XIII
CHEMICAL CONTRIBUTIONS TO PHARMACY
Chymistry. “An art whereby sensible bodies contained in vessels, or capable of being contained therein, are so changed by means of certain instruments, and principally fire, that their several powers and virtues are thereby discovered, with a view to philosophy or medicine.”—Boerhaave. Quoted as a definition in Johnson’s Dictionary, 1755.
Acids, Alkalies, and Salts.
Under the above title almost the entire history of chemistry might be easily comprehended. The gradual growth of definite meanings attached to these terms has been coincident with the attainment of accurate notions concerning the composition of bodies. To the ancient philosophers sour wine, acetum vinæ, or acetum as it is still called, was the only acid definitely known. When the alchemists became busy trying to extract the virtue out of all substances they produced several acids by distillation. These they called, for example, spirit of vitriol, spirit of nitre, spirit of salt, meaning our sulphuric, nitric, and hydrochloric acids respectively. They regarded everything obtained by distillation as a spirit. When the theorists came forward, Becher, Stahl, and their followers, they treated these acids as original constituents of the substances from which they were obtained. Thus, when sulphur was burned phlogiston was set free, and acid remained. Lavoisier believed that the acidifying principle had been discovered in oxygen, and it was on this theory that he gave that element its name. But this idea broke down when Davy proved that there was no oxygen in the so-called muriatic, or oxy-muriatic acid. It was the subsequent recognition of the law of substitution which made it clear that the acids are, in fact, salts of hydrogen or of some metal substituted for the hydrogen.
The history of alkalies is as varied as is that of acids. The distinction between caustic alkalies and mild alkalies was a problem as far back as Dioscorides. By burning limestone caustic lime is produced. It was not an unreasonable presumption that the fire had created this causticity, and this theory was held with regard to all the alkalies until it was proved by Joseph Black, in 1756, that the caustic alkali was the result of a gas, fixed air, he named it, being driven off from the mild alkali.
The ancient Jews prepared what they called Borith (translated “soap” in Jeremiah, ii, 22, and Malachi, iii, 2) by filtering water through vegetable ashes. Borith was therefore an impure carbonate of potash. It is probable that the salt-wort was generally employed for this purpose, and some of the old versions of the Old Testament give the herb “Borith” as the proper sense of the passages referred to above. In any case the alkaline solution produced from vegetable ashes was used for bleaching and cleansing purposes. The Roman “lixivium” was similarly prepared, and the process is still followed in some countries where there are dense forests. The Arabic word “al-kali” was apparently applied to the product from the word “qaly,” which meant “to roast.” The earliest known use of the term is, however, found in the works of Albertus Magnus, early in the thirteenth century. A process of making caustic potash by filtering water through vegetable ashes with quicklime is described in the works attributed to Geber, but this is in a treatise now known to have been written in the thirteenth or fourteenth century. It was only in 1736 that the three alkalies, soda, potash, and ammonia, were definitely distinguished by Duhamel as mineral, vegetable, and animal or volatile alkalies.
A formula for a solution of caustic potash was given in the P.L., 1746, under the title of Lixivium Saponarium. Equal parts of Russian potashes and quicklime were mixed, wetted until the lime was slaked, water afterwards added freely, and after agitation the solution poured off. This was ten years before Black’s classic investigation already referred to. Before Black, and for some time afterwards, there were several theories in explanation of the action of the lime on the potashes. The lime had been tamed, but the potash had become more virulent. One popular suggestion was that the lime had withdrawn a kind of mucilage from the potashes; another that it had the effect of developing the power of the potashes by a mechanical process of comminution. A German chemist named Meyer, who vigorously opposed Black’s conclusions, maintained that the lime contained a certain Acidum Causticum or Acidum Pingue, which potashes extracted from it.
In the P.L., 1788, the process was altered by increasing the proportion of the lime, and the product was described as Aqua Kali Puri. Subsequently the proportion of the lime employed was reduced.
