-I. A solution of potassa; 2. Column of pumice saturated with sulphuric acid; 3. A U drying tube of chloride of calcium; 4. The analysis tube; 5. Will's nitrogen bulbs charged with standard acid. The steel in all the experiments was used either in the form of fine powder (passed through a muslin sieve) filings, grains (the size of ordinary shot); or strips, about 3 to 4 inches long, inch to inch wide, and about th to 8th inch in thickness. The passage of the gas through the potash-bulbs varied from the rate of 50 to 150 bubbles per minute, and was continued after the heat was withdrawn until the assay tube was quite cold. Table I. exhibits the result of the first eleven experiments just mentioned; by a reference to which it will be noticed that in all these instances, excepting No. 2, nitrogen was obtained, though varying in quantity from 007 to 068 per cent. CHEMICAL NEWK, further precaution was taken of passing the gas over the soda-lime for some time before the steel was heated. It will thus be seen that if any nitrogen was present, either in the hydrogen or in the apparatus it would become converted into ammonia by passing over the soda-lime, which passing onwards would be absorbed by the sulphuric acid. There would now remain only the small space above the liquid in the sulphuric acid bottle, and the short and narrow tube between it and the assay-tube in which any air could lodge, to vitiate the results. With this arrangement, experiments 13 to 17 were made. No. 13 and 14 were made upon cast steel in thin strips similar to those previously described, and Nos. 15 and 17 upon spiegeleisen crushed to powder in a steel mortar and passed through a fine muslin sieve. It will be noticed by a reference to table No. 2 that considerable quantities of these substances were used, but in only one case was any nitrogen detected. This was in No. 15, upon spiegeleisen, but there seems to be some doubt respecting the accuracy of this experiment and it appeared likely that the assay-tube was heated before the air was entirely expelled from it, and as in the subsequent experiments upon the same substance none gave any nitrogen whatever, it is probable that this or some other error must have crept in. 25.000 2. 2 33'3345, '020 *027 TABLE II. '018 *007 These experiments were considered as merely preliminary, and, judging from the experience afterwards obtained, the authors reject altogether Nos. 1, 3, 6, and 7, from the nitrogen obtained being, at all events, in part, derived from other sources than the steel; most probably from some air lingering in the apparatus when the experiment was commenced; and when the comparatively large quantities of nitrogen obtained are taken into account, there can be but little doubt that this source of error vitiated the results in all these instances. Experiment No. 2 demands a special notice. It seems to have given what must now be looked upon as an accurate result; however, as it was only the second experiment of the kind that the authors had made, they did not feel justified in laying any very great stress upon it, although, on referring to their note-book, they could not find any further reason to doubt its accuracy. In experiments Nos. 8, 9, and 11 the amount of nitrogen found had materially decreased. This may probably have arisen from the precautions requisite to insure an accurate result becoming better understood, and especially to extra care being taken in preparing the hydrogen, and in driving out the air from the apparatus more completely before commencing the experiments. On comparing all these experiments generally together, a gradual but unmistakeable decrease in the amount of nitrogen was at once apparent. This appeared strange, and aroused a suspicion that possibly much, if not all of it, might be due to other sources than the metal under examination, and it was evident that more careful experiments were necessary to arrive at a perfectly correct result. It was then determined to try if the nitrogen present in the apparatus could not be entirely removed, so as to insure the hydrogen arriving at the assay tube in a state of absolute freedom from this impurity. The best method of doing this seemed to be to convert it into ammonia, and to absorb it in this state by dilute acid, and the apparatus was accordingly modified thus : 1. Flask containing potash as before. 14. 