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PHYSIOLOGICAL CHEMISTRY.P h y s i o l o g i c a l C h e m i s t r y .279Effects of Alkalis and Acids on Respiration. By C. LEHMANN(Landw. Versuchs-Xtat., 31, 169--171).-According to the author, t,heashes of various cattle-foods have not been sufficiently studied frortithe point of view of their effect on the transformation of tissuc inthe respiratory organs. The general opinion is that t'he increase ofalkalis in the circulation, causes increase of oxidation and consequentrapidity of tissue changes, whereas the preponderance of acids has acoritrary effect. Experiments in this direction being very rare, theauthor undertook some researches with the view of deciding thequestion ; the work of others is also noticed. The author's experi-ments were made on rabbits on which the operation of tracheotomywas performed after a fast of 18-24 hours ; they were then placed inthe respiration apparatus described in Pfliiger's Archiv, 1884.During spontaneous breathing of the animals after introduction ofalkali into the stomach by the pump, there was an increase of oxygenconsumption of more than 5 per cent., while after the introduction ofacids there.was a decrease of 8.3 per cent., the substances used beingsodium carbonate and hydrochloric acid.Tn order to obtain a more rapid action, the substances in a suitablydilute state were introduced directly into the veins (2 per cent.of Na,CO3-0*5 per cent. HCl), and in order better to observe themuscular contractions, the animals were curarised and artificial respi-ration employed ; after 1-2 hours from the time of the injection of thealkali, the consumption of oxygen had increased 4-5 per cent.and theproduction of carbonic anhydride to 7-20 per cent. ; the injection of thedilute acid on the contrary, reduced the consumption of oxygen about5 per cent., and also that of the carbonic anhydride considerably. Inanother series of experiments, using the same alkali and acid, butadding 3 per cent. of grape-sugar to each, it was shown that the non-nitrogenous mnbters were rendered more readily oxidisahle by alkalisand less so by acids ; in one case the alkali caused an increase of oxygenconsumed of 15 per cent. and of carbonic anhydride produced ofabout 24 per cent. In order to show that the injection of the solutionsinto the veins was not the cause of abnormal irritation, the authorinjected sollitions of common salt into other animals under preciselysimilar conditions, but the functions of the organism continued to becarried on normally. J.J?.By P. VIGIER (Jour. Phann. [ 5 1, 9, 398-402, 461-468 ; aiid 10, 17-2 I ) .- 1. Pepsiri.-Af ter many experi-Digestive Ferments280 ABSTRACTS OF CHEMICAL PAPERS.ments, the author proposes the following method for the estimation ofpepsin :--Medicinal pepsin powder 0.5 gram ; water 60 ; hydro-chloric acid, officinal, 0.6; mutton, pork, or veal fibrin, washed andstrained, 10 grams. Heat at 50" on water-bath for six hours, withfrequent agitation until the fibrin is dissolved ; this takes place veryrapidly, then shake every hour ; after six hours, 10 C.C.of the filteredliquor should give no turbidity on the successive addition of 30--40drops of nitric acid ; 0.2 gram of the pepsin extractive ought to givethe same results. The aptitude of a pepsin to dissolve fibrin is acharacter of no value, for a good pepsin can dissolve three or fourtlhousand times its weight of fibrin, if the amount of acidified waterpresent is proportional to the amount of fibrin ; the true test is thepower to convert the fibrin into peptone. The author asserts that theonly character which indicates in a precise manner that the digestmionis complete, is the absence of all precipitation and turbidity on theaddition of nitric acid. The fibrin employed .should be obtained byvigorously stirring up warm blood with a bundle of twigs, wash-ing in a large quantity of water until colourless, and then pressing incloth.I t may be preserved in glycerol, but the results are not sogood as with fresh material. Results obtained by the author point tothe fact that the accumulation of peptone in the solution tends toprevent further action of the pepsin, and that the action of thepepsin is considerably increased if the peptone produced be suffi-ciently diluted ; hence the necessity of drinking sufficient fluid duringa meal. These results appear to show that pepsin acts as a livingferment. J. T.Behaviour of Carbonic Anhydride, Oxygen, and Ozone inthe Human Stomach. By W. JAWORSKI (Zeits. .f: Biol., 20, 234-2.54) .-Whilst, making experiments upon the behaviour of chloride ofsodium solution in the human stomach, the author noticed that if thesolution wa's saturated with carbonic anhydride i t passed throughmuch more rapidly than if no free carbonic anhydride were present.He accordingly made the following experiments, the results of whichare briefly as follows :-All the gases increase the quantity of secretion, although in varyingproportions, a fact which proves that it is not from mechanical stimu-lation, but from the action of the gases themselves.Carbonic anhydride very markedly increased the activity ir, twocases, but only a little in a third case ; the acid secretion peptonisedalbnmin readily, and had moreover a strongly antiseptic action.Oxygen caused in one case the secretion of an alkaline fluid, whichdissolved, but did not peptonise.Ozone produced in one case a less alkaline secretion than oxygen,in another case very little change ; the largest increase in the secretionis, however, produced by ozone.Carbonic anhydride, besides producing a pleasant effect, stimulatedthe appetite. J.P. L.Formation of Fat from Carbohydrates in the AnimalOrganism. By S. CHANIEWSKI (Zeits. f. BioE., 20, 179-192).PHYSIOLOGICAL CHEMISTRY. 281Soxhlet’s experiments on pigs and Schulze’s on geese being incon-clusive, the author made the present ones, in the hope of arriving a t amore definite conclusicn. For this purpose, three geese of nearlysimilar live weight were fed for 26 days on rice and barley, at theend of which period No, 1, weighing 3219 grams, was killed and usedas the standard of comparison.No. 2 and No. 3 were then fed on adaily ration of 100 grams of a mixtare of rice and barley, their re-spective weights before the commencement of the feeding, beingNo. 2, 3283 grams, No. 3, 3581 grams. After 18 days, No. 2 waskilled, and weighed at tLhat time 3816 grams. No. 3 was not killedtill the 29th day ; its weight had then increased to 4471 grams.The total amount of prote’id and fat was determined in the driedflesh, bones, blood, feathers, &c., of each bird, and are compared ina table given in the original paper.During the period of feeding, the intake and output of nitrogenbalanced one another within the limits of experiment.The increasein prote’id in both birds was but a small percentage of the total.&faking every allowance for the fat assimilated from the food andthat which was possibly due to the decomposed proteiid of the same,i t is only necessary to subtract 75.37 grains for No. 2 and 136.52 forNo. 3 ; a balance of 193.63 grams for No. 2 and 503.68 grams forNo. 3 is still left, the origin of which apparently can only be from thecarbohydrates.A similar experiment made with two geese almost destitute of fatgave even a more striking result, 86.7 per cent. of the newly formedfat apparently being due to the carbohydrates.Alimentary Value of Oats. By A. MUNTZ and C. GIRARD (Ann.Agronomiques, 10, 524-526 ; from Ann,. de 1’Institut Agronomique,No. S).-Three horses were fed each with three varieties of oats fromSweden, Russia, and the Beauce district respectively.The rationswere weighed arid analysed before ingestion, and the excreta of theanimals were also weighed aud analysed, in order to determine thecoefficient of digestibility of each constituent in the three samples ofoats examined. Taking the coefficient of digestibility of the starch(none of which was excreted) as 100, the authors arrive a t the follow-ing conclusions :-Nitrogenous Substances.--80 per cent. (mean) of the nitrogen con-tained in the Beance sample, 77.3 of that in the Russian sample, and75 per cent. of that in the Swedish sample, was digested.Succhara’jable CelEulose.--56 per cent. of that in the Beauce oats,and about 34 per cent.of that in the other samples, was digested.“ Indigestible cfibre ’’ (the residue after successive treatment withacid and alkali).-46.2 per cent. of tliis was digested in the Beaucesample, 37.5 in the Swedish sample, and 18 5 only i n the Russiansample.The nutritive value of a sample of oats is greater the smaller theproportion of husk to kernel ; in the case8 cited, the Beauce oats con-tained much less husk than the Swedish.The authors point out the erroneous results arrived at in estimatingthe nutritive value of a food such as oats, from an ordinary analysis.J. P. L282 ABSTRACTS OF CHEMICAL PAPERS.They also mention that different samples of oats which they haveexamined, vary in the percentage of albumino’ids from 7.6 to 13.25.J.M. H. M.Digestibility of Substances used as Food for Horses. By A.MUNTZ and C. GIRARD (Ann. Agronomigues, 10, 526-527 ; from Ann.de Z’lnstitzct Agronomiqtce, No. 8 ) .-Experiments made in the mannerabove described have yielded the following results :-Horse-beans.-Horse No. 1 digested 67.64 per cent. of the nitro-genous matter, horse No. 3,77.9 per cent. ; crude fibre 46 (No. 1) and81 (No. 3) per cent.; saccharifiable cellulose 73.6 (No. 1) and 88.3(No. 3 ) per cent.Buckwheat.-Supposing the grains to be perfectly masticated, whichis never the case, the digestive coefficients are as follows :-fat 55.14,starch 100, saccharifiable celluIose 35.75, crude fibre 7.10, nitrogenousmatter 69.06, undetermined constituents 51.15.Carrots.-Digestive coefficients :-fat 56.3, sugar 100, saccharifiablecellulose 98.03, crude fibre 90.25, nitrogenous matter 89.28, pectic sub-stances 100, undetermined constituents 90.88.J. M. H. M.Composition and Methods of Analysis of Human Milk. ByA. R. LEEDS (Chem. News, 50, 263-267 ; 280-2281).-The authorhas examined 84 samples of human milk, and has tested experiment-ally the various methods employed for the analysis of human milk.In the present communication the various methods previously em-ployed are reinvestigated, and numerous sources of error pointedout.He commends highly the Gerber-Ritthausen method (Abstr., 1881,657) ; i t is the one employed in his analyses.The 84 analyses of human milk are thus summarised. They had auniformly alkaline reaction. Only normal milks were analysed afterbeing submitted to a microscopical examination :-Average.Specific gravity............ 1 0 3 1 3Albuminoids ............ 1.995Sugar.. .................. 6.936Fat ...................... 4.131Solids not fat.. ............ 9.137Ash ...................... 0.201Total solids (by addition ofconstituents) ............ 13.268Total solids (by evaporation). 13.267Water.. .................. 86.732Minimum.1.02600.855.402.1 16-570-1310.9210.9183.21Maximum.1.03534-867.926.8912-090-3716.7916.6689.08These results agree fairly well with those of earlier investigators ofthis subject. The most variable constituent of human milk is thealbumino’id, the fat coming next, whilst the sugar is the least so.The colour of the milk is no indication of its richness, the taste isusually more or less saline and somewhat disagreeable, whilst its con-Eistency is much thinner and more watery than cow’s milk.Althoughthe amount of solids is greater in human than in cow’s milk, never-theless the specific gravities of the two classes of milk vary buPHYSIOLOGICAL CHEMISTRY. 283little one from the other, that of human milk being somewhat thegreater. The milk from women under 20 years of age is richer in allrespects than that from older women, and that of the first lustrum isricher in alburninoxds: and especially in sugar than that of those sue-ceeding it. D. A. L.Relation of Phosphoric Acid to Nitrogen in the Urine duringFeeding with Brain. By G.POL~TIS (Zeits. f. Riot!., 20, 193-214).-Zulzer, Edlefsen, and others from their observations concluded thatan increased excretion of phosphoric acid denoted an increasedactivity and decomposition of brain material. Voit, however, doubtedthe correctness of this conclusion, which is left in still greater doubtby the present experiments. A dog was fed for nine days on a meatdiet consisting of 500 grams of cooked flesh, and the avemge relationof phosphoric acid to the nitrogen excreted was 1 to 6.7 ; on the loth,l l t h , and 12th days 50 grams of ox brain was included with the meat,its equivalent in meat being deducted, the relation however stillremained the same. I n another experiment the animal was fed onbrain exclusively (518 grams per day) ; the urine during the day wasanalysed five times, at intervals of three hours, from 9 A.M.to 9 P.M., andnot only did the average relat,ion remain constant, but the relation wasthe same for the whole 24 hours, The reason of the varying relationduring meat diet is owing to the fact that the phosphoric acid existsas inorganic salts (phosphates), which are easily absorbed and ex-creted ; whilst in brain it exists in an organic combination, and conse-quently undergoes resolution concurrently with the protejid.Moreover it seems unnecessary to attribute the increase, evenadmitting its truth, to increased activity of the brain solely, as thatorgan only forms 4 to 2 per cent. of the body weight, whilst themuscles, which themselves experience great activity, constitute 45 percent.J. P. L.Action and Fate of Trichlorethyl Alcohol and TrichlorobutylAlcohol in the Animal Organism. By E. KULZ (Zeits. f. Bid., 20,157-164) .-Liebreich incorrectly attributed the physiological actionof chloral hydrate to the formation of chloroform in the organism, dueto the alkalinity of the blood. Mering and Musculus found, however, anew body : " trichlorethylglycuronic acid," excreted in the urine aftertaking chloral hydrate ; this substance is l~evorotatory, and is decom-posed into trichlorethyl alcohol and dextrorotatory glycuronic acidwhen treated with mineral acids. The author has been unable toobtain this acid from the urine of patients kept under chloroform fora long time during operation, or from the urineof a dog continuouslychloroformed for five hours.He further states that the Itevorotntoryaction of the urine from chloroformed pat,ients is due to the presenceof a similar substance, " phenylglycuronic acid." In the present paper,the author has given the results of experiments with trichlorethyl andtrichlorobutyl alcohols ; both produce a marked soporific effect and areexcreted in the urine as their corresponding glycuronic acids. Boththese latter compounds have still a very strong physiological action,producing a more prolonged sleep, although they take longer to produc284 ABSTRACTS O F CHEMICAL PAPERS.the effect than an equivalent dose of chloral hydrate, butyl-chloralhydrate, or trichlorethyl or trichlorbutyl alcohols.A New Lzevorotatory Substance (PseudohydroxybutyricAcid).By. E KELZ (Zed. f. Biol., 20, 165--178).-1n the urineof diabetic patients taking chloral hydrate, after the sugar had beenremoved by fermentation, the author observed that the laevorotatoryaction of the urine in some cases exceeded that due to the trichlor-ethylglycuronic acid, and concluded that a second laerorotatory sub-stance was present, which was incapable of precipitation either by leadacetate, basic acetate, or even basic acetate and ammonia. Neitherwas it identical with the IEvorotatory body Haas has described as exist-ing in normal human urine. In order to isolate this substance, one ofthe two following methods was adopted :-1st. After fermentation,the urine is concentrated and then precipitated with normal leadacetate, basic acetate, and basic acetate and ammonia; the filtratefreed from lead is evaporated to dryness, the residue dissolved ina little strong alcohol, and then absolute alcohol added until no moreprecipitate is formed. After remaining 24 hours, it is filtered andmixed with 5 times it's volume of ether, whereupon the acid separatesout as a light yellow syrupy mass.2nd method. After fermenta-tion, the acid liquid is coucentrated to a syrup, and a large volume ofether added at once to separate the acid.The purified acid was converted into its barium salt, and from thisthe potassium, magnesium, copper, cadmium, zinc, and silver saltswere obtained ; the last named crptallises in beautiful stellateneedles, the elementary analysis of which agrees with the formulaC,H,AgO,, its specific rotatory power (using a Jellet-Corm polari-meter) is [ a ] j = -8.657.The acid obtained by decomposing thesilver salt with sixlphuretted hydrogen forms a colourless syrup.Analyses of the acid and its silver salt gave numbers agreeing withthe formula for a hydroxybutyric acid.As however it does not agree in any of its properties with any ofthe four hydroxy-acids already known, the author has assigned to itthe name of pseudohydroxybutyric acid ; it gives no colour reactionwith ferric chloride, and is not volatile with the vapour of steam.I n 52 cases under observation, the acid occurred only in the urineof the most severe, and of those which a t the same time gave theferric chloride reaction.It is besides of great clinical interest, for inone of the cases above mentioned, over 200 grams were eliminated in24 hours ; it may possibly too account for the lower percentages ofsugar sometimes obtained by the polarimetric, than by the tetrimetricmet hod of estimation.J. P. L.J. P. L.Putrefaction of Albumin in the Alimentary Canal of Her-bivora. By L. BOHM and 0. SCHWENK (Zeit. f. Biol., 20, 215-233).-The authors consider the negative results of both Brieger andMunk in their researches on oxen and horses, to be entirely due to thefact that they used too small a quantity to determine the presence ofthe volatile aromatic compounds of sepsis. They have thereforerepeated the experiments, observing at the same time the same divisioPEYSIOLOGICAL CHEMISTRY. 285of the alimentary canal as Tappeiner did in his recent experiments onintestinal gases.The results, which are entirely of a positive cha-racter, are as follows :-Phenol is present in every section of the ali-mentary canal of both horse and ox ; in the paunch and colon of oxen insufficient quantity to be weighed as tribromophenol ; indole in the smallintestine of horses and oxen, in the cmmm of horses and in the caecumand colon of oxen ; skatole in the paunch of oxen and colon of horses.There can, too, be no doubt that they owe their origin to the sepsis ofalbuminous bodies in the intestine. About 10 per cent. of the prote‘idof the food may approximately be considered as lost through putrefac-tion.I n the horse, putrefaction begins earlier, as traces of phenolare evident in the stomach; in the colon it is more actire than inany part of oxen; this is in agreement with the observations ofMunk, namely, that more phenol was contained in horse’s urine thanin that of oxen. They do not consider the variation in behaviour ofphenol when given to dogs and horses t o be due to the greater powerof oxidation in the blood of the latter, but to the fact that it is moreslowly absorbed. J. P. L.By J. GRASSET (Compt. rend.,99, 983--984).-When a 1 per cent. solution of coca’ine hydrochlorideis injected under the skin of dogs or monkeys, it produces completecutaneous anaesthesia after some minutes, and this anmthesiaincludes those muscles which lie nearer the snrface, but there is alimit to the depth to which the effect extends below the skin.Anesthetic Action of Cocahe.C.H. B.Physiological Action of Dichloromethane compared withthat of Chloroform. By J. REGNAULD and VILLEJEAN (Jozcr.P k a r z . [ 5 ] , 9, 384-389). - The researches of the authors show(1) that the methylene chloride usually supplied to surgeons issimply a mixture, owing its anaesthetic properties to chloroform ; (2)that the physiological action of dichloromet hane is different from thatof chloroform, and only resembles the latter in producing insensibility ;(3) the symptoms produced by dichloromethane are constant, and ofsuch a nature as to preclude the employment of this agent in surgery.Analysis of the Contents of a Cyst formed under the Tongue.By GUINOCHET (Jozcr.Pharm. [5], 9, 475-479). - The cyst wasabout 18 years growing, and weighed about 30 grams. Details of themethod of analysis are given; its composition was found to be asfollows :-J. T.water. ........... 21-20Soluble in ether. . cholesterin ......fatty matter. .....mineral salts. .....albuminoid mattery:;;} 74.73.... } 1:;) 4-07{Insoluble in ether100~00The large amount of cholesterin is very remarkable. J. T286 ABSTRACTS OF CHEMICAL PAPERS.Occurrence of Xanthine, Guanine, and HypDxanthine. By A. BAGINSKY (Zeits. Physiol. Che?n., 8, 395-403) .-The researches ofFischer (Abstr., 1883,354) having shown the close relation of xanthineto caffeine and theobromine, it appeared probable that it might occurin tea.The author, therefore, examined several samples of tea, andfound not only xanthine, but also hypoxanthine.A considerable quantity of the pancreas of the ox was divided intotwo portions. The first portion, examined whilst quite fresh, con-tained guanine 0.2797 per cent., xanthine 0.1145 per cent., hypo-xanthine 0,128 per cent. The second portion mas allowed to putrefyfor three weeks, and then yielded guanine 0.0069 per cent., xanthine0.0455 per cent., and hypoxanthine 0.0810. An experiment in whichin the course of three da,ys 4.28 grams of hypoxanthine was admin-istered to a dog, showed that no increase was thereby caused in theamount of hypoxanthine excreted in the urine.In cases of acuteinflammation of the kidneys in children, the urine contained quan-tities of xanthine varying between 0.0113 and 0.0285 gram per 100 C.C.of urine, whilst normal urine (of children) contains only 0.0028-0.003. A. J. G .Guanine. By A. KOSSEL (Zeits. Physiol. Chem., 8, 404410).-The separation of guanine from hypoxanthine ca’n only be effected byammonia (in which guanine is sparingly, hypoxanthine readily solu-ble) in the absence of peptonous substances and many other com-pounds. It is therefore better to precipitate both substances togetherby means of ammoniacal silver nitrate, recrystallise the mixed silversalts from hot nitric acid in the presence of carbamide, and then, afterremoval of the silver, to effect a separation by ammonia. A loss ofabout 5.5 per cmt. of the guanine is met with in this process, due to thesolubility of guanine silver nitrate in the nitric acid employed. Theamounts of guanine, hypoxanthine, and xanthine, in several animaltissues, &c., were determined with the following results, per 100 partsof the dry organ :-~~~ ~Leucheemic blood.. ................Sarcoma of t,he peritoneum of a cow .Sarcoma of the skin of the upper armEmbryonal muscle (ox) ............Muscle of adult animal (ox) ........Muscle of adult animal (dog) .......Pancreas (ox 11) ..................Spleen (ox) ......................Pancreas (ox I) ...................Liver (ox).. ......................Guanine.0 -2010 *2830 -1960 -4120.020trace0 *24l0 -7460 -2700.197IIypoxanthine.0 ’0720 ‘2720 *1370 *3590 *2300 ‘2220 -4110.3640 -2810.134Xanthine.Not determined.,>0 3110.0530 ‘0930 -84240.1300 .l520 *12

