I first tried redistilling it, but besides the loss consequent on distilling small quant.i.ties, the flavor is thereby impaired. As the oil became brighter when heated, I antic.i.p.ated that all its precipitable matter would be thrown down at a low temperature, and I applied a freezing mixture, keeping the oil at zero for some hours. No such change, however, took place.
The plan which I ultimately decided upon as the best which I had arrived at, was to shake up the oil with a little boiling water, and to leave the water in the bottle; a mucilaginous preparation forms on the top of the water, and acquires a certain tenacity, so that the oil may be poured off to nearly the last, without disturbing the deposit.
Perhaps cold water would answer equally well, were it carefully agitated with the oil and allowed some time to settle. A consideration of its origin and const.i.tution, indeed, strengthens this opinion; for although lemon otto is obtained both by distillation and expression, that which is usually found in commerce is prepared by removing the "flavedo" of lemons with a rasp, and afterwards expressing it in a hair sack, allowing the filtrate to stand, that it may deposit some of its impurities, decanting and filtering. Thus obtained it still contains a certain amount of mucilaginous matter, which undergoes spontaneous decomposition, and thus (acting, in short, as a ferment) accelerates a similar change in the oil itself. If this view of its decomposition be a correct one, we evidently, in removing this matter by means of the water, get rid of a great source of alteration, and attain the same result as we should by distillation, without its waste or deterioration in flavor.
I am, however, aware that some consider the deposit to be modified resin.[H] Some curious experiments of Saussure have shown that volatile oils absorb oxygen immediately they have been drawn from the plant, and are partially converted into a resin, which remains dissolved in the remainder of the essence.
He remarked that this property of absorbing oxygen gradually increases, until a maximum is attained, and again diminishes after a certain lapse of time. In the oil of lavender this maximum remained only seven days, during each of which it absorbed seven times its volume of oxygen. In the oil of lemons the maximum was not attained until at the end of a month; it then lasted twenty-six days; during each of which it absorbed twice its volume of oxygen. The oil of turpentine did not attain the maximum for five months, it then remained for one month, during which time it absorbed daily its own volume of oxygen.
It is the resin formed by the absorption of oxygen, and remaining dissolved in the essence, which destroys its original flavor. The oil of lemons presents a very great a.n.a.logy with that of oil of turpentine, so far as regards its transformations, and its power of rotating a ray of polarized light. Authorities differ as regards this latter property.
Pereira states that the oil of turpentine obtained by distillation with water, from American turpentine, has a molecular power of right-handed rotation, while the French oil of turpentine had a left-handed rotation.
Oil of lemons rotates a ray of light to the right, but in France a distilled oil of lemons, sold as scouring drops for removing spots of grease, possesses quite the opposite power of rotation, and has lost all the original peculiar flavor of the oil. Oil of lemons combines with hydrochloric acid to form an artificial camphor, just in the same manner as does oil of turpentine, but its atom is only one half that of the oil of turpentine. The artificial camphor of oil of lemons is represented by the formula, C_{10}H_{8}HCl; the artificial camphor of oil of turpentine by C_{20}H_{16}HCl.
According to M. Biot, the camphor formed by the oil of lemons does not exercise any action on polarized light, whilst the oil of lemons itself rotates a ray to the right. The camphor from oil of turpentine, on the contrary, does exercise on the polarized ray the same power as the oil possessed while in its isolated state, of rotating to the left. These molecular properties establish an essential difference between the oils of turpentine and lemons, and may serve to detect adulteration and fraud. It is also a curious fact, that from the decomposition of these artificial camphors by lime, volatile oils may be obtained by distillation, isomeric with the original oils from which the camphors were formed; but in neither case has the new product any action on polarized light.
In conclusion, I would recommend that this oil, as well as all other essential oils, be kept in a cool, dark place, where no very great changes of temperature occur.
BENZOIC ACID, AND TESTS FOR ITS PURITY.
BY W. BASTICK.
Dr. Mohr"s process for obtaining benzoic acid, which is adopted by the Prussian Pharmacopoeia, unquestionably has the reputation of being the best. According to this process, coa.r.s.ely-powdered gum benzoin is to be strewed on the flat bottom of a round iron pot which has a diameter of nine inches, and a height of about two inches. On the surface of the pot is spread a piece of filtering paper, which is fastened to its rim by starch paste. A cylinder of very thick paper is attached by means of a string to the top of the iron pot. Heat is then applied by placing the pot on a plate covered with sand, over the mouth of a furnace. It must remain exposed to a gentle fire from four to six hours. Mohr usually obtains about an ounce and a half of benzoic acid from twelve ounces of gum benzoin by the first sublimation. As the gum is not exhausted by the first operation, it may be bruised when cold and again submitted to the action of heat, when a fresh portion of benzoic acid will sublime from it. This acid thus obtained, is not perfectly pure and white, and Mohr states that it is a question, in a medicinal and perfumery point of view, whether it is so valuable when perfectly pure, as when it contains a small portion of a fragrant volatile oil, which rises with it from the gum in the process of sublimation.
