摘要:

101 PAPERS READ BEFORE THE CHEMICAL SOCIETY. III.-,Mineralogical Notices. By Prof. STORY-MASKELYNE and Dr. FLIGHT. 14. Cnledonite. SOME little time back a minei*al termed by the dealer who sold it to the British Museum aztrichalcite was bought by the Mineral Depart- ment. It was from Leadhills and though at first sight not unlike the mineral under the name of which it went it really bore much greater resemblance to some of the more fibrous and compact varieties of cale-donite. In the first place therefore it was analysed. The percentage composition of the mineral is given in Colurnn I in a subsequent part of this Notice. It will suffice here to say that that analysis led to a rationai formula represented by five equivalents of lead sulphate two of lead hydrate with three of cupric hydrate a composition in which a small amount of lend carbonate present in the substance is not included.A composition thus differing from that received for caledonite led in the next place to an investigation of the crystallographic elements of the mineral in question. The crystals however were microscopic and it was with some diEculty that two of them were found capable of being measured with any degree of accuracy ; one of these however when examined under the microscope in light polarised in a definite plane showed principal sections parallel to the edges of the prism in two planes which were afterwards proved to be perpendicular to each other. The measurements of the edges in the zone contaking these two faces gave angles approximately corresponding with those of the zone [100,001] of caledonite ; a zone perpendicular to this that namely of [100,010] was also measured and the angles in the two cases were :- As found.As in Caledonite. 100,101 . . * . 35" 16' to 3.5" 30' 35" 37' 101,001.. . . 54" 44'to 54' 30' 54O 23' l00,OOk * . . . 90" 90" 100,110.. . . 48" (approx.) 47" 15' 100,101.. . . 90" (approx.) 90" The crystals were too minute to afford measurements of any of the VOL. XYVII. I STORY-XASKELPNE AND FLIGHT’S angles in other zones or any more accurate determination of these ; indeed only one face that namely of 100 reflected a perceptible image into the telescope. The optical characters however prove the crystal to belong to an ortho-symmetrical system while the observed angles were sufficiently near to those established for caledoiiite to justify khe belief that the two minerals were crystallographically identical or nearly so.It was deemed desirable however that an analysis of undoubted caledonite should be made in order to see whether the received formula for that mineral was correct. The result has confirmed the goniometrical determinations by establishing for caledonite the composition above given for the mineral. In the analysis of the so-called aurichalcite it was found that the amount of lead sulphate lead oxide reckoned as carbonate and copper oxide already gave a total of one hundred although the water which the mineral contains had not yet been estimated.A determination of the actual amount of carbonic acid present mas then made and instead of 9.5 per cent. of that constituent as given in Brooke’s analysis only about 1.5 per cent. was found. The analysis of undoubted caledonite is given under I1in the follow- ing table:- I. TI. Mean. Lead sulphate ........ 60.23 59.49 59-86 Lead oxide .......... 25-12 26.19 25.66 Copper oxide ........ 9.41 9.178 9.294 Carbonic acid ........ 1.434 -1.434 Water .............. -3.701 3.701 99.949 As the mineral occurs in association with cerussite the carbonic acid is most probably present in the form of carbonate of lead. If then we eliminate this carbonic acid together with the corresponding amount of lead oxide the remaining constituents give the following equivalent ratios :-Lead sulphate ........0.395 .... 5 Lead oxide ........... 0.16 .... 2 Copper oxide ........ 0.23 .... 3 Water ............... 0.411 .... 5 which ratios accord with the formula 5PbS04 +. 3CuH20 + 2PbR2OZ indicating a composition corresponding with three equivalents of lina-rite two of lanarkite and two of water. It is not easy to ascertain how Brooke arrived at his results. In his MINERALOGICAL NOTICES. paper (Edin.Phil. JOUT., iii 117) he states that (‘the cupreous sulphato- carbonate appears . . . to consist of six atoms of sulphate of lead four atoms of carbonate of lead and three atoms of carbonate of copper if the carbonate of copper be chemically combined and not accidental.” No percentage numbers are to be found in his paper and those given by Dana (Sgstem of Mheralogy 5th ed, 626) are clearly not the re- sults of an analysis as the reader might suppose but are calculated numbers based on Brooke’s formula.15. Lanarkite. Pisani (Conzpt. rend. lxxvi 114) and Jannettaz (ibid. lxxvi 1420) and still more recently Schrauf (Mineralog. Mitt. 1873 heft 2 137) have shown that lanarkite is not a lead sulphate and car- bonate as Brooke and Thornson have stated it to be but a combi- nation of one equivalent of the sulphate with one of the oxide It seemed not improbable that the second equivalent of lead oxide might be in the form of hydrate. As this water would only constitute some- what more than 3 per cent. of the mineral and as Pisani’s analysis showed a deficiency of more than 2 per cent.it was considered advisable to analyse lanarkite with a special view to decide this point. A very pure specimen lost at loo” in one hour 0.008 per cent. ; in another hour at the same temperature the same trifling amount. When heated to just visible redness it gave off 0.149 per cent. of water and when it was exposed to a bright red heat for half an hour nothing further passed into the chloride of calcium tube. An analysis of the heated mineral gave the following numbers (PbSOI + PbO). Theory. Lead sulphate ,.... . 57.70 57.605 Lead oxide .....,.. 42.89 42.395 100.59 100~000 Lanarkite then contains no water and like caledonite no carbonic acid. It is of interest in connection with this subject to note that the maxite of Iglesias Sardinia examined last year by Laspeyres (Jour. Prakt. Chem. 1872 470) consists of lead sulphate in combination with lead carbonate and hydrate. I2

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年代:1874

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104 IV.-On the Analysis of a Meteoric Stone and the Detection qf Va?mdium it. By RICHARD M.A. T.C.D. Proelector of Chemistry APJOIIN Caius College Cambridge. BEFORE the celebrated researches of Kirchof f and Angstrom which have proved the presence in the sun and fixed stars of many elements that occur on the earth our knowledge of the chemical composition of extra-terrestrial bodies was I may say entirely derived from the exami- nation of the meteoric stones or aaroliths which occasionally fall on the surface of our planet. The analysis therefore of these bodies has for a long time engaged the attention of many of the most eminent chemists. Howard Klaprot h and Vacq uelin and more recently Berzelius Ramm e Isberg and many others have investigated their composition and have clearly demonstrated the presence in them of 18 elementary bodies identical with those which occur in terrestrial minerals viz.oxygen sulphur silicium carbon phosphorus copper aluminium chromium iron mangmese nickel cobalt, calcium magnesium sodium potassium titanium and tin. Hydrogen clilorilie arsenic antimony and lead have also in some cases been detected in these bodies. The result of recent investigations in which I have been engaged relative to the presence of vanadium in traprocks (see Chem. News October 18 1873 page 183) led me to the conclusion that this metal is probably to be found in all rocks of this class; and as the proximate constituents of meteorites are in general the same as those of traprocks it seemed likely that vanadium would be found present in the former as well as the latter.I acco~dingly selected for examination 8 meteoric stone from the Mineralogical Museum of Trinit-y College Dublin which fell at Adare in the county Limerick in the year 1810. The surface of this stone is of a dark colour and exhibits a fused appearance doubtless the effect of the heating that it underwent during its rapid transit through the earth's atmosphere. On examining its recent fracture it appeared to consist of an earthy matrix in which were imbedded numerous small shining metallic particles. Its specific gravity was 3-94. In order to ascertain if vanadium was present the following course was adopted :-12 grams of the finely powdered mineral were digested with nitric acid and the whole evaporated to dryness the object of this first step being to oxidize the metallic particles.The residue was fluxed with four times its weight of sodium carbonate and the fused mass being permitted to cool a small quantity of nitre was added. The crucible was now cautiously heated care being taken that it did not APJOHN ON THE ANALYSIS OF A METEORIC STONE ETC. 105 attain more than a dull red heat. The mass was lixiviated with water and the aqueous solution was boiled with ammonium carbonate and filtered to remove silicic acid. Hydrochloric acid being added the filtrate was evaporated and hydrogen sulphide passed in to precipitate any metals of the lead group that might be present. The filtered solu- tion was then treated with an equal volume of a concentrated solution of ammonia and hydrogen sulphide was passed in till all the free ammonia was saturated.At this stage the solution assumed a beauti-ful intense cherry-red colour n sure indication of the presence of vanadium. This coloured liquid was filtered off and saturated with hydrochloric acid ;and the precipitate consisting of sulphur and vana- dium sulphide was dried ignited and the residue then melted with a pinch of nitre From the potassium vanadate thus formed the cha- racteristic blowpipe reactions of vanadium were obtained. The re- mainder of the potassium vanadate along with the microcosmic salt bead formed in the blowpipe experiment was dissolved in water acidulated with sulphuric acid and shaken in a test-tube with hydrogen peroxide and ether.The result was the formation of a dark red colour in the aqueous portion of the solution without the slightest trace of blue in the supernatant ether clearly demonstrating the presence of vanadium and at the same time showing that chromium was entirely absent. The discovery of vanadium iuduced me to make a quantitative analysis of this stone and as all the determinations were conducted with the greatest care a brief account of the methods I employed and of the results may not be destitute of interest. The separation of the metallic particles from the silicious portion of the stone was effected in the following manner:-10 grams of the finely pulverised mineral were digested for 24 hours with an excess of iodine and the insoluble portion was separated bp filtration.The excess of iodine having been removed from the filtrate by distillation with sulphuric acid the iron was precipitated with sodium acetate and the nickel and cobalt were separated in the filtrate by the potassium nitrite process. Two grams of the metallic particles which had been removed from the earthy matrix by means of amagnet were dissolved in nitric acid and on the addition of the molybdate solution gave it decided indication of the presence of phosphoric acid. It was present however as a mere trace. The portion deprived of metallic particles by iodine was now heated with dilute hydrochloric acid evaporated to dryness and exhausted with water and the several constituents of the aqueous solution deter- mined by known methods.The residue was boiled with a solution of pnre sodium carbonate in order to dissolve out the silicic acid which had been set free by the action of the hydrochloric acid. During the digestion with hydrochloric acid it was observed that 106 APJOBN ON THE ANALYSIS OF A BIETEORIC STONE ETC. hydrogen sulphide was copiously developed which indicated the pre- sence in the aikolith of iron sulphide. In order to determine its amount 2 grams of the original mineral were fluxed with sodium carbonate and potassium nitrate and the sulphur wits estimated as barium sulphate. From the sulphur thus found the quantity of magnetic pyrites was calculated and the amount of iron corresponding to it was deducted from that of the soluble silicate.The mineral portion therefore of this meteorite soluble in hydro- chloric acid consisted of a silicate and of magnetic pyrites. The residue insoluble in hydrochloi+c acid was fluxed with sodium carbonate and potassium nitrate and its various components were deter- mined in the ordinary manner. The chromic oxide obtained from this portion is in the discussion of the analysis assumed to be present as chrome iron. The alkalis of both the soluble and insoluble silicates were determined from large separate portions in order to insure greater accuracy in the results. A search for lithium by means of the spectroscope was insti- tuted but with an entirely negative result. The following is a statement of the proximate and ultimate composi- tion of the Adare meteorite as determined by my analysis :-I.Mi?teralogica,lcomposition. 11. Metullic portioiz. p.c. p.c. Metallic portion ..... 19.07 Iron .......... 85.120 Magnetic pyrites .... 6-54! Nickel ........ 14.2 75 Chrome iron ........ 1.75 Cobalt ........ ,602 Soluble silicate ...... 35.4 Phosphorus .... trace. Insoluble silicate .... 37.07 99.87 111. Silicate sohuble i?z hydrochlo-IT.8ilicute hsolubk $7~hydrochlo-ric acid. ric acid. p.c. p.c. SiO,. ..... 42.91 SiO,.. .... 5'3.48 A1203 .... 2.35 A1203 .... 3.24 FeO.. .... 16.93 FeO. .... 7.94 MnO .... 6.26 MnO .... 8-84 CaO.. .... 5.34 CaO.. .... 4.62 MgO .... 24.32 MgO ... 13.17 NhO .... -29 NazO .... 1.86 KZO ...... -02 KZO.. .... 0.30 Loss.. .... 1.58 PZO .... trace Loss.. .... 0.55

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年代:1874

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107 V.-Note o’n the Action of .k7ric Chloride on Codeine. By C.R. A. WRIGHT, D.Sc. Lecturer on Chemistry in St. Mary’s Hospital Medical School. Ir is stated by M. atthiessen and Burnside (Proc. Roy. Soc. xix 71) that when codeine hydrochloride is heat,ed with zinc chloride to 170”-180” for 15 minutes the following reaction occurs (the empiri- cal formulae of the original and resulting substances being used) :-accordingly the term “apocodeine” was applied by them to the product. On attempting to prepare for the market “apocodeine,” according to the process described by Matthiessen and Burnside Mr. D. Brown (Messrs. Macfarlane and Co. Edinburgh) obtained a product which exhibited most of the properties ascribed to ‘‘apocodeine” hydrochloride but which when analysed by the writer gave entirely different numbers the same result occurred in several instances when the process was somewhat varied ; if the action be carried on at a low temperature and for a short time as suggested by Matthiessen and Burnside the chief product is a loose compound of zinc chloride and the hydrochloride of a base isomeric with codeine yielding amorphous salts soluble in ether and itself amorphous; i.e.of a base exactly corresponding with tyicocleiwe (PYOC. Roy. Xoc. xx 278) ; if a longer time of heating be adopted or a higher temperature there is also formed a good deal of a base insoluble in ether probably tetracodeiTie. The following numbers were obtained :-Specimen A. Prepared by D. Brown in strict accordance with Matthiessen and Burnside’s directions the substance thrown down by addition of water to the product of the action is a loose double chloride of zinc and tricodeine from which the zinc cannot be wholly separated by successive solutions in water and precipitations by hydrochloric acid dissolved in water and precipitated by sodium car-bonate ; precipitate dissolved in ether and ethereal solution agitated with a few drops of hydrochloric acid- 0.2205 gram gave 0.521 COZ and 0.129 H20.B. Prepared by D. Brown. Similar product obtained in the same way the precipitation with sodium carbonate and treatment with ether being performed twice- 0.3480 gram gave 0.821 C02 and 0.208 H20 0.1940 , 0.0845 AgC1. 108 WRIGHT ON THE ACTION OF ZINC CHLORIDE ON CODEINE.C. Prepared by C. R. A. Wright. Product from action of zinc chloride on strongly acid solution of codeine hydrochloride kept at 17Oo-18O0 for 30 minutes ; treated its before ; much base insoluble in ether formed- 0.2985 gram gave 0.707 C02 and 0.173 H20 0.1720 , 0,075 AgCI. Caleulat,ed. Found. For apocodeine For tricodeine hydrochloride. hydrochloride. A. B. C. Carbon .. . . 68.03 64.38 64-44! 64.34 64.59 Hydrogen . . 6.30 6.26 6.50 6.45 6.44 Chlorine.. . . 11.18 10.60 -10.78 10.78 Tricodeine hydrochloride when perfectly pure gives no immediate coloration with ferric chloi*ide but develops a red-purple tint on standing a short time ; “apocodeine,” on the other hand gives the reactions of aponiorphine (M. and B.) i.e.an immediate coloration with ferric chloride. Each of the three samples above mentioned yielded a pale red-purple tint immediately with ferric chloride the colour deepening much on standing. From these results it is evident that the base soluble in ether produced by the action of zinc chloride on codeine has not the composition of “apocodeine,” but consists almost wholly of tricodeine along with minute quantities of other bodies. It has already been shown (Proc. Roy. Soc. xx 282) that when tricodeine is acted on by hydrochloric acid it readily undergoes the reaction-(C18H2~~03)Il= nH2O + (CI8H19N02). (the empirical formulae of the original and resulting substances being employed) and it has been pointed out also that the resulting pro- duct agrees in all its characters wit’h the “apocodeine ” of Matthies-sen and Burnside. It hence appears probable that the substance examined by Matthiessen and Burnside was not produced solely by the action of zinc chloride on codeine but was an alteration-product of the tricodeine first formed ; notl improbably a large excess of hydro-chluric acid was used to agitate with the ethereal solution of the base and the acid liquor obtained evaporated either spontaneously or on the water-bath ; removal of the elements of water then ensued through the action of the excess of acid on the tricodeine the greater part of which must have been converted into “apocodeine ” in this way unsuspected by the operators.

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DOI:10.1039/JS8742700107

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年代:1874

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TTI.-On. the Hydrochlo&& of Narceine. By C. R. A. WRIGHT, n.Sc. Lecturer on Chemistry in St. Mary's Hospital Medical School. IT has been stated by Petit (Bull. Xoc. Chirn. Paris xviii 534) that narceine has comparatively little tendency to combine with hydro-chloric acid so that unless a large excess of acid be present in the liquor from which narceine hydrochloride is deposited the crystals which separate contain less chlorine than that calculated for the forniula N.HC1 (where = C,,H,,NO,). With certain weak solutions Petit obtained substances corresponding to 5s.HC1 and 10N.HC1 the latter being invariably formed by the action of water on either the neutral hydrochloride or substances less basic than 10N.HC1. The author can corroborate many of these statements.Thus crystals of' a basic hydrochloride deposited from a solution containing between 3 and 4 equivalents of hydrochloric acid for 1of narceine contained after drying at loo" 5.77 per cent. of chlorine whilst others thrown down from a solution containing less acid (but still in excess relatively to the narcctine) contained 3.06 per cent. of chlorine the formula R.HC1 requiring 7.11 per cent. When 8 or 10 equivalents of hydrochloric acid are present a strong solution deposits sandy crystals which give the following numbers :-A. Crystals drained on the filter-pump washed with a little cold water and well pressed between blotting-paper- 1.3490 gram lost at 100 0.1455 = 10.78 per cent. 1.6770 , , ,) 0*1810 = 10.79 , , B. Crystals washed once with cold water three times with cold alcohol and twice with ether and exposed to the air with frequent stirring until all smell'of ether had disappeared (about two hours)-1.4680 gram lost at loo" 0.1590 = 10.83 per cent.The formula B.HC1.3H20 represents a loss of 9.75 per cent. on becoming anhydrous. Petit represents the hydrochloride as N HCL. 2$H20 requiring 8.26 per cent. of loss only ; but he states that his specimens lost one-tenth of their weight at 100". The excess found is doubtless due to the hygroscopic character of the body ; although crystals A and B lost most of their water of crystallisation over sul-phuric acid yet the whole could never be thus removed from 1to 2 per cent. being always lost on further heating to 100' ; on the other hand the hydrochloride when perfectly dried at loo" always gained 110 WRIGHT ON THE HYDROCHLORIDE OF NARCEINE.1per cent. or more in weight by keeping over fresh sulphuric acid; thus :-A. 1.677 gram lost at 100" 0.1810 gram = 10.79 per cent,. Residue over sulphuric acid 18 hours gained 0.0180 = 10.7 per cent. B. 1.4680 gram lost at loo" 0.159 gram = 10.83 per cent. Residue over sulphuric acid 18 hours gained 0.0150 = 1.02 per cent. .Residue over sulphuric acid 4weeks gained 0.0153 = 1.06 per cerit. When fully exposed to the air of the laboratory the perfectly anhy- drous salt gains rapidly in weight and at the end of a week regains the whole of the 10.8 per cent. of water originally lost at 100". After drying at loo" the hydrochloride gave tche following num- bers :-0.3940 gram gave 0.798 CO and 0.233 H20.0.2890 , 0.0855 AgC1. 0.7610 , 0,2260 AgCl. Calculated. Found. c23 276 55-25 55-24! H3 30 6.01 6.57 N 14 2.80 - 09 144 28.83 - c2 35.5 - 7.11 7.15 7.35 C23H.J?09,HCl 499.5 100*00 On dissolving the crystallised hydrochloride in 50 times its weight of boiling water and cooling fine filamentous crystals formed at a temperature of 35" ; these were filtered off and washed a little on the filter-pump ; after drying at 100" they contained- Chlorine = 1.30 per cent. agreeing with 6R.HC1 which requires- Chlorine = 1.26 per cent. On digesting these crystals with cold water after rubbing them up to a fine powder in a mortar with a little water the percentage of chlorine was diminished but the whole could not thus be removed ; after seven treatments by digestion with about 100 times their weight of water for 24 hours filtering off and washing on the filter-pump the residual crystals still retained-Chlorine = 0.88 per cent.WRIGHT ON THE HYDROCHLORIDE OF NARCEINE. 111 And after recrystallisation from hot alcohol the deposited crystals retained-Chlorine = 0.75 per cent. This corresponds with Petit's formula lOE.HC1 which requires Chlorine = 0.76 per cent. ; but it is doubtful if' this is a definite body as further crystallisations diminished the percentage of chlorine to 0.5 and 0-4 per cent. Hitherto it has not been found practicable to obtain narceine absolutely free from chlorine the base having neces- sarily existed at one time as hydrochloride in the treatment of opium by the Robertson-Gregory process.Precipitation by an excess of alkali and seveyal recrystallisations from boiling alcohol fails to remove every trace of chlorine. The most natural explanation of this would appear to be that hydro- chloric acid forms a chlorinated narceine-derivative perhaps analogous to chlorocodide and difficultly separable from narceine ; but no evidence of the existence of such a body could be obtained. On digesting narceine with several times its weight of concentrated hydrochloric acid at 100" for an hour a change is produced ; but the resulting com- pound is not a chlorinated base being simply formed by the removal of the elements of water thus (employing the empirical forrnulaj of material and product) :-CZ,H29N09.HCl= HZO 3-C:,Hz,NO,.HCl.On adding water to the strongly acid liquid a tarry mass is thrown down; this is principally. the hydrochloride of the new base from which the pure hydrochloride may be obtained by dissolving the tar in hot water leaving the solution to cool and fractionally precipitating by the addition of strong bydrochloric acid. The first fraction is somewhat dark-coloured the latter ones are nearly white amorphous flakes; these cohere together on drying forming a brittle gummy mass. After drying at 100"-0.4090 gram gave 0.8590 C02 and 0.2190 HzO 0.6480 , 0.202 AgC1. Calculated. Found. c23 2 76 57.32 57.28 HZ8 28 5.82 5-93 N 14 2.91 - 08 128 26.58 - c1 35.5 7.37 7.72 - C23&~O*,HC1 481.5 100~00 The free base is amorphous and sparingly soluble in ether; it is excessively soluble in all alkaline solutions even in sodium carbonate 112 WRIGHT ON THE HYDROCHLORIDE OF NARCEINE.solution. Its salts yield with ferric chloride solution a dark-blue purple colour gradually becoming purple-brown ; chromate of potassium and sulphuric acid gives a dark red-purple colour. The physiological action of this new body is only slightly marked doses of one and two decigrammes of its hydrochloride being subcutaneously administered to cats and dogs without production of any noticeable symptoms. The narceine used in these experiments was obligingly presented to the author by David Brown Esq.(Messrs. Macfarlane and Co. Edinburgh) ; it has long been known to this gentlenian that narceine hydrochloride becomes basic on treatment with water; in some in- stances however he has found that two sorts of crystals are simul- taneously deposited on cooling a solution of the hydrochloride ; the one fine and filamentous soluble in alcohol and consisting of narceine retaining only a little hydrochloric acid ; the other consisting of hard -gritty crystals containing 6.46 per cent. of chlorine the formula N.HC1.3Hz0,requiring 6.41 per cent.