ISSN:0368-1769    

DOI:10.1039/CA8854800279

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. 287Chemistry of Vegetable Physiology and Agriculture.Chemistry of Bacillus Subtilis. By G. VANDEVELDE (Zeifs.Physiol. Cliem., 8, 367--39O).-These experiments were made toascertain the changes produced by the growth of bacilli in solutionsof extract of beef (containing 2.5, 5, and 10 grams of extract to500 grams of water). The solutions were boiled in flasks closed byplugs of cotton-wool, or where the gases evolved were to be collected,placed with a little air, in tubes over mercury. After heating, thecontents of each vessel were carefully seeded by the introduction of afew drops of a pure cultivation of Bacillus subtilis. Within 24 hours,the solution, originaIIy clear, had become clouded, after a further40-48 hours this cloudiness bad vanished, and a bacillus-film ofgreyish-white colour had formed on tbe surface of the liquid.Afterawhile, this film broke up and sank in fragments to the bottom ; some-times one or more additional films formed in succession, but were sothin as to be nearly invisible, whilst bacilli were disseminated through-out the liquid, during these latter stages. The chemical examinationof the liquids showed that ammonia and volatile fatty acids were formedat the expense of the creatinine and sarcolactic acid of the fleshextract ; the formation of the fatty acids from the latter occuri-ingespecially in the latter period of the action, when the bacillus was actingas an anaerobjc ferment.In similar solutions, to which glycerol and some calcium carbonatewere added, the formation of lactic, bntyric, and a small quantity ofsuccinic acid was noticed.The gas evolved in the earlier stage offermentation contained carbonic anhydride 22.52 per cent., hydrogen15.35, nitrogen 62.13 ; that evolved later contained carbonic anhy-dride 37.02, hydrogen 3.72, nitrogen 59.26; still later in the fer-mentation, carbonic anhydride alone was given off. Substitutinggrape-sugar for the glycerol, the formation of mannite, lactic acid,butyric acid, and (doubtfully) of caproic acid, was observed. Twoalcohols were also formed, one boiling above and one below loo", thequantity obtained was, however, too small for identification. Theformation of succinic acid was also observed in one case. An analysisof the gas evolved in the later stage of the fermentation gave carbonicanhydride 78.61, hydrogen 3.39, nitrogen 18.00.Samples of gasfrom still later stages consisted of carbonic anhydride with traces ofhydrogen. A. J. G.Sterilisation of Fermentable Liquids in the Cold. By A.GAUTIER (BzdZ. SOC. Chim., 42, 146--150).-The filter used by theauthor t o sterilise liquids in the cold, consists of a small flask ofbiscuit porcelain or faience, with a long and narrow neck. A glasstube passes down the neck to the bottom of the flask, and is cementedinto the neck by means of a lead borosilicate. This cement is madeby melting together boric anhydride 8 parts, silica 2 parts, red lead12 parts, and allowing the mass to cool. It is then powdered ver288 ABSTRACTS OF CHEMICAL PAPERS.fine, mixed with terebenthene to form a paste, applied to the joint,and heated to redness.This cement is elastic, very fusible, and canbe applied to glass, porcelain, faience, &c.The receiver for the sterilised fluid consists of a glass flask with anarrow neck, which carries a tube bent a t right angles and reachingto the bottom of the flask, and another side tube which is connectedwith the pump. The tube which passes to the bottom of the receiveris ground to fit that which passes to the bottom of the filter, and thetwo are thus connected. Between the receiver and the pump is acylinder packed with asbestos. The filter and receiver are sterilised byheat, connected together, the filter placed in the particular liquid, andthe receiver rendered vacuous.The liquid passes through the porouswalls of the filter and thence into the receiver. Diastatic granules,ferments, &c., are deposited on the external surface of the filter, butthe latter can be readily sterilised by heating it in a Bnnsen flame.I n this way solutions of egg albumin, blood serum, grape juice,peptones, milk, &c., can be sterilised without the application of heat.As a rule, acid liquids treated in this way may be kept indefinitelywithout undergoing ally change, but alkaline liquids sometimesbecome turbid after a time, b u t give off no gas or odonr, andeventually become clear again and undergo no further change.Albumin solutions, after filtration in this way through biscuitporcelain, are not coagulated by heat, nor by carbonic, acetic, or nitricacid in the cold.The hot solution coagulates in presence of nitricacid, but not in presence of acetic acid. If the albumin solution isheated to loo", allowed to cool, and then treated with a current ofcarbonic anhydride, it yields a precipitate which dissolves if thepassage of the carbonic anhydride is continued, or if air or oxygen isbubbled through the liquid. The solution thus formed is not coagu-lated by acetic acid in the cold in presence of sodium phosphate, butcoagulates when heated under these conditions.Dilute solutions of case'in seem to behave in the same way, and it isevident that i f these liquids are thus modified by filtration throughbiscuit porcelain, they may undergo much greater changes by filtrationacross vegetable or animal membranes.Employment of Plaster Filters to Sterilise Liquids.By P.CAZENEUVE (BUZZ. SOC. Chim., 42, 89-94).-Pasteur hasadopted a filter of plaster of Paris to separate the bacteria of Davainein the charbon disease. As Benoist and Miquel have pointed out thatthese filters possess the disadvantage of depositing traces of calciumsulphate in the filtrate, which exerts a certain antiseptic action, theauthor has submitted them to a more critical observation. Milk,blood, bile, and albuminous urine were completely deprived of thealbumin on filtration, this effect being due partly to a chemical com-bination of the calcium sulphate with the albumin, and partly to theretention of the latter in the capillaries of the filter.But after atime these become more or less choked, the filtration is retarded, andt,Ee albuminous substances pass through.It i s here shown by a series of experiments that these filters retainsoluble or diastatic ferments, such as the diastase of malt, the myrosinC. H. BVEGETABLE PHYSIOLOGY AND XQRICULTURE. 289of mustard, the synaptase of almonds, pepsin, and the diastase ofTomla urince.Pasteur has observed that the liquid obtained by filtering the bloodin the charbon disease, loses its virulence from the separation ofthe bacteria, which act by virtue of their physiological action, namely,their avidity for oxygen. But this explanation is here criticised asinsufficient, and jtidging from the above experiments, improbable ; itis here suggested that the bacteria owe their virulence to the produc-tion of a diastatic action.This latter is prevented by the process offiltration. V. H. V.Action of Various Compounds on Bacteria of the GenusTyrothrix and their Spores. By CHAIRY (Compt. rend., 99,980-983).-T he author has estimated the amount of various solutions(viz., sulphuric acid, chlorine-water, sulphurous acid, hydrogen sul-phide, alcohol, phenol, zinc chloride, alkaloiids) required to maintainthe transparency of solutions of animal matter when inoculated withvarious species of tyrothrix, and also the quantities required to kill thespores of these bacteria. He has also examined the action of variousgases on the spores, the latter being collected on filter-paper, driedby exposure to air, and then subjected to the action of the gas.The nature of the liquid to which the bacteria are added, has verylittle influence on the quantity of a substance required to prevent thedevelopment of the spores or to kill them.The influence of the massof bacteria present in the liquid is, however, very marked. Thosecompounds which have a pronounced acid character (e.g., sulphuricacid, chlorine-water, hydrogen sulphide) exert the most destructiveaction on the bacteria and their spores, whilst substances like alcoholand the alkalo'ids are efficient only when present in relatively consider-able quantity. It is worthy of note, in connection with this result, thatthe development of the bacteria tends to make the liquid alkaline.The action of gases on the spores depends on the acid characterof the products to which they give rise, and the behaviour of theseproducts towards the envelopes of the spores.Nitrogen peroxide ismore active than chlorine, which in its turn is far more active thansulphurous anhydride or hydrogen sulphide. The two latter do notkill the spores but simply delq their development. Ozonised air,containing 3 4 per cent. of ozone, has no appreciable effect on thespores. C. H. B.Activity of Assimilation by Leaves. By J. SACHS (AnmAgronomiques, 10, 514-517 ; from Rot. Zeit., 1884, 428).-By the useof a colorimetic method depending on the various tints assumed byleaves when stained with iodine in a certain manner, the author hasinvestigated the rapidity of formation and disappearance of starchunder various circumstances, and in many different species of plants.He estimates t'hat a square metre of leaf, during a favourable day(24 hours), produces about 24 grams of starch, to which must beadded nearly a gram lost by respiration.J. M. H. M.By A. EMMERLING(Landw. Versuchs-Stat., 31, 182--183).-Previous observations on theFormation of Albumin in Green Plants.VOL. XLVIII, 290 ABSTRACTS OF CHEMICAL PAPERS.presence of amido-acids in all parts of green plants, have left thequestion undecided, whether they arc: formed by synthesis in theassimilating organs, or are derived from the decomposition of albuminalready formed in the plant. The author has made fresh experimentsto decide the question by examining the various forms of nitrogenpresent in the experimental plants-Ticia faba-in different stages oftheir growth. The Tesults of his experiments are in favour of theformer hypothesis, namely, that it is a synthetic process.The pro-cess begins with the formation of the roots, and afterwards of theleaves ; when these are perfected, the amido-acids accumulate in thefruits and assist their rapid development. The probability of this firsthypothesis is rendered greater, when the di6culty of explaining theknown facts by the second is considered; the nmido-acid being foundin the youngest leaves is opposed to the probability of the decom-position theory, whereas the syfithetic process is harmonious and onlyrequires the supposition of one regular process during the wholegrowth of the plant.By V.v. WILM (Lardw, Versuchs-Stat., 31,202-204) .-The ordinary method of extraction by Soxhlet's apparatusdoes not remove all the fat from palm nuts in the time (3-3; hours)usnally employed with other substances, a second extraction yieldinganother 1 per cent. ; other feeding stuffs yield their €at to within aminute fraction of 1 per cent. The matter is of considerable import-ance, as in recent times the palm nut cake or meal has been morethoroughly deprived of oil than formerly, the arverage of fat being3-5 per cent. ; so that 0.5-0.7 per cent. is an important figure in ananalysis. The suggestion was made that the substance obtained bythe second extraction is not true fat', but a species of' wax; tested byappearance, smell, melting, and solidifying points, it, however, provesto be a true fat.Thinking that the fat cells of the palm nut are of adense nature and do not permit the ether to have free access to thefat, the author ground samples of the substance to different degreesof fineness, and extracted the fat in the usual way; the resultsshowed the correctness of his views, the coarser samples leaving alarge proportion untouched, whilst all the fat was obtained fromthose finely ground. J. F.Oleaginous Seeds of the Syrnphonia Fasciculata (Clusiacea?).By J. REGNAULD and VILLEJEAN (Jour. Phurm. [ 5 ] , 10,12--16).-l'heauthors give a detailed account of the analyses of these seeds fromMadagascar.They remark that-(1.) The analyses of the seedsare very interesting on account of the large amount (56 per cent.)of fatty principles not containing any substance susceptible ofmodifying their mild taste, and remarkable for the nature of theglycerides present, and their striking analogy to the glycerides of themammalia employed as food. (2.) The astringent matters isolatedare very similar to those of the cinchona, ratanhia, &c. (3.) Besidesquercetin they have only found cellulose, and pectous and albuminojidbodies, such as occur in analogous vegetable organs.J. F.Fat in Palm Nuts.J. TVEGETABLE PHYSIOLOGY AND AGRICULTURE. 291Aira csespitosa . , , . . .Molinia cserulea . . . . .Nardus st,ricta . . . . . . .Carex csespitosa... . . .Carex panicea. . . . . . . .Eriophorum vaginatumScirpus cmpitosus.. . .Juncus articulatus.. . .Juncus squarrosus.. . .Erica vulgaris . . , . . .Occurrence of Phytosterin. By H. PASCHKIS (Zeits. PJz~s~oZ.Chem,., 8, 356-357) .-The author has obtained from colchicum seedsit substance agreeing in properties with phytosterin, the homologuo (?)of cholesterin previously observed in Calabar beans by Hesse ( Ahstr.,1878, 850), and in peas by Kolbe. A. J. G.69 -1869.8256 -5868.2667 .7374 -4668 *5282 *C975 -9565 -43Composition of Maize. By SCHICHOWSKY (Ann. Agronomipues,10, 518-519).-300 grams maize grains contain 260 grams drymatter, apportioned as follows : envelope 17 grams, albumin (botani-cal) 216 grams, embryo 27 grams.The embryo is richest in mineralsand the envelope poorest, the ash per cent. of dry matter being in theenvelope 1.71, albumin 0.36, embryo 8.23. The envelope ash containsabout 23.5 per cent. each of sulphuric and phosphoric anhydrides ; thealbumin ash contains 36.4 P,O, and 14.4 SO,; and the embryo ash:41.8 P,O, and 19.4 SO,. Lime and magnesia are very unequally dis-tributed. The envelope ash contains 10.5 MgO and 2.3 CaO ; the albu-min ash 8.5 MgO and 0.06 CaO ; the embryo ash 6.6 MgO and 7.9 CaO.The albumin is richest in alkalis, then the envelope, lastly the embryo.Silica, is contained in the following proportions : envelope ash 5.5 :albumin ash 1.4 ; embryo ash 0.2 ; the distribution of the iron is liket.hat of the silica.Composition of the Food of Scotch Hill Sheep.By E.KINCH (Trans. Highland and Agric. SOC., 16, 273-280) .-The authorhas executed analyses of the species of grasses and other forageplants collected in May and June, 1883, from the hill pastures ofAuchenbrach. The results are given in the following table ; in addi-tion to the determinations of albuminoids made by Church's phenolprocess, duplicate determinations were made by the copper hgdr-oxide process ; these latter gave in all cases results slightly higherthan the former :-No part of the grain contains chlorine.J. M. H. M.Composition of Fresh Plants.I- .-I- I t I-/-I-4-40 9.04 11-14 14-446'19 9.25 0.98 12.486-05 13.52 0.63 20-856.20 8.39 0.93. 14.621-95 6-49 7-24 1.18 15-410'83 3-51 8-17 0'18 12-851.18 4.89 8-38 0.97 16.061.44 2-45 4'82 0.19 9-011.39 2.62 7.25 0'24 12.551-12 3.13 7.52 2.87 19.9292 ABSTRACTS OF CHEMICAL PAPERS.5.864'245-465.046-043.263.758.085.773-24Aim caespitosa ......Molinia ceerulea......Nardus stricta ......Carex ceespitosa ......Eriophorum vaginatumScirpus cmpitosus.. ..Juncus articulatus.. ..Juncus squarrosus.. ..Erica vulgaris.. ......Cayex panicea. .......14-12] 29-26 3.72 4'7'0420'50 30.65 3.25 41.3613.93 31.13 1.46 48-0219.56 26.43 2-92 46'0520'12 22.42 3.68 47-7413-75 31.99 0.73 50.2415.58 26-61 3-09 50.9913.68 26.90 1-04 50.3010.90 30.17 0.99 52-179.06 21.74 8.33 57-63Composition of Dry Matter.h%m % .g 2$ a g s !.-12 *2516 -009.5617 -4317 -5713.3510 -449 -127 -69-86 -7378 -0568 *6189 *1486 *8497 -0966 -9983 -6984 -83-J.M. H. M.Composition of Inferior Hay. By A. MORGEN (Landw. Versuchs-Xtat., 31, 204-20e5).-Two samples of hay were submitted to theauthor, from a farm on which the cattle were very subject to weaknessand fracture of the bones. He found No. 1 t o contain only 0.37 percent. of lime and 0.20 per cent. phosphoric acid. The botanicalexamination showed that it consisted of so-called acid grasses andweeds, and contained few of the more nutritive grasses. SampleNo. 2 contained 0.67 lime and 0.26 phosphoric; acid ; there was also alarg0 proportion of the better grasses present. The albumin wasestimated in both samples, but the author thinks, with A.Meyer, thatthe lime and phosphoric acid are of greater importance.Analysis of White Carrot Fodder. By G. KRECHEL (Jow.Pharm. [ 5 ] , 9, 28--33).-The author had occasion to analyse somesamples of white carrot grown near Corbeil in a clayey calcareoussoil manured with farmyard manure. The root only was taken, thetops having been removed, and was found to contain-J. F.Water ...................... 85.727Sugar ...................... 10.400Starch ...................... 0.351Cellulose .................... 0.850Pectic acid .................. 1.990Proteid matter. ............... 0.077Mineral constituents. .......... 0.846100*241Deduct oxygen for the chlorine. , 000.004100,237-TTEGETABLE PHYSIOLOGY AND AGRICULTURE.293Mineral constituents (directly 0’828).rSilica.. ...... 0.205 Clilorine. ........... 0.0 13Iron ........ 0.002 Carbonic anhydride . . 0.132Lime ........ 0.012 Sulphuric anhydride . 0.042Magnesia .... 0.011 Phosphoric anhydride 0.108Potash ...... 0.238Soda ........ 0.077 Total ........ 0.846Organic acids, resinous and fatty matter not estimated.The ash contains-Silica. ....... 25.40 Potash ...... 29.50Iron ........ 0-31 bod& ........ 9-55Lime.. ...... 1.50 Chlorine .... 2.42Magnesia. .... 1.40ccCarbonic anhydride ............ 16.40Sulphuric ,, ............ 5.20Phosphoric anhydride .......... 13.40Deduct oxygen for chlorine.. .... 104.080.55103.53I n beetroot it has been repeatedly observed that the phosphoricanhydride is present to the extent of 1.1 per cent.of the sugar found ;in this root, the proportion is 1-04 per cent. The sugar was estimatedby Fehliug’s solution, the pectic acid by Schloesing’s method.Starch was estimated in the residue from the preceding by digesting itwith very dilute sulphuric acid, and determining the sugar produced.I he pulpy residue was washed successively with acid and potash,then with water, and assumed to be cellulose.niJ. T.Vegetation of the Sugar-beet in the Second Year. By H.LBPLAY (Con@. rend., 99, 1030--1031).-The sugar in the root ofthe beet a t the commencement of the second year continually dimin-ishes up to the maturity of the seed, a t which point it has completelyor almost completely disappeared, Six weeks before maturity (aboutthe middle of July) the stalks, leaves, and green seeds contain nosugar.The density of the sap diminishes in the root and increasesiu the stalks, then in the leaves, and finally in the seeds in the propor-tions respectively of 2, 2.7, 3.4, and 4.2. Potassium salts of vegetableacids exist in the juice in all parts of the plant, but the amount inthe root is aimost double what it was a t the end of the first year.Soluble and insoluble calcium compounds exist equally in all parts ofthe plant. The tissues of the ascending axis of the beet in the secondyear seem to contain more calcium in insoluble organic combinationthan the same tissues in the first Sear, with the exception of the stalks,which cont,ain less than the petioles of the first year, The gree294 ABSTRACTS OF CHEMICAL PAPERS.seeds also contain a somewhat large quantity of lime in insolubleorganic combination. I n the beet in the second year, there is anascensional movement of the calcium and potassium compounds fromthe soil to the leaves and to the p i n s , similar to that observed inthe maize plant during the formationof the grain (Abstr., 1883, 366).In this movement, the bicarbonates and carbonic acid absorbed fromthe soil by the root undergo organic transformation as in the firstyear. Potassium and calcium salts of organic acids are not whollyretained by the root, but are distributed throughout the ascendingaxis, and especially in the leaves and seeds. The movement of thecalcium towards the leaves and the seeds is very strongly marked.The potassium and calcium compounds contaiiied in the root of theheet in the first year are not nearly sufficient to meet the requirementsof the plant in the second year, and the quaiitity of these basesabsorbed from the soil in the second year is ten times as great as thatexisting in the root in the first year. The potassium and calciumsalts existing in the juice in various parts of the beet seem to have tohesame ultimate functions as in the maize plant (Zoc. c i t . ) ; the potassiumsalts contribute t o the formation of the seeds, and the calcium saltsto the formation of the tissues. C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8854800287

