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MINERALOGICAL CHEMISTRY. M i n e r a1 o g i c a 1 C h e m i s t r y. 115 Analyses of Orthite, Vasite, Erdmannite, Tritomite, and Archenite. By N. ENGSTROM (Devd. Chenz. Ges. Uer., x, 1'727).- The author's analyses of ortl~ite from various localities lead t o the for- mula, 2(2RO.SiO,) + 3R,0,.4Si02, with 1 or 2 aq. Si6(R2)3RAH2026, is regarded as the true formula of undecomposed orthite. Vasite was found t o be merely decomposed orthite. Erdmanriite and tyitomzite both belong to the borates, containing 7-8 per cent. of boric anhydride. Archenite from Ytterby contains tantalic and silicic acids in about equal quantities, and appears to be a decomposition-product of the tan- talo-niobates found in the same locality. J. R. Analysis of Periclase. By A. Cossa (Dezct. Chew. Ges.Ber., x, 1'74'7).-The author found in periclase contained in predazzite from Monte Somma, 95% per cent. of magnesia and 4.4 per cent. of ferrous oxide. Cossa obtained crystallised magnesia by fusing together magnesium sulphate and sodium chloride at a very high temperature for four hours in a platinum crucible, and allowing the mass to cool slowly. Some- what larger crystals of a reddish colour were formed on adding a little ferrous sulphate to the mixture. The density of the mineral was 3.642 at 12". J. R. Chalkophanite, a New Mineral Species. By MOORE (Claenz. Ceiztr., 1877, p. 8) .-In the calamiue works of the Passaic Zinc Company at Sterling Hill, Ogdensberg, New Jersey, a deposit was found over the calamine ore, which includes more or less the decomposition- products of Praaklinite and other manganiferous and zinciferous mine- rals.The material is fissured, and contains cavities which me filled up with a crystallised mineral ; the crystals are rhombic, have a hard- ness of 2.5"; a specific gravity of 3.907, a metallic lustre, and a blue t o iron-black colour. When the mineral is heated before the blowpipe, the pale-yellow bronze colour is converted into a copper- red, and tlhe mass shows slight indications of melting, while the colour becomes darker and darker as the heating is continued. By A. S c H R A U F (Jahrb. f. Nine, 1877, 403-404).-The author confirms his previous and re- D. B. Morphological Studies of Brookite.116 ABSTRACTS OF CHEMICAL PAPERS. iterated statements that brookite crystallises in the monosymmetrical, and not in the rhombic system, and further observations point to the complete isomorphism of wolframite and brnokite, whilst the formula, TiO?, for the latter is too simple.In the Juh~b. ,f. ~W~YL., 1873, 754 (Chem. Xoc. J., 1873, 235), he described three types of brookite-crys- tals, giving their axial relations and the localities in which t,hey were found. I n the present communication the author points out that the well-known “ dispersion ” in the planes of the optical axes (although theoretically possible), is scarcely reconcilable with the optical sym- metry of the rhombic system deduced from numerous observations. This dispersion, on the contrary, as “ dispersion croisske,” is one of the principal characteristics of the asymmetrical system.The theoretical explanation of this optical phenomenon becomes easier if brookite is considered to crystallise in the monosymmetricad system, for it is an established fact that monosymmetrical crystals with an apparent rhombic symmetry very commonly exhibit the characteristics of this system parallel to, or in the position of the axis of polarisation. From this the author contends that brookite and wolframite are isornor- phous, whilst there can be no doubt that the three types of crystals of brookite are brought about by changes in chemical constitution. The few analyses which have been made of brookite are not suficient t o warrant any decided conclusions as to chemical changes in their constitution through “ vicarious constitnents,” although iron and pro- bably silica play, no doubt, an important part in these changes.The author determined the specific gravities of the three brookite types, and found them to be respectively as f o l l o ~ s , viz. :-Type I. = 4.15 ; Type 11. = 4.21 ; Type 111. = 4.11. A qiialitative examination of the substance driven off by ignition of brookite would be desirable, for if it be water, the analysis by Hermann leads to the formula, H6Fe2Ti46098, for brookite ; but other analyses of this mineral and the consideration of its isomorphism with wolframite, scarcely allow the assumption of a formula with eight valencies. Leaving out the iron and hydrogen as accidental constituents, and considering the trimor- phisrn to be polymerism, the formula, Ti20a, is arrived at for brookite. The isomorphism of brookite and wolfrnmjte compels a doubling of the molecular formula of the former, and the assumption of an equal valency in each of these bodies ; the lowest possible valency being 16.C. A. B. Bismuthospherite. By A. WEISBACH (J. f. Mim., 1877, 404- 405) .-The author instituted a further examination ipto the compo- sition of the original specimens examined by Werner, and named by him Awen-uiismuth. These specimens came from the Nengluckspath vein at Neustiidtel, near Schneeberg, and exhibited the so-called arsen- wismuth in dull brown spheriiles and hemispherules, sometimes as large as a pea, and often enclosing a kernel of bismuth. The larger spherules have a concentric, undula,ting, shell-like structure, the smaller ones a fibrous structure, both being accompanied by quartz, and cobalt-speis, and attached to bitter-spar.Sometimes the exterior of the spherules is covered with a whitish, mealy deposit, the inner- most shells exhibiting a light-yellow or light-brown colour, whilst theMINERALOGICAL CREMIYTRY. 117 outer shells vary from a dark-brown to an almost black colour. The lustre increases in intensity as the mineral becomcs darker in colour, but the fibrous structure becomes proportionately less well defined whilst the straw-yellow shells are the most distinctly fibrous and ouly exhibit a glimmering lustre. The various shell-structures gave the same streak, viz., yellowish-grey, and all of them clissolved in dilute hydrochloric acid with effervescence. No water was evolved on heat- ing the mineral in ;L mattrass, but the mineral mass assumed a beau- tiful lemon-yellow colour.Hardness, 3. Spec. gr. 7.28 to 7.32. On analysis, the mineral proved to have the following percentage-compo- sition, viz. :- Bi,O,. ( 3 0 2 . SiO,. 88.58 8.9 7 0.28 = 9'7.83 from which the formula, Bi2C05, is obtained, this formula requiring 91.34 Bi203 and 8-66 COz. Prom this result it appears that the Arsen-wismuth of Werner is in reality an anhydrous bismuthic carbonate, for which the author pro- pases the name " Bismuthospherite." All the natural carbonates of bismuth hitherto analysed were hydrated. C. A. B. A peculiar Twin-formation of Cobalt-speiss. By G. v o x RATI-I (,Juhrb. f. Nin., 1877, 405--406).-Naumann described a crystal- group of cobalt-speiss from the Daniel mine near Schneeberg, the crystals occurring in peculiar penetration-twins, the twin-axis being given by him as the normal to a face of 30$, the individuals being developed prismatically parallel to the trigonal twin-axis common to both.Vom Rath examined, some specimens of arborescent cobalt- speiss which undonbtedly exhibited the peculiar twin-forniation des- cribed by Naumann, presenting a striking example of crystalline development in the direction of the trigonal axis. The twin crystals in question occnr in a central red-like aggregdtion, with thrce twist- ing arms projecting upwards from it a t anglcs of 70".30'. The whole of this peculiar tree-like structure is built up of the above-mcntioncd twins, all having an identical position, whence it follows that the structure represents a si?iyZc twin.Whilst most of t'hese crystals appear to correspond completely with those described by Naumann, as the re-entering angles intersect one another in the terminals of the crystals, there are other isolated crystals which exhibit a normal twin- formation, according to the law " the twin axis a tringonal axis." The twins, according to the last-mentioned law, completely resemble the well-known twins of fluorspar, galena, &c., and occur as penetration- twins, with a rotation of 60" and 180", the combination observed being mOm .O. mO.202 ; all tliese faces being evenly and well-developed, most particularly the cubical faces, which are square. The author points out that the occurrence of these well-developed twin-crystals (which appear to be more inclined to isolation than to enter into the peculiar arborescent growth which was observed with tlie other pcne- tration-twius), strohgly shijws that the twin-lam of Naumann is not VOL.XXXIII. Fc118 ABSTRACTS OF CHEMICAL PAPERS. correct. The faces of the abnormal twins are always convex, pa#rticu- larly the cubicdl faces, as the terminal edges of these penetration- twins are not normal cubical edges, the interfacial angles never mea- suring go", but generally 100" to 105". It was observed throughout that the Naumann twins never exhibited well-developed terminal edges, but mostly distortions of the occurring faces. Tom Rath con- cludes by stating that the twins described by Naumann are abnormal, the crystals appearing to penetrate each other in a different position, owing to the facial distortion, whilst those crystals which possess well- defined cubical faces occur in normal twins according to the law already given above.The distorted twins exhibit an acute rhombo- hedron at their poles instead of a cube. C. A. B. Glauberite and Blijdite of Pendshab. By W. SCHTXPFR (Ja7wb. f. Mirz., 1877, 408).-GQlauberite occurs attached t o cubes of rock-salt, in forins having exactly the habit of the crystals from Westeregeln, near Magdeburg, m hich was described by von Zepharo- vich (Jahrb. f. AMivz., 1874, 543). The forms observed were 0P.-P, predominating ; then P. COP m, with small developed faces, and some- times also -$P . %Po0 . ;%' oc! occur, but only very secondary. BZodite.-These crystals fully exhibit the development described by vom Rath, Groth, and Hintze (J(chrb.f. .Win., 1872, 528) of the Stsss- furt and Magdeburg blodite. being secondary, 0323. and + €24. The forms observed were- 0P.R CO.-P.m P. e 2 , C. A. B. The Schorlomite of the Kaiserstuhl. By A. KKOP ( J d w b . f. Mhz., 1877, 408-409) .-The author came to the following coiicl-usions after his examinations of this mineral :-1. Most analyses of titaniferous silicates, particularly of the melanite of the Kaiserstuhl and of Frascati, did not lead to satisfactory results, owing to the methods for the separa- tion of this acid being imperfect. 2. The minerals from the Kaiserstuhl, which were always considered to be schorlomite, are either melnnite or pyroxene (augite). Schorloniite does not occur at the Kaiscrstuhl. 3.As the real American schorlomite occurs intergrown with mclanite (both minerals possessing the same outward appearance and the same crystalline form, viz., ~00.203), an accurate examination of the speci- mens is advisable, in order to ascertain whether the above-mentioned crystalline form is not peculiar to melanite, schorlomite being in that case amorphous. C. A. B. Some BrazilianMinerals. By A. GORCEIX (Jahrb. f. il.Zhz., 1877, 409-410). -EucZase is found accompanied by topaz in the neighbour- hood of aluminous slates, embedded in a white clay or quartz, near Ouro Preto, 14 miles from the quarries. The beautiful coZowZess uizdln- lusites and green tourmalirLes (called by the natives emeralds), are found in the north of the province &!inas Novas, on the banks of the river Doce.Blcxck toimnalines are common everywhere. Between Ouro Preto and Sabara, near the village Rio-das Pedras, there is a vein ofMINERALOGICAL CHEMISTRY. 119 granular quartz, quite filled with large crystals of black tourmaline. This variety of tourmaline is also found in the gold mines of Antonio Pereira, at the extremities of the veins. C. A. B. Hydrocastorite, a New Mineral. By G. GRATTA ROLA ( J d d . f. ilfiiz., 1867, 411).-Occurs as a mealy deposit upon kernels of castor, having the appearance of an aggregate of fine needles under the micro- scope. H., 2, spec. grav., 2.16. Colour, white. Double refractive in polarised light. Chemical composition as follows, viz. :- sio,. Al20,. CaO. HQO. 59.59 21.35 4.38 14.66 = 99.98 Hydrocastorite (which is undoubtedly a product of the decomposition of castor) is found in company with black avid red tourmaline, beryl, castor and pollux, in veins of granite at Sail Piero, Elba.Andalusite and Pinite from Elha.-Andalnsite is found in felspar, at, San Piero, in Campo. Forms observed . mP.m PkOP, also :is radiating aggregates of crystals. The greenish crystds often envelop a dark- red kernel. Spec. grav., 3.244. Chemical composition as follows, viz. :- SiOz. A1203 and Fe,03. HaO. -\ 39.16 58.53 1.58 = 99.27 The green incrustation enveloping the andalusite (which is a, pro- Hardness, 2.,5. duct of the decomposition of the latter), is pinite. Spec. grav., 2.75-2.86, Chemical composition as follows :- SiOz. &03. Fe@. K20. NazO. HzO. 49.40 18.80 16.41 6.63 2-17 6-87’ = 100.25 C.A. 13. Olivine Rock. By H. M ~ H L (,Jahrb. .f. &&., 1877, 413-414).- The rocks in which olivine is the predominating constituent are t h dunite of New Zealand, and the lherzolite of the Pyrenees. Both are light green, and contain only a trifling amount of enstatite, diallogite, chromdiopide, and chrompicotite. The olivine-rocks of the Ulthenthal, and the bombs and blocks enclosed in basalt, contain 3, considerable amount of the above-mentioned minerals. The rocks of Sweden and Norway are particularly fine, and arc only partially corn- posed of olivine, but eulysite (a rock closely related to olivine rock) consists of olivine, diallagite, garnet, and magnetite. The eruptive olivine rocks of the Fichtelgebirge, Ellgoth in Austrian Silesia, and the Hessian Hinterland, between Dillenburg arid Brilon, are T-ery dark, blackish-green in colour, and were first accurately described by Gumbo1 and Sandberger.In the Hessian district they occur in mounds or points, ridges, and veins, the general strike being that of the tran- sition-rocks. The author examined 45 points of eruption, and found that in most of them the olivire was more or less convertcd into SCT- pentine (the Dillenberg specimen consisted almost entirely of serperi tint.), k 2120 ABSTRACTS OF CHEMICAL PAPERS. and associated with it were diallagitc, magnesium-mica, chromdiopside, magnetite, chrompicotite, titanite, &c. Orthoclase and oligoclase occur in many localities, sometimes constituting about one-third of the rock, and passing over into gabbro.At Rndbach the asymmetrical felspar is more prominent, and associated with granular olivine, which is com- plctely converted into serpentine, whilst there is a diminished amount of tlie other rock-minerals already mentioned. Again at Rachelshausen and Oberdicten, the olivine rock is very closely allied to proterobase, in which the olivine has almost entirely disappeared, whilst oligoclase, augite, hornblende, ehloropite, magnetite, titanite, and occasionally mica, constitute a granitic mixture, which shows that olivine rock may belong equally to the gabbro and the diabase scries of rocks. C. A. B. The Limestones and Calcium Phosphates of Curacao. By A. STELZNER ( J a h d . f. KE., 1877, 415--416).-The calcium phos- phates occur partially in the form of loose lumps resting upon the limestone, and partially in such a form as to show that they are a pro- duct of the decomposition of the limestone itself.The limestone is sometimes massive and sometimes oolitic, and penetrated by the remains of gasteropods and bivalves, from which it, may be inferred that it is a very recent formation ; a qualitative examination proved it. to be passing gradually into calcium phosphate, the mass a t the same time becoming cellular in structure. The purest calcium phosphate is found in nests or veins disseminated throughout the limestone ; or it occurs in foliated shell-like masses, having a reniform surface, clothing, and even entirely filling the cells or 1:ollows in the cellular limestone. In its pure state this calcium phospliate is an amorphous, yellowish, greenish, or brown mass, with a dull or resinous lustre upon its con- cho'idal fractured surfaces, somewhat resembling opal in appearance.From its appearance and properties, it is undoubtedly the same sub- stance as the pyroclasite of Shepard, the sombrerite of Phipson, and the hard guano of Dana. Formerly pyroclasite was supposed to be the result of volcanic action upon the coral-limestone, but it is known a t present to have been formed by the action of water upon guano, the solution thus obtained acting upon the limestone, and causing the formation of calcium phosphates. An examination of the specimens of calcium phosphate from this locality seems to prove that the purest calcium phosphate was o~iginally a gclatinous precipitate, which sub- sequently hardened, as bubble-like spaces are found in the shell-like masses, which could only have been formed by the generation of gas inside a permeable, gelatinous mass.This theory of the formation of natural phosphates agrees well with the cheniical reaction between a solution of calcium phosphate and ammonia. Pjroclasite and the other phosphates above mentioned are therefore only hardened jellies. The occurrence of radio-fibrous crystalline calcium phosphates is very rare in Curapo ; they arc probably the same as the mineral staffelite. Curacao is an island belonging to the Antilles. C. A. B. Note on an Edible Clay from New Zealand. By M. M. P. Ici ii * r ~ (Chem. NTEZGS, xxxvi, 202).-l'he ciay is from Mackenzie County,ORGANIC CIXEMISTRY.121 South Island. sheep. It is free from diatomace=. It is largely eaten by SiO,. A1,03. Fe203. CaO. MgO. NaCl(traccof KCI). HzO. Orgtmic. ... 1 4 61.25 17.97 5.72 1.91 0.87 3-69 7.31 1 - 7 7 = 100.40 M. M. P. N. Meteorites. By J. LAWRENCE SMITII (Counpt. rend., lxxxv, 678). -A metcorite which, on the 21st December, 1876, passed over several of the States, .projected fragments, one of which was found near Rochester, Indiana. It weighed 400 grams, and exhibited a globular texture. Spherical grains of two or tlhree mm. diameter could easily be detached from the mass, with which they were identical in compo- sition. Two silicates could be distinguished, but nothing resembling anortliite. A meteorite fell at Warrenton, Missouri, on the 3rd January, 1877, of wliich the mineralogical composition was : peridote, 76.00 ; broneite and pyroxene, 18.00 ; nickeliferous iron, 2.00 ; troilitc, 3-50 ; chrome iron, 0.50 per cent.This meteorite is unlike any yet described, except that of Ornans ; it is very friable, and its crust is dull, and in parts scoriaceous. A meteorite which fell at Cynthiana, Kentucky, on the 23rd Janu- ary, 1877, weighed six kilos., and presented a great similarity to the meteorite of Parnallee. I t s composition corresponded with peridote, 50.00 ; bronzite and pyroxene, 38.00 ; nickeliferous iron, 6-00 ; trollite, 5.50; chrome iron, 0.52 per cent. R. It.MINERALOGICAL CHEMISTRY.M i n e r a1 o g i c a 1 C h e m i s t r y.115Analyses of Orthite, Vasite, Erdmannite, Tritomite, andArchenite. By N.ENGSTROM (Devd. Chenz. Ges. Uer., x, 1'727).-The author's analyses of ortl~ite from various localities lead t o the for-mula, 2(2RO.SiO,) + 3R,0,.4Si02, with 1 or 2 aq. Si6(R2)3RAH2026,is regarded as the true formula of undecomposed orthite.Vasite was found t o be merely decomposed orthite.Erdmanriite and tyitomzite both belong to the borates, containing 7-8per cent. of boric anhydride.Archenite from Ytterby contains tantalic and silicic acids in aboutequal quantities, and appears to be a decomposition-product of the tan-talo-niobates found in the same locality. J. R.Analysis of Periclase. By A. Cossa (Dezct. Chew. Ges. Ber., x,1'74'7).-The author found in periclase contained in predazzite fromMonte Somma, 95% per cent.of magnesia and 4.4 per cent. of ferrousoxide.Cossa obtained crystallised magnesia by fusing together magnesiumsulphate and sodium chloride at a very high temperature for four hoursin a platinum crucible, and allowing the mass to cool slowly. Some-what larger crystals of a reddish colour were formed on adding a littleferrous sulphate to the mixture.The density of the mineral was 3.642 at 12".J. R.Chalkophanite, a New Mineral Species. By MOORE (Claenz.Ceiztr., 1877, p. 8) .-In the calamiue works of the Passaic Zinc Companyat Sterling Hill, Ogdensberg, New Jersey, a deposit was found overthe calamine ore, which includes more or less the decomposition-products of Praaklinite and other manganiferous and zinciferous mine-rals. The material is fissured, and contains cavities which me filledup with a crystallised mineral ; the crystals are rhombic, have a hard-ness of 2.5"; a specific gravity of 3.907, a metallic lustre, and ablue t o iron-black colour.When the mineral is heated before theblowpipe, the pale-yellow bronze colour is converted into a copper-red, and tlhe mass shows slight indications of melting, while the colourbecomes darker and darker as the heating is continued.By A. S c H R A U F (Jahrb.f. Nine, 1877, 403-404).-The author confirms his previous and re-D. B.Morphological Studies of Brookite116 ABSTRACTS OF CHEMICAL PAPERS.iterated statements that brookite crystallises in the monosymmetrical,and not in the rhombic system, and further observations point to thecomplete isomorphism of wolframite and brnokite, whilst the formula,TiO?, for the latter is too simple. In the Juh~b.,f. ~W~YL., 1873, 754(Chem. Xoc. J., 1873, 235), he described three types of brookite-crys-tals, giving their axial relations and the localities in which t,hey werefound. I n the present communication the author points out that thewell-known “ dispersion ” in the planes of the optical axes (althoughtheoretically possible), is scarcely reconcilable with the optical sym-metry of the rhombic system deduced from numerous observations.This dispersion, on the contrary, as “ dispersion croisske,” is one of theprincipal characteristics of the asymmetrical system. The theoreticalexplanation of this optical phenomenon becomes easier if brookite isconsidered to crystallise in the monosymmetricad system, for it is anestablished fact that monosymmetrical crystals with an apparentrhombic symmetry very commonly exhibit the characteristics of thissystem parallel to, or in the position of the axis of polarisation.Fromthis the author contends that brookite and wolframite are isornor-phous, whilst there can be no doubt that the three types of crystalsof brookite are brought about by changes in chemical constitution.The few analyses which have been made of brookite are not suficientt o warrant any decided conclusions as to chemical changes in theirconstitution through “ vicarious constitnents,” although iron and pro-bably silica play, no doubt, an important part in these changes.Theauthor determined the specific gravities of the three brookite types,and found them to be respectively as f o l l o ~ s , viz. :-Type I. = 4.15 ;Type 11. = 4.21 ; Type 111. = 4.11. A qiialitative examination of thesubstance driven off by ignition of brookite would be desirable,for if it be water, the analysis by Hermann leads to the formula,H6Fe2Ti46098, for brookite ; but other analyses of this mineral and theconsideration of its isomorphism with wolframite, scarcely allow theassumption of a formula with eight valencies. Leaving out the ironand hydrogen as accidental constituents, and considering the trimor-phisrn to be polymerism, the formula, Ti20a, is arrived at for brookite.The isomorphism of brookite and wolfrnmjte compels a doubling of themolecular formula of the former, and the assumption of an equalvalency in each of these bodies ; the lowest possible valency being 16.C.A. B.Bismuthospherite. By A. WEISBACH (J. f. Mim., 1877, 404-405) .-The author instituted a further examination ipto the compo-sition of the original specimens examined by Werner, and named byhim Awen-uiismuth. These specimens came from the Nengluckspathvein at Neustiidtel, near Schneeberg, and exhibited the so-called arsen-wismuth in dull brown spheriiles and hemispherules, sometimes aslarge as a pea, and often enclosing a kernel of bismuth. The largerspherules have a concentric, undula,ting, shell-like structure, thesmaller ones a fibrous structure, both being accompanied by quartz,and cobalt-speis, and attached to bitter-spar.Sometimes the exteriorof the spherules is covered with a whitish, mealy deposit, the inner-most shells exhibiting a light-yellow or light-brown colour, whilst thMINERALOGICAL CREMIYTRY. 117outer shells vary from a dark-brown to an almost black colour. Thelustre increases in intensity as the mineral becomcs darker in colour,but the fibrous structure becomes proportionately less well definedwhilst the straw-yellow shells are the most distinctly fibrous and oulyexhibit a glimmering lustre. The various shell-structures gave thesame streak, viz., yellowish-grey, and all of them clissolved in dilutehydrochloric acid with effervescence. No water was evolved on heat-ing the mineral in ;L mattrass, but the mineral mass assumed a beau-tiful lemon-yellow colour.Hardness, 3. Spec. gr. 7.28 to 7.32. Onanalysis, the mineral proved to have the following percentage-compo-sition, viz. :-Bi,O,. ( 3 0 2 . SiO,.88.58 8.9 7 0.28 = 9'7.83from which the formula, Bi2C05, is obtained, this formula requiring91.34 Bi203 and 8-66 COz.Prom this result it appears that the Arsen-wismuth of Werner is inreality an anhydrous bismuthic carbonate, for which the author pro-pases the name " Bismuthospherite." All the natural carbonates ofbismuth hitherto analysed were hydrated. C. A. B.A peculiar Twin-formation of Cobalt-speiss. By G. v o xRATI-I (,Juhrb. f. Nin., 1877, 405--406).-Naumann described a crystal-group of cobalt-speiss from the Daniel mine near Schneeberg, thecrystals occurring in peculiar penetration-twins, the twin-axis beinggiven by him as the normal to a face of 30$, the individuals beingdeveloped prismatically parallel to the trigonal twin-axis common toboth.Vom Rath examined, some specimens of arborescent cobalt-speiss which undonbtedly exhibited the peculiar twin-forniation des-cribed by Naumann, presenting a striking example of crystallinedevelopment in the direction of the trigonal axis. The twin crystalsin question occnr in a central red-like aggregdtion, with thrce twist-ing arms projecting upwards from it a t anglcs of 70".30'. The wholeof this peculiar tree-like structure is built up of the above-mcntioncdtwins, all having an identical position, whence it follows that thestructure represents a si?iyZc twin.Whilst most of t'hese crystalsappear to correspond completely with those described by Naumann,as the re-entering angles intersect one another in the terminals of thecrystals, there are other isolated crystals which exhibit a normal twin-formation, according to the law " the twin axis a tringonal axis." Thetwins, according to the last-mentioned law, completely resemble thewell-known twins of fluorspar, galena, &c., and occur as penetration-twins, with a rotation of 60" and 180", the combination observed beingmOm .O. mO.202 ; all tliese faces being evenly and well-developed,most particularly the cubical faces, which are square. The authorpoints out that the occurrence of these well-developed twin-crystals(which appear to be more inclined to isolation than to enter into thepeculiar arborescent growth which was observed with tlie other pcne-tration-twius), strohgly shijws that the twin-lam of Naumann is notVOL.XXXIII. F118 ABSTRACTS OF CHEMICAL PAPERS.correct. The faces of the abnormal twins are always convex, pa#rticu-larly the cubicdl faces, as the terminal edges of these penetration-twins are not normal cubical edges, the interfacial angles never mea-suring go", but generally 100" to 105". It was observed throughoutthat the Naumann twins never exhibited well-developed terminaledges, but mostly distortions of the occurring faces. Tom Rath con-cludes by stating that the twins described by Naumann are abnormal,the crystals appearing to penetrate each other in a different position,owing to the facial distortion, whilst those crystals which possess well-defined cubical faces occur in normal twins according to the lawalready given above.The distorted twins exhibit an acute rhombo-hedron at their poles instead of a cube. C. A. B.Glauberite and Blijdite of Pendshab. By W. SCHTXPFR(Ja7wb. f. Mirz., 1877, 408).-GQlauberite occurs attached t o cubes ofrock-salt, in forins having exactly the habit of the crystals fromWesteregeln, near Magdeburg, m hich was described by von Zepharo-vich (Jahrb. f. AMivz., 1874, 543). The forms observed were 0P.-P,predominating ; then P. COP m, with small developed faces, and some-times also -$P . %Po0 . ;%' oc! occur, but only very secondary.BZodite.-These crystals fully exhibit the development described byvom Rath, Groth, and Hintze (J(chrb.f. .Win., 1872, 528) of the Stsss-furt and Magdeburg blodite.being secondary, 0323. and + €24.The forms observed were-0P.R CO.-P.m P. e 2 ,C. A. B.The Schorlomite of the Kaiserstuhl. By A. KKOP ( J d w b . f.Mhz., 1877, 408-409) .-The author came to the following coiicl-usionsafter his examinations of this mineral :-1. Most analyses of titaniferoussilicates, particularly of the melanite of the Kaiserstuhl and of Frascati,did not lead to satisfactory results, owing to the methods for the separa-tion of this acid being imperfect. 2. The minerals from the Kaiserstuhl,which were always considered to be schorlomite, are either melnnite orpyroxene (augite).Schorloniite does not occur at the Kaiscrstuhl.3. As the real American schorlomite occurs intergrown with mclanite(both minerals possessing the same outward appearance and the samecrystalline form, viz., ~00.203), an accurate examination of the speci-mens is advisable, in order to ascertain whether the above-mentionedcrystalline form is not peculiar to melanite, schorlomite being in thatcase amorphous. C. A. B.Some BrazilianMinerals. By A. GORCEIX (Jahrb. f. il.Zhz., 1877,409-410). -EucZase is found accompanied by topaz in the neighbour-hood of aluminous slates, embedded in a white clay or quartz, nearOuro Preto, 14 miles from the quarries. The beautiful coZowZess uizdln-lusites and green tourmalirLes (called by the natives emeralds), are foundin the north of the province &!inas Novas, on the banks of the riverDoce.Blcxck toimnalines are common everywhere. Between OuroPreto and Sabara, near the village Rio-das Pedras, there is a vein oMINERALOGICAL CHEMISTRY. 119granular quartz, quite filled with large crystals of black tourmaline.This variety of tourmaline is also found in the gold mines of AntonioPereira, at the extremities of the veins. C. A. B.Hydrocastorite, a New Mineral. By G. GRATTA ROLA ( J d d .f. ilfiiz., 1867, 411).-Occurs as a mealy deposit upon kernels of castor,having the appearance of an aggregate of fine needles under the micro-scope. H., 2, spec. grav., 2.16. Colour, white. Double refractive inpolarised light. Chemical composition as follows, viz. :-sio,.Al20,. CaO. HQO.59.59 21.35 4.38 14.66 = 99.98Hydrocastorite (which is undoubtedly a product of the decompositionof castor) is found in company with black avid red tourmaline, beryl,castor and pollux, in veins of granite at Sail Piero, Elba.Andalusite and Pinite from Elha.-Andalnsite is found in felspar, at,San Piero, in Campo. Forms observed . mP.m PkOP, also :is radiatingaggregates of crystals. The greenish crystds often envelop a dark-red kernel. Spec. grav., 3.244. Chemical composition as follows,viz. :-SiOz. A1203 and Fe,03. HaO.-\39.16 58.53 1.58 = 99.27The green incrustation enveloping the andalusite (which is a, pro-Hardness, 2.,5. duct of the decomposition of the latter), is pinite.Spec. grav., 2.75-2.86, Chemical composition as follows :-SiOz.&03. Fe@. K20. NazO. HzO.49.40 18.80 16.41 6.63 2-17 6-87’ = 100.25C. A. 13.Olivine Rock. By H. M ~ H L (,Jahrb. .f. &&., 1877, 413-414).-The rocks in which olivine is the predominating constituent are t hdunite of New Zealand, and the lherzolite of the Pyrenees. Bothare light green, and contain only a trifling amount of enstatite,diallogite, chromdiopide, and chrompicotite. The olivine-rocks of theUlthenthal, and the bombs and blocks enclosed in basalt, contain 3,considerable amount of the above-mentioned minerals. The rocks ofSweden and Norway are particularly fine, and arc only partially corn-posed of olivine, but eulysite (a rock closely related to olivine rock)consists of olivine, diallagite, garnet, and magnetite.The eruptiveolivine rocks of the Fichtelgebirge, Ellgoth in Austrian Silesia, andthe Hessian Hinterland, between Dillenburg arid Brilon, are T-ery dark,blackish-green in colour, and were first accurately described byGumbo1 and Sandberger. In the Hessian district they occur in moundsor points, ridges, and veins, the general strike being that of the tran-sition-rocks. The author examined 45 points of eruption, and foundthat in most of them the olivire was more or less convertcd into SCT-pentine (the Dillenberg specimen consisted almost entirely of serperi tint.),k 120 ABSTRACTS OF CHEMICAL PAPERS.and associated with it were diallagitc, magnesium-mica, chromdiopside,magnetite, chrompicotite, titanite, &c. Orthoclase and oligoclase occurin many localities, sometimes constituting about one-third of the rock,and passing over into gabbro.At Rndbach the asymmetrical felsparis more prominent, and associated with granular olivine, which is com-plctely converted into serpentine, whilst there is a diminished amountof tlie other rock-minerals already mentioned. Again at Rachelshausenand Oberdicten, the olivine rock is very closely allied to proterobase,in which the olivine has almost entirely disappeared, whilst oligoclase,augite, hornblende, ehloropite, magnetite, titanite, and occasionallymica, constitute a granitic mixture, which shows that olivine rock maybelong equally to the gabbro and the diabase scries of rocks.C. A. B.The Limestones and Calcium Phosphates of Curacao.ByA. STELZNER ( J a h d . f. KE., 1877, 415--416).-The calcium phos-phates occur partially in the form of loose lumps resting upon thelimestone, and partially in such a form as to show that they are a pro-duct of the decomposition of the limestone itself. The limestone issometimes massive and sometimes oolitic, and penetrated by theremains of gasteropods and bivalves, from which it, may be inferredthat it is a very recent formation ; a qualitative examination proved it.to be passing gradually into calcium phosphate, the mass a t the sametime becoming cellular in structure. The purest calcium phosphate isfound in nests or veins disseminated throughout the limestone ; or itoccurs in foliated shell-like masses, having a reniform surface, clothing,and even entirely filling the cells or 1:ollows in the cellular limestone.In its pure state this calcium phospliate is an amorphous, yellowish,greenish, or brown mass, with a dull or resinous lustre upon its con-cho'idal fractured surfaces, somewhat resembling opal in appearance.From its appearance and properties, it is undoubtedly the same sub-stance as the pyroclasite of Shepard, the sombrerite of Phipson, andthe hard guano of Dana.Formerly pyroclasite was supposed to be theresult of volcanic action upon the coral-limestone, but it is known a tpresent to have been formed by the action of water upon guano, thesolution thus obtained acting upon the limestone, and causing theformation of calcium phosphates. An examination of the specimens ofcalcium phosphate from this locality seems to prove that the purestcalcium phosphate was o~iginally a gclatinous precipitate, which sub-sequently hardened, as bubble-like spaces are found in the shell-likemasses, which could only have been formed by the generation of gasinside a permeable, gelatinous mass.This theory of the formation ofnatural phosphates agrees well with the cheniical reaction between asolution of calcium phosphate and ammonia. Pjroclasite and the otherphosphates above mentioned are therefore only hardened jellies. Theoccurrence of radio-fibrous crystalline calcium phosphates is very rare inCurapo ; they arc probably the same as the mineral staffelite. Curacaois an island belonging to the Antilles. C. A. B.Note on an Edible Clay from New Zealand. By M. M. P.Ici ii * r ~ (Chem. NTEZGS, xxxvi, 202).-l'he ciay is from Mackenzie CountyORGANIC CIXEMISTRY. 121South Island.sheep.It is free from diatomace=. It is largely eaten bySiO,. A1,03. Fe203. CaO. MgO. NaCl(traccof KCI). HzO. Orgtmic. ... 1 4 61.25 17.97 5.72 1.91 0.87 3-69 7.31 1 - 7 7 = 100.40M. M. P. N.Meteorites. By J. LAWRENCE SMITII (Counpt. rend., lxxxv, 678).-A metcorite which, on the 21st December, 1876, passed over severalof the States, .projected fragments, one of which was found nearRochester, Indiana. It weighed 400 grams, and exhibited a globulartexture. Spherical grains of two or tlhree mm. diameter could easilybe detached from the mass, with which they were identical in compo-sition. Two silicates could be distinguished, but nothing resemblinganortliite.A meteorite fell at Warrenton, Missouri, on the 3rd January, 1877,of wliich the mineralogical composition was : peridote, 76.00 ; broneiteand pyroxene, 18.00 ; nickeliferous iron, 2.00 ; troilitc, 3-50 ; chromeiron, 0.50 per cent. This meteorite is unlike any yet described, exceptthat of Ornans ; it is very friable, and its crust is dull, and in partsscoriaceous.A meteorite which fell at Cynthiana, Kentucky, on the 23rd Janu-ary, 1877, weighed six kilos., and presented a great similarity to themeteorite of Parnallee. I t s composition corresponded with peridote,50.00 ; bronzite and pyroxene, 38.00 ; nickeliferous iron, 6-00 ; trollite,5.50; chrome iron, 0.52 per cent. R. It

ISSN:0368-1769    

DOI:10.1039/CA8783400115

出版商:RSC    

年代:1878

数据来源: RSC

摘要:

ORGANIC CIXEMISTRY. 121Organic C h e m i s t r y .On Isodibutylene. By A l3 u T L E R o w (Lie& iy7s ArznnZeT1-, clxxxix,&--83) .-Observing the extraordinury easc with wliicli isobatyienc be-comes polyrnerised, the author was induced to undertake, in conjunctionwith Goriainow (Liebig’s Anrzahz, clxix, 1461, the study of the condensa-tion products of the simpler members of the hydrocarbon series, C,,H2,).In all cases in which the attempt bas been made to obtain ?nethyZene,CH2, condensation takes place, and etlqZene is the result (Perrot,Ann. Chirn. Phys. [3] xlix, 94; Butlerow, Bull. Soc. Chirn., 1862,xiii; and others). 3thyZene, on the othcr hand, seems incapable ofbecoming polymerised, the source of the more complex bodies obtainedwheu sulphuric acid acts upon alcohol being probably the higheralco2iols contajned in the latter: Yropy Zerie, alt bough condensable byboron fluoride, gives neit’her di- nor tri-propylene, but only products ofa higher order; nor do these bodies result from the a,ction of sul-phuric acid on normal or secondary props1 alcohol, Rerthelot’s ex-periments on this point (Bull.Xoc. Chim. [2], xi [1869], 13) notbeing decisive. The author has also found that simple condensation-products cannot be obtained from isobutyl or from secondary buty122 ABSTRACTS OF CHEMICAL PAPERS.alcohol, although by abstracting water from the former, a hydrocarbonis obtained identical with the easily condensable isobutylene fromtirimethyl carbinol.The action of sulphuric acid upon isobutyZene itself led t o no satis-factory result, since concentrated acid converts it at once into high-boiling products, and a weaker acid dissolves it, giving only a smallquantity of condensed products, the most volatile of which is probablyisotributy Zem, C12&.When strong sulphuric acid acts upon trimethyl-carbinol, the isobutylene first formed is also polymerised to high-boilingliquids. The quantity of these, however, decreases as more dilute acidsolutions are employed, and when trimethyl carbinol is heated withtwice its volume of a mixture of equal parts of sulphuric acid andwater, only isodibzctyzelze and unchanged isobuty Zene are obtained. Thesame result may be attained by enclosing isobutylene (liquitied bycold) in a tube with dilute sulphuric acid, and after some days, whenthe hydrocarbon has dissolved, heating the tube in a water-bath.Thecondensed products separate ou the surface of the acid ; when dried(finally by boiling with sodium) they are fractioned. That portionwhich boils between 102-104" consists of isodibutylene, a colourlessliquid, of sp. gr. at 0" = -734.Isodibutylene combines directly with bromine to form a rather un-stable bromide, C,H,,Br,. By boiling with caustic potash, or even bydistillation, this bromide is decomposed into HBr and CsH,,Br.Burning hydrochloric acid at 100' gives witlh isodibutylene a compound,C,H,,Cl, which is a light oily body, stable at ordinary temperatures,but partially decomposed by distillation, KCl being given off.B.p.An iodide, C,H,,I, is obtained, wit'h even greater ease, by saturatingthe hydrocarbon at 0" with hydriodic acid gas. This iodide is at-tacked, even at O", by moist silver oxide. The product of the reaction,dried by anhydrous bsryta, consists of regenerated isodibutylene and a,iiew octylic alcohol, CsHlsO, named isodibutoZ. This alcohol is a colour-less thick liquid of characteristic odour, which boils at 146*5-147*5",and solidifies at 20". Sp. gr. at Oo = -8417. Its alcoholic nature isproved by its yielding, when treated with phosphorus pentachloride,the Same chloride that is produced by the action of hydrochloric acidupon isodibutylene. It belongs to the class of tertiary alcohols, thegeneral properties of which it shares. Its iodide, when treated withsilver nitrite, gives neither a nitrolic nor a pseudonitrolic acid (VictorMeyer's test).In order t o determine its constitution, isodibutol was submitted t o theregulated actioii of oxidizing agents ; it gave, besides unaltered alcoholarid isobutylene, the same products as are furnished by oxidation ofisodibutylene, but no ketone or aldehyde, a further proof that it isneither a primary nor a secondary alcohol.It was only necessary thento study the oxidation of isodibutylene. This body was thereforereated in the cold for six days with a mixture of sulphuric acid andpotassic dichromate. Carbonic acid was continuously evolved. Themixture was then distilled, that part of the distillate which containedoily drops being collected separately from the clear acid liquid whichsubsequently passed over.This clear liquid contained principally145-150"ORGANIC CmmSTRY. 123acetic acid. The first distillate was treated with potassic carbonate,when much of the oil dissolved. The undissolved oil was removed, andthe remaining alkaline liquid again distilled. From the first portionsof liquid which now passed over acetoiie was easily separated by PO-tassic carbonate in excess ; not, however, in large quantity, probablybecause much of it had been oxidized to acetic acid. The alkaline so-lution, after removal of the acetone and oil, gave, on treatment withsulphuric acid, acetic and trimethyz-acetic acids, of which several charac-teristic salts were prepared. Since trimethyl-acetic acid does not giveacetone on oxidation, it is thus evident that the primary oxidation-products of isobutylene are acetone and trimethyl-acetic acid, thus :CsH16 + 0, = C,H,,02 + C,H,O.The acetone is partially oxidized toacetic acid.This experiment establishes the constitution of isodibutylene. For ofthe two products one contains three, the other two methyl groups ; fromwhich it must be inferred that the molecule of isodibutylene containsJiue such groups. Three of these must be united to one carbon-atom toform tertiary butyl ( CH3),C-, which appears in the trimethyl-aceticacid, the remaining two methyls forming with another carbon-atom thegroup (CH3),C 1, which by oxidation yields acetone. Prom theseconsiderations the formula of isodibntylene may be inferred to be(CH,),C-CH=C( CH,), ; and that of the corresponding tertiaryalcohol isodibutol ( CH3),C-CH2-C ( CH,>,OH. The oxidation of thehydrocarbon follows the general rule for the series CnHan, viz., thatthe carbon-atoms separate a t the junction C z C .(CH,),C-CH=U(CH,), + 0, = (CH,)C-CO,H + (CH3)ZCO.This constitution of isodibutylene granted, the mode of its formationfrom trimethyl-carbinol is the following : (1) part of the alcohol splitsup into water and isobutylene ; (2) one molecule of isobutylene uniteswith one of unaltered trimethylcarbinol, water being again eliminated.The course of the reaction is quite analogous to Collarits’ and Merz’ssynthesis of aromatic: ketones by the action of phosphoric anhydrideupon a mixture of a hydrocarbon and an acid, or to VV-ischnegradsky’ssynthesis of diamylene (Deut.C‘hern. Ges. Ber., viii, 434).To account for the second phase of the reaction, the author remarksthat methyl groups and their derivatives are in general less prone toenter into reaction than the groups =CHz or CH, and their deri-vatives. The different degrees of‘ stability are well observed in thealcohols of the three categories and the bodies allied to them, theradicles of the primary alcohols being least inclined to part with thehydroxyl or other simple radicles united to them, while in the tertiaryalcohols and their allies such separations take place with the greatestease. When therefore trimethylcarbinol is partially resolved intowater and isobutylene, the feebly- bound hydroxyl of the nndecomposedalcohol combines more readily with the hydrogen in the group 1 CH, ofthe hydrocarbon than with that belonging to the more stable methyl-groups of its own molecule, thus-(CH,),C (OH) + H CH=C(CH,)z= (CH,)3C-CH=C(CH,)z + HZO.On the other hand, when isobutyl alcohol, CH2(0H)-CH(CH3)2124 ABSTRACTS OF CHEMICAL PAPERS.separates partially into water and this same (iso-) butylene, no suchcondensation takes place, because the alcoholic hydroxyl unites withthe hydrogen of the group E C H in its own molecule, rather thanwith that of the ZI CH2 of isobutylene.These considerations, somewhat modified, will also explain whysecondary butyl alcohol, on treatment with sulphuric acid, gives, as aprincipal product, pseudo-butylene, but no dibutylene.Here the al-coholic hgdroxyl tends to combine either with the hydrogen of thepseudo-butylene, CH3-CH = CH-CH3, first formed, or with that ofthe =CH, in its own molecule. The proximity of the latter deter-mines its union with it, and consequently the complete conversion ofthe alcohol into pseudobutylene.The higher-boiling portions of the oily acids from the oxidationof isodibutylene were, after a tedious investigntion, found tlo consist oftrimethylacetic acid and a new octylic acid, CBHIGO2, the separation ofwhich was ultimately effected by preparing the cadmium salts, andfractionally distilling the acids extracted from them. This octylic acidis a colourless oily liquid, smelling like trimethylacetic acid, and boil-ing with partial decomposition a t 205-218".I t s constitution is bestexpressed by the formula, C(CH,),-CHZ-CH(CH3)COOH : since thecarboxyl group must be formed at the expense of one of the five methylgroups of isodibutylene, and it is reasonable to assume that the groupoxidised is one of those lying nearest to the point of attack of theoxidizing agent, the doubly-united carbon atoms C=C. The forma-tion of this acid from isodibutylene appears strange a t first sight, butis not without analogy, since oxidation of the hydrocarbons CI,HZn,appears in general to furnish the same products as that of thecorresponding tertiary alcohols. Thus the author has found that acertain quantity cjf isobutyric acid may be obtained by oxidation oftrimethylcarbinol. Now this octylic acid may be regarded as isobutyricacid in which hydrogen is displaced by tertiary butyl (CH,),C-, iso-dibutol and isodibutylene being similarly derived from trimethylcarbinoland isobutylene respectively.It may be assumed that in both cases,by the successive removal and addition of water, an isomeric alcoholis. first produced, which is then oxidized to the acid. Thus, whentrimethyl carbinol is oxidized--(1.) (CH,),C(OH) = CHz=C=(CH3)2 + HZO.( 2 . ) CHZIZC=(CH~), + HZO = (CH,),CH--CHzOH,which furnishes isobutyric acid ( CH3)2CH-COzH ; and when isodi-butylene is oxidized-(1.) B~-CHIIC=(CH,)Z + HZO = Bt--CH,--C(OH)(CH3)z;(2.) Bt--CH,--C(OH)(CH,)2 = B~--CH~C(CH~)IICH, + HZO.(3.) Bt-CH,--C(CH,)=CH2 + HZO =Bt-CHZ-C (CUI,) lEII-CH,OH,which yields the above octylic acid.I n support of this explanation the author mentions that he hasfound, amongst the oxidation-piaoducts of isodibutylene, a body derivedfrom the octylene, C(CH,)3-CH,-C( CH,) = CH,, whose existence isassumed in equations (2) and (3).This hydrocarbon would, upon oxiORGANIC CHEMISTRY. 125dation, separate at the doubly-joined carbon atoms, and give, as a firstproduct, a ketone, C(CH,)3-CR,-CO-CH3; and, in fact, the oilyproducts insoluble in potassic carbonate were found t o consist of amixbure of isodibutylene, and of a ketone of this composition boilingbetween 125 "and 130". The peculiar deportment of this body withmetallic sodium, which indeed first drew attention to it, is also ex-hibited by an undoubted ketone, namely, ethyZisopropyZ 7iefol.i e, preparedby acting with zinc-ethyl on isobutyryl chloride ; these bodies do notattack the metal in the cold, but dissolve it rapidly whcn warm, givingsolutions which, in contact with air, quickly assume a blood-redcolour, finally passing into brown. On the other hand, it is not oxi-dized by silver oxide ; it does not combine with acid sodium sulphite,nor does it throw down ferric hydrate when boiled with ferric cliloride,properties which distinguish it from the aldehydes and oxides of theclass t o which ethylene oxide belongs.Finally, when oxidised withsulphuric acid and potassic bichromate, it yields acetic and trimethyl-acetic acids, as follows :-This reaction is decisive with respect to its constitution.The views unfolded in this paper receive some support from theauthor's observations on the action of sulphuric acid upon amylenc(trirnethylated ethylene) from tertiary amyl alcohol.Here the suc-cessive assimilation and separation of water take place without anychange in position of the hydroxyl. In the cold sulpliuric acid con-verts this amylene into diamylene. Rut when tertiary amgl alcoholis heated t o 100" in a tube with three times its volume of a mixture ofequal weights of sulphuric acid and water, the principal product isuncondensed amylene, which floats on the surface of the acid. If nowthe tube be laid on its side for some days, and occasionally shaken, thehydrocarbon again dissolves, i.e., assimilates water to reproduce thealcohol ; and these operations may be repeated several times.Here,then, is an example of dissociation, and of gradual union of the dis-sociated bodies to form the original compound. I n thc case of isodi-butol, on the other hand, the dissociated products (isodibutylene andwater) would reunite to form, not the original alcohol: but anisomeride.Let it be supposed that, in a mixture of tertiary alcohol and sul-phuric acid, some molecules are dissociated even a t low temperatures,as Wislicenus has observed for concentrated lactic acid, and Berthelotf o r saline solutions. Under ordinary condit'ions chemical cquilibriumis established when a small number of hydrocarbon molecules and a,large number of molecules of alcohol are present ; in the -arm mix-ture, on the contrary, the hydrocarbon molecules preponderate.Itmay now be assumed, (1) that in ccrtain cases the dissociatcd productsunite to form, not the original molecules, but new ones isomeric withthem; and (2) that these new rriolecules also undergo dissociation.Under these circumstances chemical equilibrium would be establishedbetween certain quantities of the two isomeric alcohols, the hydro-carbon and water. Such a condition of equilibrium might even occurin the absence of a reagent, such as sulphuric acid, to bring it about12 6 ABSTRACTS OF CHEMICAL PAPERS.and the composition of an apparently homogeneous mixture mightthen be different at each moment of time. Between the isomericmolecules present there would be the same “ struggle ” (“ Concurrenz ”Pfaundler, Pogg.r~nnaZeiz, 1874, Jubelband, p. 189) which takesplace between niolecules of different kinds. In most homogeneousgaseous or liquid substances the number of molecules of one kind isexceedingly great, that of molecules of one or more other kinds,vanishingly small ; the chemical structure of such a body may fairly bediscussed. Cases however may occur, in which the quantity of one ofthe isomeric bodies present is not infinitesimal ; here, then, the mole-cules of the two kinds would be in a state of continual “struggle.”This, of course, renders the investigation of such a mixture dificult.since its reactions must vary with the conditions of experiment. Asexamples of such duality of structure, cyanic and hydrocyanic acidsmight be cited.From this point of view it is impossible, and indeedunnecessary, to determine whether cyanic acid is really carbimide ora hydrate of the radicle cyanogen, or whether hydrocyanic acid is anitril or a carbylamine. By the adoption of such views our concep-tions of chemical constitution would acquire a less absolute meaning ;but many phenomena, as, for example, the frequent appearance ofsecondary products in reactions, would be explicable.Constitution of Amylene from Fermentation Amy1 Alcohol.By ELTEKOFF (Ueut. Chem. Ges. Ber., x, 1904+-1905).--The authorestablishes the presence of the hydrocarbonsCh. B.( CH3),CHL.CECH and CH,.CHpCH = CH.CH3in ordina,ry amylene. The latter he regards as being formed from theoptically active alcohol, in virtue of a re-arrangement of its atoms,precisely as trimethylethylene is formed from the optically inactivealcohol.c. F. c.Formation of Allylene from Bromocitrapyrotartaric Anhy-dride. By E. I3 O U R G O I N (Cornpt. rend., lxxxv, 710).-Bromocitra-pyrotartaric aiiliydride was dissolved in water, saturated with ammonia,and to the solution excess of silver nitrate was added, then the mixturewas heated for some hours at 130°, in sealed tubes. When the tubeswere opened, a, larger quantity of gas was disengaged, consisting ofcarbon dioxide and allylene, some of which gave the characteristicyellow precipitate with ammonio-cuprous chloride. The bromocitra-pyrotartrate of silver appears to have split up, as shown by the equa-Action of Sodium on Tetrachloromethane and Bromoben-zene.By J. GUABESCHI (Deut. Chenz. Ges. Ber., x, 1748).--’CVhensodium is added to mixed ethereal solutions of these substances, aviolent reaction takes place, sodium chloride and bromide being depo-sited.diphenyl, two other substances melting at 61.5” and 83*, and chlori-nated compounds. J. R.tion:-C5H4Agl13r04 = AgBr + 2C02 + C3H4. R. &.Amongst the products are pentaphenylethyl chloride,(CsH,)&-C(C6H5),C1ORGANIC CHEMISTRY. 127On the Limits of Etherification. By M. BERTHELOT (Compt.rend., lxxxv, 883). -During the researches of the author and Saint-Gilles, on etherification, sixteen years ago, a certain number of mix-tures were put aside in sealed tubes.The author now gives the resultsof the reactions.Equivalent Weights o,f Ethyl Alcohol amd Acetic Acid.-Two specimensprepared in 1862, contained, in November, 1877, 65 and 65.4 per cent.of acetic ether respectively. These numbers approach very near tothose obtained in the original experiments ( A r m . Chim. Yhys. [3],lxviii, 239), by heating the mixtures in sealed tubes nearly full ofliquid.In presence of water the same resnlts are obtained ; a mixture ofacetic acid and akohol with 4 per cent. of water contained, after 8years, 63.8 per cent. of acetic ether, coinciding with the limit obtainedin the original experiments (Zoc. cit., p. 301).Another experiment, with equivalent weights of glycerin and aceticacid, gave, after 64 years, 71 per cent.of etherified acid. The limitobtained by heating the mixtures was 69.3.Tartayic Acid a n d Alcohol.-A mixture of 28 per cent. alcohol,11.8 per cent. tartaric acid, and 60.2 per cent. water, left for 12 years,had lost 32.2 per cent. of its original acid. The same mixture whenheated, had lost 32.5 per cent. This acid, being bibasic, existed partlyas neutral ether, partly as ekhyl-tartaric acid. The present mix-ture contained 1.3 per cent. of neutral ether, 5 per cent. of ethyltartaricacid, and 5.5 per cent. of unchanged acid. The mixture obtained byheating to 135", contained 1 per cent. neutral ether, 5.7 per cent. ethyl-tartazic acid, and 5.1 per cent. of unchanged acid. A mixture of ordi-nary alcohol and valeric acid, left at the ordinary temperature for16 years, contained ethyl-Valerie acid and water, which had separatedin the liquid form at the bottom of the tube.In this tube the per-centage of etherified acid was 81.7, instead of 65.8 Gbtained at 200".This difference is due to the fact, that at 200" the water does notseparate, whilst at the ordinary temperature it is removed from thefield of action, and thus allows the etherification to go on further.These experiments verify the general laws of etherification, and par-ticularly the identity of the limits of combiliation between alcohols andEtherification of Secondary Alcohols. By N. MEN s c H u T K I N(Deut. Chern. Ges. Ber., x, 1898--1902).--The results of this investi-gation are contained in a comprehensive table, from which it is seen :-(a.) That the absolute initial velocities of etherification of thesecondary alcohols are about 30 less than those of the correspondingprimary alcohols.They differ from one another, the velocity beinggreatest in the case of dimethyl carbinol ; less by 3 in that of ethyl-methyl carbinol, again decreasing by 3 in the case of methylisopropylcarbinol, but at this point remaining constant for all secondary alcoholscontaining four or more carbon-atoms.(b.) Whereas the absolute velocities of etherification during thefirst hours of observation are practically the same for all primaryalcohols, these observed velocities for the secondary alcohols areacids, from the crdinary temperature up to 260". c. w. w128 ABSTRACTS OF CHEMICAL PAPERS.found to differ from one another, even in cases where the initial velo-cities are identical.Further, the absolute velocities observed duringthe second and subsequent hours are greater for the secondary thanfor the corresponding primary alcohols.( c . ) Dxring the earlier hours, greater velocities are observed in thecase of alcohols of smaller molecular weights; after the lapse of36 hours these differences disappear, the etherification during thisinterval being found equal for all secondary alcohols hitherto investi-gated. Subsequently the velocities of etherification of the secondaryalcohols increase with increase of molecular weight.(d.) The relative init8ial velocities are found to decrease with increaseof molecular weight, and are much smaller than those of the corre-sponding primary alcohols.(e.) Of the secondary unsaturated alcohols, both absolute and rela-tive initial velocities are less than those of the saturated alcohols.df.) The observed limit of etherification exhibits a percentage in-crease of 1.1 for each carbon-atom added to the alcohol molecule. Thelimit is less for the corresponding unsaturated alcohols.The author finds that the etherification of methylisopropyl cai-binolfollows a somewhat abnormal course, which fact he refers to a conver-sion of the alcohol on prolonged heating into the isomeric dimethyl-ethyl carbinol. Secondary octyl alcohol exhibits a similar deviation,which is similarly explained. c. F. c.Action of Methyl Iodide upon Sulphur.By H. KLINGER(Deut. Chem. Ges. Bcr., x, 1880-1 881) .-By heating methyl iodide(2 mols.) with sulphur (1 mol.) in sealed tubes to 160-190", theauthor has obtained trimcthysulphiodide, crystallising from alcohol incolourless prisms. The corresponding free base is a t ordinary tempera-tures a heavy oil, soluble in water in all proportions ; its aqueous solu-tion exhibits strongly alkaline properties, and does not undergo decom-position on boiling.The author has obtained the plstinochloride, { (CH3),S.C1)PtCI,,crystallising in a form compounded of the cube and octahedron. c. I?. c.Brominated Ethylic Ether. By FR. KESSET, (Deut. Cheulz. Ges.Ber., x, 1667-l676).-The author has obtained, by the action ofbromine on ethylidene oxychloride, [ (CH,-CHCl),O + 16 Br], insealed tubes at 't10", the following amongst other products :-1.C4H,Br,0 (octobromether), a thickish liquid, fuming slightly inthe air, insoluble in water. It is decomposed by distillation a t ordi-nary pressure, but distils at 132-135" at reduced pressure (450-A70 mm.).2. C,H,Br,, a body crystallising in pearly scales, easily soluble inether, alcohol, and carbon bisulphide, insoluble in water. It melts at52", and boils at 220".3. Tribromacetic acid.Bromine acting on ethylidene oxychloride [ (CH,-CHCl),O + 4131-1in open vessels at 100' forms a syrupy, yellowish liquid, which fumeORGANIC CHEMISTRY. 12Yin the air, and is decomposed by distillation. Its composition agreeswith the formula, C,H,B,O (tetrabromethcr).The same substaiice isformed by saturating ethylidene oxychloride with bromine, a t 115-120".The foregoing brominated ethers (octobrom- and tetrabrom-ether)are both decomposed by heating with water, the former yielding hydro-bromic acid and bromoform, the latter hydrobromic acid, crotonalde-hyde, and resinous products. From the analogy of this behariour withthat of ethylidene chloride (which yields hydrochloric acid by decom-position with water), the author concludes that the brominated ethersboth contain the residue, -CI€Br-0-CHBr-, and accordinglyassigns to them the following formule. :-CBr3-CHBr-O-CHBr-CBr3 (octobromether) ;CH2Br-CHBr-0-C HBr-CH,Br (tetrabrome ther) .J. R.Action of Sulphuric Acid on Mixed Ethers. By ELTEKOFF(Deut.Chern. Ges. Ber., x, 1902--1904).-The author has furtherinvestigated the decomposition of ethyl-isocrotyl oxide by sulpliuricacid (1 per cent.), and has proved t h a t this ether is formed in accord-ance with the equation-(CH,),.C = CH.0C2H5 + HzO = (C€€,),.CH.COH + C2H50H,its formation being therefore analogous to the similar decompositionof the simple and mixed ethers. Ethylisopropyl oxide is entircly de-composed, on heating with the dilute acid, into ethyl and isopropylalcohols ; this property of ready decomposition the anthor regards aspeculiar to all ethers of secondary and tertiary alcohols. Ethyl-ally1oxide subjected, as a type of unsaturated compounds, to the sameaction, was resolved int'o ethyl and ally1 alcohols ; this result disprovesButlerow's view of the decomposition of the ethers of unsaturatedalcohols a t the point of union of the carbon-atoms by the dcluble bond.The author further shows that ready resolution of these bodies is con-ditioned by the presence of unsaturated radicles.The formation of ethylene by the action of Na upon CH,.CHCI,,the author regards as occurring in two stages, the first consisting inthe resolution of the latter body into CH2CHC1 + HC1; the secondin the reduction of the vinyl chloride thus formed to ethylene.c. F. c.Selenium-compounds. By L. v. PIEVERLING (Liebig's AnnaZeYz,clxxxv, 331-339) .-Ethyl 2ClponoseZenide.-The author obtains this sub-stance by digesting phosphorus pentaselenide (P,Se5) with potassiumethysulphate, potash, and water a t 50" aad submitting the product tofractional distillation.The distillate consists for the most part ofethyl monoselenide, contaminated, however, with traces of diselenide,which are removed by digesting the distillate with more potassiumethylsulphate, p.otash, and water, with the addition of a little phos-phorus, and distilling afresh130 ABSTRACTS OF CHEMICAL PAPERS.Pure ethyl monoselenide, (C2H5)$e, thus obtained is a clear, colour-less, mobile, highly refractive liquid, smelling like the light hydro-carbons and boiling at 108". It mixes with alcohol and ether in allproportions.Triethyl-seZenofiium Iodide.-Ethyl monoselenide and ethyl iodide,when mixed in molecular proportions, combine slowly at the ordi-nary temperatures to form white crystals of the compound Se(C2H5)J.This substance is stable in the air, not hygroscopic, but very easilysoluble in water and alcohol, and sparingly in ether.It sublimescompletely between 80" and 126" without melting, but undergoingdissociation into ethyl monoselenide and ethyl iodide, which collect inthe receiver and recombine in the course of 1 2 hours to form triethyl-selenonium iodide. The author finds by direct experiment that triethyl-telluronium iodide behaves in the same manner.Tyieth yZ-sdenonizwz Lfydrozide, Se ( CzH,),HO.-This substance isformed by the action of silver oxide on triethyl-selenonium iodide.It is a powerful base, forming a syrupy solution which absorbs car-bon dioxide and water with avidity.Its salts are all crystalline : theyhave the odour of leeks and a burning bitter taste. With the excep-tion of the tartrate, they all deliquesce rapidly in the air, and hencecannot well be analysed.The tartrate, Se (CzH5),C4H,O6 + 2H20, crystallises in delicateneedles of a pale rose-red colour: it dissolves very easily in water,forming an acid solution.The platinochloride, [ Se ( C2H,)SCl]2PtC14, crystallises in highly re-fractive red rhombohedrons.From the foregoing results the author arrives a t the conclusion that,selenium is an element of variable atomicity, being bivalent in thecompound ( C2H5),Se, and quadrivalent in the compounds-(C2R,),SeC-,H,I and (C2H5)2SeC2Hj(OH). J. R.Action of Alcoholic Soda on Etheric Nitro-compounds. ByFILIPP HESS and JOHANN SCHWAB (Wien.Akad. Bey., lxxv, 702).-Beckerheim has proposed to determine the amount of nitro-substitutionin such substances as nitroglycerin, nitrocellulose, &c., by saponifica-tion with standard alcoholic potash and titration of the alkali notconverted into nitrate. The authors find that this process gives resultsf a z too high, as the reaciion is a complex one, nitrite being formed andthe alcohol (and possibly the glycerin) being oxidised to acetic: andformic acids, aldehyde-resin, &c. Thus a specimen of nitroglyceringave 1Fj.72 and 15.65 per cent. of nitrogen by Dumas's method (aftercorrection by the results of a blank experiment with pure glycerin,whilst 25.3 and 26.0 were fonnd by Beckerheim's process. Analogousresults appear to be produced with nitrocellulose, nitromannite, a i dsimilar bodies. Probably Beckerheim's process would answer were thenitrite reduced to ammonia by nascent hydrogen and then estimatedas such.C. R. A. W.Sugar in Grapes. By E. MACH (Din$. p0hJt. ?7., CCXXV, 470-474) .-In investigating the formation of sugar in plants the authoORUANIC CHEMISTRY. 131and F. Kurmann have examined numerous samples of must by meansof Fehling's solution and the polarizing apparatus of Ventzke andSo 1 eil .Fifteen samples of grapes examined on October 1st) 1875, gave anaverage difference of 0.5 per cent. of sugar between the polarizingmethod, in which the sugar was calculated as inverted, and the methodby Fehling's solution. On the 15th of October an avcrage differenceof 2.02 per cent.was obtained, and on Noverrilncr 3rd, 4 per cent.Grapes preserved in a cool place gave, on November 20th, 8 per cent,of difTerence, and on December 28th) a difference of 10.5 per cent.between the two methods. Hence the later the grapes are examined,the greater the error in calculating the sugar as inverted sugar, sincethe levulose seems to predominate more and more over the dextrose.The juice of several samples of apples gave diEerences of from 1 to1.3 per cent. The juice of pears gave from 5 to 'LO per cent. difference.These show that the calculation as inverted sugar is crroneons.Experiments made on fermenting must show that the levnlose fer-ments most quickly at the first, but soon the dextrose is most rapidlyacted upon.Fresh must was set to ferment after the addition of about 1$ percent.of cane sugar. After four days 0.93 per cent. of cane sugarremained ; after ten days 0.27 per cent. ; after sixteen clays the wholehad disappeared, but thc fermentation of the sugar originally presentin the must was completed only after thirty-one days. From thisand other experiments it is inferred that must treated with canesugar will always yield wine giving a left-handed rotation, whilstmust treated with commercial grape sugar will yield wine giving aright-handed rotation. J. T.Physical Properties of Quercite. By L. PRUNIER (Compt. rend.,lxxxv, 808--810).-The specific gravity of quercite is 1.5845. Itcrystallises in the clinorhombic system, and the crystals have a dextro-gyratory power, [ a ] , = 24" 17'.R. R.Cyanogen-compounds of Gold. By C. G. LINDBAUM (Dd.Chem. Ges. Bey., x, 1725).-The author has prepared and annlysed thefollowing compounds :-Potassium Aurocyannide, KCy.CgAu.-Prepared by Himly's method.Potassium Azcricyanicle, KCy.AuCy2 + 1.t- aq.-Formed by the actionof potassium cyanide on perfectly neutral gold chloridc.Potcrssium Iodazwicyanide, KCy. C yAu12 + aq. ; bro7.izaic7.icya.rzide,KCy.CyAuRr, + 3 aq. ; and chZorauricya?zide, KCy.CyAuC1, + aq. ;the last formed by the action of chlorine on the iodine-compound.Sodium Azcrocyanide, NaCy2Au ; Fromau.ticyaizide, NaCy,AuB 1 a 2 +2 aq., formed by the direct action of bromine.Ainnzonium Awrocyanide, (NH4)Cy,Au.-Gives off ammonium cyanideat 100".Barium Aurocyanide, BaCy,.Cy2Au, + 10 aq.; iodnicyicyanide,BaCy4Au214 + 10 aq. ; Fro~~zni~roc~jaizicle, BaCy4Au2Br4 + 10 aq. ; andchlornuricyanide, BaCysAu4C14 + 8 aq.Strontium Aurocyanide, SrCy4Au2 + 3 ay., and the iodine, bro132 ABSTRACTS OF CHEMICAL PAPERS.mine, and chlorine-compounds crystallises with 10 aq., 7-10 aq., and8 aq. respectively ;CaZcizm Aurocyu?zide, CaCy4Au, with 3 aq., and the iodine- andbromine-compounds, with 10 aq. ;Cadmium ammxyanide, anhydrous, and brornauricya&de, CdCy4Au2Br4with 6 aq.Zinc Aurocyanide, anhydrous, and brom- and chlor-auricyanideswith 8 aq. and 7 aq.Cobalt Aurocyanide ; atwicyanide, CoCy4AuzCya + 9 aq. ; iod- andbrom-auricyanides, with 10 aq. and 9 aq.Dibrom-ethylcarbylamine.By M. TCHE RNIAK (Cowpt. rend.,lxxxv, 711).-According to the author's analysiF, dibrom-ethylcarbyl-amine has the formula NC3H5Br2, and may be regarded as cyanate ofethyl, the oxygen of which has been replaced by bromine.J. R.R. R.Nitrosoguanidine. By M. J o U S S E L I N (Compt. r e f d . , lxxxv, 548-5.50) .-Nitrosoguanidine is olhined by dissolving nitrate of guanidinein excess of nitrous and fuming nitric acid. After the solution hasstood f o r 24 hours, it is poured into an excess of cold water, when thenitrosoguanidine is precipitated in acicular crystals. These are colour-less and flexible, soluble in hot water and boiling alcohol, insoluble inether and chloroform. Submitted t o a gradually increasing tempera-ture, nitrosoguanidine loses ammonia a t 220°, the crystals becomingopaque without change of form.At higher temperatures cyanogencompounds are given off and a stable yellow substance remains, whlchis probably hydromellone. R. R.Action of Hydrogen Sulphide on Propyl Aldehyde. By W.ALEXEJEFF (Deut. Che7n. Qes. Ber., x, 1739).--By saturating withhydrogen sulphide an aqueous solution of propyl aldehyde acidifiedwith hydrochloric acid, the author has obtained a colourless liquid,lighter than water, agreeing approximately in composition with theformula C3H,0 + C?H,S. The further action of hydrogen sulphideresults in the production of a viscid liquid, heavier than water, andhaving the characteristic odour of the thioaldehydes. This substanceis still under examination.J. R.Thialdehydes. By H. KLINGER ( D w t . Chern. Ges. Bey., X,18 77-1880) .-By converting the amorphous or a-benzothialdehydeinto the @-modification (m.p. 225") by the action of iodine in smallquantity on its concentrated solution in benzene, and heating thelatter with metallic copper, the aathor obtains stilbene in the propor-tion of 60 per cent. of the weight of P-thiobenzaldehyde employed.By the action of methyl iodide (26 grams) upon thiacetaldehyde(10 grams) the author obtains trimethyl sulphiodide, (CH,),SI (10grams). This reaction corroborates the tri-molecular view of theconstitution of thiacetaldehyde. It appears to take place accordingt o the equation-(CH)3.S3.(CHs)3 + 3CHJ = S(C&3)31* + (CH,.CHI.S)z.CH.CH3ORCANIC CHEKCSTRY.133The a-thiobenzaldehyde dissolves with difficulty in ethyl iodide, andis converted into the 6-modification which separates in the form of fineneedles. c. F. c.Molecular Volumes of the Silver Salts of Organic Acids.By H. SCRODER (Deut. Chern. Ges. Ber., x, 1871--1875).-The authorhas continued his researches. and obtains results which further estab-lish the existence of a simple numerical ratio between the molecularvolumes of the silver salts of organic acids, that they are in factmultiples of a unit denominated by the author a " silberstere " = 5.14= one-half the at. vo?. of silver. In the case of the fatty acids themolecular increment of CH2 determines an increase of 3 steres = 15.4in the molecular volume of the corresponding silver salts.The author,however, finds that the molecular volume of normal silver caproate isless by 2 x 5.1 than that of its isomeride the salt of the fermentationacid, and that the mean of the two quantities thus differing, andnot either of the quantities themselves, is identical with the numberobtained by calculation from the observed mol. vol. of silver acetate.On the other hand, silver isovnlerate exhibits in its mol. vol. the normaJdifference of 3 x 5.14, from the mol. vol. of the normal batyrate.The author further finds the mol. vol. of silver benzoate (cryst.) to be20 x 5.14, and that of the succinate (cryst.) to be 1 7 x 5.14. c. F. c.On Brominated and Chlorinated Ethyl Acetate. By F.KRS SE L (Deut. Che?iz. Ges.Bey., x, 1~94--2000).--Dibrorneth~~l acetate,C H3-CO-O-CHBr-CHHzBr, is obtained by the action of bromineon monochlorethyl acetate a t 100-103". The product is a yellow oilyliquid fuming strongly in the air ; i t is insoluble in cold water, butdecomposes slowly on long standing; in boiling water it, dissolvescompletely with decomposition, crotonic aldehyde being evolved. Itdistils with partial decomposition at 180-240"; under a pressureof 360 mm. it boils at 132". The distillate thus obtained has the samerefractive index as glass, and a sp. gr. of 1.962 a t 17".FrirhZorethyZ acetate, C2H3O2.C2CIGH2, is produced by acting onmonocbloreth yl acetate with chlorine in presence of a little iodineat 120". It is an almost colourless syrupy liquid, and distils withpartial decomposition a t 25(3-280° On boiling with water it yieldsacetic acid and other products.T. C.Remarks on the Conversion of Chloral into DichloraceticAcid. By V. MEYER (Deut. Chem. Ges. Ber., x, 1740).-With regardto Wallach's discovery of the conversion of chloral into dichloraceticacid, the author points out that it is a general property of aldehydesin alkaline solutions to take up the elements of water, one moleculeof aldehyde being thereby reduced, while another is oxidised. Thus,benxaldehyde is converted into benzoic acid and benzyl alcohol-VGL. XXXITT. 134 ABSTRACTS OF CHEMICAL PAPERS.Glyoxal is converted by alkalis into glycollic acid-COH-COH + H2O = CHZOH-COOH.Glyoxalic acid is resolved into glycollic and oxalic acids-2(COOH-COH) + H,O = CHZOH-COOH + COOH-COOH.In the analogous reaction with chloral, the hydrogen, instead of re-ducing a second molecule of the aldehyde, replaces an atom of chlorine,with simultaneous formation of hydrogen chloride-CC&-COH + HZO = CC12H-COOH + HCl.The potassium cyanide in Wallach's reaction acts merely as a feeblebase, facilitating the separation of hydrochloric acid, as is shown bythe fact that silver oxide acts in the same manner (Compt. rend., lxi,The analogy of the reactions of aldehydes and chloral is rendered953).more apparent by writing them thus :-I.CGH5-COH + H20 = CGH5-COOH + H,;11. CGHb-COH + HZ = C,H,-CH,OH.I. CCIa-COH + H2O = CC13-COOH + H?;11. CC13-COOH + H2 = CC12H-COOH + HC1.J. R.Action of Chlorine on Butyric Acid.By L. BAZBTANO(Dewt. Chern. Ges. Ber., x, 1749).-Dry chlorine acts rapidly on warmbutyric acid in direct sunshine, the products (with 2 mol. of chlorineto 1 mol. of the aci'd) being chiefly mono- and dichlorobutyric acids.These, when etherified by means of alcohol and hydrochloric acid,yield mainly ethyZ morLocJLZorohutlJrate, the boiling point of which is168-169" under 741 mm. pressure, and its sp. gr. 1.072 a t 0". Theether is decomposed by water, even in the cold, but more rapidlywhen heated, hydrochloric acid being formed. J. R.Heptoic Acid ((Enanthylic Acid) from CEnanthol, and someof its Derivatives. By TH. MEHLJ s (Liebig's AnnaZerL, clxxxv, 358-372).-The author obtained oenanthylic acid by distilling cenanthol(from castor-oil) with twice its weight of a mixture of 1 vol.of strongnitric acid and 2 vols. of water. The product was purified by conver-sion into barium salt and fractional crystallisation, the pure cenan-thylate crystallising first. CEhantliylic acid, liberated from the bariumsalt by sulphuric acid, is a clear, colourless, oily liquid of faintly aro-rnatlic odour and burning taste, nearly insoluble in water, but easilysoluble in alcohol and ether. It boils at 219" (mercury entirely inva,pour) without decomposition, and solidifies a t - 12" to a crystallinemass, which melts at, about -5". The fol-lowing salts of the acid were prepared :-Easilysoluble in water, alcohol, and &her.Sp. gr. = 0.916 at 21".Amrnomium Sak-Formed by adding ammonia to the acid.Not crystallisableORGANIC CHEMISTRY.135Potassium Salt.-Obtained by neutralising an alcoholic solution ofthe acid with potassium carbonate. It is left on evaporation as awhite silky mass, devoid of crystalline structure. The salt dried at,100" agreed in composition with the formula C7H,,0.0K.Barium Salt, ( C7H,,02)2Ba.--Formed by boiling the acid withbarium carbonate in excess. Crystallises from hot aqueous solutionin white iridescent laminae, meltinq at 238-239" with decompositioiz.Soluble in 64 parts of water a t 22", and moderately freely in boilingalcohol of 85 per cent.Lead Salt, ( C7H1302),Pb.-Formed by donble decomposition of thcammonium salt and neutral lead acetate. Soluble in boiling water,from which it crystallises on cooling, in white silky laminae meltingat 78".C,yper Salt.-Precipitated by the ammonium salt from cupric sul-phate.A bluish-green powder, insoluble in water but soluble in boil-ing alcohol, which deposits it in blue-green prismatic crystals of theformula ( C7Hl30,),Cu.Silver Salt, C7Hl,0,Ag.-A white bulky precipitate, turning bro ~ w iin the light. Insoluble in cold water and alcohol, sparingly soluble illboiling water.Efhyl Qhmthylats, C7H130.0C2Hs.-Formed by heating the silvex.salt with ethyl iodide. A clear, colourless, highly refractive liquid,insoluble in water but soluble in ether and alcohol, having a fruityodour and a burning taste. It distils a t 186-188" without decompo-sition, and remains fluid at -14".(Enafithonitd, CiH13N.-This substance is formed, together ait!icenanthamide, by heating oenanthylic acid with potassium thiocyatiate(Letts's reaction).It is a clear, colourless, neutral liquid, insoluble it1water but soluble in alcohol arid ether. It boils a t 175-178'. Sp. gr.= 0.895 at 22". The nitril is decomposed by boiling with potash, theproducts being potassium cenanthylate and ammonia. It speedilj-undergoes alteration in the air.(Ilmanthamide, C7Hl,N0.---Formed together with the precediligcompound. When pure, it is easily soluble in watcr, alcohol, aii%tether. It crystallises from water in iridescent laininae and frorttalcohol in pointed needles. By boil-ing with water or with alkalis it is resolved into ceuanthylic acitland ammonia.The formation of the two preceding compounds is represented thco-retically by the following equations :-Sp.gr. = 0.871 at 21".The melting point is 9 4 . 4 5 "CNHS + C;H1402 = C7H13N + CO, + HZS;CNHS + CTH1402 = CTH1,NO + CSO;but in practice other decompositions go on a t the same time, whic!ivery much reduce the yield of the above products.(Enanthy lic anhydride, (C,H130)20, obtained by distilling the acil Iwith phosphorus pentachloride and heating the resulting mnanthyl;~:chloride with potassium Enantbylate, is a colonrless, thick liquid havingit neutral reaction, and boiling at 268-271" without decomposition.Sp. g:. = 0.932 at 21". It reacts with ammonia to form an arnideidentical in every respect with that described above.J. R.1 136 ABSTRACTS OF CHEMICAL PAPERS.a-Methyl-P-oxybutyric Acid and a-Methylcrotonic Acid. ByH. R o H R B E c K ( Liebig's Ani~nlen, clxxxviii, 229 -239) ,-It has beenshown (AianaZen, cxlix, 205) by Wislicenus that the ethylic ether ofaceto-acetic acid is converted by treatment with sndium amalgam andwater into the sodium salt of 6-oxybutyric acid, and that the latter onheating splits up into water and solid crotonic acid (Zeitschr. f. Chem.,1869, p. 325). The author finds that the same changes take place withthe ethylic ether of aceto-methyl-acetic acid. This body also corn-hines with nascent hydrogen and yields a-methyl-@-oxybutyric acid-CH,-CO-CH(CH,)-CO.O.CZHB + Na, + 2H20 =CH,-CH(OH)-CH(CH3)-C0.0Na + NaOH + H0.C2H5.The latter splits up on heating into water and a-metliyl-crotonic acid,identical with that obtained by Frankland and Duppa from etho-methoxalic acid ( AnnaZen, cxxxvi, 1).G. T. A.a-Ethyl-P-oxybutyric Acid and Ethyl-crotonic Acid. By E.W A L D s c H M IDT (Liebig's AnnaZen, clxxxviii, 240-248) .-The actionof nascent hydrogen on tho ethylic ether of aceto-ethyl-acetic acidgives rise to the formation of a-ethyl-P-oxybutyric acid, and this, onheating, is converted into ethyl-crotonic acid identical with that ob-tained by Frankland and I)uppa, by the action of phosphorous chlorideon the ether of diethoxalic acid. G, T. A.Action of Chloranhydrides and Anhydrides upon BibasicDiatomic Acids. By R. AN s c B u TZ (Dewt. Chenz. Ges. Ber., x, 1881-1887) .-The decomposition of anhydrous oxalic acid by benzoylchloride in excess is proved bv the author to take phce accordinr toRenzoic anhydride in the proportion of 80 per cent.of the theoreticalyield was obtained. (The author has determined the boiling point ofthe latter to be 360', the thermometer being completely enveloped byvapour.) By heating succinyl chloride (1 mol.) with succinic acid(1 mol.), succinic anhydride was formed in quantity approaching thetheoretical. From this result the author co~cludes that the formationof trichloracetic anhydride from trichloracetic acid and phosphorustrichloride is immediately referable to a similar decomposition of thetrichloracetic acid by trichloracetyl chloride, formed in the course ofthe reactions, and the truth of this he has established by direct experi-ment.By the action of acetic anhydride upon the correspondingacids, the author has prepared the following anhydride :-DipheiLic(m. p. 211-212') ; succi~~ic (118') ; phthalic (127") : camphinic (216-217"). The decompofiition is represented by the general equation :-''OH + E;g:O = R'':EO + R'.COOH. R" C 0 OHThe decomposition of gibromosuccinic acid by acetic anhydride re-sulted in the formation of monobromomaleic anhydride (m. p. 125' ;b. p. 215'), most probably in the manner indicated by the equationsORGANIC CHEMISTRY. 137(1) C4H4Brz04 + (C2HsO),0 = C4H,Rr0, + C2H,0.Br + C2H402 ; and( 2 ) C,H3Br04 + (CsH30)20 = CaHBr03 + 2C2H40,.By the action of fuming hydrobromic acid (4 mols.) upon mono-bromomaleic anhydride (1 mol.), the author obtains isobromomaleicacid, together with varying quantities of the two dibromosuccinic acids.Having also observed the decomposition a t high temperatures of iso-brornomaleic acid into water and monobromomaleic anhydride, tlicauthor draws the probable conclusion that isobromomaleic acid is moiio-bromofumaric acid.From a consideration of the results of this research the author pro-poses the inversion of the formuh now assigned to maleic and fumaricacids on the one hand, and to the two dibromosuccinic acids on theother ; but reserves the full discussion of the subject for a further-communication.C. F. C.Diethylic Acetosuccinate and its Derivatives. By MA x C o x-RAD (Liebig's An nalen, clxxxviii, 217-226) .-Ethylic acetosodacetatewas treated with a sufficient quantity of ethylmonochloracetate tosaturate the sodium with chlorine.The product obtained yielded aliquid on fractional distillation between 254" and 256", which consistedof CloH,,O,, a formula which agrees with that of diethylacetosuccinate.This body consists of a colourless liquid, which can be distilled un-changed, and possesses afaint ethereal smell. It is insoluble in water,soluble in alcohol, ether, benzene, and bisulpliide of carbon. It is notcoloured by ferric chloride, and can exuhande a hydrogen atom forsodium.No other compound was formed in the above reaction, neither theethylic ether of succinic acid, nor dehydracetic acid being able to bedetected. Diethylacetosuccinate yields on saponification with strongalcoholic solution of potash acetic and succinic acids, and this is 110doubt the way in which the succinic acid of Noldecke (Liebig's A'y~72(7,2011~,cxlvii, 224) was formed.When it is decomposed with barium hydrate,however, it yields a ketonic acid, C5H80,. This /3-acetopropionic acidconsists of large plates, which are very hygroscopic, and melt a t 31°.It is easily soluble in water, &c., and decomposes the carbonates. Itis probably identical with the levulinic acid of Grote and Tolleiis(Annalen, clxxv, 181).The ethyl ether of ,@-acetopropionic acid was also obtained its Rcolouriess liquid, heavier than water, possessing a fragrant smell, andboiling at 203" to 205". G. T. A.Synthesis of Pyrotartaric Acid from Ethyldiacetic Acid. RyMA x C o N R A D (Liebig's Annnlen, clxxxviii, 226-228) .-To a saturatedwarm solution of sodium in ethylic acetoacetate diluted with benzene,the quantity of the ethylic ether of a-bromopropionic acid correspond-ing with the sodium was added.The product of the reaction was theethylic ether of /3-methylacetosuccinate. This body is capable of takingUP an atom of sodium. On saDonification with concentrated caustic:potash, it yields pyrotartaric accd and P-acetoisobutyric acid.G. T. A138 ABSTRACTS OF CHEMICAL PAPERS.Action of Sulphuric Acid on Malic Acid. By W. WEITH(Deut. Chem. Gss. Bey., x, 17&).-Mnlic acid is resolved by boilingwihh dilute sulphuric acid (boiling point, 135") into carbon oxide,carbon dioxide, and aldehyde-COOH-CHOB-CEf2-COOH = CO + COZ + CHS-CH(OH),;CHS-CH(OH)z = H20 + CHs-CHO.J.R.Asparagin-derivatives. By J. GTJA R E s c H I (Deut. Chem. Qes.Bw., x, 1747) .-On evaporating mixed aqueous solutions of asparaginand potassium cyanate, there remains a syrupy mass, which, whensaturated with hydrochloric acid, deposits crystals of a body havingthe composition of amidosuccinuric acid-CO.NH,-CH,-CH.NH2-COOH + KCNO + HC1 =CO.NH~-CH~-CH.NH.CO.NH~-COOH + KC1.This product crystallises from water in hard, colourless prisms,sparingly soluble in water, and nearly insoluble in etlier and alcohol.1 t melts a t 137-1 38" with decomposition, a portion of it being con-rerted into arnidomaZyZureide, C0.NHz-CH2-CH.NH.C0.NH_CC),a body previously obtained by the author by fusing asparagin with car-bamide.The acid corresponding with this amide,COOH-CHZ-CH.NH.CO.NHzC0,is produced on boiling amidosuccinuric acid with hydrochloric acid.J. 8.Production of Racemic Acid in the Manufacture of TartaricAcid. By E. J u N G F L E I s c H ( Compt. rend., lxxxv, 805-808) .-Theauthor's observations and experiments lead him to explain the appear-ance of racemic acid in manufacturing operations on tartaric acid, bythe united actions on the solutions of heat and alumina, or an aiialo-gous oxide. R. It.The Distillation of Nitrobenzene, Ethylbromide, Ethylben-zoate, and Naphthalene by means of Steam. By A. NAUMANN(Deut. Chern. Ges. Bw., x, 2014--2017).-!L'his i s a continuation of theauthor's previous paper on this subject (Deut.Chew,. Ges. Bey., x,I El and 1819 ; also p. 47 of this volume).Excess of temperatureof vrtpour over thatVol. of water which distilsover with 100 C . C . of B. P. ofof the liquid. mixture. Lie substance.Nitrobenzene . . . . 0.5' 99" 700 C.C.Et'hyl bromide . . 0.0 37 1.35 C.C.Ethyl benzoate .. 0.4 99 581 C.C.Naphthalene . . . . 1.4 99 548 C.C.T. c.Propyl-isopropylbenzene. By P A T E R X ~ and SPI C A (neutORGANIC CHEMISTRY. 139Chem. Gea. Ber., x, 1746).-This substance is formed by the action ofcumyl chloride on zinc ethyl (Dezct. Cizern. Qes. Ber., ix, 581). It boilsat 211-213" (bar. at 754 mm.). Sp. gr. a t 0" = 0.8713. By oxidationwith diluted nitric acid it yields yropy7benzoic acid, C3H7.C6H,.C0,H,isomeric with cumic acid, and homoterephthalic acid, CO,H.C,H,.CH,.C0,H.Propylbenzoic acid crystallises from ether and weak spirit incolourless needles, which dissolve also in benzene and chloroform, andmelt a t 138-139". The crystalline ammoriium saZt, wliich is solublein water, alcohol and ether, gives precipitates with salts of the heavymetals.It is ayellowish PO wder, subliming a t high temperatures, without melting.The silver and barium salts have been analysed. J. R.Hornoterephthalic acid is nearly insoluble in all liquids.Reactions of Bromocymene. By PAT ERN^ and COLOMBO(Deut. Chem. Ges. Ber., x, 1749).-A solution of bromocymerie inxylene, mixed with a little ethyl acetate, is readily attacked by sodium-amalgam, the compound Hg( CloH,3)2 being formed.This substancecrystallises from alcohol in matted needles, which dissolve in benzenearid xylene, melt at 134", and sublime without decomposition.Bromocyrnene, heated to 100" with a mixture of coiiccntrated andf urning sulphuric acids, yields two crystalline sulpho-acids, which aredificult to separate. J. R.Action of Sulphuretted Hydrogen on certain Nitro-com-pounds. By F. HEILSTEIN and A. KDRBATOW (Ileut. Chem. Ges.Ber., x, 1992--1994).-When a current of sulphuretted hydrogen ispassed through a warm alcoholic solution of dinitrochlorbenzene,CsH,C1(N02)(NOz),[l : 2 : 41, m. p. = 53", to which a little strongammonia has been added, tetmmtrophenyl sdphide is precipitated as ayellow body. An alcoholic solut'ion of potassium sulphide, or better,sulphhydrate may also be used. Tetranitrophenyl sulphide crystallisesfrom glacial acetic acid in yellow prisms ; it dissolves with great diffi-culty in glacial acetic acid, and is practically insoluble in benzene,alcohol, and carbon disulphide ; it melts at 193", and, when heated to120" with fuming nitric acid, yields the sdphione, [ C6H,(N0,),],S0,(?),which melts a t 240" and crystallises in yellow prisms. The aboveresults are not what might have been expected from those previouslyobtained by Willgerodt (Deut.Chem. Ges. Ber., x, 1683), who foundthat dinitrophenyl niercapt'an was produced by the action of anilinesulphydrake on the above dinitrochlorobenzene.N~tro~a,*adichZorbellzelte, C,H3.C1.C1.NO2rl : 4 : 21, m.p. 55", treatedin a, similar manner with ammonia, alcohol, and eulphuretted hydro-gen or with potassium sulp h y drat e, gives chl oroizitrop herby lm e r c q t an,C6H3.(SH).Cl.N0,[l : 4 : 21, crystallising in yellow plates, and rnelt-ing at 212" ; it is difficultly soluble in glacial acetic acid, still less soin alcohol and carbon disulphicle, but more easily in benzene.On treating the same nitroparadichlorobenzene with alcoholic potas-sium mlphide, d~chlorodinl:tro~hanylsu~~hide is produced, cry stallising inyellow needles which melt a t 149". T. C;140 ABSTRACTS OF CHEMICAL PAPERS.Action of Aromatic Sulphonic Chlorides on Dimethylaniline.By W. MICHLER (Deut. Chenz. Gas. Ber.., x, 1742).-The reactmion ofdimethylaniline with benzene-sulphonic chloride, benzene-disulphonicchloride, and naph thalene-sulphonic chloride, .gives rise to beautifulblue colouring matters of extraordinary tinctorial power, together withcolourless sixlpho-compounds, The blue substances are basic and aredecoloriscd by mineral acids.Trichloromethyl-sulphonic chloride also reacts with dimethyl-anilineto form a colourless sulphuretted base.J. R.Action of Potassium Nitrite on Nitraniline and Aceto-nitranilide. By ARMAND M ~ ~ L L E R (Cheln. Centr., 1877,204).-~)neequivalent of nitracetaniline or nitraniline, acidified with nit.ric acid,gives, on treatment with 18 to 2 equivalents of potassium nitrite, andsubsequently with strong ammonia, a deep red crystalline precipitatewhich dries up to a red-brown powder, while the mother-liquor con-tains diazoamidonitrobenzene.In its properties this substance corre-sponds with Vogel's " zinalin," prepared from a rosamiline salt wit!hnitrous acid. It is sparingly soluble in water, but dissolves withred colour in alcohol, ether, chloroform, and carbon disulphide ; itdissolves with deep blood-red colour in caustic alkalis, and is pre-cipitated by acids in yellow flocks. It ismore easily prepared by dissolving 1 pt. of acetanilide in 8 pts. ofnitric acid at 75", adding an equal volume of boiling water, filteringthrough asbestos, and subsequent treatment with potassium nitriteand ammonia. It is probably phenol-di-diazonitrobenzene, CISHI~N~O~.It dyes silk a fine yellow.W. R.Derivatives of Triamidobenzene.By H. S AL K o w s K I (Deut.Chern. Ges. Be?.., x, 1692-1697) .