CHEMICAL NEWS, Sept. 1, 1876. Aragonite on the Surface of a Meteoric Iron. The greatest practical difficulty in the Deacon's chlorine process lies in the enormous volume of gas which has to be dealt with, and consequently in the large dimensions required for the chloride of lime chambers. But Deacon has endeavoured to combat these difficulties. He compels the gases to take such a course that they are systematically deprived of chlorine. They meet at first with chloride of lime almost saturated, then, as they lose their chlorine they pass over lime less and less chlorinised till they finally pass out into the atmosphere completely exhausted over fresh hydrate of lime. The arrangements by which this systematic saturation of the lime is produced are of a twofold nature. In the first place chambers are employed in which the lime lies on gratings and which are so connected with each other that the chlorine streams through them successively. As soon as the lime in the chamber nearest the generating apparatus is saturated it is thrown out of connection with the current of chlorine, is charged with fresh lime, and takes its place at the end of the series, whilst a chamber containing lime nearly saturated receives the concentrated portion of the gaseous current. The second kind of methodic saturation is the following, in which is applied the principle of Hasenclever and Helbig's pyrites furnace : In a tower are several stories of sloping plates of slate, forming a smaller angle with the perpendicular than the outer surface of the heaped up chloride of lime is capable of taking. In every story the direction of the plates, which are parallel to each other, cuts the plane of the plates, likewise parallel to each other, in the next higher and next lower story. Thus intervals are produced which extend in zigzag from below upwards. At the lower end of each of these intervals is a shovel-wheel by whose revolution the speed of a powder sliding over the plates can be regulated. Into this tower the lime is thrown by means of a hopper and slips from plate to plate till its further fall is stopped by the rollers. But as the falling lime cannot form so acute an angle with the perpendicular as the plates it does not completely fill the interstices, but leaves in every link of the zigzag a wedge-shaped space, through which the gases are compelled to ascend from stage to stage. Hence, as the lime moves constantly downwards in an opposite direction to the current fresh lime enters above, and saturated chloride is taken out below. To obviate incidental stoppages in the motion of the lime there are here and there in the tower openings fitted with valves. This apparatus can scarcely be adopted in practice, as chloride of lime, from its tendency to clog together, moves but slowly down an inclined plane, whence frequent stoppages would be inevitable. The last mentioned apparatus, suitably modified, is recommended by Deacon for the preparation of salt-cake from diluted chlorine, sulphurous acid, steam, and salt. Instead of lime he causes salt to glide down a tower strongly heated, whilst a mixture of diluted chlorine, sulphurous acid, and steam ascends. The hydrochloric acid thus formed is condensed and re-converted into chlorine, whilst the sulphuric acid formed by the oxidation of the sulphurous acid converts the salt into sulphate. (To be continued) ARAGONITE ON THE SURFACE OF A METEORIC IRON, AND A NEW MINERAL (DAUBREELITE) IN THE CONCRETIONS OF THE INTERIOR OF THE SAME. By J. LAWRENCE SMITH, Louisville, Ky. I. Incrustation of Aragonite. THE remarks in this communication have reference to some of the masses of iron that have been brought from that region of Mexico called the Bolson de Mapini, or the Mexican Desert, situated in Cohahuila and Chihuahua, 87 two of the northern provinces of Mexico; the Deser being 400 miles from east to west, and 500 miles from north to south, bordering on the Rio Grande. This region, so prolific in masses of meteoric iron, has been described by Prof. Burckhardt, of Bonn, as well as by myself. In 1854 I described three of the masses (Amer. Journ. of Science and Arts, vol. xxviii., p. 409): two of these have been brought to the United States, one weighing 125 kilogrms. and the other 630 kilogrms. In 1868 eight others were brought to this country, the heaviest weighing 325 kilogrms. These I described in 1869 (Amer. Fourn. of Science and Arts, Nov., 1869); and in 1871 I was enabled to give a description and an analysis of a still larger one, weighing about 3500 kilogrms., this last one remaining on the western boundary of the Desert near El Para. We have some account of one even larger than the last, located in the very centre of the Desert. So far as known there have been found in this locality not less than 15,000 kilogrms. of meteoric matter, an amount exceeding that which has been brought together in cabinets from all other sources. When I examined the eight masses in 1868, I noticed a white