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Wollaston, William Hyde

WOLLASTON, WILLIAM HYDE

(b. East Dereham, Norfolk, England, 6 August 1766; d. London, England, 22 December 1828)

chemistry, optics, physiology.

Wollaston’s family had become well known through their interests in science and theology. His great-grandfather, William Wollaston, was the author of Religion of Nature Delineated, a widely read work on natural religion published in 1724. His father, Francis Wollaston, a vicar and fellow of the Royal Society, was interested in astronomy and compiled a catalog of stars, Fasciculus astronomicus, which appeared in 1800. The famous physician William Heberden was his uncle. His father’s brother, Charlton Wollaston, who died before William’s birth, was a physician to the royal household.

William went to school at Charterhouse and in 1782 entered Caius College, Cambridge, as a medical student. There he pursued his favorite field, botany, but also studied some astronomy and, most important for his future work, became interested in chemistry. He attended the lectures of Isaac Milner, Jacksonian professor of chemistry, and performed experiments in the laboratory of his elder brother, Francis, who then held a lectureship in mathematics and who later lectured in chemistry, succeeding Milner in 1792. His interest in chemistry was also stimulated by Smithson Tennant, who was also studying medicine. William graduated in 1787 and then completed his medical studies in London. He first practiced in Hunting don in 1792, but after a few months he went to Bury St. Edmunds. He became a fellow of the Royal Society in 1793. Four years later he moved to London. In 1800, either because of his failure in a contest for the appointment of physician to St. George’s Hospital or through his dislike of the profession, he abandoned medicine and turned his attention to the other sciences. In 1802 he was awarded the Copley Medal of the Royal Society for his published papers. He became secretary of the Royal Society in 1804. As a member of numerous committees he gave advice on matters of scientific interest. He was associated with the attempts to bring uniformity into the system of weights and measures and recommended the introduction of the imperial gallon, which was accepted in 1824. Between 1818 and 1828 he was an active member of the Board of Longitude, and was particularly concerned with nautical instruments. In 1820 he was president of the Royal Society, for the interim period before Humphry Davy’s election. In 1823 he was elected foreign associate of the Académie des Sciences. Shortly before his death on 22 December 1828, he made notable donations for scientific research. He gave two thousand pounds to the Royal Society for promoting research, so initiating the Donation Fund. He also invested one thousand pounds in the name of the Geological Society, of which he had been a member since 1812. The proceeds from the first year’s income were used to cast a die for a medal bearing Wollanston’s head. The “Wollaston Medal,” first awarded to William Smith in 1832, has continued to be an annual prize of the Society.

In the same year that he left the medical profession Wollaston formed a partnership with Tennant which was to bring him fame and wealth. Tennant had traveled to Sweden and met J. G. Gahn, an adept of chemical analysis on the small scale. This may well have been the source of Wollaston’s practice of working with unusually small quantities, a distinctive feature of his chemical operations. When extent to which Wollaston had developed this art. In a letter to Gahn1 he remarked that the whole of Wollaston’s chemical apparatus consisted of no more than a few bottles standing on a small wooden board with a handle. The bottles contained the common reagents and were so stoppered that their contents could be extracted in drops. Substances were investigated on a small piece of glass. A good example of Wollaston’s small-scale chemistry was his introduction of the standard laboratory test for magnesium by the precipitation of magnesium ammonium phosphate, assisted by the scratching of a glass point.2 But his skill was best demonstrated in his important investigations on the platinum metals.

Wollaston and Tennant were both interested in platinum, which continued to resist the efforts of chemists (particularly intensive since the middle of the eighteenth century) to produce it in a satisfactory malleable state in which it might be worked. Tennant bought a large quantity of crude platinum ore, and the partners began work on the intractable metal. Tennant was soon able to announce his discovery of osmium and iridium, new elements in the crude ore; but Wollaston was the harder worker, and it was through his continuing experiments, conducted in his private laboratory, into which he was reluctant to admit anyone, that the difficult practical problem was solved.

It had become common practice to refine the crude ore by dissolving it in aqua regia and then to precipitate platinum by means of ammonium chloride, with which it forms an insoluble complex salt. To recover any platinum still in solution Wollaston added bars of iron, and treated the precipitate as before with aqua regia and ammonium chloride. Adding iron for the second time, he obtained a precipitate with unexpected properties. When it was treated with nitric acid, a red solution formed. This gave an amalgam when treated with mercury, which in turn was decomposed by heat, leaving a white metal. The new metal, which he had discovered by July 1802, he first called “ceresium” after the recently discovered asteroid. But he soon changed the name to “palladium,” after Pallas, another asteroid.

Instead of reporting his discovery openly Wollaston sent out anonymous printed notices in April 1803, describing the properties of the new metal and advertising its sale at a Soho shop. This attracted the attention of Richard Chenevix, a chemist, who suspected fraud from the way in which the discovery was announced. He bought the advertised stock and performed many experiments. In spite of his conviction that palladium was an alloy of known metals, none of his many attempts to analyze it succeeded. He claimed, however, that he had synthesized palladium by mixing a solution containing mercuric oxide and platinum in aqua regia with a solution of ferrous sulfate. When heated, this mixture produced a precipitate that fused into a button, supposedly indistinguishable from palladium, though it was in fact a compound of platinum with silicon and boron contained in the powdered charcoal used for the fusion. Chenevix concluded that palladium was an alloy of platinum and mercury. He felt he had found the key to reducing the number of the elements, whose recent rapid increase had led him to suspect their real simplicity. One critic, congratulating Chenevix, pointed out that the pursuit of alchemical transmutations was not as ridiculous as it had seemed.3Wollaston replied, again anonymously, offering a prize of twenty pounds to anyone who could synthesize palladium. The repeated failures to achieve this result soon convinced chemists that palladium was a genuine new metal. In 1804 Wollaston announced his discovery or rhodium in the crude platinum ore. Yet he withheld the identity of the discoverer of palladium until February 1805. He mentioned his fears of competing workers anticipating his discoveries, but he never fully explained his curious behavior, which according to Banks, the president of the Royal Society, had brought him into disfavor with scientists who were “open and communicative.”

