Chronicles of Pharmacy, Vol. 1 (of 2)
Part 24
Bromine, isolated by Balard in 1826, was named by the discoverer Muride, from Muria, brine. Its actual name was suggested by Gay Lussac from Bromos, a stench.
Schultzenberger relates, on the authority of Stas, that some years before the discovery of bromine by Balard, a bottle of nearly pure bromine was sent to Liebig by a German company of manufacturers of salt, with the request that he would examine it. Somewhat carelessly the great chemist tested the product and assumed that it was chloride of iodine. But he put away the bottle, probably with the intention of investigating it more closely when he had more leisure. When he heard of Balard’s discovery he turned to this bottle and realised what he had missed. Schultzenberger says he kept it in a special cupboard labelled “Cupboard of Mistakes,” and would sometimes show it to his friends as an example of the danger of coming to a conclusion too promptly.
COLLODION.
Pyroxylin was discovered by Schönbein in 1847, and the next year an American medical student at Boston, Massachussets, described in the American Journal of the Medical Sciences his experiments showing the use that could be made of this substance in surgery when dissolved in ether and alcohol. By painting it on a band of leather one inch wide and attaching this to the hand, he caused the band to adhere so firmly that it could not be detached by a weight of twenty pounds.
EPSOM SALTS.
The medicinal value of the Epsom springs was discovered, it is believed, towards the end of the sixteenth century, in the reign of Queen Elizabeth. According to a local tradition the particular spring which became so famous was not used for any purpose until one very dry summer, when the farmer on whose land it existed bethought him to dig the ground round about the spring, so as to make a pond for his cattle to drink from. Having done this he found that the animals would not touch the water, and on tasting it himself he appreciated their objection to it. The peculiar merits of the water becoming known, certain London physicians sent patients to Epsom to drink it, and it proved especially useful in the cases of some who suffered with old ulcers. Apparently the sores were washed with it. The name of the farmer who contributed this important item to medical history was Henry Wicker or Wickes.
In 1621 the owner of the estate where the spring had been found walled in the well, and erected a shed for the convenience of the sick visitors, who were then resorting to Epsom in increasing numbers. By 1640 the Epsom Spa had become famous. The third Lord North, who published a book called the Forest of Varieties in 1645, claimed to have been the first to have made known the virtues of both the Epsom and the Tonbridge waters to the King’s sick subjects, “the journey to the German Spa being too expensive and inconvenient to sick persons, and great sums of money being thereby carried out of the kingdom.”
After the Restoration Epsom became a fashionable watering-place. Before 1700 a ball-room had been built, and a promenade laid out; a number of new inns and boarding-houses had been opened; sedan-chairs and hackney coaches crowded the streets; and sports and play of all kinds were provided. Pepys mentions visits to Epsom more than once in his Diary, and Charles II and some of his favourites were there occasionally. The town reached its zenith of gaiety in the reign of Queen Anne, who with her husband, Prince George of Denmark, frequently drove from Windsor to Epsom to drink the waters.
An apothecary living at Epsom in those times, and who had prospered abundantly from the influx of visitors, is alleged to have done much to check the hopeful prospects of the Surrey village. Much wanted more, and Mr. Levingstern, the practitioner referred to, thought he saw his way to a large fortune. He found another spring about half a mile from the Old Wells, bought the land on which it was situated, built on it a large assembly room for music, dancing, and gambling, and provided a multitude of attractions, including games, fashion shops, and other luxuries. At first he drew the crowds away from the Old Wells. But his Epsom water did not give satisfaction. For some reason it brought the remedial fame of the springs generally into disrepute. Then Levingstern bought the lease of the Old Wells, and, unwisely it may be thought, shut them up altogether. The glory of Epsom had departed, and though several efforts were made subsequently to tempt society back to it, they were invariably unsuccessful. The building at the Old Wells was pulled down in 1802, and a private house built on the site. This house is called The Wells, and the original well is still to be seen in the garden. The very site of Mr. Levingstern’s “New Wells” is now doubtful. He died in 1827.
