72 ABSTRACTS OF CHEMICAL PAPERS.T e c h ni c a1 C h e mi s t r y.Production of Photographs exhibiting Natural Colours. ByW. W. ABNEF (Chem. News, 39, 282)-The author suggests thatthe natural colours in the photographs exhibited by Becquerel lastyear are produced by the oxidation of the silver compounds em-ployed, and are not due to interference.He has photographed the solar spectrum on silver plates, and oncompounds of silver held in situ by collodion, in both of which, thespectrum has imprinled itself approximately in its natural colours.In the former, the image is the brighter, but in the latter the spectrumcan be seen both by transmitted and reflected light. The colouringmatter seems to be due to a mixture of two different sizes of moleculesof the same chemical composition, one of which absorbs a t the blueand the other a t the red end of the spectrum.The author believes itwill be possible to preserve the colours unchanged when exposed toordinary daylight. W. T.Action of Phenol Vapour on Organic Matter at High Tern-peratures. By C. v. THAN (Annden, 198, 273-289).-As theresult of a series of experiments on a process for disinfection used inthe Hungarian Cusiom House, it is shown that although exposure t o atemperature of 137" for three hours retards the development oforganic germs, it is incapable of destroying them. If, however, thegerms are subjected to the action of the vapour of phenol a t 137",they are completely destroyed. The articles to be disinfected areplaced in a leaden chamber (containing phenol), which is providedwith an outer jacket.The apparatus is heated over a fire, and bymeans of an ingenious arrangement, the pTrometer which registers thetemperatures rings an electric bell when the temperature exceeds137". By opening dampers in the outer jacket, the temperature canbe rapidly cooled down to 137", when the bell will cease ringing.Written and printed matt'er, linen, cotton, quilting, lace, white andcoloured silk and woollen materials, raw wool, and plain and lacqueredleather, were exposed to this treatment without any deleterious effects,excepting the white wool, which acquired a yellowish tint..CiLarn& leather is rendered friable by exposure to phenol vapour. w. c. w.Antiseptic Action of Acids.By N. SIEBER (J, pr. Chem. [el,l9,433--444).-The presence of so small a proportion as 0.5 per cent.of hydrochloric, sulphuric, phosphoric, acetic, or even of hu tyric acidis sufficient for antiseptic purposes. Phenol is somewhat less active,whilst lactic and boric acids are much less active, 4 p.c. of boric acidbeing insufficient to prevent putrefaction.The experiments were made simultaneously with mea,t and with thepancreas of the ox, in both cases suspended in water, and without ex-ception decomposition occurred sooner in the case of the pancreasTECHNICAL CHEMISTRY. 73There was fungoid growth but no Bacteria, when using 0.5 p.c. sul-phuric acid, 1.0 p.c. phosphoric, 2 and even with 4 p.c. lactic acid.The author discusses the question whether the acidity of the gastricjuice is of itself sufficient to maintain the healthy action of thestomach, and he inclines to the affirmative opinion, a,s he found that0.25 p.c.of hydrochloric acid, about the normal quantity in thestomach, was sufficient to prevent putrefaction for 24 hours in thetissues of meat and ox-pancreas, arid when putrefaction did occur, thesolution was no longer acid, but neutral.As antiseptics, dilute solutions of acid salts mould be no doubt asactive as the acids, for G. Glaser has lately shown that in this respectaluminic acetate is equal to acetic acid. A. J. C.Antiseptic Action of Pyrogallol. By V. BOVET ( J . p r . C1Le.m. [2],19, 445-461).-From a number of experiments it has heen found thatan aqueous solution containing 1-l+ p.c.of pyrogallol, will preservemeat for a month free from micro-organisms and bad smell, and thata 2-2+ p.c. solution will arrest decclmposition in putrefying sub-stances, and prevent alcoholic fermentation of grape-sugar. In thislatter respect H. Kolbe and E. v. Meyer state in a note that they havealready shown that it is far less active than salicylic acid ( J . pr. Chern.[2], 12, 151).It also arrests the movements of Bacillus subtilis and the formationof mildew. For many antiseptic purposes, such as wound dressings,pyrogallol, it is suggested, may be substituted with advantage forphenol.It is c7 question whether the antiseptic action of pyrogallol is due toits power of absorbing oxygen or to some other property which maybe conimon to all the aromatic phenols.A. J. C.Spontaneous Oxidation of Manganous Oxides with refer-ence to the Manganese-recovery Process. By 3 . POST ( B e y . , 12,1537--1542).