Phosphorus.
Phosphorus, or its Latin equivalent, Lucifer, was the name given by the ancient astronomers to the planet Venus when it appeared as a morning star. When it shone as an evening star they called it Hesperus. Do we invent such seductive names now, or do they only seem attractive to us because they are ancient or foreign?
The phosphorescent properties of certain earths had been occasionally noticed by naturalists, but no observation of the kind has been traced in ancient writings. The earliest allusion to a “fire-stone” known occurs in the work of a gossipy French historian named De Thou. In a history of his own times this writer relates that in 1550, when Henri II made his state entry into Boulogne on the occasion of its restoration to France by the English, a stranger in foreign costume presented the king with a fire-stone which, he said, had been brought from India. De Thou narrates that this wonderful stone glowed with inconceivable splendour, was so hot that it could not be touched without danger, and that if confined in a close space it would spring with force into the air.
Sometime early in the seventeenth century, a shoemaker of Bologna, one Vincent Cascariolo, who, in addition to his ordinary business dabbled in alchemy, discovered a stone in the neighbourhood of his city which was luminous in the dark. The stone, which is now known to have been a sulphate of barium, and which the shoemaker calcined, ground, and formed into little round discs about the size of a shilling, and sold for a fancy price, was called the sun-stone. The discs, exposed to a strong light for a few minutes and then withdrawn into a dark room, gave out the incandescent light which we know so well. The discovery excited keen interest among scientific men all over Europe.
Johann Kunckel.
(From the Collection of Etchings in the Royal Gallery at Berlin.)
About 1668 two alchemists named Bauduin and Frueben, who lived at Grossenhayn in Saxony, conceived the idea of extracting by chemical processes the spirit of the world (Spiritus Mundi). Their notion was to combine earth, air, fire, and water in their alembic, and to obtain the essences of all of these in one distillate. They dissolved lime in nitric acid, evaporated to dryness, exposed the residue to the air, and let it absorb humidity. They then distilled this substance and obtained the humidity in a pure form. History does not tell us what questions they put to their spirit of the world when they had thus caught it. It appears, however, that the stuff attained a great sale. It was supplied at 12 groschen the loth, equal to about 1s. 6d. per ounce, and lords and peasants came after it eagerly. Rain-water would have been just as good, Kunckel, who tells the story, remarks. But one day Bauduin broke one of the vessels in which was contained some of the calcined nitrate of lime, and he observed that this, like the Bologna stone, was luminous in the dark after exposure to sunlight. Bauduin appreciated the importance of his discovery, and, taking some of his earth to Dresden, talked about it there. Kunckel, who was then the Elector’s pharmacist, and keenly interested in new discoveries, heard about this curious substance, and was very curious to find out all he could. He visited Bauduin and tried to draw from him the details of his process. But Bauduin was very shy of Kunckel, and the latter has left an amusing account of an evening he spent with his quarry. Kunckel tried to talk chemistry, but Bauduin would only take interest in music. At last, however, Kunckel induced Bauduin to go out of the room to fetch a concave mirror to see if with that the precious phosphorus (for Bauduin had already appropriated this name to the stuff) would absorb the light. While Bauduin was gone Kunckel managed to nip a morsel with his finger-nail. With this, aided by the fragments of information he had been able to steal from Bauduin’s conversation, he commenced to experiment by treating chalk with nitric acid, and ultimately succeeded in producing the coveted luminous earth. He sent a little lump of it to Bauduin as an acknowledgment of the pleasant musical evening the latter had given him.
It was now 1669. Kunckel was visiting Hamburg, and there he showed to a scientific friend a piece of his “phosphorus.” To his surprise the friend was not at all astonished at it, but told Kunckel that an old doctor in Hamburg had produced something much more wonderful. Brandt was the name of the local alchemist. He had been in business, had failed, and was now practising medicine enough to keep him, but was devoting his heart and soul and all his spare time to the discovery of the philosopher’s stone. The two friends visited Brandt, who showed them the real “phosphor” which he had produced, to which, of course, the other substances compared as dip candles might to the electric light, but nothing would induce the old gentleman to disclose any details of his process. Kunckel wrote to a scientific friend happily named Krafft at Dresden about the new “phosphor.” Honour seems to have been cheap among scientific friends at that time, for Krafft posted off to Hamburg, without saying anything to Kunckel about his intention, caught Brandt in a different humour, or perhaps specially hard-up, and bought his secret for 200 thalers.
According to another story, the German chemist Homberg also succeeded in securing Brandt’s secret by taking to him as a present one of those weather prognosticators in which a figure of a man and another of a woman come out of doors or go in when it is going to be wet or fine, as the case may be; a toy which had just then been invented.