15 17. Spiegeleisen in fine powder do. In all these experiments the gas issuing from the sodalime tube was tested for ammonia by placing small pieces of reddened litmus paper in the narrow tube leading from it into the sulphuric acid bottle. They invariably gave indications of its presence, and traces of it could be found even after the hydrogen had been passing through for more than an hour. The assay-tube was never heated until these traces had entirely disappeared. In the next series of experiments that were made, the soda-lime tube was dispensed with, and no means were taken to absorb the nitrogen in the apparatus. The hydrogen was prepared with every possible precaution, however, and was passed direct from the gas-holder into the assay-tube without any intervening apparatus except a wash-bottle filled as full as practicable with a solution of protosulphate of iron, made slightly alkaline with potash. As short an apparatus as possible was used, and the hydrogen passed through it for a long time before heat was applied to the assay-tube, the object being to reduce the amount of air contained in the apparatus to the least possible quantity, and to completely sweep it out, so as to prevent the nitrogen it contained interfering with the result. The protosulphate of iron was intended to absorb any oxygen that might be present, it being frequently found that the steel was slightly oxidised when the experiment was ended. It was replaced for experiments Nos. 51 and 52 by a solution of oxide of lead in potash. This was used to absorb hydrosulphuric acid, a small quantity of which was given off during some of the experiments. This method was found to answer very well in practice, although, of course, open to the objections which have been stated before; very great care was, however, requisite in making the experiments, but 2. Tube filled with soda lime at a red heat, and about when sufficient attention was given, the results might be six inches in length. 3. Dilute sulphuric acid. 4. Assay tube. 5. Will's nitrogen bulbs filled with standard acid. The distance between the sulphuric acid and the steel was made as short as possible, with the view of reducing to a minimum the quantity of air it would contain, and the relied upon. In table No. 3 a detailed account of the experiments made with this arrangement is given; a glance at it will show that in the whole series no amount of nitrogen was obtained that could be considered of any importance, even with the possible chance of the errors previously pointed out. The authors submit that th negative results obtained in these instances are very stron 52. Steel made by heating iron in CO. Spiegeleisen in grains 80'000 *0015 '000 In the succeeding experiments an important alteration was made in the apparatus, which requires to be shortly described. Two tubes, one containing the steel to be operated upon mixed with soda-lime, and the other containing soda lime only, were placed side by side in the same furnace, and heated to the same temperature, whilst the hydrogen was passed from the same gas-holder through both, the current being so regulated that an equal quantity passed through each tube in a given time. Previously to its entering the tubes the hydrogen was washed by passing successively through solution of potassa and dilute sulphuric acid, and in some cases was partially dried by passing through concentrated sulphuric acid immediately before its entrance into the steel and sodalime tubes. The first of these was made upon cast steel filings, 6.355 grm. of which were taken and intimately mixed with 6.3 grm. of soda-lime, the same weight of soda-lime alone being placed in the second tube. Both were heated to full redness for two and a-half hours. No nitrogen was obtained. The whole of the series were made in a precisely similar manner, Nos. 25, 30, and 36 upon cast steel in filings, and Nos. 32, 33, 34, and 37 upon JB. blister steel, and iron of the same brand. A reference to the following table will show the results obtained : 36. 9'980 21'040 37. 5'091 10'117 Blister steel. Cast steel in filings. do. 5'3 15.0 2 " 19:456 JB. Blister steel in filings 6'7 I "" It was invariably found that the greater part of the nitrogen, in those cases where any was obtained, was given off in the early part of the operation, and that towards the end no indication could be found. It appeared very probable from this circumstance that in those instances the nitrogen was supplied by the air in the apparatus. Having given a full description of the methods of experimenting, the authors next direct attention to the different kinds of steel and iron employed, and the quantity of nitrogen obtained from each. Excluding, for the reasons previously given, the first five experiments, there are four made upon JB. blister steel, and iron. Of these, two, Nos. 32 and 33, gave absolutely no nitrogen; whilst the others, Nos. 34 and 37, gave only 004 and 010 per cent., quantities which, in their opinion, were due to the sources of error before mentioned. Taking the average, 0036 per cent. is obtained, an amount which is too small to be considered of any moment. These experiments were all made upon the same sample in the state of filings. Next follow ten experiments upon cast steel. These were made partly on cast steel in the form of strips and partly as filings. In these a remarkable unanimity is observable in the results, for out of