--The author’s experiments were made on a small scale inordinary evaporating basins, and relat’e to the influence of “ whipping,”addition of soap, and to the use of soda or lime in the recovery ofmanganese. The only noteworthy result he obtained is, that a slightexcess of caustic alkali gives a larger yield of manganic oxide than aslight excess of lime, and that a large excess of alkali, whether lime orsoda, has no corresponding influence on the proportion of manganeseoxidised. W. R.Some Analyses of Iron. By S. KERN (Chellz. News, 39, 281).-The author states that in many cases tlie analysis of iron or steel isnot a criterion of the quality of the metal; thus a sample of boilerplate whicli he analysed and found to contain silicon 0.010 per cent.,manganese 0.120, sulphur absent, phosphorus a trace, copper 0.028,was found to be of inferior quality by the mechanical tests.Thisthe author attributes to the rolling of the metal having been badlyconducted. W. T74 ABSTRACTS OF CHEMICAL PAPERS.Separation of Phosphorus and Iron especially with referencet o the Manufacture of Steel. By T. BLAIR (Chem. News, 40,150-152, and 160--163).-The first part of the paper contains areview of the various processes which have hitherto been proposedwith this object, and whichare well known. With regard to Krupp'sor Marje's process for dephosphorising pig-iron by means of the oxidesof iron and manganese, some data are given, from which i t is probable,although it has not yet been proved experimentally, that mangani-ferous iron will work more favourably still than pig-iron.Anotherpoint which has not yet been settled is whether it will be possible byaddition of a siliceous pig to fit the refined metal for the Bessemerprocess, for which, as at present constituted, it is not suitable, sincethe dephosphorising process also eliminates the silicon.I n discussing the Thomas and Gilchrist process, the autlior mentionsthat, although it must be admitted that all the initial difficulties havenot been entirely surmounted, it is obvious that the great problem asto the dephosphorisation of iron is solved, and that nothing more iswanting than the rapid and effectual removal of the minor difficulties.Briefly the process consists of the following points:-1.A durablebasic lining. 2. The addition of basic materials. 3. Removal ofphosphorus by blowing after the carbon has been eliminated. As aset-off against the objections as to the cost of the new process may beconsidered the utilisation of the large deposits of phosphoretic ores inthis and other countries, which may be so much more cheaply workedand delivered to the works than hEmatite ores from distant countries,and the prolongation of the lease of life of inland iron-producingdistricts in all countries, which have their own coal and ironstone.D. B.Bleaching-Sugar Syrups by Ozone.By A. R. LEEDS (Clien2.News, 40, 86).--The first specimen operated on was of syrup, whichhad undergone but one filtration, and was of a brownish-yellowcolour. At the close of the bleaching with ozone, the syrup was of afaint straw colour, and of slightly acid reaction. A second trial wasmade with a syrup which had been twice filtered, but still retained ast'rong yellow tint. 20 C.C. of the syrup was introduced into aGeisler absorption apparatus, and a slow current of oxygen, ozonisedto the extent of 24 mgrms. ozone per litre, passed through it forseveral hours. When about 100 mgrms. ozone had been brought intocontact with the syrup, it had become almost colourless and almostneutral in reaction.As determined by Behr, the filtered syrup when it came from therefinery contained, in 100 parts, 50 parts of dry substance and40 parts of dry sugar.The alteration in the course of bleaching isseen in the following table :-E f e c t of Ozone upon Filtered Xymp.Dry substance contains :- Unblcached. Bleached.Cane sugar (by polariscope). . 79.7 per cent. 80.0 per cent.Inverted sugar . . . . , . . . . . . . 12.7 ,, 12.7 ,,D. BTECHNICAL CHEMISTRY. 75Experiments on Creaming. By W. K~RCHNER and others (Bied.Centr., 1879, 377--381).-As the result of numerous experiments,Kirchner comes to the conclusion that pans made of tin are betterthan wooden pnns for the cream to rise in. The other authors haveexperimented on the cooling of the milk by various processes beforechurning, and find that a larger yield of butter is usually obtainedwhen the milk has been cooled by ice.J. I(. C.Experiments on Churning. By WINKEL ( B i e d . Centr., 1879,382).