NEWS

1873. CHEMICAL NOTICES

FROM FOREIGN

SOURCES.

Under this heading will be found an encyclopædic list of chemical papers published abroad during the past week, with abstracts of all susceptible of advantageous abridgment. The two half-yearly volumes of the CHEMICAL NEWS, with their copious indices, will, therefore, be equivalent to an English edition of the "Jahresberichte."

NOTE. All degrees of temperature are Centigrade, unless otherwise expressed.

Comptes Rendus Hebdomadaires des Séances de l'Academie des Sciences, June 2, 1873. Action of the Chief Derivatives of Amylic Alcohol upon Polarised Light.-I. Pierre and É. Puchot.Amylic alcohol has an action upon polarised light resembling that of a solution of sugar of 14 per cent, but of an inverse direction. The authors found, in all the experiments to which they submitted the pure amylic alcohol of fermentation, no indication of the second amylic alcohol pointed out by Pasteur. The action of ordinary amylic alcohol upon polarised light is increased one-third by the addition of about 6 per cent of water. Amylic alcohol, reproduced from its ethers, or obtained as the residue of an incomplete oxidation, does not appear to have undergone any appreciable modification either in the direction or the intensity of its action upon polarised light. This is not the case with its ethers, nor with the compounds formed under the oxidising influence of a mixture of sulphuric acid and bichromate of potash, along with the necessary amount of water. The first of these oxidation products, amylic aldehyde, turns the plane of polarisation in an opposite direction; in the same, namely, as would be produced by crystallised sugar. With the pure aldehyde this deviation is equal to that which would be produced by a solution of crystallised sugar at 1 per cent. Its degree of purity has a great influence on the extent of deviation. A sample of crude aldehyde, saturated with water, gave a deviation three times greater than does the pure substance. The presence of the water was, however, found not to be the cause of this increased action, since a sample of pure aldehyde saturated with water exerted a rotatory power decidedly inferior to that of the anhydrous aldehyde. The second product of oxidation, valerianate of amyl, (isomeric with the aldehyde above mentioned) causes a deviation in the same direction-but seven times greater-equal to that of a solution of crystalline sugar of 6.6 per cent. The results obtained with the amylic compounds are represented in the subjoined table; the sign + being attached to the deviations similar in direction to crystalline sugar, and

to those in the inverse direction:

Detection and Determination of Sulphate of Lead in Commercial Chromates of Lead.-E. Duvillier.-The methods used to decide on the purity of a chromate of lead do not indicate whether sulphate of lead be present or absent. The author heats gently, in a flask of sufficient size, I part of the sample of chromate with 2 to 3 parts of nitric acid at 1'420° sp. gr., 1 to 2 parts of water, and of alcohol. The reaction is very strong, and must be moderated by reducing the heat. When the violent action has subsided, heat is still applied till all nitrous fumes have disappeared. In the flask will be found a violet liquid-a mixture of nitrate of lead and nitrate of chrome-and a white precipitate of nitrate of lead, along with which sulphate of the same metal may be present. Water is added and the whole boiled. If no sulphate is present the whole dissolves; but otherwise sulphate of lead remains insoluble. To determine its amount the whole is evaporated to dryness to expel nitric acid, and the products of the oxidation of alcohol, care being taken not to heat so strongly as to decompose the nitrate of chrome. On treating the residue with water the sulphate is left undissolved. This method is applicable

to all chromates.

Action of Nitric Acid upon Chromate of Lead.E. Duvillier.-In allowing nitric acid, diluted with 1 to 2 volumes of water, to act at the boiling-point upon pure chromate of lead the liquid took the colour of chromic acid, and preserved it on cooling, although the bulk of the chromate of lead remained unchanged. On concentration crystals of nitrate of lead were deposited. The mother-liquor evaporated to dryness yielded a solution of chromic acid nearly pure, but representing a very small part only of the chromic acid present in the quantity of chromate employed. The action of the nitric acid is, therefore, analogous to its behaviour with chromate of baryta. With the latter, however, the amount of water is immaterial, whilst if water be added to a solution of chromate of lead in nitric acid this salt is precipitated. On treating the chromate of lead with double its weight of nitric acid we obtain a solution of chromic acid containing only 2 per cent of lead oxide. Nitric acid, therefore, resolves chromate of lead into chromic acid and into nitrate of lead, which is precipitated at a boiling heat in presence of the excess of nitric acid employed.