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

294 ABSTRACTS OF CHEMICAL PAPERS.A n a l y t i c a1 Chemistry.Microscopic Chemical Reactions. By A. STRENG (Jahrb. f.Nin., 1885, 1, Mem., 2 1-42> ,-The author, from the frequent appli-cation of chemical methods in the examination of rocks, is enabled toimprove and simplify the methods of microscopic chemical research.It must, however, be remarked that considerable skill and practice arerequired in all these methods.Phosphoric Airhydride.-In 1876, the author proposed to determinethe phosphoric anhydride in apatite, under the microscope, by means ofa nitric acid solution of ammonium molybdate. To the application ofthis reagent, Stelzner objected, as soluble silicates may give a similarreaction. The author has thoroughly examined the matter, and findsthat it is always apatite which occasions the precipitation of theyellow granules, but t h a t the amount of the precipitate is greatlyincreased by the presence of soluble silica, so that one can be led tobelieve that the whole silicate consists of apatite, whereas the latter ispresent only in very small quantity.In order to detect the presenceof apatite in a section with certainty, even in the presence of solublesilicates, the crystal to be tested for phosphoric anhydride is isolatedby a glass cover, in which a hole is bored. The crystal is then dis-solved in a drop of concentrated nitric acid, evaporated at a gentleheat, the residue decomposed with water, the solution removed by apipette, placed in three drops on a glass and evaporated to drynessANALYTICAL CHEMISTRY.295The first residue is then treated with a drop of molybdate solution,and observed under the microscope. If a number of rhombic dodeca-hedra and octahedra are rapidly precipitated, phosphoric anhydrideis present. Silica in this case cannot act, as it is rendeyed insolubleby the evaporation. The second residue is decomposed by a drop ofdilute sulphuric acid. If needles of gypsum are formed, lime ispresent. The magne-sium ammonium chloride, suggested by Behrens as a test for phos-phoric anhydride, gives very good results, but is not so delicate as themolybdate test.Potassium.-As a test for potassium, Behrens has suggested plati-num chloride. The crystals of potassic platinochloride frequentlyoccur as cubea, with or without rhombic dodecahedra and octahedra.Full details are given for performing the test.Sodium.-The author has suggested a reaction (Abstr., 1884, 366) ofa very delicate nature.Lithium.-Various reagents have been proposed as microscopictests for lithium ; the best is potassium carbonate.The author hasalso endeavoured to employ sodium lithium phosphate, but furtherexperience is necessary before an opinion can be given as to itsmerits .CuZciuin and Strontium.-As a good microscopic reagent for calcium,dilute sulphuric acid has long been employed. Another method is touse a concentrated solution of oxalic acid, distinct octahedra beingformed. Exactly the same reaction is given by stroutium with oxalicacid. Were it, necessary to detect strontiiim and calcium together, itcould be done with dilute sulphuric acid.Barium.-A good microscopic reagent for barium is potassiumferrocyanide.If a drop of warm dilute barium chloride is mixedwith a drop of potassium ferrocyanide, allowed to cool, and diluted,yellow rhombohedra of barium ferrocyanide separate out. Witheriteand strontianite may be easily distinguished, if the dilut,e hydro-chloric acid solution is divided into two drops, one treated withpotassium ferrocyanide, and the other with oxalic acid. Witherite inthe first shows yellow octahedra, strontianite in the second colourlessoc tah e dra..Magnesium.-Sodium phosphate, recommended by Haushofer andBehrens, is very suitable €or microscopic work. The auhhor finds thatthe best crystals are obtained when ammonia is added to the sodiumphosphate, and ammonium chloride to the solution t o be test,ed;the drops of both solutions are heated to loo", then mixed, andcooled slowly.AZ~crniniunz.-As a test for aluminium, hydrogen potassium sulphatemay be employed.A more delicat'e test is cmsium chloride, as cmsiumalum is more insoluble than potassium alum.The third residue may be tested for sodium.The reagent is uranium acetate.B. H. B.Detection of Iodine, Bromine, and Chlorine. By E. HART(Chem. News, 50, 268--269).-The substance is boiled in a flaskwith a solution of ferric sulphate, a suitable bent tube with bulbscontaining starch-paste having been previously attached to the flas296 ABSTRACTS OF CHEMICAL PAPERS.by means of a perforated cork. The presence of iodine is indicatedby the production of the usual blue coloration ; the bulbs are ofcourse kept cool.When all the iodine is thus driven off, chloroformis substituted for the starch-paste in the bulbs, and a small quantityof permanganate added to the contents of the flask, which is againboiled ; the presence of bromine is shown by the usual coloration ofthe chloroform. After all the bromine is eliminated, chlorine can betested for in the solution in the ordinary way. This method has beentested experimentally and gives satisfactory results.Chem., 8, 391--394).-A reply to E. Baumann (ibid., Part IV).D. A. L.Estimation of Iodine in Urine. By E. HARKACK (Zeits. Pkysiol.Estimation of Sulphurous Anhydride.By C. L. REESE (C'lzem.News, 50, 218).-The sulphurous anhydride solution, contained in astoppered bottle, is titrated with a solution of hydrogen peroxideof known strength. A few drops of titanium sulphate solution areadded to act as an indicator, a permanent yellow colour showingwhen the titration is complete. Results are low with this method.The hydrogen peroxide solution is standardised by means of per-manganat e. IJ. A. L.Estimation of Alkalis in Silicates. By T. M. CHATARD (Chem.News, 50, 279) .-This is an improvement on Hempel's process (Abstr.,1882,552) .--The finelypowdered mineral is mixed with twice its weightof bismuth oxide, placed in a platinum crucible, and heated, a t firstgently, then gradually to full redness, a t which it is kept for ten tofifteen minutes ; decomposition is complete when the solid mass is per-fectly friable.When cool, it is transferred to a dish and treated withhydrochloric acid, and if a complete analysis is required the silicaand then the bismuth are removed in the usual way. If alkalis only areto be determined, ammonia and ammonium carbonate are added, andthe removal of magnesium and the alkali determinations are proceededwith in the ordinary way. The process gives good results. The morebasic the silicate, the less likely is it to fuse when heated with thebismuth oxide, and vice versd; therefore, to prevent the fusion of acidsilicates, and ultimately to get them in the very convenient friable con-dition, it is advantageous to add an equal weight of calcium carbonateas well as the bismuth oxide before heating.D. A. L.Volumetric Estimation of Calcium Oxide and Carbonate.By PRUNIER (Jour. Phurnz. [ 5 3, 9, 300-303) .-On titrating a solu-tion containing calcium salts with a standard solution of ammoniumoxalate, the precipitate formed does not settle quickly enough t o givegood results. The author finds that a sufficiently rapid depositionof the precipitate takes place if a little starch is added to the solu-tion after it has been neutralised with pure ammonia, and the mixtureis boiled. The solution of oxalate can be standardised with purecalcium carbonate, dissolved in dilute hydrochloric acid, neutralisedwith ammonia free from carbonate, and boiled with a little starch.The solution is heated from time to time, and allowed to stand one o ANALYTlCAL CHEMISTRY.297two minutes for the precipitate to settle. If a persistent froth formson the surface, a few drops of strong alcohol are added, and the upperportion of the liquid is heated.Estimation of Iron by Potassium Permanganate in Pre-sence of Free Hydrochloric Acid and Chlorides. By J. J. HOOD(Chem. News, 50, 278).-It is well known that the titration of ironby means of permanganate is untrustworthy in the presence of freehydrochloric acid, owing partly to the action of the acid on the per-manganate, and partly to the yellow colour acquired by the solution.The author has observed that the presence of many soluble chloridesalso produces an error in such estimations, and suggests the additionof a few C.C.of a strong solution of magnesium sulphate (1 or 2 gramsaccording to the amount of chloride present) to the iron solutionbefore titration. The titration can then be conducted just as accu-rately as if sulphuric acid bad been used instead of hydrochloric acid,or as if no chlorides were pyesent.Estimation of Antimony. By G. T. DOUGHERTY (Chew,. News,50, 278).-The following method is recommended for the approxi-mate estimation of antimony in ores, hard leads, antimony s l a p , &c. :-About 10 grams of the substance are employed. If oxides are to beassayed, they are reduced to a metallic button by charcoal or redargol; if sulphur is present,, a mixture of equal parts of potassiumcyanide and sodium carbonate should be used for the decomposi-tion.The metallic button is weighed, cut into small pieces or ham-mered out thin, and boiled with nitric acid, diluted with an equalvolume of water, until the alloy is decomposed. The solution isdiluted, the antimony tetroxide filtered off, dried, ignited, and weighed.The lead may be obtained by difference if the button was pure, or maybe determined as sulphate in the solution.Detection of Cyanogen. By 9. VOGEL (Chem. News, 50, 270).-The reaction of hydrocyariic acid with trinitrophenol is recommended ;1 in 30,000 can be detected, and the reaction is considerably morerapid than the formation or" Prussian blue. The trinitrophenol shouldbe neutralised by heating with soda or potash solution before employ-ing it for this test, otherwise the darkening of the colour of thetrinitrophenol when heated with alkali might lead to an error ofjudgment.The substance to be tested is heated with soda solution, then boiledwith the neutralised picric acid ; the appearance of a deep red colourindicates the presence of hydrocyanic acid.By this means hydro-cya,nic acid has been detected in tobacco smoke and coal gas.Ammonia, Nitrous Acid, and Nitric Acid in PotableWaters. By GREINERT (Chem. News, 50, 279).-The author remarksthat out of 126 wat,ers examined, 21 contained ammonia alone,6 nitrous acid alone, 35 nitric acid alone, 15 nitrous and nitric acid,13 nitrous acid and ammonia, 17 nitric acid and ammonia, 19 nitrousand nitric acid and ammonia, and complains thar; the present theory ofResults are accurate to per cent.J. T.D.A. L.D. A. L.D. A. L298 ABSTRACTS OF CHEMICAL PAPERS.the conversion of ammonia into nitric acid does not explain either theappearance of nitrous acid without ammonia, or the appearance ofammoniacal compounds along with nitrates without any nitrites.D. A. L.Note by Abstractor.-A full explanation of phenomena such as aredescribed above will be found in Warington’s paper on Nitrification(Trans., 1884,637-672). The first difficulties are explained on p. 639,where it is shown that. the character of the organism determinesthe production of either nitrites alone or nitrates alone, whilst the totalremoval of ammonia is ensured when all conditions are favourable fornitrification. D.A. L.Separation and Estimation of Methyl Alcohol in PresenceBoth alcohols combine readily with oxalic acid in the presence ofgaseous hydrochloric acid. Methyl oxala te is readily soluble inwater, ethyl oxalate, however, is only sparingly soluble ; by. dissolv-ing the two ethereal salts in water or alcohol, and treating wit11ammonia, insoluble amides are formed, a circumstance on which thedetermination of the methyl alcchol is based.10.8 grams of oxalic acid are dissolved in 10 C.C. of the alcohol tobe examined, and the solution is saturated with hydrogen chloride.The mixture is allowed to stand for 24 hours in a well-closed flask,after which 2 C.C. are diluted with 10 C.C. of water and filtered.Methyl oxalate being completely soluble in water, the quantity ofoxamide produced on adding ammonia to the aqueous solution will begreater than that from an equal amount of ethyl oxslate. The quan-tity of oxamide formed in the washings of the ethyl oxnlate may bedetermined by ;L series of trials.For pure alcohol, the average is6.6 per cent. For methyl oxalate, the number is betwceii 14-65 and1 5 per cent. of the qiiaritity of methyl alcohol. If instead of purealcohol a mixture of ethyl and methyl alcohol is eniploped, the quan-tity of methyl alcohol can be calculated from the oxarnide found.For every per cent. of methyl alcohol, 0.14 to 0.15 per cent. morethan 6.6 per cent. is obtained.O f Ethyl Alcohol. By C. DE POKCY (DijigZ. polyt. J., 254, 500).-D.B.Detection of Coal-tar Colours in Wines by Means of Am-monia and Amy1 Alcohol. By JAY (BuIZ. SOC. chi^^., 42, 166-167).-In testing for coal-tar colours in wines by the ordinary methodof adding ammonia to alkaline reaction and shaking with amylalcohol, it is necessary to avoid a great excess of ammonia, and theproportion of the latter should never be more t.han 3 per cent., for ifthis is exceeded, the amyl alcohol may remain colourless, even ifthe wine contains a coal-tar colour. If the amyl alcohol is colour-less it should be decanted 08, filtered, and evaporated with a smallquantity of silk, when the foreign colonring matter, if present, willbecome fixed on the silk. C. H. B.Analysis of Red Wine by Means of Electrolysis. By L. N.KROHN (Jour.Pharm. [ 5 ] , 9, 298- SOO).-If an electric current, saANALYTICAL CHEMISTRY. 299from a couple of Bnnsen cells, be passed throngh 5 to 10 C.C. ofnatural red wine diluted with 6 volumes of water acidified with 8omedrops of sulphuric acid, a red lamellar deposit soon forms on thepositive pole. It is quite visible to the naked eye, whilst under themicroscope it appears as a tissue. After 12-20 hours it is quitecompact. During the passage of the current, the odour of aldehydeis perceptible ; the red liquid gradually becomes yellow, and finallycolourless. White wines similarly treated lose their faint colour, butgive 110 deposit. On isolating the red colouring matter of wine bymeans of lead acetate, and redissolving the precipitate in alcoholand a little tartaric acid, the deep red solution gives the same reddeposit a t the positive pole.The colouring matters usually em-ployed for the adulteration of wine do not give this deposit, althoughthey are decolorised, so that electrolysis combined with a micro-scopic examination of the deposit formed affords a certain meansof ascertaining whether the colour of a red wine is natural.Estimation of Starch in Gluten Bread. By L. RICHARD(Jou'r. Yharm. [ 5],9, 27).-Direct saccharification gives results whichare too high, owing to the conversion of other principles always presentin gluten bread. Thegluten is finely powdered, washed well with water, until the wash-water carries off no inore starch. The washings containing t'he starchare evaporated to a small bulk, mixed with sufficient sulphuric acid,and heated at 105" for 10 hours in a sealed glass tube. The glucoseformed is then estimated in the neutralised liquid.Estimation of Gum Arabic in Syrup.By A. ANDOUARD(Jour. Pharnt. [ 5 ] , 9, 18--19).-The author points out defects inRoussin's method of coagulation by ferric sulphate, and in Soubeiran'smethod of precipitation by alcohol. The defects of the lattermethod are obviated by slightly acidifying the alcohol employed.The author recommeiids the following process :-Gradually dilute10 grams of the syrup with 100 C.C. of alcohol at 85", add 20 drops ofacetic acid, and stir vigorously. After standing about three hours,pour on to a double tared filter, when the gum forms a cake whicheasily drains.Dissolve in 7-8 C.C. water and repeat the prxipitation,collect on the filter before used, after washing by decantation withpure alcohol, and wash on the filter with the same alcohol. Dry a t10U" and weigh. Afterwards, as Soubeiran suggests, expose to thettir for 24 hours and weigh again, when the gum will have taken u pits normal amount of moisture. The results are very exact. Thismethod is not applicable to a product containing gum and commercialglucose, although it serves to detect the latter when alone. Thisgives a turbidity with alcohol due to the precipitation of dextrin,which may be taken for gum arabic a t the first glance, but the dextrinforms a glue-like mass on the sides of the vessel. Further testsreadily show whether the precipitate is gam or dextrin.J.T.It is therefore necessary to isolate the starch.J. T.J . T.Milk Adulteration. By SAMBUC (Jozcr. Plzarrn. [ 5 ] , 9, 95-10l).-The author published in 1879 a simple method of detectin300 ABSTRACTS OF CHEMICAL PAPERS.the addition of water to milk. The method requires from 10-20minutes, and it consists in coagulating by an acid, and determiningthe sp. gr. of the serum after filtration. This is sufficiently constantin unadulterated milk to afford a ready means of detecting the addi-tion of water. 150 C.C. of milk are warmed to 40-50°, and 10 C.C.of an alcoholic solution of tartaric acid of sp. gr. 1*030-1*032 (pre-pared with alcohol of $5') are added. The mixture is taken from thefire and agitated with a small bundle of twigs, and the serum ispassed through a linen filter ; a sliglit turbidity in the filtrate does notappreciably affect the result.After cooling to 15", the sp. gr. is takenwit'h a lactometer. Numerous experiments made in the spring of1879 at Rochefort, and in October and November of last year a tToulon, show that the sp. gr. of serum thus obtained never fallsbelow 1.0278. All milk giving 8 serum sp. gr. of 1*024r--1.025 oughtto be regarded as falsified with a t least one-tenth of water ; a sp. gr.of 1.921-1.022 would indicate two-tenths, or each tenth of waterlowers the reading by 3" to 3-25" of the lactometer. J. T.Koettstorfer's Method for the Examination of Butter forForeign Fats. By It. W. MOORE (CI2ern. News, 50, 268).-Theauthor has examined, by the Koettstorfer and the Reichert methods,numerous vegetable oils and some mixtures in order to ascertaiiiwhich, if any, could be used, without detection, for the adulterationof butter or oleomargarine.The results are :-Mgrms. KHO C.C. !!- NaHO,1 gmm of oil.required for 10Kind of oil. for 1 gram of oil.Olive ............Cotton seed.. ......Pea nut ..........Palm ............Beune ............Sweet almonds ....Rapeseed.. ........Linseed ..........Cocoa butter . . . . .Cocoanut.. ........,, washed ...Poppy ...........185.2191.2196.6196.3192.4187.9192.8183.0195-2199.8250-3246.20.20.30.40.80.60.30.50.30.21.63.72.7Koettstorfer fixes between 221.5 and 232.4 mgrms.KHO as thelimits of the amount required to saponify 1 gram of real butter. Ofthe above oils, cocoanut oil alone exceeds these limits. The washedcocoanut oil was treated with large quantities of boiling water to freeit from fatty acids. The following mixtures were then examined,1 gram of the oleomargarine requiring 193.5 mgrms. KHOANALYTICAL CHEMISTRY. 301Cocoanut Oleomar- Mgrms. KHO Washed Oleomar- Mgrms. HKO.oil. 1 garine. 1 per gram. I oil. I garine. I pergram.220.0 53.1 P.C. 46.9 p . ~ . 223 -6234.9 I 75'9 ,, I 241 ,, I 234.9~~Koettstorfer's method evidently does not detect the admixture, noris it probable that Hehner's method would do so, since the cocoanutoil yields 86.43 per cent. of insoluble fatty acids, Reichert's method,on the other hand, shows the adulteration, as genuine butter wouldrequire more than three times as much - NaHO as the mixture.N10D. A. L.Detection of Cotton-seed Oil in Olive Oil. By BECHI (Jour.Ph,arm. [ 5 1, 9, 35-36 ; from Jour. Pharm. d'Alsace-Lormine). -The methods proposed up to the present time are unsatisfactory.The author finds the following to give good results :-5 C.C. of the oil aremixed with 25 C.C. of 98 per cent. alcohol and 5 C.C. of silver nitratesolution (prepared by dissolving 1 gram of the nitrate in 100 U.C. of98 per cent. alcohol). If cotton-seedoil be present, even in very small quantity only, the mixture will becomecoloured, and ta.ke a tint more or less deep according to the amountof cotton-seed oil present. This method depends on the propertypossessed by cotton-seed oil of reducing silver nitrate.It is neces-sary to avoid heating by a direct flame, or other oils which may bepresent, such as linseed oil, colza, &c., will give colorations.The mixture is heated t o 84".J. T.Estimation of Fragrant Essential Oils. By A. LEVALLOIS(Cmpt. rend., 99, 977--980).-1f an aqueous or alcoholic solution ofbromine is added gradually to an aqueous or alcoholic solution of anessential oil (for example, rose, geranium, neroli, rosewood, bergamot,lemon, orange, lavender, marjoram, cummin, eucalyptus), the colour oft,he bromine solution is discharged up to a certain point, beyondwhich any further addition of bromine produces a permanent colora-tion.The end of the reaction is also distinctly marked by the dis-appearance of the odour of the essential oil, and, if the oil and bromineare in aqueous solution, by the sudden appearance of a whitishresinous precipitate. The amount of bromine required is alwaysproportional to the amount of essential oil present, but a correctionmust be made for the quantity of bromine solution (0-2-0.3) neces-sary to impart a distinct coloration to the quantity of liquid employedWhen an aqueous solution of an essential oil is distilled in a flaskconnected with a Liebig condenser, the whole of the oil comes overwith the first 20-50 C.C. of the distillate, according to the amount ofoil present.The author's method consists in concentrating the essential oil bydistillation, and titrating the first portion of the distillate with a(25 -30 c.c.) 302 ABSTRACTS OF CHEMICAL PAPERS.solution.of bromine, standardised by means of a standard solution ofthe particular essential oil. C. H. B.Assay of Commercial Quinine Sulphate. By J. E. DE VRIJ(Jour. Pharm. [ 5 ] , 9, 454--4S6).