-The a#uthor sums up the results of his investigations asfollows :-The more carefully the cream is skimmed off , that IS, the lessmilk it contains, the lower the temperature of churning required, thenumber and swiftness of the turnings remaining the same; or inother words, so much the more quickly will the butter separate a t thesame temperature and quickness of churning. J. K. C.A New Method of Preparing Methyl-violet. By H. HASSEN-CAMP (Deut. Chenz. Ges. Ber., 12, 1275--1276).-When a mixture ofone part of beazenesulphonic chloride and two of dimethylaniline isheated on a Fater-bath, a blue coloration is produced, which graduallybecomes more intense, and after some hours the whole is convertedinto a viscous dark-coloured mass.The colouring properties of this showit to be methyl-violet. Further, when the product is boiled with water,the presence of an oily liquid was observed, which had the characteristicodour of phenyl sulphide. The reaction, therefore, takes place as,CcH,follows:-C,H,.S02C1 -t 3C6H,NMe2 = (Me2N.C,H4),C/ 1 -+ HCl +\NMe2H20 + C6H5.8H. Benzenesulphonic chloride and methyldiphenyl-amine appear to yield diphenylamine blue.Transferring Lightfoot-black from one Fibre to Another.By J. WOLFF (Chem. News, 40, 59).-Lightfoot-black dissolves in astrong aqueous solution of aniline hydrochloride, but incompletely, andwith a deep greenish-black coloration.The solution obtained in thisway mixes with hot water, producing a black-violet liquid, which dyescotton, wool, and silk of a grey tint. Even the Lightfoot-black on thefibre dissolves in a strong solution of aniline hydrochloride. Sometime ago the author dyed a large quantity of China grass yarn withLightfoot-black, by soaking the yarn thoroughly in a stlrong solutionof aniline hydrochloride and potassium chloride. A small quantity ofthat yarn treated lately with a strong solution of aniline hydrochlorideproduced a dark greenish-black solution, whilst the remaining fibre,after washing and drying, showed a dark greenish-grey colour. Thegreenish-black solution mixed with water dyed cotton a beautifulbluish-grey, and wool and silk a blackish-grey, showing that thiscolouring-matter itself has a very great affinity f o r the fibres, withoutbeing produced on the fibre as in the Lightfoot process.The shadesthus produced on wool and silk are not bright, proving that theLightfoot-black process is unable to produce fine black shades a t allon these animal fibres. The solutions obtained in the above mannerP. P. B76 ABSTRACTS OF CHEMICAL PAPERS.contain too much acid and comparatively small quantities of colouring-matter, so that it is t-ery difficult to dye a deep black with them.As far as the author knows, this is the first case of transferringLightfoot-black from one fibre to another.If the solut,ion of Lightfoot-black in aniline salt solution is neu-tralised with caustic soda and boiled until all aniline is driven off, agreyish-black powder remains in a light brown-coloured slightlyalkaline liquid.The powder filtered from the liquid and washed onthe filter with boiling water, consists of two different colouringmatters ; the one dissolving with a bright red colour in boiling wateracidulated mit,h hydrochloric acid, and dyeing cotton and wool of adull-red shade, which by washing with clear water turns reddish-brown, and by soaping, clear brown ; the other consisting of a darkblue-black powder, insoluble in neutral and acidulated water. Thisis another proof that Lightfoot-black consists of two colouring matters-oue dark blue, the other brown. D.B.Aniline Blacks. By J. WOLFF (Clzenz. News, 39, 270-273 ; and40, 3-6).-The author divides aniline blacks into two series, thosewhich are produced in or on the fibre, and those which are first manu-factured and afterwards applied to the fibre by the usual process ofdyeing.The first was invented by J. Lightfoot, of Accrington, in 1866, andare extremely well adapted for p?.inti?zy black on vegetable tissues, butall attempts to use this process for dyeing have proved more or lessunsatisfactory, owing mainly to the difficulty of evenly distributingthe colour, and for silk and wool dyeing this difficulty becomes stillgreater. The basis of the method usually employed to dye by thisprocess is to soak the yarn or woven fabric in aniline hydrochloride,with or without free aniline, and potlassium chlorate, with or withoutthe a,ddition of other, especially metallic compounds, and afterwardsto expose