NEWS

The chlorinated liquid containing oxides of lanthanum, didymium, and a little lime, was treated by oxalate of ammonia, which precipitated the three bases as oxalates. They were weighed after being washed and calcined, then digested with very weak nitric acid by M. Mosander's method. A little oxide of cerium remained undissolved, and was added to that already obtained in the preceding operation.

The nitric acid solution of oxides of lanthanum and didymium, coloured violet red, was saturated with ammonia; the lime remained in the liquid while the other oxides were precipitated in a gelatinous state. The lime was estimated as caustic lime, after precipitation by oxalate of ammonia, and calcination of the oxalate; a little lanthanum and didymium were found mixed with it and were taken into account in the final result.

The oxides of didymium and lanthanum were re-dissolved in nitric acid, and the nitrates evaporated to dryness in a flat-bottomed capsule. The dried mass was of a pale rose tint. By exposing the capsule for a few minutes to a temperature of 400° or 500° the saline mass was fused with disengagement of nitrous vapours. The capsule was withdrawn from the fire before the decomposition was complete, and hot water was poured in. Part of the matter dissolved and part remained insoluble in the form of greyish-white flakes (with no nitrate of didymium). The whole was left to stand for a few hours, then boiled and filtered; and as the liquid still retained a feeble rose tint, the same operation was repeated three times before a colourless liquid was obtained, containing nitrate of lanthanum, separated from subnitrate of didy mium. Oxide of lanthanum was determined by evaporating this liquid and strongly calcining the residue. The oxide of didymium was also estimated after the calcination of the subnitrate thus obtained.

This process is founded on the fact that nitrate of didymium decomposes before nitrate of lanthanum, and that the first of these salts changes to the state of subnitrate, 4DIONO,+5HO (this salt has already been observed and described by M. Marignac). Several pre cautions must be observed. The bottom of the capsule containing the mixture of the two salts must not be too much heated, nor must too large quantities of material be used, as in that case it forms a thick layer at the bottom of the capsule and decomposes unequally. It is better to recommence the operation several times than to heat too strongly in attempting to separate the two oxides at the same time. The first portions of oxide of didymium obtained in this way give, with sulphuric acid, reddish-violet crystals, with traces of white needleform ones, which seem to belong to the sulphate of lanthanum. The last portions give a sulphate less colonred, but like the preceding with the same crystalline form derived from the oblique rhomboidal prisms; the needles of sulphate of lanthanum are rather more numerous; in short, the above-described colourless solution gives, with sulphuric acid, colourless crystals derived from the right rhomboidal prism characteristic of sulphate of lanthanum.

By following this method we obtain rather too high an estimation of oxide of didymium, and consequently one rather too low of oxide of lanthanum. By operating on a mixture of these oxides previously weighed, we found that the excess of oxide of didymium varied from 5 to 6 per cent.

We cannot, then, give this mean analysis as yielding precise results, but it may prove a sufficiently near approximation.

Oxide of lanthanum calcined at white heat, and put in contact with a concentrated solution of ammoniacal

nitrate readily dissolves, even without heat, disengaging ammoniacal gas; oxide of didymium similarly treated also dissolves, but somewhat more slowly; consequently this property cannot be utilised for the separation of the two oxides. To estimate the carbonic acid combined with oxides contained in parisite, a gramme of this mineral, reduced to a very fine powder, was heated to whiteness in a current of nitrogen; the decrease in its weight gave the quantity of carbonic acid disengaged; the number obtained very nearly corresponds to that already determined by M. Bunsen. The fluorides contained in the parisite are not decomposed by this calcination.

Having endeavoured to collect the proportion of water existing, according to M. Bunsen's analysis in parisite, we placed a gramme of this substance, reduced to an impalpable powder in a platinum boat, which we placed in a crucible of the same metal six centimetres long, with a screwed cover furnished with a small tube, traversing a stopper of hard asbestos in a glass tube, bent to a semicircle and tapered at the extremity opposite to that where the small platinum tube is placed. The glass tube intended to collect the water disengaged during the calcination of the mineral having been exactly weighed, we heated by an enameller's lamp the part of the platinum crucible containing the boat and the substance to be analysed. Slight vapours were disengaged and condensed inside the glass tube, but on weighing this tube it was found to have increased in weight scarcely one milligramme.