It was Wollaston’s skill in working with small quantities that made possible the isolation and characterization of the new metals rhodium and palladium. For these metals are only present in platinum ore in small amounts. From one thousand grains of crude ore he had extracted five grains of palladium and four grains or rhodium. Vauquelin, who was working with much large quantities of platinum ore at the same time, thought that Wollaston’s achievement “seems at first incredible.”4

In 1805 Wollaston stated that he had at last found a way to make platinum malleable, but he gave no details of his process until shortly before his death in 1828. His paper earned him the Royal Medal of the Royal Society. No one had yet succeeded in fusing platinum in larger quantities. Previous workers had tried the effects of heat and pressure on the platinum sponge, obtained by the ignition of the complex ammonium salt. Through trial and error, and a careful attention to detail in the treatment of his material, Wollaston brought remarkable refinements to this method. His techniques included the slow thermal decomposition of the ammonium salt, the avoidance of burnishing by gently powdering the platinum sponge, sieving, and sedimentation. This process produced a uniform powder, essential to the production of malleable platinum. Impurities were removed by washing and forming a compact mass under water. The cake so formed was powerfully compressed by a toggle press. Finally the compact metal was carefully dried and forged. These details of Wollaston’s process constitute the fundamental procedures of modern powder metallurgy. His process was not immediately adopted in industry; but it was followed, at least in part, by Liebig at the Giessen laboratory.5 Today it is recognized as a standard method for producing compact metals from powder.

Wollaston sold the laboratory apparatus which he made from his malleable platinum. He drew very fine platinum wires by a process that is still used, and superintended the construction of platinum vessels for the concentration of sulfuric acid. These are the earliest platinum boilers known. They were sold to manufacturers. According to one estimate, Wollaston’s profit up to 1826 from the sale of articles of platinum and the other platinum, metals was £15,000.6

In theoretical chemistry Wollaston influenced the way in which the new atomic theory of Dalton was received. His own attitude to atomic chemistry varied remarkably between bold speculation and complete skepticism. In 1808 he described his experiments on carbonates, sulfates, and oxalates, which proved that the composition of these substances was regulated by the law of multiple proportions. These additional instances of the law were easily verifiable and were often mentioned as standard examples. Wollaston accepted that his findings were merely particular instances of Dalton’s assertion that the atoms of elements united one to one, or by some simple multiple relation. He speculated on the possible atomic composition of the oxalates of potash. With brilliant intuition he predicted that arithmetical relations between atoms would be insufficient to explain chemical combination, and that spatial considerations would have to be introduced. He stated that a compound of four particles of one type and one of another would be stable if the four surrounding particles were arranged tetrahedrally. This surmise was confirmed much later in the century with the development of the stereochemistry of the carbon atom.

Wollaston therefore appeared to accept Dalton’s theory, pointing to its possible extension. Yet already there was a hint of reservation in his statement that the “virtual extent”7 of the particles was spherical. He discussed this idea in more detail in his paper on the structure of crystals, which was read in 1812. He remarked that the existence of ultimate Physical atoms was not established and that virtually spherical particles, consisting of mathematical points surrounded by forces of attraction and repulsion, would explain the structure of crystals equally well.8 This theory of unextended point centers of force, invented by Bošković in the eighteenth century, had already interested Davy. Later Faraday would accept it in favor of the extended mass atoms of Dalton.

In 1813 Wollaston discussed the atomic theory in a way that was to have a surprisingly wide appeal. His tone was totally different from that of his earlier treatment of the subject. He complained justifiably that there was no known way to establish the numbers of atoms present in particular compounds, but he went on to say that in any case such questions were “purely theoretical” and unnecessary for practical chemistry. He therefore proposed to draw up a scale, based on the most reliable analyses available, which would express the proportions in which the common chemical substances combined. This summary of chemical facts would provide chemists with immediate answers to the routine problems of laboratory work. Referring all combinations to a standard oxygen unit of 10, he calculated the combining proportions of various substances, and distributed their names and values on a sliding rule, along a line logarithmically divided from 10 to 320. He was thus able to compute mechanically chemical proportions that before had been obtained only by lengthy multiplication and division. Chemists were not yet employing tables of logarithms for their calculations. According to Wollaston the numbers that he had given to each substance were reliable and not “warped” by the atomic theory. He called these values “equivalents.” This use of the term earlier introduced by Cavendish was unfortunate for it implied that every chemical has a fixed equivalent, an erroneous conception that persisted until Laurent, thirty years later, pointed out how chemical equivalence varies with function.

Abandoning atoms and conjectures Wollaston had attempted to strip chemistry of all but the factual content of experimental results. There appeared to remain a purely descriptive chemistry, a body of recipes for producing desired effects, summarized on an instrument. Yet this was an illusion. Chemists, particularly in England, succumbed to this apparently factual presentation. They did not detect the intrusion of hypothesis, which later prevented Comte from recognizing Wollaston’s treatment as fully positivistic, saying that it amounted to no more than a “mere artifice of language.”9 In his calculation of representational numbers Wollaston had in fact made assumptions about composition of exactly the same arbitrary nature that he had objected to in Dalton. For example he assumed that the two oxides of carbon consisted of one equivalent of carbon united to one and two equivalents of oxygen. The same hypotheses crept, apparently unnoticed, into Davy’s calculations of “proportional numbers” ; they too relied on tacit suppositions on the constitution of oxides. Like Wollaston, he presented his numbers as deduced from experiment and free from theoretical assumptions. The skepticism of Davy and Wollaston was accepted by English chemists as embodying a sound philosophy and for many years dictated their reactions to Dalton’s theory. A typical statement came from William Brande, who welcomed Wollaston’s treatment of chemistry as “divested of all hypothetical aspect.”10 One fellow of the Royal Society objected that Wollaston and not Dalton should have been given the Royal Medal, for he had done for the atomic theory what Watt had done for the steam engine: he had rendered it useful.11 Perhaps the clearest indication of Wollaston’s influence appeared in the new Chemical Dictionary of Andrew Ure, containing the entry “Atomic Theory. See Equivalents (Chemical).”12 Wollaston’s “equivalents” continued to be used in this sense until the middle of the century. Chemists were convinced that equivalents expressed the unalterable facts of chemical proportions. Reluctant to introduce theories of matter into their science, or to accept calculations of atomic weights (Berzelius conceded these were based on unproved suppositions of atomic constitution and were therefore subject to revision), they felt the language of equivalents was safest. This circumstance accounts for the preference later given to Gmelin’s equivalents over Berzelius’ system of atomic weights. There was even a tendency to use “equivalent” and “atom” synonymously. According to this usage, “atom” synonymously. According to this usage, “atom” was regarded as a convenient alternative to “proportion” or “equivalent,” and carried on theoretical implications. It was left for later generations of chemists to distinguish between equivalents, atoms, and molecule, and to show how atomic weights could be unambiguously determined.