the ten eight gave no indications of nitrogen whatever, and the other two only ·018 and ·0023 per cent., the average of the whole being 002 per cent., an amount which may be considered as quite inappreciable in influencing the quality of steel. Then come two experiments on Bessemer steel; both these show nitrogen--one to the amount of 007 per cent., and the other o11 per cent. In both these cases large quantities (50 to 55 grms.) were used, and it may be possible that this peculiar kind of steel contains some small quantity of nitrogen; though, even in this case, it would not affect its quality, being most likely an accidental constituent, formed during the process of manufacture, from the stream of air driven in it analogous to that which nitrogen forms with through the molten iron forming some compound titanium, and which is so often found in crude pigirons. Then follow four experiments upon spiegeleisen, which show, with one exception, a total absence of nitrogen. One of these must be particularly alluded to, viz., No. 52, in which 80 grm. were submitted to experiment for four hours. At the end of this time it was found that no nitrogen whatever had been eliminated. The authors look upon this as being one of the best and most conclusive experiments they have made, and its evidence is very strong in favour of the conclusion that nitrogen is not remain to be mentioned were made upon iron of English present essentially in steel. The two experiments which manufacture, of very soft quality, and the same converted into steel by heating to full redness in a current of carbonic oxide. In both cases the results were so small as to indiwhole of the experimental results which have been decate mere traces of no importance. After reviewing the scribed, the authors adopt the conclusion that nitrogen does not exist either in steel or in iron as an essential constituent, and cannot, therefore, be made use of to explain Taking the average of the whole series of experiments, the the different commercial qualities of those substances. proportion of nitrogen amounts only to '0033 per cent., a result which the authors consider to be of no practical value. The adhesion of air to the surface of the steel would be sufficient to explain the amounts which in some instances were obtained, and in experiments carried to such a nicety, this source of error must not be overlooked, and, taken in addition to that arising from the air remaining in the apparatus, small as its amount may have been, would be, nevertheless, quite sufficient to account fully for all the nitrogen obtained. It was not to be expected that in a long series of experiments every one should be equally successful, but they have published the results, good and bad, as they occurred, rejecting only such as contained a manifest and palpable error; and, in summing up the whole of the evidence, the authors give it as their opinion that nitrogen is not an essential constituent of steel or iron, that it very rarely exists in them even as an accidental constituent, and that it has nothing whatever to do with the respective qualities of different samples of those substances. The PRESIDENT, in inviting discussion upon the subject of Mr. Baker's communication, referred briefly to the difficult nature of the investigation, and the necessity for using every precaution in the conduct of such experiments. Mr. PERKIN asked the lecturer whether he had assured himself that hydrogen was really capable of abstracting nitrogen from iron or steel; for even supposing the metals contained this element as an essential ingredient, he doubted whether the affinities of hydrogen and nitrogen were such as to permit of the formation of ammonia at a high temperature. Professor WANKLYN mentioned the result of some experiments performed by Mr. Dittmar, of Edinburgh, upon MM. Will and Varrentrap's method of estimating nitrogen. According to his experience, it was shown that ammonia 248 Chemical Society-Lectures on Chemical Philosophy. was resolved into its constituent gases by the action of a degree of temperature not much higher than that usually employed in the soda-lime process. Dr. MILLER said there was no doubt regarding the possibility of decomposing ammonia by heat; this happened especially when a current of the gas was passed over iedhot iron filings. Professor CHURCH alluded to an observation of M. Wöhler, who found that the nitride of boron might be heated for any length of time in a current of pure dry hydrogen without suffering decomposition; but if the gas be passed conjointly with the vapour of water ammonia was at once formed. Mr. BAKER replied by asserting his belief that steel was permeable by gases at a high temperature, and that if the specimens of metal, whether in filings or rolled strips, had contained nitrogen, such constituent would have been expelled in the form of ammonia. His views