In another experiment we did not pulverise, but broke up the mineral into fragments, which when treated in the same manner decrepitated and projected into the condensing tube a brown powder of great tenuity without apparently disengaging more moisture than in the preceding experiment. According to these results parisite would hold no water in combination. The presence of the 2.50 per cent. of water found by M. Bunsen may be explained by admitting the accidental interposition of the liquid in some of the interstices of the mineral. On breaking parisite crystals we find, in fact, in their interior small hollows lined with microscopic crystals. It is possible that in these cavities infinitesimal quantities of water were interposed, which would disappear when the mineral was reduced to impalpable powder.

The apparatus described as having served in the research for water in parisite had been previously employed successfully in determining the water in minerals containing but a very small proportion of it, such as euclase, idocrase, diallages, talcs, &c. It has the advantage of rendering visible the water disengaged from minerals by heat, and of allowing it to be transferred so as to undergo various tests.

The mean of these analyses has given the following numbers :—

Oxygen. Relation. 0*1708 6

0.2348 0'4252

00958 00137

'0826 0012100339

0.0285 0.0081
traces

. O'1010
0'0216

0*9895

Parasite, then, may be represented by the formula,

2CeOCO2+ (DiO.LaO) CO2+ (Ca, Ce) Fl.

-Comptes Rendus, lix., 271, 64.

232

TECHNICAL CHEMISTRY.

{CHEMICAL NEWS,

1864.

then taken from the furnace and cooled, remaining in the hydrogen current.

FRED. MARGUERITTE.

THE theory of the carburation of iron has been the subject of many controversies. Not wishing to discuss all the opinions relating to this subject, I have simply sought to ascertain whether carbon combines with iron directly by contact or by cementation.

Guyton-Morveau (Annales de Chemie et de Physique, series 1, xxviii., 19) was the first who attempted to prove that alteration takes place by simple contact. He calcined a diamond in an iron crucible placed in a Hessian crucible. After undergoing about an hour of intense heat the iron crucible was completely changed into a mass of melted steel.

Thus, says Guyton-Morveau, the diamond disappeared by the attractive force of the iron favoured by the high temperature to which they were both exposed, just as one metal disappears in forming an alloy with another metal.

Nevertheless, the transformation of iron into steel exclusively by the contact of the diamond may be contested, as the iron crucible during the whole time of calcination was exposed to the carburising action of the gases of the furnace. The question seems as yet unresolved; and M. Chevreul recently said before the Academy (Comptes Rendus, 1861, lii, 424):

"It is important to know, 1. Whether it is true, as Guyton says, that iron may be converted into steel with diamond powder; 2. Whether, if such be the case, the transformation is effected without the intervention of nitrogen."

The object of this paper is to show that iron carburises, is converted into cast iron when heated in contact with carbon, and is also transformed into steel without the intervention of nitrogen. The essential condi

into the boat beside a small globule of cast iron.

In the second operation five small diamonds traversed a soft iron plate, and in disappearing gave well melted globules of cast iron.

In the third experiment a larger diamond and a thicker iron plate were used. The diamond pierced and became inserted in the plate.

Then a fourth experiment was made for the purpose of producing steel.

The hydrogen current was directed on an iron wire 1 milimetre in diameter, half of which was covered with coarse diamond powder contained in a platinum boat.* The part of the wire plunged in the diamond dust was cemented, while the rest of it remained unaltered.

After having used diamond, we operated on plumbago and sugar charcoal calcined for a long time in a hydrogen current.

After heating strongly the tube containing the charcoal, an iron wire was introduced into it 1 millimetre in diameter. In three minutes the end of the wire in the carbon dust was transformed into cast iron, the globules of which were found. The temperature was lowered, and in the same space of time the extremity of another wire was converted into very hard fine-grained steel, while the part not in immediate contact with the charcoal showed no sign of any change. This confirms M. Berthelot's observation that if hydrogen were capable of forming acetylene or any other carbonised compound, the whole of the wire would have been cemented.-Comptes Rendus, lix., 139.

PHARMACY, TOXICOLOGY, &c.

1. With pure carbon (diamond);

2. In an atmosphere of chemically pure hydrogen ; 3. In vessels absolutely impermeable to the gases of the furnace ;

So that the possible combination of the diamond and iron was complicated by no foreign action.