crust on a small part of the surfaces of two of them, but at that time I could not make any critical examination of it. Within the past few months these irons have come under my control, and therefore I have been enabled to examine the points that had been omitted, the most interesting of which forms the subject of this communication. On one of these masses of iron, weighing 210 kilogrms., there is a small amount of a white incrustation covering about 15 square centimetres of the surface; and on another. weighing 275 kilogrms., there is an incrustation, which covered originally over 200 square centimetres of the surface, attached firmly to the iron, and when broken off (as most of it has been by careless handling of the mass) it brings away with it on the under surface a portion of the iron that has become oxidised: its thickness is from 1 to 5 m.m. It is quite hard, scratching calc spar very readily; the surface of it is irregular and granular. If broken perpendicularly to the surface of the iron, and ground down, it will receive a very good polish, showing an irregular and wavy structure on many of the pieces, and parallel to the surface of the iron, with yellow and dark brown streaks like the Gibraltar limerock; it effervesces with acids, and is an incrustation of aragonite. The following is the composition of the mineral: As regards its formation, I am satisfied that the crust has been made on the iron since the fall of the latter. Conceiving this to be the case, desired to know the nature of the rock and soil where these meteorites were found, and I have been able to gather the following particolars from Dr. Butcher, who collected the specimens under examination :-This spot is in an alluvial valley or plain between two ranges of high mountains running parallel with each other, varying in distance from 1 to 3 miles. The mountains at the base are calcareous in formation, and in the hills and plains there are large calcareous deposits. The plain in many places is cut up with deep ravines, and several of the specimens of iron were found among the stones and sand at the bottom of the ravines, and during heavy rains were washed or covered with water. It is, however, only in wet seasons that the water is found remaining in the ravines and depressions of the valley, and this water is always brackish to the taste, containing a large amount of mineral matter. Without giving any further details of the nature of this region of Mexieo where these meteorites were collected, 88 Dinitro-Para-Dibrombenzols and their Derivatives. sufficient has been stated to show the probable source of the calcareous incrustation which I discovered upon two of them. This incrustation on meteorites has been discovered but twice before, and in both instances by myself. One of them, however, is of so obscure and unsatisfactory a character that I have not given any public notice of it. The other is the case of the Newton County meteorite described by me (Amer. Journ. of Science and Arts, vol. xl., 1865). It is a meteoric stone belonging to the variety classified by M. Daubrée as Syssidères; specimens of it have been furnished by me to the museums of the Garden of Plants, Great Britain and Vienna, with this incrustation in well-defined particles of a translucent character adhering firmly to the surface. The entire amount of this meteorite yet known does not exceed 700 grms., although the primitive mass must still exist in a sparsely settled region of Arkansas, and when obtained will no doubt furnish specimens with a larger amount of the calcareous incrustation upon it. II. New Meteoric Mineral, Daubréelite. Two of the masses of iron above referred to have been cut across, the section made on one of them being over 15 square decimetres; also several transverse cuts have been made. In all of these sections a number of nodular concretions have been exposed, most of them quite small, and hardly any exceeding a centimetre in diameter. At the first glance all these nodules have the appearance of very finely crystallised troilite; but a little closer inspection reveals the fact that most of these nodules have more or less of a black mineral associated with it. I had never seen anything of the kind before, it being very evident that it was not graphite. As further examination has proved it to be a new and interesting mineral, I have thought proper to designate it after M. Daubrée, who has done so much in the study and elucidation of meteoric minerals. Daubréelite is a black lustrous mineral, highly crystalline in structure, occurring on the borders of the troilite nodules, and sometimes running across the centre of them, as may be seen in one of the specimens, where, in a nodule of troilite, a vein of the mineral traverses the very centre of the nodule, which is 2 m.m. in width and 12 m.m. long. It has a distinct cleavage, but I cannot make out its crystalline form. It is very fragile, and in the attempt to detach it from the iron