摘要:

THE QUA4RTERLY JOURNAL OF THE CHEMICAL SOCIETY. VI1.-On Compounds obtained by the Action of Anhydrous SU@~U~C Acid on the Chlorides of Hydrogen and Ethyl. BY ROBERTWILLIAMSON OF UNIVEBSITX COLLEGE LONDON. IThas been stated by Gerhardt* that the reaction which takes place between pentachloride of phosphorus and monobasic acids is not the same as the reaction between the same body and bibasic acids. In the first case two chlorides are formed viz. chloride of hydrogen and chloride of the radical of the acid thus with acetic acid the reaction is '"H3HO)O + PC15 = C2H30C1+ HC1 + YOCl3 t But according to Gerhardt the reaction between pentachloride of phosphorus and a bibasic acid consists of two stages. "When for example one atom of hydrated succinic acid is treated with one atom of the perchloride the products are anhydrous succinic acid hydrochloric acid and oxychloride of phosphorus ; but when anhydrous succinic acid is treated with an additional atom of perchloride chloride of succiny 1 and oxychloride of phosphorus are obtained.lo. C4H402.0,H20+ PClZ,Cl3= C4H402.0 + 2HC1+ POCP 20.~4~402.0 + PC1",C13 = C4H4O2.ClZ+ ~0~13 J * Compt. Rend. XXXVI 1052. I-The atomic weights used in this paper are those proposed by Berhardt vh-C = 12 S = 32; 0 = 16; H ROBERT WILLTAMSON Similarly G er h a r dt describes the action of pentachloride of phosphorus on hydrated sulphuric acid or on a sulphate as consist- ing first in the formation of anhydrous sulphuric acid (together with hydrochloric acid and oxychloride of phosphorus.) Secondly in the transformation of this anhydrous sulphuric acid by anot tier atom of pentachloride into chlorosulpliuric acid.This supposed difference in the behaviour of monobasic and bibasic acids with perchloride of phosphorus is connected by Gerhardt with the fact that the atom of a monobasic acid does not contain the quantity of hydrogen requisite for the formation of water while the atom of a bibasic acid contains the elements of its anhydride with the elements of one atom of water; and he supposes that it is on this atom of water only that the chloride of phosphorus first acts. This aacount of the action of pentachloride of phosphorus on the bibasic acids has been shown by Dr. Williamson* to be inac- curate in the case of siilphuric acid.With this acid the reaction does indeed take place by two stages but the second is an exact repetitionof the first and each is exactly the same as the one stage of the reaction between chloride of phosphorus and a monobasic acid. For the sake of comparison the reactions may be written side by side. Sulphuric acid and chlor. phosphorus. Acetic acid and chlor. phosphorus. 1") so2Ho + PC15 = C2H30C1. HO + PC15 = SOZc,1 C2H300 +poc13 + HCl + POCP 1 + HC~ + HC1 + POClJ In each case the change which the hydrated acid undergoes may be stated empirically to be the replacement of an atom of binoxide of hydrogen by an atom of chlorine. And it is evident from the above equations that this replacement can take place twice in a bibasic acid but only once in a monobasic acid.The result of the replacement of one atom of binoxide of hydrogen in *'Proc.Roy. SOC.vii. 11. ON CRLOROHYDRATED SULPHUBIC ACID &C. hydrated sulphuric acid by chlorine is the compound S03C1H which is strictly intermediate between the hydrated acid and Regnault’s chlorosulphuric acid (S02C12). The capability of forming such a compound intermediate between the hydrated acid and the chloride of the acid radical seems to be a general character distinguishing hibasic from monobasic acids. It is evident that between a hydrated tribasic acid (P04H3)and its chloride (POC13) two intermediate compounds may exist (P03H2Cl and P02HC12). As examples of bodies similarly con-stituted to Dr.Williamson.’s chlorohydrated sulphuric acid (S03HCI),there may be mentioned Chiozza’s chlorobenzoic acid (C7H5C102)*and the substance which Dumas obtained by the reac- tion of chlorocarbonic acid on alcohol. This body is to chlorocar- bonic acid and hydrated carbonic acid what chlorohydrated sulphuric acid is to chiorosulphuric acid and hydrated sulphuric acid but contains an atom of ethyl in place of an atom of hydrogen. Its formation is represented by C2H5 o + cocis = HC~+ co2 ~2~5~1. 4 Chlorohydrated sulphuric acid is formed not only by the action of perchloride of phosphorus on hydrated sulphuric acid but by the action of chloride of sulphur and chlorine on sulphuric acid by the action of chlorine on sulphurous acid in presence of moisture in contact with platinum black at a red heat and by the combination of hydrochloric acid with anhydrous sulphuric acid.The present paper contains an analysis of chlorohydrated sulphuric acid obtained by the last process and also an account of compounds similarly obtained fiom the chlorides of ethyl and methyl and anhydrous sulphuric acid. Chlorohydrated Sukhuric Acid S03C1H. -This substance was prepared by saturating anhydrous sulphuric acid with hydrochloric acid which had been dried by anhydrous phosphoric acid. The compound so formed agreed in all its properties with the chloro- * This substance has been found by Mr. Lockwood of this laboratory to give alicylate of potash and not chlorobenzoate of potash when boiled with alcoholic potash.It is therefore chlorohydrated salicylic acid C7H603 + C1 -HO = CiH’C102 Salicylic ac. Chlorohydrate of Salicylic ac. H2 ROBERT WILLIAMSON hydrated acid described by Dr. Williamson* as obtained from pentachloride of phosphorus and hydrated sulphuric acid. The composition of chlorohydrated sulphuric acid was deter- mined by decomposing a portion of it with water and estimating the. sulphuric aud hydrochloric acids formed. This was done by neutralising the aqueous solution w:th baryta-water and after filtration from the sixlphate of baryta precipitating the hydro-. chloric acid as chloride of silver. Two experiments of this kind gave *7487grm. sulphate of baryta to -43153grm. chloride of silver and *6887grm.Ba2S04 to -4189 Ag C1. These results correspond with the percentages I. 11. Cal. (S03HC1.) so3 . . 69.87 . . 68.93 . . 68.67 HCI . . 30.13 . . 31-08 . . 31.33 The process by which I obtained chlorohydrated sulphuric acid is similar to that by which Roset obtained compounds of anhydrous sulphuric acid with the chlorides of ammonium potassium and sodium. Chlorohydrated sulphuric acid is in fact the acid of which Rose’s compounds are the ammonium potassium and sodium salts; and is probably identical with the compound which Rose obtained1 by the action of anhydrous sulphuric acid (or better of Nordhausen acid) on chloride of sulphur. Chlorost@hute of Ethyl S03C2H5C1.-This substance mas obtained by the direct combination of chloride of ethyl with anhydrous sulphuric acid.Its composition was iletermiried by finding the weight of the product obtained by combining a known weight of SO3 with chloride of ethyl. The experiment was conducted in the following manner. A * In the notice of chlorohydrated sulphuric acid published by Professor William- son that substance is described as distilling witholit alteration at 145°C. ;but I am informed by him that he afterwards found that by long boiling it is partially decom- posed ;so that if a portion of chlorohydrated acid which has been distilled upwards for some time is distilled with a thermometer chlorosnlphuric acid distils first then unaltered chlorohydrated and lastly hydrated sulphuric acid. If the middle part of the distillate is again submitted to the same treatment a fresh portion of chloro-sulphuric and hydrated sulphuric acids may be obtained.Ry repeating this process a given quantity of chlorohydrated sulphuric acid may be resolved almost completely into chloro-sulphuric and hydrated sulphuric acids. The decomposition which takes place is 2 S03HC1 = SO4H2 + 802CP. ‘IPogg. Ann. XXXVIII. 117. 2 Pogg. Ann. XLIV. 291 and XLVI. 177. ON CHLOROHYDRATED YULPHURTC ACID &C. 101 bottle containing anhydrous sulphuric acid was provided with a perforated stopper to which was fused a horizontal glass tube about 2 feet in length and Q in. in diameter. This tube was drawn out before the blow-pipe at intervals along its whole length so as to form a series of narrow bulbs from 2 to 3 inches long connected by pieces of almost capillary tubing.This series of bulbs being connected with the bottle of anhydrous acid by the perforated stopper the bottle was warmed and the acid condensed in the further bulb by cooling it in a mixture of ice and salt. The freezing mixture was moved from one bulb to the next going towards the acid bottle as each one became full of the acid. When all were filled the two ends of the tube were fused and the bulbs separated from one another. One of these bulbs of acid was weighed and sealed up in a glass tube with chloride of ethyl. The bulb was broken by shak- ing the tube and when the acid was dissolved the excess of chloride of ethyl was distilled off at about 15°C. When the product ceased to lose weight the weight of the tube in which it was contained was ascertained and also that of the bulb which had held the sulphuric acid.In this way the following results were obtained I. weight of compound 7.5866 11. . * 7.4757 111. . . 7.3776 Anhydrous acid used 4-1424 grammes. Found Calc. \ 1. 11. 111.' SO 54.601 55*41 56.14 55-36 C,H,Cl 45.399 44.59 43.86 44-63 From these weighings it would appear that at the first a little chloride of ethyl remained with the sulphuric acid compound and in the last some of the chloro-ethylated sulphuric acid had distilled over. The pure compound is a colourleas oily liquid heavier than water at the bottom of which it will lie for weeks without thoroughly decomposing.Sulphuric and hydrochloric acids may however be detected immediately a€ter its immersion and on neutralising the liquid with baryta a soluble salt is formed which I believe to be sulphovinate of baryta. HUTCHINGS ON THE ACTION The compound has a peculiar sharp pungent smell. When dry ammonia is passed into it part of it is precipitated as a white solid body and if water is now added it emits a nutty odour; the solution forms a soluble barium-salt. A similar compound is formed with chloride of methyl but could not be satisfactorily examined on account of the difficulty of condensirig the chloride. I have since formed a body smelling exactly like the ethyl- compound by adding absolute alcohol to chloro-sulphuric acid. The action is probably as follows I have also tried the aetiori of chloride of othyl C,H,OCl on anhydrous sulphuric acid.It dissolves the acid very rapidly with evolution of heat and forms a colourless compound which after- wards turns yellow and then red even while sealed up. It is rapidly decomposed on opening the tube; and from this cause I was precluded from determining its composition. When dropped into water it sinlis to the bottom and gradually dissolves forming an acid liquid. This liquid forms with baryta a soluble salt which yields a gelatinous precipitate on the addition of an alkali.

ISSN:1743-6893    

DOI:10.1039/QJ8581000097

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年代:1858

数据来源: RSC

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HUTCHINGS ON THE ACTION VIII.-On a Compound obtained by the Action of Fuming Sul-phuric Acid on Chloride of Phenyl. BY L. HU'I'CHINGS OF UNIVERSITY COLLEGE LONDON. BY the action of fuming sulphuric acid on benzin (hydride of phenyl) Mi tsch er 1 ich* obtained sulphobenzidic acid C6H6S03 The substance described in the present paper was obtained in a similar manner from chloride of pheuyl. The chloride of phenyl employed was prepared from hydrate of phenyl and pentachloride of phosphorus as described by Mr.Scrugham.? .* Pogg. -41in. XXXI. 283. + Chem. SOC. Qu. J.vii. 238. OF FUMING SULPHURIC ACID ON CHLORIDE OF PBENYL. 103 When fuming sulphuric acid and chloride of phenyl are brought in contact at the common temperature they gradually combine ; and on treating the resulting liquid with excess of milk of lime a soluble lime salt is obtained which crystallises on evaporation in flat tabular crystals.0.259 grm. of this lime salt gave 0.06 grm. carbonate of lime containing 0.024grm. calcium = 9.26 per cent. 0.2744 grm. of this lime-salt gave 0.3044 grm. sulphate of baryta containing 0.042 sulphur = 15-22 per cent. These quantities agree with the formula C6H4ClCa SOs* Calc. Found. 6 C . . . 72.0 34.03 4H.,. 4.0 1.92 c1 . . . 35.5 16.78 Ca . . . 20.0 9-46 9.26 S . . . 32.0 15.13 15-22 3 0 . . . 48.0 22-68 C6H4CaC1 OS3 211.5 100*00 The acid may be regarded as a compound of anhydrous sul-phuric acid with chloride of phenyl.

ISSN:1743-6893    

DOI:10.1039/QJ8581000102

出版商:RSC    

年代:1858

数据来源: RSC

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OF FUMING SULPHURIC ACID ON CHLORIDE OF PBENYL. 103 IX.-Notes on Alum in Bread and its Detection. BY EDWARD ASH HADOW DEXONSTBATOR OF CHEMISTRY IN KING'S COLLEGE LONDON. THEREare two methods recommended in chemical works with a view to the detection of alum in bread to both of which there appear at first; sight to be theoretical objections rendering it difficult to understand how they could answer the purpose for which they were proposed. One method that of Messrs. Robine and Paris ot depends on the extraction of the alum from the bread by digestion in cold water and then testing the clear filtrate for sulphuric acid and alumina with chloride of barium and ammonia respectively. This method seems open to the objections that the detection of sulphuric acid would not prove much since it might have been derived from the common salt employed in making the bread ;and the non-precipitation of alumina wodd not make its "C = 12; S = 32; 0 = 16.104 HADOW absence certain since it might be retained in solution by organic matters extracted from the bread. The second method that recommended hy Hu hl m an consists in incinerating the bread digesting the ash in nitric acid and after filtration testing the filtrate for alumina with potash ; here again it seems questionable whether the alumina would be found capable of solution in nitric acid after the prolonged incineration of the bread. With a view to settle these points 20 grains of alnm were given to a baker to be introduced into a llb.loaf of bread which being in the proportion of 80 grains to the quartern loaf is pro-bably above the average amount employed; the loaf thus prepared was broken up and macerated in successive portions of' water for 48 hours. The expressed liquids mixed became perfectly clear by filtration through coarse paper. The filtered liquid was very feebly acid to litmus paper rendering it by long immersion purple rather than red. One portion tested with chloride of barium the other with ammonia gave moderate precipitates. The great bulk of the liquid was evaporated to dryness and ignited to get rid of a quantity of gummy organic matter. The residue which fused readily owing to the common salt present dissolved for the most part in water and wliolly on the addition of a little nitric acid.Potash (pure and free from alumina) gave on addition an abundant precipitate insoluble in excess and the filtrate remained perfectly transparent on addition of excess of chloride of ammonium proving thus the total absence of alumina. The inorganic matters extracted by water were further examined arid found in addition to common salt and sulphate of potash to contain alkaline phosphates existing in the fiised ash at first as pyrophosphates together with phos- phate of lime and a large quantity of phosphate of magnesia which fully accounts for the precipitate obtained by ammonia in infusion of bread. The glutinous mass of the bread left undissolved by water was then incinerated completely when the ash was found to be wholly soluble in dilute nitric acid.Potash was then added in excess and the whole was filtered on testing the solution with chloride of ammonium; alumina was found in abundance; the portion of the ash insoluble in potash was chiefly phosphate of iron and manga- nese with a little phosphate of lime. Thus it appears that on treating alumed bread with water no alumina is extracted even when alum is present in so large a proportion so far from it that the aqueous infusion of this bread produced an immediate precipi- ON ALUM IN BREAD AND ITS DETECTION. tate with a solution of alum becoming ahundant on gently warming the mixture and rendering it impossible that alum should exist in the solution so that this process of maceration in water only is entirely fallacious and any sample of bread thus examined will give a precipitate with ammonia; but this precipitate consists only of phosphate of lime and phosphate of magnesia and ammonia the extraction of which by water only appears somewhat remakable the acidity of the liquid being insufficient to account for their solu- tion.The removal of these phosphates by water appears to be nearly complete while the retention of alumina and phosphates of iron and manganese is no less entire. The quantity of alkaline phosphates present in the ash renders it highly probable that the alnmina is retained as phosphate which would sufficiently account for its ready solubility in nitric acid after strong ignition; at any rate Ruhlman’s method of extraction by nitric acid from the ash answers perfectly the only objection being the length of time reqnired for complete incineration of the bread to obviate which it map after charring in a capsule of platinum be deflagrated with nitrate of potash a process which can be effected over a spirit lamp.On digesting the mass in water the alumina is almost wliolly found in solution in the carbonate of potash thus produced. Nitrate of cobalt is of no use as a means of detecting alumina in the ash; since the phosphates present are capable of giving the same reaction with this reagent before the blowpipe. Since alumisa is thus obstinately retained by bread it seemed probable that its mordant properties might serve for its summary detection. With this view a proportion of pure bread mas immersed simultaneously with a piece known to contain alum in a freshly prepared and dilute decoction of logwood and set aside for some hours when a distinct difference between the two pieces was per-ceptible both in intensity arid in shade of colour which was more evident on breaking the two pieces.The pure bread was simply dtained superficially with the pale orange-red colour of the decoc- tion while the alumed piece had acquired a purple dye which had penetrated to some depth. A baker in whose bread alum had been detected acknowledged the fact when accused of it but stated that he only used loz. for a bushel of flour or loz. to about 19 quartern loaves which amounts to about 5.7 grains of alum per llb. of bread. Dr.Normandy also states that no effect is produced in improving the appearance of the bread if the quan- 106 HADOW tity of alum be reduced below 1in 906 of' flour or below loz. per bushel; hence this may be taken as the mirhimzdm probably in which this ingredient mould be added. A loaf was therefore prepared with this proportion of alum and was found to give a perfectly satis- factory reaction with the decoction of logwood a piece of pure bread having been immersed at the same time by way of com-parison. Sulphate of zinc was on one occasion detected in bread by Professor Bloxam when he was led to suspect it from observing that the ash had a yellow colour while hot which disappeared 011 cooling. It is probable that with bread of pure wheat-flour this phenomenon would not be observed in consequence of the trans- formation of the sulphate into phosphate of zinc by the alkaline phosphates present there being no excess of alkali present to pre- vent such a combination.On one or two occasions however I have fibserved a strongly alkaline reaction of the ash due in all proba- bility to the addition of potatoes ;in such a case only would such a phenomenon probably be observed. Having on one or two occasions detected small quantities of copper in brown bread and finding it left in the bread after diges- tion of the latter in water I wished to try whether sulphate of copper was in the same predicament as alum and if so whether ferrocyanide of potassium was capable of detecting its presence as it is stated to do by merely moistening the bread with its solution.A loaf was therefore prepared with the addition of this salt in proportion of 10 grains to the lb.; it mas macerated in successive portions of water in which very little copper was found to be dissolved yet the residue from which all soluble matters had been extracted acquired a decided reddish tint when treated with ferro- cyanide of potassium which was found to produce a more marked effect than ammonia or hydrosulphate of ammonia. Bread thus adulterated becomes equally with alumed bread strongly dyed by an infusion of logwood SO that this test though alone incapable of distinguishing between the two would at least indicate that some-thing was wrong. In applying this test the solution should be freshly prepared and diluted considerably ; the pieces of bread should likewise be allowed to float in the liquid for about 1.2 hours the effect being more marked than when they are entirely immersed 50 as to exclude the air.It is possible that unfermented bread might occasionally give a fallacious indication if the carbonate of soda used werc not wholly neutralized by the hydrochloric acid ON ALUM IN BREAD AND ITS DETECTION. added for the purpose by the baker ;as however the alkali would pass into the solution it seems probable that the latter would likewise be simultaneously affected and the alkaline reaction of the bread would explain the phenomenon. The only unfermented bread thus examined became unmistakeably dyed ; the bread however had a feebly acid reaction and was found to contain abundance of alum.Before concluding it may be well to remark that it is difficult to judge of the quantity of alumina present merely by observing its bulk and appearance on precipitation since its appearance varies much with its mode of precipitation. It probably appears most abundant when precipitated from its solution in potash by careful neutralization of the latter with a diluted acid or by the addition of chloride of ammonium and gentle warming ;if however the latter be boiled or the precipitation be effected by addition of ammonia to its acid solution the alumina is far more transparent and in a hasty examination might even be overlooked when present in small quantity. The decoction of logwood should also be made with water containing carbonate of lime such as that ordinarily supplied in London; for with a decoction of logwood in distilled water the differences of colour are far less marked.