The word “salt” is traced back to the Greek “hals,” the sea, from which was formed the adjective “salos,” fluctuating (like the waves), and subsequently the Latin “sal.” Marine salt was therefore the original salt, and salts in chemistry were substances more or less resembling sea-salt. Generally, the term was limited to solids which had a taste and were soluble in water, but the notion was developed that salt was a constituent of everything, and this salt was extracted, and was liable to get a new name each time. Salt of wormwood, for instance, is one of the names which has survived as a synonym for salt of tartar, or carbonate of potash. Paracelsus insisted that all the metals were composed of salt, sulphur, and mercury, but these substances were idealised in his jargon and corresponded with the body, soul, and spirit, respectively.
Lavoisier was the first chemist who sought to define salts scientifically. He regarded them as a combination of an acid with a basic oxide. But when the true nature of chlorine was discovered it was found that this definition would exclude salt itself. This led to the adoption of the terms “haloid” and “amphide” salts, the former being compounds of two elements (now the combination of chlorine, bromine, iodine, cyanogen, or fluorine with a metal), and the latter being compounds of two oxides. The names were invented by Berzelius. Since then salts have been the subjects of various modern theories, electric and other, but they are always substances in which hydrogen or a metal substituted for it is combined with a radical. In a wide sense the acids are also salts.
Alcohol.
Al-koh’l was an Arabic word indicating the sulphide of antimony so generally used by Eastern women to darken their eyebrows, eyelashes, and the eyes themselves. Similar words are found in other ancient languages. Cohal in Chaldee is related to the Hebrew kakhal used in Ezekiel, xxiii, 40, in the sense of to paint or stain. The primary meaning of alcohol therefore is a stain. Being used especially in reference to the finely levigated sulphide of antimony, the meaning was gradually extended to other impalpable powders, and in alchemical writings the alcohol of Mars, a reduced iron, the alcohol of sulphur, flowers of brimstone, and similar expressions are common. As late as 1773 Baumé, in his “Chymie Experimentale,” gives “powders of the finest tenuity” as the first definition, and “spirit of wine rectified to the utmost degree” as the second explanation of the term alcohol. As certain of the finest powders were obtained by sublimation the transfer of the word to a fluid produced by a similar method is intelligible, and thus came the alcohol of wine, which has supplanted all the other alcohols.
Distillation is a very ancient process. Evidence exists of its use by the Chinese in the most remote period of their history, and possibly they distilled wine. But so far as can be traced spirit was not produced from wine previous to the thirteenth century. Berthelot investigated some alleged early references to it and came to the conclusion indicated. Aristotle alludes to the possibility of rendering sea water potable by vaporising it, and he also notes elsewhere that wine gives off an exhalation which emits a flame. Theophrastus mentions that wine poured on a fire as in libations can produce a flame. Pliny indicates a particular locality which produced a wine of Falerno, which was the only wine that could be inflamed by contact with fire. At Alexandria, in the first century of the Christian era, condensing apparatus was invented, and descriptions of the apparatus used are known, but no allusion to the distillation of wine occurs in any existing reference to the chemistry of that period. Rhazes, who died in A.D. 925, is alleged to have mentioned a spirit distilled from wine, but Berthelot shows that this is a misunderstanding of a passage relating to false or artificial wines.
Water distilled from roses is mentioned by Nicander, about 140 B.C., and the same author employs the term ambix for the pot or apparatus from which this water was obtained. The Arabs adopted this word, and prefixing to it their article, al, made it into alembic. This in English appeared for some centuries in the abbreviated form of limbeck. The Greek ambix was a cup-shaped vessel which was set on or in a fire, as a crucible was used.
Pissaeleum was a peculiar form of distillation practised by the Romans. It was an oil of pitch made by hanging a fleece of wool over a vessel in which pitch was being boiled. The vapour which collected was pressed out and used.
Distilled waters from roses and aromatic herbs figured prominently in the pharmacy of the Arabs, and Geber, perhaps in the eighth century, describes the process, and may have used it for other than pharmaceutical purposes. Avicenna likens the body of man to a still, the stomach being the kettle, the head the cap, and the nostrils the cooling tube from which the distillate drips.
