Joseph Black Lecturing (after John Ray)(From a print in the British Museum.)
Joseph Black Lecturing (after John Ray)
(From a print in the British Museum.)
The oxide of magnesia was believed to be an elementary substance until Sir Humphry Davy separated the metal from the earth by his electrolytic method in the presence of mercury. By this means he obtained an amalgam, and by oxidising this he reproducedmagnesia and left the mercury free, thus proving that the earth was an oxide of a metal. In 1830 Bussy isolated the magnesium by heating in a glass tube some potassium covered with fragments of chloride of magnesium, and washing away the chloride of potassium formed. Magnesium in small globules was left in the tube. The metal is now prepared on an industrial scale either by electrolysis, or by fusing fluor-spar with sodium. At present the uses of magnesium and of its derivatives are infinitesimal in comparison with the vast quantities available in deposits, as in dolomite, and in the sea.
among the ancient Greeks and Romans generally meant carbonate of soda, sometimes carbonate of potash. The Arab chemists, however, clearly described nitrate of potash. In the works attributed to Geber and Marcus Græcus, especially, its characters are represented. Raymond Lully, in the thirteenth century, mentions sal nitri, and evidently alludes to saltpetre, and Roger Bacon always meant nitrate of potash when he wrote of nitre. It was not, however, until the seventeenth century that the term acquired the definite meaning which we attach to it.
At the beginning of that century there was much discussion as to the formation of nitre, as it had been held that the acid which combined with the alkali was ready formed in the atmosphere. Glauber was the first to argue that vegetables formed saltpetre from the soil. Stahl taught that the acid constituent of nitre was vitriolic acid combined with phlogiston emanating from putrefying vegetable matter.
After gunpowder had become a prime necessity of life, saltpetre bounded upwards in the estimation ofkings and statesmen. In France in 1540 an Edict was issued commissioning officials called “salpêtriers” in all districts who were authorised to seek for saltpetre in cellars, stables, dovecotes, and other places where it was formed naturally. No one was permitted to pull down a building of any sort without first giving due notice to the salpêtriers. The “Salpêtrière” Asylum in Paris recalls one of the national factories of nitre. During the French Revolution citizens were “invited” to lixiviate the soil and ceilings of their cellars, stables, etc., and to supply the Republic with saltpetre for gunpowder. The Government paid 24 sous, 1s., a pound for the nitre thus procured, though, as this was no doubt paid in assignats, it was cheap enough. It was estimated that 16,000,000 lbs. a year were thus provided.
Under the name of naphtha and other designations petroleum has been known and used from the earliest times. The Persians were the first, as far as is known, to employ it for lighting, and also for cooking. They likewise made use of it as a liniment for rheumatism. So in this country, a kind of petroleum was sold as a liniment under the name of British oil; and in America, long before the great oil industry had been thought of, petroleum was popular as a liniment for rheumatism under the name of Seneca Oil.
Asphalt, or Bitumen of Judæa, was used by the Egyptians for embalming. Probably they reduced its solidity by naphtha. Naphtha was employed by Medea to render the robe which she presented to her rival Glauca inflammable, and this legend is given to account for the name of Oil of Medea, by which petroleum wasanciently known. It was no doubt the principal ingredient in the Greek Fire of the middle ages.
Petroleum has been called by many other names. Oil of Peter or Petre was a common one, meaning, like petroleum, simply rock oil. Myrepsus, in the thirteenth century, refers to it as Allicola. The monks called it sometimes oil of St. Barbarus, and oil of St. Catherine.
Dioscorides said naphtha was useful as an application in dimness of sight. Two centuries ago it was occasionally given in doses of a few drops for worms, and was frequently applied in toothache. Petroleum Barbadense, Barbadoes tar, had some reputation in pectoral complaints in the seventeenth and eighteenth centuries, and was admitted into the P.L. as the menstruum for sulphur in the balsamum sulphuris Barbadense.