ISSN:1743-6893    

DOI:10.1039/QJ8581000103

出版商:RSC    

年代:1858

数据来源: RSC

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107 ON ALUM IN BREAD AND ITS DETECTION. X.-On the Valuation of Nitre. BY F.A.ABEL,and C. L. BLOXAM. INaccordance with a promise made by the authors at the conclu- sion of a former paper upon this snbject,* they beg to lay before the society the results of the application of their modification of the method of Gay-Lussac for determining the value of speci-mens of the commercial salt. It will be remembered that the modification alluded to consisted in the substitution of resin for charcoal in the conversion of the nitre into carbonateof potassa and in the subsequent treatment of the fused mass with chlorate of potassa in order to oxidise the cyanate of potassa and to obviate the error arising from the reduction of the sulphates. The following results mere obtained in 53consecutive experiments conducted in this manner.Mean of 53 experiments upon pure nitre; 99.7 per cent. * Chem. Soc. Qu. J. ix 97. 108 ABEL AND BLOXAM Of these results 25 exhibited a slight deficiency in the amount of nitre indicated by the standard acid; Mean of these 25 experiments . . 98.7 per cent. Mean of the remainder . . . . 100-7 , Moreover a difference arnounting to 0-3 or 0.5 per cent. was observed in the results according as the strength of the acid employed had been determined by means of pure nitre or of its equivalent of carbonate of soda proving that the process was not yet theoretically correct or the results would have coincided in the two cases. The alteration of the quantity of resin and of the temperature employed to effect tlle deflagratioii was not found to improve the results.On examining the mass obtained by the deflagration the carbon was usually found collected into large flocks and therefore me-qually disseminated ; and on examining the residues in such cases traces of undecoinposed nitre were frequently detected. In the course of subsequent experiments it was noticed that the decomposition of the nitre appeared to be more complete when the carbon was added in the form of the pure ignited finely divided graphite prepared by the recently patented process of Mr. Rrodie. Attention may be called to thc circumstance that no cyanate of potassa mas to be fourid in the deflagrated mass when the graphite had been used while it may be remembered that considerable quantities of this salt were fornied when other varieties of carbo-naceous matter wliich contained hydrogen were employed ren- dering it probable that the ammonia which was always evolved in such cases is the proximate cause of the formation of cyanogen.The use of chlorate of potassa however is still necessary in the examination of samples of nitre containing snlphates. Twenty grains of pure nitre were mixed with 5 grains of ignited graphite and 80 grains of salt; after deflagration the amount of carbonate of potassa formed was determined as usual. Considerable influence was exerted upon the success of the process by the degree of heat employed in conducting the defla- gration; if the platinum crucible be heated to moderate redness in a mufile from 8 to 10 minutes will suffice to cornplete the decom- position of the nitre a result which may also be attained when a gauze burner is used by prolonging the application of heat for 20 minutes and covering the crucible with a jacket.If too high a temperature be applied in the muffle the results always exhibit ON THE VALUATION OF NITRE. a deficiency; the heat should not be sufficient to volatilise the common salt to any considerable extent. Six experiments made with the above proportions gave as a mean result 99.98 per cent. of nitre. Eleven experiments upon a mixture containing 95 nitre 2.5 common salt and 2.5 sulphate of potassa gave a mean of 94.88 per cent. of nitre. In treating the fused mass with chlorate of potassa the crucible was removed from the muffle the chlorate sprinkled over the surface and heat applied by means of an argand burner as long as any effervescence was observed.The fused mass was then thrown upon a filter (having been loosened by pouring a little water into the crucible) and washed with hot water till the washings were no longer alkaline. In the course of the experiments upon pure nitre a fresh sample of graphite happened to be employed and the results then fell some- what short of the theoretical numbers; on enquiry this was found to be due to the presence of sulphide of iron in the specimen of graphite; after this had been removed by treatment with hydro- chloric acid correct results were again obtained.The subjoined table exhibits the results of a number of deter-minations of the value of commercial saltpetre by the graphite process the amount of nitre thus indicated being compared with that indirectly obtained by determining the various impurities in the sample. The greater number of these analyses were performed by Messrs. Dent and Brown. Saltpetre employed for each deterniination 20 grains. No. Nitre obtained No. Nitre obtained Directly. Indirectly. Directly. Indirectly. 1 94-85 94-81 14 98.45 98.33 2 98-25 98.31 15 98.65 98.60 3 98-45 98.10 16 96.05 96-00 4 95.85 95.79 17 94.00 93-91 5 98.10 97.96 18 98.75 98.43 6 96.70 96.88 19 99-50 99.72 7 96-90 96.73 20 99.35 99-49 8 95.25 95.03 21 94.85 94.66 9 95.05 95.24 22 95.35 95.27 10 97.10 97.41 23 96-05 96.18 11 99.15 99.21 24 95.00 95-05 12 93.80 94-09 25 97-10 97.32 '13 95.35 9548 26 97.10 96.90