-The author has examined nume-rous samples of commercial quinine sulphate by the method proposedby Oudemnns (Annulen, 182, 33). A boiling solution of commercialsulphate f 5 grams in 200 C.C. water) is treated with a concentratedboiling solution of Rochelle salt ( 5 grams). The crystals of quininetartrate formed on cooling are collected in a filter, washed with alittle water, and air dried. Cinchonidine tartrate does not separateout under these conditions. The results thus obtained, combined withoptical examination as detailed by Oudemans, show that the amountof cinchoriidine sulphate occurring in commercial quinine sulphatevaries from 5.47 to 18.46 per cent.J. T.New Reactions for Codeine and 2Ekm.h. Bg L. RABY(Jour. Pharm. [ 5 ] , 9, 402403).-To the code'ine placed in a watch-glass add two drops of ordinary sodium hypochlorite, dilute, a.nd thenfour drops of concentrated sulphuric acid ; after mixing with a glassrod, a superb clear blue coloration is produced. Bromine-water, inplace of hypochlorite, gives no coloration. Bromine-water employedalone causes a turbidity at the point of contact with the alkalo'id ; byagitation, the liquid becomes clear and perfectly colonrlesu, but aftera few seconds a violet coloration appears, faint but perfectly distinct.In experimenting with 50 of the most common alkalo'ids, none ofthem gave a coloration that could be confounded with the one givenby code'ine.An equally beautiful coloration is produced with acscnIin whensomewhat differently treated.Four drops of concentrated sul-phuric acid are added to the aesculin, and to the slightly colouredliquid which is formed, sodium hypochlorite is gradually added, withagitation. When sufficient of this reagent has been added, the liquidtakes an intense violet coloration; this gradually and totally dis-appears in about an hour. No coloration is produced if the additionsare made in the inverse order. Bromine-water substituted for hypo-chlorite gives a precipitate of the colour of dregs of wine ; the reac-tion is much less certain than with hypochlorite.J. T.Estimation of Tannin. By P. CARLES (Jour. Phamz. [ S ] , 9,33-35).-The author finds that i n estimating tannin by titration witha solution of gelatin, the solution can be made to clear quickly bythe addition of 2-3 grams of barium sulphate; the clearing takesplace most rapidly towards the end of the titration. To make quitesure of the finish, a little liquid is taken out, filtered, divided into twoportions, and tested with gelatin and Oannin solution respectively.The weak point of the method is the instability of gelatin solution.However, after numerous experiments, the author finds that cherry-laurel water preserves the solution for months in well-closed bottles.The solution is prepared as follows :-Gelatin 2 grams, bailing wateAXALYTICAL CHEMISTRY.3031000 ; when all is dissolved, cool, add 1.50 of cherry-laurel water, makeup to 1500 C.C. and filter ; 45 C.C. are equal to 0.05 P a m of tannin.J. T.Adulteration of Pepper. By H. RABOURDTN (Jour. Pliarm.[ 5 ] , 9, 289-297).-This paper deals mainly with the adulteration ofpepper by the addition of ground olive-stones and pepper refuse.The microscope shows the presence of these adulterants ; the authorhas devised a method of estimating the amount. 1 gram of thepepper, shown by the microscope to be adulterated with ground olive-stones, is boiled for an hour with 100 grams water and 1 gram sul-phuric acid, water being added from time t o time to replace thatevaporated.The flask is best, suspended by its neck on account ofthe bumping which takes place. The residue is cooled and thrownon to a weighed filter, washed, dried, and weighed. The presence ofolive-stone powder is shown by the reddish powder which settles tothe bottom of the flask on standing; pure pepper does not give adense reddish residue. Numerous experiments show that the fol-lowing coefficients are obtained for different varieties of pure pepper.White pepper, 0.175 ; Malabar, Tellichery, and Saigon, 0.30 ; Aleppo,0.32 ; other commercial peppers, the so-called light varieties, 0.35. Onthe other hand, the varieties of ground olive-stones of commercegive numbers closely approximating to 0.745. Pepper refuse, con-sisting largely of the epidermis, gives 0.655. Commercial peppers,guaranteed pure, of different varieties, have been found t o give0-497 = 44 per cent. of adulterant, 0.50 = 45 per cent., and so on,Samples of known purity were mixed with different amounts ofadulterant, and when examined by this method, gave results alwayswithin 2 per cent., and frequently wiOhin 1 per cent. of the truth.J. T.Estimation of Nitrogen in Urine and Faeces. By W. CAMERER(Zeit. f. Biol., 20, 255--263).-1nstead of the ordinary method ofevaporating the urine to dryness on a water-bath with oxalic acid andgypsum, the author substitutes the following plan. A piece of thin-walled glass tubing capable of holding 6-7 c.c., and passing easilydown the combustion tube, is fused a t one end, to the other is fitted asolid paraffin cap, their weight noted, and then the tube is nearlyfilled with urine, the cap replaced, and carefully melted into the tube(by means of a lighted taper), to prevent any escape of urine, andfinally weighed. The combustion is carried out in the ordinary way,the tube being placed between two long layers of soda-lime.Applying the same principle to the fresh fseces, the author has beenable to determine by comparative experiments the loss of nitrogencaused by the usual method of drying faeces at 100-105" before com-bustion. The mean result of several analyses shows that a loss ofa little over 0.1 gram occurs for every 100 grams of fresh faeces,which is an important discrepancy, considering the normal daily elimi-nation is between 150-200 grams. J. P. L

ISSN:0368-1769    

DOI:10.1039/CA8854800294

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

304 -4BSTRACTS OF CHEMICALT e c h n i c a l ChemPAPERS.i s t r y .Recovery of Sulphur from Hydrogen Sulphide. By C. P. CLAW(Dingl. p d y t . J., 254,355).--Tt has been found that on passing hydrogensulphide mixed with a quantity of atmospheric oxygen equivalentto its hydrogen, through a layer of ferric oxide, the temperature oftenrises above the point suitable for the operation, and fused masses areproduced. To overcome this difficulty, other substances which willeffect a finer division of the ferric oxide are mixed with the latter.Alumina, magnesia, lime, baryta, their sulphates 01- carbonates, oxidesof zinc, chromium, &c., may be used. Instead of ferric oxide, otheroxides, and metsllic salts capable of decomposing hydrogen sulphideat an elemted temperature may be employed.For instance, chromicoxide, chromates, the oxides of copper and manganese, manganates,&c. If a soluble salt is employed, for instance, copper sulphate,n chromate, &c,, it is best to soak porous substances such as cubes ofporous clay, pumice stone, or similar materials in its solution, and drythem. Before use, these substances are broken into sizes varyingfrom a walnut t o a pea, and are placed in a layer from 150 to300 mm. deep on the perforated bottom of an iron tank lined withclay masses. Beneath tlhe false bottom are two apertures, by one ofwhich the hydrogen sulphide is allowed to enter, and by the otheratmospheric air. The free sulphur formed i n the operation escapesthrough an opening in the tank, and is collected in suitable chambers.Purification of Sulphuric Acid.By W. J. MENZIES (DingE.poZyt. J., 254, 400).-The author obtains sulphuric acid of thehighest concentration, containing only traces of iron or arsenic, bydistilling pyrites acid in the presence of a powerful oxidising agent,such as nitric acid. For this purpose ordinary chamber a8cid of notless than 58' B. is treated with some nitric acid, and introduced intoan iron pan provided with a condenser consisting of a range of ironpipes. The pan is then heated by a flue from the fire place, soarranged that the sides of the pan only are exposed to the heat. Thedistillation is continued until the condensed acid has a concentrationof about 60° R., when the operation is stopped and the liquid allowedto settle.The acid is then withdrawn, and will be found practicallyfree from iron and arsenic, and 3 or 4 per cent. stronger than theordinary 66" Baum6 acid of commerce.D. B.D. B.Preparation of Ammonia from Nitrogenous Minerals. ByG. BEILBV (Dingl. polyt. J., 254, 342--345).-According to a tableof analyses in Watts's Dictionary, natural bitumens contain from 1 to2.3 per cent. nitrogen. The oils prepared artificially by the destructivedistillation of carbonaceous substances also contain considerable quan-titlies of nitrogen. Oils obtained by the distillation of coal contain5 bo 10 per cent. of the total nitrogen originally present in the coal,and shale oils 20 to 30 per cent. I n 1871, the anthor investigated thTECHNICAL CHEMISTRY.305distribution of the nitrogen of bituminous shales when distilled for theproduction of paraffin. It was found that 100 parts of the nitrogenin the original shale was divided in the products as follows :-In theammoniacal water 17.0 per cent., in the oil as basic tar 20.4 per cent.,nud in thc residue or coke 62.6 per cent. By subjecting the oil todistillation, free ammonia is given of€, an oil being obtained whichcontains only a small amount of nitrogen, whilst the residue showsfrom 2.8 to 3.2 per cent. nitrogen. The residue from the distillationof the basic tar contains about 4 per cent. of nitrogen.I n prosecuting these researches, the author found that an increasein the yield of ammonia was effected, when the distillation was con-ducted very slowly, as the coal was expose3 to a red heat for a longerperiod.The same effect was produced when steam was nsed for thedistillation of bituminous shales, the yield of ammonia being furtherincreased by passing steam through the red-hot residue. 100 partsof the total nitrogen originally present gave the following distri-butioti:-In the ammoniacal water 24.2 per cent., in the oil asbasic tar 20.4 per cent., and in the residue or coke 55.3 per cent.nitrogen. It was found possible, however, to obtain almost all thenitrogen of the coke as ammonia by igniting the coke in steam.Samples of coke ignited in fire-clay retorts gave the following results :-Nitrogen in the ammoniacal water 74.3 per cent., in the oil asbasic tar 20.4 per cent., and in the residue 4.9 per cent.Retorts ofsmall capacity gave unsatisfactory results, owing to the fusibility ofthe ash of various bit,uminons shales, but no difficulty has been expe-rienced with large retorts, i n which the material remains under theinfluence of heat and steam for a longer time and at a somewhatlower temperature.In 1882, the author discovered that a, certain proportion of air couldbe mixed with the steam without reducing t.he yield of ammonia. Acertain amount of heat is thereby generated within the retort, andconsequently less has to be supplied from the outside. A retortworked alternately with steam alone and with a mixture of steam andair, showcd with the latter a gain of 10 per cent. of paraffin oil and25 per cent.of solid paraffin.The author has investigated the application of this process to therecovery of ammonia and water-gas from coal. The difFiculty expe-rienced is that the temperature necessary for carbon to act on wateris a t least 1100-1200". According to Ramsay and Young, however,decomposition of ammonia begins at 500"- It is necessary thereforet o reduce the chalices of contact of the ammonia molecules withsurfaces a t the decomposing temperature; t h i s may be effected bydiluting the ammonia-gas with steam. Air may be made to take theplace of a part of the steam. Retorts have been erected a t theOakbank works for the carbonisation of coal by means of steam. Thecoal is burned i n the lower part of the retort with sfeam and air.When the heat is properly regulated, the tar is completely decomposed,only a, small amount of pitch being deposited in the condensing pipes.The apparatus worked a t Oakbank gives a yield of 40-50 kilos.ammonium sulphate per ton of dross, equal to 60-70 per cent.of thet80tal nitrogen present. The amount of steamused raries from 1116 t oVOL. XLVIII. 306 ABSTRACTS OF CHEMICAL PAPERS.1563 kilos. per ton of coal.somewhat according to the temperature and air supply.showed the following composition :-The composition of the water-gas differsA sampleco,. co. CH4. H. N.16.6 8-1 2.3 28.6 44.4D. B.Working up the Mother-liquors from Schoenite in the Pro-duction of Kainite. By VORSTER and GR~~NERERG (Ding7. poZyt. J.,254,355).-The liquors obtained in the preparation of schoenite fromkainite are evaporated to a density of about 35" B.During thisoperation, a mixture consisting of sodium chloride, calcium chloride,potassium magnesium sulphate, and magnesium sulphate is separated ;this contains the greater part of the potassium and sulphuric acidoyiginally present in the liquors. The potassium may be recoveredfrom this saline mixture in the form of potassium magnesium sulphate,by treatment with hot kainite mother-liquors,Chemical Reactions in the Setting of Hydraulic Mortars.By H. LE CHATELTER (BUZZ. SOC. Chim., 42, S2-89).-A completetheory of the setting of mortars includes the physical and the inducingchemical phenomena. As regards the former, it has already beenshown that the process of hardening results from the successive dis-solution and crystallisation of the calcium hjdroxide.The reactionstaking place between the combinations of the lime, silica, and theoxides of aluminium and iron are here studied. The principal ingre-dient in hydraulic mortars is a hydrated calcium silicate of the approxi-mate composition 2(Ca0,Si02) + 5HZO ; this is decomposed by excessof water to form another silicate of the composition 2Si02,Ca0 + H,O,although this change is arrested by the presence in the water of0.5 gram of lime in the litre. A larger quantity of water decomposesthis acid silicate to form silica, whilst carbonic acid converts it com-p.l!tely into calcium carbonate and silica. The formation of thesilicate in the hardening of the mortar results from a variety ofcauses, as by the direct combination of the lime and silica, by thedecomposition in contact with water of a basic calcium silicate, andpossibly by the hydration of anhydrous calcium silicate.Theseseveral chemical changes are here discussed ; the first occurs in thepreliminary calcination and fusion of artificial mortars, the second, ormost important, reveals itself by the separation of crystalline calciumhydroxide, whilst the third, although not reproducible in the laboratoryin the case of calcium silicate, has yet been effected in the corre-sponding barium compound.Besides the silicates there are present in the mortars calciumaluminate and ferrate, of the composition A1,O3,4Ca0,12H,O andFe,0,,4Ca0,12H20, decomposed by water and carbonic anhydride,with separat,ion of ferric oxide and alumina.Their presence is, how-ever, most important in the preliminary fusion of the mortars, asserving to melt the lime and the silica, thus effecting their combina-tions by the more immediate contact.Lastly, as regards the combination of the free lime with theD. BTECHNICAL CHEMISTRY. 307carbonic anhydride, the author shows that this change is not essentialto the setting of the mortar, but although limited to the superficiallayers, it mitterially assists its preservation. V. H. V.Roman Alunite. By C. SCHWARZ (Ber., 17, 2887--2888).-Theauthor has roasted alunite at different temperatures, and extractedthe product with sulphuric acid at different degrees of strength, inorder to ascertain the conditions for obtaining the greatest amount ofalumina and potash in solution.He recommends that the mineralbe roasted at 500", and then treated with sulphuric acid of sp. gr.1 2 9 i to 1.530 (comp. Guyot, Abstr., 1883, 250 and 397).A. K. RI.The Moulding of Porcelain. By C. LAUTH (BUZZ. XOC. Chi7)2.,42, 560-567) .-The ordinary process of porcelain moulding consistsin pouring the thin porcelain paste into dry plaster moulds ; after atime, the paste adhering to the dry porous walls of the mould becomesset and of sufficient thickness to allow of the mould being turnedupside down, and emptied of all but the thin layer of comparativelydry paste adhering to the inside ; this continues t o dry, shrinks, andcan then be easily detached.When large mouldings have to be made,special precautions must be taken ; the excess of paste is allowed torun out a t the bottom of the mould, and compressed air is driven into keep the thin layer on the walls in its position ; or the liquid pasteis extracted by means of a vacuum. In order that the shell may detachitself with perfect evenness from the mould, RBiiard first covers theinside of the mould with a piece of muslin ; by this means seams andslight imperfections do not reproduce themselves in the cast.J. K. C.Purification of Zinc containing Arsenic. By L'HOTE (Din$.polyt. J., 254, 400).-The author has examined several specimens ofzinc for arsenic, and found the following quantities in 1 kilo. of themefa1:-Zinc in sheets from Vieille Montagne...... 20 to 36 mgrme.9 7 ,, Honfleur ............ 10.5 ,,9 3 ,, the Asturien Company. . 26.0 ,,Zinc in blocks from Vieille Montagne.. .... traces not weighable.The removal of arsenic may be effected by adding to the moltenzinc 1 to 1.5 per cent. of anhydrous magnesium chloride and stirringthe mixture. The arsenic is thereby volatilised in the form of tri-chloride of arsenic, together with white vapours of zinc chloride.The mass is granulated by pouring it into water and the zinc willthen be found free from arsenic. The purification of zinc containingantimony may be effected in a similar manner.Manganese Steel. By F. GAUTIER (DingZ. polyt. J., 254,499).-Steel containing from 9 to 15 per cent.of manganese is prepared byadding ferromanganese (80 per cent. Mn) to the molten metal i n quan-tities Sufficient to produce the desired eaect. The mixture is then,> ,, Silesia .............. do.D. B308 ABSTRACTS OF CHEMICAL PAPERS.fuscd and cast. For the production of steel containing 9 per cent.manganese, 11 to 12 per cent. ferromanganese and 5.5 to 6 per cent. ofcarbon are added, so that the finished steel contains 0-6-0.7 per cent.carbon. Manganese steel is readily fusible, and offers a considerableamount of resistance to concussion, hence it is suitable for the manu-facture of projectiles and the construction of bulwarks. Axes havebeen cast from this steel, with which it was possible to split iron 15to 20 mm. in thickness without previously haGdening the castings.D. B.Preparation of Malleable Nickel and Cobalt.(DingZ. polyt. J.,254, 315.)-According to the “ Berndorf Metal Works,” fused nickelor cobalt absorbs carbon and oxygen simultaneously, and loses thegreater part of the latter on cooling, so that a porous metallic massremains, which, in consequence of the presence of varying quantitiesof carbon, cannot be welded. To overcome this difficulty, it is pro-posed to reduce pieces of pure oxide of cobalt or nickel a t a moderatetemperature, and to saturate the porous cubes thus obtained with a4 per cent. solution of a manganate or permanganate of the alkalimetals. The cubes are then dried and fused. The manganates or per-manganates are said to suppress the injurious effect of the carbonabsorbed by the castings.The oxygen may be removed by theaddition of a small amount of aluminium, calcium, or an alloy ofcalcium with zinc and wood charcoal, to the fused metal. D. B.Weiller’s Silicon Bronze. By X. M~~LLER (Di~igZ. polyt. J., 254,492-495).-The oxides contained in the mass of a metal or an alloytend to impart a want of uniformity to the mass, and may deteriorateits most essential properties. Weiller’s experiments in this directionhave shown that the presence of minute quantities of oxides in alloysoccasions a reduction in the strength and conductivity of electric wiresprepared from such alloyg. He proposes to remove the oxides pro-,duced during the process of fusion by means of silicon, which is addedto the molten mass in the form of potassium fluosilicate.This isdecomposed by sodium, the silicon which is liberated effecting thereduction of the oxides. The fluorides of potassium and sodium,together with the silica, float on the surface of the molten mass andform an excellent slag, which takes up the greater part of the un-absorbed silicon. Only small quantities of the latter are retained bythe bronze. D. B.Formation of Patina. By E. STEINER (DingZ. polyt. J., 254,355).-An important element in the production of patina is the pre-servation of the skin of the castings. Bronzes of recent origin aredefective, inasmuch as the moulds used for casting them are tooporous, and have too many seams ; the best results are obtained whenthe finest moulding sand is employed.The formation of the patinabegins with the commencement of the cooling of the fused metal, andcan be distinguished microscopically. It depends on the infusibilityof the alloy, hence silver or similar metals are often added.D. BTECHNICAL CHEMISTRY. 309-------1. Fusing point (Itudorf's method)Manufacture of Asphalt. By E. DIETRICH (Di$. p07yt. J.,254, 354).