partly received support from the well-known fact that it was possible to convert iron into true steel by heating in a current of carbonic oxide, carburetted hydrogen, or cyanogen gas. He would remind the Society of the circumstance that his experiments were merely in repetition of those of M. Fremy, and that they were negative in their character. He had himself endeavoured to produce a nitride of iron for the purpose of investigating its properties, but hitherto without result. The onus lay with those who stated that nitrogen was contained in steel to prove that such a combination was really decomposed by hydrogen. For himself, he believed that the nitrogen had been derived from other sources extraneous to the metal operated upon. The PRESIDENT said there could be no doubt that a kind of cementation went on at a high temperature, and that the steel was really permeable to gases. But, supposing even the nitrogen to be removed, he doubted whether it would take the form of ammonia. He had himself remarked the facility with which ammonia was decomposed by heat when attempting to employ iron tubes in organic analysis; but owing to a loss of nitrogen, he had been compelled to resort again to the use of the ordinary glass tubes. Hydrates. Hydrate of potassium. Hydrate of sodium. H Hydrate of methyl. H CHEMICAL NEWS, Salts. NO2 Oxides. K K Oxide of potassium. Nitrate of potassium. со Ag Ag Hydrate of ethyl. NO, H Gerhardt generalised this opinion, and brought new proofs in support of it. He had before asserted that anhydrous monobasic acids could not exist, seeing that the molecule of normal acids did not contain the elements necessary to form a molecule of water, which would have to be separated. He had not foreseen that these acids might be formed by the union of two molecules of the brilliant experiment, however, taught him that it must be hydrated acid, a molecule of water being eliminated. A so. By treating chloride of acetyle with acetate of sodium, he obtained acetic anhydride ACADEMY OF SCIENCES. November 7. which chemists to-day confound with the hydrogen type, not come quite within our province, were read at this The first of these bodies is a powerful base, the second is a neutral body, which proves that the properties of a body do not depend upon molecular arrangement only, but, beyond this, are a natural function of the elementary atoms. The influence of oxygen upon the properties of bodies which contain it are in this case clearly shown. Ethylated ammonia, which does not contain oxygen, is strongly basic; acetylated ammonia, in which the negative oxygen takes the place of H2, is neutral. Gerhardt has since described acid ammonias. According as discoveries followed one another, and the facts were elucidated, this theory has been developed and extended. Before we end this historical exposé, we have yet to mention one important point. Conceiving that it is impossible to bring under the simple type, are necessary to decompose it. We shall then have (SO2)" (SO2)", Cl2 + H2 } 02 = H2Cl2+ Chloride of Sulphuryle. H2 H2J Sulphuric Acid. We see by this that sulphuric acid is derived from two molecules of water-that is to say, it belongs to the type of doubly condensed water. This acid is diatomic, because its radical, SO, is substituted for H, or, in other words, possesses a substitution value equal to II. This idea is the origin of the theory of condensed types, of which we shall speak in a subsequent lecture. By the signs ",", "", "", "", the author as usual indicates monatomicity, diatomicity, triatomicity, &c. SOME very interesting and important memoirs, which do meeting of the Academy, and of which we need only mention the titles. One of these was by M. Tresca " On the flow of Solid Bodies Submitted to Strong Pressure." The results of numerous experiments showed the author that, without undergoing any change of state, solid bodies flowed from an orifice in exactly the same way as liquids when sufficient pressure was applied to them. He described the apparatus employed, and the materials experimented with, which were the soft metals and ceramic pastes. The results it was said went to prove the unity of the constitution of all matter, showing that masses of the most solid metals are formed of separate and mobile molecules. Another important communication was a description by M. Maissoneuve of a " New Instrument for Crushing Stones in the Bladder and Extracting the Fragments." The author calls his instrument the lithexère, or stone extractor; it will no doubt attract the attention of English surgeons. Among the papers specially within our province we may notice one by M. Weil, "On New Processes for Covering Metals with Firmly Adherent and Bright Layers of Other Metals." The method consists in dipping the metal to be coated in a saline solution of the metal to be deposited rendered distinctly alkaline with potash or soda, and