ISSN:1743-6893    

DOI:10.1039/QJ8581000107

出版商:RSC    

年代:1858

数据来源: RSC

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110 SPILLER ON THE INFLUENCE OF XI.-On some remarkable Circumstances tending to disguise the Presence of various Acids and Bases in Chemical Analysis. By JOHNSPILLER ASSISTANT IN THE CHEMICAL ESTABLISHMENT OF TEE WAR DEPARTMENT. ON commencing a series of analyses of iron ores under the direc- tion of Mr. A b el I had occasion to make a number of experiments in the endeavour to obtain a more perfect and rapid method than those hitherto employed of separating phosphoric acid from alumina. In the course of this investigation I was incidentally led to bring together in the same solution alum citric acid phosphate of soda and ammonia the citric acid being added in order to retain in solution the aluniina and phosphate of alumina. On attempting to precipitate the phosphoric acid as phosphate of baryta I was astonished to find that no precipitate was produced and on considering that there was present in the solution not only phosphoric acid but also sulphuric acid from the sdphate of alumina I was naturally led to inquire further into the cause of sulphuric acid and baryta existing together in the same solution.Since it wag evident that this extraordinary result could only be due to the .presence of citric acid a series of experiments were instituted in order to determine the influence which citric acid exerts on the formation of precipitates in chemical analysis the resnlts of which I will now proceed to describe. In order to ascertain the conditions under which the precipita-tion of sulphate of baryta may be prevented by citric acid and the &rates sulphaite of soda was taken as the source of sulphuric acid and nitrate of baryta as a convenient salt of that base.To a mixed solution of sulphate and citrate of soda a small quantity of nitrate of baryta was added; the result was the formation of a bulky white precipitate of citrate of baryta which immediately redissolved to a clear solution on agitation. On continuing the addition of successive portions of nitrate of baryta a point was at last arrived at when a permanent precipitate of sulphate of baryta made its appearance. In the next experiment the object was to ascertain the extent to which citrate of soda will prevent the precipitation of sulphate of baryta and for this purpose weighed quantities of each of the substmces were employed.CITRIC ACID ON CHEMICAL REACTIONS. Ill TOa known quantity of citrate of soda sulphate of soda was gradually added until on testing a portion of the mixture the sulphuric acid was immediately indicated by a drop of solution of nitrate of baryta; and it was found that this point was attained when the equivalents of citric acid to sulphuric acid were in the relation of 1 3. In order to confirm this result equal weights of carbonate of soda were saturated the one with sulphuric acid the other with citric acid; on mixing these the salts in solution consisted of 3(NaO,SO,) i-3Na0,Ci. In such a solution nitrate of baryta gave no permanent precipitate but on increasing the proportion of the sulphate of soda the sulphuric acid was immediately rendered apparent.With a view to determine whether citric acid exercises a similar protective action over baryta as it does over sulphuric acid the experiment was reversed and the citrate of soda added to the salt of baryta. To a known quantity of citrate of soda nitrate of baryta was added until a permanent precipitate of citrate of baryta was formed; the solution at this stage containing 2 (3Na0,Ci) + 3Ba0,G. On adding a little sulphate of soda an immediate precipitate of sulphate of baryta was produced. In conriexion with this experiment it may be stated that the solution of the double citrate of baryta and soda deposited nearly the whole of the citrate of baryta on standing.It would appear therefore that the protective action is on the side of the acid rather than that of the base. The conditions under which the precipitate of sulphate of baryta is produced in a solution made according to the first experiment are the following:-by boiling when sulphate of baryta is irnme- diately precipitated; by the addition of an excess of nitrate of baryta; by the addition of hydrochloric acetic tartaric or oxalic acid. The sulphate of baryta when precipitated from solution by either of these agents is in a peculiar flocculent condition totally dissimilar in appearance from that obtained under ordinary cir- cumstances; so finely divided is it that it readily passes through a filter of Swedish paper. Prolonged boiling with or without hydrochloric acid has little effect in changing its physical cha- racter.112 SSPILliER Oh’ THE INFLUENCE OF Citric acid itself has no effect in prevehting the precipitation of sulphuric acid by a salt of baryta; and this is probably the reason why the addition of acids to a solution containing a neutral citrate is immediately followed by a precipitation of sulphate of baryta. These results having been obtained by the use of a baryta salt it became iriterestiug to know whetlier the sulphates of strontia and lead were in like manner prevented from precipitation by citrate of soda. To a mixture of sulphate and citrate of soda nitrate of strontia was added when no indication o€ snlpliuric acid was observed the salt of strontia behaving in a precisely similar manner to that of baryta under the same circumstances.Nitrate of lead substituted for the baryta or strontia in these experiments gave the same result no sulphate of lead being pro-duced. But sulphate of lead differs from the sulphates of baryta and strontia in being soluble after precipitation in citrate of soda. My attention was next directed to the power which the citrates possess in influencing the general reactions which characterize the acids and bases in the ordinary course of chemical analysis. Baryta.-Of the compounds of baryta there is not one that is precipitated when the acid is previously combiiied with citrate of soda whether the reaction of the solution be acid or alkaline. The salts of this base which have been made the subject of experiment are besides the sulphate the phosphate carbonate borate oxalate tartrate citrate and fluoride.With the exception of the sulphate all these compounds after precipitation are again dissolved in neutral citrate of soda. 8trontia.-The acids which were tried in connexion with this base mere sulphuric phosphoric and carbonic all of which com-pounds were retained in solution. Lime.-Of the lime salts the carbonate phosphate and oxalate were found to follow the general rule both with respect to pre-vention of precipitation and in being redissolved in citrate of soda if once produced. The fact of‘ oxalate and phosphate of lime being soluble in citrate of soda suggests the possibility of this salt being employed with advantage in diseases arising from the formation of these descriptions of calculi.As lime is the reagent generally recommended for the detection of citric acid it is important to hear in mind that the citrate of CITRIC ACID ON CHWMTCAI REACTIONS. lime will not be thrown down on boiling unless the chloride of calcium be added in sufficient quantity to decompose the ‘greater portion of the alkaline citrate since the double citrate of lime and soda does not give any precipitate 011 boiling. Magnesia-The salts of this base appear to be less aEected by the presence of citrate of soda hydrate of magnesia and the ammonio-phosphate of magnesia being precipitated as usual. The phosphate and carbonate are however held in solution. The next group consisting of the sesquioxides of iron chromium and aluminium are not precipitated by their usual group-test-ammonia.The phosphates of these oxides are also retained in solution by citrate of soda. Chromium in the state of chromic acid is not detected by lead silver bismuth or baryta. The chromate of lead does not even appear on the addition of acetic acid. Sesquioxide of Iron.-A solution of sesquichloride of iron is not precipitated by ferrocyanide of potassium benzoate or succinate of ammonia; nor is the coloured reaction produced with acetate of potassa ferricyanide or sulphocyanide of potassium. The re- action between sesquichloride of iron and ferrocyanide of potassium is curiously modified. On mixing these two solutions in the presence of an alkaline citrate a yellow solution is formed which becomes deep blue in colour on largely increasing the amount of ferrocyanide of potassium ; no precipitate of Prussian blue is pro- duced until hydrochloric acid in excess is added.From the fact that a salt of iron does not precipitate benzoic and succinic acids in presence of a citrate the detection of these acids becomes exceedingly difficult as we are not able to avail ourselves of any of the methods previously adopted for the decomposition of the citrate. The group comprehendi-ng the protoxides of iron manganese nickel cobalt and zinc are variously affected by their group-test -sulphide of ammonium. The sulphides of nickel cobalt and zinc are precipitated as usual; sulphide of iron incompletely; and sulphide of manganese not at all.Protoxide of hn.-Neitlier potassa nor ammonia will precipi- tate this base in the presence of citric acid. The alkaline product so obtained gives with sulphide of ammonium if dilute a dark olive-green solution but if more concentrated an immediate pre- cipitate with a supernatant liquid of that colour. The sulphide of iron comes down however on boiling or on standing for a I SPILLER ON THE INFLUENCE OF sufficient length of time in the cold. The protophosphate of iron is held in solution and the reaction between ferricyanide of potassium and a protosalt of iron is entirely masked. Oxide of Manganese.-The most striking result observed under this head relates to the behaviour of the sulphide.The flesh- coloured precipitate usually obtained on adding sulphide of am-monium to a salt of manganese does not appear under these circumstances and the sulphide after precipitation is freely soluble in an alkaline citrate. If citrate of ammonia be the solvent employed vatpour of sulphide of ammonium is evolved on boiling. The protoxide of manganese is not precipitated by potassa nor the carbonate by carbonate of soda in presence of a soluble citrate. On exposure to air the brown binoxide of man-ganese separates from the former only of these solutions. Oxide of Nickel.-A salt of nickel gives with sulphide of ammonium the ordinary black precipitate of sulphide of nickel ; but the other reagents as potassa carbonate of soda and ferro- cyanide of potassium fail to give their usual indications.Oxide of Cobalt.-Solutions of this metal behave in a similar manner to those of nickel with the several reagents just men-tioned. The alkaline solution of protoxide of cobalt in potassa deposits the sesquioxidc on exposure to air. Oxide of Zinc.-This oxide resembles magnesia in being pre- cipitated by potassa in the presence of a citrate. The carbonate of zinc is retained in solution but the sulphide and ferrocpanide are not influenced. Sesquioxide oj Uranium.-The phosphate and ferrocyauide of uranium are not precipitated in the presence of citrate of soda. The metals of the sulphuretted hydrogen group are with the exception of arsenic precipitated as usual by their group-test. Several of their principal reactions are completely disguised as will appear on describing these metals individually.Oxide of Lead.-Besides the oxide itself the sulphate phosphate carbonate arid oxalate the bromide iodide cyanide and ferro-cyanide are all retained in solution ou the addition of their respec- tive precipitants. The only compound of lead of those experi- mented upon which made its appearance as under the usual circumstances was the sulphide. The chromate has been already referred to as having its characters completely masked. Oxide of SiZwer.-Inasmuch as the nitrate of silver is frequently ennployed for the detection and discrimination of several acids CITRIC ACID ON CHEMICAL REACTIONS. both organic and inorganic it was thought advisable to make a careful study of the more important compounds of this metal and to trace their connexion with the ordinary process of analysis.Nitrate of silver if added in small quantity to a solution of neutral citrate of soda gives rise to a precipitate which on agitation is completely redissolved but on continuing the addition of the nitrate of silver a permanent precipitate is at last produced. As this final effect can only result in the destruction of the citrate of soda and the removal of the citric acid as an insoluble silver- compound it follows that no interfering influence need be antici- pated in the ordinary course of testing for acids. Among the compounds of silver insoluble under ordinary circnm- stances but which are held in solution through the medium of citrate of soda are the carbonate phosphate oxalate tartrate and citrate.On the contrary the sulphide chloride bromide iodide ferrocyanidc and sulphocyanide are precipitated as usual. The cyanide of silver is slightly soluble in this reagent so that in its presence very dilute hydrocyanic acid is not precipitated by nitrate of silver. Oxide of silver resembles magnesia and oxide of zinc in being thrown down by potassa under all circumutances. Suboxide of Mercury.-By adding potassa to a salt of this base in the presence of citric acid the suboxide of mercury is resolved into protoxide which remains in solution and metallic mercury precipitated in the form of minute grey globules. The chloride bromide and iodide corresponding to the suboxide are precipi- tated in the usual manner.Protomide of Mercury.-The sulphide and iodide are not sensibly influenced in their precipitation; the latter is very sparingly soluble in citrate of soda so that in a highly dilute solution the scarlet iodide does not make its appearance. The oxide and carbonate are retained in solution and if to either of these alkaline liquids ammonia or one of its salts be added the white precipitate (chloride and amide of mercury) is immediately thrown down. The fact that oxide of mercury is not precipitated by carbonate of soda in the presence of certain salts and that on the addition of any compound of ammonia an immediate precipitate is pro-duced is not new. A solution of protochloride of mercury chloride of sodium and carbonate of soda has long since been employed by Mr.E. 0. Brown as a test for ammonia; and so delicate is this test that the slightest trace of ammonia is indicated by an opalescence throughout the liquid. 12 Terozide of Bisnz7n.tlt.-N either this oxide nor the carbonate is precipitated if citric acid be prescnt nor is the terchloride of bismuth decomposed by water. The aulphide is however not appreciably affected. Oxide of Copper.-This oxide and the carbonate are both retained in solution ;the sulphide and ferrocyanide are precipitated in the usual manner. Oxide of Cadmium.-The carbonate and oxide of this metal are also retained in solution but not so the sulphide which is com-pletely precipitated.Protoxide and Binoxide of Tin.-Both these oxides may be retained in alkaline solution on the addition of ammonia. The sulphides of tin are completely precipitated as under the ordinary circumstances. Teroxide of Antimany.-The addition of citric acid prevents the precipitation by water of the terchloride of antimony but does not interfere with the separation of this metal by sulphuretted hydrogen. Antizmonic Acid.-The precipitation of the pentasulphide of antimony does not appear to be so complete as in the case of the t.ersulphide ; the separation of the last portion was attended with difficulty in some of my experiments. Arsenious and Arsenic Acids.-The characteristic reactions of arsenic are modified in a remarkable manner. A solution of arsenious acid to which citric acid or a neutral citrate has been added is no longer precipitated by sulphuretted hydrogen in the cold or on boiling.The tersulphide of arsenic is also readily soluble in citric acid or a citrate. Hydrochloric acid added to either of these solutions at once separates the whole of the arsenic. The pentasulphide imitates the deportment of the tersulphide under the circumstances recorded above. The arsenites of silver copper lime and baryta and the arseniates of lead silver and baryta are entirely kept in solution. From a consideration of the circumstances under which the sulpliidesof arsenic may be preserved in a soluble form while the same compourids of tin and antimony are completely precipitated I have been induced to attempt the analytical separation of these metals by such a process.My experiments have not yet been sufficiently numerous to enable me at the present time to point m1.t the conditions under which their perfect separation may be ClTRIC ACID ON CHEMICAL REACTIONS accomplished but I have every reason to believe that a yuantita-tive method may be based upon this principle. Teroxide of Gold.-The precipitation of the sulphide of gold takes place as under ordinary circumstances but the reaction witb protoehloride of tin is modified to the extent of the production of a dingy green precipitate instead of the brilliant purple of Cassius. Binoxide of Platinum.-The bisulphide of platinum is precipi- tated on boiling but not readily in the cold.The double chloride of platinum and ammonium has an increased tendency to assume a crystalline condition perhaps on account of its formation being dig htl y retarded. Finding citric acid to exert such remarkable solvent powers in many of the iiistances enumerated I extended the inquiry to a few substances where a parallel action might have been expected. With this intention tartaric and racemic acids glycerine and the sugars were selected and their interfering action in some few cases determined. Tartaric acid prevents the precipitation of a salt of cobalt by potassa and in the form of a neutral tartrate retains in solution sulpliate of lead and the sulphide of manganese ; Prussian blue is not formed in its presence; and the precipitation of sulphate of' baryta is to a small extent retarded.Racemic acid also slightly retards the precipitation of sulphate of baryta. Glycerine has seemingly no influence in preventing the preci- pitation of Yrussian blue sulphide of manganese or sulphate of haryta. Under the head of the sugars tlie only circumstance met with worthy of record was the power of grape-sugar to prevent in the cold the formation of sulphide of manganese. Neither cane nor milk-sugar appeared to have any influence in this direction. These examples fully confirm the fact long known that many kinds of organic matter exert a very considerable influence on the formation of precipitates in analytical chemistry and suggest the necessity of eliminating all these interfering circumstances before testing for the inorganic bases.It is then good policy to carry out the instructions of the analytical tables when after treatment of the unknown substance with hydrochloric acid and sulpharetted hydrogen it is recommended to evaporate the filtrate to dryness and to clear organic matter before proceeding to search for met& belonging to eithcr of the subsequent groups. SPILLER ON THE INFLUENCE OF Before concluding the account of my experiments on the pro- perties of citric acid I cannot refrain from mentioning a difficulty early experienced in the detection of tartaric acid when mixed with a large proportion of citric acid. So imperfect is the ordinary method of proceeding-that of emplo-jing a lime-salt to precipitate in the cold the tartaric acid as tartrate of lime-that I think it possible for citric acid to be adulterated with as much as 10per cent.of tartaric acid without fear of detection. Desiring to ascertain the purity of the sample with which I worked my attention was naturally directed to this point. By the following process we are enabled to detect the presence of tartaric acid in cases where the old method would not be successfully employed. To a concentrated aqueous solution of the acid under examina- tion acetate of potassa is added and subsequently strong alcohol to the amount of an equal bulk; on stirring with a glass rod the crystalline bitartrate of potnssa separates time being allowed when small quantities only are suspected.By this means it is possible to detect a much smaller amount of this impurity in citric acid. The same mode of proceeding may be turned to useful account if the relation between these two acids be reversed. By first separating the tartaric acid as above and afterwards evaporating the alcoholic filtrate over a water bath the citric acid may be detected in the residue by boiling with excess of chloride of calcium in the usual manner. For the explanation of these curious phenomena I am not able to bring forward any hypothesis with the same degree of confidence that I have treated the facts themselves. The only possible way that has suggested itself to my mind of accounting for the pro-perty possessed by citric acid of retaining in solution substances which under ordinary circumstances are insoluble is to suppose a neutral salt of citric acid to be endowed with the power of com- bining on the one hand with another salt containing the acid of the compound whose formation is prevented in such a manner as to produce a class of double salts of the general composition :-(3M0,Ci) + 3(MO,SO,) in which the term SO is capable of being replaced by CO, CrO, BO, 0 &c.; or in the case of PO, a tribasic acid one equivalent only will be required to take the place of three equivalents of SO,.On the other hand it must be allowed that an alkaline citrate CrTmc ACID ON CHEMICAL REACTIONS. has a tendency to combine with the citrate of another base even though this latter compound be of itself but slightly soluble in water.The affinity existing between the two constituents of the double citrate taken in conjunction with that exerted in the formation of the class of double-salts just now referred to might it is suggested determine in favour of the non-precipitation of the otherwise insoluble body involved. The ascertained facts upon which this hypothesis has been prin- cipally constructed may be shortly stated to consist in the power of one equivalent of citric acid to mask the reactions of either three equivalents of sulphuric or carbonic acid or one equivalent of the tribasic phosphoric acid; while the existence of a class of double citrates as those of soda with silver lime and baryta respectively has been rendered highly probable in the course of this investigation.Additional confirmation is also derived from the circumstance that the carboriates of baryta and lead dissolve in a neutral citrate with production of an alkaline liquid the new metal remaining in solution in the form of a double citrate. And again the alkaline product of the action of carbonate of soda on a salt of manganese in presence of citrate of soda does not deposit binoxide of manga-nese on exposure to the oxidising influence of the air while another solution containing caustic potassa in place of the carbonate is constantly absorbing oxygen An analogous instance in the case of cobalt need scarcely be quoted. All these reactions are explicable in my opinion on the view advanced; the affinity of carbonic acid for these several bases though weak is strength- ened by the formation of a citrocarbonate.

ISSN:1743-6893    

DOI:10.1039/QJ8581000110

出版商:RSC    

年代:1858

数据来源: RSC

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CrTmc ACID ON CHEMICAL REACTIONS. XIL-Note on Crystaljised Binoxide of Tin. BY 3’. A. ABEL. IN the bronze gun foundery at Woolwich it is customary in cleaning out and examining the furnace employed in preparing the gun-metal to collect the small quantity of dross or slag found on the hearth and to subject it to fusion in one of the crucibles used during the day in the preparation of small castings in order to 120 ABEL ON CRYSTALLISED BINOXIDE QF TIN. recover the metal disseminated through the mass by allowing it to subside from the liquid slag. Upon breaking the crucible to remove the metal obtained in an operation of this kind a short time since a cavity was dis-covered in the slag bctween it and one portion of the metallic surface containing a number of long brilliant needles which appeared to possess a light brown colour.On careful examination under the microscope they proved to be striated four-sided pris- matic crystals of a colourless transparent substance enclosing here and there small particles of metal. The crjstals were very brittle and so hard as to scratch glass easily. Some of them were carefully selected so as to be quite free from slag and submitted to chemical examination. They proved to be perfectly insoluble in acids and when fragments of them were fused with carbonate of soda they remained unaltered for a considerable period. A few of the crystals were finely pul- verised after digestion in nitrohydrochloric acid and the enclosed metallic particles separated by levigation.The dense white powder thus obtained was readily dissolved by fused carbonate of soda and proved to consist entirely of binoxide of tin. When submitted to the highest blowpipe-heat upon a charcoal support the crystals evinced no symptom of fusion until after some time partial reductioii of the metal ensued. Upon exposing the extremity of a crystal in a platinum support for some time to the hottest portion of the blowpipe-flame it altered in form a little and when examined by a lens was found to have fused slightly to a yellowish transparent glass. These crystals of binoxide of tin were not only found in the cavity between the metal and the slag but were distributed over the entire upper surface of the metal to which they firmly adhered.The appearance of' the metallic surface wits very peculiar; the metal itself having assumed the form of tufts which were inter- laced with the crystals of binoxide of tin. The latter would seem to have separated from the gun-metal in the crystallirie form as the crucible was allowed to cool. The formation of such crystals as those described does not appear to be a matter of frequent occurrence; although the ope- ration above alluded to (i. e. the collection of the metal from the slag) has long been a customary one this is the first instance in which the crystals have been observed by those conducting this operatioil at Woolwich. ABEL ON CRYSTALLISED BINOXIDE OF TIN. Two shell-like specimens of gun-metal removed about ten years ago from some crevices above the hearth of one of the furnaces in the same foundery after a cast have been preserved by the super- intendent because tlie interior surfaces were found to be covered with crystals which prove to be similar though of inferior size to those above described. These crystals of binoxide of tin are quite similar to those described by M. Daubr6e as obtained by the action of the vapour of water upon bichloride of tin at a red heat.

ISSN:1743-6893    

DOI:10.1039/QJ8581000119

出版商:RSC    

年代:1858

数据来源: RSC

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ABEL ON CRYSTALLISED BINOXIDE OF TIN. XIK-On a New Base from the Juice of Flesh. BY A. STRECKER. LIEBIG, in his classical investigation of the juice of flesh did not as is well known make use of any heavy metallic salt to precipitate the substances which he discovered in that liquid; and it was only after he had become acquainted with the properties of creatinine which he at first obtained by artificial means,-that he demon- strated the existence of that base in flesh-juice by precipitation with chloride of zinc. As the juice of flesh in addition to the principles discovered and examined by Liebig contains a considerable number of bodies hitherto undetermined which bodies remain in the form of a thick magma when the mother-liquor of creatinine is evaporated I endeavoured to isolate some of these constituents by precipitation with different metallic salts e.y. mercuric chloride mercuric nitrate ammonio-chloride of zinc and acetate of copper. All these salts produced a considerable precipitate containing as an essential constituent a well characterised organic base which I will provisionally distinguish by the name Sarcine. The most advantageous method of preparing this base is by precipitation with acetate of copper. The mother-liquor of the creatine-crystals was diluted and mixed with a dilute solution of acetate of copper ;a copious precipitate was then produced which when decomposed by sulphuretted hydrogen yielded a substance soluble in water hut still coloured. On boiling the solution of this substance with hydrated oxide of lead the colouring matter was precipitated together with a smal! quantity of sarcine ;the 122 STRECKEIC greater part of that substance however remained in solution and after the lead had been precipitated by sulphuretted hydrogen was obtained in the crystalline form by evaporating the liquid.From a warm saturated solution sarcine gradually separates on cooling in the form of a white indistinctly crystalline powder which often covers the sides of the containing vessel with a dense coherent crust. It dissolves in 300 pts. of water at 15O C. and in 78 pts. of boiling water ;but requires 900 parts of boiling alcohol to dissolve it. The solutions do not alter the colour of litmus-paper and have no very characteristic taste.In hydrochloric acid ammonia and potash sarcine dissolves much more readily than in cold water ; dilute nitric and sulphuric acid dissolve it less readily ; concentrated nitric and sulphuric acid dissolve it abundantly without colouring or evolution of gas. The solution of sarcine in boiling concentrated hydrochloric acid deposits on cooling colourless nacreous tabular crystals containing a considerable quantity of hydrochloric acid. The concentrated solution of these crystals mixed with bichloride of platinum deposits a yellow crystalline platinum-salt which dissolves readily in warm water sparingly in cold. The solution of sarcine in concentrated nitric acid deposits 011 standing transparent colourless crystals (apparently rhombic octo- hedrons) of nitrate of sarcine which when exposed to the air or moistened with water hecome white and opaqge but without alteration of form.The solution of sarcine in concentrated sul- phuric acid likewise deposits on standing or on addition of alcohol colourless needle-shaped crystals of sulphate of sarcine which crumble to a white powder on addition of water. Sarcine is therefore a weak base capable of uniting with acids and forming a platinum double salt; its salts are however in great part decomposed by water. When the solution of bydro- chlorate of sarcine is repeatedly evaporated to dryness over the water-bath a residue is at length obtained free from hydrochloric acid. Sarcine undergoes no alteration when treated with concen- trated acids at 100'; even when its solution is mixed with aqua regia and evaporated over the water-bath the residue consists mainly of unaltered sarcine.Sarcine like other weak bases unites with metallic oxides and salts not only with the oxides of the heavy metals but likewise with the alkalies and alkaline earths. Among all these compounds the silver-compound presents the greatest interest because it is ON A NEW BASE FXOM THE JUlCE OF FLESH. 123 best adapted for detecting the presence of sarcine and for preparing it in the pure state. An aqueous solution of sarcine forms with nitrate of silver n flocculent precipitate which does not dissolve on the addition of dilute nitric acid in the cold; to dissolve it completely the nitric acid must be tolerably strong and at the boiling heat.As the solution cools the greater part of the salt separates in colourless scaly crystals so that the filtrate scarcely yields any precipi- tate on addition of hydrochloric acid. The crystals consist of a compound of sarcine with nitrate of silver. A totally different compound is obtained by precipitating an ammoniacal solution of nitrate of silver with sarcine; the flocculent precipitate which is quite insoluble in water and ammonia dries up like alumina to a hard mass on exposure to the air. Sarcine is precipitated by basic acetate of lead but only on boiling; also by an ammoniacal solution of chloride of zinc by cadmium-salts by solution of mercuric oxide by corrosive subli- mate and many other metallic salts.By alkalies on the other hand even by baryta it is dissolved. From its solutions in alka- lies it is for the most part reprecipitated by a stream of carbonic acid gas. Its solution in baryta-water deposits on addition of a larger quantity of the baryta-solution transparent colourless crystals of sarcine-baryta. These properties of sarcine mould sufficiently show it to be a base even if its basic character were not decidedly established by the existence of definite compounds with acids and of a platinum double salt. The bases which it most resembles are cafeine and guanine ; in composition it likewise exhibits a certain aiialogy to that of these bodies. The analyses of sarcine and of its compounds lead to the follow- ing formuh :-a Sarcine .. . . . . . . C10H4N402 Hydroclilorate of sarcine . . . C1,H,N402 HC1 + 2Aq Chloroplatinate . . . . . . C,,H4N402 HC1 PtCl Sarcine with nitrate of silver . . CloH4N402 Ago NO Sarcine with oxide of silver . . C,,H2Ag,N4B2 + 2Aq Sarcine with baryta . . . . . C1,H2Ba2N4O2+ 4Aq Guanine CloH5N,02 differs from sarcine only by NH and resem-bles it closely in its combining relations. Caffeine C,6Hl,N,0, contains the same number of equivalents of nitrogen. 124 ON A NEW BASE FROM THE JUICE OF E’LESI-1. Sarcine is identical in composition with hypoxmthine the base which Scherer discovered in the spleen and traces of which he has since found in the blood. The two bodies likewise agree iri certain of their properties so that I might be disposed to regard them as identical were it not that Scherer’s compound in respect of its solubility in water and insolubility in acids differs from sarcine to an extent which can scarcely be accounted for by dif- ference of purity in the preparation.According to Scherer’s statement hyposanthine dissolves in warm nitric acid with evolu- tion of gas and yields on cooling a product of decomposition; and the liquid when evaporated to dryness leaves a yellow residue which assumes a red colour on addition of potash. Sarcine on the other hand dissolves in nitric acid without evolution of gas and the solution when evaporated over the water-bath leaves a colourless residue which does not become yellow till it is strongly heated; on addition of potash this residue assumes a red colour.This reaction however is exhibited by guanine and xanthine (Marcet’s xanthic oxide) as well as by the above-mentioned bodies. Xanthine might according to its composition C,,H,N404 be regarded as a compound of uric acid with sarcine Xanthine. Uric Acid. Sarcine. but its chemical relations as I have found by experiment do not accord with such a view of its composition. By mixing a solution of hydrochlorate of sarcine with urate of soda I have prepared the isomeric compound urute of sarcine. This compound is resolved into its constituents by the action of acids and in that respect is different from xanthine. Lastly I have discovered in human urine a body identical with sarcine or at all events iery closely resembling it. This body forms with nitrate and with oxide of silver compounds resembling those formed by sarciiie it may nevertheless be not sarcine but guanine-a point to be decided by the analysis which I am about to undertake. I have as yet used only beef‘ and horse-flesh for the preparation of sarcine and have obtained it in about equal quantity from both.