The London Pharmacopoeia directs that it shall be prepared by sublimation, and does not prescribe that it shall be free from this oil, to which it princ.i.p.ally owes its agreeable odor.
By the second sublimation the whole of the benzoic acid is not volatilized. What remains in the resin may be separated by boiling it with caustic lime, and precipitating the acid from the resulting benzoate of lime with hydrochloric acid. Benzoic acid can be obtained also in the wet way, and the resin yields a greater product in this process than in the former; yet it has a less perfumery value, because it is free from the volatile oil which, as above stated, gives it its peculiar odor. The wet method devised by Scheele is as follows:--Make one ounce of freshly-burnt lime into a milk with from four to six ounces of hot water. To the milk of lime, four ounces of powdered benzoin and thirty ounces of water are to be added, and the mixture boiled for half an hour, and stirred during this operation, and afterwards strained through linen. The residue must be a second time boiled with twenty ounces of water and strained, and a third time with ten ounces; the fluid products must be mixed and evaporated to one-fourth of their volume, and sufficient hydrochloric acid added to render them slightly acid. When quite cold, the crystals are to be separated from the fluid by means of a linen strainer, upon which they are to be washed with cold water, and pressed, and then dissolved in hot distilled water, from which the crystals separate on cooling. When hydrochloric acid is added to a cold concentrated solution of the salts of benzoic acid, it is precipitated as a white powder. If the solution of the salts of this acid is too dilute and warm, none or only a portion of the benzoic acid will be separated. However, the weaker the solution is, and the more slowly it is cooled, the larger will be the crystals of this acid. In the preparation of this acid in the wet way, lime is to be preferred to every other base, because it forms insoluble combinations with the resinous const.i.tuents of the benzoin, and because it prevents the gum-resin from conglomerating into an adhesive ma.s.s, and also because an excess of this base is but slightly soluble.
Stoltze has recommended a method by which all the acid can be removed from the benzoin:--The resin is to be dissolved in spirit, to which is to be added a watery solution of carbonate of soda, decomposed previously by alcohol. The spirit is to be removed by distillation, and the remaining watery solution, from which the resin has been separated by filtration, treated with dilute sulphuric acid, to precipitate the benzoic acid. This method gives the greatest quant.i.ty of acid, but is attended with a sacrifice of time and alcohol, which renders it in an economical point of view inferior to the above process of Scheele. It is so far valuable, that the total acid contents of the resin can be determined by it.
Dr. Gregory considers the following process for obtaining benzoic acid the most productive. Dissolve benzoin in strong alcohol, by the aid of heat, and add to the solution, whilst hot, hydrochloric acid, in sufficient quant.i.ty to precipitate the resin. When the mixture is distilled, the benzoic acid pa.s.ses over in the form of benzoic ether.
Distillation must be continued as long as any ether pa.s.ses over. Water added towards the end of the operation will facilitate the expulsion of the ether from the retort. When the ether ceases to pa.s.s over, the hot water in the retort is filtered, which deposits benzoic acid on cooling.
The benzoic ether and all the distilled liquids are now treated with caustic potash until the ether is decomposed, and the solution is heated to boiling, and super-saturated with hydrochloric acid, which afterwards, on cooling, deposits, in crystals, benzoic acid.
Benzoic acid, as it exists in the resin, is the natural production of the plant from which the resin is derived. It may also be produced artificially. Abel found that when c.u.mole (C_{18}H_{12}) was treated with nitric acid, so dilute that no red vapors were evolved for several days, this hydro-carbon was converted into benzoic acid. Guckelberger has, by the oxidation of casein with peroxide of manganese and sulphuric acid, obtained as one of the products benzoic acid. Alb.u.men, fibrin, and gelatin yielded similar results when treated as above. Wohler has detected benzoic acid in Canadian castor, along with salicin. It is also formed by the oxidation of the volatile oil of bitter almonds. Benzoate of potash results when chloride of benzoyle is treated with caustic potash. Benzoic acid in the animal economy is converted into hippuric acid, which may by the action of acids, be reconverted into benzoic acid.