In 1695 Nehemiah Grew, physician, and secretary of the Royal Society, wrote a treatise “On the Bitter Cathartic Salt in the Epsom Water.” Dr. Grew names 1620 as about the date when the medicinal spring was discovered at Epsom by a countryman, and he says that for about ten years the countrypeople only used it to wash external ulcers. He relates that it was Lord Dudley North, who apparently lived near by, who first began to take it as a medicine. He had been in the habit of visiting the German spas, as he “laboured under a melancholy disposition.” He used it, we are told, with abundant success, and regarded it as a medicine sent from heaven. Among those whom he induced to take the Epsom waters were Maria de Medicis, the mother of the wife of Charles I, Lord Goring, the Earl of Norwich, and many other persons of quality. These having shown the way, the physicians of London began to recommend the waters, and then, Dr. Grew tells us, the place got crowded, as many as 2,000 persons having taken the water in a single day.
It was Dr. Grew who first extracted the salt from the Epsom water, and his treatise deals principally with that. He describes the effect of adding all sorts of chemicals, oil of vitriol, salt of tartar, nitre, galls, syrup of violets, and other substances to the solution; explains how it differs from the sal mirabilis (sulphate of soda); and writes of its delicate bitter taste as if he were commenting on a new wine. It most resembles the crystals of silver, he says, in the similitude of taste.
As to the medicinal value of this salt Dr. Grew says it is free from the malignant quality of most cathartics, never violently agitates the humours, nor causes sickness, faintings, or pains in the bowels. He recommends it for digestive disorders, heartburn, loss of appetite, and colic; in hypochondriacal distemper, in stone, diabetes, jaundice, vertigo, and (to quote the English translation) “in wandering gout, vulgarly but erroneously called the rheumatism.” It will exterminate worms in children in doses of 1½ to 2 drachms, if given after 1, 2, or 3 grains of mercurius dulcis, according to age. Epsom salts were not to be given in dropsy, intermittent fevers, chlorosis, blood-spitting, to paralytics, or to women with child.
“I generally prescribe,” writes the doctor, “one, two, or three pints of water, aromatised with a little mace, to which I add ½ oz. or 1 oz., or a greater dose of the salt.” He gives a specimen prescription which orders 1 oz. or 10 drachms of the salt in 2 quarts of spring water, with 1 drachm of mace. This dose (2 quarts, remember) was to be taken in the morning in the course of two hours, generally warm, and taking a little exercise meanwhile. This was what was called an apozem. You might add to the apozem, if thought desirable, 3 drachms of senna and 1½ oz. or 2 oz. of flaky manna.
Mr. Francis Moult, Chymist, at the sign of the Glauber’s Head, Watling Street, London, translated Dr. Grew’s treatise into English, and gave a copy to buyers of the Bitter Purging Salts. Probably he was the “furnace philosopher” referred to by Quincy (see below), though it is difficult to see what there was to object to in his action.
George and Francis Moult (the latter was, no doubt, the chymist who kept the shop in Watling Street) in about the year 1700 found a more abundant supply of the popular salt in a spring at Shooter’s Hill, where it is recorded they boiled down as much as 200 barrels of the water in a week, obtaining some 2 cwt. of salt from these. Some time after, a Dr. Hoy discovered a new method of producing an artificial salt which corresponded in all respects with the cathartic salts obtained from Epsom water, and which by reason of the price soon drove the latter out of the market, and caused the Shooter’s Hill works to be closed. It was known that Hoy’s salt was made from sea water, and at first it was alleged to be the sal mirabilis of Glauber, sulphate of soda. But this was disproved, and experiments were carried on at the salt works belonging to Lady Carrington at Portsmouth, and later at Lymington, where the manufacture settled for many years, the source being the residue after salt had been made, called the bittern--salts of magnesium, in fact. This was the principal source of supply, though it was made in many places and under various patents until in 1816 Dr. Henry, of Manchester, took out a patent for the production of sulphate of magnesia from dolomite.
It should be mentioned that it was by the examination of Epsom salts that Black was led to his epoch-making discovery of the distinction between the alkaline earths, and also of fixed air, in 1754.