ISSN:1743-6893    

DOI:10.1039/QJ8581000121

出版商:RSC    

年代:1858

数据来源: RSC

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125 x1V.-Report on Recent Patents connected with the Reduction and Puri$cation of Iron and the Manufacture of Steel. BY F. A. ABEL DIRECTOR OF THE CHEMICAL ESTABLISHMENT OF THE WAR DEPARTMENT. THE progress made during the last two or three years in the manufacture of iron would appear from a cursory inspection of the patents published within that time to relate principally to the treatment of the metal after its elimination from the ore by the agency of the blast furnace the process of the reduction of iron from its ores having undergone apparently no very important modification since the introduction of the hot blast. Although the general truth of this may be admitted it is well known to all who have devoted themselves to a more minute examination into the details of iron manufacture that many of those actually engaged in directing operations with the blast-furnace have by a careful study of the relations between the pro- duct the temperature and blast the proportions of the materials employed &c.succeeded in regulating the working of the furnace to such an extent as on the one hand almost to ensureuniformity of product and on the other to raise very considerably the quantity of iron yielded by the furnace in a given time. It is also well known though less openly acknowledged that the iron-master has within the last few years succeeded in manu-facturing a marketahle iron from materials which in former times were either considered as useless or employed only in compara-tively small quantities.It is this circumstance which has led on more than one occasion to an outcry against the hot-blast pro-cess as having placed within the reach of the iron-master the power of increasing the quantity of his product from the blast- furnace at the expense of its quality. While therefore the efforts of the iron-master have raised the manufacture of iron in Great Britain to a marvellous height as regards actual quantity of metal produced (the annual amount of which is shown upon competent authority to equal the sum of that furnished by dl other iron-making countries) they have at the same time raised within the minds of those who watched these achievements with wonder and pride the fear that British iron is in danger of losing the general reputation which it has 126 ABEL REPORT ON PATENTS possessed for high quality; a fear in great degree nourished by the opportunity afforded in 1855 for an examination of the excellent results of the labours of foreign iron manufacturers.Abundant evidence has however been recently afforded that the quality of iron is a subject not likely to be neglected in England; it has for some time past occupied an unusual share of general public attention; it has been made the subject of ingeni- ous contrivance and scientific research; and at the present time some of our most extensive iron manufacturers are actively engaged in determining by extensive trials the merits of some of our more prominent schemes for its improvement. An attempt has been made in the present report to fulfil the desire of the Council of the Chemical Society to present its Fellows with an outline of the improvements in the various pro- cesses connected with the reduction and purification of iron or its conversion into steel which have been suggested or actually carried out within the last two or three years.In a report of this description it is impossible to enter into the consideration of im- provements in the construction of furnaces or of the appliances for iron manufacture excepting in so far as they are concerned in carrying out effectually the chemical principles involved in the various proposals which will have to be referred to. The difficulties necessarily experienced even with the best opportunities at command for collecting information in the endeavour to give some account of the actual improvements effected in iron-manufacture are very considerable ; emanating as they do on the one hand from the impossibility of obtaining trustworthy information as to the full extent to which the numerous proposals made public as patents have met with successful appli- cation; and on the other from the circumstance that many of the improvements in the ordinary method of iron smelting which furnish beneficial results to the iron-master by whom or in whose establishment they have been elaborated are not published to the world through the Patent Office or through any other channel That this should be the case cannot excite surprise; the iron trade like every other must have its secrets jealously guarded by their fortunate owners; moreover it must be remembered that any peculiarities in the treatment of the ore adopted by a parti-cular iron-master may have been called forth by the nature of the materials at his command the locality in which his works are situated or the class of product which he is most desirous of KET,ATING TO IRON-MANUFACTURE.manufacturing advantageously. Or possibly he may fear that the circumstances constituting to him an important improvement in the system of iron smelting would if publicly known tend to raise a prejudice against the iron which he sends into the market. Men of science and ingenuity have however not been wanting during the last few years who have made public and secured to themselves the claim to modifications in the present method of iron smelting by the blast-furnace or to new plans for reducing the metal from its ores.It is but natural that some of the patented prwesses relating to iron smelting should not be likely to lead to any beneficial results when put to practical tests; there are many however which embrace important principles and which though individually they may not all realise the san- guirre expectations of their proprietors are likely if classified and studied collectively to lead to substantial and general im-provements in iron smelting These remarks apply even with greater force to the verynumerous processes for partially or com-pletely refining iron with economy and success or for the manu- facture of steel or other varieties of iron which have been patented during the last two or three years.The circumstances that the processes of refining puddling and balling bear no pro- portion as regards their rapidity or the scale upon which they can be conducted to the process of iron smelting by hot blast and that with the greatly increased demand for wrought iron &c. the treatment of inferior qualities of pig-iron by the refining processes is frequently a matter of necessity have combined with numerous other considerations not only to set at work the inventive facul- ties of ingenious theorists but to rivet the attention of men thoroughly acquainted with the intricacies and the requirements of iron manufacture; and as the result of this it may be fairly asserted that the system of iron refining is at the present time in a state of transition and that a proper elaboration of the prin- ciples involved in some patented processes which have of late excited the serious attention of several of our most extensive iron manufacturers will in all probability result in most important improvements in the system adopted for the purification of iron.It will be difficult in this report to separate the coilsiderations relating to the reduction of iron from its ores from those which have reference to the purification of the metal or the production of particular descriptions of iron; as many of the patents to which 2'. 128 ABEL REPORT ON PA4TENTR it may be necessary to allude arc connected with more than one branch of iron manufacture such for example as those which relate to the application of particular agents at different stages of the manufacture or which propose methods for combining the smelting and refining processes.Any attempt at classification must therefore rather have reference to the principles involved in the various patented processes discussed than to the separate stages in the manufacture of iron. The most simple modifications proposed of late in connection with the smelting process relate 1'. To the construction of the blast-furnace ; To the application of the blast ; 3'. To the mixture of ores &c. with a view to ensure uniformity in the working of the furnaces; 4". To the preparation and state of division of the ore and its mixture with the fuel and flux; 5'.To the description of fuel employed in the blast-furnace. 6". To the economisation of the fuel employed. Of such modifications those included under the first four and the sixth classes which have been made public as patents within the last two or three years arc scarcely of such a nature as to rank as improvemcnts of high importance; neither can it be sup- posed that they fairly represent the general progress which has been made in the details of iron smelting. It will therefore suffice to mention as examples of these classes of patents That Mr. Charles Howard (1854) proposes to cleanse thoroughly and to granulate the ores to mix them in proper pro- portion with the fuel and flux in a divided condition and to convert the mixture into a suitable form for smelting by compression into cakes ; Sir Francis Knowles (1852) and Mr.C. Cowper (1853) have patented proposals for mixing rich ores with slags from copper- works; for the use of schist in admixture with similar ores; and for the employment of other minerals with ores of different classes in order to ensure uniformity of product from the blast-furnace; Mr. Crane (1854) proposes to employ additional blasts at some distance above those passing from the usual tuykres into the furnace ; Messrs. Lea and Hunt (1852) and Mr. Prideaux (1853) apply the gases obtained in the preparation of coke for the blast- RELATING TO IRON-MANUFACTURE. furnace as a source of heat in the puddling and other processes and Mr.Mickfe (1855) conducts tlic gases thus collected after their admixture with the air necessary for their combustion into the blast-furnace in which the smelting process has been carried on as usual with coke. Mr. Onions proposes to collect the waste gases from boiler fires and other soiirces in iron works for the same purpose. The proposals which relate to the description of fuel to be employed in the smelting process posscss considerable interest as they include patents for the application of peat in various forms and proposals for the employment of gaseous fuel for the reduction and treatment of iron. In Ireland there appear to exist immense deposits of clay- ironstone which are not worked or only to a very small extent on account of the scarcity of mineral fsel but which have been worked in former times in districts which were then covered with wood.Proposals have been heard of from time to time and even very recently for establishing extensive smelting works in Ireland in which peat-charcoal was to be employed as the fuel and I have had occasion to examine some very excellent specimens of pig-iron in the reduction of which Irish peat-charcoal had been employ ed. In Bohemia iron is profitably smelted with carbonisen peat and from the statements which have been publicly and privately made by Ah. Ommaney Mr. Dewar and others,it appears rea- sonable to expect that a similar result may be obtained in Ireland. Two recent patents may be referred to in order to point out the modes in which peat may be expected to be made available as fuel for the production of iron.The one taken out by Mr. R. McC all of Limerick (185S) relates firstly to the construction of a modification of the blast furnace with closed top and a lateral exit-pipe for the escape of the gases; and secondly to the use (for smelting refining and pu6dling) of peat either in its natural or in a cornpressed state or of a mixture of equal parts of peat and small anthracite coal compressed into cakes. He also proposes to work up the refuse turf or peat by forming it into pulp and then moulding it. The other patent to which I refer applies to the manufacture of iron with any description of fuel vegetable or mineral and appears particularly adapted to iron districts where the attainable fuel is rich iu mineral constituents.The patentee Dr. Gurlt of Prussia ABEL REPORT OK PA'l'ENTS (1856) proposes to effect the reduction and requisite csrbonisation of the ore entirely by the gases evolved from the fuel which is submitted to destructive distillation in gas generators immediately attached to the furnace. It is well known that id several of the iron districts in Germany the refining puddling arid welding processes are accomplished without allowing the metal to come into contact with the solid fuel; the coal wood or peat being in the first instance converted into gases in generators which either form part of the furnaces or are connected with them by conducting pipes.The so-called gas-furnaces wliich have been planned by Th om a Eck Bisc11 of and other experienced metallurgists diifer somewhat in their construction accorcling to their particular object or the descrip- tion of fuel with which they are to be worked; their principle may however be exemplified by a few words descriptive of Eck's gas-refinery furnace which is very simple of construction and has met with most successful application for some years past at the Government iron worlrs in Upper Silesia wliere 1 had an oppor-tunity of inspecting one in operation a short time ago. The general construction of the finery is that of a reverberatory furnace the fireplace of which is replaced by an oblong chamber nearly four feet wide and about six feet high and tapering slightly towards the top so as to facilitate the descent of the fuel which is introduced through a lateral opening in the upper part of this retort or gas generator.The air necessary for the production of the gas from the fuel placed in this chamber is supplied by a feeble blast and enters the generator from the two openings or tnykres of a long air-chest of iron plate fixed at the back of the chamber near the bottom. The spacc between the air-chest and the sole of the chambers serves as a receptacle for the slag aid ash from thc fuel. There is an opening Eelom the air-chest through which fire is introduced into the chamber when the furnace is set at work and which is then bricked up until at the expiration of &out fourteen days it becomes necessary to let the fire die out when the slag and ashes which have accumulated on the sole of the generator are removed through this opening.When a brisk fire has been kindled in the generator aid the lower opening closed up a moderate supply of air is admitted through the tuysre into the chamber which is filled with coal after a sufficient quantity has become thoroughly ignited. It is evident that the fuel is in this \ray made to fiwnish the maximum quautity of infiammablc gas undergoing destructive distil1atio;i as it gradually descends in the generator and furnishing carbonic oxide as the secondary pro-duct of the combustion of the coke or charcoal fiirniecl. As the gases rush towards the hearth of the furmce they meet with a supply of air passing from a series of tuykrea which enter from an air-chest into the top of the furnace just over the fire-bridge at an angle of 30°; the resulting flame being thrown upon the metal on the hearth in front of the bridge.Both air-chests communicate with an accumulator and the supply of air to the taykres admits of perfect regulation by means oi stopcocks. The pressure of air employed is about 4lbs. to the square iiich. When the charge of iron on the liearth is ascertained to be thoroughly fused a small quantity of. crushed limestone is thrown over its surface and two tuykres are then introduced into the furnace at an angle of 254 through mi opening on each side of the hearth riot far from the bridge; the width of the nozzle employed depends upon the power of the blast used.The air rnshing from these tuy&res,impinges with violence upon the iron and the two currents meeting an eclclying motion is imparted to the fused metal. In a short time the motion produced in the mass is considerable ; the supernatant slag is blown aside by the blast and the surface of iron thus exposed undergoes refinement while it changes continually the temperature of the whole mass being raised to n full white heat by the action of the air. The iron is also stirred occasionally in order to ensure a proper change in the metal exposed to the action of the blast. A shovelful of limestone is occasionally thrown in (the total quantity used being about I per cent. of.the crude iron employed). The duration of the treatment in this furnace after the fusion of the metal with a charge of about 40 cwt. varies from two and a half to five ~QU~S according to the product to be obtained. When the charge is to be withdrawn from the furnace the side tuykre nearest the tap-hole is removed so that the blast from the opposite tuykre may force the metal towards the hole. The flui6 iron as it flows from the tap-hole is fully white hot and perfectly limpid ; it chills however very rapidly and soon solidifies. The loss of metal during the treatment is said not to exceed 5 per cent. The extent to which the iron is purified by treatment in a furnace of this description may be discussed hereafter. The above brief description has been given to demonstrate the sim-a2 132 ABEI, HEPOIL'I' ON PATENT3 plicity of the arrangements the great facilities which they present for regulating the temperature and the oxidizing effects of the flame and the economy in fuel which must attcnd its employment in such a manner as that described.It must also be remembered that the fluid metal is not allowed to come in contact with the mineral constituents of the fuel. The arrangements proposed by Dr. Gurlt for the reduction of iron by gaseous fuel are based upon those above described. The roasted ore is reduced to fragments presenting a certain uniformity of size and placed .in a sloping cylindrical shaft or cupola the lower portion of which communicates with two such generators as that just described.The gases as they pass from these into the furnace are supplied with air just suficient to kindle them ; the ore is raised to a dull red heat and zt that temperature undergoes in the first instance reduction and then the requisite carbonisation by Cementation. The product gradually sinks into a cooler portion of the furnace below the openings of the generators and upon subsequent removal is subjected to fusion with the necessary flux in a simple modification of Eck's furnace provided with two gas-generators and blast appliances at the opposite ends of the hearth. Dr. Gurlt considers that the process of which the above is an outline will furnish products of a high degree of purity whatever be the description of fuel used and that the nature of the iron obtained may be regulated by the duration of the process of cementation in the first furnace and by the subsequent treatment in the smelting furnace.It is scarcely necessary to enumerate the advantages which he claims for his process such as the possibility of using any kind of fuel; the complete separation of the mineral constituents of the fuel from the metal; the more perfect carbon- ising action of gases upon the porous metallic mass obtained; the possibility of arresting this process of cementation at any point 80 as to regulate the nature of the product; the economisation of fuel; the ease with which large quantities of steel may be rapidly fused in his smelting furnace &c. It is to be hoped that these most important advantages the theoretical correctness of which cannot be disputed may eventually be fully confirmed by practice.The possibility of effecting the reduction of' iron and its purifi- cation or conversion into the particular description required by one continuous process is a problem which has engaged very considerable attention of late ; all exwninaticn ho~evcr,of the patented processes for attaining ahis object does not lead to the RELATING TO IRON-.MANUFACTffKE. conclusion that a process has as yet been elaborated which can compete successfully with the present system. The gexerd nature of' the plans suggested may be illustrated by the following examples :-Rdr. Augustus Bellford (183~)proposes tlie treatment of a mixture of ore carbon and flux in tubulated vessels and subse-quent fusion of the reduced metal in crucibles.Mr. W. E. N e IV t on (1855) places in a cementing oven alternate layers of coal and ore with flux if necessary arid maintains the furnace at a white heat for about 48 hours. The layers of ore will then be found to liave formed themselves into sheets by agglu-tiuation ; the metal which these COII tain is mechanically separated from dross and fused or welded for employment as spring steei. Mr. Rogers (March 1855) and Mr. Congreve (April 1855) both of Kew York have patented coiitrivaiices almost exactly alike for reducing and purifying iron ; which consist in placing the mixture of ore and coal in a revolving cylinder which is so constructed internally that the mixture is made to travel slowly along from end to end being esposed during that time to the heat requisite for the reduction of the metal.When the powder arrives at the further extremity of the cylinder it falls through a hopper on to the hearth of' a puddling furnace situated beneath the cylinder. Mr. J. 11. Johnson (1853) effects the deoxidation of the ore on successive tables placed one above another passing it gradually down to the hotter tables until it arrives upon the lowest whence it falls into a reverberatory furnace beneath. The ore on the tables is submitted to the action of the gases from this furnace and is subjected to additional heat from an nuxilkry stove or f11rnace. Mr. Mrtckay (1853) has patented tlic use of a reverberatory furnace with thrce hearths and with an arrangement for project-ing hot air on to the hearths.The ore and carbon are subjected in the first instancc to the waste heat from thc furnace and then gradually passed from hearth to hearth until the reduced and partially refined metal reaclics the hearth nearest the fire-place where it is submitted to the usual puddling process. The arrangements extensively adopted in various parts of the TLTnitcd States for the manufacture of wrought iron directly from the ore are far more simple in their nature than any of the pro- posals ahore alluded to; it must be borne in mind however that the only ores which are fonnd to be profitably worked arid to furnish products of a proper quality in this manner are tllc maqnetic aid sgecular ores and the purer description of hematites.'I\Tost of the American furnaces employed for the direct pro-duction of wrought iron are only slight modifications of the Catalrtii forge; they are worked with a blast of the nsual blast-furnace-pressure and which is fimequeiitly heated by the wade heat from the blooirzery-fire (as these forges are called). The fuel employed is cliarcoal and the method is acknowledged to be a wasteful one. In the various patented projects relating to iron-nianufacture already referred to in this report the points of novelty are all connectcd with the method of effecting the reduct,ion and purifi- cation of the metal by the usual agents-fuel in the solid or gsrseous form and air-with the addition of such mineral snb-stances as are generally employed as fluxes when necessary.It could scarcely be imagined that other well known and powerful chemical agents the efficacy of which for effecting the purification of iron is predicted by theory should escape trial or even appli-cation in that direction. Among such agents chlorine stands prominent