-The author prepares R raw material suitable for asphaltpaving by adding pure bitumen, Trinidad ipure', Goudron, or hardbitumen, to ordinary limestone or asphalt stone during the process ofdisintegration. On heating the mixture in drums, the bitumen isabsorbed by the limestone granules, any light oils which may be pre-sent in the asphalt employed being simultaneously volatilised.Process for Solidifying Mineral Oils. By L.ROTH (Dingl.polyt. J., 254, 398).-The author converts mineral oils into a solidform by dissolving a fatty acid therein, then adding a small amountof sulphuric or hydrochloric acid, and mixing with water containingabout 2 per cent. of alkali, By treating crude petroleum in a similarmanner, three layers are said to be obtained, the lowest containingthe mechanical impurities, the middle layer the heavy hydrocarbons,such as paraffins, &c., and t'he upper layer the light hydrocwhonswhich are worked up for lighting oils. The author claims as iioveltyhhe separation of the light and heavy hydrocarbons from crude petro-l m m by this method, which is said to take the place of fractionaldistillation.D. B.D. B.~~Cowv's milk(Isigny ) .36.5"Substance employed to Colour Wines. By JAY (BUZZ. XOC.Chinz., 42, 167-168). -A substance known as Tirhtura por 10s vinosis largely used in the district of Huesca for colouring Spanish wines.It contains two coal-tar derivatives, one of which is that form ofBiebrich red which is turned blue by sulphuric acid, whilst the other,which exists in smaller proportion, closely resembles the colonringmatter know as cerise. The composition of the Tintura is :-Organicmatter, mainly Biebrich red, 66.4 ; sodium sulphate, anhydrous,26.10 ; arsenious oxide, 1.62 ; loss, iron, lime, &c., 5.88 = 100. Thepresence of arsenic is of special importance.Composition of Butter from Cow's, Goat's, and Ewe'sMilk.By E. SCHMITT ( A m . Agrowmiques, 10, 496-500). Theauthor gives the composition of four samples of genuine butter ofknown origin, according to analyses and calculations made in themanner finally recommended by him :-C. H. B.Goat'smilk.Ewe'smilk.2. Proximate analysis (Gtrandeau'sF a t ......................Water ....................Casei'n ....................Ash ......................Not determined, and loss ....method)-33 * 5 O75.022'401.750.180.6786 a259 .so2 *2250.101.62537'5"---- -Butter fromCow's milk(Flanders:~.36 '5"---86.5010 *541 .420 -850 -69I- -310 ABSTRAUTS OF CHEMICAL PAPERS.4.453. Fixcd and insoluble fatty acids(Hehner and Angell's method) ,4.Busing point of fixed fatty acids5. Volatile and soluble fatty acids,reckoned as butyric acid (Le-chartier's process, modified) . .6. Composition of the fat (calcu-Butyrin.. ..................Olern .....................Margarin ..................lat ed) -4'505 4.77Cow's milk(Isigny) .88 *5f39 -8"4 -452560355.5064.030.50Butter from65836Corn's milk Goat's Ewe's(Flanders). milk. milk.40"56035The composition of the fat is calculated from the anal-yses with theaid of the cable given by Chevreul (Agenda du chimiste, 1883, 256).J. ill. H. M.Separation of Soap from the Leys by Centrifugal Means.(Dinql. polyt. J., 254,399).-According to the Fabrilc chemischm PTO-diicte in Berlin, the soap separated by salt instead of being cooledthoroughly, so as t o effect the separation of the soap from the leys,is subjected whilst hot t o centrifugal force in a drum. The soap sepa-rated in this way is said to contain no leys, only traces of salt, and lesswater, and is denser and perfectly neutral.D. B.Preparation of a Yellow Rosaniline Dye. By P. MACHEN-EIAUER (DingZ. yolyt. J., 254, 272).-On treating a hot solutionof 1 part azuline in 20 parts glacial acetic acid, with 3 parts nitricacid or a corresponding amount of nitrous acid, nitrate, or nitrite, theblue is converted into a yellow colour. A similar result is obtainedon nitrating an aqueous solution of the sulphonic acid of azuline.For this purpose, 20 parts of the siilphonic acid, obtained by treating1 part azuline with 5 parts of sulphuric acid are dissolved in 20 partsof water and treated with 2 parts nitric acid at 100".D. B.Preparation of New Colouring Matters. (Dilzgl. poZyt. J.,254'389--396.)-A process for preparing violet, blue, arid green dye-stuffs of the rosaniline group has been patented by tho BndisclzeAnilin und Soda Pabrih, which is essentially an extension of Caroand Graebe's synthesis of aurin from phenol and hydroxy-derivativesof benaophenone in the presence of phosphorus trichloride (Abstr.,1879, 60). The following derivatives of benzophenone are used :-Tetramethyldiamidobenzophenone, tetrethyldiamidobenzophenone,Climethylamidobenzophenone, and the diethyl-derivative of paramidoTECHNICAL CHENISTRP. 311benzophenone.Aromatic amines :-Diphenylamire, phenyl-a-uaph-thylamine, a-dinaphthylamine, and the tertiary alkyl-derivatives ofaniline, orthotoluidine, a-naphthylamine, orthanisidine, metaphenyl-enediamine, and quinoline.The action of the carbonyl group of amidobenzophenone, like that ofthe corresponding hydroxy-ketones on hydrocaybon residues, does nottake place directly, but is effected through the medium of phosphorustrichloride or phosphorus oxychlorid e. Carbonyl chloride, phosphoruspentachloride, the bromine and iodine compounds of phosphorus,phosphorus oxybromide, and phosphorus sulphochloride act in asimilar manner. The condensation takes place also in the presenceof aluminium chloride. The dyes obtained by the condensation ofthe tetra-alkyl diamidobenzophenones with the above-named aromaticamines give violet o r blue colours resembling methyl-violet, whilstkhe corresponding colouring matters of the di-alkyl amidobenzo-phenones are green and resemble malachite-green in properties.Thegreen dye-st uffs from quinoline and the alkyl-derivatives of diamido-benzophenone belong to the latter category.The preparation of a new group of basic dyes called auramines islikewise described by the Baden aniline works. The simplestmembers of this group are yellow dyes formed from tetra-alkyldiamidobenzophenones by the action of animonin on the methaneresidue. When these dyes are heated with aniline, its homologues, ornaphthylamine, &c., phenyl, tolyl, naphthyl auramines, &c., are ob-tained, which give redder or browner colours.Ewer and Pick prepare sulphuretted dyes by heating equalmolecular proportions of sulphur and paranitraniline, paranitrethyl-aniline, or paranitrodimethylaniline, thus forming the correspondingthio-compound, which is converted into thiotetramine by reduction.The latter is then subjected to oxidation, and accordingly as it hasbeen formed from a primary, secondary, or tertiary paranitramine,violet, blue, or greenish-blue colouring matters are produced.The deri-vatives of ort hotoluidine, orthami doanisoil, and ort h amidop hene toy1may be used in the place of aniline. By introducing alkyl-groupsinto the primary or secondary amido-group of thioparanitramines,the corresponding secondary and tertiary amines are obtained.For the production of azo-colours from tetrazo-diphenyl, Bottgermixes aqueous solutions of tetrazodiphenyl salts with salts of a- or6-naphthylaniine, or a- or P-naphthylnmine sulphonic acids.Thecolouring matters obtained in this way impart a permanent red colourto wool and cotton, in the case of the latter, without the use ofmordants. D. B.Benz aldehyde-green. (Dingl. poly t. J., 2 54, 3 1 6 .)-Accordingto Dittler and Co. in Griesheim a bluish-green dye is obtained hydissolving a salt of benzaldehyde-green in water, acidifying withacetic acid and adding chloride of lime. 25 kilos. of tetramethyl-diamidotriphenylcarbinol oxalate are dissolved in I 000 litres coldwater, acidified with 50 kilos. acetic acid, and treated with 7 kilos.chloride of lime made into a slndge witah water.The mixture isallowed to stand for half an hour and filtered. The solution i312 ABSTRACTS OF CHEMICAL PAPERS.neutralised with ammonia, filtered, the colour base dried, dissolved inhydrochloric acid, and treated with sodium chloride to precipitate tliegreen dye. It is also proposed to dissolve 53 kilos. of the oxalstegreen in 2000 litres of water, acidify with 100 kilos. hydrochloric:acid, treat with an alkaline solution cont'aining 18 kilos. bromine, andprecipitate with ammonia. The base produced has a bronze colourand gives up the dye on the addition of an acid. The salts oftetrethyldiamidotriphenyl carbinol give similar colouring matters.D. B.Preparation of Dyes from Alizarin and other AnthraceneColouring Matters suitable for Calico Printing.(Uingl. p o l ~ t .J., 254, 224-226.)-1n printing cotton goods with alizarin, nitro-alizarin, or alizarin-blue, Gagenburg of Rydboholm (Svveden) andLeverkus of Cologne recommend the use of preparations whichrender the mordanting of the fabric needless. For this pui*pose, com-mercial alizarin, nitroalizarin, or alizarin-blue (10-20 per cent. paste)is pressed by hydraulic pressure into a mass containing from 40 to 50per cent. solid matter, and subsequently dried a t 130-140". The drypowder is then ground in a colour mill with 4 parts of oil, and themixture passed through Matter's straining machine (ibid., 25 2, 111).A colour for red is then prepared in the following manner:-Thickening material : 6 kilos.starch, 6 kilos. flour, 60 litres water,and 10 litres acetic acid of 8". Colour : 2750 grams thickening agent,470 "fatty alizarin" (20 per cent. paste), 30 stannous chloride (24"),548 aluminium acet'ate (lo'), and 280 calcium acetate. Instead ofaluminium acetate, thiocyanates may be used. The other alizarin-dyes are prepared in a similar manner.It is stated that the proposal to treat alizarin with fatty substancesbefore use in dyeing is not new. About 10 years ago Forster, inAugsburg, suggested that the alizarin should be dissolved in an alka-line saline solution of the fatty acid and precipitated by means of anacid, an intimate mixture of dye with fatty acid being obtained whichgave good results in dyeing.By L.LAND-SHOFF (Dirzgl. poZyt. J., 254, 232).-In order to convert the hydroxyl-group of naphthyl compounds of the /3-series into the amido-group,it is necessary to work with a pressure of from 30 to 40 atmospheres.'Po avoid using this pressure, the author recommends to heat the:blkali salt, of 6-naphtholsulphonic acid for 12 hoiirs a t 200-250", andpass a slow current of gaseous ammonia through the solution. ThereactionsD. B.Preparation of Naphthylamine Compounds.CiH.CloH6.S03Na + NH3 = NH2.C,,H6.S03Na + HzO, orOH.C,oH,(S0,Na)2+ NH3 = NH2.CloHb(S03Na)2 + HtO, orOH.CloH4(S03Na)3 + NH3 = NH,.CloH4(SO3Na), + H20.take place. D. B.-According to the Frankfort Aniline Works, Gans and Co., 27.5kilos. sodium ~itroso-P-nnphtholmoxzosulplionate are dissolved inPreparation of Naphthol-green.( D i q l . polyt. J. 254, 184.TECHNICAL CHEMISTRY. 313100 litres of water and treated with 20 litres of a solution contain-i n g 5 kilos. of ferric chloride. The excess of iron is then removedby the addition of an alkali, and the filtrate evaporated to dry-ness. The resulting green dye is purified by recrystallisation fromweak alcohol. Instead of using Schaeff er’s monosulphonic acid, allother naphtholsulptionic acids, excepting the /3-naphthol-a-monosul-phonic acid and the P-naphthol- ydisulphonic acid, may be employed.By replacing the ferric chloride by equivalent quantities of a salt ofcobalt or nickel, brown or yellow colouring matters are produced.D. B.Turkey-red Oil. By A. M~~LLER-JACOSS (Dingl.polyt. J., 254,302-312) .-In the Mittheiluiigen des Technologischen Gewerbemusaumsin, Vienna, 1884, 59, Liechti and Suida give a reply to the author’stheories regarding the composition and mode of action of Turkey-redoil (see A bstr., 1884, 946). The present communication deals withthe author’s criticism on this reply. Liechti and Suida base theirtheory as to the formation of the “ compound soluble in water ” onthe evolution of large quantities of sulphurous anhydride thus :-6S02, although they arrive at a different result in a, more recentequation, 2C,H5(CleH,302)d + 7H,SOI + 8H20 = CI2Hs2O,?S +4C,,H3,03 + 6H2S 04. The evolution of sulphurous anhydride indicatesthat the process of saponification has not been conducted in a propermanner, in which case only would deoxidation of the sulphuric acidbe effected. The same applies to the treatment of oleic acid with sul-yhuric acid.This reaction is also explained differently by Liechti andbuida in their reply, and more in accordance with the views of theauthor; but although they appear to confirm the opinion that thebest yield of soluble substance is obtained when the action of thesulphuric acid is not carried too far, they decline to accept Muller-Jacob’s process, and stipulate that the sulphuric acid should remainin contact with the oil for twelve hours as before. They doubt, more-over, the presence of unaltered oil (triglyceride) in the products ofthe reaction. The presence of this compound can, however, be esta-blished by dissolving the products of the reaction in 10 to 12 timesthe volume of alcohol, when the mixture becomes turbid and graduallydeposits a precipitate of the triglyceride.The autlior, in the second part of the paper, criticises the chemicalquestions raised by Liechti and Suida.Muller- Jacob’s Investigations on Turkey-red Oil.By H.SCHMID (Dingl. p o l y f . J., 254, 346--350).-The author is of opinionthat the researches by Liechti and Suida (ibid., 1883, 250, 543) andA. Muller-Jacobs (Abstr., 1884, 946, and preceding Abstract) onTurkey-red oil do not fully solve the problem of the constitution andmode of action of the above-mentioned compound. According toLiechti and Suida, the conversion of olive oil depends on the forma-tion of soluble glyceryl sulphate hydroxyoleate, the sulphuric acidacting both as oxidising and saponifying agent.An important factwhich these investigators failed to observe is the production of2C3H,(C,eH,O?), + 7H28Or = C42Hi8012S + 4CJLO3 + 4H2O +D. B314 ABSTRACTS OF CHEMICAL PAPERS.hy d roxystearic acid, C18H360Y, discovered by Miiller- Jacobs. It hasrecently been dernonstlrated by Liechti and Suida that the decomposi-tion products of their compound contain, in addition to hydroxyoleicacid, large quantities of hydroxystearic acid. The latter, however,differs from oleic acid by containing more of the elements of water,C18H3102 + H,O = C1flH3603, so that the action of sulphuric acid onoil must now be regarded in a different manner fmm that originallyindicated by Liechti and Suida.The oxidising action of sulphuricacid, and consequent evolution of sulphurous anhydride, thereforedqends only on the amount of hydroxyoleic acid formed besideshydroxystearic acid, as the latter is produced by the addition of waterto the former. The author submits that this correction, that is restric-tion or complete suppression of the oxidising influence of sulphuricacid, does not invalidate the theory upheld by Liechti and Suida, asit is easy to imagine that by the action of sulphuric acid an oil,glyceryl sulphate hydroxy stearate, accompanied or not by glycerylsulphate hydroxyoleate, is formed.According to Muller- Jacobs, Turkey-red oil is a mixed solutionof sulpholeic acid, c,&,( SO,H) O2 (soluble in water) hydroxyoleicamd hydroxystearic acids (soluble in alcohol), and unaltered triglg-ceride (soluble in ether).It is also stated that decomposition takesplace when sulpholeic acid is boiled with water, a mixture of hy-droxyoleic and hydroxystearic acids being obtained, thus :-2C,H,SO, + H2O = C1eH3403 + CI,H~,O~ + H2SO4.Hydroxyoleic Hydroxy stearicacid. acid.The incorrectness of this formula is shown by the fact that theoxidising influence of the sulphuric acid has been disregarded inthe formation of these acids. The production of hydroxystearicacid by the decomposition of sulpholeic acid can be expressed bythe formula C18H,(S03H)02 + 2H,O = H,SO* + Cl8H3&I3 ; hydroxy-oleic acid can, however, be formed from sulpholeic acid only by as-suming that the oleic acid separated is oxidised at the expense of thesulphuric acid thus :--C18H3Y(S03H)02 = SO3 + Cl8H3,O3.Miiller-Jacob’s formula must therefore be altered to the following :-2C,,H3*SO, + 2HZO = H2SO4 + SO, + C J 3 3 4 0 3 + CieH360.3.The same chemist believes that Turkey-red oil contains 30 per cent.or more of unaltered glycerides, and attributes the principal action ofthe mordanting to the presence of this compound. The unaltered oilis said to enter the colour lake and surround it in a manner, keepingit damp and protecting it from exterior influences, thus impartingbrightness, softness, and solidity to the colour, an opinion whichS. Jenny has already expressed, and which Miiller-Jacobs has appliedto the new Turkey-red oil.The action of the latter as a mordant isdue to its yielding oil to the fibre in a finely-divided form, and in thebest processes the remaining substances (sulpholeates) are said to beremoved by washing. Nevertheless, the author has succeeded in dye-ing alizarin without Turkey-red oil, by the application of ammoniuTECHNICAL CHEMISTRY. 315ricinolente, and although finely-divided triglycerides were not presentthe reds produced compared favourably with alizarin-red as obtainedby the Turkey-red process.Composition of Turkey-red Oil. By L. LIECHTI and W. SUIDA(Dingl. polyt. J., 254, 550-352) .-A brief reply to Muller-Jacob'scriticism of the author's researches on the constitution of Turkey-redoil. D. B.Behaviour of Different Ferric Oxide Mordants with Silk.By L.LIECHTI and W. SUIDA (Dingl. poZyZ. J., 254, 437--439).-Forthe purpose of comparison, the following iron mordants were pre-pared :-(1) Fe2(S04)2.50H of 30" B. ; (2) Fe2(S04),(N0,)OH of30.5" B. ; and (3) Fe,(SOa)a(OH)2 of 31" B. The quantities of ferricoxide fixed to the animal fibre by dissociation were determined bysteeping a weighed quantity of silk in these solutions, washing thesilk, drying and incinerating it, and estimating the iron in the ash.The mordant (3) gave the best result, 1 2 per cent. of ferric oxidehaving been taken up by the silk fibre as compared with 8 per cent.absorbed from the mordant (1). This result was expected, as thecompound (3) has a tendency to split up into more basic salts, all ofwhich are too unstable to be of practical utility.It is a remarkablecoincidence that the mordant (2) gives a result which is almost asfavourable as that of the compound ( 3 ) , giving up 11 per cent. offerric oxide. But before arriving a t a conclusion as to the practicalutility of this mordant, the experiment should be repeated. Most ofthe iron mordants examined by the authors had the formulaFez( SO,),.,OH, and sometimes contained a considerable amount ofnitric acid.Referring to the influence of ferrous oxide in iron mordants, it hasbeen ascertained by experiment that, with an increase in the per-centage of this oxide, the degree of dissociation on dilution with waterdiminishes. The authors have, however, found that the dissociationeffected by the animal fibre is the same for ferrous and ferric oxidemordants. New trials should, therefore, be made to solve thisproblem before the use of mordants containing ferrous oxide is corn-plet el y rejected.By A. GACON (DingZ.polyt. J., 254, 355).-1 kilo. of this powder is said to blow up 12 to 15 cubic metres ofrock. It requires for ignition a temperature of 480°, and cannot beexploded by concussion, not even when hammered on an anvil. It isobtained by mixing 69 parts of potassium or sodium nitrate with19 parts of sulphur and adding ash (?) ii:li in potash or soda to themixture. It is proposed to obtain this ash by burning dead leaves.200 grams of tannin dissolved in 8 litres of water are then added tothe mixture. D. B.D. B.D. B.Blasting Powder.Preparation of Weatherproof and Incombustible Paper. ByW. HERRE (BingZ.poZyt. J., 254, 315).-The materials used for t1i.emanufacture of incombustible and weatherproof paper or pasteboardare treated with saline solutions, for example, a solution containiri316 ABSTRACTS OF CHEMICAL PAPERS.15-18 grams zinc sulphate or chloride in 1 litre, and ground to apulp in a rag engine. 100 kilos. of the prepared pulp are then mixedwith 1 to 5 kilos. tallow soap, 1 t o 5 kilos. size, and 4 t o 16 kilos.alum, and made into paper or pasteboard in the usual manner.Before the final drying the treatment wit,h zinc sulphate is repeated.To render the paper weatherproof, it is steeped in a solution ofcatechu. D. B.Enamelling Casks. By F. G. SPONNAGEL (DingLpolyt. J., 254,443).-Instead of coatin5 the wood of casks with the enamel, thelatter is allowed to form in the wood in the following manner :-Thecask or vat is in the first place treated with an aqueous solution of anenamel obtained by fusing 100 parts of pure silica with 50 parts ofalkali. It is then filled with a solution of aluminium acetate in watermixed with sulphurous acid in the proportion of 4 : 2 : 1. The solu-tion acts on the enamel which has penetrated into the wood, and pro-duces a neutral enamel of silica within the pores of the wood.D. B

ISSN:0368-1769    

DOI:10.1039/CA8854800304

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