-Triamidobenzene, when boiled forsome hours with twice its weight of glacial acetic acid, is convertedinto acety Zetheny Z-tr.iamidobenxene, C6H,(NH. C2H30)(NH.C2H3)( NH,) +2Hz0. This substance crystallises in prisms, which dissolve very freelyin hot water, but scarcely at all in cold. It melts at 85-90", andwhen carefully heated gives off its water at 100". When treated withhydrochloric acid, it does not form the hydrochloride, but is resolvedinto acetic acid and ethenyltriaiilidobenzeiLe hydrochloride. The lattersubstance forms brilliant reddish triclinic cqstals, easily soluble inwater. Its composition agrees with the formula C,H,(NB,),(NH.C,H,),2HC1 + 1iH20.J. R.Orthonitro- and Orthamido-Benzonitril. By HE BN E R (Dem~t.Chern. Oes. Ber., x, 1713) .-Orthonitrobenzoyl chloride reacts wit!hstrong aqueous ammonia to form orthonitrobenzamide, which crystal-lises in long colourless needles melting a t 174'. This substance, whenheated to 180" with phosphorus pentoxide, yields orthonitrobenzonitril,CsH4N02.CN, a colourless crystalline body dissolving easily in waterand alcohol, and melting a t 109".Orthonitrobenzonitril, when treated with tin and hydrochloric acid,is converted into orthamidobenzonitril, CsH4NH,. CN, which crystal-lises in yellowish needles, meltiug at 1U3', and dissolving easily iORGANIC CHEMISTRY. 141water, alcohol, and ether.ammonium orthonitrobenzoate. J. R.The same product is obtained by heatingAction of Phosphorus Trichloride on Carbamides.By W.WE I T H (Deut. Chem. Qes. Ber., x, 1743j.-Phosphorus trichloride actsviolently on cnrbamide when heated with it over the water-bath.Ammonia is eliminated in the form of phosphamide-compounds, theother products being biuret and an amorphous substance, which fromits composition appears to be triuret.Monophenylcarbamide yields, by similar treatment, r/oolar~hen?/l-bl:uret,a crystalline subst'ance sparingly soluble in water, but easily in alcoholand ether. The reaction is as follows :-2(NH2-CO--NHCsH,) = NH7,C,H5 + C20ZN,H,C,H5.When mcnophenglbiuret is boiled with aniline, ammonia is expeiled,and a fine crystalline substance, probably diphenylbiuret, is produced.J.R.Action of a-Dinitrochlorobenzene on Thiocarbamide. ByWILLGERODT (Deut. Chem. G'es. Ber., x, 1686-1688).-a-Dinitro-chlorobenzene dissolved in 90 per cent. alcohol reacts with thiocar-bamide, when heated therewith in sealed tubes, in such a manner thatthe chlorine-atom of the benzene-compound is replaced by the groupHS, the chief product of the reaction being a-di?Litr0~~zen?/Z-nzerc~~~tn?z,HS .C6H,(N02),. This substance crystallises iii short yellow needles,which melt a t 275-280" Its formation may be represented by theequation :-(NH,),CS + C,H,OH + HZO + C~H~(NO,)ZC~ = C6Hs(NOz),SH +2NH3 + C,H,C'l + CO,.J. R.Action of a-Dinitrochlorobenzene on Carbanilide. By WILL-G E R O D T (Deut. Chern. Ges. Ber., x, 1689--1691).-When these sub-stances are heated to 200" with water in sealed tubes, the followingreaction takes place :-(NHCsH,),CO + CsH,(NOz)zC1 + H2O = NH(GH,)CsH,(N0,)2 +NH,C,H5.HC1 t- CO2,the products being dinitrophenylmiline, aniline hydrochloride, andcarbon dioxide in theoretical proportions. J.R.Conversion of Nitrils into Imides. By A. PI N N E R and FR.ELEIN (Deut. Chem. Ges. Bw., x, 1889--1897.)-When dry hydro-chloric acid gas is passed into a mixture of benzonitril (1 mol.) andisobutyl alcohol (1 mol.), 2 mols. of the former are absorbed, and acrystalline body is obtained, which appears to be the chloride of apeculiar amide, having tbe formula ~,H5.C(~l).OCaH,.NH,.HCL. Thiscompound, if left over sodium hydrate, loses 1 mol. HC1, and isconverted into a body whose constitution may be represented by theformula c6H5.c(o.C4H,).(NH)".HC1.The latter salt is insoluble inether, slightly soluble in benzene, and is freely dissolved by bot142 ABSTRACTS OF CHEMICAL PAPERS.alcohol and water; it is but very slowly decomposed by the latter.It is entirely decomposed a t a temperature of 130-160" into benz-amide and isolnutyl chloride.Compounds of this class are denominated by the authors salts (8benxarnidoisohutyl ether.By the action of alcoholic ammonia upon this salt, a body is obtainedcrystallising in coloiirless silky needles, which is the chloyhydrate ofbensimidamide, C7H6.C. (NH)".NH,.HCl ; and in addition a thickoily liquid, the free base corresponding to the original salt, viz., benz-imidobutyl ether, C',H6.C.(NH)".0.C1H,.The authors have attempted,b u t without success, to prepare compounds of the form R'.C (NH)".OH,isomeric with the amides, by passing HCl gas into the mixture of ztnitril with the necessary quantity of water. c. F. c.Reactions of Para-, Meta-, and Ortho-nitrobenzanilide. By H. H ~ B N E R (Deut. Chern. Ges. Ber., x, 1708-1710).-1. With NitricAcid.-The so-called paranitrobenzanilide (melting at 199") is con-verted by the action of nitric acid into a triqzitrobenxa~ailide, whichmelts at 165", and may be resolved into metanitrobenzoic acid anddinitraniline melting at 176". Hence its probable formula is-Orthonitrobenzanilide melting at 94" yields the same trinitro-benzanilide, thus confirming the correctness of the foregoing formula.Metanitrobenzanilide melting at 154" gives with nitric acid threetrinitrobenzanilides melting at 178", 20'L", and 212".The first ofthese only has been fully examined. It may be resolved into anitraniline melting a t 175", and orthonitrobenzoic acid.2. With Bromine.-Paranitrobenzanilide, wlien treated with bro-mine, yields orthoDroruio~ara8aitrohenauniZi~e, which crystallises in longcolourless needles melting at 160". This substance is resolved bypotash into benzoic acid and orthobromoparanitraniline, which last isconverted, by substitution of hydrogen for the amido-group, int,o nitro-bromobenzene (C,Ha.NO,.Br = 1 : 31, crystallising in small yellowishprisnis, and melting a t 56". The bromoriitrobenzanilide yields byreduction orthobromoparamidobenzanilide, which crystallises in colour-less laminm, melting a t 205".Together with orthobromoparanitrobenzanilide there is alwaysformed a little paranitrodibromaniline melting at 203-204".Orthonitrobenzanilide, when treated with bromine, yields orthonitro-parabromobenzanilide, which crystallises in fine yellow tablets, meltingat 137".The mrne compound is formed when parabromobenzanilideis treated with nitric acid. At the same time a dibromo-orthonitro-benzanilide, C,H,Br2( NO2)NH.COC6H5, is formed.Dibromobenznnilide, obtained by the action of bromine on benzani-lide, crystallises in colourless laminae, arid, when treated with fumingnitric acid, yields monobromodinitrobenzanilide, crystalli sing in colour-less needles, arid melting a t 221".The same compound is producedon treating orthonitromonobromobenzanilide with fuming nitric acid.J. RORGANIC CHEMISTRY. 143Reactions of Amides with Cyanogen Iodide. RJ H. H ij B N E R(Deut. Chern. Qes. Ber., x, 1715-1720).-1. The author has shownpreviously (Deut. Chein. Ges. Ber., ix, 7.7'6) that orthamidobenzene andcyanogen iodide react together to form a base having the formula( C6H4.N2H2),C. When this base, suspended in water, is treated withnitrous acid, an evolution of nitrogen dioxide takes place, and a redsubstance, &H8N6O3, is precipitated, which dissolves readily in potashand ammonia, and forms with the latter a yellow crystalline com-pound. The formula assigned to the base is-2. Benzanilide, heated with cyanogen iodide, yields iodobenzanilide3.Paranitraniline, heated to 110-120" with cyanogen iodide, re-in reddish needles melting a t 210".acts in the following manner :-4(C,H,N02.NH,) + CNI = NHJ + (C6H,NO2.?JH),C.The latter product, which the author calls carbi)~%r.anitrotetrnmiclo-benzene, forms small red crystals, melting above 300". By reductionwith tin and hydrochloric acid it yields the corresponding arnido-compouml ( C6H4NH2.NH)$, which crystallises in colourless tables,melting a t 138", dissolves easily in water, and volatilises without de-composition. The last Substance reacts with nitrous acid to form acompound of the formula (C,H,OH),.N,O. (NO)$.4. Metanitraniline and cyanogen iodide yield ci~~bometanItrotatramido-hewwze, a green precipitate dissolving in aniline aid alcoholic soda,and melting at 286".It reacts in the same manner as the preccdingpara-compound. J. R.Anhydro-bases. By H. HCBNER (Deut. Chew. Ges. Ber., x, 1710-1713).--1. When xylidine obtained from coal-tar xylene boiling a t138-140" is treated with benzoyl chloride, the product is a-ben-zoyZcyZidine C6H3( UH,),. (NH,COC6H5), which crystallises from alcoholin colourless needles melting at 192'. On boiling this substance withstrong nitric acid, a nitro-compoun d, C6H2N 02. (CH,) ( NH. C 0 C6H,),is formed, which melts at 184*5", crystallises from alcohol in yellowneedles, and yields, by reduction with nascent hydrogen, a-anhydro-diamido- benzoylxylene-C6H2( CH3)2\ / N \ /CC6H5-NHThis substance crystallises from alcohol in colourless needles, meltinga t 195".It forms crystallisable salts with hydrochloric, nitric, sul-phuric, and oxalic acids.f-3-Xylidine, boiling a t 198-210", forms with benzoyl chlorideP-be7~zoyZxyZicli7~e, melting a t 140", and crystallising in colourlessneedles. The nitro-compound crystallises from alcohol in long needlesmelting at 178" ; it yields by reduction an anhydro-compound, th144 ABSTRACTS OF CHEMICAL PAPERS.hydrochloride of which crystallises in tables represented by theformula-2. Benzomesidine, when subjected to the action of nitric acid,yields, together with trinitrobenzomesidine, a mon,onitrobenzo.mesidine,Cs( CH,),H.NO,.NHCOC,H,, the colourless crystals of which melt at168.5". From this compound hitromesidine, cry stallisingin golden-yellowneedles, and melting a t 75", may be separated.The last-named sub-stance reacts with metnnitrobenzoyl chloride to form metartitrobenzo-mesidine, C,( CH,),H,. (NH.COC6H4.N02), which crystallises in colour-less prisms, melts a t 205*, and when treated with nitric acid yieldsmetan itrobenzodi~nitromes.idirze, Cs (CII,) , (NO,) , (NH. CO C6H4.N0,), (co-lourless needles, melting a t 307"), and nzetanitrober~,zo-monitro-mesidine, C,( CH3),.N02€I(NH COC6H*.NO,), (colourless crystals, melt-ing a t 207"). The last substance is resolved by heat into nitromesidineand metanitrobenzoic acid.3. Metanitrobenzo-paratoluide, C6( CH3)H4.NH( COC6H4.N02), formscolourless needles, melting rtt 162".With nitric acid it yields thecompound C6(CH,)H,No2. ( NHCOC6H4.N02), which crystallises inyellow needles melting a t 188.5". The last is readily converted intonitrotoluidine, c6H3 : CH, : NO, : NH,(= 1 : 3 : 4), and metanitro-benzoic acid ; it yields by reduction an anhydro-compound-which crystallises with 1 mol. of water in colourless lamin% meltingat 228'.4. Anhydrototuy7diamidobenzene, C6H4<"H?/C.C6H4.cH,, a colourlesscrystalline base melting at 268", is formed,?.together with ditolyldi-amide, hy the reaction of orthamidobenzene and paratoluic chloride,or better by the action of orthonitraniline on paratoluic cbloride. Ityields by oxidation an acid, crystallising in long colourless needles, ofthe formula-C6H4\ PH\ / C .CRHj. COOH.NThe analogous bases, anh~drotoluyl-diarnidotolzceize and anl~ydrotoluyl-diamidoxylene (melting point 217") are obtained by similar reactions.They are both colourless crystalline bodies.J. R.Action of Amy1 Iodide on Anhydrobenzoyl-diamidobenzene.By H. IJGBNER (Ueut. Chern.. Gas. Ber., x, 1720--1722).-These sub-stances react together to form a dark-red comp'ound, which crystallisesin very thin tables, soluble in alcohol and glacial acetic acid, anORGANIC CHEMISTRY. 145melting at 111-112".by the formula-The constitution of this body is represented//C.c6H6\I N 2 \ C6H,'N( CbH11)21.When its alcoholic solution is boiled with lead hydrate, it loses thewhole of its iodine, and yields a base which crystallises from alcohol inlamina? melting at 90-91".When recrystallised from water, how-ever, the base melts a t 164".An ethyl-compound analogous to the above is produced by sub-stituting ethyl iodide for amyl iodide. It forms reddish-brown laminamelting a t 154-155". J. R.Replacement of the Diazo-group by the Group S0,H. ByH. HUBNER (Dead. Chem. Ges. Ber., x, 1715). Dry metadiazoimido-benzoic acid, treated with alcoholic solution of sulphurous acid, yjeldsmetasulphobenzoic acid, C6& C'OOH.S03H. Similarly the prtradiazo-compound yields parasulphobenzoic acid. J. R.New Mode of Formation of Phenetol. By AD. KASTROPP(Deut. Chern. Ges. Ber., x. 1685)-The methods hitherto employed forthe preparation of phenetol have involved the previous preparation ofphenol-potassium and ethyl iodide.The author finds, however, thatphenetol may be okhained directly in large quantity by heating a mix-ture of phenol and alcohol with zinc chloride, or by heating a solutionof phosphorus pentoxide in phenol with alcohol. J. R.Compound of Sodium and Iron with a Derivative of Pyro-gallol. By addingpyrogallic acid to a solution of an equal weight of ferric chloride, andthen adding sodium carbonate, a nearly black precipitate is obtainedcontaining soda and iron oxides, in the proportion of 2Na20 + 2Pe0 + Fe203, combined with an acid derived from pyrogallic acid.By G. C. WITTSTEIN (Chein. Centr., 1871, 621).M. Jf. P. M.The Formula of Quinhydrone. By C. LIERERMANN (Deut.ClLenz. Ges. Ber., x, 2000-2002). I n a paper by Wichelhans (Derd.C'henz. Ges.Ber., x, 1781) the latter attempts to show that quinhydronehas the formula ClsH1406, and that it is formed from one molecule ofquinone and one of hydroquinone. The author contradicts these re-sults, and points out that, assuming the formula C,sEX:,,06 as correct,quinhydrone must be formed from two molecules of qninone and oneof hydroquinone; but this cannot be so, since the author has shownexperimentally that it is formed from an equal number of moleculesof quinone and hydroquinone, and that Wichelhaus' attempt to explainthis latter fact by the equation 2C6H402 + 2CtiH602 = ClsH,,06 +C6H602, is untenable. The author believes that the true formula isC,,H,,,O,, and that it is formed thus-CGH402 + C6H602 = C12H1,,01T. C146 ABSTRACTS OF CHEMICAL PAPERS.On Quinhydrone.By R. NIETZKI (Deut. C h t . &a. Ber., x,2003-200-5) .-B.y the action of sulphurous acid, quinone is convertedeasily and entirely into hydroquinone. In order, therefore, to ascer-tain the quantity of qninone present, it is only necessary to know theamount of sulphurous acid required, and this can be done by using astandard solution of the latter and titrating the excess with iodine,for the author finds that iodine has no action on the hydroquinoneformed. This method is employed to settle the formula of quinhy-drone, which, according to Wohler and Liebermann, is represented hyCI2Hl0O4, and according to Wichelhaus, by C1,Hl4O6 ; or for comparironthese formuh may be written respectively Cl8H1506 and CIRHl4O6.Now since sulphurous acid reduces quinhydrone as well as quinoneto hydroquinone, 4 atoms of hydrogen would he required according tothe formula ClaHI4O6, and only 3 accordinq to c1881506, to convert thesebodies into hydroquinone 3(C6H602).By titrating as above, it wasfound that only 3 atoms of hydrogen were required, and, therefore,that C12H,,0* is the correct formula for quinhydrone.A modification of the method (Deut. Chenz. Ges. Bey., x, 834) ofobtaining hydroquinone from aniline is given, by means of which amuch larger yield is got, 30 grams of aniliiie giving 10 grams ofalmost perfectly pure hydroquinone.Investigations are being continued with regard to the action ofsolutions of toluquinone and hydroquinone on one another, and like-wise of quinone on hydrotoluquinone.The Formula of Quinhydrone.By H. WICHELHAUS (Deut.Chem. Ges. Ber., x, 200.5--9006).-This is a short reply t o the twoprevious papers by Liebermann and Nietzki. The author believes" that phenoquinone, quinhydrone, and pyrogalloquinone are producedin such a manner that each molecule of quinone drives out two atomsof hydroqen from two molecules of phenol, hydroquinone, or pyro-gallic acid, and then unites, by means of its own oxygen-atoms; withthe affinities of the hydroxyl-oxygen-atoms thus set free.'' The hydro-gen driven out as above is not liberated, but combines with the redu-cible substances (qninone and quinhydrone) present in the mixture.This is the answer to Liebermann's objections.Wichthlhaus thinks that the experiments of Nietzski are most fittedto settle the question, and intends to repeat them himself.T.C.T. C.Derivatives of Rhenish Beech-wood Creasote. By W. B R B U-N I N GE R (Liebig's AnwaZen, clxxxv, XB-358).-The specimen ofcreasote examined by the author had the sp. gr. 1.04. It boiIedbetween 180 and 21G0, the greater part of the distillate passing ovei'at 199-203". I t was found to contain traces only of phenol, andabout 1.3 per cent. of cresol. By distillation over heated zinc-dust, ityielded anisol and a little toluene.The portion of the distillate boiling at 199-203", was violentlyattacked by melting potash, yielding pyrocatechin, but no traces of theoxybenzoic acids.The creasote, when treated with potassium chlorate and hydrochloricacid, yielded tetrackZorotoZzcq~~r~o~e, C6Cl3.CH,C1.O2, a body previouslORGANIC CHEMISTRY.147obtained from beech-wood creasote by Gorup-Besanez, who describedit as tetraclilorogaaiacone. This substaace is converted, by the actionof sulphur dioxide into tetruchZorotoZ~~h~/dro~uinone, CsCl,.CH,Cl. (HO),,which sublimes in brilliant white brittle needles, soluble in alcohol andether, and sparingly in water.Tetrachlorotoluhydroquinone is converted by the action of dilutepotash into d;chZo?.ocliox7_Jtolzcrluinoiae-~otassiuvn, C7H,C1,( OK),O,, a redcrystalline substance which is converted by dilute sulphuric acid intoa brick-red crystalline powder, consisting of dic7zloro~ioayfoZ?~~~z~~non,e,C,H,Cl,( OH)zO,. J. R.Nitracetophenone.By H. H ~ B N E R (Dad. Chem. Ges. Ber.,x, 1714) .-Mononitro-acetophenone ( CGH*.NO,) C0.CH3, is formed bythe slow action of nitric acid on acetophenone a t a low temperature.It is a colourless crystalline body, melting at 80--81", and volatilisingwith steam. When treated with tin and hydrochloric acid, itis converted into amidacetophelzon,e, the hydrochloride of which,CGH4.NH3Cl.C0.CH3, is a very deliquescent body.Nitracetophenone is converted by oxidation into meta-nitrobenzoicacid. J. R.Some Derivatives of Acetophenone. By H. HUNNIUS(Deut. Chem. Qes. Ber., x, 2006-2011). - Aceto-phcnone hroniide,C6H5.C0.CH,Rr.-Xmmerling and Ehgler, by the direct action ofbromine on acetophenone, obtained the compound C6H4Br.C0.CH3,which, on oxidation, gave monobromobenzoic acid (Deuf. Clzenz.Ges.Ber., iv, 148).--The author 6nds that on dropping 1 molecule ofbromine into 1 molecule of acetophenone dissolved in carbon disul-phide, a compound is produced, identical in percentage composition andsimilar in properties to the above, except that on oxidation it yieldsbenzoic acid ; nevertheless, for stated reasons, he thinks tlmt the twoare identical.Acetophenone bromide is easily soluble in alcohol, ether, benzene,and chloroform ; crystallises in colourless prisms, and melts at 50".Nitracetophenone bromide, C6H4(N02).C0.CHzBr, is obtained bynitratting the above, in small needles, which melt a t 96", and dissolvein alcohol, chloroform, and carbon disulphide ; they are very littlesoluble in ether and insoluble in watcr.On oxidation, i t gives meta-nitroben zoic acid.Amidacetophenone, CGH~.NH~.CO.CH~, is obtained by reducing thelast compound with zinc and hydrochloric acid, in the form of yel-low crystals. The hydrochloride crystallises in colourless needles,which are very soluble in water.Acetophenone acetate, benzoate, and alcohol were prepared, andagreed in all respects with those obtained by Huniius and Zincke(Deut. Chem. Ges. Ber., x, 1486).Acetophenone dibronzide, C6H5.C0.cI~Brz, is formed on treating aceto-phenone dissolved in carbon-disulphide with 2 molecules of brominein the cold. It melts a t 36" and is soluble in all ordinary solvents,except water. On boiling with caustic potash it yields benzoic acid,but with caustic soda an acid which appedrs to be benzoyl-formi148 ABSTRACTS OF CHEMICAL PAPERS.acid.B y the action of alcohol and potassium acetate on the dibro-mide, th;! acetic ether is apparently {roduced, c6H5.Co.cH(C,H30)2.T. c.Dinitrobenzoic and Nitramidobenzoic Acids. By H. H ij B N E R(Deut. Chenz. Ges. Ber., x, 1702-1'704) .-When dinitrobenzoic acid,obtained by the action of nitric acid on metanitrobenzoic acid, is con-verted into the nitrnmido-acid, and the NH,-group in the latter isreplaced by hydrogen, metanitrobenzoic acid is reproduced ; andwhen the NH,-group in nitramidobenzoic acid is replaced by chlorine,and the N02-group by hydrogen, metachlorobenzoic acid is formed.It follows, therefore, that both the NO,-groups. and all the radiclesreplacing them, occupy the meta-posi tion in relation to the carboxyl-group.Moreover, it becomes probable that negative groups or ele-ments iu general, in replacing hydrogen in benzoic acid, take the meta-position.Manyof its salts and the ethyl-ether have been examined. By reduc-tion with ammonium sulphide, it yields nitrnmidobenzoic acid,C,H,.NO,.NH,COOH. This substance nielts a t 208", and crystal-lifies from water in long golden-yellow needles. It yields byGriess's reaction metanitrobenzoic acid, and this, by further reduc-tion, is converted into metamidobenzoic acid. Nitramidobenzoic acidlikewise yields, through the diazo-compound, a chloro~itrobenzoic acid,C,H,.NO,.CI.COOH, which crystallises in small, colourless, sparinglysoluble needles melting at 147".This body is converted by re-duction with tin and hydrochloric acid into chloramidobenzoic acid,which crystallises from water in long colourless needles melting atMetanitro-metamidobenzoic acid reacts with ethyl bromide to formnitro-ethylimido-benzoic acid, C6H,NOz.NHC2H5. COOH, a bodycrystallising in small needles, dissolving sparingly in water, andmelting a t 208". Its barium salt forms red needles.Dinitrobenzoic acid obtained as above, melts at 204-205".215-216".J. R.Di- and Tri-bromobenzoic and Dibromosalicylic Acids. ByH. HCBN E R (Deut. Chern. lj'es. Bei-., x, 1704--1708).-Metabromo-benzoic acid, when acted on by nitric acid, yields a- and P-metabromo-orthonitro-benzoic acids. When the NOz-groups in these latter arereplaced by bromine (t>hrongh the diazo-compounds) the followingacids are formed :-1.a-,~eta-ortho-h7.o?nohen,zo7'c ucid (from a-metabromo-orthonitro-benzoic acid) .-This substance crystallises in long needles, whichdissolve sparingly in water and melt at 228". Jts barium salt,( C6H,Br,C02)2Ba + 4&H,O, crystallises in colourless needles.2. 0- Meta- ort ho- bro mobmzoic Ac;d (from P-m etabromo- ort honitro-benzoic acid) forms colourless needles melting at 153" and dissolvingrather more freely than the a-acid. The bamhn-sdt (C,H3BrzCO2),Ba + 6+Hz0, is easily soluble in water and weak spirit, and crystallisesin broad colourless needles. The potassi?cm-saZt crystallises in longneedles. The lead-sa It crystallises in small sparingly soluble needles,containing 5 mols.of waterORGANIC CHEMISTRY. 149Together with the @-acid there are formed a tm'bromobenzoic acid,which crystallises in colourless needles melting a t 178", and a dibro-rnosalicylic acid, which crystallises in colourless needles, melting a t221", and colours ferric chloride a deep violet.Parai?aetabromo-?Litrobenxoic Acid.-This acid is produced by theaction of nitric acid on parametabromobenzoic acid melting at 2.29".It forms delicate colourless needles, which melt a t 162". Whentreated with tin and hydrochloric acid it yields : -Pummetatr~onzanz.~~ idobenaoic Acid, C6H2 Br,.N H,. C 0 OH. -T hi s sub-stance forms colourless needles melting a t 2254 Its diazo-compoundgives with hydrobromic acid a trihomotrenzoic acid which crystal-lises from alcohol in small colourless needles, melting at 195", andforms a barium salt crystallising with 5 mols.of water.Together with these two acids there is formed a d;bromosalicyllcacid, CsH2Br,( OH)COOH, cryst'allising in colourless needles and melt-ing a t 218". Its solution colours ferric chloride violet.The dibrornobenzoic acid produced by converting orthobromonitro-benzoic acid into amido-acid, and replacing the NHz-group in thelatter by bromine, crystallises in colourless needles melting apparentlyat 1.50'.When parabromobenzoic acid melting at 248-251" is convertedsuccessively into parabromonitrobenzoic acid and parabromamido-benzoic acid, and thc bromine in the last is then replaced by hydrogcn,the product, is a metamidobenzoic acid which crystallises in needlesmelting at 173-174".It forms a very soluble barium salt with4 mols. of water, a beautiful green copper salt, and a hydrochloridecrystallising in needles.The same parabrornobenzoic acid yields a crystalline eldoride,C6H4Br.COC1, and, through the latter, an anilide, C,HJ3r.C0.NI-I.C6H5,crystallising in colourless lamine which melt a t 197".DihomosaZicy lie Acid.-This Bubstame, produced by the action ofbromine on salicylic acid, forms colourless needles which dissolvesparingly in water, easily in alcohol, and melt at 219". Its solution iscoloured violet by ferric chloride. The barium, lead, and ammoniumsalts bave been examined. Neither this acid nor monobromosalicylicacid appear to form dibasic salts.Tribronzobenxoic A c i d , C6H2Br3COOH, obtained by acting on met-amidobenzoic acid with bromine, and replacing the NH2-group in theresulting tribromamidobenzoic acid by hydrogen, melts at 186.5".Itcrystallises in needles and dissolves only slightly in water. Thebariz~nz sult crystallises with 54 mols. of water.Orthazobenzoic Acid. By PETER GRIESS (Deut. Chem Ges.Ber., 18CjS-l871).-The author has prepared orthazobenzoic acid, andfinds in opposition to the statement of Claus and Fittica, that boththe acid and its salts dif€'er essentially from their respect'ive isomerides.The acid is soluble in cold, very easily soluble in h o t alcohol, andcrystallises from this solution on cooling in slender dark-yellow needles ;it is somewhat soluble in ether, slightly in water, but insoluble in ben-zene.It melts at 237".Barium orthaxoberuoate crjstallises in two distinct forms, viz., inVOL. XXXIIL rnJ. R150 ABSTRACTS OF CHEMICAL PAPERS.bright yellow shining needles, of the composition C,,H8N20,Ba.9Hz0,and in large pale yellow prisms, C,4H8Na04Ba.71X,0. This salt, inboth modifications, is freely soluble in hot water, but almost insolublein alcohol.Siher orthazobenzoate, CI4H8N,O4Ag,, occurs as an amorphous,orange-coloured precipitate.I n the preparation of the orthonitrobenzoic acid necessary for theabove investigation, the author has employed Gerland's met,hod, whichhe finds to yield the acid in the proportion of 17.4 per cent. of theweight of benzoic acid employed.C. F. C.Nitrosalicylic Acids. By H. Hi7 B N L R (Deut. Chem. Ges. Be]-., x,1697-1 702).--1. Mononitro-salicylic Acids.-In former papers (Deuf.Chem. Ges. Ber., vii, 1329; viii, 1215) the author has shown thatsalicylic acid yields two nitro-derivatives melting at 280" and 145" ;these bodies he now calls a. and P-nitrosalicylic acids.a-Nitrosalicylic acid yields a diethyl-compound; which, by treatmentwith alcoholic ammonia, is converted intoa- Orth am idoin etafiitro benxoic acid, C6H3 NH,.NOz. CO OE.-T his sub-stance forms very long delicate golden-yellow needles, melting at 263".Its bm-izctrz salt forms bron-nish-yellow crystals. The potassium andlead s a h have also been examined. The acid is converted by treat-ment with nitrous acid into a white diazo-compound, and this, whentreated with alcohol, yields a metanitrobenzoic acid which melts at140°, and is converted by reduction with tin and hydrochloric acidinto an amido-acid melting a t 173".Hence the nitro-group in theacid occupies the meta-position in relation to the carboxyl-group, asthe name implies.Together with the foregoing amidonitrobenzoic acid, there is formedan nrnide, C6H3.N0,.NH,.CONH2, which crystallises in long colourlesssparingly soluble needles melting a t 225". Solutions of this substanceproduce a deep-red colour with ferric chloride. It forms colourlesscomponnds with nitric and hydrochloric acids.,B-Pu'itrosalicylic acid, when pure, melts a t 131", not a t 145", as statedin former papers.P-Ort72amidometlx~itrobenzoic acid, obtained in the same manner asthe a-compound (see above), forms long yellow needles melting a t204", and volatilises easily with steam.It is converted by treatmentwith nitrous acid and alcohol into metanitrobenzoic acid melting a t142", and yielding, by reduction with tin and hydrochloric acid, anamido-acid melting at 174". The amide formed together with thenitro-acid, melts atj 109".It is shown by the results of this investigation that in one nitro-salicylic acid the NO,-group occupies the meta-position in relation tothe carboxyl-, and the ortho-position in relation to the hydroxyl-group; whilst in the other acid the NO,-group occupies the meta-position in relation t o the carboxyl-, but the para-position in relationt o the hydroxyl-group.Hence it may be said that the NO,-groups ofthe two acids replace two diff'erent meta-hydrogen atoms.2. Dinitro-saZicyZic acid.-Both the nitrosalicylic acids describedabove are converted by treatment with fuming nitric acid into the samORGANIC CHEMISTRY. 15 Idinitrosalicylic acid, C6Hz(OH) (NO,),COOH + H20, a body crys-tallising in thick needles, which become turbid on dryinq. I t issparingly soluble in cold water, and still more so in dilute acids. Theaqueous solution is coloured red by ferric chloride. The potassiumsalt is not decomposed bg dilute hydrochloric or nitric acid. Theethyl-ether melts a t 99-100".3. Szc&holzic ncicls.-a-Nitros~licylic acid is converted by heatingwith fuming sulphuric acid into a sulphonic acid,C6H2( OH j(N0,) (COOH)SO,H,the calcium and barium salts of which crystnllise in hair-like needles.This acid yields by reduction the corresponding amido-acid,CsHz(OH)(NH,)~SO,H)C00H + HZO-a-Metamidosalicylic acid, when heated with fuming sulphuric acid,yields colourless needIes of the sulphonic acid,C,Hz(OH)(NH2)(SOJI)COOH + 3H2O,the calcium salt of which cyystallises with 5 mols.of water,J. R.Action of Salicylic Acid on Iron. By S. BARTLARI (Deu-t.Chem. Qes. Ber., x, 1746).-A warm solution of salicylic acid, pro-tected from the air, attacks iron filings, evolving hydrogen and forminga greenish solution of ferrous salt, which turns red in the air, owingto oxidation. When boiled, the ferrous salt throws down flocks of agreenish basic salt, which oxidise in the air. J.R.Amides of Phenylglyoxalic Acid. By L. CLAISEN (Dsut. Chem.Ges. Ber., x, 1663--1667).-1n a former paper (Beut. Chem. Ges. B e y . ,x, 429) the author showed that;, in the reaction of hydrochloric acidwith benzoyl cyanide to form phenylglyoxalic acid, two stages maybe distinguished, the formation of phenylglyoxalic acid being precededby that of the corresponding amide, as represented in the followingequations :-C,H,CO.CN + H,O = C,H5.C0.C0.NH2 ;CsH,.CO.CO.NH, + H,O + HC1 = C,H,.CO.COOH + NHdCl.I n point of fact, this amide is always obtained in considerablequantity in the preparation of phenylglyoxalic acid. The author hasnow prepared it free from the acid by agitating benzoyl cyanide insmall portions with twice its weight of strong hydrochloric acid tillsolution is complete, and pouring the clear liquid into water, where-upon the arnide is thrown down in delicate white prisms.A simplerplan is to agitate the hydrochloric acid solution with ether, whichtakes up the arnide and leaves it in crystals when evaporated.The compound thus obtained-a-p hen y Zg Zy oxmnide-melts at 90-9 1 O,dissolves easily in ether, alcohol, benzene, and chloroform, slowly inwater, and has a peculiar acrid and bitter taste. It dissolves easily indilute alkalis in the cold, without decomposition ; but on warming them 152 ABSTRACTS OF CHEMICAL PAPERS.solution it gives off ammonia, and the liquid afterwards gives up phe-nylglyoxalic acid to ether.Alkaline solutions of the 'amide, when treated with carbonic acid,deposit crystals of an isomeric body-p-phenplglyoxarnide-whichmelts at 64-65", dissolves sparingly in water, but easily in alcohol,and forms an intensely yellow solution with sulphuric acid.An alcoholic solution of the a-amide, when dropped into dilutehydrochloric acid, deposits a snow-white powder, consisting of 8 thirdisomeride - yphenylglyoxamide - distinguished from the 6-amidechiefly by melting a t 130".It is a tasteless inodorous substance,nearly insoluble in ether, benzene, and chloroform. Its hot saturatedaqueous solution deposits after some time beautiful four-sided tables.With sulphuric acid it behaves in the same manner as the a-amide,into which i t may be converted by passing carbon dioxide into itsalkaline solution.All three amides are converted into the same phenylglyoxalic acidby heating them with alkalis.Ethers of Terephthalic Acid.By J. BERGER (Deut. Chem. Ges.Her. , x, 1 742) .-Prop y E terep hthte Eat e, C6H4 (C0,- C H,-CH,-CH,),,formed by the action of propyl iodide on silver terephthalate, crys-tallises in long white needles, which dissolve easily in hot alcohol andin ether, and melt a t 31".The isopropyZ-ether, C6H4[ C0,- CH (CH,),],, obtained by a similarreaction, forms brilliant white laminae melting at 55-56".IsobutyZ terephthalute, C,H4[ C02-CH2-CH( CH,),],, best obtainedby the action of terephthalic chloride on isobutyl alcohol, crystallisesin dazzling-white, fatty laminre, which melt at 52*5", and dissolveeasily in ether.The nor?naZ bzctyl-etlzer, obtained in the same manner as the last, is acolourless oil.The following are the melting-points of the ethers of terephthalicacid hitherto prepared :-J. R.Meth3;l-ether .. 140" Isopropyl-ether. . 55-56"Ethyl-ether .. 44 Isobutyl-ether . . 52.5Propyl-ether . . 31 J. R.Amaric Acid. By T H. Z I N I N (Deut. Chew. Ges. Ber., x, 1735) .-This acid, formed, together with deoxybenzoh, by prolonged boilingof benzamarone with alcoholic potash, was at, first represented by theformula Ci2H4,)O6, but further investigation has shown that its formulais C46H4206. The acid crystallises from alcohol with 2 mols. of water,which it loses at 100". A t 140-150" it is converted into the anhy-dride, Cd6H&-a transculent colourless resinous mass, which becomessemi-fluid below loo", and in that state dissolves in alcohol ; the solutionthus formed, however, speedily changes t o a pulpy mass of smallcrystals, the change from the amorphous t o the crystalline form beingattended with considerable rise of temperature.The pure anhydrideinelts at 140.5" and distils in small portions without decomposition.The alkali-salts of the acid are completely decomposed by heat, in pre-sence of free alkali, in the manner indicated by the equation :ORQANlC CHEMISTRY. 153C4,H,,Oa + 4KH0 = 2C16H15KOz + 2C7HSKOz + H,.Potassium pyramarate.Pyramaric acid dissolves easily in ether, and crystallises on spon-taneous evaporation of its solution in thick rhombic plates or prisms.It is easily soluble in alcohol, but sparingly in water. The acid meltsat 49", and distils in small quantities without decomposition. Thealkali-salts crystallise badly.Amaric acid is formed, as stated above, by heating benzamaronewith alcoholic potash.On substituting isobutyl alcohol for ethylalcohol in the reaction, a honiologue of' amaric acid-isobutzJZmmaricacid, ~ 5 0 ~ , 0 6 - i s formed. This substance dissolves readilg in causticalkalis and carbonates, forming uncrystallisable salts. The bariumsalt, C5,H,,BaO6 + 2H20, crystallises from weak spirit in tufts of longneedles. The acid is nearly insoluble in water, but dissolves easily inether, and also in alcohol, from which it crystallises in rhombic plates.It melts at 175-1 79", and i s thereby converted into an amorphous anhy-dride, C50H4604, which dissolves in ether, but is speedilg deposited inthe crystalline form. The anhydride melts at 137" and distils withoutdecomposition.When heated with excess of alkali, it undergoes de-composition in the following manner :-c50H4604 + 4KHO = 2C,,H,,I<02 + 2C7H5K(0, + H,.The new acid thus formed melts at 172", distils without decom-position, and crystallises from alcohol in short four-sided prisms. Itis nearly insoluble in water, but dissolves freely in hot alcohol andether, and in aqueous alkalis. The ammoniacal solution deposits thefree acid when heated.The author considers that pyramaric acid is isomeric with dibenzyl-acetic acid, and that it is represented by the €ormula,C6H5.C7H7. CzH5. C 00 H,whilst the homoloffous acid obtained from isobutylamaric acid is to beNaphthalene-Derivatives. By P. T. C: LEVE (Deut. Chew. Ges.Ber., x, 1722) .--a:-Nitron~~~hthnlene-sulplhonic acid is formed by theaction of nitric acid on the a-sulphonic acid, but it is best prepared byacting with sulphuric acid on nitronaphthalene. It crystallises with4 eq. of water in long straw-yellow prisms, easily soluble in water,but only sparingly in presence of sulphuric acid. The salts are readilycrystdisable and of yellow colour. The potassium salt crystallises inlarge tables with + eq. of water ; the amwionium salt in needles with 18 eq. of water ; the silver salt in anhydrous monoclinic prisms ; thebarium and lead salts with 3 eq.of water. The ethyl-ether melts at101", the chloride a t 113". The amido-acid is a light crystallinepowder, yielding, when treated with nitrous acid, a-Jiazonaphthnlicacid, CloH6N2S03. This last crystallises in yellow needles ; whenheated with water it is converted into u-dioxyn~~hthalane, C,,H6( OH),,a crystalline substance, alkaline solutions of which absorb oxygen andturn brown.regarded as benzyliso butylbenzoic acid. J. It154 ABSTRACTS OF CHEMICAL PAPERS.,~-Nitronn~htTLalene-sulphonic acid is formed by the action of nitricacid on P-eulphonic acid. It forms easily soluble yellow needles. Thesalts are for the most part sparingly soluble. The potassium anda~nrnonizcm salts are anhydrous; the barium salt contains 1 eq.ofwater. The ethyl-ethev melts at 114", the chloride at 125.5". Theamide crystallises in anhydrous tables, or in prisms with 2 aq.In the preparation of 6-naphthalene-sulphonic acid two other bodies,sulphonaphthalide and sulpphonaphthaiene, are formed, as was first ob-served by Berzelius. The former of these, (C,,H,)aS02, is the moreabundant. It crystallises in white needles, melting at 1'75.5". Bytreatment with phosphorus pentachloride it yields /3-sdphonic chZoridcmelting at 212", and a 6-chloronaphthalene, C,,H,Cl, melting at 53",which is also formed by the action of phosphorus pentachloride on&naphthol.The author describes also two dichloronaphthalenes, distinguishedas 6- and e-compounds, obtained by distilling a- and /3-sulphonic chlo-rides with phosphorus pentachloride. The former melts at 114", thelatter at 135".J. R.The substance is, therefore Pa-solphonaphthalide.Methylquinizarin. By R. NIETZKI (Deut. Chem. Ges. Ber., x,2011-2014) .-When equal numbers of molecules of hydrotoluquinoneand phthalic anhydride are heated with an excess of concentrated sul-phuric acid, methyl-quinizarin is produced. This body forms a brown-red crysballine mass, with a green lustre ; it is soluble in alcohol, ether,glacial acetic acid, and benzene, forniing fluorescent liquids. It sub-limes on heaking, with partial decomposition, and melts at 160". Bydistillation with zinc dust, it yields methylanthracene, convertible byoxidation with chromic acid into anthraquinone-carbonic acid, togetherwith a large quantity of anthraquinone, a circumstance in which itagrees with the rnethylanthracene obtained from enlodin and chryso-phanic acid.From the results above detailed, viewed in connection with the knownconstitution of anthracene, and the fact established by Baeyer (Berichte,vii, 974), that the C,O, group of anthracene, occupies in both benzene-rings the position 1 : 2, it follows that methylanthracene and methyl-quinizarin must be represented by the following constitutionalformulae :-H OHIC \CO-C/ b H 3C 6 d \CO-C, It , C H IC /1 OHI HMeth yl-anthracene.Methyl-quinizarin.T. c.Retene-sulphonic Acids. By A. G. EKSTRANU (Deut. Chem. Ges.Ber., x, 1725).-Retene, submitted to the action of sulphuric acid atthe ordinary temperature, forms a disulphrmic acid, C,,H,,( SO,H),,crystnllising in easily soluble needles, with 10 aq.The salts generallORQANIC CHEMISTRY. 155crystallise in needles ; the barium and lead salts are sparingly soluble.The chloride, Cl8Hl6SO2C1, crystallises in prisms melting at 175".A retene-trisdphunic acid is formed on heating retene with sulphuricacid over the water-bath. It is even more soluble than the precedingcompound. J. R.By G. GOLDSCHMIEDT (Deut. Ohem. Ges. Rer., x, 2022-8030).-The idryl obtained by Bodecker (Ann. C'hem. Pharm., lii, loo),was a mixture of phenanthrene and pyrene. From crude idryl theauthor has isolated the following :-Anthracene, phenanthrene, chry-sene, pyrene, and a new hydrocarbon, having the same composition asBodecker's idryl, but different properties. The name " idryl" isretained for this body.Analysis and vapour-density led to the formula, CL5H10.Idryl meltsat 110", sublimes, crystallises in needles, and dissolves easily in benzene,carbon disulphide, chloroform, ether, and boiling alcohol, but is littlesoluble in cold alcohol. On slightly warming with strong sulphuricacid, it dissolves, and the liquid assumes successively a greenfsh-blue,a deep blue, and finally a brown colour. It yields acrystalline bromo-compound, and a compound with picric acid, the latter of whichforms yellow needles melting at 184'. The quinone was also pre-pared ; it consists of reddish-yellow needles, melting at 18Y0, which onheating with soda-lime yield diphenyl.Constituents of Cinchona-bark : Cusconine and Aricine.By 0.HESSE (Liebig's Annden, clxxxv, 296-323).-1n this paper theauthor gives the results of his examination of a Cusco cinchona-bark,apparently identical with that examined by Liverkohn (Bepert. €'harm.,33, 357), who found it to contain aricine. The bark gives off brownvapours when heated, and yields a t last a brown tar, thereby differingfrom barks containing quinine or isomeric alkaloids, all of which giveoff red vapours when heated. The author has found in the bark:aricine, a new base called cusconime, and a small quantity of an amor-phous alkaloid, which he believes to be derived from the other two.These bases do not exist, in the bark in the free state, since they can-not be extracted by chloroform.They mere isolated in the followingmanner :-An alcoholic extract of the comminuted bark was snper-saturated with soda and shaken with ether; and the ethereal liquidwas agitated with acetic acid, which took up the greater part of thealkaloids. The acetic solution was partially nentralised with ammonia,which threw down aricine acetate, and the filtrate from this substancewas then mixed with a strong solution of ammonium sulphate, where-upon the cusconine was precipitated as sulphate. The mo ther-liquorcontained the amorphous alkaloid, which has not been further examined.The percentage of alkalo'ids contained in the bark was about 0.62 ofaricine, 0-93 of cuaconine, and 0.16 of amorphous substance.CUSCONINE is thrown down from the sulphate by ammonia as anamorphous precipitate, crystallising from ether in white lamin=, andfrom alcohol or acetone in larger crystals. It dissolves in 35 times itsweight of ether, more easily in alcohol and acetone, and very freely inchloroform, but is nearly insoluble in water.Strong nitric and sul-Idryl.T. C156 ABSTRACTS OF CHEMICAL PAPERS.phuric acids dissolve it with greenish coloration. A little cusconineadded to a warm solution of ammonium molybdate in strong sulphuricacid colours it a dark blue, changing t o olive-green when heated, andagain turning blue as the liquid cools. This reaction is characteristicof cusconine and aricine. Cusconine rotates a ray of polarised lightl tothe left; in the ethereal solution = - 27". The formula of thecrystallised substance is C2,H,6N204 + 2H20, the water being givenoff a t 80".It is a feeble base,forming,salts which have a more or less acid reaction. The followingsalts have been prepared :-Neutral subhate, 2C23H26N204, S04H2. Crystdlises from alcohol inlamins.Hydrochloride.--Not crystallisable. Forms with mercuric chloridea white pulverulent precipitate.Plntinocliloride, 2 ( C,3H2,Nz04,HCl) + PtC14 + 5H20.-Amorphous,flocculent dark-yellow precipitate.A~~~~ochZor.ide.-Dirty-yellow amorphous flocculent precipitate, de-composing when wai-med.H~clrobromide.-Colourless ; amorphous ; soluble in water, fromwhich it is precipitated by potassium bromide.Eydriodide.-Pale-yellow amorphous precipitate, freely soluble i nwater, but sparingly soluble in solution of potassium iodide.Thiocyanute, C23Hz6N20a.CNSH + 2H20.-Pale yellow amorphouspowder.The nitrate, acefate, citrate, tns.traie, oxalate, thiosulpkate, and snlicy-late are all gelatinous and non-cry stallisable.The anhydrous alkaloid melts a t 110".The acid suZphate is gelatinous and uncrystallisaJble.ARICINE is obtained i n the free state by decomposing the acetatewith soda.It crystallises in white prisms, which dissolve very easilyin chloroform, and less freely in ether and alcohol, but not in water.It melts a t 188", and decomposes a t higher temperatures. With strongnitric and sulphuric acids it behaves in the same manner as cusconine.Its taste is slightly astringent, not bitter.In alcoholic or etherealsolution it rotates a ray of' polarised light to the left. Anslyhes ofaricine lead to the formula, C23H261T204, which is that of anhydrouscusconine. The neutral salts have a more or less acid reaction, andare partially decomposed by water. Solutions of the salts turn yellowafter a time, the alkaloid becoming converted into a coloured amor-phous substance.The hydrochloride, C23H26N204,HC1 + H20, separates from its aqueoussolntion, on evaporation, in the form of a jelly, which afterwardscrystallises.The yZutimchZoride, 2( C23H26N20a.HCl)PtC14 + 5H20, is an amor-phous, orange-coloured precipitate, sparingly soluble in water.The nurochlode is a dirty-yellow aniorphous ppecipitate, easilydecomposed.The neutrul szdphate, 2C2,H,,N204,S04H2, is precipitated as a whitegelatinous mass, made up of delicate needles.The acid suZptiute is thrown down in small white prisms on addingsulphuric acid to a solution of the hydrochloride.The neutrnZ ozalute is a granular white crystalline powderORGANIC CHEMISTRY.157The acid oealate, C?3H26N20A,C2H204 + H20, is precipitated byoxalic acid, from a solution of the hydrochloride. It crystallises inprisms, which soon change to rhombohedrons. The salt requires forsolution 2025 parts of water at 18", and hence affords a means of sepa-rating aricine from cusconine.The nitrate, C23H26Nz0a,N03H, is precipitated by nitric acid from awarm solution of the hydrochloride. It forms delicate white prisms,easily soluble in alcohol.The hydrobro?nide is a white amorphous powder. The hydriodideforms small white prisms.The thiocyanate, C2,H2,NZ04, CNS& crystahes in small whitepri sms.The sahyzate, C23H26N",4.C7H603 f 2H20, is a pale yellow puhe-rulent precipitate, sparingly soluble in water, easily in alcohol.The acetate, C2,H2,N2O4.C2HB02 + 3H20, is obtained by precipitatingthe hydrochloride either with sodium acetate, or with acetic acid, a re-action which distinguishes aricine from all other alkalo'ids. It formswhite granular crystals, very sparingly soluble in cold water. At 100"the acid is cxpelled, leaving the free alkalojid.The acid citrnte and the neutral tartrate are both crystalline salts.J. R.Cinchonine. By H. SKRAUP (Chern. Uentr., 1877, 629).-Theauthor regards Laurent's formula for cinchonine, C19N22N20, as correct.By fractional precipitation from alcohol of commercial cinchonine, andpreparation of the tartrate, a base, probably identical with Zorn'shydrocinchonine, has been obtained.This base is oxidised by perman-ganate to formic acid and cinchotenine-CJT,ZN,O + 0 4 = CISHZONZO, + CH202.M. M. P. M.Alkaloids contained in the Red Poppy. By 0. HESSE(Liebig's AlznaZen, clxxxv, 329) .-The milk-ss,p of the unripe capsulesof Pupaver Rhceas leaves on evaporation about 34 per cent. of dryresidue, which the author finds to contain no trace of morphine, or anysimilar alkalojid. The residue conta'ins 2.1 per cent. of rhceadine, andtraces of otlier, partially cry stallisable alkaloids.J. R.Essence of Tansy. By M. BRUYLANTS ( J . Phamz. China. [4],xxvi, 393--4OO).--Essence of tansy is a yellowish, mobile liquid,readily becoming brown when exposed to air and light; it has astrongly marked camphoraceous odour, and tastes bitter and burning,with an acrid after-taste. Its sp. gr. a t 15" is 0.923, aid its firstboiling point, 192", the thermometer rising boon to 2U4--20'i0, betweenwhich limits the greater part passes over ; a little distillate then passesover as the temperature gradually rises to 270--28O", when a resinousmass remains in the retort, constituting about 10 per cent. of theessence employed. By fractional distillation it is not practicable toisolate any substance of constant boiling point ; but by treating theessence with sodium-hydrogen sulphite, a separation of the constituentsis effected, crystals of an aldehyde-compound separating, whilst a smal158 ABSTRACTS OF CHEMICAL PAPERS.quantity of a terpene (about 1 per cent.) can be obtained from theuncombined portion by fractional distillation over sodium ; this terpeneboils at 135-160" ; it combines with iodine, evolving much heat, andforming a product from which much hydriodic acid is evolved on heat-ing.The bisulphite compound forms light, nacreous scales, insoluble inbenzene and ether, soluble in dilute, but almost insoluble in strongalcohol ; on heding with alcohol or water, or better with sodium car-bonate solution, it is decomposed, forming a liquid readily soluble inether and alcohol, and having the formula, CloH,,O.[No analyses arequoted, though it is stated that the carbon and hydrogen agree with thisformula.] 'lhe vaponr-densities found in two experiments were 5.07and 5.11 respectively, corresponding with the molecular weights, 147and 148 ; the sp. gr. a t 4' is 0.918, and the boiling point, 195-196". Tothis substance the author applies the term tuwacetyZ hydride [ fansoZwould appear to be a more convenient designation.--(:. It. A. W.]When it is dissolved in alcohol, and brought into contact with 1 perceut. sodium-amalgam, a body is formed, boiling at 205-21U0,which, when treated with acetyl chloride, evolves hydrochloric acid,and forms a compound ether boiling near 2'20"; this body formspotassium acetate on sapoiiification with caustic potash, but does notappear to have been analJsed.Bromine and iodine attack tansol, theformer violently ; from the products of the action of the latter, cymenewas isolated, boiling a t 170-175". Hydrochloric acid gas forms aliquid compound, Cl,Hl,O.HCI, decomposed by water, with formationof hydrochloric acid and tansol. Strong sulpkiuric acid removes theelements of water, forming cymene and other products; the sameresult is brought about by heating with phosphorus pentasulphide thecymene boiling a t 175-176", and forming by the action of nitric acidan acid which melts a t 176" (toluic acid), and by that of sulphuricacid and potassium dichromate an acid volatile without fusion(terephshalic acid). Phosphoric anhydride forms impure cymene,and phosphoric pentachloride gives rise to the chlorinated derivatives,Cl0HI6Cl2, C,,H,,Gl, and cymene.None of these derivatives appear tohave been analysed, as no figures are quoted,That tansol is an aldehyde is indicated by the formation of thecrystalline sodium sulphite derivative, and by its giving a mirror whenheated with ammoniacal silver nitrate. In a list of conclusions drawnfrom these results the author states t>hat, besides the hydrocarbon,Cl0HI6, essential oil of Tanmetrun vulguw consists of about four-fifthsof the aldehyde, C1,H160, and one-fifth of an alcohol, CloHl,Q, togetherwith two resins, one acid, one without action on bases. This alcohol, hestates, forms ordinary laurel camphor on oxidation. C. R. A. W.Contributions to the Chemistry of the more importantResins, Gums, and Balsams. By ED. HIRSCHSOHN (Chem.Cmtr., 1877, 182-183) .-Galbanurn and the ammonia-resins, saga-panum and opoponax, may be divided into three classes. Sagapenums,containing sulphur, and yielding by dry distillation umbellifrone,together with other products ; yalhanwm and African ammonia, not con-taining sulphur, but yielding umbellifrone ; and Persian ammonia anORGANIC CmiMISTRY. 159opoponux, which neither contain sulphur nor yield umbellifrone. Gal-banum may be distinguished from African ammonia by its propertyof giving a yellowish-red or violet colour with hydrochloric acid ; andPersian ammonia fkom opoponax by the orange-yellow colour it giveswith Q solution of bleaching powder.From a good Persian galbanum light petroleum oil should extractat least 15 p.c. ; from granular Levant galbanum at least 6 p.c. ; andfrom the same variety in lumps, at least 7 p.c.Persian and African ammonias must have 3 p.c. of soluble consti-tuents, and Persian sagapas 15 P.c.; that from the Levant 16 P.c.,and lastly, opoponax 1 p.c. At%er the solutions are evaporated andheated to 120”, the residue, in the case of galbanum and ammonias,should riot exceed 1 p,c. ; that of Persian sagapenums 5 p.c. ; that ofLevantine sagapas, 12 P.c.; and that of opoponax 3 p.c. of theweight of the drug, that is, the light oil should extract from galbanumand ammonias only ethereal oil, and from the remainder also resinoussubstances. The reactions of a large number of resins, he., are said tobe described in the original paper ( Y h a r n ~ Zeitschr. j: Russlawd, xvi, l),from an extract of which the above facts are drawn. W. R.Chemical Compounds contained in Liquid Storax. ByWILHXLM v. &’IILLER (Liebig’s Awualen, clxxxviii, 184-216).--Thefirst part of the papel. is historical, and the following references (inorder) are made to the literature of the subject-in addition to a pre-vious communication of‘the author (Ueut. C‘hen2. GTes. Ber., ix, 274) :-Liebiy’s A’rLnulerb, lix, 316, and liii, 321 ; Armales de Chimie, xxvi,203 ; Journal d. H a r m . [LS], xiii, 149 ; Liebig’s A ~ ~ r m h , xxxi, 267 ;J: ,pr. Chem., xxxvii, 281 ; Jahresberkht f. C‘hem., 1849, 451 ; Lie-bag s Anrmlen, lv, 1 ; xcix, 376 ; clxiii, 123 ; clxxiii, 10 ; J . pr. C’henz.,xxiii, 321 ; Liebiig’s Aimalelz, liii, 292 ; J. pr. Chem., xxxvii, 281 ;Cowapt. rend., xxi, M i 6 ; Inebig’s Awnden, xcvii, 185 ; Jahresbericht f.Chem., 1860, 303 ; Liebig’s AiinaZen, cxxxv, 122 ; cxli, 181, 377 ; cxlii,251, and Suppl., v, 368; Compt. rend., lxiii, 515, 518, 788, 834, andlxv, 465 ; Deut. Chem. Ges. Ber., vi, 255 ; ix, 1339 ; Liebig’s Annalen,lxx, 1 and % ; lxxv, 297 ; clxiv, 289 ; clxxii, 122 ; cxx, 66.The results of the author’s researches contained in the second partof the paper (too long for abstraction) show that, iii addition to styro-lene, cinnamic acid and styracin, storax contains-(1 .) Phenylpropyl cinnanaate in considerable quantities.(2.) Ethyl cinnarriate in small quantities.(3.) A body which smells like vanilliw, and forms a crystalline com-This body melts at 65”, and may(4.) A resinous body which accompanies the last in small quantities.( 5 . ) ‘l’wo alcoholic bodies (a- and @-storesin) in very considerable(6.) Compounds of these bodies with cinnamic acid also in con-(7. j A sodium compound of storesin in very small quantities.Storesin (from storax and resina) is the name proposed by thepound with sodium bisulphite.possibly be ethylvanillin.Its composition has not been determined.quantities .siderable quantities.It occurs in small quantities160 ABSTRACTS OF CHEJIICAL PAPERS.author for the body obtained from the residue left on extracting re-fined storax successively with caiibtic mda, cold alcohol, cold petro-leum naphtha, hot petroleum naphtha (using an upright condenser).It melts between 160" and 168", and has the composition, €&H5&03.G. T. A

