摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 97 Chemistry of Vegetable Physiology and Agriculture. Influence of the Chemical Composition of the Soil on the Growth of the Chestnut. By P. FLICHE and L. GRANDEAU (Ann. Chim. et Phys [5] ii 354-379). THEauthors point out the difference in the growth of chestnut trees in the Wood of ChampAtu on the sanie soils as those concerned in their experiments with Pinus pitiaster (vide ibitl. [4] xxix 383 and last volume p. 382). Chatin (BzdZetiiz Xoc. Botnl~.,1870 194) has shown that the chestnut naturally disappears from soiis containing more than 3 per cent. of lime. The authors found that on a soil of this locality containing about 55 per ceii t. of calcium carbonate chestnixts would not grow; on the calcareous soil No.11 page 382 the growth was very poor and sickly ; whilst on the silicious soil No. I it was vigor- ous. Analyses of the ash of the leaves and of the stem and branches from trees grown on the silicious and on the calcareous soil were made with the following percentage results. The well grown specimens from the silicious soil were taken from a plantation about twelve years old and the badly grown specimens from the calcareous soil from one twenty-three years of age. Loaves. Prom sili-From calca-Prom sili-From calca-cious soil. reous soil. cious soil. reous aoil. P205 .................. 12 -32 12 -50 4'53 4-27 Si04 .................. 5.79 1.46 3 -08 1 '36 CaO .................. 45 *37 74 *55 73 '26 87 '30 Fe,03.. ................ 1*07 '83 2 '04 1'27 MgO ..................6.63 3 *70 3 '99 2.07 K20 .................. 21 *67 5 "76 11-65 2 '69 NaaO .................. 3 -86 -66 -.28 I so3 ................... 2 *97 1 '43 -64 c1 .................... *30 -52 -08 99 -98 1 99.98 99 '98 99.96 Percentage of ash.. ...... 4*80 '7 '80 4.74 5.71 i The percentage of ash in both the leaves and axes (sterns and branches) is greater in those plants grown on the lime soil and in these there is a marked increase in the percentage of lime and decrease in that of the potash and also of the silica. The percentage of iron is also deficient in those grown on the lime soil. Sodiumand chlo- rine which are present in the leaves are nearly or quite a'bseiit from the wood. The leaves from the trees on the lime soil were much smaller and a microscopical examination showed that they contained far less starch VOL.XPVIII. H ABSTRACTS OF CHEMICAL PAPERS. and ch'Iorophyl1 than those from the vigorous-growing trees. In a11 these respects the analogy is complete between the chestnuts and the cluster pines grown on these soils the only difference observed being that in the case of tlie cliestnuts grown on tlie lime soil the lower leaves were fair17 developed whilst the upper ones became less and less vigorous and at the top quite incapable of their functions; in the pines the leaves were uniformly weak. Malatguti and Durocher (Aim. Cl~im.Phys. [3] liv 257) found that several plants assimilated much more lime and much less potash when grown on a calcareous soil arid more recently Rothe (Bot.Zeit. 1873 240) has observed the same facts with Hemiaria glabra,. E. K. Contributions of Volcanic Rocks to the Formation and Fertility of Soils. By BOUSSTWGAULT (Ann. Chim. Phys. [5] iii 390-41 7). TK this paper the author compares the analyses of numerous crystalline rocks more especially with regard to their contents in alkalis and points out the valuable soil-forming properties of trachytes basalt's and lavas due to the alkalis and phosphoric acid they cont'ain arid their comparatively easy disintegration. The amount of the alkalis in a cubic meter of many of the minerals is calculated. E. K. Field Experiments on Permanent Pasture. By A. V o E r c K E rr' (Journ. Roy. Agri.SOC.,1874 429-443). THE author describes the results of' applying the same series of manures to several different pastures. Common salt had an injurious effect. Crude potash salts applied alone were injurious or of little value. The effect of quick-lime and of bones was generally beneficial but not in every case ; the behaviour of grass land to such manures should be ascertained by experinlent before they are emplopd on a large scale. Superphosphate with crude potash salts was generally bene- ficial. Nitrogenous manures (guano) gave the largest increase of mop. In one experiment with a pasture on a cold clay the effect of the manures was recorded for three years afLer their application. Super-phosphate with potash salts produced the greatest effect in the subse- quent years.R. W. Composition of New Peruvian Guanos. By A. VOELCKER (Journ. Roy. Agri. SOC.,1874 541). THEsamples of these as yet unworked deposits were taken during the survey of H.M. ship "Petrel ;" t8he percentage compositions were as follows :- V EG ET-iBLE PIXYSlOLOGY ASD AGRICULTTJRE. Guano from Papillon de Pica. La San Cueva del Rinconacla. Barloverita La Cueva Lorenzo, white 25 ft. from 15ft,.from 50ft. from gnaiiofrom surface. sui*face. Surface. surface. surface. --. -~~ Moisture ........... 4 *13 5 .45 9 .23 6 90 Organic matter ard 59.01 449 40 41.32 55 '10 ammoninm salts.. 1 Earthy phosphates ... 21 -82 27 -01 23 -80 24 *55 Alkali salts.. ........ 9 00 15 *99 23 -30 12*lo Sand ...............6 04 2 -15 2'35 1*55 Phosphoric acid.. .... 11*67 14 -06 11.57 14-72 Total Nitrogen. ...... 15 08 9 -15 6 '68 11-02 Nitric acid .......... 44 .61 -90 1-20 IIusnillos guano. Purita de Lobos guano. B 06 8ai 52 &8 u% 22 g2 e ---. -1- 3loisture ........... 8 -23 14.53 j 4.79 14'06 Organic matter and ammoniurn salts. . } Ihrthy phoapliates ... 1.6'46 35.77 17'14 $9 7s 32 .4,5 10.21 24.71 26.50 23.09 21 -40 Alkali salts .......... 19 22 16.73 23 .09 20.35 12'7-04 13 -45 Sarid ............... 3 -64 5-91 2.GO 2.85 127.9% 1-35 -1- Phosphoric acid.. .... 15.62 15 .30 .12.93 L1.01 Total nitrogen ....... LO '40 7.43 6.65 9 '99 Nitric acid .......... 2 .S7 2 -46 *25 3 *50 -The total amount of these deposits is about 7,301.000 tons to which the deposits at Papillon de Pica contribute 5,000,000.With one ex- ception the guanos are not equal to the old Chincha guano which contaiiicd 14 per cent. of nitrogen but they are mostly in excellent condition dry and free from lumps. Guano .does not seem to alter steadily in composition witjh the depth from surface its composition apparently depending less on its age than on other circumstances. The author thinks that t'he nitric acid of the Peruvian nihe beds may pos-sibly be derived from ancient guano. It. w. RRSTR-4CTS OF CHEMICAL PAPERS. Eighth Note on Guano. By E. CHEVREUI (Compt. rend. lxxix 273-276). THEinvestigation of guano has led to the discovery of the existence of ammonio-sodic phosphate (microcosmic salt) in several forms of which two are prominent namely :-1.Bulky colourless crystalline masses as limpid as rock-crystal perfectly free from chlorides and sulphates but containing rather less than 1per cent. of calcium phosphate. 2. Obtained by successive washings in perfectly colourless octo-hedrons. Both were free from potash. In all the guanos examined potassium sulphate was found which in the majority of cases existed as ammonio-potassic sulphate. It was found diEcult by successive washings when operating on small quan- tities of substance to separate the ammonio-potassic nxalate and the ammonio-sodic phosphate from the arnmonio-potassic sulphate. The following salts have been isolated :-1. Carbonate of ammonium.2. Chloride of ammonium. 3. Phos-phate 4.Oxalate and 5. Urate of calcium. 6. Avate of potassium. 7 8 and 9. Two or three salts of potassium combined with a volatile and odorous organic acid. Double salts :-A mmonio-potassic oxalate. Ammonio-po t assic sulph ate. Ammonio-sodic phosphate. Ammonio-magnesic phosphate. The portion rcputed to be insoluble in water gave at a sIightly higher temperature avate and carbonate of ammonia. C. H. P. Chemical Analysis of Jaborandi. By M. RABUTEAU (Pharni. J. Trans. [3] iv 911). JABORANDI is the native name for the leaves and small branches of Pilocarps pinizatus a shrub grown in the northern provinces of Brazil. To try the eflcct of these leaves on his own person the author reduced 2.90 grams to powder and prepared from them an or.dinary teacupful of infusion.This he drank when nearly cold about t’en o’clock in the evening. one half alone and the rest with the addition of a little sugar. Ten or fifteen minutes afterwards his forehead became moist and he went to bed. Sweating came on shortly after and at the same time an abundant salivation,. which continued for nearly two hours. The sweating hegan to diminish in about an hour and a-half from the com- mencement of the experiment and ceased at nearly the same time as the salivation. The temperature of the mouth was found to oscillate between 28.8 and 37.1 the thermometer being placed under the tongue. There was therefore scarcely any abnormal heat yet the temperature was highest when the effects of the medicine were most active about three- quarters of an hour after the infusion had been taken.After changing his shirt about midnight the author slept well. VEGETABLE PHYSIOLOGY AND AGRICULTURE. 101 The author has made a chemical examination of the leaves which however he does not consider complete on account of the small quan- tity at his disposal. They do not appear to contain any alkalo’id %nd their odour seems to be due to a volatile bitter principle soluble in water and alcohol. H. J. H. Microchemical Examination of Angustura Bark. By P. CAZENEUVE (Pharm. J. Trans. 131 v 7). WHENthin transverse sections of true Angustura bark are examined under the microscope and compared with seotions of the false bark both being moistened with glycerin irregularly scattered cells will be observed in the true bark whereas the false bark presents two zones of sclerogenous cells entangled with one another.When the sections are moistened with water cells containing calcium oxalate are seen in thc true bark but they are absent in the false bark. When true Angustura bark is moistened with nitric acid a granular substance supposed to be cusparin melts in each cell with disengagement of gas into a red liquid which finally disappears with excess of acid ; but in the false bark the coloration spreads through the tissue. When a thin section of the suberous layer of false Angustura bark first treated with nitric acid is immersed in glycerin the cells aye observed to be rounded empty and coloured emerald-green on the sides ; this appearance is not observed in the suber of true Augustura bark.E.w. P. Means of Promoting the Germinating Power of Seeds. By R.BOTTGER (Chem. Centr. 1874 405). A MODERATELY concentrated solution of caustic soda or potash promotes the germinating power of seeds to an extraordinary degree. If a handhl of common coffee-berries are shaken up in a tumbler with a weak solution of caustic potash snow-white shoots one or two milli- meters long appear often within two or three hours. G. T. A. Modifications produced by the Phylloxera in the Chemical principles of Vines. By M. BOUTIN (Compt. rend. lxxix 515). THEbark of the root of a healthy vine contains crystallisable or cane-sugar only whilst in the vine attacked by the insect glucose or un-crystallisable sugar only is present.In the attacked vine the sugar amounts to about one-half and the albumin and calcium oxalate (raphides) to but one-fourth of the quantity of these substances present in the healthy vine. The ash of healthy leaves gives about one-sixth of its weight of potassium carbonate whereas that of leaves of a diseased vine gives only one-twelfth. H. J. H. ABSTRACTS OP CHEMICAL PAPERS. Behaviour of Yeast in Media free from Oxygen. By M. TRAUBE(Deut. Chem. Ges. Ber. vii 872-887). EXPERIMENTS are described which tend to prove Pasteur’s doctrine that yeast may be originated in the absence of free oxygen to be erroneous for when care was taken to exclude free oxygen by means of a stream of carbonic anhydride no yeast was formed even in the case of fer- mentable liquids which rapidly developed yeast on exposure to the air.Ready-formed yeast can however increase when free oxygen is excluded but there is reason to believe that the oxygen required for this increase is not derived from sugar but from albumino‘id substances as the yeast was found to cease growing while unaltered sugar remained in the liquid. When oxygen is excluded yeast can produce fermentation in pure sugar-solution but in this case the yeast does not increase. All the author’s experiments confirm the view that fermentation is not a purely chemical but a vital process. T. B.

ISSN:0368-1769    

DOI:10.1039/JS8752800097

出版商:RSC    

年代:1875

数据来源: RSC

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ABSTRACTS OP CHEMICAL PAPERS. Analytic a1 C h emi s t r y. Detection of Phosphates and Oxalates of Calcium &c in the Ammonium Sulphide Group. By A. HILGER (Zeitschr. Anal. Chem. 1874,133-137). THEprecipitate is dissolved in hydrochloric acid or in aqua regia if nickel and cobalt are present and a small portion of the solution after sulphuretted hydrogen is thoroughly expelled is tested for phosphoric and oxalic acids. To the remainder of the solution excess of alkali is added ; the precipitate is collected washed and dissolved in hydro-chloric acid (the alkaline liquid being tested for zinc chromium aluminium &c.). Ammonium chloride and ammonia in excess are added and the precipitate is collected (nickel cobalt &c. are tested for in the filtrate) treated with warm ammonium carbonate solution to remove uranium &c.and again dissolved in hydrochloric acid. A small portion of this liquid is tested for iron; another portion for barium and strontium ; and to the third and greater part crystallised sodium acetate is added whereby calcium oxalate and ferric phosphates are precipitated ; these are afterwards specially tested for in the preci- pitate. To the filtrate excess of ammonium oxalate is added to preci- pitate any calcium that may be combined with phosphoric acid. If a precipitate forms it is removed and the filtrate is mixed with excess of tartaric acid and of ammonia, whereby magnesium if present is thrown down as magnesium-ammonium phosphate. In a note Fresenius makes the following objections to the above process :-(1.) After the addition of alkali in excess in order to separate zinc &c.the precipitate may contain the greater part of both the zinc and chromium originally present. ANALYTICAL CHEMISTRY. 103 (2.) On the addition of ammonium chloride and ammonia basic ferric phosphate may be precipitated unaccompanied by calcium barium strontium and magnesium salts so that the alkaline earths must be looked for in the filtrate containing the nickel and cobalt. (3.) Thc addition of sodium acetate to precipitate ferric phosphate &c. may not bring about this result ;under certain circumstances a red solution will be produced consisting of ferric acetate holding ferric phosphate in solution. M. M.P. M. Detection of Selenious and Tellurous Acids. By A. HILGER (Zeitschr. Anal. Chem. 1874 132-133). THESEacids or their alkaline salts are entirely precipitated by magne- sium chloride or sulphate and ammonia in presence of excess of ammo- nium chloride. The precipitation takes place on standing or on brisk agitation of the liquid. In the case of selenious acid the precipitate is crystalline ;with tellurous acid it is non-crystalline. The precipitates contain seleriious or tellurous acid magnesium and .ammonium ; they are soluble in ordinary acids but their constitution is not yet fully determined. M. M. P. M. On the Formation of Alkaline Chlorides from their Sul-phates by Ignition with Ammonium Chloride. By FRANCIS C. P H I L L I P s (Zeitschr.Anal. Chem. 1874 149-153). H. ROSE asserts in his work on analytical chemistry that alkaline sul- phates are totally decomposed by ammonium chloride. E. Nicholson states that the decomposition is confined to a small fraction of the total amount of sulphate. The discrepancy of these statements is owing to the different temperatures to which tlie mixture of sulphate and chlo- ride has been submitted. When aqueous solutions of the two salts are evaporated in a porcelain crucible and gently heated the ammonium chloride may be volatilised without any mutual reaction. If they are more strongly heated in a platinum crucible the decomposition is nearly complete after ammonium chloride has been added fourteen to sixteen times. At a low red heat the decomposition is thorough but at a bright red heat some of the sodium chloride is volatilised.The sodium or potassium chloride should therefore not be fused. W. R. Chemical Examination of the Air in Rooms covered with Arsenical Wall-papers. By N. P. HAMBERG (Pharm. J. Trans. [3] iv 81-83). POISONING by arsenical wall-papers being commonly attributed to fine particles of the paper in the air removed by mechanical causes an investigation was made of the air in a room the wall-paper of which was very old and dry having a light green ground with an ornamental brownish-yellow pattern. The room being kept carefully closed 80 as 104 ABSTRACTS OF CHEMICAL PAPERS to prevent change of atmosphere the air wa,s drawn by means of aspirators through various tubes containing cotton-wool and silver nitrate ; the air entered first by an empty U-tube to collect any possible dust.On examination scarcely any solid particles could be discovered. The cotton-wool after fusion with sodium nibrate and carbonate gave a little ferric oxide and a trace of arsenic; but in the silver nitrate tubes decided evidences of the presence of arsenic were obtained as also some silver sulphide. The amount of arsenic present in the air of the room was so slight that it had not been noticed by the occupiers. E. w. P. Estimation of Water in Paraffin Residues and Crude Paraffin. By J. CARTERBELL(Chem. News xxx 57). THEdiscrepancies in the analytical resiilts are attributed to careless selection of samples. The water exists in the residues in a mechanical state therefore care should be taken before analysing that the residues are well agitated.The paraffin should be digested for two or three hours at loo" and then distilled at 120° the light oil and water which distil being measured. When the residues are distilled on the large scale the water is condensed in the crude paraffin to the amount of 5-11 per cent. E. W. P. Note on the Analysis of Sugar BYJ. M. MILNE (Chem. News xxx 104). As Presenius' method of determining the fruit-sugar in raw sugars does not answer for all sorts as much fruit-sugar being found in the solution after as before the addition of lead acetate the following method is recommended:-About 5 grams of the sample are treated with hot water and the insoluble portions are collected on a weighed filter and washed To the filtrate in a 100 C.C.flask about three-quarters full is added tri- basic lead acetate. When an excess of acetate has been added the liquid after agitation is cooled and diluted to 100 c.c. then after the precipitate bas subsided it is filtered through a dry filter into a dry glass it is then ready for determination of the fruit-sugar. E. W. P. The Analysis of Pyrolignate of Lime. By R. FRE s E N I u s (Zeitschr. Anal. Chem. 1874 153-161). THISis a process similar to that devised by Fresenius for the analysis of lead pyrolignate (p. 921 of last volume). 5 grams of calcium pyro-lignate are introduced into a 250 C.C. flask which has also a mark at 252.1 C.C. 150 C.C.of water are then added for solution and 70 C.C. of standard solution of oxalic acid. The flask is then filled to the higher mark corked up and well shaken. After the precipitate has settled 200 C.C. are filtered off. 100 C.C.of the filtered fluid are drawn 0% and the total amount of acid determined with normal sodium hydrate litmus and turmeric paper being used to test the end of the reaction. ANALYTICAL CHEMISTRY. 105 Multiplication by 2.5 gives the total amount of acid in the 5 grams used. A solution of pure calcium acetate is added to another 100 c.c. and the precipitate of calcium oxalate filtered off and weighed as calcium carbonate. If y be the amount found the equation 100 250 y :~t gives the amount of calcium carbonate obtained from 5 grams of calcium pyrolignate.The amount of calcium carbonate found is cal-culated to anhydrous oxalic acid (C,Os) by the equation 100 72 y' (calcium carbonate found by the previous equation) x. The amount of anhydrous oxalic acid f(ound is calculated to normal sodium hydrate 1000 1000 by multiplication with 2.5 X 36 X The product y x 50 x 36 1. 36 is however the same as y x 50. If it be desired to avoid the weighing of the calcium carbonate obtained by gently igniting the precipitated oxalate the precipitate may be strongly ignited and the calcium in the residue whether it exists its caustic lime or as carbonate estimated by titration with normal hydrochloric acid and back-titration with soda. W. R. Note on Procter's Reaction for Gallic Acid.By I?. A. FL~~CKTGER (Pharm. J. Trans. [S] iv 83). THE statement that an alkaline arsenate and gallic acid in aqueous solutions develop a green colour requires some modification. The fact is well known and recorded? but the arsenate has nothing to do with the reaction as phosphates boiates &c. give the same reaction. The reaction is developed by any alkali provided it is present in minute quantities. This reaction distinguishes gallic acid from gullotarinic acid and pyrogallol. Another reaction suffices to distinguish gallic acid. A dilute solution of ferrous sulphate with an aqueous gallic acid solution remains colourless provided tannic ac; d and ferric salts are absent. The violet colour of ferrous gallate does riot appear if the acid present be powerful but it appears when only a weak acid is present such as acetic acid.E. W. P. Simplification of Bunsen's Method of Estimating Urea. By G. BUNGIG (Zeitschr. Anal. Chem. 1874 128-132). THEauthor does away with the many weighings required in Bunsen's method by adding a measured quantity of ammoniacal barium chloride solution to a measured quantity of urine filtering and heating a measured quantity of the filtrate in a sealed tube. The temperature need not be raised above 200". If 100 C.C. of urine and 50 C.C.of barium chlcride solution have been used 15 C.C.of the filtered liquid may be assumed to contain 10 C.C. of urine ; the small inaccuracy here introduced is fihown to have but a very slight influence on the final results. The barium carbouate produced is transferred as far as possible to a filt,er well washed and dissolved in hydrochloric acid ; that portion which adheres mechanically to the tabe is likewise washed until free ABSTRACTS OF CI-IE;?IIIC,lL PLPERS. from barium chloride and dissolved in hydrochloric acid and the two acid liquids are mixed. The barium in this liquid is now precipitated as snlphate collected and weighed. M. 31. P. M.