In Quincy’s “Dispensatory” (1724), medicinal waters like those of Epsom are described as Aquæ Aluminosæ. It is stated that there are many in England, scarce a county without them. The principal ones about London are at Epsom, Acton, Dulwich, and North-hall. They all “abound with a salt of an aluminous and nitrous nature,” and “greatly deterge the stomach and bowels.” But it is easy to take them too frequently, so that “the salts will too much get into the blood, which by their grossness will gradually be collected in the capillaries and glands to obstruct them and occasion fevers.” After some more advice Quincy adds--
“It is difficult to pass this article without setting a mark upon that abominable cheat which is now sold by the name of Epsom waters. Dr. Grew, who was a most worthy physician and an industrious experimenter, made trial how much salt these waters would leave upon evaporation, and found that a gallon left about two drams, or near, according to my best remembrance, for I have not his writings by me. He likewise found the salt thus procured answered the virtues of the water in its cathartic qualities. Of this an account was given before the Royal Society in a Latin dissertation. But the avaricious craft of a certain furnace-philosopher could not let this useful discovery in natural knowledge rest under the improvement and proper use of persons of integrity; but he pretended to make a great quantity for sale; and to recommend his salt translated the Doctor’s Lecture into English to give away as a quack-bill.”
Quincy proceeds to tell us how other competitors came in, and how the price was so reduced that what was first sold at one shilling an ounce, and could not honestly be made under (Quincy apparently refers to the salt made by evaporation), came down in a short time to thirty shillings per hundredweight.
ETHER.
The action of sulphuric acid on spirit of wine is alluded to in the works of Raymond Lully in the thirteenth century, and in those attributed to Basil Valentine, by whom the product is described as “an agreeable essence and of good odour.” Valerius Cordus, in 1517, described a liquor which he called Oleum Vitrioli Dulce in his “Chemical Pharmacopœia.” This was intended to represent the Spiritus Vitrioli Antepilepticus Paracelsi. It was prepared by distilling a mixture of equal parts of sulphuric acid and spirit of wine, after this mixture had been digested in hot ashes for two months. Probably the product obtained by Cordus was what came to be called later the sweet oil of wine, and not what we know as sulphuric ether.
The first ether made for medicinal purposes was manufactured in the laboratory directed by Robert Boyle, and it is said that he and Sir Isaac Newton made some experiments with it at the time. A paper describing his ether investigations was published by Newton in the “Philosophical Transactions” for May, 1700. In 1700 a paper on ether was published by Dr. Frobenius in the “Philosophical Transactions,” and in the same publication in 1741 a further paper appeared giving the process by which Frobenius had prepared his “Spiritus Vini Ethereus.” Equal parts of oil of vitriol and highly rectified spirit of wine by weight were distilled until a dense liquid began to pass; the retort was then cooled, half the original weight of spirit was added, and the distillation again renewed. This process was repeated as long as ether was produced. Frobenius had been associated with Ambrose Godfrey in Boyle’s laboratory, and Godfrey had been supplying ether for some years, but he does not seem to have published his process. It was in Frobenius’s first paper, published in 1730, that the name of ether was first proposed for the product, which had been previously known as Aqua Lulliana, Aqua Temperata, Oleum Dulce Paracelsi, and such-like fancy titles. Frobenius, it was understood, was a _nom de plume_. Ambrose Godfrey Hanckwitz, Boyle’s chemist, sharply criticised Frobenius’s article, said it was a rhapsody in the style of the alchemists, and that the experiments indicated had been already described by Boyle. Godfrey was, in fact, at that time making and selling this interesting substance. In France, the Duke of Orleans, a clever chemist, who was suspected to have had some association with the famous poisonings of his time, and whose laboratory was at the Abbaye Ste. Genevieve, was the first to produce ether in quantities of a pint at a time.
Hoffmann’s “Mineral Anodyne Liquor,” the original of our Spiritus Ætheris Co., was a semi-secret preparation much prescribed by the famous inventor. He said it was composed of the dulcified spirit of vitriol and the aromatic oil which came over after it. But he did not state in what proportion he mixed these, nor the exact process he followed.
