SOME EARLY PUBLICATIONS ON PHOSPHORUS WILHELM PRANDTL University of Munich, Munich, Germany (Translated by Ralph E. Oesper, University of Cincinnati)
T h e discovery of phosphorus by Henning Brand in Hamburg and its preparation by Kunckel and by Boyle have been discussed often and a t length. THISJOURNAL has published papers on this topic by Davis1 and by week^.^ Accordingly, there has been ample opportunity to become acquainted with the early history of phosphorus. However, the first printed documents regarding this important and successful discovery seem never t o have been published. The purpose of this paper is to fill this gap, a t least t o the extent of the material available to the present writer. During the seventeenth century, in fact as late as the time of Davy and Berzelius, light was thought to be an imponderable material which united with ponderable substances and could be released from such comhinations. Substances that readily set free their fixed light material a t ordinary or slightly elevated temperatures were known as phosphors (Gr. 46s light 4ipw to bear). Such light-bearers were of great interest to the scientists (natural philosophers) of those times, since 1 DAVIS, T. L., THISJOURNAL, 4, 1105-1113 (1927). . WEEKS,M. E., ibid., 9, 16-21 (1932); 10,302-6 (1933). See also her "Discoverv of the Elements." 5th ed.. Mack Printine Company, Easton, Pennsylvania, 1945, pp. 34-57.
+
Figun, 1. supplement to Bdduin'e A u r v m Superius and infsrius Aurae Suparioris and Inferioris
1 ?
they hoped to be able to isolate the light material itself from such substances. Glowworms and fireflies, and the luminescing organisms in sea water or on decaying flesh and wood were, of course, long frlmiliar sights. However, the inherent difference between these natural phosphors and the so-called Bolognese stones, prepared from heavy spar, wm quite apparent. Hence, these artificial products, which after exposure released the absorbed light when placed in the dark, aroused much excitement from the time of their discovery a t the beginning of the seventeenth century. A new variety of luminescent stones was accidentally discovered in 1674 a t Grosshain, Saxony. It resulted from the strong ignition of the residue obtained by evaporating a solution of chalk in nitric acid. The discoverer, Christoph Adolph Balduin, was a member of the Imperial Academy of Sciences, and as such received the cognomen Hermes. He therefore named his preparation Phosphorus Hemeticus or, alternatively, Magnes Luminaris, because it attracted light as a magnet attracts iron particles. In 1675, he issued a booklet (Figure 1) describing this phosphor, but did not disclose the method of preparation. The procedure was published for the first time by Kunckel in his "Lahoratorium Chymicum." About this time, a t Hamburg, a new phosphor was 4114
AUGUST, 1948
415
Figure 2e.
Page 8 of the Elsholt= Pamphlet
ity a t the court of the Elector of Brandenburg was the physician and chemist Johann Sigismund Elsholtz (1623-88), see frontispiece. In May, 1676, he had printed a t Berlin a pamphlet (Figure 2a) in which he described what he had seen at the time of Krafft's visit. This is the earliest publication concerning elementary phosphorus, but it seems to have been completely forgotten or overlooked since it is never mentioned by writers on this subject. Only Kunckel, in a letter to Brand (Wittenberg, June 25, 1676) earnestly requesting the latter to disclose his method of preparing phos-
Figures 2b. c. d
obtained by Brand from urine. He sold his product for 200 reichsthalers to Johann Daniel Krafft, a commercial agent from Saxony. The latter exhibited this wonderful new substance st various courts but did not tell where he had obtained it. Consequently, he made it appear as though he were the real discoverer. In the spring of 1676 he came to Berlin. The scientific author-
JOURNAL Of CHEMICAL EDUCATION
Figure 6. Plate from Cohevsen Illustrating Various Kinds of Phos~horus
friends, have almost become enemies over this, because he boasted so brazenly a t Berlin, and permitted a physician t o print a pamphlet about it spreading the impression that the discovery is really Krafft's. I have refuted this."