ISSN:0368-1769    

DOI:10.1039/CA8783400121

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年代:1878

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160 ABSTRACTS OF CHEJIICAL PAPERS. P h y s i o l o g i c a l C h e m i s t r y . Chemical Changes in the Liver. By C. FLUGGE (Ze&chr$tf. BioZogie, xiii, 133--171).-Lehmann’s analyses of the blood ff owing through the portal and hepatic veins respectively were made by methods open to so many objections, that the results he obtained can- not form the basis of any theory concerning the functions of the liver. The author therefore determined to make a series of estimations of such constituents of the blood flowing through these veins as could be estimated accurately and with certainty, viz., the water, ash, and ash- constituents. The results of these analyses agreed so closely, that what- ever differences existed were plainly caused by the unavoidable minute errors of manipulation.No difference in chemical composition exists therefore so far as regards these substances between the blood of the portal and hepatic veins. Estimations were next made of the amount of water and of haemoglobin in arterial, portal, and hepatic blood, the haemogloloin being estimated by Prey er’s spectroscopic method. No difference existed in the amount of hzmoglohin in the various kinds of blood, or in their water contents. Recent experimenters have been unable to detect any difference between the amount of sugar, fibrin, and urea contained in the blood of the portal vein and that of the hepatic vein. It therefore follows that these constituents of the blood su-ffer no change in their passage through the liver, and that neither an absorption nor yet a formation of these substances belongs to the functions of that organ.By parity of reasoning, and upon the basis of the experiments recorded by the author, the water, salts, and haemoglobin crf the blood suffer no change in their passage through the liver, and therefore these substances have no relation to its activity. To what extent then may the blood be changed by the liver without our being able to detect it analytically ‘r‘ To answer this question, two $actors are needed, lstlp, the amount of change in the individual constitue‘nts of the blood which can be detected analytically; and secondly, the amount of change in the same constituents which the blood in passing through $he liver con- stantly undergoes. Should the latter be less than the former, then the impossibility will be seen of proving analytically any change of blood in the liver.To answer these questions, we require to know what quantity of blood passes through the liver in 24 hours. This depends upon the quantity of blood held by the organ and the rate of its flow. Such a conclusion is not tenable.PHYSIOLOGICAL CHEMISTRY. 161 With regard to the flow of the blood through the liver, nothing is at present known. It occurred to the author that by means of Vierordt's infusion method, some knowledge might be obtained. Hav- ing determined the rates of the flow of blood through a dog from the crural vein through the system to the crural arterv, the flow was next determined on the same dog from a vein of the intestines or stomach through the liver. By this means the difference in the times taken to complete the circulation would equal the rate of flow through the liver.This latter equalled in time the ordinary flow of the blood from a vein through the lung t o an artery. Of course these results wcrc only proximate. The quantity of blood held by the liver may be taken at 20 per cent. of its weight. With these data we may calculate as follows. The change in the blood of the liver of a dog of 20 kilos. mcight may be estimated as requiring 16 seconds. The blood contained in the liver is 20 per cent. of the 1ivtfl"s weight, and therefore 3.5 per cent. of the weight of !he body, or about 140 gr. Thus in 16 seconds there flows through the liver 140 gr. of blood ; in one minute about 500 grams ; in an hour 30 kilo. ; and in 24 hours 720 kilo.In the estimation of the water in blood, results can at the best be insured only within 0.5 per cent. This in 720 kilo. equals 3600 grains. Therefore by calcu- lation a dog could secrete at least 3600 prams of water through the liver without our analyses of the blood detecting it with certainty. A dog of 20 kilo. weight would secrete at the most only 400 grams of bile in the 24 hours. In like manner, in the estimation of chlorinc, there is an error of 0.02 per cent. which equals in 24 hours 144 grams, whilst only 3 grams of sodium chloride are secreted in the bile during the same time ; and if we distribute this 3 grams over the whole quantity of the blood, we should find in the 50 C.C. taken for analyses, differences so slight as to fall f a r within the limits of error of the most exact analyses.Thus the material changes in the liver can cause only such slight changes in the composition of the blood as lie within the limits of error of our methods of investigation, so that we cannot hope by a compari- son of the blood flowing to m d from the liver to come to any conclu- sions as to the functions of that organ. F. J. L. Action of Biliary Acids on the Alimentary Canal of Dogs. By hl. S C I ~ ~ L E I N (Zeitschr. f. Biologic, xiii, 172--192).--The bile and salts of the biliary acids, when brought into the alimentary canal, greatly increase the peristaltic action of the intestines. If the dose be large, the stomach is affected, and vomiting accompanies the diarrhea. Finally, should the dose be very large, the action on the mucous mem- brane of the stomach is so rapid that violent vomiting ensues and the dose is ejected before the acids reach the int'est,ines.The dose required by a dog of from 4-6 kilo. to produce diarrhma is 0-5 grm. of sodium cbolate, whilst 1.0-1.2 grm. produces vomiting. The action of cliolic acid is the most intense, whilst taurocholic acid is more powerful than gly cocholic. B. J. L.162 ABSTRACTS OF CHEMICAL PAPERS. Oxalic Acid in the Urine. By P. FGRBRYNGER (Chem. Centr., 1877,197).-Theauthor’s observations lead to the following conclusions. 1. Oxalic acid is a normal and perhaps constant constituent of urine. 2. The quantity normally excreted appears not to exceed 20 mgrm. per day. 3. The amount of calcium oxalate which separates even after standing for 24 hours affords no criterion of the total amount of oxalate in the urine.4. The chief solvent for calcium oxalate in the urine is acid sodium phosphate. 5. The amount of oxalic acid is diminished by taking a dose of sodium bicarbonate, and is not increased by lime water or mates. . 6 . There is no constant relation between a large increase of oxalic acid and the stoppage of the normal process of oxidation ; neither is the elimination of the acid hindered by fever. W. R.160 ABSTRACTS OF CHEJIICAL PAPERS.P h y s i o l o g i c a l C h e m i s t r y .Chemical Changes in the Liver. By C. FLUGGE (Ze&chr$tf.BioZogie, xiii, 133--171).-Lehmann’s analyses of the blood ff owingthrough the portal and hepatic veins respectively were made bymethods open to so many objections, that the results he obtained can-not form the basis of any theory concerning the functions of the liver.The author therefore determined to make a series of estimations ofsuch constituents of the blood flowing through these veins as could beestimated accurately and with certainty, viz., the water, ash, and ash-constituents. The results of these analyses agreed so closely, that what-ever differences existed were plainly caused by the unavoidable minuteerrors of manipulation.No difference in chemical composition existstherefore so far as regards these substances between the blood of theportal and hepatic veins. Estimations were next made of the amountof water and of haemoglobin in arterial, portal, and hepatic blood, thehaemogloloin being estimated by Prey er’s spectroscopic method.Nodifference existed in the amount of hzmoglohin in the various kinds ofblood, or in their water contents.Recent experimenters have been unable to detect any differencebetween the amount of sugar, fibrin, and urea contained in the bloodof the portal vein and that of the hepatic vein. It therefore followsthat these constituents of the blood su-ffer no change in their passagethrough the liver, and that neither an absorption nor yet a formationof these substances belongs to the functions of that organ. By parityof reasoning, and upon the basis of the experiments recorded by theauthor, the water, salts, and haemoglobin crf the blood suffer no changein their passage through the liver, and therefore these substances haveno relation to its activity.To what extent then may theblood be changed by the liver without our being able to detect itanalytically ‘r‘To answer this question, two $actors are needed, lstlp, the amountof change in the individual constitue‘nts of the blood which can bedetected analytically; and secondly, the amount of change in thesame constituents which the blood in passing through $he liver con-stantly undergoes.Should the latter be less than the former, then theimpossibility will be seen of proving analytically any change of bloodin the liver.To answer these questions, we require to know what quantity ofblood passes through the liver in 24 hours. This depends upon thequantity of blood held by the organ and the rate of its flow.Such a conclusion is not tenablePHYSIOLOGICAL CHEMISTRY.161With regard to the flow of the blood through the liver, nothing isat present known. It occurred to the author that by means ofVierordt's infusion method, some knowledge might be obtained. Hav-ing determined the rates of the flow of blood through a dog from thecrural vein through the system to the crural arterv, the flow was nextdetermined on the same dog from a vein of the intestines or stomachthrough the liver. By this means the difference in the times taken tocomplete the circulation would equal the rate of flow through the liver.This latter equalled in time the ordinary flow of the blood from a veinthrough the lung t o an artery. Of course these results wcrc onlyproximate.The quantity of blood held by the liver may be taken at20 per cent. of its weight.With these data we may calculate as follows.The change in the blood of the liver of a dog of 20 kilos. mcight maybe estimated as requiring 16 seconds. The blood contained in theliver is 20 per cent. of the 1ivtfl"s weight, and therefore 3.5 per cent.of the weight of !he body, or about 140 gr. Thus in 16 seconds thereflows through the liver 140 gr. of blood ; in one minute about 500 grams ;in an hour 30 kilo. ; and in 24 hours 720 kilo. In the estimation ofthe water in blood, results can at the best be insured only within 0.5per cent. This in 720 kilo. equals 3600 grains. Therefore by calcu-lation a dog could secrete at least 3600 prams of water through theliver without our analyses of the blood detecting it with certainty.Adog of 20 kilo. weight would secrete at the most only 400 grams ofbile in the 24 hours.In like manner, in the estimation of chlorinc, there is an errorof 0.02 per cent. which equals in 24 hours 144 grams, whilst only 3grams of sodium chloride are secreted in the bile during the sametime ; and if we distribute this 3 grams over the whole quantity ofthe blood, we should find in the 50 C.C. taken for analyses, differencesso slight as to fall f a r within the limits of error of the most exactanalyses.Thus the material changes in the liver can cause only such slightchanges in the composition of the blood as lie within the limits of errorof our methods of investigation, so that we cannot hope by a compari-son of the blood flowing to m d from the liver to come to any conclu-sions as to the functions of that organ.F. J. L.Action of Biliary Acids on the Alimentary Canal of Dogs.By hl. S C I ~ ~ L E I N (Zeitschr. f. Biologic, xiii, 172--192).--The bileand salts of the biliary acids, when brought into the alimentary canal,greatly increase the peristaltic action of the intestines. If the dose belarge, the stomach is affected, and vomiting accompanies the diarrhea.Finally, should the dose be very large, the action on the mucous mem-brane of the stomach is so rapid that violent vomiting ensues and thedose is ejected before the acids reach the int'est,ines. The dose requiredby a dog of from 4-6 kilo. to produce diarrhma is 0-5 grm. of sodiumcbolate, whilst 1.0-1.2 grm. produces vomiting. The action of cliolicacid is the most intense, whilst taurocholic acid is more powerful thangly cocholic. B. J. L162 ABSTRACTS OF CHEMICAL PAPERS.Oxalic Acid in the Urine. By P. FGRBRYNGER (Chem. Centr.,1877,197).-Theauthor’s observations lead to the following conclusions.1. Oxalic acid is a normal and perhaps constant constituent of urine.2. The quantity normally excreted appears not to exceed 20 mgrm.per day. 3. The amount of calcium oxalate which separates even afterstanding for 24 hours affords no criterion of the total amount of oxalatein the urine. 4. The chief solvent for calcium oxalate in the urine isacid sodium phosphate. 5. The amount of oxalic acid is diminishedby taking a dose of sodium bicarbonate, and is not increased by limewater or mates. . 6 . There is no constant relation between a largeincrease of oxalic acid and the stoppage of the normal process ofoxidation ; neither is the elimination of the acid hindered by fever.W. R

ISSN:0368-1769    

DOI:10.1039/CA8783400160

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年代:1878

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摘要:

162 ABSTRAOTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Elimination of Oxygen from Green Twigs under Boiled Water in Sunlight. By Jos. BORM (Liebig's Anrhalen, clxxxv, 248-258) .-The author summarises the results of his experiments on this subject as follows :- 1. When green twigs of woody plants, such as privet, are enclosed in a limited atmosphere containing oxygen, in the dark, there ensues at first a diminution, but afterwards an increase, in the volume of the enclosed gases ; and this increase takes place before the oxygen present is completely absorbed. 2. The diminution in the volume of gas which takeg place when green twigs are enclosed in an atmosphere containing oxygen, in feeble light, is not due t o assimilation of oxygen, as in the germina- tion of seeds rich in oil, but is caused by absorption of carbon dioxide formed in normal respiration.3. When portions of fresh plants are enclosed in an atmosphere of carbon dioxide, there takes place at first a diminution (contrary t o Saussure's statements) and afterwards an increase in the volume of the gas, due to internal respiration. 4. The absorption of carbon dioxide by fresh plants is not due to the action of cellular liquids (ZeZZsaft) exclusively, since it takes place also in twigs previously dried at 100". 5. When fresh green shoots of privet are exposed t o sunlight, under boiled water, they give off more oxygen than corresponds with the volume of air contained in them. This oxygen is for the most part derived from carbon dioxide formed in the shoots by internal respira- tion.In prolonged experiments the evolutlion of oxygen becomes slower and slower, and after 3 or 4 days ceases entirely, although the shoots still appear fresh and sound. After a week, however, the shoots begin to turn brown, and butyric fermentation sets in. J. R. Action of Sunlight on the Vine. By H. MA CAGNO (Compt. rend., lxxxv, 810--812).-Two rows of vines were covered in April,VEGETABLE PHYSIOLOGY AND AGRICULTURE. 163 one with a black, the other with a white cloth. The green branches and leaves were submitted t o analysis at the beginning of August. The results lead to the following conclusions :-The diminution of solar light by the black cloth prevented the production of glucose in the leaves, and tartaric acid and mineral matters were found in direct pro- portion to the intensity of the light.R. R. On the Pathology of Fruit Trees. By DR. EBERMAYER (Land. Versuchs Stationem, xx, 392).-In the preparation of cellulose for paper pulp, the sawdust, &c., is usually digested under pressure with soda- ley, and from the alkaline liquors containing resin, &c., the soda is regained by evaporation and incineration. During this process vapours are evolved alkaline in character, and depositing wdium carbonate : these act very injuriously on vegetcction in the vicinity, causing the leaves of the fruit trees of the neighbourhood to become reddish- brown, and finally black, when they die. By acting on leaves of dif- ferent kinds with soda-solution of sp. gr. 1.01, the author found that similar effects are produced ; humus-like matters are developed by the decomposition brought about by the alkali.It is noticeable that apple leaves are affected sooner than pear, and pear sooner than plum leaves ; and that, if the alkaline solution be allowed to dry on thc leaves, the alkaline reaclion is wholly or almost destroyed by reason of the formation of acid decomposition-products. Nitrification by Organised Ferments. By S c H L O E s I N G and M ~ N T Z (Compt. rend., lxxxv, 101%--1020).-1n continuation of their pyevious research (this JOTLYW~, 1877, ii, 215), the authors show that vegetable earth will not nitrify in an atmosphere containing chloro- form-vapour. Nitrification is also stopped by heating the earth for an hour to 100". Earth so heated may afterwards be exposed to a current of air purified by ignition, without nitrification taking place. Nitrification recommences if a little vegetable mould diffused through water is applied.Oxidation of organic matter still proceeds in earth which has been tr'eated with chloroform or heated to 100'; under these circumstances carbonic acid and ammonia are produced, but no nitric acid. A porous medium is not necessary for nitrification. Sewage, or rz solution containing sugar, and the phosphates and sul- phates of ammonium, potassium, and calcium, can be nitrified by passing over polished pebbles. Sewage clarified by alum and filtra- tion, and then treated with a few particles of vegetable earth and some carbonate of calcium, may he nitrified in a closed vessel through which filtered air is conducted.When raw sewage is thus treated with air, without previous seeding wit'h vegetable earth, the result is uncertain, as sewage contains a multitude of organisms, and in the struggle for existence the nitrifying ferment may be destroyed. Vegetable earth suspended in fresh water or in sea-water is easily nitrified by passing air through the water ; the nitrification takes place equally in light or darkness. On boiling the mixture of soil and water, nitrification ceases if pure air be afterwards supplied. Fermentation of Norwegian Fish-guano and Steamed Bone- C. R. A. W. R. W.I64 ABSTRACTS OF CHEMICAL PAPERS. meal. By A. PAGET (Ckenz. Centr., 1877, 206).-As the action of these manures is too slow, and as dirty products are obtained by the action of sulphuric acid, the insoluble nitrogenous compounds are de- composed by moistening with water and urine, and leaving the mass to ferment.For 50 kilos. of manure 39 litres of urine or water are necessary; 5 kilos. of gypsum are added, and the heaps are covered with gypsum or earth to prevent loss of nitrogen. The temperature rises to above 40°, and when it begins to fall the fermentation is over. W. R. Purification and Utilisation of Sewage. By A. M ~ ~ L L E R (Land. Versuchs. Sfationen, xx, 391) .--Irriga8tion processcs are viewed by the author with favour. In winter when plants hybernnte, the purification is less efficarious than in spring and summer, when vegeta- tion shows the maximum of activity. Self-purification by settling and asration, although successful with small quantities in a laboratory, does not appear likely to give good results on the large scale ; whilst precipit'ation processes a,re too costly.Irrigation must be intermittent t o permit of aiiration and oxidation of the deposited fcccal solid mat- ters from time to time ; and in winter this will often be impracticable, unless ' combined with a partial precipitation process, or unless large reservoirs be constructed. C. R. A. W.162 ABSTRAOTS OF CHEMICAL PAPERS.Chemistry of Vegetable Physiology and Agriculture.Elimination of Oxygen from Green Twigs under BoiledWater in Sunlight. By Jos. BORM (Liebig's Anrhalen, clxxxv,248-258) .-The author summarises the results of his experiments onthis subject as follows :-1.When green twigs of woody plants, such as privet, are enclosedin a limited atmosphere containing oxygen, in the dark, there ensuesat first a diminution, but afterwards an increase, in the volume of theenclosed gases ; and this increase takes place before the oxygen presentis completely absorbed.2. The diminution in the volume of gas which takeg place whengreen twigs are enclosed in an atmosphere containing oxygen, infeeble light, is not due t o assimilation of oxygen, as in the germina-tion of seeds rich in oil, but is caused by absorption of carbon dioxideformed in normal respiration.3. When portions of fresh plants are enclosed in an atmosphere ofcarbon dioxide, there takes place at first a diminution (contrary t oSaussure's statements) and afterwards an increase in the volume ofthe gas, due to internal respiration.4.The absorption of carbon dioxide by fresh plants is not due tothe action of cellular liquids (ZeZZsaft) exclusively, since it takes placealso in twigs previously dried at 100".5. When fresh green shoots of privet are exposed t o sunlight, underboiled water, they give off more oxygen than corresponds with thevolume of air contained in them. This oxygen is for the most partderived from carbon dioxide formed in the shoots by internal respira-tion. In prolonged experiments the evolutlion of oxygen becomesslower and slower, and after 3 or 4 days ceases entirely, although theshoots still appear fresh and sound. After a week, however, theshoots begin to turn brown, and butyric fermentation sets in.J.R.Action of Sunlight on the Vine. By H. MA CAGNO (Compt.rend., lxxxv, 810--812).-Two rows of vines were covered in AprilVEGETABLE PHYSIOLOGY AND AGRICULTURE. 163one with a black, the other with a white cloth. The green branchesand leaves were submitted t o analysis at the beginning of August.The results lead to the following conclusions :-The diminution of solarlight by the black cloth prevented the production of glucose in theleaves, and tartaric acid and mineral matters were found in direct pro-portion to the intensity of the light. R. R.On the Pathology of Fruit Trees. By DR. EBERMAYER (Land.Versuchs Stationem, xx, 392).-In the preparation of cellulose for paperpulp, the sawdust, &c., is usually digested under pressure with soda-ley, and from the alkaline liquors containing resin, &c., the soda isregained by evaporation and incineration. During this process vapoursare evolved alkaline in character, and depositing wdium carbonate :these act very injuriously on vegetcction in the vicinity, causing theleaves of the fruit trees of the neighbourhood to become reddish-brown, and finally black, when they die.By acting on leaves of dif-ferent kinds with soda-solution of sp. gr. 1.01, the author found thatsimilar effects are produced ; humus-like matters are developed bythe decomposition brought about by the alkali. It is noticeable thatapple leaves are affected sooner than pear, and pear sooner than plumleaves ; and that, if the alkaline solution be allowed to dry on thc leaves,the alkaline reaclion is wholly or almost destroyed by reason of theformation of acid decomposition-products.Nitrification by Organised Ferments.By S c H L O E s I N G andM ~ N T Z (Compt. rend., lxxxv, 101%--1020).-1n continuation of theirpyevious research (this JOTLYW~, 1877, ii, 215), the authors show thatvegetable earth will not nitrify in an atmosphere containing chloro-form-vapour. Nitrification is also stopped by heating the earth foran hour to 100". Earth so heated may afterwards be exposed to acurrent of air purified by ignition, without nitrification taking place.Nitrification recommences if a little vegetable mould diffused throughwater is applied. Oxidation of organic matter still proceeds in earthwhich has been tr'eated with chloroform or heated to 100'; underthese circumstances carbonic acid and ammonia are produced, but nonitric acid.A porous medium is not necessary for nitrification.Sewage, or rz solution containing sugar, and the phosphates and sul-phates of ammonium, potassium, and calcium, can be nitrified bypassing over polished pebbles. Sewage clarified by alum and filtra-tion, and then treated with a few particles of vegetable earth and somecarbonate of calcium, may he nitrified in a closed vessel through whichfiltered air is conducted. When raw sewage is thus treated with air,without previous seeding wit'h vegetable earth, the result is uncertain,as sewage contains a multitude of organisms, and in the struggle forexistence the nitrifying ferment may be destroyed.Vegetable earthsuspended in fresh water or in sea-water is easily nitrified by passingair through the water ; the nitrification takes place equally in light ordarkness. On boiling the mixture of soil and water, nitrification ceasesif pure air be afterwards supplied.Fermentation of Norwegian Fish-guano and Steamed Bone-C. R. A. W.R. WI64 ABSTRACTS OF CHEMICAL PAPERS.meal. By A. PAGET (Ckenz. Centr., 1877, 206).-As the action ofthese manures is too slow, and as dirty products are obtained by theaction of sulphuric acid, the insoluble nitrogenous compounds are de-composed by moistening with water and urine, and leaving the mass toferment. For 50 kilos. of manure 39 litres of urine or water arenecessary; 5 kilos. of gypsum are added, and the heaps are coveredwith gypsum or earth to prevent loss of nitrogen. The temperaturerises to above 40°, and when it begins to fall the fermentation is over.W. R.Purification and Utilisation of Sewage. By A. M ~ ~ L L E R(Land. Versuchs. Sfationen, xx, 391) .--Irriga8tion processcs are viewedby the author with favour. In winter when plants hybernnte, thepurification is less efficarious than in spring and summer, when vegeta-tion shows the maximum of activity. Self-purification by settlingand asration, although successful with small quantities in a laboratory,does not appear likely to give good results on the large scale ; whilstprecipit'ation processes a,re too costly. Irrigation must be intermittentt o permit of aiiration and oxidation of the deposited fcccal solid mat-ters from time to time ; and in winter this will often be impracticable,unless ' combined with a partial precipitation process, or unless largereservoirs be constructed. C. R. A. W

ISSN:0368-1769    

DOI:10.1039/CA8783400162

出版商:RSC    

年代:1878

数据来源: RSC

摘要:

I64 ABSTRACTS OF CHEMICAL PAPERS. An a1 y t i c a1 C h e m i s t r y. Estimation of the Free Oxygen Dissolved in Water. By J. KOKIG and L. MUTSCHLER (Detct. Chem. Gcs. Ber., x, 2017-2022). -The method proposed by Schiitzenberger (Ann. Chim. Phys. [4J, xx, 351) for this purpose, by means of sodium hyposulphite, ammoniacal copper solution and indigo, cannot be recommended, on account of the considerable alteration which takes place in the strength of the stand- ards on keeping, and also because there is no convenient and safe method for eiandardising these solutions. Mohr's method, by the use of an ammoniacal solution of ferrous oxide arid titration of the excess witli permaiiganate, is much more exact and requires less time. Attempts to arrive at conclusioiis as to the value of a water for drinking purposes from the quantity of dissolved oxygen, led to no results .T. C. Estimation of Atmospheric Carbonic Acid at Tabor, Bohe- mia, in 1874 and 1875. By FR. PARSKY (Clzein. Centr., 1877, 198).--10,000 vol. air at 0" C. and 160 mm., coiitained vols. of car- bonic acid:-ANALYTICAL CHEMISTRY. 163 Month. October. ........... November. ......... December. ......... January .......... February .......... March ............ April. ............. May .............. June .............. July .............. August ............ Maximum. 3-75 3.91 3.67 3.77 3-62 3.75 3.67 3-53 3.61 3.09 4-07' Minimum. 3-19 3.17 3.10 3-22 3.21 3.15 3.19 3.19 3-02 3.15 3.19 Mean. 3.12 3.42 3.3 7 3.43 3.43 3.43 3.53 3-55 3.29 3.31 3.43 The amount of carbonic acid varied during the month, and appeared to depend on the weather.North-west and south-west winds lowered the proportion, while the opposite took place with north and north- east winds. w. R. Estimation of Carbonates in presence of Sulphites and Hyposulphites. By E. POLACCI (Deut. Chem. Gas. Ber., X, 1747). -The author decomposes tlie carboiiates by means of po tzssium bi- tartrate at a gentle heat in an ordinary carbonic acid apparatus. Carbon dioxide alone is liberated, sulphites and hyposulphites remaiii- ing undecomposed. J. R. Estimation of Nitrogen in the Nitroglycerin of Dynamite, By SAUER arid E. ADOR (Ileut. C ' J m x . Qes. Ber., x, 1982-1984).- The estimation of nitrogen in the nitroglycerin of dynamite by treat- ment with potash gives results which are always too low, owing to the occurrence of the following secondary reaction :- C,H,( O.NOa), + 3KHO = 3KN0, + c3n5(oH)3, Correct resuits can be obtained only by using Dumas' method.By this means the percentage of nitrogen in three different samples of nitro-glycerin. from dynamite was found. to be from 18.35 to 18.52. The calcuhted percentage of N in pure nitro-glyccrin being 18.50 proves, therefore, that dynamitc contains only trinitrin. T. C. ( D i w ~ l . poZyt. J., ccxxv, 560--561.)--IEd. Hart recommends potassium permangan- ate as the best reagent for titration. He heats the ore to redness in a porcelain tube, for three hours at least, in a stream of hydrogen; then cools, and adds it to boiling dilute sulphuric acid, a t the same time passing a stream of hydrogen through the liquid, and titrates with permanganate in the ordinary way.Coal-gas is inapplicable, as some of its constituents absorbed by the acid act on the per- manganat e s o h t ion. Some brown hixmatites, reduced by this method, yield an iron almost insoluble in the acid. Dr. T. 111. Drown proposes to heat such ores in air or oxygen, to burn off carbonaceous matter before passing hydrogen over them; the iron then reduced dissolves easily. Moat magnetic ores yield an insoluble portion containing iron; for such ores this method is no better than ordinary ones. Dr. Drown dissolves iron ore in hydrochloric acid, evaporates nearly VOL. XXXILI. n Volumetric Estimation of Iron in Iron Ores.166 ABSTRACTS OF CHEMICAL PAPERS. t o dryness, adds a little water, and then stannous chloride from a burette.The excess of stannous chloride is estimated by adding starch and standard iodine solution. The iron solution should be tolerably conceutrated and warm ; the tin solution should be freshly prepared: 1 C.C. = 0.012 gram iron = 3 C.C. iodine solution. Ten assays gave a mean of 38.235 per cent. ; two assays with perrnnngan- ate gave 38.17, and two gravimetric deteriniiiiations gave 38-14 per cent. of iron. The author made four simnltaiieoms assays in eiFhty minutes, the tin solution being prepared whilst the ores wcre dissolving. Metallic iron dissolved in hydrochloric acid with a little potassium chlorate, the solution being evaporated to dryness nearly, is used t o standardise the t)in solution. A solution of iron chloride some months old, which gave 0.1024 and 0.1025 of iron per volume by precipitation with ammonia, gave 0.2017, 0.1012, 0.1010, and 0.1007.Estimation of Phosphorus in Iron and Iron Ores (two papers). By KOSCHELT, and by C A I R X ~ (Clrein. Ceubh., 1877, 487).- Koschelt prepares a molybdic solution by dissolving one part of pure rnolybdic acid together with one part of caustic potash in six part's of water, adding, after cooling, a solution of $ part of tartaric acid in two parts of water, followed by addition of 7+ parts of nitric acid ; heating the whole to boiling and filtering while hot. About onc gram of the iron is dissolved in the smallest possible quantity of nitric acid (the solution should not measure more than 50 c.c.), and the filtered liquid is allowed to flow into about 30 C.C.of the rnolybdic solution placed in a basin on the watw-bath ; after complete precipitation tbe whole is warmed for a short time, the precipitate is collected on a weighed filter, washed with dilute nitric acid (2 : 3 ) and alcohol, dried a t 120-130" and weighed; it contains 1.73 per cent. of phosphorus. The process of Cairns is very tedious; it consists in precipitating the ferric phosphate with ammoiiia, redissolving, precipitating with ammonium molybdate, redissolving, reprecipitating, again dissolving, and filially J. T. precipitating with magnesia mixture. M. &I. P. n!t. Aluminium Plate as a support in Blow-pipe Work. By W. M. HUTCH I N G S (Ch,ena. News, xxxvi, 208 and 217).-Detailed directions for using ROSS'S aluminium plate ; accounts of various metallic subli- mates are also given.Estimation of Reducing Sugar in Commercial Products. By A. GIRAR D (Cornpt. reid., lxxxv, 800-802).-The author deter- mines the amount of reducing sugar by weighing the quantity of rnetal- lie copper which it will precipitate from a cupropotassic solution. The copper is rapidly washed on a filler, which is burnt in the air on a pla- tinum boat, and this is afterwards ignited in a current of hydrogen, iu order to reduce the copper oxide. The saccharose present in the pro- ducts is estlirnatpd by inverting it, finding the weight of copper preci- pitated, and deducting from this the amount previously determined as due to reducing sugar. One gram of copper is reduced by 0.569 gram of reducing sugar ; but a correction represented by +$+ has to be ap- plied for saccharose, on account of the difference of the equivalents.R. R. M. &I. P. M.ANALYTICAL CHEZ\!ISTRT. 167 Sacchariunetry. By H. 31 o it IN (Compt. Tend., lxxxv, 802-805) .- The author's results go to prove the optical inactivity of the reducing sugar contained in commercial products. The slight rotatory power, which in some exceptional cases this kind of sugar may posscss, is too small to affect the saccharinietrical detcrrnination of commercial sugars. R. R. On some Quick Methods for testing Milk ( I l i n ~ Z . p d ~ t . J., ccxxvi, 418-421)-Ritthauscn ( J . pi'. Cheiiz., 1877 [2], xv, 329) states that 20 or 10 C.C. of milk is diluted to 20 times its volume, and 10 or 5 C.C. of solution of copper (63.5 gr.of siilphate of copper in 1 Iitrc) added. Then as much potash is added as is sufficient t o dccompose the coppel. salt added. The precipitate so011 settles, the supernatalit liquid is decanted off, and the washed precipitate is placed on a filter. The filtrate contains thc sugar, which can he estimated. The precipitate contains the proteid and the fat. This latter can be dissolved out by ether, after washing with absolute alcohol, t h e cther evaporated, and the fat weighed. The precipitate is again waslied with absolute alcohol, dried over sulphuric acid, and then at 125" for t w o or three hours, and weighed. The dry powdery product is thcn well ignited, tthe loss giving the quantity of prcteid. Schmen oC hfunich uses an carthenw;we plate, m-liich he heats to IOO", and tlicii allows to cool, qiiickly iinses it with a little water, and then places it ovcr a glass vehsel contaiiiinq somc coiiceritrateil salplinric scitl.The milk, which is tliliiterl with a n equal bulk of tlistillcd water, and contained in a kind of wash-bottle (spritz-ghs) is then poured over the ceiitre of this earthenware plate, and, to prevent evaporatiou, covered with a ground clock-qlass. Nine t o ten parxis of milk are sufficient. After one or two hours the serum is absorbed by the plate, arid the cascin and fat can be scraped 08 with a horn spstula, and then placed in a weighed watch-glass. This is heated to 105" iii an air-bath and weighed. The fat can be dissolved out by ether, a d estimated. A. Kaiser ( 8 c h u e i z .Lat~dwi~th. Zcituvq, from the iWilclL-Zeitung, 394) gives a ine.ihud of finding the yuaritit)y of fat by means of a formula into which the sp. gr. of pure and skimmed milk, of milk-fat, and of milk-serum, enter. The sp. gr. of the serum is taken to be sp. gr. of skimmed milk, + 0.0011, The sp. gr. of fat is assumed to be the same or nearly the same in all milks. The accuracy of this method depends on the degree of skimming, and the exactness of the reading of the specific gravity. The author has invented a lactometer and a skimmer for these purposes. S. Test for Xantonin. By DAVID LINDO (Chem. News, xxxvi, 222). -'l'he crystals are dissolved in strong sulphoric acid without heating, small successive quantities of a very dilute solution of ferric chloride are added, and the dish is agitated : a red colour, changing to pinrple, and subsequently to violet, i s produced.I f the quantity of santonin be very small, the ferric chloride solution should be mixcd with :in equal bulk of strong sulphuric acid, the mixed liquid should be added to the santonin, aiid Lent should be applied. M. M I?: &I. 12 2168 ABSTRACTS OF CHEMICAL PAPERS. Detection of Saffron. By W. STODDART (Chem. Centr., 1877, 477). Very small quantities of this colouring matter may be detected by boiling with dilute hydrochloric acid, containing a strip of copper- foil with a little piece of platinum touching it, and a little sugar; the colour changes to red. Saffron is unchanged by alkalis. 31. 31. P. M. Detection, by the Spectroscope, of the Adulteration of Red Wines.By F. v. LEPET, (Deut. Chwa. Ges. Ber., x, 1875-1877).- The juice of the beet-root (Beta vuZgcwis) which is used for imparting colour to red wines, exhibits an absorption-spect rum cliaracteri sed by two distinct bands. The author finds that a white wine to which an alcoholic infusion of the root has been added, gives this spectrum un- changed; the colouring matter present in pure red wine, which prevents the recognition of the characteristic bancis of thc juice of the beet when present a s an adulteration, may be removed by means of tannin and gelatin (Faure’s reagent, which leaves the colouring matter of the beet unchanged. Characteristic modifications of the spectrum are determined by cupric sulpliate, the alkalis, and other reagent<. These are carefully described by the author as affording additional evidence of thc presence of beet-juice. c.1’. c.I64 ABSTRACTS OF CHEMICAL PAPERS.An a1 y t i c a1 C h e m i s t r y.Estimation of the Free Oxygen Dissolved in Water. By J.KOKIG and L. MUTSCHLER (Detct. Chem. Gcs. Ber., x, 2017-2022).-The method proposed by Schiitzenberger (Ann. Chim. Phys. [4J, xx,351) for this purpose, by means of sodium hyposulphite, ammoniacalcopper solution and indigo, cannot be recommended, on account of theconsiderable alteration which takes place in the strength of the stand-ards on keeping, and also because there is no convenient and safemethod for eiandardising these solutions. Mohr's method, by the useof an ammoniacal solution of ferrous oxide arid titration of the excesswitli permaiiganate, is much more exact and requires less time.Attempts to arrive at conclusioiis as to the value of a water fordrinking purposes from the quantity of dissolved oxygen, led to noresults .T. C.Estimation of Atmospheric Carbonic Acid at Tabor, Bohe-mia, in 1874 and 1875. By FR. PARSKY (Clzein. Centr., 1877,198).--10,000 vol. air at 0" C. and 160 mm., coiitained vols. of car-bonic acid:ANALYTICAL CHEMISTRY. 163Month.October. ...........November. .........December. .........January ..........February ..........March ............April. .............May ..............June ..............July ..............August ............Maximum.3-753.913.673.773-623.753.673-533.613.094-07'Minimum.3-193.173.103-223.213.153.193.193-023.153.19Mean.3.123.423.3 73.433.433.433.533-553.293.313.43The amount of carbonic acid varied during the month, and appearedto depend on the weather.North-west and south-west winds loweredthe proportion, while the opposite took place with north and north-east winds. w. R.Estimation of Carbonates in presence of Sulphites andHyposulphites. By E. POLACCI (Deut. Chem. Gas. Ber., X, 1747).-The author decomposes tlie carboiiates by means of po tzssium bi-tartrate at a gentle heat in an ordinary carbonic acid apparatus.Carbon dioxide alone is liberated, sulphites and hyposulphites remaiii-ing undecomposed. J. R.Estimation of Nitrogen in the Nitroglycerin of Dynamite,By SAUER arid E. ADOR (Ileut.C ' J m x . Qes. Ber., x, 1982-1984).-The estimation of nitrogen in the nitroglycerin of dynamite by treat-ment with potash gives results which are always too low, owing to theoccurrence of the following secondary reaction :- C,H,( O.NOa), +3KHO = 3KN0, + c3n5(oH)3, Correct resuits can be obtainedonly by using Dumas' method. By this means the percentage ofnitrogen in three different samples of nitro-glycerin. from dynamitewas found. to be from 18.35 to 18.52. The calcuhted percentage ofN in pure nitro-glyccrin being 18.50 proves, therefore, that dynamitccontains only trinitrin. T. C.( D i w ~ l . poZyt.J., ccxxv, 560--561.)--IEd. Hart recommends potassium permangan-ate as the best reagent for titration.He heats the ore to redness in aporcelain tube, for three hours at least, in a stream of hydrogen;then cools, and adds it to boiling dilute sulphuric acid, a t the sametime passing a stream of hydrogen through the liquid, and titrateswith permanganate in the ordinary way. Coal-gas is inapplicable,as some of its constituents absorbed by the acid act on the per-manganat e s o h t ion.Some brown hixmatites, reduced by this method, yield an ironalmost insoluble in the acid. Dr. T. 111. Drown proposes to heat suchores in air or oxygen, to burn off carbonaceous matter before passinghydrogen over them; the iron then reduced dissolves easily. Moatmagnetic ores yield an insoluble portion containing iron; for suchores this method is no better than ordinary ones.Dr.Drown dissolves iron ore in hydrochloric acid, evaporates nearlyVOL. XXXILI. nVolumetric Estimation of Iron in Iron Ores166 ABSTRACTS OF CHEMICAL PAPERS.t o dryness, adds a little water, and then stannous chloride from aburette. The excess of stannous chloride is estimated by addingstarch and standard iodine solution. The iron solution should betolerably conceutrated and warm ; the tin solution should be freshlyprepared: 1 C.C. = 0.012 gram iron = 3 C.C. iodine solution. Tenassays gave a mean of 38.235 per cent. ; two assays with perrnnngan-ate gave 38.17, and two gravimetric deteriniiiiations gave 38-14 percent. of iron. The author made four simnltaiieoms assays in eiFhtyminutes, the tin solution being prepared whilst the ores wcre dissolving.Metallic iron dissolved in hydrochloric acid with a little potassiumchlorate, the solution being evaporated to dryness nearly, is used t ostandardise the t)in solution. A solution of iron chloride some monthsold, which gave 0.1024 and 0.1025 of iron per volume by precipitationwith ammonia, gave 0.2017, 0.1012, 0.1010, and 0.1007.Estimation of Phosphorus in Iron and Iron Ores (twopapers).By KOSCHELT, and by C A I R X ~ (Clrein. Ceubh., 1877, 487).-Koschelt prepares a molybdic solution by dissolving one part of purernolybdic acid together with one part of caustic potash in six part's ofwater, adding, after cooling, a solution of $ part of tartaric acid in twoparts of water, followed by addition of 7+ parts of nitric acid ; heatingthe whole to boiling and filtering while hot.About onc gram of theiron is dissolved in the smallest possible quantity of nitric acid (thesolution should not measure more than 50 c.c.), and the filtered liquidis allowed to flow into about 30 C.C. of the rnolybdic solution placed ina basin on the watw-bath ; after complete precipitation tbe whole iswarmed for a short time, the precipitate is collected on a weighed filter,washed with dilute nitric acid (2 : 3 ) and alcohol, dried a t 120-130"and weighed; it contains 1.73 per cent. of phosphorus. The processof Cairns is very tedious; it consists in precipitating the ferricphosphate with ammoiiia, redissolving, precipitating with ammoniummolybdate, redissolving, reprecipitating, again dissolving, and filiallyJ.T.precipitating with magnesia mixture. M. &I. P. n!t.Aluminium Plate as a support in Blow-pipe Work. By W.M. HUTCH I N G S (Ch,ena. News, xxxvi, 208 and 217).-Detailed directionsfor using ROSS'S aluminium plate ; accounts of various metallic subli-mates are also given.Estimation of Reducing Sugar in Commercial Products.By A. GIRAR D (Cornpt. reid., lxxxv, 800-802).-The author deter-mines the amount of reducing sugar by weighing the quantity of rnetal-lie copper which it will precipitate from a cupropotassic solution. Thecopper is rapidly washed on a filler, which is burnt in the air on a pla-tinum boat, and this is afterwards ignited in a current of hydrogen, iuorder to reduce the copper oxide. The saccharose present in the pro-ducts is estlirnatpd by inverting it, finding the weight of copper preci-pitated, and deducting from this the amount previously determined asdue to reducing sugar.One gram of copper is reduced by 0.569 gramof reducing sugar ; but a correction represented by +$+ has to be ap-plied for saccharose, on account of the difference of the equivalents.R. R.M. &I. P. MANALYTICAL CHEZ\!ISTRT. 167Sacchariunetry. By H. 31 o it IN (Compt. Tend., lxxxv, 802-805) .-The author's results go to prove the optical inactivity of the reducingsugar contained in commercial products. The slight rotatory power,which in some exceptional cases this kind of sugar may posscss, is toosmall to affect the saccharinietrical detcrrnination of commercialsugars.R. R.On some Quick Methods for testing Milk ( I l i n ~ Z . p d ~ t . J.,ccxxvi, 418-421)-Ritthauscn ( J . pi'. Cheiiz., 1877 [2], xv, 329)states that 20 or 10 C.C. of milk is diluted to 20 times its volume, and10 or 5 C.C. of solution of copper (63.5 gr. of siilphate of copper in 1 Iitrc)added. Then as much potash is added as is sufficient t o dccomposethe coppel. salt added. The precipitate so011 settles, the supernatalitliquid is decanted off, and the washed precipitate is placed on a filter.The filtrate contains thc sugar, which can he estimated. The precipitatecontains the proteid and the fat. This latter can be dissolved out byether, after washing with absolute alcohol, t h e cther evaporated, andthe fat weighed.The precipitate is again waslied with absolutealcohol, dried over sulphuric acid, and then at 125" for t w o orthree hours, and weighed. The dry powdery product is thcn wellignited, tthe loss giving the quantity of prcteid. Schmen oC hfunichuses an carthenw;we plate, m-liich he heats to IOO", and tlicii allowsto cool, qiiickly iinses it with a little water, and then places itovcr a glass vehsel contaiiiinq somc coiiceritrateil salplinric scitl. Themilk, which is tliliiterl with a n equal bulk of tlistillcd water, andcontained in a kind of wash-bottle (spritz-ghs) is then poured overthe ceiitre of this earthenware plate, and, to prevent evaporatiou,covered with a ground clock-qlass. Nine t o ten parxis of milk aresufficient. After one or two hours the serum is absorbed by the plate,arid the cascin and fat can be scraped 08 with a horn spstula, andthen placed in a weighed watch-glass.This is heated to 105" iii anair-bath and weighed. The fat can be dissolved out by ether, a destimated.A. Kaiser ( 8 c h u e i z . Lat~dwi~th. Zcituvq, from the iWilclL-Zeitung,394) gives a ine.ihud of finding the yuaritit)y of fat by means of aformula into which the sp. gr. of pure and skimmed milk, of milk-fat,and of milk-serum, enter. The sp. gr. of the serum is taken to besp. gr. of skimmed milk, + 0.0011, The sp. gr. of fat is assumed tobe the same or nearly the same in all milks. The accuracy of thismethod depends on the degree of skimming, and the exactness of thereading of the specific gravity.The author has invented a lactometerand a skimmer for these purposes. S.Test for Xantonin. By DAVID LINDO (Chem. News, xxxvi, 222).-'l'he crystals are dissolved in strong sulphoric acid without heating,small successive quantities of a very dilute solution of ferric chlorideare added, and the dish is agitated : a red colour, changing to pinrple,and subsequently to violet, i s produced. I f the quantity of santoninbe very small, the ferric chloride solution should be mixcd with :inequal bulk of strong sulphuric acid, the mixed liquid should be addedto the santonin, aiid Lent should be applied. M. M I?: &I.12 168 ABSTRACTS OF CHEMICAL PAPERS.Detection of Saffron. By W. STODDART (Chem. Centr., 1877,477). Very small quantities of this colouring matter may be detectedby boiling with dilute hydrochloric acid, containing a strip of copper-foil with a little piece of platinum touching it, and a little sugar;the colour changes to red. Saffron is unchanged by alkalis.31. 31. P. M.Detection, by the Spectroscope, of the Adulteration of RedWines. By F. v. LEPET, (Deut. Chwa. Ges. Ber., x, 1875-1877).-The juice of the beet-root (Beta vuZgcwis) which is used for impartingcolour to red wines, exhibits an absorption-spect rum cliaracteri sed bytwo distinct bands. The author finds that a white wine to which analcoholic infusion of the root has been added, gives this spectrum un-changed; the colouring matter present in pure red wine, whichprevents the recognition of the characteristic bancis of thc juice of thebeet when present a s an adulteration, may be removed by means oftannin and gelatin (Faure’s reagent, which leaves the colouring matterof the beet unchanged. Characteristic modifications of the spectrumare determined by cupric sulpliate, the alkalis, and other reagent<.These are carefully described by the author as affording additionalevidence of thc presence of beet-juice. c. 1’. c