Wollaston’s chemical slide rule, in some form, was in general use in laboratories for over twenty years. The instrument was reportedly sold in the bookstores of New York and Vienna. Schweigger, the editor of the Journal für Chenzie und Physik, reproduced two copies of Wollaston’s scale in one issue, so that one copy could be cut out and pasted on a slider.13 Berzelius said that he used the instrument constantly. Faraday, in his practical manual, described it as a commonly used calculating device.14 But the instrument began to fall into disuse around 1840 on account of the increasing demands for more accurate calculations. In 1842 Thomas Graham said that Wollaston’s instrument was “not of much practical value” and gave instead the logarithms of atomic weights.15

In 1822, in spite of his earlier firm skepticism, Wollaston returned by a most unusual route to the full acceptance of Dalton’s theory. With startling boldness he asserted that conclusive tests on the existence of atoms could be made through the observation of planets. He argued that the particles of the atmosphere of the earth were subject to the opposing forces of their mutual repulsion and gravity. If there were a limit to the divisibility of atmospheric matter, The weight of these ultimate particles would prevent further atmospheric expansion. But if matter were endlessly divisible into lighter and lighter particles, the force of repulsion would overcome gravity. Then the atmosphere of the earth would not terminate at a finite height, but would expand freely into celestial space and collect about the planets through gravitational attraction. Wollaston therefore believed that the classical problem of the divisibility of matter could be decided by a crucial test in astronomy. In May 1821 Venus was passing very close to the sun in superior conjunction. He carefully followed the path of the planet with a small telescope. He was unable to detect any apparent retardation in the motion of Venus that might be attributable to refraction by the solar atmosphere. He added that Jupiter possessed no sensible atmosphere, since the occultation of its satellites was also unretarded. He was in no doubt that the atmosphere of the earth was of finite extent. Therefore he concluded that it was composed of ultimate atoms. He argued that since the laws of definite proportions were true for all kinds of matter, not just the elastic atmosphere but all substances could be regarded as composed of indivisible atoms. He asserted that the equivalents of chemistry really did express the relative weights of atoms, but curiously he made no mention of the problem, which had earlier troubled him, of estimating the numbers of atoms that entered into combination.

There was a surprising delay before the weakness of Wollaston’s logic was exposed. Meanwhile the popular expositions of the atomic theory given by Turner and Daubery accepted the attractive new argument as a clear proof of atomism. Graham pointed out that the atmosphere of the earth could be limited simply through condensation at low temperatures and that Wollaston’s explanation in terms of atoms was unnecessary.16 But it was not realized until much later that Wollaston had put forward a circular argument.17 He had assumed from the start that if there were atmospheric particles of limited divisibility, these must be the ultimate Daltonian atoms that participated in chemical change; but the particles of oxygen and nitrogen in the atmosphere need not be monatomic. The carbon dioxide and water vapor of the atmosphere were clearly not chemically simple particles. In fact, the height of an atmosphere is controlled by the weight of polyatomic molecular particles, and by the temperature.

In general, chemists did not share Wollaston’s concern to test the divisibility of matter. They were content to deal with combining weights as they found them, without speculating on their further divisibility outside of chemistry. Wollaston’s paper continued to be referred to in connection with the existence of a universal ether.18

Some of Wollaston’s best work was in crystallography, another field of study intimately connected with the structure of matter. The fundamental laws of crystallography had been discovered toward the end of the eighteenth century. In part this was the work of Haüy, who had created a system of crystallography in a spirit of mathematical idealism. It was a problem for Haüy’s contemporaries to determine how far the details of his thought, inspired by a belief in the simplicity of nature, were representative of reality. Haüy had constructed algebraic formulas that related the various occurring crystalline forms of a given substance to the primitive form, which could be extracted by mechanical cleavage from each of them. For example, the primitive form of calcium carbonate was a rhomboid, which could be extracted from the secondary forms with hexagonal and pentagonal faces by appropriate cleavages. Once the dimensions of the primitive form were known it was possible to deduce the angles of any related secondary form. Where the primitive form was a regular solid, such as the cube, the required dimensions could be inferred from considerations of symmetry; but with less regular forms such as the obtuse rhomboid the dimensional ratios had to be calculated from measurements of angles. This was approximately performed by the contact goniometer, which consisted of a hinged pair of arms attached to a protractor. It was difficult to make the arms coincide with the crystal faces, and Haüy never claimed an accuracy beyond twenty or thirty minutes of arc. Within this wide margin afforded by approximate measurement, Haüy was able to consider various possible dimensional ratios and select those that most satisfied his metaphysical beliefs. He asserted that the dimensions of the regular solids, which were correctly expressed as ratios of square roots of small integers, reflected Nature’s simplicity. This, he argued, must be discernible in the irregular forms also. Accordingly, in his discussion of these he chose the simplest possible ratios consonant with measurement, and then adjusted the angles, by calculation.

In 1809 Wollaston described his newly invented reflective goniometer, which allowed a far greater accuracy in the measurement of crystals. It consisted of a graduated circle, vertically fixed on a horizontal axle. The crystal was attached by wax to a small leveling device joined to the axle. An object was viewed by reflection in one face of the crystal, and then the crystal was rotated until the same object appeared in the adjacent face. The angle through which the graduated circle had moved was read off. This procedure gave the angle of the crystal to the nearest five minutes. In this way Wollaston showed the angle of rhomboidal calcium carbonate to differ by over thirty minutes from that given by Haüy. He detected even greater discrepancies in other carbonates, but if he had shown the way he was not prepared to carry out the extensive determinations needed to correct Haüy’s data. Doing so was largely the work of William Phillips, a printer and bookseller, whom Wollaston had instructed in the use of his instrument. Employing the new goniometer with graduations of half-minutes, Phillips compiled the most accurate body of crystal data that had hitherto existed. The results showed that Haüy’s values for the irregular primitive forms, based on conceptions of simplicity, were incorrect. By 1824 several continental authorities, including Mohs and Mitscherlich, had rejected Haüy’s data. It was fitting that John Herschel later mentioned Wollaston’s goniometer as an illustration of the influence of instrumentation on the progress of science.19 The modern goniometer is the result of extensive refinements of Wollaston’s original design.