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 costumepresented 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.)
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, andwas 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 scientificfriend 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 hisreturn 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” werethe 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.”
“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 itscareer, 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.
The hypophosphites in the form of syrup were introduced by Dr. J. F. Churchill, of Paris, as specifics inconsumptive diseases about 1857. His preference of these salts over the phosphates was based on the theory that the deficiency in the system in a phthisical condition was not of phosphates, which had been completely oxidised, but of a phosphide in an oxidisable condition, and this requirement was fulfilled by the hypophosphites. The latter he compared to wood or coal, the phosphates to ashes, so far as active energy was concerned. Dr. Churchill’s interest in a special manufacture of the hypophosphite syrups prejudiced the medical profession against his theories, and it is not certain that he got a fair hearing in consequence. The general verdict was that his results were not obtained by other experimenters, but for a good many years past syrups of the hypophosphites have been among the most popular of our general tonics.
Phosphorus is soluble in alcohol, ether, chloroform, bisulphide of carbon, and to a very small extent in water.
Phosphor paste as a vermin killer was ordered by the Prussian Government to be substituted for arsenical compounds in 1843, and it is probable that to some degree the alteration has been successful, though in France it was found that phosphorus in this form became a popular agent for suicide and criminal poisoning.
was at one time in high esteem, as it was believed that by the process adopted for making it the nitre was specially purified. Purified nitre was melted in an iron pot and a little flowers of sulphur (1 oz. to 2 lb.) wassprinkled on it, a little at a time. The sulphur deflagrating was supposed to exercise the purifying influence on the nitre. The actual effect was to convert a small part of the nitrate of potash into sulphate. It was first called Sal Prunella in Germany from the belief that it was a specific against a certain plum-coloured quinsy of an epidemic character. Boerhaave advised the omission of the sulphur, but believed that melting the pure nitre and moulding it was of medicinal value by evaporating aqueous moisture.
Nitre and flowers of sulphur were deflagrated together before the Sal Prunella theory was invented, equal quantities being employed. The resulting combination, which was of course sulphate of potash, was known as Sal Polychrestum, the Salt of Many Virtues.
Sal Gemmæ or Sal Fossile was the name given to rock salt, particularly to the transparent and the tinted varieties. It was believed to be more penetrating than the salt derived from sea water, and this property Lemery ascribed to the circumstance that it had never been dissolved in water, and therefore retained all its native keenness.
Spiritus Salis Marini Glauberi was one of the products discovered by Glauber, to whom we owe the name of spirit of salt. He was a keen observer and remarked on the suffocating vapour yielded as soon as oil of vitriol was poured on sea-salt. It is astonishing to his biographers that he just missed discovering chlorine. The spirit of salt was highly recommended for many medicinal uses;for exciting the appetite, correcting the bile, curing gangrene, and dissolving stone. Its remarkable property of assisting nitric acid to dissolve gold was soon observed and was attributed to its penetrating power.
Tartarus was the mythological hell where the gods imprisoned and punished those who had offended them. Virgil represents it as surrounded by three walls and the river Phlegethon, whose waters were sulphur and pitch. Its entrance was protected by a tower wrapped in a cloud three times as black as the darkest night, a gate which the gods themselves could not break, and guarded by Cerberus.
There is nothing to associate this dismal place with the tartar of chemistry, except that in old books it is said that Paracelsus so named the product because it “produces oil, water, tincture, and salt, which burn the patient as Tartarus does.” Paracelsus did not invent the name of tartar; it is found in many alchemical books long before his time. The earliest found use of it is in an alchemical work by Hortulcuus, an English alchemist of the eleventh century.