On a Base Isomeric with Piperidine, and on the Nitro Derivatives of the Hydrocarbons of the Formula C2mH2m.-H. Gell.-Meyer and Stuber have lately prepared isomeric compounds of the nitrogenous ethers formed by wood-spirit, alcohol, and oil of potatoes. These new substances behave like nitro derivatives of hydrocarbons of the general formula C2mH2m+2. This discovery of these compounds tends to disprove the essential difference which had been assumed between these carbides and those of the aromatic series, C2mH2m-6, the only group whose nitro derivatives were known. The author endeavoured to obtain analogous compounds of another family, still resulting from the substitution of an equivalent of hyponitric acid for one of hydrogen. He sought to prepare the nitro derivatives of the hydrocarbons CamH2m. Having added to nitrethane the quantity of potassa dissolved in alcohol necessary for its transformation into potassic nitrethane, it was placed in contact with an equivalent of iodide of allyl. On adding water to the filtrate an oily liquid was obtained which could not be purified for analysis as it was decomposed on volatilisation. On treating it with hydrochloric acid and fragments of zinc the insoluble oil disappeared, and on distilling the residual liquor with an excess of potassa a colourless liquid was obtained which, on the addition of some fragments of potassa, gave an odour of piperidine. The new substance differs from that base in several important respects. It boils at 85°, and its isomer at 106°. It is soluble in water and alcohol, and combines energetically with acids. If poured upon bisulphide of carbon it gives rise to a brisk reaction, but the liquid does not crystallise

NEWS

June 27, 1873

Note on the Transit of Venus in 1882.-M. Pinseux. -The author gives a number of particulars as to the circumstances of observation. He points out that the shortest transit will be observed in the neighourhood of New York, and the longest (in accessible regions) in Terra del Fuego and adjacent islands, the difference of duration being about sixteen minutes. The most retarded ingress will be observed in Canada and New Britain; the most accelerated in the island of Kergualen, between which and Montreal the difference will be more than fifteen minutes. The most accelerated egress will be observed in the Antilles and Euzana; the most retarded in the eastern part of Australia, e.g., Sydney; the difference from the time of ingress being about fifteen minutes. The determination of parallax by observations of contact will be in less advantageous circumstances than in 1874. In the latter case, with accessible regions the differences of duration of transit reach twenty-six minutes, the differences of times of ingress twenty-one minutes, and those of times of egress eighteen minutes; while in 1882 the differences will be reduced, the first to sixteen and the two others to fifteen minutes. Instead of observing the hours of contact, however, the parallax might be deduced from measurements made during the transit, and giving at various instants either the angular distances of the centres of Venus and of the sun, or the angle of position of Venus. M. Puiseux illustrates these points.

