A Practical Treatise on the Manufacture of Perfumery. C. Deite
19.
The absorption process is employed for the flowers of the jasmine (jasminum oderatissimum), the mignonnette (réséda odorata), the violet (viola tricolor), the tuberose (polianthes tuberosa), etc.
Storage of volatile oils.—In storing volatile oils, they should be carefully protected from light and air. Some oils become darker on exposure to light, while others, for instance, lemon oil, become colorless. Most volatile oils, as previously mentioned, absorb oxygen from the air with avidity and combine chemically with it. Thinly-fluid oils become perceptibly more thickly-fluid and finally even rigid, the product of oxidation being a resinous body. Some volatile oils containing aldehydes are converted, by the absorption of oxygen, into acids, cinnamic acid being, for instance, formed in cinnamon oil, and benzoic acid in oil of bitter almonds.
To prevent evaporation, as well as the above-mentioned effects of light and air, the volatile oils should be preserved in not too large glass bottles kept as full as possible, and closed with a good cork, over which it is best to tie a piece of bladder. The bottles should be stored in a cool, shady place. The preservation of the oils is assisted by the addition of 0.5 to 1 per cent. of anhydrous alcohol.
CHAPTER III.
TESTING VOLATILE OILS.
Volatile oils are much adulterated, the adulterations consisting chiefly in mixing an expensive oil with a cheaper one and with alcohol; more rarely with chloroform and fat oils. To these adulterations, which have been common for many years, has recently been added the previously mentioned hydrocarbon called terpene or camphene, which is separated in the preparation of concentrated oils.
For the recognition of the quality of a volatile oil, serve first of all its physical properties, especially its color, odor and taste. The specific gravity varies too much and is not always a sufficient criterion. Reagents can only be employed with a few oils. The chemical detection of adulterations is rendered especially difficult by the fact, that most of the volatile oils form a mixture of terpenes with other combinations, in which the separate constituent parts do not appear in fixed, but in changeable proportions, and in which the constituents themselves suffer alteration by storing, air and light.
Odor and taste are so characteristic for every volatile oil as to suffice in most cases. For testing as to odor, bring a drop of the oil to be examined upon the dry palm of one hand and for some time rub with the other, whereby the odor is more perceptibly brought out. To determine the taste, vigorously shake one drop of the oil with 15 to 20 grammes of distilled water and then test with the tongue.
An adulteration with fat oil (poppy oil, castor oil) may be recognized as follows: Place a drop of the suspected oil upon blotting paper and expose it to the heat of the water bath. If it evaporates completely and no stain is perceptible, the oil is pure. But frequently a transparent stain remains with old oils without their being adulterated, which is due to the resin formed by the absorption of oxygen and remaining dissolved in the oil. In this case a transparent ring is generally formed by the concentration of the resin on the edges of the stain. If no tangible results are obtained by this test, pour a few cubic centimeters of the oil upon a watch-crystal and heat it very slowly upon a piece of sheet-iron, until all the odor has disappeared. If the watch-crystal becomes empty in a short time, nothing but volatile oil was present; but if a viscous residue remains, this may consist either of fatty oil or resin, or of both. Treat the residue with strong alcohol; if it dissolves it may be resin or castor oil. Dilute the solution with much water; a white flocculent turbidity indicates resin; the separation of an oily liquid, after standing, castor oil. If the residue remains undissolved, it consists of a fatty oil, generally oil of almond or olive.
The presence of castor oil can be accurately determined by bringing the residue from the watch-crystal into a test-tube by means of a glass-rod, and compounding it with a few drops of nitric acid. A strong development of gas takes place, after the cessation of which, solution of carbonate of soda is added as long as there is any sign of effervescence. If the added oil was castor oil, the contents of the test-tube will show a peculiar odor due to œnanthylic acid formed by the action of nitric acid upon castor oil.
Another method of establishing the presence of fat oil consists in mixing the suspected oil with eight times its quantity of 90 per cent. alcohol (specific gravity 0.823). If the oil is unadulterated a clear solution is formed; if it contains fat oil, the latter remains undissolved. The presence of castor oil, which of the fat oils is chiefly used for adulteration, is, however, not shown by this method, it being also soluble in alcohol.
A permanent stain upon the paper may, however, also be formed by fresh oils obtained by expression from the respective parts of the plant. Thus, lemon oil obtained by expression from the peel, and which has a far more agreeable odor than that produced by distillation, always leaves behind a slight grease-stain.
Detection of alcohol or spirit of wine.—Independent of the alcohol added to assist the preservation of some oils, adulteration with alcohol frequently occurs, especially in expensive oils. With a content of not more than 3 per cent. of alcohol, it suffices to allow one to two drops of the suspected oil to fall into water. In the presence of alcohol, the drop becomes either immediately surrounded with a milky zone, or it becomes turbid or whitish after being for some time in contact with the water. Dragendorff's test is based upon the fact that oils, which are hydrocarbons, suffer no change by the addition of sodium (ten drops of oil and a small chip of sodium), while oils containing hydrocarbons and oxygenated oils cause with sodium a slight evolution of hydrogen gas, and suffer but a slight change during the first five to ten minutes of the reaction. If, however, the oil is adulterated with alcohol, not only a violent evolution of hydrogen gas takes place, but the oil in a short time becomes brown or dark brown, thickly fluid or rigid.
The detection of alcohol by means of fuchsine, which has been frequently recommended, requires special precautions. It must first be ascertained that the oil is free from acids and water; if such is not the case, they must be removed by means of caustic potash. After settling, bring, by means of a dry pipette, about five cubic centimeters of the oil into a dry test-tube about ten millimeters in diameter, without moistening the walls of the upper half of the tube. Then bring, by means of a paper gutter, a few milligrammes of coarsely-powdered fuchsine into the dry part of the obliquely held tube, at a distance of one centimeter from the oil. Now heat gradually over a lamp until the tube begins to tarnish. With pure oil no evaporation is observed, but if the oil contains only 0.1 per cent. of alcohol, every speck of fuchsine will, after heating to boiling and setting aside, be surrounded by a stain produced by the alcoholic solution. The chief requirement for this test is that the oil be free from water. If such is not the case, vapors will be observed, which condense in the upper portion of the test-tube, and dissolve fuchsine, and, after flowing back, sink below the oil with a crackling noise. If the oil contains alcohol, the condensing vapors dissolve fuchsine with greater ease, and in flowing back mix without crackling.
Hager's tannin test is very reliable. Bring into a test-tube 5 to 10 drops of the oil to be examined, add a piece of tannin the size of a pea, shake so that the tannin is moistened by the oil, and let the whole stand at a temperature of 59° to 68° F. In most volatile oils tannin is insoluble, and, if the oil is pure, floats for days on the surface without change. If, however, the oil contains alcohol, the tannin absorbs the latter, according to the quantity present, in 3 to 48 hours, and forms with it a more or less transparent, viscous, tough, or smeary mass resembling a soft resin, which settles on the bottom, and adheres so firmly to it, as well as to the sides of the tube, that it cannot be moved by shaking. The mass may be examined as to its consistency with a knitting needle. Traces of moisture in the oil are not detrimental to the test, the tannin mass separating in the form of a hyaline mass only in few oils, and if this mass is tested with the knitting needle it will be found not tough or smeary,