Haüy had concluded, from the polyhedral fragments produced in cleavage, that the crystal kingdom was constructed from three molecular forms: the tetrahedron, the triangular prism, and the parallelepiped. His conclusions were criticized by others, including Wollaston, who objected that a stable crystal could not result from such arrangements as the grouping of tetrahedral particles hanging together at their edges. Regarding this as precarious masonry, Wollaston in 1812 proposed alternative spherical crystal units, joined together as closely as possible by mutual attraction. His close-packed formations of triangularly arranged spheres imitated the commonly occurring crystal forms. From a rhomboid of spheres, tetrahedral groups of spheres could be removed, leaving an octahedron. This accounted for the cleavage of rhomboidal fluorspar. Wollaston was surprised to learn that the beginnings of his theory were to be found in the thirteenth observation of Hooke’s Micrographia. He also constructed other forms from spheroids, earlier considered by Huygens. The most original part of his theory concerned the cubic form. He explained this in terms of two different kinds of sphere, which he referred to as “black and white balls,” so arranged that each black ball was equidistant from all surrounding white balls; balls of the same type were also equidistant from each other. This produced a cube from two interpenetrating tetrahedra. In the twentieth century the lattice structure of sodium chloride was shown to be of this type; but in 1812 Wollaston’s theory was an unverifiable speculation.

The most enthusiastic supporter of Wollaston’s theory was John Daniell, professor of chemistry at King’s college, London. He brought forward variours arguments, none of which was successful, to show that this theory was the only one that would explain the facts of crystallography. For example, he tried to interpret his observations on crystal etching in this way. Etched forms are indicative of crystal symmetry, but they could not have provided the crucial data on internal structure that Daniell believed he had found. The American mineralogist James Dana also adopted Wollaston’s spheres and spheroids but grouped them differently according to supposed discrete polarities. This development represented some steps toward the conception of the space lattice.

Discussions of the type initiated by Haüy and Wollaston were not favorably received in the early nineteenth century. At the time crystallography was largely concerned with the geometrical treatment of external symmetry. The important physical study of internal structure was not revived until the middle of the century. Wollaston’s speculations provided an early example of how, in the absence of direct experimental investigation, remarkably close approximations to the actual internal structure of crystals could be derived through the arrangement of spheres.

The mineral wollastonite was named by a French admirer of Wollaston’s work in crystallography.20

A large part of Wollaston’s published work was devoted to optics, notably in the design of instruments. His early papers on atmospheric refraction discussed the phenomena of the mirage. His theoretical treatment was muddled and made no advance on existing theories, which had similarly exaggerated the effects of water vapor. But his imitation of the phenomena by mixing liquids of different density was frequently referred to.21 Further, his own careful observations across heated surfaces and description of a mirage, which he was surprised to observe while sitting in a boat near Chelsea, provided Biot with data for his mathematical treatment of the phenomenon.22 Wollaston was particularly interested in such irregular refraction for the difficulties it created in navigation. Altitudes were taken with reference to the horizon, and the necessary dip correction was difficult to assess in cases of unusual refraction close to the horizon. He therefore designed a dip sector, a modified sextant, which allowed the dip to be measured by simultaneous observation of opposite points of the horizon. The commissioners of the Admiralty directed Ross, and later Parry, to make observations on the dip of the horizon during their arctic voyages, taking with them Wollaston’s instrument.23 But they reported that the dip sector was of limited use, since the atmospheric conditions were not uniform on the opposite sides of the horizon. Wollaston Island, in Baffin Bay, was named for him by Ross; it was the first of several arctic christenings in his honor.24

In 1802 Wollaston introduced the important method of determining refractive indices by total internal reflection. The alternative method of minimum deviation, however, continued to be used in the early part of the century. His observations on an impure spectrum led him to conclude that there were only four colors in the solar spectrum. This influenced Thomas Young, who was led by it to alter his own theory of color vision. At the same time Wollaston discovered the dark lines in the solar spectrum, later to be known as Fraunhofer lines. Also in 1802 he presented convincing experimental support for Huygens’ wave theory. Using the technique he had invented, he measured the refractive index of Iceland spar in different directions and showed that for different planes of incidence the extraordinary ray was refracted exactly as Huygens’ theory predicted. He did not commit himself, however, to a firm statement of belief in the wave theory. This later brought Wollaston charges of timidity and undue caution; but there was no reason why he should have gone further, particularly since Young’s impressive evidence had not yet appeared.

In 1803 he described his “periscopic spectacles,” designed to allow clear vision in oblique directions. He substituted meniscus lenses for the generally used biconvex and biconcave forms. Contemporary opticians were mistaken in supposing the elimination of spherical aberration to be the prime consideration in the design of spectacles. As Wollaston correctly pointed out, the eye looks through only a small part of the lens at any instant, and the chief requirement is sharp vision in all directions. Meniscus lenses had been recommended since the seventeenth century. It is uncertain to what extent Wollaston’s spectacles were used; the general introduction of meniscus spectacles did not occur until after the work of F. Ostwalt at the close of the nineteenth century.

In 1807 Wollaston described his camera lucida, a quadrilateral glass prism, which by two total internal reflections sent horizontal rays from an object vertically upward into the eye viewing above the prism. This device was widely used as an aid in drawing.25 It was also commonly attached to the eyepiece of microscopes for sketching images. He also improved the camera obscura by introducing a meniscus lens and an aperture, so reducing the curvature of image of a laterally extended object. In this form it was employed as an early camera by Niepce and Daguerre.

His well-known microscopic doublet was described posthumously. Dissatisfied with the performance of the compound microscope, which was soon to receive essential improvements from Lister, Wollaston proposed the use of a combination of two planoconvex lenses to reduce the aberration of the simple microscope. This suggestion had been occasionally adopted since the seventeenth century, and more recently John Herschel had worked out formulas for the aberration of spherical surfaces in combination. But Herschel’s suggestion of a biconvex lens combined with a concavo-convex type presented difficulties in grinding. Wollaston’s doublets were easier to make, particularly since two surfaces were plane. The improved resolution impressed workers and led to further developments. A diaphragm was placed between the lenses, and triplet combinations were introduced. While there were continuing attempts to improve the compound microscope, the simple microscope, improved through Wollaston’s suggestions, continued to be used. His improvements in illumination, involving the reduction of glare by a type of field stop, were also adopted.

