Chapter VII: Section 3: This Act shall not take effect until the first day of July, (4)
This brings us to the practical question, What is to be done? All agree that there ought to be a reform. On this point we can do no better than quote the close of Mr. Alexander’s preface.—“Finally,” says he (page vii.) “if I may be allowed, in connection with this work and its appropriate applications, to allude to certain dreams of my own, (as they may be; although I consider them capable, without undue effort, of a more prompt and thorough realisation than seems to be ordinarily anticipated,) as to the prevalence, some day, of an universal conformity of weights and measures, I must acknowledge that such a result was one of the ends I had in view in the original collection of materials. Not that such a work was going to show more emphatically than business men feel, and reflecting men know, the importance of such an universal conformity; or that a book whose pages deal in discords, could, of itself, produce unison; but the first step to any harmonious settlement is, to see clearly, and at a glance, where the differences lie, and what they are.—If a millennial period for this world is ever to come, as many wise have deemed, and pious prayed, it must be preceded by one common language, and one common system of weights and measures, as the basis of intercourse. And the way to that is to be built, not by the violent absorption of other and diverse systems into one, but rather by a compromise into which all may blend. When the Earth, in her historical orbit, shall {139} have reached that point, (as it stood ere mankind were scattered from the plain of Shinar) and not till then, may we begin to hope that her revolutions will be stilled, and that before long the weights and measures of fleeting Time will be merged and lost in the infinite scales and illimitable quantities of Eternity.” We are not sure that we precisely understand the last sentence, and we are sure we dissent entirely from the one that precedes it. No compromise can be of service in bringing about a uniformity in weights and measures. We must either make a better system than the best extant, and ask all men to adopt it, or if the best that human ingenuity and science can devise is already in use, so much the better; let us adopt it with all our heart. Is the French system this best one? We believe it is, nor have we ever heard it called in question.—Why then speak of a new one as desirable? We fear the suggestion is the offspring of a national vanity, which ought to be beneath us. We would not oppose such a motive even to the introduction of the centigrade thermometer, which is much more inconvenient than Fahrenheit’s, and has _no one_ advantage over it in any respect; still less should it bar the progress of a system against which no fault can be alleged, but that it is _foreign_.
We agree with our author that the introduction of a new system is much easier than is generally supposed. It will not be like the change of a monetary system, where the old coins remain, mingled with the new, to perpetuate the old names.—The change could be, by law, effected next New Year’s day, and all inconvenience from it would be over in a month, save some awkwardness from habit, and two more serious difficulties. One is from the human propensity to _bisection_. Thus the old hundredweight of 112 pounds is bisected down to 7 pounds, and the grocer will sell half this quantity, 3 1/2 pounds, at a cheaper rate than he will sell 3 pounds or 4. Unfortunately in bisecting 100 we run down too soon to the fractions 12 1/2 and 6 1/4. The French have been obliged to give way to this propensity, and divide the kilogramme in a binary manner, {140} with an unavoidable irregularity, reckoning 31 1/4 grains as 32. Would that 32 × 32 = 1000! Our only remedy is to change the radix of numeration from 10 to 16, a thing impossible but to a universal dictator. The other difficulty is in our measure for land. This must remain in all surveyed tracts in such a shape that 40 acres, and also 5 acres, shall be some multiple of unity.
But shall the apothecary wait the action of government?—This is neither necessary nor desirable. Some relief he ought to have speedily. If he dare not make so great an advance as to adopt the French system, (his truest and most honorable policy,) let all subdivisions of the avoirdupois pound be discarded, except the grain. Introduce the chemists’ weights of 1000, 500, 300, 100, 50, &c. grains, and let all prescriptions be written in grains alone. This, perhaps, is the only feasible course.
We must return once more to our author before taking leave of our readers. The motive for making the collection was one that strikes us as new. It was for ethnological and historical purposes. As the carat points to India as the origin of the diamond trade, so we find in the names, mode of subdivision, and amount of weights and measures evidences of the migrations of races, and of the ancient and obsolete channels in which trade once flowed. The care with which Mr. Alexander seems to have corrected these tables, and adjusted the discordant elements of which they are composed, and corrected the discrepancies between them, makes them more worthy of reliance than anything that has preceded them, and leaves little to be desired that is within the reach of human attainment. After the alphabetical arrangement, are given the weight and measure systems of the “principal countries of the world,” beginning with Abyssinia and ending with Würtemberg. And we have only to add that the mechanical execution of the volume is worthy of the care and labor the author has spent upon it, unsurpassed, in fact, by any book made for use we have ever seen.
{141}
QUINIDINE.
BY MR. ROBERT HOWARD.
This alkaloid, which gained a prize in the Great Exhibition, has scarcely yet attracted much attention. Some of the cheaper barks now largely imported from New Grenada contains so much of it that it is, perhaps, as well that it should be more studied. The _Cinchona cordifolia_, from this part of the continent, is particularly rich in it. It is, however, contained in larger or smaller quantities in the Bolivian and Peruvian barks—the _Cinchona Calisaya_, _Boliviana_, _rufinervis_, and especially _ovata_.
Referring your readers to a very able paper in your Journal,[10] I beg to add a few facts from my own observations.