and the proposals for the eiiiployment of that agent in one form or another have been correspondingly numerous. In 1851 Mr. Crace Calvert patented the use of chlorine chlorides liydrochloric acid and hypochlorites in connexion with iron smelting and the purification of coke. In his patent lie proposed to bring chlorine as a gas or a compound (chloride of sodium being preferred) in contact with the ore when roasted or with the niaterials in the blast furnace; the gas being passed into the furnace about ten feet from the top of the charge before the reduction of the metal takes place or the compounds of chlorine being thrown into the top of the fiirnace with the other materials.If a compound were used he considered that its base would also exert a purifying action tending to the removal of the sulphur and phosphorus from the metal. The idea of purifying or preparing the coke to be employed for iron-smelting by chlorine and bases has been acted upon with a slight modification by PulCr. Prideaux (1853) who in a patent already alluded to proposes to drench the glowing coke with lime- water containing either common salt or carbonate of soda or other similar salts.In the production of cast steel M. Fontaine of Paris (1855) RELATING TO mON-MANUFACTURX. has proposed to pass clilorine or hydrochloric acid over the surface of the metal or to treat it with a mixture of a chloride or hypo-chlorite of an earth or alkali iron-scale and binoxide of manganese. This treatment is to be carried on either in pots or in the puddling furnace. Mr. Martien of New Jersey (185G) has very recently taken out a patent for tbe employment of various materials for the purification of iron which are to be passed through the liquid metal ; and among these chlorine is specified. Mr. Tilghman of Philadelphia (1856) follow-s close in the footsteps of Mr. Calvert by proposirig to introduce powdered chloride of sodium together with the blast or by other convenient means into the lower part of the furnace.Various compositions of which clilode of sodium or chlorides form aii essential constituent have also becn patented for employ- ment as A~isesiii tlie mariufactuie of' steel and of malleable iron. Chloride of sodium appears also to be very iiequently used on the Coiitinent in the puddling ~nocess,and iu tlie manufacture of cast steel. A statement recently made by Mr. Keriyon Black- well in a paper read before the Society of' Arts to the eEect that chloride of sodium was much used under those circumstances at the Seraing Works in Belgium elicited the observation from Mr. David Mushet that his father had patented the use of chloride of sodium in the puddling process about thirty-three years ago.Binoxide of manganese is another agent included in many recent patents connected with the manufacture of iron and very frequently in association with chlorides. Mr. Broom an (1854) has patented a mixture of two-thirds chloride of sodium and one- third binoxide of manganese for purifying and softening steel ; and more recently (1856) another for the conversion of bar-iron into cast steel by a single melting and which contains binoxide of manganese chlorides of sodium and ammonium and ferrocyanidc of potassium. Mr. Leachman (1853) adds a mixture of binoxide of manganese chloride of sodium and calcined clay to iron during the boiling process. In several patented processes for the manufacture of steel the addition of small quantities of binoxide of manganese is also recommended.hfr. J. Crowlcy of ShefEeld (1855) produces malleable cast iron from charcoal pig-irou by melting it with a very small proportion of scrap-iron and a mixture of chloride of sodium binoxide of manganese carbonate of lime and charcoal. Although the employment of binoxide of manganese in small ABEL REPORT ON PATENTS quautities particularly iu the manufacture of steel has long been a practice frequently resorted to no very concordant opinioiis have been pronounced by authorities on iron as to the functions actually exercised l)y that substance. It has been fully denion- strated by analysis that t’hc quantity of combiiied carbon in iron reduced froni ores rich in niauganese is always considerable and that it is so in direct proportion to the amoinit of mangmesc which has entered into the constitution of the iron.It is also well known that iron of siicli a description is particularly adaptcd for the manufacture of natural steel. The Westphalian and Silesian irons may be quoted as examples. That the facility with which superior steel may be manufactured from rnanganiferouv iron is not occasioned by the retention of a portion of the man- ganese in the steel as an irnportant constituent is proved by the circumstance that the existence of that metal in the steel is demonstrated by analysis to be exceptional; and that steel (such as the Styrian) remarkable for its hardness and elasticity which has been obtained from ores very rich in manganese is not found to contain a trace of that metal.The most satisfactory explana- tion of the beneficial effect of manganese is afforded by the pro- tracted treatment to which it is found necessary to submit iron containing much of that metal in order to effect its proper de-carbonisation and the facility thus afforded for its more complete yuri ficat ion. It appears possible that the beneficial effects of binoxide of manganese when added to iron in the manufacture of steel or in the production of malleable iron mag also be due in some measure to tlic formation of carbide of manganese and tlie con- sequent more obstinate rcterition of a prtiou of tlic carbon in the iron. Other advantages may be ascribed to the greater fusibility of the slag produced vhen manganese is employed and also to a diminution under these circumstances of the destructive effect of the slag ~~pon the crucible or hearth during the operation of smelting and decarbonising.It is also stated that the presence of a small quantity of manganesc in the steel has the effect of improving the texture and colour and of imparting to it the property of welding readily to wrought iron. While referring to manganese in connexion with iron it may be meutionccl that some attempts appear to have been made within the last few years to examine into the influence exerted over the properties of iron by the presence of small quantities of other RELATING TO IRON-MANUFACTURE. metals and to ascertain whether iron may not be advantageously hardened or toughened or its properties in any other way modified by being alloyed with small quantities of such metals as zinc copper tin lead &c.Several proposals were made public not long since through various channels for the employment of copper nickel and zinc for increasing the tenacity of iron and thus improving its quality for such purposcs as the manuftcture of ordnance. These propos:tls appear however to have been the result of inference rather than of experiment ; the arguments in their favour being sought in stcch circumstances as the reported superior toughness of iron made from Franklinite ;the peculiar cliaracter of nieteoric iron; the existence of an appreciable amount of copper in the highly tenacious steel from Solingen &c.Messrs. T alab ot and St ir lin g appear however to have devoted some attention to the subject and have patented proposals in which the addition of small quantities of various metallic oxides (e.g. those of tin zinc barium calcium) to the iron is recom-mended for the purpose of modifying its properties in different ways. The method generally suggcsted for their application is to line the sole of the puddling furnace 01" the pig-moulds or chills with sawdust bitumen or tarry matter mixed up with a small quantity of the particular oxide and with oxide of iron. The uniform alloy is supposed to be formed in the subsequent treat-ment of the metal. Although it is not on record that these and similar proposals have led to any practical results there is little doubt that the influence of foreign metals upon iron will receive the serious attention of some of the metallurgists who are just now zealous in the cause of iron-manufacture and that results of intercst and importance may be expected from a farther prosecu- tion of such experiments as those instituted by Faraday and St o rt art some years ago with particular reference to steel.Attcntioii is naturally directed by the discussion of the subject of alloys to the successful results wliich appear to have attended experiments made with a view of producing steel or other specific varietics of iron by the veqr simple process of mixing together in proper proportions iron-varieties of different composition.Several patents have been published within these last two years for the preparation of mixtures of this kind thus Mr. Bessemer (1855) in two patents relating to the melting of steel and its manufacture by cementation claims the production of a mixture ABEL REPORT ON PATENTS of cast iron and steel prepared by adding together the two liquid materials or by immersing the solid steel in tlie fused cast iron. The products are susceptible of' annealing or hardening like steel. Dr. Price and Mr. Nicholson (1855) have found that il very superior de3cription of metal is produced by mixing grey pig-i-iron with the so-called finery-metal which though it still retairis nearly the wlde of the carbon originally contained in the iron is comparatively free from silicium mid has also parted with a certain proportion of its other impurities.Tho product tiins obtained containing as it does a considerable portion of the carbon in 8 combined state bears great rwernblance to the description of iroii manufactured for ordnance at all the Contiaetita! gun fouiidries by careful mixture of pig-irou with partly refined prodrrcts arid subsequent protracted treatment in the reverberztory furnace. Messrs. Price and Kicholson (1855) havc besides sccurcd a patent for the manufacture of steel of excelhit quality by melting together finery-metal and wrought iron. Nr. G. 13row n (1856) also proposes to make steel by a mixture of metals but employs charcoal-pig-iron and wrought iron made from the same material.Ah. hfanevy (1856) prepares cast steel by fusing together white cast iron and malleable iron both previously reduced to small fragments and with the addition of the oxides of iron and OC calcium potassium or sodium in some form. There car1 be no doubt that provided the necessary precautions be taken to ensure the uniformity of the materials employed the production of cast steel by the simple mixture of iron-varieties of a known compo-sition should possess considerable advantages over tlie process of decarbonisat'1011. Before proceeding fiirther with the examination of the recent improvements in the manufacture of steel it is advisable to com- plete the review of the patented proposals relating to modifications of the ordinary methods of refining and puddling.Mr. Kenyon Blackwell in his paper on the manufacture of iron already referred to alludes to the difficulty experienced in tlie treatment of grey iron in the puddlingfurnace on account of its fluidity and the tenacity with which it retains its carbon; and in pointing out the great loss of iron sustained by the iiitermediate treatment in the coke-finery which it is necessary to adopt suggests that the partial decarboriization of the metal might be far more economically effected by its treatment in a small blast- furnace similar to the cupola used for remelting with the addition perhaps of minerals consisting of nearly pure oxides of iron. That some such treatment has occasionally been adopted is shown in a subsequent communication from Mr.D. Mushet who states that his father patented in 1817 the use of the cupola for re-melting and partially refining iron and employed the method in Staffordshire and Wales. l’he adoption of a siniilrtr treatment is also referred to in one or two comparatively recent patents con-nected with rcfining. Xr. D. hlushet moreover claims for his father the first patent for employing hzematite in the refining or puddling of grey iron cz method of treatment which is also brought forward in several forms in recent patents. It has been noticed in connexiori with Rlr. Calvert’s patent that importance is sometimes attached to the effects of the metals of the alkalies and earths as agents for the removal of such im-purities as sulphur and phosphorus from iron.Various proposals have been patented within the last two years for the employment of alkalies and similar agents as fluxes. Mr. Hampton (1855) slakes quick-lime with the solution of an alkali or alkaline salt and employs it in the refining and puddling furnaces. MM. Du Motay and Fontaine (1856) purify and decarbonise iron in the refining and puddling furnace by the employment of fluxes pre- pared from the scoriz of the puddling furnace from oxides of iron and silicates or carbonates of alkalies or other bases. Mr. Pope (1856) proposes to add the residue obtained by the distilla.. tion of Boghead or Torbane mineral to such fuel as is employed in the refining of iron and also includes the use of spent oxide of mangariese in his patent.Mr. Sanderson of Sheffield (1855) employs for the refining of iron such substances as sulphate 04 iron capable of disengaging oxygen or other elements -which will act upon the silicium aluminium &c. contained iri the metal. The specification of the objects of the latter patent leads me to the consideration of a patent granted to Mr. J. Nasmyth in 1854 for an improvemeiit in the puddling process which is parti-cularly worthy of notice as being the first application of the principle upon which several interesting patents connected with iron-refining are based to which I shall shortly refer. The patent claims the treatment of iron with a current of steam which being introduced into the lower part of the iron in the puddling furnace passes upwards and meeting with the highly heated metal undergoes decomposition both elements actiiig as purifying 140 ABEL REPORT ON PATENTS agents.The steam employed is at a pressure of about five pounds per square inch and passes into the metal through a species of' hollow rabble the workman moving this about in the fused metal until the mass hegins to thicken which occurs in from five to eight minutes after the introductiori of the steam; the steam-pipe is then removed and the puddling finished as usual. The advantages claimed consist in the time saved in each heat or puddling opera- tion (from ten to fifteen minutes) ; tlic very effective purificatioii of the metal and the possil>ility of treating highly carboriised pig-iron at once in the pucldhg furnace the prclirninwy rdiiiiiig being thus avoided.It is said that this ivetlioil of treatmcnt after haring been used with great advantage for two years at the Bolton Iron Works is gradually extending itself to other large manufactorics. Another though less striking application of water in refining iron is rnadc by Ah. W. Taylor (1855),who after puddling the metal until it is pasty runs it into water ; the spngy mass thus produced is ground by rollers separated into powders of different degrees of fineness by sifting and melted. The portion of metal oxidised by this treatment is to serve as the final purifying agent. The quality of the product varies with the fineness of the powder. Mr. Martien of New Jersey (1855) proposes to use a very similar mode of treatment for the conversioii of ore reduced to spongy metal into steel.The water into which he throws the heated mass contains in sdution saline matters such as chloride of sodium borax soda &c. The principle of employing oxides of iron 8s ageuts for decar- bonking the metal sufficiently to produce steel has recently oceu-. pied the attention. of several metallnrgists. One or two patents involving its application have alreacly been published ; other modifications are in couwe of elaboration; and it is considered likely by competent authorities to receive in some form or other ex ten sive application. In 183-1Slr. St ir3iag proposed to produce cast steel by adding to fused mst iron n qmiitity of the oxides or carbonates of iron the operation being pd'ctrmed in crucibles or reverberatory furnaces and heiiig repeated with successive quantities of the ore until the proper description of steel had been produced.From five to seven per cent. of the oxides were to be employed in the first melting and smaller quantities in successive operations ; manganiferous ores were to be selected in preference to others and exceedingly sruail quantities of other oxides might be added together with the ore such as those of zinc or tin for strengthen-ing tougliening or hardening the nieta!. It will be observed at oncc that this process differs only in its details from that more recently patented by Captain Uchatius of the Austrian Service (1855),which attracted considerable attention last autumn mlien a successful cxperimerit mas made Kith it at the works of Messrs.Rennie. The irnporhnt point in the process of Captain U c h a tius is the great acceleration of the decarbonising effect of oxide of iron upon the pig-metal by exposing as large a surface as possible to contact with the ore employed. The metal is thus converted into steel in one operation and with considerable rapidity. The mode of proceeding is to granulate the iron by running the fused metal into water aud beating it with a broom. The globular particles thus obtained are mixed with about 20 per cent. of roasted spathose ore and 4 per cent. of fire clay and subjected to the heat of a steel-furnace. The employment of oxide of manganese is not specified; a certain proportion is hom-ever generally added.The granules of iron are partially decar- bonised and melted and a portion of iron from the ore is also reduced; the increase of yield upon the metal employed amount- ing generally to about 6 per cent. The granules are sorted in the first instance as the finer particles produce a softer steel. The addition of a small quantity of wrought iron in fragments is re-commended for the production of soft welding cast steel and harder products are obtained by adding various proportions of charcoal to the mixture. The average time necessary for the conversion of such a quantity of iron as was operated upon at the works of Messrs. Rennie (24 Ibs.) is said to be about two hours. It is specified that the best description of pig-iron should be employed and the experiments appear to have always been made with East India pig-iron; but it is believed by the patentee that numerous descriptions of ordinary English pig- metal may be con-verted without difficulty.The results obtained by Captain Uchatius appear to have been even surpassed by a modification of his process in which partially refilled iron is employed. Improvements in the conversion of wrought iron into steel by €usion or cementation have also been made the subject of several recent patents. In one or two processes (e.g. for the nmnufacture of cast steel by Mr. Brooman and for the production of steel direct fmm the me by Mr. Newton,) cyanogen is proposed as an 142 ABET, REPORT ON PATF:N'I'8 agent for carbonising; it is either employed in the form of a cyanogen-compound (ferrocyanide of potassium) in a flux or its production during the cementation process is effected by the presence of an alkali and animal matter in the cementing oven.31. Boullet of St. Denis (185li) proposzs to use a cementing compound consisting of glucose or other saccharine matter ;horn shavings dried blood or other descriptions of animal matter and wood-charcoal. As an improvement on the ordinary cementation-p~occss RIr. Lucas of Sheffield (1854) has patented a method for the convey- sioii of bar-iron into steel in the presence of iron ore which shall at the same time become converted into steel. Tlie ore is mixed with animal- or vegetable-charcoal and a small quantity of binoxide of manganese ; alternate layers of this mixture iron fragments and charcoal are piled in the converting furriace.When the con- version of thc iron into steel is effected the reduced orc is melted and furnishes cast steel. In 1855 Mr. Bessemer obtained three patents for the niann- facture of steel. Tlie first two which have already been alluded to as including the preparation and treatment of mixtures of steel and cast iron relate to particular arrangements for carrying on continuously the cementation process by alloving the cut bar graiiulated pnddle-iron or other refined metal and charcoal eithcr to travel gradually along a horizontal heated cylinder (which is divided into chambers by plates linked together and moved slowly along by a winding apparatus) ;or to dcsceiid gra-rlually in a vertical cylinder or retort which is charged with material from above.Various irriprovements in the arrangement and construction of the furiiaces and crucibles are included in these patents. The third patent dated October 3 855 relates to the treatment of iron €or its conversion into steel upon the principle applied by Mr. Nasmyth to the puddling process in May 1854. The system proposed is as follows :-The liquid iron to be converted is taken from a comnion finery or cupola-furnace and filled into skittle-pots provided with tap-holes at the bottom and arranged in a suitable furnace. A pipe passes through a hole in the cover nearly to the bottom of the crucible and is connected with a larger pipe over the furnace into which highly heated air alone or air and steam or steam alone also highly heated is forced under a pressure exceeding that of a column of metal equal to RELATING TO IRON-MANUFACTURE.the depth of fluid iron in the pots. Thus the air or steam is made to pass up throngii thc liquid metal and to effect its purifi- cation When the latter becomcs pasty or has been treated to the requisite extent its temperature is raised so as to render it sufficiently fluid for casting. It is observed in the specification that the iron is liable to becoaie pasty by treatment mith steam which may be avoidzd by properly maintaining the heat in the pot-furnace; but that it is found advisable to use steam only at; an early stage of the ~PQCCSS,and to conclude the treatment with air which readily maintains tfic iron in a liquid condition and also rapidly raises its temperature when it has become much lowered by the trcatment with steam.In the specification of this patent Mi*. Be s s em er intimates his kncwledge of Mr. Nasmyth’s prucess for yudclling with steam and of a patent taken out by Mr. Martien of New Jersey earlier in 1855 for effecting the partial purification of iron by causing air or steam to pass up through the liquid metal as it flows along gutters from the tap-hole of the blast-furnace or finery-forge but especially from the former. By this treatment no more than the partial purification of the metal is attempted and Mr. B e s sem er therefore lays claim in the above patent to the conver- sion of crude iron into malleable metal or steel by the treatment with air and steam in tLe manner described.This patent of Mi. Bessemer’s is followed by two others (in December 1855 and July 1856),in which the treatment of iron by air and steam is carried out in various mays and which are in a manner preparatory to the patent for the refining of iron without fuel on the subject of which a paper was read by Mr. Bessemer at the British Association last year and which for some time excited the general attention of the ironmanufacturers and the p uhlic. In the first of these patents it is prclposed to refine the iron by passing air or steam into the liquid metal which has been trans- ferred from the blast-furnace to a species of ladle on trunions and then to submit