Although he left the medical profession Wollaston continued to be interested in physiology. In 1797 he characterized the principal constituents of urinary calculi, and in 1812 identified a new and rare type of stone, which he called “cystic oxide” since it occurred in the bladder. This was later renamed cystine, the first of the amino acids to be discovered. Fourcroy and Vauquelin reported similar investigations, but unaccountably gave no recognition to Wollaston. This led Alexander Marcet, a physician, to set matters right in a popular work dedicated to Wollaston, his friend.26

In his Croonian lecture of 1809 Wollaston stated for the first time the vibratory character of muscular action. He had been led to this discovery by considering the sound heard when a finger is put in the ear, which he compared to the sound of distant carriages. He reproduced the sound by rubbing a pencil over notches on a board and thus determined the frequency of the vibration. With one finger against his ear he found the number of notches which the pencil had to pass over in five seconds to produce the same sound. His value of 20–30 vibrations per second was later shown by Helmholtz to be the first overtone of the fundamental frequency of muscular murmur.

In 1811 he announced that in spite of the known presence of sugar in the urine of diabetics he had failed to detect it in the blood taken from victims of this disease. He adopted the eccentric theory, proposed by Charles Darwin (d. 1778), the son of Erasmus Darwin, that there existed an unknown route between the stomach and bladder, allowing the sugar to avoid the blood and pass directly into the urine. The failure to detect the sugar was due to the use of stale specimens. Claude Bernard later pointed out that quick tests on fresh serum were essential, since sugar is unstable in blood.

In 1820 Wollaston read an interesting paper on the physiology of the ear. Hiding in the library of Sir Henry Bunbury he had produced high notes from pipes and looked to see which of the company present had heard them. He discovered that there was a sharply defined upper limit to audibility and that this varied noticeably with the individual. He also speculated that some insects might communicate by high notes inaudible to humans. His correct conclusions were challenged by the French authority Savart, who erroneously stated that the inaudibility of the high notes was due, not to their frequency, but to their low intensity.

In 1824 Wollaston discussed a traditional problem in physiology, that of binocular vision. In the eighteenth century it had been debated whether this faculty of combining two images was inherited or acquired. Newton had argued for the former possibility in the fifteenth query of his Opticks, postulating an arrangement of the optic nerves in which corresponding points of the retinas were connected by nerve fibers that joined before entering the brain. The same theory was proposed by Wollaston, who supposed it to be new. The intricate structure of the human chiasma was still not known. Wollaston was led to adopt the correct arrangement of “semi-decussation,” also given by Newton, as a result of his experiences of hemianopia, a disease in which there is a loss of sight in symmetrical parts of each eye. This relation of hemianopia to semi-decussation had also been noticed before; but Wollaston’s was the fullest description of the disease that had yet appeared. As a theory of binocular vision it was opposed by those who favored alternative nervous arrangements in the chiasma, and by those who continued to insist that an explanation in terms of acquisition was required. The invention of Wheatstone’s stereoscope emphasized the psychological character of binocular vision which had been ignored in the physiological explanations of Newton and Wollaston.

Wollaston and Humphry Davy both died within a few months of each other. It became common to contrast the soaring poetic imagination of Davy with the cautious approach of Wollaston. It is clear from his letters to Young that Wollaston warned against speculation and advised staying close to the facts. It is equally clear from his work that he did not practice what he preached. George Peacock, the Victorian biographer of Young, said of Wollaston that “posterity is not likely to maintain the same high estimate of his powers which was made by his contemporaries,”27 There is growing evidence that this prediction will not stand.

NOTES

1.Jac. Berzelius Bref, H. D. Söderbaum, ed, IV, pt, 9 (Uppsala, 1912–1941), p. 73.

2. W. Saunders, A Treatise on the Chemical History and Medical Powers of Some of the Most Celebrated Mineral Waters, 2nd ed. (London, 1805), 391–392.

3. “Inquiries Concerning the Nature of a Metallic Substance. Lately Sold in London . . .,” in Edinburgh Review, 4 (1804), 168.

4. N. Vauquelin, “Mémoire sur le palladium et le rhodium,” in Annales de chimie, 88 (1813), 170.

5. J. Pelouze, “Note sur la fabrication du platine,” in Annales de chimie et de physique, 62 (1836), 443–444.

6. L. F. Gilbert, “W. H. Wollaston MSS at Cambridge,” in Notes and Records of the Royal Society, 9 (1952), 326.

7. Wollaston, “On Super-acid and Sub-acid Salts,” in Philosophical Transactions of the Royal Society, 98 (1808), 101.

8. Wollaston, “The Bakerian Lecture, On the Elementary Particles of Certain Crystals,” ibid., 103 , (1813) 61.

9. A. Comtse, Course de philosophie positive, III (Paris, 1830–1842), 149.

10. “Proceedings of the Royal Institution,” in Quarterly Journal of Literature, Science and the Arts, 21 (1826), 109–110.

11. “On the Recent Adjudgment of the Royal Medals . . .,” ibid., 1 (1827), 15.

12. A. Ure, A Dictionary of Chemistry (London, 1821).

13. “Synoptische Scale der chemischen Aequivalente,” in Journal für Chemie und Physik, 12 (1814), 105.

14. Faraday, Chemical Manipulation (London, 1827), p. 551.

15. T. Graham, Elements of Chemistry (London, 1842), 117, 1071.

16. T. Graham, “On the Finite Extent of the Atmosphere,” in Philosophical Magazine, 1 (1827), 107–109.

17. G. Wilson, “On Wollastons’s Argument From the Limitation of the Atmosphere, as to the Finite Divisibility of Matter,” in Transactions of the Royal Society of Edinburgh, 16 (1849), 79–86.

18. A. V. Humboldt, Kosmos, III (Stuttgart-Tübingen. 1845–1862), p. 52.

19. J. F. W. Herschel, Preliminary Discourse on the Study of Natural Philosophy (London, 1833), p. 354.

20. S. Léman, “Meionite,” in Nouveau dictionnaire d’historie naturelle, XX (Paris, 1816–1819), 28–31.

21. A similar treatment is given in the fifty-eighth observation of Hooke’s Micrographia.

22. J. Biot, “Recherches sur les réfractions extraordinaires,” in Mémoires de l’Institut national des sciences et arts, 10 (1810), 6–7.