317General and Physical Chemistry.The Second Spectrum of Hydrogen. By B. HASSELBERG (PhiZ.,Mug. [ 5 ] , 17, 329--352).-The author’s observations tend to showthat Wullner’s so-called acetylene spectrum is in reality the spectra ofhydrogen and of carbonic oxide superposed. The second hydrogenspectrum has been attributed to the formation of acetylene in conse-quence of the presence of traces of carbon-compounds in the hydrogentubes. The author, however, has made experiments which disprovethis. With a tube filled with pure hydrogen, he observed mere tracesof the second spectrum when the tube was observed transversely ; butthe spectrum was fully developed when the tube was viewed longi-t udinall y .Spectral Lines of Metals Developed by Exploding Gases.By G.D. LIVEING and J. DEWAR (Phi2. Mug. [5], 18,161-173).-Theresearches of Berthelot have shown that the velocity of an explosionof oxygen with hydrogen is about m&m of that of light; conse-quently if such an explosion were advancing towards the eye, thewave-lengths of successively illuminated particles would be shortenedby this fraction. In the case of the sodium lines such an effect wouldproduce a shifting of the lines towards the more refrangible end ofthe spectrum of about AT of the space between the two lines. Con-versely, a receding explosion would prodnce an opposite effect.In this paper, an account is given of the spectroscopic observationsmade with a Romland grating on explosions occurring in a tube bentin the form of a U, so that images of the receding and advancing explo-sive wave could be obtained simultaneoudy. The authors were, how-ever, unable to substantiate any displacement of the relative positionsof the lithium lines, owing to their breadth and diffusiveness.In theadvancing flash, however, the iinage of the lithium lines was reversed,that is, showed a dark line down the middle, whilst the receding flashgave as broad a bright band without such a dayk line. These reversalsshow that in the explosive wave, the temperature of the gas does notreach its maximum a t once, but that the front of the wave is coolerthan its successive portions. It is further established that thebreadth of the lithium lines is dependent on the quantity of lithiumpresent. I n order to further study the spectra developed by ex-ploding gases, various metals such as iron, copper, lead, cadmium,zinc, aluminium, silver and magnesium mere introduced into the tubecontaining explosive mixtures of oxygen with hydrogen, carbonicoxide or methane, or the hydrogen-compounds of sulphur, selenium,and antimony. A description is given of the lines characteristic ofeach metal brought out by the explosion ; among the observations, itis noticed that metals 80 little volatile as iron, nickel, and cobaltdevelop many lines, whilst more volatile metals show fewer or none.R.R.VOL. xLvrn. 318 ABSTRACTS OF CHEMICAL PAPERS.On the whole, it may be said that the spectra so formed are similarin character to those produced by the combustion of these metals ina jet of oxygen and coal-gas.The observations of Berthelot andVieille have shown that the temperature of the exploding gases is about3000" ; then at this temperature iron, nickel, and cobalt are completelyvaporous, and a great'er number of rays emitted lie between G andP. It is suggested that the appearance of certain lines is condi-tioned by certain temperatures, and that it might be possible to con-struct a spectroscopic scale of temperature by observation on thesuccessive development of lines concomitant with the rise of tempera-ture. V. H. V.Spectroscopic Examination of the Vapours Evolved onHeating Iron, &c., at Atmospheric Pressure. By J. PARRY(Chem. News, 50, 303-304).Double Refraction of Liquids. By E. v. FLETSCHL (Ann.Phys.Chem. [2], 24, 127--144).-Inasmuch as circular polarisation is aphenomenon common alike to doubly refracting crystals and to certainliquids and solutions of solids, the problem presents itself whetherchange in direction of the light rays producible by so-called opticallyactive liquids, is due to a difference in phase of two circular polarisedrays as iu the case of crystals, or t o some qiiite independent cause. Inthis paper, the author examines the question whether such opticallyactive liquids are doubly refractive, though & priori calculations showthat the degree of double refraction corresponding with their specificrotatory power is so small that it would be impossible to estimate itby any known method. A particular apparatus was constructed €orthe purpose, consisting of 22 hollow glass prisms within parallelglass plates ; of these prisms, 20 had a refractive angle of 120", andtwo of 60"; these were arranged alternately, so that ten of the onekind and one of the other were situated with their refracting angle inthe one direction, and the remainder in the other direction.Therefractive angle of the whole system was equal to 2520". The one setof prisms was then filled with some dextrorotatory solution, the otherset with a laevorotatory. If then this liquid system were doublyrefractive, a homogeneous ray of light should be decomposed into theordinary and extraordinary ray. This was found to be the case: foron projecting spot of light, through this combination of prisms con-taining solutions of dextrose and levulose of equal and opposite rota-tory power, there was observed not one but two images, side by side,A similar result was obtained with a dextrorotatory orange oil and alsevorotatory terpene.From these observations, it follows (i) thatthere are doubly refracting liquids, and that the ordinary and extra-ordinary rays undergo circular polarisation in opposite directions ;(iij that from the unequal velocity of both rays in the liquid there is pro-duced a difference of phase proportional to the path of liquid traversed ;this is the cause of the circular polarisation of the liquid. Such doublyrefracting liquids have no optical axis, but the wave-surfaces of lightin these liquids consist of two concentric spherical surfaces.V.H. 8GENERAL AND PHYSICAL CHEMISTRY. 31 9Amount of Atmospheric Absorption. By S. P. LANGLEY (Phil.May. [ S ] , 18, 289--307).-Numerous observations made under dif-ferent conditions and in different localities have given for the absorp-tion, whether of heat or of light from the sun, a value of about 20 percent. These values have been based on two assumptions, namely,(i) that the emanating r a p are homogeneous in kind, and (iij thatthe absorption by the successive strata of the terrestrial atmosphereis homogeneous in degree. But by laboratory experiments Mellonihas demonstrated that like proportions are not absorbed by likestrata; hence it follows that the coefficieut of transmission is trulyconstant only in the case of the absolute homogeneous ray, which canbut approximately be discerned, much less discriminated, by the mostdelicate instruments.It is here shown by mathematical reasoningthat the coefficient of transmission is (i) never a constant; (ii) alwaystoo large ; (iii) increases as one approaches the horizon. But apartfrom mathematical considerations, the photographic spectrum near theD line, taken at 3.30 P.M., shows many more telluric lines than aspectrum taken at noon; this indicates a very small coefficient oftransmission. Further, many of the telluric lines appear a t greataltitudes even in the clearest atmosphere. It would thus appear thatthere is a certain selective absorption of solar rays, and that practicallybetween telluric lines and the general absorption there is every coefi-cient of transmission from unity to zero.The author believes thatthe actual mean absorption of sun and starlight a t the sea level isprobably over 40 per cent. a t its minimum ; and that fine dust particles,both near the surface and a t a great altitude, play a more importantlpart in the absorption, both general and selective, than has hcretoforeheen supposed. By a complete solution of this complex question, thephenomena of meteorology would become predictable.V. H. V.Method of Measuring the Chemical Effect of Radiation. ByL. OLIWER (Compi. rend., 100, 178--181).-1n order to time photo-graphic exposures, the author employs a radiometer which is providedwith screens so arranged that light is only allowed t o fall on theinstrument during the time that the photographic plate is beingexposed.The number of revolutions made by the radiometer duringan exposure sufficient to give a good negative is determined oncefor all, and each subsequent exposure is continged until the radiometerhas made the same number of revolutions. I n cloudy weather themotion of the radiometer is slower, and the exposure is proportionallylonger ; in bright weather the motion is quicker and the exposure isproportionally shorter ; but in every case the quantity of light whichfalls on the photographic plate remains the same.The radiometer may be used in a similar manner to determine therelative sensitiveness of different plates, or the effect of different ex-posures on the same plate.Note by Abstractor.-This method was suggested several years agoby Crookes in one of his earlier papers on the radiometer (see Chem.News, 51, 75).C.H. B.2 320 ABSTRACTS OF CHEMICAL PAPERS.A Diffusion Photometer. By A. CROVA (C~mpt. rend., 99, 1115-1118).-This photometer is designed for measuring luminoussources of high intensity, and is based on the principle that when8 translucent screen is placed in a uniformly illuminated field in adirection normal to the incident rays, each point of the screen may beregarded as a luminous source and transmits light, the intensity ofwhich depends on the nature of the translucent material, in accordancewith a law which also varies with the material, but in every case therays diffused in a direction closely approaching the normal are equalin intensity. If there is placed behind the diffuser an opaque screenwith an opening, the size of which can be varied a t will, the intensityof the light normally emitted by this opening is proportional to theintensity of the luminous field in which the diffuser is placed, to acoefficient which depends on the nature of the translucent substance,and to the area of the opening, and varies inversely with the squareof the distance.The author employs a Foucault’s photometer, one-half of the screen being illuminated by a standard light of one Camellamp placed at the end of a blackened tube 1 metre in length, whilstthe otber half is illuminated by the light to be examined. The latterpasses down a tube which is movable on a graduated circle fixed atright angles to the axis of the first tube.At the further end of thistube there is a rectangular opening, the breadth of which remainsconstant, a-liilst the length can be varied by means of a micrometerscrew. This opening is placed against the diffuser, and the size of theopening is altered until the two halves of the screen of the photo-meter are equally illuminated. For intensities up to 400 Carcels thediffuser is made of ground glass, whilst for higher intensities opalglass is used.The Pupil Photometer. By J. GORHAM (PYOC. Roy. SOC., 37,Sunshine Recorder. By H. MCLEOD (Phil. Mag. [ 5 ] , 18, 141-142).-1n this paper a preliminary account is given of a sunshinerecorder, in which the light, not the heat, of the sun is the agent inthe production of chemical change. The apparatus consists of acamera whose axis is parallel to the polar axis of the earth, the lenspointing northward ; opposite the lens is a silvered sphere.The solarrays are reflected from the latter through the camera lens on sensitive(“ ferroprussinte”) paper.By the earth’s motion the image is carried round in a circular arc,tracing a curve on the paper ; a time scale is made by drawing fromthe centre of the circular band radial lines enclosing angles of 15”,each division representing one hour of time. The paper is sufficientlysensitive to register short gleams of sunshine. When the sun isshining through light clouds, a blurred impression is produced of amuch less intense blue colour than that obtained by direct sunlight.V.H. V.Formuh for calculation are given in the paper.C. H. B.425-426).Note.-For further details and drawings of the apparatus, seeMore than six months’ experience of its working Nutwre, 31, 319.has confirmed the usefulness of the results obtained by it.-A. J. GGENERAL AND PHYSICAL CHEMISTRY. 321New Standard of Illumination. By W. H. PBEECE (Proc.Roy. Soc., 36, 270-275). - After alluding to the unsatisfactorymethods in vogue for meaquring the intensity of illumination, theauthor suggests as a staudard the space illuminated by a standardcandle a t 12.7 inches distant. For a comparison of the relative illu-mination of surfaces, use is made of a Swan’s incandescent lamp,giving a light of 24 candles with a current of 5 volts, enclosed wit’hinR box with blackened walls, over the end of which is stretched adiaphragm of paper; the latter has a grease spot a t its centre.Atabout 12 inches from the tube is a screen of paper as a reflectingsurface. The current is supplied from a secondary battery. Fromexperiments detailed in the paper, it appears that the illuminatingI’ower of the glow lamp inweases in the ratio of the sixth power of.the current: hence a determination of its strength gives the necessaryequivalent for ascertaining the degree of illumination. Though thereare certain difficulties arising from alteration of the glass envelope ofthe lamp, deterioration of the carbon fibres, and failure of vacuum,yet the light emitted from the passage of a given current is moreeasily reproducible and probably more uniform than any other arti-ficial standard.V. H. V.Disturbing Phenomenon observed in Polarising Operations.By SCHMIDT and HANSCH (DirqZ. polyt. J., 255, 119).-In makingobservations with polarising apparatus, it is occasionally found that afilled tube, when placed in the polarimeter, does not always give thesame reading when turned round the axis ; this difference is observedeven on filling the tube with distilled water. The causes of thesedisturbing influences are said t o be-(1) want of uniformity of thesolution ; (2) dirt in the tubes ; (3) imperfect parallelism of the planeof the glasses ; and (4) non-parallel edging of the observation tubes.D.B.Relation between the Electromotive Force of a Daniell’sCell and the Strength of the Zinc Sulphate Solution. ByH. S. CARHART (Amer. J. Sci. [3], 28, 374--377).-The investigationdescribed was undertaken with a view to ascertain to what extent thevariation in the strength of the zinc sulphate solution affected theelectromotive force. The method employed was essentially Poggen-dorff’s compensation method. The table (p. 322) exhibits theresult 8.The values of the electromotive force, given in the seventh columnin arbitrary units, were reduced to volts in the following manner:-The ratio of the Siemens unit to the legal ohm (this vol., p. 2) is50 : 53, and according to Lord Rayleigh, a current of one amperedeposits 67.08 mgrms.of silver per minute. Then if C, R, and Nrepresent current strength, resistance, and electromotive force i nampBres, ohms, and volts, and e the electroniotive force in the arbi-trary unit of the table, we have the following equation :-(€Q%)(C x 67.08) = e.e whence RC = - - L = E .x 67-08 71.10Per cent.ofZnSO,.013 {5 {7 . 5 {lo {l5 {2o {25 {73.997 }:::::} 81 -216} '79 -620) 79 -490} 79 -305} 78 -997} 79 -008-Temp-erat meof rheo-stat.--20 -oo18 '818'019 * 517 *817 *317.31s -317 -019.320 *o18 -317 -317 -516 - 316 .€I- :::::1 -1421 -1201 -1181 -1151 *1111 -111ABSTRACTS OF CHEMICAL PAPERS.ResistanceinSiemensunits.---11111112111111111111111111111111Silverdepositedin oneminute.mgrms.6 "7277 -2777 -3396 -7107 -4237 -3587 *2397 *2507 -2247 -2397 *2197.2057 -1707 -2107 *19Y7 -1%Productof resist-ance andsilver.--73 -99780.03780 *72980 * 52081 *65380.93879 -63279 -75079 -46479 $3479 -40979.25578 -87079 -31079.18979 -030Cor-rected€ 0 ~ tem-perat ureof rheo-stat.73 -99780 *00080 *664SO .SO481 *58180 *85179 -54679 *69479 -36979.62279 *40979 -201'78 *7S579 '23179 *07278 *923 -E.M.F.in valueofproduct.It is only necessary to divide the quantities in column 7 by 71.105to reduce them to volts.The method employed is fully sustained bythe results obtaiued with a Latimer Clark standard cell.The meanof all the values in the last column of the table is 1,122, which is thevalue obtained by Sir W. Thomson by the electrostatic method, if t h evelocity expressing the ratio between the electrostatic and electro-maguetic units be taken as 3 X 10'0.From the results of tjhe investigation, it appears that the variationin the concentration of the zinc sulphate sohition is sufficient toaccount for the discrepancr between the results obtained by differentexperimenters in measuring the electromotive force of a Daniell cell.It therefore seems desirable that a standard Daniell cell should be soconstructed as to admit of employing a zinc solution of known con-centration. B. H. B.Experimental Researches on the Electric Discharge withBy W.DE LA RUE and H. W. the Chloride of Silver Battery.M~?LLIGR (Proc. Roy. Sot., 36, 151-157, and 20S--S07.)Electric Conductivity of Impure Mercury and Methods ofPurification. By C. MICHAELIS (Chem. Centr., 1884, 48i-484) ,-The metallic impurities of mercury are divided by the author intothree groups, according to their action and the mode of separatingthem. The first group contains magnesium, potassium, and sodium ;these may be completely removed by agitation with sulphuric acid.The second group contains zinc, lead, cadmium, and bismuth, whichare best separated by boiling the mercury with concentrated snl-phuric acid containing a few drops of nitric acid, and subsequentlGENERAL AND PHYSICAL CHEXISTRY. 323treating it with dilute nitric acid.The metals of the third group aregold, silver, and copper, the last of which may be separated in thesame way as the metals of the second group.An excellent way of purifying mercury is to submit it to surfacedistillat'ion in a vacuum. A. K. M.Electric Conductivity and other Properties of the Copper-Antimony Alloys. By G. KANUENSKY (Phil. Mug. [5], 17, 270-275).-The paper gives determinations of the electric conductivitiesand of tlhe specific gravities of a graduated series of alloys of copperand antimony. A maximum of conductidy was found in the alloyvorresponding with the formula SbCuz ; from this point, the curvefalls very rapidly with increase of copper until it reaches SbCul,whence i t again rises very rapidly as pure copper is approached.The specific gravities rise evenly from antimony to the alloy CulSb(sp.gr. = 8*871), and then diminish to copper. R. R.Electric Conductivity of Water. By F. KOHLRAUSCH (Phil.Mag. [ 51, 18, 542--544).-The question of the conductivity of watercannot be considered to be settled, inasmuch as there are diffi-culties in purifying it from dissolved gases, and from solids derivedfrom the vessels used in its distillation. The water used in the expe-riments described in this paper was distilled a t a temperature of 30-45" under a pressure of G.001 mm., and quickly condensed in theresistance apparatus. Observations were made a t once, inasmuch asit was found that the conductivity increased with the time.Themean of eight observations gave a value of about 30*10-'2 ohms,or practically about 72 billionths of that of mercury, or, t o put thestatement in another form, a thread of water 1 mrn. in length has thesame resistance as a thread of mercury of the same thickness encir-cling the earth. Water may thus be considered to be practically anon-conductor of voltaic electricity. The value obtained in theseexperiments is almost one-third of that found in previous researches ;the water was thus presumably three times as pure.Electric Conductivity of Acids. By W. OSTWALD (J. p r .Chern. [2], 30, 225--237).-1n a former paper (this vol., p. 3) theauthor has shown that a direct ratio exists between the rapiditv withwhich certain acids take part in a, reaction, and the rate a t which theyconduct, electricity.This latter property depends greatly on the stateof dilution of the acid, as the appended table shows. The numbers incolurrin I represent the electrical conductivities of the acids in normalsolutions, hydrochloric acid being taken as 100 ; those under columns11, 111, and IV, give the conductivities €or normal solutions dilutedwith water, 10, 100, and 1000 times respectively.The weaker monobasic acids show a rapid increase in their electricalconductivities with increasing dilution, and apparently all convergetowards the same limit, Pomething above 100, which the strongeracids reach a t an early stage. The bibasic acids, with the exceptionof sulphuric acid, appear to tend towards a maximum conductivity ofabout 52, or half the number attained by the monobasic acids, whilstV.H, V324 ABSTRACTS OF CHEMlCAL PAPERS .Hydrochloric ...................Ethylsulphonic .................Ethyleulphuric ..................Phenylsulphonic ...............Butyric ........................Hydrobromic ...................Xitric .........................Isethionic ......................Formic .......................Acetic ........................Isobutjric .....................Monochloracetic ................Dichloracet. ic ..................Trichloracetic ..................Glycollic ......................Lactic .........................Met hylglycollic ................Ethylglgcollic ..................fl-Hydroxypropionic ............Glyceric .......................Pyroracemic ....................Hydroxy isobuty ric ..............Sulphuric ......................Oxalic .........................Malonic ........................Succinic ......................Malic ..........................Tartaric ......................Diglycollic .....................Pyrotartaric ..................Citric ..........................Phosphoric .....................Arsenic ........................I .100 *o101 -499 -480 *388 *675 -373 -61 *71S0'4360 *3330 -3295-0624 -7561 -11.3901 -7871.0850 -6501 *5566 -011 *316-65 -019 -503 *160 -6951 *4012 *3702 '6211 -1091 *728'7'165 -3211 .118 -0119 *8116 -7106 *€i108'5103 -8104 *85 *311 -5571 -4041 -40315.2664.2100 -34 *65G '615.464 -252.315 '5019 -264.217s *238 -79 *522 *0614 *796.897 *953 -315 *4915 -3912111 .123-8125.9122 *5113 -5116.6110 -2111 -315 754 -964 *454 -4138.979 *6110 -213 -9019.1916 '4913'076 9 916 '2746.111.80102 *753 -024 '356.1613.8820.9021 *168 -2614 3228 *4025.49I V .112'2112 -5107 -4101 -8111.6101.797*242*714 *4512 -9012 -6578.2103 *O104.437'147-743.935.419 -5242 *tj76'432*5113 -452-843-916 '9133'245.546*120 *2228 *8231.430.8the limit reached by the tribasic acids is a third.or about 35 . Inother words. the conductivities of the three kinds of acids are thesame when compared according to their molecular weights .In verydilute solutions. therefore. during electrolysis. only one of the replnce-able hydrogen-atoms in each molecule is influenced by the current .J . K . C .Some New Phenomena of Electrolysis . By G . GORE (Proc .Roy . SOC., 37, 24) .Unequal Electric Conduction Resistance at Cathodes .By (2. GORE (Proc . Roy . SOC., 37, 35-36) .Relation of Chemical Corrosion to Voltaic Current . By G .GORE (Proc . Roy . Soc., 36,331-341).