The sulphate of quinidine, or β quinine as it is called by some, (Van Heijninger and others,) is so like the sulphate of quinine, that the eye or the taste can with difficulty distinguish them. It forms the same light fibrous crystallization, and occupies as large a bulk. It corresponds in appearance with the description given by Winckler, of “chinidine.” (See _Pharm. Journ._ for April, 1845, vol. iv., p. 468.) He notices that it has “a remarkably white color and a peculiarly faint lustre.” Its most striking characteristic is its extreme solubility. Pure sulphate of quinine requires nearly thirty times its weight of boiling water for solution, whilst the sulphate of quinidine dissolves in four parts. On the other hand the pure alkaloid crystallizes readily out of proof spirit and out of ether, whilst quinine does not crystallize out of either. A very good test for the presence of cinchonine in sulphate of quinine is also capable of being applied to detect the presence of β quinine. On this point I would refer for very interesting details to a paper by M. Guibourt, in the _Journal de Pharmacie_ for January in this year.
[10] _Pharmaceutical Journal_, vol. ix., p. 322, January, 1850.
In your Journal of April, 1843, I gave a test for sulphate of quinine, to which I would again advert, because subsequent {142} experience has proved it to be a tolerable easy, and at the same time exact means of ascertaining its purity. Put 100 grains in a Florence flask with five ounces of distilled water, heat this to brisk ebullition; the sulphate of quinine ought not to be entirely dissolved; add two ounces more water, and again heat it to ebullition; ought to make a perfectly clear solution. If this be allowed to cool for six hours, and the crystals carefully dried in the open air on blotting paper, they will be found to weigh about ninety grains, the mother-liquor may be evaporated and tested with ether, when any cinchonine or β quinine will be easily detected. On examining sulphate of quinine of commerce from several leading manufacturers, I have found all of them give, within a grain or two, the same result, and, in each, indications of a β quinine, though to an unimportant extent.
The above quantity of water (seven ounces) readily dissolves 800 grains of sulphate of β quinine; and if 100 grains of this salt are dissolved in seven ounces of water, the crystals as above weigh only fifty-four grains, thus leaving forty-six grains in solution instead of about ten grains.
The medical effects of β quinine deserve investigation, the chemical constitution and the taste appear to indicate a great similarity if not identity.
ON THE ADULTERATION OF SULPHATE OF QUININE, AND THE MEANS OF DETECTION.
Mr. Zimmer, manufacturer of sulphate of quinine in Frankfort-on-the-Maine, has published the following circular and paper to his correspondents abroad:
_Frankfort-on-the-Maine, Feb._ 6th, 1852.
You are doubtless, aware that various and partly spurious kinds of sulphate of quinine have for some time past found their way into the market. The substance now frequently {143} mixed with quinine is quinidine. But little positive is as yet known of the medicinal properties of this alkaloid, and whatever may be the result of future experiments, its arbitrary substitution is, under any circumstances, unwarrantable, and renders all fair and honest competition almost impossible.
The importance of the subject has induced me to address a few words to you, that I may submit a simple experiment by means of which the most usual adulterations of quinine may readily be detected.
I have the honor to be, with much respect, &c. C. ZIMMER.
* * * * *
The high price of genuine Bolivian _Cinchona Calisaya_, through the monopoly of its export, has given occasion to imports, from other districts, of _Cinchonas_, the quality of which widely differs from that of the Calisaya, inasmuch as they contain principally quinidine. The lower prices of these barks, regardless of their different constituents, have brought them quickly into use in many factories of quinine, whereby a large quantity of quinine, containing quinidine, has got into the market, causing an undue depreciation in the price of quinine.
The existence of this third cinchona-alkaloid is now established beyond a doubt by ultimate analysis, by the peculiarity of its salts, and by important distinctive tests; and there can be no further question, that quinidine must, equally with cinchonine, be distinguished from quinine. The external characters of sulphate of quinidine differ from those of sulphate of quinine; it has a greater specific gravity and less flocculent crystallization. In dry warm air it parts with its water of crystallization, without deliquescing or losing its crystallized aspect; lastly, it is far more soluble than sulphate of quinine in cold water and in alcohol.
One of the distinctive properties of the three alkaloids in question, _viz._, their behavior with ether—places in our hands a ready means of detecting the mixture of cinchonine and {144} quinidine, with quinine. Schweitzer (_Lond. Med. Gazette_, vol. xxi., p. 175) has already employed ether for the detection of cinchonine with complete success, and his process has, with justice, been subsequently quoted in most manuals, as it answers its purpose completely; cinchonine is known to be entirely insoluble in ether, whatever may be the quantity of ether employed. The solubility of quinidine in ether, as compared with that of quinine, is but slight; ten grains of pure sulphate of quinine dissolve in sixty drops of ether, and twenty drops of spirit of ammonia, while only one grain of sulphate of quinidine is soluble in the same quantity of the fluid; and in proportion quinine containing quinidine will always be less soluble than pure sulphate of quinine.
Guided by this fact I can recommend the following simple and very convenient process for the detection of quinidine and quinine:―
Ten grains of the salt to be examined is to put into a strong test tube, furnished with a tight-fitting cork, to this are to be added ten drops of diluted sulphuric acid, (one acid and five water) with fifteen drops of water, and a gentle heat applied to accelerate the solution. This having been affected, and the solution entirely cooled, sixty drops of officinal sulphuric ether with twenty drops of spirits of ammonia, must be added, and the whole well shaken while the top is closed by the thumb. The tube is then to be closely stopped and shaken gently from time to time, so that the bubbles of air may more readily enter the layer of ether.
If the salt examined be free from cinchonine and quinidine, or contain the latter in no greater proportion than ten per cent., it will be completely dissolved; while on the surface, where contact of the two layers of clear fluid takes place, the mechanical impurities only will be separated (in which respect the various sorts of commercial quinine differ.) After sometime longer the layer of ether becomes hard and gelatinous, after which no further observation is possible.