ISSN:0368-1769    

DOI:10.1039/JS8752800102

出版商:RSC    

年代:1875

数据来源: RSC

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106 ABSTRACTS OF CI-IE;~IIC,lL PLPERS. Technic a1 Chemistry An Apparatus for recovering the Iodine disengaged in the Manufacture of Superphosphate of Lime. By P. THIBAULT (Compt. rend. lxxix 384-387). CERTAINphosphates from the departments of Tarn and Garonne-et- Lot have been shown by several chemists to contain iodine the greater part of which is in the form of a compound soluble in water probably calcium iodate. The author describes an appa'ratus by which the iodine which is volatilised when these phosphates are treated with sulphuric acid may be collected. It consists of a cast-iron mixer (malaxeur) which receives the powdered mineral and the acid. The mixture falls into brick chambers where it solidifies. A powerful aspirator draws the acid vapours through a sheet-iron tower filled with coke wetted with water.The same liquid passes several times through the coke and ultimately contains as much as 8 grams per litre of iodine in the form of iodide of iron. To this solution sulphate of copper is added arid the cuprous iodide thus obtained is distilled with sulphuric acid. W. A. T. On the Causes which modify the Setting of Plaster. New Cements of Plaster and Lime. By E. LANDRIN (Compt;. rend. lxxix 658-660). l'tm actions which occur during the setting of plaster are three anti may be seen with a microscope. 1. The burnt plaster in contact with nter becomes crystalline. 2. The water surrounding the crystals dissolves a certain quantity of the calcium sulphnte. 3. A portion of t!ie water is evaporated by the heat of combination and a crjstal forms which determines the cry stallisation of the whole mass just as when a crystal of sodium sulphate is dropt into a supersaturatetl solution of that salt; but it is only after some time that tbe mass acquires its maximum hardness and the plaster then contains the pro- portiori of water required by the formula CaSO4.2H,O.This amount of water does not diminish by evaporation. Only about 12 per cent. of water should be added as ordinary plaster elways contains about 8 per cent. ; yet in practice never less than 33 per cent. is added in order to prevent setting before the plaster can be used ; the effect is to produce very porous slowly-drying plasters which rapidly determine nitrification.To diminish the rapidity of setting is to delsly the crys-tallisation which can be effected by adding gum gelatin guirnanve pol.r.der glycerin and similw bodies ; while inert substances such as TECHXIGAL CHEMISTRY. sand baz.inin sulphate &c. diminish the solidity of the material with- out in the least effecting the desired end. In over-burnt plasters crystallisation may bc determined by admixture with ordinary plaster the setting of the latter occasioning the setting of the whole. A similar effect is produced bg simply placing t<he two plasters in con- tact. Lime has a favourable effect on plaster occasioning mor6 rapid setting and giving hardness. With 10 per cent. of lime the plasters are susceptible of a polish ; samples with 75 per cent.of lime have beon made ;they are tery hard yet light and may perhaps be utilised. C. H. P. Russian Coals and Lignites. By A. Sc HE UR E R-KESTN E R and C. MEUSIER-DOLFUS (Ann. Chim. Phys. [5] ii 325-332). MUCHof the coal from the immense deposits in the basin of the Donetz is of exceptional purity leaving only 2 or 3 per cent. of residue in the grate. The following are the results obtained with three samples of coal and one of ligiiiti from this region:-I. From Groiichesski is a greyish-black coal having a very brilliant metallic lustre. It is very hard and compact and keeps its form while burning. It burns with- out flame 01-decrepitation. It contains pyrites. 11. From Mioucki is deep black and very brilliant. It is very friable and burns without much smoke.It is well adapted for blacksmiths and is equal to and in some respects superior to the Welsh coal much used in the English Navy the analysis of which appears in this JouwmZ ([2] x 91). 111. From Galoubosski is black and brilliant with a slightly conchojidal fracture. It is compact and burns with more smoke than IT. IV. A lignite from Riazan is known as Toula lignite. It occurs in slabs which break down with conchojidal fracture into laminated fragments. It coutains abuudance of' pyrites. It generally contains more water than the sample analysed and often leaves 30 per cent. of residue on the grate. Pure. ?\later. .... . . 4 -08 1'39 -4-88 -9.39 -Ash .. . ..,... 1.57 -0.23 -1-42 -16.86 -Hydrogen .... 1-27 1.35 4.43 4.50 4-75 5.07 4.49 6.09 Carbon ...... 91*20 96 *6(i 89-97 91.45 77-47 82-67 54-37 73.72 0,N S ...... 1'88 ~-1 -99 3 -98 4,05 11-48 12.26 14-89 20-19 -___----~-100 -00 100'00 100'00 100*00 100'00 100-00 100'00 100'00 -Per cent. of coke.. 91*04 Heat -units per 86-95 8091 76'87 substance.. .. B. J. G. ABSTRACTS OF CHEMlCAL PAPERS. Evolution of Red Fumes during the Evaporation of Sugar Solutions in the Vacuum-pans. [By E. J. MAUM ENG (Compt. rend. lxxix 663-665). THEauthor having noticed during the late sugar harvest the evolution of red fumes during the boiling of the syrups in the vacuum-pans especially at the moment when the air-pumps began to act determined to investigate the cause. Beetroot-juice contains a notable proportion of nitrates and it is evidently from these that the red fumes are evolved.In order to determine the cause of the evolution very pure sugar-candy was treated in solution with nibrates of potash soda magnesia and lime in various proportions without effect ; but on boiling 50 grams of sugar with 100 of water and 2 of ammonium nitrate (or a maximum of 12*5) the liquid rapidly becomes coloured and at 125" swells up arid evolves a quantitg of rapours having a cyanic odour almost entirely condensable but containing nitric oxide. The sugar there-fore is the cause or one of the causes tending to produce the red fumes whenever the juice contains ammonium nitrate or any nitrate and an ammoniacal salt and the ammonium nitrate is very certainly one of the most active causes of the discoloration of the concentrated syrups (musses cuites*) and the production of molasses towards the end of the evaporation.The remedy is to treat the juices (syrups) with lime and keep them at least 24 hours in order to evolve the ammonia as suggested by the author in 18.55. The preliminary out- lay for tanks for storage would be quickly repaid by the increased yield and facility of working. c. R.P. Action ofAlimentary and Medicinal Liquids on Vessels made of Tin containing Lead. By J. FORDOS (Compt. rend, Ixxix 678-680). WHENwine vinegar or other acid liquid remains in such vessels for some hours it dissolves an appreciable quantity of lead. Hence the da,nger of using alloys of tin and lead for making drinking-vessels or for lining culinary utensils. R. R. Thum's Gas-generator in Sunderland. (Dingl. polyt. J. ccxiii 121.) On Mechanical Puddling. By P. TTJNNER (ibid. 123). Loew's Apparatus for the industrial preparation of Ozone. By A. OTT (ibid.,130). * The name given in English works to syrups after evapomfion in the v~cuu~n-pans.

ISSN:0368-1769    

DOI:10.1039/JS8752800106

出版商:RSC    

年代:1875

数据来源: RSC

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3 09 PAPERS READ BEFORE THE CHEMICAIJ SOCIETY. VL-On the Composition of Awturzite. By A. H. CHURCH. THE recent discovery of a new locality in Cornwall for autunite induced me to make a fresh examination of this mineral species. The crystals from Cornwall though distinct and perfect being very thin I was obliged to content myself with the employment of a quantity of the material rather insufficient for a satisfactory quantitative analysis. However as a remarkable peculiarity concerning the condition of the water in this mineral presented itself I availed myself of two fine specimens from the well-known French locality of St. Symphone near Autun. One of these hereinafter designated "Autun A," consisted of a crust half an inch thick of large crystals irregularly massed together in fan-like aggregations and was of a citron-yellow colour ; the other specimen was similar but the crystals were smaller and their yellow tint approached that of sulphur.This specimen is named "hutun B." The Cornish specimen occurred in thin isolated rhombic tables translucent to sub-transparent and was sulphur-yellow. All the samples were prepared for analysis by careful selection so that no foreign matter or gangue was introduced. The crystals were then finely ground and submitted to the following treatment :-Imme- diately after grinding the powder was weighed ; it was again weighed after the lapse of some hours. This was done to see whether exposure to air varying within natural limits both as to temperature and humiditr would cause any Toss or gain in the weight of the freshly powdered mineral.No gain ever occurred but a loss never reaching 1per cent. however was occasionally recorded. This loss might have been due to the escape of interstitial water but I am disinclined to accept that conclusion in the light of the results presently to be mentioned. In the next place the powdered specimens were (ixsually) submitted to dry air confined in a bell-glass over oil of vitriol. The result of this treat- ment was most striking for in the case of both the Cornish and the Autun specimens a loss of water then took place at ordinary tempera- tures of from 8.24 to 9.08 per cent. When uninjured crystals of the several specimens were submitted to the same condit'ions an almost complete loss of transparency OccurTed accompanied by increased fragility.The physical changes wrouglit in the mineral by exposum to dry air indicate that the water thus removed is not mere accidental VOL. XXVIIT. I 110 CHURCH ON THE COMPOSITION OF AUTUNITE. or interstitial moisture but is absolutely essential to the integrity of the compound-to the constitution of this mineral species. And this indication is confirmed by the constancy in the amount of water so lost in every analysis it reached a maximum practically identical beyond which no further exposure to the same conditions could push it. Had this loss of water and this appearance of opacity occurred in a soluble crystalline salt like ordinary sodium phosphate it would have been accepted at once and named cfllorescence.An insoluble mineral like autunite placed under novel conditions dissimilar to those of its for-mation might not unreasonably be regarded as liable to some corre- sponding change. But the definite loss of water suffered by autunite in dry air is not the only peculiarity of this mineral for it sustains a further loss in vacuo. Placed over oil of vitriol in a nearly perfect vacuum it soon loses an amount of water which is fairly definite and constant when the pre- vious drying over oil of vitriol has been properly carried out. This loss amounted to 4.95 per cent. in one case and to 5.28 in another. If the vacuum be bad then little or no loss occurs until the powdered mineral is heated to loo" when the water which should have been removed by the absence of the atmospheric pressure is driven off by heat.But if autunite be duly dried im vacuo it loses nothing more at loo" although that temperature suffices to dry it as effectually as a vacuum. In the table that follows I have collected my analytical results. I would first obeerve however that I did not always ascertain separately the amount of water lost under the various conditions specified not having made the earlier analyses so complete as some of the later ; and in one instance marked * I found that the air-pump had leaked and conse- quently no loss occurred until the material employed had been after- wards heated to 100". For reaching this temperature a large double air-bath with a regulator was used instead of a steam-bath.Aisalyses of Autunite. Specimen analysed. Cornwall. Autun A. Autuii B. I. 11. 111. IV. v. Substance taken (gram). ..... *134 *3885 -303 -398 "728 H20lost over H2SO4........ -*032 -0275 *0335 '069 H20 lost ia vacuo .......... H20 lost at looo.. .......... -0195 *027 none ,016 '029" - *036 '0055 H20lost at red heat ........ -0055 -016 -016 -016 '0375 CaC03 )) ............. MgZP,O , ............. U304obtained ............. '079 -012 *029 -- *180 '028 '0'7 --085 *4345 '069 -1697 ~~ * Of this wat,er *012was giren off at 180"C. CHURCH ON THE COMPOSITION OF AUTUNITE. 111 Translated into percentages the preceding numbers become- I. 11. 111. IT. V. H20lost in vacwo .......... -H20lost at 100"............13*8 -H20lost over H@04........ 8.24 -6 '90 9 '08 5 -28 - 8'38 7 '29 - 9-48 4 *95 *75 €TzOlost at red heat ........ 4 *85 4 '12 5 *28 4.02 5.15 u203...................... 60.00 - 61 *34 - 60 *84 CaO ...................... 5.01 - 5 *24 -5 *31 P,O,.. .................... 13.84 - 14 -97 13.66 13-40 Confining our attention to the main point under discussion namely the relation in which the water of autunite stands to this mineral we may summarize ths foregoing percentages thus- Total percentage of water lost in dry 13 8 15.14 15 .36 15.6~ 15 .18 air in vacuo and at 100" ........ Water lost at red heat ............ 4 *85 4 *12 5 '28 4'02 5 *15 Total percentage of water. ....... 18-65 19 *26 20 -64 19 *69 20 '33 If we calculate these numbers into mean percentages we conclude that ilk v(x,cuoautunite loses 1-5-03per cent.of water and at a red heat 4.68 per cent. making altogether 19.71 per cent. We say that this 15.03 per cent. is lost in vacuo because as before explained this always happens when that method of drying the mineral is the only one adopted and when therefore the substance has not had the oppor-tunity of giving up some 8.8 per cent. of its water to dry air at the ordinary temperature. In conclusion one point remains to be considered-how many mole- cules of water do autunite crystals naturally contain and what number of the molecules is removed during those processes of disintegration and change which take place in dry air or in vccczm ? Now Berze- lius's analysis of autunite gave but 15.48 per cent.of water; Pisani on the other hand found 20 per cent. On the strength of the former result we should assign 8Hz0 (requiring 15.77 per cent.) t'o the mole- cule of autunite but the latter result corresponds more nearly with 1OH,O which demands 18.96 per cent. of water. It is this latter theory of 10H,O which is so thoroughly confirmed by the analyses given in the present paper. I conclude then that the following formuh represent the composition of the mineral autunite :-Autunite as it exists in the unaltered crystals- ]P,05.1013,0. Antnnite dried iz.vacuo-I2 :;$ CHURCH ON THE COMPOSITION OF AUTUNITE. The difference between these two formula of 8Hz0corresponds with 15.18 per cent. of water. My experiments gave as a mean 15.03 ; a closer accordance of experiment with theory could not be required.The closely allied uranium-copper phosphate torbernite did not show analogous results as the following numbers prove :-*819gram pure torbernite in powder lost -003 , H,O in dry air nothing in vacuo. &091gram H,O at 100" = 11.11per cent. *035 , , at red heat = 4.25 per cent. The formula deduced from these numbcrs are :-Torbernite as it exists in the iinaltered crystals Torbernite dried at loo" ;!$ } P,05.2H,O. Thus the loss of 11.11per cent. H,O at 100' corresponds with 6H20 (theory requires 11.54 per cent.) ; while the mineral thus dried retains 2H,O more intimately united but driven off at low redness when a loss of 4.25 per cent. is experienced theory indicating a.loss of 3-84! per cent. Thus it will be seen that autunite and torbernite so long considered isomorphous differ slightly in composition as they do in form. I must ask the forbearance of the Society for the prolixity of my present paper. I felt that unless I placed the whole evidence in the present case before chemists they would have been as unwilling to admit as I myself once was the conclusions which I have deduced from analysis. I now consider that there are cases in which the drying of minerals in vacm removes essential water and not as I formerly believed accidental moisture only and I further believe that abso- lutely dry air does in still rarer instances effect a similar alteration. I have already obtained such a result with two ot'her mineral species.

ISSN:0368-1769    

DOI:10.1039/JS8752800109

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

11s VII. The Action of Buryta on Oil of Cloves. By A. H. CHURCH. THE several observations which have been made from time to time on the action of caustic baryta on eugenol being discordant I have endea- voured by operating on large quantities of material to reach a satis-factory conclusion. I was specially induced to take up the subject from having incidentally recorded in a paper published some 20 years ago that I had made a preliminary trial of the reaction in question. On repeating the experiment on a larger scale and with eugenol from oil of cloves of ascertained genuineness though I failed to obtain confirmatory evidence of my former view I secured some results which I trust may be deemed worthy of the attention of the Society. Between 5 lbs. and 6 Ibs.of English clove oil chiefly supplied by Messrs. Hopkins and Williams were employed in the present in-quiry which was commenced several years ago and concluded only in October last. I will first describe some experiments as to the physical characters of pure eugenol itself and of the terpene with which it is associated in clove oil. The eugenol was prepared by saturating the oil with caustic potash in solution and siphoning off the undissolved terpene some of which however will dissolve in the strong potassium-eugenol solution. On supersaturating the latter with hydrochloric acid the eugenol sepa- rates and is drawn off by a tap-funnel when it has stood for some time. By several distillations in a current of dry hydrogen it wits gradually freed from water and most of the admixed terpene still remaining.Before the residue in the retort became resinous and semi- solid it was noticed that a liquid came over having a more oily appearance than eugenol and a higher boiling point while a strong creasotic odour was also observed in the very last portion of this dis- tillate. Pure eugenol was found to have the specific gravity 1so66 at 15" C. while its uncorrected boiling point was 244". On applying the corrections (as described in Watts's Dictionary vol. iii p. 85) for which the following are the data it becomes 251.8" :-Barometer = 744.5mm. To= 244 = observed temperature by principal thermometer. to = 25 = temperature of second thermometer. 6 = -0001545 = coefficient of expansion of mercury.N = 214 = length in degrees of that mercury-column of principal thermometer which has mean tem- perature 25". CHURCH ON THE ACTION OF BARYTA With a carefully prepared and dried sample of eugenol distilled in dry hydrogen with every precautions to endme accuracy the boiling point did not vary more than 1"on either side of 244". Although the quantity of terpene in clove oil is relatively small yet the several pounds of material operated upon enabled me to prepare some ounces of this bydrocarbon. It was noticed that the range of temperature within which it distilled after having been simply treated with stick potash was much lower than that observed with the same terpene after it had been cohobated with sodium-a useful method of purifying hydrocarbons which I published in 1855.On the first dis- tillation the dry clove terpene came over between 126" and 165" the largest fraction being collected between 160" and 164" while on the second distillation of this fraction most liquid was collected between 215" and 221". This terpene must have been nearly pure though it had not been treated with sodium for it had the spec. grav. -9064 at 15O and gave the following numbers on analysis :-I. -33 gram of terpene gave- 1.0622 gram carbon dioxide and -3439 , water. 11. ,3609 gram of terpene gave-1.1595 gram carbon dioxide and a3794 , water. Experiment and theory are here shown in percentages :-Experiment I. Experiment 11. Theory (C,H8). Carbon . . . . . . 87.79 87-62 88.23 Hydrogen... . 11.59 11.68 11.77 -4 99.38 99.30 100~00 When however the terpene was distilled twice from sodium it boiled chiefly at 247" to 250" (uncorrected) and was almost constant at 247". This temperature when corrected becomes 253.9O the data being :-Barometer = 744 mm. T" = 24'7". to = 35". 6 = *0001545. N = 193". * Draughts of air were prevented by suitable metal screens round the retort the mean temperature (to) of the exposed portion of the principal thermometer was ascertained by keeping the bulb of the second thermometer in a small trough of zinc powder surrounding a particular part of the stem of the principal thermometer a perforated disc of mica preserved this trough from receiving heat from currents of hot air. ON OIL OF CLOVES.The specific gravity of the terpene at 15" wa8 now -905 instead of -9064 as before. A not very successful vapour-density determination in the vapour of boiling mercury by means of the apparatus described by Greville Williams gave the following data :-Balloon and air.. . ,.. . . 21.5564 grams at 16" Bar. vapour . .. . 21.8180 ? , 350") 752 mm. Residual air .. . . . . . . . . *2C.C. at 19". Capacity of balloon.. . . 82.3 C.C. Vapour-density . . . . . . 7.7 air = 1(or 114 if H = I). The formula CI5Hz4demands 7.05 (or 102 if H = From these resuits it may be concluded that whatever be the nature of the terpene as it naturally exists in the clove oil it certainly has the formula, CI5H2$, after prolonged treatment with sodium possessing moreover the high boiling point 253.9" and the specific gravity 0.905 which are concomitants of that formula.It now becomes necessary to revert to the main subject of the inquiry the nature of the product or products resulting from the action of the baryta on engenol. After several trials the experiment was thus made. At each operation (and there were more than 30) 60 grams of eugenol 90 of caustic baryta and 30 of powdered zinc (together with 30 grams of the residue of former operations) were distilled in Florence flasks with bent necks. About 10 to 15 parts of an oily distillate were obtained for each 100 parts of eugenol employed this oil being unaffected by baryta when once or twice redistilled from that substance in a current of dry hydrogen.When about 2,000 grams of engenol had been used the mixed distillates were purified and sub- mitted to fractionation all the distillations being performed in a stream of dry hydrogen. It is not necessary to give the results of the earlier analyses of the several fractions for unfortunately they were all vitiated by the presence then unsuspected of traces of the clove ter- pene but it may be mentioned that the (uncorrected) boiling point of the chief fractions collected were between 222" and 251" and that the main portion came over at 244". After several further fractionations the higher portions were found to be free from any terpene although it could not be eliminated from the lower fractions. The largest quan- tity of the new product was found to boil between 255" and 260" (uncorrected) and came over almost entirely at 255" which corrected becomes 262.5'.This oil was colourless neutral of specific gravity 1.046 at 15" and gave on analysis the following results :-I. *3843gram gave-1.0430 gram GO, and ,2793 , H,O. 1). CHURCH ON THE ACTION OF BARYTA IT. -3722 gram gave-1.009 gram GOz and 2.723 , H20. Translated into percentages of carbon and hydrogen and compared with the nearest theoretical proportions the above numbers are as follows :-Experiment I. Experiment 11. Theory (Cl1HI4O5). Carbon ...... 74.02 73-93 74.16 Hydrogen.. .. 8-07 8.13 7-87 Oxygen.. .... 17-91 17.94 17.97 lOO.OC 100.00 100~00 Eugenol itself C10H1202, requires 73.17 p. c. C.7.32 p. c. H. and 19.51 p. c. O. while the formula given above that of methyl-eugenol presents just that slight excess of carbon and deficiency of hydrogen which is usually shown in comparison with the results of experiment. On tlhe other hand ethyl-eugenol C12Hls02,contains 75.00 p. c. C. 8.33 p. c. H. and 16.67 p. c. O. numbers which are quite incompatible with the results of my analyses. There is however one serious diffi-culty in accepting the conclusion that the neutral oil now under con-sideration is methyl-eugenol. For this compound as obtained by means of the reaction of sodium-eugenol on methyl iodide boils not at 262*5",but between 237" and 239"; whereas it is ethyl-eugenol CI2Hl6O2, that has a boiling point (251" uncorrected) near that of my new product.One explanation suggests itself namely that the product above detscribed is isomeric but not identical with methyl-eugenol ;the results of its oxidation favour this view to a certain extent as we shall presently see. A determination of the vapour-density of the new product threw no light on the matter since a serious amount of oxidation occurred even though the balloon used had been filled with hydrogen ;this determination is here given however for what it is worth :-Balloon + air.. ...... 18.6743 at 12" Bar. , + vapour .... 18.906 at 350") 753.2 mm. Capacity of balloon .. 88.7 C.C. Residual air. ......... 0.8 C.C.at 17" and 751 mm. Vapour density ...... 6.88 air = 1 (or 99.6 if H =1). CllH1402 ..........- 6.16 (or 89 if H = 1).Had the substance been ethyl-eugenol its vapour would have been 96 times as heavy as hydrogen and although my result nearly reached 100 yet the dark-coloured resinified oil which remained in the balloon ON OIL OF CJIGVES. 117 showed clearly enough that the high density deduced from the experiment must have been inuch in excess of the truth. There still remained a method of testing the constitution of the new product (boiling at 262.5 corr.) namely if,s conversion into dimethoxy- benzoic acid. Following the directions of Graebe and Borgmann (Am.Chem. Yharm. clviii 282) I digested the several fractions of the product from eugenol with glacial acetic acid and potassium dichromate for several daya at 100". In each case an acid was obtained agreeing in properties and composition with dimethoxybenzoic acid C9HI00d, or CsH3(0CH3)ZCOZH.It would be tedious to give all the analytical details and methods of purification adopt,ed but I may state that tshe pure acid which I obtained fused at 179*5" and partially sublimed at a higher tempera- ture giving out at the same time a strong odour of creasote. Its recryatallised silver salt gave the following results on analysis :-The acid prepared from the fraction boiling between 255" and 2GO" (uncorrected) gave a silver salt which on ignition yielded this result :-*1871 gram of silver salt gave- -0698 gram of silver = 37.30 p. c. The acid prepared from the fraction boiling between 190' and 230" (uncorrected) gave a silver salt which on ignition yielded this result :-*1141 gram of silver salt gave- -043gram of silver = 37-68 p.c. The acid from the fraction 235" to 240" gave a silver salt which 011 ignition yielded this result :--1985gram of silver salt gave- so75 gram of silver = 37.80 p. c. The formula of silver dimethoxybenzoate demands 37.37 p. c. of silver; it is evident therefore that this was the salt obtained in each case. The action of the oxidising mixture was however most rapid and effective upon the fraction 235" to 240" a fraction which corre- sponds in boiling point with that of ordinary methyl-engenol; and although the acid from the higher fraction 255" to 260" was pro-duced more slowly yet no other acid could be detected as accompanying the dimethoxybenzoic acid from this fraction.A combustion of a silver saltl made from the purified acid pre- pared by oxidising a fraction boiling between 251"and 255O gave the following results :- 118 CHURCH ON THE ACTION OF BARYTA ETC. 0.4 gram of silver salt gave- -5465 gram GO2 and -119 ? H2O. These amounts correspond with the following percentages :-Experiment. Theory (C9H,AgO4). Carbon.. ...... 37.26 37.37 Hydrogen .... 3.31 3.11 Silver ........ -37.37 Oxygen ...... -22.15 Taking all these observations into consideration together with the results of all the analyses which I have made I conclude that the action of baryta on eugenol is not a precise or definite one ;that the greater part of the eugenol is carbonised and destroyed; and that from the products of such destruction a minute proportion of the remaining eugenol receives an addition of CH2 becoming thereby converted partly into methyl-eugenol and partly into another body of the same empirical formula and possibly isomeric with that ether.These con- clusions are not as definite as I could wish but I may perhaps be permitted to plead in excuse for not pursuing the investigation fur-ther the very large expenditure of material and of time which even such results as I have obtained have demanded. Slender though the interest of the inquiry may be one thing is clear that none of the former conclusions as to the nature of the action of baryta on eugenol are correct. Should I be able to resume the present investigation there are several points which might be worth attention.Among these I would include the nature of the cresol-like body which distils over towards the end of the rectification of large quantities of eugenol ; the com- position of the fraction a little lower than this but higher than eugenol and the volatile base resembling propylamine which accompanies the crude oily distillate obtained by the action of impure baryta (from igni-tion of the nitrate) on eugenol. In conclusion I have much pleasure in expressing my thanks to Mr. R. C. Woodcock for the care with which he has performed all the analytical work as well as the specific gravity and boiling point determinations recorded in the present paper.