M. Berthelot gives the following from the Book of Fires of Marcus Grecas, which he says could not be earlier than 1300, as the first definite indication of a method of producing what was called aqua ardens. “Take a black wine, thick and old. To ¼ lb. of this add 2 scruples of sulphur vivum in very fine powder, and 2 scruples of common salt in coarse fragments, and 1 or 2 lbs. of tartar extracted from a good white wine. Place all in a copper alembic and distil off the aqua ardens.” The addition of the salt and sulphur, M. Berthelot explains, was to counteract the supposed humidity.
Albucasis, a Spanish Arab of the eleventh century, is supposed from some obscure expressions in his writings to have known how to make a spirit from wine; but Arnold of Villa Nova, who wrote in the latter part of the thirteenth century, is the first explicitly to refer to it. He does not intimate that he had discovered it himself, but he appears to treat it as something comparatively new. Aqua vini is what he calls it, but some name it, he says, aqua vitæ, or water which preserves itself always, and golden water. It is well called water of life, he says, because it strengthens the body and prolongs life. He distilled herbs with it such as rosemary and sage, and highly commended the medicinal virtue of these tinctures.
It is worth remarking that when Henry II invaded and conquered Ireland in the twelfth century the inhabitants were making and drinking a product which they termed uisge-beatha, now abbreviated into whisky, the exact meaning of the name being water of life.
Raymond Lully, who acquired much of his chemical lore from Arnold of Villa Nova, was even more enthusiastic in praise of the aqua vitæ than his teacher. “The taste of it exceedeth all other tastes, and the smell all other smells,” he wrote. Elsewhere he describes it as “of marveylous use and commoditie a little before the joyning of battle to styre and encourage the soldiers’ minds.” He believed it to be the panacea so long sought, and regarded its discovery as evidence that the end of the world was near. The process for making the aqua vitæ as described by Lully was to digest limpid and well-flavoured red or white wine for twenty days in a closed vessel in fermenting horse-dung. It was then to be distilled drop by drop from a gentle fire in a sand-bath.
The chemical constitution of alcohol was speculated upon rather wildly by the chemists who experimented on it before Lavoisier. It was held to be a combination of phlogiston with water, but the phlogiston-philosophers disagreed on the question whether it contained an oil. Stahl, however, later supported by Macquer, found that an oil was actually separated from it if mixed with water and allowed to evaporate slowly in the open air, after treating it with an acid. Lavoisier, in 1781, carefully analysed spirit of wine and found that 1 lb. yielded 4 oz. 4 drms. 37½ grains of carbon, 1 oz. 2 drms. 5½ grains of inflammable gas (hydrogen), and 10 oz. 1 drm. 29 grains of water. It was de Saussure who later, following Lavoisier’s methods of investigation, but with an absolute alcohol which had been recently produced by Lowitz, a Russian chemist, showed that oxygen was a constituent of alcohol. Berthelot succeeded in making alcohol synthetically in 1854. His process was to shake olefiant gas (C2H4) vigorously with sulphuric acid, dilute the mixture with eight to ten parts of water, and distil. Meldola, however (“The Chemical Synthesis of Vital Products,” 1904), insists that an English chemist, Henry Hennell, anticipated Berthelot in this discovery.
Alum.
Alum is a substance which considerably mystified the ancient chemists, who knew the salt but did not understand its composition. Ancient writers like Pliny and Dioscorides were acquainted with a product which the former called alumen and which is evidently the same as had been described by Dioscorides under the name of Stypteria. Pliny says there were several varieties of this mineral used in dyeing, and it is clear from his account that his alumen was sometimes sulphate of iron and sometimes a mixture of sulphate of iron with an aluminous earth. It is the fact that where the various vitriols are found they are generally associated with aluminous earth.
Alum as we know it was first prepared in the East and used for dyeing purposes. Alum works were in existence some time subsequent to the twelfth century at a place named Rocca in Syria, which may have been a town of that name on the Euphrates, or more probably was Edessa, which was originally known as Roccha. It has been supposed that it was the manufacture of alum at this place which bequeathed to us the name of Rock or Rocha alum, but the Historical English Dictionary says this derivation is “evidently unfounded.”