23. J. Ross. A Voyage of Discovery . . . (London, 1819), pp. xviii, 10, app.

24.Ibid., p. 206.

25. B. Hall, Forty Etchings From Sketches Made with the Camera Lucida in North America in 1827 and 1828 (Edinburgh-London, 1829).

26. A. Marcet, An Essay on the Chemical History and Medical Treatment of Calculous disorders (London, 1817).

27. G. Peacock, Life of Thomas Young (London, 1855), p. 470.

BIBLIOGRAPHY

I. Original Works. In 1949 a collection of Wollaston’s notebooks was discovered in the Department of Mineralogy and Petrology, Cambridge. A report containing the essential new information is L. F. Gilbert, “W. H. Wollaston MSS. at Cambridge,” in Notes and Records of the Royal Society of London, 9 (1952), 311–322. There are also some of his notes and letters in the Science Museum, London, concerning his work on the production of rhodium alloys, platinum wires, and boilers. Additional information on the controversy over palladium is contained in the letters between Chenevix and Banks in volumes XIV and XV of the Dawson Turner copies of the Banks correspondence. Natural History Museum, London, Wollaston’s activities on the Board of Longitude are recorded in the minutes on the board at the Royal Greenwich Observatory, Herstmonceux Castle, Sussex. The Royal Society possesses some of Wollaston’s letters to Thomas Young, in which he stated his reluctance to speculate. One of these has been published in D. Turner, “Thomas Young on the Eye and Vision,” in Science, Medicine and History, E. A. Underwood, ed., II (Oxford, 1953), 251. Other letters, in which he commented on the wave theory of light, can be found in T. Young, Miscellaneous Works G. Peacock, ed., I (London, 1855), 233, 261.

Wollaston’s published scientific work appeared in the journals. The list given in the Royal Society Catalogue of Scientific Papers is almost complete. The following are not mentioned there: “On Gouty and Urinary concretions,” in Philosophical Transactions of the Royal Society, 87 (1797), 386–400; “Report from the Select Committee on Weights and Measures,” in parliamentary Papers, 3 (1813–1814), 140–141; and “Instructions for the Adjustments and Use of the Instruments Intended for the Northern Expeditions,” in Journal of science and the Arts, 5 (1818), 233–26. some interesting information on the background of Wollaston’s work was related by a close acquaintance, the Reverend H. Hasted, in his “Reminiscences of Dr. Wollaston,” in Proceedings of the Bury and West Suffolk Archaeological Institute, 1 (1849), 121–134.

II. Secondary Literature. No satisfactory study of Wollaston’s work as a whole has yet been published. A discussion of his work on the platinum metals is included in D. Mc. Donald’s excellent A History of Platinum from the Earliest Times to the Eighteen-eighties (London, 1960). Useful as general introductions to nineteenth-century crystallography are L. Sohncke, Entwickelung einer Theorie der Krystallstruktur (Leipzig, 1879), pp. 5–18; and P. H. von Groth, Entwickelungsgeschichte der Mineralogischen Wissenschaften (Berlin, 1926). Wollaston’s work in crystallography has been discussed in D. C. Goodman,. “Problems in Crystallography in the Nineteenth Century,” in Ambix, 16 (1969), 152–166. For his fluctuating views on atoms, see D. C. Goodman, “Wollaston and the Atomic Theory of Dalton,” in Historical Studies in the Physical Sciences, 1 (1969), 37–59. Wollaston’s meniscus lenses have been discussed by M. V. Rohr, who states that Wollaston’s spectacles were sold in Vienna by Voigtänder. See his “Der grosse Streit bei des Einführung des periskopischen Brillengläses,” in Central-Zeitung für Optik und Mechanik, 43 (1922), 490–491; “Contributions to the History of English Opticians in the First Half of the Nineteenth Century (With Special Reference to Spectacle History),” in Transactions of the Optical Society, 28 (1926–1927), 117–144; and “Meniscus Spectacle Lenses,” in British Journal of Physiological Optics, 6 (1932), 183–187. Another useful article is H. C. King. “The Life and Optical Work of W. H. Wollaston,” in British Journal of Physiological Optics, 11 (1954), 10–31. A Herschel MS, which tells of the intrigues involving Wollaston in the election of a successor to Banks, has been discussed in L. F. Gilbert, “The Election to the Presidency of the Royal Society in 1820,” in Notes and Records of the Royal Society, 11 (1955), 256–279.

D. C. Goodman

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Wollaston, William Hyde

WOLLASTON, WILLIAM HYDE

(b. East Dereham, Norfolk, England, 6 August 1766;

d. London, 22 December 1828), metallurgy, chemistry, optics, instrumentation, physiology. For the original article on Wollaston see DSB, vol. 14.

Research since the 1970s has drawn heavily on the original laboratory notebooks, letters, and documents held by Cambridge University Library to reveal much new information about Wollaston’s unhappy career as a physician, his business partnership with Smithson Tennant, and their entrepreneurial activities in the production and marketing of malleable platinum and organic chemicals. In addition, a more complete understanding has been gained of Wollaston’s influential role in the development of atomistic thinking, his methods of scientific research, and his reports of the visual disturbances known as hemianopsia.

Francis Wollaston married Althea Hyde in 1758, and over the years 1760–1778 they had seventeen children, of which fifteen survived into adulthood; William was the seventh child and third son. Francis was made rector of East Dereham, Norfolk, in 1761 but relocated to Chisle-hurst, Kent, as rector in 1769; the family continued to reside there until his death in 1815. William received his early education at Lewisham and Charterhouse before moving to Caius College, Cambridge, in 1782 to study medicine.

An Unhappy Physician. As described in the main article, Wollaston qualified as a physician and began his practice in Huntington in 1792, but within a few months he relocated to Bury St. Edmunds, where his uncle Charleton had practiced three decades previously. In 1797 he moved his practice to Cecil Street in London, where another uncle, the famed clinician William Heberden, had begun forty years earlier. By the time he left Bury, William had gained the necessary experience and maturity and seemed destined to advance his reputation in the capital. But he was miserable. In a letter to his lifelong Bury friend Henry Hasted, Wollaston wrote that “the practice of physic is not calculated to make me happy … [and] I have fully determined & now declare that I have done with it. … even if I turn waiter at a tavern ready to say “Yes Sir” to everyone that calls at any hour of the day or night, I cannot be a greater slave” (29 December 1800, Hasted correspondence, University College Library).