The experiment was thus effected :-Hydrogen was prepared with distilled zinc, and pure sulphuric acid, purified and dried with the greatest care, in the way indicated by MM. Dumas and Sainte Claire Deville; that is to say, that the gas traversed successively apparatuses filled with acetate of lead, sulphate of silver, pumice stone saturated with potash, and cold sulphuric acid, after having passed through spongy platinum heated to dull redness.

Thus purified and dried the hydrogen was carried through a doubly glazed porcelain tube, whose perfect impermeability had been tested, which was heated to the melting point of cast iron. In the tube was a small porcelain boat, on the edges of which rested a very fine plate, which had been previously and for a long time heated in a current of hydrogen, so as to free it from its sulphur and nitrogen.

On the iron plate was placed a diamond which had been slightly heated; a cold hydrogen current was passed through the apparatus for several hours, to free it from air, that is to say, from oxygen and nitrogen. The temperature was then rapidly raised to red heat, and kept at this point for some time. The tube was

Almonds, by M. Dragendorff.

THIS test consists in acting on the adulterated oil with sodium in the presence of alcohol. This metal, in contact with pure oil of bitter almonds, disengages gas, which is augmented by the addition of alcohol, and white flocks are formed. Nitro-benzol under the same circumstances with alcohol becomes deep brown or black and viscid.

In testing the adulterated oil, take ten or fifteen drops of it, add four or five drops of alcohol, and a fragment of sodium; a brown deposit, approaching black, in proportion as the nitro-benzol is in excess, occurs. This reaction is instantaneous, and when the oil contains from 30 to 50 per cent. of nitro-benzol_one_minute is sufficient to obtain a thick brown liquid.—Journ. de Pharm,

On a New Falsification of Saffron, by M. GUIBOURT, M. VESQUE, Pharmacien of Lizieux, has received recently from a house in Paris, under the name of "Safran du Gatinais," 250 grammes of a saffron of inferior quality, containing about 30 per cent. of a material judged to be the stamens. Professor Decaisne, who has examined this substance, has recognised in the length of the filaments the cylindrical form of the anthers and the large size of the pollen grains, that these stamens are those of a Crocus. But they are not the

powder boiled in nitric acid to free it from any metallic particles, and

Several good diamonds were pounded in a steel mortar, the

then slightly heated.

NEWS

stamens of the mother plant, which have been inadvertently collected with the stigmata, the colour of which is yellow and easily distinguishable. They are evidently collected intentionally, dyed artificially, and twisted so as to deceive the eye, and in quantity equal to nearly a half of the article. The adulteration is recognised by throwing a certain quantity into a glass of water. The stamens are instantly decolorised and float, whilst the true stigmata fall to the bottom of the water. On comparison with the figures of Hayne, these stamens belong to the Crocus vernus, by the cylindrical form of their anthers, rounded at the summit, whilst the anthers of Crocus sativus are terminated like an arrow. Finally, this saffron contains also little marigold petals, coloured red like the stamens; these sink in water with the stigmas of the saffron, and are recognised by their base, their longitudinal nervures, and three-pointed terminations. I do not know what opinion to give of a merchant who thus falsifies saffron; the man who takes your purse from your pocket is not more culpable. Journ. de Pharm., Juin., 1864.

PROCEEDINGS OF SOCIETIES.

CHEMICAL SOCIETY.
Thursday, November 3.

Professor A. W. WILLIAMSON, Ph.D., F.R.S., President, in the Chair.

AT this the opening meeting of the Society during the present session there was an unusually large attendance of members, and a sufficient amount of business to occupy the Society until a very late period in the evening.

The minutes of the last ordinary meeting (in June) having been read and confirmed, and a very long list of library contributions acknowledged, Mr. Wm. Baker, of Sheffield, and Mr. G. W. Knox were formally admitted as Fellows of the Society. The names of several candidates for the same honour were then read over for the first time; amongst them were Colonel H. Y. D. Scott, Royal Engineers, South Kensington Museum; Lieutenant Hosier, 2nd Life Guards; Dr. Hermann Sprengel; Mr. John Berger Spence, Manchester; Mr. J. G. F. Richardson and Mr. Daniel Harvey Jay, Leicester; Mr. Henry Haywood, Broom Hall Park, Sheffield; Mr. Charles Eken, Bath; and Mr. William White Rouch, Norfolk Street, Strand.