mixed with some organic matter, such as tartaric acid or glycerine. At the same time, it is necessary in some cases to set up a weak voltaic current by keeping a piece of zinc or lead in contact with the metal. In this way the author obtains a firm layer of copper on iron and steel, and procures various and beautiful effects according to the thickness of the copper deposited. Silver, nickel, and other metals can be applied in the same way. The process, it will be seen, is susceptible of numerous applications. A curious fact mentioned is that a clean surface of copper may be coated with zinc by placing the two metals in contact in a solution of caustic soda or potash. In the cold the deposit of zinc takes place slowly, but at 100° it is effected rapidly. M. Lamy contributed a paper "On Thallic Alcohols," which we shall translate at length. At present we may remind our readers that M. Lamy has already described a compound of thallium and ethylic alcohol, a very dense liquid of great refractive power. In the hope of obtain ing a still denser and more refractive body, he sought for a compound of thallium and amylic alcohol; this liquid, however turned out to be lighter than the ethylic compound. He then formed methyl-thallic alcohol; this is a solid body at ordinary temperatures. The general properties of these componds, and the methods by which they were prepared, will be described at length in an early number. M. Le Guen presented a note “ On Tungsten Steel." The author's experiments go to show that the addition of tungsten up to 2 per cent. greatly increases the tenacity of the steel. The effect, however, is rather less when the iron is cemented with wood charcoal than when coke is used. In a note "On the Production of Formamide by means of Formiates and Oxalates," M. Lorin shows that formamide may be obtained by the distillation of chloride of ammonium and a formiate, the sodic formiate more particularly; and further, that the same body is produced in the The formamide will be found among the liquids which pass above 130° C. careful distillation of acid or neutral oxalate of ammonia. Among the papers which may be of interest to our sitic worm, which makes itself a home for a tine under the medical readers are a description, by M. Guyon, of a paraconjunctiva of negroes, but which, according to the author, is a sort of bird of passage, moving about according to its necessities. The paper will be of interest to surgeons and 250 Notices of Books-Notices of Patents. naturalists. M. Pouchet announced his "Discovery of Bacteries and Vibros in Bronchial Mucus, and Discharges from the Nose and Ear." Lastly, M. Decaisne presented a note "On the Effects of Tobacco-smoking on Children,' ascribing to that indulgence the chloro-anæmic condition he constantly remarks in French boys. NOTICES OF BOOKS. Annalen der Chemie und Pharmacie. October, 1864. We have in this journal several papers which have already appeared in the CHEMICAL NEWS, including Marignac's "Researches on the Silico-tungstic Acids," Pisani's "Analysis of Pollux," and Mr. Bassett's paper "On Quadribasic Carbonate of Ethyl," as well as papers by Wurtz, Berthelot, and others from the Comptes Rendus. Of the original papers, the most important is by Heintz " On Ethyl-diglycolamidic Acid, and some Compounds of Ethylglycocol.' We must refer readers interested in these bodies to the original paper. Another original contribution is by Braun, "On the so-called Xanthocobalt Compounds." The author differs from Gibbs and Genth as to the constitution of the ammoniacal compounds of cobalt to which they gave the above name, and gives analyses and reasons in support of his own views. Dr. Wickelhaus has a communication in which he shows that the acid obtained by the action of sodium amalgam on aconitic acid is identical with the acid obtained by Mr. Simpson from the cyanide of allyl, and which Kekulé has named carballylic acid. The formula of this acid is H,. It is soluble in water, alcohol, and ether: the salts could not be obtained crystallised. The reaction with salts of peroxide of iron is peculiar. At first only a cloudiness appears, but on long standing, or on boiling, a bulky precipitate forms, which analysis seemed to prove a mixture of a bibasic and tribasic salt. Submitted to a high temperature, the acid at first sublimed, but about 200° it lost water, and left in the retort a crystalline residue, which again attracted water. We have also in this number the continuation of a series of papers giving an account of original researches made in the laboratory at Marburg. The first is "On the Action of Nascent Hydrogen on Benzoic Acid," by Dr. Herrmann. On distilling an excess of benzoic acid in water with sodium amalgam, a distillate is obtained, which smells of bitter almond oil, and contains an oil which partly settles at the bottom and partly remains suspended in small