it breaks up into small fragments resembling small particles of molybdenite. It is feebly attracted in very fine part:cles when a strong magnet is brought in contact with it. This may arise from the presence of a minute quantity of troilite, which it is very difficult to get rid of. Pulverised, it furnishes a perfectly black powder, the smallest particle of which gives before the blowpipe a very strong reaction of chromium. Heated very intensely, it loses its brilliant colour and becomes a dull black. The powdered mineral is dissolved completely in nitric acid. The solution is intensely green, and furnishes a strong reaction of sulphuric acid and oxide of chrome. The other strong acids attack it but slightly. This solubility in nitric acid readily distinguishes it from chrome iron. The quantity of mineral I was enabled to obtain pure, or nearly so, was very small. the reaction of the acids on the mineral being nearly the same as on troilite. I am enabled to separate them only by varying the strength of the acids, and the length of the time they are in contact with the minerals. Less than 100 m.grms. were obtained of sufficient purity to make out its composition, and this amount furnished me 36-48 per cent of sulphur; the remainder was chrome, with nearly 10 per cent of iron and a little carbonaceous matter. This mineral, when obtained pure and in sufficient quantity for a thorough analysis (which I hope to make before long, will, I am satisfied, prove to be a protosulphide of chrome; the iron present being mixed with the Daubréelite. The following, therefore, would {CHEMICAL NEWS, Sept. 1876. Two kilogrms. of pure crystallised solid (para) dibrombenzol were divided into portions of 250 grms., and each portion added to a mixture of 800 grms. of fuming nitric acid and an equal volume of concentrated sulphuric acid, and then heated on a sand-bath, when a violent action set in, during which it was found advisable to remove the burners. A reddish yellow oil settled in the bottom of the flask. After boiling three hours the mixture was allowed to cool, and then poured in a thin stream into a large excess of cold water. The oil sank to the bottom and gradually solidified, an operation which may be greatly accelerated by vigorous stirring with a glass rod. The nitrited product from 500 grms. of the dibrombenzol, after the washing out the acid with water, was dissolved in about a kilogramme of glacial acetic acid, filtered, and allowed to stand about seventy hours. A copious separation of the first (a) dinitro-para-dibrombenzol, containing a considerable amount of the second (3) isomer, and but a small amount of the third (7), took place. By repeated crystallisation, first from carbon disulphide and then from glacial acetic acid, it was obtained perfectly pure. The acetic acid filtrate from the first separation contained the B- and y-isomers and some of the a. The solution was treated with a large excess of water, and the substances in solution were thus precipitated in the form of a yellow oil, which was then separated from the water by means of a stop-cock funnel, heated on a water-bath until it was entirely dry, dissolved in about 1 kilos. of carbon disulphide, and allowed to stand. By standing, a small separation of impure a-isomer generally occurs. The carbon disulphide was then distilled off in portions of 200 c.c., and the respective crystallisations, which consisted of the B-isomer containing a good deal of the a-isomer and traces of the y, collected. When no more separated the thick oil was heated on a water-bath until the carbon diiulphide was entirely volatilised, after which it was exposed to a temperature of 5° for three days, when it became solid. The mass was carefully rubbed in a mortar with ether, at the same temperature, and this ethereal extract (consisting of much y and little ẞ) separated by a filter-pump. The ether was then evaporated, the oil again exposed to the same temperature, and the operation repeated until the substance dissolved in the ether without leaving a residue. The oil was then exposed to a temperature of about -8° to -10° for nearly two weeks, during which small amounts of the B-isomers crystallised out, and were separated by filtering the oil directly with the filter-pump. Finally no more separated from the oil, which then appeared to contain only an exceedingly small amount of the ẞ-isomer. Alpha-dinitro-para-dibrombenzol. The alpha-dinitro-para-dibrombenzol, containing traces of the B-isomer, crystallises from glacial acetic acid in beautiful siriated transparent needles, often attaining a length of 25 c.m. and a diameter of 3 m.m. When perfectly pure, however, it crystallises from the same solvent in short, compact, white, glittering needles, or small prisms. From carbon disulphide it separates in the form of small, hard, white crystals. The compound is inso CHEMICAL NEWS,} Sept. 1, 1876. Dinitro-Para-Dibrombenzols and their Derivatives. luble in water, easily soluble in boiling absolute alcohol and glacial acetic acid, as well as in benzol and acetic ether. It is slightly volatile in steam. Fuses at 159° to a transparent slightly yellow liquid. 