From the above statement respecting the solubility of {145} quinidine in ether, it appears that the ten grains of the salt to be examined, may contain one grain of quinidine, and still a complete solution with ether and ammonia may follow; but in this case the quinidine will shortly begin to crystallize in the layer of ether. The last trace of quinidine may be yet more definitely detected by employing, instead of the ordinary ether, some other, previously saturated with quinidine, by which means all of the quinidine contained in the quinine must remain undissolved. It is particularly requisite in performing this last experiment to observe, after the shaking, whether all has dissolved, for owing to the great tendency of quinidine to crystallization, it may become again separated in a crystalline form, and be a source of error.
If more than a tenth of quinidine or cinchonine be present, there will be found an insoluble precipitate at the limits of the two layers of fluids. If this be quinidine, it will be dissolved on the addition of proportionately more ether, while cinchonine will be unaffected.
It is expressly to be remarked, that the necessity for testing sulphate of quinine, in search of other fraudulent adulterations is not superseded by the above described process.
We have particularly to determine upon the absence of inorganic substances, which may be effected by subjecting to red heat on a platinum dish, or simply by solution in alcohol. Gypsum, chalk, magnesia, &c., will be left undissolved. Boracic acid will be dissolved by alcohol, but its green flame will indicate its presence in the alcoholic solution when ignited.
The absence of organic substances, such as salicine, sugar, stearic acid, &c., may be inferred from the formation of a colorless solution with pure concentrated cold sulphuric acid; it is as well to leave the sulphuric acid to act for some hours.
The presence of sal-ammoniac may be detected by the addition of caustic potash to the suspected salt, when, if present, it will be known by the diffusion of the ammoniacal odour.—_Pharmaceutical Journal, March, 1852._
{146}
REMARKS ON THE ENVELOPEMENT OF PILLS.
BY DORVAULT.
The envelopement of pills is a minute question, an accessory in this form of administering medicines, but as it is a frequent cause of trouble to practitioners, and as their successful operation is often due to their peculiar mode of exhibition, we shall perhaps be pardoned for devoting a short space to the subject.
In order that pills may not adhere to one another, they are rolled in an inert powder, such as marsh-mallow, liquorice, and above all, lycopodium. Carbonate of magnesia is now particularly used for pills of turpentine and copaiba. To disguise the peculiar odour of the pill mass, German practitioners use iris powder, or cinnamon.
To render pills more pleasing to the eye, as well as to disguise their taste, instead of rolling them in the before named powders, they are frequently covered with gold or silver leaf. The mode of doing this is too well known to need repetition. We will only remark that those pills which contain iodine, bromine, sulphur, iodides, bromides, sulphides, salts of mercury, gold, platina, &c., cannot be silvered.
These methods conceal but imperfectly the unpleasant taste and smell of certain pillular compounds. M. Garot, to obviate this inconvenience, has proposed to cover pills with a layer of gelatine, by means of a process which he has made public, and into the details of which we think it needless to enter. The gelatinous layer conceals the bad taste and smell perfectly, but it is attended with one inconvenience; in time it shrinks, cracks, and the pill mass exudes. Besides, much skill is required in its manipulation. After gelatinization comes sugaring. This is frequently preferable to the former modes, and can be equally well applied to pills of a repulsive taste and smell, (copaiba, turpentine, musk, assafœtida, &c.,) or to those which are changed by air or light, (proto salts of iron,) or deliquescent, (iod-hydrargyrate of iodide of potassium,) or caustic, (croton oil.) It can extemporaneously be performed in the following manner:—Put the pills into a vase with a round bottom, {147} or into a box lined with silver, moisten them with a little syrup of sugar, clear mucilage, or white of eggs, agitate them so as to moisten them uniformly; add a mixture of equal parts of gum, sugar and starch; again rotate them, so as equally to enclose all the pills. If a first layer be not sufficient, add a second and third in the same manner. Dry them in the air or in a stove. In damp weather, these pills should be enclosed in corked bottles. Gelatine of carragheen or caseine dried and powdered may be substituted for the above powdered mixture. This method is more expeditious than gelatinisation, and it has besides the advantage of the material being always perfectly soluble. Collodion has been proposed for enveloping pills, but seems never to have been used.
The last method we shall call _toluisation_. It appears to possess many decided advantages over the others. M. Blancard, its originator, employs it particularly for pills of proto iodide of iron. It is to induce its more general use that we make these remarks. The following is the mode of proceeding, which can be modified to suit the daily wants of practice:
Dissolve one part of balsam of tolu, in three parts of ether, (the balsam which has been used in the preparation of syrup of tolu will answer perfectly;) pour some of this tincture into a capsule containing the pills, to favor the evaporation of the ether. When the pills begin to stick together, throw them on a mould of tin passed through mercury, or simply on a plate, taking care to separate those which stick together. Set them in the air to dry. The drying may be completed in a stove of moderate heat, especially if several layers have been found necessary. This mode of enveloping may take the place, or nearly so, of all the others. An important point in it, is, that it resists the effects both of damp and dryness on the pill mass. Its balsamic odour is generally agreeable; but should it not be so, the tolu might be replaced by some inert resin soluble in ether, as mastic tears for example. The layer of resinous matter is so thin, that we apprehend no obstacle in its influence on the medicine. {148}
We will, however, make one general remark, namely: that as each method possesses some peculiar advantages, we thought it right to give them all.—_Bulletin Gen. Ther. Med. et Chir. January, 1852._
ON THE APPLICATION OF ORGANIC CHEMISTRY TO PERFUMERY.