Stimulated perhaps by Brandt’s obstinacy and Krafft’s treachery, Kunckel set to work and in time succeeded in manufacturing phosphorus. It may be taken as certain that he had picked old Brandt’s brains a little, and his own skill and shrewdness enabled him to fill up the gaps in his knowledge. However he acquired the art, he soon became the first practical manufacturer of phosphorus.
Brandt discovered phosphorus because he had arrived at the conviction that the philosopher’s stone was to be got from urine. In the course of his experiments with that liquid, phosphorus came out unexpectedly from the process of distilling urine with sand and lime.
The new substance excited great curiosity in scientific circles all over Europe, but the German chemists who knew anything about it kept their information secret, and only misleading stories of its origin were published. Robert Boyle, however, who was travelling on the Continent when the interest in the discovery was keenest, got a hint of the method of manufacture, and on his return to England proceeded to experiment. His operator and assistant in these investigations was Ambrose Godfrey Hanckwitz, who became the founder of a London pharmaceutical business which still exists. Ultimately Boyle and Hanckwitz were completely successful, and for many years the “English phosphorus” supplied by Hanckwitz from his laboratory in Southampton Street, Strand, monopolised the European market. According to a pamphlet published by him, entitled “Historia Phosphori et Fama,” the continental phosphorus was an “unctuous, dawbing oyliness,” while his was the “right glacial” kind.
In 1680 Boyle deposited with the Royal Society, of which he was then president, a sealed packet containing an account of his experiments and of his process for the production of the “Icy Noctiluca,” as he called his phosphorus.
It is related in the Memoirs of the Academy of Sciences of Paris for 1737 that in that year a stranger appeared in Paris and offered for a stipulated reward to communicate the process of making phosphorus to the French Government. A committee of the Academy, with Hellot as its president, was appointed to witness the stranger’s manipulation. According to the report of this committee, the experiment was completely successful.
It only remains to add, to complete the history, that in 1769, Gahn, a Swedish mine owner, discovered phosphorus in bones, and that working from this observation Scheele in 1775 devised the process for the manufacture of phosphorus which is still followed.
Such a remarkable substance as phosphorus, extracted as it had been from the human body, was evidently marked out for medical uses. Experiments were soon commenced with it. Kunckel’s “luminous pills” were the first in the field, so far as is known. His report was published in the “Chemische Anmerkungen” in 1721. He gave it in three-grain doses, and reported that it had a calmative effect! Subsequently it was tried in various diseases by continental practitioners. Mentz commended it in colic, Langensalz in asthenic fevers, Bonneken in tetanus, Wetkard in apoplexy, and Trampel in gout.
In 1769 Alphonse Leroy, of Paris, reported a curious experience. He was sent for to a patient apparently on the point of death from phthisis. Seeing that the case was hopeless, he prepared and administered a placebo of sugared water. Calling the next day, Leroy found his patient somewhat revived, and on examining the sugar which he had used for his solution, he found that some phosphorus had been kept in it for a long time. The patient was much too far gone to recover, but she survived for fifteen days, and Leroy attributed this amelioration to the phosphorised water which he had accidentally given her.
Gahn discovered phosphorus in the bones in 1768, and in 1779 another German chemist named Hensing ascertained its presence in a fatty matter which he extracted from the brain. Medical theories were naturally based on these observations. Couerbe, a French chemist quoted by Dr. Churchill, wrote thus in 1830:
“The want of phosphorus in the brain would reduce man to the sad condition of the brute; an excess of this element irritates the nervous system, excites the individual, and throws him into that terrible state of disturbance called madness, or mental alienation; a moderate proportion gives rise to the sublimest ideas, and produces that admirable harmony which spiritualists call the soul.”
British practitioners took but very little notice of phosphorus as a remedy in the first century of its career, although it remained for a large part of that period an English product.
It is rather curious, too, that neither in this country nor on the Continent did it get into the hands of the empirics, as mercury, antimony, and other dangerous drugs did. It may be supposed that it was not so much the danger that checked them as the pharmaceutical difficulties in the way of preparing suitable medicines. The earliest preparations of phosphorus, such as Kunckel’s pills, were a combination of it in a free state with conserve of roses. This method was gradually abandoned on account of the difficulty of subdividing the phosphorus so perfectly that the dose could be measured accurately. But as Dr. Ashburton Thompson remarks,[3] “although it is not so specifically mentioned, the uncertainty of action which imperfectly divided phosphorus exhibits” had something to do with the rejection of the old formulas. That is putting it very gently. The three-grain doses must have killed more people than they cured. The author just quoted says that in the early days “the dose employed seldom fell below 3 grains, while it occasionally rose as high as 12 grains.” Even Leroy, he adds, instituted his experiments by taking a bolus of 3 grains, and he did not seriously suffer from it. The recommended dose has been regularly declining. In 1855 Dr. Hughes Bennett gave it at one-fortieth to one-eighth of a grain. The Pharmacopœia now prescribes one-hundredth to one-twentieth of a grain.