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年代:1874

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113 ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. General and Physical Chemistry. Spectra of Gases in GeisslerJs Tubes. By A. WUELLNER (Pogg. Ann. cxlix 103-112). THE following results of Schuskr’s experiments (1) that pure nitrogen allows only the spark-discharge to pass and yields the line-spectrum only ; and (2) that the silent discharge and the band-spectrum can only be produced in presence of small quantities of other gases were tested by the author who in order to remove the last traces of oxygen from the nitrogen suspended in the gas a coil of iron wire which was for a considerable time kept red-hot by a gRlvanic current. He found that he could obtain either the one or the other spectrum by varying the pressure.On purifying the nitrogen in the same way as Schuster by sodium he was also able to obtain both spectra and when the pressure was reduced to 5 mm. he noticed exactly those changes in the light of the discliarge described by Schuster ; but he found the spect<rum to be not the line-spectrum of nitrogen but the spectrum of carbon. He thinks that his experiments furnish a new proof that the line-spectra and the band-spectra of gases are produced respectively by the spark- discharge and by the silent discharge. R. S. Absorption-spectrum of a Solution of Nickel Nitrate. By H. EWSMANN (Pogg. Ann. vi 334). NICKEL nitrate solution absorbs the red and violet ends of the spectrum. h flat bottle filled therewith serves as a means of distinguishing certain kinds of otherwise similar colours inasmuch as objects treated with them present different appearances when viewed through the solution.C. R. A. W. On the Electro-Chemical Equivalent of Silver. By F. KOHLRAUSCH (Pogg. nun. cxlix 170-186). THE object of this investigation was to determine with the highest refinements of modern apparatus and methods the ratio of the mag- netic to the chemical unit of current-force. This memoir is divided iuto three parts. In the first are recorded the details and results of three determinations of the electro-chemical equivalent of silver. 114 ABSTRACTS OF CHEXIIcAL PAPERS. The variation in the horizontal intensity of the earth's magnetism, T,was observed during each experiment and reduced to a mean.The galvanometer was read every twenty seconds during the half to three- quarters of an hour occupied by each determination. To eliminate variations in declination the current was commuted in the galvano- meter every five minutes. The electrolyte was a 15 per cent. solution of silver nitrate contained in a large silver crucible as cathode with a rod of silver covered with muslin for anode. The following are the numbers obtained :-I. 11. 111. Duration of the current,. . t 1979.7 2399.6 26995 sec. Mean deviation on scale .... a 636.99 526.42 521.59 mm. Precipitated siIver ........ M 1135.52 1139.05 1269.29 mgr. Mean position of the Bifilar-+ 19.5 + 7.8 +5.9 div. magnetometer .......... 1 Horizontal intensity of earth's l,.8422 1.8400 1.8396 magnetism ............I Twas calculated from by the formula- T = 1.8985 (1 + 0.000105 6). The distance of the millimeter scale from the galvanometer mirror was 3687.1. mm. Therefore putting 9 for the angle of deviation a = tan 2.3;. The strength of the current in absolute measure 3687.1 i was obtaiiied by introducing these values into the expression .i = 31.959 Ttan 9 which according to previous determinations' (Pogg. Ann. cxxxviii 7), denotes for the particular galvanometer used the current strength corresponding with the angle of deviation 9. 1M The silver deposited in 1 sec. m = - consequently m is the quan- t z tity of silver precipitated in 1 sec. by the unit-current or in other words the electro-chemical equivalent of silver.The results are as follows :-m -i m i f ............... 5-0482 0.57359 0.11362 11. ............ 4.1767 0.47469 0-11365 111. ............ 4.1377 0.47017 0.11363 Now the chemical equivalent of silver according to the exact deter- minations of Stas is 107.93. Multiplying therefore 0.11363 into 107.93,we obtain for the electro-chemical epuivalent of water the number 0.009476 which is about 1+per cent. larger than that gene- rally received viz. 0.00933. The older determinations are then discussed and the probabi1it.y GENERAL AND PHYSICAL CHEMISTRY. shown thah in all of them the estimation of the terrestrial intensity was inaccurate the general result being to raise them when corrected. The mean of all the most trustworthy gives 0.009421.The second part of the memoir deals with the choice of a galvanic current-unit. The use of Jacobi’s unit is deprecated on account of its being based on purely chemical considerations bearing no relation to the other properties of the current. it is however pointed out that by re-ducing the volume of gas to 0” and 800 mm. (801.3 exactly) instead of to 760 mm. the units of Jacobi and Weber would become identical. For rough estimations the unit may be taken as precipitating 1mgr. of cop- per in half a minute ; but for accurate work the absolute unit derived from magnetic measurements is the only one admissible. Electromotive force is most conveniently expressed by the product of the current-strength into the resistance ; and if Siemens’ resistance- unit be employed the electromotive force of 1 Bunsen (or Grove) cell will Le expressed by the round number 2.00 (Pogg.Ann. cxli 458) and (taking the mean of the author’s determinations and those of von Waltenhofen) 1Daniel1 element = 11.57. In the third section these and some previous results of the author are combined with Favre’s measurements of the electromotive force of Daniell’s and Grove’s cells in heat-units to deduce the mechanical equivalent of heat. The results are respectively 456.5 and 407.2 kilo-grammeters. That obtained from the Daniel1 element is of course the more trustworthy and even this is probably too high in consequence of the electromotive Dower beinn determined in a cornBensated cell, 1 0 A whilst the calorimetric measurements were made witrha cell in a state of activity.M. J. S. Pyrometric Researches. By A. WEI N H o LD (Pogg. Ann. cxlix 1863-235). THISpaper contains a detailed examination of several methods which have been proposed or used for the measurement of high temperatures. The air-thermometer upon the indications of which all the other deter- minations were based consisted essentially of a porcelain vessel holding about 20 c.c. in conimunication with a manometer which indicated the pressure whilst the volume was kept constant. Dry air was found to be the only gas suitable for filling the thermometer. It was necessary to refill each time and also after each heating to control the pressure at a normal temperature. Minute descriptions of the apparatus and mode of using it are given also the formula for the corrections due to the capacity and temperature of the air in the tubes connecting the porcelain vessel with the manometer.A trial determination of the boiling point of zinc gave 1035”. The coefficient of the cubical expan- sion of porcelain was found to be 0*0000305-0.0000359 which num- bers are higher than that generally received. Pyrometers depending on fhe .Expansion of Solids.-Three such Sauntlett’s Bock’s and Oechsle’s were tested they all proved utterly ABSTRACTS OF CHEMICAL PAPERS. useless. Attempts were also made to construct pyrometers in which the differential expansion of silver and platinum and of steatite and platinum should communicate angular motion to a mirror but they were equally futile owing in the former case to the fact that the silver tube did not return to its original dimensions on cooling and in the latter to a continually increasing contraction of the steatite even after sixteen re-heatings.The change of shape exhibited by a prism of quartz on being heated was also investigated. The section of the prism used was a right-angled isosceles triangle and the method adopted was to observe with a telescope the position of the images of an object placed in front of the hypothenuse and reflected internally by the faces forming the right angle. On heating to about 400' these images moved away from one another regularly and considerably and on cooling they returned to their origiiial positions ; but above that temperature their relative motion diminished and at 8 strong red heat became reversed owing apparently to a change in the relation of the two coefficients of expan- sion.The quartz was found on cooling to be full of fissures which rendered it useless. Zircon is suggested as probably more suitable. The applicability of the calorimeter to pyrometry was studied. The apparatus used is minutely described and the sources of error pointed out. A series of determinations of the specific heat of platinum showed that it increased slightly between 100" arid 250" diminished between 2.50" and about 500" and then again increased the peatest difference beiiig about 10 per cent. on the mean value. The specific heat of wrought iron increases considerably with rise of temperature being about 40 per cent.higher at 900" than at loo" but it is suffi-ciently regular to admit of the employment of the following interpola- tion formulzt in which C indicates the specific heat at to:-C = 0.105107 + 0*00006538t + 0~000000066477t2. The temperature of a mass of iron may therefore be determined by the calorimeter. Lamy has proposed to estimate high temperatures by obsewing the tension of dissociation of a solid substance vvhich evolves a gas on heat- ing and re-absorbs it on cooling. The author has re-examined Lamy's experiments with calcium carbonate and has ~lso studied the compound of calcium chloride with ammonia CaC1.8NH3. With the latter sub-stance complete re-absorption of the ammonia on cooling coiild not be attained and with the former many remarkable irregularities were observed which rendered it quite inapplicable to the present purpose.The author concludes that the dissociation of bodies consisting of a solid and a gas does not follow the law announced by Lamy and Debray. Lastly Siemens' resistance pyrometer was compared with the air thermometer at various temperatures betweerl 98" and 992". Up to 400" the differences were trifling; from 5;30° to 550" the Siemens indicated 26"-28" above the air thermometer ; above 900" it showed 32"-35" below. The determinations above 500" depend each on one experiment only. GENERAL AND PHYSICAL CHEXISTRP. The author considers tchat the Siemens is the only serviceable pyro- meter ready for immediate reference.In a postscript the acoustic pyrometer of Mayer and that of Caignard Latour and Demonferrand are discussed and their unsuitability for high temperatures demonstrat'ed. M. J. S. Some Calorimetric Problems and Values. By M. B E RT H E LOT (Compt. rend. lxxvii 971-976). 1. THE author in his thermochemical inrestigations had found that the action of sodium borate on ammonium sulphate both in solution gave rise to an absorption of heat equivalent to -2-25 heat-units whilst Fane and Valson found only -1.16. The author has repeated his experiments which were made by the direct method of mixing the solutions and obtains results agreeing sensibly with those previously found; he attributes the different results obtained by Fame and Valson to their having obtained their numbers by an indirect method namely the difference of the heat of solution of sodium borate in pure water (-11.04) and in water charged with ammonium sulphate (-12.20).2. By the method of reciprocal double Gecomposition that is by acting 011 sodium borate with hydrochloric acid and on sodium chloride with boric acid it was ascertained that the saturation of soda by boric acid takes place at once as in the case of other acids and not by successive steps. 3. When silver nitrate is precipitated by potassium iodide the whole of the heat developed by the formation of the argentic iodide is not at once rendered sensible in the calorimeter ; thus in one experiment at the end of the first minute the effect was equivalent to 23.1 heat-units whilst at the end of three or four minutes it had risen t 26.4 so that in general the thermic effect duo to the formation of a solid body cannot be represented by a constant co-efficient unless the substance produced is cryst,alline.This is an important point for consideration n the discussion of problems in which precipitates are produced. 4.Owing to an error in the calculation of the number formerly given (+ 20.6) for the action of potassium iodide on mercury chloride it should be + 13.67. A recent experiment has given + 13.61 so that HI (dissolved) + HgO (precipitated) disengages + 23.0. The heat developed in the formation of crystallised mercury iodide is greater than that of any other iodide. 5. The numbers obtained for the action of a solution of oxalic acid on calcium hydrate vary as much as 2.0 units; this the author believes to be owing to the formation of hydrates of calcium oxalate of various composition.Probably the variations observed by Favre in the precipitation of barium sulphate are due to the same cause. 6. The constitation of a salt recently dissolved is not necessarily the same as that which it acquires after the lapse of a certain time. In the experiments of Reischauer (Ann. Chem. Phnym,. cxv 116) on fused sodium acetate it was found that the salt deliquesced when exposed to the air absorbing as much as 7H,O ; this supersaturated POL. XXVIT. K ABSTRACTS OF CHEMICAL PAPERS. solution suddenly crystallism depositing the ordinary hydrated acetate CzH3Na02.3Hz0, and then the 4H20in excess which it had absorbed passes off by spontaneous evaporation.This phenomenon the author believes may be explained by snpposing that the sodium acetate which is present in solution in the anhydrous state suddenly becomes hydrated and separates in the crystalline form. Although in this instance the change takes place suddenly it is possible that in others it may take place gradually ;this appears to be the case with the formates of strontium calcium &c. The probable cause why certain solutions require the lapse of a longer or shorter period of time before they pass from a state of supersaturation to the normal state is that the salt iu solution is only slowly transformed into the hydrate ultimately depo- sited.C. E. G. Specific Heat of Zirconium Silicon and Boron. By W. G. MIXTERand E. S. DANA(Ann. Chom. Pharm. clxix 388-392). THEdeterminations were made by means of Bumen’s ice-calorimeter with the following results:- Specific heat. (1 .) Pure silver .................... 0.0549 (2.) Crystallised silicon (Si 98.7 Fe 0.6 0.16995 Zn 0.7). ................... ] 0.1704 (3.) Zirconium (Homogenous plates re- sembling graphite and contain- 0.1313 0.1321 ing Zr 54.53 Si 5.44 A1 40.36) 1 0.2472 Crystallised boron (B 0.2489 A1 9.92). ................... } Prom these numbers the following specific heats of the pure elements were calculated (specific heat of iron 0.1138 Zn 0.0955 A1 0.2143) :-Silicon = 0.171. Zirconium 0.066.Boron 0.2518. These numbers show that silicon and boron do not obey Dulong and Petit’s law as already observed by Regnault and Kopp while the atomic heat of zirconium is nearly the same as that of silver. c. s. Frigorific Effects produced by Capillarity combined with .Evaporation of Carbon Disulphide on Bibulous Paper. By C. DECHARME (Compt. rend. lxxvii 998-1000). ON dipping the end of a piece of bibulous paper into carbon disulphide the liquid rises on the paiper owing to capillary attraction. Small crystals like hoarfrost may be observed on the highest point of the mpillarised liquid. Whether these are n compound of carbon disulphide with water or whether they are ice the author has not been able to determine. The temperature falls from + 20 to -12 or -15.A similar phenomenon is produced by chloroform but not by ether. W. R. GENERAL AND PHYSICAL CHEMISTRY. Researches on Explosive Substances. By MM.Rous and SARRAU (Compt. rend. lxxvii 478-481). THE authors have made a number of experiments with different kinds of gunpowder by exploding them in a manometer. The compression of gas from 3 4,and 5 grams of powder was measured for example at 27" by 64 86.5 and 106.0 mm. of mercury. These numbers reduced to 1 gram of powder give 21.3 21.6 and 21.2. The contents of the gauge being 108 c.c. the gas from 1gram of powder occupies at 0" and 760 a volume equal 271 c.c. which is found by the following for-mula :-V' = 0.102 214 x 273 = 0.271. 76 x (273 + 27) The resu1t.s obtained are tabulated as follows :-Atmospheres.Sporting powder. .. SO7 -3 4654 234 3989 2,687,909 Cannon powder .... 752 -9 4360 261 4168 2,524,317 Rifle powder. ...... 730 -8 4231 280 4339 2,45 1,987 Ordinary powder. .. 694 -2 4042 281 4160 2,343,492 Blasting pow-der. ... 5'70 -2 3372 307 3792 1,952,910 The second column refers to the number of heat-units evolved by the gases in passing from the temperature of combustion to the ordinary atmospheric temperature of 17". The third gives the abso- lute heat of combustion obtained by the formula T = 273 + 17 +-9 Q when c repyesents the mean specific heat at a constant volume of the products of combustion. The number c = 0.185 formed by Bunsen and Schischkoff has been adopted. The fourth columa shows the volume of gas in litres at Oo and 260 mm.from 1 kilo. of powder. The pressure of expansion of the gas compressed into the bulk of 1litre is to be found in the fifth column. The sixth column gives the extreme theoretical amount of work in foot-pounds. Experiments have also been made with gun-cotton &c. with the following results :-VOl. of gas for 1kgr. Gun-cotton. ........................ 1056 *3 0 *a53 720'"litres. Dynamite 75 per cent. nitroglycerin. .. 1290 .O 0 ~600 JJ Picrate of potassium.. ............... 787 -1 0.740 576 )I Mixture of 55 parts picrate of potas-916 '3 0 *4S5 334 tf sium and 45 nitrate of potash .... } Mixture of equal parts of picrate and 1180 *2 0 *466 329 ,¶ chlorate of potash.. .............W. R. K2 ABSTRACTS OF CHEMICAL PAPERS. Action of Heat on Gases and Vapour condensed by Charcoal and the Behaviour of Charcoal with certain Liquids. By MELSENS (Conipt. rend. lxxvii 781). WHEN wood-charcoal saturated with dry chlorine is placed in the longer branch of Faraday's syphcn gas-condensing tube and the heat of boiling water is applied to it the shorter branch being placed in a freezing mixture a portion of the gas is volatilised. Pressure being thus developed liquefied chlorine soon appears in the tube. The expe- riment is well adapted for a lecture-demonstration. The author has liquefied in this manner ammonia sulphur dioxide hydrosulphuric acid hydrobrornic acid ethyl chloride and cyanogen. Wood-charcoal retains so firmly the vapours of the volatile liquids bromine hydrocynnic acid carbon sulpliide ether and alcohol that upon repeating with them the experiment just described no liquid is obtained.* Youillet observed a slight evolution of heat when water oils ethyl acetate and alcohol were absorbed by mineral powders and still more marked effects with organic powders The author finds that with charcoal still more heat than in the above cases is given out when it ahsorbs liquids upon which it has apparently no chemical action.Thus 17 ith 5-10 grams of charcoal and 40-80 grams of brorrtine the temperature was raised 30" C. If the charcoaJ had been previously heated to expel gas and then cooled in vaem the absorption of bromine being also conducted in VCICUO,no doubt the rise of temperature would have been still greater.B. J. G. Researches on Crystalline Dissociation Valuation and Dis-tribution of Work in Saline Solutions. BF P. A. FAVRE and C. A. VALSON(Compt. rend. lxxvii 577-584; 802-808; and 907-915). THEsolution of a salt in water is usually accompanied by a contraction of the salt and of the solvent ;this can readily be determined by com- paring the density of the solution with that of the salt and solvent. The mechanicd value of this contraction can be calculated since we know that at a temperature of' 15" a contraction in water of iG1m of its bulk corresponds to 7576 heat-units. In making these esti-mations the authors have determined with the greatest care the specific gravity of 16 various salts both anhydrous and contain- ing water of crystallisation; also the density of a solution con-taining one equivalent of the salt-reckoned in gi ams-in one litre of water.They 'have observed that the circumstances under which the hydrated salt wsumcs the crystalline state slightly influences its density which cannot therefore be regarded as absolutely inva- riable. Three tables accompany the first memoir giving for 16 salts -I. The density of the anhydrous salt of the hydrated salt and of its aqueous solution prepared as above described. 11. Gives the total * With regard to alcohol this observation is implied in the fact recorded by Hunter in this Journal [IS] vi 187 that 1 volume of charcoal at 100°C.,absorbs 141.1volumes of alcohol vqiour.GENERAL AND PHYSICAL CHEMISTRY. contraction in volume produced by the solution of the anhydrous salt ; the contraction due to the formation of the hydrated salt; the con- traction due to the solution of the hydrated salt thus found ; and also the mechanical equivalent correspondiiig with these contractions expressed in heat-units. 111. Tabulates the amount of heat rendered sensible in the calorimeter by the solution of the anhydrous and hydrated salts and also that corresponding with the formation of the hydrated crystal. From an inspection of the last-mentioned table it will be observed that with the exception of strontium nitrate all the anhydrous salts dissolve with disengagement of heat whilst all the hydrated salts with the exception of aluminium sulphate with 18H,O lower the temperature.The second communication gives the results obtained from a com-parison of the coercive effects produced by the solution of anhydrous salts of different kinds in water accompanied by a tabular arrangement of the experimental results and the numerical consequences deduced from them. An inspection of this table shows :-1. That with the exception of amnionium chloride bromide and iodide all the salts examined give rise to a contraction of volume on being dissolved. 2. With respect to their coercive energy the salts of the various acids may be arranged in the following groups :-lst. Carbonates and borates ; 2nd sulphates and fluorides ; 3rd chlorides nitrates and bromides ; 4th iodides. The corresponding arrangement according to the metal they coctain is lst aluminium and copper; Znd strontium barium and calcium ; 3rd sodium and potassium ; 4th ammonium.3. When R salt dissolves two opposed effects may be simultaneously produced lstly the contraction of the solvent under the influence of the salt ; Zndly an increase in volume in the salt caused by dissocia-tion. Of these the first is generally the most c~nsidera~ble. 4. When a salt is dissolved each of its saline radicals produces an increase of density proper to itself and quite independent of the other radical with which it is associated. 5. As ammonium chloride bromide and iodide when dissolved produce an increase in the total volume a result iiot observed with salts of other metals the author thinks it probable that the ammonium salts in solution are in a much more advanced state of dissociation than any of the other salts which have been examined.It is possible that the phenomena of coercion may be due to the molecular surfaces of the salt in the extreme state of division in which it is in solution acting on the water so as to give it a density greater than that which it possesses in the liquid or even in the solid state somewhat similar to that produced by the action of charcoal on car-bonic anhydride when the latter is condensed within its pores ; here the development of heat is greater than that which would be produced by the solidification of the gas. In the third memoir the authors observe that when several salts of strong acids are dissolved in a sufficient amount of water the thermic results are such that we may suppose each of the acid radicals to be associated indifferently with any of the metallic radicals ; this is the result of the phenomenon of therrnoneutrality as deduced from the ABSTRACTS OF CHEMICAL PAPERS.existence of 8 thermic modulus. The variations in volume which accompany solution also satisfy these relations ; and when this is the case the author designates it by the term delzsi?zezdratiity. There are however certain exceptions. Berthelot has already treated this ques- tiou from the point of view of the calorific effects aiid the author's results obtained from the determinations of the density of the solutions agree with these thus sodium nitrate produces sensibly the same calorific effect whether it is dissolved in pure water or in a solution containing equivalent quantities of sodium chloride or ammonium sulphate.The increase of density is also practically the same. In the case of certain double salts such as copper-pot,assium sulphate the results show that the double salt no longer exists in solution and therefore the conditions of thermoneutrality hold good ; with acid salts however which in the crystalline state are true double salts the case is different; here their state when in solution as shown by their density is the same as that produced by a mixture of a solution of the normal salt with a solution of the acid. Thomsen has ascertained that this causes an absorption of heat.Amongst those salts which do not satisfy the conditions for thermo-neutrality the authors have examined two cases namely the solution of 1 equivalent of sodium carbonate in water containing 1equivalent of ammonium szlyhate; and the solution of 1 equivalent of sodium borate in water containing 1 equivalent of ammonium sulphate ; in both these instances the theymic results show that there has been an almost complete interchange of acids by the bases. C. E. G-. Verification of Baumci's Hydrometer. By BE RTH ELOT Cou L IF:R and D'ALN E r DA (Compt. rend. lxxrii 9 70-9 71). THEgraduation of this instrument having been altered so that it was no longer in conformity with the original definition the authors under- took to re-establish the graduation and in the course of their investi- gations have obtained some numerical results which they think may be useful.The solution of salt which serves as the standard is made by dis- solving 15 parts of sodium chloride in 85 parts of distilled water. A litre of this at the temperature of 12.5" and at 760 millimeters weighs lll0*57grams the weighings being made in air with brass weights. The apparent weight of a litre of water weighed in this manner is 998.084 grams at 15" 998.404 grams at 12-5" and 998-876 grams at 4". C. E. G. An Improved Form of Gas Generator. By C. J. WOODWARD (Chem. News xxviii 209). Two forms of apparahs are suggested available respectively for large or small quantities of gas. They are simple in character. A small vessel for the solid reagent is placed above and in connection with a larger vessel containing the acid.By various modes of pressure the INORGANIC CHEMISTRY. 123 acid is forced into. the upper vessel containing the solid (chalk, zinc &c.> and the gas generated is drawn off for use. When sufficient gas has been obtained the pressure is relieved and the acid flows back into the lower vessel. J. B. On the Nature of Electricity. By E. EDLUND (Pogg. Ann. Erganzungs-band vi 241-262). A New Electrical Machine according to Holtz’s Principle. By H. LEYSER (Pogg. Ann. cxlix 587-591). On the Secondary Current. By K. W. KNOCKENHAUER (Pogg. Ann. Erganzungs-band vi 302-314). On Temperature and its Measurement. By G. RECKNAGEL (Pogg. Ann. Erganzungs-band vi 275-302). Application of Solar Heat as a Source of Mechanical Power. By A. BERGH(Pogg. Ann. Erganzungs-band vi 591-595).