drops. By extracting the alkaline residue with ether, a dense aromatic oil is separated, which in a short time becomes a crystalline mass. By treating the residue exhausted by ether with hydrochloric acid a yellowish offensive oily acid is separated, which can be isolated with ether. The smell of the distillate was, of course, due to the presence of bitter almond oil; the oily drops separated from it on analysis gave results which corresponded with the formula of hydrated oxide of tolyl, CHO. The crystalline mass extracted from the alkaline residue by ether gave results which accord with the formula C1H,O,, or C2H4O4. On heating this body with concentrated sulphuric acid it changed into a crystalline mass, which, on dry distillation, was completely converted into bitter almond oil. On distillation in a stream of carbonic acid it gave a crystalline sublimate, which may be benzoic acid. The body appears to be isomeric with hydrobenzoin, which Zinin obtained by the action of hydrogen on benzoic aldehyd. As it changes to bitter almond oil on dry distillation, we may suppose it a compound of benzoic aldehyd and an aldehyd two atoms richer in hydrogen, since these two atoms of hydrogen are easily removed by the oxygen of the air. The oil obtained on decomposing the exhausted alkaline solution with hydrochloric acid is an acid having the formula CH,O,,HO, the characters of which are not yet Nov. 19, 1864. atoms clearly made out. Reviewing the whole of the phenomena, the author says that by the action of hydrogen on benzoic acid we must believe that the greater part of the acid is at first, by the loss of 2 atoms of oxygen, changed into aldehyd, and then, by taking up 2 atoms of hydrogen, becomes the alcohol, while a small portion of the acid takes up of hydrogen directly without any change in the oxygen contained. The next papers are by Oefele, "On a New Class of Organic Sulphur Compounds," which has already been communicated to English chemists, and on CH "Diethylsulphan," CH[8,9], or sulphuric acid, in which the two extra-radical oxygen atoms are replaced by two atoms of ethyl. It is a crystalline body soluble in alcohol and water. We must postpone a notice of other papers in the Annalen until next week. NOTICES OF PATENTS. Communicated by Mr. VAUGHAN, PATENT AGENT, 54, Chancery Lane, W.C. Grants of Provisional Protection for Six Months. 2156. Jacques Fuliraud Pascal Hugouneuq, town of Lodève, Département de l'Herault, France, "An improved method of obtaining indigo from textile materials, either yarns or fabrics, previously dyed by the blue soaking process.”—Petition recorded September 2, 1864. 2354. George Printy Wheeler, Abinghall, Gloucestershire and John Fox Gloyn, Manchester, Lancashire, "Improvements in the preparation and application of certain materials for the purpose of cleaning or polishing the surfaces of metals, and also applicable to other purposes."Petition recorded September 26, 1864. 2522. Edouard Moride, Nantes (Loire Inférieuse), and Boulevart St. Martin, Paris, France, "Improvements in the treatment of sea-wrack grass, for the extraction of the carbon and the salts contained therein." 2526. Richard Archibald Brooman, Fleet Street, London, "Improvements in the manufacture of prussiates of ammonia, and in the application of prussiates of ammonia to dyeing, printing, and photography."-A communication from Arthur Baudesson and Paul Houzeau, Rheims, France. -Petitions recorded October 13, 1864. 2552. William Clark, Chancery Lane, Middlesex, "Improvements in the preparation of artificial wax.” A communication from Jules Montier, Lambert Dietzenbacher, and Abraham Worms, Boulevart Saint Martin, Paris.Petition recorded October 15, 1864. 2560. John Cassell, La Belle Sauvage Yard, London, "Improvements in apparatus for the carburation of gas and atmospheric air." A communication from Jean Best, Paris, France.-Petition recorded October 17, 1864. 2581. William Taylor, Shiffnall, Henry Harrison Hollinswood, and George Brown, Hollinswood, aforesaid, all in the county of Salop, "Certain improvements in the manufacture of iron."-Petition recorded October, 19, 1864. 2598. William Littell Tizard, Birmingham, Warwickshire, "Improvements in brewing and distilling, and in apparatus employed therein, parts of which are applicable to the separation of liquids from solids."-Petition recorded October 20, 1864. 2628. Richard Hookham, Regent's Park, Middlesex, "Improved powder magazines and receptacles for storing or keeping gunpowder or other explosive materials, and improved vessels and vehicles for transporting explosive materials from place to place." 2634. William Clark, Chancery Lane, Middlesex, "Improvements in apparatus for concentrating and distilling sulphuric and other acids, and all solutions in general." A communication from Eugéne Alphonse Cotelle, Boulevart Saint Martin, Paris.-P etitions recorded October 24, 1864. |