BY DR. A. W. HOFFMAN.
Professor to the Royal College of Chemistry, London.
Cahours’ excellent researches concerning the essential oil of gaultheria procumbens (a North American plant of the natural order of the Ericinæ of Jussieu,) which admits of so many applications in perfumery, have opened a new field in this branch of industry. The introduction of this oil among compound ethers must necessarily direct the attention of perfumers towards this important branch of compounds, the number of which is daily increasing by the labors of those who apply themselves to organic chemistry. The striking similarity of the smell of these ethers to that of fruit has not escaped the observation of chemists; however, it was reserved to practical men to discover by which choice and combinations it might be possible to imitate the scent of peculiar fruits to such a nicety, as to make it probable that the scent of the fruit is owing to a natural combination identical to that produced by art; so much so, as to enable the chemist to produce from fruits the said combinations, provided he could have at his disposal a sufficient quantity to operate upon. The manufacture of artificial aromatic oils for the purpose of perfumery is, of course, a recent branch of industry; nevertheless, it has already fallen into the hands of several distillers, who produce sufficient quantity to supply the trade; a fact, which has not escaped the observation of the Jury at the London Exhibition. In visiting the stalls of English and French perfumers at the Crystal Palace, we found a great variety of these chemical perfumes, {149} the applications of which were at the same time practically illustrated by confectionery flavored by them. However, as most of the samples of the oils sent to the Exhibition were but small, I was prevented, in many cases, from making an accurate analysis of them. The largest samples were those of a compound labelled “Pear oil,” which, by analysis, I discovered to be an alcoholic solution of pure acetate of amyloxide. Not having sufficient quantity to purify it for combustion, I dissolved it with potash, by which free fusel oil was separated, and determined the acetic acid in the form of a silver salt.
0,3080 gram. of silver salt = 0,1997 gram. of silver.
The per centage of silver in acetate of silver is, according to
Theory. Experiment.
64,68 64,55.
The acetate of amyloxide which, according to the usual way of preparing it, represents one part sulphuric acid, one part fusel oil, and two parts of acetate of potash, had a striking smell of fruit, but it acquired the pleasant flavor of the jargonelle pear only after having been diluted with six times its volume of spirits of wine.
Upon further inquiry I learned that considerable quantities of this oil are manufactured by some distillers, from fifteen to twenty pounds weekly, and sold to confectioners, who employ it chiefly it flavoring pear-drops, which are nothing else but barley-sugar, flavored with this oil.
I found, besides the pear-oil, also an _apple-oil_, which, according to my analysis, is nothing but valerianate of amyloxide. Every one must recollect the insupportable smell of rotten apples which fills the laboratory whilst making valerianic acid. By operating upon this new distillate produced with diluted potash, valerianic acid is removed, and an ether remains behind which, diluted in five or six times its volume of spirits of wine, is possessed of the most pleasant flavor of apples.
The essential oil most abundant in the Exhibition was the pine-apple oil, which, as you well know, is nothing else but the butyrate of ethyloxide. Even in this combination, as in {150} the former, the pleasant flavor or scent is only attained by diluting the ether with alcohol. The butyric ether which is employed in Germany to flavor bad rum, is employed in England to flavor an acidulated drink called pine-apple ale. For this purpose they generally do not employ pure butyric acid, but a product obtained by saponification of butter, and subsequent distillation of the soap with concentrated sulphuric acid and alcohol; which product contains, besides the butyric ether, other ethers, but nevertheless can be used for flavoring spirits. The sample I analyzed was purer, and appeared to have been made with pure butyric ether.
Decomposed with potash and changed into silver salt, it gave
0,4404 gram. of silver salt = 0,2437 gram. of silver.
The per centage of silver in the butyrate of silver is according to
Theory. Experiment.
55,38 55,33.
Both English and French exhibitors have also sent samples of cognac-oil and grape-oil, which are employed to flavor the common sorts of brandy. As these samples were very small, I was prevented from making an accurate analysis. However, I am certain that the grape-oil is a combination of amyl, diluted with much alcohol; since, when acted upon with concentrated sulphuric acid, and the oil freed from alcohol by washing it with water, it gave amylsulphuric acid, which was identified by the analysis of the salt of barytes.
1,2690 gram. of amylsulphate of barytes gave 0,5825 gram. of sulphate of barytes. This corresponds to 45,82 per cent. of sulphate of barytes.