Benzoic acid should be completely volatile, without leaving any ash or being carbonized when heated. When dissolved in warm water, to which a little nitric acid has been added, nitrate of silver and chloride of barium should produce no precipitates. Oxalate of potash should give no turbidity to an ammoniacal solution of this acid. When heated with an excess of caustic potash it should evolve no smell of ammonia, otherwise, it has been adulterated with sal ammoniac. In spirit, benzoic acid is easily soluble, and requires 200 parts of cold and 20 parts of boiling water to dissolve one part of it.
ON THE COLORING-MATTERS OF FLOWERS.
BY FREMY AND CLOEZ.
Chemists possess only a very incomplete knowledge of the coloring matters of flowers. Their investigation involves difficulties which cannot be mistaken. The matters which color flowers are uncrystallized; they frequently change by the action of the reagents employed for their preparation; and, also, very brilliantly-colored flowers owe their color to very small quant.i.ties of coloring matter.
On the nature of the coloring matters of flowers several opinions have been expressed. Some observers have a.s.sumed that flowers owe their color to only two coloring matters, one of which is termed anthocyan, and the other anthoxanthine. Others will find a relation between the green coloring of leaves, the chlorophylle, and the coloring matters of flowers. They support their opinion generally on the results of the elementary a.n.a.lysis of those different bodies; but all chemists know that chlorophylle has not yet been prepared in a pure condition.
Probably, it retains various quant.i.ties of fatty and alb.u.minous bodies.
Further, the coloring matters of flowers are scarcely known, so that it is impossible to establish relations supported by the necessarily uncertain composition of impure bodies.
Some time since the blue color of flowers was ascribed to the presence of indigo; but Chevreul has shown, in a certain way, that the blue substance of flowers is always reddened by acids; and that with indigo it is quite different, which, as is known, retains its blue color even when the strongest acids are allowed to act on it.
It is thus seen that the coloring matters of flowers have heretofore only in a superficial manner been examined, and that it is important to again undertake their complete examination, as these bodies are interesting to the chemist, because they are employed as reagents in the laboratory for the recognition of alkalies; and by an improved knowledge of them the florist might find the way by which he could give to cultivated flowers various colors.
We have believed that before undertaking their elementary a.n.a.lysis, methods must be carefully sought for which can be followed for the obtainment of the coloring matters of flowers, and that it should be proved whether these substances are to be considered as independent bodies, or whether they proceed from one and the same matter, which is changed in various ways by the juices of the plant.
We now publish the results of our first investigations.
_Blue Coloring Matter of Flowers (Cyanine)._--The blue coloring matter of flowers we propose to call cyanine. To obtain this substance we treat the petals of _Centauria cya.n.u.s_, _Viola odorata_, or _Iris pseudacorus_, with boiling alcohol, by which the flowers are decolorized; and the liquid acquires immediately a fine blue color.
If the coloring matter is allowed to remain some time in contact with alcohol, it is perceived that the blue of the liquid gradually disappears, and soon a yellow brown coloration takes its place. The coloring matter has in this case suffered an actual reduction by the prolonged action of the alcohol, but it will again a.s.sume its original color when the alcohol is allowed to evaporate in the air. Nevertheless, the alcohol must not be allowed to remain in contact too long with the coloring matter, because the alcoholic extract will not then again a.s.sume its blue coloration by the action of oxygen.
The residue remaining from the evaporation of the alcohol is treated with water, which separates a fatty and resinous substance. The watery solution which contains the coloring matter is then precipitated by neutral acetate of lead. The precipitate, which possesses a beautiful green color, can be washed with plenty of water, and then decomposed with sulphuretted hydrogen; the coloring matter pa.s.ses into the watery solution, which is carefully evaporated in a water-bath; the residue is again dissolved in absolute alcohol; and lastly, the alcoholic solution is mixed with ether, which precipitates the cyanine in the form of blue flocks.
Cyanine is uncrystallizable, soluble in water and alcohol, insoluble in ether; acids, and acid salts color it immediately red; by alkalies it is, as known, colored green. Cyanine appears to behave as an acid, at least it forms with lime, baryta, strontia, oxide of lead, &c., green compounds insoluble in water.
Bodies absorbing oxygen, as sulphurous acid, phosphorous acid, and alcohols, decolorize it; under the influence of oxygen its color is restored.