the goods to the air in a warm room nntil they are changedto a dark green colour.They are then passed through a warm bath ofsoda, which develops the black in a short time, or they are passedthrough a bath of chrome and hydrochloric acid, which produces amuch deeper and finer black, which does not turn green.The Lightfoot blacks can be divided into (1) those which turngreen and (2) those which remain black on exposure to the air. Thefirst are the common and the second the oxidised Lightfoot blacks.The shades of these series of blacks run from blue of different shadesof grey, and of browii-black to black-brown.The first link of theseseries is the blue invented by the late F. Grace-Calivert, and obtainedby the action on aniline hydrochloride of a smaller quantity of potas-sium chlorate than that required for the black with use of ferroussulphate t o moderate the oxidation.The aniline blacks are mixtures of at least two distinct colouringmatters, the one a very deep blue, the other browns of differentshades. The less toluidine the aniline contains, the bluer will be theblack produced by this process ; hence i t would appear that the browncolouring matter is derived from the toluidines. Again, from theirability to increase the strength of the oxidation, copper, cerium, yanaTECHNICAL CHEMISTRY. 77dium, and other metallic compounds, even in very minute quantities,have the property of deepening the dark blue-black to a veryfine blue-black.Little is known respecting the chemical constitution of theLightfoot black; Reinbeck says it is a powerful Fiolet-black baseforming with acids green-coloured compounds. Muller gives to theblack the formula C,,H,,N,OII, but on account of the large proportionsof hydrogen and oxygen the anthor considers i t an improbable one.A more trustworthy elementary analysis by Goppelsrmder leads to theformula C21H20NC for the common Lightfoot black, which he interpretsas = 4(C6H,)N. The chemical constitution of the oxidised black herepresents as (CsH5N),0, and of the reduced common black asHN(C6H,).N(C6H,).N(C6H5). (C,H,)NH. With potassium-hydrogensulphate he produces naphthalene pink from this black, thus, 5C24H20N4) + 16HKS01 = 8N + EH20 + 8S0, + 4 of naphthalene pink,Another chemist, by treatment of Lightfoot's black with aniline, hasobtained a fine aniline pink of the formula C,,H,,N,.All these formule of aniline blacks show that they are the productsof powerful oxidation taking place simultaneously with considerablecondensation.Another interpretation of these results may be given,supported by the production of naphthalene pink above mentioned,and by the property the black has of forming substitution-productswith aniline, such as aniline pink. (CsH~),(NH)4(C6H4),. The oxidisedTightfoot black (c6H,.NH),~(c6H~.~H)2. The reduced Lightfoot black,In the aniline blacks which are mauufactured first, and then appliedto the cloth or yarn, there are two, known by the commercial names'' indulin " and " nigrosin." The latter name was given to a productinvented by the author in 1862.He also discovered the first link ofthe indulin series in 1865, by treating the bases of magenta refuse withaniline and acetic acid. The spirit-soluble indulin thus produced wasconverted by sulphuric acid into water-soluble indulin, fraudulentlycalled by some firms " nigrosin."C30H2&.H2N. (CsK),(NH),( CsH,)2-NHz*Indulin may be manufactured by several methods.(1.) Prom magenta refuse, which is treated with boiling wateracidulated with hydrochloric acid, to extract completely the salts ofmauvaniline, rosaniline, and chrysaniline, and to leave the violanilinesalt undissolved, which is then decomposed with impure caustic soda.10 parts of the impure violaniline thus left are treated with 6 parts ofcommercial acetic acid (of the equivalent lSO), and 20 parts of " anilinefor blue," and heated to between 140" and 160", as long as ammoniais given off and until the mass dissolves and gives the desired shade,in alcohol acidulated with acetic acid.Caustic soda is then added insufficient quantity to neutralise the 6 parts of acetic acid, and theliberated aniline is driven off by steam. The indulin base thus ob-tained may then be separated from the soda acetate solution anddried. To convert it into the water-soluble form, 1 part of the baseis introduced slowly into 3 or 4 parts of sulphuric acid of 66" B., heatedto loo", and kept agitated; the acid solution is then heated at 120-140" for about five hours until a sample when taken out, washed withwater, and treated with ammonia, a t 