Amylsulphate of barytes, crystallized with two equivalents of water, contains, according to the analysis of Cahours and Kekule, 45,95 per cent. of sulphate of barytes. It is curious to find here a body, which, on account of its noxious smell, is removed with great care from spirituous liquors, to be applied under a different form for the purpose of imparting to them a pleasant flavor. {151}
I must needs here also mention the artificial oil of bitter almonds. When Mitscherlich, in the year 1834, discovered the nitrobenzol, he would not have dreamed that this product would be manufactured for the purpose of perfumery, and, after twenty years, appear in fine labelled samples at the London Exhibition. It is true that, even at the time of the discovery of nitrobenzol, he pointed out the striking similarity of its smell to that of the oil of bitter almonds. However, at that time, the only known sources for obtaining this body were the compressed gases and the distillation of benzoic acid, consequently the enormity of its price banished any idea of employing benzol as a substitute for oil of bitter almonds. However, in the year 1845, I succeeded by means of the anilin-reaction in ascertaining the existence of benzol in common coal-tar-oil. In his essay, which contains many interesting details about the practical use of benzol, he speaks likewise of the possibility of soon obtaining sweet scented nitrobenzol in great quantity. The Exhibition has proved that this observation has not been left unnoticed by the perfumers. Among French perfumeries we have found, under the name of artificial oil of bitter almonds, and under the still more poetical name of “essence de mirbane,” several samples of essential oils, which are no more nor less than nitrobenzol. I was not able to obtain accurate details about the extent of this branch of manufacture, which seems to be of some importance. In London, this article is manufactured with success. The apparatus employed is that of Mansfield, which is very simple; it consists of a large glass worm, the upper extremity of which divides in two branches or tubes, which are provided with funnels. Through one of these funnels passes a stream of concentrated nitric acid; the other is destined as a receiver of benzol, which, for this purpose, requires not to be quite pure; at the angle from where the two tubes branch out, the two bodies meet together, and instantly the chemical combination takes place, which cools sufficiently by passing through the glass worm. The product is afterwards washed with water, and some diluted solution of carbonate of {152} soda; it is then ready for use. Notwithstanding the great physical similarity between nitrobenzol and oil of bitter almonds, there is yet a slight difference in smell which can be detected by an experienced nose. However, nitrobenzol is very useful in scenting soap, and might be employed with great advantage by confectioners and cooks, particularly on account of its safety, being entirely free from prussic acid.
There were, besides the above, several other artificial oils; they all, however, were more or less complicated, and in such small quantities, that it was impossible to ascertain their exact nature, and it was doubtful whether they had the same origin as the former.
The application of organic chemistry to perfumery is quite new; it is probable that the study of all the ethers or ethereal combinations already known, and of those which the ingenuity of the chemist is daily discovering, will enlarge the sphere of their practical applications. The caprylethers lately discovered by Bouris are remarkable for their aromatic smells (the acetate of capryloxide is possessed of the most intense and pleasant smell,) and they promise a large harvest to the manufacturers of perfumes.—_Annalen der Chemie.—In An. of Pharmacy._
ON TESTS FOR THE IMPURITIES OF ACETIC ACID.
Pure acetic acid is colorless, possesses strong acid properties and taste, and no empyreumatic flavor. It should have, according to the new London Pharmacopœia, a specific gravity of 1.048, and one hundred grains should saturate eighty-seven grains of crystallized carbonate of soda; consequently the pharmacopœial acid consists of thirty-one per cent. of the anhydrous acid, and sixty-nine per cent. of water. It should leave no residuum by evaporation. Sulphuretted hydrogen, nitrate of barytes, ferrocyanuret of potash, and nitrate of silver, should produce no precipitate in it. When it contains empyreumatic {153} matter, which besides being evident to the smell, concentrated sulphuric acid causes its color to darken. Sugar, in a more or less changed condition, is frequently one of the impurities of the German diluted commercial acid, and may be recognized by the taste of the residuum left upon its evaporation.
When sulphuretted hydrogen produces in acetic acid a milky turbidity, it shows that sulphurous acid is present, the presence of which is due to the decomposition of coloring and other organic matters, contained as impurities in the acetates, from which the acetic was prepared, when treated with sulphuric acid. The turbidity is caused by the separation of sulphur from the sulphuretted hydrogen, and from the sulphurous acid by reason of the hydrogen of the former combining with the oxygen of the latter, and forming water (Wittstein.) If the sulphuretted hydrogen produces a black precipitate, either lead or copper may be present. The lead may be recognized by sulphuric acid giving a precipitate of sulphate of lead; and the copper, by the blue reaction which ensues, with an excess of ammonia. Sulphuric acid can be readily known when present by nitrate of barytes producing a white precipitate, insoluble in mineral acids. Nitrate of silver detects muriatic acid by throwing down a white precipitate, which changes, under the influence of light, to a violet color, and is insoluble in nitric acid, but soluble in ammonia. Ferrocyanuret of potassium will indicate the presence of salt of iron when by its addition, a blue precipitate results.
The above tests are not applicable to the same extent to detect the impurities of the brown vinegar of commerce, because manufacturers are allowed by law to add to it a small per centage of sulphuric acid, and there are always sulphates and chlorides and other salts present in it, derived from the water used in its manufacture; therefore, in testing for its impurities, an allowance must be made for those which arise from the necessary process of the manufacture, and those considered only as adulterations which are over and above such fair allowance. To detect such impurities as cayenne pepper, {154} &c., it is merely necessary to neutralize the vinegar with carbonate of soda, when their presence will be palpably evident to the taste.
Acetic acid may be purified by distillation from those substances which are not volatile. By adding acetate of lead previously to its distillation, sulphuric and muriatic acids can be separated from it; and sulphurous acid can be removed by peroxide of manganese, which converts it into sulphuric acid. It can be freed from empyreumatic impurities by agitation with charcoal, subsequent filtration and distillation.
The strength of acetic acid and vinegar cannot be determined by the specific gravity. The power of saturating an alkaline carbonate is the best criterion of the quantity of anhydrous acid present in any given sample. This method will only give correct results when the acid is pure, or when the quantities of free mineral acids have been estimated previously by precipitation, so as to make the necessary deductions for their saturating power when the acid is neutralized with an alkaline carbonate. It would be well if pharmaceutists were more frequently to try the strength of their acetic acid, which is constantly sold with very plausible labels, about one part of the acid to seven parts of water, making the distilled vinegar of the Pharmacopœia, which statement we have oftentimes proved to be a very pretty fiction.—_An. of Pharmacy, March, 1852._
A TEST FOR ALCOHOL IN ESSENTIAL OILS.