The Elsholtz pamphlet Figure 2b opens with a description of the previously known phosphors: I, Bologna stone; 11, BaldGn's phosphor;. and 111, emerald phosphor. The latter is a green fluorspar which glows in the dark when gently warmed. The effect is now known t o be due to radioactive action. and this is the earliest description of the phenomenon. Then follows: IV, phosphorus fulgurans, the flashing ph&phor. "All the previously named species of phosphors are left fitr behind by the fourth and most reoent, for which t,he name 'flashing phosphor' is fitting because of its special activity. A doubtless, diligent natural philosopher, who from his early youth was on intimat* terms with Helmont's son, with Taeke, Glauber, Beeher, and other noted chemists, not only in Europe but also in India,and u.ho therefore gained the favor of many princes, Johann or Daniel Krafft, who because of public affairs is now IivinginDresden, and whb recently on his way baok from Holland passed through Berlin, showed our gracious Elector in tho presence of numerous courtiers on lmt April 24 (1676) a t 9 P.M. a luminescing material, which was enclosed in a small, hermetically sealed, bulbous glass vessel, and which he himsolf called 'eternal fin:.' For demonstrat,ion, he oponed the glans and placed t,he substance on dark paper; aftcr thc candles u w e rernovcd, it not only lit up itmlf as do the glowworms that fly through
AUGUST, 1948 hoen rubbed. I f anyono had rubbed himself all over with it, his whole figure would havc shone, as once did that of Moses when he eamc down irom Mt. Sinai (if the comparison with such sacrcd matters is permissible hero). "Tho next day, the demonstrator again enclosed his material. not in the glass hulh hut in a small tube of the form and sisc as illustrated, and he closed both ends with Spanish wax. The particlo, which in the illustration (Figure 2b) is shown outside thc glass on a. saucer a t A , roscmblcd, in color and hardness, yellow, not quite transparent ambcr. I t remained sticking in the middle of the before-mentioned tubo. That same day a t dusk he brought the particle thus onelosed to my house. In my study, with the windows closed, wc watched it together for several hours and observed that i t did not glow as it did the previous day when it, lay out,sideof the glass, an the paper, hut, on the contrary sent out intermittent sparks, like summer lightning without thunder. The int,ervals were hriof. ahout one-ouarter of the nulse-beat. of the t o push out the wax plugs and was angry at being confined in such a small space. This spectacle quite properly greatly astonished not only me but also the domonstrstor who up to then had nevcr seen thisshility tospark. "The latter came to my home on the third evening to rcpcat our observations, and wo noticed that the particle no longer spsrkcd on both sides or both onds, but only on one, i. e., in the direction toward B of tho illustration. Therefore, I turned that end R, whieh in my hand was pointed t,oward the west, t o the east, expecting that tho reversed partiele would send its flashes of light likowisc in that direction. I t was amazing, however, to see how, instcad of sparking toward the east, as we expected, it, quite indepondcntly and obstinately, threw out its flashes toward the west, w e n though we rcvcrsed the tube about one hundred timcs. Owing to the departure of Mr. I h f f t , we were unable t o msko further observations a t that time. However, still other and varied phonomena can he expeetcd from this luminescing and 0x2 tremcly wonderful littlo stone."
The next year, on January 29, 1677, Elsholtz gave an account of a fifth phosphor. This liquid preparation was exhibited by Dr. Martin Weise, Electoral Councillor and Senior Body-physician. After a private showing to the Elector id theiatter's bedroom, the wonderful
Figure 8
prcpmation was demonstrated in the doctor's home the next day to invited guests, friends, and colleagues. The niaterial was called ignis frigidus, i. e., cold fire, since it glowed but did not burn. "Picture a small glass containor with the neck tied shut, and containing a. liquid, which has stood quietly for several hours so that s. dcnscr, darkcr portion has sctt,le& out with a lighter, clertrcr layor above. The farmor has ttie color of impure sulfur,
=:- .-e-ix--*. -
Figure 7
Figure 9
JOURNAL OF CHEMICAL EDUCATION with a finger of the other hand, a bluish flame, similar t o that of burning alcohol, will suddenly appear in the cupped hand as well as on the finger which is rubbing the liquid. This flame will persist so long as any of the material remains and all except a smsll residue is consumed. If the material is spread over one's hair, beard, or eyebrows, they will appear to be in flames but undamaged: hence the name 'cold fire' s e e m t o be very apprapriate. I n addition, this Liquid s e e m not t o be ignited by ordinary fire, because paper dipped into it did not catch fire, hut a n the contrary, when it was hrushed over with the liquid, and placed in the dark, i t glowed most oxeellently, as though it were actually on fire. This could also be seen a t the point where a little of the liquid adhered to the thread with which the glass was tied shut."