ISSN:0368-1769    

DOI:10.1039/JS8752800113

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. General and Physical Chemistry. Variability of the Spectra of Incandescent Gases. By 0. SCHENK (Zeitsclzr. Anal. Chem. 1874 386-390). THEauthor supports the opiniou that a gas may exhibit more than one spectrum and considers that the circumstances which most defi-nitely produce modification are :-1. The density of the gas. 2. The strength and nature of the electric discharge and the tem- perature to which the gas is thereby brought. 3. The thickness of the radiating layer. 4. The chemical constitution and purity of the gas. The description of the changes taking place on rarefying hydrogen is almost the same as that given by Wullner with the exception that the spectrum of six bands is said to appear before the highest degree of exhaustion is attained and that when the utmost limit is reached one or other of the bands is replaced by a group of fine lines which every now and then reverts to the band spectrum.The effect of the different kinds of discharge is that with the silent discharge and a high pressure the same spectrum may be obtained AS with the spark discharge at a lower pressure. At the same tension the only difference is that with the spark discharge the spectral lines come out more brilliantly. It is to be noted that the layer of gss heated by the spark is ex-tremely thin whilst with the silent discharge the entire mass of the gas is rendered incandescent though the temperature is lower.0 The general conclusion to be drawn from the researches of Angstrom and Wullner is that the band spectrum belongs to the luminous envelope of the spark and the line spectrum to the spark itself. As regards the fourth point the author admits that it is impossible to ensure absolutely the purity of the gases employed. M.J. S. The Spectrum of the Light of Exploding Gun-cotton. By 0. LOHSE (Pogg. Ann. cl 641). THE following lines were measured :-1 -meters. 109 Faint ......n. ,........ ...... . ..... . .. 644.6 oo Broad band.. ,.....,,.................. .. .. 120 ABSTRACTS OF CHEMICAL PAPERS. -1 meters. 109 Broad band weaker ....................... do. the very bright Na lines .......... {El Faint ....................................572.8 Faint but sharply defined.. .................. 568.7 Very bright broad line without sharp edges.. .. 554.8 Rather less bright do. do. .... 550.4 A very faint continuous spectrum was also observable. The most remarkable feature is the widening of the sodium lines especially the more refrangible so that in some cases the space between them is quite obliterated. This appears to be connected with the violence of the explosion. 31.J. S. On the Light reff ected from Potassium Permanganate. By E. WIEDEMANN (Pogg. Ann. cli 625-628). THEauthor has extended the experiments of Stokes on the spectrum of the light reflected from the surface of potassium permanganate. This surface was obtained by burnishing the powdered salt on a glass plate by means of an agate burnisher.This prepared plate was then inserted in a hollow right-angled prism which could be filled with benzene or carbon bisulphide so that the light reflected from the sur- face of the perrnanganate immersed in the fluid could be examined by the spectroscope. Tables are given of the absorption spectra of the reflected and also of the transmitted light from which it appears that no bands in the latter cover even partially those of the former nor do any of them lie exactly intermediate between any two of the former. The position of the bands is independent of the angle of incidence both with ordi- nary light and with tLat polarised parallel to the plane of incidence When the light however is polarised at right angles to the plane of incidence the bands occupy the same position as above up to a cer- tain angle which is 58.5" for air and 52" for benzene or carbon bisul- phide but with a slight increase of the angle of incidence they suffer a sudden displacement towards the blue.C. E. G. Behaviour of certain Fluorescent Bodies in Castor-oil. By CHAS.HOENER (Phil. Mag. [4],xlviii 165). CERTAIN natural organic colouring matters which exhibited no fluor-escence when in aqueous or alcoholic solution were observed to fluoresce brightly when dissolved in castor-oil ; while other substances possessing naturally a faint fluorescence were found to have this pro- perty considerably augmented. In this solvent cudbear exhibited a brilliant orange-coloured light GENERAL AND PHYSICAL CHEMISTRY.and extracts of logwood and camwood a powerful apple-green fluor-escence. The well-known fluorescent light of turmeric solutions was increased in brilliancy at least threefold and is described as a vivid emerald-green fluorescence comparably only with the appearance pre- sented by the best uranium glass under similar circumstances. It is suggested therefore that in studying the phenomena of fluorescence advantage should be taken when possible of the solvent property of castor-oil. J. W. Electric Conductivity of Woody Bodies and other Bad Conductors. By TH. DU MONCEL (Compt. rend lxxix 41-44 110-114 154-159 295-299 356-360 591-594 753-757 945-949. THESEresearches were undertaken with a view of determining how far the conductivity of various kinds of wood &c.is dependent upon the moist,ure with which they are more or less charged even when appa- rently quite dry. Themode of experiment was to place a small bar of the substance in the circuit connecting the poles of a constant battery of six cells and including a delicate galvanometer. A plate of plati-num was pressed strongly against each extremity of the bar thus forming electrodes for the entrance and exit of the current. The deflection was read after the circuit had remained closed for five minutes and each bar of wood was made the subject of experiment lst as received from the joiner ; end after drying for two hours in a stove ; 3rd after exposure out of doors for a night ; 4th after expo- sure for hours to an atmosphere saturated with humidity.The results show that the conductivity of woods is in proportion to the amount of moisture imbibed into their pores. A piece of oak placed permanently in the circuit constituted a kind of hygrometer for it exhibited variations of conductivity which followed at an interval of some hours corresponding changes in the humidity of the atmo- sphere. It was found much more difficult to expel moisture from the harder than from the softer woods and in the former it was observed that moisture which had apparently been removed by a superficial drying reappeared in a short time. But when hard woods are once thoroughly dried they absorb moisture from the air much more slowly than the sofher kinds do under the same circumstances and the moisture which the hard woods have imbibed they obstinately retain even in a dry place.The resistances to the current offered by rods of the same wood but of different lengths and sections are in accordance with Ohm’s law or at least the deviations therefrom of the experiniental figures are readily explicable and the conductivity appears to be greater along the fibres than across them. In the tenacious compact solid produced by strongly compressing hardwood sawdust agglutinated with blood the author has found an ex- cellent insulator for electric currents and one possessing qualities which promise to render it more valuable than ebonite for certain purposes. Prolonged exposure in ail atmosphere saturated with moisture left it a perfect non-conductor even when it was tested without a previous wiping 122 ABSTRACTS OF CHEMICAL PAPERS.of the surface. A series of experiments on various kinds of woods im-pregnated with paraffin yielded some curious results and appeared to show that the effect of moisture in giving conducting power to wood is diminished and by several repetitions of the process of alternately stoving and steeping in paraffin almost annulled. Mechanical com- pression at first augments the conductivity of wood by giving more continuity to its conducting moisture but afterwards the conductivity progressively diminishes for the atmospheric moisture finds its way with less facility into the compacted mass. By similar experiments with mineral substances the author has found that in so far as these are porous some part of the observed effects are analogous to those presented by woods.Minerals however differ entirely from the latter by the very marked polarisation which occurs in them. Thus with a sample of Caen stone the initial devia- tion always decreased rapidly and even after the current had been interrupted for some hours the deviation of SO" observed when the current was again established fell in ten minutes to 18O but a reversal of the electrodes sent it up to 85'. The most porous stones exhibit the greatest variation in their conductivity according to their hygro- metric state while the harder stones like hard woods retain moisture more obstinately and absorb it less readily.A certain kind of flint occurring near Caen was however found to have a conductivity quite exceptional and even comparable with that of liquids. The state of aggregation of the particles of the substance as modified by fusion or crystallisation powerfully influences its conductivity ; for example porcelain which had been exposed to a very high temperature gave no deviation even after prolonged exposure to moisture. Crystallised bodies insulate almost perfectly ; gypsum however gave a deviation of 5" and quartz and Iceland spar 2.5"; but in the last two substances the effect was probably due to surface moisture. By interposing between the platinum electrodes a thickness of various fabrics such as silk woollen linen cotton the author has found in these also a conductivity varying so much with their hygro-metric state that it may be said to be dependent on the hour of the day and the state of the thermometer.Contrary to expectation he has observed that silk stuffs and especially black silk stuffs show a higher conductivity than woollen. Some black silk in his experi-ments yielded a deviation of 81O. By inquiries among the silk dyers of Lyons he has traced this exceptional conductivity of black silks to the salts of iron &c. with which they are dyed. Good black silks are charged with from 10 to 60 per cent. of their weight of dye-stuff; but the author also lets us into the secret that the weight of the iron dyes fixed on black silk is sometimes three times that of the silk itself.He suggests the galvanometric method used by himself as a possibly useful mode of detecting excess of dye. Linen absorbs moisture more readily than the other stuffs and it has therefore a high conducting power except when it is quite dry. The galvanometric indications are so precise that it is possible readily to detect admixtures of the various materials in the fabrics experimented upon. Polarisation phe- nomena show themselves with fabrics but not nearly to the same extent as with minerals. GENERAL AND PHYSICAL CHEMISTRY. From the results of a series of experiments on minerals the author has arrived at a novel view of polarisation namely that for a certain direction of the battery current polarisation may give rise to a pro-gressive augmentation of the int,ensity while for the opposite direction the result may be a decided and rapid weakening of the current.R. R. The New Contact Theory of the Galvanic Cell. By J. A. FLEMING (Phil Mag. [4] xlvii 401-4111. THEauthor points out that several of the able physicists who have lately advocated this theory have put forth contradictory statements on several points ; but its fundamental principles are that when two different metals are immersed in one liquid there is no difference of potential or electromotive force due to chemical affinity ; and that the chemical action in the battery is the result and not the cause of the difference of potential which is due to the contacts of dissimilar metals. Several experiments of Faraday De la Rue and others are cited as directly combating this theory and the author describes a new form of battery he has devised in which dissimilar metallic conkacts are entirely avoided.An element of this battery is formed of two vessels one containing dilute nitric acid the other solution of sodium persulphide. A sheet of lead twice bent at right angles is made to dip into both vessels in each of which there is also a copper plate and these copper plates being connected by a copper wire a current circu- lates in the sodium persulphide from the copper to the lead and from the lead to the copper in the nitric acid. By repeating the arrange- ment with allemate acid and sulphide cells connectsd with bent copp2r and lead plates the author formed a battery of 60 elements having 211 electromotive force equal to that of 15 Daniell’s cells.In this was observed a I*egular rise in potential from cell to cell which could tnlre place only at the surface of contact of the metal with the electrolj-te namely at the seat of the chemical action. R. R. Researches on Galvanic Polarisation and the Distribution of the Current in Electrolytes. By C. (3. MELLER(Pogg. Ann. cli 286-303). INthis first instalment of his communication the author gives full details of a new method he has devised for estiinahing the force of polarisation. The determinations can be much more qixickly made than by any process hitherto employed and the possible errors fall within very iiarrow limits. R.R. On the Electromotive Force of Palladium in the Gas Battery.By E. VILLABI (Pogg. Ann. cli 608-619). As Graham considered the hydrogen combined with psllndiuin to be in t,hc active form and Beetz has shown that tlm electromotive force of ABSTRACTS OF CHEMICAL PAPERS. the gas battery depends not only on the nature of the gases but also 011 the power of condensing them possessed by the electrodes it seemed to the author that the couple with palladium electrodes would have a greater electromotive force than that with electrodes of pla-tinum. The author after giving ihe details of the apparatus employed and the method used for perfectly cleaning the electrodes describes the series of experiments which he found it necessary to make in order to avoid the inaccuracies attendant upon a direct comparison of the electro- motive force of two gas couples one furnished with platinum and the other with palladium electrodes.In the first series of experiments the couple was formed of two electrodes one of platinum and the other of palladium immersed in hydrogen. In all these experiments the palla- dium appeared as the negative,* or more easily oxidisable electrode of the couple. This always occurred not withstanding the conditions were varied considerably. This result is quite in accordance with Graham's opinion that hydrogenium is readily oxidisable. When a couple was formed with two platinum electrodes one of which was in an atmo-sphere of hydrogen prepared from zinc by the action of dilute acid and the other in hydrogen obtained by electrolysis a powerful deflec- tion of the galvanometer was observed indicating that the electrolytic hydrogen was the more readily oxidizable.When the couple of plat'i-num and palladium above mentioned was charged with oxygen pre- pared by the decoinposition of potassium chlorate no perceptible effect was produced neither was there any permanent deflection of the gal- vanometer needle with a couple with two platinurn electrodes one of which was in an atmosphere of oxygen and the other immersed in acidulated water. If however one of the platinuni electrodes be in the oxygen and the other in oxygen obtained by electrolysis the latter electxode becomes strongly electropositive ; this is owing to the ozone present in the electrolytic oxygen.With palladium electrodes the action is complicated by the formation of palladium oxide on the sur-face of the palladium which has been made the posit'ive electrode in the voltameter and this oxide acts as a strongly oxidizing agent. The following method was employed for a comparison of the two couples. One with platinum and palladium electrodes was charged with chemically prepared hydrogen which gave a deflection showing the palladium to be the electro-negative element ;a similar one charged with chemically prepared oxygen gave no current. On re-arranging these to form two couples the one with platinum and the other with palladium electrodes opposing them and completing the circuit through the galvanometer a current was observed indicating the superiority of the palladium couple but this gradually decreased until it became zero.On arranging the elements however in the original order the platinum and palladium couple charged with hydrogen showed a powerful current in the original direction whilst the corre- sponding oxygen couple gave one indicating that the palladium element was attacked. This seems to arise from a secondary polarisa- * According to English usage the niore oxidisable element of the couple is called posi fire. GENERAL AND PHYSICAL CHEMISTRY tion. Similar results were obtained with electrolytic oxygen and hydrogen. The results of these experiments prove that the element with palla- dium electrodes has a greater electromotive force than a Grove’s element the hydrogen in contact with palladium being much more readily oxidizable than when it is in contact with platinum.C.E.G. Internal Latent Heat. By M. AVENARIUS (Pogg. Ann. cli 303-316). ON gradually heating an hermetically sealed tube partly filled with ether the aut’hor observed that at about 196” the liquid lost its trans- parency assuming a yellow red or brown tint and began to rise in the tube. In a few seconds the coloration and turbidity disappeared and the column of liquid defined only by a nebulous zone rapidly ascended and the whole tube became filled with a clear fluid in which a temperature bordering on 350Oproduced no further change. On the temperature being allowed to fall the same changes took place in the inverse order.When the quantity of ether sealed up in the tube was diminished to a certain point the liquid column on becoming turbid instead of rising sank rapidly and disappeared. But on cool- ing the interior of the tube showed a dimness at the same tempera- ture as before and the liquid then made its appearance at the lower end. The author believes that this temperature marks the abrupt and total conversion of the liquid into the gaseous form ;and as it does not change with the proportion of the capacity of the tube occupied by the liquid it is independent of the pressure. Similar results were ob-tained with carbon sulphide carbon chloride and acetone and the critical temperatures were carefully noted. Empirical formulae for the calculation of the intwna latent heats of these substances at any given temperature were arrived at frm the re-sults of Regnault’s observations and certain deductions of Zeuner’s.By equating each of the expressions to 0 the temperature at wkhich the latent heat of the substance becomes nil is calculated. The figures so found are in complete accordance with the temperatures directly observed by the author as the following table shows :-Observed temperature. Calculated temperature. Ether. .............. 196.2 196.8 Carbon sulphide ...... 276.1 274.0 Carbon chloride ...... 292.5 298.7 Acetone.. ........... 246.1 230.4 The want of agreement in the last case is exptained by the discre- pancies among the data given by different observations ; from another set of data the temperature 271.7” may be deduced.R.R. vOL. xxVIII. ABSTRACTS OF CHEMICAL PAPERS. Gaseous Liquid and Solid States of Water Substance. By JAMESTHOMSON (Phil. Mag. [4],xlvii 4A7-457). IF,representing temperatures and pressures by ordinates to a pair of rectangular axes we lay down three curves expressing the relations between these two conditions (1)for a gas in contact with its own liquid (2) for gas with solid (3) for liquid with solid the three curves must as the author has shown all meet in one point termed therefore by him the triple point. He bats also deduced from theore- tical considerations that the curves for gas-solid and for gas-liquid must intersect at the triple point in an angle re-entrant from the side of the axis of pressures.The latent heats of ice and of steam supply data for a calculation proving that for any very small fall in temperature from the triple point (where the pressure of steam-ice is the same as that of steam-water) the former pressure fa<lls off 1.13times as much as the latter. On closely examining Regnault’s experimental results on the pressures of steam at different temperatures the author finds distinct indications of the re-entrant angle and he has even calculated from Regnault’s figures the ratio of the inclinations of the tangents at the point of intersection of the two curves obtaining thus the value 1.10 which agrees well with the former a remarkable result when we consider that Regnault himself was fully persuaded of the continuity of the curve of pressures through the freezing point as elsewhere.R.R. Experimental Researches on Explosive Substances. By Roux and SARRAU (Compt. rend. lxxix 757-760) THEauthors have previously shown that two different kinds of explo-sion can be produced by dynamite according as the substance is made simply to deflagrate (explosion of the second order) or to detonate by the percussion of fulminate of mercury (explosion of the first order) and that the force of the explosion produced by the same quantity is very different in t’he two cases. They now find that the majority of explosive substances gunpowder included possess the same remark- able property. The reciprocal of the weight (due corrections made) of each sub-stance which when exploded in one and the other manner sufficed to rend similar small cast-iron shells gave the relative explosive forces.Some results of the experiments are given in the following table the explosive force of gunpowder ignited in the ordinary manner being taken for unity:- GENERAL AND PHYSICAL CHEMISTRY. Name of substance. Explosive force. 2nd Order. 1st Order. Mercury fulminate. ........... -9.28 Gunpowder. ................. 1.00 4.34 Nitroglycerin ................ 4.80 10.13 Pyroxyl (gun-cotton) ........ 3.00 6.46 Picric acid .................. 2.04 5-50 Potassium picrate ............ 1.82 5.31 Barium picrate .............. 1-71 5.50 Strontium picrate ............ 1*35 4 51 Lead picrate.. ................ 1.55 5.94 Of the highest practical importance is the discovery of the detona- tive explosion of gunpowder induced by the detonation of nitro-glycerin (itself set off by fulminate of mercury) for the force of the explosion is more than fourfold greater than that obtained by igniting gunpowder in the ordinary manner.* The authors observe that the mass of the substance employed for exciting detonation must usually bear a certain proportion to that of the substance to be exploded but in some cases the action is propagated throughout the latter when once up at any point.R.R. The Mathematical Theory of Isornerides. By Prof. CAYLEY (Phil. Mag. [4] xlvii 444-447). THISpaper describes a mode of so representing the linking of the atoms in chemical compounds as to permit of treating mathematically the determination of the number of possible isomeric combinations in a given case.The method is however practically limited in its applica- tion by the great complexity of the question. R. R. On Diffusion between Dry and Moist Air. By E. REUS c H (Pogg. Ann. cli 365-366). THEnotice by Dufour (Naturforscher vii 242) on the diffusion through a porous septum between dry and moist air recalled to the author an observation that he had made witha diffusion tube closed by a plate of hydrophane. The tube was filled with hydrogen and after the level of the water had risen to a maximum it gradually sank the level inside ultimately being below that of the outside. This is now satisfactorily explained by the more rapid diffusion through the porous septum of the exterior dry air than of the interior air which is moist.C. E. G. * The increased force of gunpowder and gun-cotton when exploded by the agency of detonation was fully demonstrated by Abel six years ago (PhiZ. Trams. 1869; Chem. SOC.J. xxiii 41).-E~. w 2 ABSTRACTS OF CHEMICAL PAPERS. An Improved Apparatus for Fractional Distillation. By J. A. LE BELand A. HENNINGER (Deut. Chem. Ges. Ber.,vii 1084-1086). THEapparatus which it is not easy to describe without the aid of the figure consists of a tube having two or more bulbs blown upon it. The lower end of the tube is inserted into the neck of the flask in which the liquid is boiled whilst from near the upper extremity a lateral tube conveys away the vapour to the condenser.lmmediately below each bulb there is a slight contraction so that as the less volatile constituents of the vapour condense in passing through the bulbs the liquid formed may lodge there and the vapour in order to pass higher must bubble through it. The accumulation of the liquid in the bulbs beyond a certain height is prevented by sealing into the lower part of each bulb a narrow tube which curving downwards in the form of an inverted syphon carries the excess of condensed liquid into the bulb beneath. In the hands of the authors this apparatus hams been found very effective. W. A. T.