60" or 70" dissolves quickly an78 ABSTRACTS OF CHEMICAL PAPERS.completely.When the process is finished, the whole is washed withwater, filtered, and boiled with sufficient soda solution to dissolve andform a neutral salt with it. The solution is then evaporated, and theresidue, which is the water-soluble indulin, is dried at a, temperaturenot exceeding 70".Another way of preparing indulin is by heating 10 parts of piireaniline with 20 of syrupy arsenic acid a t 185" or 190°, until it formson cooling a dull, yellowish, bronze-ccloured, brittle substance, whichis composed principally of violanilin.Caustic soda is added to thefused mass, to combine with the arsenious and arsenic acids, the freeaniline driven off by steam, and the base after being powdered anddried is converted by aniline and acetic acid into indulin in the man-ner described.It may also be prepared by a number of different methods based onthe action of suitable oxidising or dehydrogenating agents, such aschlorine, nitric acid and its compounds, on pure aniline or suitableaniline salts at a temperature of 185" to 190". The author gives equa-tions in explanation of these reactions.I n the most soluble indulin blues, the triphenyl-violaniline predo-minates in quantity, Gut in many, the mono- and di-phenyl-violanilineand mauvanilines accompany it.Thus indulin may be principallytriphenyl-violaniline hydrochloride.By treating these bases with sulphuric acid, they are converted intothe corresponding conjugated acids, from which salts map be obtainedby neutralisation. Thus there may be formed sodium triphenyl-violaniline monosulphonate ; and the di-, tri, and tetra-sulphonntesmay also be obtained. The monosulphonates are insoluble in water,the disulphonates are sparingly, and the tri- and tetra-sulphonateseasily soluble. The alkaline salts of all are easily soluble.These, together with the phen-ylated mauvanilines, form the prin-cipal constituents of water-soluble indulins ; they sometimes, how-ever, contain nigrosin-sulphonic acids and their salts.Spirit-soluble indulin dyes wool, silk, and cotton of different shadesof grey.Tn dyeing, the acidulated alcoholic solution is added to anacidulated cold bath, the goods t o be dyed are immersed, and thewhole heated to the boiling point and kept there until the desiredshade is obtained.Spirit-soluble indulin dissolves a t 11.5" in 2 to 3 parts of its weightof glycerine aciclnlated with 5 per cent. of hydrochloric acid, butdyeing. with these products is not satisfactory, owing to the liabilityof their separating from solution and rendering the dyed shades un-even.The water-soluble indulins dye fabrics of good light and dark shadesof grey, even approaching black, but the blacks are not satisfactoryeither in colour or " fastness."The third series of aniline blacks is the one of which nigrosin is alink; they are used for dyeing blacks and greys on wool, silk, andleather.They resist well the action of light and air, and their alco-holic solutions are employed with varnish producing oils and resinsfor making black varnish.Nigrosin was first manufactured by heating a mixture of 44 partsAmmonia is sometimes used instead of sodaTECHNICAL CHEMISTRY. 79of aniline, 20 of stannous chloride, and 11 of nitrobenzene durinqfour hours a t 190", and afterwards at 220" or 230" for five t o eighthours more, until a sample poured into water gives to the latter a paleyellcw coloration. At this point, the unaltered aniline in the " melt "was driven off by a current of steam. The "melt" separates fromthe condensed steam, and when powdered and dried.constitutes thenigrosin of commerce. The author soon found that the presence ofstannous chloride was unnecessary, and assuming that the nitroben-zene acted simply as an oxidising agent, he made experiments, andfound that, by the action of arsenic acid on a mixture of aniline andaniline salt, a fine nigrosin could be produced. In trying to make thewater-soluble nigrosin from a product produced from aniline contain-ing toluidine, a brown-yellow extract was obtained by boiling withwater acidulated with hydrochloric acid, and no nigrosin was dis-solved, but when boiled with fresh quantities of acidulated water thebrown-yellow substance was ultimately removed, and then the nigrosinbecame soluble.I n the first stage of the process in the production of nigrosin, viol-aniline is produced, and a t this stage a mixture of violaniliiie andaniline salts remains.When these are heated a t 220" or 230", thecolour of the melted mass changes gradually from