ISSN:0368-1769    

DOI:10.1039/CA8783400164

出版商:RSC    

年代:1878

数据来源: RSC

摘要:

168 ABSTRACTS OF CHEMICAL PAPERS. T e c h n i c a l C h e m i s t r y . Purification of Water for Boilers by Haen’s and Bohlig’s Pro- cesses. By %‘ E RD. F I s c H E R (Diy~yZ. Polyt. J., ccxxvi, 94-100) .-The following are analyses of water before (I) and after (11) the purXying process by Hazn’s method, and 111 shows an analysis of water in a, boiler at work :- 1 litre contains- I. Chlorine ................ 22 mg. Sulphnric anhydride ...... 55 Nitric anhydride.. ........ 42 Nitrous acid. ............. trace Ammonia ................ slight, trace Organic matter .......... 35 Magnesia ................ 9 Lime.. .................. 175 Percipitated by boiling : Lime.. .............. 141 11. 78 trace 41 strong trace 33 trace 80 111. 2765 147 1260 trace 0 trace 2240 very large trace Qr, CaC03 ............252 0 0 CaS04 ............ 83 trace 250 Na,S04.. .......... 11 0 0 ............ trace MgCI, 21 trace CaCI, .............. 0 121 4236 NaY03.. .......... 66 65 1983 The barium chloride employed contained BaCI, 82.18 ; CaC12 0.39 ;TECHNICAL CHEMISTRY. 169 MgCl, trace ; insoluble 0-48 ; water 15.71 ; chlorides of alkali-metals 1-24, The purified water reacted nentral, and still contained some sulphuric acid, as sufficient chloride of barium had not been adclcd. It is advisable to add sufficient lime, after the addition of the barium chloride, to make the solution alkaline, so as to prevent the chlorides, he., from attacking the cocks and sidcs of boilers. A sample from another person had the following composition before (1) and after ( 2 ) :- 1 litrc contzzins- 1.2. Chlorine.. .............. 142 mg. 391 mg. Sulpliuric acid ............ 209 0 Nitric acid ................ 63 G 0 Nitrous acid .............. trace trace Ammonia ................ 7 9 Baryta .................. 0 53 Magnesia ................ 22 12 Lime ................... 294 241 Precipitated by boiling : Organic matter.. .......... i’7 39 Lime ................ 137 Magnesia ............ trace One litre of purified water showed by neutralisntion that it was equivdcnt to 21 mg. hydrate of carlcium, or 1 7 mg. of hydrate of magnesium. CaCO3 CnS04 CaC1, MgC1, BaCl, MgH,O, 245 341 3 3 52 0 0 0 0 477 0 7 2 1 7 The followiiig may be taken as the composition :- The chloride of barium used bald the annexed composition :- Chloride of barium 76.75; chloride of calciuin 1-86; chloride of magnesium trace ; water i9.72 ; chlorides of alkali-metals 1-67.‘llie water is heated, and the chloride of bariurn and lime added. I n three or four minutes tlie solution kmc;mes clear, and the purification is perfect. The aiitlior then deals with Bohlig‘s preparation, and combats at tlie same time the remarks of the manufacturers of this article on tlie HaBn process. He finds the preparation called “ Bohlig’s A!Iagnesia prepara- tion,” to consist of burnt magnesia. The use of it requires a consider- able time for the clearing of the liquid, and carbonic acid lias at times t o be passed through the liquid to separate the lime. Much magnesia is introduced in this process, and altogether tlie author considers the HaEn process to be the better, aiid advises, if magnesia has to be used, t o employ ordinary magnesia, and not the costly prepwation of Uohlig.S. Manufacture of Iodine. Ry C. C. STANFORD (Dit~gZ. polyt. J., ccxxvi, 8&-94).-After a short history of iodine and an account of the fluctuations of the trade in kelp and iodine, the autbor goes on to describe the manufacture of this latter substance. The kelp is broken up into fragments, and the soluble matter extracted by water.170 ABSTRACTS OF CHEMICAL PAPERS. This solution is evaporated, allowed to stand a t 40" or 45" F., and the crystals whicl) form are fished out. At 62" F. a hard salt, containing 50 per cent. of potassium sulphste, together with Glauber's salt and sodium chloride, is deposited. The liyuid is again heated, when tlic kelp salt (sulphate of potassium and sodium) again forms.The liquid is again cooled, and so on. The resulting liquor is mixed with + Nordhausen sulphuric acid (145" F.) ; oxide of manganese is atldecl, and on distillation iodine is obtained ; afterwards, on addition of niow oxide, bromine comes over. The author Yefers t o the fluctuation in the demand for kelp in con- sequence of the discovery of Spanish soda aiicl the Stassfurt salt de- posits. He shows that about 0.16 per cent. of iodine is got from kelp. The quantity of iodine in the sea is as 1 : 250,000, or 1 cuhic milc con- tains 11,072 tons. Other chemists estimate the proportion to be 1 : 30,000,000. Seaweeds possess tlie power of taking tlie iodine from the sea-water, but in different degrees, as the following table will show.Thev take UB ten times more iodine than bromine. of.dried a l p contain- 100 parts Lam. digitata.. ............ ,, saccharina ........... FUCUS serratus ............ ,, nodosus ............ ,, vesiculosus .......... Zostera niariiia ............ Rhodomcla pinnastroydes.. .. Hyderix siliquoso .......... Hymantlialia loreo. ......... Chordaria flagelliformis .... Cladophlora glornerata ...... Sarphat. 0 -135 0 -230 0.124 0 '001 0.0005 - - - - - - 3chmeit- zer. Stanford. These specimens came from Larne, Ballina, Sligo, Galway, Shet- land, Tyree, Coll, Colonsay, from the Isle of Man, Denmark, &c. The first five are those from which kelp is gcnerally made. The best is the Lcrrni.i.iaria cligitata, which grows on rocks and always undcr water.Tlie laminaria? in general form the best source and are found thrown on the shore by storms. The rest are cut generally as they rise out of water and are poorer in iodine. The method of preparing kelp is wasteful in the highest degree. Exposed to weathering, heated too stroi~gly in burning, and mixed with sand, the product does not contain what more careful manipulation would render certain. The author read a paper before the Society of Arts (Chemical News, March, 7 862, p. 167) in which he describes a method of destructive distillation. The pro- ducts were ammoaia, naphtha, tar, acetic acid, &c., and a coke or char- coal, which gives by treatment with water the compounds of iodine and other bodies. The charcoal then left resembles animal charcoal in appearance, costs only 2 as much, and is a good deodorizer-TECHNICAL CHEMISTRY.171 ~~ 21-6 34 0 40-2 41.3 28’0 - - - Laminaria. Carbon .................. 52.54 Phosphate ................ 10% Carbonate of lime. ......... 15.56 ,, magnesia. ..... 11.34 Alkalis .................. 5.70 Alumina ................ 3.94 L Sulphate of lime .......... 67.9 5 0 . 2 34.2 30.0 12% - - - Fucus. 70.32 1.90 10.35 7.92 1.93 1 -84 5-74 100.00 100.00 S. Decomposition of Soda-waste for the Production of Sul- phur. By CARL KRACJSHAAR (D17agZ. pdyt. J., ccxxvi, 41%- 41S).--Schaffner’s melhod (Dhgl. 1869, cxcii, 308, and cxciii, 42) is to throw the residue in hcaps, and after leaving it Some months, to strew these heaps about, whereupon chemical action sets in.The author has in this paper followed out this chemical action, and for t)his purpose took a sample, 1 yard below the surface of the heap, and treated 1.5 kil. with 850 C . C . of water ; 30 kil. of the same sample he made into a little heap, and after half an hour treated a second portion with 850 C.C. of water. A 3rd, 4th, 5th, 6th, 7th, and 8th samples were taken at intervals of 1 liour and treated with matcr as before. The samples were left for 24 hours in the wa,ter and the solution con- taine d- First qnant i ty ........ After + hour .......... )) 1& ,, .......... )) 24 ,, .......... )) 3% ), .......... )) 4* ), .......... ) ) 5+ ), .......... ,, 6 + , , .......... Sample No. 1. 5.6 33 ‘0 31 -3 21 -5 14 -6 - - - No. 2. 10 -5 15 *8 25 *6 28 *7 59 ‘2 - - -I 7 2 ABSTRACTS O F CHEMICAL PAPERS.First quantity ........ ,Qfter hour .......... ,, 1i ,) .......... ,, 2 i ,, .......... ,, 3+ ), .......... .. 5Q )) .......... ) ) GB ), .......... 4" ) , 2 , , . . . . . . . . . . No. 3. No. 4." 12 *7 20 2 51.8 79 -1 77 -0 83 *O 86.2 - It can be seen from this that the snlph-hydrate forms tlie greater I n This salt is proportion before tlie air is admitted and oxidntiori conirncances. the later stages CaX203 is the most abundant compound. probably formed as follows :- CaH2S, + 0 = H,O + CaS,; CnS, + 0, = CaS,O,, or CaH& + 0, = CaS,C13 + H,O. Thc sulphiclc in the fresh soda-residue is undoubtedly CaS, but this, by the action of water, is converted into CaH& : 2CaS + H,O = CaH2S2 -t CaO, When this has taken place the heap is broken up and air admitted, when the reactions already given cornmencc.If we can stop the oxidation at such a point that the polysulphicles, the suJp?l-i-hydrate, and the thiosulphate are present in such proportions as give the following reactions, we get the greatest yield of sulphur :- CaH2Sz + CaS203 + 4HC1 = 3H20 -t 2CaC1, + S1, and 2CaS2 + CaSgOJ + GHC1 = 3CaG12 + 3H20 + S,. I f the oxidation goes beyond this, the quantity of so:uble sulphur decreases, as sulpliite and sulpliate of calcium are formed. The quan- tity of sulphur in thc solutions of tlie four samples, which were taken from different parts of the heap, and which thus show that the heaps have not a uniform composition, was as follows :- * This sample was taken nearer the surface of the he:ip.TECHNICAL CHEMISTRY.Pemeiztnge Amount of Sui$hur. 173 First quantity .......... After + hour.. .......... ), 18 )) ............ )) 29 ,, ............ ), 3% )) ............ )) 4+ ,) ............ ,) 54 .............. .. 6+ .............. 1. 2. 3 *24 3.03 2 9 6 3 '00 3.04 - - -- 3. 4. 2 -60 2 -58 2 .El5 2 '73 2 '13 2.19 2 -25 - When the CaSzOj is present in slight excess, above the quantity shown by the above equations, the precipitation can be performed in open vats instead of being precipitated in closed vessels as in the Schaffner process. The process, as carried out a t Thann, takes place in a vat 2 meters in diameter and 1.5 meter deep. The liquor passes into the vat just above the bottom, and the hydroclJoric acid enters by a wooden pipe, which is so arranged that the hydrochloric acid and the liquor impinge together on the bottom of the vat.The vat is half filled with water and then heated by steam to 70". A stirrer is set in motion, and the hydrochloric acid and liquor allowed to enter in such pr-oportions tlint the mixture is slightly acid. The overflow is situatcd about 3 c.m. below the edqe of the vat. The chloride of calcium and the sulphur pass out by this overflow. The vat' is always kept full, so that any sulphuretted hydrogen that' may be formed is decomposed before it rises to the surface in the sulphurous acid. An improvement on the above process is to add sufficient watcr to the fresh soda-residue in an iron cylinder to allow of the action of a stirrer, and then to treat it with steam a t 5 at. 90 per cent.of the sulphur can thus be brought into solution. The slinie from this is allowed to dry and then broken into lumps, when oxidation rapidly sets in. The result is then treated as bcforc. The author tliinks this would spare much labour. The solution of CaH,S2 obtained in this way could also be applied in tanning to remove the hair froin hides. It would do this in 24 hours and not harm the leather. x. Presence of Arsenic in the Sulphuric Acid Manufactured from Arseniferous Pyrites and in the various Soda Salts Manufactured from this Sulphuric Acid. By C. H J E J,T (DiqZ. p o l y t . J., ccxxvi, 174--181).--The author refers to H. A. Smith's book on the chemistry of the manufacture of sulphuric acid, and remarks that, though the quantity of arsenic in the pyrites is given, no special notice is taken cf the amount of arsenic in the sulphuric acid manufactured therefrom.1. Arsenic in ITOYL Pyl-ites.-The arsenic is probably present as (FeS.As), but fincly diffused, as it cannot be dissolved out by the solvents for arscnide of iron. Spanish pyrites gave 0.90 per cent. of arsenic, Westphalinn 0.30 per cent., and Norwegian only a, trace. Smith gires the following :-174 ABSTRACTS O F CHEMICAL PAPERS. Spanish ( a ) .............. 1.651 per cent. As,O, .. (6) .............. 1.745 .. I , West phali an .............. 1 -8 7 8 .. 7 7 Norwegian ( a ) , hard ...... 1.649 .. 9 , ? j ( b ) , soft ...... 1.708 .. 1, Richardson and Watts give in “ Chemical Technology ”- Spanish.. ............. 0.21 to 0*31 per cent.As Westphalian .......... trace Norwegian ............ - The method employed for the determination of araenic was fusion wit,h fusion-mixture and nitre, and precipitation of ammonia-magne- sian- arsenate. 2. Quantity of arsenic in sulphuric acid-- Present a s arsenic Arsenic. acid. Chamber acid ................ 0‘202 p. c. 0.040 p. c, Acid from Glover’s tower ...... 0.331 .. 0.041 ,, 9 7 Gay-Luasac’s tower . . 0.334 ,, 0.132 ,, The chamber acid, before einployrnent, in sal t-cake manufacture, is concentrated in Glover’s tower. A part of this acid goes to the Gag- Lussac tower for the purpose of absorbing the nitrous gases. These nitroiis gases oxidize the arsenious to arsenic acid, and this accounts €or the larger proportion of arsenic acid shown by the analyies, (A4sz03 + 2N,03 = As20S $.4NO). The total amount of nitric acid used in this manufacture is 1.62 per cent. of the sulpliuric acid pro- duced. Calculating according tlo the above equation aiid by the result of analysis, the loss of nitric acid due to arsenic is 3.18 per cent. of total sulphuric acid produced. Westphalian pyrites with 0.30 per cent. of arsenic used 1-32 per cent. (of nitric) of total sulphuric acid manu- factured, while, as above stated, with Spanish pyrites the proportion was 1-62 per cent, Other examples a’re, a t Preiberg, 1.7 per cent. of nitric acid ; arsenic iu sulphuric acid = -05 to *30 per cent. At Grew- enbruck, 1.10 per cent. is amount used ; the pyrites is poor in arsenic. At tJhe Rhenania works in Stolberg, 1 per cent. in amount, the pyrites poor in arscnic.In a chemical works a t Benel, where pyritcln with 1 per cent. to 1 ~ ~ 5 per cent. of arsenic, 1.5 per cent. to 2.0 per cent. of nitric is used. l’abulated, we have- Nitric acid need with pyrites poor in arsenic. Rich in amenic. 1*:-12 p. c. 1.10 ,, 1.70 ,, 1.62 p. c. 1-00 ,, 1.5-2.0 p. C. The last sulphuric acid chamber has the purest acid with, in case cited hy author, 0.019 per cent. of arsenic. This, by concentration in pans, can be used f o r many purposes to which the other cannot be applied, The passage from the fire to the Glover’s tower contains a white deposit with much arsenic. The longer this passage is the purer theTECHNICAL CHEMISTRY. 175 acid, as much arsenic is deposited. The burnt pyrites contain 0.19 per cent.of arsenic. Arsenic iw, the svlphnte and fiodn manufactured with this sulphuric acid. Smith found in the sulphate manufactured from sulphuric acid with 1.051 per cent. of As 0.029 per cent,, but found none in the soda. Fresenius has fouiid it; in both. The author found the sulphate quite free from arsenic. He thinks that the arsenic goes off as chloride, and that i€ excess of sulphuric acid be not used, the result will be free from arsenic. Arseuic i!v, Hydrochloric Acid from, Xodn-manufnct7cre.-The raw acid has much arsenic in it. The longer the passage from the hearth or furnace t o the condensing chamber, the freer the acid is from arsenic, as it is deposited on the way. Smith found 0.691 pcr cent. As203 in the hydrochloric acid. Pilhol and Lasassin Eound 0.081 per cent.As, 0.174 per cent., 0.428 per cent. ; so it can bc seen that quantity varies much. Amenic in chloride of lime win& f r o m this Iychochloric acid, none. S. Ultramarine. By J. PH I I, [ P P (Dh$. pohyt. ,J., ccxxiv, 635- 639).-The author notices somc experiments made t o ascertain if the oxxgen-compounds of sulpliur obtained by thc treatment of bluc ultra- marine with acids, are esseutial constituents of the colour, and to ascertain the relation between blue and green nltramarine (Dcut. (J"hew7. Qes. Iler., 1876, 1109 ; Chew. S'oc. J., l g i 5 , ii, :383). He conclndes that the sulphuric acid obtained by treating ultramarine witli hydro- chloric acid arises, in part a t least, from the dcconiposition of' penta- tlrionic acid formed by the action of sulphurous acid and sulphnretted hydrogen upon each other.Hlrie inltramarine, ignited in air and well washed, gave a tolerable amount of sulphuric acid; still more was found in a sample formed on the wdl of a sulpli>ate furnace. It thus appears that this acid, found when ultramarine is treatccl with acids, arises in part from over oxidation, by which some of the coloiir is decomposed. Repeated heating with water in a sealed tubc, even up to 200°, failed to remove the oxyyen-compounds completely. These compounds are not essential t o the constitution of blue ultramarine, for the blue variety can be ohtained from the green wit liout auy change in the distribution of the sulphur. Green niay be conver1t.d into blue ultramarine 'by the following, besides other methods : by repeated heating w i t h iodine in air; by heating to 140" or 160" with iodine solution ; by fusing wit,h boric acid, or by repeated evaporation with solution of this acid ; by heating t o 160" with water; by heating with concentrated ~olutions of some metallic salts.These changes find their simlilest cxplanstioii in the supposition that the green ultramarine lias lost sulph uric acid. When t'he method of heating to 160" with water is used, the blue product has the same composition and weight as the original, and the sulphur- compounds obtained on treating with acids agree exactly, whilst the water used in the tube takes up only small quantities of sodium corn- pounds. Hence the oxidation-products obtained from ordinary blue are by no means essential to its constitution.The difference between176 ABSTRACTS OF CHEMICAL PAPERS. blue and green ultramarine appears to be that the latter contains a little sodium sulphide, mechanically or chemically, which hides its colour ; on removing tliis the blue colour appears. On fusing blue ultjramarine with sodium sulpliate and charcoal, the green substance is obtained. Green ultramarine boiled with zinc sulphate solution increases in volume and becomes blue, zinc being taken up by the mass and much sodium passing into the solution. Blue ultramarine thus treated also takes up zinc without changing colour essentially j herc sodium is not removed simply, but free silica, alumilia, and zinc oxide, removable by alkalis, are found. J. T. Testing of Portland Cement. (Dlngi. pdyt.J., CCXXV, 565 570) .-Dyckerhoff (Jourtiul j2r Gmheleuchtuirg, 1877, 75) shows that the seven days' test of Portland cement is untrustworthy, and that the 28 days' test, ihough better than the first, does not indicate the bind- ing quality of the cement when mixed with sand. From results oh- tamed by adding four parts of sand to various ccrnents, arid determin- ing the tenacity of test-picces after one, two, four and twelve weeks, he recommends, as the best test, to add a considerahle amount of sand and test after 28 days. For good results the well burnt cement must be finely ground, C. Heintzel (hTotizb. des deut. Ver. fiw. Pahrik. won Ziegeln,, 1876, 199) concludes generally that : 1. Portland ceinent of proper composi- tion bccomes gradually harder, either in air or water.All oscillations in the tenacity of test pieces are due to faults in their preparation. 2. The greater the amount of water used, the less the tcnacity of the product. 3. The finer the grain, the greater the tenacity. 4. Of purc cements of the same grain, those which ha,ve the greatest tenacity will give similar results when mixed with sand. 5. The coarser the sand used, the greater will be the tenacity of the be't0'12 produced. 5. The tenucity can be determined after seven days by 1lichai':lis' absorption method, either for pure cement, or for mixed cement and sand. The specific gravitiy, determined by Seyer and Aron, ranges from 2.99 t o 3-08 The best method of testing is still an open question. Formation of Manganiferous Iron in Blast Furnaces.(Dim$. y o l y t . J., ccxxvi, 53-55) .-Ward compares the Austrian with the American processes. At Reschitza 1-37 tons (1400 k.) of manginese ores gave .98$ cwt. (50 k.) of manganiferous iron, 35 per ceiit. being manganese. The 1-37 tons contain 37.2 per cent. of htn2O3, or 25.89 per cent. of manganese = 362 k. (7.12 ewts.). The amount of manganese which passed into the manganiferous iron was -344 cwt. (17.5 If.). This shows that 95.5 per cent. of manganese passes into tlhe slag. The following is the composition of the mixtures fused in Austria:- J. T.TECHNICAL CHEMISTRY. 177 1 5 per cent. limestone. 85 per cent. manganese ores. ...................... For production of manganiferous iron with 25 per cent. of %In Por production of manganiferous iron with For production of manganiferous iron with The slag having a composition in the last case of- Silica .....................23.1 Lime ...................... 335 Oxide of iron ............... 11.6 AIumina ................... 6.1 7 9 7 7 ,, 29 per cent. of Mn ...................... 7 9 ...................... { :; 35 per cent. of Mn Hydrate of manganese ....... 2.5.7 The fluidity of slag depends on the amount of manganese in it, but on the other hand, ifthe slag be stiff, particles of manganiferous iron be- come enclosed. and so the loss is the same. I n America, Ward has obtained better results in a furnace 10.5 meters high, and with a blast, 76 mm. in diameter. The melting point of the slag is nearly the same as that of the metal. -After 3 months’ work, 270 k.(5.3 cwt.) of ore with 35 per cent. of manganese yielded 100 k. (1.9 cwt.) of mnnganiferous iron with 35 per cent. (1.045 cwt.) of manganese. This shows a loss of 59.5 per cent. (.8.55 cwt.) of manganese, or a yield of 58.1 per cent., or 12 times as much as ia obtained in Austria. S. Uses of Manganiferous Iron. (Chenz. Centr., 1877, 204).- Gautier believes that the niariganese acts as a reduciiig aqent, which removes iron oxide from the metallic iron, and prevents it fi.om becom- ing ‘‘ hot short.” Henderson, of Glasgow, discovered a process of preparing manganese-iron containing 25 to 75 per cent. of mangaiiese, thus lowering the cost of preparing manganiferous iron. The amount of manganese required for reduction is usually 1 per cent., if added as manganese-iron ; the rcsulting iron is extremely soft ; its coefficient of elasticity is 22 to 25 kilos.; its resistance to strain, 45 kilos., and its expansion, for 200 mm., 20 to 25 kilos. The p r d u c t of the resist- ance to strain multiplied by end-expansion is nearly 7 times that of ordinary iron, and more than twice that of hard steel. This iron is used in plating ships. Addition of li per cent. of manganese to inferior iron counteracts the influence of phosphorus. Addition of 1 per cent. of manganese to cast steel gives it great rcsisting properties. W. R. Chromium Crucible Cast-Steel. By S. KE R N ( C~EIU,. News, xxxvi, 198) .-Directions and receipts are given for manufacturing crucible steel from Bessemer steel, iron, chrome ore, and limestone. The product is good and the price moderate.It does not become hard by tempering. M. M. P. M.178 ABSTRACTS OF CHEMICAL PAPERS. Electrogilding by means of Potassium Ferrocyanide. By E. E B E R 11 AYE n (DkgZ. polyt. .J., ccxxiv, 63l--6%).-T0 avoid the use of potassium cyanide baths, the author dissolves 300 grams potassium ferrocyanide, 100 grams of potassium carbongt'e, and 50 grains of s d - ammoniac in 3-& litres of water at, 39" to 40" C. To this is slowly added 200 C.C. of neutral gold chloride solution cnntaiiiing 20 grams of gold; after boiling about 30 minutcs, and leaving the solution to cool, the liquid is filtered and made up to 5 litrcs. To increase tlie conductivity and t o prevent tlie separation of iron oxide a t the anodc, a littlc potassium cyanide is added.TVhen about 0.4 of the gold has been deposited, tlie bath is renewed by adding a second 2Q0 C.C. of gold- solution aid proceeding as at first ; this can be repeatetl. three o r four times, after 3vliich it is necessary to add about 30 grams of ferrocy- anide and tlie same proportion of the other salts. This rcnewitig is repeated as long as good results arc ohtained. Tho gold froin spent liquids is recovered, aftel. filtering off any separntctl iron oxide, by depositing 011 a largc copper plate totally immersed as cstlioclc. With the same current a warm bath gives a more copious deposit than a cold one. From many experiments the author concludes that, in a bath rich in gold, very little of the anode is dissolved, whilst the latter is more strongly attacked in a poor bath, so that a plntinum anode may be used with a rich bath.J. T. New Method of recovering Gold from Toning Baths. Ry FR. HAUGH (Chenz. Ceictr., 1877, 201).--'l'he liquid is filtered into a flask of white glass, made alkaline with sodium bicarbonate, a i d coloured deep red with solution of aniline red. On exposure to light for 6 o r 8 hours, the gold not used in toning is precipitated as a violet powdcr. The supernatant fluid is ponred off, and whcn a saficient qimntity of the powder has been collected, it is transformed into gold chloride. ?V. R. Drawing of fine Platinum Wires. By A. GAIFFE (C0~7pt. rend., lxxxv, 625).-The author has so arranged an apparatus for drawing fine platinum wires, that they are protected from contact with any parlicles of clust that nray be floating in the air.This permits of wires only &- of a millimeter in diameter, to be drawn without rnp- turing at the draw-hole, an effect traced to the contact of foreign matters. R. R. Purification of Coal-gas. By H. RUNTE (Ohern. Cent?.. 1877, lS5-192).-1. The ammonia existing i n the gas-water is too dilute t o be used with profit for purifying the gas. IC does not contain enough NH, to absorb CO, and HzS, even though acid salts were formed. This is, however, not the case, as the temperature of the water is so high :is to decompose any acid salt that might be formed. The '( regenerating " of dilute gas-water involves an amount of fuel disproportioned to thc irripurities it, absorbs ; consequently (a), a stroiig ammoniacal liqnor, prepnred by known methods, should bc used ; the strength of tliis liquor should be about 36.21 grams, or 47-46 litres NH, per litre of liquor ; it then absorbs 39.2 ~ 1 * i ~ ~ ~ s , or 19.8 litres of COz, arid 14.8 grams or 9.7 litr-s of H2S.By Hill's recovery processTECHYICAL CHEMISTRY. 179 $ OF the carbonic acid and 9 of the sulphuretted hydrogen arc re- moved from the liquor, which is passed over iron oxide to free it com- pletely from sulpliuretted hydrogen. The liquor intended for the purification of the gas is not to be allowed to mix with the gas liqnor. JV. a. Purification of Gas. By H. SCHWARZ (DinyZ. p o l y t . J., ccxxvi, 307) .--The author suggests a centriiugal machine for the scparation of tar from gas. A fan with sieve-like vaiies revolves at high speed.The gas enters a t the centre of the case surrounding the fun and passes out a t the opposite side. The globules of tar are brolien by the wires of t'he sieves and the tar is thrown to tlic periphery, where it ag- glomerates into liquid tar. centre on opposite side to the entrance t o avoid the sucking-in of gas, which would result The gas passes out if the gas were allowed to escape at the periphery. S. Two Methods of getting Sugar from Molasses. By H. SCHWARZ (Dingl. polyt. J . , ccxxvi, 182-193 and 4(34--412).--The amount of molasses yearly produced in Europe from beet-root is ~7ery great. The author reckons that 250,000 tons of molasses are yearly produced, and this is equivalent t o 125,000 tons of crystallisablo sugar. He considers this equivalent t o a loss of S265,OOO ycwly.Several chemiFts have tried to attack this question, some by cndeil- vouring to precipitate a compound of sugar with lime, baryta, and strontia ; others by endeavouring t o get rid of tlre impurities which prevent the sugar from crystallising. The former methods me costly, and the latter cause much loss. The best method inicler the latter plan is t h a t of osmose proposed by Dubrunfaut. Warm pure water and concentrated solution of molasses are dialysed through parch- ment paper. Some of the molasses goes to the water and some of the water to the molasses. The chief part of the salts and a small quan- tity of sugar pass into the water, and the remaining solution contains the sugar in a crystallisable state. 15 per cent. of the molasses is thus made useful as crystallised sugar.Dr. Stammer saw that the diffeyence of sugar and salt in dialysing power was not sufficiently great to give good result's, arid he proposed the addition of lime to the molasses, so as t o make its passage through the parchment more difficult. The author, by means of' a dinlysing apparatus (see Dingl. poZyt. J., 1875, ccxviii, ZlS), has made many experiments on this method. (1.) Dialysis of pure Sz~grnr.-lOOgrams of loaf-sugarwere dissolved in 0.5 litre. As 400 C.C. = 80 grams of sugar in the apparatus, 460 C.C. were employed outside. After IG hours there were 540 C.C. with 60.75 grams sugar inside, and 320 C.C. with 19.20 grams of sugar out- side, In this time, therefore, 19-20 grams of sugar or 24 per cent. had passed through the parchment. The size of' paper was 1388 q.c.I n 1 q.c. -9 mg. of sugar passed per hour. (2.) Pwe Suym- with, Lime.-To 67.2 grams of s u p r 7.168 grams of lime were dissolved, or 3 eq. of sugar to 2 eq. of lime. 320 C.C. of sugar solution were put in the centre of apparatus, and 440 C.C. of water outside. After 18 hours there was in the centre part of the appa- ratus 58.05 grams sugar in 460 C.C. of solution ; outside 320 C . C . with180 ABSTRACTS OF CHEMICAL PAPERS. 6.750 grams of sugar. Inside there was 6.025 CaO; outside -432 gram of' CaO, 11.8 per cent. of sugar diffused, and 1.7 per cent. of lime. For 1 q.cof parchment 0.02 mg. diffused. (3.) iWolass~s from a Sugar .ieJiizery was dissolved in water, and lime added. and filtered. A portion after separation of lime gave 24.15 per cent.of solid matter, or 15.01 per cent. of sugar, so that of the solid substancc 61.3 per cent. was sugar. The percentage of salt was 22.0. After 12 hours there was- Solid matter. Sugar. Sugar qnotient." Per cent. Inside ........ 17.0 11.77 69.2 Outside ...... 6-25 3.01 49.6 so that the amount of sugar had rclatively increased. (5.) Molasses saturated with lime and dialysed with flowing water. The outer part of vessel was so arranged that fresh water ran through it constantly but slowly. This flowing water was evaporated after the process was finished, and both portions were analysed :- Solid substance. Sugar. Sugar quotient. Centre of apparatus ...... 16.00 11-40 71.2F; Outer portion of apparatus 28.00 7.0 25.00 (6.) The molasses from the inner portion dialysed again with running water :- Inner portion ...........14.6 11.4 78.0 (7.) Raw molasses from Barzdorf, in Austria, Silesia, contained- Solid matter. Sugar. Salt. Sugar quoticnt. Salt quotient. 78.9 43.6 10.0 55.1 23.0 (8.) 80 grams of the molasses was dissolved to 200 C.C. without lime, and placed in the inner portion of the apparatus. 400 C.C. of water in outer. After 16 hours 350 C.C. foundin the inner and 250 in the outer portions :- Solid matter. Sugar. Salt. Sugar quotient. Salt quotient. Inner.. ...... 10.83 6.03 1.17 55.7 19.2 Outer ...... 8.90 4.56 1.44 51.2 31.6 grams of sugar and 8 grams of salt, there wcre found :- Of the 80 grams of molasses with 63.12 grams of solid matter, 34.86 Solid matter. Sugar. Salts. Grams.Per cent. Grams. Per cent. Grams. Per cent. Inner.. .. 39.6 = 62 7 22.00 = 63.2 4.27 = 5:3.3 Outer.. .. 23.0 = 36.5 11.81 = 33.9 3.73 = 46.6 From this it may be seen that the principle of dialysing with a neutral solution is wasteful, 33.9 per cent. of sugar has to be lost in order to get rid of 426.6 per cent. of the salts. (9.) The same molasses (7) was rubbed with excess of lime, and after removing the lime from a portion, the amount of solid matter, * The sugar quotient is the percentage of sugar in the solid substance.TECHNICAL CHEMISTRY. 181 sugar, and salts was obtained. 220 C.C. of lime-molasses was dialysed with 400 C.C. of water for 16 hours. I n the portion employed there were 35.69 grams of solid matter (26.60 grams sugar and 4.36 salt) :- Solid matter.Sugar. Salts. Grams. Per cent. Grams. Per cent. Grams. Per cent, .... Inner 27.5 = 76.7 20.60 = 80 2.06 = 46.8 Outer .... 8-34 = 23.3 5.13 = 20 2.34 = 53.2 In this latter the sugar quotient is 74.9. (10.) Molasses with much lime dialysed for two days with running water :- Solid matter. Sugar. Salts . Grams. Per cent. Grams. Per cent. Grams. Per cent. Inner .... 63.073 = 74.5 43.713 == 90.6 3.203 = 32% Outer.. .. 21.527 = 25.5 4.496 = 9.4 6.615 = 67.4 The sugar and salt quofients (or percentage of sugar and salt in the solid matter) were :- Sugar. Salts. Interior .......... 69.3 7.3 Outer .......... 20.9 14-7 The product crystallised easily and well. (11.) A similar experiment gave:- Solid matter. Sugar. Salts. Grams. Per cent. Grams. Per cent. Grams.Per cent. Inner.. ...... 37.6 = 59.6 31.5 = 79.3 1.856 = 20.6 Outer.. ...... 25.5 = 40.4 8.2 = 20.7 7.130 = 79.4 Sugar quotient. Salt quotient. Inner ............ 83.8 5.9 Outer ............ 32.1 86.9 (12.) An experiment in which st little more than 1 eq. of lime was added to 1 of sugar, gave:- Solid matter. 8 ugar . Salts. Grams. Per cent. Grams. Per cent. Grams. Per cent. } 63.2 34.88 8.04 80 grams of molasses.. Inner.. .... 39.65 = 62.0 24.79 = 68.00 3-42 = 41.6 Outer. ..... 24.30 = 38.0 11.66 = 32.00 4.70 = 58.4 I n n e r . . .......... 62.5 13-7 Outer.. .......... 47.9 40.3 Sugar quotient. Salt quotient. (13.) The same with running water:- Inner.. .......... 77.2 3-13 Outer.. ......... 30.3 89.60 (14.) The outer solution in (12) was evaporated, lime added, and dinlysed with runnihg water :- VUL.XXXITI. 0182 ABSTRACTS O F CHEMICAL PAPERS. Solid matter. Sugar. Salts. Grams. Ycr ccnt. Grains. Per cent. Grams. Per cent. Inner.. .. 41.20 = 56.2 20.120 = 89.9 5.360 = 31.4 Outer.. , . 32.06 = 43.8 2.314 = 10.1 11.400 = 68.6 Sugar quotient. Salt quotient. Inner ............ 48.8 26.6 Outer ............ 7.2 4920 (15.) Nothing particular. (16.) With a large quantity of lime (as much as can be added) and rlialysing with running water, the author got one of the best results. With a sacrifice of 10.5 per cent. of sugar, 65.3 per cent. of non-crys- tallisable sugar (Nichtzucker) and 81.6 per cent. of salt separatcd :- Solid matter. Supr. Salts. Inner ........ 78.78 56.27 2.74 Outer ...... 39.22 9.75 12.17 Grams. Grams. Grams.Sugar quotient. Salt quotient. Inner ............ 71.4 4.8 Outer ........... 17.2 180.0 (17.) Nothing particular. (18.) In order to find the amount of salt that passed out of the sugar in stated times, 200 grams of molasses (with 157.8 grams of solid matter, 87.2 sugar, and 20 grams of salts) werc shaken and saturated with lime and then diluted to 3% C.C. This was dialysed, the outer solution taken away and analysed after three hours (A), then after a second three hours (B), and at end of 16 hours (C). The inner solutioc was analysed at the end, too :- Solid matter. Sugar. Salts. Grams. Per cent. Grams. Per eciit. Grams. Per cent. A , . .... 20.23 = 13.1 4.5 = 5.1 6.24 = 34.0 I B.. .... 14-91 = 9.1 5.4 = 6.1 3-76 = 20a-5 C.. .... 19.54 = 12.6 10.8 = 12.3 2-94 = 16.0 D...... 99.52 = 65.2 67.2 = 76.5 5.40 = 29.5 Sugar quotient. Salt quotient. A .............. 22.1 138.7 B .............. 36.2 69.6 C .............. 55.2 27.2 D.. ............ 67.5 8.0 This shows that the salt passes out in largest quantities in tlie first The author draws the following conclusions :- (1.) The diffusion of sugar by the addition of lime is made slower. (2.) The lime-holding molasses gains a higher sugar-quotient reln- tive t o the salt quotient by diffusion, and this result is better tIhm when neutral molasses is dialysed. six hours. (3.) Running ivvttter acts better than standing water.TECHNICAL CHE'MISTRY. 183 (4.) In general 70 to 90 per cent. of thc salts are successfully got rid of, with n loss of only 20 to 30 per cent. of the sugar. The re- maining sugar is then in a condition t o crystallise to some extent. (5.) The sugar or molasses which passes'into the outer liquid can, by evaporation and addition of lime, be again dialysed and more sugar recovered.The success of the above experiments encouraged the author to make experiments on a larger scale. The following is a brief descrip- tion of the apparatus:-A long four-sided box, lined with galvanised iron, is provided with two tubes or pipes. One conducts the niolasses to the bottom of the box ; the other is an overflow pipe. In this box, wedged in, are a number of cells of the following construction :-A frame of wood 80 mm. wide has a parchment sheet laid on each side. Two frames, screwed, one on each side, fasten the parchment in its place and make this box water-tight at the joints.The edges of the parch- ment, where they rest on the frame, are covered with linseed-meal to make it even t,ighter. Into this cell n tube passes through the wooden frame and allows water t o enter at the top of the cell. Another pipe leads the water off from the bottom of the cell. As the dialysis goes on, the salts pass into the water which sinks, and more fresh water entering at the top, it is forced out by this pipe. The authorthinks it preferable t o have a series of water cells, so that as one loses in dialys- ing power, a new one can be put in. As a sign of the molasses being puritied, the sp. gr. can be taken. The supply should be so arranged t'hat the molasses which passes off at the overflow should have a sp.gr. of 12" to 13" B. When the molasses is dialysed, the question is the getting ridof the lime, Ton Sebor has proposed to add i t to the liquor from the beet- root in the manufacture of sugar. The result is to give a, bad colour to the sugars. On evaporation the lime settles out as a slime, taking with it some of the colonr of the molasses. The liquor is filtered through bone- ashes, and then evaporated to crgstallisation. The author has tried it in two or three manufactories with varying success. I n the method above described, the salt and much su,yar are lost, and so, after a great many experiments, the author suggests a new plan. The molasses is diluted with 50 to 60 per cent. of water with gentlc heating. On cooling, a quantity of lime equivalent t o the potassium oxide in the molasses is added.An analysis has to be made to deter- mine this, or it may be assumed that the molasses contains 10 per cent. of soluble salts, and that 60 per cent. of this is carbonate of potassium. Sufficient sulphuric acid (diluted and cooled) is then added to preci- pihate a double salt of potassium and calcium. Instead of adding lime, gypsum may be used, and then only so much sulphuric acid is added as will convert the carbonate of potassium into sulphate. Magnesium sulphate can also he used, and this promises to give good results when it can be obtained cheaply, as near Stassfurt. The precipitate of sulphate of calcium, potassium (and in cases of magnesium), is very rich. Part of fluid is filtered off, and the rest pressed out of the precipitate.Thc liquor is cleared of lime by car-184 ABSTRACTS O F CHEMICAL PAPERS. bonic acid and heating. abn ndance of sugar-cr y stals. The liquor on being left at 40" deposits The following are laboratory experiments :- (1.) 400 grams of molasses mixed with 150 grams of water, 12 grams of lime dissolved in 50 grams of water added (3 per cent.), and then 40 grams (10 per cent.) of sulphuric acid in 80 grams of water added. The precipitate after pressing weighed 100 grams, and contained 16 per cent. potash, equal to 4 per cent. of molasses. (2.) In a similar experiment in which 3.83 per cent. of potash was found. (3.) 300 grams of molasses dissolved in 90 grams water ; 39 grams of magnesium sulphate dissolved in 60 grams hot water added ; and then 25.8 grams of gypsum, 71 grams of pressed precipitate was obtained.In this was found potash amounting to 3.63 per cent. of the molasses used. (4.) 300 grams of molasses, 150 grams water, 39 grams of bitter salt, and 30 grams of gypsum. 90 grams of precipitate, with potash, equal to 4.18 per cent. of molasses. I n the Klein-Kletschkau manufactory, near Schweidnitz, experi- ments were carried out on the sulphate of magnesium and gypsum principle ; 50 cwt. of molasses were employed. 18 cwt. of moist pre- cipitate were obtained. From one experiment 6 cwt. of sugar were obhained. I n another, owing to the temperature, although performed in a vacuum, inversion set in, and the sugar would not crystallise. S. Behaviour of Wool towards an Ammoniacal Solution of Fuchsine.By R. BOTTGER (Chew%. Centr., 1877, 576).-A colonr- less Qmmoniacal solution of fuchsine dyes wool red. It has been supposed that the wool causes the decomposition of a compound formed by the action of ammonia upon fuchsine; but the author's experiments showed that fuchsine is merely mechanically dissolved by ammonia; when wool is soaked inthis liquid, the ammonia evaporates. M. M. P. 31. Glazing of Paper. By C. WURSTER (Dingl. polyt. *J., ccxxvi, 75 -82, 310-316, and %1--389).-The old method of sizing or glazing paper was superseded by the method of mixing a resin soap with the pulp, and then precipitating by alum, The theoretical opinion is that a salt of aluminium with the acid of the resin is formed, and that this closes the capillary pores of the paper. The author of this paper considers, however, from the following reasons, that this is not the correct view.When, as in the glazing process, an excess of alum is added to the resin- or fat-soap, a thick, gelatinous precipitate is obtained. This, by treatmcnt with warm alcohol, or with ether or chloroform, yields up the resin, which can be reprecipitated by water, or recovered by evaporation of the solvent. A different result is obtained when an excess of resin-soap is used. In this case a true aluminium salt is formed, which does not yield up its resin. From this it can be seen that alumina decomposes this salt. Another proof lies in the fact that the ash before and after treatmentTECHNICAL CHEMISTRY. 185 of the glazed paper with ether is the same, free resin being alone extracted, and then the paper allows ink to run. Ash before Substance treatment with Ash after.extracted. I.. ...... 1.68 ether 1-63 3.35 11.- ...... 2.29 ,, 2.19 4.72 111. ....... 2.19 ,, 2.18 3.70 IVa ...... 1.93 ,, 1.81 4.*w IVb ...... 1:95 benzol 1-88 4.59 V.. ...... 1.71 ether 1-66 2.11 The author shows, too, that an ethereal solution of resin will glaze paper, but the aluminium salt remains as a powder on the surface. 'l'he alkaline salt of resin or colophoniuni is easily decomposed by COa in water, a milk resulting. This consists of finely divided particles of resin. The addition of starch makes it less easy for the resin to agglomerate, and the action of the hydrate of aluminium or of basic sulphate of aluminium is the same. Free resin acid, or acid of colophonium, does not glaze paper well.In summing up, the author observes that, to obtain a good result', there must be as much free resin present as possible, and to obtain this he recommends the addition of sufficient excess of alum to produce free resin and a basic sulphate of aluminium, the water having a neutral, or slightly acid reaction. The resin used in the glazing of paper is colophony, the dry residue left in the distillation of turpentine. It consists mainly of sylvic or abietic acid, C20H3002. It varies from light yellow t o dark brown in colour, according to the method pursued in the process of distillation. An American specimen began to soften at 54" ; it retained this tem- perature for some time ; at rj5" it was softer ; at 63" it formed a thick fluid.The temperature then rose rapidly to 90", when the substance was quite liquid. Powdered colophony unites into a cake when ex- posed to summer heat. The sp. gr. of the resin is 1-07 to 1.08. The art of glazing the paper consists in filling up the capillary pores of the paper with resin. The substances chiefly used for dissolving the resin are caustic soda, Crystalline carbonate, and calcined carbonate of sodium. Theoretically the solution by caustic soda is the best, as the alkali is purified by t'he precipitation of the carbonate of calcium during its manufacture, the latter carrying all the impurities down with it. Caustic soda, however, acts very injuriouslyon the paper, if it be present in excess. Calcined soda is most frequently adopted. Impurities are present to a large ex- tent in this substance, so that not only is a chemical analysis requisite to ascertain the amount of soda in each sample, but a solution has t o be made, and the impurities filtered off.Crystallised carbonate of sodium appears to be the best, but then its price is high. The author recom- mends manufacturers to prepare crystallised carbonate from the cal- cined soda. The proportion of soda to resin depends on the nature of the required product. The addition of sufficient soda to dissolve all the resin, though unnecessary, defines one limit of the quantity. The amount of soda necessary to dissolve the resin and to take up the rest186 ABSTRACTS OF CHEMICAL PAPERS. mechanically is the other limit,. formula, G2,H,,)O2, we have this reaction- Assuming resin to be an acid of the 2CzcH3,O, + Na,COJ = 2C,,H2,02Na + GO, + H,O.The molecular weight of the CnoH300, is 302 ; of the carbonate, 106 ; and of crystallised carbonate, 286. From this we get the proportions of 100 of resin to 16.5 of anhydrous, o r 45.6 of crystallised carbonate. As the resin is never pure, this becomes 40 to 41. The amount of free resin that can be taken up by the sodium salt of resin is not quite known. Muller (i?a,bdcation des Papieres, Berlin, 18'17) gives the pro- portions as 100 of resin t o 25 of soda (crystallised). The soap result- ing from this contains therefore, 35 to 38.5 per cent. of free resin. The solution of the resin takes place in copper vessels. The different methods of making the glaze depending on the differ- ent proportions of resin and soda, can be clmsified under two heads :- 1.The production of a salt< of sodium which is entirely soluble in water. 2. The production of a resin-soap, with much free resin, ~ l i i ~ l ~ on dilution is precipitated, and gives a milky appearance to the solution. The production of the resin-soap for the brown glaze is very simple. 40 to 42 of crystalline, or a proportionate quantity of calcined soda is dissolved in 80 to 150 litres of water, and heated to boiling. 100 k. of resin are added and broken up. As soon as the resin melts, carbonic acid is evolved. The process takes from a quarter of an hour to one hour. A specimen of the soap added to distilled water should dis- solve completely. The soap is allowed to stand, and the supernatant liquid taken off.If the soap requires to be washed for the removal of some of the colour, the author suggests the solution in a little water with soda, by aid of gentle heating. The soap can be againpreci- pitttted by addition of chloride of sodium. This repeated several times removes much of the objectionable colour. For the glazing of paper of medium thickness, 5 t o 6 k. of resin to 100 k. of paper are required. The soap is dissolved in water, with the addition of a little starch, and then filtered. More important, but also more difficult, is the preparation of the white glaze. It can be prepared in three ways :--1. By treatment of the resin with a quantity of alkali lnsufiicient to combine with it chemically. 2. Treatment with excess of alkali, but stopping tlhe action when a certain quantity of free resin is present, and then removing the excess of alkali by skimming.3. By production of ft perfectly soluble resin-soap, and addition of free resin to it. The first and second are used in the manufactory ; the third is not. In the brown glaze the concentration plays but an unimportant part, whereas in the preparation of the white glaze it is very important. The first method is t o be considered here. The view of the author that the glaze is better the more free resin it contains, makes it import- ant to add as much free resin as possible. The amount of free resin depends on the degree of eoncentration of the soap. The concentra- tion of the soap by hcating over fires is recommended as an easier plan than the employment of steam, especially if the latter be of low pres- sure.This is the brown glaze. This is the white glaze.TECHSICAL CHEMISTRY. 187 Good results are obtained by heating 65 litres of water by steam, adding 34 k. of soda, and then slowly 100 k. of resin. The heat being continued, carbonic acid is slowly evolved, and the operation lasts fyom 1 to 3 hours. The heat has to be still continued, in order to dissolve the free resin, The soap is ready when, on being taken out on a spatula, it shows the following properties. A clear, transparent, thick liquid, without bubbles, brcak- ing off short, and not drawing out into threads. On addition to ail equal volume of hot water, it should assume a brownish, gelatinous appearance, and not show yellow stripes.A portion stirred in luke- warm water should give a milky cloudiness, but no flockiness. The soap is diluted until 1 litre of liquor contains 20 t o 25 grams of resin. Where such a dilute solution cannot be used, by reason of size of machinery and vessels, this proportion may be raised to 50 grams of resin. When resin soap with much free resin is used, the difference of the result, whether dilute or more concentrated soap is used, is not very great ; but if 36 to 38 k. of soda are employed in the formation of the soap, it is different. It is well to add a little starch to the soap, as it renders the suspension of the resin-milk easier. The boiler is three-fourths filled with water, and strongly heated, the starch pre- viously suspended in lukewarm water added, and the whole stirred.Cold water is added to cool it, and then the resin-soap. It is skirred, and again heated t o such a degree that the hand can be held in it. The solution is then run through a flannel sack into the glazing vessels. The glaze so obtained has a fine, milk-nThite colour, the amount of suspended resin being 15 to 20 per cent. The author then quotes, from Miiller’s book, a method in which caustic soda is employed, and says that whilst caustic soda is disadvantageous in the production of brown glaze, its advantages are great when white glaze is required. One objection to the white glaze is the fact that the resin becomes precipitated on the sides of the glazing vessel, and so large masses may get into the paper. Absolute cleanliness and frequent filtration of the solution will avoid this in a great measure.The precipitation of the resin is the next point to be examined. Sulphate of aluminium added in excess gives free resin, a basic salt of aluminium and resin, and sulphate of sodium. Sufficient sulphate must be added to remove the alkalinity of the paper-pulp. The quan- tity of sulphate required to effect the above two results is best d.cter- mined by experiment. For 100 parts of resin, 52.4 parts of alum are re- quired by this reaction 6(CzoH2,0z)Na + Alz(SOa)3 = (c20H2902)6A1z + (YNazS04). This is for the decomposition of the salt of soda only. In practice 1 k. of alum is the least quantity that is added for 1 k. of resin. This allows the excess of sulphate of aluminium to act on the resin salt first produced, thus: (~20H2goz)6A~2 + 2AlZ(SO4), + 3H20 = 6C,,,H,,O, + 3AlZO(SO4),, a basic sulphate being the result.As a rule more alum even than this is employed. According t o 0. Hoffmann, 2 to 3, and even 5 k. are used. The only useful ingredient in the alum is the sulphate of aluminium, and this is obtained from several sources. If the resin be employed as white glaze, with 20 per cent. of free resin, 2.5 k. will suffice for 100 k. of paper. In the form of brown The whole occupies from 3 to 8 hours.188 ABSTRACTS OF CHEMICAL PAPERS. ghze, 5 k. is required ; thus the 20 per cent. of free resin, or 0.5 k., is equivalent to 3 k. of resin precipitated by the sulphate of aluminium. The action of the alumina and starch is again referred by the author as to its prevention of the agglomeration of the resin, at temperatures above its melting point, and is thus mechanical.He thinks that all the qualities of starch point in a different direction to its being of direct utility as a glaze for the paper. ' s. Substitution of Chlorophyll for Copper Salts in the Preser- vation of Fruits and Green Vegetables. By A. GUILLEUARE ( Compt. rend., lxxxiv, 685-686) .-In the preservation of vegetables by Appert's method, some of tthe clilorophyll is unavoidably destroyed. Manufacturers have therefore been induced, in order t o improve the appearance of the preserved article, to restore the green colour by the addition of a salt of copper. A much more harmless and equally effective colouring agent has been obtained by the author, by dissolving the chlorophyll from parsley or other similar plant with a solution of caustic soda.From the liquid thus obtained the chlorophyll is preci- pitated by the addition of alum, and the " lake," after washing, is dis- solved in a solution of sodium phosphate. A definite quantity of this liquid is added to the water in which the operation termed " blnnchis- sage " is conducted ; the excess of chlorophyll is quickly absorbed by the immersed vegetable, and the natural green colour of the latter is thus restored. J. W. Technico-Chemical Communications. By H. S c H w A R Z (Dingl. polyt. J., ccxxvi, 305--507).-1. Analysis of the Smoke qf Virginian Cigars.-Gas contained 12 to 12.85 per cent.. of COz, and 4.0 to 4.76 per cent. CO. 2. Lead from, IZaibZ, too hard for rolling or pressing into pipes.Analysis:-Fe 0.012 per cent. Cu with Ag and Bi = 0.005 per cent. Arsenic, 0.143. 3. Brass-coZouring.-A solution of oxide of lead in potash and red prussiate of potash is taken. The brass when dipped in receives a golden-yellow colour. Compare Bohl (1875, ccxv, 191). On heating to 40" or 50" it becomes brown. S.168 ABSTRACTS OF CHEMICAL PAPERS.T e c h n i c a l C h e m i s t r y .Purification of Water for Boilers by Haen’s and Bohlig’s Pro-cesses. By %‘ E RD. F I s c H E R (Diy~yZ. Polyt. J., ccxxvi, 94-100) .-Thefollowing are analyses of water before (I) and after (11) the purXyingprocess by Hazn’s method, and 111 shows an analysis of water in a,boiler at work :-1 litre contains- I.Chlorine ................22 mg.Sulphnric anhydride ...... 55Nitric anhydride.. ........ 42Nitrous acid. ............. traceAmmonia ................ slight, traceOrganic matter .......... 35Magnesia ................ 9Lime.. .................. 175Percipitated by boiling :Lime.. .............. 14111.78trace41strongtrace33trace80111.27651471260trace0trace2240very large traceQr,CaC03 ............ 252 0 0CaS04 ............ 83 trace 250Na,S04.. .......... 11 0 0 ............ trace MgCI, 21 traceCaCI, .............. 0 121 4236NaY03.. .......... 66 65 1983The barium chloride employed contained BaCI, 82.18 ; CaC12 0.39 TECHNICAL CHEMISTRY. 169MgCl, trace ; insoluble 0-48 ; water 15.71 ; chlorides of alkali-metals1-24, The purified water reacted nentral, and still contained somesulphuric acid, as sufficient chloride of barium had not been adclcd.It is advisable to add sufficient lime, after the addition of the bariumchloride, to make the solution alkaline, so as to prevent the chlorides,he., from attacking the cocks and sidcs of boilers.A sample from another person had the following composition before(1) and after ( 2 ) :-1 litrc contzzins- 1.2.Chlorine.. .............. 142 mg. 391 mg.Sulpliuric acid ............ 209 0Nitric acid ................ 63 G 0Nitrous acid .............. trace traceAmmonia ................ 7 9Baryta .................. 0 53Magnesia ................ 22 12Lime ................... 294 241Precipitated by boiling :Organic matter............ i’7 39Lime ................ 137Magnesia ............ traceOne litre of purified water showed by neutralisntion that it wasequivdcnt to 21 mg. hydrate of carlcium, or 1 7 mg. of hydrate ofmagnesium.CaCO3 CnS04 CaC1, MgC1, BaCl, MgH,O,245 341 3 3 52 0 00 0 477 0 7 2 1 7The followiiig may be taken as the composition :-The chloride of barium used bald the annexed composition :-Chloride of barium 76.75; chloride of calciuin 1-86; chloride ofmagnesium trace ; water i9.72 ; chlorides of alkali-metals 1-67.‘llie water is heated, and the chloride of bariurn and lime added. I nthree or four minutes tlie solution kmc;mes clear, and the purificationis perfect.The aiitlior then deals with Bohlig‘s preparation, and combats at tliesame time the remarks of the manufacturers of this article on tlie HaBnprocess.He finds the preparation called “ Bohlig’s A!Iagnesia prepara-tion,” to consist of burnt magnesia. The use of it requires a consider-able time for the clearing of the liquid, and carbonic acid lias at timest o be passed through the liquid to separate the lime. Much magnesiais introduced in this process, and altogether tlie author considers theHaEn process to be the better, aiid advises, if magnesia has to be used,t o employ ordinary magnesia, and not the costly prepwation of Uohlig.S.Manufacture of Iodine. Ry C. C. STANFORD (Dit~gZ. polyt. J.,ccxxvi, 8&-94).-After a short history of iodine and an account ofthe fluctuations of the trade in kelp and iodine, the autbor goes onto describe the manufacture of this latter substance.The kelp isbroken up into fragments, and the soluble matter extracted by water170 ABSTRACTS OF CHEMICAL PAPERS.This solution is evaporated, allowed to stand a t 40" or 45" F., and thecrystals whicl) form are fished out. At 62" F. a hard salt, containing50 per cent. of potassium sulphste, together with Glauber's salt andsodium chloride, is deposited. The liyuid is again heated, when tlickelp salt (sulphate of potassium and sodium) again forms. The liquidis again cooled, and so on. The resulting liquor is mixed with +Nordhausen sulphuric acid (145" F.) ; oxide of manganese is atldecl,and on distillation iodine is obtained ; afterwards, on addition of niowoxide, bromine comes over.The author Yefers t o the fluctuation in the demand for kelp in con-sequence of the discovery of Spanish soda aiicl the Stassfurt salt de-posits.He shows that about 0.16 per cent. of iodine is got from kelp.The quantity of iodine in the sea is as 1 : 250,000, or 1 cuhic milc con-tains 11,072 tons. Other chemists estimate the proportion to be1 : 30,000,000. Seaweeds possess tlie power of taking tlie iodine fromthe sea-water, but in different degrees, as the following table willshow. Thev take UB ten times more iodine than bromine.of.dried a l p contain-100 partsLam. digitata.. ............,, saccharina ...........FUCUS serratus ............,, nodosus ............,, vesiculosus ..........Zostera niariiia ............Rhodomcla pinnastroydes....Hyderix siliquoso ..........Hymantlialia loreo. .........Chordaria flagelliformis ....Cladophlora glornerata ......Sarphat.0 -1350 -2300.1240 '0010.0005-- ----3chmeit-zer. Stanford.These specimens came from Larne, Ballina, Sligo, Galway, Shet-land, Tyree, Coll, Colonsay, from the Isle of Man, Denmark, &c. Thefirst five are those from which kelp is gcnerally made. The best is theLcrrni.i.iaria cligitata, which grows on rocks and always undcr water.Tlie laminaria? in general form the best source and are found thrown onthe shore by storms. The rest are cut generally as they rise out of waterand are poorer in iodine. The method of preparing kelp is wastefulin the highest degree. Exposed to weathering, heated too stroi~glyin burning, and mixed with sand, the product does not contain whatmore careful manipulation would render certain.The author read apaper before the Society of Arts (Chemical News, March, 7 862, p. 167)in which he describes a method of destructive distillation. The pro-ducts were ammoaia, naphtha, tar, acetic acid, &c., and a coke or char-coal, which gives by treatment with water the compounds of iodineand other bodies. The charcoal then left resembles animal charcoalin appearance, costs only 2 as much, and is a good deodorizerTECHNICAL CHEMISTRY. 171~~21-634 040-241.328’0---Laminaria.Carbon .................. 52.54Phosphate ................ 10%Carbonate of lime. ......... 15.56,, magnesia...... 11.34Alkalis .................. 5.70Alumina ................ 3.94L Sulphate of lime ..........67.95 0 . 234.230.012% ---Fucus.70.321.9010.357.921.931 -845-74100.00 100.00S.Decomposition of Soda-waste for the Production of Sul-phur. By CARL KRACJSHAAR (D17agZ. pdyt. J., ccxxvi, 41%-41S).--Schaffner’s melhod (Dhgl. 1869, cxcii, 308, and cxciii, 42) isto throw the residue in hcaps, and after leaving it Some months, tostrew these heaps about, whereupon chemical action sets in. Theauthor has in this paper followed out this chemical action, and fort)his purpose took a sample, 1 yard below the surface of the heap, andtreated 1.5 kil. with 850 C . C . of water ; 30 kil. of the same sample hemade into a little heap, and after half an hour treated a second portionwith 850 C.C.of water. A 3rd, 4th, 5th, 6th, 7th, and 8th sampleswere taken at intervals of 1 liour and treated with matcr as before.The samples were left for 24 hours in the wa,ter and the solution con-taine d-First qnant i ty ........After + hour ..........)) 1& ,, ..........)) 24 ,, ..........)) 3% ), ..........)) 4* ), ..........) ) 5+ ), ..........,, 6 + , , ..........Sample No. 1.5.633 ‘031 -321 -514 -6---No. 2.10 -515 *825 *628 *759 ‘2- -I 7 2 ABSTRACTS O F CHEMICAL PAPERS.First quantity ........,Qfter hour ..........,, 1i ,) ..........,, 2 i ,, ..........,, 3+ ), .......... .. 5Q )) ..........) ) GB ), ..........4" ) , 2 , , .. . . . . . . . .No. 3. No. 4."12 *720 251.879 -177 -083 *O86.2-It can be seen from this that the snlph-hydrate forms tlie greaterI nThis salt isproportion before tlie air is admitted and oxidntiori conirncances.the later stages CaX203 is the most abundant compound.probably formed as follows :-CaH2S, + 0 = H,O + CaS,; CnS, + 0, = CaS,O,, orCaH& + 0, = CaS,C13 + H,O.Thc sulphiclc in the fresh soda-residue is undoubtedly CaS, butthis, by the action of water, is converted into CaH& :2CaS + H,O = CaH2S2 -t CaO,When this has taken place the heap is broken up and air admitted,when the reactions already given cornmencc. If we can stop theoxidation at such a point that the polysulphicles, the suJp?l-i-hydrate,and the thiosulphate are present in such proportions as give thefollowing reactions, we get the greatest yield of sulphur :-CaH2Sz + CaS203 + 4HC1 = 3H20 -t 2CaC1, + S1, and2CaS2 + CaSgOJ + GHC1 = 3CaG12 + 3H20 + S,.I f the oxidation goes beyond this, the quantity of so:uble sulphurdecreases, as sulpliite and sulpliate of calcium are formed.The quan-tity of sulphur in thc solutions of tlie four samples, which were takenfrom different parts of the heap, and which thus show that the heapshave not a uniform composition, was as follows :-* This sample was taken nearer the surface of the he:ipTECHNICAL CHEMISTRY.Pemeiztnge Amount of Sui$hur.173First quantity ..........After + hour.. ..........), 18 )) ............)) 29 ,, ............), 3% )) ............)) 4+ ,) ............,) 54 ................ 6+ ..............1. 2.3 *243.032 9 63 '003.04-- --3. 4.2 -602 -582 .El52 '732 '132.192 -25-When the CaSzOj is present in slight excess, above the quantityshown by the above equations, the precipitation can be performed inopen vats instead of being precipitated in closed vessels as in theSchaffner process. The process, as carried out a t Thann, takes place ina vat 2 meters in diameter and 1.5 meter deep. The liquor passes intothe vat just above the bottom, and the hydroclJoric acid enters by awooden pipe, which is so arranged that the hydrochloric acid and theliquor impinge together on the bottom of the vat. The vat is halffilled with water and then heated by steam to 70".A stirrer is set inmotion, and the hydrochloric acid and liquor allowed to enter in suchpr-oportions tlint the mixture is slightly acid. The overflow is situatcdabout 3 c.m. below the edqe of the vat. The chloride of calcium andthe sulphur pass out by this overflow. The vat' is always kept full, sothat any sulphuretted hydrogen that' may be formed is decomposedbefore it rises to the surface in the sulphurous acid.An improvement on the above process is to add sufficient watcr tothe fresh soda-residue in an iron cylinder to allow of the action ofa stirrer, and then to treat it with steam a t 5 at. 90 per cent. of thesulphur can thus be brought into solution. The slinie from this isallowed to dry and then broken into lumps, when oxidation rapidlysets in.The result is then treated as bcforc. The author tliinks thiswould spare much labour. The solution of CaH,S2 obtained in thisway could also be applied in tanning to remove the hair froin hides.It would do this in 24 hours and not harm the leather. x.Presence of Arsenic in the Sulphuric Acid Manufacturedfrom Arseniferous Pyrites and in the various Soda SaltsManufactured from this Sulphuric Acid. By C. H J E J,T (DiqZ.p o l y t . J., ccxxvi, 174--181).--The author refers to H. A. Smith'sbook on the chemistry of the manufacture of sulphuric acid, andremarks that, though the quantity of arsenic in the pyrites is given,no special notice is taken cf the amount of arsenic in the sulphuricacid manufactured therefrom.1.Arsenic in ITOYL Pyl-ites.-The arsenic is probably present as(FeS.As), but fincly diffused, as it cannot be dissolved out by thesolvents for arscnide of iron. Spanish pyrites gave 0.90 per cent. ofarsenic, Westphalinn 0.30 per cent., and Norwegian only a, trace.Smith gires the following :174 ABSTRACTS O F CHEMICAL PAPERS.Spanish ( a ) .............. 1.651 per cent. As,O, .. (6) .............. 1.745 .. I ,West phali an .............. 1 -8 7 8 .. 7 7Norwegian ( a ) , hard ...... 1.649 .. 9 ,? j ( b ) , soft ...... 1.708 .. 1,Richardson and Watts give in “ Chemical Technology ”-Spanish.. ............. 0.21 to 0*31 per cent. AsWestphalian .......... traceNorwegian ............ -The method employed for the determination of araenic was fusionwit,h fusion-mixture and nitre, and precipitation of ammonia-magne-sian- arsenate.2.Quantity of arsenic in sulphuric acid--Present a s arsenicArsenic. acid.Chamber acid ................ 0‘202 p. c. 0.040 p. c,Acid from Glover’s tower ...... 0.331 .. 0.041 ,,9 7 Gay-Luasac’s tower . . 0.334 ,, 0.132 ,,The chamber acid, before einployrnent, in sal t-cake manufacture, isconcentrated in Glover’s tower. A part of this acid goes to the Gag-Lussac tower for the purpose of absorbing the nitrous gases. Thesenitroiis gases oxidize the arsenious to arsenic acid, and this accounts€or the larger proportion of arsenic acid shown by the analyies,(A4sz03 + 2N,03 = As20S $. 4NO). The total amount of nitric acidused in this manufacture is 1.62 per cent.of the sulpliuric acid pro-duced. Calculating according tlo the above equation aiid by the resultof analysis, the loss of nitric acid due to arsenic is 3.18 per cent. of totalsulphuric acid produced. Westphalian pyrites with 0.30 per cent. ofarsenic used 1-32 per cent. (of nitric) of total sulphuric acid manu-factured, while, as above stated, with Spanish pyrites the proportionwas 1-62 per cent, Other examples a’re, a t Preiberg, 1.7 per cent. ofnitric acid ; arsenic iu sulphuric acid = -05 to *30 per cent. At Grew-enbruck, 1.10 per cent. is amount used ; the pyrites is poor in arsenic.At tJhe Rhenania works in Stolberg, 1 per cent. in amount, the pyritespoor in arscnic. In a chemical works a t Benel, where pyritcln with 1per cent.to 1 ~ ~ 5 per cent. of arsenic, 1.5 per cent. to 2.0 per cent. ofnitric is used. l’abulated, we have-Nitric acid need with pyritespoor in arsenic. Rich in amenic.1*:-12 p. c.1.10 ,, 1.70 ,,1.62 p. c.1-00 ,, 1.5-2.0 p. C.The last sulphuric acid chamber has the purest acid with, in casecited hy author, 0.019 per cent. of arsenic. This, by concentrationin pans, can be used f o r many purposes to which the other cannot beapplied,The passage from the fire to the Glover’s tower contains a whitedeposit with much arsenic. The longer this passage is the purer thTECHNICAL CHEMISTRY. 175acid, as much arsenic is deposited. The burnt pyrites contain 0.19per cent. of arsenic.Arsenic iw, the svlphnte and fiodn manufactured with this sulphuricacid.Smith found in the sulphate manufactured from sulphuric acidwith 1.051 per cent. of As 0.029 per cent,, but found none in the soda.Fresenius has fouiid it; in both. The author found the sulphate quitefree from arsenic. He thinks that the arsenic goes off as chloride, andthat i€ excess of sulphuric acid be not used, the result will be free fromarsenic.Arseuic i!v, Hydrochloric Acid from, Xodn-manufnct7cre.-The raw acidhas much arsenic in it. The longer the passage from the hearth orfurnace t o the condensing chamber, the freer the acid is from arsenic,as it is deposited on the way. Smith found 0.691 pcr cent. As203in the hydrochloric acid. Pilhol and Lasassin Eound 0.081 per cent.As, 0.174 per cent., 0.428 per cent. ; so it can bc seen that quantityvaries much.Amenic in chloride of lime win& f r o m this Iychochloric acid, none.S.Ultramarine.By J. PH I I, [ P P (Dh$. pohyt. ,J., ccxxiv, 635-639).-The author notices somc experiments made t o ascertain if theoxxgen-compounds of sulpliur obtained by thc treatment of bluc ultra-marine with acids, are esseutial constituents of the colour, and toascertain the relation between blue and green nltramarine (Dcut. (J"hew7.Qes. Iler., 1876, 1109 ; Chew. S'oc. J., l g i 5 , ii, :383). He conclndesthat the sulphuric acid obtained by treating ultramarine witli hydro-chloric acid arises, in part a t least, from the dcconiposition of' penta-tlrionic acid formed by the action of sulphurous acid and sulphnrettedhydrogen upon each other.Hlrie inltramarine, ignited in air and wellwashed, gave a tolerable amount of sulphuric acid; still more wasfound in a sample formed on the wdl of a sulpli>ate furnace. It thusappears that this acid, found when ultramarine is treatccl with acids,arises in part from over oxidation, by which some of the coloiir isdecomposed. Repeated heating with water in a sealed tubc, even upto 200°, failed to remove the oxyyen-compounds completely. Thesecompounds are not essential t o the constitution of blue ultramarine,for the blue variety can be ohtained from the green wit liout auy changein the distribution of the sulphur.Green niay be conver1t.d into blue ultramarine 'by the following,besides other methods : by repeated heating w i t h iodine in air; byheating to 140" or 160" with iodine solution ; by fusing wit,h boricacid, or by repeated evaporation with solution of this acid ; by heatingt o 160" with water; by heating with concentrated ~olutions of somemetallic salts.These changes find their simlilest cxplanstioii in thesupposition that the green ultramarine lias lost sulph uric acid. Whent'he method of heating to 160" with water is used, the blue producthas the same composition and weight as the original, and the sulphur-compounds obtained on treating with acids agree exactly, whilst thewater used in the tube takes up only small quantities of sodium corn-pounds. Hence the oxidation-products obtained from ordinary blueare by no means essential to its constitution.The difference betwee176 ABSTRACTS OF CHEMICAL PAPERS.blue and green ultramarine appears to be that the latter contains a littlesodium sulphide, mechanically or chemically, which hides its colour ; onremoving tliis the blue colour appears. On fusing blue ultjramarinewith sodium sulpliate and charcoal, the green substance is obtained.Green ultramarine boiled with zinc sulphate solution increases involume and becomes blue, zinc being taken up by the mass and muchsodium passing into the solution. Blue ultramarine thus treated alsotakes up zinc without changing colour essentially j herc sodium is notremoved simply, but free silica, alumilia, and zinc oxide, removable byalkalis, are found. J. T.Testing of Portland Cement. (Dlngi. pdyt. J., CCXXV, 565570) .-Dyckerhoff (Jourtiul j2r Gmheleuchtuirg, 1877, 75) shows thatthe seven days' test of Portland cement is untrustworthy, and that the28 days' test, ihough better than the first, does not indicate the bind-ing quality of the cement when mixed with sand.From results oh-tamed by adding four parts of sand to various ccrnents, arid determin-ing the tenacity of test-picces after one, two, four and twelve weeks,he recommends, as the best test, to add a considerahle amount of sandand test after 28 days. For good results the well burnt cement mustbe finely ground,C. Heintzel (hTotizb. des deut. Ver. fiw. Pahrik. won Ziegeln,, 1876,199) concludes generally that : 1. Portland ceinent of proper composi-tion bccomes gradually harder, either in air or water.All oscillationsin the tenacity of test pieces are due to faults in their preparation.2. The greater the amount of water used, the less the tcnacity ofthe product.3. The finer the grain, the greater the tenacity.4. Of purc cements of the same grain, those which ha,ve the greatesttenacity will give similar results when mixed with sand.5. The coarser the sand used, the greater will be the tenacity of thebe't0'12 produced.5. The tenucity can be determined after seven days by 1lichai':lis'absorption method, either for pure cement, or for mixed cement andsand.The specific gravitiy, determined by Seyer and Aron, ranges from2.99 t o 3-08The best method of testing is still an open question.Formation of Manganiferous Iron in Blast Furnaces.(Dim$.y o l y t . J., ccxxvi, 53-55) .-Ward compares the Austrian with theAmerican processes. At Reschitza 1-37 tons (1400 k.) of mangineseores gave .98$ cwt. (50 k.) of manganiferous iron, 35 per ceiit. beingmanganese.The 1-37 tons contain 37.2 per cent. of htn2O3, or 25.89 per cent. ofmanganese = 362 k. (7.12 ewts.).The amount of manganese which passed into the manganiferousiron was -344 cwt. (17.5 If.).This shows that 95.5 per cent. of manganese passes into tlhe slag.The following is the composition of the mixtures fused in Austria:-J. TTECHNICAL CHEMISTRY. 1771 5 per cent. limestone.85 per cent. manganeseores. ...................... For production of manganiferous iron with25 per cent. of %InPor production of manganiferous iron withFor production of manganiferous iron withThe slag having a composition in the last case of-Silica .....................23.1Lime ...................... 335Oxide of iron ............... 11.6AIumina ................... 6.17 97 7 ,,29 per cent. of Mn ...................... 7 9...................... { :; 35 per cent. of MnHydrate of manganese ....... 2.5.7The fluidity of slag depends on the amount of manganese in it, buton the other hand, ifthe slag be stiff, particles of manganiferous iron be-come enclosed. and so the loss is the same. I n America, Ward hasobtained better results in a furnace 10.5 meters high, and with a blast,76 mm. in diameter. The melting point of the slag is nearly the sameas that of the metal.-After 3 months’ work, 270 k.(5.3 cwt.) of ore with 35 per cent. ofmanganese yielded 100 k. (1.9 cwt.) of mnnganiferous iron with 35per cent. (1.045 cwt.) of manganese. This shows a loss of 59.5 percent. (.8.55 cwt.) of manganese, or a yield of 58.1 per cent., or 12times as much as ia obtained in Austria. S.Uses of Manganiferous Iron. (Chenz. Centr., 1877, 204).-Gautier believes that the niariganese acts as a reduciiig aqent, whichremoves iron oxide from the metallic iron, and prevents it fi.om becom-ing ‘‘ hot short.” Henderson, of Glasgow, discovered a process ofpreparing manganese-iron containing 25 to 75 per cent. of mangaiiese,thus lowering the cost of preparing manganiferous iron. The amountof manganese required for reduction is usually 1 per cent., if added asmanganese-iron ; the rcsulting iron is extremely soft ; its coefficient ofelasticity is 22 to 25 kilos.; its resistance to strain, 45 kilos., and itsexpansion, for 200 mm., 20 to 25 kilos.The p r d u c t of the resist-ance to strain multiplied by end-expansion is nearly 7 times that ofordinary iron, and more than twice that of hard steel. This iron isused in plating ships. Addition of li per cent. of manganese toinferior iron counteracts the influence of phosphorus. Addition of1 per cent. of manganese to cast steel gives it great rcsistingproperties. W. R.Chromium Crucible Cast-Steel. By S. KE R N ( C~EIU,. News,xxxvi, 198) .-Directions and receipts are given for manufacturingcrucible steel from Bessemer steel, iron, chrome ore, and limestone.The product is good and the price moderate.It does not become hard by tempering.M.M. P. M178 ABSTRACTS OF CHEMICAL PAPERS.Electrogilding by means of Potassium Ferrocyanide. By E.E B E R 11 AYE n (DkgZ. polyt. .J., ccxxiv, 63l--6%).-T0 avoid the useof potassium cyanide baths, the author dissolves 300 grams potassiumferrocyanide, 100 grams of potassium carbongt'e, and 50 grains of s d -ammoniac in 3-& litres of water at, 39" to 40" C. To this is slowlyadded 200 C.C. of neutral gold chloride solution cnntaiiiing 20 grams ofgold; after boiling about 30 minutcs, and leaving the solution tocool, the liquid is filtered and made up to 5 litrcs. To increase tlieconductivity and t o prevent tlie separation of iron oxide a t the anodc,a littlc potassium cyanide is added.TVhen about 0.4 of the gold hasbeen deposited, tlie bath is renewed by adding a second 2Q0 C.C. of gold-solution aid proceeding as at first ; this can be repeatetl. three o r fourtimes, after 3vliich it is necessary to add about 30 grams of ferrocy-anide and tlie same proportion of the other salts. This rcnewitig isrepeated as long as good results arc ohtained. Tho gold froin spentliquids is recovered, aftel. filtering off any separntctl iron oxide, bydepositing 011 a largc copper plate totally immersed as cstlioclc.With the same current a warm bath gives a more copious depositthan a cold one. From many experiments the author concludes that,in a bath rich in gold, very little of the anode is dissolved, whilst thelatter is more strongly attacked in a poor bath, so that a plntinumanode may be used with a rich bath. J.T.New Method of recovering Gold from Toning Baths. Ry FR.HAUGH (Chenz. Ceictr., 1877, 201).--'l'he liquid is filtered into a flaskof white glass, made alkaline with sodium bicarbonate, a i d coloureddeep red with solution of aniline red. On exposure to light for 6 o r8 hours, the gold not used in toning is precipitated as a violet powdcr.The supernatant fluid is ponred off, and whcn a saficient qimntity ofthe powder has been collected, it is transformed into gold chloride.?V. R.Drawing of fine Platinum Wires. By A. GAIFFE (C0~7pt.rend., lxxxv, 625).-The author has so arranged an apparatus fordrawing fine platinum wires, that they are protected from contact withany parlicles of clust that nray be floating in the air.This permits ofwires only &- of a millimeter in diameter, to be drawn without rnp-turing at the draw-hole, an effect traced to the contact of foreignmatters. R. R.Purification of Coal-gas. By H. RUNTE (Ohern. Cent?.. 1877,lS5-192).-1. The ammonia existing i n the gas-water is too dilutet o be used with profit for purifying the gas. IC does not containenough NH, to absorb CO, and HzS, even though acid salts wereformed. This is, however, not the case, as the temperature of thewater is so high :is to decompose any acid salt that might be formed.The '( regenerating " of dilute gas-water involves an amount of fueldisproportioned to thc irripurities it, absorbs ; consequently (a), a stroiigammoniacal liqnor, prepnred by known methods, should bc used ; thestrength of tliis liquor should be about 36.21 grams, or 47-46 litresNH, per litre of liquor ; it then absorbs 39.2 ~ 1 * i ~ ~ ~ s , or 19.8 litres ofCOz, arid 14.8 grams or 9.7 litr-s of H2S.By Hill's recovery procesTECHYICAL CHEMISTRY. 179$ OF the carbonic acid and 9 of the sulphuretted hydrogen arc re-moved from the liquor, which is passed over iron oxide to free it com-pletely from sulpliuretted hydrogen. The liquor intended for thepurification of the gas is not to be allowed to mix with the gas liqnor.JV. a.Purification of Gas. By H. SCHWARZ (DinyZ. p o l y t . J., ccxxvi,307) .--The author suggests a centriiugal machine for the scparationof tar from gas.A fan with sieve-like vaiies revolves at high speed.The gas enters a t the centre of the case surrounding the fun andpasses out a t the opposite side. The globules of tar are brolien by thewires of t'he sieves and the tar is thrown to tlic periphery, where it ag-glomerates into liquid tar. centre on oppositeside to the entrance t o avoid the sucking-in of gas, which would resultThe gas passes outif the gas were allowed to escape at the periphery. S.Two Methods of getting Sugar from Molasses. By H.SCHWARZ (Dingl. polyt. J . , ccxxvi, 182-193 and 4(34--412).--Theamount of molasses yearly produced in Europe from beet-root is ~7erygreat. The author reckons that 250,000 tons of molasses are yearlyproduced, and this is equivalent t o 125,000 tons of crystallisablosugar.He considers this equivalent t o a loss of S265,OOO ycwly.Several chemiFts have tried to attack this question, some by cndeil-vouring to precipitate a compound of sugar with lime, baryta, andstrontia ; others by endeavouring t o get rid of tlre impurities whichprevent the sugar from crystallising. The former methods me costly,and the latter cause much loss. The best method inicler the latterplan is t h a t of osmose proposed by Dubrunfaut. Warm pure waterand concentrated solution of molasses are dialysed through parch-ment paper. Some of the molasses goes to the water and some of thewater to the molasses. The chief part of the salts and a small quan-tity of sugar pass into the water, and the remaining solution containsthe sugar in a crystallisable state. 15 per cent.of the molasses is thusmade useful as crystallised sugar.Dr. Stammer saw that the diffeyence of sugar and salt in dialysingpower was not sufficiently great to give good result's, arid he proposedthe addition of lime to the molasses, so as t o make its passage throughthe parchment more difficult. The author, by means of' a dinlysingapparatus (see Dingl. poZyt. J., 1875, ccxviii, ZlS), has made manyexperiments on this method.(1.) Dialysis of pure Sz~grnr.-lOOgrams of loaf-sugarwere dissolved in0.5 litre. As 400 C.C. = 80 grams of sugar in the apparatus, 460 C.C.were employed outside. After IG hours there were 540 C.C. with60.75 grams sugar inside, and 320 C.C. with 19.20 grams of sugar out-side, In this time, therefore, 19-20 grams of sugar or 24 per cent.had passed through the parchment.The size of' paper was 1388 q.c.I n 1 q.c. -9 mg. of sugar passed per hour.(2.) Pwe Suym- with, Lime.-To 67.2 grams of s u p r 7.168 grams oflime were dissolved, or 3 eq. of sugar to 2 eq. of lime. 320 C.C. ofsugar solution were put in the centre of apparatus, and 440 C.C. ofwater outside. After 18 hours there was in the centre part of the appa-ratus 58.05 grams sugar in 460 C.C. of solution ; outside 320 C . C . wit180 ABSTRACTS OF CHEMICAL PAPERS.6.750 grams of sugar. Inside there was 6.025 CaO; outside -432gram of' CaO, 11.8 per cent. of sugar diffused, and 1.7 per cent. oflime.For 1 q.cof parchment 0.02 mg.diffused.(3.) iWolass~s from a Sugar .ieJiizery was dissolved in water, and limeadded. and filtered. A portion after separation of lime gave 24.15per cent. of solid matter, or 15.01 per cent. of sugar, so that of the solidsubstancc 61.3 per cent. was sugar. The percentage of salt was 22.0.After 12 hours there was-Solid matter. Sugar. Sugar qnotient."Per cent.Inside ........ 17.0 11.77 69.2Outside ...... 6-25 3.01 49.6so that the amount of sugar had rclatively increased.(5.) Molasses saturated with lime and dialysed with flowing water.The outer part of vessel was so arranged that fresh water ran throughit constantly but slowly.This flowing water was evaporated after the process was finished,and both portions were analysed :-Solid substance.Sugar. Sugar quotient.Centre of apparatus ...... 16.00 11-40 71.2F;Outer portion of apparatus 28.00 7.0 25.00(6.) The molasses from the inner portion dialysed again withrunning water :-Inner portion ........... 14.6 11.4 78.0(7.) Raw molasses from Barzdorf, in Austria, Silesia, contained-Solid matter. Sugar. Salt. Sugar quoticnt. Salt quotient.78.9 43.6 10.0 55.1 23.0(8.) 80 grams of the molasses was dissolved to 200 C.C. without lime,and placed in the inner portion of the apparatus. 400 C.C. of water inouter. After 16 hours 350 C.C. foundin the inner and 250 in the outerportions :-Solid matter. Sugar. Salt. Sugar quotient. Salt quotient.Inner.. ...... 10.83 6.03 1.17 55.7 19.2Outer ......8.90 4.56 1.44 51.2 31.6grams of sugar and 8 grams of salt, there wcre found :-Of the 80 grams of molasses with 63.12 grams of solid matter, 34.86Solid matter. Sugar. Salts.Grams. Per cent. Grams. Per cent. Grams. Per cent.Inner.. .. 39.6 = 62 7 22.00 = 63.2 4.27 = 5:3.3Outer.. .. 23.0 = 36.5 11.81 = 33.9 3.73 = 46.6From this it may be seen that the principle of dialysing with aneutral solution is wasteful, 33.9 per cent. of sugar has to be lost inorder to get rid of 426.6 per cent. of the salts.(9.) The same molasses (7) was rubbed with excess of lime, andafter removing the lime from a portion, the amount of solid matter,* The sugar quotient is the percentage of sugar in the solid substanceTECHNICAL CHEMISTRY. 181sugar, and salts was obtained.220 C.C. of lime-molasses was dialysedwith 400 C.C. of water for 16 hours. I n the portion employed there were35.69 grams of solid matter (26.60 grams sugar and 4.36 salt) :-Solid matter. Sugar. Salts.Grams. Per cent. Grams. Per cent. Grams. Per cent, .... Inner 27.5 = 76.7 20.60 = 80 2.06 = 46.8Outer .... 8-34 = 23.3 5.13 = 20 2.34 = 53.2In this latter the sugar quotient is 74.9.(10.) Molasses with much lime dialysed for two days with runningwater :-Solid matter. Sugar. Salts .Grams. Per cent. Grams. Per cent. Grams. Per cent.Inner .... 63.073 = 74.5 43.713 == 90.6 3.203 = 32%Outer.. .. 21.527 = 25.5 4.496 = 9.4 6.615 = 67.4The sugar and salt quofients (or percentage of sugar and salt in thesolid matter) were :-Sugar. Salts.Interior ..........69.3 7.3Outer .......... 20.9 14-7The product crystallised easily and well.(11.) A similar experiment gave:-Solid matter. Sugar. Salts.Grams. Per cent. Grams. Per cent. Grams. Per cent.Inner.. ...... 37.6 = 59.6 31.5 = 79.3 1.856 = 20.6Outer.. ...... 25.5 = 40.4 8.2 = 20.7 7.130 = 79.4Sugar quotient. Salt quotient.Inner ............ 83.8 5.9Outer ............ 32.1 86.9(12.) An experiment in which st little more than 1 eq. of lime wasadded to 1 of sugar, gave:-Solid matter. 8 ugar . Salts.Grams. Per cent. Grams. Per cent. Grams. Per cent. } 63.2 34.88 8.04 80 grams ofmolasses..Inner.. .... 39.65 = 62.0 24.79 = 68.00 3-42 = 41.6Outer. ..... 24.30 = 38.0 11.66 = 32.00 4.70 = 58.4I n n e r . . .......... 62.5 13-7Outer............ 47.9 40.3Sugar quotient. Salt quotient.(13.) The same with running water:-Inner.. .......... 77.2 3-13Outer.. ......... 30.3 89.60(14.) The outer solution in (12) was evaporated, lime added, anddinlysed with runnihg water :-VUL. XXXITI. 182 ABSTRACTS O F CHEMICAL PAPERS.Solid matter. Sugar. Salts.Grams. Ycr ccnt. Grains. Per cent. Grams. Per cent.Inner.. .. 41.20 = 56.2 20.120 = 89.9 5.360 = 31.4Outer.. , . 32.06 = 43.8 2.314 = 10.1 11.400 = 68.6Sugar quotient. Salt quotient.Inner ............ 48.8 26.6Outer ............ 7.2 4920(15.) Nothing particular.(16.) With a large quantity of lime (as much as can be added) andrlialysing with running water, the author got one of the best results.With a sacrifice of 10.5 per cent.of sugar, 65.3 per cent. of non-crys-tallisable sugar (Nichtzucker) and 81.6 per cent. of salt separatcd :-Solid matter. Supr. Salts.Inner ........ 78.78 56.27 2.74Outer ...... 39.22 9.75 12.17Grams. Grams. Grams.Sugar quotient. Salt quotient.Inner ............ 71.4 4.8Outer ........... 17.2 180.0(17.) Nothing particular.(18.) In order to find the amount of salt that passed out of thesugar in stated times, 200 grams of molasses (with 157.8 grams ofsolid matter, 87.2 sugar, and 20 grams of salts) werc shaken andsaturated with lime and then diluted to 3% C.C. This was dialysed,the outer solution taken away and analysed after three hours (A), thenafter a second three hours (B), and at end of 16 hours (C). Theinner solutioc was analysed at the end, too :-Solid matter.Sugar. Salts.Grams. Per cent. Grams. Per eciit. Grams. Per cent.A , . .... 20.23 = 13.1 4.5 = 5.1 6.24 = 34.0 IB.. .... 14-91 = 9.1 5.4 = 6.1 3-76 = 20a-5C.. .... 19.54 = 12.6 10.8 = 12.3 2-94 = 16.0D.. .... 99.52 = 65.2 67.2 = 76.5 5.40 = 29.5Sugar quotient. Salt quotient.A .............. 22.1 138.7B .............. 36.2 69.6C .............. 55.2 27.2D.. ............ 67.5 8.0This shows that the salt passes out in largest quantities in tlie firstThe author draws the following conclusions :-(1.) The diffusion of sugar by the addition of lime is made slower.(2.) The lime-holding molasses gains a higher sugar-quotient reln-tive t o the salt quotient by diffusion, and this result is better tIhmwhen neutral molasses is dialysed.six hours.(3.) Running ivvttter acts better than standing waterTECHNICAL CHE'MISTRY.183(4.) In general 70 to 90 per cent. of thc salts are successfully gotrid of, with n loss of only 20 to 30 per cent. of the sugar. The re-maining sugar is then in a condition t o crystallise to some extent.(5.) The sugar or molasses which passes'into the outer liquid can,by evaporation and addition of lime, be again dialysed and more sugarrecovered.The success of the above experiments encouraged the author tomake experiments on a larger scale. The following is a brief descrip-tion of the apparatus:-A long four-sided box, lined with galvanisediron, is provided with two tubes or pipes. One conducts the niolassesto the bottom of the box ; the other is an overflow pipe.In this box,wedged in, are a number of cells of the following construction :-Aframe of wood 80 mm. wide has a parchment sheet laid on each side.Two frames, screwed, one on each side, fasten the parchment in its placeand make this box water-tight at the joints. The edges of the parch-ment, where they rest on the frame, are covered with linseed-meal tomake it even t,ighter. Into this cell n tube passes through the woodenframe and allows water t o enter at the top of the cell. Another pipeleads the water off from the bottom of the cell. As the dialysis goeson, the salts pass into the water which sinks, and more fresh waterentering at the top, it is forced out by this pipe. The authorthinks itpreferable t o have a series of water cells, so that as one loses in dialys-ing power, a new one can be put in.As a sign of the molasses beingpuritied, the sp. gr. can be taken. The supply should be so arrangedt'hat the molasses which passes off at the overflow should have a sp. gr.of 12" to 13" B.When the molasses is dialysed, the question is the getting ridof thelime, Ton Sebor has proposed to add i t to the liquor from the beet-root in the manufacture of sugar. The result is to give a, bad colourto the sugars.On evaporation the lime settles out as a slime, taking with it someof the colonr of the molasses. The liquor is filtered through bone-ashes, and then evaporated to crgstallisation.The author has tried it in two or three manufactories with varyingsuccess.I n the method above described, the salt and much su,yar are lost, andso, after a great many experiments, the author suggests a new plan.The molasses is diluted with 50 to 60 per cent.of water with gentlcheating. On cooling, a quantity of lime equivalent t o the potassiumoxide in the molasses is added. An analysis has to be made to deter-mine this, or it may be assumed that the molasses contains 10 per cent.of soluble salts, and that 60 per cent. of this is carbonate of potassium.Sufficient sulphuric acid (diluted and cooled) is then added to preci-pihate a double salt of potassium and calcium. Instead of addinglime, gypsum may be used, and then only so much sulphuric acid isadded as will convert the carbonate of potassium into sulphate.Magnesium sulphate can also he used, and this promises to give goodresults when it can be obtained cheaply, as near Stassfurt.The precipitate of sulphate of calcium, potassium (and in cases ofmagnesium), is very rich.Part of fluid is filtered off, and the restpressed out of the precipitate. Thc liquor is cleared of lime by car184 ABSTRACTS O F CHEMICAL PAPERS.bonic acid and heating.abn ndance of sugar-cr y stals.The liquor on being left at 40" depositsThe following are laboratory experiments :-(1.) 400 grams of molasses mixed with 150 grams of water, 12 gramsof lime dissolved in 50 grams of water added (3 per cent.), and then40 grams (10 per cent.) of sulphuric acid in 80 grams of water added.The precipitate after pressing weighed 100 grams, and contained 16per cent.potash, equal to 4 per cent. of molasses.(2.) In a similar experiment in which 3.83 per cent. of potash wasfound.(3.) 300 grams of molasses dissolved in 90 grams water ; 39 gramsof magnesium sulphate dissolved in 60 grams hot water added ; andthen 25.8 grams of gypsum, 71 grams of pressed precipitate wasobtained. In this was found potash amounting to 3.63 per cent. ofthe molasses used.(4.) 300 grams of molasses, 150 grams water, 39 grams of bittersalt, and 30 grams of gypsum. 90 grams of precipitate, with potash,equal to 4.18 per cent. of molasses.I n the Klein-Kletschkau manufactory, near Schweidnitz, experi-ments were carried out on the sulphate of magnesium and gypsumprinciple ; 50 cwt.of molasses were employed. 18 cwt. of moist pre-cipitate were obtained. From one experiment 6 cwt. of sugar wereobhained. I n another, owing to the temperature, although performedin a vacuum, inversion set in, and the sugar would not crystallise.S.Behaviour of Wool towards an Ammoniacal Solution ofFuchsine. By R. BOTTGER (Chew%. Centr., 1877, 576).-A colonr-less Qmmoniacal solution of fuchsine dyes wool red. It has beensupposed that the wool causes the decomposition of a compoundformed by the action of ammonia upon fuchsine; but the author'sexperiments showed that fuchsine is merely mechanically dissolved byammonia; when wool is soaked inthis liquid, the ammonia evaporates.M. M. P. 31.Glazing of Paper. By C. WURSTER (Dingl.polyt. *J., ccxxvi, 75-82, 310-316, and %1--389).-The old method of sizing or glazingpaper was superseded by the method of mixing a resin soap with thepulp, and then precipitating by alum, The theoretical opinion is thata salt of aluminium with the acid of the resin is formed, and that thiscloses the capillary pores of the paper.The author of this paper considers, however, from the followingreasons, that this is not the correct view. When, as in the glazingprocess, an excess of alum is added to the resin- or fat-soap, a thick,gelatinous precipitate is obtained. This, by treatmcnt with warmalcohol, or with ether or chloroform, yields up the resin, which can bereprecipitated by water, or recovered by evaporation of the solvent.A different result is obtained when an excess of resin-soap is used.Inthis case a true aluminium salt is formed, which does not yield up itsresin. From this it can be seen that alumina decomposes this salt.Another proof lies in the fact that the ash before and after treatmenTECHNICAL CHEMISTRY. 185of the glazed paper with ether is the same, free resin being aloneextracted, and then the paper allows ink to run.Ash before Substancetreatment with Ash after. extracted.I.. ...... 1.68 ether 1-63 3.3511.- ...... 2.29 ,, 2.19 4.72111. ....... 2.19 ,, 2.18 3.70IVa ...... 1.93 ,, 1.81 4.*wIVb ...... 1:95 benzol 1-88 4.59V.. ...... 1.71 ether 1-66 2.11The author shows, too, that an ethereal solution of resin will glazepaper, but the aluminium salt remains as a powder on the surface.'l'he alkaline salt of resin or colophoniuni is easily decomposed by COain water, a milk resulting.This consists of finely divided particles ofresin. The addition of starch makes it less easy for the resin toagglomerate, and the action of the hydrate of aluminium or of basicsulphate of aluminium is the same.Free resin acid, or acid of colophonium, does not glaze paper well.In summing up, the author observes that, to obtain a good result', theremust be as much free resin present as possible, and to obtain this herecommends the addition of sufficient excess of alum to produce freeresin and a basic sulphate of aluminium, the water having a neutral,or slightly acid reaction.The resin used in the glazing of paper is colophony, the dry residueleft in the distillation of turpentine.It consists mainly of sylvic orabietic acid, C20H3002. It varies from light yellow t o dark brown incolour, according to the method pursued in the process of distillation.An American specimen began to soften at 54" ; it retained this tem-perature for some time ; at rj5" it was softer ; at 63" it formed a thickfluid. The temperature then rose rapidly to 90", when the substancewas quite liquid. Powdered colophony unites into a cake when ex-posed to summer heat. The sp. gr. of the resin is 1-07 to 1.08.The art of glazing the paper consists in filling up the capillary poresof the paper with resin.The substances chiefly used for dissolving the resin are caustic soda,Crystalline carbonate, and calcined carbonate of sodium.Theoreticallythe solution by caustic soda is the best, as the alkali is purified by t'heprecipitation of the carbonate of calcium during its manufacture, thelatter carrying all the impurities down with it. Caustic soda, however,acts very injuriouslyon the paper, if it be present in excess. Calcinedsoda is most frequently adopted. Impurities are present to a large ex-tent in this substance, so that not only is a chemical analysis requisiteto ascertain the amount of soda in each sample, but a solution has t o bemade, and the impurities filtered off. Crystallised carbonate of sodiumappears to be the best, but then its price is high. The author recom-mends manufacturers to prepare crystallised carbonate from the cal-cined soda.The proportion of soda to resin depends on the nature ofthe required product. The addition of sufficient soda to dissolve allthe resin, though unnecessary, defines one limit of the quantity. Theamount of soda necessary to dissolve the resin and to take up the res186 ABSTRACTS OF CHEMICAL PAPERS.mechanically is the other limit,.formula, G2,H,,)O2, we have this reaction-Assuming resin to be an acid of the2CzcH3,O, + Na,COJ = 2C,,H2,02Na + GO, + H,O.The molecular weight of the CnoH300, is 302 ; of the carbonate, 106 ;and of crystallised carbonate, 286. From this we get the proportionsof 100 of resin to 16.5 of anhydrous, o r 45.6 of crystallised carbonate.As the resin is never pure, this becomes 40 to 41.The amount of freeresin that can be taken up by the sodium salt of resin is not quiteknown. Muller (i?a,bdcation des Papieres, Berlin, 18'17) gives the pro-portions as 100 of resin t o 25 of soda (crystallised). The soap result-ing from this contains therefore, 35 to 38.5 per cent. of free resin. Thesolution of the resin takes place in copper vessels.The different methods of making the glaze depending on the differ-ent proportions of resin and soda, can be clmsified under two heads :-1. The production of a salt< of sodium which is entirely soluble inwater. 2. The production of a resin-soap,with much free resin, ~ l i i ~ l ~ on dilution is precipitated, and gives amilky appearance to the solution.The production of the resin-soap for the brown glaze is very simple.40 to 42 of crystalline, or a proportionate quantity of calcined soda isdissolved in 80 to 150 litres of water, and heated to boiling.100 k.of resin are added and broken up. As soon as the resin melts, carbonicacid is evolved. The process takes from a quarter of an hour to onehour. A specimen of the soap added to distilled water should dis-solve completely. The soap is allowed to stand, and the supernatantliquid taken off. If the soap requires to be washed for the removal ofsome of the colour, the author suggests the solution in a little waterwith soda, by aid of gentle heating. The soap can be againpreci-pitttted by addition of chloride of sodium. This repeated several timesremoves much of the objectionable colour.For the glazing of paperof medium thickness, 5 t o 6 k. of resin to 100 k. of paper are required.The soap is dissolved in water, with the addition of a little starch,and then filtered.More important, but also more difficult, is the preparation of thewhite glaze. It can be prepared in three ways :--1. By treatmentof the resin with a quantity of alkali lnsufiicient to combine with itchemically. 2. Treatment with excess of alkali, but stopping tlheaction when a certain quantity of free resin is present, and thenremoving the excess of alkali by skimming. 3. By production of ftperfectly soluble resin-soap, and addition of free resin to it. The firstand second are used in the manufactory ; the third is not.In the brown glaze the concentration plays but an unimportant part,whereas in the preparation of the white glaze it is very important.The first method is t o be considered here.The view of the authorthat the glaze is better the more free resin it contains, makes it import-ant to add as much free resin as possible. The amount of free resindepends on the degree of eoncentration of the soap. The concentra-tion of the soap by hcating over fires is recommended as an easier planthan the employment of steam, especially if the latter be of low pres-sure.This is the brown glaze.This is the white glazeTECHSICAL CHEMISTRY. 187Good results are obtained by heating 65 litres of water by steam,adding 34 k. of soda, and then slowly 100 k. of resin. The heat beingcontinued, carbonic acid is slowly evolved, and the operation lasts fyom1 to 3 hours.The heat has to be still continued, in order to dissolvethe free resin, The soap isready when, on being taken out on a spatula, it shows the followingproperties. A clear, transparent, thick liquid, without bubbles, brcak-ing off short, and not drawing out into threads. On addition to ailequal volume of hot water, it should assume a brownish, gelatinousappearance, and not show yellow stripes. A portion stirred in luke-warm water should give a milky cloudiness, but no flockiness. Thesoap is diluted until 1 litre of liquor contains 20 t o 25 grams of resin.Where such a dilute solution cannot be used, by reason of size ofmachinery and vessels, this proportion may be raised to 50 grams ofresin.When resin soap with much free resin is used, the difference ofthe result, whether dilute or more concentrated soap is used, is notvery great ; but if 36 to 38 k. of soda are employed in the formation ofthe soap, it is different. It is well to add a little starch to the soap,as it renders the suspension of the resin-milk easier. The boiler isthree-fourths filled with water, and strongly heated, the starch pre-viously suspended in lukewarm water added, and the whole stirred.Cold water is added to cool it, and then the resin-soap. It is skirred,and again heated t o such a degree that the hand can be held in it. Thesolution is then run through a flannel sack into the glazing vessels. Theglaze so obtained has a fine, milk-nThite colour, the amount of suspendedresin being 15 to 20 per cent. The author then quotes, from Miiller’sbook, a method in which caustic soda is employed, and says that whilstcaustic soda is disadvantageous in the production of brown glaze, itsadvantages are great when white glaze is required. One objection tothe white glaze is the fact that the resin becomes precipitated on thesides of the glazing vessel, and so large masses may get into the paper.Absolute cleanliness and frequent filtration of the solution will avoidthis in a great measure.The precipitation of the resin is the next point to be examined.Sulphate of aluminium added in excess gives free resin, a basic salt ofaluminium and resin, and sulphate of sodium. Sufficient sulphatemust be added to remove the alkalinity of the paper-pulp. The quan-tity of sulphate required to effect the above two results is best d.cter-mined by experiment. For 100 parts of resin, 52.4 parts of alum are re-quired by this reaction 6(CzoH2,0z)Na + Alz(SOa)3 = (c20H2902)6A1z +(YNazS04). This is for the decomposition of the salt of soda only. Inpractice 1 k. of alum is the least quantity that is added for 1 k. of resin.This allows the excess of sulphate of aluminium to act on the resinsalt first produced, thus: (~20H2goz)6A~2 + 2AlZ(SO4), + 3H20 =6C,,,H,,O, + 3AlZO(SO4),, a basic sulphate being the result. As arule more alum even than this is employed. According t o 0. Hoffmann,2 to 3, and even 5 k. are used. The only useful ingredient in thealum is the sulphate of aluminium, and this is obtained from severalsources.If the resin be employed as white glaze, with 20 per cent. of freeresin, 2.5 k. will suffice for 100 k. of paper. In the form of brownThe whole occupies from 3 to 8 hours188 ABSTRACTS OF CHEMICAL PAPERS.ghze, 5 k. is required ; thus the 20 per cent. of free resin, or 0.5 k., isequivalent to 3 k. of resin precipitated by the sulphate of aluminium.The action of the alumina and starch is again referred by the authoras to its prevention of the agglomeration of the resin, at temperaturesabove its melting point, and is thus mechanical. He thinks that allthe qualities of starch point in a different direction to its being of directutility as a glaze for the paper. ' s.Substitution of Chlorophyll for Copper Salts in the Preser-vation of Fruits and Green Vegetables. By A. GUILLEUARE( Compt. rend., lxxxiv, 685-686) .-In the preservation of vegetablesby Appert's method, some of tthe clilorophyll is unavoidably destroyed.Manufacturers have therefore been induced, in order t o improve theappearance of the preserved article, to restore the green colour by theaddition of a salt of copper. A much more harmless and equallyeffective colouring agent has been obtained by the author, by dissolvingthe chlorophyll from parsley or other similar plant with a solution ofcaustic soda. From the liquid thus obtained the chlorophyll is preci-pitated by the addition of alum, and the " lake," after washing, is dis-solved in a solution of sodium phosphate. A definite quantity of thisliquid is added to the water in which the operation termed " blnnchis-sage " is conducted ; the excess of chlorophyll is quickly absorbed bythe immersed vegetable, and the natural green colour of the latter isthus restored. J. W.Technico-Chemical Communications. By H. S c H w A R Z(Dingl. polyt. J., ccxxvi, 305--507).-1. Analysis of the Smoke qfVirginian Cigars.-Gas contained 12 to 12.85 per cent.. of COz, and4.0 to 4.76 per cent. CO.2. Lead from, IZaibZ, too hard for rolling or pressing into pipes.Analysis:-Fe 0.012 per cent. Cu with Ag and Bi = 0.005 per cent.Arsenic, 0.143.3. Brass-coZouring.-A solution of oxide of lead in potash and redprussiate of potash is taken. The brass when dipped in receives agolden-yellow colour.Compare Bohl (1875, ccxv, 191).On heating to 40" or 50" it becomes brown.S