ISSN:0368-1769    

DOI:10.1039/JS8752800119

出版商:RSC    

年代:1875

数据来源: RSC

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ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. The Formation in Nature of Nitrous Acid Nitric Acid and Hydrogen Peroxide By L. CARIUS(Ann. Chem. Pharm. clxxiv 31-55). CONTINUING his former line of investigation the author states that experiments to ascertain whether ozone in presence of aqueoiis vapour can at higher temperatures (120"-210") act upon free nitrogen gave completely negative results for no nitrogen-acids or ammonia. could be detected. The alleged formation of ammonium nitrite by the evapora- tion of water in air or by the condensation of its vapour was tested by causing purified air to stream through water in a retort heated to temperatures ranging from 45"to 100". Each experiment lasted several days but not the least trace of the nitrogen compound was found.After having made ozonised oxygen pass for a long time through a very dilute solution of ammonia the author was able to prove the pre- sence in the liquid of nitric acid nitrous acid and hydrogen peroxide. During the experiments a thick white smoke or cloud formed of part of the oxidation-products was observed above the liquid and the author refers to the great inconvenience this smoke occasioned him wying that it repeatedly caused violent coughing and illness. The equation representing the formation of the nitrous acid is- (NH3)2 + ((&)*= N(NHJ02 + OzHz + (OZ)~ while the nitric acid may originate thus- (NHJ)~+ (03)d = N(NH,)Os + OH2 + (02)a; but it is more probably prodnced wholly or in part by oxidation of IXORGANIC CHEMISTRY.the nitrous salt through the well-known action of the hydrogen peroxide The first equation gives a satisfactory explanation of the observed simultaneous occurrence in nature of ammonium nitrite and hydrogen peroxide and the experiments prove that ozone must play an important part in the production of nitrous and nitric salts. One result of the author’s researches is to reduce the known natural pro-cesses by which these acids are formed to the following five:- From free nitrogen (1)by electrical discharges ; (2) in the oxidation of other bodies. From ammonia through its oxidation (1) by electric discharges ; (2) by the presence of alkaline substances ; (3) by ozone. R. R. Polythionic Acids. By W. SPRING (Deut.Chem. Ges. Ber. vii 1157-1163). WHENbenzene-sulphonic chloride acts on potassium sulphide sulphur is separated at first but this soon disappears with production of a salt of benzene-hyposulphonous acid. This separation of sulphur renders it probable that the reaction does not take place as Blomstrand supposes but in two stages as follows:- (1.) c6H’,.sO2.c1 + K2S = C6Hs.SOZ.K + KCl + S. (2.) C6Hs.SOzK + S = C~HS-S~O~K. As a confirmation it may be mentioned that the liquid filtered from the precipitated sulphur was found to contain a salt of benzene-sulpho- nous acid and this readily unites with sulphur and form benxene- hyposulphonous acid. Phosphorus sulphide acts on ammonium sulphate with production of ammonium sulphide which sublimes and ammonium hyposulphite (thio- sulphate) with a small proportion of ammonium trithionate.Ammo-nium thiosulphate can also be formed by the direct action of ammonium sulphamate on sulphydric acid but an attempt to form it by the action of sulphuric anhydride ammonia and sulphydrio acid on one another failed a crystalline substance which is now under investigation being formed. These results appear to support the old view as to the con- stitution of hyposulphurous (thiosulphuric) acid. The ammonium trithionate which is formed during the action of phosphorus sulphide on ammonium sulphate probably arises from the decomposition of ammonium thiosulphate- This reaction is confirmed by the fact that many double thiosul-ghates partially split up into sulphides and trithionates when their solutions are boiled.2AgKS20 = hgaS + I<2S3060 When a solution containing sodium sulphide and sodium sulphite is treated with iodine a thiosulphate is formed Na2S + Na,S03 + 1 = Na2S,03+ 2Na1 and when a solution containing sodium sulphite and ABSTRACTS OF CHEMICAL PAPERS. sodium khiosulphate is similarly treated a trithionate is formed, Na$3O3 + N&SZO3+ I = N+S306 + 2NaI. Dithionates were not formed by the action of iodine on sulphites sulphates being formed by oxidation. Sodium amalgam converts a solution of a thiosulphate into sulphite and the author does not regard this as the simple abstraction of sulphur but as the breaking up of the group Sz by the insertion of sodium between the atoms of sulphur this view being founded on the following reaction in which two double salts are formed KzS203 + Na,=KNaS + KNaS03.Sodium dithionate is very slowly acted on by sodium-amalgam sulphite being formed N&Se06 + Naz =2NhS03 while trithionates yield thiosulphates and sulphites K2S30s+ Naz = KNaSZO3+ KNaS03. When a mixture of mercaptan and sodium sulphite is treated with iodine the sodium salt of the acid ether of thiosulphuric acid remains. This is identical with the salt obtained by Bunte and when it is heated with sodium-amalgam mercaptan and a sulphide are repro-duced C2H5.Na.S2O3 +Na + K =CzR5.SH + Na2S03. But its treat- ment with phosphorus pentachloride leads to the production of a very unstable chloride which probably contains C2H5S2OzCI2, and easily splits up into ethyl disiilphide sulphurous anhydride and sulphuryl chloride.With soda it yields the original salt. An ethyl-hyposulpho- nite of sodium CZH5S2O2Na can be formed by the action of ethyl-sulphonic chloride on sodium sulphide and the action of sodium-amalgam on this may be represented as follows :-(1.) C2H5.SZOzNa + Na2 = C2H5.SNa+ Na2SO2. (2.) N&S02 + 2Naz + 2H20 = Na2S + 4NaHO. Its treatment with phosphorus-pentachloride gives rise to a chloride which probably contains C2H5SzOCl,and easily decomposes with depo- &ion of sulphur ; but soda converts it into the original salt. T. B. Formation of Sulphates by Gas-flames. By E. PRIWOZNICK (Ding]. Polyt. J.,ccxiii 223-229). A WHITE incrustation is always formed after some time on tiis glass covers hung over gas-flames consisting of small crystals of neutral ammonium sulphate with a trace of soda and potash.The sulph~r which when burned produces the sulphuric acid does not exist as sulphuretted hydrogen but as carbon disulphide. The ammonia is not a product of combustion for if a basin whose lower surface is moistened with hydrochloric acid be held over a burning gas-flame no fumes are visible and even with Nessler’s reagent no ammonia is found. But gas unburnt contains a small quantity enough to give a yellow colour to Nessler’s reagent. The author supposes that the ammonia arises from the nitrogen of the air for Saussure has shown that ammonia is formed when hydrogen is burnt in oxygen containing nitrogen.Schonbein proved the presence of ammonium nitrite in the products of combustion of fat and coal-gas. The carbon disulphide in the gas would burn to carbonic and sulphurous anhydrides. But INORGANIC CHEMISTRY. sulphurous anhydride cannot exist in presence of ammonium nitrite but is immediately oxidised to sulphuric acid and combines with the ammonia. The glass cylinder of an argand lamp is also often covered with a white incrustation. This consists mainly of potash soda lime &c. from the ash of particles of dust derived from the air. W. R. Aotion of Sulphur on Calcium Carbonate. By E. POL LA c c I (Gazzetta chimica italiana iv 177-1 79). THE author found that if a mixture of sulphur and calcium carbonate be moistened with water and allowed to dry repeating this operation several times it will contain calcium sulphate.Cossa (ibid.,26) on the contrary finds t,hat an intimate mixture of sulphur calcium car- bonate and water does not contain any calcium sulphate even after standing for three days at the ordinary temperature or after being boiled for eight or ten hours. This apparent discrepancy is accounted for by the fact that the calcium sulphate results from oxidation of the snlphur by the oxygen of the atmosphere during the drying of the mixture. It is generally stated that the ~ulphuret~ted hydrogen which passes into the atmosphere from various natural sources combines directly under the influence of a gentle heat arid B moist atmosphere and in presence of porous substances with oxygen to form sulphuyic acid.The author however believes that the first action is to form water and liberate sulphur which in prmence of the calcium carbonate of the soil becomes oxidised with production of calcium sulphate. C. E. G. Action of Sulphur on Calcium Carbonate. By G. BELLUCCI (Gazetta chimica italiana iv 179-182). INorder to obtain evidence as to the action of sulphur on calcium car- bonate at the ordinary temperature the author made experiments with mixtures of sulphur both commercial and that precipitated by hydro-chloric acid from sodium polysulphide with precipitated calcium car- bonate crushed marble and a calcareous earth containing 18-61per cent. of calcium carbonate and 9.29 of organic matter. All the sub-stances were proved to be free from sulphuric acid and the mixtures were kept constantly moist and covered with glass.The results of various experiments made under these circumstances tend to show that calcium sulphate is produced after a long time (75 to 80 days) whilst with the calcareous earth in presence of organic matter the action takes place in less time (30 to 35 days). The amount of snlphate formed however is but small. c. E. G. Precipitation of Zinc by Water. By J. L. Dnvi E s (Chem. News xxx 163). IFto a solution of zinc chloride a quantity of ammonia be added just sufficient to redissolve the precipitate at first formed the addition of ABSTRACTS OF CHEMICAL PAPERS. water throws down zinc in the form of a gelatinous and bulky precipi-tate.In the cold the precipitation of the zinc is not complete. H. J. H. Compounds of Mercuric Sulphide. By KARL HEUMANN (Deut. Chem. Ges. Ber. vii 1388-1390). CINNABAR when treated under water with copper powder yields a black mixture of copper sulphide metallic mercury and unchanged metallic copper which after prolonged boiling with nitric acid is converted with an almost sudden change of colour to white into a molecular combination 2HgS.Hg(N03)2 identical with that obtained by precipi- tating a mercuric nitrate solution with a small quantity of hydrogen sulphide. On addition of alkalis this compound blackens in conse-quence of its breaking up into RgS and HgO from which mixture the original combination 2HgS,Hg(N03)2 can be regenerated by boiling with nitric acid.Palm’s statement that red molecular combinations can also be obtained by several hours’ treatment of cinnabar with concentrated solutions of HgC12 Hg(NO& HgSOh Hg(C2H30& has not been confirmed by the author. R.S. Action of Cupric Chloride on Mercuric Sulphide. BF KARLHEUMANN (Deut. Chem. Ges. Ber. vii 1390-1392). BY digesting cinnabar or precipitated mercuric sulphide with cupric chloride and hydrochloric acid sufficiently concentrated to favour the formationof cuprous chloride the author obtained a brilliant orange- jellow powder to which from its analysis and reactions he assigns the Hg-S-Cu-C1 formula I whilst the formation of the compound is Hg-S-Cu-Cl explained by the equation- SHgS + 2CuC12 = Hg2S2CuzC12 + HgCIz -+ S Concentrated boiling hydrochloric acid dissolves out C uC1 and Hg Cl,? and boiling sulphuric acid decomposes the compound with evolution of HC1 and SO2.No effect is produced by these acids in the cold On the addition of sodium hydrate the substance is con-verted into a black powder from which warm hydrochloric acid extracts much mercury and little copper thus indicating the presence of HgO and Cu2S R decomposition which would not be in agreement with the formula given above. But as it was found that a mixture of HgS and Cu20 soon yields HgO and Cu2S,it may be concluded that the primary products of the decomposition were indeed mercuric sul-phide and cuprous oxide which then ky their mutual action passed into a mixture of HgO and CU~S which to hydrochloric acid would yield mercury but no copper.R. S. INORGANIC CHEMISTRY. Behaviour of Cuprous Sulphide to a Solution of Silver Nitrate. By R. SCHNEIDER (Pogg. Ann. clii 471473). A SOLUTION of silver nitrate of known strength was added to a weighed quantity of cuprous sulphide until a drop of the supernatant liquid gave with a drop of hydrochloric acid a distinct silver reaction. It was then determined how much silver could be extracted from the greyish precipitate by nitric acid of sp. gr. 1.18 and how much re-mained undissolved. The numbers obtained show t'hat the decom- position between cuprous sulphide and silver nitrate takes place according to the equation- CUZS + 2(AgJT20 = ~(CUN~O~) + AgzS + 2Ag.R.S. Action of Iodine on Arsenious Acid. By M. WEGN E R (Ann. Chem. clxxiv 129-133). ACCORDING to Zinno an iodarsenic acid is formed by adding iodine to a hot aqueous solution of arsenious acid as long as it dissolves without colour and evaporating the solution to crystallisa,tion. The crystals thus obtained are however nothing but arsenious oxide containing a trace of hydriodic acid. When iodine is dissolved in a hot solution of arsenious acid the latter is oxidised and arsenic acid and hydriodic acid are formed which act on each other again when the solution is concentrated free iodine and arsenious acid being regenerated. c. s. Bismuth Bromide. By R. W. E. MACIVOR (Chem. News xxx 190). BISMUTH bromide is prepared by heating finely powdered bismuth with dry bromine in a hand-glass tube closed at the end.It is a dark-grey solid melting at 198"-200" to a dark red liquid which boils below a dull red heat. It is insoluble in carbon disulphide alcohol and ether. Hydrochloric acid dissolves it but it is decomposed by heating with nitric acid. On treatment with water it is decomposed into free hydro- bromic acid and a white amorphous oxybromide and the latter by long continued washing is converted into hydrobromic acid slid bis- muth oxide. H. J. H. Alleged Nuclear Action of Gold upon Gold reduced from Solution by Organic Matter. By W. SKEV(Chem. News xxx 162). INa paper on the formation of gold nuggets which appeared in the Tynnsactions of the Royal Society of Victoria,the author Mr.Wilkinson states that '(Mr. Daintree formerly of the Geological Survey of Victoria had on one occasion prepared for photographic use a solution of gold chloride leaving in it a small piece of metallic gold undissolved. ABSTRACTS OF CHEMICAL PAPERS. Accidentally some extraneous substance supposed to have been a piece of cork had fallen into the solution decomposing it and causing the gold to precipitate which was deposited in the metallic state as in the electro-plating process around the small piece of undissolved gold increasing it in size to two or three times its original dimensions.” The author has made numerous experiments to reproduce a similar effect but with negative results. From the careless way in which the above solution appears to have been kept and from the fact that the size of the piece of gold was judged only by the eye he considers tlie evidence as to its alleged enlargement to be very unsatisfactory.H. J. H. Note on a Palladium Salt. By F. W~HLER (Ann. Chem. clxxiv 199-200). ON adding sulphurous acid to a solution of palladium dichloride the liquid becomes pale-yellow ; on the addition ofsoda a bulky precipitate is formed which soon becannes crystalline. It is soluble in an excess of soda and sulphurous acid and is decomposed by boiling water and by heat. Its composition is PdSO + 3Na2SO3 + 2H20 and corre- sponds therefore with the known platinum-salt. c. s.

ISSN:0368-1769    

DOI:10.1039/JS8752800128

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

ABSTRACTS OF CHEMICAL PAPERS. 134 Min er a1o gi c a1 C h e mi s t ry. The Vermiculites ; their Crystallographio and Chemical Relations to the Micas ; together with a discussion of the Cause of the Variation of the Optic Angle in these Minerals. By J. P. COOKX,Jun. (Phil. Mag. [4],xlvii 241-2 72) VERMICULITE is the name given by Webb to a mineral from Millbury near Worcester Mass. which "when heated exfoliates prodigiously the scales opening out into long worm-like threads made up of the separate lam in^," According to an analysis of Crossley it consists of- Oxygen. Ratio. Silica.. ........ 35.74 true. 19.06 19.06 VP. 11 Alumina ...... 16.42 7-65 7.65 4 Ferric oxide .,.. Magnesia ...... Water ........ Ferrous oxide . . 27.44 10.30 9.16 -10.02 li::i} 9.16 -13.21 5 -7 99.92 The author finds however that the iron exists almost entirely in the ferric date.and that the anaiysis should be :- MINERALOGICAL CHEMISTRY Oxygen. Ratio. true. &PP* Silica. ......... Alumina ...... Ferric oxide. ... Ferrous oxide . . 35.74 16.42 11.13 - 19-06;:ti} - 19.06 10.99 - 2 1 - Water ........ Magnesia ...... 10.30 27.44 9.16 10-98 9.16 10.98 1 1 101.03 From this it results that the true atomic ratio is 2 1 1 1. The author applies the term vermiculite as a generic name and in- cludes under it several other minerals such as Jeff erisite Culsageeite and Hallite the whole forming a family of hydrous silicnt es closely allied and parallel to the family of anhydrous silicates known as micas.The exfoliation of these minerals is due to the escape of water of crystal-lisation and is analogous to the intumescence which takes place on heating alum borax &c. That this water is water of crystallisation and not of constitution is shown by its being driven off at a tempera- ture below a red heat by the complete disintegratiou of the mineral when the water is expelled and by the fact that the amount of the basic radicals exclusive of the hydrogen is sufficient to saturate the silicon and that the amount of hydrogen is wholly in excess of the amount which the atomic ratio 1 1requires. The vermiculites are probably orthosilicates. The variation of the optic angle is shown to be due to the macling of the ~rgst~als. A plate which presented the largest optic angle was divided into as thin laminae as possible and these laminae were then superimposed so that the planes of the optic axes were inclined at an angle of 60".The result was that a symmetrical ring system mas obtained in which the optic sngle was very small. By introducing laminae into the compound crystal in the position of the third member of the macle (that is with the plane of the optic axes in the position of the third diagonal of the hexagon) the apparent angle could be reduced still further so that the plate was apparently uniaxial. From hexagonal laminae cut from other specimens of mica and opti- cally parallel plates were prepared showing the familiar system of rings as perfectly as could be expected. The best results were obtained with plates consisting of from twelve to twenty-four laminae and the character of the resulting plate whether left or right-handed mas found to depend on the order of the spiral arrangement.If in building up the pile the marked side of each successive lamina is turned through an angle of 60" in the direction of the motion of the hands of a watch the result corresponds with left-handed quartz ; if it is turned in the reverse direction with right-handed ; and on super- posing two dissimilar plates thus prepared the spirals of Airy were obtained in great perfection. Thus with micas of the widest optic angle we can build up a structure which is optically uniaxial. Since the process of twinning produces hexagonal crystals in external form as well as in optical characters may not the hexagonal crystals of other minerals be formed in a similar way ? that is may they not be ABSTRACTS OF CHEMICAL PAPERS.developed from twinned molecules which though in their aggregate producing hexagonal structure singly would develope into biaxial crystals ? May not the whole difference between a hexagonal and a rhombic form arise from a slight difference of dimensions which deter- mines a molecular macling in the one case and a normal development of the single molecules in the other ? A further account of the author's theory would require the reproduc- tion of' the plate which accompanies the paper. The composition and mineralogical characters of the varieties of vermiculite and other minerals are detailed at length in the paper and it is shown that the observations of SBnarmont (Ann.Chim.et Phys. [S] xxxiv 171) on the variation of the optic angle of the micas are not necessarily invalidated by the new theory. G. T. A. Association of Garnet Idocrase and Datolite. By J. LAWRENCE SMITH(Compt. rend. lxxix 813). MASSES of calc-spar containing the above three minerals were found in Santa Clara California. The datolite is colourless and crystalline. Sp. gr. = 2.988. It has the composition:- Si02. B03. CaO. HzO. 38.02 21.62 33-57 5-61 = 99.12 The garnet is the variety called cinnamon-stone. It occurs in very large and perfect dodecahedra1 crystals green at the exterior and of a cinnamon colour in the interior. Sp. gr. = 3.59.Its composition IS :-XiO* Also$. Fez03. MnO. CaO. MgO. 42.01 17.76 5.06 0.20 35.01 0.13 = 100.17 The idocrase occurs in fibro-compact green crystals. It penetrates the garnet but there is no possibility of distinguishing the limits of either so imperceptible is the gradation. Its specific gravity = 3.445. Composition :-SiOz. A1203. Fe,03. MnO. CaO. MgO. K20. HZO &c.. 36.56 17.04 5.93 0.18 35.94 1.07 0.51 2.00= 99.23 Smith considers the above to be an unexpected association especially when the respective formulae of garnet and idocrase are compared. Des Cloizeaux states however that the greyish limestone of the Hautes- Pyr&n&es contains crystals of brown garnet penetrated by dull green idocrase. B. J. G. Tellurium Ores of Colorado.By B. SILL~MAN (Amer. J. of Sci. [3] viii 25-29). AFTER a short account ofthe geological position of the ores the follow- ing species are described :-Hessite. -Sp.gr. = 8.6. Lustre bright metallic when Au~fe~ous OROA NIC CHEMISTRY. fresh. Fracture conchoidal. Brittle yet slightly malleable. Lami-nates under the pestle and leaves streaks resembling plumbago. Colour telluric ; tarnishes blackish on exposure. Heated in a closed tube it decrepitates then fuses evolves a white sublimate which melts to clear colourless globules. Alone on charcoal in either flame it gives a globule surrounded by an areola of tellurium and tellurous acid ; with soda it gives a bead of silver which on solution in nitric acid leaves gold in powder. By cupellation it yielded gold 6.4 and silver 50.9 per cent.XyZvanite.-Sp. gr. not determined. Ileated in an open tube it iudi-cates selenium and tellurium ; alone on charcoal the same ; probably contains lead and antimony. Its reactions differ from those given by Berzelius for sylvanite. By assay it yielded gold and silver in the proportions of 1.7 to 1. These metals exist in the ore as minute particles or so finely divided as to produce the effect of R stain upon the rocks. One specimen yielded by assay 1,890 ounces gold and 5,300 ounces silver per ton of 2,000 lbs. Native TeZZurium.-Occurs only in very small quantities ; cleavage perfectly hexagonal. Contains no selenium and but a trace of gold. C. H. P.

