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to 200° in a sealed tube for several hours. EC1, +2.0=EOC1+ ZnCly. The product, however, is mostly destroyed by the action of the zincic oxyd thus: €8012+Zno=ZnCl2 +€0,

(2.) By passing a mixture of carbonic tetrachlorid vapor and carbonous oxyd gas over pumice heated to about 400°.

(€C1,)2+€0=eCl2 +€,C1,. (3.) By similarly treating a mixture of carbonic tetrachlorid vapor and carbonic dioxyd. €C1, +€0,=(€0C1, 2: (4.) By acting on carbonic disulphid with hypochlorous oxyd:

€5,+(C1,0)3=(SoCl2)2+COClą. Bull. Soc. Ch., II, X, 188, Sept. 1868.

G. F, B. 13. On the relation between boiling point and constitution of hydrocarbons.—The saturated hydrocarbons whose constitution is known with more or less certainty, SCHORLEMMER divides into four groups. The members of each group show a very regular difference of boiling-point. (1) The first group comprises hydrocarbons in which the carbon atoms form a simple chain; i. e., those in which no carbon atom is united to more than two others. Beside the first three members of the series, di-ethyl, hexylic hydrid from suberic acid, and heptylic hydrid from azelaic acid also belong in this group, since their boiling-points are higher than those of their isomers; it being a fact that compounds whose carbon atoms are thus arranged, boil at a higher temperature than isomeric borlies in which any of the carbon atoms are united to more than two others. Moreover, the formation of these bodies also places them in this group; the acids from which they are derived being produced by the splitting up of compounds richer in carbon; and as the hydrocarbons come from these acids in the same way they must possess a simple constitution. The difference of boiling point between the mernbers of this group is 31° C. The hexylic hydrid from suberic acid, that from petroleum, and that from mannite appear identical. (2) The next group includes those which may be viewed as derived from propylic (tritylic) hydrid by annexing a simple chain to the middle carbon atom. To this group belong trimethylformene, some hydrocarbons derived from the butylic and amylic alcohols produced in fermentation, and octylic hydrid from caprylic (octylic) alcohol. The difference of boiling point here also is 31° C., amylic €H

2
at 91°, and octylic hydrid él(CH),

LEH, at 124°. (3) The third group contains the isopropyl grouping twice, instead of once; i. e., there are two atoms of carbon in it, each of which is united to three others. The difference of boiling point in this group is 25° C. It includes di-isopropyl }

€H (CH3)2 boiling at 58°, di-butyl-amyl-isopropyl €,H boiling at

€H (CH3)2

62°, ethyl-amyl { € (€II.),

,

. { €H (CH3);

l

CH(CH3)2 109°, (the second member being wanting) amyl-butyl €,

Củ (CHỊ). ( €H(€Hz), at 132°, and di-amyl €,I, at 158o (4) The fourth group

€H (CH3)2 includes hydrocarbons in which one carbon atom is united with four others. Thus far only one member of this group is known, the carbo-dimethyl-diethyl of Friedel and Ladenburg €(CH3)2 (€,H,), which boils from 86° to 87° C.*

From this classification it is easy to see that in the marsh-gas, as in the benzol series of hydrocarbons, conclusions as to the constitution of the bodies may be drawn from their boiling points. Ann. Ch. Pharm., cxlvii, 214, Aug. 1868.

G. F. B. 14. On a nero source of octylic alcohol.-Silva has examined in the laboratory of Professor Wurtz, a sample of fixed oil, derived, like castor and croton oil, from the family of the euphorbiacea, the plant yielding it having been described by Adanson about the middle of the last century under the name Curcas purgans. This plant exists in great abundance in certain parts of Africa, and especially in the Cape de Verd islands; and from the fruit, considerable quantities of the fixed oil are obtained, the physiological properties of which are analogous to those of castor oil, though it is more active. The similar origin and analogous properties of this and castor oil suggested its distillation with an alkali, as had been * These groups may be more clearly shown by a graphic representation. Tak

н--н ing propylic (tritylic) hydrid as a representative of the first H-C-H, the second