Trial during a Solar Eclipse of the New Spectroscopic Method Proposed for the Approaching Transit of Venus.-P. Secchi.-His method is as follows:-A highly dispersive direct-vision prism is placed about 25 c.c. before the slit of an ordinary spectroscope supported on the same tube. This gives in the plane of a slit a coloured image of the sun in the form of a very impure spectrum. The rays transmitted thence through the spectroscope form in the field of the small telescope a very distinct solar image, in which not only the border of the disc, but also the spots and the faculæ are quite visible. The sun is seen, in fact, as with coloured glass. When the image is received so that it is formed by red rays, then by putting the Fraunhofer line C near the sun's border at the exterior, one sees the chromosphere as a bright line separated from the solar disc by a distance equal to the height of the chromosphere; but one may at will displace this line according to the part of the chromosphere to be observed, even to contact with the sun's border. Hence, when the dark star covers the chromosphere in points situated in the field of the telescope, one will see this bright line interrupted, and be advised that the star approaches contact. One may then follow its movement by placing the slit near the border, and as the border itself is distinctly seen may estimate very exactly the instant in which (the line disappearing) the border of the dark star eats into the disc of the bright star. P. Secchi observed the recent eclipse thus, and found the results fully up to his expectations. P. Rosa and P. Ferrari also made observations at the same time; the former with a Weil refractor, magnifying 80 times, the latter with a Cauchoix telescope magnifying 120 times; and from comparison of the mean result with P. Secchi's it appears that first contact was anticipated by P. Secchi by 119 seconds, while the egress was retarded by 12.2 seconds; the method gives more precision. Comparing his results with those of M. Respighi, who used an ordinary spectroscope according to a method proposed by Zollner, P. Secchi finds M. Respighi in advance of him at the commencement and behind him at the close, the difference of duration being 34'2 seconds; but he gives reasons for thinking this result excessive; chiefly the sun's border seen by Zollner's method is imperfectly defined.

notice of the phenomenon use the ordinary spectroscope as for observation of protuberances; (2) having ascertained the ingress of Venus on the chromosphere mount the prism before the slit to obtain a distinct and direct solar image in the field of the spectroscope (an objective prism is preferable to a direct-vision prism); (3) for the second interior contact use either this method or the ordinary.

Action of the Electric Fluid on Flames, Liquids, and Powdery Substances.-Second note by M. Neyreneuf.-The writer examined flames containing no solid particles. In pure hydrogen there was a sensible attraction by a negative print; in carbonic oxide and sulphide of carbon the attraction was more maiked, and to both points. Alcohol behaves like ordinary gas. Retreat of the flame is most marked with essence of terebenthin (burnt in a lamp). If the electric point be directed normally to the surface of liquids in a conducting cylindrical capsule an umbilicus is produced for both fluids in water, oil, sulphide of carbon, essence of terethe point after having immersed it some millimetres, a benthin. With badly conducting liquids, if one withdraws liquid cone remains adherent as long as the electricity Few powders give distinct effects. The blue passes. sand used for drying with is best. Either electric point held a little way off produces centrifugal effects, while if the negative point be held very near there is a centrifugal On contact aspiration. one may, as with liquids, raise and maintain a cone of grains during passage of the

current.

the molecular theory of gases only the movements of translation have been considered, and as if these molecules were small globes perfectly elastic; whereas they are composed of several atoms held at some distance from each other. The author deduces from mechanical laws that these non-globular molecules have a movement of rotation about the natural and principal axis, for which the moment of inertia of the molecule is a maximum. A knowledge of the moment of inertia of molecules has led him to calculate the boiling-points of isomers, and details will be given in his forthcoming work on molecular mechanics.

Molecular Rotation of Gases.-M. Hinrichs.-In

General Results of Analysis of the Glyserian Springs in the Island of San Miguel (Azores).—M. Fouqué.-Chemical analysis reveals in all the waters of portions, of saline compounds identical with those San Miguel the original existence, but in various proobtained by condensing the fumes of a volcano in action, or lixiviating cold lava; and also the presence of the most common volcanic gases.

Berichte der Deutschen Chemischen Gesellschaft zu Berlin, May 26, 1873.

Arcmatic Amide Acids with Alcohol Radicals.Peter Griess.-The author has previously shown that in certain aromatic amide acids 1, and also 2 atoms of hydrogen can be easily replaced by alcohol radicals. He has since attempted to substitute a third atom in the same manner, and in some cases successfully. The compounds thus obtained differ very essentially from the amide acids previously described, and containing 1 or 2 atoms of an alcohol radical. The latter still possess the double attributes of acid and base, whilst the amido acids with 3 atoms of an alcohol radical have entirely lost the power of forming metallic salts, and, strictly speaking, cannot be classed as acids. They behave more like organic bases, and seem most closely connected with a little known class of basic bodies, to which Liebreich's oxyneurine and Scheibler's betaine, C5H11NO2, belong. The first of the compounds obtained, trimethyl-benzo-betain, C10H13NO2, forms small white acicular crystals containing I atom of crystalline water, deliquescent in the air, insoluble in ether, very soluble in alcohol, of bitter taste, and without reaction upon vegetable colours. If heated alone to fusion