violet-blue to darkblue, and later on to greenish-black, whilst ammonia is formed. Tri-phenylviolaniline (the base of spirit-soluble indulin) when heated withaniline salts as above described, yields also nigrosin in both thesoliible and insoluble form, but witbout the formation of ammonia.Pure nigrosin is prepared by heating 22 parts of pure aniline hydro-chloride with 10 parts of pure syrupy arsenic acid (containing 70 percent. of dry acid) for four or five hours at 190" in glass or enamellediron vessels, the liquid being agitated from time to time, and after-wards heated at 220" to 230" until a sample when drawn off dissolveswith a faint yellow colour in boiliug water.The unaltered aniline isliberated with soda, and it, in company with diphenylamine, is re-moved with a current of steam; the remaining nigrosin base iswashed with boiling water, then dissolred in boiling water acidulatedwith excess of hydrochloric acid, and precipitated with soda. Theprecipitated nigrosin is collected on a filter, washed, and again dis-solved in acidulated boiling water, and when cold is precipitated byadding common salt. It is further purified by dissolving it in boilingwater, filtering, and allowing it to cool, when the nigrosin separates,the process being repeated several times.Nigrosin has a blue colourif pure aniline is used, but if toluidine is present even in small quan-tities, the black shades of nigrosin are obtained. The author foundthe formula for the pure nigrosin base to be C36H27N3, and fornigrosin itself, C36H2iN:,C1H, but this is also the formula for triphenyl-violaniiine, the conversion of the one into the other being broughtabout by intramolecular change.By dry distillation, nigrosin yields substances belonging to the de-rivatives of di- and tri-phenyl-diamine, whilst triphenylviolanilineyields diphenylamiiie and aniline. and from this the author infers thedifference in the molecular constitution of these two bodies.Pure blue nigrosin dissolves in water, producing a dull blue soh80 ABSTRACTS OF CHEMICAL PAPERS.tion, becoming brighter and greener on the additlion of hydrochloricacid.It possesses a remarkable blood-red fluorescence, and all theblue and black nigrosins have this property more or less, and someso strongly that when so little is dissolved i n water that no colour canBe seen by transmitted light, the solution has the appearance by re-flected light as if particles of bright metallic copper were movingabout in it. The nigmsins dye yarns and goods slowly and evenly ofblue, or blue-black colours, mhich when deep enough will stand light,air, and soap well, but not the fulling process.The following mixtures treated in the manner above described, inwhich aniline salts and arsenic acid are made to react on each other,produce the different shades of blue and black nigrosins.60 parts of pure aniline hydrochloride, and 10 parts of pure nitro-benzene, yield a dark blue dyeing nigrosin, whilst the same mixturewith 1 part of cuprous or cupric chloride added to it yields a fineblue-black.60 parts of aniline hydrochloride (prepared from aniline containing2 per cent.of toluidine) and 10 parts of nitrobenzene (made from ben-zene containing 2 per cent. of toluene) yields a blue-black dyeingcolouring matter, which by addition of certain metallic compounds(such as cupric chloride) is much deepened.I n the manufacture of nigrosins, the careful regulation of the tem-perature is of great importance, otherwise a considerable quantity ofbye-products would be formed.The nigrosins are slightly soluble in weak boiling alkaline solutions,easily soluble in benzene, petroleum, and certain oils, especially whenalkaline, with ;t bright purple colour, and when acid, with a fine green-blue shade. Oxidising agents convert nigrosins on the fibre into dulland reddish-grey violets, whilst reducing agents render them colour-less, forming leuco-nigrosins. Nitric acid, even of 1.5 sp. gr., hasvery little action on these colouring matters. The author givesformulae showing the typical relations which he assumes to existbetween nigrosin and Lightfoot black.Nigrosin is specially well adapted for dyeing silk a fine blackcolour without injuring the gloss of the fibre or increasing its weightmore than a few per cent.Production of the Red Colour in Salting Meat. By A. HART-W. T.DEGEN ( B i e d . Cent?.., 1879, 478).-Salt added in large quantities pre-vents the appearance of the red colour, but if it is applied a little at atime, and the meat is afterwards smoked, a better red is obtained.J. K. C