[ 43 1 VII. Examination qf Cetine Ethal Oils of Laurel Turpen-tine Hyssop and Assnfmtida. By Dr. JOHNSTENHOUSE. Read November 17th 1841. Cctine. CHEVREUL gave the name of Cetine to spermaceti when rendered absolutely pure. The spermaceti of commerce always contains more or less of a yellowish oil which it re- tains wit11 great tenacity and by which its rnelting point is greatly lowered. The best means of purifying spermaceti is to treat it two or three times with boiling alcohol in which however it is very slightly soluble and then to subject it to nine or ten crystallizations in aether. These solutions and crystallizations must be repeated till the temperature at which the cetine solidifies reaches 120° F. or 121' F. when it may be regarded as perfectly pure.The cetine which I subjected to analysis was prepared in the manner just described and solidifies at 121O F. The following are the results :-(I.) 0.236 gramme gave O*ci805carbonic acid and 0-2831 water. (2.) 0.3198 gramme gave 0.9223 carbonic acid and 0.378 water. (3.) 09593 gramme gave 0*7286carbonic acid and 0'3008 water. (4.) 0-2928gramme gave 0-8468carbonic acid and 0.3476 water. 1. 2. 3. 4. Carbon. . . . . . 79.72 79-74 79.53 79-96 13ydrogen . . . . 13.32 13*13 Oxygen . . . . . 6.96 7-13 13.19 75%- 13*19 6*85 100'00 100'00 1oo*oo 100'00 ~ These analyses differ considerably from that of Chevreul though I have repeated them with every attention to accuracy. Chevreul found Carbon . . . . 81.660 Hydrogen .. . 12.862 oxygen . . . . 5.578 -100'000 It is needless however at present attempting to deduce any formula from these analyses as the acids which spermaceti contains have not been accurately determined. Sperniaceti is usually supposed to corisist of margarate and oleate of ethal. From experiments I have reason to think that one of thein is mnrgwic acid but as spermaceti when distilled yields no Chem. Soc. &fern6 VOI.. I. 13 Dr. Stenhouse on Cetiiie Ethal &c. trace of sebacic acid there is every reason to conclude the other acid it contains the quantity of which is extremely small is certainly not the oleic acid. In order to ascertain how far cetine differs in composition from ordinary spermaceti I was induced to submit a portion of the latter also to analysis.The melting point of the crude spermaceti analysed was only 107' F. (1 .) 0.3279 gave 0.9499 carbonic acid and 0.8904 water. (2.) 0*349 gave 1.0065 carbonic acid. (3.) 0.3755 gave 1*0887carbonic acid and 0*4399water. 1. 2. 3. Carbon. . . . . 80*10 7974 80-16 Hydrogen . . . Oxygen . . . . 13'23 6-67 13'01 6-83 100'00 100~00 It is evident from these analyses that the composition of crude spermaceti is precisely the same with that of the purest cetine. The small quantity of oil therefore which accompa- nies the former is probably isomeric with the more solid fat. Ethal. The ethal which I analysed was prepared by saponifjring spermaceti with powdered potash. The saponification was twice repeated in order that none of the spermaceti might escape decomposition.The lime-soap was then formed by precipitation with chloride of calcium. It was dried with a gentle heat and the ethnl extracted by aether alcohol was found inadmissible as a large quantity of the lime-soap was also dis-solved by it. I also found it advantageous to mix the lime soap with a considerable quantity of pounded glass as this prevented its adhering to the sides and bottom of the vessel when heated and thus enabled the aether to act more equally on every part of the mass. The ethal first obtained was again boiled with milk of lime again extracted with aether and repeatedly crystallized. Its melting point was 119' F. (1.) 0'5307 gave 1.519 carbonic acid and 0-665 water.(2.) 0'2881 gave 0.8295 carbonic acid and 0.361 water. (3.) 0.302 gave 0*8645carbonic acid and Om383water. 1. 2. 3. Carbon . . . 79*14 79-61 79-15 Hydrogen. . 13.92 13'02 14.08 Oxygen . . . 6-94 6.47 6-77 -I___ 100*00 100~00 100~00 These analyses agree very closely with the calculated num-bers and with the analyses of Chevreul and Dumas. Dr. Stenhouse on Lawel Turpentine &c. Calculated numbers. Atoms. Per cent. Carbon ....... 32 = 79.69 Hydrogen. ..... 34 = 13-82 Oxygen ...... 2 = 6-51 Laurel Turpentine. For some years past an essential oil to which the name of Laurel has been improperly given has been imported in considerable quantities from Demerara and some other parts of South America. It has been successfuliy employed as an external application for the cure of rheumatism.It is also an excellent solvent for caoutchouc as it dissolves that substance very readily and leaves it in a firmer and less altered state than either naphtha or oil of turpentine. Its comparatively high price however IS. per oz. precludes its employment fbr this purpose. The botanical nature of the tree which pro- duces it is unknown. The Spaniards call the tree ''acaita de sassefras." I think it probable that it is a species of pine. These