ISSN:0368-1769    

DOI:10.1039/CA8783400168

出版商:RSC    

年代:1878

数据来源: RSC

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189 G e n e r a l a n d P h y s i c a l Chemistry. On some Points connected with the Chemical Constituents of the Solar System. By J. H. G L A D S T O N E (Phil. Nus. [5], iv, 379-385) .-The formation of the solar system by thc condensation of a nebulous mass made up of many different chemical elements, will have resulted in a distribution of those elements dependent on the two followina considepations :- (1.) During the process of cooling the least volatile constituents will condense first and sink towards the centre of gravity, while thc rest will arrange themselves inore or less in the order of their volatility. (2.) As mas pointed out by Mr. C. J. Stoneg, in an atmosphere de- creasing in temperature from within outwards, the lightest molecules will be the farthest from the centre of gravity.The most volatile elements, and those of least vapour-deiisity, will therefore be the outermost in a hot nebulous mass. This distribution is seen to occur in the sun, where hydrogen forms the bulk of the outer atmosphere, mixed with small quantities of sodium and magnesium, while the vapoui* of iron is found only in a lower stratum of the sun’s atmosphere, and platinum has not been detected at all. According to the nebular theory, the planets wcwe formed by the separation of some of the outer portion of the original mass; we should therefore expect them to contain a preponderance of the more volatile elements, and those of least vapour-density ; and this is in- deed the case. Of thecnori-metallic elements, those which are plentiful have an average vapour-density of 19.8, while those wliich are com- paratively rare have an average vapour-density of 63 : grouping the metals into four classes-plentiful, common, rare, and very rare, we find that the average vapour-densities of each class are, 37.8, 104.5, 106.7, and 122.9 respectively.The meteoric stones which fall to the earth from interplanetary spaces show this preponderance of the lighter elements still more strikingly. There are, however, in both cases many exceptions to thc rule, for in- Etance, glucinum and lithium are both rare, while lead is w r y common ; such exceptions may be cxplained by supposing these elements to have been combined with others forming compounds of g1-catcr or less volatility than themselves ; thus carbon is very difficult to volatilise, but its compounds with oxygen, hydrogen, &c., are gases at the ordi- nary temperature.The heads of comets emit light giving band spectra which are usually referred to carbon ; the volatilised carbon of the electric lamp was also found to give these band spectra ; in cornets, however, the carbon is probably combined with oxygen or hydrogen. The Influence of Temperature upon the Coefficients of Refraction of the Natural Sulphates of Barium, Strontium, and Lead. By A. ARZRUNI (Jahrb. f. J&., 1877, 52t;--527).--The author considered it desirable to ascertain whether the coefficients of F. D. €3. VOL. XXXlV. 2’190 ABSTRACT8 OF CHEMICAL PAPERS. refraction remained constant or varied with the temperature a t which the determination was made.Three isomorphous sulphates, viz., barium salpliate, strontium sulphate, and lead sulphate were selected for the investiption ; firstly, because Descloiseaux observed in them a great variation of the angle of the optical axis with the temperature, from which it might justly be inferred that any change in the co- efficient of refraction could easily be determined ; and, secondly, it was desirable to ascertain if isomorphous cornpounds with analogous optical characteristics still remained analogous to an increase of temperature. F o r these observations the author prepared prisnis out of a barytes crystal from Dufton, a cmlestine crystal from Lake Erie, and an anglesite crystal from Monte Poni, the results of the investiga- tions being briefly as follows, vie.:-(1.) The principal coefficients of refraction of the above-mentioned isomorphous sulphntes differ from each other with the temperature, but all of them decrease with an increase of temperature. (2.) The decrease in the coefficient of re- fraction of the three sulphates is an analogous one, and can he ex- pressed thus, viz., Further, y approaches the two others, whilst u withdraws from 6. (3.) With anglesite the refraction is inversely as the temperaftme, whilst the dispersion increases for dif- ferent colours. (4.) The directions of the maximum, medium, and minimum expansicjn of the three compounds by heat do not staid in any relationship to the values of the directions of optical elasticity in them, or to the alteration of the velocity of light in these three direc- tions.C. A. B. > u > 6. On the Law of Absorption and its Employment in Quantita- tive Spectrum Analysis. By G. Govh (Conyt. r m r l . , lxxxv, 1046- 1049).-The author at first alludes to the phenomena of absorption, and compares tlie increase and dilatation o€ absorption-bands ‘‘ due to thickening in the absorbing medium,” to the increase in the bright lines in the spectra of incandescent gases caused by increase in the temperatiwe aEd pressure. He says tliat it is not possible to determine the absorbing power of a body, unless the coefficients of absorption are known f o r all wave-lengths which can be studied. He thinks, however, tlhatj the absorbing power of bodies may be determined, either by direct comparison of the curves of chroniatic absorption, or by measuring tlie intensity of the light along the whole length of the spectrum.To use the first of these methods, lie employs the ab- sorbent in tlie shape of a prism, and by placing one of its plane faces against the slit, with the centre angle touching one end of it, he ob- tains a gradually increasing thickness of the absorbing medium throughout the whole leiigth of the slit, any deviation heing ncu- tidised by a prism of the smallest absorbing power. When white light is passed through the arrangement described above, the spectrum shows more or less wavy shadows, representing to the eye the law according to which tlie coefficient of absorption of the medium varies with the wave-length of the incident light. Should the slit be divided longitudinally into two equal parts, i t is easy t o compare the two chromatic absorption-spectra produced.By using solar light the absorption-curves may be compared with E’raunhof er’s lines. TheGENERAL AND PHYSICAL CHEMISTRY. 1'31 author concludes by saying that in cases requiring great accuracy &is method is not' applicable. J. M. T. Theory of the Action of certain Organic Substances in increasing the Sensitiveness of Silver Haloids. By M. C. L E A (Amer. J. of Xci. [3], xiv, 96-99).-Explanations of this action of certain organic substances have been offered by Poitevin and by H. Vogel, who suggest that' it' is due to their af€inity for the halogen. The author, however, .points out that all the organic suhstances pos- sessing the property in question are reducing agents, and argues that.i t is their affinity for oxygen which, aiding as it does the affinity of tlie halogen for hydrogen, determines the decomposition of the silver-salt. That this is so is provcd by the fact that when pyrognllol is acided to recently precipitated silver iodide, and the mixture exposed t o sun- light, it exhibits a distinctly acid reaction at tlie end of 15 minutes. Had the first-mentioned explanation been the true one, an iodo-substi- tution-product would have been formed, but no acid. Substances which have a great affinity for iodine, as potassinm carbonate and starch, do not increase the sensitiveness of the silver haloid. These facts support tlie views of the author, as does also the process of alkaline development, tlie alkali, 11y ncutralising the acid produced, assisting the development of the image.Y. D, B. A Battery in which the Carbon Electrode is the one At- tacked. By P. JABLOCHKOFP (Conzpt. rend., lxxxv, 1052-1053).- The electricity produced by electro-magnetic machines is due t o the combustion of carbon. The author has attempted to produce electricity by direct action on carbon. As carbon is not attacked by liquids atj ordinary temperatures, he has constructed a hot liquid electro-chemical battery. For this purpose lie uses either potassium or sodium nitrate in which ordinary coke is used as one electrode, and for thc other platinum-iron, or any metal not attacked by the liquid in lwesence of carbon. By the addition of various metallic salts the electro- motive force may he modified, the nietals being deposited on the unattacked electrode.The electromotive force of the battery the author states to vary between 2 and 3 uiiits, while the Runscn battery gives a maximum of 1.8, and Gernet 2.1. To start the action of the battery, a piece of iiicandescent coke is placed in contact with the crushed nitrate, heat) is pyoduced, and the action commences. A large quantity of carbon dioxide and other gases are evolved, which the author proposes to use as a motive power. A description of the appa- ratus is given. J. 31. T. The Movements of Electrified Mercury. By HE R M AS N HE R W I G (8w.n. Ph?ys. Chem. [Z], i, 73--95).-Earlier experiments on the capillary depression of electrified mercury (this Journal, 1877, i, 677) had rendered it probable that the surface of the glass tube in which the mercury was contained was attacked. I n the experiments here detailed the mercury contained in a capillary tube vas electrified by connecting it with one pole of a Holtz machine, while the other pf!192 ABSTRACTS OF CHEMICAL PAPERS.pole was connected with the earth, sparks being meanwhile allowed to pass between the poles which were not too far apart. When the mercury was connected with the positive pole, i t rorc gradually in the tube when the machine was set in motion, forming, a t the highest point to which it reached, and where the surface remained for some time, a dirty ring, which was not removed by repeatedly pouring dean quicksilver through the tube ; this ring held up the thread of mercury when it was no longer electrified.When, on the other hand, the mercury was connected with the negative pole of the machine, it did not rise so high in the tube, no ring was formed unless the electrification was continued for a long time, and on its ceasing the quicksilver sank immediately to its former level ; this latter fact clearly shows that the cohesion of the quicksilver is diminished by electrifica- tion. Drops of mercury placed upon a horizontal glms plate, and posi- tively electrified, rapidly formed a ring of dirty mercury on the plate : when, however, both the plate and the metal hid been carefully dried, these rings were only obtained with great difficulty. The quicksilver is therefore oxidised if water he present. That the diminution of the rapillary depression is not caused by such oxidation alonc is, liowever, shown by the fact that when tm-o similar tubes were filled, the one with hot, dry quicksilver, the other with the same substance inten- tionally moistened, both tubes being closed at the top, the S~TIIC phe- nomena were observed in each on electrification.Furtlicr, when the space above the quicksilver -as filled with dry hydrogen, the same effects were produced as with air, though not so rapidly, although all chance of oxidation was removed. When the mercury of a barometer is positively electrified in thc same manner, the discharge from thc upper surface being facilitated by connecting the outer surface of the glass with the ground, it ap- pears to boil violently, and glowing particles are projected against the sides of the tube ; the effect is much inferior with negative elcctricity.The diflerent action of the two electricities is explained by sup- posing that where a break occurs in a series of conductors, the nega- tive electricity flows more easily, while the positive collects on the surface till a far greater tension has been attained, thus occasioning, on at length passing off, a much greater disturbance. When the mercury is connected with the positive pole the entire 1-acuous space is filled with bluish-green light, which, examined with the spectroscope, is shown t o be mercury light ; close to the mercnry meiiiscus a yellowish-green fluorescent light is also observed which gives an almost continuous spectrum ; when connected with the nega- tive pole the bluish-green light is less developed, while the fluorescent light fills the upper part of the vacuum.The above liypothesis cx- plains these facts also, since the negative electricity passing more easily from the quicksilver surface, the charge would accumulate a t the upper portion of the tube where its presence would be indicated hy the fluorescent light, whereas the positive would be found close to the surface of the mercury. The same explanation applies to the movement of threads of mer- cury in horizontal capillary tubes : it was found, for instance, thatGENERAL AND PHYSICAL CHEMISTRY. 193 when a platinum-wire, connected with the negative pole of the machine, was placed near one end of the thread, the merciiry rapidly approached the wire, whereas i&en it was connected with the positive pole the mercury was almost always repelled.0 bservations made with tubes containing threads of mercury bounded a t each end by water, were attended with like results. The results o€ the experiments already made are summed up as follows :- (1.) Powerful charges of electricity diminish the cohesion of mer- cury more than the adhesion between mercury and glass, thus lessen- ing the capillary depression in glass tubes. (2.) When positive electricity a t high tension escapes from the sur- face of mercury in glass vessels, tlie surface being exposed to the air, oxidation takes place, more especially when moisture is present. Nega- tive electricity has a reducing action. (3.) The passage of electricity (particularly positive) at high tension from mercury to glass occasions decomposition of the glass.(4.) The three facts above mentioned are the united cause of the observed diminution of the capillary depression. ( 5 . ) Negative electricity escapes from highly charged conductors at a less tension than positive. (6.) When surfaces of mercury are charged with electricity, the formation of mercury-vapour is greatly facilitated. Positive electricity has by far the greatest effect. (7.) Mercury-vapour is relatively an excellent conductor of elec- trici ty . F. I). B. On the Specific Heat of Vapours and its Variations with the Temperature. By E. WIEDEMANN (Am. Phys. C h n . [2], ii, 1'35-21 7) .-In Regnault's researches upon specific heats of vapours, he determined the specific heats at high temperatures by finding the qiiantities of heat given up in each case in condensing the gas from two different high temperatures to the same lower temperature, the difference between the two quantities giving the specific heat between the two high temperatures.He found that the specific heat et a t a temperature t, might be represented by the formula c, = c, + gat, when c, is the specific heat a t 0" and 2u the alteration of specific heat for one degree of temperature. His method is objectionable in this : that though the amount of heat given up in each case may be large and capable of determination with only a small proportiorlate error, nevertheless a small error may bear a, large proportion to the dif- ference between two determinations, and so considerably affect the result.Wiedemann avoids this difficulty by using an arrangement in which he can obtain the vapours a t low pressures and therefore at lower temperatures, and he observes directly the heat given off in cooling a vapour from a higher to a lower temperature. He has investigated thus the values of c, and u in Regnault's formula for chloroform, ethyl bromide, benzene, acetone, acetic ether, and ethyl oxide. His resulting specific heats differ from those of Begnault by from 3 to 5 per cent., but agree much more closely among them-194 ABSTRACTS OF CHEMICAL PAPERS. selves, the variations from Regnault's results being probably clue to i 111 purities . He finds in general that the greater the specific heat of a 1iqu:d thfl greater is that of its vapoin. The coefficient a is o€ tlic same order of magnitude for the liquid and its vapour, and in some cases nrarly the same for the two, but it varies greatly for dif-ferent vapours.J. H. P. The Internal Condition and Latent Heat of Vapours.. By P. C. PUSCHL (Chem. Centr., 1877, p. 318).-Bg a metliod incle- pendent of the second law of thermodynamics, the author deduces the general equation which holds for saturated vapours. Hc further shows that, in the cycle of operations upon a mixture of liquid and rapour, which consists (I), in allowing the same to expand at a con- stant temperature; ( 2 ) ' heating a t the rolumc attained and kept constant; (3), allowing it to contract to its initial volume a t this increased temperature; and (4), allowing it to cool to the init'ial temperature while maintaining its volinme constant at t,his point,-the work expended is not the equivalent, but is in excess of the heat ob- tained.There has therefore been a gain in internaJ work, the qnnntitg of which may be determined in the case of water and its vapour from Regnault's experimental data. The values of the forces which deter- mine the volume of water vapour, under the external pressure, may easily be determined for temperatures between 0" and 200". Respect- ing the function pv, the author finds that, with decreasing temperatnrc and pressure, it does not increase indefinitely to a limiting value, bnt attains a msximum value at a temperature near 0" C., and then de- creases. If the vapour be removed from its point of saturation by expansion at a constant temperature, the product 2v.j is found first to increase, a t ordinary temperatures, to attain a maximum value at a certain point of dilution of the vapour, and then to decrease, whereas a t very low temperatures a progressive decrease from the point of saturation is observed.The deviation of diluted aqueous vnpour from Boyle's law is therefore essentially different from that of ordinary gases and vapours, and is rather of the nature observed by Mendelejeff in the case of rarefied atmospheric air. C. P. c. Abnormal Vapour-densities. By J. GUAR E s c H I ( A h . d.' Acad. cl. Eolog'za [3], viii, 193).-The author gives a general view of the experimental investigations which have any bearing on the .question of the so- called abnormal vapour-densities. He endeavoiirs to show that in most cases of abnormal vapour-densities a partial or total decom- position can be proved with more or less certainty, and therefore that they are not really exceptions to Avogadro's law.Some Properties of Boric Acid. By A. I) I T T E ( Co??zpt. retad., lxxxv, 1069--1072).-1n this paper the author has determined the heat disengaged by the hydration of boric anhydride, which he finds to be 6300 thermal units a t 14;' per one equivalent boracic acid to three of water. I n the case of solution of the hydrated acid an absorptioii of heat, amounting to 3181 thermal units per equivalent, takes place T. C.GENERAL AND PHYSICAL CHEMISTRY. 195 011 the formation of a saturated solution, the solution of tlic hydrous acid thus absorbing about half the heat disengaged by its hydra- tion.The author then gives tables of the specific gravity of the acid a t various temperatures, both in the hydrated and anhydrous condi- tion ; he also determines the coemcient of dilatation between 12" and 80' as 0.0014785, and between 12" and 60" as 0.0015429, amcl gives tables of the solubility of both kinds of acid a t different tcmperatures. I n conclusion he calls attention to the use t o which this action may be put as a lecture experiment to show evolution of heat by chemical action, 100 grams of the anhydride mixed with 125 grams of water being able to melt in a few minutes an ingot of Dtwcet's alloy. J. IT. T. Surface-tension of Aqueous Solutions of Alcohols and Fatty Acids. By 31. DUCLAUX (Compt. rend., lxxxv, lOG8--1069).-'l'he author states that, by allowing different solutions of alcohols and fattj- acids t o flow from a tube having an orifice of known diameter, under constant pressures, and counting the number of drops given by the different solutions, he can obtain the superficial tension of thcse solu- tions by a simple calculation.By comparing these tensions he arrives at the following result :-If solutions of difl'erent den& ties of alcohols or fatty acids having the same superficial tension are compared, the volume-percentages of alcohol or acid whicli they contain have a constant ratio independent of the tension. Tlius, let x be the per- c:entage of alcohol or acid in a liquid, the superficial tension of which = y, and let TC = f (y) be the equation representing the curve of the tensions for a given substance, then x = kf (y) will be the equation of the same curve for any other substance ; or, the function of 1~ in the above expression is the same f o r all bodies of the same organic series, and is modified only from one to the other by the introduction of a constant coefficient, k , which characterises each body.J. M. T. On the Capillary Angle and the spreading out of Liquids upon Solids. By G. QUINCKE (Am. Phys. Chem. 121, ii, 145-194). --The author has published previous investigations upon the surface- tensions and capillary angles of liquids by different methods, but the result of one method did not agree with those of another. He has therefore adopted a direct measure of the angle of capillarity, by ob- serving the angle between the reflections of the same ray from the two surfaces near the dividing edge.He was in this way able t o make very accurate measures. The angle between the same substances was found to vary from different causes. That of a, drop in contact with a glass plate was less the greater the height of fall of the drop on to the plate. This is explained by the fact that if a drop is once spread out it does not contract again properly, and so makes a smallcr angle a j t h the plate than it would otherwise. But the most important modifjing cause was the greater or lesser cleanliness of the plate. The best method of cleaning a surface was to heat it in sulphuric acid, wash it, and allow it to stand in distilled water, and then t o dry it in the colourless flame of a Bunsen's burner.Upon a surlace thus pre- pared fluids like water, alcohol, &c., seemed to spread out a t once and to have a capillary angle of zero. But a few seconds sufficed for the196 ABSTRACTS OF CHEMICAL PAPERS. condensation of air or moisture on the surface and a consequent altem- tion of the angle. The longer the surface was exposed to the air tlie less clean it became and the greater was the angle. The slightest trace of oil was sufficient to affect the surface, and when once present was difficult to remove. It seems probable that the angle for liquids, such as water, alcohol, &c., upon clean glass, crystal, or metal surfaces is zero, and that the liquids immediately spread out, but that when i t has a different value, a layer of some substance is present, upon the solid surface. This layer may be excessively thin, too thin even to show the interference colours.It may consist of foreign solid, liquid, or gaseous substances, or part of the liquid which is being invcstigatetl may itself spread out over the surface, and form a very thin layer mitlt a different snrface-tension from the rest of the liquid which may then rest upon it in a lenticular form. The presence of Ghese layers may be proved by the so-called creeping of salts, or by their conduction of electricity. If two liquids, miscible in all proportions, are in contact with one another and with a third solid body, they will have no definite common surface with a surface-tension, and therefore the one which has the greater surface-tension at the solid surface will be driven by the other away from the solid.By this may be explained some of the phenomena, of diffusion of salts through membranes, &c. Studies on Chemical Volumes. By W. OSTWALD (Chew. Centr., 1877, 25-32 and 42--43).-Several attempts have been made to answer the question how two acids divide themselves towards a base in aqueous solutions. Berthelot and St. Martin adopted a chcrnical method (Ann. Ch+m Phys. [4], xxvi, 433, 1872), which, however, is open t o many objections. The calorimetrical method of A. Muller (Pogg. ATZ'Y~., Suppl. vol., vi, 123, 1875), and that of J. Thomsen, de- pending on the evolution of heat (Pogg. Ann., cxxxviii, 65, 1869), give much more satisfactory results. The method now proposed by the author depends on the measure- ment of the specific gravities of the solutions.Since alterations of volume generally take place during chemical processes in aqueous solutions, it follows that if these are different in one case from what they are in another, the relative magnitudes of action of two bodies acting simultaneously may be measured by the alteration in volume. For instance, the sp. gr. of an equivalent of N a P in solution is 104051, and that of an equivalent of SO3* in solution is 102970 com- pared with water at 20" ; hence the sp. gr. of NaO.SO, in solntion should be 207021. It is found to be 205218 ; hence a difference of - 1103. With NaO and NO5 the difference is found to be - 1868. They will account for Moser's pictures (Hanchbilder) . J. H. P. Thus- NaO.. ..........= 104Q51 sp. gr. NO, ........... = 103083 Sum.. ...... 207134 Na0.N05 found . . 205266 - 1868 * 0 = 8 : S = l G .INORGANIC CHENISTRY. 197 The difference between the contractions in the two cases aniounts to -7’765. I n this way a series of numbers is obtained which may be compared with those obtained by Thomsen by means of the formula The agreement of the numbers obtained by the shown in the following table :- Found by author’s method. NaO SO3.2SO3 ............ - 129 N&OSO3.+SO3 ............ - 213 NaOSO3. so3 ............ - 320 NaOXO3.2SO3 ............ - 398 NaOS03.4S03 ............ - 452 two methods is C:hdatcd b j iornllllu. - 132 - 213 - 309 - 396 - 463 n n + U.8 Thornsen’s formula is - x const. In other experiments Guldberg’s formula (Guldberg et Waage, Etudes szw les Afinite‘s c h i m i p e s , Christiania, 18767) is employed, and the results are shown to agree.The analogy between the change of volume and evolution of heat is very striking, as in the following cases :- Evolution of heal,. Condensation. Na0.S03-Na0.N0, ...... - 2072 - 765 Na0.S03--Na0.HC1 ...... - 1949 - 740 Na0.S03.$S03 ............ - 631 - 213 Na0.S03.+N05 ............ - 1292 - 472 Na0.S03.2N0, ............ - 2026 - 748 Na0.S03.2HC1.. .......... - 1878 - 688 K. Hofmnnn proposed a method somewhat similar to t,hat of the author to solve a similar question (Pogg. Ann., cxxxiii, 5 i 5 ) . G. T. A.189G e n e r a l a n d P h y s i c a l Chemistry.On some Points connected with the Chemical Constituentsof the Solar System. By J.H. G L A D S T O N E (Phil. Nus. [5], iv,379-385) .-The formation of the solar system by thc condensationof a nebulous mass made up of many different chemical elements, willhave resulted in a distribution of those elements dependent on the twofollowina considepations :-(1.) During the process of cooling the least volatile constituents willcondense first and sink towards the centre of gravity, while thc restwill arrange themselves inore or less in the order of their volatility.(2.) As mas pointed out by Mr. C. J. Stoneg, in an atmosphere de-creasing in temperature from within outwards, the lightest moleculeswill be the farthest from the centre of gravity.The most volatile elements, and those of least vapour-deiisity, willtherefore be the outermost in a hot nebulous mass.This distributionis seen to occur in the sun, where hydrogen forms the bulk of the outeratmosphere, mixed with small quantities of sodium and magnesium,while the vapoui* of iron is found only in a lower stratum of the sun’satmosphere, and platinum has not been detected at all.According to the nebular theory, the planets wcwe formed by theseparation of some of the outer portion of the original mass; weshould therefore expect them to contain a preponderance of the morevolatile elements, and those of least vapour-density ; and this is in-deed the case. Of thecnori-metallic elements, those which are plentifulhave an average vapour-density of 19.8, while those wliich are com-paratively rare have an average vapour-density of 63 : grouping themetals into four classes-plentiful, common, rare, and very rare, wefind that the average vapour-densities of each class are, 37.8, 104.5,106.7, and 122.9 respectively.The meteoric stones which fall to the earth from interplanetary spacesshow this preponderance of the lighter elements still more strikingly.There are, however, in both cases many exceptions to thc rule, for in-Etance, glucinum and lithium are both rare, while lead is w r y common ;such exceptions may be cxplained by supposing these elements to havebeen combined with others forming compounds of g1-catcr or lessvolatility than themselves ; thus carbon is very difficult to volatilise,but its compounds with oxygen, hydrogen, &c., are gases at the ordi-nary temperature.The heads of comets emit light giving band spectra which areusually referred to carbon ; the volatilised carbon of the electric lampwas also found to give these band spectra ; in cornets, however, thecarbon is probably combined with oxygen or hydrogen.The Influence of Temperature upon the Coefficients ofRefraction of the Natural Sulphates of Barium, Strontium,and Lead. By A.ARZRUNI (Jahrb. f. J&., 1877, 52t;--527).--Theauthor considered it desirable to ascertain whether the coefficients ofF. D. €3.VOL. XXXlV. 2190 ABSTRACT8 OF CHEMICAL PAPERS.refraction remained constant or varied with the temperature a t whichthe determination was made. Three isomorphous sulphates, viz.,barium salpliate, strontium sulphate, and lead sulphate were selectedfor the investiption ; firstly, because Descloiseaux observed in them agreat variation of the angle of the optical axis with the temperature,from which it might justly be inferred that any change in the co-efficient of refraction could easily be determined ; and, secondly, itwas desirable to ascertain if isomorphous cornpounds with analogousoptical characteristics still remained analogous to an increase oftemperature.F o r these observations the author prepared prisnis outof a barytes crystal from Dufton, a cmlestine crystal from Lake Erie,and an anglesite crystal from Monte Poni, the results of the investiga-tions being briefly as follows, vie. :-(1.) The principal coefficients ofrefraction of the above-mentioned isomorphous sulphntes differ fromeach other with the temperature, but all of them decrease with anincrease of temperature.(2.) The decrease in the coefficient of re-fraction of the three sulphates is an analogous one, and can he ex-pressed thus, viz., Further, y approaches the two others,whilst u withdraws from 6. (3.) With anglesite the refraction isinversely as the temperaftme, whilst the dispersion increases for dif-ferent colours. (4.) The directions of the maximum, medium, andminimum expansicjn of the three compounds by heat do not staid inany relationship to the values of the directions of optical elasticity inthem, or to the alteration of the velocity of light in these three direc-tions. C. A. B.> u > 6.On the Law of Absorption and its Employment in Quantita-tive Spectrum Analysis.By G. Govh (Conyt. r m r l . , lxxxv, 1046-1049).-The author at first alludes to the phenomena of absorption,and compares tlie increase and dilatation o€ absorption-bands ‘‘ due tothickening in the absorbing medium,” to the increase in the brightlines in the spectra of incandescent gases caused by increase in thetemperatiwe aEd pressure. He says tliat it is not possible to determinethe absorbing power of a body, unless the coefficients of absorptionare known f o r all wave-lengths which can be studied. He thinks,however, tlhatj the absorbing power of bodies may be determined, eitherby direct comparison of the curves of chroniatic absorption, or bymeasuring tlie intensity of the light along the whole length of thespectrum. To use the first of these methods, lie employs the ab-sorbent in tlie shape of a prism, and by placing one of its plane facesagainst the slit, with the centre angle touching one end of it, he ob-tains a gradually increasing thickness of the absorbing mediumthroughout the whole leiigth of the slit, any deviation heing ncu-tidised by a prism of the smallest absorbing power.When whitelight is passed through the arrangement described above, the spectrumshows more or less wavy shadows, representing to the eye the lawaccording to which tlie coefficient of absorption of the medium varieswith the wave-length of the incident light. Should the slit be dividedlongitudinally into two equal parts, i t is easy t o compare the twochromatic absorption-spectra produced.By using solar light theabsorption-curves may be compared with E’raunhof er’s lines. ThGENERAL AND PHYSICAL CHEMISTRY. 1'31author concludes by saying that in cases requiring great accuracy &ismethod is not' applicable. J. M. T.Theory of the Action of certain Organic Substances inincreasing the Sensitiveness of Silver Haloids. By M. C. L E A(Amer. J. of Xci. [3], xiv, 96-99).-Explanations of this action ofcertain organic substances have been offered by Poitevin and by H.Vogel, who suggest that' it' is due to their af€inity for the halogen.The author, however, .points out that all the organic suhstances pos-sessing the property in question are reducing agents, and argues that.i t is their affinity for oxygen which, aiding as it does the affinity of tliehalogen for hydrogen, determines the decomposition of the silver-salt.That this is so is provcd by the fact that when pyrognllol is acided torecently precipitated silver iodide, and the mixture exposed t o sun-light, it exhibits a distinctly acid reaction at tlie end of 15 minutes.Had the first-mentioned explanation been the true one, an iodo-substi-tution-product would have been formed, but no acid.Substances which have a great affinity for iodine, as potassinmcarbonate and starch, do not increase the sensitiveness of the silverhaloid.These facts support tlie views of the author, as does also theprocess of alkaline development, tlie alkali, 11y ncutralising the acidproduced, assisting the development of the image.Y. D, B.A Battery in which the Carbon Electrode is the one At-tacked. By P. JABLOCHKOFP (Conzpt. rend., lxxxv, 1052-1053).-The electricity produced by electro-magnetic machines is due t o thecombustion of carbon. The author has attempted to produce electricityby direct action on carbon. As carbon is not attacked by liquids atjordinary temperatures, he has constructed a hot liquid electro-chemicalbattery. For this purpose lie uses either potassium or sodium nitratein which ordinary coke is used as one electrode, and for thc otherplatinum-iron, or any metal not attacked by the liquid in lwesenceof carbon. By the addition of various metallic salts the electro-motive force may he modified, the nietals being deposited on theunattacked electrode.The electromotive force of the battery theauthor states to vary between 2 and 3 uiiits, while the Runscn batterygives a maximum of 1.8, and Gernet 2.1. To start the action of thebattery, a piece of iiicandescent coke is placed in contact with thecrushed nitrate, heat) is pyoduced, and the action commences. A largequantity of carbon dioxide and other gases are evolved, which theauthor proposes to use as a motive power. A description of the appa-ratus is given. J. 31. T.The Movements of Electrified Mercury. By HE R M AS NHE R W I G (8w.n. Ph?ys. Chem. [Z], i, 73--95).-Earlier experiments onthe capillary depression of electrified mercury (this Journal, 1877, i,677) had rendered it probable that the surface of the glass tube inwhich the mercury was contained was attacked. I n the experimentshere detailed the mercury contained in a capillary tube vas electrifiedby connecting it with one pole of a Holtz machine, while the otherpf192 ABSTRACTS OF CHEMICAL PAPERS.pole was connected with the earth, sparks being meanwhile allowed topass between the poles which were not too far apart.When the mercury was connected with the positive pole, i t rorcgradually in the tube when the machine was set in motion, forming, a tthe highest point to which it reached, and where the surface remainedfor some time, a dirty ring, which was not removed by repeatedlypouring dean quicksilver through the tube ; this ring held up thethread of mercury when it was no longer electrified.When, on theother hand, the mercury was connected with the negative pole of themachine, it did not rise so high in the tube, no ring was formed unlessthe electrification was continued for a long time, and on its ceasing thequicksilver sank immediately to its former level ; this latter fact clearlyshows that the cohesion of the quicksilver is diminished by electrifica-tion.Drops of mercury placed upon a horizontal glms plate, and posi-tively electrified, rapidly formed a ring of dirty mercury on the plate :when, however, both the plate and the metal hid been carefully dried,these rings were only obtained with great difficulty. The quicksilveris therefore oxidised if water he present. That the diminution of therapillary depression is not caused by such oxidation alonc is, liowever,shown by the fact that when tm-o similar tubes were filled, the onewith hot, dry quicksilver, the other with the same substance inten-tionally moistened, both tubes being closed at the top, the S~TIIC phe-nomena were observed in each on electrification. Furtlicr, when thespace above the quicksilver -as filled with dry hydrogen, the sameeffects were produced as with air, though not so rapidly, although allchance of oxidation was removed.When the mercury of a barometer is positively electrified in thcsame manner, the discharge from thc upper surface being facilitatedby connecting the outer surface of the glass with the ground, it ap-pears to boil violently, and glowing particles are projected against thesides of the tube ; the effect is much inferior with negative elcctricity.The diflerent action of the two electricities is explained by sup-posing that where a break occurs in a series of conductors, the nega-tive electricity flows more easily, while the positive collects on thesurface till a far greater tension has been attained, thus occasioning,on at length passing off, a much greater disturbance.When the mercury is connected with the positive pole the entire1-acuous space is filled with bluish-green light, which, examined withthe spectroscope, is shown t o be mercury light ; close to the mercnrymeiiiscus a yellowish-green fluorescent light is also observed whichgives an almost continuous spectrum ; when connected with the nega-tive pole the bluish-green light is less developed, while the fluorescentlight fills the upper part of the vacuum.The above liypothesis cx-plains these facts also, since the negative electricity passing moreeasily from the quicksilver surface, the charge would accumulate a tthe upper portion of the tube where its presence would be indicatedhy the fluorescent light, whereas the positive would be found close tothe surface of the mercury.The same explanation applies to the movement of threads of mer-cury in horizontal capillary tubes : it was found, for instance, thaGENERAL AND PHYSICAL CHEMISTRY. 193when a platinum-wire, connected with the negative pole of the machine,was placed near one end of the thread, the merciiry rapidly approachedthe wire, whereas i&en it was connected with the positive pole themercury was almost always repelled.0 bservations made with tubescontaining threads of mercury bounded a t each end by water, wereattended with like results.The results o€ the experiments already made are summed up asfollows :-(1.) Powerful charges of electricity diminish the cohesion of mer-cury more than the adhesion between mercury and glass, thus lessen-ing the capillary depression in glass tubes.(2.) When positive electricity a t high tension escapes from the sur-face of mercury in glass vessels, tlie surface being exposed to the air,oxidation takes place, more especially when moisture is present. Nega-tive electricity has a reducing action.(3.) The passage of electricity (particularly positive) at high tensionfrom mercury to glass occasions decomposition of the glass.(4.) The three facts above mentioned are the united cause of theobserved diminution of the capillary depression.( 5 .) Negative electricity escapes from highly charged conductors ata less tension than positive.(6.) When surfaces of mercury are charged with electricity, theformation of mercury-vapour is greatly facilitated. Positive electricityhas by far the greatest effect.(7.) Mercury-vapour is relatively an excellent conductor of elec-trici ty . F. I). B.On the Specific Heat of Vapours and its Variations withthe Temperature. By E. WIEDEMANN (Am. Phys. C h n . [2], ii,1'35-21 7) .-In Regnault's researches upon specific heats of vapours,he determined the specific heats at high temperatures by finding theqiiantities of heat given up in each case in condensing the gas fromtwo different high temperatures to the same lower temperature, thedifference between the two quantities giving the specific heat betweenthe two high temperatures.He found that the specific heat et a t atemperature t, might be represented by the formula c, = c, + gat,when c, is the specific heat a t 0" and 2u the alteration of specific heatfor one degree of temperature. His method is objectionable in this :that though the amount of heat given up in each case may be largeand capable of determination with only a small proportiorlate error,nevertheless a small error may bear a, large proportion to the dif-ference between two determinations, and so considerably affect theresult.Wiedemann avoids this difficulty by using an arrangementin which he can obtain the vapours a t low pressures and therefore atlower temperatures, and he observes directly the heat given off incooling a vapour from a higher to a lower temperature. He hasinvestigated thus the values of c, and u in Regnault's formula forchloroform, ethyl bromide, benzene, acetone, acetic ether, and ethyloxide. His resulting specific heats differ from those of Begnault byfrom 3 to 5 per cent., but agree much more closely among them194 ABSTRACTS OF CHEMICAL PAPERS.selves, the variations from Regnault's results being probably clue toi 111 purities .He finds in general that the greater the specific heat of a 1iqu:d thflgreater is that of its vapoin.The coefficient a is o€ tlic same order ofmagnitude for the liquid and its vapour, and in some cases nrarly thesame for the two, but it varies greatly for dif-ferent vapours.J. H. P.The Internal Condition and Latent Heat of Vapours.. ByP. C. PUSCHL (Chem. Centr., 1877, p. 318).-Bg a metliod incle-pendent of the second law of thermodynamics, the author deduces thegeneral equation which holds for saturated vapours. Hc furthershows that, in the cycle of operations upon a mixture of liquid andrapour, which consists (I), in allowing the same to expand at a con-stant temperature; ( 2 ) ' heating a t the rolumc attained and keptconstant; (3), allowing it to contract to its initial volume a t thisincreased temperature; and (4), allowing it to cool to the init'ialtemperature while maintaining its volinme constant at t,his point,-thework expended is not the equivalent, but is in excess of the heat ob-tained.There has therefore been a gain in internaJ work, the qnnntitgof which may be determined in the case of water and its vapour fromRegnault's experimental data. The values of the forces which deter-mine the volume of water vapour, under the external pressure, mayeasily be determined for temperatures between 0" and 200". Respect-ing the function pv, the author finds that, with decreasing temperatnrcand pressure, it does not increase indefinitely to a limiting value, bntattains a msximum value at a temperature near 0" C., and then de-creases.If the vapour be removed from its point of saturation byexpansion at a constant temperature, the product 2v.j is found first toincrease, a t ordinary temperatures, to attain a maximum value at acertain point of dilution of the vapour, and then to decrease, whereasa t very low temperatures a progressive decrease from the point ofsaturation is observed. The deviation of diluted aqueous vnpour fromBoyle's law is therefore essentially different from that of ordinarygases and vapours, and is rather of the nature observed by Mendelejeffin the case of rarefied atmospheric air. C. P. c.Abnormal Vapour-densities. By J. GUAR E s c H I ( A h . d.' Acad.cl. Eolog'za [3], viii, 193).-The author gives a general view of theexperimental investigations which have any bearing on the .questionof the so- called abnormal vapour-densities.He endeavoiirs to showthat in most cases of abnormal vapour-densities a partial or total decom-position can be proved with more or less certainty, and therefore thatthey are not really exceptions to Avogadro's law.Some Properties of Boric Acid. By A. I) I T T E ( Co??zpt. retad.,lxxxv, 1069--1072).-1n this paper the author has determined theheat disengaged by the hydration of boric anhydride, which he findsto be 6300 thermal units a t 14;' per one equivalent boracic acid to threeof water. I n the case of solution of the hydrated acid an absorptioiiof heat, amounting to 3181 thermal units per equivalent, takes placeT. CGENERAL AND PHYSICAL CHEMISTRY.195011 the formation of a saturated solution, the solution of tlic hydrousacid thus absorbing about half the heat disengaged by its hydra-tion. The author then gives tables of the specific gravity of the acida t various temperatures, both in the hydrated and anhydrous condi-tion ; he also determines the coemcient of dilatation between 12" and80' as 0.0014785, and between 12" and 60" as 0.0015429, amcl givestables of the solubility of both kinds of acid a t different tcmperatures.I n conclusion he calls attention to the use t o which this action may beput as a lecture experiment to show evolution of heat by chemicalaction, 100 grams of the anhydride mixed with 125 grams of waterbeing able to melt in a few minutes an ingot of Dtwcet's alloy.J.IT. T.Surface-tension of Aqueous Solutions of Alcohols and FattyAcids. By 31. DUCLAUX (Compt. rend., lxxxv, lOG8--1069).-'l'heauthor states that, by allowing different solutions of alcohols and fattj-acids t o flow from a tube having an orifice of known diameter, underconstant pressures, and counting the number of drops given by thedifferent solutions, he can obtain the superficial tension of thcse solu-tions by a simple calculation. By comparing these tensions he arrivesat the following result :-If solutions of difl'erent den& ties of alcoholsor fatty acids having the same superficial tension are compared, thevolume-percentages of alcohol or acid whicli they contain have aconstant ratio independent of the tension.Tlius, let x be the per-c:entage of alcohol or acid in a liquid, the superficial tension of which= y, and let TC = f (y) be the equation representing the curve of thetensions for a given substance, then x = kf (y) will be the equationof the same curve for any other substance ; or, the function of 1~ in theabove expression is the same f o r all bodies of the same organic series,and is modified only from one to the other by the introduction of aconstant coefficient, k , which characterises each body. J. M. T.On the Capillary Angle and the spreading out of Liquidsupon Solids. By G. QUINCKE (Am. Phys. Chem. 121, ii, 145-194).--The author has published previous investigations upon the surface-tensions and capillary angles of liquids by different methods, but theresult of one method did not agree with those of another.He hastherefore adopted a direct measure of the angle of capillarity, by ob-serving the angle between the reflections of the same ray from the twosurfaces near the dividing edge. He was in this way able t o makevery accurate measures. The angle between the same substances wasfound to vary from different causes. That of a, drop in contact with aglass plate was less the greater the height of fall of the drop on to theplate. This is explained by the fact that if a drop is once spread outit does not contract again properly, and so makes a smallcr anglea j t h the plate than it would otherwise. But the most importantmodifjing cause was the greater or lesser cleanliness of the plate.The best method of cleaning a surface was to heat it in sulphuric acid,wash it, and allow it to stand in distilled water, and then t o dry it inthe colourless flame of a Bunsen's burner.Upon a surlace thus pre-pared fluids like water, alcohol, &c., seemed to spread out a t once andto have a capillary angle of zero. But a few seconds sufficed for th196 ABSTRACTS OF CHEMICAL PAPERS.condensation of air or moisture on the surface and a consequent altem-tion of the angle. The longer the surface was exposed to the air tlieless clean it became and the greater was the angle. The slightesttrace of oil was sufficient to affect the surface, and when once presentwas difficult to remove. It seems probable that the angle for liquids,such as water, alcohol, &c., upon clean glass, crystal, or metal surfacesis zero, and that the liquids immediately spread out, but that when i thas a different value, a layer of some substance is present, upon thesolid surface.This layer may be excessively thin, too thin even to showthe interference colours. It may consist of foreign solid, liquid, orgaseous substances, or part of the liquid which is being invcstigatetlmay itself spread out over the surface, and form a very thin layer mitlta different snrface-tension from the rest of the liquid which may thenrest upon it in a lenticular form. The presence of Ghese layers may beproved by the so-called creeping of salts, or by their conduction ofelectricity.If two liquids, miscible in all proportions, are in contact with oneanother and with a third solid body, they will have no definite commonsurface with a surface-tension, and therefore the one which has thegreater surface-tension at the solid surface will be driven by the otheraway from the solid.By this may be explained some of the phenomena,of diffusion of salts through membranes, &c.Studies on Chemical Volumes. By W. OSTWALD (Chew.Centr., 1877, 25-32 and 42--43).-Several attempts have been madeto answer the question how two acids divide themselves towards a basein aqueous solutions. Berthelot and St. Martin adopted a chcrnicalmethod (Ann. Ch+m Phys. [4], xxvi, 433, 1872), which, however, isopen t o many objections. The calorimetrical method of A. Muller(Pogg. ATZ'Y~., Suppl. vol., vi, 123, 1875), and that of J. Thomsen, de-pending on the evolution of heat (Pogg. Ann., cxxxviii, 65, 1869),give much more satisfactory results.The method now proposed by the author depends on the measure-ment of the specific gravities of the solutions. Since alterations ofvolume generally take place during chemical processes in aqueoussolutions, it follows that if these are different in one case from whatthey are in another, the relative magnitudes of action of two bodiesacting simultaneously may be measured by the alteration in volume.For instance, the sp. gr. of an equivalent of N a P in solution is104051, and that of an equivalent of SO3* in solution is 102970 com-pared with water at 20" ; hence the sp. gr. of NaO.SO, in solntionshould be 207021. It is found to be 205218 ; hence a difference of- 1103. With NaO and NO5 the difference is found to be - 1868.They will account for Moser's pictures (Hanchbilder) .J. H. P.Thus-NaO.. .......... = 104Q51 sp. gr.NO, ........... = 103083Sum.. ...... 207134Na0.N05 found . . 205266- 1868* 0 = 8 : S = l G INORGANIC CHENISTRY. 197The difference between the contractions in the two cases aniounts to-7’765. I n this way a series of numbers is obtained which may becompared with those obtained by Thomsen by means of the formulaThe agreement of the numbers obtained by theshown in the following table :-Found byauthor’s method.NaO SO3.2SO3 ............ - 129N&OSO3.+SO3 ............ - 213NaOSO3. so3 ............ - 320NaOXO3.2SO3 ............ - 398NaOS03.4S03 ............ - 452two methods isC:hdatcd b jiornllllu.- 132- 213- 309- 396- 463nn + U.8Thornsen’s formula is - x const.In other experiments Guldberg’s formula (Guldberg et Waage,Etudes szw les Afinite‘s c h i m i p e s , Christiania, 18767) is employed, andthe results are shown to agree.The analogy between the change of volume and evolution of heat isvery striking, as in the following cases :-Evolution of heal,. Condensation.Na0.S03-Na0.N0, ...... - 2072 - 765Na0.S03--Na0.HC1 ...... - 1949 - 740Na0.S03.$S03 ............ - 631 - 213Na0.S03.+N05 ............ - 1292 - 472Na0.S03.2N0, ............ - 2026 - 748Na0.S03.2HC1.. .......... - 1878 - 688K. Hofmnnn proposed a method somewhat similar to t,hat of theauthor to solve a similar question (Pogg. Ann., cxxxiii, 5 i 5 ) .G. T. A

ISSN:0368-1769    

DOI:10.1039/CA8783400189

出版商:RSC    

年代:1878

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 197 I n o r g a n i c C h e m i s t r y . The Reducing Action of Hydrogen. By D. TOMMASI (Isti- tuto Lowzhardo [2], x).-The author concludes that, for the explanation of certain reducing actions of hydrogen, it is not necessary to make the assumption of an allotropic modification of the element. In most instances a sufficient explanation is obta'ined if we suppose that tlhe evolved hydrogen possesses various quantities of heat in the digerent phenomena observed. This supposition he endeavours to substnntiakc by a number of experiments. T. C. The Gases dissolved in Sea-water. By J. Y. BUCHANAN (Chem. Cemtr., 877, 742).-The author describes the apparatus used by him for determining the oxygen, nitrogen, and carbonic anhydride198 ABSTRACTS OF CHEMICAL PAPERS.on board of the “ Challenger.” His conclusions are, tlmt the amount of oxygen and nitrqen in sqa-water is less than that contained in river-water, but the proportion of the two elernents to each other is nearly the same; that the absolute amount of gas deperids on tihe temperature ; and that water a t a great depth has all the physical pro- perties of surface water. Nevertheless the belicf that water from a great depth parts with gas when relievcd from pressure is true, inas- much as biibbles appear on the side of the vessel in which it is con- tained, when it is allowed to stand for some time. Surface water contains 33 to 35 per cent. of its volume of oxygen ; water from the Trade Winch’ regions gave the first figure, and tllat from the Antarctic Circle the second.Water covering diatomaceoils mud contains most, and covering red clay least oxygen. The amount of oxygen decreases up to a depth of 1,800 feet, and then increases. It apparently depends on the presence of animal life. ?V. R. Action of Oxalic Acid on Sodium Silicate. By E. MOBIF: R (Compt. T e d . , lxxxv, 1053-1054) .-The author introduces a solution o€ oxalic acid, 75 grams to the litre, into a vessel containing 500 C.C. solution of sodium silicate. The liquors do not mix, and a crust is formed a t their point of contact, consist,ing of amorphous hydrated silica. This layer increases in thickness in certain cases, having reached 7 to 8 mm. after standing two months. The crust sets quite hard, and when heated decrepitates, giving a fine white sand hard enough to polish glass.J. M. T. The Action of Phosphoric Acid on Calcium Carbonate. By H. RITTHAU s F N (Land. VersziclwXtat., xx, 401-407).---An aqueous solution of pliosplioric acid acts on precipitated chalk, forming small needle-shaped crystals of di-calcium phosphate, Ca,H2P,08 ; the tri- phosphate is never formed. The crystalline character of the phosphate renders i t possible to detect very small quantities of this substancc, even in presence of a large excess of calcium carbonate, by means of the microscope. The finely divided chalk contained in marl deposited in the beds of streams or ponds is easily attacked by phosphoric acid. Deme particles of calcium carbonate in marl, which arc scarcely acted on by phosphoric acid, are converted into di-calcium phosphate by the simultaneous action of carbonic and phosphoric acids.On the Formation of Ultramarines and their Colorations. By E. GUIMET (Cowzpt. rend., lxxxv, 1072--1074).-When ultrama- rine is being prepared, tb e mixture becomes successively coloured brown, green, blue, violet, red, and white, in the order named. These changes the author ascribes to the gradual oxidation of the mixture of kaolin, sulphur, and sodic carbonate and sulphate. The brown colour appears with the blue flames due to the combustion of sulphur, the green just after the sulphur flames have ceased, and the blue is first seen at a temperature of about 700”. If, after this point is reached, heat is still applied, and free access of air permitted, the mixture becomes violet, red or rose-coloured, and finally white. When Llie white ultra- marine is heated to redness with carbon, the red, violet, blue, green, or W.C. W.INORGANIC CHEMISTRY. 199 brown varieties are reproduced, according to the quantity of carbon used, and these colours may again be made to pass through changes in the same order as before by fbrther oxidation. Hydrogeii, ammonium chloride, and other reducing agents act in the same manner a,s carbon. These facts, the author thinks, show that tlic changes of colour are due to different degrees of oxidation, as also that they may be due to the sulphur in the mixture, this being shown by the fact that the colours differ when other bodies of the same group are used. He thinks also that the soda, though not producing the colours directly, is neccssary, since any attempt to replace it by another substance prevents the formation of the colours. He considers that several varieties of ultra- marine exist, and that a further study of these bodies will be of advan- tage.J. 35. T. Silver Ultramarine. By J. PHILIPPS (Deut. Chern. Ges. L'e.., x, 2031).-The product obtained by the action of silver nitrate on ultra- marine blue (p. 113 of this volume), evolves sulphnretted hydrogen when treated with an excess of hydrochloric acid ; there is no action, however, with a small quantity of acid. T, C. Oxidation of Metallic Sulphides. By P H. DE C L E R M o N T and H. GUIOT ( C o q ~ t . rend., lxxxv, 714).-If moist manganese sulphide is suddenly compressed and powdered, rapid oxidation takes place, and the temperature of the mass rises several degrees.R'ecently precipi- tated nickel and ferrous sulphides oxidise even more violently than manganese sulphide : when strongly compressed and then powdered between the fingers, the temperature of the sulphide rapidly rises through 35 or 45 degrees, and aqueous vapour is disengaged. The sulphides of cobalt,, copper, and zinc, when treated in a similar manner, do not oxidise rapidly enough to give rise to a disengagement of heat. J. W. The Behaviour of Iodine to Amido-mercuric Chloride, in Presence of Alcohol; and a Safe Method of Preparing Iodide of Nitrogen. B y R. BOTTGER (Cihenz. Ce7xtr., 1877, G51).-Although iodine may be ground in a mortar along with amido-mercuric chloride, with no other action than the formation of mercuric iodide, yet in presence of alcohol, an explosion always takes place in thirty or forty minutes, preceded by evolution of nitrogen, and sometimes separation of mercuric chloride.I n presence of chloroform or arnyl alcohol, gas is evolved, but no explosion occurs. The author's process for preparing nitrogen iodide consists in treat- ing a solution of iodine chloride, obtained by heating iodine with nitro- hydrochloric acid, with ammonia. Thus prepared, it never explodes when moist, and when dry, only when touched with a piece of wood, or some similar substance. W. R. Anhydrous Sodioferric Pyrophosphate. By S. 31. JO R G E pt's E s (J. pr. Chem. [a], xvi, 342- 344).-The brownish-coloured glass, obtained by strongly heating a mixture of microcosmic salt and ferric oxide, is slowly melted in a platinum dish by the heat of a Bunsen's200 ABSTRACTS O F CHEMICAL PAPERS.burner. The fused mass is treated with dilute hydrochloric acid, which dissolves out sodium phosphate, and leaves R bluish pearly crystalline residue of sodioferricpyrophospbste, Na2FcVi,P4O,,. This compound crystallises in rhombic tables, and also in prisms terminated by acute pyramids ; it can be recrystallised by solution in molten micro- cosmic salt. It is decomposed by fusion with sodium carbonate, or by boiling with strong sulphuric acid, concentrated hydrochloric or nitric acids have scarcely any action on this body. w. c. w. Action of Silver Nitrate on Hydroplatinic Chloride. By S. M. J~RGENSEN ( J . p r . Chern., [Z], xvi, 345-35t;).--The addition of silver nitrate in excess, to a cold solution of hydmplatinic chloride, throws down the whole of tthe platinum in the form of a yellow pre- cipitate, having the composition 2AgCl.PtC1,.This substance has not beeii obtained in the pure state, as it is slowly decomposed by cold, and rapidly by hot water, into a solution of Norton’s salt, PtC1,5H,O (J. pr. Chenz., [a], ii, 469 ; v, 36.5)) and an insoluble residue, consisting of impure silver chloride. Norton’s salt loses four molecules of water a t loo”, the fifth molecule cannot be expelled without decomposing the compound. The aqueous solution of this substance has an acid reaction, decomposes carbonates, and produces with silver nitrate a yellow precipitate of AffaPtCl4(OHl2. With ammonia, it forms a precipitate of ammonio-platinic chloride, and the filtrate yields on evaporation a black, amorphous, hygroscopic residue of platinum hydroxychloride. The relation between these bodies is shown thus :- Hydroplatinic chloride. Norton’s salt.Platinum hydroxy- chloride. The action of silver nitrate on a hot solution of hydroplatinic chlo- ride may be represented by the following equations :- H2PtC16 + ‘LAgNO, = AgzPtC1, + 2HN03. AgzPtC1, + H20 = HPtCl*.OH + 2Ag:CI. H2O + HPtCl4.OH + 2AgN03 = AgAPtC14(0H)t + 2HN03. The silver salt obtained by adding silver nitrate to Norton’s salt is not analogous to the acid from which it is derived, since it yields by double decomposition with ammonium chloride platinosemidiammo- nium chloride, C12Pt(N2H6c1), and silver chloride. w.c. w. c1 Platinosoplatinic Oxide. By S. M. J o R G E N s E N (J. p Y. Chenz. [a], xvi, 344).--Platinosoplatinic oxide, Pt304, is o btained by heating one part of anhydrous sodium platinochloride with four parts of dry sodium carbonate, nntil the mixture begins to fuse. (The platino- chlorides of pot,assium and ammonium cannot be substituted for the sodium salt.) The black residue which remains after treating the fused mass with water, and with dilute nitric acid, is repeatedly washedMINERALOGICAL CHEMISTRY. 201 by decantation with hot nitric acid, and finally with water acidified with nitric acid, and is then dried at 110". This oxide is converted into platinum black by formic acid ; it is not attacked by mineral acids, not even by boiling aqua regia.It slowly loses oxygen at a red heat, but it is rapidly reduced in an atmosphere of hydrogen or coal gas, even a t the ordinary temperature. w. c. w.INORGANIC CHEMISTRY. 197I n o r g a n i c C h e m i s t r y .The Reducing Action of Hydrogen. By D. TOMMASI (Isti-tuto Lowzhardo [2], x).-The author concludes that, for the explanationof certain reducing actions of hydrogen, it is not necessary to make theassumption of an allotropic modification of the element. In mostinstances a sufficient explanation is obta'ined if we suppose that tlheevolved hydrogen possesses various quantities of heat in the digerentphenomena observed. This supposition he endeavours to substnntiakcby a number of experiments. T. C.The Gases dissolved in Sea-water. By J.Y. BUCHANAN(Chem. Cemtr., 877, 742).-The author describes the apparatus usedby him for determining the oxygen, nitrogen, and carbonic anhydrid198 ABSTRACTS OF CHEMICAL PAPERS.on board of the “ Challenger.” His conclusions are, tlmt the amountof oxygen and nitrqen in sqa-water is less than that contained inriver-water, but the proportion of the two elernents to each other isnearly the same; that the absolute amount of gas deperids on tihetemperature ; and that water a t a great depth has all the physical pro-perties of surface water. Nevertheless the belicf that water from agreat depth parts with gas when relievcd from pressure is true, inas-much as biibbles appear on the side of the vessel in which it is con-tained, when it is allowed to stand for some time. Surface watercontains 33 to 35 per cent.of its volume of oxygen ; water from theTrade Winch’ regions gave the first figure, and tllat from the AntarcticCircle the second. Water covering diatomaceoils mud contains most,and covering red clay least oxygen. The amount of oxygen decreasesup to a depth of 1,800 feet, and then increases. It apparently dependson the presence of animal life. ?V. R.Action of Oxalic Acid on Sodium Silicate. By E. MOBIF: R(Compt. T e d . , lxxxv, 1053-1054) .-The author introduces a solutiono€ oxalic acid, 75 grams to the litre, into a vessel containing 500 C.C.solution of sodium silicate. The liquors do not mix, and a crust isformed a t their point of contact, consist,ing of amorphous hydratedsilica.This layer increases in thickness in certain cases, having reached7 to 8 mm. after standing two months. The crust sets quite hard, andwhen heated decrepitates, giving a fine white sand hard enough topolish glass. J. M. T.The Action of Phosphoric Acid on Calcium Carbonate. ByH. RITTHAU s F N (Land. VersziclwXtat., xx, 401-407).---An aqueoussolution of pliosplioric acid acts on precipitated chalk, forming smallneedle-shaped crystals of di-calcium phosphate, Ca,H2P,08 ; the tri-phosphate is never formed. The crystalline character of the phosphaterenders i t possible to detect very small quantities of this substancc,even in presence of a large excess of calcium carbonate, by means ofthe microscope. The finely divided chalk contained in marl depositedin the beds of streams or ponds is easily attacked by phosphoric acid.Deme particles of calcium carbonate in marl, which arc scarcely actedon by phosphoric acid, are converted into di-calcium phosphate by thesimultaneous action of carbonic and phosphoric acids.On the Formation of Ultramarines and their Colorations.By E. GUIMET (Cowzpt.rend., lxxxv, 1072--1074).-When ultrama-rine is being prepared, tb e mixture becomes successively colouredbrown, green, blue, violet, red, and white, in the order named. Thesechanges the author ascribes to the gradual oxidation of the mixture ofkaolin, sulphur, and sodic carbonate and sulphate. The brown colourappears with the blue flames due to the combustion of sulphur, thegreen just after the sulphur flames have ceased, and the blue is firstseen at a temperature of about 700”.If, after this point is reached, heatis still applied, and free access of air permitted, the mixture becomesviolet, red or rose-coloured, and finally white. When Llie white ultra-marine is heated to redness with carbon, the red, violet, blue, green, orW. C. WINORGANIC CHEMISTRY. 199brown varieties are reproduced, according to the quantity of carbonused, and these colours may again be made to pass through changes inthe same order as before by fbrther oxidation. Hydrogeii, ammoniumchloride, and other reducing agents act in the same manner a,s carbon.These facts, the author thinks, show that tlic changes of colour are dueto different degrees of oxidation, as also that they may be due to thesulphur in the mixture, this being shown by the fact that the coloursdiffer when other bodies of the same group are used.He thinks alsothat the soda, though not producing the colours directly, is neccssary,since any attempt to replace it by another substance prevents theformation of the colours. He considers that several varieties of ultra-marine exist, and that a further study of these bodies will be of advan-tage. J. 35. T.Silver Ultramarine. By J. PHILIPPS (Deut. Chern. Ges. L'e.., x,2031).-The product obtained by the action of silver nitrate on ultra-marine blue (p. 113 of this volume), evolves sulphnretted hydrogenwhen treated with an excess of hydrochloric acid ; there is no action,however, with a small quantity of acid.T, C.Oxidation of Metallic Sulphides. By P H. DE C L E R M o N T andH. GUIOT ( C o q ~ t . rend., lxxxv, 714).-If moist manganese sulphideis suddenly compressed and powdered, rapid oxidation takes place, andthe temperature of the mass rises several degrees. R'ecently precipi-tated nickel and ferrous sulphides oxidise even more violently thanmanganese sulphide : when strongly compressed and then powderedbetween the fingers, the temperature of the sulphide rapidly risesthrough 35 or 45 degrees, and aqueous vapour is disengaged.The sulphides of cobalt,, copper, and zinc, when treated in a similarmanner, do not oxidise rapidly enough to give rise to a disengagementof heat. J. W.The Behaviour of Iodine to Amido-mercuric Chloride, inPresence of Alcohol; and a Safe Method of Preparing Iodideof Nitrogen.B y R. BOTTGER (Cihenz. Ce7xtr., 1877, G51).-Althoughiodine may be ground in a mortar along with amido-mercuric chloride,with no other action than the formation of mercuric iodide, yet inpresence of alcohol, an explosion always takes place in thirty or fortyminutes, preceded by evolution of nitrogen, and sometimes separationof mercuric chloride. I n presence of chloroform or arnyl alcohol, gasis evolved, but no explosion occurs.The author's process for preparing nitrogen iodide consists in treat-ing a solution of iodine chloride, obtained by heating iodine with nitro-hydrochloric acid, with ammonia. Thus prepared, it never explodeswhen moist, and when dry, only when touched with a piece of wood,or some similar substance.W. R.Anhydrous Sodioferric Pyrophosphate. By S. 31. JO R G E pt's E s(J. pr. Chem. [a], xvi, 342- 344).-The brownish-coloured glass,obtained by strongly heating a mixture of microcosmic salt and ferricoxide, is slowly melted in a platinum dish by the heat of a Bunsen'200 ABSTRACTS O F CHEMICAL PAPERS.burner. The fused mass is treated with dilute hydrochloric acid,which dissolves out sodium phosphate, and leaves R bluish pearlycrystalline residue of sodioferricpyrophospbste, Na2FcVi,P4O,,. Thiscompound crystallises in rhombic tables, and also in prisms terminatedby acute pyramids ; it can be recrystallised by solution in molten micro-cosmic salt. It is decomposed by fusion with sodium carbonate, or byboiling with strong sulphuric acid, concentrated hydrochloric or nitricacids have scarcely any action on this body.w. c. w.Action of Silver Nitrate on Hydroplatinic Chloride. By S.M. J~RGENSEN ( J . p r . Chern., [Z], xvi, 345-35t;).--The addition ofsilver nitrate in excess, to a cold solution of hydmplatinic chloride,throws down the whole of tthe platinum in the form of a yellow pre-cipitate, having the composition 2AgCl.PtC1,. This substance has notbeeii obtained in the pure state, as it is slowly decomposed by cold,and rapidly by hot water, into a solution of Norton’s salt, PtC1,5H,O(J. pr. Chenz., [a], ii, 469 ; v, 36.5)) and an insoluble residue, consistingof impure silver chloride.Norton’s salt loses four molecules of water a t loo”, the fifth moleculecannot be expelled without decomposing the compound.The aqueoussolution of this substance has an acid reaction, decomposes carbonates,and produces with silver nitrate a yellow precipitate of AffaPtCl4(OHl2.With ammonia, it forms a precipitate of ammonio-platinic chloride, andthe filtrate yields on evaporation a black, amorphous, hygroscopicresidue of platinum hydroxychloride. The relation between thesebodies is shown thus :-Hydroplatinic chloride. Norton’s salt. Platinum hydroxy-chloride.The action of silver nitrate on a hot solution of hydroplatinic chlo-ride may be represented by the following equations :-H2PtC16 + ‘LAgNO, = AgzPtC1, + 2HN03.AgzPtC1, + H20 = HPtCl*.OH + 2Ag:CI.H2O + HPtCl4.OH + 2AgN03 = AgAPtC14(0H)t + 2HN03.The silver salt obtained by adding silver nitrate to Norton’s salt isnot analogous to the acid from which it is derived, since it yields bydouble decomposition with ammonium chloride platinosemidiammo-nium chloride, C12Pt(N2H6c1), and silver chloride. w. c. w. c1Platinosoplatinic Oxide. By S. M. J o R G E N s E N (J. p Y. Chenz. [a], xvi, 344).--Platinosoplatinic oxide, Pt304, is o btained by heatingone part of anhydrous sodium platinochloride with four parts of drysodium carbonate, nntil the mixture begins to fuse. (The platino-chlorides of pot,assium and ammonium cannot be substituted for thesodium salt.) The black residue which remains after treating thefused mass with water, and with dilute nitric acid, is repeatedly washeMINERALOGICAL CHEMISTRY. 201by decantation with hot nitric acid, and finally with water acidifiedwith nitric acid, and is then dried at 110". This oxide is convertedinto platinum black by formic acid ; it is not attacked by mineral acids,not even by boiling aqua regia. It slowly loses oxygen at a red heat,but it is rapidly reduced in an atmosphere of hydrogen or coal gas,even a t the ordinary temperature. w. c. w