the product to further treatment with air on the hearth of the puddling furnace or in long retorts.Or the metal is treated with steam or air in a large crucible enclosed in a circular re\-erberatory furnace. A clay pipe serves to conduct the steam or air to the bottom of the crucible. It is again ob-served that steam should only be used at the commencement of the operation and that if the metal becomes pasty the heat of the furnace should be raised prior to tapping. Tlic patent iidudes a proposal for recarbonising iron in this crucible by raising the heat of the metal in the first instance by the injection of air or steam and by then forcing carbonaceous gases or solid carbonaceous matter into the iron through the same channel.The second patent is for the exposure of liquid iron in a finely divided condition to the action of n current of air. One method proposed for effecting this is to have two cupo1as so arranged that they may be alternately lifted and deprcssed. Both being charged with highly heated fuel and the one containing a ciuan-tity of fluid metal; they are so arranged that the latter may be run from the tap-hole into the top of the second cupola. As the iron descends in a shower through the fuel in this cupola it meets with a powerful current of air passing upwards. W'hen the whole of the iron has been run out from the up1m cupola the relative position of the two furnaces is changed and the metal is poured back upon the fuel in the first cupola which is now lowest and through which a blast is also passing.This operation is repeated until the metal has been snificiently refined. Or the iron is fused in a furnace which may be provided with internal projections and which is made to revolve on horizontal axes so that the metal when fluid may be raised by the projections or by centrifugal force and allowed to fall upon the heated fuel through which air circulates. The axes are hollow a blast being admitted through the lower while the upper one provides for the escape of the products of combustion. It is stated that coke may be used as the fuel and that if the object is to obtain steel an addition of from 1 to 2 per cent. of binoside of manganese and a similar proportion of chloride of sodium should be made to the metal.Immediately upon the above patents followed the proposal of Mr. Bessemer to produce steel and malleable iron from the crude metal without the uee of fuel to the details of which it is scarcely necessary to allude as the process in question has not only been very fully discussed in public but also witnessed by a great number of persons interested in iron manufacture. It will be sullicient to bear in mind that a suitable vessel proriided near the bottom with several tuykres in connection with a blast-cylinder capable of compressing air to about eight or ten pounds to the square inch is placed in the immediate vicinity of a cupola or blast-furnace so that the liquid metal may at once run into it.The vessel which is closed at the top is provided with lateral RELATING TO IRON MANUFACTURE. openings to be used for the introduction of the metal and the removal of the product. The blast having been turned on into the furnace or converting vessel the fluid metal is allowed to run in. The iron is at once violently agitated and a considerable number of sparks issue from the furmace accompanied by a small carbonic oxide-flame. When this operation has been carried on for about fifteen minutes the temperature of the metal gradually increasing the action of the air appears to become more intense; the metal rises considerably above its actual level; the heat ia raised to full n-hiteness and a frothy slag is thrown off from the siirface in considerable quantities.In a few minutes the size of the flame issuing from the furnace increases considerably and it is steadily maintained for about ten minutes when it rapidly diminishes and the process is then considered complete. Upon tapping the furnace the metal runs freely and is perfectly white hot but it chills very rapidly and from the number of cavities generally observed in the masses cast it appears to solidify before the air-bubbles carried into the metal as it pours inti the mould have time to rise to the surface. Mr. Bessemer claims the production by this operation of pure homogeneous malleable iron and also the preparation cf hard or soft steel and of a particular product called semi-steel by arresting the operation at certain periods indicated successively by the phenomena above alluded to.In discussing the theory of these processes in his paper read to the British Association Mr. Bessemer considers that during the first part of the treatment the oxygen of the air combines with the graphite in the iron producing carbonic acid thus rais- ing the temperature considerably Subsequently when the metd has become very highly heated and the flame is observed to increase the combined carbon undergoes oxidation. At this stage of the process as the quantity of carbon present is but small a portion of the iron is stated to undergo oxidation being imme- diately fused and disseminated through the metal upon which it acts as a powerful solvent of the silica and earthy bases.The sulphur and other volatile matters are also supposed to be oxidised and removed at this period. The iron is stated to undergo com- plete purification by this treatment while the loss of metal during the operation is considered to be about 10 per cent. below that usually sustained in its purification. Before examining into the extent to which the views of Mr. L ABET, SEPORT ON PATENTS Bessemer have been borne out by practice it is necessary to state that the patent last alluded to was followed shortly afterwards by another providing for the adaptation of the process just described to the furnaces used for smelting re-melting and refining iron. Another form of converting vessel was also pro- posed for ensuring the contact of thn air with a larger surface of metal previous to its escape.In order to obviate the injurious effect upon the malleability of' the prodnct which the presence of any oxide of iron mould exert it was proposed to treat the refined metal with some form of carbonaceous matter or to add the latter towards the completion of the refining process. Treatment with carburetted hydrogen or carbonic oxide ; the introduction of a pole into tlie liquid metal; or the addition of charcoal anthracite or carbonate of iron are the methods specified. It has already been stated that Mr. Bessemer does not stand alone in proposing the purification of iron by treatment with steam or air. Tlic patelit of Mr. Martien for passing air and steam througb fluid iron has alrertcly been noticed.A subsequent patent by the same gentleman inclndes the application of other purifying agents together with tlie air and steam ; such as chlorine hydrogen and coal-g,zs. Oxides of manganese and zinc are pro-posed bp him to he blown into tile iron to assist in the removal of the silicium ; spathose ore is to bc similarly applied to assist in decarlloriising the iron ; and a small quantitj- of clay to facilitate the working of the nictal. Mr. John Birch of Bradford patented in June 1855 pro-posals for refining crude iron immediately upoil its removal from the blast-furnace in a molten state by allowing it to flow into an improved refinery-furnace adjoining ; and for smelting and refin-ing iron in one oper'atioii by the ernploymelit of what he terms reducing and osidising tuybes in connection with a peculiarly constructed blast-furnace so arranged that the metal as it is reduced collects in a deep hearth and is them at once submitted to the refining action of the air from the osidising tnykre.The employment of steam in admixlure with cold blast in the smelting furnace and finery-forge was made the subject of a patent by Messrs. hrmitage and Lee of Leed? in October 1856 and in Augirst a pateiit was taken out by XIr. G. Parry furnace manager at the Ebbw Vale works for the purification of iron by means of highly heated stearn. l'he fluid iron is allowed to rim into a reverberatory furnace previously heated and the steam is either made to iiqinge upon it from several tuygres or to pass through the metal.Steel is to be obtained by treating highly carburetted iron with the steam and then either running it into water and fusing it with the addition of purifying agents or adding to it iii the furnace a sniall quantity of clay and after-wards about 10 or 15 per cent. of calcined spathose ore. It would be quite out of place in this report to enter into any discussion with reference to the respective claims to originality of the different patentees who propose the partial or complete purifi- cation of iron and the production of steel by the passage of air and steam through the metal ; but it will be generally admitted that to Mr. Bessemer the credit is due of first directing the attention of iron manufacturers and the scientific world prominently to this mode of treatment and of amakirig a spirit of niorc scruti- nizing inquiry than had before existed into the extent to which iron is purified by being subjected to the action of air or steam.The announcement so convincingly demonstrated by experiment on a large scale that the heat evolved hp the action of air upon iron when once liquid was sufficiently intense not only to main- tain the fluidity of the metal but to raise it to a heat attained only in the most porvcrfiil filriiaces,-so that the purifying action of oxygen in the gaseous state was promoted to the fullest extent -was received with general astonishmerit and by the chemist with wonder that a fact so self-evident should furnish such im- portant results as those described bp 3Ir.Bessemer in his paper and yet so long have escaped application. The simplicity of the process the positive statements made by Mr. Bessem er in support of his arguments for proving that the purification of the metal must be complete and his very attractive assertions with respect to the econoniy of liis process ; all combined to raise to the highest the general expectations of the important results to he attained by its adoption in iron-manufacture. It need scarcely be stated that these expectations have not yet been realised and that the ultimate product which &Ir.Re ssern er obtains by the pmcess just now described has been found to differ in sonie very material respects from the malleable iron obtained by the old puddling process.Both the economy and efficacy of Mr. Be s sem er's method for purifying iron have been contested by the publication of facts resulting from experiments with the process and the product and from chemical investigation. L2 AJIEL REPORT ON PATENTS I will not attempt to enter into any discussion of the technical objections raised against the adoption of such a process as that of Mr. Bessemer’s as a good method for obtaining malleable iron but will confine myself to a few remarks bearing upon the chemical questions involved in the proposed system of refining some of which I venture to offer vith considerable hesitation as the results of limited observation and experiment. It has been amply demonstrated that the constituent of cast iron which may be regarded as generally exercising the greatest influence over its quality namely the silicium is also that which may be most readily and completely abstracted from the metal by its subjection to oxidising influence.Those specimens of iron refined by Mr. Bessemer’s process which hare been chemically examined were found perfectly free from silicium. Iron which has been subjected to a less searching treatment with oxygen in the Siiesian gas-finery furnace of Eck has been found to be almost perfectly freed from silicium and the pig-iron generally operated upon in these furnaces contains from 45 to 5 per cent. of that constituent. The patents of Messrs. Price and Nicholson which have been referred to are based upon the observation that the product ofthe ordinary finery obtained from iron of moderate quality contains only a very small portion of silicium.The statements of these gentlemen that the actual amount of carbon. existing in finery-metal differs little from that originally contained in the pig-iron substantiates similar observations made by me with reference to products of the refining process. It may therefore be considered as very probable that no appreciable amount of carbon is oxidised upon treatment of pig-iron by such a process as that of Mr. Bessemer until as a first effect of the high temperature the graphite has become con- verted into a carbide of iron; and that during the interval which elapses before the carbide undergoes decomposition the silicium is almoot or entirely osidised.It will be generally admitted that among the elements in the pig-iron with which the oxygen meets at a high temperature the iron itself will be one of the first to undergo oxidation and that the increase of temperature resulting from the contact of air with the fluid metal is in the first instance almost entirely due to this oxidation of iron which will be partially checked for a time when the temperature is sufficiently high to favour the oxidation of the combined carbon. RELATING TO IRON MANUFACTURE. The compounds formed by sulphur and phosphorus in iron appear to be far less easy of decomposition than would have been imagined h priori. From an examination of the finery metal from the English or Silesian furnace it appears that at the period when the carbon begins to undergo oxidation the sulphur and phos- phorus remain almost untouched ; the analyses of several speci- mens of Mr.Bessemer’s ultimate product have shown moreover that these elements as they exist in the metal have not undergone oxidation to any important extent even when the carbon has been almost entirely removed; although the action of the air is assisted as Mr. Bessemer describes by the oxide of iron produced during the treatment which becomes to a certain extent mixed up with the agitated metal.* The important obstacle to the successful purification of iron by subjection to treatment with air even in the most complete manner evidently consists in the difficulty of effecting the decom- position of the compounds of sulphur and phosphorus to a suffi-cient extent ; or perhaps still more in the impossibility of removing their oxides when produced from the reducing influence of the highly-heated metal.There is some reason to believe that the effect of nascent hydro- gen from steam upon the sulphur and phosphorus in iron is more energetic than that of oxygen from air; but the use of steam appears as might have been expected to have the effect of cooling the metal rapidly to such an extent as to dimiuish its fluidity; hence M r. B e ss e m e r’s reason for only recommending its applica-tion at the outset of the process. It is stated however that Mr. Parry has by the use of highly-heated steam recently obtained very successful results.The phenomena observed on the treatment of iron by Mr. Bessemer’s plan added to the inferences drawn from the facts above alluded to would appear to lead to the following explanation of the effects successively produced by the passage of air through the liquid metal In the first instance a portion of the iron undergoes oxidation it 1 am unaware whether Mr. Bessemer ever caused the amounts of sulphur and phosphorus to be determined in metal before and after treatment ; the specimens of his products which I have examined contained from 0.4 to 0.5 per cent. of phos- phorus and from 0.05 to 0.06 per cent. of sulphur. These specimens were stated to have been preparedf rom Bloenavon iron in which the percentage of phosphorus has been found to be about 0.5 and the sulphur 0.06.I have been informed that similar results have been obtained by obher chemists. ABEL ICEPOET ON PATENTS the temperature of the mass beiiig thereby very considerably raised. At the same time the conversion OF the graphite into carbide of iron gradually takes place while the siliciuin undergoes oxidation and contributes to the formation of slag. When the scintillations are observed to diminish in quantity while a steady flame makes its appearance aiid the actiovi becomes more tumultuous the decomposition of the carbide of' iron coimneiices ; the oxidation of the iron still contiiiuiiig lio~i-evei* diiriug the production of the carbonic oxide. Wheii the flame ceases to appear the purifying functions of the air seem to have attained their limits; but the sulphur and phosphorus still remain iii the mctnl in hut slightly diminished quantities.If tlicrcfbre the original proportion of these elements in the iron operated upon are incoiisiderable thc product niag exhibit most of the attrihutes of the best malleable iron; but if the percentage of sulphur or phospliorus in the crude metal be at all considerable the iiiflueiice exerted by these substanccs over the properties of iron must bc cshibited in the product even iri ail exaggerated degree. Without eiitering into the question 01' ec'oiioiriy with reference to sucli a niode of treatment as tliat proposed by Mr. Bessemer it is evident that urile.ss means are uitimately devised in con riectioii with it for promoting the removal to il considerable esteiit at any rate of the sulphur and pliosphorus from the iron it cannot com- pete as regards the quality of the product with the old puddling process; in which the decomposition of the sulphur and phos- phorus compounds in the iron and the rerrioval of these elements from the metal is mainly effected by prolonged contact of the latter with the osidiuing slag.The tedious mid laborious iiaturc of tlie puddling process and the circumstance that the skill and indwtry of the operator deter- mine in great measure the quality of the product are alone reasons sufficiently powerful to induce all interested in the maiiu- facture of iron to cherish the hope that the unceasing attention and study which Mr.13es sem er aiid many other metallurgists are at the present time devoting to the subject of iron refining may result in the elaboration of a process really capable of fulfilling the high expectations entertained in the first ~~~ti~nce, of the system of treatment which associated with tlie rianie of' Mr. Bessemer enjoyed for a brief' period so 1arg.e it share of' popularity; but wliich must undergo some vital modifications ere it can ofl'er a pyospcc*t of lncttlising thr prophwy of 311.. Kasmyth that a new- RELATIXG '10 I RON XAB UFACTURE. era would be established by it in R most important branch of our manufactures. In the course of the discussion which followed the reading of Mr. Abel's paper Mr. P. J. Worsley said that Dr.Gurlt's patent contemplated rather making steel and the higher classes of iron than competing with our present manufacture of cheap iron although it would seem from all calculations that this process would be very eco- nomical both of fuel and of labour to say nothing of the power it gives of using any fuel whatever with little risk to the iron. The division of Dr. Gurlt's patent into two processes corre-sponding to the upper ard lower parts of' the high fxirnaces gives the power of performing each conipletely 1% ithout unnecessary heat; a very great advantage as too high a heat injures the quality; the tendency of hot blast being to give a coarsegained iron full of large crystals of graphite from the quarter carburet being decomposed by an exccssive temperature into the one-eighth carburet and carbon beside favouring the absorption of silicium.The furnace in which Dr. Gurlt proposes to melt the carbonised ore diff'errj f'rom common reverberatory furnaces in having means to control the atmosphere of the furnace by regulating the .supply of wind so that this furnace is in fact a gigantic blow-pipe with its oxidisirig and rcducing flames and with what will be still more useful its neutral flame. With this Dr Gurlt hopes to melt steel in quantity without altering its quality and thus be able to cast large pieces of the same metal an object never hitherto attained. Ah. John Taylor observed- The process proposed by Mr. B e sse m e r for the conversion of cast into wrought iron having been noticed by the Society in connectiors with the subject of the paper now read and I having witnessed that process at the Dowlais Iron Works may perhaps be permitted to observe that the general result obtained at those works was that it was quite iiripossible to make malleable iron from the same description of pig iron that is usually employed for the manufacture of rails.It is doubtless well known to the great majority of the mem-bers present that iron as it runs from the furnace may be roughly divided into two kinds-one in which nearly if not the whole of ABEL REPOIZT ON PATENTS &C. the carbon is in chemical combination with the iron forming rc white brittle iron and which by proper treatment is readily con- verted into malleable iron.This species is known by the name of white forge pig. The other species of iron is termed grey foundry pig; in it the carbon exists not only chemically combined with the iron but also diffused mechanically through the mass in a more or less crystalline state this species is almost wholly employed by the founder. It is however to be observed that between these two varieties which I take as the two extremes of the scale there are numerous sub-species varring in their relative proportions of combined and uiicombined carbon their purity their crgst alline texture and other particulars all of which possess peculiar com- mercial values and are known to the trade under certain technical designtit’ions. It was found at the Domlais works that when grey foundry iron was submitted to Mr.Bessemer’s process in a cupel made after his plan and air blown into it at a pressure of about 7Ibs. on the square inch a pig of malleable iron was obtained which possessed all the characters that have been assigned by Mr. Bessemer to the iron manufactured by his plan ;but when white forge pig the same iron from which rails were then being made was the subject of experiment the pig on being transferred to the rollers broke into several pieces; nor could any of thesc by any treatment whatever even when gently and carefully hammered on the anvil be brought into the malleable state. In fact as expressed by one of the overseers it crumbled like sand. The experiments were conducted by Mr. Riley the chemist to thc works and on one or more occasions in the presence of Mr.Bessemer. In an economical point of view it cannot therefore be said that the process has succeeded at least at present as the greater price of grey foundry iron over wliite forge pig would pre- clude malleable iron made from the former even by the more rapid process of Mr. B e sse mer from competing in the market with iron made in the ordinary way from white forge pig. In reference to the phosphorus and sulphur contained in iron X believe I am not violating any confidence if I say that Mr. Ri 1e y informed me from analyses made by him that these substances are riot removed from the iron made by Mr. Rcssemer. There can be also I think no doubt that the great source of heat in the Bessemer cupel is due to the combustion of the iron itself The colour and appearance of the flame together with the ON THE JUICE OF BEEF.large proportion of scoria aud its richness in oxide of iron together with the relatively smaller amount of iron confirms this view. I have the honor of laying before the Society some specimens illustrative of the different stages of iron-making as proposed by Mr. Bessemer a process which has at least the merit of ingenuity and may at some future time lead to greater results.