trees are not very abundant but the quantity of oil they contain is exceedingly great. It runs out abundantly when incisions are made near the root of the tree and it also not unfrequently exudes spontaneously. The oil as it occurs in commerce is transparent but of a slightly yellow colour owing to its containing a little resinous matter which is easily re- moved by distilling it with water.The smell of this oil reminds oiie of that of turpentine but it is much iriore agreeable and approaches more nearly that of oil of lemons; its specific gravity is 0.8646 at 56' F. Oil of laurel is accompanied with a volatile acid the quantity of which however is extremely small. When this acid is boiled with nitrate of silver the oxide is reduced to the metallic state. The acid is probably therefore the Formic. To prepare the oil for analysis it was distilled with water to remove the resin it contained and then rendered anhydrous by fused chloride of calcium. When rectified on the oil-bath it began to hoil at 301' F.but the boiling point gradaally rose to 325O I?. It was then transparent and colourless. The first portion that distilled over was set aside but the second and third which contained nearly an ounce each were sepa- rately collected and subjected to analysis with oxide of copper. (1.) 0.2677 gramme boiling at 301" I?. gave 0.857 carbonic acid and 0.2'79 water. (2.) 0-2839 gramme boiling at 32.5' F. gave 0,9062 car-bonic acid and 099.56 water. HS) Dr. Stenhouse 012 Oils #Hyssop 4.c. 1. 2; Calculated numbers. A toms. Carbon. . . . . 88.51 88.29 88*46 = 5 Hydrogen. . . 11-57 11.57 11-54 = 4 100*08 99*83 100*00 It is evident from these analyses that oil of laurel consists of two or more isomeric oils belonging to the numerous tribe of carburetted hydrogens of which oil of turpentine is the type containing carbon and hydrogen in the proportion of 5 to 4.The action of the reagents on oil of laurel is so similar to that on oil of turpentine as to render details unnecessary. The reason which has induced me to change the name of oil of laurel to that of laurel turpentine is that there are two oils of laurel already one fixed and the other volatile with which it might otherwise be easily confounded. Oil OfHyssop. The essential oil of hyssop is easily obtained by the usual process of distilling the plant with water. The quantity which it yields is pretty considerable. The oil has the smell ofthe plant and its taste like that of the other essential oils is very pungent.When fresh it is transparent and colourless but when kept some time especially if the air is not carefully ex- cluded it becomes yellowish owing to the formation of a small quantity of resin. Oil of hyssop is lighter than water and quite neutral; its boiling point is not at all fixed; it be- gins to boil at 288' F. but the boiling gradually rises till it reaches 325O soon after which it begins to pass over coloured it is evidently a mixture of several oils. In order to deter- mine this more certainly the anhydrous oil was rectified and the product of its distillation at different temperatures collected separately and subjected to analysis. The following are the results :-1.) 0.289 gramme boiling at 288' F. gave 0.8794 carbonic acid and 0*2875 water.(2.) 0*3022gramme boiling at 299O F. gave 0'8885 car-bonic acid and 0'298 water. (3.) 052338 gramme boiling at 335' F. gave 0.8243 car-bonic acid and 0'2671 water. 1. 2. 3. Carbon. .. . . 84*13 81-29 80.31 Hydrogen. .. 11.05 10.95 10.45 Oxygen.. ... 4*82 7-76 9-24 100*00 1oo*oo 100'00 It will at once be perceived from these results that the por- Dr. Stenhouse on Oils of Hyssop Assafmlida 4.c. 41 tion of the oil richest in carbon and hydrogen distils over at a comparatively low temperature and that as the quantity of oxygen in the oil increases its boiling point rises. This is what usually takes place with oils which consist of a mixture of,&carburetted hydrogen and more or less oxygenated oils.I was induced therefore to try if these different oils could be separated by treating them with fused potash-the method so successfully employed by Messrs. Gerhardt and Cahours with oil of cumin and which promises to be extremely useful in the investigation of this class of bodies. The oil of hyssop was dropped upon the potash through a capillary opening in the tubes of a retort. As soon as the oil came in contact with the melted potash the greater portion of it was converted into a brownish resin but a part of it passed into the receiver. This portion was again subjected to the action of the potash when still more of it was converted into resin. What di-stilled over was considerably different in taste and smell tiom ordinary oil of hyssop.When subjected to analysis 0'3047 gramme gave 0,955 carbonic acid and 0'3 13 water = Carbon. ..... 86-65 Hydrogen. .... 11'41 Oxygen. ..... 