ISSN:0368-1769    

DOI:10.1039/JS8742700113

出版商:RSC    

年代:1874

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Cheznis try. The Polythionic Acids. By W. I€. SPRING (Deut. Chem. Ges. Ber. vi 1108-1111). THE author has examined the action of the chlorides of sulphur S'LC12,SC12, on certain of the metallic sulphites. If the chloride S2C1 (b. p. 138') beadded drop by drop to a solution of pure potassium sulphite a slight rise of temperature is observed and the solution remains perfectly clear but after a time abundantly deposits potassium trithionate. The mother-liquor then contains- beside potassiiim chloride-potassium thiosulphate (hyposulphite) but in proportionately very small quantity. If the amount of S2C12 neces- sary to convert potassium sulphite into trithionate be added at once to the concentrated solution a considerable quantity of flocculent amor- phous sulphur separates.On the addition of S2C12to barium sulphite suspended in the smallest possible quantity of water a slow action accompanied by rise of temperature was observed sulphurous anhy- dride was evolved and the solution contained barium chloride and trithionate ; but the quantity obtained of the latter salt was small. From these observations it appeared probable that the action of the chloride SCl on sulphites would giye rise to the formation of trithio-nates without secondary products and this experiment shows is the case. On addition of this chloride to a concentrated solution of potas-sium sulphite the mixture became warm and %~r crystalline mass of potassium trithionate was soon deposited. If an excess of the chloride ABSTRACTS OF CHEMICAL PAPERS.was added the rise of temperature was greater sulphurous anhydride was evolved and white sulphur separated. This mode of formation renders it extremely probable in the author's opinion that the constitu- tion of trithionic acid is given by the formula H-0-0-0-S-S-S-0-0-0-H. Thiosulphuric acid may with considerable probability be regarded as H-S-S-0-0-0-H ; and since by the action of iodine it may be converted into tetrathionic acid it appears almost established that the formula of tetrathionic acid is H-0-0-0-S-S-S-S-0-0-0-H. The author considers that some light is thrown on the constitution of pentathionic acid by the following experiment :-On the addition of SJ.3 in small quantities to a pasty mixture of barium thiosulphate and water eulphur separates ; if the mass be then at once brought on a filter and the filtrate allowed to drop into diluted sulphuric acid barium sulphate is precipitated but no sulphur.After eliminating the free sulphuric acid by the addition of precisely the required quantity of barium hydrate a solution is obtained which exhibits all the reactions of pentathionic acid. This mode of forming penta- thionic acid leads to the formula H-0-0-0-S-S-S-S-S-O-O-O-H. As characteristic of trithionic acid and as a meam of distinguishing if from dithionic and tetrathionic acid it is stated that the salts of this acid when heated with solution of cupric sulphate cause the separation of cupric sulphide. This is observed only when sulphites are either absent or present in very small quantity only ; if the solution contain much sulphitle the cupric salt is reduced but no sulphide precipitated.To ascertain whether during the reduction caused by the sulphite the trithionate underwent alteration the author mixed concentrated solu- tions of potassium sulphite and trit'hionate then added cupric sulphate and heated. The liquid became colourless and on cooling deposited fine white glistening needles having the composition (cu2)S306.K&06 + aq. This salt is difficultly soluble in water and insoluble iu alcohol. H. E. A. Decomposition of Nitric Acid by Heat. By I;. CARIUS (Ann. Chem. Pharm. clxix 273-343). NITRIC acid as is well known is decomposed by heat yielding red vapours.The object of the present research has been to ascertain the nature and degree of this decomposition at vai*ious temperatures princi- pally by determining the specific gravity of the vapours. The specially prepared acid employed contained 99.55 per cent. HNOs and 0.45per cent. H20. No further dehydration could be attained. The determina- tions were all made in tubes of hard glass which was proved to be unacted on by the acid. In the first series the following process was INORGANIC CHEMISTRY. used A small quantity of the acid was sealed up in a weighed tube together with air and the tube then heated to the required temperature in an air or vapour bath. The baths employed are minutely described and figured. The tube which was placed horizontally was frequently rotated in order to mix the contents.The whole of the liquid being concerted into vapour the capillary point of the tube was opened in the flame and the pressure allowed to equalisc itself very slowly with that of the atmosphere. The tube was then re-sealed cooled weighed opened under water and the residual air + oxygen measured. The oxygen not reabsorbed during the cooling was calculated from a sub-sidiary research (vide infm). The actual amount of acid in the tube when weighed was also controlled by conversion into a barium salt and only those determinations accepted in which the two methods gave concordant results. The tabulated results of the determinations made by this method at about every 10" between 129" and 312" show that the decomposition increases up to about 256" above which temperature the density of the vapour is appreciably equal to 18 (H = l), which is 4 of that of HNO (31*5) as it should be if the decomposition takes place according to the equation 2HN03 = 2N02 + H20 + 0.For lower temperatures the density (air = 1) is given by the two interpolation formulce- s = 1.68619 + 0.0069874tF -0.000044'736t2+ 0*0000@0029869t3.,I. s = 17.1814 -0.2015215 + 0*00087296t2 -0~0000012848t3.... 11. The first is used for temperatures between 1'70" and 180" the second for temperatures above 190". Below 160"a third formula derived from the second series was used owing to the larger number of the deter- minations upon which it was based. In the second series the method was modified.A known weight of nitric acid was introduced (in a closed bulb) into a tube of known capacity filled with air. The tube was then sealed and after break- ing the little bulb the whole was heated opened and resealed as before. From the measurement of the residual air the volume of the vapour at the given temperature could be calculated. Numerous pre- cautions requisite for obtaining accurate results are described as are also the details of determinations of the density of benzene bromine and chloride of sulphur vapours made according to the above methods to show the degree of accuracy which they would afford. The formula derived from this series was- s = 2.14494 + 0.0003402t -0~000016154t2.e.. . . 111. which agrees well with formula I.The determinations of the amount of oxygen remaining unabsorbed on cooling were made by a process in every respect similar to the second method except that the tube was not opened at the high tem- perature. The increase in the volume of the permanent gas over that originally contained in tlie tube was regarded as oxygen. It was ABSTRACTS OF CHEMICAL PAPERS. found that the amount of residual oxygen increased with the tempera- ture and also with the relative volume of air up to certain limits. For correcting the first series of determinations the assumption was made that the limit occurred when 500 C.C.of air were present with 1gram of nitric acid and further that the increase of the residual oxygen up to this point was regular.The corrections calculated from these assumptions are apparently as accurate as if the free oxygen had been determined each time. These experiments also showed that above 200' the proportion of re-sidual oxygen becomes constant evidently owing to the re-formation of nitjric acid during the cooling of the sealed tubes so that above 200" the decomposition assumes the character of true dissociation. The reason why the oxygen is not entirely reabsorbed on cooling is evidently that the presence of water is necessary and that as the amount of HNO formed increases it unites with the excess of water to form a compound which no longer influences the combination of N20aand 0. This takes place when the reconstituted acid contains about 17 per cent.of water. It would follow from this tliat abore the limit of the increase of air (e.g. with 1200 C.C. to 1gram of HNO,) and below 200" the whole of the oxygen set free would remain so ; and on calculating by the first method the specific gravity of the vapours and from that the extent of the decomposition a very close accordance was observed between the amounts of oxygen thus obtained and those actually observed. The corrections for the residual oxygen in the second series in which this excess of air was always prasent were made in accordance with this supposition. A few experiments were made respecting the vapour-density of dilute nitric acid in order to correct the experiments with the strong acid for the amount of water it contained.The presence of water was found to hinder the decomposition but not to such an extent as to make the correction for 0.45 per cent. larger than the errors of observation. Even acid so dilute as 0.15 per cent. is decomposed to some extent by being heated to 260". Finally a variety of considerations and experiments are brought to bear on the inquiry whether the decomposition is accurately represented by the equation given above and it is shown to be in the highest degree probable (though data do not exist for absolute proof) that none of t,he other oxides of nitrogen are present. The following portion of a table shows the percentage decomposition at every 10" above the boiling point of the acid. 86". 90". 100". 110". 120". 130". 140°. 150". 160". T * ~ ~ o ~11.05 ~11.44 ~ ~ ~ ~12.86 1465 -}16.74 19.05 21-86 25.48 28.96 170".180". 190". 200". 210". 220". 230O. 240". 250". 256". composition.. } 35.25 41.23 49.39 58.83 66.12 72'0'7 '7'7.67 8422 93.03 100.0 I.-Per cent. de-M. J. S. INORGANIC CHENISTRY. 1.27 The Dioxides of Barium Strontium and Calcium. By EM.SCHONE (Deut. Chem. Ges. Ber. vi). THE author refers to a communication made by him seven years ,ago in which he pointed out some of the properties of these dioxides. He prepares them by the original method of Thitnard and assigns to them the formulz Ba02.8H,0-Sr02.8H20-and Ca02.8H20 respectively. The author generally confirms the results obtained by Conroy (see this Journal [2] xi 808) but differs from him in saying that the anhydrous oxides are snow-white not "pale buff," as stated by Conroy.Barium dioxide melts at a strong red heat oxygen being given off; at the same temperature the dioxides of strontium and calcium do not melt but they lose one atom of oxygen. The three hydrated dioxides crystallise in isomorphous forms belong- ing to the quadratic system the most ordinary combination being mP. oP the crystals being tabular from predominance of oP. M. M. P. M. Preparation of Crystalline Borates in the Dry Way. By A. DITTE (Compt. rend. Ixxvii 783-786 and 892-896). WHENboric acid is heated with an oxide or a carbonate the borate formed is generally in the form of a more or less transparent glass varying in composition with the proportion of each ingredient em- ployed.The great impediment in the preparation of crystalline borates in the dry way is in fact the ready fusibiiity of these bodies. This difficulty has now been overcome by adding the borate to be crystal- lised or its constituents to a mixture of alkaline chlorides in equivalent proportions contained in a platinum crucible so arranged over the lamp that the bottom only is at a red heat. The borate sinks and dis- solves in the chlorides which are only just in a state of fusion on the surface. On reaching the surface again by convection the borate becomes crystalline. It is easily detached from the cooled mass and is then washed with hot water. Cnlciz~n~ Bomtes.-A saturated boiling solution of boric acid readily attacks Iceland spar marble chalk or dolomite forming small needles.These crystals present the same appearance as the crusts of natural calcium borate which are found in Tuscany on the limestone and which Beudant supposed were formed by the action of borax upon the carbonate. The author has not however succeeded in decomposing limestone at the ordinary pressure with a hot saturated solution of borax. The composition of the borate formed by the action of boric acid on a carbonate is expressed by the formula Ca"H2B408.(H,B03)2 or monocalcic tetrametaborate pZus 2 mols. of boric acid. This com- pound loses its water at 20@",and fuses at 450". When it is intro-duced into the crucible containing the alkaline mixture kept at as low a heat as is compatible with fusion the crystals which form on the surface have the following composition :-Limo =44.57,boric oxide =r 55.42 corresponding with the formula CaB204 or calcium metaborate.The same result is obtained with the precipitate-a sesquimetaborate ABSTRACTS OF CHEMICAL PAPERS. according to Rose-which is formed on adding borax to a soluble calciiim salt. The addition of a small quantity of calcium chlo-ride to the fused mass in the above experiments causes crystallisation to take place more quickly but with no alteration in composition. The crystalline borate appears in the form of four-sided prisms often flattened out into plates and arranged in fluted masses. It is colour-less transparent very fusible readily soluble at 50' in concentrated hydrochloric or nitric acid diluted with its own bulk of water but insoluble in boiling concentrated acetic acid.If the calcium chloride employed in hastening the formation of the crystals amounts to a fourth of the whole mixture a borate is crystallised having the formula Ca3Ba0 (= Clt3B206+ B20s),or calcium orthoborate plus one mol. of boric oxide. This is zlso formed when a little boric acid is added to a fusing mixture of 2 parts of potassium chloride 2 parts of sodium chloride and 1part of calcium chloride. The crystals have the form of long prisms st-riated parallel to the side-edges. They are soluble in all acids except acetic. The third crystalline calcium borate formed has the composition lime = 34.67 boric oxide =65.32 corresponding with the forniula Ca2B,01,( = Ca2B,OS.B2O3), or 2 mols.of calcium meta- borate plus l mol. of boric oxide. It is obtained by adding to the mixed chlorides in fusion precipitated calcium borate,* or the prodixct of the reaction of boiling boric acid solution on caic-spar with the addition of one-third its weight of fused boric acid. The crystals are long silky slender needles. The same salt is obtained in flattened pearly needles when boric acid is simply fused with chalk. If in the former operation the boric acid instead of being one-third of the weight of the borate employed be in peat excess the crystallisation is retarded and the salt formed which is in flat needles soluble in cold nitric acid is the calcium analogue of borax. Strontizcm Berates.-Strontium carbonate behaves like calcium car- bonate with a boiling solution of boric acid.But if the product of the reaction or the precipitate produced by mixing borax with a soluble strontium salt be added to the heated chlorides it does not fuse but is converted into strontium borax containing strontia = 42.66 boric oxide = 57.33 corresponding with the formula SrB,07. Even when a slight excess of strontium chloride is present the same result is obtained. If in the last case a jet of steam be directed upon the top of the melting contents of the crucible crystals are formed which do aot differ in composition from those last mentioned. This compound forms long needles sduble in cold nitric acid. If caustic strontia be added in excess in either of the last three experiments opaque striated four-sided prisms crystallise out.These are very soluble in acid and have the composition Sr2B6Ol1.When one equivalent of boric acid and one equivalent of caustic strontia are heated strongly in a carbon crucible brilliant needles are obtained which when added to the mix- ture of heated chlorides containing a little strontium chloride are con- verted into short striated crystals consisting of SrBzOa. If in the last operation caustic strontia be also added in excess small flat prisms are obtained. They are coloured yellow by a trace of iron and they f Composition not given. INORGANIC CHEJlISTRT. have the composition Sr3B,0g. This compound dissolves in all dilute acids except acetic. Barium Berates.-When the precipitate formed by adding borax to a soluble barium sdt is dissolved in the fused chlorides needles are obtained which show a tendency to group themselves in crosses or stars the branches of which are inclined to each other at an angle of 60".The composition of these crystals is barium 52.37 boric oxide 47.63 corresponding with the formula BaBa07. Boric oxide and caustic baryta when brought to a strong red heat in equivalent quanti- ties in a carbon crucible yield a grey crystalline mass which when submitted to the action of the mixed chlorides with the addition of barium chloride furnishes white six-sided prisms terminated by pyra- mids. They are readily soluble in warm dilute acids and contain barium 58.46 boric oxide 41-54 corresponding with the formula B&B,O,,.The addition of caustic baryta to the crucible prevents all crystallisatioii. Magnesium Berates.-When a mixture of' magnesia and boric oxide the latter in large excess is brought to a white heat in a carbon crucible bard white opaque masses are left on cooling surrounded by the glass of boric acid. These masses consist of long needles radiating from centres. They are soluble in all warm dilute acids except acetic and they contain magnesia 30.00 boric oxide 70.00 corresponding with the formula Mg3B,0,,(= 3MgBz0,.B,0,j which is the formula of the boracite from Lunebuig. When this compound is introdiiced into the fused chlorides it loses half its boric oxide the freed oxide forming in transparent drops attached to the portions of salt which are yet unaltered.The crystals which form are large trans-parent flattened needles terminated by points. They dissolve in warm dilute nitric and sulphuric acids and contain magnesia 46.40 boric oxide 53.60 corresponding with the formula Mg3BaOg.The same compound is produced if the operation is commenced with one equi- valent of magnesia and two equivalents of boric oxide. If the artJificial boracite be heated very strongly with the mixed chlorides it loses a fourth only of its boric oxide. The crystals thus obtained are in the form of needles or of prisms which contain magnesia 36.85 boric oxide 63.15 corresponding with the formula MgBzOa. The constitution of the borates of barium strontium and mag- nesiu? above described is similar to that of the analogous calcium compounds.Double Berates.-If the artificial boracite be heated in the mixed chlorides with a large excess of calcium chloride the crystals form very slowly and the salt is obtained in prisms terminated by regular pyramids. It contains lime 29.78 magnesia 21.34 boric oxide 48.87 corresponding with the formula C&Mg3R,O,,[ or Ca3BaOg.&!g3B,0g]. If strontium chloride be substituted for the calcium chloride the compound Mg13,04 is alone obtained. But if caustic strontin be substituted a double salt of strontium and magnesium exactly analogous to the magnesio-calcic salt described above is obtained containing strontia 43-60 magnesia 16-40 boric oxide 40.00. Both these double salts dissolve easily in dilute acids. The author could not obtain a similar double salt containing barium.l3. J. G. ABSTRACTS OF CHEMICAL PAPERS. Iodarsenic Acid a Compound of Iodine with Arsenious Acid and its Compounds with Basic Oxides and Alkaline Iodides. By SILVESTRO (N. Repert. Pharm. xxii 385-390). ZI,NNO THEauthor showed in a former paper (Chem. Xoc. J. ['zf,ix 1164) that iodine under certain circumstances combines with sulphurous acid to form a kind of sulphuric acid in which the iodine replaces oxygen ; that certain salts are formed from this iodo-sulphuric acid ; and that the decolorization of iodide of starch by sulphurous acid depends on the formation of the above acid and not upon that of hydriodic acid and sulphuric acid as commonly supposed. In the present paper the author describes the formation of a similar acid from arsenious acid which he calls iodo-arsenic acid.Using the old notation he assigns to it the formula As03T2,and explains its con- stitution as the replacement of two atoms of oxygen iu arsenic acid by two atoms of iodine. It is prepared as follows :-To a boiling solution of arsenious acid iodine suspended in water is added as long as it dissolves and the liquid is filtered through charcoal and evaporated on the water-bath till it begins to lose its transparency. It is then left in a cool place for several days during which time the iodarsenic acid is deposited in very small brilliant colourless crystals. Iodarsenic acid has the following properties. It is more soluble in water than vitreous arscnious acid it is also soluble in alcohol but not in ether or benzene.It is decomposed by air and light and more especially by direct sunlight. If heated in the dry state it is partly decomposed into iodine and arsenious acid. Its solut'ion also by continued boiling is partly decom- posed into hydriodic acid and amenious acid. Chlorine-water and nitric acid set free iodine with formation of arsenic acid. Sulphuric and hydrochloric acids set free iodine. Sul-phuretted hydrogen gives the usual yellow precipitate while hydriodic acid is formed. Alkalis dissolve the acid and on concentration of the solution iodarsenates are deposited. Copper sulphate produces in the solution of the acid a dirty-white precipitate which gradually becomes brown.Ammoniacal copper sulphate gives a green precipitate ; silver nitrate a yellow ; mercuric chloride a red ; lead acetate a yellow ; chloride of gold a rose-coloured precipitate which is dissolved by excess of the reagent. If a solution of potassium iodide be poured into a hot soliition of iodarsenic acid (containing undissolved acid) a compound is formed of iodo-arsenic acid with potassium iodide while on cooling a part of the iodarsenic acid precipitates in the form of extremeIy minute silvery plates. If the solution is concentrated the compound of the acid and potassium iodide separates out in the form of a crystalline powder-the crystals being cubes. The salt thus obtained is very soluble in cold wster and shows the characteristics of the poluble iodides as well as of arsenious acid.Its formula (old notation) is KI.AsOsT2. The author has also obtained the corresponding ammonia salt. We must therefore conclude that when iodine acts upon arsenious INORGANIC CHEMISTRY. acid this new acid is formed and not as commonly supposed arsenic acid and hydriodic acid. Traces of the last two are indeed found but this is due to a secondary reaction. The author is extending his researches to produce similar compounds of iodine with nitrous phosphorous and antimonious acids i.e. wit,h the alkali-salts of these acids and has already obtained some favourable results. G. T. A. Bismuth its Alloys with the Alkali-metals and its Purification. By C. MBlriu (Pharm. J. Trans. [3] iv 341). BISMUTH contaminated with sulphur and arsenic may be purified to a considerable extent by keeping it melted at a sufficiently high tempe- rature and exposed to the air and throwing the oxide of bismuth upon the sides of the vessel as fast as it is formed.Arsenic and sulphur are volatilised as arsenious and sulphurous acids. The arsenic and sulphur may be more perfectly removed by fusing the roasted metal with potassinm or sodium tartrate when an alloy will be formed of bismuth and potassium or sodium as the case may be. The alkali- metal may be removed by melting the alloy in a porcelain capsule exposing a large surface. If the alloy contains potassium a liquid layer of canstic potash forms on the surface of the bismuth and pre- serves it from oxidation.It is necessary to throw the layer of melted potash on to the sides of the crucible and this may be done more readily if from time to time fragments of wood paper &c. be thrown in ; these convert it into the less fusible carbonate. When the bismuth contains no more potassium it begins to oxidize and should then be run off. It is diflicult to remove the last traces of arsenic. A mixture of alkaline carbonate and charcoal may be used instead of the alkaline tartrate. J. B. Chlorovmadates. By P. HAUTEFEU~LLE (Compt. rend. lxxvii 896). WHEN vanadic oxide mixed with litharge and lead chloride in large excess is brought to a dull-red heat then cooled and the excess of lead chloride washed out yellow transparent six-sided prisms are obtained having the composition represented by the formula 3Pb3V2Os.PbC1,.The angle-measurements give numbers which as well as the above observations show the identity of this compound with vanadinite. There are but few chlorides which can be made to combine in this way with vanadatcs. Thus with magnesium chloride vanadium oxychloride and magnesia are formed. With calcium chlo- ride however white crystals of an adamantine lustre are obtained containing vanadic oxide 39.07 lime 36-66 calcium chloride 23.75 = 99.48 corresponding with the formula Ca3V,0,.CaCl, or vanadium-wagizerite. The specific gravity of this compound = 4.01. It is amor- phous with wagnerite. The following .angles were measured :-M M = 97" 6' ; M h' = 138"43'. B. J. G. ABSTRACTS OF CHEMIOAL PAPERS.Chlorides of Molybdenum. By L. PAULLIECHTI and B. KEMPF (Ann. Chem. Pharm. clxix 344-359). 1. Molybdenum Pentachloride MoCI5.-Metallic molybdenum is heated in a glass tube in a current of dry hydrochloric acid gas until it sub-limes and dry chlorine is then passed through the tube. This salt forms a crystalline black mass which melts at a gentle heat and sub-limes unchanged in a stream of chlorine. Heated in the air it for-ms the oxychloride MoO2Cl2. 2. Trichloride MoCI,.-This salt which is formed by heating the pentachloride to about 250" in a stream of dry hydrogen is an anior- phous dmk brown powder unchangeable in the air at ordinary tem- peratures but when heated it forms at first a white sublimate which changes to brown and eventually gives off dark blue vapours impure dichloride remaining.It is insoluble in water in the cold but is decomposed on boiling in this liquid. 3. l'etrackloride MoCI+-When the last-named salt is heated in a stream of dry carbon dioxide yellow vapours are given off which condense on the cold part of the tube to form a brown slightly crys-talline powder. The tetrachloride thus prepared cannot be again snb- limed in an atmosphere of carbon dioxide without decomposition the products of decomposition being the penta- and tri-chlorides the last of which is again broken up into di- and tetrachloride. When heated in an open tube this salt yields a mixture of two salts whose formula are respectively MoO,H,CI and No02C12. 4. Dichloride MoC12.-The impure salt is produced when the tetra- chloride is sublimed in carbon dioxidtt (see above) ; it is purified by gentle warming with dilute nitric acid washing and drying.As thus prepared it forms tt yellow amorphous powder unchangeabIe in the air at ordinary temperatures but decomposed on heating a white sub-limate being produced while black oxide remains behind. Heated in a stream of hydrogen it is decomposed metallic molybdenum remaining. This salt is easily soluble in warm hydrochloric acid a salt having the formula Mo&l*.3H20 crystallising out on cooling. M. M. P. M. The Atomic Weight of Molybdenum. By L. METER (Ann. Chem. Pharm. clxix 360-366). INthis paper which is appended as a note to the foregoing on the chlorides of molybdenum tbe author deduces the number 95% as the mean atomic weight of molybdenum.He points out the regular gradation in the atomic weight of the metals belonging- to vanadium chromium and copper groups thus- DZ. Diff. Diff. TT = 51.2 Cr = 52.4 Cu = 63.3 43.0 43.2 4A.4 Nb = 94.0 88.0 No = 95.8 88.8 Ag == 107.7 88-5 Ts = 183.0 W = 184.0 Au = 196.2 M. M. P. M. MINERALOGICAL CHEMISTRY. Chromium Dioxide. By E. HINTZ (Ann. Chem. Pharm. clxix 367-372). THISsalt is best prepared by the method of Schweitzer which consists in passing nitric oxide into a dilute solution of acid potassium chro-mate ; the resulting hydrated oxide is collected and washed first with water then with alcohol and dried until it ceases to lose weight.It is a black very hygroscopic powder (Cr02). When it is acted on by chlorine a small quantity of chromium chlorochromate (Cr30,C12) is produced while the temperature gradually rises to 250". The action of dry hydrochloric acid gas is to produce water chlorine and green chromium oxide which is eventually decomposed forming the violet chloride. Phosphorus pentachloride is almost without action on chromium dioxide. M. M. P. M.