ISSN:0368-1769    

DOI:10.1039/CA8783400197

出版商:RSC    

年代:1878

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. M i n e r a1 o g i c a 1 C h em i s t r y . 201 The Growth and Twin Development of Crystals of Diamond. By J. HIRSCEWALD (Jahrb. f. Mh., 1877, 520--525).-The author's independent investigations of the phenomena observed in the growth of diamond crystals, fully confirm those of Sadebeck (J~hrb. f. Ilfin., 1877, 197)' pvoying completely that a parallel nggrcgntion occurs in the growth of diamonds, resulting in a rectangular inclentatioii of the octohedral edges. He further shows :--1. That there is no evidence of any penetration having taken place, all signs of such an occurrence being wanting. 2. The absence of a uniform and symmet,rical develop- ment of the individual portions of the intergrown edges. 3. The commoii occurrence of indentations which do not differ from each other in the slightest degree.4. The iridepcndent development of the octohedral segments occurring in the opposite octants. 5. The ana- logy of these peculiar developments with other well defined holohedral species, exhibiting a Eimilar formation by aggregation. 6. The inden- tations observed on the edges of diamond crystals are not due to any twin-formation. Hirschwald states, therefore, that from henceforth the diamond must be considered R holohedral species. The aggregated construction of some diamonds was made very apparent by examination in polarised light, most of them exhibiting a distinct depolarising effect parallel to a trigonal axis when examined with a delicate selenite plate in the polarising apparatus. C. A. B. Report on a Memoir by Stanislas Meunier, entitled Com- position and Origin of the Diamond-bearing Sand from Du Toit's Pan (S.Africa). (Cow@ re?Ad., lxxxiv, 1124-1130).- According to the report, the investigation of St. Meunier respecting the composition of the diamond-bearing sand of Southern Africa, and his deductions therefrom as to its origin, which are given in this Jourmd (1877, ii, 280), correspond in the main with the results ob- tained by previous geologists ; a t the same time the report expresses no decided opinion respecting his original proposition, viz., that the very varied rock-fragments composing the sand must have been derived from wholly different sources, and have been mechanically carried to the spot where the mixture actually took place. A memoir was published by E.S. Dana, in 1874, on the '' dry mines " of Southern AfKca, in which he proves that from the disposition of the sands in vertical layers, and from the nature of their component202 ABSTRACTS OF CHEMICAL PAPERS. fragments, it is scarcely possible to arrive at any other conclusion than that the diamond has had a deep-seated origin, a i d that it has proceeded from below upwards. I n tliis opinion Prof. RamSaT, Prof. Forbes, and Mr. Stow, who lias examined the “ pans’’ of Griqualand West, unanimously concur. Attention is drawn to the fact that the “ vertical allurial deposits ” of the author, which are supposed by him t o be closely related to the diamond-beering sand-wells, are also closcly relatcd t o the geyser deposits of Belgium, whicli mere carefully studied by cl’Riillo>* about 30 years ago.B’urther, that thc angles and edges of the crpstals of c~1~?10?zado, or black diamond of Brazil, are almost invariably abraded, rounded, and even polished, which shows that thcy must have beeu submitted to energetic and prolonged attrition ; that their faces arc not unfrequently marked by mirror-like strize, which seem to indicate that before arriving at the surface they had been violently pressed together against each other, probably in a manlier similar to that which has often been observed in eruptive breccias, and in many congl omerates. With respect to the rocks associated with diamonds, the specimeiis from South Africa differ from those of Brazil and India, in the fact that with the former quartzose rocks predominate, while with the latter magnesiau rocks are chiefly found ; in many deposits also, such as those of Borneo, Ural, Australia, and Brazil, the diamond is found nssociated with platinum and gold, which does not appear t o be the 3ase with the African specimens, at least as far as the former metal is concerned.J. W. The Brown-Goal of the Bauerberg, near Bischoffsheim, vor ler Rhdn. 13y A. EILGER ( J a h ~ b . fur. 112i’.n., 1877, 420-421).- A brown-coal deposit occurs in the south-western slope of the Hohen Rhon, in four or five thick strata, separated from each other by a thin ayer of a bituminous mixture of iron pyrites, clay, and basaltic tufa. I!he brown-coal is partly earthy and partly inassive or dense, stems of bssil trees, 5 or 6 feet thick, being often found in the strata. The ,hicknew of the individual strata varies from 3 t o 16 feet, the total hickpess of the dcposit being 50 feet.The uppermost stratum con- lists generally of a dense lignite, then follows earthy brown-coal, the owermost stratum consisting, however, of lustrous black bituminous hod, and resting upon basalt. A former examination of these brown :oals, made by Klinger, prored them t o be composed as follows, ‘1Z. :- Carbon. Hydrogen. Oxygen and Nitrogen. Lignite . . . ... . 64.22 5-56 23-52 = 93.30 Brown-coal . . . . 61-74 4-94 20.60 = 87.28 Bituminous coal 76.43 8.88 13.99 = 99.30 The author determined! the amount of ash and water in the above, obtaining the following results :-MINERALOQlCAL CHEMISTRY. 203 Water. Ash. Bituminous coal ........11.6 8.5 Brown-coal ............ 12.4 10-4 Sandy-coal ............ 16.2 77.94 Clayey-coal . . . . . . . . . . . . 14.4 %;*lo Lignite.. .............. 15.2 9.8 A greyish or yellowish mass is found in the d6'b~is of the exhausted mines, the greater part of which is found to be C T ~ ~ ~ ~ / O ? L ; U ~ uZuiiz con- taining a small quant)ity of sulphur, ferric oxide, and clay. I t is, of course, a product of the completely weathered brown-coal " slack," and of great importance to the alum trade. The author also analysed a, granular, crystdline, ochrey-yellow efflorescence, which occiirs 011 the clay-substance interposed between the brown-coal strata, arid four,d it t o have the following composition, vie. :- Al20,. Fc~O;~. FeZO. MgO. SO,. H,O. 16.7 4-2 2.9 2.3 39.3 33.3 = 98.7 from which it appears to be kcramohalite.It is soluble in water. C. A. B. On the Production of Artificial Corundum, Ruby, and dif- ferent Crystallised Silicates. By E. F IL i nr Y and V J; IT, ( CYC,~~zpt. yewi., lxxxv, 1025--1035).-Synthetical mineralogy or the artificial production of minerals throws, the authors think, the greatest light O n the natural production of mineral substances, and. enables us t o solve certain problems in their composition which analysis leaves to a certain extent undecided, as the purest minerals contain foreign bodies impossible of distinction by analysis, but which their synthe- tical production eliminates. A large number of minerals hsve already been produced in the wet way, and the important results of Bccqucrel and Hautcfeuille show the advantage of this line of research.Coriindum is, perhaps, the mine- ral which has been most investigated by chemists, as the names of Ebelmen, de Scnarmont, St. Claire Deville, Caron, Gaudin, arid De- bree show. The authors think, therefore, that the metliods they liavc employed for pruoducing crystallised alumina colouretl by Tarions pigments will be of intercst, and may find an application in the arts ; they further add that the methods they employ may be used for the production of other minerals. Wishing to approach as nearly as possible the natural conditions for the production of corundum, they have used furnaces capable of pro- ducing the highest temperature and of maintaining it for a long time ; they have also acted on masses of 20 to YO kilogi~ims.Among other furnaces they have employed a regenerative gas furnace, used in the production of plate-glass. The method whicii produced the largest quantity of crystallised alumina was the following :-A fusible alumirmte is heated to a bright redness in contact with a silicious substance. The alumina being gradually disengaged from combination, crystallises in presence204 ABSTRACTS OF CHEhfICAL PAPERS. of a flux. The authors attribute this crystallisation to different causes. n. The datilisation of the base united to the alumina. b. The reduction of this base by the gases of the f’urnace. c. The formation of a fusible silicate by the combination of the d. A plienomenori of liquidation, producing a very fusible silicate All these cases have occurred during the experiments.The authors think that the best method of crystallising alumina is to replace it by silica (c). Aluminate of lead, the authors have, up to the present, found to be the one best suited for this purpose. Equal weights of alumina and minium are heated to a bright red- ness in zt fire-clay crucible ; on cooling two products are found, one vitreous, consisting mainly of lead silicate, tlic other crystalline and containing pcodes filled with fine crystals of alumina, the sides of the crucible itself supplying the silica necessary for the rcaction ; by this mctliod cqstals of white cormdun1 are obtained : when rubies are required, 2 to 3 per cent. of potassium bichromate are added to the mixture, and oxide of‘ cobalt gives sapphires.T’he crystds found in the geodes have the composition, adamantfine lustre, hardness, density, and form of natural rubies ; they scratch quartz and topaz. Specific gravity 4-4.1, like natural rubies they lose colour on strong ignition. and regain it on cooling. Lapidaries have found them quite as hard as the natural stones. When polarised they show a black cross and coloured rings. The crystallised silicates shown by the authors a t the same time were obtained by means of fluorides, and M. Daubray’s observations were fully confirmed that fluorine takes a most important part in the formation of mineral deposits. They have found that in this direction aluminium fluoride is the most active. Equal weights of silica and aluminium fluoride heated to redness for several hours give a crystal- line body, probably disthene, and fluoride of silicon.These crystals have the composition SiO, = 417*65,Al20, = 51.85, loss = -50. and closely resemble natural disthenc. The crystals appear t o belong to one of the oblique systems. The action of aluminium fluoride on boric acid gave a crystallised aluminium borate which corresponds with disthene. Thc authors are now engaged in a series of cxperirnents on the action of aluminium fluoride on other inorganic acids. When equal weights of alumina and barium fluoride, together with 2 or 3 per cent. of potassium bichrornate, are treated a t a high temperature for a considerable time in a crucible covered by another so as to form a condenser, two kinds of crystals are obtained ; some, which appear to have been volatilised, are long colourless prisrns with the appearance of antimony glance ; the others are regular crystals of ruby of a fine rose colour. The long prismatic crystals are a double silicate of barium and aluminum, having the composition SiO, = 34.32, RaO = 35.04, A1,0, = 33.37.These two substances seem to be the result of the following trans- formations. The calcination of the mixture, forming aluminium silica with the base. and refractory alumina.MINERALOGICAL CHEMISTRY, 205 fluoride and bnryta, the fluoride of alumina probably acting in two different ways. (a.) Decomposed by the gases of the furnace, it formed hydrofluoric acid and corundum. ( b . ) By acting on the silica of the crucible, i t formed aluminium silicate, which, by its action on the baryta, produced the double silicate above mentioned.The authors call attention to the fact that these crydals occupy a position in the crucibles pointing to their having undergone volatili- sntion, and yet it is impossible to alter them when obtained, even a t the highest temperatures ; this they think is due to the action of fluo- rider which act as carriers of less volatile substance.;;. I n support of this they recall the remar.kable crystals of orthose felspar found in the upper part of a copper furnace at Mmsfeld, which were due to the fluoride of calcium used as a flux. This action of barium fluoride on alumilia in presence of silica is probably one example of a general pheno- menon of the decomposition of fluorides by different bases.The authors hope to describe other crystallised double silicates produced under the same conditions as the one above nientioned, and will then give the general forniuh of these compounds. In conclusion the authors say that they have carried out tliese investigations simply for their scientific int'erest, and that they therefore publiski them without reserve, and will be happy to hear of any appiication in the arts which may result from them. J. M. T. Artificial Formation of Albite and Orthose. By P. HAUTF:- F E U I L L E (Cow@. r.eud., lxxxv, 1043--1046).-~elspars the author considers to be a most important group of minerals, as they are the principal constituents of almost all eruptive rocks. Up to the present time it had not been possible to produce tlrcm artificially, a t least in well-defined crystals ; they have, however, been acciden tally procliiccd in copper furnaces both a t Mmsfeld and in the H a r k These the author thinks must have been formed by sulnlimation with the aid of the calcium fluoride employed its flux.As orthobe is fusible, attempts have been made to crystaliisc ir by slow cooling, but without success. M. Hautefeuille, having pi-epared successfully the principal minerals of titanium, has also succeoded in obtaiiiing orthose arid albite, amd hopes soon to prepare the other sprcies of the same group. His process consists in heating the elements of these minerals in presence of certain fused salts, sach as tungstic acid or alkaline tung- states : thus a mixture of silica and alumina in presence of acid potas- sium tungstatc, at a temperature between 900 and 1,000", produces tridymite, orthose, and triclinic felspars.If the potash and alumina are in the proper proportions, the tridymite and triclinic felspari; dis- appear after 15 to 20 days' heating, and the orthose alone remains. A highly alkaline silicoaluminate of potash containing one of Al,O, to six SiO, mixed with tungstic acid gives the same result. When soda is substituted f o r potash, other conditions remaining the same, albite is formed. The analyses of these products give the proportions of oxygen contained in the alkali (K or Na), in the alumina and in the silica as 1 : 3 : 12, these being the proportions characterising VOL. XXXIV. !?206 ABSTRACTS OF CHEI\IICAL PAPERS. orthose, microcline, and albite.Like the natural ones, the crFstnls artificially obtained are not attacked by acids ; their sp. gr. respec*- tively being 2-61 and 2.55. The crystallographic examination of the artificial albite shows that it almost exactly resembles the natural crystals from Dauphin6 and thc Tyrol. The crystals having thc cornposition of orthose appear to be analogous to those described b,y &Ir. Mallard found in the St. Gothard. The author thinks that the orthose and albite having been obtained under exactly the same con- ditions, the pseudomorphism of this group of silicates is simply due to the nature of tlie alkali. While showing the interest attached to the preparation of these minerals in tlie dry way, he in no wise wishcs to deny that the wet way may have often been employed by nature in the formation of the same species..J. M. T. Chemical Constitution of Hatchettolite and Samarskite from Mitchell County, North Carolina. €37 0 S C A R D. RLLKS (Amer. J. qf Sci. [3], xiv, 128-131).-I. €Tcitchettoklte.-In IParch, 1876, Dana described a mineral which was associated with the samar- skite of Mitchell county, and in May, 2877, Lawrence Smith pub- lished an analysis of this mineral for which he proposed the name of hatchettolite. The specimen obtained by the author was from the same source, and corrsisted of a large but imperfect crystal, of which about 12 grams appeared sufficiently pure for analysis. Pieces ftoir: different parts of tlie mass gave the specific gravities 4.77, 4.84, 4.82, 4.990, 4.76 ; the mineral described by Dana had a specific gravity of 4.794.The results of two analyses by the xuthor are given in thc first two columns ; the third column cont:%iiiins the number;.; given by Luwrencc Smith. wo3 li’ttrin slid Ta20,. CbnO,. TiOz. u. SnO,. U-oxide. CaO. Ccriuiv 0xitlc.s. I. .. 29-89 34.240 1.61 0.30 15.50 8.87 - 8.89 - 11. .. 29.60 35.96 - 111.. 67.86 - 0.60 15-63 7-09 0,813 - - K20 and Water easily PeO. MgO. Na20. heated. I. ........ 2.19 0.15 1.37 4,449 = 98.55 11. ........ 2.33 IIJ.. ....... 2.51 - 1-21 4.42 = 100.18 I and I1 also contained a trace of lead. - - - The separation of tantalic and columhic acids was effected Iny Marignac’s method. The composition of tlie mineral may be repre- sented by the formula Rii2RV207 + 2LbiiRV206 + 4Ef,O, where Rii re- presents one atom of a bivalent basic radicle or two of sodium, and RV represents Ta or Cb.Hatchettolite may have resulted from alte- ratiou of a mineral having essentially the samc chemical constitution, aty -Tell as crjstnlline form, as pyrochlore, an alteration consisting of hydration a,n<f removal of alkaline fluorides. 11. Su;?zarskifc:.-T2ie analysis of this mineral gave results as fol- lows :--MINERALOGICAL CHEMISTRY. 207 Cb,O,. Ta,O,. SnOz. YzOp Uranium Cerium oxides. oxide. I. .. . . 37.81 17.79 - 14.5‘2, 4.10 12.63 11.. . . . 37.20 18-60 0.08 14.45 4.24 12.46 MnO . FeO. CaO. HZO. I. . . . . 0.@0 10.60 - - 11. . .. . 0.75 10.90 0.55 1.22 = 100.45 These results do not differ materially from the first publihhecl ann- lysis of samarskite from the same locality by Miss E.H. Swallotv. They agree sufficiently well with the formula Ei12Rv207 + Rl11iv2Os. 3’. D. B. Occurrence of Tinstone at Truro. By C n o z E TI (Clmu. Cei/,ti*., 1877, 120) .-A valuable deposit of tiiistone is sitxatcd under the water of the small drift of Eestronguet, near Truro. It is covered with mud and sand. After working this ore at various periods, it was given up in 1843. I n 1871, however, the working was again commenced. The ground was examined hy boring in tlio opcn sea, and it was found that the deposits, which rested irnrnediatcly on the rocky bottoni, had a tliickncss of 0.4; to 1-20 meters, and wcre covered with mud and said to a dcpth of 18 meters. The richest porttiom of’ the ore formed pure crystals of stannic oxide (BUZZ. SOC.de Z’id. m i i / i r ; 8. u. Hutteiinb-Z., xxx, 443). D. 33. Galenite from Habach in Salzburg. By V. VON 2; E P I I A R O V I C I I ( & d i d . f. Uin., 1877, 529).-The galenite from this locality is re- markable, firstly, for its very complete octoheclral cleavage, with a lcss complete cubical cleavage ; and secondly, through the occurrencc of numerous interpolatcd twin lamell= parallel to a facc of 303. The unusual cleavage mentioned above has been obscrvcd before only in the case of galenite from Pennsylvania. There was no appreciable difference in tbc lustre of the two kinds of cleavage-surf:xes. ‘l’hc beliaviour of this galenite, on being heated in a rnattrass, is striking, as it does not c1ecrepit:ite ; whilst the heated poitioils have a ready cubical and only an indistinct, octohedral cleavage.Sp. gr., 7.50; them. corn. = 58-03 per cent. of lead sulphide aiid 1.97 per cent. ot bismut)h sulpliide. Thc jnterpolated twin l a r n d l e are grnei*ally so thin that they are scarcely discwniblc with tlic u;tked eye, and are ob- served also on the respective cleavage-faces of the large crjsta! ex- hibiting identical cleavage faces. C. A. B. An Aragonite Crystal from Oberstein on the Nahe. 13y H. LASPEYRES (Jahrb. f. M ~ I L . , 1877, 527).-Calcite is often fourid amygd&icIal cavities in rnelapliy~, but aragonite was nriknowii to it until the author discovered it in the abovc-mentioned locality. The crystal in quest>ioii has a length of 13 c.m., and a thickness of 4,s C . m . It is a penctrntion quadding, tllc twin planc being a, face of‘ ml’, and tJ1e conibinution is co 1’ .co k’ c% . $ I’ . 1’s . UP ; the latter fncc is not striated ill the direction of the bracbgdisgonsl. c. A. l3. y:!208 ABSTRACTS O F CHEMICAL PAPERS. A Polysynthetical Augite-twin from Bell, near Laach. By H. LASPEYRES (Jahrb. f. M&., 1877, 527, .52P).---A polysynthetical twin - development in the monosymmetrical system is of rare oc- currence. It, is most common with epidote, arid more rare wit,h orthoclase and augite. G. vom Rath (Jahrh. f. AIin., 1876, 404) described a. crystal of fassaite from Traversella, which consisted of one large individual, with two interpolated twin-plates of the same substance. The author observed an anpite-twin from 13~11, exhibitinp the usual forms, with a tw-in-plate (interpolated parallcl to tlie ortho- pinaroid), having half the thickness of the two halves of the principal individual.C. A. B. Analysis of a Trachyte from Wolferdingen, in the Wester- wald. By A. HI r,Gb:R (,Tahrb. f . &%,., 1877, 421, 422).-The specific gravity of this spccirnen was found to be 2.68, aud its chemical com- position as follows, viz. :- SiO,. A1203. Fe20. FeO. MnO. CaO. MgO. 59.87 22-52 0.32 2.52 0-13 2-5 0.46 K20. Na20. P20,. H20. 4.42 5-78 0.3 2.24 = 101.06. with traces of C1, S04H2, Li, Ba, and Sr, Before this the presence of these bodies had rarely been proved, von Lasaulx describing a trachyte from Mont Dore, which contained Li and Ba. C. A. B. The Primary Rocks of the Northern Schwarzwald. By C. HKBENSTRE I T (Juhrb.f. Xin., 417-419).--The author undertook the task of a,scertaining the composition of the basic and acid rocks of the wide-spread gneiss district of the Kinzigthal. Three varieties of these rocks were examined, viz. : (1.) A granular gneiss, rich in silica and poor in mica; ( 2 . ) A hornblendic rock, enclosed in the gneiss; ( 3 . ) A garnet-graphite-aneiss, rich in mica. Garnet-gneiss was known to occur often in the Schwarzwald ; but ~arnet-graphitc-gneiss was hitherto unknown, the latter being formerly known by the riame of Kinzigite. This rock is found at Schenkenzeil, near Wittichen, in a lajer scarcely I+ feet in thickness, enclosed in ordinary gneiss. It is coarsely laminated, macroscopically distinctly striated plapioclase ; black mica, violet-red garnet, mid lamince of graphite are recognisable. Colourless needles of apatite, fine aggregates of iron-pyrites and red- dish specks of specular-iron were detected in the felspar, on examining the rock under the microscope.The presence of quartz could riot be detected. An analysis made of a pure, fresh specimen furnished the following results, viz. :- (1.) By experiment; (2.) Calculated from No. 1, after dcducting Its specific gravity was found to be 3.00. iron-pyrites, apatite, graphite, and iron-glance. SiO,. AI,O,. Pe,O,. FeO. CaO. MgO. K20. No. 1 . . 44.53 17.55 5.38 12.60 3-36 5-68 3-54 Xu. 2 . . -46.68 18.40 3.54 12.87 3.32 5.95 3.72MINERALOGICAL CHEMISTRY. 209 Na20. H20. P. S. Graphite. No. 1.. . . . . . . 3.60 1.66 0.17 0.29 4-33 = 100.69 - = 100.00 NO.2 ... . . ... 3.77 1.75 - - The author also examined the asymmetrical felspar and garnet ob- served i n the rocks, atid found the former to be colourless strongly lustrous oligoclase, with a specific gravity of 2.1357, slid cxhibitirig a fine twin striation ; whilst the latter was true almandine, coiitaining many enclosures (particularly niicrolitic quartz), arid had a specific gravity of 3.96. The analyses of these minerals furnished the fol- lowing results, viz. :- SiO,. Fc,O,. FcO. CaO. MgO. Oligoclase .. . . 62.90 22.23 trace - 4.45 - Garnet . . . . . . . 37.40 21.08 2.01 28.49 3.05 8-22 K,O. Na,O. Oligoclase.. . . . . . . 2 09 8.48 = 100.15 Garnet . . . . . . . . . . - - = 100.25 Hebenstreit gives a tablc of analyses of gneissoid rocks, comparing them a t the same time with analyses of rocks from the same neigh- bourhood, the result of which serves to show that the hornblendic rocks and the garnet-giieiss (which is intirnntely associat'ed with the hornblcndic rocks) have been sepzrated from tlle very common snd widely-spread graqular striat$eJ gneiss, and are equally basic in cha- racter.An examination of tlie granite of Tryberg proved i t to resemble very closely the granites from the northern Schwarzwald. The composi- tion of the gneiss from the neighloourhood of Tryberg was feud to difter considerably from that of the granite from the northern Schwarzwald. C. A. B. Analysis of the Water of the Warm Spring at Assmanns- hausen. By R. YRESJCXIUS ( J . pr. Chem. L2], xvi, 278-2!W).- This water was found to contain in 100,000 parts (salts all anhy- NaLC03.Li,CO,. CaC03. BaC03. SrCO3 MgCO,. 9.7486 1,711160 12.2307 0.0989 0.1978 4.0066 FeC0,. MnCOJ. K2S01. 0.2239 0.1326 4.3068 The granular gneiss is the most acid of these rocks. drous) :-- C0.J co, KCl. NaCl. NaBr. NaI. NaJIPO,. Si02. (combined). (free). 0.4522 57.1764 0.0971 0.0004 0.0301 3.1539 12,7780 18.5800 The sp. gr. of the water was 1.000832 a t 15", and its temperature The water is distinguished from all others of similar cha- 31.1" C. racter by the relatively large quantity of lithium which it con&ns. Analysis of the Acid Well (Sauerbrunnen) at Bilin. J. R. By H u PPE: ET (Chem. Cei~tr., 1877, 137).-'l'his is a newly-discovered spring, and tlie analysis of one of the older springs, the Josefsquelle, is added for comparison.210 ABSTRACTS OF CHEMICAL PAPERS .K.60. .............. Na.SO. .............. NaC 1 ................ Na.&O, .............. caco, .............. MgCO, .............. Li,CO, . . . . . . . . . . . . . . FeCO, .............. MnCO, .............. Iodine .............. Al,O,.P,05 . . . . . . . . . . SiO, .............. Josef squolle . 2.3496 7.2 762 3.8135 33.3085 4.1295 1.71 91 0.1133 0*0284 0.0305 trace 0*0057 0.4340 New spring . 2.5418 7.0767 3. 7191 32.6 5 7 C 4.2 8 2 .i 1 * P9 5 4 0.1 2 5 3 0 02.79 0.0105 trace 0.0 0 .-, 6 0.43 5 7 Total solids .......... 53.2088 52.7761 Half-combined COz . . Free CO. ............ Total of conatituerits . . 16.7303 14.2697 84.2083 Total CO. .......... 47.5565 16.5087 15-53 16 841-6164 48.3480 .- G . T . A .MINERALOGICAL CHEMISTRY.M i n e r a1 o g i c a 1 C h em i s t r y .201The Growth and Twin Development of Crystals of Diamond.By J.HIRSCEWALD (Jahrb. f. Mh., 1877, 520--525).-The author'sindependent investigations of the phenomena observed in the growthof diamond crystals, fully confirm those of Sadebeck (J~hrb. f. Ilfin.,1877, 197)' pvoying completely that a parallel nggrcgntion occurs inthe growth of diamonds, resulting in a rectangular inclentatioii of theoctohedral edges. He further shows :--1. That there is no evidenceof any penetration having taken place, all signs of such an occurrencebeing wanting. 2. The absence of a uniform and symmet,rical develop-ment of the individual portions of the intergrown edges. 3. Thecommoii occurrence of indentations which do not differ from eachother in the slightest degree.4. The iridepcndent development of theoctohedral segments occurring in the opposite octants. 5. The ana-logy of these peculiar developments with other well defined holohedralspecies, exhibiting a Eimilar formation by aggregation. 6. The inden-tations observed on the edges of diamond crystals are not due to anytwin-formation. Hirschwald states, therefore, that from henceforththe diamond must be considered R holohedral species. The aggregatedconstruction of some diamonds was made very apparent by examinationin polarised light, most of them exhibiting a distinct depolarisingeffect parallel to a trigonal axis when examined with a delicate seleniteplate in the polarising apparatus.C. A. B.Report on a Memoir by Stanislas Meunier, entitled Com-position and Origin of the Diamond-bearing Sand from DuToit's Pan (S. Africa). (Cow@ re?Ad., lxxxiv, 1124-1130).-According to the report, the investigation of St. Meunier respectingthe composition of the diamond-bearing sand of Southern Africa, andhis deductions therefrom as to its origin, which are given in thisJourmd (1877, ii, 280), correspond in the main with the results ob-tained by previous geologists ; a t the same time the report expressesno decided opinion respecting his original proposition, viz., that thevery varied rock-fragments composing the sand must have been derivedfrom wholly different sources, and have been mechanically carried tothe spot where the mixture actually took place.A memoir was published by E.S. Dana, in 1874, on the '' dry mines "of Southern AfKca, in which he proves that from the disposition ofthe sands in vertical layers, and from the nature of their componen202 ABSTRACTS OF CHEMICAL PAPERS.fragments, it is scarcely possible to arrive at any other conclusionthan that the diamond has had a deep-seated origin, a i d that it hasproceeded from below upwards. I n tliis opinion Prof. RamSaT, Prof.Forbes, and Mr. Stow, who lias examined the “ pans’’ of GriqualandWest, unanimously concur.Attention is drawn to the fact that the “ vertical allurial deposits ”of the author, which are supposed by him t o be closely related to thediamond-beering sand-wells, are also closcly relatcd t o the geyserdeposits of Belgium, whicli mere carefully studied by cl’Riillo>* about30 years ago.B’urther, that thc angles and edges of the crpstals ofc~1~?10?zado, or black diamond of Brazil, are almost invariably abraded,rounded, and even polished, which shows that thcy must have beeusubmitted to energetic and prolonged attrition ; that their faces arcnot unfrequently marked by mirror-like strize, which seem to indicatethat before arriving at the surface they had been violently pressedtogether against each other, probably in a manlier similar to thatwhich has often been observed in eruptive breccias, and in manycongl omerates.With respect to the rocks associated with diamonds, the specimeiisfrom South Africa differ from those of Brazil and India, in the factthat with the former quartzose rocks predominate, while with thelatter magnesiau rocks are chiefly found ; in many deposits also, such asthose of Borneo, Ural, Australia, and Brazil, the diamond is foundnssociated with platinum and gold, which does not appear t o be the3ase with the African specimens, at least as far as the former metal isconcerned.J. W.The Brown-Goal of the Bauerberg, near Bischoffsheim, vorler Rhdn. 13y A. EILGER ( J a h ~ b . fur. 112i’.n., 1877, 420-421).-A brown-coal deposit occurs in the south-western slope of the HohenRhon, in four or five thick strata, separated from each other by a thinayer of a bituminous mixture of iron pyrites, clay, and basaltic tufa.I!he brown-coal is partly earthy and partly inassive or dense, stems ofbssil trees, 5 or 6 feet thick, being often found in the strata. The,hicknew of the individual strata varies from 3 t o 16 feet, the totalhickpess of the dcposit being 50 feet.The uppermost stratum con-lists generally of a dense lignite, then follows earthy brown-coal, theowermost stratum consisting, however, of lustrous black bituminoushod, and resting upon basalt. A former examination of these brown:oals, made by Klinger, prored them t o be composed as follows,‘1Z. :-Carbon. Hydrogen. Oxygen and Nitrogen.Lignite . . . ... . 64.22 5-56 23-52 = 93.30Brown-coal . . . . 61-74 4-94 20.60 = 87.28Bituminous coal 76.43 8.88 13.99 = 99.30The author determined! the amount of ash and water in the above,obtaining the following results :MINERALOQlCAL CHEMISTRY.203Water. Ash.Bituminous coal ........ 11.6 8.5Brown-coal ............ 12.4 10-4Sandy-coal ............ 16.2 77.94Clayey-coal . . . . . . . . . . . . 14.4 %;*loLignite.. .............. 15.2 9.8A greyish or yellowish mass is found in the d6'b~is of the exhaustedmines, the greater part of which is found to be C T ~ ~ ~ ~ / O ? L ; U ~ uZuiiz con-taining a small quant)ity of sulphur, ferric oxide, and clay. I t is, ofcourse, a product of the completely weathered brown-coal " slack," andof great importance to the alum trade. The author also analysed a,granular, crystdline, ochrey-yellow efflorescence, which occiirs 011 theclay-substance interposed between the brown-coal strata, arid four,d itt o have the following composition, vie.:-Al20,. Fc~O;~. FeZO. MgO. SO,. H,O.16.7 4-2 2.9 2.3 39.3 33.3 = 98.7from which it appears to be kcramohalite. It is soluble in water.C. A. B.On the Production of Artificial Corundum, Ruby, and dif-ferent Crystallised Silicates. By E. F IL i nr Y and V J; IT, ( CYC,~~zpt.yewi., lxxxv, 1025--1035).-Synthetical mineralogy or the artificialproduction of minerals throws, the authors think, the greatest lightO n the natural production of mineral substances, and. enables us t osolve certain problems in their composition which analysis leaves to acertain extent undecided, as the purest minerals contain foreignbodies impossible of distinction by analysis, but which their synthe-tical production eliminates.A large number of minerals hsve already been produced in the wetway, and the important results of Bccqucrel and Hautcfeuille show theadvantage of this line of research.Coriindum is, perhaps, the mine-ral which has been most investigated by chemists, as the names ofEbelmen, de Scnarmont, St. Claire Deville, Caron, Gaudin, arid De-bree show. The authors think, therefore, that the metliods they liavcemployed for pruoducing crystallised alumina colouretl by Tarionspigments will be of intercst, and may find an application in the arts ;they further add that the methods they employ may be used for theproduction of other minerals.Wishing to approach as nearly as possible the natural conditions forthe production of corundum, they have used furnaces capable of pro-ducing the highest temperature and of maintaining it for a longtime ; they have also acted on masses of 20 to YO kilogi~ims.Amongother furnaces they have employed a regenerative gas furnace, usedin the production of plate-glass.The method whicii produced the largest quantity of crystallisedalumina was the following :-A fusible alumirmte is heated to abright redness in contact with a silicious substance. The aluminabeing gradually disengaged from combination, crystallises in presenc204 ABSTRACTS OF CHEhfICAL PAPERS.of a flux. The authors attribute this crystallisation to differentcauses.n. The datilisation of the base united to the alumina.b. The reduction of this base by the gases of the f’urnace.c. The formation of a fusible silicate by the combination of thed. A plienomenori of liquidation, producing a very fusible silicateAll these cases have occurred during the experiments.The authorsthink that the best method of crystallising alumina is to replace it bysilica (c). Aluminate of lead, the authors have, up to the present,found to be the one best suited for this purpose.Equal weights of alumina and minium are heated to a bright red-ness in zt fire-clay crucible ; on cooling two products are found, onevitreous, consisting mainly of lead silicate, tlic other crystalline andcontaining pcodes filled with fine crystals of alumina, the sides of thecrucible itself supplying the silica necessary for the rcaction ; by thismctliod cqstals of white cormdun1 are obtained : when rubies arerequired, 2 to 3 per cent.of potassium bichromate are added to themixture, and oxide of‘ cobalt gives sapphires. T’he crystds found inthe geodes have the composition, adamantfine lustre, hardness, density,and form of natural rubies ; they scratch quartz and topaz. Specificgravity 4-4.1, like natural rubies they lose colour on strong ignition.and regain it on cooling. Lapidaries have found them quite as hardas the natural stones. When polarised they show a black cross andcoloured rings.The crystallised silicates shown by the authors a t the same timewere obtained by means of fluorides, and M. Daubray’s observationswere fully confirmed that fluorine takes a most important part in theformation of mineral deposits.They have found that in this directionaluminium fluoride is the most active. Equal weights of silica andaluminium fluoride heated to redness for several hours give a crystal-line body, probably disthene, and fluoride of silicon. These crystalshave the composition SiO, = 417*65,Al20, = 51.85, loss = -50. andclosely resemble natural disthenc. The crystals appear t o belong toone of the oblique systems.The action of aluminium fluoride on boric acid gave a crystallisedaluminium borate which corresponds with disthene. Thc authorsare now engaged in a series of cxperirnents on the action of aluminiumfluoride on other inorganic acids. When equal weights of aluminaand barium fluoride, together with 2 or 3 per cent. of potassiumbichrornate, are treated a t a high temperature for a considerable time ina crucible covered by another so as to form a condenser, two kindsof crystals are obtained ; some, which appear to have been volatilised,are long colourless prisrns with the appearance of antimony glance ;the others are regular crystals of ruby of a fine rose colour.The longprismatic crystals are a double silicate of barium and aluminum,having the composition SiO, = 34.32, RaO = 35.04, A1,0, = 33.37.These two substances seem to be the result of the following trans-formations. The calcination of the mixture, forming aluminiumsilica with the base.and refractory aluminaMINERALOGICAL CHEMISTRY, 205fluoride and bnryta, the fluoride of alumina probably acting in twodifferent ways.(a.) Decomposed by the gases of the furnace, it formed hydrofluoricacid and corundum.( b .) By acting on the silica of the crucible, i t formed aluminiumsilicate, which, by its action on the baryta, produced the double silicateabove mentioned.The authors call attention to the fact that these crydals occupy aposition in the crucibles pointing to their having undergone volatili-sntion, and yet it is impossible to alter them when obtained, even a tthe highest temperatures ; this they think is due to the action of fluo-rider which act as carriers of less volatile substance.;;. I n support ofthis they recall the remar.kable crystals of orthose felspar found inthe upper part of a copper furnace at Mmsfeld, which were due to thefluoride of calcium used as a flux. This action of barium fluoride onalumilia in presence of silica is probably one example of a general pheno-menon of the decomposition of fluorides by different bases.Theauthors hope to describe other crystallised double silicates producedunder the same conditions as the one above nientioned, and will thengive the general forniuh of these compounds. In conclusion theauthors say that they have carried out tliese investigations simply fortheir scientific int'erest, and that they therefore publiski them withoutreserve, and will be happy to hear of any appiication in the artswhich may result from them. J. M. T.Artificial Formation of Albite and Orthose. By P. HAUTF:-F E U I L L E (Cow@. r.eud., lxxxv, 1043--1046).-~elspars the authorconsiders to be a most important group of minerals, as they are theprincipal constituents of almost all eruptive rocks.Up to the presenttime it had not been possible to produce tlrcm artificially, a t least inwell-defined crystals ; they have, however, been acciden tally procliiccdin copper furnaces both a t Mmsfeld and in the H a r k These theauthor thinks must have been formed by sulnlimation with the aid ofthe calcium fluoride employed its flux. As orthobe is fusible, attemptshave been made to crystaliisc ir by slow cooling, but without success.M. Hautefeuille, having pi-epared successfully the principal mineralsof titanium, has also succeoded in obtaiiiing orthose arid albite, amdhopes soon to prepare the other sprcies of the same group.His process consists in heating the elements of these minerals inpresence of certain fused salts, sach as tungstic acid or alkaline tung-states : thus a mixture of silica and alumina in presence of acid potas-sium tungstatc, at a temperature between 900 and 1,000", producestridymite, orthose, and triclinic felspars.If the potash and aluminaare in the proper proportions, the tridymite and triclinic felspari; dis-appear after 15 to 20 days' heating, and the orthose alone remains.A highly alkaline silicoaluminate of potash containing one of Al,O,to six SiO, mixed with tungstic acid gives the same result. Whensoda is substituted f o r potash, other conditions remaining the same,albite is formed. The analyses of these products give the proportionsof oxygen contained in the alkali (K or Na), in the alumina and inthe silica as 1 : 3 : 12, these being the proportions characterisingVOL.XXXIV. !206 ABSTRACTS OF CHEI\IICAL PAPERS.orthose, microcline, and albite. Like the natural ones, the crFstnlsartificially obtained are not attacked by acids ; their sp. gr. respec*-tively being 2-61 and 2.55. The crystallographic examination of theartificial albite shows that it almost exactly resembles the naturalcrystals from Dauphin6 and thc Tyrol. The crystals having thccornposition of orthose appear to be analogous to those described b,y&Ir. Mallard found in the St. Gothard. The author thinks that theorthose and albite having been obtained under exactly the same con-ditions, the pseudomorphism of this group of silicates is simply dueto the nature of tlie alkali.While showing the interest attached tothe preparation of these minerals in tlie dry way, he in no wise wishcsto deny that the wet way may have often been employed by nature inthe formation of the same species. .J. M. T.Chemical Constitution of Hatchettolite and Samarskitefrom Mitchell County, North Carolina. €37 0 S C A R D. RLLKS(Amer. J. qf Sci. [3], xiv, 128-131).-I. €Tcitchettoklte.-In IParch,1876, Dana described a mineral which was associated with the samar-skite of Mitchell county, and in May, 2877, Lawrence Smith pub-lished an analysis of this mineral for which he proposed the name ofhatchettolite. The specimen obtained by the author was from thesame source, and corrsisted of a large but imperfect crystal, of whichabout 12 grams appeared sufficiently pure for analysis.Pieces ftoir:different parts of tlie mass gave the specific gravities 4.77, 4.84, 4.82,4.990, 4.76 ; the mineral described by Dana had a specific gravity of4.794.The results of two analyses by the xuthor are given in thc first twocolumns ; the third column cont:%iiiins the number;.; given by LuwrenccSmith.wo3 li’ttrin slidTa20,. CbnO,. TiOz. u. SnO,. U-oxide. CaO. Ccriuiv 0xitlc.s.I. .. 29-89 34.240 1.61 0.30 15.50 8.87 -8.89 - 11. .. 29.60 35.96 -111.. 67.86 - 0.60 15-63 7-09 0,813- -K20 and Water easilyPeO. MgO. Na20. heated.I. ........ 2.19 0.15 1.37 4,449 = 98.5511. ........ 2.33IIJ.. ....... 2.51 - 1-21 4.42 = 100.18I and I1 also contained a trace of lead.- - -The separation of tantalic and columhic acids was effected InyMarignac’s method.The composition of tlie mineral may be repre-sented by the formula Rii2RV207 + 2LbiiRV206 + 4Ef,O, where Rii re-presents one atom of a bivalent basic radicle or two of sodium, andRV represents Ta or Cb. Hatchettolite may have resulted from alte-ratiou of a mineral having essentially the samc chemical constitution,aty -Tell as crjstnlline form, as pyrochlore, an alteration consisting ofhydration a,n<f removal of alkaline fluorides.11. Su;?zarskifc:.-T2ie analysis of this mineral gave results as fol-lows :-MINERALOGICAL CHEMISTRY. 207Cb,O,. Ta,O,. SnOz. YzOp Uranium Ceriumoxides. oxide.I. ... . 37.81 17.79 - 14.5‘2, 4.10 12.6311.. . . . 37.20 18-60 0.08 14.45 4.24 12.46MnO . FeO. CaO. HZO.I. . . . . 0.@0 10.60 - -11. . .. . 0.75 10.90 0.55 1.22 = 100.45These results do not differ materially from the first publihhecl ann-lysis of samarskite from the same locality by Miss E. H. Swallotv.They agree sufficiently well with the formula Ei12Rv207 + Rl11iv2Os.3’. D. B.Occurrence of Tinstone at Truro. By C n o z E TI (Clmu. Cei/,ti*.,1877, 120) .-A valuable deposit of tiiistone is sitxatcd under thewater of the small drift of Eestronguet, near Truro. It is coveredwith mud and sand. After working this ore at various periods, itwas given up in 1843. I n 1871, however, the working was againcommenced. The ground was examined hy boring in tlio opcn sea,and it was found that the deposits, which rested irnrnediatcly on therocky bottoni, had a tliickncss of 0.4; to 1-20 meters, and wcre coveredwith mud and said to a dcpth of 18 meters.The richest porttiom of’the ore formed pure crystals of stannic oxide (BUZZ. SOC. de Z’id. m i i / i r ;8. u. Hutteiinb-Z., xxx, 443). D. 33.Galenite from Habach in Salzburg. By V. VON 2; E P I I A R O V I C I I( & d i d . f. Uin., 1877, 529).-The galenite from this locality is re-markable, firstly, for its very complete octoheclral cleavage, with a lcsscomplete cubical cleavage ; and secondly, through the occurrencc ofnumerous interpolatcd twin lamell= parallel to a facc of 303. Theunusual cleavage mentioned above has been obscrvcd before only inthe case of galenite from Pennsylvania.There was no appreciabledifference in tbc lustre of the two kinds of cleavage-surf:xes. ‘l’hcbeliaviour of this galenite, on being heated in a rnattrass, is striking,as it does not c1ecrepit:ite ; whilst the heated poitioils have a readycubical and only an indistinct, octohedral cleavage. Sp. gr., 7.50;them. corn. = 58-03 per cent. of lead sulphide aiid 1.97 per cent. otbismut)h sulpliide. Thc jnterpolated twin l a r n d l e are grnei*ally sothin that they are scarcely discwniblc with tlic u;tked eye, and are ob-served also on the respective cleavage-faces of the large crjsta! ex-hibiting identical cleavage faces. C. A. B.An Aragonite Crystal from Oberstein on the Nahe. 13y H.LASPEYRES (Jahrb.f. M ~ I L . , 1877, 527).-Calcite is often fouridamygd&icIal cavities in rnelapliy~, but aragonite was nriknowii to ituntil the author discovered it in the abovc-mentioned locality. Thecrystal in quest>ioii has a length of 13 c.m., and a thickness of 4,s C . m .It is a penctrntion quadding, tllc twin planc being a, face of‘ ml’, andtJ1e conibinution is co 1’ . co k’ c% . $ I’ . 1’s . UP ; the latter fncc is notstriated ill the direction of the bracbgdisgonsl. c. A. l3.y:208 ABSTRACTS O F CHEMICAL PAPERS.A Polysynthetical Augite-twin from Bell, near Laach. ByH. LASPEYRES (Jahrb. f. M&., 1877, 527, .52P).---A polysyntheticaltwin - development in the monosymmetrical system is of rare oc-currence. It, is most common with epidote, arid more rare wit,horthoclase and augite.G. vom Rath (Jahrh. f. AIin., 1876, 404)described a. crystal of fassaite from Traversella, which consisted ofone large individual, with two interpolated twin-plates of the samesubstance. The author observed an anpite-twin from 13~11, exhibitinpthe usual forms, with a tw-in-plate (interpolated parallcl to tlie ortho-pinaroid), having half the thickness of the two halves of the principalindividual. C. A. B.Analysis of a Trachyte from Wolferdingen, in the Wester-wald. By A. HI r,Gb:R (,Tahrb. f . &%,., 1877, 421, 422).-The specificgravity of this spccirnen was found to be 2.68, aud its chemical com-position as follows, viz. :-SiO,. A1203. Fe20. FeO. MnO. CaO. MgO.59.87 22-52 0.32 2.52 0-13 2-5 0.46K20.Na20. P20,. H20.4.42 5-78 0.3 2.24 = 101.06.with traces of C1, S04H2, Li, Ba, and Sr, Before this the presence ofthese bodies had rarely been proved, von Lasaulx describing a trachytefrom Mont Dore, which contained Li and Ba. C. A. B.The Primary Rocks of the Northern Schwarzwald. By C.HKBENSTRE I T (Juhrb. f. Xin., 417-419).--The author undertookthe task of a,scertaining the composition of the basic and acid rocks ofthe wide-spread gneiss district of the Kinzigthal. Three varieties ofthese rocks were examined, viz. : (1.) A granular gneiss, rich in silicaand poor in mica; ( 2 . ) A hornblendic rock, enclosed in the gneiss;( 3 . ) A garnet-graphite-aneiss, rich in mica. Garnet-gneiss was knownto occur often in the Schwarzwald ; but ~arnet-graphitc-gneiss washitherto unknown, the latter being formerly known by the riame ofKinzigite. This rock is found at Schenkenzeil, near Wittichen, in alajer scarcely I+ feet in thickness, enclosed in ordinary gneiss.It iscoarsely laminated, macroscopically distinctly striated plapioclase ;black mica, violet-red garnet, mid lamince of graphite are recognisable.Colourless needles of apatite, fine aggregates of iron-pyrites and red-dish specks of specular-iron were detected in the felspar, on examiningthe rock under the microscope. The presence of quartz could riot bedetected. An analysismade of a pure, fresh specimen furnished the following results, viz. :-(1.) By experiment; (2.) Calculated from No. 1, after dcductingIts specific gravity was found to be 3.00.iron-pyrites, apatite, graphite, and iron-glance.SiO,.AI,O,. Pe,O,. FeO. CaO. MgO. K20.No. 1 . . 44.53 17.55 5.38 12.60 3-36 5-68 3-54Xu. 2 . . -46.68 18.40 3.54 12.87 3.32 5.95 3.7MINERALOGICAL CHEMISTRY. 209Na20. H20. P. S. Graphite.No. 1.. . . . . . . 3.60 1.66 0.17 0.29 4-33 = 100.69- = 100.00 NO. 2 ... . . ... 3.77 1.75 - -The author also examined the asymmetrical felspar and garnet ob-served i n the rocks, atid found the former to be colourless stronglylustrous oligoclase, with a specific gravity of 2.1357, slid cxhibitirig afine twin striation ; whilst the latter was true almandine, coiitainingmany enclosures (particularly niicrolitic quartz), arid had a specificgravity of 3.96. The analyses of these minerals furnished the fol-lowing results, viz.:-SiO,. Fc,O,. FcO. CaO. MgO.Oligoclase .. . . 62.90 22.23 trace - 4.45 -Garnet . . . . . . . 37.40 21.08 2.01 28.49 3.05 8-22K,O. Na,O.Oligoclase.. . . . . . . 2 09 8.48 = 100.15Garnet . . . . . . . . . . - - = 100.25Hebenstreit gives a tablc of analyses of gneissoid rocks, comparingthem a t the same time with analyses of rocks from the same neigh-bourhood, the result of which serves to show that the hornblendicrocks and the garnet-giieiss (which is intirnntely associat'ed with thehornblcndic rocks) have been sepzrated from tlle very common sndwidely-spread graqular striat$eJ gneiss, and are equally basic in cha-racter. Anexamination of tlie granite of Tryberg proved i t to resemble veryclosely the granites from the northern Schwarzwald. The composi-tion of the gneiss from the neighloourhood of Tryberg was feud todifter considerably from that of the granite from the northernSchwarzwald. C. A. B.Analysis of the Water of the Warm Spring at Assmanns-hausen. By R. YRESJCXIUS ( J . pr. Chem. L2], xvi, 278-2!W).-This water was found to contain in 100,000 parts (salts all anhy-NaLC03. Li,CO,. CaC03. BaC03. SrCO3 MgCO,.9.7486 1,711160 12.2307 0.0989 0.1978 4.0066FeC0,. MnCOJ. K2S01.0.2239 0.1326 4.3068The granular gneiss is the most acid of these rocks.drous) :--C0.J co,KCl. NaCl. NaBr. NaI. NaJIPO,. Si02. (combined). (free).0.4522 57.1764 0.0971 0.0004 0.0301 3.1539 12,7780 18.5800The sp. gr. of the water was 1.000832 a t 15", and its temperatureThe water is distinguished from all others of similar cha- 31.1" C.racter by the relatively large quantity of lithium which it con&ns.Analysis of the Acid Well (Sauerbrunnen) at Bilin.J. R.ByH u PPE: ET (Chem. Cei~tr., 1877, 137).-'l'his is a newly-discoveredspring, and tlie analysis of one of the older springs, the Josefsquelle,is added for comparison210 ABSTRACTS OF CHEMICAL PAPERS .K.60. ..............Na.SO. ..............NaC 1 ................Na.&O, ..............caco, ..............MgCO, ..............Li,CO, . . . . . . . . . . . . . .FeCO, ..............MnCO, ..............Iodine ..............Al,O,.P,05 . . . . . . . . . .SiO, ..............Josef squolle .2.34967.2 7623.813533.30854.12951.71 910.11330*02840.0305trace0*00570.4340New spring .2.54187.07673. 719132.6 5 7 C4.2 8 2 .i1 * P9 5 40.1 2 5 30 02.790.0105trace0.0 0 .-, 60.43 5 7Total solids .......... 53.2088 52.7761Half-combined COz . .Free CO. ............Total of conatituerits . .16.730314.269784.2083Total CO. .......... 47.556516.508715-53 16841-616448.3480.-G . T . A

ISSN:0368-1769    

DOI:10.1039/CA8783400201

出版商:RSC    

年代:1878

数据来源: RSC

摘要:

210 ABSTRACTS OF CHEMICAL PAPERS.O r g a n i c C h e m i s t r y .Decomposition of Organic Liquids by the Electric Spark,with production of the Fundamental Hydrocarbons. By P.‘I’ nu c H o T (C‘on7pt. rend., lxxxiv, 714-7’16~.-According to Berthclot,when a hydrocarbon of high molecular weight is submitted to de-structive distillation, the four fundamental hydrocarbons, ncctylene,ethene, methane, and etliaiie arc first separated, aiid thesc, imme-diately entering into combination with each other, producc tlre morecornplcx hyc1rocarl)ons which are actually obtained. It is obviousthat this assumption would be greatly st,rcngt,hened if thc decomposi-tion ccdd be effected in such a maliner that,, recombination being pre-vented, the simpler hydrocarbons were obtained in the free state.This tbe author has succeeded in doing by passing a powerful iiiduc-tion spark tlrrougli the liquid itself, and collecting the resulting gases.Volatile liquids, such as pentnne, pentpne, aqd ethyl oxide giveabout one litre of gas per hoixr, but conipounds of higher boilingpoint give considerably less.The gas invariably contained hy Jrogenin a,ddition t o the 11ydrocal;bons already mentioned, bnt no compoundcontaining more than two atoms of carbon in the molecule was prcscnt.With the liquid paraffins, no deposit of carbon occurred during thedecomposition, provided the liqiiid WRS kept, slightly warm ; and atrace of carbon only was obtained in the case of an olefine. With theless saturated hydrocarbons, however, such as the turpentines anORUANIC CKENISTRP.21 IFerizene-derivatives, zt tolerably abundant. deposit of carbon alwaysresulted. Componnds containing oxygen, such as aIcohol, ether, andthe ddehydes give no carbon; but, in addition t o the fundamentalh ydrocarboiis, evolve carbon monoxide, unaccompanied by carbonAction of Aluminium Iodide on various Organic Corn-pounds containing Chlorine. By G. G u s TAT SON (GYhem. C B ~ T . ,dioxide or water-vapour. J. w.1877, 19).-Aluminium iodide has no action even with the aid ofheat on C6C16 and C2Cl, (C,Cl,(?)). It acts easily 011 C,C16 according tothe equation 3cZc16 + &I6 = :3C12C14 + Al2CI, + 31,. But there isalso former? an amorpli ous carbon compound containing iodine.Aluminium iodide acts energetically on trichlorhydrin, yjeldiiig iodine,alIyl iodide, and aluminium chloride. In the benzene series the chlorineof the lateral chains only is replaced by iodine, when they are actedon by aluminium iodide.G. T. A.Action of Sodium upon Monochlorethylene Chloride. ByH. BRUNNER and R o o . BRANDENBURG (Dsut. Che?ir.. Ges. B c T . , ’ ~ ,14Y6--1499).--Thc authors have demonstrated that, monochlorethyleneclilori cle is decomposed by sodium into acetylene, ethylene, andethylene dicbloride, according to the equation-CHtCl4 1 + 4Na2 = 8NaCl t HCGCH + H2C1CH2 +CHC1,S(CLIIC~CuIC1) + Hz.This is in keeping with the observation of Fuchs on the decomposi-tcion of vinyl bromide by sodium into acctyJene and ethylene, and afhrdsa sufficient explanation of the failure of the author’s at,tempts to intro-duce the vinyl molecule into the benzene nucleus by means of theaction of sodium upon a mixture of chlorethylene chloride and benzenebromide.c. P. c.The Preparation of Propyl Glycol. CBy 0. HARTMANN (J. p r .Chetiz. [2], xvi, 383).-The author obtained 5 grams of propyL glycolfrom 125 gmms of propylene bromide (b. p. 141”) by Zeller andHufner’s reaction. Hence Voelker’s statement (Deut. Chem. Gos.Ber., ix, 924) that potassium carbonate has no action on prop-yltlnebromide is incorrect. w. c. w.Compounds of Quercite with Butyric and Acetic Acids.By L. PRCXIER (Cow~it. rend., Txxxiv, 1318).--The compounds ofquercite with sfearic: benzoic, and tartaric acids have been describedby Berthclot.The author describes the following cornpounds of quer-cite with bntyric acid :-C&i,oO,(C,H,O,) = CsHlZOj + C4HSOZ - HZO.&Ionobutyrin. Quercite. 3 utj-ric acid.CJI,O?(CJ&O,), = C&I,,05 + 3C,H,O, - 3HZO.Tri butpin212 ABSTRACTS OF CHEMICAL PAPERS.C6H,(C4H,o2), = C6H,,0, + 5CaH,02 - 5H,o.Pentabutyrin.The three corresponding ncetins are also described.The mo.lzob?dy~i~ is produced when 1 part of quercite is heated with3-4 parts of butyric acid to 110--120° for twelve hours in scaledtubes. It is mixed with some higher compouiids, and with a largequantity of uncombined quercitc.The tributy-in is produced when the mixture is heated to 150-160".The peiafabutyrirb is produced a t 17'0-1Sr>0.All these ethers are solid or viscid bodies, amorphous, colourless,and slightly deliquescent, of bitter taste ; wry solahle in ether, less soin alcohol, and very slightly in water, unless this latter contains alpexcess of butyric acid, in which case the ethers dissolve, and bycautious addition of water the pentabutyrin aiid trihutyrin are sepa-rated as an emulsion, the former being precipitated, and the latterrising to the top.The methcd of separation of these bodies is prcciselp the same asthat, used by Berthlot in the separation of the acetins, butyrins, &c.,of glycerin, except that, potash must be added to slight alkaline reac-tion, so a s to remove the free acid which these bodies dissolve andretain obstinately.The following are the analytical results, which were in each casecontrolled by titration with baryta-water :-Monobutyrin.Tributyrin. Pentabutyrin./ \-----?Pound. Calc. for Found. Calc. for Found. c':ilc. f'orCSH1004 (C'IK302) * CBH,O,(C4H,O2)3. CGH, (C'ZHy,O,),.C . . 51.3 51.1 57.9 57.70 60.1 60.70H . 7.8 7% 8.2 8.02 8.3 8.15The first two contained small quantities of higher compounds.Acetins.-Crystallisable acetic acid heated t o 100-1%0" with quer-cite combines with it slowly to form the monoacetin. If a small quan-tity (about -01) of acetic a u h y d d e be added, and the mixture heatedto 130-1410", the triacetin is formed. The pentacetin is formed whenquercite is heated with acetic auhydride. The method of purificationis the same as with the butyrins.The acetins of quercit'e resemble the butyriris ; they are amorphous,colourless, solid arid brittle, or viscid bodies, of bitter taste and some-what agreeable odour.The following are the analytical results :-Pent acetin, C6Hz ( C21140z) 5.7- -.Triacctin, C6H602 ( C2H,00) 3.Found.Calculated. Found. Calculated.C .. . 51.15 51.30 49.3 49.65H . . . 6.10 6.00 6.4 6.20c. w. wORGANIC CHEMISTRY. 213Substituted Crotonic Acids from the Pyrocitric Acids. ByT. M ORAWSKI (Chem. Ceutr., 11377, 131-133).-Tlie author pointedout in a paper on mesaconic acid (Chena. Cent?.., 1876, 262-294), thattlie monobromocrotonic acid which is formed from mesaconic acid bymeans of the intermediate mesadibromopyrotartaric acid, is convertedby the action of sodium amalgam iiitn isobutyric acid, as is the case onsimilar treatment with KekulB's nionobromocrotonic acid from citra-conic acid.The supposition that the two acids are identical has beenconfirmed by the author by a comparison of their salts. 'l'he first saltsformed with tlre rnonobromocrotonic acids derived from citracoriic andmesaconic acids were the calcium arid copper salts.The calciunz salt of both acids is moderately solublc in water, andcrystallises on evaporation of the solutions. It is stable iu air, andloses its water of crystallisation quickly and periectly at loo", but onlyslowly in a vacuum over sulphuric acid. The copper salt is in eachcase of a bright blue colour; becomes lighter on drying, and hasthe corriposition of a basic salt. The cadnLiuut salt of each acid crys-tallises in briliiant prisms, and appears to be hydrated.The crystals,dried a t looo, were of a faint yellow a t the edges, and the amount ofcadmium corresponded with the anlLydrous salt. With the monobro-mocrotonic acid dei-ived from citraconic acid a barium salt was obtainedwhich was easily soluble in water, and separated from concentlratedsolutions in prismatic crystals. An amnioiiium salt was also preparedfrom the same acid, whicli crystallised easily, arid seemed to be volatilein a vacuum over sulphuric acid. l'he soluble salts of the acids fromboth sources gave with ferric chloride bright flesh-coloured precipi-tates.The author next examined the monocl~lorocrotonic acid whichGottlieb obtained by ruearis of zinc from triciilorobutyric acid, aiidthat which Swarts obtained by decomposition of citraciichloro~yrotar-taric acid with bases, and found them to be identical.The followingsalts mere prepared from Gottlieb's acid. Tlie calciz~m sult, when i tseparates from a cold solution on slow evaporation, forms liglit, loose,efflorescent crystals, which overtop the side of the vessel ; but when de-posited horn a hot concentrated solution, i t crystallises in distinctneedles, which adhere to tlie sides of the vessel, giving them a finesilky lustre. The copper salt is a bright blue powder, which dissolveswith great dificulty in water. It is a basic halt, and consists of(C4H4C102)2Cu + CU(O€€)~. The sodi'LtwL stilt is e w l y soiuble in water,but not without dificulty in alcohol.It crgstallibes imperfectly, andseems to be hydrated. It gives a bright flesh-coloured precipitate withferric chloride. The ethyl-r o r u r p i d of moliochlorocrotonic acid is amobile liquid, obtaiiied by treating ail alcoliolic solution of the acid withhydrochloric acid gas, washing with water arid caustic soda, aid dry-ing over calcium chloride. l'he etlier is sparingly soluble in water,has a pleasant fruity smell, can be distilled withbut change, and boilsat 155-158".A few salts were also prepared from diclilorocrotonic acid, obtainedfrom trichlorobutyric acid by the action of alkalis. 'I'he putusstuw saltcrystallises in very fine large rhombohedrons. The c o p e r salt has anintensely green coiour. It is less soluble in hot than in cold water, s214 ABSTRACTS OF CHEMICAL PAPERS.that, if a, solution saturated a t ordinary temperatures is raised to boil-i n g it becomes turhid, and a t last is filled with the separated greensa1 t.The crmmoniutn salt dissolves with extraordinary ease in water.A crystalline mass was obtained by evaporating the solution over sul-phuric acid, which was neutral and ar;hydrous. It gives a light flesh-coloured precipitate with ferric chloride. The burlurn salt is veryeasily soluble in water, but crystallises with difficulty. An alcoholicsolution deposits very small crystlals 011 the side of the vessel, which,however, appear to be very deliquescent. G. T. A.Action of Chlorocarbonic Ether on Sodium Cyanamide. ByPAUL BXBSLER ( J . p*.Chcin: [el, xvi, 125--16!3).--When chlorocar-bonic ether is gradually added to dry sodium cjaiinmide suspended inanhydrons etlier, a reaction begins which a t first requires moderating bycooling, but which must be completed on the water-bath. The filtrate,after evaporation of the ether, forms a thick, very sour syrup, containingmuch cyanamidocarbonic ether. On being heated to over 140' it yieldsa ncw body, cya,iic2midodicarbonic ether, together with cyanamide andits pol y 1yi erisation product, die y ~ ~ 7 7 odiant ide.C~'/?La"idr/d;(:rC~~~~;c ether, C,H,,N,O, = N(CN) ( CO0C2Hr,),, con-sists of very large glittering crystals, which melt a t 32.8" to an oilyliquid, resolidifying only at a much lower temperature. It is readilysoluble in alcohol, ether, chloroform, and benzene, less soluble in car-bon bisulphide and sulphuric acid, but insoluble in water.On dry dis-tillation i t yields carbon dioxide and cyanic ether, together with thedecomposition products of the 1;ttter. Water gradually resolvcs i tinto carbon dioxide, alcohol, and cyanamidocarbonic ether, which lastis in turn split up into carbon dioxide, alcohol, and cyanamide. R'ithammonia it yields cyananlidocarbonic ether and ehhyl carbamate.Heated to 150" with sodium ethylate in sealed tubes it yields ether,sodium, ethylcarbonate, and the sodium salt of cyi~namidocarbonicether.Cyanamidocn~boicic efker, C4H6N202 = N(CN)(COOC,H,)H. is pre-pared by the action of concentrated sulphuric acid on 6odium cyana-midocarhonic cther.When pure it is an oily thick syrup, of a yellowcolour, and with a strong sour reaction and burning taste. I t has anethereal odour. It is soluble in alcohol, ether, chloroform, and ben-zene, less soluble in carhon disnlphide, and somewhat soluble i n water.Boilin5 water converts it into carhon dioxide, alcohol, and cyanamide,and boiliiig dilute h~-drochloric acid into ethyl allophmate. Or1 beingheated i t yields cyanamide and cyanamiclodicarbonic ether. C j anami-docarbonic etlicr readily forms stable salts, which are gencdly charac-terised by forming magnificent cq-stals with a peculiar satiny Iuctre.SodZu?n-~ym nwzkloc 7,r.lmnic ethe.;, N(C;N) (COOC,H,)Na, crystallisesin splendid glittering crystals, melting a t .t41", and soluble with greatease in water, less soluble in hot absolute alcohol, and still less in coldalcohol.On liesting it splits up into a mixture of ethyl and sodiumcyanates.Polcc.s~iz~m-c~~a~2anzidocar~~nie ether, N( CN) (COOC,H,)K, is formedwhen cyanamidodicarbonic ether is treated with alcoholic potassiumhydrate. It crystallises in magnificent white glittering needles of verORGANIC CHEMISTRY. 215voluminous character. They melt at 199", and are readily soluble inwater, slightly soluble in absolute alcohol in the cold, but more easilyon warming.S;lver-c?/ana?lpiclocn,l.boiiic ethey, N( CN) (COOC,H,)Ag, is obtained asa, curdy white precipitate by adding either of the previous compnndst o a solution of silver nitrate. It is easily solublc in ammonia anddilute nitric acid.Eth!/7-cy"?Ln1,2idoca,i.bonic ethw, N( CN) (COOC?H,).C,H,, is formedby heating in sealed tubes t o 150" a mixture of ethyl iodide and potas-sium cyanamidocarbonic ether.It is a colourless, neutral, oily liquid,boiling a t about 213", and miscible in all proportions with alcohol andether. It is slightly soluble in cold water, but rather more soluble inhot water. It can be inflamed witli difficulty, and burns with a violet-red flame. This new body is isomeric, with dicyanic ether and R poly-meride of ethyl cyanate.By E. BLANKEN-E. N.Action of Thiocyanic Acid on Alcohols.H O R N ( J . p r . Chem., [el, xvi, 358-~3t;3).--Etliylic clithiosllophanate,C4H8N,S,0, was obtained by Tiksner ( J . p r . Clmn., [a], vii, %i4), bythe action of phosphorons chloride on ail alcoholic solution of potassiumthiocyanate, and was considered by him to be C,H,,N,S,O.It is bestprepared by adding fuming Iiydrochloiic acid to a hot concentratedalcoholic solution of potassium thiocyannte ; potassium cliloritle sepa-rates out, and the filtrate, after concentration, deposits crystals of cthylicdithioallophanate. An excess of hydro(-hloric acid must, be avoided,as its prcserice is favourable to the prcduction of tliiourethancs.Ethylic dithioallophanste floats on the surface of cold water withoutdissolving; it is soluble in boiling water, in boiling ether, and inalcohol. The alcoholic solution deposits regular prismatic crystals,melting with decomposition at l7O-1'iSo, and having a, bitteu.taste.It is decomposed by the action of alcoholic :tmmonia a t the ordinarytemperatiire, into urea, mercaptan, and tJiiocarl)amide, but w lien heatedto 15Uo, in sealed tubes, i t forms tliiocarbamide and etbpl alcoliol.Aniline converts i t into thiocarbamicle, dlipheii3ilci~rbamide, and mer-captan, and baryta o r alcokiolic potash decomposes it, formiiig merc.np-tan, tliiocarba,mide, and carbon dioxide. From these reactions it followsthat the probable constitut>ion of ethylic dithioallophanate may bcrepresented by the formula, NH,--CS--NH-CO--SC,H,. The ituthorhas not yet succeeded in preparing methyl- aud butylthioa1lo~)liarri~tes.A mixture of two isonieric tl~lourcth~~?aes is obtainccl by acting onalcoholic solutions of potassium thiocyanate, with an excess of stronghydrochloric acid, e.g., xanthnnaide and cal-bo.1Ly2t~~iciethylunzl,r,e, describedby Conrad and Salomon (J.yr. C'lmi?., [ 2 ] , x, 28), are obtained byadding hydrochloric acid to a solution of potassium thiocyanate inet1,yl alcohol. Ry substituting metlryl for ethyl alcohol, a mixture ofme th ylxant ha<mide, N H2-C S--0 CH3, and curbony 1 t8 hiome t hylamine,NH,-CO-SCH,, is produced. The last,-mentioned substance is de-posited from its alcoholic solution in large, monoclinic prisms, whichmelt a t 95-98'.A mixture of isobutylxanthamide, NH2--CS-OC4H9, and carbonyl-monothioisobutylamine, NH2--C;O-SC,H,( CH,),, is formed by th216 ABSTRACTS OF CHEMICAL PAPERS.action of an aqueous solution of potassium thiocyanate on isobutylalcohol which has been saturated with hydrochloric acid gas.w. c. TV.On the Constitution of Pyrrol. By ROBERT SCHIFF (neut.Chem. Ges. Ber., x, 1500--1503).-By the action of acetyl anhydrideupon pyrrol (b. p. 133"), the author obtains an acetill p y r d (m. p. W").Fiiiding that both ethyl iodide and the alkali metsls, in preserice ofanhydrous ether, fail to exert> any action upon this compound, and thattherefore there is no second atom of hydrogen in uiiiori with the nitro-gen, he appears t o have established the presence of the N11 group inBy the action of bromine on this compound, a 6ibromacetyZpyrroZ ispyrrol .formed, to which the author assigns the constitution :-CH-CHBrC,H,O .N/\CH-CHB~.The preparation arid investigation of the derivatives of this bodyare in progress. c.I?. c.Peculiar Formation of Phenyl Isocyanide. By C. 0. C ECHand P. SCIIW E B E L (Clmm. Cmtr.. 1877, 134).-When dicliloraceticacid is brought into contact with aniline, the mixture solidifics, withstrong evolution of heat. This solid, rccrystallisecl from alcohol,yields yellowish, brilliant needles, which melt a t 1'25", and consist ofaniline dichloracetiite. On treatment o€ this body with dilute causticsoda, no aniline is liberated, but on boiling the liquid, phenjlisocyanicleis formed, together with formic and hydrochloric acids. G. T. A.Cyanoguanidines. By OSCAR LAXGREBE (Deist. Chem. Ges.Bey., x, 1587- 1596).-Hofmmn has shown that auiline, toluidine,and cumidine form addition-products with cyanogen, and that melani-line (diphenglguanidine) also possesses tlic same propel ty ; the authorhas examined the action of cyanogen on ditolylguanidine ; corn biiiationreadily takes place whcn cyariogen is pabsed through a cooled etherealsolution of the base, a magma of crystals being formed after recrystal-lisation from \.c arm alcohol (a terriperature of UPM aids of' 50" producesdecomposition).These have the composition of'i~icllcnnotlitol!/ly /(mridr'ne,CI7H,,N5. This body is very difficultly soluble in water, more readilyin ether; a t about 7c)-80° i t begins to decompose; by the artiori ofdilute acids it gives rise to dltolllloxal~lgzslxlz.idilLe, C,,H,,N02, meltingat l88.5", the reaction being-C17H17Nj + 2HzO = c,iH,5hT,Or + 2NH3.This body is nearly insoluble in water, difficultly soluble in ether andcold alcoliol, readily in hot alcohol.Boiling with hydrochloric acidconverts dicyanoditolylguanidine into diLoL3 Lparabanic acid, CL7HIJN2O3,by the parallel reaction-C,;H,,N, + 3HXO = C1THJT20J + 3NHSORGANIC CHEMISTRY. 217This substance melts at 144", and i s readily soluble in alcohol andbenzene, less easily in ether, carbon disrxlphide, and glacial ;teatic acid,and almost insoluble in water. Jn all these reactions the tolylgimnidinederivative behaves in a, Cishion pi.ecisely parallel to that exhjbited bymelaniline ; similarly when subjected to the lonq-continued action ofboiling concentrat,ed acids, i t forms toluidine, oxalic acid, and carbondioxide. Alcoholic ammonia a t the ordinary terripcrature did notform an oxaluric derivative, but gave rise to d i t d y l - u r e a , C1511,6N,0(melting a t 250-260"), and oxalic acid.To these aild analogous bodies the author attributes the forrnu1~-Sub stit u t e d osal yl Substituted para- Cyanogen combinatioiigunnidines. banic acids.products.NEE-CO NR-CO NR-C=NH'ER-CO 'NR-CO 'XK--O=NH 'NH=C' I O=C' I NH=C' Iit heing assumed that ditolylguanidine and similar bodies are NH =By Leatirig ditolyloxalylguanidine with aniline, a phenylated deri-vative is formed, of basic charactcrs, Eorrninq a hytlroc'nloride,C,,H,,N,O,,HCl; on similarly heating dic~anodiphenylgnanidine andaniline hydrochloride, the hydrochloritls of dir,?/nrttri?ilieir!/Z!/urr,n7:17ine isformed, indicated by the formula, C,,H,,N,.HCI,SH,O, after crystallisa-tion from hot, alcohol.The free base crystallises in needles. containingC21H17N5, iH20, melting atl72.5" when anhydrous; it is insoluble in water,solnble in alcohol, ether, benzene, and carbon disulphide : with lipdro-chloric, sulpliuric, nitric, and acetic acids it forms well cr~stallisedsalts ; the platinochloride also is crystalline. This base is not identicalwith the isomeride mhich Hnfmann prepared by passing cyanogeninto a-triphenylguanidine, for Hofmann's product gave no hydrochlo-ride, and formed by the action of dilute acids a yellow tviphenyloxalyl-gunnicline, whilst the author's substance does not thus break LIP, saveon long-continued boiling with coilcentrated acids, when diphcnyl-parabanic acid is formed with difficulty.Hofmann's product readilyformed diphenylparabanic acid on boiling with acids. On the otherhand, Hofinann obtitined a dicyantriphenylguanidine as a bye-product,with preparbation of cyeniline, by acting on aniline Mith cyanogen,which is apparently identica,l in all respects witth the author's product( D e z d . Chew. Qes. Bey.. iii, i64). The author hence proposes to namethe product from a-triphenylguanidine, a - d r ' c ? / l l c r ? c t r ~ ~ ~ ~ ~ e ~ ? ? / l ~ u whilst the other isomeride from aniline hydrochloride and dicyandi-phenylguanicline (or from cyanagen and aniline) is distinguished as/3 - d i c y IX n t rip h e y i y lg u anidii L e .Aniline hg drochl orid e produces similar bodies with dicyancl i tolyl-guanidine, and diphenyloxalylguanidine.These are now under inves-tigation. C. R. A. W.C{N(C,H,)H} 2'Action of Carbonic Oxide on Aniline, Toluidine, Acetylene,&c. By G A R ~ I I ' T S C H - G A R N ~ ~ ~ Z K Y (Cltern. Cenir., 1877, 22).--Car-honic oxide dissolved in an ammoniacal solution of cuprons chloride,forms with the above bodies tolerably stable crystalline compounds218 ABSTRACTS OF CHEMICAL PAPERS.which probrtbly belong to the ammonia type, and contain the copper inthe same condition as the iron in tlie ferro- and ferricyanides. Ammo-niacal solutions of cuprous chloride, free from carbonic oxide, alsoform crystalline conipounds, with considerable evolut,ion of heilt ; butthey are unstable, and rapidly undergo oxidation in tlie air, whichshows that they belong to the suboxide type.Mono- and Dimethyltoluidine.By A. L. T H o M s E ? r ~ (Dcut.0. T. A.Cl?mz. Ges. Bw., x, 15S2--1Sd7).-Methyl chlc,ride was prrp:iwl bypassing hydrochloric acid into pure metbylic alcohol containing ziiicchloride ; the evolved vapouvs were passcd successively througli causticsoda, water, and sulphuric acid, and finally into 350 gmms of piircfused toluidine, contained in a cohobator, through which steam waspassed, so that the toluidine was kept fluid, but yet was condensedand prevented from escaping. After 29 hours methyl chloritle vapou1.swere copiously e ~ o l ~ e d , diowiiig the niethylatiori to be ncarly entl~tl.On shaliiny with ether, I81 grams of pure toluidine liycllrochlori~lewere left undissolved, liilst on nqitating the ethereal sohition withdilute snlphuric acid, 126 grams of toluidine sulpliate were formcd, sothat little more than one-third of the toluicline had been methylntcd.The ethereal solution thus deprived of toluidine was evaporated, andthe oily base left was trented with acetic anhydride, whereby muchheat was evolxTed, and much acrfonzrtli~~Zto77ridin e produceti.Yrom thismethyltoluidine was easily p r e p r e d by boiling with coriceiitratetl 11ytl~'o-chloric acid, and precipitatiiig w i t h soda. From the quarititim oftoluidine 11 y drocliloride and t c e i onicthj~l toliiidiue obtained, tlir ;in thorcalculates that nbont 2 parts of'clirnetli~ltoluidine wcre foimeil for every7 of monomethgltoluidii~e : but lie does not ?,escribe the rnode of st'px-ration of the former body, or even distinctly state that its formationwas directly observed.Aretornetbyltoluicline, C7H;.N( CH,) (CJ130), crystallises from amixture of alcohol and ether in large plates, which fuse a t 83", midboil at 283* ; t>he rrit~thyltoluidine thelice prepared boils a t 208".Ondissolving this in hydrochloric acid, and aclcling potassium riitrite,with careful cooling, nitrocoiuirt7i!/lfo7?cidine, C7H7.N( CH,) (NO), isformed, crystallising from a mixture of alcohol and etlicr i n wclldefined pi'isnis, melting a t 54". By nitration, metliyltoludine formsa dinitro-derivative, crystnllising in fine liglit red needles, me1 tirig at129", and unaltered by solution in hot acetic or hydrochloric acitl.By treating paratoluidine with methyl iodide, trL'ii~rth!/7jl/t~,-i4t~)l~/Z-awmouiwrz iorlidc., TU(CH,),( C7H7'i1, is readily obtained, from wlrichdiinethy1toluid;~ie can be formed by treatment with silver hydr;rt~, anddistilljng the ammoilium hydrate thus p~oduced ; it boils at 208" (A4,W.Hofrriann fourid 210" for tlie dimethyltoluidine similarly 1)ropar(~dfrom paratoluidine). In order to compare this with dimetliylortlio-toluitlinc, this body was prepared iii a similar fashioii from p3ui.e ort lro-tolnitline (the accto-derivative of whicii melted i1 t 107") ; tlte J i ? n r l / / ! / l -o~thotoliridine thus obtaimd boiled at 185". A. W. Hofmaiin obtaineda dimethyltoluidine boiling at 186", by the action of heixt, on ti~iinetliyl-phenyiammonium iodide, arid states in a footnote that he rt.g;wds thisas identical with the ortho-derivative just described, attributiiig thORGANIC: CHEMISTRY.219slight,*difference in boiling point to thermometric errors ; a t the sametime a dimethyltoluidine, boiling a t 205", was formed; query the cor-responding meta-derivative ? ( V i d e Deut. Chsn7. Clies. B e r . , v, 711.)C. R. A. W.Diazobenzene-derivatives. By P. G. W. T Y P K E (Dezst. Cl~em.Gea. Rer., x, 1576--1582).-Baeyer and Jagcr have shown that whenaqueous solutions of resorcin and azobenzrne are mixed, a red solids e p r a t e s which melts at 166" : the author finds that this substance isa mixture of two isomerides which he terms rcspectively a- and p-diocc?ycrzobenzeiie (or azobe?~ze?2e-diozijlbe?zzelzr).The two differ in theirsolubility in alcohol, and can thus be separated ; the a body is readilysoluble in alcohol, ether, acetic ether, chloroform, and benzene, bntinsoluble in water, which precipitates it from nlcoliolic solution in siriallred needles : it is soluble in dilute alkalis, and p ~ c i p i t s b l e from thesolutions unchanqed by means of acids : i t melts a t 161". Thc @-corn-pound is formed in much less quantit'y ; it melts at 215 ) (not eorrectcd),resembles the a-modification, but is only sparingly soluble in coldalcohol, though readily soluble in hot spirit. The analytical numbeibslead to the formula C,H,--N=N-C6H,(OH), for both sub,taiiccs.On dissolving a-dioxpazobrnzcne i n glacial acetic acid iriid acitlingexcess of bromine, a magma of crystals results consisting of thc tri-bronio-derivative, fusing a t 186" : long-continucrl coiitact with the acidand bromine, or boiling for a short time, breaks up this bromiiiaterlbody, forming t~lbmw,oreso~ci?l (just as iliazotei~zt~~c itself s\)J its ixp) :thus C,H,-N~N-C,Br,(OH), + H,O = CJ€,.OH + C,HUr,(OIi>, + N,; the phenol thus produced is converted into brornopl~eriol bythe excess of bromine present.When orcin i s substituted for resorcin in the above experiment,m e thy I - d ;ox!/ ax o benzene ( az o /J en z e i / e - d iox y "17.7 e f h !/ 1 h I: 1 I z e ?&e) is pro cl I I c c d , i n-dicated by the formula C,H,--N=N-C;H,( OH), ; like dioxyazoben-zene, this substance possesses grcat tinetorial power ; i t melts at 18Y,arid is solnble in alcohol, ether, chloroform, and alkalis, being preci-pitated from tihe latter solution bg acids. and from its solution inglacial acetic acid by water.On bromination, a diioromo-dcrivativemelting at 183" is formed.Alpha-naphthol gives rise to a similar derivative, probably to twoisonierides. oiie more soluble in alcoliol tlinri the other. The moresoluble substance, a z o b e n z e ~ ~ e - u - i r ~ ~ ~ l ~ t ? ~ o l , does not crystnllise iwdily ;it has powerful tinctorial properties : acids dihsolve it, f'ormiiig solu-tions which are decolorised by natscent hydrogen. B ~ o t ~ ~ i n i ~ ted tlerirn-tives could riot be formed, the body being clt~composed by bromine :sulphuric acid appears to form a sulplionic acid not yet 0bt:iined pnre.C.It. A. W.Action of Sulphurous Acid and the Sulphuric Acids uponDiazo-compounds. By W. KONIGS (Ihzct. (!horn. Ges. jh., X, lX31-15:34). Bg the action of aqueous sulpliurous acid upon a solutionof diazobeiizene sulphate or chloride, a coinpixrid is ohtninetl \.I liivh,both in its poperties and constitution, the nutlror slioms to bc itlenticdwith the hyclrazine derivstive--CGH,.NIl.N~i.80,~Gll,, which Pische220 ABSTRACTS OF CHEMICAL PAPERS.prepared by the action of benzenesulphochloride upon phenylhgdrazine.The course of tbe reactiorl appears to be-(1) the conversion of aportion of the diazobenzene into beneenesulphinic acid, which (Z),unites with the undecomposed diazobenzene ; and (3), the reductionof the product of this union by the siilphurous acid.I n older to snbstantiate h i s deduction, the author has tried theaction of sodium benzenesnlpbinxte upon diazobenzene nitrate, andfound in effect that a body corrwpondinc in composition with diazo-benzene benzenesulphinat~e-CGH5".SO,.C,;H,--is foruied. Itmelts a t 75-76', it is insoluble in water in tlre cold, but soluble inalcohol, ether, and benzene. Its constitution is rezarded by tlie aulhoras that of a phen~1-diazophenylsuIphone, S02<N2.c,LI,. C6~H5 "By the ac-tion of reducing agents it is converted into the hydrazine-derivativefirst described.The yellow potassium diazober,eencsulphonate, C,H,N.N.S03K, isalso converted. by reduction, into a hydrazine-derivative, the colourlessbody, C,H:,.NH.NH.SO,K.The three compounds described in this paper all yield on treatmentwith mercuric oxide, according to Fischer's method, crystals of theyellow diazobenzenebenzolsulphinate.The author is engaged in the experimental generalisation of theseobservations. C. F. C.Decomposition of Substituted Benzene-sulphonic Acids byWater and by Acids at High Temperatures. By H. L I M P R IC 11 T(Deut. Chem. Ges. fjer., x, 1538-1542) -Para- anci meta-dibrorno-benzenesulphonic acids are completelp resolved by the action of con-cent,rated HBr at temperatures of 250" and 190" respectively, into sul-nhuric :reid and the corresponding dibromobenzene.The ortho-acid isikrnilarly, but only partiall$ decomposed at 250".SO.<HTqmib.ro?nobenzene - sulphonic acid, Br ('1 Br , is completely re-\/Brsolved by the action of concentrated HC1 at 150" into sulphuric acidand tribromobenzene (m.p. 118.5").SO,HTribronzobenxene - sulphonic a&d, , is decomposed by (,) BrBrconcentrated HBr at 200" into sulphuric acid and tribromobenzene(small needles ; m.p. &kO").SO,HB 1'centrated HBr or HC1 to 150°, forms sulphuric acid and tetrabro-mobenzene (m.p. 98.5")0RC;IANIC CHEMISTRY. 221Br /\ BrNitrotribroinobenxene-~~lpl~o~~ic acid, , is resolved by i,! NO,Brconcentrated HC1 a t 185", for the greater part, into sulphuric acid andni trotribrorno benzene (m. p. 12 5 ") .BoaThe isomeric acid, , is decomposed a t 220", with evolu-tion of red vapours and formation of t body crystallising from alccjliolin small needles which melt a t 53", which, however, is not nitro&-S03II('1 bromobenxene.The behaviour of the third isomeride,Br ,/ BrBris similar ; the product of the decomposition, although crystallising inbeautiful needles, is a mixture of compounds melting between 141)"and 230".Dibr o man2 id ob enzew-s ulp ho&c acid, Br nBr , is decomposed byheating with water t o 150", with formation of sulphuric acid and twoisomeric dibromanilines (melting points 70" and 84" respectively) ;tribroxnaniline and bromaniline are also formed, pi.obably by the actionof sulphuric acid upon the dibromanilines.N H2SO?.HTr ib 1'0 ma?? Lido b e m e n e - s t d p h o k e acid, , is rapidly con-verted by heating with water, a t 150", into the dibromamidobenzerieSOaHBr /\sulphonic acid, , wliich, at, 250°, is resolved first into () KH,Br80,H/\bromamidobenzene-sulphonic acid, , and finally into met-amido benzene-sulphonic acid.In this case, therefore, bromine, and not the S03R group, is replacedby hydrogen.c. P. c.VOL. XXXIV. 222 ABSTRACTS OF OHEMICAL PAPERS.Structure of the Diazo-compounds of BenzenesulphonicAcids. By H. LIM pr: CCHT (De7tt. C h m . Ges. Ber., x, 1534-1538).--From the fact' that the ethyl ether of amidobenzoic acid, C,H,.NH,.C0.0CzH5, yields a corresponding diazo- compound, which must beconstituted according to the formula, C6H3.N3.COOCZH5, Griess hasshown (Ber., ix, 1653) that diaxobenzoic acid is formed from amido-benzoic acid by the substitution of one N-atom for the two H-atoms oftlie NH, molecule and of 1 H-atom of the benzene nucleus, thus :-The author has investigated the applicability of similar reasoningto the analogous diazo-derivatives of benzeriesulphonic acid.He findsthat they are incapable of forming compounds with acids. He alsofailed in attempts to prepare the ethyl ether. of amidobenzenesulpbonicacid, and therefore to solve the problem by Griess's method of deter-mining t h constitution of diazobenzoic acid. Reckurts, however, bypreparing the diazo-derivative of tetrabromobenzencsulpEloiiic acidfiom the corresponding amido-acid ( B e y . , ix, 479), has supplied thenecessary proof that the hydrogen atoms replaced in this conversioiiare those of tlie NH, and SO,H groups, thus :-NH Co.Br4so,~ yields C6.Br4.N=N--SOJ.This view is much strengtliened by a further observation of theauthor's, vie., that by the action of nitrous acid upon the ayueonssolutions of the neutral potassium and harinm salts of P-amidobenzene-sulphoiiic acid, the same diazo-compounds arc formed as from thecorresponding acid salts : these are respectively :-i .~ . , that diazo-compounds dcrived from the neutral salts of benzenedi-sulphonic acid, do not exist, and hence a serious objection to thehT L lformula C6H/ 'N, as represcntiiig tlie constitution of diazobcnzene- so,'sulphonic acid is removed. C. F.C.Action of Sulphuryl Chloride on Resorcin. By G. RE I N H A R D(Dsut. Ch~rn. Ges. Ber., x, l5'24.--1525).-Dubois found some yearssince (Jahb., 1866, 283), that, by the action of sulphuryl chlorideupon phenol, two monochloroyhcnols, hydrochloric acid arid sulphuricauhydride were formed. The autlior has extended this observation toresorcin, and obtains, by the action of sulpliuryl chloride upon thisbody, a compound of the formula C6H,C1202. It is easily soluble inwater, alcohol, and ether, melts at 100" to a clear liquid, and a t ahigher temperature may be distilled unchanged. Whether the conORGANIC CHEMISTRY. 223stitution of this body .is that of resorcin in which the hydrogen of theOH-molecules is replaced by chlorine, the author is not yet in a posi-tion to state.C. F. c.On certain Pinacones and Pinacolins. By W. T H ~ R N E R andTH. ZINCKE (Deut. Chem. Qes. Ber., x, 1473-1477).--1. Bewpina-cone, C26Hzzoz (m.p. 185-186") .-This compound, on fusion or dis-tillation, is not converted into a physical isomeride, as stated by Linne-mann, but is decomposed into benzophenone and benzhydrol, thus :-C,,H2,0z = CI3Hl00 + C1,H,,0. The decomposition is complete evena t the fusion temperature of the pinacone. Alcoholic potash effectsthe same resolution : Linnemann's observation, therefore, of the pro-duction of benzhydrol by the action of sodium-amalgam on thealcoholic solution of the pinacone, is probably referable to this cause.Benzpiiiacone is usually regarded as tetraphenylglycol, ( C,H,),.OH.C-C.OH. (C6H5)2 : all attempts, however, to denionstrate the presenceof two OH-mol., by the formation of mixed ethers, have proved urisuc-cessf ul. Benzpinacone is converted into the corresponding pinacolineby the action of acids and chloranhydrides.By acetic anhydride,however, i t is resolved into benzophenone and benzhydrol. Hcnzpina-coline is somewhat soluble i n hot a81cohol, a,nd crystallises from thissolution, on cooling, in small shining needles ; these melt at 178-1 79"t e a colourless liquid which cools t o an amorphous mass. It is furthersoluble in benzol, chloroform, and carbon disulphide, and also to someextent in ether. The constitution of this body is probably the follow-ing :-( c6H,),c-co-c6Htr,.2. Tdylphenylpinacone, C2HH2602, (m.p.164-165°).-Closely re-sembles tlie preceding in physical properties, and in undergoing, a t itspoint of fusion, resolutic )n into tolylphenyl ketone and the correspond-ing hydrol, thus:-C2,Hz60z = C,,Hl,O + C1,H140. By the action ofchromic acid it is decomposed according to the equation, C2&L6OZ + 0= 2C14HlZ0 + H20. Compound ethers of this body, also, could no$be obtained.,El-Tolyl-phenylpinacoline (m.p. 136-137"), which is the more stable, resultsfrom tlie action of acetyl and beiizoyl chlorides, and of concentratedacetic and hydrochloric acids upon the piiiacone. The rL-modificationis obtained in the pure state by adding hydrochloric acid t o thealcoholic solution of the pinacone, and leaving it for some time atthe ordinary temperature. By the action of acetic and benzoic anhy-drides, on the other hand, the pinacone is decomposed in the mannerdescribed above.From their observations on this pinacone t h eauthors conclude that pinacones are formed as intermediate productsThe corresponding pinacoline occurs in two modifications.in the production of pinacolins from ketones. c. J?. c.Styrolene Alcohol (Phenyl-glycol). By P. HUN A u s and T H.Z I N c K E (DeutLt. Cl~em. Ges. Ber., x, 1486-1491) .-Phenyl-glycol isfound by the authors to yield on oxidation successively benzoyl-car-binol and formobenzoic acid ; thus :224 ABSTRACTS OF CHEMICAL PAPERS.C,H,CH.OH CGHSCO C,H,COICOOH.IH.CH.OH 'IHCH.OH 'Pheny lgl ycol. Benzoylcarbinol. Formobenzoic acid.The oxidation of the secondary alcohol-group, therefore, prccedes thatof the primary.Be~zoyZ carbind, C6H,C0.CH20H, crystallises from its solution inalcohol and in ether, in large six-sided tables ; from its aqueous solu-tion in large shining plates which retain water.These latter melt at73-74', the anhydrous modification at 86". This body is a powerfulreducing agent, probably b j reason of its tendency to decompositionaccording to the equation :-CGBjCOCH,OH = C,H,COH + HCOH.The acetic ether, C6H,C/OCH20C2H,0 (m.p. 49O), and the benzoicether, CGH,C0.CH,.0.C7H,0 (m.p. 117"), of this carbinol are de-scribed.Formnbenxoic acid, C,H,CO.COOH, has also been prepared by oxi-dizing mandelic acid, CGH,CH.OH.COOH, with nitric acid. Thebarium and silver salts of the acid are described.The strongly reducing properties of benzoyl carbinol seem rather toindicate that its constitution is that of mandelic aldehyde, CGH,-CH.OH-COH. That this view, however, is iiicorrect, follows from thefact that by the action of silver benzoate upon the cldoricle of methyl-phenyl ketone, C,H,.CO.CH,Cl, a benzoic ether is obtained which isidentical with that described above.The constitution of beiizoyl-carbiiiol is thus established. I n conclusion, the authors express theopinion, that the reducing properties of many complicated bodies,which are assumed to be aldehydes, possessing the characteristic COH-group, may be referred to the presence of this same CO.CH,OH-group. c. F. c.Compounds of Salicylic Acid with Albuminoids.By FR.FARSKY (Chern. Cewtr., 1877, 148).-The author has prepared com-pounds of eggalbumin, casein, fibrin, and syntonin with salicylic acidby several methods. Either the albuminold and the acid were mixedtogether and allowed to stand with constant stirring, or the two werecombined in a dialyser, or the vapour of the acid was made to act onthe finely powdered substance. Whichever method of preparationwas adopted, the solid substance was finally extracted by pure ether,which was shaken up with it as long as the filtrate gave a reactionwith ferric salts. The albumin-conipound was then washed with hotwater, and dried in an air- bath a t 12~--130~.Analyses showed that on tlie average 14.16 per cent. of salicylicacid was combined with 85.84 per cent.of the alb-umino'id, whichpoints to the formula C72HlL2N1&3022 + 2C7€1603. Thesc compoundsare found to be quhe as easily digestible as the uncombined albumi-nolds, so that salicylic acid might possibly be used for the preservationof f eeding-st uffs.In connection with the above researches the author has been enableORGIANIC CHEMISTRY. 225to make a more accurate investigakion of salicylic acid, and he givesthe following account of it. i t crys$allises from concentrated solu-tions in slender. almost colourless needles, from dilute solutions inlarger prismatic, very hard crystals, often very prettily grouped. If,liowerer, other bodies are present in the solution, and more espcciallyif they are orgaiiic bodies, regular crystals are not formed, but, ac-cording to the nature and quantity of the admixed body, either crescent-shaped, anuular, or tufted forms which scarcely resemble crystals, areobt ni ned.When the foreign body is removed the acid gradually regains thecapability of forming acicular crystals.Preczing the solution alsobriiigs about the change. The acid melts a t 157*5", and sublimes a t203", but even at 80" a considerable quantity volsttilises. Perfectlypure crystals may be obtained by heating a solid body containing theacid, or a solution of the acid, at this temperature in the air- or water-bath. The acid, as is well known, splits up on boiling into carbondioxide and phenyl-alcohol ; but it is quite sufficient to heat the solu-tion of the acid or certain salts, especially in presence of other acids,for a long time on the water-bath, to bring about this change.Hy-drated sulphuric acid decomposes salicylic acid only when it is addedall a t once to the solid acid or its solution.Permangannte of potassium, espccially in presence of sulphuricacid, osidises salicylic acid, and among other products of the decom-position are found formic and carbonic acids and water. A similardecomposition is effected by boiling the acid with potassium loichro-mate and sulphuric acid. If the solution of the acid is heated withthe bichromate without addition of siilphuric acid, a body passes overwith the steam which has an unpleasant odour ; it has not been ex-amined. When salicylic acid is brought into contact with ferricacetate, it combines with the iron, the liquid becomes of a violet colour,and deposits a dirtg violet precipitate of Fe,H204.This hydrate dissolves in water and forms a golden-yellow liquid,which can be concentrated, but is decomposed by contact with acids,bases, salts, alcohol, ether, and even filter-paper, and rendcred in-soluble. If, however, the solution of the ferric salt is tolerably con-centrated, and especially if the mixed solution is not too acid, a brownsalicylate separates out.The acid behaves in a similar way t o leadacetate ; l c a l saliaylate is formed, and very strong vapours of aceticacid are evolved in the cold.Salicylic acid forms three salts with ferric oxide, a normal salt, abasic salt, and a so-called ferric ferro-salicylate.Conipare the author's paper on the " Application of these salts toacidirnetry and alkalimetry " ( Wkn.Sitzwzysber, lxxiv, 49).Ortho- and Para-aldehydosalicylic Acids, Ortho-aldehydo-paroxybenzoic Acid, and the Phenoldicarboxylic Acids thenceobtained. By FERD. TIEMANN and K. I;. REINER (Deut. Cl~cm.GYes. Be]-., x, 1.562-l57G).-l1he authors give further details as t o thepreparation of the acids produced by the action of chloroform onstrongly alkaline solutions of salicylic anti paroxybenzoic acids : thebest yield is obtained by dissolving 30 grams of salicylic (or paroxy-G. T. A226 ABSTRACTS OF CHEMICAL PAPERS.benzoic) acid in 100 C.C. of caiistic soda solution of sp. gr. 1.35 (con-taining about 43 grams of sodium hydroxide), and cohobating with5-10 grams of chloroform, further quantities of tlle last substancebeing from time to time added (20-%5 grams in half an hour).Whena little chloroform condenses and drops back, more caustic soda-solutionis added, so fhat in the course of 4 to 5 hours about 1.50 C.C. of tilesoda-solution and 45-46 grams of chloroform have been used alto-gether: no appreciable increase in the yield is noticed after thisperiod.The resulting deep-red liquid is cautiously nentralised with hydro-chloric acid, whereby a dark resinous decomposition-product is throwndown : the filtrate is strongly aciddated with hydrochloric acid, andthe resulting liqnid (containing in suspension a white precipitate)agitated with ether ; the concentrated ethereal extract is then shakenwith 100 C.C.of solution of sodium-hydrogen sulphite of sp. gr. 1.35,diluted with 40-50 C.C. of water; this quantity suffices to take up allthe aldehydo-bodies found. By means of sulphuric acid and steam(40 grams concentrated acid diluted with 40 C.C. of water) the sulphitecompounds are decomposed, the whole being thrown on a filter aftercooling to 60". If paroxybenzoic acid is used in the first instance,o ~ ~ t h o - c ~ Z d e h y d o - ~ ~ a r o ~ ~ ~ e ~ z z i ~ i c ucid remains on the filter, a little more ofthis acid being contained in the filtrate togetlier with a little r/a/-uxy-benzoic a7clehyde ; the yield of the aldehydo-acid is about 20 per cent.of the paroxybenzoic acid employed.If salicylic acid was originallyemployed, pu~a-nldel~yclo-.srtlicylic clcid remains on the filter, the filtratecontaining small qnantities of the same, together with o,,tl~o-ulrlel/llt7u-salicylic acid. Scilic;7/lic aldehyde is also produced in small quaiititywhen the sodium hydrate solrition origiiially used was more dilutethan that recommended, and especially if the mixture was not heatedt o a higher temperature than the boiling point of chloroform, a largequantity of that substance being ardded at first: this product is easilyisolated by distillation with steam, the qnantity not exceeding 1 or 2per cent. of the salicylic acid used : possibly it is formed by the split-ting up of the salicylic acid into phenol and carbon dioxide, the formerbeing then aldehydated ; or possibly it is produced by the decomposi-tion of the ortho-aldehydo-salicylic acid ; or, again, and more probably,it may result from a direct exchange of carboxyl for aldyl (the groupCOH characteristic of aldehydes).To separate ortho- and IDara-aldehydo-salicylic acids, the methodformerly described (methodical crystallisatiou) does not suffice, tracesof the para-acid being always retained by the ortho-acid thus prepared.The following process ariswers well :--The solution of the mixed acidsis shaken with ether, the ethereal extract evaporat,ed, and the residuedissolved in considerably diluted ammonia-liquor : copper sulphatesolution is then added, and sufficient ammonia to dissolve a portion ofthe precipitate with a blue colour ; the whole is then heated to boiling,when almost the whole of the ortho-acid separates as a hasic coppersalt of a bright green colour, containing when -dried at loo",C6H,d 0 > cu ; on treatment with dilute hydrochloric acid, this saltCO2\COORGANIC CHEMISTRY.227furnishes pure ortbo-aldehydo-salicylic acid, crystallising from waterin fine interlaced needles resern bling salicylic acid, and melting at 173"when perfectly pure (166" was given as the melting point in a formerpaper): by careful heating it can be sublimed unchanged, but ifquickly heated to 220" in the fused state, it splits up into carbondioxide and salicylic aldehyde : when crystallised it is reprcsented bythe formula CaHH01,H20 ; the crystals becoming anhydrous at 100".Alcoholic so111 tions of the acid exhibit a feeble bluish-violet fluores-cence: in caustic soda it dissolves with a yellow colour.Ferric chlo-ride strikes a red tint, and sodium carbonate dissolves the acid witheFervescence.Two classes of salts are formed by each one of the three aldehydoacids, viz., neutral salts, and basic salts in which the phenolic hydroeenis also replaced ; the points a t which the neutral salts are formed wlthalkalis and the two salicylic derivatives are easily determined by meansof litmus, a red coloration being given to the litmus as long as theamount of alkali added is less than that requisite to form the neutralsalt, and a blue with the slightest excess: with the puroxybenzoicderivative, however, the point of neutrality cannot be thus determined,as the litmus becomes green before the amount of alkali requisite toform the neutral salt is added; further addition of alkali deepens thegreen, but there is no characteristic colour change marking the pointof neutrality. The alkaline salts of all these acids .are very soluble,and crystallise only from extremely concentrated solutions ; tlie neutralsalts of the two salicylic derivatives are colourless by transmittedlight, appearing to possess R grecn fluorescence with reflected light ;traces of excess of alkali gives a yellow coloration.Tables of thereactions of the neutral and basic ammoniuni salts of the three acidswith calcium and barium chlorides, silver nitrate, copper sulphatle, andlead acetate are given, precipitates being formed in most cases eitherat once or on standing.Ortho-aldehydo-salicylic acid dissolves in 1500-1 600 parts of watera t 23-2.5", and in 15-16 parts a t 100" ; para-aldeliydo-salicylic acidin 2600-2700 parts at 25", and in 14-5-150 parts a t 100" ; ortho-aldehydo-paroxybenzoic acid is slightly more soluble in cold water thanthe latter.When fused with 10-15 parts of potassium hydroxide these threealdehydo-acids are readily converted into the corresponding phenol-dicarboxgi acids, 6 to 8 minutes' fusion sufficing with potash to whiclia little water has been added (ternpcrature of fusing mixture notstated). On cooling, solution in water, and addition of hydrochloricacid, the dicarboxyol acids are mostly precipitated, the remainder beingreadily obtainable by shaking with ether.No " molecular inter-change" takes place during the fusion, as the same acids respectivelyare produced by oxidising the aldehydo-acids with permanganate inalkaline solution. To effect t)liis oxidation, 1 part of aldehydo-acid isdissolved in a little caustic soda, and 200-250 parts of water areadded ; 3-4 parts of solid potassium permanganate are then throwni n , and the whole left for 16-24 hours with occasional stirring: theliquid is then heated to boiling, filtered off from precipitated man-ganic hydrate, and evaporated to a small bulk: on adding hydro228 ABSTRACTS OF CHXXICAL PAPERS.chloric acid and sliaking with ether, the dicarboxyl acids are ex-tracted, together with unaltered aldehydo-acids, wliich are removedby agitatifig the ethereal liquids with sodium-lqdrogen su!phite :finally the ether is evaporated off and the residue crystallised fromwater.In this way para-,zldehydo-s,licylic acid is the most oxidised,ortho-aldehydo-parnxyhenzoic acid being much less completely con-verted, whilst oiily 1-2 per cent. of dicarfoox,)-l acid is obtained fromortho-aldehydo-sslicylic arid ; a somewhat M t e r result is obtained inthe last case by substitating silver oxide for pernianganate, a mirrorbeing copiously deposited./3- Ph eno 1 ( T i 1 8 wr h onic CI cid (P- oay ;sop 11 t h a7ic c( c id j thus 011 tnine d fromortho-aldehydo-salicylic acid, crystallises wilh one rnolecizle of water inhair-like white needles and well defined prisms : when air-dry it meltsat 139"; when thoroughly dried a t 100' a t 245-244." Watery andalcoholic solutions fluoresce blue-violet, the f'lnorescence disa ppearingon addition of cauptic alkali ; ferric chloride strikes a cherry-red tint.By cautiously heating, a little of the acid cam be sublimed unclianged ;the greater part, however, splits up into carbon dioxide and salicylicacid.It fiirrns three classes of salts, acid, neutral, and basic ; litmusis blued only when alka,li is added in qusntity just sufficient to formthe neutral salt and a t i x e over. The sohbilitj in watcr is 1 ~ m * t in:3.5-40 of water a t lOO", in 700 of water atl 24" ; in alcohol and etherit readily dissolves, less easily in chloroform.a- Phemoldicarbon,ic acid (cc-omjisophfhnhk acid) is obtained by theoxidation of either i~lar~-Rldeliydo-salicylic acid or ortho-aldehydo-paroxybenzoic acid, a fact indicated by the formuh :-Ortho-aldehgdo- Para-aldehydo- Ortho-ddehydo-proxy-salicylic acid.salicylic acid. benzoic acid.8-phenol-dicarbonic acid. a-phenol-dicarbonic acid.A CO.OHC0.OHI t is identical with the oxyisophthalic acid obtained some short timeago by Ost ( J . pr. Clmn,., N. P., xiv, 93; xv, 3O1), melting a t 30@",and crystallising anhydrous. Ost obtained this acid along with oxy-t rimesic acid, [) OH , by treating salicylic acid withalkali and carbon dioxide ; whence it should result that oxytrimesicacid is obtainable from either u- or 6-oxyisophthalic acid. On com-paring the reactions of oxytrimesic acid and these two acids (both 8sneutral and basic ammonia salts) with calcium and barium chlorides,CO.OH \ CO.OHCO.OORGANIC CIIEMISTRY.229magnesium sulphate, silver nitrate, and lead acetate (a table of wLicliis given), it is noticeable that there is a greater resemblance betweenoxytvimesic acid and the 6-oxyisophthalic acid, than between oxytri-mesic acid and the a-oxyisophthalic acid. All three give cherry-redcolorations with ferric chloride ; the solubilitics in water aze : a-oxy-isoplithalic acid ; 1 in 5000 a t lo", in 3000 at 24", in 14F;-158.5 a t100" : /%oxyisophtha:ic acid ; 1 i n 700 at 24', in 35-40 at 100" : oxy-trimesic acid, 1 in 200 at 10". By the action on salicylic acid ofcarbon tetracliloride in alkaline solurion, cxperiments now in progressby G.Hasse show that there is formed not only a- but also /3-oxyisoph-t'cialic acid. Reimer a l ~ o firids that by hydrogenation thcse sltlehydoacids are convertible into alcoholo-acids containing the gronp CW,.OH :similarly Tiemann is investigating the acids formed by the action ofcli 1 o ro f o mi on creosol (12 on? o c a I icyj i i c and ?I om op a ~ o q lien zoic ( I C ids) , andthe phenol dicerboxyl acid formed from meta-oxybenzoic acid.C. IFt. A. W.Action of Dehydrating Agents upon Acid Anhydrides. J3y s. GABRIEL and A, h1JCHAF;L (Ueut. C'henz. Ges. IIe?'., x, 1551-156a).-The authors have improved their method for the preparation ofphthnlylacetic acid by the action of phthalic aiihydride upon a mix-ture of acetic anhydride and anhydrous sodium acetate.The constitti-tion of the acid is expressed by the formula C,H4<Co>CH.C0.0H, coand is deduced from a consideration of a number of its reactions :-1. If the acid is dissolved t o a neutral solution by cold caasticpotash it is precipitated from this solution unchnnpd on the additionof hydrochloric acid, but if the alkali be atldecl in excess the additionof the acid causes no precipitation ; the alkaline solution, however, onstanding, deposits a crystalline body, which OCCUTS in shining needlesmelting a t go", and is shown on investigation t o be phttialylaceticacid + 2 mol. H,O, and to be constituted according to t h e formulaC,H4(~~($~,,COOH} + H20. It may therefore be designatedbenznc~,to(o~t7r,o)cnl.bo,ric acid.By boiling the aqueous solution ofthis acid i t is converted, wit11 loss of CO, + H,O, into a monohasic acid,a crystalline compound melthg at 114-116', which is found to bectcetoy henon e( o h n ) co rhon ic acid, C6H4E8gg3. This same acid isobtained directly from phthalylacetic acid by heating the latter withwater to 200".2. By the action of bromine on phthalylacetic acid in presence ofglacial acetic acid, a bocly i s obtained crystallising in long colourlessneedles which melt a t 1W". Its composition is expressed by tlieformula CgHSBr303. It is completely decomposed by alkalis accordingto the equation C9H,Rr30, + H20 = CHBI-3 + CHH604. From t h i s re-solution it is concluded t o be tribroinncetopJ~s?zonc(ortl7Lo)carbo?iic acid,C0.CBr3C6H4C0.0H *The decomposition in question is similar to that of pentabrornacetoneby ammonia into browqfurm and dihrowacdarnide. The action of chlo-rine upon phthalylacetic acid under the same conditions is entirel230 ABSTRACTS OF CHEMICAL PAPERS.analogous ; the resulting trichloracetophenone (ortho) carbonic acidmelts at 144".3.By dissolving phthalylacetic acid in ammonia and adding hydro-chloric acid to the solution, a white precipitate is obtained, which issomewhat soluble in hot water, separating from this solution 011 cool-ing in colourless silky needles (m. p. 20U"). This body is shown t o bephthnZ~/Zaceta~nide, C,H,(CO),.CH.CO.NH,.4. By the action of' concentrated sulphuric acid upon phthalyl-acetic acid a compound is obtained crystallising in slender yellowneedles, which are soluble in nitrobenzene but not in alcohol, ether, norin glacial acetic acid.The same body is obtained, but in very smallquantity, as a by-product in the preparation of phthalylacetic acid.For the constitution of this body tlie authors propose the formula coCt?Hd< 2 -5. As products of reduction of phthalylacetic acid, by means ofsodium-amalgam two crystalline bodies are obtained, melting re-spectively a t 173-175" and 150-251" ; of these, however, the firstpasses on fusion into the second, with which it is indeed isomeric.Their empirical composition is represented by the formula CI,H,04.The first is a bibasic acid, probably ciir ~za.rno.uthooarbonic m;d, the lattera monobasic acid, and at the same time probably an anhydride ofZ, enzhy d ry 1 a ce to r f h occcr ;Ilon,ic: a cid .The authors have further investigated the action of sodiam acetateupon a mixture of plrthalic anhydride and succinir: acid ; this they findt o yield a compound crystallising in long yellow necdles, which meltat a teniperature above 350".This body is soluble in aromatic liquidsof high boiling point : its constitution is that of e f 1 z i r i o r f h u ~ h e ~ i y l c ~ ~ e ~ ~ ~ ketone or ethi?idz)~lithulyZ, C,H4<CO>CH-C~< >C,H,, iiidicat-ing therefore that it is a prodiict of the condensation of phthalic andsuccinic anhydrides.I n contact with aaueous alkalis at 100" it is converted.bv the ad-co coLO1 , . I dition of 2 mol., H,O, into (ortho) p h e r i y l ~ t h y l ~ ? z e k e t o ~ ~ e ~ ~ r L o ~ ~ ~ c mid,Ho.oc>C6H4, crystallising in prisms which C O-CH,-CH,-CQC8H4< c OOHmelt a t 166" and arc: freely soluble in alcohol. By the action of bro-mine a t 100" on ethindiphthalyl in presence of acetic acid, two of itsH-atoms are replaced by bromine, and by the simultaueous additionof 1 mol., H,O, is converted into the compound-This body crystalliaes in colourless, shining octohedrons, which melt a t285--28i", arid are soluble in alcohol. c. 3'. c.Trimellitic Acid. By G. KRINOS (Deut. Chenz. Ges. Ber., x,1491-1495) .-By the regulated oxidation of xylidic acid by meansof potassium permsnganate in a,lkaline solution, the author has sucORGANIC CHEMISTRY.231ceeded in realising its conversion into trimellitic acid, according to theequation-C6H3(C02K),CH3 + 2KMnOl = C6H,( CO,K), + KOH + H,O + 2Mn02.Since the (1, 2, 4) position of the substituting groups in tlie formeracid has been established beyond doubtj, a similar constitution must beassigned to the derived acid. The view expressed by Baeyer someeight years since of the constitution of trirnellitic acid is thus experi-mentally corroborated.Isophthnlic acid also occurred as a product of the oxidation ofxylidic acid, resulting. most probably from the removal of C 0 2 fromthe molecule of trimellitic acid. C. F. C.Conversion of o-Benzyltoluene-derivatives into Anthracene-derivatives. By W. THORNER and TH.ZINCKE ( U e d CI~ei-rz. G'rs.Ber., x, 1477--1481).-By the acttion of chlorine upon liquid tolyl-phenyketone, CfiH5-CO-CfiH,. CH,, the authors obtain an anthra-quinonedichloride, CfiH,<CCl,>C6H4, co crystallising from its solutionin benzene in tlie form of brilliant transparent prisms, which melt a t132-133". In presence of water it is at once tlocoiriposed into antlira-qiiinone arid hydrocliloric acid. It is dissolvcd unclianged in the coldby absolute alcohol and by glacial acetic acid, but, on warming tlicsesolutions complete decomposition of the ellloride into anthraquinoneensues : hence the formula for this body given above.The dichloride is attacked by PCl, a t a temperature of 150-160",with formation of a tetrachloride, CILH8C14, crystallising from ether insmall colourless needles, which melt a t 203-2041" : their solutions ex-hibit a beautiful blue fluorescence.By the action of PCl, npono-benzyl- arid o-benzoyl-benzoic acids chlorinated derivatives of anthra-quinoiie are obtained.Nitro-alizarin.These the authors have not yet investigated.C. F. C.By A. ROSENSTIEHL (Any?,. C'hi~7. Plys. [S], xii,519--529).-The author has studied the action of nitrous fumes onalizarin, which was first observed by Stivhel, namely, that whcn apiece of cloth, printed or dyed with gwancin or artificial alizarin-red,is dipped into a flask filled with nitrous fumes, the colour is changedto orange, which is not atlacked by soap. Wlien alizarin paste istreatled with nitrous fumes, a portion is converted in a mononitro-alizarin, which forms a sodium compcurid insoluble in alkalis ; thissubstance, on decomposition with acids, yields a crj-stalline bodywhich, according to its analysis, has tlie formula ClIH,(NO2)O4. Itis scluble in chloroform, from which it crystallises in orauge-colouredplates, appearing green by reflected light.It is sparingly soluble inwater, melts a t 2YOo, and a little above this temperature sublimes,forming orange needles and yellow plates possessing a green reflection.The former body resenibles alizaiin in its properties, but its alkalinesolution has a reddish-violet colour, whilst that of alizarin is colouredbluish-violet ; their spectra closely resemble each other.WitJb calcium bicarbonate, nitroalizarin forms a precipitate which isnot decomposed by carbon dioxide: by this means alizarin can b2 32 ABSTRACTS OF CHEMICAL PAPERS.separated from nitro-alizarin, inasmuch as the precipitate formed byR lizarin and calcium bicarbona tc: is decornpoqed by cnrbon dioxide withliberation of alizarin.The compounds of nitro-alizarin with bases areexceedingly stable; ferric oxide prodimes a fine hlack colour. Onreduction nitro-alizarin yields an amido-compound.When an alkaline solution of nitro-alizarin is treated with plios-phorins, the colour changes first to blue, then t o green, and finally toyellow ; if the reaction be stopped when the liquid becomes blue, abody may be isolated which gives a garnet-red prccipitate withalumina, but if it' be allowed to proceed until ihe rrtlnction is com-plete, a suloshnce is obtained which gives a brown colour wit11 alumi-nium niord ants.Pseuilo-pinrpurin, p urpurin, and 811 t hrn-pu rpurinare bleached by nitrous fumes. L. T. 0's.Methyl Derivatives of Anthracene. By C . IV A c T-E F: N D o R F Fand TH. ZKNCKE (netit. Chem. Ges. Rer., x, 1481--1486).--Froni asubstance closely resembling anthraccnc, obtained as a product of theaction of a high-boiling aniline oil upon carbazol, the authors haveisolated a hydrocarbon, C,,H,,, yieldiny on oxidation a quinone,CI6Hl2O2: and also two acids, a vz2cino- and di-carbon acid, CliH,02.CQOHand C11H,02(COOH),. The hydrocarbon is therefore c Z ) : ~ ~ ~ c t ? i ~ ~ I ~ t u i t l ~ ~ C P Y L P , C14H,(CH,),.It is soluble in hot alcohol, benzol, and g1aci:tlacetic acid, and crystaliisgs from these solutions on cooling in small,yellowish, shining plates, which melt a t 224-225", and may be readilysublimed.D;?neth?/7n??thrn~?Ainor~e, Cl,H,02( CB,)?, is obtained, together withthe COOH derivatives mentioned above, by long boiling of the hytllrv-cnrbon with glacial acetic and chroniic acids. It crystallises from hotalcgbol in small, bright, yellow needles, which melt at 155", and snb-lime a t higher temperatures in colourless feathery needles.nlethyl-cc.latl2raqzci.rionecai-7,onic acid, Cl,H,02co~H, crystsllises fromits solution in hot alcohol in snow-white flocks. It melts at 244-246",and sublimes at higher temperatures.COOH, occurs in indefi-nite crystalline masses, which melt at a temperature exceeding 300".It is much less easily soluble in alcohol, ether, and benzene than thepreceding acid.The oxiclising act'ion of chromic acid upon the hydrocarbon is of avariable nature, and yields, in addition to the compouiids namcdabove, products which result from the replacement of one OT bothmethyl-groups by hydrogen.In one experirnciit dimetliylantlzracenewas found to be oxidised directly t o anthraquinonc.The authors have further isolated froin certain aniline residues ahydrocarbon which appears to be i?iethyl-anthracene, C,,H,.CH,. Itcrystallises from its solution in hot alcohol in yellowish shining .plates,which melt at 208-210". On oxidation with chromic acid it yields aquinone, which crystsllises in small needles melting a t 160-162", andexhibits close resemblance to Yischer's methyl-anthraquinone (m.p.CHA~zthraqui~~c~nedicarbo72ic acid, Cl,H,02 {By fusion with potash alizarin appears t o be formed.162-163")ORGANIC CHEMISTRY. 233As to the identit,y of the methyl-anthracenes described in this paperwith compounds previously described as such, the authors are not, pre-pared to pronounce definitely. C. p. c.Juglone (Nucin). By C. REISCHAUER (Dad. C7mz. Qes. Bw., X,1542--154$).-This body, prepared from the green shells of walnuts(JuyZm~x regin), has been analysecl by the author, who assigns to it theempirical formula, C~6€I12010.A compound of this body with copper is obtained by adding its alco-holic solution to a solut!ioii of neutral cupric acetate either in water oralcohol.It occurs in small bronze-coloured shining crystal Y, and afterdrying a t 100" contains 15.83 per cent. Cu. Sufiicient data are notyet a t hand for tlie determination of the constitution of these coin-pounds.This paper also contains details of certain modifications of the ordi-nary method of combustion which had to be adopted in the analysisCantharadin and an Acid Derivative thereof. By J. PICCAR Dof juglone, in consequence of its volatility. c. 3'. C.(Deut. Chem. Ges. Bey., x, 1504--1506).-Three determinations ofthe vapour-density of cantharidin gave the numbers 6-36, 6.60, and6.41; the empirical formula of this body is therefore CloH,,O,. Itenters into complete fusion at 2i8", and not at 250," as usually stated.By the action of hydriodic acid a t a temperature of 100" in seaiedtubes it is converted into a body, which, altliough possessing the sameultimate composition, differs essentially from canthuriclin.It crystal-lises in needles, which melt at 278", , ~ ~ i c l are soluble in 12 parts boilingwater ; they are freely soluble in alcohol, slightly in ether, and insolublein benzene. The solution of this body in glycerin does not blister theskin.In its chemical properties it differs from cantharidin in being astrong acid, dissolving in and completely rieutralising alkaline solutions,decomposing carbonates with effervescence, and being but partiallyexpelled from its salts by acetic acid. The salts of cunihnric acid, asthis body is termed by the author, contain 1 atom of metal to 10 atomsof carbon ; the union of the acid with bases is attended with the elimi-nation of H,O ; it is therefore a monobesic hydrate ; its equivalent, asdetermined by titration (cryst.oxalic acid = 63) is 196.The lead The general formula of its alkaline salts is Cl,,HllO,.OR'.salt crystallises in long needles. I t s formula is (CloHl104)2Pb.C. F. C.Capsicin. By J. C. THRESH ( C l m ~ Cwtr., 1877, 68--6!3).--Ryextracting powdered cayenne pepper with ether, evaporating theextract, dissolving it in hot alcoholic potash-lye, diluting the solutionwith water, and treating with barium chloride, a precipitate is obtainedwhich, when washed, dried, treated with ether, and evaporated, leavesan oily red liquid, which Buchheim calls cirpricol, exhibiting all theacrid properties of the fruit.Assuming this body t o be a mixture,and knowing that castor oil, for example, renders other fatty oils moresoluble in alcohol, the author dissolved the red oil in twice its volumeof almond oil, and agitated this solution three times with stron234 ABSTRACTS OF CHEMICAL PAPERS.alcohol. The acrid body was thus taken up by the alcohol, and theremaining oil was tasteless. The alcoholic extracts left 2 reddish-brown fatty mass having a strong pungent taste. This mass dissolvesin dilute potash-lye, but forms a turbid soapy mixture with ammonia.By allowing the latter to stand for some time, numerous colourlessprismatic crystals are obtained, which may be separated hy filtration,washed, and dried.These crystals have a pungent taste, are but littlesoluble in cold water, more soluble in hot water, the solution giving aprecipitate with strmg acids. The peculiar beliaviour of this sub-stance, which the author calls capsaicin, led him to suppose that it wasa fatty acid, which formed a soluble soap with potash, an insolublesoap with ammonia. This, hoFvever, was not correct, since pure crys-tals dissolved in potash p v e , when treated with excess of ammoniumchloride, a milky solution, which after some time yielded crystals ofthe pure substaiice. By boiling a solution of the crystals in absolntealcohol with sodium carbonate, filtering, and evaporating, an oilyresidue was formed, free froin soda, which hegrtn to crystallise in a f e ndays.This oily residue was quite insoluble in watcr (the formerlyobserved solubility was probably due to adhering traces of alkali). itwa,s readily soluble in strong alcohol, the solution giving w i t h bayiumand cdcium chlorides precipitates which dissolved in cther. Silvernitrate forms a precipitate soluble in dilute ammonia. Ferric chlorideforms a reddish precipitate when warmed. Dilnte sulphuric acid aridpotassiilm bichromatc destroy the pungent taste when heated with thesubstance. The same result is obtained with dilute nitric acid andpotassium permanganate. The above reagents behave in a similarmanner with capsicum preparations.Itbegins to voliitilise at 100". Water distilled froin it lias a pungenttaste.Capsaiciii may be isolated by dissolving tlie oil (capsicol) indilute potash, treating the solution with ammonium chloritle, collect-ing the precipitate, redissolving in potash, aud treating it with ammo-nium chloride a t 50". The crystals obtained after a few days are, ifnecessary, treated once more in the same manner. The author hasfurther obtained this substance in a pure state by dialysis. A fewounces of the conceiitrxtcd tirrcture of cayenne pepper were pouredinto a dialyser of parchment paper and surrounded by strong alcohol.The latter absorbed tlie pungent constituent, and .yielded, when em-porated, crystals agreeing with those formerly obtained.By P. SCH~?TZENBEKGEB (Chem. Cmtr., 1877, 73).-By boiling fresh yeast with water, and washing the boiled mass, aresidue is obtained, the weight of which seems constant, varying onlyfrom 20 to 21.4 1).c. on the yeast used. But on agitating frcsh yeastwith water and exposing it to a temperatui'e of 35-40", tlie yeastloses 17-18 p. c. of soluble substances, while the undissolvcd portionafter drying a t 100" weighs 12.5 to 13 p. c. Fresh yeast thereforeloses 8-9 p. c. of solid substarices when treated with boiling water,and after digestion, 17-18 p. c. This fact depends on some physio-logical action that takes place in the substance of the yeast, and isnot due to putrid fermentation. It may be further stated that thisCapsaicin may be volatilised with ease without decomposition.ID. 13.Beer-yeastORGANIC CHEMISTRY. 235action does not go beyond a certain st'age. The following method wasused :-The digested yeast was boiled with much water, and filtered,arid the slightly acid filtrate evaporated to a syrup on the water-bath,and then left to cool. The crystalline mass was then well boiled witli92 p. c. alcohol, whereby a pitch-like rnass was separated, adhering tothe sides of the flask. The alcoliolic extract gave, when concentratedand cooled, a copious crystallin2 deposit, which, when washed andpressed, formed a white mass of crystals partly in the form of thinlaminac and partly as transparent globnles. This crystallisation con-sisted almost entirely of pseudo-leucine with traces of tyrosine. Themother-liquor separated from the secoiid crystnllisation was heatedover tlie water-bath to remove tlie alcohol ; it was then diluted withwater, treated with baryta-water in order to separate the phosphates ;the filtrate was treated with carbonic acid to remove excess of baryta;and this second filtrate boiled with cupric acetate. The brownishflocculent precipitate formed was filtered off (it contained carnine,guanine, and xanthine in combination with cupric oxide), and thefiltrate treated with alcohol in excess, when a bluish-white precipi-tate was obtained, soluble in water. After washing it with dilutealcohol, it yielded, on treatment witJh hydrogen sulphide, arabin com-bined with baryta, which was removed wit,h sulphuric acid. Thefiltrate from the bluish-white precipitate, after being freed fromalcohol, was treated with hydrogen sulphide, and the filtrate evapo-rated to a syrup, which on coolinq solidified to a crystalline mass.J3y treating the latter with cold alcohol, leucine free from sulphurwas obtairied, probably containing butalanine. By evaporating thealcoholic liquid, a nitrogenous syrupy mass of a sweet taste was ob-tained. The above-mentioned precipitate of copper was washedwith hot water and treated with hot dilute hydrochloric acid, thesolution depositing on cooling a large proportion of the copper-com-pound. This deposit was decomposed by hydrogen sulphide, wlierebycarnine was obtained. The mother-liquor gave, after removing thecopper and concentrating, crystals of xanthine h~drochloride, thencrystals of guanine. Sarciae was obtaiiied by precipitating thenitric acid solution of the first copper precipitate with ammonia andsilver nitrate, wasliinq with ammoniacal water, crystallising from hotnitric acid (12" Bk), and decomposing the silver-compound withsulphuretted hydrogen. The pitch-like residue mentioned abovegave, when dissolved in hot water, crystals of tyrosine, which werefurther purified with acetate of lead, precipitation, and decompositionwith hydrogen sulphidc. Urea, uric acid, creatine, and creatinine,also inosite and inosinic acid, were absent. D. B.Lacto-protein. By 0. HAMXSRSTEN (Chem. Centr., 1877, XI).-BIillon and Commaille maintained that, after precipitation of thecasein and albumin of cows' milk, a third incoagulable albuminoussubstance could be obtained by addition of mercuric nitrate. Bielhas since confirmed this statement for mares' milk. The authorshows that the so-called lacto-protein is nothing more than a mix-ture of casein, acid-albumin, and probably traces of peptone. (SeeKuhne, Lehrb. der Physiol. Chern., 568.) G. T. A

ISSN:0368-1769    

DOI:10.1039/CA8783400210

出版商:RSC    

年代:1878

数据来源: RSC