ISSN:0368-1769    

DOI:10.1039/JS8752800134

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

OROANIC CHEMISTRY. Organic Chemistry. On the Processes which take place in the Imperfect Com-bustion of Illuminating Gas and on the Behaviour of Coal Gas when heated without Access of Air. By R. BLOCHMANN (Ann. Chem. Pharm. clxxiii 167-191). TEEexperiments were made with a Bunsen's burner so arranged that the mixture of gas and air burned inside the tube and the unburnt gases were drawn off at the top. The following table shows the com-position of the gas itself of the gases drawn off from the top of the burner above the flame and of the air :-Gases from top Gas. of burner. Air. H.. ........................ 49.04 11-63 - CH ........................ co ........................C,H ...................... 36.52 5-57 - 17.16 5.91 0% I - CZH4 ......................3.88 0.80 - C,H ...................... 0.......................... 2.96 - 0.33 - 20-96 - N .......................... 0.96 59.24 79.00 CO,.. ...................... 1.07 3.97 0.04 100~00 100*00 100~00 H,O ...................... 1.76 22.05 0.91 -.__ 101.76 122.05 100.91 'pecific gravity Found .....{Calculated.. 0.412 0.410 0.815 0.818 -1.000 138 ABSTRACTS OF CHEMICAL PAPERS. The relative volumes of gas and air used were 58.91 to 41.09 iind the composition of this gaseous mixtme with respect to its several constituent,s before and after combustion was as follows :-Before combustion. After cornbustion. H ............ 19.91 9-14 CH .......... 14.82 13.49 co .......... 2-26 4-54 C2H .......... -0.75 C2H4 ..........1-57 0.63 CIH,. ........ 1.20 0.26 N ............ 46-54 46.54 0 ............ 12.25 co .......... 0.45 3.02 H,O .......... 1.00 17.33 100~00 95.80 ConOrsc tion. ....... . 4.20 The acetylene and part of the carbonic oxide are no doubt formed from the decomposition of the heavy hydrocarbons and it will be noticed that the oxygen during this imperfect combustion has not acted on any single and definite constituent of the mixture but has influenced all. The acetylene is formed from ethylene thus :-C2H,= C2Hq+H2. The peculiar smell of the reduced flame is due to this formation of acetylene and may serve to detect flames which would otherwise escape notice and which gradually poison the air by the production of carbonic oxide.The way in which the gas and air mix inside the tube may be watched by replacing the metal tube by a glass one of similar proportions. Coal gas was next passed through a porcelain tube heated to nearly 1000”,as was estimated by means of srnall pieces of metals and alloys the melting points of which are known. .The following table shows the composition of t.he gas before and after the expei*imeiit :-Before passing through the heated tube. Sfter. H .......... 49.57 61.96 CH,.. ........ 36.92 30.49 co .......... 5.63 5-26 CZHa ........ 3.92 CIH ........ 2.99 N ............ 0.97 100*00 100*00 CZH ........ 0.06 0.11 The increase in the amount of hydrogen during combustion arises from decomposition of the heavy hydrocarbons and on careful exami- nation of the tube a deposit of carbon was found inside.In the glass tube leading from the porcelain tube a deposit of ORGAXIC CHEMISTRY. 139 naphthalene was found the production of which is explained by the equations :-EiCZH = 5CzH2 + 10H. 5CzH2 = CIOHLO = CIoH + H,. G. T. A. Preparation of Iodine Substitution-products. By P. WEs E L s K Y (Ann. Chem. Pharm. clxxiv 93-111). THEauthor finds that the method proposed in 1869 by Hlasiwetz and himself of obtaining these compounds by treating organic bodies with iodine together with such oxides as HgO PbO is applicable only to certain classes of bodies belonging to the aromatic group. The process is however remarkable for the facility with which the products are obtained and he describes the preparation by it of iodine-compounds of salicylic oxybenzoic and para-oxybenzoic acids and of other bodies.He has also thus obtained for the first time iodine substitution-pro- ducts of the mono-nitro derivatives of these three isomeric acids. Each of the new iodated nitro-acids forms in the pure state bright yellow crystals and gives rise to potassium and barium salts of a deep red colour. R.R. Action of Bromine on Methyl Acetate. By A. STEINER (Deut. Chem. Ges. Ber. vii 1284-1286). THE author formerly stated that by acting with bromine on ethyl acetate ethyl bromide and bromacetic acid are produced while methyl acetate is but slowly attacked and yields substitution-products of which a crystalline hex-compound was isolated.He has now found that this compound is nothing but pentnbromacetone which was derived from some acetone contained in his supposed pure acetate. Acetone adheres obstinately to this ether and cannot be removed by washing with water or by distillation. If in a product thus purified an acid sulphite does not show the least trace of acetone its presence can easily be detected by bromine. Pure methyl acetate can be obtained only by using methyl alcohol prepared from the oxalate. c. s. On the Constitution of Ethyl Sulphite. By A. MICHAEL IS and G. WAGNER (Deut. Cbem. Ges. Ber. vii 1073-1075). ACCORDING to Strecker's formula for sulphurous acid SO2 ffiro isomeric compounds may be produced by the replacement Gf an atom of hydrogen by B metallic or other radicle.When both ato IS of hydrogen are replaced by the same radicle oftly one compound can 1 esult. Thus there can be only one ethyl ether of the formula ~ ~ SO,. ~ o Two isomeric compounds of this composition are however knowr ;the one ethyl sulphite which boils at 16l",the other the ethylic ether of ethyl 140 ABSTRACTS OF CHEMICAL PAPERS. sulphonic acid boiling at 207". The latter considering its formation from sodium ethylate and sulphuric chlorethylate must have the formula SO,{ OC,Hs' Hence the former must be represented as SO C2H5 corresponding with the normal acid SO { EE. This constitution is established by the experiments detailed in the present paper. The action of phosphoric chloride on ethyl sulphit,e may be repre-sented by the following equation :-The ethoxyl-thionyl chloride thus obtained is a colourless liquid the greater part of which distils over at 122".It is isomeric with ethyl sulphonic chloride which boils at 171". It is easily decomposed by water into sulphurous and hydrochloric acids and alcohol. It is not attacked by phosphoric chloride below 180" at which temperature it yields phosphoric oxychloride ethyl chloride and thionyl chloride SOCI,. From thionyl chloride ethyl sulphite can be obtained by the action of alcohol. Thus it has been shown that ethyl sulphite contains two ethoxyl groups exchangea,ble for chlorine ad henAe its formula must be SO { E::?. W. A. T. Action of Phosphorus Pentachloride on Ethene-disulphonic Acid.By W. KOENIG(Deut. Chem. Ges. Ber. vii 1163-1164). WHEN potassium ethene-disulphonate is treated with phosphorus pen- tachloride the corresponding chloride is obtained. Ethene-d-isdphonic chEoride melts at 91" decomposes at 150" and separates from ether in needles. Alcohol decomposes it with production of ethyl chloride and sulphurous acid and when it is heated to 150"-160" with phosphorus pentachloride a liquid is produced which boils at 125"-127" and has the composition of chlorisethionic chloride ; and when chlorisethionic chloride is heated to 200' with phosphorus pentachloride ethene chloride and other products are slowly formed. T. B. Singular Formation of an Ethidene-compound. By F. BATJMSTARK (Deut. Chem. Ges. Ber.vii 1172-1175). WHENethene di-iodide is prepared by passing ethene into a warm mix- ture of absolute alcohol and iodine an odour resembling that of mustard-oil is given off which is due to the formation of an oily bye-product. To obtain this body in quantity etheiie is passed into a solution of iodine in absolute alcohol containing an excess of iodine at 60"-65" until all the iodine is combined. Then the solution is heated to 70"- ORGANIC CHEMISTRY. 75" as long as ethene is given off and after adding more iodine the whole process is repeated several times. After precipitating the oil with water it is washed dried and distilled. It has the composition C,H,IO and when freshly prepared is a colourless oil having a peculiar sweetish pungent and stupefying odour and boiling at 154"-156".It has a burning taste and its vapours produce giddiness and headache. On heating it with sodium ethylate to 150" it yields acetal and some aldehyde and ether. This reaction shows that it is an ethidene-cornpound CH3.CHI(OC2H,). As it is also obtained by heating ethene diiodide with alcohol to 70° it seems to be formed according to the equation CzHa.I2,+2(CzH,.OH) = C2H4 + HI + H20 + C2HJ.OC2H5. c. s. Some Derivatives of Secondary Butyl Alcohol. By S. REYbTANN (Deut. Chem. Ges. Ber. vii 1287-1290). HALF a hundredweight of Roc.ce1la timctoria var. fucvormis yielded by Stenhouse's method 430 grams of erythrite and from 300 grams of this body 410 grams of secondary butyl iodide were obtained. B.utyl mercaptan was prepared by digesting the iodide with an alco- holic solution of potassium sulphhydrate.It is a mobile liquid smelling like asafcetida boiling at 84°-850 and having at 17' the spec. grav. 0.8299. On mixing its alcoholic solution with one of mercuric chloride a white amorphous precipitate is formed which crystallises from boiling alcohol in greasy scales melting at 189" and consists of (C4H9S)Hg. The silver mercaptide C4H95Ag is a similar body forming very small and slender needles. The copper compound is a yellow precipitate which easily decomposed and the lead-salt farms a yellow smear. Butyl sulphide (C,H,),S is a mobile liquid boiling at 165" and having an alliaceous odour ; its spec. grav. is 0.8317 at 23". By the action of methyl iodide no dibutylmethylsulphine iodide was formed but a complete decomposition took place and a crystalline solid pro- bably trimethylsulphine iodide was formed besides other products.Hofmann has shown that the mustard-oil or sulphocarbimide of the secondary butyl is identical with the oil of scurvy-grass ; as a further proof of this the author found that both yield the same butylamine which boils at 63". It precipitates the salts of lead magnesium copper silver and aluminium like the normal amine; but while the latter re- dissolves the silver- and copper-precipitate the secondary amine dis- solves only the hydroxides of silver and aluminium but neither that of copper nor that of zinc which is fioluble in isobutylamine. From the latter it differs also by not acting on oxalic ether even at looo while isobutylamine forms with it isobutyloxamide in the cold.When the secondary butylamine is heated with the iodide a large quantity of butene and its polymerides is formed together with a small quantityof the diamine and triamine but not a trace of the quarternary base could be obtained. While therefore the normal alcohols readily yield the four ammonia-bases the primary isobutyl alcohol can be converted only into the three amines ; the secondary alcohol yields the triamine only VOL. XXVIIT. L ABSTRACTS OF CHEMICAL PAPERS. with difficulty and the tertiary alcohol can only indirectly be converted into the monamine. c. s. Derivatives of Malonic Acid. By C. OSTERLAXD (Deut. Chem. Ges.Ber. vii 128G-1287). MethyZ m.aloaate CsH2(CH,),Od which was obtained by treating the silver-salt with methyl iodide is a mobile liquid having an ethereal smell and boiling at 175"-180°. Its spec. grav. at 22" is 1.135 ; it is insoluble in water and gradually decomposes when left in contact with it. By the action of aqueous ammonia it is converted into mdonnmide C3H,(NH2)O2, crystallising from hot water or alcohol in silvery needles. On boiling it with dilute ammonia it is gradually converted into ammo- nium malonamate. c. s. Non-chlorinated Derivatives of Monochlorocitramalic Acid. By T. MORAWSKI (J.pr. Cbem. [el x 68-89). THEsalts of monochlorocitramalic acid and likewise the acid itself are decomposed by boiling with water with production of an acid identical with the citratartaric acid of Carius C,H806.If monochlorocitramalic acid be dissolved in boiling water baryta water added in excess and the liquid be boiled a,s long as carbon dioxide is evolved then quickly filtered a salt crystallises out on cooling from which by decomposition with hydrochloric acid an acid is obtained which the author calls ooycitraconic acid. This acid has the composition C5H6O5, forms two series of salts C,H,RO and C,H4&0, in which R represents one atom of a univalent metal. The author describes the sodium potassium ammonium calcium barium and okher salts of this new acid. Bro-mine has no action on this acid; neither is it acted upon by sodium amalgam. M. M. P. M. Action of Ammonium Sulphide on Chloral Hydrate.By EDMUND DAVY(Phil. Mag. [4] xlviii 247-251). WHEN ammonium sulphide is added to an aqueous solution of chloral hydrate the mixture rapidly acquires a yellow tint and passing through several shades of colonr becomes finally dark brown. From this liquid dilute sulphuric acid separates a voluminous brown precipitate. The latter having been purified by washing &c. in the usual way was submitted to examination. It was exhausted with carbon sulphide in order to remove free sulphur and then dried at 100" until it ceased to lose weight. After this treatment it presents the appearance of an amorphous light brown earthy powder slightly soluble in water alcohol and carbon sulphide,.practically insoluble in chloroform and benzene but readily soluble in solutions of caustic alkali and alkaline sulphides from which it is reprecipitated on the addition of an acid.When ORGANIC CHEMISTRY. ignited on platinum foil it evolves a peculiar odour and taking fire produces a large carbonaceous residue which slowly burns away. From the results of its analysis the formula CleH,S13N406is cal-culated from which it is supposed that the following reaction takes place-9(C,HC13O.H,O) +I6(NH4),S + 2H2S = C,~H,,SI~N,O~ + 27NH4Cl + NH3 + S + 12HzO. The actual numbers obtained in the analysis are not given. The author states that this sulphur-compound prepared in the above manner does not agree in its properties with the yellow substance described by Walz as the result of the action of ammonium sulphide on chloral hydrate but as the latter substance was not analysed he is unable to draw any further comparison between them.J. W. Dibrornacrolein. By L ou I s HEN RY (Deut. Chem. Ges. Ber. vii. 1112-1113). THEauthor prepared dibromacrolein C3H40Br2,in tlhe hope of obtain-ing a dibromopropionic acid from it by oxidation and thus settling the constitution of acrolein. Dibromacrolein is however polymerised by the action of nitric acid. The polymeride crystallises in prisms melting at 59" and is soluble in alcohol and hot water. The solution of this body in alcohol gives when treated with hydrochloric acid a product not yet analysed which is heavier than and insoluble in water and boils at 200" with partial decomposition. To this body the author ascribes the formula C,H,Br{ OC2H5.c1 W. H. P. Barium Sulphocarbonate. By P. TH~NARD (Compt. rend. lxxix 673-676). WHENa solution of barium sulphide is added to carbon disulphide barium sulphocarbonate BaCS3 is quickly deposited in the form of a canary-yellow crystalline powder. In working on a manufacturing scale the yield is 90 of dry sulphocarbonate for 100 put in; the mother-liquors may also prove useful in which case the above yield would be increased. Dumas has suggested the use of the sulpho- carbonates against the phylloxera in wine-districts. Thenard thinks the barium salt though very little soluble would probably be injurious to the soil. He proposes to convert it into the potassium salt by adding potassium sulphate to its solution.B. J. G. L2 ABSTRACTS OF CHEMICAL PAPERS. Methene Sulphocyanate. By JULIELERMONTOFF (Deut. Chem. Ges. Ber. vii 1282-1284). Methene su.?phocyamate CH,( SCN), is obtained by heating an alcoholic solution of potassium sulphocyanate and methme iodide on a water- bath for 2-3 hours. It is almost insoluble in cold water more easily in boiling water Rind freely in alcohol and ether and crystallises in beautiful white long prisms or needles or in rhombic plates melting at 102". Qn boiling it with water it gives off a very pungent vapour which atfiacks the mucous membrane. Nitric acid converts it into metheme disdphonic (disulphometholic) acid CH,( SO,H), forming a barium salt which crystallises in beautiful pearly rectangular plates.c. s. Ethene and Methene Selenieyanates. By B. PROSKANER (Deut. Chem. Ges. Ber. vii 1279-1282). Ethene selenicyanate C2H4( SeCN), is easily obtained by heating an alcoholic solution of ethene bromide and potassium selenicyanate. It is insoluble in ether and cold water sparingly soluble in hot water and alcohol and crystallises in white needles which melt at 128" decom-posing at the same time. On boiling it,with nitric acid it yields diselenetholic acid C2H4(S03H), a deliquescent crystalline solid which easily decomposes with separation of selenium. Its lead- and silver-salt are insoluble in water but the barium-salt dissolves in hot water. Metheme selenicyanate CH,( SCN), is obtained by an analogous reaction from methene iodide.It crystallises from alcohol in rhom-bohedrons melting at 132" and easily decomposing with separa-tion of selenium. Nitric acid converts it into the corresponding sulphonic acid. c. s. The Nitril and Amide of Oxycaprylic Acid and the Amide of Amidocaprylic Acid. By E. ERLENMEYER and 0. SIGEI. (Deut. Chem. Ges. Ber. vii 1108-1109). THEauthors have obtained the nitril of oxycaprylic acid as an inter- mediate product in the preparation of this acid (p. 981 of last volume) from anhydrous hydrocyanic acid and oenanthol. It is a colourleas oily liquid lighter than water and soluble in alcohol and ether. It is con- verted by concentrated hydrochloric acid into oxycaprylamide with great evolution of heat. The amide crystallises in brilliant leaflets which melt at 15U0,and are easily soluble in alcohol and ether and difficultly soluble in water.The nitril of amidocaprylic acid could not be obtained in the pure state by the action of anhydrous hydrocyanic acid on cenanthol-ammonia. Amidocaprylamide is formed by treating the crude nitril with con- centrated hydrochloric acid. It is a powerful crystalline base which absorbs carbonic acid from the air and forms a difficultly soluble car- bonate. The hydrochloride is crystalline but does not form a double salt with platinum chloride. W. H. P. ORGCAKIC CHEMISTRY. 145 The True Nitril of Leucic Acid. ByE. ERLENMEYER~~ 0. SIGEL (Deut. Chem. Ges. Ber. vii 1109). THE authors have obtained the nitril of leucic acid by the action of hydrocyanic acid on amyl aldehyde.This body differs materially from the so-called nitril discovered by Bopp. It is a colourless oil lighter than water and soluble in alcohol and ether. It cannot he distilled as it is decomposed at temperatures above 100" into hydrocyanic and amyl aldehyde. Potash and soda solutions also separate it into these products ; concentrated hydrochloric acid however converts it at once into leucic acid and ammonium chloride. The constitution of this nitril and of the leucic acid prepared from it may be represented by the formula- CH3-CH-CH and CH3-CH-CH3 I I CHOH CHOH I I CN COOH. The authors intend to examine the isomerides of this acid. W. H. P. Action of Methene Iodide on Amines. By JULIE LERMONTOFF (Deut.Chem. Ges. Ber. vii 1252). WHENpure ethylamine is digested with alcoholic methene iodide in sealed tubes at 100" for some hours a difficultly volatile liquid base is formed apparently tetrethyl-tetrarn ethene-tetramine [:3!} N4. This unites with two proportions of hydrochloric acid ; the hexmethenarnine of Butlerow is solid and crystdline and unites with only one proportion of hydrochloric acid. Methylamine seems to unite with methene iodide forming the corn- pound (C2H5)sN.CH212, or N CH21 ; only half of the iodine pre-i:C2=,l3 sent in this body is precipitated by silver nitrate ; when it is acted on by freshly-precipitated silver chloride a crystallisable chloride is pro- ( (C2H5)3 duced which gives rise to the platinum salt 2N CHJ .PtC14. 1c1 Aniline acts on methene iodide forming a fluid base which yields soluble salts for the most .part not readily crystallisable ; the sulphate is precipitated by alcohol from its aqueous solution as an indistinctly crystalline body; it has the composition N2 (C,H5)2 . H,SO4 i.e. it is {Z the sulphate of met7~ene-di23henyZ-dliamine. This base does not resemble the ethene-diphenyl-dinmine obtained by Hofmann from ethenedi-bromide-aniline but it has considerable reEemblance to the isomeric ABSTRACTS OF CHEMICAL PAPERS. ethidene-diphenyl-diamineobtained by Schiff from ethidene chloride and aniline also from aldehyde and aniline. Aniline treated with excess of methene iodide yields a similar pro-duct possibly dimethene diphenyl diamine; the sulphate of this is not thrown down by alcohol from its aqueous solution; methene iodide and methene-diphenyl-diamine give an unpromising tarry product as do also ethylaniline and diethylaniline when treated with methene iodide.C. R. A. W. Compounds of Urethane with Aldehydes. By C. €3 IS c H o FF (Deut. Chem. Ges. Ber. vii 1078-1054). THEauthor has already shown in a former paper (this Journal p. 890) that urethane combines with the aldehydes generating water and crystallisable compounds. This character belongs not only to ethyl-urethane but also to the other carbamic ethers. Compounds have been obtained from cinnamic aldehyde and we-thane melting between 135" and 143" from anisic aldehyde and urethane melting at 171"-172" ; from furfurol and urethane melting at 169" ; from aldehyde and propyl-urethane melting at 115"-116" ; from benzoic aldehyde and propyl urethane melting at 143'; from vnleral and xanthamide melting at 108"; besides several others which were less particularly examined.Salicylous acid was found to dissolve urethane but the compound could not be obtained in a state fit for analysis. W. A. T. A Compound of Sarcosine and Guanidine. By E. BAUMANN (Deut. Chem. Ges. Ber. vii 1151-1152). WHENsarcosine is fused with guanidine hydrochloride and the pro-duct is crystallised from alcohol beautiful tabular crystals are obtained consisting of a compound of sarcosine and guanidine hydrochloride. This substance may also be obtained by boiling an alcoholic solution of its constituents.Silver hydrate decomposesit with production of a deliquescent base; while mercuric hydrate acts on its boiling solu-tion with formation of the white mercuric compound of guanidine. Treatment of the double hydrochloride with platinum chloride leads to the production of the platinum salts of guanidine and sarcosine. The new compound is probably anaIogous to a double salt and may /NH2 NH; be constituted as follows :-C= NHZ \(CH,)N-CH2-C0.H0. T.T. B.B. Sarcosine-uric Acid. By E. BAUMANN (Deut. Chem. Ges. Ber. vii 1152-1153). WHENuric acid is gently heated with fused sarcosine a product is obt,ainedwhich crystallises from water in beautiful prismatic crystals ORGANIC CKEMISTHY. I47 containing the elements of sarcosine and uric acid minus one molecule of water.The crystals contain 2H20. The author intends to study the new substance in detail. T.B. Contributions to the Constitution of the Aromatic Compounds. By R. PITTIG and E. MAGER(Deut. Chem. Ges. Ber. vi< 1175- 1180). THE autlhors have proposed to themselves to prepare the three dioxy- benzenes from benzene at the same time to obtain all the intermediate products as pure as possible and to examine carefully all the bye- products if any. They have so far obtained the following results. Pure paranitrobromobenzene which by repeated crystallisations from alcohol was completely freed from the ortho-compound crystallises in very slender long and almost colourless needles melting at 126O- 127" and boiling at 255"-256'.The parabromaniline obtained from it forms large colourless regular octohedrons which melt at 63". The colourlesa liquid when more strongly heated suddenly becomes bluish- violet ; then a colourless liquid distils over ; and afterwards crystals condense in the neck of the retort while a dark mass dissolving in alkalis with a beautiful blue colour is left behind. The li uid dis- tillate fast yields on redistillation a base boiling between lSC?'-190° which is probably aniline and then the same phenomena repeat them- selves. Besides bromaniline a small quantity of a base crptallising in long needles was always found in the mother-liquors. To convert parabromnniline into bromophenol the diazobromobenzene nitrate cannot be used as it yields a considerable quantity of a resinous body; but by boiling the sulphate with water parabromophenol is readdy obtained.It forms large transparent crystals belonging probably to the monoclinic system melting at 63"-64" and boiling almost without decomposition. In presence of water the melting point is much lower. This bromophenol is identical with that wliich Hubner obtained from phenol and from bromosalicylic acid. On fusing it with potash and a little water at as low a temperature as possible pure resorcin is formed without a trace of its isomerides. Pure resorcin which is readily obtained by crystallisation from benzene melts at 110". Orthobromonitrobenzene forms pale-yeliow transparent large needles melting at 41"-41.5' and boiling at 261".Orthobromaniline is a colourless crystalline mass melting at 31"-31*5" and boiling without decomposition at 229". Hubner and Alsberg found that this compound does not solidify at once but onlyat a low temperature and must then be rapidly pressed to keep it solid at the common tempera- ture. The authors found thesame the cause being that a small quan- tlityof a liquid base is present. c. s. ABSTRACTS OF CHEMICAL PAPERS. Aldehyde and Benzene. By A. BAEYER (Deut. Chem. Ges. Ber. vii 1190). DIPHENYLTRICHLORETHANE is formed when 1-li parts of paraldehyde are added drop by drop to 100 parts of well-cooled sulphuric acid and the solution is then shaken with a little more benzene than is required by the equation CH3.CHO + 2C6Ht5 = C&.CH(CJ€,)Z + H2O.The same hydrocarbon appeam to be produced by mixing benzene and sulphuric acid with concentrated lactic acid the latter body being partially converted into aldehyde by sulphuric acid. C&&O,= C2&0 + COZ + HZO. c. s. Compounds of Chloral with Bromobenzene and Chloroben- zene. By 0. ZEIDLER(Deut. Chem. Ges. Ber. vii 1180-1181). Dimoltobromophe?LyltrichZorethane,CC13.CH(C6H4Br)~,is produced by gently heating a mixture of 1part of bromobenxene 2 parts of chloral and 4-5 vols. of sulphuric acid. It is insoluble in benzene sparingly soluble in cold alcohol and glacial acetic acid more freely in hot alcohol ether and chloroform and very freely in carbon snlphide. From alcohol it crystallises in silky needles and from ether-alcohol chloroform or carbon sulphide in large compact crystals melting at 139°-1410.On boiling it with alcoholic potash it is converted into dimonobromophenyldichlorethene cCI,.c( C6H4Br)z,crystallising from hot alcohol in needles and from ca,rbon sulphide in large glistening crystals melting at 119°-1200. Dinitrodimonobron~ophenyltrichlorethane crystal-C14C13Brz(N02)2H7, lises from alcohol in yellowish prismatic needles melting at 168'-170". Dimonochlorphenyltrichlorethane CCI,.CH( C,H4C1), was prepared from chlorobenzene. It resembles the bromo-compound and crystallises from ether-alcohol in fine interwoven needles melting at 105". Dimonochlorphenylchlorethane crystallises from alcohol in .well-de-fined brilliant crystals.Dinitrodi~onochlorphenyltrichlorethane separates from nitric acid in needles melting at 143". c. s. Diphenyl. By G. SCHULTZ (Ann. Chem. clxxiv 201-235). THEbest method for preparing diphenyl in quantity is that of Ber-thelot giving about twice as good a yield as that of Fittig if 100-200 grams of benzene are passed through a porcelain or iron tube which is heated by charcoal to a very high temperature falling short however of an intense white heat. Pure diphenyl boils at 254" if the whole mercurial column be immersed in the vapour. Bromodiphenyl C12H8Br,is formed by adding the calculated quantity ORGANIC CHEMISTRY. 