ISSN:0368-1769    

DOI:10.1039/JS8742700123

出版商:RSC    

年代:1874

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. lbl in er a1o g i c a 1 Ch emi s try. Syngenite. By V. v. ZEPHAROVICH (Jahrbuch. fur Mineralogie 1873 638-642). THISmineral from the salt-beds of Kalusz in Galicia having the com- position CaS04.K2S04 -+ H20,was originally supposed hy the author from its optical characters to belong to the rhombic syst.em although the external character is decidedly monoclinic. Further examination of the optical characters has shown however that the crystals are really monoclinic and this result is confirmed by exact measurement of the angles. The most frequently occurring forms are co em CORm OP COP4 OOPS COP.2 COP COP2-Pm7 .Pm 2Pm, 3R GO P 2P. The most exactly determinable angles are oc!42 co P m = 156"6' ; oP cog GO = 104'; P GO co P co = 100" 38' whence the ratios of the axes are- Clinodiagonal.Orthodiagonal. Principd axis. 1.3699 1 0.8738 lnclination of the clinodiagonal to the principal axis = 76". The crystals 'cleave perfectly parallel to co P 00 and co P. The plane of the optic axis is parallel to the orthodiagonal. The specific gravity of the mineral is 2.603 ; hardness = 2.5. In the flame of a Bunsen burner syngenite becomes turbid colours the flame violet and melts easily to a transparent bead which when cold is white and faintly lustrous and has a crystallogranular struc- ture. Heated in a tube the mineral decrepitates violently gives off water and melts after prolonged ignition to a milk-white mass. It is easily attacked by water 400 parts of cold water dissolving 1part of it.The clear solution becomes turbid when heated from deposition of gypsum. H. w. VOL. XXVII. L ABSTRACTS OF CHEMICAL PAPERS. Potassium Salt from India. By G. TSCHERMAK (Jahrbuch. fur Mineralogie 1873 642). THIS salt is a white or reddish hard granular mixture of sylvin (KJ3O.J rock-salt and kieserite (MgS04.H,0) occurring in the " Salt-range " in the northern Punjaub which belongs to the Silurian formation and is therefore perhaps the oldest of all known salt-deposits. The sylvin and rock-salt are easily recognised by their cleavage and flame-reactions. The kieserite which occurs in grains not exceeding 12 mm. in diameter is colourless and exhibits the hardness and density of that from Hallstadt ; here and there also it occurs massive ; when heated it gives off 12.99 p.c.water which agrees with the calculated quantity (13.04). As kieserite is converted by contact with moist air into bitter salt (MgS04.7H,0) the lumps of the mixture become pul- verulent on the surface and continually throw off crusts. Many of the lumps consist chiefly of sylvin. H. W. Schrockingerite a new Mineral from Joachimsthal. By A. SCHXAUF (Jahrbuch. fur Mineralogie 1873 646). THISis a calcio-manic carbonate crystallising in small soft thin six- sided plates implanted on pitch-blende in compact spherical or floccu-lent masses. It has a light greenish-yellow colour and nearly nacreous lustre. It contains scarcely perceptible traces of sulphuric acid. At a rcd heat it becomes orange-red like liebigite and gives off carbonic anhydride and water to the amount of 36.7 p.c. In forin it resembles the micas appearing yder t4he microscope as six-sided tables terminated by the faces 00 P 00 and 00 P. One of the principal planes of optical vibration is perpendicular to co I? 00 showing that crystals belong to the rhombic system. These characters show that schrockingerite as distinct from all the calcio-uranic carbonates pre-viously known. H. w. Jordanite from Imf'eld in the Binnenthal. By L. LIPOCZ (Jahrbuch. fur Mineralogie 1873 644). Two analyses of this mineral gave the following results- As. Pb. 5. I ...... 12.78 69-99 18.18 == 109.95 11... . . . 12.86 68.93 18.13 = 99.94 showing that its formula is As,Pb&. H. W. Titanic Iron Ore of Abnormal Composition.By HILGER (Jahrbuch. fur Mineralogie 1873 643). THEmaterial in question was taken from a splendid crystal of titanic iron in the mineralogical cabinet of the University of Wurzburg, supposed to come fi-om Norway. Analysis showed it to contain- MINEltXL00ICAL CHEXISTRY. 135 TiO? Fe203. FeO. 46.42 52.67 1-07 == 100.16 Reckoning the small quantity of iron nionoxide as sesquioxide the ratio of the latter to the titanic acid becomes Fe203 TiOz = 3 504 giving for the mineral the formula Fe20,.5Ti02. Rammelsberg distinguishes three principal classes of titanic iron ore viz. I. 11. 111. FeO.TiO,. iFe0 $MgO }TiO,. Different from these are- 1. A titanic iron from Harkau near Chemnitz analysed by Hesse having the formula 3Fe,0,.9Ti02.2. Iserin described by Rammelsberg having the composition Fe0.Ti02 + Fe20,.3TiOz. 3. From Uitkel on the Rhine described by Rammelsberg ; composi-tion 2(FeO.TiOZ) f 3(3Fe0.2FeZO3). H. W. Buchonite. By Ii’. SANDBERGER (Jahrbuch. fur Mineralogie 1873 647). A DESCRIPTION of this rock belonging to the nephelin group has already been given (p. 608 of last volume) together with an analysis by C. Gmelin of the variety occurring at Sinsheim. The medium- grained variety from the Calvarienberg at Poppenhausen on the Rhon has lately been analysed by E. v. Gerichten. Its specific gravity is 2-85. Its proximate constituents are nephelin partly in course of transformation into natrolite ; hornblende ; a micaceous minerd ; magnetic iron ore; triclinic and orthoclastic felspar ; apatite and augite.A large portion of it (40.73 P.c.) is decomposed by hydro- chloric acid with very distinct separation of gelatinous silica. This portion is therefore to the undecomposible portion in the ratio of 2 3 whereas in the Sinsheim rock this ratio is 3 4. The residue of the treatment with hydrochloric acid contains after the silver has been removed by sodium carbonate a very small qumtity of augite trans- parent colourless orthoclast ic felspar and a small quantity of triclinic felspar. Quantitative analysis gave a. Portion soluble in hydro-chloric acid (calculated to 100). b. Insoluble portion (calculated to 100). G. Total constituents- Si02. P205. Fe203.81203 FeO.CaO. MgO. K20. Na20. H20. a. 33.19 2.50 15.80 9.3’7 11.56 0.84 2.78 2.16 12.08 2-77 6 54-64 -14.46 10.68 2.34 7-15 0.44 5.25 5.04 -c. G.84 0.66 14.32 10.18 6-42 8.m 1.47 3.56 8.77 1*21-100*83 The small amount of magnesia and the large amount of iron in the insoluble residue show that the rock contains not basaltic hornblende but a hornblende rich in iron and poor in alkalis like arfvedsonite and L2 ABSTRACTS OF CHEMICAL PAPERS. the hornblende occurring in the ziivon-syenite of Brevig. Orthoclase occurs abundantly in the residue and is an essential constituent of the rock. Notwithstanding the difference of mineralogical character the total result of the analysis of buchonite is very much like that which Rosen- busch obtained for the porphyritic nephelinite of the Katzenbuckel (Jnhrbmh.1869 47). H. W. Analysis of two Minerals from Greenland. By 5.V. JANOVSKY (Deut. Chem. Ges. Ber. vi 1230-1232). THE first mineral (from the interior of Greenland) may from its mineralogical characteristics be regarded as one of the chlorite group. It has a dark green colour and gives a white streak. Before the blowpipe it mejts only at the edges. It is but imperfectly decomposed by hydrochloric acid even after long boiling. It contains-SiOP A120p FeO. CaO. MgO. H20. PZO,. F. S03. I.. 30.32 1'7.90 7.71 1.28 29.88 12.28 0.11 -= 99.48 11.. 29.82 17.96 '7.47 1.22 29-40 -tmce tmce leading to the formula- %&". + 4Aq or A12Si05+ R",Si20 + 4Aq. Err6Si3O16 The second specimen (from the island of Kikkertarsursurok) is a mineral similar to zircon-syenite.It contains quartz a hornblende-like mineral eudialite nephelin some magnetic iron and a triclinic felspar. The hornblende-like mineral is black transparent and green at the edges dark green when powdered. Before the blowpipe it easily melts into a black bead. It consists of Loss by SiOz. A1203. FeJ03.FeO. MnO. CaO. MgO. E20. N%O. P205ignition. I,. 4424 1.80 4-27 29.46 2.20 8.88 3.11 1.31 0.83 2.33 1*35=99.74 11.. a.06 --8.'78 --111.. 4427 -29.33 -8.82 3.03 --The formula which agrees most nearly with the above results is R~iR'&3,~0,~, or R'*Si207 + 15(RrrSi03). G. T. A. Examination of English Chalk. By A. VOGEL (N. Rep. Pharm. xxii 391). A SPECIMEN of English chalk used in the preparation of cement con- tained 98.5 per cent.of calcium carbonate 0.46 per cent. of calcium phosphate 0.786 per cent. of matter insoluble in hydrochloric acid. This insoluble residue contained 48 per cent. of organic matter and the organic matter contained 1.1per cent. of nitrogen answering to 7 per cent. of protein bodies. MINERALOGICAL CHEMISTRY. The incrustation produced in vessels supplied with water from the well at the University of Munich contains on the average 0.05 per cent. of phosphoric acid. G. T. A. Titanium and Vanadium in the Basalts of Clermont-Fer-rand (Auvergne). By V. ROUSSEL (Compt. rend. lxxvii 1102). THE percentage of titanium in the basalts of this locality is greater than that given in any published analysis of basalt.The lowest per- centage obtained in ten analyses was 0.707 and the highest 2.378 the mean being 1.501. The titanium is best determined as follows :-The basalt is fused with sodium carbonate the cooled mass dissolved in hydrochloric acid the solution evaporated to dryness and the silicic acid dehydrated as usual. The whole is then boiled with dilute acid and the silica filtered off both precipitate and fiItrate contain titanium. The silica is ignited and then treated with warm oil of vitriol for several hours. The pure silica is left insoluble after this operation and the titanium is precipitated froin the solution by ammonia. The original filtrate from the silica is boiled with sodium sulphate sul- phurous acid and sodium hyposulphite.The impure titanic oxide is gentlyignited and then mixed with that obtained from the silica and the whole digested in a sealed tube with warm concentrated hydrochloric acid. The residue is titanic oxide. The same basalts contain vanadic oxide the percentage of which varied in ten analyses from ,006 to *023,the mean being ,014. B. J. G. The Carbonic Acid of Vesuvius. B~DIEGO FRANCO (Ann. Chim. Phys. [4],xxx 87-114). THE author has made observat,ions of carbonic acid at the centre of Vesuvius under the lava of the great eruption of the 15th Kovember 1868 and in the stream of lava of the eruption of 1871. The details of his observations are too minute to be given but the results may be summarised as follows :-In every case the presence of carbonic acid has been demonstrated ; it is often but not invariably accompanied by sulphurous acid.Car-bonic acid is always to be found in the crater showing that it is not an " expiring effort " of the eruption but accompanies it constantly. None however was found in the extinct funlaroles at the foot of the mountain where the atmosphere was dry. It appears also that the evolution of aqueous vapour ceases after extinction. In the fumaroles resulting from the eruption of 1868 a large amount of carbonic acid is present which may be proved by passing the mixture of gases through lime water whereupon an abundant precipitate is thrown down. Carbonic acid was found ouly in small quantity in the lava from the eruption in 1871 and but a small amount of oxygen (from 6-12 per cent.).Nitrogen was the most abundant constituent of the gas evolved. The presence of CO may be explained by the amount of aqueous vapour present as it is always associated therewith. W. R. ABSTRACTS OF CHEMICAL PAPERS. Relation of Lime to Carbonic Acid in Well Water. By A. MATER (Landw. Versuchs-Stationen xvi 274-277). TESTborings into the gravel of the Rliine valley were made by the method employed for the Abyssinian wells with a view to the supply of Mannheim with water. Determinations of calcium existing as carbo- nate acd of total carbonic acid were niade in txenty-five samples of water thus obtained. The mean quantity of lime was 15.12 grams and of carbonic acid 31.09 grams per 100,000 parts. The mean proportion between them was 1 2.06 and the extreme proportions 1 1.57 and 1 2.45. The smallest proportion of carbonic acid to lime (1.57 1) is exactly that required to form calcium dicarbonate R. W.

ISSN:0368-1769    

DOI:10.1039/JS8742700133

出版商:RSC    

年代:1874

数据来源: RSC

摘要:

ABSTRACTS OF CHEMICAL PAPERS. Organic Chemistry. On the Polymerisation of the Olefines and the Production of Ethyl Alcohol from Ethylene. By W. GORJAINOW and A. BUTLEROW (Ann. Chem. Pharm. clxix 196-149). XTHYLENE is not taken up by sulphuric acid at ordinary temperatures but at looo and still better between 160" aiid 175O the gas is rapidly absorbed and by subsequently diluting and distilling the acid liquid a considerable quantity of' alcohol may be prodnced. Elevation of tem-perature then being necessary to the absorption of ethylene by sul- phuric acid it appears not improbable that in Berthelot's well-known experiment the violent and continued shaking serves not only to bring the gas into intimate contact with the acid but to develop the heat necessary.Contszct of ethylene with sulphuric acid at the temperatures above mentioned did not result in condensation of the hydrocarbon. Neither did a still further elevation of temperature or the employment of fuming sulphuric acid or of fluoride of boron produce signs of poly-merisation. This remarkable stability in circumstances under which its higher homologues are easily affected indicates that the constitu- tion of ethylene is symmetrical and not analogous to that of propyleiie isobutylene &c. Propylene and isobutylene are readily polymerised by the action either of sulphuric acid or of boron fluoride. A preliminary experiment with isobutylene gare besides trimethyl-cerbinol oily condensation pro- ducts a fraction of which boiled at 113"-176" and had a vapour-density corresponding with the formula CI,H,,.Diisobutylenc seemed not to be formed under these circunistances. W. A. T. Isomeric Amylenes, Ey F. FLAVITZKY (Ann. Chem. Pharm. clxix 205-206). FERMENTATION amylic alcohol boiling at 131" and non-rotatory was converted into iodide and this iodide wlicii treated with alcoholic pot- ORGANIC CHENISTRY. ash yielded ethyl-amyl ether and an amylene boiling at 25". When this amylene is heated t80 100" with fuming hydrochloric acid it is con-verted into an amyl chloride boiling at 85"-86" ; moreover this chlo-ride is decomposed by water with production of an alcohol boiling below 100". When the above-mentioned ethyl-amyl ether is treated with phosphoric anhydride a liquid substance boiling at 35" is pro-duced together wit>h a gas which appears to be ethylene.This liquid is regarded by the aut.hor as an amylene; he intends however to continue his investigations. T. B. Preparation of Active Amyl Alcohol. By J. A LE BEL (Compt. rend. lxxvii 1021-1024). THE author proposes to act upon commercial amyl alcohol contain-ing both the active and inactive varieties with hydrochloric acid gas until the greater part of the alcohol is converted into amyl chloride. The unaltered part of the alcohol appears to consist principally of the active modifications but the author's experiment,^ have been thus far only partly successful and are at present incomplete. W. A. T. New Amyl Alcohol. By G. H. BEIGNESBAKHOVEN (Pogg.Ann. Erganzungsbund vi 325-332). THE author estimated by the polariscope the amount of active alcohol in the fractions distilling between 12-5" and 135" derived from fuse1 oil from potatoes and fi-om barley and found them to be respectively 23.68 and 38.4 per cent. the inactive alcohols being 76.4 and 61%; to these alcohols respectively he added 23.6 and 76.4 per cent. of sulphuric acid and 38.4 and 61%per cent. so as to have four mixtures ; half of each of these mixtures was made at the ordinary temperature half was previously cooled. After from two to three days these mixtures were shaken with water whereby part was taken up part left as an oily film ;from each of the eight specimens examined three kinds of barium salt were made :-(1) from the oily layer (2) , aqueous liquor separated fi-om the oily layer (3) mixed with the oily layer.9 9 All the 24 salts thus prepared had the same composition the most soluble one being that obtained from the oily layer in the case where the mixture was cooled whilst being made. Some of the salts were dextro- others Itevo-rotatory the specific rotatory power being 3.7 times as great as that of the alcohol prepared from the salt and being at a maximum where the lesser quantity of sulphuric acid was added (23%or 38.4 per cent. in the two cases respectively) the mixtures being cooled; the left-handed niaxinium was obtained in this case with the salt from the oily layer (No. 1) ; the right-handed maximum with the salt from the aqueous layer (No.2) ; the minima were found when the larger quantities of sulphuric acid were used (76.4 and 61.6 respectively) without cooling. 140 ABSTRACTS OF CHEMICAL PAPERS. With cooling. Without coolimg. (1.) With 38.4 per cent. Ralt from oily layer Salt from aqueous layer.. .,..... liquor ....... . } -0.149 Alcohol from oily layer -4.85. (2.) With 23.6 per cent. H2SO4-(2.) With '76.4per cent. ]ET$04-Salt from oily layer -18.36 Salt from oily layer +0*07 more or less completely separated from one another C. R.A. W. Action of Polyatomic Aleohols upon Oxalic Acid and its Application to the Industrial Preparation of Formic Acid. By LORIN (Hull. SOC.Chim. [Z] xix 241-244). Continuation see this Journal [2] xi 1219.THEtemperature at which the acid decomposes varies for each poly- atomic alcohol. The final product is sometimes as with dulcite a solid sometimes as with mannite a liquid. The hydrake of turpentine-oil is simply dehydrated by oxalic acid. 0RGA.NIC CHEMISTRY. 141 The following results were obtained in the preparation of formic acid on the large scale. 65-25kilograms of ordinary oxalic acid (containing *5kilogram of solid impurity) were gradually added to 1.12 kilogram of glycerin and yielded 23.004 kilograms of real formic acid or 97.3 per cent. of the quantity required by theory to be formed in the reaction. It was estimated that 2.2 per cent. was required to saturate the glycerin leaving 0.5 per cent. unaccounted for. The carbon dioxide evolved agreed with theory.The water was above theory. This was due to the fact that the glycerin contained a little water and the oxalic acid contained water of' interposition as well as of constitution. The organic liquid formed weighed 1.45 kilogram or 3.43 per cent. above the quantity theoretically required if monoformin were alone pro- duced. The idea originally entertained (An~t. Chi?n. Phys. [3] xlvi 477) that the action of polyatomic alcohols upon oxalic acid whereby the latter is split up into carbon dioxide water and formic acid is simply a catalytic one must now be abandoned. The action is analogous to that which takes place with sulphuric acid and monatomic alcohols with this exception that with the monatomic alcohol it is the acid which is stable and the alcohol which is broken UD but with the Dolvatomic alcohol the acid is split up and the alcohol &the stable bod;.B. J. G. Tribromacetic Acid. By H. GAL (Compt. rend. lxxvii 786-788). THISacid which was formerly obtained by the author (Compt. rend. Ivi 1257) by a rather difficult process may be more easily prepared by a reaction analogous to that which furnished Clermont with tri- chloracetic acid viz. by the oxidation of bromal hydrate with fuming nitric acid. The hydrate dissolves in the acid and occasions a fall of temperature. The solution is heated till vapours are abundantly evolved. The sourc~ of heat is then removed and the reaction allowed to proceed spontaneously. On cooling crystals are formed which after recrystallisation from water have the form of oblique rhombic prisms.Tribromaeetic acid thus formed has all the properties of the acid already described by the author. The dry acid may be touched with impunity but if any moisture be present a violent inflammation is the result of its contact with the skin. B. J. G. A New Synthesis of Propionic Acid. By J. H. VAN'T HOFF (Deut. Chem. Ges. Ber. vi 1107). ON distillation of a dry mixture of potassium oxalate and sodium ethy- late oily products pass over which have not yet been investigated ; the residue supersaturated with sulphuric acid and distilled yields an acid distillate. The distillate was neutralised evaporated to dryness, and converted into a silver salt by double decomposition ; this salt was boiled with water to decompose the formate present ; and the solution filtered.On standing a silver salt was deposited in the form of small ABSTRACTS OF CHEMICAL PAPERS. nodules containing 59.9 per cent. of silver. Silver propionate requires 59.7 per cent. of silver. No benzoic acid could be detected amongst the products of the action of potassium oxalate on potassium phenate. The author was led to make these and other experiments by Pfanltuch's statements (t'l-tis Journal [2] ix 895)) that diphenyl is produced on fusing a ben-zoate with potassium phenate ; that toluene is produced when a mixture of potassium phenate and potassium acetate is heated ; and that ethyl- berizene is formed by heating a mixture of potassium ethylate and a benzoate.He finds indeed that diphenyl is produced in small quantity by the first of these reactions ; but although he worked with moderately large quantities of material and under various conditions he could not obtain either toluene or ethylbenzene by Pfankuch's methods. H. E. A. Oxyacetic Acid (Glycollic Acid). By CONSTANTIN RG FAHLBE (J. pr. Chem. [2] vii 329-346). THEexperiments of Wurtz Drechsel and Kobe have rendered it not improbable that there may exist two acids having the composition C,H,O, viz. :-Methyl-carbonic acid c{ ;:i"' and Glycollic acid C{ :*OH Dessaignes Wurtz Schulze and Kekul6 have obtained crystalline acids of this composition whilst SGcoloff and Strecker and Kekul6 have also obtained acids that would not crystallise ; otlier differences also especially as regards volatility have been noticed by these observers.The author has prepared glycollic acid from the mother-liquors of fulminating mercury (by Cloez's method). The liquors are treated successively with sulphuretted hydrogen and milk of lime whereby mercury oxalic and glyoxylic acids are separated the latter being decomposed by boiling the liquor into glycollate and oxalate of cdcium ; carbonic acid is passed through the filtered liquid to precipitate excess of lime and the filtrate is evaporated to a syrup ; calcium glycollate then separates in crystals or if not can be thrown down by addition of an equal volume of alcohol ; by pressure the calcium salt is obtained free from acetate formate &c.and is piirified by crystallisation. From a concentrated solution an anhydrous calcium salt separates but from a more dilute liquid a hydrated salt Ca(C2E,0,) + 2H20; on recrystallisation the former salt becomes changed into the latker which dissolves in 80 parts of water at 1-5" in 19 parts at 100". The same salts were also obtained fi.om the product of the action of nitric acid on alcohol and of nascent hydrogen on oxalic acid. ORGANIC CHENISTRT. To obtain the acid the calcium salt is treated with oxalic acid and the filtrate with fresh lead carbonate. The solution of lead salt thus obtained is decomposed by sulphuretted hydrogen and the liquors are evaporated to a syrup whereby crystals are obtained which are anhy- drous after drying in vacuo and melt at 80" ; thy are quite non-volatile.Exactly the same substance is obtainable from nioiiochloracetic acid by KekulQ's process and from alcohol and nitric acid ;without doubt therefore the volatility of the specimen examined by other observers was due to the pmsence of impurities. When this acid is heated or allowed to stand in contact with vapours CO. CH,. OH of sulphuric anhydride glycollic anlyilride 0 ,is formedas a CO.CH,.OH white powder insoluble in cold water ether and alcohol ;the presence of a small quantity of this substance in molten glycollic acid prevents the liquid from becoming solid on cooling and standing. It melts at 128" CH, -130" so that as glycollic acid melts at 80° and glycolide { co } 0 at 180° the melting point of this anhydride is just midway between the two.A neutrallead salt Pb(C2H,03)2 and a basic salt Pb(C,H302)2.Pb0 ; a copper salt Cu(C,H,O,), and a thallium salt T1C2H302 are described all anhydrous ;the ethylie ether is readily obtained by heating equiva- lent quantities of calcium glycollate and potassium ethylslilpliate ; it boils at 150°9and has the sp. gr. 1.0333; water decomposes it into alcohol and glycoltic acid. -Its analysis agrees with idhe formula CR,.OH . CO.O.C,H The action of hydrochloric acid on pure glycollic acid does not yield chlomcetic acid ; the substance obtained by Kekul6's process from silver or potassium chloracetate however yields chloracetic acid in this way; but the author finds that this is simplyyi-eeontained in the inipure acid employed.Kekul6's production of bromacetic acid by the action of hydrobroniic acid on this impure glycollic acid is simply due to the reaction of the liydrobromic acid on the chloracetic acid actually present. By heating glycollic acid with alcohol saturated with hydro- chloric acid to 150° glycullic ether is formed but no chloracetic acid. The action of phosphorus pentachloride on calcium glycollate is CHzCl stated by Perkin and Duppa to give rise to chloracetyl chloride COCl The author could not obtain this body in this way but got it by treat-ing glycollic acid and phosphorus pentachloride to 120" in a scaled tube ; the product of the reactiou yielded chloracetic ether on treat- merit with alcohol. At 80" only the chloride of glycollic acid CH,.OH COCl ' was formed.By the action of phospliorus pcntachloride on glyco'Ilic ether at 150° chloracetic ether is formed the oxethyl group being unaffected. The author concludes from his research tliat glycollic acid from all sources crystallises when pure the same salts anhydride and ether beiiig obtainsble in each case and the acid being slwaj-s uoii-volatile. C. R. A. W. ABSTRACTS OF CHEMICAL PAPERS. Formation of Ethyl Acetate. By W. MARKOWNIKOPF (Deut. Chem. Ges. Ber. vi 117). ETHYL acetate is readily formed by distilling acetic acid with a concen- trated solution of ethylsulphuric acid. The same ether is therefore obtained by running a mixtare of equal molecules of alcohol and acetic acid into a small quantity of sulphuric acid heated to 130".By using 10 grams of sulphuric acid 232 grams of crude acetic ether were pro- duced. The same method may be used for preparing the ethers of bibasic acids but in this case the process is not continuous owing to the high boiling point of the product. On boiling a mixture of 1gram of sulphuric acid 8 grams of alcohol and 20 grams of succinic acid for two hours in a flask connected with reversed condenser 25 grams of crude ethyl succinate were obtained. By using more sulphuric acid neither is the duration of the reaction shortened nor does it take place at a lower temperature. c. s. Action of Phosphorus Pentachloride on Ethyl Diethoxalate. By W. MARKOWNIKOFF (Deut. Chem. Ges. Ber. vi 1175-1178).PEIOSPHORGS pentachloride converts ethyl diethoxalate into the ethylic ether of monochlorinated diethylacetic acid which by the action of sodium amalgam is converted into diethylacetic acid. This acid could not be obtained piire because the chlorinated ether is resolved by dis-tillation into hydrochloric acid and the ether of ethylcrotonic acid ; and the latter acid boils at nearly the same temperature as diethyl- acetic acid. c. s. Action of Phosphorus Pentoxide on Ethal. By W. MARKOWNIKOFF (Deut. Chem. Ges. Ber. vi 116). WHENethal is distilled with phosphorus pentoxide no pure cetene is obtained but a mixture of olefines. (Note by the Abstractor.-Heintz has already shown that the alcohol obtained by the saponification of spermaceti contains besides cetyl alcohol probably three other alcohols.) c.s. Action of Sulphuric Acid on Isobutaldehyde. By W. MARKOWNIKOFF (Deut. Chem. Ges. Ber. vi 116). BY acting on isobutaldehyde with sulphuric acid gaseous hydrochloric acid or phosphorus pentachloride it is converted into the polymeride C,H,,02 crystallising from alcohol or hot water in needles melting at 59"-60". It boils at 194O and sublimes in needles. c. s. 145 ORGANIC CHEMISTRY. A New Derivative of Valeral. By A. BORODIN (Deut. Chem. Ges. Ber. v 982-98.5). BYthe action of solid potassium hydrate at 0" on valeral and oenan- tho1 the author has obtained polymeric compounds which are evidently homologues of aldol. Both are colourless viscid liquids which when heated are converted wit.h elimination of water into con- densation-products the polymeride of valeral yielding an aldehyde C10H180,and a neutral body C2*HB03; the polymeride of oenanthol the corresponding homologues Cl*Hz60and CZ8H5,Os.According to Wurtz aldol is entirely resolved into water and cro- tonic aldehyde on heating; the author finds however that acetalde- hyde is also produced and that the polymerides of valeral and oenanthol behave similarly yielding together with the above-mentioned products more or less of the original aldehjdes. Wurtz has stated that aldol deposits crystals when kept. Similarly, the author has observed that the polymeride of valeral when allowed to stand in contact with about an equal volume of very dilute soda- solution often deposits crystals ; this does not take place in all cases however and the amount formed and the rate of formation varies greatly in diff eront experiments conducted apparently under precisely similar conditions ; in fact the conditions under which these crystals may be obtained at will have not yet been ascertained.The composi- tion of the air-dry crystals is represented by the formula (CloH2002)20H2; when heated they melt slowly to a colourless liquid which if not heated too long solidifies to a crystalline mass on cooling. If it be heated above the melting point decomposition takes place valeral passes over first then the aldehyde CloHlsO,and finally the compound C2,H,03 ; these products are obtained quite colourless and no residue remains in the retort.The crystals are similarly decomposed when heated with water or very dilute sulphuric acid; they are also decomposed with loss of waier when exposed over sulphurk acid. H. E. A. A Polyacetone. By W. HEINTZ (Ann. Chem. Pharm. clxix 11&120). WHENacetone is mixed with water and a sufficient quantity of caustic potash-solution is added to form with the water a solution having it specific gravity of 1.25-1.30 the acetone is separated as an oily layei-. On neutralising this acetone with sulphuric acid filtering from the sepa- rated potassium sulphate and distilling it is found that towards the end of the distillation the temperature rises and an oily liquid boiling at about 130"passes over this being followed by a small quantity of a substance of high boiling point which is probably phorone.The liquid passing over at about 130"appeared-to consist of mesityl oxide contami- nated with a substance containing more oxygen. Its specific gravity is 0.861 at 18" and its odour suggests that of acetone rather than that of peppermint and when the liquid has almost all evaporated it smells like cat's urine. When impure commercial acet,one was employed in the above experi- ABSTRACTS OF CHEMICAL PAPERS. ment the portions passing over between l~Oo-18O" were found to yield a substance to water and this substance was separated from its aqueous solution by the addition of calciuin chloride and agitation with ether. When the ether was renioved by distillation the new sub-stance was obtained as a thin syrupy fluid soluble in water and boiling between 166"-1.68".This siibstance appears to be the impurity which was contained in the mesityl-oxide previously obtained and analysis showed it to have the same composition as acetone. The author regards it as the oxy-analoguc of tlie duplosulphacetone of Wislicenus ; but this surmise was not proved as an attempt to take its vapour-density failed and the author could not obtain any more of the acetone which yielded the substance in question. Pure acetone treated as described at tlie conimencement of this paper did not yield a trace of the polyacetone but it yielded a portion of the substance boiling at 130° and a small quantity of the body sup- posed to be phorone. Impure acetone when treated with caustic potash evolves basic vapours which form a crystalline platinum salt.This however was not analysed. T. B. Nitro-compounds of the Fatty Series VI. By V. MEYER and C. WURSTER (Deut. Chem. Ges. Ber. vi 1168-1172). BY the action of ethyl iodacetate on a solution of nitroethane in alcoholic potash no ethyl nitrobutyrate is produced but an oil having a fruity smell and containing nitrogen. This compound could not be obtained in the pure state nor could the expected synthesis be effected by using other iodides or bromides. The cause of this failure is that. nitroethane does not form a potas-sium-compound inasmuch as on dissolving this body in alcoholic potash diluting with water and adding sulphuric acid no nitroethane is precipitated.By shaking the acid liquid with ether and evaporating the solution beautiful prisms resembling prehnite are obtained. They have a sweet taste and deflagrate by heat. When they are heated to 82" a copious evolution of gas takes place and a liquid remains behind. There exists hardly any other reaction in which potash and soda behave so differently as in their action on nitroethane and its homologues. When nitroethane is dissolved in well-cooled fuming sulphuric acid and the mixture is then gently heated a very violent reaction sets in gases being evolved and etheizeclisulphonic acid being formed. A solution of nitroethane in common sulphuric acid undergoes on standing a violent decomposition if the quantity of acid is not large.But by using an excess (about 15 times) and working with small por- tions a reaction sets in only when the liquid is boiled carefully for a few minutes. The products consist of acetic acid and a small quantity of another acid forming an amorphous barium salt. The latter acid is produced in larger quantity by acting on nitroethane with well-cooled fuming acid for several days. c. s. ORGANIC CHEMISTRY. Thallium Cyanide. By C. F R oN M ii L L E R (Deut. Chem. Ges. Ber. vi 1178-1180). THIScompound is conveniently prepared by precipitating a coricen-trated boiling solution of the sulphate with a saturated boiling solution of baryta and adding to the cold filtrate first concentrated hydro- cyanic acid and tlien a lavge quantity of alcohol and as much ether as will dissolve.An amorphous white precipitate is formed which is quickly washed with ether-alcohol arid dried in a vacuum. Thallium cyanide crystallises from a hot coucentrated solution in small glistening plates ; it smells strongly of hydrocyariic acid and is readily soluble in water ; 100 parts at 28.5" d'issolve 16.8 parts. When heated it melts and decomposes a non-inflammable gas being given off and metallic thallium mixed with carbonaceous matter being left behind. The aqueous solution has an alkaline reaction and is readily decomposed by carbonic acid. When the solution is heated in a sealed tube for some time the salt is completely decomposed into ammonia and thallium formate. Thallium cyanide forms with the cyanides of zinc and silver double salts which crystallise well and are more stable than the pure salt.c. s. Metallic Derivatives of Cyanamide. By F. B E I Ls TE IN (Deut. Chem. Ges. Ber. vi 1185). THE silver salt and copper salt of cyanamide recently described by Mulder have been previously investigated by the author in conjunc-tion with Geuther (Arm. Chem. Pharw. cviii 94). T. B. Cyano-Derivatives of Acetaldehyde and Acetaldehyde-ammonia. By F. URECH(Deut. Chem. Ges. Ber. vi 1113-1117). THEauthor has previously shown (this Journal [2] xi 60) that when a mixture of acetone potassium cyanide and potassium cyanate is treated with hydrochloric acid acetoityZ-wecc is produced by the conjunction of the acetone hydrocyanic acid and cyanic acid thus CJ&O + KCN + KOCN + 2HCl = C5HBNZO2 + 2KCl.He has now prepared in a similar manner from acetaldehyde the cop responding compound lactyZ-urea. In place of aldehyde its ammonia compound was employed however { CH3 CH(OE)(NH2) + ICCN + KOCN + 3HC1= {CH.NH co :r:NH } + 2KC1 + NH4Cl. Lactyl-urea thus obtained contains one molecule of water of crystal-lisation which is rapidly lost even on exposure to the air; it melts at ABSTRACTS OF CHEMICAL PAPERS. 145". The lactyl-urea which the author obtained from pure lacturamic acid (this Journal [2] xi 380) was anhydrous and melted at 125". It remains to be decided whether the two products are isomeric or identical. Both are resolved into xlanine carbonic anhydride and ammonia when heated with hydrochloric acid { EiE } co + 2H20 = Attempts to prepare from aldehyde-ammonia and nascent hydro- cyanic acid the compound corresponding with diacetone-cyanhydrin (this Journal [2] xi 60) were unsuccessful but instead thereof a body of the composition C,H,N was obtained :-2C2H,0N + 2KCN + 3HC1 = C6H,N3+ 2KC1 + NH4Cl + 2H20.It crystallises in white needles melting at 67"-68". On the addition of silver nitrate to the aqueous solution silver cyanide separates and at the same time the odour of aldehyde is perceptible On heating it with acids aldehyde and hydrocyanic acid are separated ; if the heating take place in sealed tubes alanine is also obtained On adding hydrochloric acid to a mixture of potassium cyanide potassium sulphocyanate and acetone the compound C5H70,NSis obtained When heated with hydrochloric acid it is resolved into acetonic acid carbonic anhydride and ammonia.With silver nitrate it yields the silver derivative C5H6Ag02NS. H. E. A. Synthesis of Taurocarbamic Acid. By E. SALKOWSKI (Deut. Chem. Ges. Ber. vi 1191-1193). AFTER several experiments made with the view of obtaining taurocar- bamic acid synthetically it was found that the potassium salt of this acid could be easily procured by mixing aqueous solutions containing molecular proportions of taurine and potassium cyanate evaporating and mixing the concentrated solution with alcohol the salt being then deposited in small needles. By decomposing this with sulphuric acid adding alcohol and evaporating the filtrate the free acid was ORGANIC CHEMISTRY.obtained and it appears to be identical with that obtained from urine. These results confirm Kolbe's assumption that taurine is an amido- acid. Sarcosine will probably yield similar results and the author intends to study the effect of replacing potassium cyanate by potassium sulpho- cyanate ; also to investigate the changes which taurocarbamic acid undergoes in the animal body especially in the case of rabbits. When an aqueous solution containing urea and taurine is evaporated no taurocarbamic acid is obtained. T. B. The Preparation of Alanine by Potassium Cyanide and the Simultaneous Formation of Lactyl-urea. By W. HEIN TZ (Ann. Chem. Pharm. clxix 120-130). POTASSIUM cyanide may be used instead of hydrocyanic acid for the pre- paration of alanine by Strecker's method.For this purpose hydro- chloric acid is added to aldehyde-ammonia and potassium cyanide dissolved in water and after some days the solution is evaporated in order to allow ammonium chloride and potassium chloride to separate. The syrupy liquid is treated with ether-alcohol to dissolve the alanine md after the removal of the alcohol and ether by distillation the sub- stance is saturated with ammonia. The addition of alcohol now causes the separation of alanine contaminated with sal-ammoniac and the alcoholic liquid separated from this was found to contain several substances one of which was separated as follows :-The potassium and ammonia were precipitated by sulphuric acid after which the alcohol was removed by distillation and the chlorine was separated by silver hydrate the excess of silver being then precipitated by hydro-sulphuric acid.After the small remaining portion of ammonia had been removed by boiling with baryta and the baryta had been sepa- rated by sulphuric acid a syrupy residue was obtained on evaporation. This syrupy liquid dissolved in alcohol from which it was separated by the addition of ether. The alcoholic filtrate separated from this syrup was freed from alcohol by distillation and the acid residue was neutralised by lime. Under these circumstances the author expected to obtain calcium lactate but instead of this long needles were de- posited and when this substance was rendered pure by crystallisation and pressure it formed large colourless rhombic prisms efHorescing in tjhe ail.and containing C4H6N202+ H20. When deposited from a strong hot solution it forms anhydrous microscopic needles. This sub-stance is probably identical with the Zactyl-urea of Urech and it evidently arises from the presence of cyanate in the potassium cyanide employed considerable quantities of it being formed when a solution containing potassium cyanate potassium cyanide and aldehyde-ammonia is treated with dilute sulphuric acid. Lactyl-mbea melts at 140" (125" Urech) and slowly sublimes at a somewhat higher tem- perature the melted mass becoming brown at the same time. Its taste is bitter it is easily soluble in water or alcohol less sohible in ether and it is neutral to litmus.When it is heated to 100"-145" with barium hydrate much ammonia is evolved and the residue was found TOL. XXVIT. M ABSTRACTS OF CHEMICAL PAPERS. to contain alanine and barium carbonate. A similar decomposition takes place when lactyl-urea is boiled for a very long time with baryta-water ; but when lactyl-urea is boiled with baryta-water for half an hour barium lactamate is formed. Lactyl-urea combines with silver hydrate to form a compound almost insoluble in watm but soluble in ammonia. This compound is precipi- tated as a white powder from its smmoniacal solution by nitric acid. Its composition is expressed by the formula C4H5AgNzOz. Lactyl-urea does not appear to combine with silver nitrate. T. B. Production of Methylamine in Methyl Alcohol.By C. VINCENT (Compt. rend. lxxvii 898-900). THEmethylamine found in methyl alEohol after the ordinary redistilla- tions (Cliem. Soc. J. [2] xi 498) is increased in quantity and is accompanied by dimethylamine and trimethylamino if the alcohol is redistilled for a still longer time. The crude spirit before these distil- lations contains traces only of methylamine but abundance of ammonia which gradually disappears. The ammonia is therefore an agent in the production of the methylamine. .The ammonia does not act directly upon the methyl alcohol for these two substances may be heated together for several hours without any methylamine being formed. The reaction takes place between ammonia and acetone which is always present in crude wood spirit as expressed in the following equations :-(1.) c3H60 + NH3 = CJ&O + NHZ(CH3).(2.) C3H6O + IIJHZ(CH3) = CzHdO + NH(CH3)Z. (3.) C3H6O +-IIJJ&(CH3)2 = CJhO + N(CH3)B. The aldehyde found in methyl alcohol is derived from the above reaction. B. J. G. Action of Bromal and Chloral on Benzene. By GUIDOGOLDSCHMIEDT (Deut. Chem. Ges. Ber. vi 985-990). Dipheny Ztribronaethnme is obtained when bromal and benzene in the proportion of one to two molecules are mixed with about double the volume of concentrated sulphuric acid + CBraCOH = CH(C6H,)2.CBr3 + HzO. Crystals gradually separate from the mass and after two or three days the action is complete. Diphenyltribromethane crystallises in mono- clinic prisms (ineasurements of the angles by Dr.Hintze are given) easily soluble in ether chloroform and carbon disulphide. It melts at 89". When heated it is decomposed with evolution of hydrobromic acid. Ui-phenyldibrornethylene c(C6H&CBr2 is produced by heating di- phenyltribrometliane with an alcoholic sorution of potassium hydrate ORGANIC CHEMISTRY. or with alcoholic ammonia or with silver acetate and some acetic acid and by the dry distillation of diphenyltribromethane. It crystallises in needles melting at 83" ; it boils with very slight decomposition above 300". Diphenyldibromethylene does not combine with bromine even when heated with it at 140". L)~l~eiz~E~icliZoretl~~Eeiie, C(C,H,),CCl, the preparation of which from diphenyltrichlorethane has been previously described by Baeyer (this Journal [el xi 885) is also a product of the dry distillation of diphenyl- trichlorethane.Diphenyltrichlorethane is also converted into diphenyl- dichlorethylene when heated to 200" with alcohol and potassium hydrate and on boiling with an alcoholic solution of potassium cyanide. Diphenyldichlorethylene crystallises from hot alcohol in long flat prisms from cold alcohol in well formed short columns from ether- alcohol in very long needles. All these forms belong to the monoclinic system. By the long continued action of sodium amalgam on alcoholic solu-tions of dipheuyltribromethane and diphenyltrichlorethane the author has succeeded in removing the halogen ; the product an oil boiling at about 267" is still under examination.Heated with hydriodic acid and phosphorus to 170° diphenyl-tribromethane yields a product which is a mixture of a crystalline and a liquid body ;the former is either diphenyl- dibromethane or diphenyldibromethylene. Heated with hydriodic acid and phosphorus at 210" the product consisted entirely of the liquid body. Analysis gave numbers intermediate between those required by the formub C14Hl,Brand C14Hl*. By heating dipbcnyltrichlorethane with zinc dust the author has obtained stilbene CIAH,,. H. E. A. Metabromotoluene. By H. HUEBNER and E. A. GRETE (Deut. Chem. Ges. Ber. vi 801-803). EXPERIMENT has proved that whereas two isomeric monosulphonic acids are obtained on treatment of parabromotoluene with Nordhausen sul-phuric acid orthobromotoluene yields but a single acid.The authors have examined the behaviour of Ilzetabromotoluetze-prepared from bromacetparatoluid-which according to Wroblevsky (this Journal [21, ix 129 xii 52) furnishes three isomeric bromotoluenesulphonic acids on treatment with fuming sulphuric acid. The aqueous solution of the sulphonic acid prepared in the usual manner was saturated with barium carbonate and fractionally crystal- lised. The first crystallisation consisted of naphthalene-like plates which remained unaltered in appearance after five recrystallisations from water. This salt when air-dry gave on analysis numbers agree- ing with the formula (C,H,Br.CH,.SO&Ba. The various subsequent fractions presented the same appearance and had the same composition ; hence the authors conclude that metabromotoluene furnishes only one monosulphonic acid when acted upon by fuming sulphuric acid.H. E. A. ABSTRACTS OF CHEMICAL PAPERS. Action of Chlorine and Nitric Acid on Benzylene Dichloride.* By H. HUEBNER (Deut. Chem. Ges. Ber. vi 803-and F. BENTE 806). HUEBNER and Heinzerling were led by their experiments to return a decided affirmative to the question Is the behaviour of all elements or groups of decidedly similar character Le. of all pronounced chemically negative (acid) or chemically positive (basic) elements or groups pre- cisely similar when they replace hydrogen in hydrocarbons or in other words do they replace the same hydrogen-atom ? A few exceptions to this rule have been noticed however.Thus Beilstein and Kuhl- berg state that whereas benzylene dichloride CeH,CHCI, is converted by chlorine into a chlorober,zylene dichloride yielding parachloro- benzoic acid on oxidation it is converted by nitric acid into a nitro-benzylene dichloride yielding nietanitrobenzoic acid on oxidation and not paranitrobenzoic acid .as might be expected. But inasmuch as benzylene dichloride is converted by the action of water alone and still more readily in presence of oxidising agents into benzaldehyde and benzoic acid it appeared not improbable that the formation of rnetanitrobenzoic acid was the result of the action of nitric acid on these latter bodies. The authors show that this explanation may confidently be accepted.They find that the nitration-product of benzylene dichloride does yield paranitrobenzoic acid on oxidation and that therefore nitric acid and chlorine exert a precisely similar action inasmuch as both give rise to the formation of para-derivatives. It appears probable that the product of the action of chlorine (in presence of iodine) on benzylene dichloride contains besides para- chlorobenzylene dichloride more or less of an isomeric compound. The authors had occasion in the course of their experiments to heat benzylene dichloride with an xlcoholic solution of ammonia and thus obtained the compound CGH5.CHCl.0CzH as a liquid boiling at 210"-212°. It is readily converted by concentrated nitric acid into ethyl metanitrobenzoate. Ethyl metanitrobenzoate is readily obtained by treating ethyl benzoate with nitric acid.H. E. A. Cpene. By F. BEILSTEIN and A. RUPFFER (Deut. Chem. Ges. Ber. vi ll8l-l18S) (a.) CUMIN-OIL cont,ains a terpene which was first observed by Warren and Fittig but; appears to have becn since forgotten. The presence of this terpene is the cause that the derivatives of the cymene from cumin- oil do not crptallise so well as those of cymene from other sources. To remove the terpene the crude cymene is repeatedly shakeu with a mixture of four volumes of sulphuric acid and one volume of water and then with coldconcentrated acid until it no longer leaves a residue on distillation. Pure cymene boils at 175" and has the specific grarity 0.8708 at 0" and 0.8572 at 20.2".The compound CGH5CHCl2 which the authors term benzjl dichloride also known as chlorobenzol is more appropriately termed benzylene dich1oride.-H. E. A. ORGANIC CHEMISTRY. (b.) Cymene from camphor after being treated with caustic soda still contains camphor which is best removed by shaking the well- cooled liquid with small quantities of concentrated sulphnric acid. It boils at 175" and has at 0" the specific gravity 0.8732. These two cymenes are identical the salts of their eulphouic acids having the same composition and solubility. -t-3H20fornis small glistening plates. 100parts of (C10H13S03)2Ba water dissolve at 16.Z0 2.503 of a and at 16*8",2.599 of b; and 100 parts of alcohol of 93 per cent. dissolve at 17*5O 5.3 of a and 5.46 of b.(CloH,3S03)~Pb + 3H20crystallises like the barium salt. 100 parts of water at i6" dissolve 1-34of a and 1-94of 6. (C,oH,3S03)2Ca+ 2H20 forms large brilliant monoclinic plates and is much more soluble than the barium salt. c. s. Oil of Wormwood. By F. BEILSTEIN and A. KUPFFEII (Deut. Chem. Ges. Ber. vi 1183-1184). COMMERCIAL oil of wormwood yielded by distillation the same products which Gladstone has observed viz. a terpene boiling at 160" absiizthol C1,Hl,O boiling at 195" and a dcep-blue oil boiling at 270"-300" and seemingly identical with the blue compound in oil of chamomile and galbanum. Absinthol treated with nitric acid does not yield camphoric acid ; on fusing it with potash a resin is formed but no acid. By the action of carbon dioxide and sodium no camphocarbonic acid is found but phosphorus sulphide converts it into common cymene.The authors point out that it seems to be forgotten that Devillc and C. G. Williams converted oil of turpentine into cymene some time ago the former by acting on it with moist cm=bon dioxide at a dull red heat the latter by treating the oil with bromine and then with sodium. c. s. On Terebene Hydrochloride and on a Method of Distinguish-ing from one another the Isomeric Bodies having the Formula C,H,,.HCl. By J. RIBAN(Bull. SOC.Chim. "21 xix 244-248). TEREBENE (this Journal [2] xi 1137) is converted into the hydro- chloride by the action of a slow and prolonged current of dry hydro- chloric acid. The vessel in which the rsaction takes place is kept cool by a stream of water.The hydrochloride is obtained in white crystals which are easily reducible to powder thereby distinguishing this hydrochloride from that of terebenthene the crystals of which are soft and waxy. Theory requires that terebene hydrochloride CloHIG.HCl should contain 20.57 p.c. of chlorine. But this substance ra.pidly undergoes a partial decomposition into hydrochloric acid and camphene which is still more quickly effected by the necessary washing of the crystals with water. It isrequisite therefore to bring the com- pound prepared as above to its state of full chlorination. This may ABSTRACTS OF CHEJlICAL PAPERS. be done in three ways (1.)By melting it at 230' in a current of hydrochloric acid.In this operation however liquid compounds are also formed. (2.) Sublimation at 150" in a current of hydrochloric acid. In this case too the chloride is contaminated with impurity owing to a portion undergoing decomposition into camphene and hydro- chloric acid which but imperfectly recombine in t?he cool part of the apparatus. (3.) Sublimation in an atmosphere of dry hydrochloric acid by the heat from a water-bath whereby the temperature does not exceed 70". This yields the best results and furnishes the hydrochloride in the form of feathery crystals having the odour of camphor and inactive to polarised light. With all these precautions the chlorine is still 0.59 p.c. below theory in the freshly prepared substance. The loss increases even in a dry atmosphere till the percentage of chlorine is reduced to l?to 18 when it ceases.Terebene hydrochloride melts at 125". The melting point must be determined in very thin sealed tubes containing dry hydrochloric acid. Water at 100" completely de- composes it into hydrochloric acid and a liquid. Terebene hydrochloride dissolves in warm absolute alcohol. If the temperature does not exceed 55"-60° transparent plates are obtained often a centimeter in length. These are not the pure chloride the percentage of chlorine being only 17-18 and the alcohol is strongly acid. Boiling alcohol rapidly decomposes the hydrochloride a volatile liquid 'being formed which has a formula probably analogous to that of terpinol. The behaviour with water furnishes a means of distinguishing the different isomerides of the formula CIoH,,.HCI.Thus terebenthenc hydrochloride is not decomposed by cold watei* and but slightly at looo The camphene hydrochlorides are slowly decomposed by cold water and more rapidly at looo with regeneration of crystalline cam- phene. The two borneol hydrochlorides undergo similar changes but with less in tensity. Lastly terebene hydrochloride decomposes in dry air of the ordinary temperature and still more rapidly when water especially if hot is present. This decomposition yields liquid com-pounds the other isomerides giving solids. B. J. G. Compounds derived from Camphor. By J. EACHLER (Ann. Chem. Pharm. clxix 168-205). PIMELIC acid was prepared from camphoric acid by the method of Hlasiwetz and Grabowski and after purification it was found to form clear transparent crystalline crusts.Single crystals were examined by Ditscheinar and they were found to belong to the triclinic system the axes a b and c being to each other as 1,0.64591 and 0.61443 ; more-over the angles x y x 2 and y z were found to be 73" 22' 82" 46' and 98" 5'. Pimelic acid melts at 114O is verysoluble in water alcohol or ether and has a taste like that of tartaric acid. The ammonium salt forms very soluble hygroscopic leaflets containing C7Hlo( NHJ204. The sodium salt is very soluble and contains C7H,,Na204. The barizm salt is exceedingly soluble and when the solution is evaporated under the air-pump it first deposits plates and then dries up to a porous mass which when dried at 200" contains C7H10BaOI.The ORGANIC CHEMISTRY.magnesium salt dries up to an amorphous mass containing C7Hl0MgO4. The copper salt was obtained as a green precipitate which when dried at 160" contained C7HloCu04. A solution of the ammonium salt is not precipitated by the salts of manganese ferrous oxide zinc cobalt nickel chromium cadmium or mercurous oxide but it is precipitated by the salts of ferricum aluminium lead or bismuth. The ethyZ ether C7Hl,(C2H5),04 was prepared by passing hydro- chloric acid into an alcoholic solution of pimelic acid. It forms a heavy oil having a fruity odour and boiling at 236"-240". When pimelic acid is distilled its anhydride C7H10O3 is produced which is a colourless liquid boiling at 245"-250" and reconverted it into the acid by hot dilute alkalis.Pirnelic chZoride C7H,,C120z,was obtained by treating the acid with phosphoric chloride and heating the product to 120" to drive off phos-phorus oxychloride. Pimelic chloride distils with partial decomposition at 210'. When pimelic acid is treated either with bromine or with bromine and water amorphous products are obtained and in the former case butyric acid is also formed. This acid is likewise produced when pimelic acid is fused with potash hence it is highly probable that the higher fatty acids which accompany pimelic acid in its production from camphoric acid result from its decomposition. Assuming this the reaction may be represented as follows :-CioHmO4 + 04 = C~H~ZO, + C2H402 + CO,.Camphoric Pimclic .thetic acid. acid. acid. The pimelic acid which has just been described differs from all other so-called pimelic acids which have been. from time to time obtained from fatty sources. Sdphocasnphoric acid was prepared according to the method of Walter the mode of purification being somewhat modified. An acid lead salt C,H,,PbS06 C9Hl,SOs + 4H20 was obtained by partially decomposing the neutral lead salt with hydrosulphuric acid and evaporatirtg the filtrate. It forms almost colourless flat prisms. When sulphocamphoric acid is treated with iiitric acid (1.25) an energetic action takes place and besides oxalic acid a substance having the composition of sulphopimelic acid C7HL2S07 is produced. It forms groups of crystals very soluble in water.C,H1oSO4 + 06 r~=:c7H12so7 + CZH204 + H2O. The distillation of sulphocamphoric acid with potassium cyanide and its treatment with phosphoric chloride led to unsatisfactory re-sults and several attempts to remove the S0,H group of sulphocam-phoric acid by means of nascent hydrogen were fruitless. When potassium sulphocamphorate is fused with potash and the product is neutralised with sulphuric acid a brown resinous substance separates yielding to ether an oily body which on distillation solidifies to a mass of crystals. The new substance separates from hot water in feathery crystals easily soluble in alkalis precipitated by acids and melting at 148". Analysis indicated the formula CgHI2O2. This ABSTRACTS OF CHEMICAL PAPERS.highly interesting substance is not an acid and it reduces alkaline solutions of silver or copper. Its oxidation led to the production of acetic acid oxalic acid and carbonic acid together with resinous pro- ducts. No acetyl derivative was obtained but when treated with phosphoric chloride it yieIded an oil which reacted on water with reproduction of the original Rubstance. The body C9H,202,appears to combine directJy with bromine and phosphoric anhydride at first converts it into a violet mass but afterwards carbonisation takes place. The author regards camphor as a ketonic body having the composi- tion-and this view is supported by a general comparison of acetone deriva- tives with those of camphor. Moreover there are good grounds for believing that the group C,H7 exists as normal propyl but there is at preseltt no evidence to show what position this and the group CO occupy ou the closed ring.When camphoric acid is formed the CO group becomes COOH and the normal propyl becomes C2H,COOH. CH Borneo1 is regarded as having the same relation to camphor that pseudopropyl alcohol has to acetone while campholic acid is viewed as a mono-carbon-acid of propyl-hexylene. Endeavours are being made to obtain the dicarbon-acid of propyl-hexylene as the author regards camphor as the ketone of this acid. He is also engaged in studying the products obtained during the distillation of calcium camphorate other compounds besides phorone being produced. T.B. Derivatives of Benzophenone.By F. URECH (Dent. Chem. Ges. Ber. vi 1112-1113). THEauthor finds that by the action of fuming sulphuric acid on ben-zophenone there is produced together with Staedel's benzophenone- ORGANIC CHEMISTRY. disulphonic acid a substance having the composition Cl3H8SO3,and apparently related to benzophenone in somewhat the same manner as sulphobenzid to benzene. The new compound is soluble in alcohol and very soluble in ether and chloroform from which it crystallises in needles or prisms melting at 156"-187". By distilling sodium benzophenonedisulphonate with PCI, the author CsH,.SOzCl has obtained the acid chloride CO { C6H4.S02C1,which separates from chloroform in small white crystals melting at 134". It appears thnt this chloride yields the corresponding mercaptan on reduction ;and that by the continued action of PC15 it is converted into CCI,( CsH4.So&l)p H.E. A. Metachlorophenol and its Nitro-Derivatives. By HERMANN (Arch. Pharm. [3] iii 103-125). M~LLER THE two isomeric mononitrophenols formed the starting point of this research. They were prepared and separated from each other by tlie method of Cook and Schmitt (KekulB Benzolderivate). Ortho-.nitrochZorophenol.