-The object of the experimentsdescribed in this paper was to ascertain the amounts of voltaic currentproduced by the chemical corrosion of known weights of variousmetals in different liquids . The method employed was based upon acomparison of the loss of weight of two similar plates immersed inthe same liquid contained in two glass vessels .One of the pieces waGENERAL AND PHYSICAL CHEMISTRY. 325employed as the positive pole of a battery, the negative pole being asheet of platinum. The current from the cell decomposed a solutionof silver cyanide. The results obtained with different metals andliquids are given in a long series of tables. The amount of corrosionof the positive plate is in nearly all cases greater than that of thecomparison phte, and the proportion of gas to corrosion was frequentlyless with the former than with the latter, A marked exception tothis rule was copper in nitric acid. The proportion of corrosion of thepositive plate accompanying external current to that produced by localaction may be approximately arrived at, either by the difference inthe loss in weight experienced by the two plates, or by the amount ofsilver deposited.The results also show that the proportion of cor-rosion attending external current to that caused by local action,depends on (1) the kind of metal ; (2), the kind of liquid, and on itsconcentrat#ion. The rate of total corrosion of the positive plate appearsto be related to tbe degree of electromotive force.Use of Moist Electrodes. By W. N. HARTLEY (Chem. News, 49,149) .-A controversial note (cornp. Abstr., 1884, 801).Determination of Chemical Affinity in Terms of Electro-motive Force. By C. R. A. WRIGHT and C. THOMPSON (Phil. .Mug.[5], 17, 282-301, and 377-391).-These papers relate to theelectromotive forces set up during the interdiffusion of two liquids ina Daniell cell of a certain construction.The experiments, which arefully described, verify the following general laws :-( 1.) The potentialdifference is increased by an increase in the strength oE the solutionsurrounding the plate of higher potential, and diminished by anincrease in the strength of the other solution. (2.) The total effectof a series of changes i n the strength of the solution is equal to thealgebraic sum of the effects of' the several changes. (3.) The effect ofa given change of strength is independent of the actual strength ornature of the solution, and of the nature of the metal immersed in it,.(4.) But it varies with the condition of the surface of the metal.(5.) The E.M.F. of a Daniell cell with copper and zinc plates, bothamalgamated, is practically invariable, no mattel.what may be theactual strength of the solutioiw of copper sulpbate and of zinc used,provided that these are of the same molecular strength. (6.) TheE.M.F. corresponds with an amount of heat greater than thatdeveloped by the intermixture of the solutions. R. I1.Relation between Electric Energy and Radiation in theSpectrum of Incandescence Lamps. By W. DE W. ABNEYand R. FESTING (Proc. Roy. Xoc., 37, 157--173).-(Comp. Abstr.,1884, 249.)Relations of Heat to Voltaic and Thermoelectric Action ofMetals in Electrolytes. By G. GORE (Proc. Roy. SOC., 37, 251-290).The Constant of Electromagnetic Rotation of Light inCarbon Bisulphide.By LORD RAYLEIGH (PTOC. Roy. SOC., 37,V. H. V.146-148)326 ABSTRACTS OF CHEMICAL PAPERS.Measurement of the Solar Heat. By G. FR~HLICH (Ann. Chim.New Method of Measuring the Heat of Combustion ofCharcoal and Organic Compounds. By BERTHELOT and VIEILLE(Compt. rend., 99, 1097--1103).-Tbe determination of the heat ofcombustiou of carbon and carbon-compounds is very difficult, mainlybecause combustiou in a current of oxygen requires a considerabletime, and, moreover, is never complete. Much better results areobtained by burning the substance in oxygen under a pressure ofabout 7 atmos. in a calorimetric bomb (8ur Za force des matibres Ex-plosives, i, 225). The substance is ignited by means of a metallicthread heated by an electric current.Combustlion takes place in threeor four minutes, and is always complete, provided that the proportionof oxygen Consumed is not more than 3 0 4 0 per cent. of the originalamount. If, however, more than half the oxygen is consumed,carbonic oxide and other products of incomplete combustion arefound in the gases produced. This method gives the heat of combus-tion a t constant volume, and the heat of combustion a t constantpressure is obtained by making the necessary corrections.The authors have determined the heats of combustion of celluloseand several samples of charcoal by this method with the followingresults :-Cellulose.-The combustion of 1 gram develops 4,200 cal., and theheat of combustion (1 mol.= 162 grams) is 680.4 cal. This numberagrees well with Gottlieb's determinat'ion and with the value deducedErom Sarrau and Vieille's experiments on gun-cotton. It is 117.8 cal.in excess of the heat of combustion of the carbon contained in thecellulose, and it follows that the carbohydrates possess energy inexcess of that calculated from the amount of carbon and water whichthey can yield on decomposition. The same conclusion was deducedby one of the authors from his researches on the heat developed byanimal life and by fermentation.Charcod-The following t,ables give the analyses of the samples ofcharcoal used, and their heats of combustion at constant volume :-Phys. [S], 3, 500-540).C. H. Ash. 0.Red charcoal, 1 .. 69.35 5.28 0.63 24.747 7 ,, 2 . . 64-82 5-60 0.83 28-85Black charcoal, 1 . 90.13 3-37 1.76 4.747 7 ,, 2 . 90.92 3.35 1.48 4.25Elder pith ch:tr-coal .......... 70.90 5.06 2.21 21-83H2at of Atomic heat ofcombustion, combustion1 grain. (C = 12).Red charcoal, 1 ...... 6.660 102.027, 98.5 ,, 2 ...... 5970?9 95.4 ,, 2 .... 8090Elder pith charcoal. ... 6.105 91.3Black charcoal, 1 .... 8.087 95.GENERAL AND PH Y STCAL CHEMISTRY. 32 7The last column was calculated on the assumption that the oxygenwas present in the form of water, and that any excess of hydrogenwas in the free state. From these results, it follows that red charcoalpossesses energy in excess of that corresponding with the carbon andfree hydrogen which it contains, but that this excess is less than in thecase of cellulose, a portion of the energy having been lost in the pyro-genic decomposition.I t would seem, therefore, that pyrogenic decom-positions are exothermic, a coiiclusion which agrees with the knowncomplexity of these decompositions and the ease with which they takeplace. Charcoal obtained by the action of more regular heat, suchas that of elder pith burnt inside the branch, has lost its excess ofenergy, whilst black charcoal obtained by the action of a high tem-perature approaches pure carbon in its heat of combustion. The heatof combustion of a sample of charcoal, and consequently of gun-powder made from it, cannot be calculated from the percentage com-position of the charcoal, but varies with the temperature and otherconditions of its mode of preparation.Heats of Combustion of Ethereal Salts of some FattyAcids. By W.LOCGUININE (C'ompt, rend., 99, 1118--1120j.-Theheats of combustion were determined by the methods previouslydescribed (Ann. Chinz. Phys. [5], 27). The following results wereobtained :-Molecular heat of655,828 cal.C. H. €3.Heat of combustionfor 1 gram. combustion.6558.28 cal. Ally1 acetate. . . . . .Diethyl oxnlate . . 4905.05 :, 716,203 ,,Diethyl succinate.. 5791.26 ,, 1007,679 ,,Diethyl malonate. . 5378.95 ,, 860,632 ,,In every case, the heat of combustion of the ethereal salt is practicallyequal to the sum of the heats of combustion of the acid and alcoholfrom which it has been formed. It follows that the heat of conibus-tion of the acid is equal to the heat of combustion of the ethereal salt,minus the heat of combustion of the alcohol.This agrees with Rer-thelot's earlier results (A92n. Ohirri. Phys. 151, 9, 338). A determina-tion of the heat of combustion of an ethereal salt may be substitutedfor the determination of the heat of combustion of the acid itself incases where the latter is non-volatile or is difficult to purify.In the last three compounds in the above ta.ble, the difference in theheat of combustion for each increment of CH, is about 145,000 cal.C. H. B.Heats of Combustion of certain Carbon-compounds. ByW. LOUGUININE (Compt. rend., 100, 63-66) .--rlcetaZ.-Heat of com-bustion for 1 gram, 7784.81 cal. ; for 1 gram-molecule, 918,583-98 cal.Heat of formation, 128.0 cal.This differs by only 0.5 cal. from thesum of the heats of formation of aldehyde and ethyl ether, and hencethe formation of acetal from these compounds is accompanied by avery slight thermal disturbance. There is the same difference (0.5)between the actual heat clf formation of acetal and that calculated o328 ABSTRACTS OF CHENICAL PAPERS.the supposition that it is produced by the union of 1 mol. of alde-hyde and 2 mols. of alcohol, with elimination of 1 mol. of water.Mesityl oxide, C,H,,O.-Heat of combustion f o r 1 gram, 8634.06 cal. ;for 1 gram-molecule, 846,137.88 cal. Beat of formation from itselemenh, 63.00 cal., a value 2.0 cal. higher than the heat of for-mation of 2 mols. of acetone minus the heat of formation of 1 mol.of water.CrotorLaldehyde.-Heat of combustion for 1 gram, 7747.37 cal.; for1 gram-molecule, 542,316 cal. Heat of formation, 41.0 cal. Thisnumber is 3 cal. less than the heat of formation of 2 mols. of alde-hyde minus the heat of formation of 1 mol. of water.Isobutyric acid.-Heat of combustion for 1 gram, 5884.04 cal. ; for1 gram-molecule, 517,796 cal. Berthelot found for the heat of com-bustion of normal butyric acid, 497,000 cal.It is important to observe that the heats of combustion are givenin minor calories, whilst the heats of formation are in major calories.C. H. R.Thermochemistry of Phosphorus Trifluoride. By B mrHELorr(Compt. rend., 100, 81--85).--When phosphorus trifluoride isabsorbed by a dilute solution of potassium hydroxide, there is a de-velopment of heat of + 107.7 cal.per gram-molecule (88 grams). Thisis much lower than the heat developed by the decomposition of phos-phorous bromide and phosphorous chloride under similar conditions.As a matter of fact, phosphorus trifluoride does not yield simply aphosphite and fluoride, but a fluorphosphorous acid is formed analogousto hydrofluosilicic and fluorboric acids. If it be assumed that fluorphos-phorous acid is similar in composition to fluorboric acid, the simplestdecomposition of the trifluoride would be represented by the equation2PF3 + 3H20 = H,PO, + PII’,HE’ + 2HF. Titration of the alka-line liquid afier absorption of the trifluoride (using as indicatorshelianthine A and helinnthine B, which behave towards phosphorousacid in the same way as towards phosphoric acid (this vol., p.345),indicates that the decomposition by alkalis takes place in accordancewith the equation 5PF3 + 12H,O = PF,HF + llHF + 4H3PO3. It ispossible, however, that the nature of the decomposition varies undervarying conditions, and this would explain the slight want of agree-ment between the individual thermoohemical determinations. Theresults obtained by titrating the alkaline liquid also agree with thesupposition that, an oxyfluoride, POF, is formed.Whatever may be the composition of the fluorphosphorous acidformed, it is a somewhat stable compound, for its potassium salt canbe hoiled for some time in presence of an excess of alkali withoutsplitting up into a phosphite and a fluoride.C. H. B.Thermal Equivalent of a Solution of Urea. By M. R 8 i j ~ ~ : ~ ~(Zeit. f. B i d , 20,414-418) .--The author has accurately determined,by means of two different calorimeters, the amount of heat renderedlatent during solution of carbamide. He finds that the heat renderedlatent by 1 gram of carbamide is equal to 61.318 calories, or for tIiemolecule 3769 calories. In order, therefore, to arrive at the true calorificvalue of muscle-protejid, it becomes necessary to take into consideratioGENERAL AND PHYSICAL CHEMISTRY. 329not only the calorific value of fseces and urea, but the loss of heatcaused by the solution of the latter. J. P. L.Eutexia. By F. GUTHRIE (Phil. Mag. 151, 17, 462--482).-Thepaper relates to substances made up of two or more constituents.insuch proportions that the resultant compound (which is neitheratomic nor molecular) has the minimum temperdtnre of liquefaction.Such substances are called by the author ezhtectic (w T ~ K G L V ) , and theproperty in question he names eutezia. The methods of obtainingvarious eutectic alloys of bismuth, lead, tin, cadmium, and zinc aredetailed in the paper, the general principle being that the portion of a,fused mixture that solidifies last on cooling is the true eutectic alloy.Previous experimenters have been misled by the notion that the alloyof minimum fusing point must have its constituents in some simpleatomic proportions ; but the author’a experiments show that this isnot the case, and his eutectic alloys have lower fusing points thanhave yet been obtained by any mixtures of the same metals.He has applied the same methods to mixtures of fused salts thathave no chemical action on each other, such as nitrates of potassium,calcium, strontium, barium, and lead.The sulphates of calcium, ofbarium, and of lead dissolve readily in fused pot,assium nitrate, and theeutectic salt, alloys so formed contain in the latter case 4.6 per cent,,and in the former cases nearly 1 per cent. of the sulphates.The significance of these facts in geology and mineralogy is pointedout, and also the manner in which eutexia explains the order ofsolidification and disposition of the saline constituents of the earth’scrust. R. R.Melting Points and Boiling Points as related to ChemicalComposition.By E. J. MILLS (PM. -Mag. [ 5 ] , 17, 173-187).-The general law of chemical change first enunciated by the authorthat “ chemical effect is directly proportional to the product of theactive masses, and inversely proportional to the sum of their residues’’has been expressed in the equationa . x!y e = ~___X r + Y rand in the present paper this equation is adjusted to meet the case ofmelting point and boiling point as related to chemical composition,beat being regarded as having the same effect as a substance enteringinto the reaction. The equation thus takes the following form :-and is applied to the calculation of the boiling and melting points ofmembers of organic series having the general formula pX . xCH,.The three constants of the equation are calculated from the experi-mental determinations in regard to three members of each series, andthe values then found for the other members to which the equation isapplied, approximate usually within the small portion of a degree t330 ABSTRACTS OF CHEMICAL PAPERS.the observed temperatures.The series discussed in the paper arechiefly normal paraffins, ketones, ketates, ethines, pyridines, mon-amines, a,nd fatty alcohols. Certain interesting general deductionsare ma,de from the results. R. R.Melting Point of Substances in Contact. By 0. LEHMANN(Ann. Phys. Chem. [2], 24, 1--27).-A homogeneous solid isseparated trom a fluid either in the ci-ystalline or amorphous state,the former process being discontinuous, the latter continuous ; thesize of the crystals formed depends on the solubility or diffusibilityof the solid in the liquid.Such generalisations are based on twohypotheses: lst, that the molecules of solids differ in kind fromthose of liquids ; and 2nd, that a molten substance near the point ofits solidification contains the solid Substances in a state of solution.I n the case of solidification of mixtures, there often occurs a separationinto two conditions of equilibrium, leading to the formation of dropscontaining presumably the one substance, while the remaining solutioncontains the other. On the other hand, the crystallination of a sub-stance from a menstruum containing another, will often determine analteration of the crystalline form of the first substance.In order tothrow light on these and allied phenomena, the author has moreparticularly examined the appearance under the microscope of theliquefaction of two substances a t their point of contact. Far example,silver chloride crystallises in the trigonal form, silver iodide in octa-hedra, but the mixed substance when melted presents under themicroscope the appearance of a dark ring ; the mixture also melts ata lower temperature than either of its constituents. I n other cases,such as a mixture of silver bromide and iodide, the mutual layer oncooling presents the appearance, not of an amorphous mixture, but ofinterlaced crystals of either substance. In the original paper, anaccount is given of the phenomena observed in the case of mixturesof the bromides, iodides, and chlorides, and the nitrates of var.iousmetals, as also of various organic substances.The experiments leadto the result that the mixture of the substances in the liquid state issufficient to lower the melting point, and the mass when solidified isgenerally not homogeneous, but a mechanical mixture, even when thesubstances are isomorphous, or to some degree morphotropic.An account is also given of experiments on the electrolysis of silveriodide, viewed under the microscope ; on the passage of the current,metallic silver separates out in denditric crystals on the negativepole, while the iodine renders the portion of salt in contact with thepositive pole of a brown colour.On continuing to pass the current,the particles of silver are seen to travel towards the pole along acanal, the width of which depends on the intensity of the current,while the iodine volatilises for the greater part. The crystallinestructure of the silver iodide, however, remains practically unaltered.Experiments on the electrolysis of a solution of silver iodide betweenelectrodes of the same material are also described ; during this processit appears to undergo an extension in the direction of lines of current.V. H. VGENERAL AND PHYSICAL CHEMISTRY. 33 1Boiling Points of Saline Solutions. By W. W. J. NICOL(Plzil. Mug. [ 5 ] , 18, 364-371).-1n this paper, an account is fiven ofsome preliminary experiments on the pressures under which saturatedsalt solutions boil at different temperatures. The results show thatincrease in solubility of a salt with temperature is attended with agreater rise in boiling point, and conversely diminished solubility isaccompanied by a less marked rise.The exception to the generalisa-tion is potassium nitrate, whose solutions even of the same strengthshow with varied pressure a regular rise of boiling point. If, then,the solubilit'y of the salt incrcases with rise of temperature, theeffect of heat will be to weaken the attraction of salt f o r salt and ofsalt for water ; but the diminution in the attraction of salt for saltmay be so great as t o be practically equal to an increase in the attrac-tion of salt for water. Such a result probably obtains in the case ofpotassium nitrate mentioned above.This is not the case with con-fitantly saturated solutions, inasmuch as the attractions of salt forwater and of salt for salt respectirely are in a state of equilibrium insuch solutions. V. H. V.Employment of Condensation in Fractionating Apparatus.By E. CLAUDON (Bull. Xoc. Ch&n., 42,613-617).-A comparison wasmade between the Winssinger and Le Bel-Henninger forms of apptt-ratus for fractional distillation. Various mixtures of alcohol andwater were simultaneously distilled in the two kinds of apparatus,care being taken that the same quantity was distilled in each in agiven time, the rates being in two experiments 3 and 6 C.C. perminute. In the first-named apparatus, the alcohol came over weakerthan in the second, the separation being not nearly so good at anypoint of the distillation, the washing of the vapour in the latter appa-ratus as it passes through the condensed liquid playing a very im-portant part in the separation.By twisting a spiral of copper wireround the cold water tube in the Winssinger fractionater, an artificialcondensation and washing of the vapours was set up, and experimentshowed that with this modification the separation of the two liquidswas greatly improved. The temperature at which different liquidsdistil has of course to be taken into consideration, the bulbs beingsurrounded with paper or wadding as the temperature rises.Critical Volumes of Liquids. By J. DEWAR (Phil. -$lay. 151,18, 2lO--SlG).-In this paper, there is described R convenient form ofapparatus for demonstrating the liquefaction of oxygen.I t is pro-posed to substitute for liquid ethylene, either solid carbonic anhydrideor liquid nitrous oxide, by means of which temperatures of -115"and -125' respectively can be produced. At a pressure of 80-100atmospheres, and with the means of producing a sudden expansion,the oxygen may readily be liquefied. By means of the npparatns,determinations can be made of the density of the liquefied gas by~b measurement of the volume of the liquid, the volume and thus theweight of the gas given by the liquid plus vapour, and the weight ofgas given by the vapour. The difference between these two last quan-tities corresponds with the weight of the substance in the liquid state.J.I(. C332 ABSTRACTS OF CHEMICAL PAPERS.A rough experiment with oxygen near the critical point gave 0.65for the value of its density. It is pointed out that the ratio of thecritical temperature to the critical pressure is proportional to themolecular volume, and a table is given of this ratio - for a number ofsubstances, from which the following may be selected as new :-frPCritical temp- Critical Terature, T. pressure, P.Ammonia ........ 