This preparation consisted of impure phosphorus, whose melting point was lowered below room temperature by dissolved contaminants, presumably sulfur. The supernatant liquid was a water solution of the oxidation products. The low purity of the phosphorus of those times made it possible to carry out with little danger exveriments such as those described by Elsholti. In 1677, he again described these observations in the "Ephemerides der deutschen Naturforscher." A French translation of this account appeared at Paris in 1678. An extended description was published by Elsholtz at Berlin in 1681 (Figure 3). This pamphlet I I i I I . .Is l w g a': r h v h 4 ron1aint.r iu left contains a plate (Figure 4) which pictures along with 1t11 undist~rb~d , flamr llr xltwn) i~ s(.tv1, I,uI ti 1I.e gln~dis.~t.lllIy phosphorus fulgurans, three alleged new varieties: phos~ h a k wi l l a darkenrcl nmnl idthe Iwilvi~rporlim iuixvd wit11tlw lighter, a circular flame soon appears, which, however, quickly phorus stellatus; phosphorus nubilosus; phosphorus vanishes. If a t the same time the glass is opened, a vapor is literatus. Starry phosphorus appears when the burning exuded which has the odor of garlic and if the movement of the substance spatters. One method of securing this result opened container should be continued, the vapor would become so was to drop a bit of material into a flask containing dense that the whole of tho liquid would be consumed. concentrated sulfuric acid and -then add water. The "Furthermore, if even a single drop of the shaken liquid is resultant heat ignited the pkibsphorus and caused it t o allowed to fall into the hollow oi the hand, and is rubbed gently
AUGUST, 1948
be thrown about. The illustration of the so-called cloudy variety shows plainly that the phosphorus contained phosphide, probably calcium phosphide. On contact with water, spontaneously inflammable phosphine was produced and it burned t o form the familiar and characteristic smoke rings so clearly shown here. "Learned phosphorus" was the fruit of a joke by Elsholtz. Brought up under the influence of the baroque school, Elsholta blackened the bulb of a flask and then scratched a design through the coating. If a little phosphorus was put into the flask, the pattern became visible in the dark. J. H. Cohausen's "Lumen Novum Phosphoris Accensum," published at Amsterdam, 1708 (Figure 5 ) , contains a picture of a darkened room where these varieties of phosphorus are on display (Figwe 6). Tubes containing sparking phosphorus are shown on both tables; liquid phosphorus is in a flask on the floor, to the left. A large gilded flask, in the form of an imperial orb, hangs from the ceiling. The inscription "Leopoldus" refers to the German emperor. On the table to the right stands an imperial eagle outlined with luminescent colors; a luminous barometer is against the rear wall. The first pamphlet by Elsholtz in 1676 was followed closely in this same year by "Noctiluca constans et per vices fulgurans diutissime quaesita, nunc reperta." The author, Georg Caspar Kirchmaier, was Professor of Eloquence at the University of Wittenberg. His friend Kunckel probably persuaded him to publish this dissertation which contains statements about Brand's phosphorus. In 1680 Kirchmaier published a more extensive treatise, which, however, contained no new observations (Figure 7). It consists wholly of a learned compilation of the extant knowledge about phosphorus together with a discussion of the various views concerning the nature of light and fire. Despite persistent requests, Brand, in the meantime, had refused to reveal the secret of the preparation of phosphorus to Kunckel. However, the latter, working a t Wittenberg, discovered for himself how,to prepare it from urine and other animal and vegetable materials. He published in 1678 his boastful "Von dem Phosphoro Mirahili, etc." (Figure 8). Though this tract contains statements about the properties of his phospho~uspreparations, the method of preparation is not disclosed. There is no doubt that Kunckel, even then, was able to make fairly pure phosphorus. He states, among other things, that when his purest specimens were burned they left an orange-red residue. Hence, he was the first t o observe the orange-colored modification of phosphorus. In the main, though, he emphasized and extolled his phosphorus pills and gave directions for their medical use. He assigned the privilege of selling them
t o the Leipsic apothecary Linck. Surely the reason that no great harm resulted is that the pills, quite soon after their preparation, contained nothing but the nontoxic oxidation products of the phosphorus. The earliest really scientific observations of phosphorus were due to Robert Boyle. He had learned about this amazing material when Krafft exhibited it a t the English court. Boyle, like Kirchmaier, called it nocti2uea. He described its preparation from urine in his books, published a t London in 1682, (Figures 9, 10) and in German translation a t Hamburg- (Fieure 111.. Bovle's uapers are writ,. .ten quite in the modern scientific spirit: -
The first doctoral dissertation (Figure 12) dealing with phosphorus was submitted on November 9, 1688, by J. C. Kletwitch to the medical faculty of the University of Frankfurt. In July, 1759, the licentiate in medicine, F. J. Kikinger, presented to-the medical faculty of the University of Munich, which was then situated in Ingolsfadt, an inaugural dissertation (Figure 13) on English phosphorus. This name came from the fact that 'it was first prepared on a considerable scale in England by Gottfried Hanckwita, a German, and was exported from there for commercial purposes. Both of these dissertations contain much information concerning the history of phosphorus.