0*3034 grm. substance gave o‘0190 H2O and o°2452 CO2. o'1749 grm. substance, after the method of Carius, gave o'1998 AgBr and 0'0027 Ag. In a preliminary notice I mentioned that a-dinitropara-dibrombenzol, by treatment with ammonia, formed a dinitro-bromaniline, which under the influence of amylnitrite gave a dinitro-monobrombenzol. By repetition of the experiments, however, with much larger amounts and perfectly pure substances, I find that the reaction is different. By treating the a-dinitro-para-dibrombenzol with strong alcoholic ammonia the crystals take on a light strawyellow colour. By heating in a closed tube at 100° for three hours the reaction is completed. The red solution obtained was precipitated with water, and the resulting yellow precipitate crystallised from dilute alcohol. The filtrate from the precipitate produced by water gave no trace of bromine with silver nitrate, but starch and potassium iodide proved the presence of a considerable amount of nitrous acid. By repeated crystallisations from alcohol the substance was obtained pure. It forms orange, yellow, and red needles, which fuse at 75°, and are quite volatile with steam. It is very soluble in most solvents, with the exception of water, in which it dissolves with difficulty. o'28 grm. substance, third crystallisation, gave o'0426 H2O and 0.2536 CO2. 0'2092 grm. substance, fifth crystallisation, gave, after the method of Carius, o'2644 grm. AgbBr and 0'0008 Ag. Calculated for CH,Br2(NO).NH2. C =24°32 H ΙΟΙ Found. II. I. 24.69 54'06 | 89 alcohol with a deep red colour, but separated from the solution as a slimy mass from which no product suscep tible of analysis could be obtained. By the action of natrium-hydrate solution on the alphadinitro-para-dibrombenzol I have obtained a substance forming red salts, which I take to be a nitro-bromphenol, give full particulars.-Amer. Journ. of Science and Arts. and concerning which I shall, at the earliest opportunity, Royal Laboratory of Berlin. NOTICES OF BOOKS. The Textile Colourist. Edited by C. O'NEILL, F.C.S. Vol. I. Manchester: Palmer and Howe. THIS is the first half-yearly volume of a monthly paper whose object, as declared in the introductory notice, is "to give an account of what is doing or has been done by practical or scientific men in connection with the dyeing, printing, bleaching, and finishing of textile fabrics and materials." Its editor remarks that "some of the existing journals do give a little space to articles connected with textile colouring," which is certainly not overstating the truth. Among the most prominent articles we may notice "Critical and Historical Notes upon Turkey Red" taken from the Moniteur Scientific Quesneville, manuscripts of Jehan le Begne, a work on dyeing compiled as early as 1431, and giving an interesting account of the tinctorial arts as practised at that time. It proves that a species of calico-printing was in use in London as early as 1410. The translation, executed by Mrs. Merrifield, must have been a task of no small difficulty as the receipts are given in old French with notes in Latin, doubtless of the mediaval type. In one of the receipts quoted we find mention of "Brazil." The red wood then used cannot, of course, have been obtained from South America, but must have been the product of some Asiatic Casalpinia. There is also a list of British and Irish calico printers in 1840, and a paper on the "Manufacture of Carmine or Extract of Indigo," from Dingler's Journal. We regret to see the continental solecism of applying the term "carmine" to preparations of indigo adopted in an English journal, sometimes even without the qualifying word "indigo." The expression "English sulphuric acid" used on the Continent to express ordinary sulphuric acid in contradistinction to the fuming or Nordhausen kind is unusual in England. The term in general use is "oil of vitriol." We hope that the existence of the "Textile Colourist " may be considered as a proof of a widening and deepening Amyl-nitrite acts at ordinary temperatures on the nitropara-dibromaniline, and forms, not as I formerly supposed, a dinitro-monobrombenzol, but the ordinary mononitro-interest in applied science. para-dibrombenzol. All the properties of the nitrodibrombenzol (fusing-point 84°) obtained in this manner agreed perfectly with those of the well-known mononitropara-dibrombenzol. This, as far as I know, is the first case in which the nitroxyl of a nitro-haloid-benzol is substituted by the , amido-group in preference to the haloid atom. In the first series there is, among others, the well-known formation of guanidine from nitro-chloroform by action of ammonia, effected by Hofmann.