The PRESIDENT then read a resolution of the Council to the effect that the names of several members of the Society who had allowed their subscriptions to lapse for the three last years be removed from the list of Fellows. After the third reading of this resolution it was proposed to ascertain the feeling of the Society with regard to it by ballot.

A paper was read by Professor WANKLYN "On Valery?, the Radical of Valerianic Acid." The author began by referring to some very old researches of Löwig and Wiedmann, wherein it was shown that when acetic ether is acted upon by potassium or sodium it does not evolve ethyl, but gives ethylate of sodium and other products. According to the prevalent opinion, acetic ether should yield ethyl just as iodide of ethyl yields ethyl when it is acted upon by a metal. Mr. Wanklyn had repeated Löwig and Weidmann's experiment with acetic ether, and confirmed their result in so far as the non-evolution of ethyl was concerned. With valerianic ether and sodium or potassium he got likewise no evolution of ethyl. From a review of the chief reactions of acetic ether, Mr. Wanklyn came to the conclusion that it was more correctly described as ethylate of acetyl than as acetate of ethyl. Of course, the same would apply to other ethers, and thus valerianic ether should be ethylate of valeryl. Experiments made

0+

Na

;}

=2

Na

}+CHO}

*CH,0}

with sodium and valerianic ether gave this result. One molecule of valerianic ether is decomposed by one atom of sodium yielding one molecule of ethylate of sodium and one equivalent of valeryl. Or doubling— C2H2O 2C2H2 Na 2C,H, In the experiments described, a weighed quantity of valerianic ether was sealed up with a weighed quantity of sodium and some dry common ether. After action in the water bath the tube was opened, no gas escaped. The residual unacted upon sodium was then cleaned and weighed; the difference between this weight and the weight of the sodium taken gave the sodium actually consumed. The amount of ethylate of sodium formed was determined by titrating the caustic soda produced by reIt was found that the quantity of action with water. valerianic ether taken, the quantity of sodium consumed, and the quantity of ethylate of sodium formed were what the above equation requires. The oil formed had the composition of valeryl. In conclusion the author promised to make a minute examination of valeryl, and of several of the acid-forming radicals, and remarked that the result of the research was the disclosure of a new general law in organic chemistry.

An explanation of the formation of carbonic ether from oxalic ether was also given.

The PRESIDENT remarked upon the unexpected nature of the reaction discovered by Professor Wanklyn; he should rather have anticipated the elimination of hydrogen; the formation of the acid radical in this simple manner was a fact of great interest and importance.

Dr. FRANKLAND made a similar remark, and inquired of the author whether he had yet tried the action of chlorine upon the radical? The speaker was now engaged conjointly with Mr. Duppa in a somewhat similar line of research; the experiments were not, however, sufficiently advanced to enable him to make a statement on the present occasion.

Professor WANKLYN, in reply to Dr. Odling, said that he had not yet succeeded in making the valeryl-sodium; and that time had not permitted of his examining fully the action of chlorine; so far it appeared to be split up into a hydrocarbon and a valerate.

Sheffield, to give an account of some experiments made by The PRESIDENT next called upon Mr. William Baker, of himself and Mr. Graham Stuart "On the Existence of Nitrogen in Steel."

This research was directed to the repetition of M. Fremy's investigations, using, however, the characteristic varieties of Sheffield steel, Bessemer steel, "J. B." iron, and other British brands, besides the well-known Spiegeleisen now largely used in the manufacture of steel. A full account of these results must unavoidably be deferred until next week, but it may be stated at once that the important conclusion to which the authors have arrived is

to the effect that there is no clear evidence of the existence

of nitrogen in steel, nor in any of the brands of iron which they have examined. The authors referred incidentally to the possible existence of the nitride of titanium in steel and titaniferous iron, which might under such special circumstances account for the appearance and detection of nitrogen amongst other normal constituents.

Mr. WILLIAM BAKER, Associate of the Royal School of Mines, then read the following paper, entitled "On the Occurrence of Nickel in Lead, and its Concentration by Pattinson's Process."