ISSN:1743-6893    

DOI:10.1039/QJ8581000125

出版商:RSC    

年代:1858

数据来源: RSC

摘要:

ON THE JUICE OF BEEF. XV.-On the Jaice of Beef. By CHARLESL. BLOXAM PROFESSOR OF PRACTICAL CHE3lXSTRY AT KING'S COLLEGE. THEfollowing paper contains an account of an examination of the juice of beef originally nndertakeii with the intention of preparing a specimen of flesh lactic acid. 1. 30 lbs. of roiznd of beef purchased in the market and of excellent quality were freed from external fat chopped very fine in a sausage-machine and stirred up with 3 gallons of cold distilled water ;after standing for an hour or two the mixture was strained and the meat well sqneezed in linen bags. The mass was then again stirred up with 2 gallons of cold water and after being squeezed the operation was repeated a third time with 3 gallons the last portions of liquid being finally squcezed out of the fibre by a powerful press.2. The 8 gallons of infusion of beef were then plwed in jugs which were heated in a water-bath till a small portion having been filtered was found to remain clear when boiled. The coagu- lated albumen was separated by a linen strainer and the clear solution was mixed in tall jars with baryta-water till it had an alkaline reaction to turmeric papm ;the precipitated phosphate of baryta was allowed to subside the clear liquid drawn off as far as possible with a syphon and filtered. The filtered solution was evaporated to about 2 quarts on a water-bath and again filtered through a hot-water funnel (for through an ordinary filter the filtration was extremely slow). It was then further evaporated on the water-bath to a syrup which was kept for some hours at 90°F.and then set aside for four days. It had then becoive a semisolid mass of crystals of kreatine which were purified in the usual manner. In this way 127 grs. of pure kreatiue mere obtained and by boiling the amorphous powder 154 BLOXAM ON obtained in the purification of the above crystals with their mother liquor and a little animal charcoal upwards of 70 grs. more kreatine were extracted giving a total amount of 197 grs. from 30 lbs. of beef. Liebig's estimate of 0.697 gr. from 1000 of ox-flesh would give 160.5 grs. from 30 lbs. 3. The syrupy mother-liquor originally poured off from the crystals was set asidc for some clays but since only orie or two more crystals were deposited it was mixed with alcohol till it became permanently milky (wliich required four or five times its volume of alcohol) and set aside.After some days a scanty crop of crystals had been deposited. These were carefully examined for Scherer's inosite but no evi-dence of the presence of that body could be obtained. The deposit was heated with water the solution filtered from the con-siderable undissolved residue and gradually evaporated when it left a syrupy mass containing a few crystals of kreatine. The liquid waslied from these crystals was mixed with chloride of barium when a scanty precipitate was obtained which did not present any of the characters of inosate of baryta as described by Liebig. 4. The alcoholic liquid from which the crystals liad separated was allowed to stand for smie weeks but having then deposited very little more it was mixed with an equal volime of alcohol of' 90 per cent.and again set aside. After two or three days a portion of' the supenlataut liquid was tested with alcohol and being found to give a very slight milkiness it was poured off aiid distilled. The partly viscid partly crystalline deposit formed in the strongly alcoholic liquid was dissolved in water and a part of the solution was precipitated by chloride of barium ; the precipitate did not appear crystalline under the microscope was scarcely soluble even in hot water aiid did not at all rcsemble the inosate of baryta. On allowing the aqueous solittion of the deposit to evaporate spontaneously no traces of crystals were perceived-a dark brown resinous mass was left not affected by ether but very readily soluble in water.5. The brown syrupy liquid left in the retort after distilling off the alcohol was set aside for ten or t\!elve weeks when it was fburid to have deposited a few crystals. 6. The liquid clccanted from these crystals WLS mixed with 1000 'FHN JUICE OF BEEP. grain measures of dilute sulpiiuric acid (1 lb. concentrated acid to 4 lbs. water) which produced a copious crystalline precipitate. Enough water was added to dissolve this and the liquid was dis-tilled fresh portioiis of water being continually added until the distillate was very feebly acid when 200 gr. measures of dilute sulphuric acid mere again added and the distillation continued ; no more acid however passing over the liquid remaining in the retort was violently shaken with 8 flclid ounces of ether.After repeated agitation for several days the ethereal layer was decanted and distilled; but very iittle acid being thus obtained 1 fluid ounce of dilute sulphuric acid was added to the original liquid which TTas tlien repeatedly agitated with fresh portions of ether. When the amount of acid cstracted by the ether appeared to be quite insignificant the aqueous liquid was mixed with alcohol till it became decidedly milky (which required more than an equal volume of alcohol) when it was set asidc. '7. After the lapse of a week very iittle deposit having been formed niore alcoliol was added from time to time until its quan- tity amounted to about five times tiiat of the liquid.On standing a considerable crystalline deposit was formed. 8. The solution decanted from this deposit was distilled to scparate the alcohol diluted cdh IF ater aid heated withi excess of carbonate of lime ;the solution filtered arid evaporated left an amber-yellow syrupy liquid which did not crystallize 011 standing but became opaque when briskly stirred minute prismatic crystals being then disceriiible uiider the microscope ; it was dissolved in water and careftilly decomposed with oxalic acid so as to leave a little lime unprecipitated. The filtrate from the oxalate of lime was evaporated to a syrupy corisistence and since it exhibited no tendency to crystallize it was reconverted into a lime-salt by saturation with carbonate of lime in the hope of obtaining some well defined crystals by very careful evaporation; but only the same viscid mass was obtained becoming confusedly crystalline when briskly stirred.The lime-salt was then dissolved in water and mixed with a strong solutioii of sulphate of zinc ; no sulphate of lime separated at firstz but on boiling it was deposited as a crystalline powder. The filtered solution when evaporGted deposited yellow crystalline crusts very similar to those formed by the lactate of zinc prepared from sugar-lactic acid but contrary to E 11 g c 1h a r d t's st atcment 156 BLOXAM ON with respect to the lactate of zinc from flesh these crystals were insoluble in alcohol.The crystals were freed from adhering mother-liquor and dried in vacuo over sulphuric acid. 22.17 grs. of the salt when heated in the water-oven lost 0.24 gr. and in the air-bath at %Oo lost in addition 0-48 gr. As this loss was so small and as the brown colouring matter adhering to the salt appeared to have been changed by the heat I was led to believe that the salt contained no water of' crystallisation. The 21-45grs. of zinc-salt dried at 280° dissolved with con-siderable difficulty in boiling water ; the solution was decomposed by sulphuretted hydrogen. The sulphide of zinc when converted into the oxide weighed 4.71 grs. giving 21.96 per cent. of zinc in the salt dried at 280'. 8. The filtrate from the sulphide of zinc when evaporated on the water-bath left a yellow crystalline very acid residue con- taining nitrogen and burning entirely away when heated.It was very readily soluble in cold water and the solution was not preci-pitated by alcohol or by acetate of copper indicating the absence of inosic acid. The acid was dissolved by hot alcohol and was deposited on cooling in oblique rhombic piisms of considerable size. The alcoholic solution when mixed with ether deposited a crys- talline powder appearing under the microscope to consist of beautiful tabular crystals. The aqueous solution when neutralised with ammonia and evaporated deposited rectangular plates. After drying in vacuo the crystals suffered no further loss in the water-oven.This same acid was found in the ethereal solution obtained at an earlier stage and supposed to contain the whole of the lactic acid procurable from the beef employed. After distilling the ether from this solution the brown somewhat syrupy acid liquid remaining in the retort was saturated with oxide of zinc boiled with animal charcoal filtered and evaporated. The zinc- salt was deposited very slowly even from the syrupy solution. On evapo-rating in vacuo I) viscid mass was obtained containing a few crystals ;this was treated with water ; and the crystals washed and dried in vacuo. Heated in the air-bath to 2154 the crystds suffered no appre-ciable diminution in weight. THE JUICE OF BEEF. 12*49grs. of the salt were dissolved though with some diffi-culty in boiling water and the solution was decomposed with sulphixret ted hydrogen.The precipitate when converted into oxide of zinc gave 2.80 grs. = 22.42per cent. First zinc-salt 21.96 per cent. ZnO Second , 22-43 , 1) Mean 22.19 , 97 Assuming the salt to contain an equivalent of the acid for each equivalent of ZnO and taking Zn = 32.52,this would give 142 for the equivalent of the anhydrous acid. (That of anhydrous inosic acid C1,H6N,0, (Liebig) would be 174). The filtrate from the sulphide of zinc when evaporated left a residue which possessed all the properties of the acid obtained from the first zinc-salt. The mother-liqiior from the crystals of the second zinc-salt which would contain any lactate of zinc was evaporated in vacuo; it left a transparent viscid mass which became opaque when briskly stirred and was insoluble in boiling alcohol.This mass was dissolved in water and decomposed by sulphuretted hydro- gen ; the filtrate when evaporated left a brown viscid acid residue which was miscible with alcohol but not to any great extent with ether. This residue was dissolved in water and neutralised with baryta- water. The solution of the baryta-salt slowly evaporated left a gummy mass exhibiting no signs of cry stallisation. It mas decomposed with sulphate of magnesia. (The sulphate of baryta thus preci- pitated was found to weigh only 17 grs. showing the quantity of acid present to be exceedingly small.) The solution of the mag- nesia salt when evaporated to a small bulk deposited what appeared to be a gelatinous mass wliich when pressed in blotting paper to free it from adhering mother-liquor became indistinctly crystalline.This salt when heated with alcohol did not dissolve but broke up into distinct prismatic crystals. When heated with hydrate of potassa the salt evolved abundance of ammonia. I had not succeeded therefore in oljtaining any lactic acid from the 30 lbs. of beef. It would not be just to assume that the viscid acid liquid last spoken of contained an acid different from the crystalline acid previously described since it was evidently associ- ated with much so-called extractive matter which would account for its not crystallising. 8. The last and most abundant deposit produced by alcohol in the solution which had been agitated with ether to extract the lactic acid (7),was now very carefully examined.This deposit contained in addition to the confused mass of crystals of sulphate of potassa a number of rectangnlar tables which were most abundant in the later portions of the deposit formed when the alcohol greatly predominated. 9. The mass was treated with warm water by which it was only partially dissolved; the dark brown solution was evaporated to a small bulk on the water-bath when it deposited a peculiar tena- cious mass showing no signs of crystallisation. The mother-liquor was evaporated to a syrupy consistence but no crystals of incsite could be obtained nor did I succeed in eliciting any of the reactions pointed out by Scherer as distinguishing that substance.10. The residue left bp warm water was boiled xith water Then it almost entirely dissolved.” The solution deposited crystals of sulphate of potassa and the mother-liquor from these gave large crystals of sulphate of soda. 11. The first aqueous extract (9) obtained by treating the deposit with warm water when saturated mi th carbonate of baryta filtered arid evaporated gave a syrupy brown liquid which had an alkaline reaction and was not miscible Fith alcohol or ether. This liquid was dissolved in water the solution mixed with alcohol till it became turbid heated till clear again and allowed to stand; merely a viscid liquid was deposited. The alcohol was then distilled off the sulphuric acid removed by ail excess of baryta-water.the barpta precipitated by carbonic acid and the solution evaporated. It left a brown viscid residue nearly free from inorganicmatter very readily soluble in water yielding a solution which WRS strongly alkaline to litmus and turmeric; it also now dissolved though slowly in alcohol and was precipitated from the solution on adding dilute siilphuric acid. On standing for a day or two this iiscid liquid solidified to a * The small quantity which remained undissolved appeared to be a compound of sulphate of potash with some organic suhst,ance; it was dimolved only by nitro-hydrochloric mid. THE JUICE OP BEEF. crystalline mass which only partly dissolved in alcohol even on boiling leaving white prismatic crystals.Hydrochloric acid dissolved them at once with evolution of heat. The whole of the crystalline mass was thoroughly washed with alcohol which left a brownish white crystalline powder more of which was afterwards recovered from the alcoholic washings. This substance dissolved very readily in water ;the solution was decidedly alkaline to red litmus but not to turmeric. It dissolved very sparingly even in boiling alcohol which sufficed to distinguish it fyom kreatiniue. Ether did not dissolve it. When heated in a test-tube it resisted a considerable degree of heat without change but finally fused evolved ammonia and left a very bulky coal. None of the substance sublimed unchanged proving that it was not sarcosine.The aqueous solution was not precipitated by alcohol even 0x1 adding sulphuric acid. When dissolved in a drop of hydrochloric acid and evaporated upon a slip of glass no well-marked crystals were obtained; but on adding a little bichloride of platinum and again evaporating very distinct cubes were perceptible. The concentrated solution of the base in hydrocliloric acid was not precipitated by bichloride of' platinum. The hydrochloric solution eraporatcd in vacuo left a gummy mass. Chloride of mercury (corrosive sublimate) added to the aqueous solution gave a white precipitate which coagulated in a curious manner when heated. (10.36 grs. of this compound dried in vacuo lost no more at 212'. Diasolvcd in nitric acid the mercury determined as sul-phide gave 58-08per cent.The chlorine amounted to 11.45 per cent). Terchlsride of gold gave a yellow flocculent precipitate in the aqueous solution. The crystals suffered no appwciable diminution when dried in vacua and in the water-oven.* * Although I have made an ultimate analysis of this base the circumstances of my having so small a quantity to operate upon of my not being able to obtain a trustworthy determination of the equivalent number and ahove all my doubt au to 160 BLOXAM ON 12. Being desirous of satisfying myself as to the nature of the volatile acids contained in the juice of beef I examined the acid liquid above alluded to as obtained by distilling the aqueous infu- sion with sulphuric acid (6). This liquid was mixed with an excess of baryta-water eraporated to a small bulk filtered from the separated carbonate and further evaporated in vacuo when it deposited a hard crystalline salt.17-01 grs. of the crystals dried in vacuo and incinerated gave 10.76 grs. carbonate of baryta representing 49.09 per cent. of baryta. Butyrate of baryta (BaO. C,H,03) should have furnished 49-19 per cent. The properties of the salt also agreed perfectly with those of the butyrate.* The mother-liquor from the crystals of butyrate of baryta was evaporated to dryness in vacuo. 21-22grs. of the residue when incinerated gave 14.13 grs. carbonate of haryta = 51.7 per cent. of baryta. Metacetate of baryta (BaO. C6H,0,) would have given 54.1 per cent. so that there is room for the supposition that the salt was a mixture of the butyrate with a little metacetate of baryta though I was rather inclined from other circumstances to attri- bute the observed excess to a little carbonate of baryta which the salt was found to contain.I bad not sufficient to enable me to the absolute purity of the small specimen analysed makes me very diffident in quoting the results although they appear to agree passably well with those calcu- lated. I.-5.88 grs. of substance ignited with soda-lime gave 23.13 grs. of the double chlo- ride of platinum and ammonium = 1.4508 nitrogen = 24.67 per cent. (The platinum,salt when ignited gave 10.17 grs. platinum instead of 10-22.) II.-3*69 grs. burnt with oxide of copper gave 6.20 grs. carbonic acid and 2-18 grs.water ; 45.82 per cent. carbon and 6.56 per cent. hydrogen. TII.-2*24 grs. gave 33'3 grs. carbonic acid and 1.38 grs. water representing 45-41 per cent. carbon and 6'84 per cent. hydrogen. The mean of these analyses would give the empirical formula C, H, N 0,. Calculated. Found. Carbon 13 45.61 45-61 Hydrogen 11 6.44 6-70 Nitrogen 3 24.56 24.67 Oxygen 5 23-39 23'02- 100.00 100~00 * It if3 worthy of remark that this salt was perfectly anhydrous although cryshllised in the cold ; I do not remember that any form of crystallised butpte of baryta but those with 2 mid 4 eqs. Aq. had yet been noticed. THE JUICE OF BEEF. decide the point. When this salt was again dissolved in water and the solution was evaporated in vacuo it gave a transparent viscid liquid which became opaque and solid when briskly stirred being converted into a mass of minute crystals which appeared under the microscope precisely similar to those of the butyrate.When distilled with dilute sulphuric acid it furnished a liquid closely resembling an aqueous solution of' butyric acid. 13. The crystals which were deposited from the aqueous fluid before distillation with sulphuric acid on standing for ten or twelve weeks (5),deserve a few remarks. They were exceedingly heavy and although they burnt entirely away when heated on platinum they were insoluble in boiling water alcohol and ether. Under the microscope they appeared to be four-sided rectan- gulai-prisms. Heated on the water-bath they fused to minute globules having a crystalline fracture.Heated on platinum they evolved a very decided odour of nitrogenised organic matter. Dissolved on heating with hydrochloric acid ;not reprecipitated by ammonia. Dissolved by potassa on boiling; the solution was not altered by hydrochloric acid and gave no dark precipitate with acetate of lead. Ammonia dissolved it with some difficulty on boiling. Dilute sulphuric acid dissolved it on boiling. Concentrated siilphuric acid dissolved it ;the solution was not precipitated by water. Concentrated nitric acid rendered the crystals white and opaqne but dissolved them with difEculty; on allowing the solution to evaporate slowly upon a water-bath it deposited on cooling very lustrous crystals apparently oblique rhombic prisms.(No oxalic acid vas found in the nitric solution.) These prisms became opaque when washed with cold water; they dissolved on heating with water; the solution gave a white precipitate with nitrate of silver which was insoluble in cold concentrated nitric acid but dissolved (in heating and was deposited again in delicate needles when the solution cooled. The following are the chief points to which it has been espe-cially desired to call attention by these remarks. 1. That in this particular case the quantity of lactic acid must M MARCRT ON THE FATTY MATTERS have been so small that even its existence in the juice has not been satisfactorily made out. 2. That instead of lactic acid a crystallised acid containing nitrogen has been obtained though its composition has not been determined.3. That a crystallised base has been obtained very rich in nitrogen and sparingly soluble in alcohol though readily dis- solved hy mater. 4. That; the volatile portion of the acid constituents of the juice of beef consists almost if not quite entirely of butyric acid. 5. That there was extracted from the juice an easily fusible crystalline organic substance containing nitrogen insoluble in water alcohol and ether aiid yielding a crystalline compound when boiled with concentrated nitric acid. I have been induced to submit these results to the Society less by attributing to them any merit in their present incomplete state tban by the hope that T might have thus acted as a pioneer for some investigator with more leisure who might add an exact description of these substances to the records of chemical science.I must beg my friend Dr. Miller to accept my thanks for the kind advice which I have received from him in prosecuting these experiments.