† It seemed extremely improbable that aniline could act in a satisfactory manner on the alpha-dinitro-paradibrombenzol, since the disengaged nitro-group would, without doubt, exert a decomposing influence on the aniline itself as well as on the new compound formed. The dinitro-dibrombenzol was treated with an excess of aniline, and the mixture boiled. A strong reaction, attended with a characteristic deep red colour, occurred. Chlorhydric acid precipitated an oil, and, by stirring, brown flocks were obtained. The product was soluble in Ber. d. Chem. Ges., viii., 1183. + Ann. Chem. Pharm., cxxxix., 107. A Course of Practical Chemistry Arranged for the Use of WHEN a scientific text-book has reached its fifth edition 90 Flame of Chloride of Sodium in a Common Fire. We cannot, however, approve of the omission of so many of the elements from the plan of the work. It may be argued that as these substances occur neither in medicines nor in articles of food, and are not likely to be employed whether accidentally or maliciously as poisons, a knowledge of their reactions and their detections is of no direct value to the medical man. This is, however, we submit, a somewhat narrow view of the subject. Furthermore, new substances are continually pressed into the service of manufacturing industry and may become the subjects of toxicological inquiry. To take an instance-Vanadium and its compounds were till lately amongst the rarest of laboratory curiosities. Now they have been introduced into dye and print works and may fall into the hands of those ignorant of their highly poisonous nature. Is not a knowledge of the properties of vanadium and the method of its recognition likely to become of importance to the medical practitioner ? CHEMICAL NEWS, remedy would be found much worse than the disease. The true method of dealing with plastered and fortified wines is to let them severally alone till Andalusian yinegrowers banish gypsum from their premises and give us the pure blood of the grape. Among the genuine, natural wines now coming into use in England, at least, among those who seek in the glass flavour and not intoxicating power, a high rank belongs to those of Greece. Mr. Denman deserves great credit for his persevering attempts to bring them under the notice of the public. No part of the world is better adapted for the cultivation of the grape than the "Isles of Greece," and the wines imported thence are worthy of their old classic fame. CORRESPONDENCE. Part V., 1876. THE FLAME OF CHLORIDE OF SODIUM IN A Bulletin of the Bussey Institution. Hunyadi János; Aperient Natural Mineral Water. By Wine and its Counterfeits. By JAMES L. DENMAN, 20, Piccadilly, London. WE have here a pamphlet which all wine drinkers should read and remember. The author points out clearly and truthfully the real and unpleasant nature of those concoctions known as port and sherry which were forced upon the nation by an unsound system of duties during the latter part of the 18th and the beginning of the 19th century. The "plastering" process, i.e., the addition of sulphate of lime to the grapes-an operation practised for some mysterious reason upon all sherries-he holds up in its true light as utterly destructive of all real vinous flavour. How any man can drink a liquid containing more than an ounce of an alkaline sulphate per gallon, how he can call the mixture wine and profess he likes it, are to us mysteries inscrutable. Would it not be better to send us the wines pure and allow those consumers who admire the flavour of "Epsoms" or "Glaubers" to add these delicious ingredients to their own liking. While Mr. Denman, however, denounces "plaster," he is no friend to the recently patented deplastering process. It is no doubt possible to ascertain by careful analysis the exact quantity of sulphate of potash present in sherry, and to add tartrate of baryta till all the sulphuric acid is precipitated. But suppose that by some inadvertence a slight excess of baryta remained in the solution! The To the Editor of the Chemical News. SIR,-Some time ago a correspondent of Nature (No. 328 Feb. 10, 1876) enquired for an explanation of the fact that while common salt (chloride of sodium) colours the fame of an ordinary spirit-lamp yellow, the same substance thrown upon a common coal fire gives rise to a blue flame. In the next number (329) Dr. Schuster stated that the origin of the blue flame was still involved in mystery, and if my memory is correct, for I have not the number at hand-that he and Dr. Schorlemmer had been engaged on an investigation of the same. Dr. Schuster's letter shows that the point is not an unimportant one, and as I have lately made a few experiments which seem to confirm the assumption on which my explanation was based, I beg to solicit space for it in the CHEMICAL NEWS. The theory I put forward is that the blue flame noticed in the instance of a coal fire (bituminous) on which salt has been thrown is possibly due simply to the presence of carbonic oxide (CO), produced by a series of reactions through which the common salt is