It is now known how Wollaston was able to escape his unhappy profession. His uncle West Hyde had died in 1797 and, without surviving children of his own, willed his considerable estate to his sister Althea’s second-oldest son, George. In March 1799 George transferred £8,000 in Bank of England stock to William, who decided that he would use the money to establish a chemical business in secret partnership with an older Cambridge schoolmate and fellow London resident, Smithson Tennant. Tennant was the antithesis of Wollaston in many ways; he was parentless, eccentric, gregarious, and undisciplined but a competent chemist with ideas on how to make a living by converting abundant, low-cost materials into high-value commercial products.

Chemical Business. Tennant and Wollaston began their entrepreneurial activities with the purchase of nearly 6,000 troy ounces of granular alluvial platinum ore in December 1800 at a cost of £794. The two men had decided to keep all aspects of their partnership and research interests secret; not even their closest friends knew of the partnership, and details have only become known by study of the Cambridge notebooks. Evidence in the notebooks suggests that Wollaston assumed responsibility for the research and development side of the business while Tennant was to look after marketing and sales. In November 1800 Wollaston optimized the chemical process for the production of a purified platinum powder that he was able to compact into a solid, malleable mass in April 1801. Then, confident of commercial success, Wollaston purchased a house on the outskirts of London and converted its rear rooms into a large chemical laboratory.

Wollaston and Tennant knew that commercial production of malleable platinum had the potential to be a lucrative business, but only if they could secure access to the crude ore (then available only from the Spanish-controlled viceroyalty of New Granada and legally only through Spain) and protect the chemical and metallurgical details of the production process. They achieved these ends by committing to buy all platinum ore that became available in Kingston, Jamaica, after being smuggled out of New Granada, and by imposing rigorous security on Wollaston’s production process (Usselman, 1980, 1989). Over a period of twenty years Wollaston, assisted only by his manservant, processed more than 47,000 troy ounces of crude platinum ore in a series of 16-to-30-ounce batches. Malleable ingots of platinum were sold for seventeen shillings per ounce by the London instrument maker William Carey, who received a 10 percent commission for his role (Chaldecott, 1979). The finest-quality platinum was used primarily for chemical apparatus, but the biggest markets were the gunnery business, where platinum replaced gold in the touchholes of firearms, and the sulfuric acid industry, where platinum boilers were used for the concentration of the corrosive acid. Total profits from the platinum business totaled about £17,000 by the time Wollaston closed down the business in 1820. Wollaston, who did all the processing work and even ended up superintending most of the marketing due to Tennant’s increasing lack of focus, received 10 percent of the profits before equal division.

As Wollaston purified thousands of ounces of platinum, he accumulated large amounts of chemical byproducts. Wollaston gave the portion of the ore insoluble in aqua regia to Tennant for investigation (the discovery of osmium and iridium followed in 1804), and he himself studied the portion of the ore that remained in solution after platinum had been precipitated from acidic solution. In 1802 he isolated and characterized the new metal palladium, which was present in the original crude ore in amounts of less than 1 percent. Wollaston was credited by his contemporaries as a chemical wizard for discovering an element so scarce in natural ores; they did not know that he was working with large amounts of ore much enriched in palladium, and Wollaston did not correct them. But his need to keep his platinum work secret created a dilemma. He wished to publicize his discovery of a new chemical element and stake a claim to his priority, but he believed an honest account of the discovery process would draw others into platinum purification while he was slowly and tediously building up a supply of the metal for first sale in 1805. He decided to offer palladium for sale anonymously through a mineralogical shop with the consequences described in the main article (also Usselman, 1978). Chastened by the unfavorable publicity this mode of action occasioned, Wollaston announced his 1804 discovery of a second new element, rhodium, in an article in the Philosophical Transactions of the Royal Society, although without clues to the enabling platinum work.

Although Wollaston has been criticized for keeping the details of his platinum purification process secret, the strategy was a sound one. No one else was able to market platinum of Wollaston’s quality until his process was published shortly before his death—it had been generally and erroneously believed that some unknown chemistry was the key to success. It is now understood why Wollaston restricted access to the rear of his house, where the furnaces, glass vessels, and chemicals were spread along benches; guests with an interest in chemistry were shown only portable equipment for chemical analysis in an anteroom.

Contributions to the Atomic Hypothesis. Wollaston and Tennant also hoped to convert the dregs left behind by wine production, known as argol (containing a large proportion of tartaric acid salts), into higher-value organic acids. As with the platinum work, Wollaston did all the exploratory chemistry and from 1802 until 1812 converted about 15,000 pounds of crude argol into tartaric acid, oxalic acid, and salt of sorrel (acid potassium hydrogen oxalate), all for subsequent sale. The organic business was even more labor-intensive than the platinum work and, when brought to a halt on Tennant’s death in 1815, had netted the partners a profit of only £700. Although not financially lucrative, the work did draw Wollaston into a study of the composition of tartaric and oxalic acid salts and examples of multiple combining proportions. In 1803 and 1804 Wollaston found that potash could form three different salts with oxalic acid, and the amounts of acid relative to a fixed weight of base in the salts were in the ratio of 1:2:4. After reading the account of John Dalton’s atomic hypothesis in Thomas Thomson’s 1807 edition of A System of Chemistry, and learning of Thomson’s forthcoming paper in the Philosophical Transactions on multiple proportions in two salts of oxalic acid, Wollaston quickly prepared his paper “On Super-Acid and Sub-Acid Salts” to follow Thomson’s in early 1808. Wollaston recognized that the law of integral multiple proportions was a logical consequence of atom-to-atom combination, and he accepted Dalton’s hypothesis as an adequate explanation. Wollaston’s paper gave further examples of multiple proportions in the salts of carbonic and sulfuric acids and procedures for determining the ratios. Near the end of the paper (and confounding the mistaken view of him as a cautious thinker) Wollaston proposed that after the combination of atoms became better understood “we shall be obliged to acquire a geometrical conception of their relative arrangement in all the three dimensions of solid extension” (1808, p. 101). Wollaston’s examples (coupled with his reputation for careful and correct analysis) gave atomic theory heightened credibility.