-Ortho-nitrophenol was dissolved in hot water and chlorine passed into it till a yellowish oil solidifying on cooling separated out. This converted into barium salts gave on crystallisation first long red flat needles of Seyfarth's baxium dichlo- ronitrophenate then long dark yellow shining needles of the barium salt of ortho-nitro-chlorophenol whilst in the mother-liquor remained unchanged ortho-nitrophenol.Orthonitrochlorophenol thus obtained is identical with the P-chloro- nitrophenol obtained by Faust from the chlorodinitrophenol which melts at 111". The barium salt has the formula (C,H3N02C10)zBa + 7H20. OrthonitrodichloropherLol.-This body has been examined by Sey- farth. The author describes two modifications of its barium salt the solu- tions of which are at first red and deposit a red salt with 4H20,then become yellow and yield crystals of a salt containing 8H20. Ort?ronitroc?LZoronit.l.ophenol.-Orthonitrochlorophenol treated with nitric acid of sp. gr. 1.36 takes in another nitro-group and is converted into a yellow body melting at 111* and forming a barium salt which crystallises with 9-10 molecules of water.This is iden-tical with the $-chlorodinitrophenol of Faust and Saame. Cidoropheizol @om the 'Volatile Nitropheno1.-Schmitt has described a chlorophenol obtained from the volatile nitrophenol by reducing it to amidophenol converting this into diazophenol and distilling the platinochloride of the base. The author has repeated these experiments and has suceeeded in obtaining a colourless oil boiling between 175" and 177" which he believes to be the same. A portion of this chlorophenol acted upon by nitric acid gave the P-chlorodinitrophenol of Faust and Saame. MetachlorophenoL-The fact thnt isomeric nitro- and sulpho-phenols are simultaneously produced by the action of nitric and sulphuric acids ABSTRACTS OF CHEMICAL PAPERS on phenol rendered it probable that chlorine would give rise to corre- sponding isomerides.Phenol treated with chlorine till its weight had increased by about the theoretical amount and then submitted to repeated fractionation gave about a tenth of its weight of an oil boiling at 175.5"-177" and exhibiting all the properties of Schmitt's chlorophenol. This chlorophenol has the chlorine in the same position as the nitro- group of the volatile nitrophenol. It has always been assumed with- out however sufficient evidence that this nitro-group occupied the metaposition. The author is now in a position to supply the necessary proof for the chlorophenol in question yields pyrocatechin when fused with caustic potash.This metachlorophenol treated with nitric acid and the product with barium carbonate gave a mixture of two barium salts one crystallising in red masses and but slightly soluble either in hot or cold water ; the other forming dark yellow shining needles. These barium salts belong to two isomeric chloromononitrophenols the former of which is new and is called by the author nzetachZoronitrcrphenoZ while the latter is metachlororthonitrophenol which has been studied by Faust and afterwards by Armstrong. iMetachZoronitrophe~~oZ.-This compound is deposited from hot solu- tions partly in yellow drops partly in fine white needles. It is easily soluble in chloroform and crystallises therefrom in yellow flat needles. It is very volatile in vapour of water.It has a strong saffron-like smell and melts at 70". The potassium salt crystallises in dark-red shining long flat needles and is easily soluble in water. The calcium salt forms short reddish- brown prisms and the barium salt copper-coloured scales both com- pounds containing H20. The silver salt is anhydrous and forms crimson shining scales which are with difficulty soluble in water. Metachlororthoizitrophen~l.-This compound melts at 110-11lo and is somewhat volatile in vapour of water. The author has analysed the following salts :-CfiH~CIN020I(.H,O ( C,H3ClN020)2Ca.4H20. (C6H3C1NO20),Ba.7H20. CfiH3ClNOZOAg. He has also prepared the hydrochloride of the amido-derivative formed by the action of tin and hydrochloric acid.MetuchZol.odi~~itro~7zenol. -Metachlorophenol introduced drop by drop into nitric acid of sp. gr. 1.36 furnishes this compound. It crystallises from chloroform in characteristic irregular six-sided tables which melt at 111'. 14letachlorodinitrophenol has been obtained by Faust (a) by passing one atom of chlorine gas into dinitropheno1,-melting at 114"; (6) by reduction of picric acid to amidonitrophenol conversion of this into diazodinitrophenol and boiling with hydrochloric acid ; (c) also by nitration of a mixture of meta- and para-sulphodichlorophenol. Armstrong has also studied its formation by (a) the action of chlorine on dinitrophenol (melting point 114') in presence of antimony penta- ORGANIC CHEHISTRT. 159 chloride ; (b) by nitration of dichlorophenolparasulphonic acid ; (c) by further nitration of orthonitrodichlorophenol (melting point 125') ; and (d) by nitration of orthonitrochlorophenol.The author has re-examined the barium salt of metachlorodinitro-phenol and believes that it contains 10 molecules of water a little of which it parts with very readily. He has also obtained it crystallised in thick yellow prisms containing 5*H20 and a double salt having the formula- [ C6HzCl(N02)z0]2Ba+ 2C6HzC1(N02)20NH4+ 12H20. Sulphztte of metachloramidonitrophenol crystallises in yellowish shining flakes which are moderately soluble in water but are partially decomposed by boiling. The hydrochloride is easily soluble in water and crystallises in short yellowish needles.Metachloramidonitrophenate of barium has the formula- ( C,HzC1NH2N0,0)2Ba.4H20. The following derivatives of metachlorophenol are now known :-1. Metachloronitrophenol melting at 70". 2. Metachlororthonitrophenol melting at 110-111". 3. Metachlorodinitrophenol melting at 111". 4. Metachlororthonitrochlorophenol melting at 125'. The following arc derived from orthochloropheno1:- 1. Orthochlormetaiiitrophenol melting at 86"-87". 2. Orthochlorometanitro-nit8rophenol,me1 ting at 81". 3. Orthochloroniet'anitrochlorophenol melting at 121"-122". W. A. T. Nitronaphthalenes. By F. BEILSTEIN and A. KUHLBERG (Ann. Chem. Pharm. clxix 81-100). Mono?titronapi~t7zale~?,e.-Themethod of Piria was found to be most advantageous for the preparation of this substance and carbon disul- phide was found to be well adapted for its purification as it is very soluble in this solvent whereas the higher nitro-derivatives are but slightly soluble.Mononitronaphthalene melts at 58-5*,and 100 parts of 87.5 per cent. alcohol dissolve 2.81 parts of it at 15". a-and P-di-nitron~phtl~ale.rze were obtained by adding naphthalene to well-cooled nitric acid boiling the mixture for three or four hours and precipitating by water. The product is extracted with alcohol until the undissolved portion melts at 211" and this after crystallisation from acetic acid consists of pure a-dinitronaphthalene. The alcoholio extracts deposited a substance which on fractional crystallkation from acetic acid yielded P-dinitronaphthalene melting at 167".100 parts of benzene dissolve 0.72 parts of it at 17" while under similar cireum- stances 100 parts of chloroform dissolve 1-09parts and 100 parts of 88 per cent. alcohol dissolve 0.188 parts. Both modifications of dini-tro-naphthalene resist the action of strong boiling chromic acid mix- ture. ABSTRACTS OF CHEMICAL PAPERS. a-Anzidonitronap7thalenewas obtained by treating a cold solution of a-dinitronaphthalene in alcoholic ammonia with hydrosulphuric acid until the increase of weight corresponded with the equation :-CioHti(NO,) $. 3HzS = C,oHti(NOz)NH2 f S2 f 2HzO-The purified base separates from water in red shining prisms melting at 118°-1190. The suZphafe [CloH6(NO,)(NHz)]z.H2S04+ 2H20 forms long shining needles slightly soluble in water.By converting a-nitro-amidonaphthalene into the corresponding azo-derivative and heating the sulphate of this with absolute alcohol a nitronaphthalene which appeared to be identical with the ordinary mononitronaphthalene was obtained. All attempts to amidise p-dinitronaphthalene failed to give a definite result. TrinitronaphthaZenes,-When the portion of crude dinitronaphthalene which dissolves in alcohol is treated with cold benzene a resinous substance is extracted which after repeated crystallisation from nitric acid benzene and acetic acid melted at 101°-1030 and gave numbers indicating that it consisted of a trinitronaphthalene contaminated with a small proportion of dinitronaphthnlene.This modification is called by the author 6-trinitro.nnphthalerie and it appears to be identical with Lament's nitronaphthaleke. For the preparation of P-trinitronaphtha-lene the author employs nitro-sulphuric acid the 6-dinitronaphtha- lene being boiled with this acid for about five minutes. The product is then precipitated with snow washed with ether and crystallised from nitric acid from which it separates in large crystals melting at 213". opt rinit~ormp7LthaZme was obtained by boiling a-dinitronap h thal ene with nitro-sulphuric acid precipitating with snow and crystallising from nitric acid from which it separates in bright yellow leaflets while alcohol deposits it iu tufts of needles. 1,000 parts of the under-mentioned solvent dissolve the indicated quantities of y-trinitronaph-thalene at 18.5" ether 3.84 ligro'in (loo") 0.00495 carbon disul- phide 0,249 chloroform 6.39 alcohol (90 per cent.) 1.12 benzene 10.52.ytrinitronaphthalene melts at 147". a-tetranitronaphthalene.-ln preparing this body it is advantageous to use a larger proportion of nitric acid than that recommended by Aguiar. T. B. Nitronaphtol. By RUD.BIEDERMANN (Deut. Chem. Ges. Ber. vi 1117-1120). THE author and Andreoni have previously shown that when nitro- acetonaphthylamine is heated with a concentrated aqueous solution of sodium hydrate nitronaphtol is produced whereas Liebermann and Dittler by employing an alcoholic solution of potassium hydrate obtained aitronaphthylamin. Nitroacetonaphthylamine is also con-verted into nitronapktol by strong aqueous potash the conversion being the more complete the more concentrated the solntion; on the other hand the amount of ammonia evolved is less and the amount of nitronaphthylamine formed proportionally greater the less concent,rated ORGANIC CHEMISTRY.the solution. The author describes the following metallic derivatives of the nitronapbtol thus prepared :-Potassium nitronnpktol ~,,H6(~O2)O~.-~ma~1 orange-red deep crystals easily soluble in water moderakely soluble in alcohol and ether. Sodium nitroiiuphtol CloHI;(N02)ONa+ Zaq.-Fine crimson-red needles easily soluble in water and alcohol. Ammonium Izitroizaphtol C,,H,( NOL) ONHI is sometimes deposited from the solution of nitronaphtol in very concentrated ammonia solution in yellow-red star-shaped groups.It is decomposed on evapo- ration into nitronaphtol and ammonia. Barium ~iitronaplitol,(C,,H,(NO,)O),Ba + aq.-Glistening dark-red pointed needles which exhibit a beautiful blue dichroism. It is easily soluble in water difficultly soluble in alcohol. Calcium nitronaphtol (C,,H,( NOz)O),Ca + 3aq.-Dark red slender interlaced needles easily soluble in water. Lend viitronaphtnl (CloH6(N02)0)2Pb,is precipitated on the addi- tion of a solution of a lead salt to ti solution of sodium nitronaphtol as a scarlet-red difficultly soluble powder. Silver nitronaphtol,C,,H,( NO2)OAg. is a crimson-red powder. Attempts to prepare nitronaphtol by nitration of a-naphtol were unsuccessful ; in all cases a tarry product was obtained.The attempt to nitrate acetyl-a-naphtol was equally unsuccessful. a-Naphtol (1mol.) dissolved in thrice its weigh5 of glacial acetic acid and treated with bromine (1mol.) dissolved in thrice the weight of acetic acid gave dibro?izo?znp7~tol. Dibromonaphtol crystallises in colourless pliable silky needles which melt at 111"; it is insoluble in water easily soluble in alcohol ether and glacial acetic acid ; it yields crystalline metallic derivatives. Dibromonaphtol cannot be distilled unchanged. It is readily converted into a dioxynapbtol by treatment with alcoholic potash The author did not succeed in obtaining more than very small quantities of a nitro-product (probably nitrodibromo- naphtol) by the action of nitric acid.The reduction-product from nitronaphtol was found to be of so unstable a character that its examination was not pursued. H. E. A. Cumic Acid. By F. BEJLSTEIN (Deut. Chem. and A. KUPFFER Ges. Ber. vi 1184). THISacid is conveniently prepared by adding cumin-oil drop by drop to fused potash contained in au iron retort adding water as soon as the evolution of hydrogen ceases and distilling off the cymene. The residue is decomposed with hydrochloric acid and the crude cumic acid purified by converting it into the calcium salt. (C?,,H,,02)2Ba+ 2H,O forms pearly plates. 100 parts of water at 20.5" dissolve 0.996 parts of anhydrous salt ; (C~oH~lOz)zCa + 5Hz0 crystallises in silky needles grouped in semiglobular masses ; 100 parts of water dissolve at 20.5" 0.81 parts of anhydrous salt ; (C,,H,,O,)Mg + 6HzO forms thin pearly plates ; 100 parts of water at 20.5 dissolve 0.825 of anhydrous salt.c. s. 162 ABSTRACTS OF CHEMICAL PAPERS. Diphenylacetic Acid and Benzilic Acid. By R. SYMONS and T.ZINCKE (Deut. Chem. Ges. Ber. vi 1188-1191). DIPHENYLACETIC acid was obtained by heating phenylbromacetic acid with benzene and zinc. The acid obtained by this method separates from hot water in slender shining needles slightly soluble in cold water and very soluble in alcohol or ether ; it melts at 145"-146" yields benzo- phenone on oxidation and appears to be identical with the diphenyl- acetic acid prepared from benzilic acid by Jena's process. The silver- salt was found to be anhydrous and thus appeared to differ from Jena's but on preparing the latter it was also found to be anhydrous.The ethyl ethe.1; C14Hl102C2H5, separates from alcohol in colourless rectangular prisms and dissolves readily in ether alcohol or carbon disulphide. When diphenylacetic acid is acted on by bromine-vapour and the product is boiled with water or barium hydrate benzilic acid is formed. These results tend to support Stadeler's formula for benzilic acid. During the preparation of diphenylacetic acid a small quantity of an acid is formed which has the composition- 1 C02H-CH-C,H,. This acid was separated from diphenylacetic acid by taking ad-vantage of the fact that the barium salt of the former is insoluble in alcohol and by adding hydrochloric acid to this barium salt the new acid was obtained in yellow drops which slowly solidified after which they melted at 110'.In order to gain further insight into the benzo'in group the authors intend to compare deoxybenzoyn with tolylphenyl ketone. T. B. Cholic Acid. By F. BAUMSTARK (Deut. Chem. Ges. Ber. vi 1185-1 18'7). CHOLICacid appears to be monobasic but diatomic and the ether obtained by the action of hydrochloric acid on an alcoholic solution of cholic acid forms a soft mass which dries up to a resinous solid having the composition CaH39(C2H5)05.It is insoluble in water soluble in alcohol or ether and when heated with soda-solution yields sodium cholate and ethyl alcohol but when heated with alcoholic ammonia it yields cholamide CzaH3,O4.H2N a resinous brittle mass insoluble in water but soluble in acids alcohol or ether and identical with the amide obtained by heating ammonium cholate. Attempts to obtain an ether containing 2 atoms of ethyl were unsuc- cessful aud similarly only one hydrogen in cholic acid was found to be capable of replacement by acetyl; but on digesting cholic acid with ORGANIC CHEMISTRY. 163 benzoyl chloride a benzoyl-ethyl ether was obtained as a resinous mass insoluble in water but soluble in alcohol or ether. Alkalis convert it into benzoic acid and cholic acid together with ethyl alcohol. In pursuing the analogy between lactic acid and cholic acid the author compares dilactylic acid with chdoi'dic acid and the product resulting from the dry distillation of cholic acid with lactide.The author is coutinuing his investigations. T. B. Action of Carbon Sulphochloride on Amides. By B. RATHKE and P. SCHAFER (Ann. Chcm. Pharm. clxix 101-111). Action of CSCI onAnzidobenxoil:Acid.-Amidobenzoic acid was digested for 12 hours with two molecules of carbon sulphochloride and the solid product was treated with carbon disulphide which dissolved out a sub-stance that after crystallisation from alcohol was found to be identical with the dicarboxylsulphanilide of Merz and Weith. This substance may also be obtained by heating sulphurea to 130' with amidobenzoic acid. As the substance in question is but slightly soluble in carbon disulphide,.itis probable that the corresponding chloride is first formed and that this is decomposed by the alcohol employed.Omitting this intermediate stage the reaction may be represented as follows :-CSCI + 2(NH,.C,R,.COzH) = CS(NH.C~HA.CO~H>~ + HCL The author calls the product sulphurea-be?zzoic acid [better sulpho-ca~bamidobenzoic]. It begins to melt at 300" and is decomposed at a somewhat higher temperature. Dilute alkalis dissolve it without change but no definite salts were obtained while strong and hot potash decomposes it with formation of potassium sulphide. Diges-tion with mercury oxide and water removes its sulphur and replaces it by oxygen carbnmidobenzoic or area-benxoic acid cO(NH.C6H,C0,H), being formed. This substance is moderately soluble in water from which it separates in colourless crystalline crusts.That portion of the original product which remained undissolved by carbon disulphide was found to consist partly of the hydrochloride of amidobenzoic acid ; and after this had been removed by water there remained a substance which proved to be mustard-oil benzoic acid [sul~hocarbiiiziclobenzoicacid] CSN.C6H*.C02H but it is better to pre- pare this substance either by heating amidobenzoic acid or sulphurea-benzoic acid to 140"with carbon sulphochloride. CSCI + NHz.CsH*.COzH = CSN.C6Hd.C02H + 2HC1. CSCIZ + CS(NHC~H~.COZH)~ = Z(CSN.C6H,CO&I) + ZHC1. On opening the tubes not only hydrochloric acid was evolved but also carbon oxysulphide ; the product is then treated successively with carbon disulphide and hot water.The residue which is almost in- soluble in the usual solvents dissolves in dilute alkalis and may be puri- fied by adding a small proportion of lead acetate to its solution in sodium carbonate and removing this by a stream of hydrosulphuric acid. Under these circumstances the lead sulphide carries down the 164 ABSTRACTS OF CHEMICAL PAPEXS. impurit'ies and on adding an acid to the clear solution the mustard.. oil-benzoic acid is obtained as an amorphous precipitate having a slight tinge of red. It remains unmelted at 310" and is decomposed at a higher temperature. Sulphocarbimido-benzoic acid is a well-marked acid capable of separating carbonic acid from its salts but strong alkalis decompose it with facility an alkaline sulphide being produced.Sulphocarbimido-benzoic acid is also formed together with the hydro- chloride of amidobenzoic acid by boiling sulphocarbamido-benzoio acid with strong hydrochloric acid. CS(NH. CsH4. C02H)z + HCI= CSN.CsH4CO2H+ NH,.CsHI,CO2H.HCl. When sulphocarbimido-benzoic acid is digested with water and mercury oxide the sulphur is replaced by oxygen and a compound is formed which is easily soluble in water and is doubtless the cyanic acid derivative of benzoic acid CON.C6H4.C02H. Sulphocarbimido-benzoic acid unites with aniline to form the compound- NH. c6H5 I cs and this was found to be identical with the substance which Merz and Weith obtained by the action of phenyl-sulphocarbimide on aniline. It melts at 190"-191".Action of CSC12 on Benzamide.-These substances were heated together for some hours at a temperature of 150",and on opening the tubes large quantities of hydrochloric acid and carbon oxysulphide escaped and these gases carried away the whole of a liquid substance which was contained in the tubes. The solid residue which possessed an odour like that of benzonitrile dissolved without residue in water and on fractional crystallisation undecomposed benzamide a sub-stance having the composition C14H15NOa and sal-ammoniac were ob- tained. In order to gain some insight into the nature of the fluid sub-stance formed the operation was conducted in a flask provided with a condenser and two receivers containing water. An oily fluid which collected on the surface of the water was found to consist of carbon disulphide carbon sulphochloride and carbon tetrachloride.The con- tents of the digestion flask deposited benzamide on cooling and the mother-liquor from this was found to consist principally of benzonitril held in solution by carbon disulphide aud caybon tetrachloride. In this case about three-fourths of the benzamide remains unaltered and the substance C14lEf,5NO4,which is formed when the materials are heated to 150° appears to arise from the action of hydrochloric acid on benza- mide. This reaction is treated of in the following communication on dibenzamide. The principal reaction may be represented as follows :-CeH5CONHZ + CSCl2 = CsH5.CN + CSO + 2HC1 2CSClz = cs2 + CCl4. The reaction represented by the second equation does not take place ORGAN10 CmMISTHY.when carbon sulphochloride is heated to 100"-120" or when it is heated to 130' with crystallised gypsum but in the latter case hydro- chloric acid and carbon oxysulphide are produced hence the decom- position of the carbon sulphochloride is best regarded as a contact action although it may be due to the formation of an unstable com- pound of CSC12and benzonitril. T. B. Dibenzamide. By P. SCHAFER (Ann. Chem. Pharm. clxix 111-114). INorder to ascertain if the substance C14H15NOa, referred to in the last paper is formed by the action of hydrochloric acid on benzamide a stream of this gas was passed into benzamide heated to 130". Sal-ammoniac soon separated from the fused mass and when after six hours' treatment the whole was dissolved in hot water the solutionon cooling deposited first benzoic' acid next benzamide then the substance ClrH1,NOa in transparent crystals and finally sal-ammoniac.The substance C,Hl,NOa appears to be dibenzamide crystallised with two molecules of water. It melts at go" is easily soluble in water alcohol ether or chloroform and its aqueous solution has an acid reaction. Ebullition with dilute alkalis decomposes it with liberation of am-monia and formation of benzoic acid. Sublimation appears to cause its decomposition as follows :-NH(C7H,0)2 + 2H2O = C,H,O + 'P;TH,C7HjO+ HZO. An attempt to obtain anhydrous dibenzamide by ciystallising the crude product from ether failed owing to the absorption of water from the air ; and it is wopthy of note that the ethereal solution did not de- posit henzoic acid this substance being probably formed by the action of water and hydrochloric acid on the unaltered benzamide contained in the crude product- NH2.(27H50 + HCl + HZO = c7H602 + NH4Cl.T. B. Isomeric Bromotoluidines. By H. HUEBNER and P. F. Roos (Deut. Chem. Ges. Ber. vi 799-801). IThas been shown that the liquid so-called ortiiobrornotolziene produced together with parabromotoluene by the action of bromine on toluene yields a single sulphonic acid. The authors have endeavorired to ascer-tain whether in like manner it furnishes a single nitrobromotoluene on nitration. As it is impossible entirely to separate orthobromotoluene from parabromotoluene they first re-examined the nitration-products of the latter and have thus occasion to correct the previous observa- tions of Wroblevsky in some particulars.Pure parabromotoluene (m. p. 28") yields two isomeric mononitro- derivatives the less fusible of which in the pure state melts at 45.5"; on reduction it is converted into a-parabromotoluidine which crystal- lises in needles melting at 32" (-2" Wroblevsky). The more fusible VOL. XXVIT. N ABSTRACTS OF CHEMICAL PAPERS. nitroparabromotoluene could not be completely separated from the isomeride but on reducing the mixture and distilling the product wit'h water a-parabromotoluidine first passed over and afterwards @para- bromotoluidine. The latter melts at 75" (67" Wroblevsky).To ascertain the nature of the product formed on nitration of ortho- bromotoluene the mixture of para- and ortho-bromotoluene obtained from bromine and toluene was nitrated the product reduced with tin and hydrochloric acid and the bromotoluidine hydrochlorides separated by fractional crystallisation. In addition to a-and p-parabromo- toluidine hydrochlorides the hydrochloride of an isomeric base [a-(ortho-) bromotoZzcidi.rze] was obtained which although present in larger proportion than the parabromotoluene derivatives was separated with difficulty from the isomeric salts. It thus appears that but a single nitro-orthobromotoluene results from the action of nitric acid on orthobromotoluene. The following salts of the above-mentioned bases were obtained :-a! CsH3Br.CH3.NHz.HC1.This salt crystallises from the last mother- liquors of the mixed bromotoluidines in large coarse rectangular (?) plates. Prepared from pure a-parabromotoluidine it forms large rhombic six-sided plates. 1 part dissolves at 16" in 59.17 parts of water. a C6H3Br.CH3.11bHz.H~03.Large rhombic plates. 1 part dissolves at 13"in 185.18 parts of water. a (CsH3Br.CH3.NHz)zHzSC~4. Colourless scales. CsH3Br.CH3.NH,.HC1. Crystallises in long needles. 1part dis-solves in 10.54parts of water at 16". B C6H3Br. CH3.NHz.HN03. Coarse needles or small rhombic plates. 1part dissolves in 31.08 parts of water at 16". (3 (C6H4Br.CH3.NH[z)2H2S04. Very small difficultly soluble rhombic plates. v C6H3Br.CH3.NHz.HC1. Small rhombic plates.1part of this salt dissolves in 32.7 parts of water at 14"-15" ; in 31.84 parts at 16.5". -/ C6H3Br. CH3.NHz.HN03. Small rhombic plates. 1part dissolves in 82.64 parts of water at 17" ; in 79.36 parts at 19". (C6H3Br.CH,.NH,),HZSO,. Slender needles united to compact half-balls ; very difficultly soluble in water. 7-(ortho-) bromotoluidine separated from these salts remains liquid at 0";it appears to agree in properties with the base which Wroblevsky terms metabromorthotoluidine. H. E. A. Orthotoluidine-sulphonicAcid. By B. GERVE R (Ann. Chem. Pharm. dxix 373-388). WHENorthotoluidine (pseudotoluidine) is heated with twice its weight of fuming sulphuric acid to 160"-180" two isomeric sulphonic acids are formed. One of them is very soluble in water and forms warty crystals.Its salts also dissolve freely in water and alcohol and do not crystallise well. The silver salt C7H8NS03Ag is a precipitate con-sisting of microscopic needles. The second acid which is always obtained in niu& Inrgcr quantity ORGANIC CHEHISTRP. crystallises from water in yellowish oblique rhombic prisms or plates, C7H8NS03H+ 2H20 which lose their water at 120" and crumble down to a yellowish-white powder. It is readily soluble in hot water but does not dissolve in absolute alcohol ether benzene 01-chloroform. C,H8NS03K + $H,O is readily soluble in water and dilute alcohol and forms silky crystals.-C7H8NS03Na + H20 forms feathery crystals and dissolves freely in water and more sparingly in dilute alcohol.(C,H8NS03)2Ba+ 3H20 is readily soluble in water sparingly in boiling dilute alcohol and crystaliises in long striated six-sided prisms.- (C7H8NS03)2Pb+ l$H,O crystallises from dilute alcohol in compact white six-sided prisms. C7HBNS03Ag is a white precipitate consisting of small plates. When boiled with water it dissolves with partial de- composition which may be prevented by adding a few drops of nitric acid. On cooling the salt crystallises in white plates. Orthotoluidine-sulphonic acid dissolves in sulphuric acid and on heating this solution atrongly sulphur dioxide is given off. When the acid is distilled with potash orthotoluidine passes over and the residue contains sulphuric acid and only a trace of sulphurous acid. On adding bromine in small quantity or in excess to the aqueous solution tribromorthotoluidinp is precipitated and the solution contains dibromorthotoluid ine-sulphonic acid hydrobromic acid and sulphuric acid.Tribromorthotoluidine crystallises from alcohol or ether in white silky needles. It can be distilled with steam and when carefully heated sublimes in dazzling white long needles melting at 112O and solidifying atgainat 98"-99". It does not combine with acids and by adding sodium amalgam to its alcoholic solution all the bromine is eliminated. Tribromorthotoluidine is also formed by the direct action of bromine on the base. The compound thus obtained possesses all the properties of that from the sulphonic acid but melts even after recrys- tallisation and sublimation at 105°-1060.When one molecule of bromine is added to a well cooled dilute alcoholic solution a mixture of the di- and tribromo-compound is precipitated and the solution con- tains some unchanged orthotoluidiue and monobromorthotoluidine. Dibronzort7Lotolzcicl~~~e-su~l~oiiic acid C7H4Br2(NH2)S03H+ H,O crystallises from alcohol in long white needles losing their water at 120" and decomposing when more strongly heated without melting It is insoluble in ether and chloroform sparingly soluble in cold water and alcohol but freely at the boiling point. Its salts are less soluble than those of toluidine-sulphonic acid. (C7H,Br,NS03),Ba + 4H20 crystallises in long white needles. (C7H6Br2NS03)Pb+ 3H20 forms long needles or prisms. The silver salt is a white precipitate consisting of needles.The acid is not altered by boiling it with strong potash- lye but on distilling it with potash triliromotoZuuidine is formed. When nitrogen trioxide is passed into the aqueous solution nitrogen is given off and on evaporation a yellow syrup having a very bitter taste is left behind; but when the anhydrous acid is suspended in well cooled alcohol of 95 per cent. and the gas passed into the liquid the diazo-compo?md C7H,N,S03 is formed consisting of white microscopic crystals which explode by percussion or when heated to 110". It js insoluble in absolute alcohol and not changed by boiling therewith under the common pressure. In water and dilate alcohol It is freely N2 ABSTRACTS OF CHEMICAL PAPERS.soluble. These solutions soon decompose even at the ordinary tern- perature. Toluene-sdphonic acid C7H,S03H was obtained by boiling the diazo-compound with absolute alcohol under pressure. The free acid as well as its chloride forms a syrup but the amide C7H,SOz(NHz), crystallises from hot water and ether in beautiful prisms melting at 148". This compound appears to be differelit from the two amides which Anna Wolkow has described. Byornotoluene-sulphoizic acid C7H6BrS03H was prepared by decom- posing the diazo-compound with concentrated hydrobromic acid and obtained as a brown syrup. (C71-f6Br803)zBa+ 9Hz0 separates from water and dilute alcohol in warty crystals. The lead potassium and sodium salts do not cryst'allise well and the chloride is a syrup.The amide C7H6ErSOZ(NHz) is sparingly soluble in cold water more readily in boiling water freely in alcohol and ether and forms micro-scopic crystals melting at 15fjo-157". This acid differs from all other bromotoluene-sulphonic acids that are known. Cre.sol-suZphonicacid,C7H70 S03H,is formed by the decomposition of the diazo-compound with water. It forms a crystalline and very deli- quescent magma. (C7H70S03)2Ba+ 2$Hz0 is obtained from water in small pointed crystals and from dilute alcohol in tufts of silky needles. Its solution gives with ferric chloride a violet colour. (C7H70S03),Pb+ 23H20 is obtained from water in microscopic crystals and from dilute alcohol in tufts of needles. c. s. A New Quinine Hydrate. By A. C. OIJDEYAXS, jun, (Deut.Chem. Ges. Ber. vi 1165). ON two occasions a quinine hydrate containing 9 molecules of water was obtained by adding an alkali to an ammoniacal solution of quinine. The new hydrate is amorphous and has a molecular Po-tatory power of -110". Subsequent attempts to obtain it were unsuccessful. T. B. Aromatic Phosphorus Compounds. By A. M I c HA E L I s (Deut. Chem. Gee. Ber. vi 816-819). PhosphelzyZ chloride PClz(C6H,) (this Journal [2] xi ll48) is a colour-less highly refractive liquid boiling at 222" (uncor.) ; sp. gr. 1.319 at 20". Phospheny1 tetrachloride PC14( C6H,) prepared by passing chlorine into well cooled phosphenyl chloride and purified by crystallisation from PCl or PClz(CsH,) is a white crystalline body melting at 73".Heated to a higher temperature it partly sublimes but is in part re- solved into its generators. PhosphenyZ chlorobromide PC12Brz(C6H,) is obtained by the addition of one molecule of bromine to one molecule of phosphenyl chloride as a solid yellowish-red mass. It is a remarkably stable compound melt- ing at about 208" but subliming from 130" onwards without the least decomposition in yellow-red crystals groupccl in fan-like forms. ORGAMIC CHEMISTRY. Phosphenyl chlorotetrabronaide PCln,Br4(C6H5),is produced on the addition of one molecule of bromine to phosphenyl chlorobromide. The mixture solidifies after a time to a fine red dry mass. PhosphenyZ oxychlo~ide POCl,( C6H,). Phosphenyl chloride readily absorbs oxygen especially on warming and is converted into this compound.It is a colourless syrupy liquid which boils at 260" (uncor.) with slight decomposition ; sp. gr. 1.375 at 20". It possesses a faint fruity by no means unpleasant odour. Phosphenyl oxychloride is decozl=posed by water far less rapidly than phosphorus oxychloride and converted into phenylphosphoric acid ; on exposure to the air it is converted into a crystalline mass which is a mixture of phenylphos- phorous and phosphoric acids. Phosphenylic (pliemjlphospho~ic) acid PO( OH)2(C6H5); is the end- product of the action of water on all the above-mentioned compounds. It crystallises from water in snow-white glistening scales melting at 158" and much resembling the fragments of gypsum obtained by cleavage; water and alcohol dissolve it readily.The silver salt PO(OAg)2( C6H,) is obtained when silver nitrate is mixed with the aqueous solution and then ammonia car.efully added as a white bulky precipitate ; it is very difficultly soluble in water but readily soluble in nitric acid and in ammonia. H. E. A. Matezite a Volatile Sugar obtained from Madagascar Caout- chouc. By A. GI RARD (Compt. rend. lxxvii 995-998). THEauthor has previously given an account of two saccharine sub- stances which he has named "Dambonite " (obtained from the caout- chouc from the Gaboon called n'dambo by the natives) which has the formula C4H803 and ''. Bornesite," C7H,406,both of which on treat-ment with hydriodic acid yield sugars dambose and Borneo dambose respectively isomeric bodies having the formula C3H603 with forma- tion of methyl iodide.Caoutchouc from Madagascar also yields a saccharine substance which the aut,hor has named "matezite," from the native word for caoutchouc. Matezite is white very soluble in water less soluble in alcohol from which it crystallises in tufts. It melts at 181" to a vitreous mass which does not crystallise on cooling and may be sublimed at 2OO0-21O0 without decomposition. It deposits in drops. Its formula is CIoH2,O9 and on treatment with hydriodic acid it undergoes a decomposition analogous to the others forming a sugar called by the author matezodambose-C,oH2,09 + HI = CHJ + CgHi,Og. The rotatory power of rnatezite is 79" to the right. Matezodambose rotates the plane of polarisation 6" to the right ; it melts at 235".The results may be tabulated as follows :- ABSTRACTS OF CHEMICAL PAPERS. M.-P. Rotatory power. Dambonite CaH,03 ......... Bornesite C7Hlt06............ 205 200 0 32 right Matezite CloH,,OS............ Dambose C3H603............ Borneo-darnbose C6H1206...... 181 212 220 79 0 0 9 Matezo-dambose CgH,,09 ...... 235 6 right W. R. Glycyrrhizin or Liquorice-juice. By P. GRIESSMAYER (Dingl. polyt. J. ccix 228-230). Irhas been suspected that sugar extracted from liquorice-root has been used for the purpose of adulterating beer and yet the opinion of chemists has been 'that such sugar is not fermentable. Glycyrrhizin is a glycoside which on boiling with acids decomposes into glycyrretin and sugar. Even after boiling it with water sugar maybe detected by Feh!ing's test.The sugar obtained in this manner was treated with yeast and after three days the fermentation was complete and alcohol was found in large quantity by means of the well-known reaction con- verting it into iodoform. During the latter stage of the fermentation apeculiarly disagreeable putrid odour was perceived and the substance emitting it passed over into the distillate ; the disagreeable taste of some German beers is doubtless owing to this body. TV. R. Triticin. By HERMAXN (Arch. Pharm. [3] iii 1). M~LLEK ITis impossible to obtain triticin free from nitrogen from 0.54 to 0.75 per cent. being contained in all the specimens prepared by the author. Neglecting this the composition is indicated by the formula C12H22011 i.e.the body is an isomeride of cane-sugar. -When pure triticin is a gummy transparent body without taste or smell neutral and very hygroscopic taking up 10-12 per cent. of moisture from the air. It is readily soluble in water but insoluble in absolute alcohol and ether; it is lavo-rotatory ; in four experiments-[a]y = -49.7 -50.8 -49.6 and -50.3 At 160" it becomes transformed into a caramel-like substance soluble in alcohol. When digested with hot water it is partially transformed into I~vulose and when heated with water in sealed tubes to 105"-110",it is wholly transformed ; thus-~d32,0,1 + H.20 = 2CEHI2O6 the author .has quantitatively verified this reaction by weighing the sugar found by titrating it and by estimating its rotatory power.Triticin does not undergo the alcoholic fermentation with yeast ; dia-stase however converts it into sugar as does boiling with dilute sul- phuric acid or treatment with hydrochloric acid ; concentrated sulphuric acid seems tco form a sulpho-acid and does not colour it ORGANIC CHEXISTRY. much. Strong nitric acid converts it into oxalic acid weak nitric acid into sugar; a mixture of nitric and sulphuric acid forms a non-explo- sive nitro-product melting at 65"-68". Alkalis and alkaline earths form unstable salts the barium compound being C21H42Ba012 i-4Hz0 and the lead salt C12H20Pb011 after drying at 110". Manganese dioxide and sulphuric acid convert triticin into formic acid as does also lead dioxide.The quantity of triticin present in the dried roots of couch-grass varies from 3.5 to 7.8 per cent. ; from 2.4 to 3.3 per cent. of sugar being present together with perceptible quantities of malates. In a postscript to the above Reichardt draws comparisons between the results of Miiller and those obbained by Scheibler (p. 1124 o€ last volume). C. R. A. W. Occurrence of Quercetin and Quercitrin in Catechu and Sumach. By JULIUS LOWE(Zeitsch. Anal. Chem. xii 127). THEauthor found that all kinds of catechu contain more or less quer- cetin. He obtained this body by agitating aqueous extracts of catechu wit.h ether and extracting the ethereal residue repeatedly with large quantities of boiling water. The insoluble residue which is left was dissolved in alcohol of 90 per cent.and the yellow alcoholic solution mixed with boiling water when the quercetin which is almost insoluble in cold water crystallised out in light-yellow needles. The analysis gave 59% C. and 3.48 H. The insolubility of quercetin in water-the catechu extracts were made' with cold water-appeared to be influenced by the presence of catechu-tannic acid. Quercitrin obtained from Sicilian or Tyrolese sumach differed from quercetin by its solubility in boiling water. On cooling it crystallised out in light-yellow needles sometimes in yellow flakes. The analysis gave 52.6 C. and 4.83 H. The cryst;als showed all the reactions of yuercitrin. w. v. Tannic Acid from Sumach. By J u L I u s L ow E (Zeitschr. Anal. Chem. xii 128-136).THE author found on re-examination that the tannic acid obtained from nut-galls is identical with that obtained from Sicilian sumach." He treated Sicilian sumach with hot alcohol of 90 per cent. ; the-extract was filtered through flannel ; the alcohol distilled off; the syrupy residue extracted with water of 50° and after standing fur 12 hours filtered through flannel. On shaking the aqueous extract-which should not be too concentrated-with acetic ether the tannic acid was taken up and could thus be separated. Tannic acid from nut-galls shows a like behaviour. On distilling off the acetic ether in a water-bath a light- yellow syrupy residue was left. Dissolved in water to a clear liquid the tannic acid was separated by saturation with pure sodium chloride in the form of yellowish-white globiilar masses which fell out from * The same result was obtained in 1861 by Dr.Stenhouse (Proc. Roy. SOC.,xi 4.01).-$D. ABSTRACTS OF CHERIICAL PAPERS. the solution in a well-stoppered flask placed in the dark for 48 hours. The separation of tannic from any gallic acid that may be present can thus be effected ; the latter remains in the salt solution together with a little tannic acid. The precipitation is repeated and the tannic acid dissolved in warm water and again shaken up with aceticether. Treatment with ether removes small quantities of quercitrin extracted from the sumach by the alcohol. Three layers are obtained viz. an ethereal layer containing quercitrin and a little tannic acid an aqueous layer with a little titanic acid and a lower syrupy layer consisting for the most part of tannic acid.This latter is obtained pure by one more treatment with ether and drying on glass plates over sulphuric acid in a dark room. It resembles in every respect tannic acid obtained from nut-galls. The analysis of t8he substance dried at 120"gave 52.28 per cent. C. and 3.55 H. Dried at 140"it gave 52-47 per cent. C. and 3.42 of H. Although the identity of the acid with tannic acid from nut-galls appeared thus sufficiently proved the author established it further by digestion with or without dilute sulpliuric acid in sealed tubes in a salt-bath whereby it is converted into gallic acid. The formation of ellttgic acid was also studied-a further proof of the identity of the two acids.The reactions which it gave with tartar-emetic with ferric cupric cadmic &c. acetates were identical. The analysis of the lead tannste agreed satisfactorily Yith the numbers found by Liehig (Ann. Chem. Phaym. xxvi lZS) and the author assigns to it the empirical formula C,4H,,0,.3Pb0. It is recommended to employ- Sicilian sumach for the extraction of tannic acid instead of nut-galls ; likewise acetic instead of sulphuric ether. w. v. On the Proteids. By H. HLASIWETZ and J. HABERMANN (Ann. Chem. Pharm. clxix 150-166). WITH the view of getting some insight into the constitution of these bodies the authors have studied the products of decomposition fur- nished by them under the influence of stannous chloride.Casein heated with ordinary hydrochloric acid gives a violet-coloured liquid the colour of which changes to pale-brown on the addition of crystals of tin chloride. After heating the concentrated and highly acid liquid for several days the tin is precipitated by sulphuretted hydrogen and the hydrochloric acid evaporated away over a water-bath The syrupy liquid which remains sets after a time into a crys- talline mass. The crystals and mother-liquor submitted to an elaborate examinatiou the details of which cannot here be followed yielded glutamic and aspsrtic acids leucine tyrosine and ammonia. Corn-pound ammonias could not be detected. The formation of glutamic acid from an albumino'id of animal origin is contrary to the experiments of Kreusler (J.pr.Chefm.cvii 240). Albumin legumin and vegetable albumin submitted to the same process furnish the same products of decomposition. The authors think that if they succeed in making a quantitative determination of t.hese products they may probably be able to show that the different PHYSIOLOGICAL CHEXISTRP. proteids yield different proportions of them for they consider it possible that the differences in properties of the bodies belonging to this group are due to the presence of the same atomic groups in different proportions. W. A. T.