149 of bromine to a solution of diphenyl in carbon sulphide which has to be kept cold until the first; reaction is over and then heated on a water- bath as long as hydrobromic acid escapes.By fractional distillation and crystallisation from alcohol it is separated from unaltered diphenyl and dibromodiphenyl. It is moderately soluble in cold alcohol more freely in hot alcohol and acetic acid and very easily in ether carbon sulphide ethyl bromide and benzene. From alcohol it crystallises in thin plates melting at 89" boiling at 310" and smelling like oranges. On oxidising it with a solution of chromic trioxide in acetic acid it yields parabromobenzoie acid. ChZorodiphenyZ CI2HgC1 is obtained by converting diphenylsulphonic acid into the phenol and distilling it with phosphorus pentachloride. It is freely soluble in alcohol and ether and forms crystals melting at 75" and smelling like oranges.On oxidation it yiel'ds parachloro- benzoic acid. Nitrodiphenyl C,zH9NOz, is prepared by boiling 5 parts of the hydro- carbon with 10 parts of glacial acetic acid and 4of concentrated nitric acid or by treating 2 parts of diphenyl with 3 of the acid in the cold. It is sparingly soluble in cold more freely in hot alcohol and crystallises in long needles melting at 113" and boiling at 340O. On oxidation it yields paranitrobenzoic acid and by reduct'ion it is converted into amidodiphenyl CI2H9NH2, which is identical with Hofmann's xenyl-amine. Biphenylcarbonic or pnra~henylbemoicacid C,,H,CO.OH is obtained by boiling diphenylbenzene with acetic acid and chromic trioxide. It is sparingly soluble in water more freely in alcohol and ether and crystallises in tufts of needles melting atl 216"-217" and subliming in long needles.All its salts are sparingly soluble in water and the barium salt is almost insoluble. On distilling it with lime it is con- verted into diphenyl and by oxidising it with chromic acid it yields terephthalic acid. The same diphenylcarbonic acid has also been obtained by Doebner from diphenylsulphonic acid. These results show that all the monosubstitution-products of diphenyl which are formed directly belong to the para-series and diphenyl behaves therefore like toluene. DibronzodiphemyZ boils at 355"-360" and yields by oxidation para- bromobenzoic acid. If is as Griess has already shown identical with the dibromodiphenyl obtained from benzidine.Bromonitrod+henyZ CI2HsBrNO2,is obtained by heating equal parts of bromodiphenyl and concentrated nitric acid exhausting the crude product several times with boiling alcohol and crystallising the residue from toluene. The same compound is formed by boiling diazonitro- phenyl perbromide with alcohol. It crystallises in long white needles melting at 173" and boiling above 360". On oxidation it yields para- bromobenzoic acid and a little paranitrobenzoic acid. 1sabro.monitrophenyZ. This isomeride is formed together with the preceding compound. It is readily soluble in alcohol and forms fine crystals melting at 65O and boiling at about 360". The same compound is also produced by treating isodiazonitrophenyl perbromide with alcohol.Din1:trod@hefiyZ,C12H,(N02)2, is best prepared by adding 6 parts of concentrated nitric acid and 1 part of snlpburic acid to 3 parts of 150 ABSTRACTS OF CHEMICAL PAPERS diphenyl and when the violent reaction is over boiling the mixture for a short time. The crude product is exhausted with boiling alcohol to remove isodinitrodiphenyl. The pure compound crystallises in needles melting at 233" and not at 213" as Fittig found. It is soluble in hot sulphuric acid and crystallises again on cooling. A solution of chromic trioxide in glacial acetic acid does not oxidise it and may be used for purification the compound separating on the addition of water as a pure white precipitate. By the action of hydrogen sulphide it is reduced to amidonitrodiphenyl CIJ&(NO~)NH,,possessing all the pro- perties of Fittig's compound with the exception of the melting point, which was found to be 198" instead of 160".On oxidation it yields paranitrobenzoic acid. By passing nitrous acid into a mixture of amido-nitrodiphenyl and hydrochloric acid cooled by snow nntil all is dis-solved and then adding a mixture of bromine and hydrobromic acid a perbromide is obtained as it dark-red precipitate which by boiling absolute alcohol is converted into the bromonitrophenyl melting at 173". Now as amidonitrodiphenyl yields paranitrobenzoic acid and the corresponding bromonitrodiphenyl yields parabromobenzoic acid it follows that all the di-subst'itution-products of diphenyl which are described in the paper without an affix are dipara-co~npozcnds.Isodinitrod@henyl crystallises from alcohol in long colourless needles melting at 93.5". Like its isomeride it may be purified with chromic acid although it appears that some of it is completely oxidised by this treatment. Isoamidonitrodiphenyl is produced by passing hydrogen sulphide into a mixture of the dinitro-compound ammonium sulphide and alcohol. It is almost insoluble in water readily in alcohol and cry- stallises in short red prisms melting at 97"-98". cI2H8(NO2)NH2, ClH crystallises from hot water in long white needles. When diparadinitrodiphenyl is completely reduced it yields benzidine which gives the following characteristic reactions :-potassium perman-ganate colours it blue ; chromic acid converts it into a black body ; and chlorine converts these as well as benzidine into a red substance having the appearance o€ ferric hydrate.It is insoluble in water and acids and is converted into an acid by oxidising it with potassium dichromste and sulphuric acid. Benzidine from azobenzene gives the same reactions and is con- verted by Griess' reaction into paradibromodiphenyl. When diphenyl is prepared by Fittig's method a high-boiling thick oil containing bromine is obtained as a bye-product. On standing long white needles separate out containing no bromine and consisting of C&,,. The same body which melts at 196" is also produced by act,ing on the oil with sodium. The bye-products contained in the diphenyl obtained by the met,hod of Berthelot consist of Berthelot's chqsene benxerythrene and bitumerze.The chrysene is a mixture of diphenylbenaene isodiphenylbenzene and a yellow oil. The two latter are removed by alcohol or ether and thus a perfectly white diphenylbenzene is obtained as the chief pro- duct ;it crystallises from boiling alcohol in plates melting at 205" and boiling above 360". This compound is identical with Riese's hydro-carbon. ORGANIC CHENEl'RY. 151 The formation of diphenylbenzene may be explailled by the tclua-tion-3C6H6 = Ci&14 + 2H2 or by C6H6 + C12H10 = C~J314-I-H,* The latter equation appears however improbable as on passing the two hydrocarbons through a red-hot tube hardly any diphenyl-benzene was formed. When diphenylbenzene is oxidised it yields as already mentioned paraphenylbenzoic acid and is therefore also a dipara- compound.Isodiphenylbenzene crystallises from hot dilute alcohol in long white needles grouped in stars. It is readily soluble in alcohol ether benzene and acetic acid melts at 85" and boils at about 360". With picric acid it does not combine; on oxidation it yields benzoic acid. Berthelot's benzerythrene consists chiefly of diphenylbenzene but also contains another hydrocarbon melting at 266"; and the yellow oil yields with a hot alcoholic solution of picric acid reddish yellow needles melting at 212'; the hydrocarbon contained in it forms needles melting at 196". Chrysene could not be detected among the products. c. s. Action of Methylal on Toluene Benzyl Chloride and Diphenyl.By J. WEILER (Deut. Chem. Ges. Ber. vii,1181-1189). To prepare dimethyZpheqLyZm,ethane,CH2( CGH~CH,)~ a mixture of equal volumes of glacial acetic acid and sulphuric acid is added to a solu- tion of 25 grams of methylal and 75 grams of toluene in 300 grams of glacial acetic acid until most of the toluene has separated out. After 12 hours a mixture of 900 grams of sulphuric acid and 300 grams of glacial acetic acid is gradually added and the solution again left for 12 hours. After diluting with water the hydrocarbon is extracted wit,h ether and purified by distillation. Dimethylphenylmethane is a colourless liquid having an aromatic smell and showing a faint bluish-violet fluorescence. It boils at 290" and yields with bromine dibromocZimethy~he?zyl-methane,Cl5Hl4Br2? crystallising from alcohol in brilliant white needles melting at 115".Well-cooled nitric acid converts the hydrocarbon into the dinitro-compound which melts at 164". Chromic acid solution oxidises the hydrocarbon to dinaethyk C6H4.CH3 benzophenone CO { c6H4:cH totylbenxoic acid { C6.&.CO2H' and C6H1 CH acid GO { ~ ~ ~ The phenone crystal- benzo~heno~Ledicarbonic :~~~$ lises from alcohol in beautiful rhombic crystals melting at 95". Nascent hydrogen converts it into rlimeth.yZbeizzhydroZ CH.OH( G6'H4. CH3)2,crystallising from a concentrated alcoholic solution in fine white needles melting at 69". ToZyZBenxoic acid is sparingly soluble ir1 water and crystallises from methyl alcohol or acetone in fine glistening needles melting at 220".C15HllK03crystallises from a hot solution in tufts of long white needles. Benzophenonedicto.bo,Lic acid has not been obtained quite pure. ABSTRACTS OF CHEMICAL PAPERS. When dimethylphenylmethane is passed through a red-hot tube filled with fragments of porcelain it loses 4atoms of hydrogen and methyZanthmcene C15H12 is formed which is sparingly soluble in alcohol ether and acet.ic acid and crystallises in glistening yellowish or white plates melting at 198'-201" and dissolving readily in chloroform benzene and carbon sulphide. It sublimes in large white plates exhibiting a fine blue fluorescence and forms a picric acid compound having the greatest resemblance to anthracene-picric acid.Chromic acid oxidises it to nnflL7.apu/inone-carbonic acid CI5Hl8O4, which sublimes in yellow needles melting at 282". On boiling it with zinc- dust and soda it yields a red solution like anthraquinone and when it is heated with soda-lime the latter compound is formed. When chlorine is passed into boiling dimethylphenyimethane brown resinous products are formed but by adding sulphuric acid carefully to a well-cooled mixture of methylal and benzyl chloride dichloro-dirnethy~?tenyZmethane,CH,( C6Ha.CH2C1)2 is formed. It crystallises from a chloroform methyl alcohol or acetone in brilliant white plates melting at 106"-108". D@henyZphenyZmethune CH2(C,Ha.C6H6)2, is obtained by adding a little of a mixture of equal volumes of acetic and sulphuric acids to a solution of 15 grams of diphenyl and 5 grams of methylal.After 24 hours a mixture of 100 grams of acetic and 100 grams of sulphuric acid is gradually added and after standing for 12 hours the liquid is mixed with 200 grams of sulphuric acid then water is added and the precipitate purified by distillation. Diphenylphenylmethane is readily soluble in benzene chloroform and acetone and crystallises in small transparent monoclinic crystals melting at 162" and distilling above 360". Like dimethylphenylmethane it does not combine with picric acid In fuming sulphuric acid it dissolves with a beautiful greenish- blue colour which disappears on the addition of water. Chromic acid solution oxidises it to dipheny7231)enyZketone CPBHIBO, crystallising from acetone &c.in small needles or generally in granular masses melting at 226". Nascent hydrogen converts it into diphenylbenxlydrol, Cz6Hzo0, crystallising from benzene or alcohol which dissolve it very freely in white needles melting at 151". c. s. Synthesis of Triphenylmetham and Methylphenyl-diphenyl- methane. By W. HEMILIAN (Deut. Chern. Ges. Ber. vii 1203-1210). TRIPHENYLMETHBNE, CH( C6H5)3,which Kekul6 obtained from henzylene dichloride and. mercury-phenyl is also formed by heating a mixture of benzene benzhydrol and phosphoric pentoxide for four hours to 130"-140'. Sulphuric acid converts it into a sulphonic acid forming a very soluble barium-salt which when precipitated with alcohol has the composition [CH( CGH4SO3),],Ba3 + 8H20.When the sulphonic acid is fused with potash a phenol is formed crystallising in slender needles which on exposure to the air soon turn red and resinous. More stable is its acetyl-compound which crystallises in thin plates melting at 180". Fuming nitric acid converts the hydrocarbon into nitro-products of ORGANIC CI-IEMISTRY. 153 which the compound CH(C6H4N02)3 could be isolat'ed ; it crystallises from benzene in yellow scales melting at 203". By the action of bromine on triphenyl-methane oxidation takes place and the body Cl9HIGO, is formed. The same compound is more conveniently pre- pared by boiling the hydrocarbon with a chromic acid solution. Tt is readily soluble in alcohol ether and benzene and crystallises in brilliant mrd hexagonal plates belonging to the monoclinic system melting at 157" and boiling above 360".The reactions of this body show that it is triphenyl carbinol (CsH5),C.0H. Its properties are as singular as its mode of formation. It is not changed by distilling it with soda-lime or by acting on it with alkalis dilute acids or sodium-amalgam or by dissolving it in cold concentrated sulphuric acid. With bromine and nitric acid it yields substitution-products. Acetyl chloride and acetic anhydride as well as benzoyl chloride convert it into the corresponding ethers which are so unstable that they are decomposed by water. When it is boiled with toluene and sodium an insoluble sodium-com- pound is formed which is very hygroscopic and at once resolvcd by water into soda and the carbinol.By the action of phosphorus penta- chloride an unstable crystalline chloride is obtained which cannot be dist'illed and is slowly decomposed by cold and rapidly by boiling water. By pouring the fused chloride into absolute alcohol the ethgl- ether (CGH,),COC2H5 is produced forming small indistinct crystals which melt at 78" and may be distilled by heating them carefully in a current of air. When the chloride is distilled it splits up into hydro- chloric acid and di~henylp23he?Lyleie~~ethalze (C~,H,),CIICGH, crystal- lising from acetic acid in brilliant silky needles melting at 138". When tlriphenyl carbinol is heated with benzene and phosphorus pentoxide diphenyl and triphenylmethane are formed- (CsH,),C.OH + 2CGHG = (CsH5)sCL-I + C12HIO + HZO.CH { &!:&:d% ~~he~ylirtethyICphenylmetliane is readily formed by boiling benzhydrol and toluene with phosphorus pentoxide. It forms an oily liquid having a peculiar smell. Chromic acid oxidises it to C.OH { LC&HgbpH,crystallising from alcohol in indistinct needles 64 melting at 187". (C20H1503)2Ba + 7H,O crystallises in long silky needles. The potassium and sodium salts are precipitated by alcohol as heavy oils which crystallise on standing. fla u. n. Thiobenzene and Thioaniline. By F. KRAFPTS (Deut. Chem. Ges. Ber. vii 1164-1165). THEordinary phenyl sulphide and that obtained from thioaniline are identical and are converted by bromine into bronao-thiobemene or bromophenyl sulphide (CsHaBr),S,which forms pearly leaflets melting at 109"-110".Phenyl sulphide yields a clzloro-derivative (c6H4c1)2s which resembles the last described body and melts at 88"-89" and it may also be formed by heating the platino chloride of diazothiobenzene. 154 ABSTRACTS OF CHEJIICAL PAPERS. Jodothiobemzene or iodophenyl sulphide (C6H11),S was obtained by KekulB's method ; it resembles the derivatives which are described above but melts at 130"-139" and it can also be obtained by the addition of hydriodic acid to a solution of diazothiobenzene sulphate. The action of water on diazothiobensene sulphnte gave rise to the for- mation of an oxythiobenzene (thiophenol) which is precipitated in shiuing leaflets when its alkaline solution is neutralised.It melts at 143°-144". A sulpho-acid which contains (C6H4S03H),S and crystallises well was obtained by dissolving phenyl sulphide in fuming sulphuric acid. T. B. Some New Organic Selenium-compounds. By C. L. JACKSON(Deut. Chem. Ges. Ber. vii 1277-1279). RATHKE has shown that on reducing sodium selenite with charcoal not the monoselenide but the diselenide is formed. When this compound is boiled with beiizyl chloride it yieIds cZibibenzy1 diselenide (C,H,),Se, a yellow crystalline body melting at go" and turning red on exposure to light. It is sparingly soluble in ether and cold aloohol more freely in boil- ing alcohol and is oxidised by fuming nitric acid to benxylselenious acid C,H7.Se0.0H which is sparingly soluble in cold water freely in hot water and crystallises in flat prisms melting at 85".It has a strongly acid reaction and a faint but not unpleasant odour. The ammonium sodium and barium salts are readily soluble ; the silver salt is a white precipitate cry stallising from hot water in slender needles and the lead-salt is a flocculent crystalline precipitate. On treating bensyl disclenide with methyl iodide no benzyl-selenin was formed but a trivnethylselenin iodide and probably benzyl iodide. Action of Chloral and Aldehyde on Toluene By 0. FISCHER (Deut. Chem. Ges. Ber. vii 1191-1197). Dimeth.y~he.IzyltrichZorethane (C6H4CH3),CH.CC& is obtained by adding sulphuric acid to a mixture of one mol. of chloral and two mol. or more of toluene. The mixture which becomes hot and reddish-brown is then cooled and more acid is added until the mass becomes pasty.By boiling it with water and orystallising the residue from ether-alcohol the pure hydrocarbon is obtained in fine crystals melting at 89". It dissolves in about 2 parts of ether and 40 of adcohol. Boiling alcohol potash converts it into d~~methy~he~zyldicl~lorethane, Cl6Hl4Cl2 crystal- lising in very brilliant needles which melt at 92O and dissolve in 2 parts of ether and about 35 of alcohol. Dim~trodimeth~~henyltrichlorethane is formed by dissolving the tri-chloro-compound in fuming nitric acid on a water-bath. It forms yellowish short brilliant prisms melting at 120"-122". On adding bromine to a solution of the trichloro-compound in carbon sulphide dibromodimethylphenyltrichloyethameis formed crystallising from alcohol in iridescent plates melting at 148".When the trichloro- compound is boiled for several days with a chromic acid solution it is ORGANIC CHEXIISTRP. 155 crystallising from alcohol and acetic acid in small plates melting at 173"-174O. The alkali-salts of this monobasic acid crystallise well but those of barium calcium and magnesium are flocculent precipitates. DirnethyZphenyZethane CH,.CR(C,&.CH,), is prepared from toluene and paraldehyde in the same wayas phenylethane from benzene. The yield is about the same as the quantity of aldehyde employed. It is a very refractive aromatic oil boiling at 295"-298". Besides this hydrocarbon another is formed but in small quantity only having probably the composition C25HZ8.The oxidation-products of dimethyl- phenylethane are the same as those of dirnethylphenylmethane and by passing it through a red-hot tube it also yields methylanthracene which may thus be obtained in quantity. Dibronzomethylnlzthracene is easily formed by adding bromine to a solution of the hydrocarbon in carbon sulphide. It forms golden-yellow needles melting at 156". c. s. Observations on the Researches of Hubner and Grete on Metabromotoluene. By E. W R oB L E v s K Y (Deut. Chem. Ges. Rer. vii 1063). H~BNER and Grete maintain that by introducing the sulphoxyl group into metabromotoluene only one acid is obtained the barium salt of which crystallises without water. The author's experiments lead him to conclude that hhis salt contains 1&H,O.He also finds that by the nitration of metabromotoluene two isomeric nit robromotoluenes are obtained the solid melting at 55' and he believes that the product of higher melting point obtained by Grete results from the presence of dibromotoluene in the bromotoluene operated upon. W. A. T. Secondary Products obtained during the Preparation of Benzyl-toluene. By WEBER (Deut. Chem. Ges. Rer. and ZIINCKE vii 1153-1157). WHENthese secondary products were distilled a hydrocarbon Cz1H2, was obtained together with anthracene and toluene the two latter being probably formed by the breaking up of highly benzylated toluenes. The hydrocarbon CZ1H2,, forms an aromatic fluorescent oil boiling at 392"-396" under the ordinary pressure or at 280"-285" under a pressure of 30 or 40 mm.and having a specific gravity of 1.049. It dissolves in the usual solvents and does not form a compound with picric acid but nitric acid converts it into an amorphous nitro-deriva- tive. When passed through a red-hot tube it yields anthracene and an isomeride of anthracene while its oxidation leads to the production of ketone-like bodies and three acids. One of these acids contains or C6H5-cO-C6H,{ ~~$, C15H1005 and does not melt at a high temperature while it yields an easily soluble barium salt. The remain- l5G ABSTRACTS OF OHENTCAL PAPERS. ing two acids are isomeric dibenzglbenzoic acids C6H5C0 C6H,.CO,H, c,&iCo} which may be respectively designated a-and 6-.The a-acid is resin- ous melts at 80"-82" and most of its derivatives are amorphous. The B-acid forms needles which melt at 210°-212" and it is almost insoluble in water but easily soluble in alcohol ether or chloroform. In most cases its compounds are slightly soluble and easy to purify. The etJLyZ ether forms white needles melting at 106"-107". When the a-acid was distilled with baryta unsatisfactory results were obtained but its fusion with potash led to the formation of benzoic acid and a small proportion of an acid containing Cl5HlOO5, but different from the isomeric acid previously described. During the fusion with potash the odour of diphenyl was noticed. The ketone-like bodies referred to above were obtained as a yellow viscous product easily soluble in alcohol and distilling at 300"-305" under a pressure of 30-40 mm.but distillation at the ordinary pressure caused it to split up into water toluene bitter almond oil anthracene anthraquinone and the isome- ride of anthracene already mentioned as derived from the hydrocarbon CzlHzo. This isomeride of anthracerie is tolerably soluble in the mual solvents and it forms yellowish leaflets which melt at 133s50-134*5" and are not easy to sublime. It can be oxidised to a quinone CllH802 which forms long white needles melting ab 211"-212". This quinone forms a blue mass when fused with potash and dissolves in sulpliuric acid more easily than anthraquinone. T.B. Metachlorophenol and its Nitro-derivatives. By A. PAu sT and H.MGLLER(Ann. Chem. Pharm. clxxiii 303-317). WHENphenol is converted into the monochloro-derivative by direct chlorination and the product is fractionated a monochlorophenol is obtained which boils at 175.5"-177". This product does not solidify at -15" and it is identical with the monochlorophenol which Schmitt obtained by distilling the platinum-salt of the diazophenol prepared from volatile nitrophenol. These results show that the chlorophenol in quest'ion is metachlorophenol. When metachlorophenol is fused with potash it is readily converted into pyrocatechin ; the relation between metanitrophenol metachlorophenol and pyrocatechin being thus proved. Strong nitric acid converts metachlorophenol into the dinitrochlorophenol melting at 11I" while dilute nitric acid converts it into a mixture of two isomeric chloronitrophenols which may be easily sepnrat)ed by fractional crystallisation of their barium salts.The more soluble barium salt forms dark yellow needles and yields a ineta-nitro-parachlorophenol identical with that of Faust (Zeits. fur Chem. 1871 339) and of Armstrong (Chent. Xoc. Jozcr. [2] x 12) ; while the second barium salt forms red nodules and yields a metachloroinetanitro~henol which separates from it,shot solution either as an oil or in fine yellow needles which are slightly soluble in water but easily soluble in chloro- form which deposit,s it in flat yellow needles. Metanitrometachloro-phenol appeaps to be converted into metanitro-dichlorophenol (m.p. 122") by the action of chlorine it melts at 70" has a saffron-like odour ORGANIC CHEMISTRY.157 and is very volatile with water-vapour while metachloroparanitro- phenol is only slightly volatile. Strong nitric acid converts both mononitromonochlorophenols into metachlorodinitrophenol melting at 111". Salts of Metanitrometachlorophenol Potassium salt :dark red flat needles readily soluble. Calcium salt (C6H3C1N020)2Ca+ H20 red prisms not very soluble in water. Ba&m saZt,(CsH,ClNOz0)2Ba+H20 tufts of short brown leaflets. Silver salt C6H3C1N0,0Ag carmine red leaflets which are slightly soluble in water. Metachloroparanitrophenol yields an amide whose hydrochloride forms white needles easily soluble in water and the chlorination of metachloroparanitrophenol gives rise to Seifart's dimetachloropara-nitrophenol.In addition to the barium salts described by Seifart the author has noticed the foimation of one containing 8 molecules of water and forming long clear-yellow needles. The metachloropara-?aitrometan,itro~lLenoZmelting at 111" (obtained by the action of strong nitric acid on either of the above-mentioned mononitromonochloro- phenols) was found to yield occasionally a barium salt containing 5+H20 and a double salt containing (C6H2C1(N02)z0)2Ba + (C6H2C1 (N02),0)NH4 + 12H20 was obtained in short pale yellow needles by adding barium chloride to an a;mmoniacal solution of the acid. Meta-chlorometamidopara~it~-ophenol was sulphate (~6~~~1~~2~H20)2S04H~ obtained by treating the last-mentioned acid with alcoholic ammonium sulphide and digesting the product with dilute sulphuric acid.It separates from water in moderately soluble yellowish leaflets while the corresponding hydrochzoride forms short yellow needles. These com-pounds stain the skin brown. The barium compound (CsH3C1NOz. NH20)2Ba + 4Hz0,was obtained in small black needles by decom- posing a solution of the sulphate with barium carbonate and evaporating the solution. T. B. Metachlorophenol and its Sulphonic Acids. By T. G. KRA11E R s (Ann. Chem. Pharm. clxxiii 331-341). THE metachlorophenol of Faast solidifies when cooled to -12"and melts at + 7. It8s acidified alcoholic solution is not acted on by sodium amalgam. When metachlorophenol is added gradually to a cooled mixture of one part of fuming sulphuric acid and two parts of oil of vitriol a mixture of y-chlorophenol-sulphonicacid and 6-chlorophenol-sulphonic acid is produced ; but if fuming sulphuric acid is used alone the y-acid is obtained almost free from the &acid.By fractional crystallisation of the mixed calcium salts that of the 8-acid was obtained in small needles containing C6H3CIS04Ca + 2H20 while that of the yacid is much more soluble and forms grape-like clusters containing CsH3C1SO~ + 3+H20. r-Ch~orophenol-su~llzonic acid fornis cubes or leaflets the latter containing C6H3C1.OH.SO2.OH + H2O. It decomposes at 80" with production of an odour like that of chlorophenol and it is easily soluble in water alcohol or ether but slightly soluble in benzene VOL. XXVIII.M ABSTRACTS OF CHEi\lICAL PAPERS. ligroh or chloroform. This acid strikes a violet-colour with ferric chloride does not reduce -silver nitrate and its fusion with caustic potash gave unsatisfactory results. Armstrong obtained a potassium salt of metachlorophenol-sulphonic acid by fractionating the mixture of potassium salts derived from the mixed monochlorophenols but he does not describe it.-Potassium salts. Two were obtained containing respec- .~~.~~2. ~ tively ~ 6 ~ 3 ~ ~+ &HzOand C6H3Cl.0K.SOzOK ~+ +H20. The mono-potassium salt forms large shining prisms which belong to the triclinic system lose water at 120" and dissolve in '7.11parts of water at 90". The di-potassium salt is very soluble and forms delique- scent plates.The nzorto-sodium saZt is very soluble while the disodium salt C6H3CI.0Na.S02.0Na2 + 3H20 is also very soluble and forms ill-defined white crystals. The calcium saZts (C,H3.0H.S020),Ca + Hzoand (C6H3Clso2~ca + 3iH20 were obtained. The former is soluble in alcohol and water while the latter is soluble in 2.6 parts of water but almost insoluble in alcohol. The mono-bahm saZt (C6H3CI.0H.S020)2Ba + 1&H20,forms masses of white crystals soluble in alcohol. The lead saZts (C6H3CI.0H.S020)2Pb 3-4E20 and c6H3c1s02~Pb+ H20,were obtained the former consisting of hard rhombic crystals soluble in water or alcohol and yielding chloro- phenol when heated to 130°,while the latter forms a slightly soluble white powder. A basic lead salt was also obtained in small leaflets containing 56 to 57per cent.of lead. The mono-cup& salt (~6~3c1.0~.so20)2cu+ 4H20,was obtained in rhombic efllorescent prisms which yield chloro- phenol when heated to 120". 8-ChloropherzoZ su7,pphoitic acid was not obtained in the pure statme but its mono-potassium salt c6H3C1.0H.SO2OK forms small soluble leaf- lets and its di-caZcizcm salt c6H3clSo2~ca+ 2Hz0 forms tufts of small yellowish needles which are permanent in the sir. It is insoluble in alcohol but soluble in 44.58 parts of water at ll" and it is not decomposed at 250'. T. B. Compounds of Phenols and Aldehydes.. By E. TER MEER (Deut. Cheni. Ges. Ber. vii 1200-1203). BYacting on anisol and methylal with a mixture of glacial acetic and sulphuric acids dimethoxyZ~heny is formed Zmethame CEz(C6H4.0CH3)2, crystallising from alcohol in white rhombic plates which melt at 52" and boil at the same temperature as mercury.When chloral and phenol are treated in the same way dioayphenyZtrichlorethnne CCl,. CH(C,l&.OH) is produced forming small white crystals which melt at 202" with decomposition. On boiling it with acetic anhydride it yields the diacetyl-compouud CzHC13(C6H4. OCZH3O), crystallising in small needles which melt at 138'. When an alcoholic solution of dioxyphenyltrichlorethane is boiled with zinc-dust it is converted into dioxyphemyZethane CH2.C(C6H4.0H), which forms small ciyt,als, melting with decomposition at 280". It forms a crystalline potassium- phenate and a crystalline diacetyl-compound melting at 213".c. s. ORGANIC CHEMISTRY. 