The alchemists were familiar with alum and knew it to be a combination of sulphuric acid with an unknown earth. Van Helmont was the first to employ alum as a styptic in uterine hæmorrhage, and Helvetius made a great reputation for a styptic he recommended for similar cases. His pills were composed of alum 10 parts, dragon’s blood 3 parts, honey of roses q.s., made into 4 grain pills, of which six were to be taken daily. Alum and nutmeg equal parts were given in agues. Paris says the addition of nutmeg to alum corrects its tendency to disturb the bowels. It has also been advocated in cancer and typhoid, but these internal uses have been generally abandoned. Spirit of Alum is occasionally met with in alchemical writings. It was water charged with sulphuric acid obtained by the distillation of alum over a naked fire.
Until the fifteenth century the only alum factories from which Europe was supplied were at Constantinople, Smyrna, and Trebizonde. Beckman relates that an alum factory was founded in the Isle of Ischia, on the coast of Tuscany, by a Genoese merchant named Bartholomew Perdix, who had learnt the art at Rocca. Very soon afterwards John de Castro, a Paduan who had been engaged in cloth dyeing at Constantinople but had lost all his property when that city was captured by Mahomet II in 1453, was appointed to an office in the Treasury of the Apostolic Chamber, and in the course of his duties found what he believed to be an aluminous rock at Tolfa, near Civita Vecchia. He asked the Pope, Pius II, to allow him to experiment, but it was some years before the necessary permission was granted. When at last the truth of Castro’s surmise was established the Pope was greatly interested. He looked upon the discovery as a great Christian victory over the Turks, and handsomely rewarded de Castro, to whom, besides, a monument was erected in Padua inscribed “Joanni de Castro, Aluminis inventor.” The factory brought in a splendid revenue to the Apostolic exchequer, and the Pope did his utmost to retain the monopoly, for when in consequence of the extravagant prices to which the Tolfa alum was raised merchants began again to buy the Eastern product his Holiness issued a decree prohibiting Christians from purchasing from the infidels under pain of excommunication. Later, when, in Charles I’s reign, Sir Thomas Challoner discovered an aluminous deposit near his home at Guisborough in Yorkshire, and persuaded some of the Pope’s workmen to come there to work the schist, he and those whom he had tempted away were solemnly and most vigorously “cursed.”
Meanwhile the nature of the earth with which the sulphuric acid was combined remained unknown to chemists. Stahl worked at the problem and came to the conclusion that it was lime. The younger Geoffroy, a famous pharmacist of Paris, ascertained (1728) that the earth of alum was identical with that of argillaceous earth and Alumina was for some time called Argile. Marggraf observed that he could not get alum crystals from a combination of argile and sulphuric acid, but noting that in the old factories it had been the custom to add putrid urine to the solution, for which carbonate of potash was subsequently substituted, went so far as to make the salt, but did not appreciate that it was actually a double salt. The name alumina which the earth now bears was given to it by Morveau. It was Vauquelin (another pharmacist) who clearly proved the composition of alum, and Lavoisier first suggested that alumina was the oxide of a metal. Sir Humphry Davy agreed with this view but failed to isolate the metal. Oersted was the first to actually extract aluminium from the oxide, but his process was an impracticable one, but in 1828 Woehler, and in 1858 Deville, found means of producing the metal in sufficient abundance to make it a valuable article of industry.
Ammonia.
The chemical history of ammonia commences in Egypt with Sal Ammoniac. This is mentioned by Pliny under the name of Hammoniacus sal. Dioscorides also alludes to it; but in neither case does the description given fit in satisfactorily with the product known to us. Dioscorides, for instance, states that sal ammoniac is particularly prized if it can lie easily split up into rectangular fragments. It has been conjectured that what was called sal ammoniac by the ancient writers was, at least sometimes, rock salt.
The name is generally supposed to have been derived from that of the Egyptian deity, Amn or Amen, or Ammon as the Greeks called him, and in the belief that he was the same god as Jupiter he is referred to in classical literature as Zeus-Ammon or Jupiter-Ammon. The principal temple of this god was situated in an oasis of the Libyan desert which was then known as Ammonia (now Siwah), and if, as is supposed, the salt was found or produced in that locality its name is thus accounted for. Gum ammoniacum was likewise so called in the belief that it was obtained in that district, though the gum with which we are familiar and which comes from India and Persia, is quite a different article from the African gum the name of which it has usurped. Pliny derives the name of the salt from the Greek “ammos,” sand, as it was found in the sand of the desert; an explanation which overlooks the fact that the stuff was called by a similar name in a country where the sand was not called ammos. In old Latin, French, and English writings “armoniac” is often met with. This was not inaccurate spelling; it was suggested by the opinion that the word was connected with Greek, armonia, a fastening or joining, from the use of sal ammoniac in soldering metals.