The chemical nature of sulphuric ether was long in doubt. Macquer, who considered that ether was alcohol deprived of its aqueous principle, was the most accurate of the early investigators. Scheele held that ether was dephlogisticated alcohol. Pelletier described it as alcohol oxygenised at the expense of the sulphuric acid. De Saussure, Gay-Lussac, and Liebig studied the substance, but it was Dumas and Boullay in 1837, and Williamson in 1854, who cleared up the chemistry of ethers.
Ether is alcohol, two molecules deprived of H_{2}O [alcohol, C_{2}H_{5}O HO; ether, (C_{2}H_{5})_{2}O]. Distilling spirit of wine and sulphuric acid together, it seemed obvious that the sulphuric acid should possess itself of the H_{2}O, and leave the ether. But on this theory it was not possible to explain the invariable formation of sulphovinic acid (a sulphate of ethyl) in the process, nor the simultaneous distillation of water with the ether. Williamson proved that the acid first combined with the alcohol molecule, setting the water free, and that then an excess of alcohol decomposed the sulphovinic acid thus formed into free sulphuric acid and ether, this circuit proceeding continuously.
SPIRIT OF NITROUS ETHER.
This popular medicine has been traced back to Raymond Lully in the thirteenth century, and to Basil Valentine. But the doctor who brought it into general use was Sylvius (de la Boe) of Leyden, for whom it was sold as a lithontryptic at a very high price. It first appeared in the P.L., 1746, as Spiritus Nitri dulcis. In English this was for a long time called “dulcified spirit of nitre,” and in the form of sweet spirit of nitre still remains on our labels. In the P.L., 1788, the title was changed to Spiritus Ætheris nitrosi, and in that of 1809 to Spiritus Ætheris nitrici. The process ordered in the first official formula was to distil 6 oz. (apoth. weight) of nitric acid of 1·5 specific gravity, with 32 fluid oz. of rectified spirit. Successive reductions were made in the proportion and strength of the acid in the pharmacopœias of 1809, 1824, and 1851, to 3½ fluid ounces of nitric acid, sp. gr. 1·42, with 40 fluid ounces of rectified spirit, and a product of 28 fluid ounces. The object of these several modifications was to avoid the violent reaction which affected the nature of the product.
ETHIOPS.
Æthiops or Ethiops originally meant a negro or something black. The word is alleged to have been derived from aithein, to burn, and ops, the face, but this etymology was probably devised to fit the facts. There is no historical evidence in its favour. Most likely the word was a native African one of unknown meaning. It became a popular pharmaceutical term two or three hundred years ago, but is now almost obsolete, at least in this country. In France several mercurial preparations are still known by the name of Ethiops. There are, for instance, the Ethiops magnesium, the Ethiops saccharine, and the Ethiops gommeux; combinations of mercury with magnesia, sugar, and gum acacia respectively. These designations echo the mysteries of alchemy.
Ethiops alone meant Ethiops Mineral. This was a combination of mercury and sulphur, generally equal parts, rubbed together until all the mercury was killed. It was a very uncertain preparation, but was believed to be specially good for worms. “Infallible against the itch,” says Quincy, 1724. Its chemical composition varied from a mere mixture of the two substances to a mixture of sulphur and bisulphide of mercury, according to the conditions in which it was kept. It was formerly known as the hypnotic powder of Jacobi.
Ethiops Martial was the black oxide of iron. It was a mixture of protoxide and sesquioxide of iron. Lemery’s process was the one usually recommended, but perhaps not always followed. It was to keep iron filings always covered with water and frequently stirred for several months until the oxide was a smooth black powder. Lemery’s Crocus Martis was a similar preparation but contained more of the sesquioxide. The Edinburgh and Dublin Pharmacopœias of 1826 ordered simply scales of iron collected from a blacksmith’s anvil, purified by applying a magnet, and reduced to a fine powder. This was a favourite preparation of iron with Sydenham. Made into pills with extract of wormwood, the Ethiops Martial constituted the pilula ferri of Swediaur.