ISSN:0368-1769    

DOI:10.1039/JS8742700138

出版商:RSC    

年代:1874

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEXISTRP. Physiologic a1 Chernistry. The Action of Alkaloids on the Organic Substratum of the Animal Body. By M. J. ROSSBACH (N. Rep. Pharm. xxii 512-544). VARIOUS experimenters the author included having found that the vegetable alkaloids restrain or annihilate oxidation-processes in organic solutions Rossbach set himself to inquire-upon what substances of the protoplasm and of the animal body is it that the alkalo'ids act by diminishing oxidation-processes ? and by what actions is it that oxida- tion is decreased or altogether annihilated in these substances ? Do the alkalo'ids render the protoplasm unsusceptible of oxidation or do they e.g. so change osmosis in the cell-membrane that no oxygen can reach the protoplasm ? In what manner do the alkaloids weaken the ozoiie reaction of the blood ? By adding neutral salts of the alkalo'ids (quinine veratrine strych- nine morphine and atropine) to solutions of egg-albumin the author found (1)that dilute solutions of albumin were coagulated at a much lower temperature with than without the salts of the nlkaloids ; (2) that a solution of albumin so highly diluted that it did not become turbid when boiled became turbid at 59"-62" when a trace of a neutral salt of an alkaloid was previously added ; (3) that with the alkaloids much more turbidity was produced on heating the solutions of albumin than with simple aqueous solutions.It was ascertained that the altered coagulability of the solutions after the addition of the salts of the alkaloids was due neither to the presence of free acid the precipitation of the alkalo'ids by the alkaline solutions of albumin nor the action of a neutrul salt in solution.Rossbach adduces experi- ments to show that a true chemical Combination and not a physical union takes place between the albumin and the alkaloids and he found the coagulum produced when a solution containing the neutral salt of an alkaloid and albumin is heated to have the properties of an alkaloid. At temperatures of 1"-10" no combination took place between the albumin and the alkaloids. Similar results were obtained by adding alkaloidal salts to the juice of muscle and to the serum of blood; and it is concluded that dis- solved albumin is converted by the alkalo'ids aided by the application of heat into a less soluble modification which is a chemical compound of albumin with an alkalo'id.When alkaloids were added to blood it was found that at 40"-50° the two absorption-bands of oxyhsmoglobin required a higher tempera- ture for their disappearance than in blood free from alkaloids ; the 174 ABSTRACTS OF CHEXICAL PAPERS. alkalo'ids formed a compound with haemoglobin but this w;ts not deprived of its property of being an ozoniscr and carrier of ozone. The aut,hor reconciles his own experiments with those of Binz by saying that the alkaloids render the combination of ozone with bamo- globin more stable and so this latter gives up its ozone less readily to other bodies than when the haemoglobin is not combined with an a1kalo'id.The relations of the alkaloids to albumin and ozone were also studied and it was found (1)that the alkaloids augment the aEnity of albumin for ozone; (2) that between 30' and 40" albumin is changed by the aJkaloYds and this is shown by a loss of affinity for ozone; (3) that the alkaloids are capable of precipitating ozonised albumin from its solutions. The author's conclusions are summarised thus :-1. The various albuminates found in solution in the tissues of the animal body and in the protoplasm are influenced and altered by the alkaloids. At temperatures of 30"-40" they lose their affinity for ozone ; and at higher temperatures yet still below their ordinary coagulating points they lose their solubility allialoi'd albuminntes being formed.. 2. These changes in albuminntes are produced by the alkaloi'ds generally though variations in the phenomena are observed by ope- rating with different alkaloids. 3. The alkaloids whilst they leave the properties of haemoglobin unchanged as a generator of ozone bind the ozone more firmly to hmmoglobin and cause it to be less readily yielded up to other bodies. 4. The degradation of the oxidability of the protoplasm brought about by the alkaloids is determined by two conditions by the change in the albuminates already described and by the more stable combination of ozone with hamoglobin. T. S. Physiological Action of Amylammonium Chloride. By DUJARDIN-BEAUMETZ (Compt. rend. lxxvii 1247-1249). AMYLAMMONIUM chloride introduced under the skin of the rabbit guinea-pig and dog causes in small doses a marked diminution of the pulse and some fall in temperature.In larger doses convulsions are produced which end in death. With man a dose of a half to one gmm lowers the pulse 10 to 20 beats per minute and occasious a fall in temperature. The author has administered this salt with advantage in some cases of typho'id fever. Amylamine has not the sedative action on the nervous system which trimethylamine possesses but surpasses it greatly in its effect on the pulse and in its toxic action. R. W. Action of Zinc on Blood-solution. By HELWRICH STRUVE (J. pr. Chem. [2] vii 346). SCHOWBEIN has shown that by agitating certain metals with water and air traces of hydrogen peroxide are formed.The author finds that the PHYSIOLOGIC,AL CHEBIISTRY. presence of air is not essential and that perceptible quantities of hydrogen peroxide are readily formed when zinc acts on water all dis- solved oxygen and air being excluded from the solution and the vessels used by means of hydrogen or carbon dioxide. When diluted and defibrinized blood is treated with zinc a clear solution is obtained con- taining neither hajmatin nor blood. albumin provided the action has gone far enough these substances separate as a precipitate wholly insoluble in water ; peroxide of hydrogen is present in the filtrate and also gelatin easily detected by means of tannin. Neither egg-albumin nor gelatin is thus precipitated by zinc ; peroxide of hydrogen is however formed in each case.C R.A. W. Australian Concentrated Mutton-Soup as a Food for Pigs. By A. VOELCKER (Jour. Roy. Agri. Soc. 1873 428-437). THE liquor obtained by boiling down sheep for tallow is strained and concentrated to a thick extract. A single sheep yields 1lb. of superior extract sold for human food and 2$ lbs. of second quality suitable for pigs and dogs. Analyses of three samples gave the fallowing per- centage results :-First quality. Second quality. Water.. ..................... 29-20 31 -29 29 '70 Pu'itrogcnous organic matter.. ... 60 '48 64*62 66 *29 10 *32 Ash ......................... --4 -09 - Nitrogen. .................... 8 *68 10 -96 8oluble in 80 per cent. alcohol.. . 33 *51 20 '27 17 -89 The first feeding experimeut with pigs lasted seven days.It appeared that & lb. of mutton-soup was quite incapable of replacing 1 Ib. of peas and its use resulted in the pigs losing weight. The second experiment lasted nineteen days. In this case the pigs received a very liberal diet and the lot which had mutton soup in addition gained nearly twice as much in weight as the other and realised a larger profit notwithstanding the greater cost of the food. From these results the soup appears to act as a condiment rather than as a true foo3. R.W Influence of Certain Substances on the Preservation of Eggs. By F. C. CALVERT (Compt. rend. lxxvii 102Lf026). EGGS, either entire or pierced at the end by a fine needle may be kept for three months without change in an atmosphere of nitrogen, hydrogen or carbonic anhydride.In dry oxygen entire eggs undergo no change but if the gas is moist the egg becomes covered with a white filamentous mould. ABSTRACTS OF CHEMICAL PAPERS. An egg pierced at the extremity soon becomes putrid either in dry or in moist oxygen the amount of oxygen consumed and of carbonic anhydride and nitrogen evolved being much greater in the latter case than in the former. New-laid eggs immersed in weak chlorine water contained in a stoppered bottle underwent no change for nearly eight months but on leaving the bottle open for a week they became covered with Per& cillium ylaucurn. Eggs kept in a weak solution of chlorinated lime soon began to show signs of change externally by the growth of penicillium. With lime water and with calcium sulphite similar results were observed. Eggs kept in solution of phenol exhibited no change for three months. They were then slightly coated with penicillium but their contents were perfectly sweet. W. A. T.