That Pliny did sometimes meet with the genuine sal ammoniac is conjectured by his allusion to the “vehement odour” arising when lime was mixed with natrum. Probably this natrum was sal ammoniac. Among the Arabs the term sal ammoniac often means rock salt; but in the writings attributed to Geber, some of which may be as late as the twelfth or thirteenth century, our sal ammoniac is distinctly described. It is also exactly described by Albertus Magnus in the thirteenth century, who mentions an artificial as well as a natural product, but does not indicate how the former was made. From this time sal ammoniac became a common and much-prized substance in alchemical investigations, as from it chlorides were obtained. The “volatile spirit of sal ammoniac” was made by distilling a solution of sal ammoniac with quicklime, and of course the same product was obtained in other ways, especially by distilling harts’ horns, and this was always regarded as having peculiarly valuable properties. A “sal ammoniacum fixum” was known to the alchemists of the fifteenth century. It was obtained as a residue after sal ammoniac and quicklime had been sublimed. It was simply chloride of calcium.
The so-called natural sal ammoniac was for centuries brought from Egypt, and was supposed to have been mined in the earth or sand of that country. In 1716 the younger Geoffroy came to the conclusion that it must be a product of sublimation, and he read a paper to the French Academy giving his reasons for this opinion. Homberg and Lemery opposed this view with so much bitterness, however, that the paper was not printed. In 1719 M. Lemaire, French Consul at Cairo, sent to the Academy an account of the method by which sal ammoniac was produced in Egypt, and this report definitely confirmed the opinion which Geoffroy had formed. It was, said M. Lemaire, simply a salt sublimed from soot. The fuel used in Egypt was exclusively the dung of camels and other animals which had been dried by the sun. It consisted largely of sal ammoniac, and this was retained in the soot. For a long time an artificial sal ammoniac had been manufactured at Venice, and a commoner sort also came from Holland. These were reputed to be made from human or animal urine. The manufacture of sal ammoniac was commenced in London early in the eighteenth century by a Mr. Goodwin.
A formula for Sal Ammoniacum Factitium in Quincy’s Dispensatory (1724) is as follows:—Take of Urine lb. x.; of Sea-salt lb. ii.; of Wood soot lb. i.; boil these together in a mass, then put them in a subliming pot with a proper head, and there will rise up what forms these cakes. Dr. James (1764) states that at Newcastle one gallon of the bittern or liquor which drains from common salt whilst making, was mixed with 3 gallons of urine. The mixture was set aside for 48 hours to effervesce and subside. Afterwards the clear liquor was drawn off and evaporated in leaden vessels to crystallisation. The crystals were sublimed. A sal ammoniacum volatile was made by subliming sal ammoniac and salt of tartar (or lime or chalk) together. Sometimes some spices were put into the retort. This salt was used for smelling-bottles. Aqua regia was made by distilling sal ammoniac and saltpetre together.
Sal Volatile Oleosum was introduced by Sylvius (de la Boe) about the year 1650. It became a medicated stimulant of the utmost popularity, and there were many formulas for it. One of the most famous was Goddard’s Drop. (See page 319).
Ammonia in gaseous form was first obtained by Priestley in 1774. He called it alkaline air. Scheele soon after established that it contained nitrogen and Berthollet proved its chemical composition in 1785.