C6H4

CoH_{CO_CH, N(CH3)2

a liquid of faintly aromatic odour and yellowish colour, insoluble in water. Another compound of this class, trimethyl-anisbetaine, CH15NO3, forms large vitreous prisms, containing 5 atoms of crystalline water. It is easily soluble in water, especially if hot, sparingly in alcohol, and insoluble in ether. At elevated temperatures it is entirely resolved into dimethyl-amido-anisic acidC6H3CO2 CH3

O CH3 N (CH3)2

a yellowish fluid of faint aromatic odour, insoluble in water, and boiling at 288°.

On Diallyl, and on Attempts to Prepare AllylBenzol.-R. Wagner and B. Tollens. - The authors have attempted unsuccessfully to substitute allyl for hydrogen in benzol. In course of their researches they obtained the tetrabromide of diallyl, C6H10Br4, in foursided prisms of camphor-like odour, and fusing at 62.5° to 63.5°. As its melting-point is given at 37° the cause of the discrepancy was examined. The authors prepared diallyl by Oppenheim's method (heating the allyl-iodide of mercury with solution of cyanide of potassium) and obtained a product boiling at 58° to 60°. On the addition of bromine a product was obtained, which behaved quite similarly to that prepared by means of the bromide of allyl.

Note on the Detection of Sulphur Compounds by Means of the Blowpipe.-B. Tollens.-One of the simplest methods of testing substances for sulphur compounds is to heat them upon charcoal with soda in the inner blowpipe flame. Remarkably enough it is nowhere pointed out that this test must be performed not with the flame of coal-gas but with an oil-lamp or a candle. Coalgas contains so much sulphur that soda upon which its flame has been driven for a minute blackens silver strongly, which is never the case with the flame of a candle.

Crystallographic Examination of the Derivatives of Naphthalin.-C. Hintze.-The author, having undertaken a revision of Laurent's labours in the same field, which he pronounces "totally useless for science," remarks that in the substitution of chlorine for hydrogen in the tetrachloride of naphthalin the angles of one crystal zone (pp) remain almost equal, just as has been shown by Groth to be the case with the derivatives of benzol. Here also, therefore, the morpho-trophic action extends only in certain crystallographic directions, with the distinction that this action is stronger in the derivatives of benzol than with those of naphthalin. This fact agrees perfectly with Groth's view that the morpho-trophic action of a substance depends not alone on its chemical nature, but on the structure of the compound into which it enters by way of substitution. Elements are often isomophous in complex compounds, but not in those of more simple structure.

On Enanthylic Acid and Normal Heptyl Alcohol. -H. Grimshaw and C. Schorlemmer.-Comparative examination of the cenanthylic acid obtained from œnanthol and that prepared from normal heptane gave the following results. The ethylic ether of the acid from œnanthol is a liquid of a pleasant fruity smell, boiling at 186° to 188°. The barium salts of the two acids have the same crystalline form and the same solubility in water. The calcium salts contain I atom of crystalline water, and are equally soluble, both forming slender needles arranged in tufts. The copper salts are obtained as somewhat soft precipitates, which on standing become granular. They are insoluble in water, but soluble in absolute alcohol. On evaporating the solutions the salt obtained from œnanthol separates out in small green needles or prisms. On the other hand, that obtained from heptane separates first in a

The copper salt of Franchimont's heptylic acid was likewise separated at first in little drops, which congealed to crystals. In other respects the compounds obtained by the authors were very similar to the corresponding salts of heptylic acid.

Whether the distinctions observed in the

cupric salts are essential must be determined by further experiment. Enanthylic acid indubitably belongs to the normal series, and as its aldehyde is readily obtained it forms the best material for preparing the normal heptyl compounds hitherto scarcely known.