J. J. Bernoulli recommends for this purpose acetate of potash. When to an etherial oil, contaminated with alcohol, dry acetate of potash is added, this salt dissolves in the alcohol, and forms a solution from which the volatile oil separates. If the oil be free from alcohol, this salt remains dry therein.
Wittstein, who speaks highly of this test, has suggested the following method of applying it as the best:—In a dry test {155} tube, about half an inch in diameter, and five or six inches long, put not more than eight grains of powdered dry acetate of potash; then fill the tube two-thirds full with the essential oil to be examined. The contents of the tube must be well stirred with a glass rod, taking care not to allow the salt to rise above the oil; afterwards set aside for a short time. If the salt be found at the bottom of the tube dry, it is evident that the oil contains no spirit. Oftentimes, instead of the dry salt, beneath the oil is found a clear syrupy fluid, which is a solution of the salt in the spirit, with which the oil was mixed. When the oil contains only a little spirit, a small portion of the solid salt will be found under the syrupy solution. Many essential oils frequently contain a trace of water, which does not materially interfere with this test, because, although the acetate of potash becomes moist thereby, it still retains its pulverent form.
A still more certain result may be obtained by distillation in a water bath. All the essential oils which have a higher boiling point than spirit, remain in the retort, whilst the spirit passes into the receiver with only a trace of the oil, where the alcohol may be recognized by the smell and taste. Should, however, a doubt exist, add to the distillate a little acetate of potash and strong sulphuric acid, and heat the mixture in a test tube to the boiling point, when the characteristic odor of acetic ether will be manifest, if any alcohol be present.
CHEMICAL EXAMINATION OF RESIN OF JALAP.
BY B. SANDROCK.
It is a well known fact that when resin of jalap is treated with ether, we obtain two kinds of resin, one soluble, and the other insoluble in ether. Dr. Kayser chose first for his analysis that part of the resin which is insoluble in ether. This resin, purified by means of charcoal, was friable, almost colorless, without smell or taste, insoluble in ether and water, but easily {156} dissolved by spirit of wine; the alcoholic solution reddens litmus slightly. The resin, again precipitated by water, was perfectly soluble in solution of caustic ammonia and acetic acid. This resin was dissolved with difficultly in cold solutions of caustic potash and soda, but was perfectly soluble when hot, and could again be readily precipitated from the alkaline solutions by acids. The solution of this resin, in ammonia was of a bright brown color, and became neutral by volatizing the superfluous ammonia. It is consequently a resinous acid, which is distinguished from other resinous acids, by the facts that it does not precipitate the bases from metalic salts, such as nitrate of silver, sulphate of copper; it afforded only a precipitate when acted upon by basic-acetate of lead. A question arose, whether the resin of jalap, dissolved in alkaline fluids, undergoes any changes in its constitution. To answer this question, Kayser undertook several analyses, the results of which were as follows: The uncombined resin of jalap gave C 42, H 35, O 20.—The resin, precipitated by oxide of lead, gave C 42, H 36, O 21. It is evident that resin of jalap, combined with the bases of salts, acquires the elements of one equivalent of water. Dr. Kayser, has named the unchanged resin of jalap, rhodeoretin, and that modified by bases of salts, hydro-rhodeoretin.
By dissolving rhodeoretin in absolute alcohol and submitting the solution to the action of chlorine, and subsequently adding water to it, Kayser obtained an oily fluid, dark yellow, possessing a pleasant smell, easy to be volatilized by heat, soluble in water, which he called rhodeoretin oil.
The part of the resin soluble in ether, possesses eminently the disagreeable smell of jalap, a prickly taste; its solution reddens litmus, and in drying leaves a greasy spot on paper; it is soluble in alkaline fluids. If the alcoholic solution is allowed to stand, mixed with water, for a lengthened period, prismatic crystalline needles are precipitated. According to these properties, Kayser includes the soluble jalap resin among the fatty acids. Sandrock in general agrees with Kayser; but, according to his analysis, the jalap can be resolved in three {157} different resins, one soluble in ether, the second obtained by precipitating the alcoholic solution by oxides of lead; the third remains unprecipitated in this solution.
That part of the resin which is insoluble in ether, but is precipitated from the alcoholic solution by oxide of lead, Sandrock calls alpha resin; that which is not precipitated, beta resin; that part which is soluble in ether he calls gamma resin.
The alpha resin agrees in its properties with Buchner’s and Herberger’s jalapine. Sandrock calls ipomic acid, the produce of this resin when treated by boiling carbonated alkaline solution; and the one obtained in the same way from beta resin, jalapic acid. The gamma resin forms in ether a yellow solution, and a purple one in concentrated sulphuric acid.—_Archiven der Pharmacie._
ON THE PREPARATION OF CHLOROFORM FROM THE ESSENCES OF LEMON, COPAIBA, PEPPERMINT AND BERGAMOTTE.
BY M. CHAUTARD,
Professor of Chemistry at the Lyceum of Vendome.
M. Chautard, after having completed his experiments for the production of chloroform by means of oil of turpentine instead of alcohol, led by analogy, proceeded to try by a similar method to prepare it by means of the essences of lemon, bergamotte, copaiba and peppermint, and succeeded. However, the quantity of essences upon which he acted was too small to carry on a minute analysis. In the meanwhile, his researches led him to discover formic acid in the calcareous residuum of the operation. It was already known, M. Chautard observes, that oil of turpentine, when old and exposed a long time to the action of the air, was transformed into formic acid, which observations is due to M. Wappen. On the other hand, M. Schneider, by collecting the volatile products of the oxidation {158} of turpentine, by means of nitric acid, detected therein the presence of acetic, metacetic, and butyric acids. Finally, a few years ago, Mr. William Bastick[11] showed that hypo-chlorite of lime, by reacting upon neutral unazotised bodies, such as sugar, starch, &c., gave rise to the formation of a certain quantity of formate of lime; hence, turning to advantage the details given by this chemist, M. Chautard continues—I thus have carried on my operation:―
[11] “Journal de Pharmacie,” 3^e serie, 1. 14.