Paracelsus was writing about “tartarous diseases” (“De Morbis Tartareis”), those, that is, which resulted from the deposit of concretions. Stone, gravel, and gout were among these diseases of tartar, and evidently it was this morbid tartar which he associated with the legendary Tartarus. The word tartar, applied to the deposit from wine, is sometimes supposed to have descended from an Egyptian term, dardarot, meaning an eternal habitation, and etymologists generally prefer it as the origin of the name. If it was, the sensedevelopment of the term as applied to the chemical is not clear. The Greek wordtartarizein, meaning to shiver with cold, does not help much in tracing the history of the word. Another frequently advocated derivation is the Arab,durd, dregs, sediment, which it is said was actually applied to the tartar of wine. It appears, too, that the Arabs used this term also as we do to represent the deposit on teeth; they also had a word,dirad, to mean a shedding of teeth, and bydardathey signified a toothless old woman. Some etymologists consider, however, that the transition from durd to tartar would be most unlikely.
When the alchemists began to experiment with tartar their first process would be to distil it. The residue left in their retorts they called the salt of tartar. They knew this substance under other names, salt of wormwood, for instance, but they did not recognise the identity. By treating tartar with vinegar they produced acetate of potash, which they called regenerated tartar. Oswald Crollius, the compiler of the first European pharmacopœia, gave the name of vitriolated tartar to what we now know as sulphate of potash.
The iatro-chemists of the next century, who obtained it by various methods, gave to sulphate of potash distinct names which show in what esteem it was held. Among other designations it appears as Specificum purgans, Arcanum duplicatum, Nitrum fixum, Panacea holsatica, and Sel de duobus. Glaser, who produced it from sulphur, saltpetre, and urine distilled together, sold it as Sal Polychrest of Glaser.
Cream of tartar was known to the ancients under the name of Fæx Vini, which is the designation for it used by Dioscorides.
The tartar of wine was found to be only soluble inwater with difficulty; but if boiled in water a turbid liquor was yielded which in the boiled condition continually threw up a sort of skin or scum. This was taken off with a skimmer and dried; it was naturally called Cream of Tartar.
Paracelsus and other chemists distilled this cream and got an oil from it which they called oil or spirit of tartar. It was chiefly a pyro-tartaric acid with some empyreumatic constituents. It was a thin, light yellow, bitter tasting but rather tart, and pleasant smelling oil, and was credited with remarkable penetrating powers. It was used in disorders of the ligaments, membranes, and tendons. Particularly surprising to them was the fact that the residue of a distinctly acid substance was a strong alkali. This “salt of tartar” was found to yield another oil called oleum tartari per deliquium, or lixivium tartari, which was the name by which it was called in the Pharmacopœia. Salt of tartar and cream of tartar together yielded the tartarum tartarisatus. It was when making this that Seignette produced by accident his double tartrate of potash and soda, now familiarly known as Rochelle salt.
Visitando Interiora Terræ Rectificando Invenies Occultum Lapidem Veram Medicinam. (Visiting the interior of the earth you may find, by rectifying the occult stone, the true medicine.) This acrostic is first found in the works attributed to Basil Valentine.
The vitriols enjoyed an enormous reputation in medicine, at least until their chemical composition was definitely explained by Geoffrey in 1728. It was certainly known that the green vitriols contained iron,and they were sometimes named vitriol of Mars; that the blue vitriols contained copper, which obtained for them the designation of vitriol of Venus; and the white was understood to be associated with calamine, though by some it was supposed to be only green vitriol which had been calcined.
The name of vitriol cannot be traced further back than to Albertus Magnus in the thirteenth century. He expressly applies the term to atramentum viride, the Latin name for sulphate of iron. Presumably it was given to the salt on account of its glassy appearance. The alchemists, on distilling these vitriols found that they always yielded a spirit or oil, to which they naturally gave the name of spirit or oil of vitriol.