Affinity of Bromine for Oxygen.-H. Baumhauer.Thomsen, in an essay on the affinity of oxygen for chlorine, bromine, and iodine, has concluded from thermo-chemical determinations that-in opposition to the prevailing opinion-the affinity between the constituents of bromic acid is considerably less than that between the constituents of chloric acid. This result he pronounces unexpected. In fact several manuals of chemistry state that bromine expels chlorine from chloric acid with formation of bromic acid (see Roscoe's "Outlines of Chemistry"). The author heated a solution of chlorate of potassa with bromine, but on evaporating the residue no bromate could be detected. Neither was any bromate of potassa formed on allowing bromine water to act upon chlorate of potassa with the addition of a little nitric acid-an adjunct which, under parallel circumstances, promotes the formation of iodate of potassa. It seems, therefore, decided that the affinity between oxygen and bromine is less than that between oxygen and chlorine.

Contribution to the History of Sulpho-Urea.-M. Nencki.-If a cold saturated aqueous solution of sulphourea is mixed with a solution of cyanide of mercury in equivalent amount, a crystalline double salt is thrown down which, when washed and dried over sulphuric acid, yielded results agreeing with the formulaCSN2H4C2N2Hg.

This compound is sparingly soluble in cold water, and cannot be re-crystallised from hot water, since on heating the aqueous solution a black precipitate of sulphide of mercury is formed, and an odour of hydrocyanic acid is given off. If the solution is boiled till all sulphur is deposited the filtered liquid yields on evaporation crystals of dicyanamide. If sulpho-urea is gently heated with anhydrous acetic acid it dissolves and yields monoacetylic sulpho-urea in yellowish prisms, which can be obtained colourless by repeated crystallisation. Its composition is

agreeing with the formula C3H6N2SO, or— CS(C2H3O) H3N2.

This substance is readily soluble in alcohol and hot water, sparingly in cold water and ether. It melts at 11.5° to a colourless liquid. The aqueous solution has a neutral reaction, and forms with the chloride of platinum a crystalline salt sparingly soluble in water

CS(C2H3Ó)H3N22HCl,PtC14.

If acetylic sulpho-urea is distilled with anhydrous phosphoric acid an oil of a pungent odour, heavier than water, distils over.

Determination of Chloral.-V. Meyer and H. Haffter. -The authors remark that chloral hydrate is often found very impure, whence a simple and accurate method for its quantitative examination becomes needful. With aqueous solutions of alkalies chloral hydrate is completely resolved into chloroform and alkaline formiate according to the equation, C2C13H3O2+ NaOH=CHCl3+HCO2Na+H2O. I equivalent of chloral hydrate neutralises 1 equivalent of soda, or 1655 grms. of the former require 1000 c.c. of normal solution of soda. If, therefore, a weighed amount

If free

a denoting the number of c.c. of normal soda consumed, and b the c.c. of normal acid used for titration. hydrochloric acid is present as an impurity, it is neutralised by shaking up the aqueous solution with pure carbonate of lime, and expelling the free carbonic acid by prolonged agitation in the measuring cylinder.

Aromatic Phosphorus Compounds.-A. Michaelis. -Two of the aromatic phosphorus compounds, corresponding to those of nitrogen, are peculiarly interesting; phosphoraniline, PH2C6H5 and PO2C6H5, both of which had not been obtained. The author passed a mixture of the vapours of benzol and chloride of phosphorus through a glass tube filled with pieces of pumice, and heated nearly to redness. The distillate was returned, and again passed over until 1000 grms. of a liquid, boiling at temperatures higher than 80° was obtained. By fractional distillation a colourless liquid, PC12C6H5, was obtained, boiling at 222°. This substance -phosphenyl-chloride is a very permanent liquid, refracting light strongly, and fuming in the air with an intense odour resembling both phosphuretted hydrogen and hydrochloric acid. It affords the prospect of a new series of interesting aromatic derivatives.