Ethiopic pills were similar to Plummer’s pills (pil. calomel. co.). Guy’s ethiopic powder was once a well-known remedy for worms. It was composed of equal parts of pure rasped tin, mercury, and sulphur. Vegetable ethiops was the ashes of fucus vesiculosus which were given in scrofulous complaints and in goitre before iodine was discovered. The ashes contain a small proportion of iodine. Dr. Runel (“Dissertation on the Use of Sea Water,” 1759) says it far exceeds burnt sponge in virtue.
Huxham recommended an Aethiops Antimoniale, composed of two parts of sulphide of antimony and one part of flowers of sulphur. The older Aethiops Antimoniale was a combination of antimony chloride with mercury, and was given in venereal and scrofulous complaints. Mercury with chalk was sometimes called absorbent ethiops, or alkalised ethiops.
IODINE
was discovered by Bernard Courtois in 1811. Courtois, who was born at Dijon in 1777, was apprenticed to a pharmacist at Auxerre named Fremy, grandfather of the noted chemist of that name, and was afterwards associated as assistant with Seguin, Thénard, and Fourcroy. He had worked with the first-named of these in the isolation of the active principle of opium, whereby Seguin so nearly secured the glory of the discovery of the alkaloids. In 1811 Courtois was manufacturing artificial nitre, and experimenting on the extraction of alkali from seaweed. He had crystallised soda from some of the mother liquor until it would yield no more crystals, and then he warmed the liquor in a vessel to which a little sulphuric acid had been accidentally added. He was surprised to see beautiful violet vapours disengaged, and from these scales of a grayish-black colour and of metallic lustre were deposited.
Courtois was too busy at the time to follow up his discovery, but he brought it to the notice of a chemist friend named Clement. The latter presented a report of his experiments to the Academy of Sciences on November 20th, 1813, two years after Courtois’s first observation. No suggestion was made by Courtois or Clement of the new substance being an element.
This deduction became the occasion of an acrimonious dispute between Gay-Lussac and Humphry Davy. The English chemist happened to be in Paris (by special favour of Napoleon) at the time when Clement read his paper. He immediately commenced experimenting, and was apparently the first to suspect the elementary nature of iodine. His claim was confirmed by a communication he made to Cuvier. But Gay-Lussac forestalled his announcement in a paper he read at the Academy on December 6th, 1813. Davy complained of the trick Gay-Lussac played him, and Hofer, who investigated the circumstances, came to the conclusion that Davy was certainly the first to recognise iodine as a simple _body_, and to give it its name from the Greek, Ion, violet. Ion was originally Fion, but had lost its initial. The Latin viola was derived from the original word.
Jean Francois Coindet, of Geneva (an Edinburgh graduate), suspected that iodine was the active constituent of burnt sponge, which had long been empirically employed in goitre and scrofula, and having proved that this was the case, was the first physician to use iodine as a remedy. The pharmaceutical forms and the medical uses of iodine have been very numerous during the century which has almost elapsed since its introduction, but it would be impossible even to detail them here.
Iodoform was first prepared by Serullas about 1828, and its chemical composition was elucidated by Dumas soon after. It was first used in medicine by Bouchardat in 1836, and then dropped out of practice for about twenty years, when it again appeared in French treatises, and its use soon became general as an antiseptic application.
Bernard Courtois was awarded 6,000 francs by the Academy of Sciences in 1832, but he died in Paris in 1838 in poverty. He had been ruined in 1815 by the competition of East Indian saltpetre with the artificial nitre which he was manufacturing. In that year the prohibitive duty on the native product was removed. When the Academy awarded 6,000 francs to Courtois it also voted 3,000 francs to Coindet, who had so promptly made medical use of Courtois’ discovery.
LITHIUM.
Lithium, the oxide of which was discovered in 1807 by Arfwedson, was first suggested as a remedy for gout by Dr. Ure in 1843. He based his proposal on an observation by Lipowitz of the singular power of lithium in dissolving uric acid. Dr. Garrod popularised the employment of the carbonate of lithium in medicine. Most of the natural mineral waters which had acquired a reputation in gouty affections have been found to contain lithium.
MAGNESIA.