After having ascertained, by means of the solution of indigo, that the residuum contained in the alembic did not contain any hypochlorite of lime, the presence of which would have prevented the extraction of formic acid, I threw the whole upon a cloth, and added sulphuric acid to the filtered liquor to precipitate the lime retained in a state of chloride or formate.—This liquor, after having been filtered anew, was distilled, and the product was a mixture of formic and hydrochloric acids, which I saturated by means of carbonate of soda. By subsequent evaporation to dryness, I succeeded, by adding afterwards a little water, in separating the formate of soda from the chloride. By means of the formate of soda, I proved the principal properties of formic acid, and besides, produced from it the formate of silver, which is decomposed by a boiling heat, leaving a precipitate of metalic silver.
In finishing this communication, I must observe that fixed oils, treated in the same way by hypochlorite of lime, do not produce chloroform; however, the reaction which occurs is so strong, and indicative of interesting results, that it induces me to continue my experiments.—_Journal de Pharmacie._
ON DRY EXTRACTS.
BY DR. MOHR.
Every one is aware of the utility of possessing dry extracts, particularly of narcotic plants, so as to be able to administer them as powders. This able pharmaceutist gives the following {159} formula for their preparation; and as it seems to answer all purposes, and is adopted in Berlin, and other continental towns, it deserves to be made public.
Take of any extract, and of powder of licorice equal parts, mix them well in a mortar; when well mixed, put the paste in an earthenware evaporating dish, and then put this vessel over an iron pan, which has been filled with chloride of calcium, previously dried in the vessel by a strong fire without melting; the iron vessel must have a cover to enclose both vessels, so that the chloride of calcium can absorb the vapor from the extract without communication with the air, and must be put on as soon as the extract has been placed on the chloride of calcium. Let it stand for some days. Remove the extract, and add an equal weight of licorice powder to it in a mortar, mix well, and preserve it in bottles.
EDITORIAL.
PHARMACEUTICAL CONVENTION. The apothecaries of the United States are in an anomalous and exceptional position. Exercising functions which concern the life and health of those who require their services, the public expects them to possess the experience, the varied requirement, the high moral qualities which the proper exercise of their profession demands; yet this same public, itself incapable of discriminating between knowledge and ignorance, furnishes them no aid in the pursuits of their studies, and yields them no protection against quackery and imposture. Everything is left to the spirit of trade, and to the laws of supply and demand. The advances that have been made in pharmacy have come from within itself, unaided by any assistance from the state governments, and looked upon often with coldness or distrust by the public. In this way, in some of the large cities, with the influence of the sister profession of medicine, something has been done; but, even there, how much remains to be accomplished before pharmacy can assume the rank it holds in France and Germany!
As heretofore, so now, the best and the only prospect of progress in the profession lies in itself. It best knows its necessities and requirments, and it can best devise the remedies that will meet them. It is in the union of its members, in mutual association and intercourse, in the formation of a public opinion of its own, which, {160} operating first upon the members of the profession, will necessarily have its weight upon the public opinion of the community, that lie our best hopes. Pharmacy is at once a liberal art, and a trade. In individuals, particularly in a community like ours, the spirit of trade is apt to be in the ascendant. Science is estimated at its money value, for what it brings in, rather than for what it is. But when the best men of a profession meet together, science resumes its proper position; they are encouraged in their noblest aims, and that encouragement is spread widely among their fellows. Individuals struggling, isolated throughout the country, feel that there is a tribunal to which they can appeal, and by which they will be judged, and its influence will be felt too by another class, as a restraint, if not an encouragement. Success, obtained by worthy means, loses much of its value, when it costs the esteem of those with whom we are most intimately connected.
It is from such considerations that we look upon the approaching convention at Philadelphia, as a step in a very important movement. A great deal depends upon its success, and every one who has the interest of pharmaceutical science at heart, should do all he can to promote it.
To prove all that is hoped for by its friends, the convention should be a national one, not only in name, but in reality. Every institution and society entitled under the requisitions of the call, should appoint delegates, and above all, they should appoint delegates who will attend. But there are many apothecaries scattered through the country, in places not entitled to appoint delegates, who may be enabled to be present at the meeting of the convention, and we are glad to see that our Philadelphia brethren are prepared to welcome them in a liberal and cordial spirit. They will both receive and communicate benefit. Their presence will add weight and authority to the convention; while, independent of its official proceedings, they cannot but derive advantages from acquaintance and intercourse with the numerous able members of the profession who will, as delegates, attend the meeting.
Great care should be exercised in the selection of delegates; they should not only, above all, be men who will attend, but men who have at heart the position and advancement of pharmaceutists.
We hope that their election will take place as early as possible, that they may have time fully to consider the objects of the convention, and the wants and wishes of the institutions they represent. It would be well, too, if early notice of their election should be communicated to Mr. Proctor, or some other of the members residing at Philadelphia, and their names should be published. The convention will have much to discuss and determine upon, while its duration will necessarily be limited. Were the names of its members early announced, an interchange of opinion might take place between, not to forstall the active of the convention, but to promote and expedite it. For this purpose, if deemed desirable our own columns are freely tendered.