In Greek the vitriols were called chalcanthon, as they were extracted from brass; the common name in Latin was atramentum sutorium, because they were employed for making leather black. Dioscorides states that this substance is a valuable emetic, should be taken after eating poisonous fungi, and will expel worms. Pliny recommends it for the cure of ulcers, and Galen used it as a collyrium. There was a good deal of confusion between the vitriols and the alums, and the Greek stypteria and the Latin alumens were often an aluminous earth combined with some vitriol. Pliny gives a test for the purity of what he calls alum, which consists in dropping on it some pomegranate juice, when, he says, it should turn black if it is pure. Evidently his alum contained sulphate of iron.
Paracelsus declared that, with proper chemical management, vitriol was capable of furnishing the fourth part of all necessary medicine. It contained in itself the power of curing jaundice, gravel, stone, fevers, worms, and epilepsy.
Mayerne was another strong advocate of the medicinal virtues of vitriol. According to him it possessed the most diverse properties. It was hot and cold, attenuative and incressant, aperitive and astringent, coagulative and dissolvant, corroborative, purgative, and sudorific.
A multitude of medicines were made from the vitriols. A vitriolum camphoratum was included in the P.L. of 1721 by distilling spirit of camphor from calcined vitriol; but Quincy remarks:—“Its intention I am not acquainted with, nor have ever met with it in prescription.” In Dr. Walter Harris’s “Pharmacopœia Anti-Empirica,” 1683, allusion is made to a remedy made by one Bovius, which consisted of spirit of vitriol, and was designed to lie a universal remedy. Added to an infusion of balm, marjoram, and bugloss, it would cure headache and vertigo; with rose water, fevers; with fumitory water, itch; with fennel water it would restore decayed memory; with plantain water it was a remedy against diarrhœa; and with lettuce water it became a narcotic. “A rare fellow,” quaintly comments the doctor. Homberg’s narcotic salt of vitriol was a combination of green vitriol and borax made after a very complicated process. The Gilla Vitrioli was a purified white vitriol used as an emetic. Spiritus Vitrioli dulcis was an imitation of Hoffmann’s Anodyne. This distilled with hartshorn made the Diaphoretic Vitriol.
One of the precious secrets of the alchemists, occasionally sold to kings and wealthy amateurs, was that of converting iron into copper by means of blue vitriol. A strong solution of the salt was prepared, and an iron blade, or any iron instrument, was immersed in it for a certain time. When taken out it appeared to be ablade or instrument of copper. Kunckel was the first chemist to explain the fallacy.
Elixir of Vitriol was devised by Adrian Mynsicht, a famous German physician, in the early part of the seventeenth century. He published an Armamentarium Medico-Chymicum which became very popular. His Elixir (under the name of Elixir Vitrioli Mynsichti) was first given in the P.L. of 1721 as follows:—cinnamon, ginger, cloves, of each 3 drachms: calamus aromaticus, 1 oz.; galangal root, 1½ oz.; sage, mint, of each ½ oz.; cubebs, nutmegs, of each 2 oz.; lign. aloes, lemon peel, of each 1 drachm; candied sugar, 3 oz. Digest in spirit of wine, 1½ lb., and oil of vitriol 1 lb. for twenty days. Then filter.
In the P.L. 1746 the formula was simplified by mixing 4 oz. of oil of vitriol with 1 lb. of Aromatic Tincture, and the title was changed to Elixir Vitrioli Acidum. In the P.L. 1778 there was no Elixir of Vitriol, dilute sulphuric acid taking its place. This was then called Acidum Vitriolicum Dilutum. Under the name of Acidum Sulphuricum Aromaticum, however, an acidulated tincture, flavoured with ginger and cinnamon, was retained, and this, with the synonym of Elixir of Vitriol, is still in the B.P.
Quincy (1724) states that this medicine had lately come greatly in practice, and deservedly. “It mightily strengthens the stomach,” he says, “and does good service in relaxations from debauches and overfeeding.”
The alga “nostoch,” so-called by Paracelsus, who also described it as flos cœlorum, acquired the name of vegetable vitriol, and sometimes spittle of the stars, because it appeared after rains in places where it had not been seen before.