H-C-1
HHH

HHH
H-6-6-6-H

H-CEL may be ropresented by H | I trimethyl-formene, the third by mi H-C-H

H H I

H-C-C-Cн

Á Úk
H-C-H

H-6-1
H

H

H-C di-isopropyl, and the fourth by

carbo-dimethyl-diethyl. In

H

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LC-H, ,

[blocks in formation]

the first the middle carbon atom is united to two others, in the second the upper carbon atom is connected with three others, in the third both the main carbon atoms are so united, and in the fourth all four bonds of the middle carbon atom are saturated by carbon.--G. F. B. AM. JOUR. SCI. -SECOND SERIES, VOL. XLVII, No. 141.- MAY, 1869.

G. F. B.

G. F. B.

done with the latter by Bouis. The sample of oil-obtained from the Portuguese commissioner at the Paris Exposition-was small, but on saponification and distillation it yielded a complex liquid, which was inflammable and possessed an agreeably aromatic odor. On fractional distillation, the portion passing between 178° and 180° was a colorless, slightly oleaginous, aromatic liquid, whose analysis gave numbers corresponding to octylic alcohol. It is insoluble in water, easily soluble in alcohol and ether, and is turned yellow by light. No attempt was made to determine its constitution by oxydizing it. The purgueira” oil—by which name the oil is known in the Portuguese colonies-contains 6.1 per cent of nitrogen, which is evolved as ammonia on distillation.-Bull. Soc. Ch., II, xi, 41, Jan. 1869.

15. Tritylic (propylic) alcohol produced by fermentation.-Some doubt existing in the minds of chemists as to the actual production of tritylic alcohol in the ordinary alcoholic fermentation of beet root, ISADORE PIERRE and Puchor have prepared in this way nearly a dekaliter of this substance remarkably pure. The alcohol itself has a density of 0.820 and it boils at 98° C. Propylic iodid obtained from it has a density of 1.784 and boils at 104.5°. The acetate boils between 104° and 105°.Bull. Soc. Ch., II, xi, 43, Jan. 1869.

16. On the reduction of acetic oxyd to ethylic alcohol.-LINNEMANN has succeeded in effecting this reduction by acting upon acetic oxyd (anhydrid) with finely pulverized sodium-amalgam. An energetic action takes place, evolving if moisture be present, an odor of aldehyd; on adding water and continuing the action, the aldehyd odor, which at first becomes stronger, disappears entirely and in the liquid is found acetate of sodium and ethylic alcohol. The reduction takes place as follows;(1.) €2H20 O-O

€,,Ꮎ
€ Hje €,HO €, e)

HSP
€2H20
H

H -Ann. Ch. Pharm., cxlviii, 249, Nov. 1868.

17. On the alcohol obtained by the saponification of castor oil. The question whether heptylic or octylic alcohol is produced by the saponification of castor oil, has been re-investigated by Schor

The product was obtained in the usual way by distilling the oil with an excess of potassic hydrate. The distillation was effected as rapidly as possible in a thin flask of copper. The distillate was rectified from fused potash so long as any action took place.* The mass of the distillate boiled between 160° and 178°, the boiling point being constant for a considerable time at 170°. It contained no methyl-ænanthyl or other ketone, sodic bisulphite being without action upon it. Upon treating it with phosphorus and iodine, the alcohol was converted into iodid, and

G. F. B.

* Beside the alcohol itself, compounds having higher and lower boiling points were also obtained. The latter consisted of various unsaturated hydrocarbons, principally octylene, boiling at 125° C.