159 A Compound of Chloral and Thymol By E. JAGE R (Deut. Chem. Ges. Ber. vii 1197-1200). BYthe action o€ sulphuric acid and glacial acetic acid on these bodies dithymyltrichloretlzane CCl,.CH( C,,H,,.OH), is formed a crystalline solid which combines with one molecule of alcohol forming a com- pound crystallising in long pointed monoclinic needles. On boil-ing it with zinc-dust and alcohol it is reduced to dithymy7ethai?7~e, CH~.CH(C~oH12.0H)2, and dithymyZethene CH2.C(C,,-,H,2.0H)2.When a mixtare of these two hydrocarbons is oxidised with a neutral solution of potassium ferricyanide coloured bodies are obtained which seem to consist of quinones and quinhydrones. c. s. Fluorescein and Phthalein-orein By E.FI s c H E R (Deut. Chem. Ges. Ber. vii 1211-2116). FLUORESCEIN is best obtained by heating resorcin and phthalic anhydride to 195°-200" until the mass becomes quite solid. After being boiled out with water the residue is converted into the acetyl-compound which is purified by crystallisation and then decomposed by alcoholic potash. The pure compound is a red crystalline powder which is almost insoluble in water ether and benzene sparingly soluble in wood-spirit alcohol and acetone. On slowly evaporating a solution in methyl-alcohol it was obtained in pale yellow needles grouped in stars. The beautiful and intensely green fluorescence of its ammo- niacal solution is so characteristic that it may be used for the detection of small quantities of resorcin.The constitution of fluorescein is- On boiling it with acetic anhydride it is converted into diacetyl- fluorescein CZoHlOO3( C,IJ,O), which when alcohol is added to the solution thus formed crystallises out in yellow plates but becomes colourless by recryatallisation from acetone and melts at 200". Diben-zoyZjluoresceir? is a very similar compound which melts at 21Fi". By the action of phosphorus pentachloride on fluorescein the compourid C20H,,03C12is obtained in small colourless prisms melting at 252'. It is not decomposed by aqueous or alcoholic potash but by heating with milk of lime to 230° it is reconverted into fluorescein and when it is heated with fuming hydriodic acid to 150' for 5-6 hours the com- pound C,,H,,O,Cl is obtained crystallising from alcohol in rhom- bohedral plates melting at 229"-230".It dissolves in dilute alkalis showing that it contains hydroxyls and is probably a derivative of fluorescein which is known only in its alkaline solution. Fluorescein combines with sulphur trioxide forming a compound containing 7.88 per cent. of sulphur which is obtained by heating the compound with sulphuric acid on a water-bath. It crystallises from methyl alcohol in pale-red prisms and is easily decomposed by boiling water or alkalis. Cold fuming nitric acid acts violently on fluorescein phthalic acid and fetrnnitro@,6oresceinbeing formed ; the latter crystallises from acetic acid in pale-yellow small prisms which deflagrate violently when &I 2 160 ABSTRACTS OF CHEMICAL PAPERS.heated and dye in an aqueous solution an intensely reddish-yellow on wool. Phthaleim-orcirz C22H1605, is prepared by heating 3 parts of phthalic anhydride and 5 parts of distilled orcin with 5 parts of sulphuric acid to 135",no sulphur dioxide being formed which curiously enough is always the case at a lower temperature. after two hours the melt is dissolved in dilute potash boiled and precipitated by acetic acid. Phthalein-orcin crystallises from acetone in colourless needles dissolving in alkalis with a red colour. When it is boiled with sulphuric acid and the solution is diluted with water a body is precipitated resembling coerulein. Phthalein-orcin forms with boiling acetic anhydride diacetyZ-phthalein orcin crystallising from alcohol in fine needles which melt at 219"-230".When an alcoholic solution of phthalein-orcin is boiled down with concentrated hydrochloric acid dark-red flakes separate out having the composition Cz2H1605 + HCl. Similar unstable compounds it forms with other mineral acids. When bromine is added to a solution of the phthalein in boiling acetic acid the tetrabromo-corn- pound is formed while in a cold alcoholic solution pentabi omophthalein- orcin is produced ; both compounds are pale-yellow powders which are almost insoluble in all solvents. The red solution o€ phthalein-orcin in dilute soda becomes colourless when heated with zinc-dust and on adding dilute sulphuric acid phthaZiry-orciry C2zH2005, is precipitated in white flakes which when heated in the air are oxidised again to the phthalein.Its diacetyl-compound Cz2HI604( C2H30)2,which is formed by boiling it with acetic anhydride is much more stable and crystal- lises from benzene in cubes melting at 211'. The constitution of phthalin orcin is expressed by the formula- '0 9 'CH(OH)-c6H2 c OH CH3 and that of the acetyl-compound which is formed according to the equation-C22HzoOs + 3(CzH30)20 = C22Hdh( CZH~O)~ + 4(C,H,O.HO) is therefore,-c. s. Synthesis of Purpurin and Analogous Colouring Matters. By A. ROSENSTIEHL (Compt. rend. lxxix 764-768). A HOT alkaline solution of purpurin dissolves phosphorus without evolution of gas and the purpurin is quickly reduced to purpuro. ORGANIC CHENISTRY.xanthin which can easily be separated from the solution and obtained as a bright yellow crystalline powder. It sublimes in needles of the same colour as pure alizarin ; it dissolves in acetic acid alcohol and benzene but does not dye with iron or alumina mordants. Its compo- sition being CICH8O4, it is an isomeride of alizarin. The beautiful red colour of its alkaline solutions is turned brownish by reducing agents but the red reappears on pouring it into acidulated water. Boiling with hydriodic acid and phosphorus first reduces it to a greenish yellow substance (C14HloOlor C,aH,,04) which dyes alumina mordant like quercitron ; but by prolonging the action anthracene is obtained as is also the case when purpuroxanthin is treated with zinc-powder.On boiling its alkaline solution purpuroxanthin is oxidised into purpu- rh,identical with that of madder and with that which results from the oxidation of alizarin. Thus alizarin yields by oxidation purpurin which however by reduction does not reproduce alizarin but its iso- meride purpuroxanthin. By t,he similar oxidation of two other isomerides of alizarin viz. chrysophanic acid and anthraflavone the author ob-tained various substances forming stable colours with mordants but none of them were identical with purpurin. The author divides these and other bodies depived from anthra- quinone into two classes according as their hydroxyls may be regarded as attached to one or both of the C6H4groups of the hndamental anthraquinone CsH4.CO.C6H4.Pseudopnrpurin. ..... C8H402.C6(HO)4 Pnrpurin ............ C~H~OZ.C~H(HO)~ Alizarin ............} C8H& CGH2 (HO), Purpuroxanthin.. .... Quinizarin .......... -- Anthraffavone ...... C6H,(HO).C0.C0.C,H3(Ho) Anthrachrysone ...... C6H,(H0)2.C20~.C6H2(HO), Rn6opin ............ Rufigallic acid ...... C6R(H0)3C~02.C6H(HO)s He thinks that in all the stable colouring-matters derived from anthraquinone three of the hydrogen atoms of the same C6H4group are replaced by (HO). R. R. e Mesityl Oxide and Phorone. By L. CLAISQN (Deut. Chem. Ges. Ber. vii 1168-1170). THEphorone obtained by the action of hydrochloric acid on acetone can be readily oxidised to acetic acid and oxalic acid while its solution in carbon disulphide readily absorbs bromine to form the compound C9H,,OBr4 which is easily soluble in ether slightly soluble in cold alcohol and melts at 86"-88O.When an alcoholic solution of the above-mentioned phorone or of the tetrabromide is treated with zinc and sulphuric acid a substance containing C18Hz80is produced. It forms colourless quadratic prisms which melt at 108",and volatilise ABSTRACTS OF CHEMICAL PAPERS. either alone or with water-vapour. These results tend to support the formula which Kekul6 and Baeyer attribute to phorone. Holtmeyer's assertion that the action of strong sulphuric acid on phorone or on mesityl oxide gives rise to the production of mesitylene was con- firmed and it is probable that acetone is first formed as it was found to be produced when phorone or mesityl oxide is boiled with very dilute sulphuric acid.T.B. Mixed Sulphones. By P. CHRUSTSCHOFF (Deut. Chem. Ges. Ber. vii 1167-1168). WHENbenzene-sulphonic chloride is heated with naphthalene and zinc-dust a product is obtained which separates from ether in crystals melting at 121" and containing C6H,.S02.C,oH7.By proceeding in a similar manner the author hopes to obtain other mixed sulphones. T. B. Ethyl-phenol- and Ethyl-benzene-sulphonic Acids. By P. CHRUSTSCHOFF (Deut. Chem. Ges. Ber. vii 1165-1167). WHEN ethyl-phenol is heated with phosphoric anhydride ethylene is evolved and phenol is formed. Two sulpho-acids are produced by the action of fuming sulphuric acid on ethyl-benzene and that which yields the least soluble potas- sium salt is converted into a chloride by the action of phosphorus pentachloride.This chloride yields an amide melting at 108" while the amide similarly prepared from the more soluble potassium salt was found to have a lower but variable melting point. When the less soluble potassium salt was fused with potash a solid ethyl- phenol was obtained together with a portion of a fluid phenol but the crude mixture of potassium salt? yielded principally the solid ethyl- phenol. Tolueneswlphonic acid.-When concentrated sulphuric acid flows slowly into boiling toluene only para-toluene sulphonic acid is formed. The amide from this melts at 180'. T.B. A new formation of Phthalic Acid. By W. WEITHand R. BINDSCHEDLER (Deut. Chem.Ges. Ber. vii 1106-1108). A CONSIDERABLE quantity of a crystalline body which proved to he phthalic acid was obtained during the preparation of anthraquinone- sulphonic acid in the alizarin manufactory of Bindschedler and Busch in Basel. A careful examination of the anthraquinone used showed that it contained no trace of phthalic acid. The authors find more- over that phthalic acid is formed at the same time as anthraquinone- sulphonic acid by heating perfectly pure anthraquinone with fuming sulphuric acid and for the reaction they suggest the equation :- ORGANIC CHEMISTRY. If benzenedisulphonic acid is formed in this reaction and if it is converted into a dioxybenzene during the conversion of the anthra- quinone to alizarin it will be contained in the mother-liquors from which the alizarin has been precipitated.This formation of phthalic acid affords further proof that anthraquinone is the ketone of phthalic acid. In a note to the above the authors add that they have found beneoic acid in considerable quantities in the alizarin mother liquors. This acid may have resulted from the action of the alkalis either on the anthraquinone or on the phthalic acid. W. H. P. On Metasantonin and the action of Hydriodic Acid on and D. AMATO Santonic Acid. By S. CANNIZZARO (Deut. Chem. Ges. Ber. vii 1103-1106). INthe expectation that the acid ClaHl,-COOH would be formed the authors have examined the action of hydriodic acid on santonic acid In no case however could this acid be obtained.The products of the reaction are a hydrocarbon C16Hd,boiling under a pressure of 5 mm. of mercury at 110°-112" and under the ordinary pressure between 235" and 245",and an iodide Cl5H,,I which boils at 143"-145"under 5 mm. pressure and when heated under the ordinary pres- sure is converted into a hydrocarbon C15H24. The authors are of opinion that this fact makes the presence of a COOH group in santonic acid improbable and that one of' the forrnul~e CIOH I PH O'bH I O< 1 1 C-OH CH, 0<1-OH \/ 'O/ O<&. represents the constitution of this acid. They give the name metasamtonin to a crystalline body which as well as the two preceding compounds they obtained by the continued action of hydriodic acid and amorphous phosphorus on santonic acid.It has the composition CI6Hl8O3,and crystallises in needles or prisms, soluble in ether alcohol and water. It melts at 160.05" and distils un- altered under a pressure of 10 mm. of mercury between 238"-240". Boiling potash dissolves it without alteration. Metasantonin is not formed at the commencement of the reaction and is produced by the elimination of water from santonic acid. W. H. P. ABSTRACTS OF CHEMICAL PAPERS. Action of Sulphuric Acid on substituted Anilines. By G. A. SMYTH (Deut. Chem. Ges. Ber. vii 1237). WHENdimethylaniline is heated to 180"-190" with somewhat more than the equivalent quantity of sulphuric acid until a sample almost ceases to give a precipitate with caustic soda dimethyltslLiline-szL1phonl:c acid is formed the barium salt of which is [C6H4{ ~&~H3))"]2Ba.3H20 the free acid C6H4 -,I WH ; SO,H )2,Hz0,crystallises from water and melts at 149"-150° (not Eorrect,ed).Attempts to form dimethylaniline-di-sulphonic acid by long-continued action of fuming sulphuric acid on dimethylaniline did not succeed only the monosulphonic acid being formed. Crystallised methyl-acetanilide is acted on by sulphuric acid with the formation of two acids the one apparentlv methane-di-sulpkonic acid CH2(SOBH)S,the 'other methyia;Lilines~lp~onicacid, { FEgH3) C6H4 ; the latter crystallises anhydrous ; its barium salt is [C6H4 { ~~(CH)3]SBa.H20.If methylnniline containing aniline be treated- with sulphuric acid the same sulphonic acid results also sdphanilic acid derived from the aniline ; ethylaniline treated in the acid C H4(so3H same way yields et722/Zaniliize-su~~on~c NH(C2H5) ; the 6 sulphanilic acid observed by Armstrong as the product of this action was due to the presence of anilins in the ethylaniline none of this acid being formed with pure ethylaniline.Diethylaniline yields after five days' treatment with sulphuric acid at 2OO0-21OQ the corresponding diethylan.ilineszl~7~01'~ic CsH4{ f&y6H5)2; acid the barium salt of this is [C6H4{ lzBa.2H,O. C. R. A. W. Action of Aniline on Fulminates. By A. STEINER (Deut Chem. Ges. Ber. vii 1244). AMMONIA acts on mercuric fulminate giving a clear solution from which shining crystals separate on standing consisting of a compound of ammonia and the fulminate; these detonate with great force.Aniline has at first no action but after some time a rapid action takes place much heat being evolved so that with large quantities an ex-tfosion may result ; if however moist fulminate be used and aniline c iluted with its own bulk of alcohol the action is somewhat moderated although care must be taken to cool the vessel containing the mixture as soon as heat begins to be evolved i.e. in about half an hour. Finely divided metallic mercury and a substance resembling amor-phous phosphorus result ;on treating the mixture with dilute hydrochlo- ric acid a substance is dissolved which after crystallisation from the liquid previously alkalised with ammonia to remove dissolved mercury and then again acidified with hydrochloric acid constitutes a neutral substance difficultly soluble in cold water but readily soluble in ORGANIC CHEMISTRY.165 alcohol ether and hot water ; it melts at 149O does not combine with acids or alkalis and gives the aniline reaction with bleaching powder together with a smell of chloropicrin on allowing the whole to stand awhile. This body has the formula C7HeN202,and is probably nitro-N the presence of the NO2group causing H the basic properties to disappear. Besides this product dipheny 1-guanidine melting at 146O is formed ; these two products result from the reactions- CHg(NOZ)(CN) + 2(CsH,.NH,) = Hg + CsH,.NH(CN) + C,jHa.NH( CH2.NO2) NH. CSH5 and CcH,.NH(CN) + C,jH,.NH2 = C NH. C6H.5 whereby cyan-aniline is formed as an intermediate product.C. R. A. W. Nitrophenylamines. By P. T. AUSTHN (Deut. Chem. Ges. Ber. vii. 1248). METANITRANILINE and picryl chloride act on one another when dissolved in boiling absolute alcohol with formation of parapicryl-metanitrani-(where p T,and w indicate respectively mefa para, and ortho) ; this compound crystallises from glacial acetic acid in small orange-g ello w transparent crystals melting at 205O and insoluble in water and ethers and only difficultly soluble in boiling absolute alcohol. Similarly para~icr?ll-paranitraniline,N ing at 216" is formed when picryl chloride acts on paranitraniline ; this compound closely resembles the previously described isomeride but is slightly more soluble in most solvents.On nitration these two bodies furnish respectively paray icry lmet apicry 1arnine and dipura-melting at 261O and 238"respectively and exploding violently when heated ; parapicryl-metapicrylamine regenerates parapicrylmetanitraniline when water is added to its solution in glacial acetic acid. Paradinitrop71enzJ 1met aid ranililz e and p a/radinitrop12.en,y Zp ar anitrani- are obtained by acting on alcoholic solutions of meta- and para-nitraniline respectively with paradinitrobromobenzene (obtained by nitrating bromobenzene and melting at 72") in sealed tubes at 100" these melt at 189" and 181" ABSTRACTS OF CHEMICAL PAPERS. respectively ; the former is sparingly soluble in glacial acetic acid whilst ihe latter is readily soluble.Dinitraniline and picryl chloride apparent17 yield an analogous penta- nitrodiphenylamine-diparapicrylamine,although a substituted ammonia nevertheless acts as a kind of acid this character being communicated by the presence of the numerous nitro-groups ; thus on treatment with barium hydrate or carbonate it forms Barium d~unrapicr~ldicc~~~ine C6H2(N02)3T {~~~$~$;seems to be this body sufficiently basic to Ba{ {C6H2(N02)3T form a salt with hydrochloric acid; it crystallises in fine needles and is soluble in water and alcohoL By the action of picryl chloride on an analogous metallic derivative C6H,(NO,),P sodium-dipicrylamine the compound N C6H2(N02),7r may be obtained. C6H2 (NO,) 3~ C. R.A. W. Nitroderivatives of Sulphoearbanilide.By A. BR .ijo KN E R (Deut. Chem. Ges. Ber. vii 123G-1237). DINITROSULPHOCARBANILIDE is best obtained by adding potash and an excess of caybon sulphide to an alcoholic solution of nitraniline from dinitrobenzene. Treated with lead oxide it yields dinitrocnr-banilide CO(NHC6H4N02)2,which forms small yellow needles but could not be obtained pure. Lead oxide and ammonia convert the sulpho-compound into diinitrodi.phenzJlgua.12.dine,C(NH)(NHCsH4N02)2 crystallising from alcohol in small yellow brilliant plates melting at 190". When phenylic mustard-oil and nitraniline are heated to loo" the rnononitrosulphurech CS {ggg:$No2,is obtained forming cry-stalline yellow crusts which melt at 145'. Lead oxide converts it into forming pale yellow needles mo.lzo.fzitrocarbni~ilide,GO {NH*C6H4N02 NHC6H5 melting at 187O and with lead oxide and ammonia it yields a yellow crystalline mononitrod~henzJl~uanid~n~, melting at 132".If the desul- phuration takes place in presence of aniline a monofiitrotripheny Z-gua.lzidine is formed. c. s. The Constitution of the Diazo-Compounds. By E. ERLENMEYER (Deut. Chem. Ges. Ber. vii 1110-1112). THEaut'hor regards the diazo bodies as ammonium compounds with R-N-R the general formula 111 . The relation between aniline nitrate N :md diazobenzene nihate will then be expressed thus- 167 ORGANIC CHEMISTRY. c,H,-N-0 -NO, Ill Ill H9 N C,H,-N-OH Free diaeobenzene is either an ammonium oxhydrate Ill N CGH5-N-0-N-CtjH5 or its anhydride Ill Ill N r The compounds with metals potassium for instance and the diazo- amidobenzene will have respectively the formu1~- whilst the perbromide and the diazobenzenimide derived from it may be represented thus- C6H5-N-Br and C6H5-N, Ill lll,p.N.Br2 N W. H. P. On the Dyes produced by the Action of Nitrous Acid on the Aromatic Oxy-Compounds. By C. LIE'BERMANN (Deut. Chem. Ges. Ber. vii 1098-1102). THEauthor's analyses of the dyes from phenols and nitrous acid de- scribed by him (Chem. Xoc. J. xxrii 693) lead to formuhe different from those proposed by Baeyer and Caro (p. 66 of this volume) for t.hese bodies. A direct comparison showed that the phenol dye from nitrosophenol is identical with that prepared by the author's method.The dyes produced from nitrosophenol with orcin or resorcin are also apparently the same as those from the action of nitrous sulphuric acid on phenol and orcin or phenol and resorcin. Since the dyes cannot be obtained in the crystalline state great pre- cautions as to quantities temperature &c. must be taken to ensure pure products and it is better to prepare them in small quantities. It is possible with some practice to judge of the purity of the substances frbm the colour of the alkaline solutions. The reagent used for the preparation was in every case a mixture of sulphuric acid with 5 per cent. of potassium nitrite. Dye from Phenol.-For the preparation of this dye the author recommends the following method :-5 grams of phenol are mixed with an equal volume of sulphuric acid the mixture being cooled to avoid the formation of phenolsulphonic acid ; and 20 grams of the reagent mentioned above are then added ;the temperature during this operation should be allowed to rise to and not exceed 40"-50".The mixture becomes first brown and then blue at the last stage and slight evolu- tion of gas takes place. un cooling the solution is poured into a 1(i8 ABSTRACTS OF CHEMICAL PAPERS. large quantity of cold water and the precipitate filtered off and dried. The dye cousists of a brown powder easily soluble in alcohol and giving with alkalis a pure deep blue solution. The analyses of this body agree with the formula C18H,5N03, and not with C12H12N02, as proposed by Baeyer and Caro.Its formation may be expressed by the equation- SCGHGO + NOzH .=C,&15N03 + 2H20. 0rc.Cn Dye.-To 10 grams of orcin in 10 grams of sulphuric acid 40 grams of the reagent are gradually added. The solution should become a fine purple red. It is then poured into a large quantity of water and the orange-red precipitate formed is washed and dissolved in alcohol. After the alcohol has been evaporated off a green mass is left having the formula C2,H18N206. The equation- 307H802 + 2NO2H = C2,H,eNzO6 + 4H20 expresses its formation. This dye is homologous with Weselsky's diazoresorcin which is formed from resorcin thus- 3CsH602 f 2NOzH = CisH1zN206 + 4HzO. Orcin treated as above give rise in most cases to several colouring matters which amre differently soluble in alcohol.The least soluble sub- stance gives with alkalis a bluish-violet solution with a brown fluo- rescence and contains less nitrogen than the preceding body. The orcin dye lately described by Weselsky also possesses a different com-position. ThynioZ Dye.-10 grams of finely powdered thymol are mixed with 10 grams of sulphuric acid and 30 to 40 grams of the reagent added immediately. The solution becomes first green and then blue. No gas should be evolved. As soon as the reaction is complete twice the volume of sulphuric acid should be added to convert unattacked thymol into thymol-sulphonic acid and after standing for some hours the solution is poured into water as before. The dye consists of a violet-coloured resinous mass which gives a violet-red solution with alcohol.Its formula is C30H,N20a,and its formation may be expressed thus- 3CJT1,O + 2NOJ3-= C30H36N201 + 3HZO. The formation of these bodies is possibly analogous to that of the phthaleins thus- Diiiitroso-orcin. Orciu dye. ORGANIC CHEMISTRY. But since picric acid does not yield such bodies it ismore probable that the nitroso-group is the important factor in the reaction as ex- pressed by the equations- Orcin dye. f-I OH = C6H + H20. C6H( g27 + Thymol dye. W. H. P. A Colouring Matter Analogous to Magdala-Red. By M. L~cco (Deut. Chem. Ges. Ber. vii 1290-1293). IN preparing azodinaphthyldiamine (amidazonaphthalene) by Church and Perkin's method and using a cold saturated solution of naphthyl-amine hydrochloride a product containing much resin is obtained while if the solution be too dilute no action will take place.As the formation of the resin depends also on the temperature it is best to find the proper conditions by a few trials and to prepare a larger quantity only when the precipitate has a brownish red and not a dark colour. The product is purified by dissolving it in boiling ether-alcohol and adding to the filtrate hot water until a colour appears. After a few moments the pure compound crystallises in reddish-brown needles with a green reflection and melting at 173"-175" and not at 135" as Perkin has found. On heating it with paratoluidine hydrochloride to 17Oo-18O0 it yields a colouring matter corresponding with XagdaZa-red.Its hydrochloride C27H21N3.HCl crystallises in small needles with a bottle-green lustre and showing in an alcoholic solution the same fluorescence as Magdala-red. c. s. 170 ABSTRACTS OF CHXMICAL PAPERS. Behaviour of Infusorial Earth (Kieselguhr) to Aniline Dyes. By R. BOTTGER (Chem. Centr. 1874 396). WHEN an alcoholic solution of any of the aniline dyes is shaken up with a sufficient quantity of infusorial earth some water added and the whole thrown on a paper filter the liquid which runs through is perfectly colourless the pigment being retained by the siliceous earth. 0. 1'.A. Xylidein. By C. LIE B E R 31 AX' N (Deut. Chem. Ges. Ber. vii 1102-1lo3). XYLIDE~X is a name given by E'ordos and Rommier to a green colouring matter examined by them which is produced in the decaying wood of beech oak and birch under the pathological influence of Pexixa aarugimosa.In some cases large blocks of wood of a dark blue-green colour are obtained. To extract the colouring matter the author treats the wood with cold phenol ;a dark green solution is thereby obtained from which the dye may be precipitated in green flocks by alcohol or ether. Dried in a vacuum the substance contains 58.65 p. c. C. 5.66 p. c. H. and 2.45 p. c. N. (Fordos and Rommier found 50.23 p. c. C. 5.33 p. c. H. and 2.63 p. c. N.). The substance dissolves in the least possible quan- tity of phenol at SO" and separates on cooling in small four-sided plates with a copper-like glance resembling coerulignone or sublimed indigo The crystals are insoluble in most solvents but are dissolved by concentrated sulphuric acid with a grass-green colour and by phenol and aniline with a dark green colour ; dried at 110" they con- tain 65.48 p.c. C. 4.71 p. e. H. and 1.0 p. c. N. The nitrogen is obviously due to impurity. The substance analysed in the first instance was precipitated by aqueous alcohol and is possibly a hydrate of the crystalline body. The author intends to continue his investigation. W. H. P. Essential Oil of Lepidium Sativum. By A. W. HOFMANN (Deut. Chem. Ges. Ber. vii 1293-1294). THEoil of the common cress consists like that of the garden-nastur- tium chiefly of phenlllacefonitril. c. s. Aromatic Phosphorus Compounds.Part 1V.-Phosphenylic Acid and Derivatives. By A. MICHAELIS and C. MATHIAS (Deut. Chem. Ges. Ber. vii 1070-1073). PHOSPHENYLIC phenyl-phosphinic acid C,H,PO( OH), is pro-acid or duced by the decomposition of phosphenyl tetrachloride tetrsbromide or oxychloride by water. 23.5 parts of the acid dissolve iri 100 parts of water at lj" but it is much less soluble in water containing hydro-chloric acid and crystallises therefrom very readily. Its melting point according to the present paper is 18" in a former paper by ORGANIC CHEMISTRY. Michaelis (p. 168 of last volume) it was stated to be 158". When quickly heated to about 250° it decomposes into benzene and meta- p%phoric acid. By prolonged heating to about 203" phosphenylic acid loses water and furnishes di- or pyrophosphenylic acid.OH C,H&d 2C,H,PO3H-H2O = '0 C6H5d 'OH At 210" three molecules of the acid lose two molecules of water in the same way and triphosphenylic acid is produced (C6H5)3(PO)302( 0H)z. Di-or pyrophosphenylic acid forms a colourless transparent tenacious mass which in moist air recovers water and is reconverted into phos- phenylic acid. When dissolved in water phosphenylic acid is at once reproduced Triphosphenylic acid behaves in the same way. Phosphenylic acid is a powerful bibasic acid forming acid and neutral salts. The free acid precipitates neither barium chloride nor silver solutions but on addition of a little ammonia white precipitates are thrown down. The addition of sodium acetate also determines the precipitation of the silver salt.2'hospheyZates.-The neutral potassium salt C6H5P03K2, is uncry- stallisable and very soluble. The acid salt C6H5P03KH is precipitated from its aqueous solution by alcohol as a crystalline powder. Neutral sodium phosphenylate C6H5P03Na2.12H20 resembles the corresponding sodium phosphate. The acid salt crystallises less easily in simi1;tl. forms. Calcium phosphenylate C6H5P03Ca.2H20,is a white amorphous precipitate soluble though with difficulty in acetic acid. By evapo-rating this solution the acid salt (C6H,PO3),H2C2, is obtained crystal- lising in beautiful shining scales which are anhydrous. The acid strontium salt (C6H5P03)2H2SrH20, resembles the calcium salt. Zinc phosphenylate has the formula CsH,P03Zn.bIz0.Copper phosphenylate is C,H5P03Cu. Silver phosphenylate c6&Po3Agz is a light white powder not changed by light. Ferric phosphenylate (C6H5P03)3Fe2.2$H20, is a yellowish white pre- cipitat e. Ethyl phosphenylate C6H5P0.0H. OC2H5,is a non-volatile oily liquid which is decomposed by water. It is a monobasic acid furnishing a silver salt C6H5.P0.0Ag.0C2H5. The neutral ether and the amides will be described hereafter. The paper concludes with an enurnerahion of the reactions observed on the addition of various metallic salts to a solution of neutral sodium p hos phen ylat e . W. A. T. The Spectrum of Chlorophyll. By J. CHAUTARD (Ann. Chem. Phys. [5],iii 1-56). THEobject of this paper is to show the variations in the chlorophyll spectrum according to the circumstances under which it is examined.ABSTRACTS OF CHEMICAL PAPERS. It is stated that before trustworthy deductions from the phenomencm can be made it is indispensable to take into consideration the nature of the plant from which the chlorophyll has been obtained its rank in the vegetable kingdom its age the climate temperature season situation Roil the solvent mode of illumination degree of concentration of the solution &c. Many of the views now expressed have been given by the author in previous papers abstracts of which have appeared in this Journal. The general conclusions now given are- 1. The spectrum of chlorophyll is characterised by a certain number of bands amongst which is one in the red the following special pro-perties of which are sufficient to distinguish the substance :-a.Sensibility having a clear outline a fixed position and a re- markable permanence even in a solution diluted to the one-ten- thousandth. b. Certainty being divided into two under the inhence of alkalis a character which does not belong t,o the rays of blood bile or any other organic liquid. c. Constancy being always present wherever there is chlorophyll either pure or altered. 2. Chlorophyll can be perfectly recognised by the spectroscope whether it has been obtained from young leaves old leaves or dead leaves which have been subject to the action of light and air. a. In young leaves by temporilry accidental bands under the action of hydrochloric acid.b. In old leaves by permaned n.ccidenta1 bands in an alcoholic solution with the same acid. c. In dead leaves by permanent accidental bands which appear imme- diately without the intervention of hydrochloric acid. 3. Chlorophyll is much less alterable than is generally believed ; it resists the action of iodine acids alkalis and the animal digestive powers and preserves under the influence of these agents if not its composition and primitive character at least some properties which permit of its recognition in the most complex and varied mixtures even after a considerable lapse of tlime. H. J. H. Colour-reactions of Albumin. By ALBERT ADAMKIEWICZ (Pfluger’s Archiv. ix 156-162). AN investigation of the colour-reactions which albumin gives when heated with sulphuric acid alone and when albumin dissolved in acetic acid is treated with sulphuric acid.The varying effects of the quantity of substance in proportion to amount of acid present are specially noted; and it is shown that when certain percentages of albumin are reached the colour disappears. Whatever may be the tint produced with albumin by sulphuric acid-yellow orange violet &c.,-it is always associated with a broad absorption-band lying between the E and F lines of the solar spectrum. 1’. s.