converted into sulphide of sodium, as in the manufacture of crude carbonate of soda (black-ash); all the reactions being performed in one furnace instead of two, and almost simultaneously. re Leblanc's process consists in-(1) Converting common salt into sulphate of sodium. (2) The "salt cake sulting is then mixed with coal and limestone, placed in a furnace, and heated strongly, during which part of the process a blue flame of carbonic oxide is observed to play upon the surface. In the case we have under consideration the only difference is that the salt is converted into sulphate of sodium by the oxidation of the iron pyrites, from which no coal is free (and, in fact, it has been proposed to use such a process commercially, viz., by roasting salt with iron pyrites). At this stage, then, the reaction going on in the fire will be expressed by the equation 4NaCl+2FeS+O11=2Na2SO4 + Fe2O3+Cl4. into play, reducing the sulphate to sulphide, with evoluSimultaneously with this the carbon of the coal comes tion of carbonic oxide CHEMICAL NEWS, Sept. 1, 1876. Blowpipe with Spectroscope for Mineralogists. 91 through the necessary changes. Moreover, the slightest trace of salt in such a mixture gave the yellow colour in the naked flame, while the mixtures used in the crucibles contained fully 15 per cent of salt, so that the supposition as to the effect of difference of temperature seems plausible. &c., proved at once by experimenting on a fire of anthracite, With a spirit lamp or a Bunsen burner there is no free carbon, nor is there any iron pyrites to react on the salt, consequently the complicated processes just sketched out cannot go on, and the flame only exhibits the sodium colouration. Dr. Schuster, in the note above mentioned, referred to a letter published by Dr. Gladstone in the Phil. Mag. (vol. xxiv., p. 417), giving a sketch of the similar behaviour of certain chlorides in imparting a blue colour to flames of various kinds. I find that in this paper the violet colour given by the chlorides of sodium, of potassium, and of barium to the flame of red-hot coals is noticed. Dr. Gladstone says, however, that "a doubt must rest on such observations made with a common coal fire, as it is quite conceivable that these chlorides may give up their chlorine to the alkalies or the earths of the ash." It struck me that it would have some bearing on the matter to ascertain whether other salts of sodium exhibited the same property of tinging the flame blue, and I find that in these is no difference. A little pure carbonate or sulphate of sodium thrown upon a common coal fire gives exactly the same blue colour as the chloride does; thrown on an anthracite fire they do not alter its bluish flame. Both give the intense yellow flame in the Bunsen burner. It is clear, therefore, that the blue flame given by common salt cannot be ascribed to a property inherent to chlorides alone, and the solution I have given seems to be the most likely one. Of course the carbonate and the sul phate will give rise to much the same reactions as those stated above. The following laboratory experiments were made with a view to check the above conclusions: (1.) A small porcelain crucible was half filled with com- No difference could be observed in these experiments, whether the air was turned on or off. When these mixtures were exposed in the naked flame on platinum wire they only gave the intense sodium colour. This is doubtless to be ascribed to the stronger heat volatilising same of the salt before it had time to pass * Every cook knows that throwing salt on a fire "clears renders it smokeless. .e. EDWARD T. HARDMAN. Kilkenny, Aug. 25, 1876. BLOWPIPE WITH SPECTROSCOPE FOR MINERALOGISTS. To the Editor of the Chemical News. SIR,-I enclose a sketch of an upright blowpipe with spectroscope adapted to its little lamp, the whole very portable. My object is discrimination in travelling between potass and soda and many other minerals. With hammer, chisel, lens, bottle of acid, magnetic penknife, and a little patience one can be far more independent of a laboratory than might be imagined. It is far more interesting to be able to determine a mineral on the spot, more especially as regards petrology, than to have to collect extensively and defer examination except with the blowpipe, which, as every one has to his aggravation experienced, leaves one sadly in the lurch when one gets amongst impure alkalies MARSHALL HALL. 0 2065 grm. gave o°1297 grm. of BaSO4. o'1377 grm. gave 0.1307 of CO2, and 0'0300 of H2O. I do not see how this data can furnish the amount of O. What is the formula of the salt and corresponding acid?" I venture to add some other questions, which cannot well be solved without some approximative grasp of the generic nature of the reactions involved; hence it is that they have more than a mere numerical interest. II. M. Grimaux has synthesised the following ureides. What are the types and genetic equations (without further data)? |