Spiritus Ammoniæ Aromaticus
was first inserted in the P.L. 1721, under the title of “Spiritus Salis Volatilis Oleosus.” Cinnamon, mace, cloves, citron, sal ammoniac, and salts of tartar were distilled with spirit of wine. In 1746 the process was altered, sal ammoniac and fixed alkali being first distilled with proof spirit to yield “spiritus salis anmioniaci dulcis,” to which essential oils of lemon, nutmeg, and cloves were added, and the mixture was then re-distilled. In 1788 the spirit became spiritus ammoniæ compositus, and the redistillation when the oils had been added was omitted. The name spiritus ammoniæ aromaticus was first adopted in the P.L. 1809, and has been retained ever since, though the process of making it has been frequently varied. That title was first given to it in the Dublin Pharmacopœia of 1807. Spiritus Salinus Aromaticus was the first title adopted in the Edinburgh Pharmacopœia. It was a preparation similar to that of the P.L., but angelica, marjoram, galangal, anthos flowers, orange, and lemon were additional flavours.
Quincy (1724) credits Sylvius with the invention of this spirit, which he refers to as “mightily now in use,” and as “a most noble cephalic and cordial.” It had “almost excluded the use of spirit of hartshorn.” This preparation, invented by Sylvius, was called the Carminative Spirit of Sylvius.
Mindererus’s Spirit, made from distilled vinegar and the volatile spirit of hartshorn, is believed by many competent authorities to have possessed virtues which are not contained in the modern liquor ammonii acetati. The late Professor Redwood was one of these. He believed that the old preparation contained a trace of cyanic ether. The new liquor, he said, made from strong caustic solution of ammonia and strong acetic acid, “is but the ghost of the old preparation. It is as unlike the true Mindererus’s Spirit as a glass of vapid distilled water is unlike the sparkling crystal water as it springs from a gushing fountain” (Pharm. Jnl., Vol. V., N.S. p. 408). Mindererus was a physician of Augsburg who died in 1621. It was Boerhaave in 1732 who advocated the use of Mindererus’s Spirit and made it popular.
Eau de Luce, which was official in the P.L. 1824, under the title of Spiritus Ammoniæ Succinatus, was an ammonia compound which became popular in France, and, in some degree all over Europe, about the middle of the eighteenth century, and was apparently first sold for removing grease from cloth and other fabrics. It is said that one of the pupils of Bernard Jussieu, having been bitten by a viper, applied some of the preparation, and was cured by it. It thence acquired a medical fame, which it still retains. The P.L. formula ordered 3 drachms of mastic, 4 minims of oil of amber, and 14 minims of oil of lavender to be dissolved in 9 fluid drachms of rectified spirit, and mixed with 10 fluid ounces of solution of ammonia. In some of the Continental pharmacopœias a much larger proportion of oil of amber is prescribed, and sometimes only that and spirit of ammonia. In some soap is ordered. In the P.L., 1851, the oil of amber was omitted. It has been recommended for external application in rheumatism and paralysis.
It has been generally asserted that this preparation was devised by a pharmacist of Lille (some say of Amsterdam), of the name of Luce. It is also asserted that a Paris pharmacist named Dubalen originated it, and that he and his successor Juliot made it popular; that Luce of Lille imitated it, but that not being able to get it purely white added some copper and gave it a blue tint which came to be a mark of its genuineness. Among the names applied to it have been Aqua Luccana, Aqua Sancti Luciæ, Aqua Lucii, and Eau de Lusse.
Bromine.
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.
Dr. Nehemiah Grew.
Born, 1628; died, 1711.
(From an engraving by R. White, from life.)
Dr. Grew was for many years secretary of the Royal Society and editor of the Philosophical Transactions. He was one of the pioneers of the science of structural botany and author of The Anatomy of Plants.
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 H2O [alcohol, C2H5O HO; ether, (C2H5)2O]. Distilling spirit of wine and sulphuric acid together, it seemed obvious that the sulphuric acid should possess itself of the H2O, 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.
The first use of carbonate of magnesia medicinally was in the form of a secret medicine which must have acquired much popularity in the beginning of the eighteenth century. It was prepared, says Bergmann, by a regular canon at Rome, sold under the title of the powder of the Count of Palma, and credited with almost universal virtues. The method of preparation was rigidly concealed, but it evidently attracted the attention of chemists and physicians, for it appears that in 1707 Valentini published a process by which a similar product could be obtained from the mother liquor of “nitre” (soda) by calcination. In 1709 Slevogt obtained a powder exactly resembling it by precipitating magnesia from a solution of the sulphate by potash. Lancisi reported on it in 1717, and in 1722 Hoffmann went near to explaining the distinction between the several earthy salts, which in his time were all regarded as calcareous.