We must here mention that Moroz has prepared a beautiful blue substance from _Centauria cya.n.u.s_ by treatment with absolute alcohol.
_Rose-red Coloring Matter._--We have employed alcohol to extract the substance which colors rose-red certain dahlias, roses, poeonias, &c.
For the procuration of this coloring matter the method pursued is exactly as that for the preparation of cyanine.
By an attentive comparison of the properties of this coloring matter with those of cyanine, we have found that the rose-red coloring matter is the same as the blue, or at least results from a modification of the same independent principle. It appears in the rose-red modification, when the juice of the plant, with which it exists in contact, possesses an acid reaction. We have always observed this acid reaction in the juices of plants with red or rose-red coloration, while the blue juices of plants have always exhibited an alkaline reaction.
We have exposed most of the rose-red or red-colored flowers which are cultivated in the Paris Museum to the influence of alkalies, and have seen that they first become blue and then green by their action.
It is often perceived that certain rose-red flowers, as those of the _Mallow_, and in particular those of the _Hibiscus Syriacus_, acquire by fading a blue and then a green coloration, which change, as we have found, depends on the decomposition of an organic nitrogenous substance, which is found very frequently in the petals. This body generates as it decomposes ammonia, which communicates to the flowers the blue or green color. By action of weak acids, the petals can be restored to their rose-red color.
The alteration of color of certain rose-red flowers can also be observed when the petals are very rapidly dried, for example, in _vacuo_, by which it cannot be easily a.s.sumed that a nitrogenous body has undergone decomposition to the evolution of ammonia. But, before all things, it must be mentioned that in this case the modification of color pa.s.ses into violet, and never arrives at green; and, further, that it is always accompanied with the evolution of carbonic acid, which we have detected by a direct experiment. Petals which were before rose-red, and have become violet by slight drying, evolve carbonic acid, and on that account it may be a.s.sumed that the rose-red color is produced in the petals by this carbonic acid, and that by its expulsion the petals a.s.sume the blue color, by which the flowers with neutral juices are characterized.
We believe that we are able to speak with certainty that flowers with a rose-red, violet, or blue color, owe their coloration to one and the same substance, but which is modified in various ways by the influence of the juices of plants.
Scarlet-red flowers also contain cyanine reddened by an acid, but in such cases this substance is mixed with a yellow coloring matter which we will now describe.
_Yellow Coloring Matter._--The simplest experiments show that no a.n.a.logy exists between the substance which colors flowers yellow and that of which we have already spoken. The agents which generate so easily with cyanine, the rose-red, violet, or green coloration, cannot in any case impart these colors to the yellow substance obtained from flowers.
By the examination of the various yellow-colored flowers, we have ascertained that they owe their coloration to two substances, which differ from one another in their properties, and appear not to be derived from the same independent principle. One is completely insoluble in water, which we have termed xanthine, a name which Runge has given to a yellow matter from madder. As this name has not been accepted in science, we have employed it to denote one of the coloring matters of yellow flowers. The other substance is very soluble in water, and is by us termed xantheine.
_Xanthine, or the Yellow Coloring Matter insoluble in water._--We have prepared this coloring matter from many yellow flowers, but chiefly from _Helianthus annuus_.
To obtain it we treat the flowers with boiling absolute alcohol, which dissolves the coloring matter in the heat, and by cooling almost completely allows it again to precipitate. The yellow deposit which is obtained in this way, is not pure xanthine, as it contains a rather considerable quant.i.ty of oil. To separate this oil we have recourse to a moderate saponification; thus, we heat the yellow precipitate with a small quant.i.ty of alkali to saponify the fatty body mixed with the xanthine, which even contains the xanthine dissolved. As the coloring matter is soluble in the soap solution, we do not treat the ma.s.s with water, but decompose it with an acid which isolates the xanthine and the fatty acids resulting from the saponification. This precipitate we treat with cold alcohol, which leaves behind the fatty acids, and dissolves the xanthine. This substance is a fine yellow color, insoluble in water, but soluble in alcohol and ether, which are thereby colored golden yellow. It appears to be uncrystallizable, and possesses the general properties of resins.
Xanthine, in combination with cyanine, modified by the various juices of plants, communicates in variable proportions orange-yellow, scarlet-red, and red colors to flowers.
_Xantheine, or the Coloring Matter soluble in water._--By the preparation of the substance which colors yellow certain dahlias, it is at once perceived that it has no a.n.a.logy to xanthine. The latter is as known insoluble in water, while the coloring matter under consideration is readily soluble in water.