ISSN:1743-6893    

DOI:10.1039/QJ8581000153

出版商:RSC    

年代:1858

数据来源: RSC

摘要:

MARCRT ON THE FATTY MATTERS XVI.-On the Fatty Matters of Human Excrements in Disease. By W. MARCET,M.D. F.C.S. ASSISTANT PHYSICIAN TO THE WESTMINSTER HOSPITAL ETC. ETC. IThas often been noticed that excessive quantities of fats are voided by the motions in certain diseases; but 110 attempt having been made to separate these fatty substances from each other and obtain them in the form of Immediate Principles I have under- Laken this task in one case by adopting a method of investigation similar to that which I had made use of for the analysis of healthy excrements. The case in question is that of a man who was for a long time my patient at the Westminster Hospital labonring OF ITUMAN EXCRENENTS IN DTSF,ASE. apparently under disease of the kidneys.From his excessive emaciation it was evident that the assimilation was very defective and with the view of endeavouring to obtain some further insight into the nature of thc disease his faxes were submitted to exami- nation. They had the consistence of putty a yellow grey colour and a strongly acid reaction. When boiled with alcohol theF formed an homogeneous mass which being squeezed in a muslin bag yielded a turbid alcoholic fluid ; this was now filtered through filtering paper and the insoluble residue exhausted with boiling alcohol. On cooling an abundant crystalline deposit quite free from colouring matter occurred in the solution. In order to analyse the deposit it mas collected on a filter and the filtrate was left to evaporate spontaneously.I removed the deposit to a flask arid then treated it with ether until nothing more was dis-solved; by so doing the crystalline mass was divided into a sub-stance insoluble in ether and one which was soluble in this fluid. The substance insoluble in ether dissolved in hot alcohol but was sparingly soluble in cold alcohol ; the solution had an acid reaction. The crystals were soluble in hot water; but the addition of cold water to the alcoholic solution induced the formation of a cloudy precipitate and the fluid gradually became neutral. This compound fused at a temperature ranging between ZOO' and 103' C. When the aqueous solution was mixed with hydrochloric acid the liquid deposited white flakes ;these were collected on a filter and the acid filtrate being evaporated to dryness left a residue which did not clear on the application of a strong heat and was found to consist of nothing but chloride of sodium.The white precipitate being washed with water till the washings ceased to give a precipitate in a solution of nitrate of silver was treated with ether when it dissolved resuming its crystalline form by spontaneous evaporation ; thc crystals were also soluble in hot alcohol. They fused at 66'C. and reappeared at 64O C. When burnt on a platinum spatula this substance charred ignited and left no residue. In short there could be no doubt but that it was stearic acid ; consequently it appeared very probable that the original compound insoluble in ether was the bistearate or the stearate of soda.The fact was placed beyond doubt by a quantitative analysis of the substance. For this purpose a sample of the compound thoroughly exhausted with ether was dried over sulphuric acid under the air-pump until it ceased to lose weight; it was then found to weigh M2 MAEZCET ON THE FATTY MATTERS 0.275 grammes. The substance was now dissolved in hot water (being insoluble in cold water) and decomposed with hydrochloric acid in excess when an abundant fiocculent precipitate of fatty acid occurred. The precipitate collected on R filter and washed with distilled water (till the washing ceased to produce a hazi- ness in a solution of nitrate of silver) was removed into a weighed match-glass to be dried over sulphuric acid under the air-pump.In order to avoid losing a trace of the fatty acid the filter itself was treated with ether and the solutiori evapo-rated to dryness in a weighed watch-glass which when dried under the air-pump gave only 0.006 grammes of the substance. The whole weight of the perfectly dry fatty acid was 0,259; therefore 0.275 grammes of the compound submitted to analysis consisted of 0.259 grammes of stearic acid and 0.016 grammes of soda. or 100 parts contained 94-18 of stearic acid and 5.82 of soda. Chevreul found 100 parts of bistearate of soda to consist of' Stearic acid . . . 94.33 Soda . . . . . 5.67 100~00 Consequently the substance under examination was bistearate of soda. It is the first time I believe that bistearate of soda has been extracted directly from the animal body and consequently in the form of an Immediate Principle.Its separation from the other fatty acids is very easy on account of the circumstance that this compound is insoluble in ether; and it is readily distinguished from the other soaps by its property of crystallising in a concen-trated alcoholic solution as soon as the fluid has become cold whilst the other compounds of fatty acid and soda solidify from their solution in alcohol in the form of a gelatinous deposit which OF HUMAN EXCREMENTS IN DISEASE. crystallises on standing after some time has elapsed. Bistearate of soda was first obtained by Chevreul by dissolving 1 part of stearate of soda in 2000 or 3000parts of hot water filtering the liquor when cold washing the deposit drying it and treating it with hot alcohol ;the solution when cold deposited bistearate of soda.* In no case have I detected this compound as an Immediate Principle of healthy human evacuations ; it is consequently a morbid product resulting in all probability from the action of abnormally large quantities of' free acids in the intestinal canal the very acid reaction of the excrements supports this view.Healthy human faxes yield margarate of lime and margarate of magnesia; if they contain any soda or potash soap at all it must be in very small quantities. Free fatty acids do not exist in healthy human evacuations unless a comparatively large amount of vegetable food has been taken; and in these cases I have not detected the presence of any bistearate.The excrements in the present instance yielded not only bis- tearate of soda but a considerable quarmtitp of free fatty acids which most probably depended as I shall presently show on the functions of the pancreas and liver being arrested. The alcoholic filtrate from the bisteai-ate of soda gave on stand- ing another crop of crystals consisting of a mixture of bistearate of soda and of fatty acid. By treating these various deposits with ether a substance was dissolved which crystallised by spontaneous evaporation and proved to be a mixture of stearic and margaric acids the former being in excess. The crystallised deposit pos- sessed the following characters. The crystals occurred under the form of small white masses exhibiting under the microscope groups of needles radiating from the centre to the periphery.They fused at a temperature of 60°C which according to Gottlieb corre- sponds to a mixture of eighteen parts of stearic with ten parts of rnargaric acid; they mere soluble in cold ether and in hot alcohol and insoluble in water; the substance dissolved in potash and could be precipitated in this alkaJine liquor by means of hydro-chloric acid; when heated on the platina-knife the crystals fused ignited and finally left no residue. These characters are precisely those of the above-mentioned fatty acids ; the amount of the mix- ture at my disposal did not allow of the complete separation of these acids being effected. * Recherche3 Chimiques Bur les corps grag d'origine snimaIc.Par M.1,. Che7 reul. BUCKTON ON SOME OF The clear alcoholic fluid being allowed to stand undisturbed for twenty-four hours yielded another crop of beautifully white glis- tening crystals. These were submitted to examination and proved to be maryaric acid apparently free fi-orn stearic acid. These crystals dissolved in ether and hot alcohol and crystallised from these solutions; the ethereal and alcoholic fluids had an acid reac- tion; the substance was insoluble in water but dissolved in aqua potass=. Hydrochloric acid induced its precipitation from the alkaline liquor. It fused at 53' Cent. am1 crystallised on cooling at 49* this low fusing poiiit beiiig due probably to the admixture of a small quantity of oleic acid ; the crystals occurred in the form of small radiating masses peculiar to margaric acid; they burnt with a fuliginous flame leaving no trace of ashes.The occurrence of such quantities of fatty acids in this case being considered in connection uith the condition of the body of the patient is of' great interest not only in a chemical but also in a physiological and pathological point of view. The pancreas of the patient was found at a post mortein examination entirely dis- organised by malignant disease and it apparently so compressed the duct of the gall bladder that no bile could flow into the intes- tines. Consequently the two alkaline intestinal secretions were wanting and the fatty acids contained in the alimentary canal could riot be neutralised. This is an important fact in favour of Ber p1 ard's view respecting the properties of the pancreatic juice. I avail myself with pleasure of this opportuuity to acknowledge the valuable aid I have received from my assistant Dr. Frederick Dupr6 in these and other investigations.

ISSN:1743-6893    

DOI:10.1039/QJ8581000162

出版商:RSC    

年代:1858

数据来源: RSC