Hoffmann’s process to obtain the powder was to add a solution of carbonate of potash to the mother liquor from which rough nitre had been obtained (solution of chloride of magnesium), and collect the precipitate. This being yielded by two clear solutions gave to the carbonate of magnesia precipitated the name of Miraculum Chemicum.
Magnesia was the name of a district in Thessaly, and of two cities in Asia Minor. The Greek “magnesia lithos,” magnesian stone, has been frequently applied to the lodestone, but this can hardly have been correct, as the magnesian stone was described as white and shining like silver. Liddell and Scott think talc was more probably the substance. The alchemists sometimes mention a magnesia, but the name seems to have been a very elastic one with them. The Historical English Dictionary quotes the following reference to the word from “Norton Ord. Alch.,” 1477:—“Another stone you must have ... a stone glittering with perspicuitie ... the price of an ounce conveniently is Twenty Shillings. Her name is Magnetia. Few people her knows.”
Paracelsus uses the term in the sense of an amalgam. He writes of the Magnesia of Gold. In Pomet’s “History of Drugs,” 1712, magnesia meant manganese. Hoffmann, 1722, first applied the name to oxide of magnesia, adapting it from the medical Latin term, magnes carneus, flesh magnet, because it adheres so strongly to the lips, the fancy being that it attracts the flesh as the lodestone attracts iron.
Hoffmann’s observations on magnesia and its salts, which were published in the first quarter of the eighteenth century, were very intelligent, and undoubtedly it was he who first distinguished magnesia from chalk. He says “A number of springs, among which I may mention Eger, Elster, Schwalbach, and Wilding, contain a neutral salt which has not yet received a name, and which is almost unknown. I have also found it in the waters of Hornhausen which owe to this salt their aperient and diuretic properties. Authors commonly call it nitre; but it has nothing in common with nitre. It is not inflammable, its crystallising form is entirely different, and it does not yield aqua fortis. It is a neutral salt similar to the arcanum duplicatum (sulphate of potash), bitter in taste, and producing on the tongue a sensation of cold.” He further states that the salt in question appears to proceed from the combination of sulphuric acid with a calcareous earth of alkaline nature. The combination “is effected in the bosom of the earth.” In another of his works Hoffmann distinguishes the magnesian salt from one of lime, showing particularly that the latter was but slightly soluble and had scarcely any taste. Crabs’ eyes and egg shells he notes combine with sulphuric acid and form salts with no taste. The sulphate of this earth (Epsom salt) he found had a strong bitter taste.
The true character of magnesia and its salts was not clearly understood until Joseph Black unravelled the complications of the alkaline salts by his historic investigation, which became one of the most noted epochs of chemistry by its incidental revelation of the combination of the caustic alkalies with what Black termed “fixed air,” subsequently named carbonic acid gas by Lavoisier in 1784. When Black was studying medicine at Edinburgh a lively controversy was in progress in medical circles on the mode of action of the lithontriptic medicines which had lately been introduced. Drs. Whytt and Aston, both university professors, were the leaders in this dispute. Whytt held that lime water made from oyster shells was more effective for dissolving calculi in the bladder than lime water prepared from ordinary calcareous stone. Alston insisted that the latter was preferable. Black was interested, and his experiments convinced him of the scientific importance of his discoveries. He postponed taking his degree for some time in order to be sure of his facts. His graduation thesis, which was dated June 11, 1754, was entitled “De humore acide cibis orto et magnesia alba.” His full treatise, “Experiments upon magnesia alba, quicklime, and some other alkaline substances,” was published in 1756. It had been previously believed that the process of calcining certain alkaline salts whereby caustic alkalies were produced was explained by the combination with the salt of an acrid principle derived from the fire. Now it was shown that something was lost in the process; that the calcined alkali weighed less than the salt experimented with. The something expelled Black proved was an air, and an air different from that of the atmosphere, which was generally supposed to be the one air of the universe. He identified it with the “gas sylvestre” of Van Helmont, and named it “fixed air.” Magnesia alba first appeared in the London Pharmacopœia of 1787 under that name.