ISSN:0368-1769    

DOI:10.1039/JS8752800137

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. The Formation of Fat in the Animal Body. By H. W EIS KE and E. WILDT (Zeitschr. f. Biologie x 1-20). THISmemoir begins with an excellent historical summary of the different views which have been held and ‘the experiments by which such views have been supported since the discovery was made that the fat taken by animals in their food is insufficient to account for all the fat laid up in their organisms. Liebig’s view that the carbo- hydrates form in such cases the source of fat was strengthened by the researches of Gundlach Huber Dumas Milne-Edwards Boussingnult Lehmann Grouwen Lawes and Gilbert and Pasteur. C. Voit howevor,.advanced the hypothesis in opposition to Liebig that the sources of animal fat other than the ready-formed fat of food are the nitrogenous coiistituents of food and not the carbohydrates.Voit’s experiments and views were confirmed by the researches of Stohmann and G. Kuhn. Experiments made with Pettenkofer and Voit’s respiratory apparatus strengthened Voit’s hypothesis ; the for- mation of adipocere showed the possibility of a conversion of nitro- genous tissues int’o fat ; the fatty degeneration of whole organs was an instance of such conversion taking place during life ; and the ex- periments of Blondeau Hoppe Kemmerich and Fleischer according to which fat was formed at the expense of casein pointed in the same direction. J. Bauer’s researches wit,h dogs whilst undergoing slow poisoning by phosphorus where fat was generated in abundance and Subotin’s experiments relative to the composition of the milk of bitches according to which the milk richest in fat is secreted when a diet rich in flesh is administered tend to confirm Voit’s supposition.Subotin’s experimeii ts are however irreconcilable with those of Bensch and Playfair. F. Hofmann’s experiments prove that the fat taken in food can pass unchanged into the animal cells and be stored up there; but Toldt and Subotin deny that this actually occurs ; and Radziejewsky thinks that the absorption and deposition of the fat of the food must first be preceded by its saponification by the secretions of the intestinal canal and that the stored-up fat is again synthesised from the soap thus produced. Weiske is of opinion that the above researches prove that in the carnivora the fat stored up in the tissues may be derived partly from the ready-formed fat in the food ingested and partly from the trans-formation of nitrogenous nutritive materials into fat and other pro- ducts.Experiments were instituted to determine whether in t,he omnivora and herbivora the sources of fat are the same as in the carni-vora or whether the carbohydrates are with those classes of animals sources of fat. Young pigs were the animals chosen for the purpose of experiment. The research appears to have been conducted with much care. The experimental period extended over six months and the animals VOL. XXVTII. N ABSTRACTS OF CHEMICAL PAPERS. were subjected to a monthly weighing when fasting.The daily allowance of food was weighed and its composition determined by analysis. The faxes were collected periodically weighed and aiia-lysed. Finally the bodies of the animals when slaughtered were subjected to analysis endeavours being made to determine the mean composition of the whole carcase. The details are too long for abstraction. Four similar pigs six weeks old were taken. Two of these were at once slaughtered and the composition of their bodies *determined. The other two animals were fed for six months the one on food poor in nitrogenous materials (ratio of nitrogenous to non-nitrogenous material 1 9.0 and later 1 8*6),and the other on food rich in nitrogenous constituents (nitro- genous to non-nitrogenoiis 1 2.9). The result of the research in the opinion of Weiske and Wildt does not afford a direct proof that in the onznivorn there is a conversion of protejids into fat when food rich in nitrogen is administered ; but that in this case as also when a food deficient in nitrogen is given the digested proteids sufficed to cover not only the increase in flesh but also the whole of the fat laid up in the body.T. S. The Colouring Matter of the Blood. By A. BBCHAMP (Ann. Chim. Phys. [5] iii 340-342). B~CEAMP claims to have isolated the red colouririg matter of the blood in a soluble form and perfectly free from all other albuminold matters. In order to effect this defibrinated blood is mixed with just so much water as is necessayy to rupture the corpuscles and dissolve the pig- ment.A solution of basic lead acetate is then added as long as a pre-cipitate falls; the precipitate is filtered off and the filtrate treated with a solution of basic lead acetate to which 10 per cent. of solution of ammonia has been recently added as long as a precipitate is formed. The very bulky precipitate is allowed to subside the access of carbon dioxide being carefully excluded during the whole process and the precipitate is filtered off. This precipitate like the first is decoloriscd by washing with water. The filtrate which contains all the blood- pigment is deprived of lead either by ammonium carbonate or by a current of carbon dioxide and dried in thin layers at a temperature of 35"-40". It then forms garnet-red laminae which are soluble in water containing a trace of ammonium carbonate.It still contains however traces of acetates of the alkalis and probably urea. In order to obtain the pigment free from these impurities the red solution which was filtered off after precipitation by ammoniacal lead sub- acetate is mixed with half its volume of alcohol of 50 per cent. and is then treated anew with ammoniacal lead acetate as long as a precipi-tate continues to form. The brick-red precipitate is filtered off and washed with 40 per cent. alcohol access of carbon dioxide being pre-vented. The washed precipitate is mixed with water a small quan- tity of ammonium carbonate being added and is then decomposed by means of a current of carbon dioxide. The filtered solution coagulates PHYSIOLOGICAL CHEMISTRY.17.5 at Gl" and must be dried below that temperature in order to obtain the pure solid pigment. In opposition to Vindschgau BBchamp asserts that the albumino'id of haemoglobin differs from that of white of egg not only in its rota- tory power but also in the reactions of its lead compounds. T. S The Relations of Fibrin to Colourless and Red Blood-cor-puscles and on the origin of these Corpuscles. By ALEX. Sc HNIDT (Pfluger's Arcliiv. f. Physiol. ix 353-357). AN exposition of the author's well-known views on the formation of fibrin during coagulation from two constituents of the blood-plasma- the fibrino-plastic substance and the fibrirogenous substance. He asserts that l-memoglobin has not'hing to do with the coagulation of blood but that the source of its coagulation is to be looked for in the protoplasm.T. s. The Influence of Alkaloids on certain Properties of Hzmo-globin. By ED. SCHAER (Deut. Chem. Gei. Ber. vii 1345-1348). A TREORETICAL discussion of the researches of Binz M. Muller Ross-bach and Schonbein on the influence of alkalo'ids and of quinine espe- cially upon the so-called organisatjon of the blood. The experi-ments of the above observers are regarded from Schonbein's st,and-point i.e. the existence of antozone and a'ntozonides is assumed. T. S. On the Decomposition of Eggs. By W. THOXPSON (Chem. News xxx 159). THE contents of eggs when their shells are intact can only be decom- posed by one two or all of three different agencies.The first or putrid ceZl ferment is capable of being developed within any egg no matter how effectually its shell may be protected. It is generated from the yolk and spreading to the albumin sets up true puhefaction. Oxygen facilitates its development while coal-gas and carbon dioxide seem to retard its growth. It is capable of penetrating the shell of other eggs when the latter are immersed in water containing it. The second or decomposition by the agency of vibrios is bronght about by an animalcule like a worm which niultiplies by division. The germs of these vibrios do not exist in the egg originally but in all cases have to penetrat,e the shell. Eggs kept dry are never attacked by these vibrios but if the shell becomes wet or moist the germs float- ing in the atmosphere fall on it develop in the moisture penetrate the shell and attack hhe contents.The third is decomposition by fungi the principal one of which is PeniciZZium gZaucunz. The spores of this fungus exist largely in the atmosphere and seitling on the shell of the egg begin to develop, N2 ABSTRACTS OF CHEMICAL PAPERS. sending their filaments through the shell into its contents. The growth of this fungus is entirely prevented in an atmosphere of carbon dioxide. In hydrogen and nitrogen a few fine filaments were observed on the shell but none penetrated to the contents. In oxygen its growth was luxuriant. H. J. H.

ISSN:0368-1769    

DOI:10.1039/JS8752800173

出版商:RSC    

年代:1875

数据来源: RSC