LEMMER.

the fluid was separated by fractional distillation into hydrocarbons boiling below 160°, and into octylic iodid whose boiling point was 210° to 215°. No heptylic alcohol was present in the above mentioned liquid therefore, which consisted entirely of octylic alcohol mixed with hydrocarbons. To ascertain the character of this alcohol, it was oxydized with sulphuric acid and potassic dichromate. After the action ceased, the fluid was distilled and the distillate neutralized with sodic carbonate. An oily layer floated on the surface, which was neutral in its reaction, possessed the characteristic odor of methyl-enanthyl, and united readily with sodic bisulphite to form a crystallized compound. This substance, pressed between folds of paper and dried, yielded, when distilled with sodic hydrate, the pure ketone, boiling between 170° and 172o. By continuing the action of the oxydizing agent the methyl-ænanthyl was converted into a mixture of sodic caproate and sodic acetate. The above facts prove conclusively the truth of the opinion expressed by Kolbe that the alcohol obtained from castor oil is a secondary alcohol, since it yields a ketone on oxydation, which ketone by further oxydation, falls apart into caproic and acetic acids. Its constitution is represented by the formula

€ H CHOH; it is methyl-hexyl iso-octylic alcohol. The constitution

CH, of the radical hexyl €6H13, is next discussed by Schorlemmer. The caproic acid prepared from fats is identical with that prepared synthetically from amylic cyanid, and both correspond precisely with that obtained above by the oxydation of the iso-octylic alcohol. And as, according to Erlenmeyer, the carbon atoms in amyl

€ 6

1 3

have the following arrangement,

it follows that this grouping

must exist in caproic acid and in the secondary alcohol from which it was obtained. To establish this point, Schorlemmer prepared from the alcohol the hydrocarbon €,H,, by converting it into the iodid, and reducing this with zinc turnings. From its boilingpoint which was 124° C., he shows that its constitution must be | CH(CH3)2. Hence, the iso-octyl alcohol from castor oil has the formula

CH,CH,

€,

€Н

€н, ,

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€Hөн

€H, -Ann. Ch. Pharm., cxlvii, 222, Aug. 1868.

G. F. B.

18. On Sulpho-carbamid.-REYNOLDS has succeeded in isolating the sulphur compound corresponding to urea, by heating ammonic sulphocyanate to 170° C. in an oil bath for two hours. On solution in water and crystallization, orthorhombic prisms were obtained which were not deliquescent, were very soluble in alcohol and water, sparingly so in ether, and which yielded on analysis the formula of sulphur-urea, (ES)H Nz; its derivatives establish its rational constitution.-J. Ch. Soc., Dec. 1868.

G. F. B.

II. GEOLOGY.

1. On a Mineral Phosphate from the island of Redonda, W.I.; by CHARLES UPHAM SHEPARD.—This substance has lately been brought to my notice by receiving through Messrs. Willis and Chisolm of this city, a few pounds of it, sent them by Mr. Crichion of Baltimore, the proprietor of the island. Its

ineralogical characters, equally with its chemical composition, place it strongly in contrast with the pyroclasite or stoneguanos of the West Indies and of South Carolina, to which it was supposed to be related; and on the ground of these differences, I have thought it worthy of notice.

Mineralogical description.- Massive, amorphous, minutely vesicular, or sub-amygdaloidal; resembling allophane or an eartly opal. The cavities (not always present) are not much above the size of mustard seeds. They are nearly spherical, and have a white opaque lining, in consequence of which they contrast with the translucent compact mass of the stone, and appear to be foreign oolitic bodies, imbedded therein. Translucent (like flint or hornstone) to opaque, color grayish or yellowish white, -rarely milkwhite in spots. H. 3-5-4, sp. gr. 1.90–2:07. Fracture even, sub-conchoidal to earthy, brittle, luster dull. The white and earthy variety adheres strongly to the tongue, like certain altered chalcedonies; but emits no argillaceous odor on being wetted.

Chemical description. Before the blow pipe, turns white at first, and then becomes rusty, without melting. The flame becomes yellow, even after the mass is moistened with sulphuric acid, though faint green tints are occasionally visible. With solution of cobalt, the heated mass becomes deep blue.

It contains no carbonic acid and only traces of sulphuric acid and chlorine. Its solution is easily effected in the strong acids; and the solutions are turbid with flocculent silica. Ammonia throws down a copious precipitate of the phosphates of alumina and iron, and the clear supernatant liquid gives additional strong precipitates with either the chlorid of calcium or chlorid of barium; in the former case, of the phosphate of lime, and the latter, of the phosphate of baryta,-showing the mineral to be unusually rich in phosphoric acid.

On analysis the following results were obtained:

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