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NEW YORK
JOURNAL OF PHARMACY.
JUNE, 1852.
ON THE PREPARATION OF PURE BARIUM COMPOUNDS.
BY HENRY WURTZ.
The preparation of the compounds of barium in a state of absolute purity is a subject which has not generally received much attention from Pharmaceutical chemists, in consequence of the hitherto limited application of these compounds, except in chemical analysis. The time, however, is undoubtedly close at hand, when new developments in the arts, will create a demand for pure barium compounds, as well as for very many other products now considered as pertaining exclusively to the laboratory. Indeed, efforts have already been made to introduce the _chlorate of barytes_ to the notice of pyrotechnists as a means of producing a green fire unequalled in beauty, and the pure carbonate has been for some time in use in England, in the manufacture of superior varieties of plate and flint glass. The precipitated or purified native sulphate is also preferred as a water color pigment to white lead, being far more durable than the latter. I may here be permitted to mention a practical application of the carbonate which has occurred to myself. I have found that sulphate of lime is totally precipitated from its solution by mixing therewith an equivalent quantity of the precipitated or finely pulverized natural carbonate of barytes, {162} of course with the formation of sulphate of barytes and carbonate of lime. It is by no means improbable that this property may be made available in removing sulphate of lime from spring or sea water which is to be used in steam boilers, thus preventing the formation of the troublesome incrustation which so often occurs, especially when it is considered that the sulphate of barytes which would be formed, might easily be reconverted into carbonate and used over again. Again, sulphate of lime might be removed in the same way from the brine in salt works, thus contributing to the purity of the salt produced.
Recent improvements in chemical analysis have greatly increased the usefulness of barium compounds in the laboratory, especially of the carbonate, to which the late investigations of Professor H. Rose, and of Ebelmen have given a place in the very first rank among the reagents valuable to the chemist. Any suggestion, therefore, concerning the preparation of barium compounds in a pure state, cannot be considered as useless.
The sulphate of baryta is the only compound which occurs in sufficient abundance to be an economical source of the other barium compounds, and the enormous though illegitimate use of this substance in the adulteration of white lead, is so far fortunate as to render it an easy matter to obtain it in any required quantity, already in a state of fine powder which is so desirable in chemical operations.
The sulphate of baryta is always reduced to the state of sulphide of barium, by exposing it to a red heat in intimate admixture with some carbonaceous substance, such as powdered charcoal, rosin, oil or flour. It is exceedingly difficult, however, if not impossible, to effect in this manner a complete decomposition of the sulphate. Indeed, it is probable that in most cases the quantity of sulphide obtained, is not more than half that which is equivalent to the sulphate employed. A modification which promises to be far more economical was proposed by Dr. Wolcott Gibbs. His proposal was to submit the sulphate to the action of a current of common coal gas at a red heat. It is evident that in this way a perfect decomposition {163} may readily be accomplished, especially if the powdered sulphate is stirred during the operation, so as to expose fresh surfaces to the action of the gas.
The mass obtained after the reduction of the sulphate is submitted to the action of boiling water, and a solution obtained, which, according to Professor H. Rose,[12] contains principally hydrate of baryta and sulphohydrate of sulphide of barium BaS. HS. formed by the reaction of equal equivalents of water and proto-sulphide of barium. It almost invariably contains also a quantity of lime, probably in the form of sulpho-hydrate of sulphide of calcium, or of hydrate of lime, proceeding from the almost constant concurrence of sulphate of lime with native sulphate of baryta. From the presence of this lime originates the principal difficulty in preparing pure barium compounds from this substance. Thus when the carbonate is prepared from the solution by precipitation, with carbonate of soda, or a current of carbonic acid gas, it is found contaminated with carbonate of lime, which is fatal to its use as a reagent in analysis. Also in examining many specimens of commercial _chloride of barium_, which is prepared from this solution by the addition of chloro-hydric acid, boiling to separate sulpho-hydric acid gas which is evolved, filtration to separate the sulphur which is precipitated and crystallization, I have always found it to contain a small quantity of chloride of calcium, which I have found it impossible to separate entirely by repeated recrystallizations. It has been proposed[13] to separate the chloride of calcium from chloride of barium by the use of very strong alcohol, in which the latter when anhydrous, is insoluble. This method is rather expensive and troublesome as it involves the evaporation to dryness of the chloride of barium solution, the reduction of the previously ignited residue to a very fine powder and digestion in strong alcohol. Attempts were made after some previous experimentation, in which it was found that an {164} aqueous solution of _oxalate of baryta_ precipitated chloride of calcium, but not chloride of barium, to separate the lime from a chloride of barium solution by addition of oxalate of baryta, or simply of a little oxalic acid, but it was soon found that oxalate of lime was somewhat soluble in a solution of chloride of barium, so that a solution of oxalate of baryta, gave no precipitate in a mixture of solutions of chloride of barium and chloride of calcium. It was found also that the precipitate formed by a little oxalic acid in a lime solution, could be re-dissolved by addition of chloride of barium. It may also be mentioned, though irrelevant to the subject, that it was found that oxalate of lime was soluble in solutions of chloride of calcium, of ammonia, and of chloro-hydrate of ammonia.
[12] Poggendorff’s Annalen, 55,416.
[13] Gmelin’s Handbuch, 2,158.
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New York Journal of Pharmacy, Volume 1 (of 3), 1852Chapter VII: Section 3: This Act shall not take effect until the first day of July, (4)
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