It is well known that for certain manufactures lead of a high degree of purity is required. The presence of a very small amount of copper especially is injurious for making white lead and glass makers' red lead. Investigating the cause of a peculiar tint in glass which was sometimes sufficiently marked to be called blue, and was readily accounted

for by the presence of copper, I sought carefully for cobalt, but only found nickel. In all the samples of English lead which I have examined I have never detected a trace of cobalt. On the contrary, traces of nickel have frequently been found in various samples of Derbyshire lead, in Yorkshire lead, and lead from Snailbeach, Shropshire. Operating upon 2000 grains I have found the following quantities of nickel in the pig lead as delivered by the smelter: Per cent. oz. dwts. grs. 0.0023 =0 14

Derbyshire lead, 1st sample

2nd 3rd

8 per ton.

0'0023 O Snailbeach lead. 0'0007 Softened slag lead 0*0057 I 16 On submitting lead containing these quantities of nickel to Pattinson's process, I find a concentration of the nickel in the fluid portion. Crystals of lead were taken out in the proportion of 9-10ths, leaving 1-10th fluid lead of a five ton charge.

Samples of the fluid lead, or "bottoms," upon analysis,

contained nickel as follows:

In all cases a weighable quantity could be obtained from 2000 grains of lead.

Per cent. ozs. dwts. grs. Five tons of lead contained '0068 4 =2 10 per ton. Four and a-half tons were removed as crystals, and when Per cent. ozs. dwts. grs. melted contained only '0047 = I 10 I per ton. These figures show that nickel remains to a great extent with the fluid portion, much as copper does, and I have reason to suppose that when it reaches a certain amount, as in the case with copper, the separation is no longer effected, or only in a very small degree. In the case of copper, this is easily understood when it is seen that, at a low temperature, copper (in the absence of antimony and arsenic) will separate and be found in the dross on skimming, leaving the fluid lead containing about 20 ozs. per ton 0.06 per cent. To effect a separation of the copper by Pattinson's process the amount at the commencement should not be

more than 10 ozs. per ton.

found.

=

A sample of lead from five tons, when analysed, gave no indications of the presence of nickel; on crystallising 9-1oths, the remainder gave distinct traces of the metal. Ín refined lead I have only once succeeded in obtaining a weighable quantity, and only rarely found traces in nickel. That it is not removed by oxidation is proved by the larger quantity found in the fluid portion of the lead when crystallised, as well as by the fact that in the softened slag lead which is submitted to the powerful oxidising action of nitrate of soda a considerable quantity of nickel is still Professor A. H. CHURCH then read a paper " On the Blue Colour of Forest Marble." This rock, which is a well known member of the oolitic series, is externally of a fawn colour, but always contains a darker-coloured, bluish grey interior portion, to which the author's remarks particularly referred. The common explanation was to the effect that the iron, existing to the amount of about one per cent., was in the form of protoxide in the interior and peroxidised without; but a more critical examination showed that the blue colour was due to the occurrence of bisulphide of iron, which had become converted in the external portions into a soluble sulphate of iron, which, reacting upon the carbonate of lime in the presence of air, formed sulphate of lime and hydrated peroxide of iron. The analytical | examination proved that sulphur existed wholly as sulphate of lime in the external crust, whilst, by digesting the blue interior mineral in dilute hydrochloric acid, an

(CHEMICAL News, Nov. 12, 1864.

insoluble residue remained, which was composed, to the extent of 16 per cent., of bisulphide of iron, and there was some sulphate of lime in solution. By mixing together iron pyrites and carbonate of lime, both in the state of very fine powder, the author succeeded in imitating the bluish tint of the natural rock.

Professor Church then proceeded to give an account of some experiments he had lately been making upon “The Effect of Ignition on Garnets, &c." In the Proceedings of the Royal Society, vol. xiii., p. 241, would be found recorded some extraordinary statements tending to show that certain minerals of the idocrase and garnet family underwent expansion when exposed to a red heat, but only went back again to their normal dimensions after the lapse of a month or other considerable period of time. That, in fact, the specific gravity of lime garnet, originally 3'35, was reduced to 2.98 by being heated to redness for a quarter of an hour, and allowed to cool; and that the mineral being left at rest for a month regained its original density. Professor Church then proceeded to challenge the accuracy of these observations, and described the results of his own experiments upon the same minerals, by which it was proved that in no single instance was there any indication of the "intermittent molecular change" which the author lays claim to having discovered. Amongst the numerous results brought forward by Mr. Church were the following:

=

The specific gravities of beryl, chrysoberyl, and topaz were likewise identical before and after ignition. Many of these minerals became permanently reduced in density by the action of a temperature sufficiently high to cause fusion. Thus, the specimen of idocrase originally 3'40 was diminished to 2.937 by fusion, and the brown-red iron garnet from Arundel became reduced to 3.395, and even to 3 204 by longer fusion. It is well known that heat is sometimes employed as a means of altering the colour and imparting increased brilliancy to natural gems. A large Indian zircon in the possession of the speaker, which weighs between 2 and 3 grammes, has a specific gravity M. Damour obtained by heating to redness a natural zircon = 4·696—a number not widely different from 4'534, which of original gravity 4.183. Mr. Church concluded by stating his conviction that the remarkable assertions communicated to the Royal Society in May last were not founded upon correct observation, and before publishing this as his final conclusion he had made upwards of seventy experiments, so that it is obvious there must be some occult however, that he (Mr. Church) failed to comply with some cause for results so anomalous. It must be admitted, of the conditions set forth by the author, viz., "The diminution of density being noted, the specimens were carefully dried, enveloped in several folds of filtering paper, and put aside in a box along with other minerals."

Mr. PERKIN having suggested that the anomalous gravities might be accounted for by the specimens having been weighed whilst yet warm, the meeting was adjourned by the President until the 17th instant.

The name of the author was not mentioned by Professor Church. On turning to page 240 of the Proceedings of the Royal Society, vol. xiii., we find a "Note on the Variations of Density produced by Heat in Mineral Substances," by Dr. T. L. Phipson, F.C.S., &c. Communicated by Professor Tyndall.

NEWS

In a word, Dumas recognised that acetic acid and terchloracetic acid, which are derived one from the other by the substitution of Cl, for H3, and which contain the same number of atoms, grouped in the same manner, possess also the same fundamental properties. He expressed these facts by saying that these two acids belonged to the same chemical type. He endeavoured also to demonstrate that the chemical properties of a compound depend less upon the nature of the constituent elements than upon the way in which these elements are grouped. Chlorine, he said, although endowed with properties quite opposite to those of hydrogen, may be substituted for the latter in a compound without modifying its fundamental properties, because the grouping may remain the same.

This was a novel and bold idea, and perhaps rather exaggerated in form, for certain facts of substitution which have been discovered since have demonstrated that the properties of bodies depend at once upon the nature of the atoms and the manner in which they are grouped. Regnault came afterwards bringing the idea of mechanical types, and placing in the same group all bodies which contain an equal number of atoms, whether their fundamental properties are the same or not.

The idea of an ammonia type arose out of my own studies and those of Hofmann on the compound ammonias. In the communication in which I announced the discovery of compound ammonias, I remarked that these bodies might be regarded as ammonias in which one equivalent of hydrogen is replaced by methylium or ethylium. I represented these relations in the following way :NH2H NH,CH, NH,C,H.

Hydramide. Methylamide. Ethylamide.

A few months later Hofmann discovered diethylamine and triethylamine, which he represented thus:C2H5 C2H H N C2H N H

H HN H

Ammonia.

H

C2H, C2HN. C2H2

Ethylamine. Diethylamine. Triethylamine. He thus formulated the typical idea more clearly than I had done it myself.

The ammonia type was adopted by chemists without difficulty, but still only from an isolated point of view; the doctrine was not yet constituted in its entirety. Towards this end the labours of Williamson gave the most decisive movement. These labours relate to etherification and the constitution of ethers.

When sulphuric acid, H,SO4, reacts on alcohol, CHO, sulphovinic acid is formed by a double substitution.

H

}○

C,H CH11

}0.

It regards each primitive compound as a particular type

immense developments; but in its first form it was susceptible of no great extension.

ether

C,H, 0 CH3

Laurent was the first who compared hydrate of potassium with water. He showed that hydrate of potassium results simply from the substitution of one atom of potassium for one atom of hydrogen in a molecule of water. HHO+K=KHO+H

If we take this hydrate, and treat it with potassium, we have KHO+K=KKO+H

KKO or K,O is anhydrous potash: it only differs from water by the substitution of K, for H,.

C2H2O+CH2I=NaI+ C.H CHO