1-94 100-00 It is evident therefore that I did not succeed in converting oil of hyssop into a pure carburetted hydrogen though the quantity of the oxygenated oil was considerably diminished. Oil of Assafatida . It is to this oil that asafetida owes its highly offensive smell. The quantity of oil which the resin yields varies ac- cording to its freshness. A pound of the resin generally yields about one-third of an ounce of oil which is obtained by distilla- tion with water in the usual way. It is advisable to mix the resin with pounded glass as this prevents the resin from ad- hering to the bottom of the retort and both hinders it from burning and diminishes the violence of the succussions with which the distillation would otherwise be attended.The oil has usually a slightly yellowish tint its specific gravity is 0*9428at 60' F. ;its taste is first mild and then acrid. When exposed for some time to the air it oxidizes and a resinous matter forms in it. In order to prepare it for analysis the oil which had been twice distilled with water to remove all the resin was rectified over chloride of calcium on the oil-bath. Its boiling point is by no means constant; it began to boil at 325' F. and continued to rise till it reached 370' F. The re- ceiver was changed three times during the distillation,' and the Dr. Stenliouse on Oil qf Assafmtida &c.products separately collected and analysed. The presence of sulphur in oil of assafmtida was first noticed by Zeise. It dif- fers from oil of mustard by containing 110 nitrogen. The carbon and hydrogen were estimated by analysis with oxide of copper and the sulphur was determined by passing the oil in vapour over a mixture of nitre and carbonate of baryta at a red heat. The following are the results :-(1.) Analysis of 1st quantity 09967 oil boiling at 325' F. gave 0.710 carbonic acid and 0'2625 water. (2.) Analysis of 1st quantity 0.2915 gave 0.6935 carbonic acid and 0-253 water. Per cent. 0.382 oil gave 0-635 sulphate of baryta = 22-93 sulphur. 0.391 oil gave 0'639 sulphate of baryta = 22.54 sulphur. 1. 2. Carbon .. . . 66.16 65-78 Hydrogen . 9'83 9.64 Sulphuq . . -22.93 22.54 Oxygen . . 1.08 2-04 100'00 100~00 (I.) Analysis of 2nd quantity of oil boiling at 341' F. 0.2312 gave 0*523carbonic acid and 0.1967 water. (2.) Analysis of 2nd quantity 0.2728 gave 0-6177 carbonic acid and 0*2224water. (3.) Analysis of 2nd quantity 0*2889gave 0.6461 carbonic acid and 0'2447 water. 0.413 oil gave 0.601 sulphate of baryta = 20.12 per cent. sulphur. 0-421 gave 0-610 sulphate of baryta = 19*99per cent. sulphur. 1. 2. 3. Carbon. . . . . 62*54 62.60 61-83 Hydrogen. . . 945 9-05 9.4 1 Oxygen . . . . 7-89 Sulphur . . . . 20.12 8.36 19.99 1oo*oo 1oo*oo (1.) Analysis of 3rd quantity of oil boiling at 370° F. 0'3036 gave 0*6415carbonic acid and 0.2493 water.(2.) Analysis of 3rd quantity of oil 09947 gave 0*6185 carbonic acid and 0.241 3 water. 0-344 gave 0*421sulphate of baryta = 16*88 per cent. sul-phur. 0'382 gave 0.436 sulphate of baryta = 1-5.74per cent. SUE-phur. Prof. Bunsen on the Radical of the Cacodyl Series. 49 1. 2. Carbon. . . . . 58.42 58.03 Hydrogen . . . Sulphur . . . . Oxygen . . . . 9*12 16-88 15.58 9'09 15.74 17.14 100~00 1oo*oo It is evident from these results that oil of asafoetida is a mixture of various oils one or more of which consist probably only of carbon hydrogen and sulphur with other oils con- taining more or less oxygen. The less oxygenated portion is the most volatile. It is therefore unnecessary to attempt to deduce any formula fiorn these analyses.Though oil of as-safetida was twice treated with fused potash in the same man- ner as oil of hyssop the greater portion of the sulphur was removed but I could not succeed in getting rid of the whole. The greater portion of the oil was converted into a blackish resin. This resinous matter is soluble in alkali from which it is precipitated by acids. It is not in the least degree cry- stalline. The action of reagents on oil of assafcetida was as follows :-salts of silver lead and protoxide of mercury gave black precipitates. When brought in contact with peroxide of mercury heat was evolved and a part of the oxide was converted into a greenish yellow mass which was insoluble in water. A very small portion of the oil was acted on however.Corrosive sublimate immediately produced a copious flocculent white precipitate. It was insoluble in water alcohol and Ether. It was soluble in nitric acid and when boiled with solution of potash the mercury was precipitated in the state of protoxide. Oil of assafoetida does not combine with am-monia. It is very little acted on either by aqueous or alco- holic solutions of potash. Nitric acid acts on this oil with great energy and the evolution of deutoxide of azote. It is converted into a resin and on adding a salt of baryta an abundant precipitate of sulphate of baryta is obtained. Sul-h ric acid first reddens and with the assistance of heat chars i." It dissolves iodine readily but without explosion. Glssgow 14th October 1841.