In later papers that involved atomistic ideas Wollaston was consistent in his acceptance of material atoms as the best available explanation for a wide range of chemical phenomena. However, until some mode of investigation could give concrete evidence of the reality of atoms, he believed that experimental results ought not be skewed to fit the hypothesis. Thus although he explained crystal structures by the ordered packing of particulate spheres and oblate spheroids, he admitted that point-centered force fields of similar peripheral extent could yield the same result, and although combining weights were consistent with atom-to-atom combination they were not incontrovertible evidence for material atoms. Wollaston was not so much an early positivist as he was someone willing to entertain multiple hypotheses until the experimental superiority of one of the contenders became compelling. And he believed he provided that evidence for atomic theory with his paper on the finite extent of the atmosphere in 1822.

Wollaston’s interest in the visual disturbance known as hemianopsia emanated from his own episodes of visual problems. In 1800 he lost the left half of his visual field in both eyes for several minutes, and in 1822 he temporarily lost the right half of his vision. Wollaston correlated these afflictions with the upset stomachs and headaches suffered by others who reported similar occurrences, a grouping of symptoms now known to be associated with migraine. That Wollaston suffered from migraine is substantiated by an 1828 notebook record of zigzag lines in his visual field, an early record of the “fortification spectra” that George Airy later connected with migraine. Although Wollaston’s death from a brain tumor was confirmed by a postmortem examination, his earliest visual problems were likely unrelated to that lesion.

Character. Comments written by his closest friends and associates portray Wollaston as a publicly quiet and austere figure who treasured uninterrupted time to pursue his scientific interests. But when in the frequent company of friends, family, children, and the genuinely and unaffectedly curious, he became sociable, generous, warmhearted, informative, and occasionally even mischievous. Unfortunately the most reliable contemporary portraits were removed from the public record by Henry Warburton, who collected all of Wollaston’s notebooks, letters, and memorials after his friend’s death, kept them out of others’ hands, and died without publishing a planned biography. Until the Warburton material was rediscovered in Cambridge in 1949, Wollaston’s historical persona had been shaped by a sprinkling of anecdotes told by a few contemporaries who did not know him well, and his reputation suffered as a result. However, subsequent research has begun to corroborate the opinion of many of his contemporaries, who judged Wollaston to be the leading natural philosopher of his time.

SUPPLEMENTARY BIBLIOGRAPHY

The L. F. Gilbert papers at University College Library, London, contain several original letters to and from Wollaston, together with typed copies of important correspondence between Wollaston and Henry Hasted, and Wollaston and Alexander Marcet. Another valuable series of letters from Wollaston to Edward Daniel Clarke is held in private hands.

WORKS BY WOLLASTON

“Reward of Twenty Pounds for the Artificial Production of Palladium.” Journal of Natural Philosophy, Chemistry and the Arts 7 (1804): 75.

“On Super-Acid and Sub-Acid Salts.” Philosophical Transactions 98 (1808): 96–102.

“Extract of a Letter from Dr. Wollaston.” Annals of Philosophy 2 (1813): 316.

“Letter from W. H. Wollaston … Together with a Report of Mons. Biot. … upon Periscopic Spectacles.” Journal of Natural Philosophy, Chemistry and the Arts 36 (1813): 316–321; also in Philosophical Magazine 42 (1813): 387–390.

“Crimson-Coloured Snow, and Meteoric Iron.” Appendix iii in John Ross, A Voyage of Discovery … for the Purpose of Exploring Baffin’s Bay. London: J. Murray, 1819.

PATENTS

1804, No. 2752. “Spectacles,” for concavo/convex spectacle lenses.

1806, No. 2993. “Drawing Apparatus,” for the camera lucida.

OTHER SOURCES

Chaldecott, John A. “William Cary and His Association with William Hyde Wollaston.” Platinum Metals Review 23, no. 3 (1979): 112–123.

Coatsworth, L. L., B. I. Kronberg, and M. C. Usselman. “The Artifact as Historical Document. Part 2: The Palladium and Rhodium of W. H. Wollaston.” Ambix 28, no. 1 (1981): 20–35.

Kronberg, B. I., L. L. Coatsworth, and M. C. Usselman. “Mass Spectrometry as an Historical Probe: Quantitative Answers to Historical Questions in Metallurgy.” In Archaeological Chemistry–III, edited by Joseph B. Lambert, 295–310. ACS Advances in Chemistry Series no. 205. Washington, DC: American Chemical Society, 1984.

McDonald, Donald, and Leslie B. Hunt. A History of Platinum and Its Allied Metals. London: Johnson Matthey, 1982.

Usselman, Melvyn C. “The Platinum Notebooks of William Hyde Wollaston.” Platinum Metals Review 22, no. 3 (1978): 100–106.

———. “The Wollaston/Chenevix Controversy over the Elemental Nature of Palladium: A Curious Episode in the History of Chemistry.” Annals of Science 35, no. 6 (1978): 551–579.

———. “William Wollaston, John Johnson, and Colombian Alluvial Platina: A Study in Restricted Industrial Enterprise.” Annals of Science 37, no. 3 (1980): 253–268.

———. “Merchandising Malleable Platinum: The Scientific and Financial Partnership of Smithson Tennant and William Hyde Wollaston.” Platinum Metals Review 33, no. 3 (1989): 129–136.

———. “William Hyde Wollaston’s Platinum Process: The Bicentenary of the Platinum Industry.” Chemistry in Britain(December 2001): 38–40.

Melvyn C. Usselman

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Wollaston, William Hyde

William Hyde Wollaston, 1766–1828, English scientist, M.D. Cambridge, 1793. His wide-ranging scientific achievements include the discovery (1802) of the dark lines (Fraunhofer lines) in the solar spectrum; invention of the reflecting goniometer (an instrument by which the angles of crystals are measured) and of the camera lucida; a method of making platinum malleable; the discovery of the elements palladium (1803) and rhodium (1804); and establishment of (1801) the equivalence of galvanic and frictional electricity. He created an endowment with the Wollaston medal to be awarded annually by the Geological Society, London, for outstanding research. Wollastonite, a mineral compound of calcium, silicon, and oxygen, was named in his honor.

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