Behaviour of Ozone with Water.-C. Rammelsberg. -Schoenbein, Marignac, and Andrews pronounce ozone insoluble in water; whilst Soret, Meissner, and Houzeau maintain the opposite view. Carius proved that at low temperatures (0.5° to 5°) oxygen gas, rich in ozone, obtained by electrolysis, forms with water a liquid which gives the reactions of ozone. Engler and Nasse have also convinced themselves of the solubility of ozone. The author examines whether ozoniferous oxygen or air when passed at ordinary temperatures through water would give a liquid capable of producing the reactions of ozone. The result showed that when chlorine was absent the reaction with starch and iodide of potassium was obtained very slightly in one case only, and that with indigo and thallium salt not at all. The so-called "ozone water" of Krebs, Kroll, and Co. contains chlorine, and is pronounced by Dr. Jacobsen to be a dilute solution of hypochlorous acid.

Hydrates of Monobasic Acids.-A. Henninger.-A reply to Geuther's claim of priority for the theory of the hydrates of the fatty acids. He quotes the following formula which Geuther has given for acetic acid :

Ο

IV. H H2

C IV. OH C

NEWS

Dyeing Straw Hats.-The articles are boiled in a mixture of 1 lb. sulphate of alumina, lb. prepared tartar, lb. sulphuric acid, to which orchil, extract of indigo, and turmeric are added as required.

Carminate of Lime. The compound of carminic acid-the colouring principle of cochineal-with lime is, according to Guignet, distinguished by its black colour There is consequently always a black precipitate formed from the other cochineal lakes, which are mostly violet.

when a decoction of cochineal comes in contact with a solution of lime, or even with calcareous water. Pure

carminic acid does not, indeed, precipitate gypsiferous water. The reason why decoction of cochineal produces this effect is because it is slightly alkaline. The black carminate of lime can be produced by mixing bicarbonate of lime in solution with decoction of cochineal. The black precipitate is probably neutral carminate of lime, insoluble in water and alcohol. An excess of lime colours the precipitate a deep violet. Concentrated acetic acid dissolves the precipitate with a deep red colour.

same

on

No. 19.

on

The number commences with receipts for sizing linen, for producing ponceau and aniline blue on mohair yarns, superior black cotton yarns, flamed effects on red material, deep madder the wool, naphthalin yellow on woollen yarn, reddish drabs on wool, iodine green on woollen yarn, light and dark maize flesh colour and mulberry on cotton, pensé, crimson, Bismarck, drab, and grey on jute. be carefully avoided in all operations with cochineal, as the compounds of this metal with carminic acid are black. Guignet's opinion that the black spots sometimes found on grain dyed goods are derived from carminate of lime is probably erroneous, as the flot in which these colours are dyed is so acid that any carminate of lime would be at once re-dissolved. Such spots the author considers due to iron present as an impurity in the tin mordants.

Black Spots in Grain Dyeing.-Traces of iron should

Birls in Woollen Tissues. To remove birls Descoubet saturates the cloth with steam, and conducts it through a narrow slit into a chamber filled with hydrochloric acid gas. Here the cloth is passed several times up and down, and is then conducted into another chamber and dried at a somewhat elevated temperature. It is then run into an alkaline bath, which removes all traces of the acid that has destroyed the vegetable matter.

Aniline Red-Violet.-Hobrecker prepares a reddish aniline by treating rosaniline with iodide of methyl and chloride of benzyl, (C14H-Cl). The metallic green acicular crystals, insoluble in water and sparingly soluble in cold alcohol, are rosaniline, in which 3 atoms of hydrogen are replaced by benzyl, C14H7, the whole being combined with I atom of iodmethyl.

Patent Mixture for Cleansing Carpets.-In noticing an English patent for cleansing carpets-which, by the way, prescribes 3 lbs. soda, and 4 ozs. washing crystals the editor very properly remarks that a final treatment with dilute oxalic acid would improve the colours.

Impurities in Tin Crystals.-Bronner recommends dyers to prepare their own bichloride of tin from commercial tin crystals, which, he thinks, are rarely contaminated, except with sulphates of soda and magnesiasubstances easily detected by means of chloride of barium. The editor points out that tin crystals are often adulterated with alkaline chlorides, forming double salts much less easily detected.