ISSN:0368-1769    

DOI:10.1039/JS8742700173

出版商:RSC    

年代:1874

数据来源: RSC

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ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. The Oleo-resin of the Sunflower. By M. CHARDON (Pharm. J. Trans. [S] iv 322). THEsunflower (.€lcZian&ts an?mus) as found in Algeria yields an oleo- resin which appears in transparent and colourless drops on the ex- tremities of the projecting palee or bracts before the flower is full grown. The drops are more abundant in proportion as the growth of the stalk is more vigorous which excludes the idea of their origin in a diseased state of the plant. This substance has been collected and found to present the following characters. Its consistence was semi-hid and pitchy; its odour much resembled that of the product of Pinus maritima with which it might easily be confounded.Its burning and aromatic taste was persistent because of its insolubility and it was not at all sweet. It did not reduce Fehling’s liquor and when exposed to the air in a thin layer it dried on the surface and after two or three days ceased to adhere to the fingers. Heated care- fully by itself it gave off an essential oil its odour was intensified and the residue was a hard matter resembling colophony. In boiling water also it hardened and left a white opaque resin. It was completely soluble in alcohol. J. B. Sugar in Asparagus. By A. VOGEL (N. Rep. Pharm. xxii 391). THEextremities of the shoots contain no sugar though the stem three or four inches below contains 1.7-2 per cent. The explanation is that the sugar is used up in the formation of cells which goes on so actively in the shoots.The same is the case with potato- shoots. G. T. A. VEGETABLE PHYSIOLOGY AND AGRICULTURE. 177 Amount of Fat in Ergot of Rye. By 0. FIGINUS (Arch Pharm. [3] iii 219). ERGOT contains 30 per cent. of fat. It would be a good plan to extract this fat by ether and reduce the dose by one-third or else supply the place of the fat by liquorice or milk-sugar. Prof. Reichardt is investi- gating this fat. G. T. A. Relation of the Camphor Group to Plant Life. By A. VOGEL. (N. Repert. Pharm. xxii 545-547). CAMPHOR is found to have a marked effect in stimulating the germina- tion of seeds both by shortening the period of germination and causing more seeds to sprout. Turpentine has a similar action but seems to exert a hurtful influence on the further development of the plant which is not the case with camphor.E. K. Researches on Alcoholic Fermentation. By A. MAYER (Landw. Versuchs-Stationen xvi 277-305). THE author in continuation of his previous labours (ibid,xiv l) has studied the action of hydrocyanic acid on fermentation already noticed by Schaer and Schonbein. The amount of hydrocyanic acid necessary to prevent fermentation is in proportion to the amount of healthy yeast present a small quantity of the acid sufficing if very little yeast has been added ; when fermentation is thus stopped the yeast is appa- rently killed. Hydrocyanic acid does not prevent the inversion of cane sugar by yeast-water; a temperature of 60" also fails to destroy this faculty.The author endeavoured to ascertain by means of gradual additions of hydrocyanic acid whether the various reactions exhibited by yeast namely fermentation evolution of oxygen from hydrogen- peroxide and reduction of nitrates to nitrites (beer-yeast does not as supposed absorb ozone from ozonized oil of turpentine) had all the same origin or if one could be destroyed without the other. Other experiments having the same aim were made by subjecting yeast to a gradual rise of temperature. It appeared from both investigations that all the properties in question suffered SL nearly equal diminution as the life of the plant was attacked and were all extinguished at its death which in the temperature series took place at asbout 60".The existence therefore of a fermentive power distinct from the life of the plant is negatived. According to Pasteur the growth of yeast is much increased by the presence of free oxygen this increased growth not being however attended by a more active production of alcohol. The author found that when fermentation was produced by minute additions of beer- yeast to artificial solutions the continual passage of air or of carbonic acid through the liquid made no practical difference in the propor- tions of the alcohol and yeast produced. The author believes that the amount of sugar decomposed is strictly proportional to the growth of the yeast-plant and shows that in artificial solutions both the growth of yeast and the production of 178 ABSTRACTS OF CHEMICAL PAPERS.alcohol are limited by the amount of nitrogenous and cinereal plant- food present. In his experiments the production of yeast varied from 1.38-2.03 per cent. of the alcohol formed; Pasteur's results gave 2.0-3.4 per cent. Experiments have been published in which the yeast appears to have actually diminished during fermentation ; when however the yeast employed is free from soluble matter or when the soluble matter is taken account of there is always an increase of yeast during fermentation. When yeast undergoes self-fermentation it suffers no loss but a small portion becomes soluble. The proportion of yeast produced in distilleries and in the fermenta- tion of grape-juice is far greater than that already quoted.Grape-juice fermented with wine-yeast yielded 18.2 and when fermented with beer-yeast 13.4 of dry yeast for 100 of alcohol. The cause of this enor&ous growth of ieist has yet to be determined. R. W. On the Origin of Acetic Fermentation. By VV. V. KNIERIEM . and A. MAPER(Landw. Versuchs-Stationen xvi 305-329). A HISTORY of the opinions held on this subject is given. Modern views raise the question-Is the acetic fermentation a simple oxidation brought about by porous bodies or is it a function of a vital process ? Platinum-black oxidises alcohol under circumstances in which a fe-ment has no effect ; thus it acts on strong alcohol as well as weak and at high temperatures even more than at low ones. It is unsafe to argue from similarity of product to similarity of process.Taking purified filter-paper pulp as the type of a porous body the authors spread it on the surface of 9 per cent. alcohol and caused alcohol to filter through a mixture of pulp and glass for six weeks but obtained only a trace of acetic acid; even the addition of iklycoderina aceti failed to produce acetic acid until the inorganic salts requisite for plant growth were added. Again when weak alcohol is passed con-tinuously over string (purified by acid and alkali) no acid is produced if Mycoderma aceti be excluded. A 9 per cent. solution of alcohol in yeast-water may be freely exposed to air without developing acetic acid if kept in a balloon free from germs. Flasks in which acidifica- tion had been started and good films of Mycoderma aceti formed mere heated to 60"-70" without breaking the film and their necks closed with heated cotton wool ; acidification was completely stopped by this treatment' though the action of the film as a porous body must have remained unchanged and no alteration in its structure could be detected by the microscope.The authors have never obtained acetic fermentation without the presence of living 4f'coderrrza aceti. Ozone does not convert alcohol into acetic acid. The rapidity of the acetic fermentation depends on the strength of the alcohol which should be 3-10 per cent. ; it depends still more on the presence of ready-formed acetic acid the best proportion being per cent. ; the ferment should also come from a solution of similar acidity to that into which it is brought.The most favourable tempe- rature is 20"-30" ; there is hardly any action at lo" and it ceases at 35". Germs in the fluid are destroyed a little below 50" but strong 2". VEGETABLE PIIYSIOLOGY AND AGRICULTURE. 179 films require 70”. Inorganic salts will support the growth of the ferment but it is more vigorous iu the presence of organic nitrogen. Mycoderma aceti is a lower organism than ordinary fungi ; it is allied to the bacteria and propagates by simple division only. When the fermentation is slow the cells are at rest and connected together but when active acidification is in progress the cells are single are in rapid motion and continually undergoing division. Some bacteria forms also convert alcohol into acetic acid.R.W. Report of Twenty Years’ Experiments on Barley. By J. 13. LAWES and J. H. GILBERT(Jour. Roy. Agri. SOC.,1873. 89-186 and 275-374). ON a field at Rothamsted barley has been grown continuously since 1852. The soil is a heavy loam with clay subsoil resting on chalk ; it was exhausted by previous cropping before the commencement of the experiments. The authors discuss the results obtained in each of the twenty seasons. The produce is largest when the growth is unchecked by drought or sudden alterations of temperature but is regular and long continued ; the rather cool but uniform season of 1854 gave the heaviest crops. In dry seasons the yield from farmyard manure and from sodium nitrate is somewhat less affected than that from ammo-nium salts ; this is due to the accumulation of water-holding organic matter on the farmyard manure plot xnd to the ready distribution of the sodium nitrate (see this Journal 1871 430).The barley receiving phosphates ripens 1-2 weeks earlier than the rest. The average produce per acre of a few of the principal plots is given helow. The “ammonium salts ” are a mixture of equal parts sul-phate and chloride ; the alkali-salts consist of the sulphates of potas. sium sodium and magnesium ; the “ cinereals ” consist of alkali-salts plus superphosphate :-Manures per acre. Ibs. lbs. per cent. Unmanured .................... 2454 86 *6 52 -3 -23 -6 Mixed cinereals .................. 3162 96 -4 53 *4 -20.2 Ammonium salts 200 lbs......... 3919 89 *2 52 *l -9.7 Ammonium salts 200 lbs. 4317 86.3 52.8 -5’3 alkali-salts ..................} and Ammonium salts 200 lbs. 5760 86 *8 53.5 + 2.7 superphosphate .............. and 1 Ammonium salts 200 lbs. 581’7 83 -2 54 .O -*3 cinfreals .................... and / Rape cake (mean 1,300 lbs.) ....... 5571 8’7 ,3 53 .8 - Farmyard manure 14 tons.. ....... 5933 88.5 54 *3 + 14.8 ABSTRACTS OF CHEMICAL PAPERS. These figures will speak for themselves. The small result obtained from cinereal manures when used alone illustrates the falsity of the old "mineral theory," according to which plants possess a sufficient source of nitrogen in the atmosphere. The total produce of barley without manure is greater than the produce of wheat (2364 lbs.) under the same circumstances and where cinereals are applied alone the barley considerably exceeds the wheat which averages 2746 lbs.As these barley crops contain more nitrogen than the corresponding wheat crops it appears that barley is better able than wheat to supply itself with nitrogen notwithstanding the deeper roots of the latter With both wheat and barley the produce is slowly falling off under these conditions. With ammonium salts alone and with sodium nitrate alone there is much less falling off than without nitrogenous manure; the falling off is least with the nitrate. The nitrate gives a rather larger crop for the same amount of nitrogen supplied ; this is also true when both nitrate and ammonia are applied with cinereals.The addition of superphos-phate to ammonium salts or sodium nitrate Featly increases the produce ; the further addition of potassium sodium and magnesium salts is almost without effect. The barley has clearly therefore obtained an ample supply of potash from the natural soil but an in- sufficient supply of phosphoric acid. When ammonium salts are used alone and the quantity of ammonia does notl exceed 501bs. per acre 3-68lbs. of ammonia will yield an average increase of 1bushel of corn and 63 lbs. of straw total 115lbs. ; the extremes in twenty years were 2*25-18*05 lbs. When ammonium salts are applied with super- phosphate 2.21 lbs. of ammonia will produce the same result; the extremes were 1.47-5-36 lbs. In the experiments with wheat about 3i lbs.of ammonia (with cinereals) were required to produce the same weight of increase. In making this comparison it is to be recollected that the manures are applied to wbeat in the autumn to the barley in the spring ; any loss of manure from winter drainage falls therefore on the wheat. Experiments with 4OOlbs. of ammonium salts per acre showed that this quantity was excessive for barley ; with wheat this dressing yields as good a return as the smaller amount. Sodium silicate has been applied for eight years to half the barley plots receiving ammonia ; no increase has resulted where ammonia and superphosphate are applied but on the other three plots an increase has taken place which in the case of the plot receiving only ammonia and alkali-salts is very considerable.This irregular action seems to show that the silicate has not produced its effect by furnishing silica to the crop but by some reaction upon the plant food of the soil. The rape cake supplied considerably more nitrogen than the ammo- nium salts and also some phosphates and potash. Rape cake alone gives a better return than either ammonium salts or sodium nitrate applied alone but when the three manures are mixed with superphos- phate the results for equal amounts of nitrogen show the rape cake to be decidedly inferior. The experiments prove that a supply of carbo- naceous matter does not increase the crop. The farmyard manure was from the open yard and contained about 64 per cent. of nitrogen; it would supply far more plant food than any of the other manures.Owing to its slow decay in the soil its VEGETABLE PHYSIOLOGY AND AGRICULTURE. 181 effect on the crop is distinctly cumulative. On an average of the twenty years it requires about 8 lbs. of ammonia in the form of dung to produce 1 bushel of barley with its equivalent of straw. The nitrogen in the experimental crops of wheat and barley during twenty years and in crops of oats during three years has been deter- mined. The amount of nitrogen recovered in the increase of crop for 100 supplied in the manure is shown in the following bable :-Manures per acre. Wheat. Barley. Oats. --____1 I 32 *4 48*1 Cinereals and ammonium salts (41lbs. nit~~~,~i-Cinereals and ammonium salts (mean 53.3lbs. nitrogen) -49 *8 Cinereals and ammonium salts (82 lbs.nitrogen). . . . 32 *9 Cinereals and ammonium salts (123 Ibs. nitrogen). . . . 31 -5 Cinereals and ammonium salts (164 lbs. nitrogen). . . . 28 -5" Cinereals and sodium nitrate (82 lbs. nitrogen) . . . . . 45 *3 -Cinereals and rape cake (mean 61.75 lbs. nitrogen). .. -36 3 Barmyard manure (about 200 lbs. nitrogen). . . . . . . . . 14 -6 10-7 The manures foy oats and barley and the sodium nitrate for wheat were applied in spring the other wheat manures were applied in autumn. In all cases which are comparable the barley appropriates more of the nitrogenous manure than wheat saTe with farmyard manure; this dressing is however far more excessive in the case of barley than of wheat. It is evident froni the figures that a large amount of the nitrogen applied in manure is not taken up by the crop ; what becomes of the remainder? Experiments in the barley field prove that large residues from ammonium salts and sodium nitrate show a small but distinct effect upon succeeding crops the influence extending over many years.In the whea;t field on the other hand very much larger residues from ammonium salts have produced only very small and ripidly diminishing results. Analysis of the soils of the wheat field to a depth of 27 inches proved that a considerable part of the unconsumed nitrogen was actually present in the soil though apparently in a condition little available to the plant; a still larger portion of the nitrogen had however disappeared. The authors believe that the nitrogen which has thus disappeared has passed into the subsoil in the form of nitrates.The wheat field is tile-drained 2-43 feet deep each drain pipe passing under the middle of a plot. Analyses of the drainage water have been made by Dr. Voelcker (this Journal 1871 286) and more recently by Dr. Frankland. The ammonium salts are applied to the plots in the autumn. The winter drainage-water from these plots is rich in nitrates the quantity being nearly proportional to the amount of ammonia applied generally exceeding 1part of nitrogen in 100,000 and reaching in one instance to 7.841 parts. The late spring and summer drainage contains only traces of nitrates. The sodium nitrate is applied to the land in the spring. The drainage-water yields most nitrate shortly after the application of the manure ; the amount reached in one instance to 5.83 of nitrogen per 100,000.The drain of the Jc Mean of 13 years only. VOL. XXVII. 0 ABSTRACTS OF CHEMICAL PAPERS. plot receiving farmyard manure seldom runs from the great porosity of the soil due to organic accumulations; the water contains less nitrate than that from plots receiving ammonium salts. Calculation shows that if the drainage-water contains 1part of nitrogen in 100,000 there will be a loss of 2.26lbs. of nitrogen per acre for each inch of rain passing beyond the reach of the roots. ‘l’he practical conclusion from these facts is obviously that ammonium salts (as well RS sodium nitrate) will be more economically applied in the spring than in the autumn.Manures containing organic nitrogen are clearly not so liable to loss from drainage. Residues of cinereal manures unlike residues of ammonia are shown by experiments in the wheat field to remain in a condition available for subsequent crops ; their effects are however only slowly mani- fested. Experiments have been made both on the growth of barley after turnips and also in an ordinal-y four-course rotation. After growing turnips ten years consecutively with purely cinereal manures and carting off the produce the yield of barley was much smaller than in the experimental field where barley was grown after barley. The turnips though very small crops had exhausted the available nitrogen of the soil to a greater extent than corn crops would have done.On one plot where rape cake had been applied to the turnips the produce of barley was €32 bushels more than where none had been used showing that the residue of the rape cake was avaiIable for a succeed- ing crop. In the rotation experiments barley is grown after turnips (carted off) and is followed by beans and wheat. In one series all the crops are unmanured ; in another the turnips receive superphosphate ; in a third the turnips receive an abundant cinereal and nitrogenous manure. The mean produce of the six crops of barley obtained in twenty-four years of rotation is as follows :-I I Character of rotation. Dressed corn. Straw and chaff. _ _ _-~ bushels. cwts. j The unmanured turnips me so very small in quantity that the barley in the first series is practically grown after a fallow; this barley is however a much larger crop than that grown after turnips manured with superphosphate only the available nitrogen of the soil being in this case exhausted by the turnips.In the last series the residue of the abundant manure applied to the turnip crop suflices to produce a good crop of barley. R. W. VEGETABLE PHYSIOLOGY AND AGRICULTURE. 183 Influence of .an Abundant Nitrogenous and Phosphatic Manuring upon the Composition of Spring Wheat. By H. RITTHAUSEN and R. POTT(Landw. Versuchs-Stationen xvi 384-399). THE experiments were made in the summer of 1872. Three plots received no manure; three superphosphate at the rate of 1to 1$ ton pel.acre ; three ammonium sulphate sodium nitrate or a mixture of the two 134 cwts. of ammonium sulphate and 16 cwts. of sodium nitrate being applied per acre ; three other plots received about 1ton per acre of superphosphate in addit?ion to the nitrogenous manures just mentioned. The land mas clearly in high condition as even these enormous applications of manure had little effect on the quantity of the crop. The greatest yield both of corn and total produce was obtained from superphosphate alone ; the nitrogenous manures di-minished the yield of corn and increased the straw. The crops on the nitrogenous plots were all laid; the grain produced by them was smaller in size than in the other cases and in the last series there pias a good deal of imperfectly developed corn.The followi~lg table shows the mean percentage composition of the dry matter analysed. The samples of the green crop were taken at the end of June. Green plant. Straw. 1 Grain. Meal. -1 -?? 4 34 z4 4 6 -29 '57 2-80 1 -27 2 *74 16 -17 7 "70 -62 2'41 1 -41) 2 '90 16 90 5 *64 .83 2-93 1 -08 3 *63 22 -71 Nitrogenous and phos-5.97 -94 2.81 1 *12 3 '84 24 *20 phatic .. ....,... }/-I-The gluten was determined by kneading 20 grams of the meal with solution of gypsum washing with hard water and drying at 120". Gluten var'ies somewhat in its percentage of nitrogen being associated with variable quantities of gliadin a substance containing as much as 18.01 nitrogen per cent. The authors conclude that the proportion of nitrogen is increased both in the plant and grain by liberal nitrogenous manuring ; a part of the increase obtained in the grain was however clearly due to defective ripening which checked the formation of starch.Compare Jour Chem. SOC.[Z] x 1. Rl. W. 02 ABSTRACTS OF CHEMICAL PAPERS. Some of the Effects of Cropping upon the Subsequent Con- dition of the Soil. By R. WARINGTON (Agricultural Economist 18'73 146). Chemical Composition of the Parenchyma of certain Vege- tables. By M. MAUDET (Compt. rend. lxxvii 1497). RICE-PAPER, the pith of Aratia papyrifera contains from 47 to 50 per cent. of cellulose-like bodies and from 50 to 53 per cent. of pectic compounds. The cellulose-like bodies are principally the cellulose of Payen and medullose.These two bodies are generally found in the ratio of 37 per cent. cellulose and 10 per cent. medullose. The pectic compounds soluble in potash contain from 35 to 40 per cent. of lime pectate and the remaining 10 or 15 per cent. appear to be principally pectose. Elder pith contains no pectic compounds but there is present from 25 to 30 per cent. of a substance named by FrQrny,vasculosa. These two species of pith are found in a great number of vegetables rice-paper in its composition resembles the parenchyma of barks while elder pith appears to be constituted like wood itself. J. B. Action of the Volcanic Earth of the Solfatara of Puzzuoli on the Diseases of the Vine. By S. DE LUCA(Compt. rend. lxxvii 1431). FROM further experiments with this earth (vide Chm.Xoc. J. [Z],xi 523) the author concludes that from its mechanical and chemical com- position it Rcts beneficially on vineyards by destroying or averting insects rendering the vegetation more vigorous augmenting the pro- duce of grapes and furnishing to the ground the necessary elements for the growth of the vine. E. K. Cinchona Cultivation in Java. By It. W. VAN Go R KOM (Pharm. J. Trans. [3] iv 341). THEfollowing are the results of analyses made in the second quarter of 1873 :- .C 2 Cinchona. Leaf. Locality . 2 ." k 6 -------.-...-I-26 Officinalis,. ................ Broad. ............ Lembaiig ....... 1870 12 '77 6.35 2.33 3.13 none 0.71 0.80 6.97 3.13 27 , .................. , .............Raouggunung .. 1868 13 *32 6 *25 3.27 1*59 trace 0.21 0.80 5.87 4'30 28 , .................. Average ........... .. , 12.77 8.34 5.19 1.58 Y 0.86 0'20 7.83 6.98 >9 29 , .................. Very small.. ....... 1; .. , 13.07 7.90 5.86 0.74 9; 0.62 0.45 7-67 7.89 30 , .................. Sinall very pointed . .. , 13-37 7.20 5-42 0.39 Y 0.44 0'64 6-89 7-29 9, 31 , .................. Three varieties mixed Kawak Tjiwidai. . 1865 13 '74 3-87 1.75 1-38 , 0 '34 0'26 3-73 2-35 32 , .................. Broad. ............ , , .. 1868 12.17 8-64 2.68 4.29 none 0'21 0.67 7.85 3.61 33 , .................. ) ............. Rantia Bolang. . , 9 -07 5.35 2-71 1.61 trace 0 *35 0.96 5 *63 3 $4 34 , .................. ............... Tjiburrum ...... , 9 *14 5 -99 4-25 0.76 none 0 *20 0.69 5.90 5.72 35 , ..................Small very pointed . Raong-gunung .. , 14.48 10.36 5.92 2.47 0.19 0.91 9.49 '7.98 " I 36 Calisaya (Schuhkraft) ....... > 1 *. Lembang ....... 1863 14 *45 1*07 0.40 0 *46 trace 2.74 0.631 4.23 0.55 37 , (crop) ............. ,I ** Nagrak. ........ , 13 '32 4'18 1-80 1-56 0 -40 0.32 0.171 4.25 2-42 9 38 , (Schuh kra ft) ....... 7 Y *. Tjomas ......... , 14*OO 1-28 1.04 trace 0*48 2.03 0.661 4.21 1.40 39 , (crop) ............. ¶ ' -Lembang ....... 1867 13 '59 1'43 0 ,56 0.59 trace 0.09 0'20 1*44 0.75 77 44 , (Ledger) ........... Long fruit.. ....... Nagrak ......... ) 14 '49 5.18 2 '28 1.91 0.33 0% 5 .22 3 -07 41 ,> ) .......... ........... Tjiburrum ...... , 8 +51 6.24 5'07 none 0 Tbl 0.50 0.63 7.11 6.82 42 3 , ..................... Raoug-gunung. .. , 13 *85 4-90 3.88 , 1-02 0.96 0.99 6.85 5.22 43 ,> , .......... ........... ,I 44 9 ............ ........... .. , 14'73 11 -20 9 '90 9 0 *17 1*2110 -4.7 12 *23 45 Caloptera (seed plank). ...... ........... Tjiniruan ....... 8-63 2.65 1-83 0%7 , 0.17 0.79 3.06 2 *46 " 46 , (crop of 1872) ..... ........... , .. ..*...I.. , 14'41 10.88 8-83 , none 0'10 0.9 9.8411 -88 ........ : 112.71 2 .03 1'38 0 26 ,> 2-28 2-00 5.92 1.86 47 , (young plant). ..... ........... 1865 14-37 1'02 0 *65 0.16 >> 2 -78 1.23 4.72 0.87 48 Lancifolia (from a dead tree) . ........... .......... 13'25 2.66 0.79 1.35 0.72 0.47 3 *33 1*06 49 , .................. ........... .......... 7.10 6.08 4.75 0.19 0 'b6 0.93 1.03 6.96 6.39 50 Succirubra ............................ Lembang ....... 1869 15 -00 9.98 1'67 6.36 none 0 *70 1*83110 -56 2 .25 51 , .................. ........... Kawak Tjiwidai. . , 12 *98 7.44 1'06 4.39 9 0.53 1.33 7-85 1-42 521 Pahudiana. ................ ........... Tjiboddas.. ..... 1854 13.20 1.24 0.30 0.73 -> trace 0.46 1.49 0.40 No. 29 is from a tree which is probably identical with the Cinchona oflcinalk Bonplandia var. august$'olia of British India. J. B. ABSTRACTS OF CHEMICAL PAPERS. Spontaneous Ignition of Hay. By L.A. BUCHNER (N. Repert. Pharm. xxii 449-459). THEpartially burnt residue of a heap of hay which had spontaneously ignited on attempting its removal about two months after harvesting was a kind of tinder of a brown-black colour in which every blade could be detected; it gave off aqueous and empyreumatic vapours on heating and was generally of the nature of a partially formed coal.If heated to between 250" and 330" it ignited when brought into contact with air. The author and H. Ranke also found that hay or grass heated to between 228-350" turned to charcoal possessing pyrophoric properties. E. K.

ISSN:0368-1769    

DOI:10.1039/JS8742700176

出版商:RSC    

年代:1874

数据来源: RSC