130" 115 3.5Hydrogen sulphide. 100.2 92 4.0Methane .......... - 99.5 50 3.5Etihane .......... 35 45.2 6.8Cyanogen ........ 124 61.7 6.4The few substances on the type of which the greater majority ofcompounds are built up, namely, hydrochloric acid, water, ammonia,and methane have practically the same molecular volume, whilstthe more complex derivatives show an increased volume, bearing asimple relation to that of the parent substance.If the values of' be taken as proportional to the molecular volumes, then the densitiesPof fluids a t their critical temperatures can be inferred, provided that thedensity of one standard substance is known, fdr = 9- +-, where S' v w'v" wS and S' are the densities of the two substances, W W' and V V'their molecular weights and volumes respectively. Thus, taking thedensity of carbonic anbydride as the standard, and calculating there-from the densities of hydrochloric acid and acetylene, the results soobtained are in accordance with the experimental results.V.H. V.Method for Estimating the Specific Gravity of Solid Sub-stances soluble in Water. By J. L. ANDREAE (J.pr. Chem., 30, 312-315).-The author employs as the medium for this purpose asaturated solution of the substance in question, and measures thevolume of a given weight of solution and excess of salt in the dilato-meter described on p. 334 of this volume. A slight error creeps intothis method, owing to the fact that after a change of temperature,the liquid in the capillary tube, which is not in contact with the excessof salt, is not of the same composition as that in the bulb. In thecase of common salt, which was the subject of these experiments, itssolubility varies so little a t different temperatures, that this source oferror may be neglected, but where the solubility increases rapidlywith the temperature, the first reading should be made at the highestwmperature.The sp. gr. of common salt was found to vary from2.1654 at 10" to 2.1543 at 50" C. J. K. C.Easy and Rapid Method of determining the Specific Gravityof Solids. By J. J. DOBB~E and J. B. HUEHESON (Phil. Nag. [ S ) , 17,459-462) .-A U-tube has one limb narrow and graduated ; the otheGEK'ERXL AND PHYSICAL CHEMISTRY. 333wide with only a line engraved a t the zero level of the graduations.The narrow limb is open; the other is fitted a t the top with an air-tight cap provided with a stop-cock. Distilled water is poured in upto the zero level, the solid is dropped into the wider limb, the cap isreplaced, and by blowing through the stop-cock the water in that limbis brought to its original level, when the rise of the water in thenarrow limb will show the volume of water that has been displaced bythe solid, whence its sp.gr. may bo calculated from its previouslyascertained weight. Determinations made by this method approxi-mate very closely to determinations by the ordinary method. If thesolid is lighter than water or soluble in that liquid, it is only neces-sary to fill the tube with some other appropriate liquid. R. R.Specific Gravity of Substances in the Solid State and inAqueous Solution. By J. A. GROSHBNS (Plzil. Mag. [5], 18, 405-416).-This paper is a continuation of the author's investigations onthe relations existing between the specific gravities n€ compounds ofnnalogous composition, whether in the solid state or in the state ofsolution (comp.Abstr., 1884, 143). Firstly, attention is called to thefact that although the specific gravities of sodium compounds in thesolid state are greater than those of the corresponding potassium com-pounds, yet in solution this relation is reversed. Secondly, althoughthe sp. gr. of the fluorine compounds in the solid state is greaterthan that of the corresponding chlorine compounds, yet the specificgravities of their solutions, provided that they are sufficiently dilute,are practically identical.A solution may be regarded as a compound of 1 part by weightof the soluble substance with a variable number of parts by weight ofwater. The density of such a solution may be represented with suffi-cient accuracy by the formula d = 1 + A in which oc and p areconstants. Threecases are presented :-(1.) The increase of volume of the solution isexactly equal to the added volume of the water, then a + P = 1.(2.) The increase of volume can be less than the added water, whichis the ordinary case, then a + /3 > 1.(3.) The volume of the solu-tion is increased by a greater quantity than the added water, thena + t3 < 1. If molecular solutions are used, then the equation will, in which V = a/l8a, X = a/18/3, and take the form d =A = a/lSaq. The results obtained by Gerlach with sugar solutionsare compared with those calculated from the above formuh. Thevalues are concordant. If aq or A = 0, the formulae becomed = 1 + - = 1 + - = 6, or the sp.gr. of the dissolved substancein the anhydrous state. The results calculated from the equationare, in the case of a few enumerated compounds, in agreement withthe observed results.Analogous salts of isomorphous metals such as iron, manganese,and chromium, have practically the same density when in solution,VOL. XLVIII. 2 aaq + P'I n this formula the sum a + ,f3 is of importance.+ A T 1a vB 334 ABSTRACTS OF CHEMICAL PAPERS.and, secondly, it is possible from observations on the densities in solu-tion of one set of salts, to deduce the densities of its analogiies.Specific Gravity of Saturated Solutions of Solid Sub-stances at Various Temperatures. By J. L. ANDREAE (J. pr.Ckem.[ 2 ] , 30, 305-312).-To obtain the sp. gr. of saturatedsolutions of various substances, two methods were employed, the fimtconsisting in measuring the volume of a concentrated solution ofknown strength a t various temperatures, and calculating therefromthe volume at the temperature of saturation, and the second in weigh-i n g directly a certain volume of solution saturated a t a given tempera-ture. In the first method, a dilatometer was used, consistingof a bulbwith capillary graduated tube attached, the tube having three o r fourenlargements in its bore at various places, and being connected with awider tube a t its other extremity. Through this wider tube the saltunder investigation was washed into the bulb by alternately coolingand heating the latter.After weighing the whole apparatus, im-mersing in a water-bath, and reading off the volume a t different tem-peratures, the sp. gr. of the saturated solution was calculated bymeans of an empirical formula (cornp. Abstr., 1884, 1090).In the second method, a quantity of the saturated solution measur-ing a certain volume was weighed directly in a pyknometer. Theonly subst,ance employed so far has been common salt, and the resultsof the two methods are given in the appended table :-V. H. V.Specific gravity. Molecular7 volumeof NaCl. -----. Temperature. First method. Second method.15" 1.20249 1.2025320 1.20036 1 -2003430 1.19604 1.1960140 1.191 79 1-191 7450 1.18758 1.1874960 1.18339 1.1832870 1.17924 1.1791280 1.17513 1.1 7499From these figures it will be seen that thesolutions of sodium chloride decreases with20.9621.2121.6221.9322.1622.3222-3922-41sp- gr.of saturatedrising temperature,while the reverse is the case with the molecular volume of the samesalt in saturated solution. J. K. C.Density of Porous Bodies. By G. FLEURY (J. Pharm. [ 5 ] , 10,255-257).-A tube 22 mm. in diameter is fitted with a narrow sidetube, as in a Gay-Lussac's burette ; mercury is poured in until it flowsout a t the side tube. The weighed piece of porous wood or othermatter is then forced under the mercury by a wire, and the mercuryruming out is weighed.Molecular Volume of Saline Solutions. By W. W. J.NICOL (Phil. Mag. [ 5 ] , 18. 179--193).--From experiments on themolecular volumes of certain salts of potassium and sodium, theH. BGENERAL AND PHYSICAL CHEMISTRY, 335author has inferred that in the case of suficiently dilute solutions, thevolume of the metal is independent of its associated non-metallicradicle, and conversely the volume of the latter is independent of thatof the former (comp.Abstr., 1884, 658). I n this paper, this generalisa-tion is extended to the halogen compounds of the alkali metals andalkaline earths. In the course of these investigations, it was observedthat water of crystallisation has no effect on the molecular volume ofa salt in solution, and a series of tables of the densities of salt solutionscontaining 100-400 molecular proportions of water added, are givenillustrating this fact.It is thus probable that the so-called water of constitution can berecognised in a solution of the salt, but owing to experimental diffi-culties this point coiild not be determined with exactitude.It is heresuggested that water of crystallisation does not exist in solutions, fora1 though the thermochemical investigations of Thomsen and otherswould tend to show that, as in a number of instances, a hydrated saltdissolves in water with absorption of heat, but when dehydrateddissolves with evolution of heat, yet i t is possible that the act ofsolution of a dehydmted salt consists first in the taking up of waterwith formation of a hpdrat,e, and subsequently this hydrate onsolution parts with its water ; which thus becomes indistinguishablefrom the rest of the water.V. H. V.Cohesion Figures. By W. P. BEZOLD (Ann. Phys. Chew. [TI,24, 27--37).-1t has been observed that figures similar to those ofLichtenberg can be produced by sprinkling a jelly of tragacanth withfine drops of colouring matter. I n this paper, adescription is given ofradiating and arborescent cohesion figures formed by touching asurface of water with a pointed instrument containing an aniline dyemade up with glycerol. The regularity of the radiation o r arbor-escence depends on the relative temperature of the wat,er and theatmosphere, and the shape of the containing vessel. For example, ifa source of heat be placed on one side of the vessel the colouringdrops, instead of spiseading vertically down the geometrical axis of theglass, will be deflected towards the cooler side ; or again, if the tem-perature of the water is higher than its enviyonments, the dropsspread neither vertically downwards nor radiate Peplarly outwardsin every direction, but collected portions travel towards and thenascend the walls of the containing vessel.Solubility and Fusibility in the Oxalic Acid Series.By L.HENRY (Compt. rend., 99, 1157-1160, and 100, 60-63).--Thefollowing table shows the solubility of the acids of the oxalic seriesin 100 parts of water :-V. H. V.Oxalic acid (anhydrous) ...... at 10" 5.3 parts ...... f , 20 10-2 ,,Malonic acid ................ ,, 15 139.0 ,,Succinic acid (normal) ........ ,, 8-5 4-22 ,,,, ........ ,, 14.5 5.14 ,,Pyrotartaric acid (normal) ,, 14 83 1 9Adipic acid.................. ,, 15 i.44 ,,9 , 7,99 ....2 a 336 ABSTRACTS OF CHEMIChL PAPERS.Pimelic acid, the next term, is described as very soluble in water,whilst suberic (C,) and sebacic (C,,) acids are very slightly soluble.The variations in solubility are not progressive but alternating.Acids containing an even number of carbon-atoms are only slightlysoluble, whilst those containing an odd number are readily soluble.When the acids are grouped in two series, one containing those withan even number of carbon-atoms and the other those with an oddnumber, it is found that in each series the solubility diminishes as themolecular weight of the acid increases.Malonic acid, intermediate between oxalic and succinic acids,diff'ers from both of them by its much greater solubility, and thisproperty is also common to all derivatives formed by the substitutionof a hydrocarbon radicle for the hydrogen in the CH, group inmalonic acid, for example, methyl-, ethyl-, isopropyl-, and allyl-malonicacids.Methylmalonic or isosuccinic acid, CHMe(COOH),, is readilysoluble, whilst succinic acid, COOH.CH,.CH,.COOH, is but slightlysoluble. Fumaric acid is only slightly soluble, and corresponds withthe succinic acid type, whilst maleic acid is very soluble, and corre-sponds with the malonic acid tjpe. These relations are expressed bythe formulte generally given to these acids. Maleic acid is methylene-mslonic acid, but the author was unable to obtain it by the action ofmethylenc iodide on ethyl disodium rnal onate.I n 1877, Raeyer pointed out that in the oxalic series between C4and C1,, the acids containing an even number of carbon-atoms have ahigher melting point than those with an odd number, and i n the odd-carbon series the melting point continualIy rises, whilst in the even-carbon series it continually falls.The following table gives the melting points of the first five termsof the series, these being the only members the constitution of whichis definitely known.Mol.wt. Melting point.Oxalic acid.. ...... 90 21.2"Malonic acid ...... 104 132Snccinic ,, ...... 118 180Pyrotartaric acid . . 132 97.5Adipic acid. ....... 146 148Examination of these numbers shows that the addition of CH,, con-verting an even-carbon acid into an odd-carbon acid, lowers themelting point by about 80°, whilst the addition of CH,, converting a nodd-carbon acid into an even-carbon acid, raises the melting pointabout 48".If the acids are grouped into an even-carbon and an odd-carbon series, it is found that in both the melting point is lower thehigher the molecular weight, tbe difference for each increase of(CH,)z being about 32". It would seem that these relations do nothold good amongst the higher members of the oxalic series, but theconstitution of such higher members as are known, has not yet beendefinitely determined. Similar relations are, however, found to holdgood aniongst the dimethyl salts and the amides of the first threemembers of the series.C . H. 13QENERAL AXD PHYSICAL CHEXISTRY. 337Salt Solutions and Attached Water. By F. GUTHRIE (PhiZ.Ma!]. [5], 18, 22-35, 105--120).-1n these two communications, anaccount, is given of a continuation of the author's researchesregarding the cryohydrates, with especial reference to the behaviour ofammonia and its derivatives with water.Prom a solution of ammonia, no cryohydrate could be obtained, forn 33.3 per cent. solution does not crystallise a t - 80", and from moredilute solutions ice alone separates.EthyZamirie.-The following are some of the results obtained withsolutions of ethylamine :-Per cent. of Temperature of Nature ofethylamine. solidification, solid.20 - 13.3" Ice.20.64 - 13.9 Cryohydrate.25 - 9<5 S u bcryohydrate.The last-named substance is minutely crystalline, and its solution isprone to supersaturation.The existence of these solid hydrates,formed at about - 10": of a substance which by itself cannot be solidi-fied in a carbonic acid freezing mixture, would tend to show thatthey are honiogeneous entities, and not juxtapositions of independentcrystals of the two constituents.Diethylunaine in aqueous solution gave the following results :-diet 11 y lamine. so1idific;rtion. solid.22 9.9" Ice.22.5 11 Cry oh ydrate.23 9.9 Subcryo hydrate.35 8 Pure solid.Per cent. of Temperature of Nature ofTriethylairzhte in aqueous solution gave the following results :-Per cent. of Temperature of Nature oftriethTlamine. solidification. solid.18 - 3.4" Ice.19.1 - 3.8 Cry ohy drate .20 - 3.5 Su bcryo hydra te.Triethylamine possesses the remarkable property of being more soInbIeill cold water than in hot.Determinations are given of the criticaltemperature between clearness and turbidity of aqueous solutions oftriethylarnine, of which the following may be selected a s an example :10 parts by weight of triethylamine with 90 of water form a whiteemulsion which on standing sepflrates into two distinct layers, theupper one of which is triethylamine saturated with water, and the lowerwater saturated with t,riethylamine. On heating to 28", both layersbecome turbid and after some time are clarified, whilst the line ofLieinarcation is shifted towards the centre of the mass. It is proposedto apply this property of triethylamine for the diagnosis of fevers, foi.a, mixture of one part of triethylamine with 24.76 of water requires cztemperature of 41" C., that of fever hest, t o cause it to become turbid33s ABSTRACTS OF CHEMICAL PAPERS.The radiation from an electric arc passing into an 8 per cent.solutionrenders it turbid, and a thin film of it spread out on glass forms asensitive plate. Determinations are also given of the relative volumesat various temperatures of water and triethylamine, the mixture con-taining 46.5 per cent. of the latter.Salts ofAni1ine.-The appended results were obtained with solutionsof ithese salts :-Per cent.of salt.Hydrochloride . . 3097 .. 31.8619 .. 35Nitrate ........ 10,, ........10.61, ........ 10-94,, ....... 4.83 . . . . . . . . . 4.91Oza Zat e ........ 0.14,? ........ 0.29Xalicylate ...... 0 24 ...... 0.28Sulphnte ....... 4.57,Pyrogallnte .... 201, .... 23.3 .... 33.6 9 9Temperature ofsolidification.- 91"- 10.7- 8- 2- 2.20 - 0.6 - 0-9- 0 - 1.40 - 0.060- '2.7 - 4.60Natureof solid.Ice.Cryohy drate.Salt.Ice.Cryohydrate.Salt.Ice.Cry0 hydrate.Salt.Cry o h y drat e .Salt.Cry0 hydrate.Salt.Ice.Cry oh ydrate.Salt .This last-named substance was obtained by adding aniline to pyro-gallic acid, and crystallising the product from benzene ; it forms longcrystals melting at 12", soluble in water, alcohol, and ether. Itturns brown on exposure to air.Injinite XoZubiZity.-From an examination of the curves of solubilityof salts in water, it would appear that in some cases at a certaintemperature a finite mass of water will dissolve an infinite mass ofsalt.In order to study the question experimentally, an alloy ofpotassium and lead nitrates was heated without and with small per-centages of added water, and it was shown that the phenomenon offusion, per se, is continuous with and is merely an exaggerated case ofliquefaction by solution. Results are given of the points of solidifica-tion and the nature of the substance separated from an aqueoussolution of potassium nitrate, a cryohjdrate of which is formed withan 11 per cent. solution at - 3". Attention is also drawn to thecontinuity in liquid condition between strong solution and anhydrousfusion in the case of potassium acetate and ammonium nitrate," and tothe bearing of these phenomena on the determination of the meltingpoints of organic substances.Such results also show that it may bean error to infer marine iufluence in the formation of rocks from the8 The Abstractor (Trans., 1883, 3'74) has noted in the case of ammoniumnitrate the continuity between the state of solution and that of fusion, and hasattributed to this phenomenon the discrepancy in the determinations of the meltingpoint of this salt.-V. H. VGENERAL AND PHYSICAL CHEMISTRY. 339presence of water in them, inasmuch as obsidian, for example, if meltedunder pressure, will presumably mix freely with water, which, by aquick release of pressure, will be more or less vaporised.Thermal and Volume Changes attending Mixture.By F.GUTHRIE (Phil. i i u g . [ 51, 18, 495--517).-The phenomena observedin mixtures of triethylamine and water (preceding Abstract) led theauthor to examine more particnlarly the behaviour of its homologuediethylamine. Similar results were obtained in that the liquid, atabout 128-130", was separated into two layers, although owing tothe slight difference between the refractive indices of diethylamineand water, the characteristic milkiness is not observable. In connectionwith similar experimer? ts on tetrethylammoniuni hydroxide, it isobserved that even a 10 per cent. solution of this substance is decom-posed a t 180", with formation of ethylene.Experiments are also described on the thermal and volumechanges produced by the mixture of alcohol, ether, carbon bi-sulphide, amylene, chloroform, and benzene, with each other, and asa general result it may be stated that a gain of volume is accom-panied by an absorption of heat, and consequently a diminishedheat- tension, and conversely, diminished volume is attended with aliberation of heat and increased tension. As an instance of the lattermay be mentioned the admixture of ether with chloroform, and of theformer that of chloroform with carbon bisulphide.The greatestchange of volume in the case of the first pair of liquids is observablewhen they are mixed in monomolecular ratio (CHCl, : C4H,,0), andfurther, the increase of vapour-tension with increase of the proportionof ether is diminished at the point corresponding with this same ratio.These results would seem to point to the existence of the combinationC4H,,0,CHC13.Similar experiments with chloroform and carbonbisulphide pointed to the formation of a similar compound, CS,,CHC13.Ethyl iodide and bromide when mixed together present a, case ofalmost absolute non-interference. inasmuch as the vanour-tension ofV. H. V.L such a mixture decreases regularly with increased proportion of ethyliodide. V. H. V.Thermal Relationship between Water and Certain Salts.By B. ILLINBWORTB and A. HOWARD (Phil. Mag. [S], 18, 123-127).-As the study of the relationship of the homologous salts of a seriesof acids towards water might throw light upon the general relationbetween salts and water, as regards the formation of cryohgdrates,the aut'hors have observed the temperatures at which potassiummethyl, ethyl, and amyl sulphates form cryohydrates. The resultswere as follows :-Temperature WaterPotassium methyl sulphate.., . - 11.3" 60.16Salt. of the cryogen. per cent.,, ethyl sulphate . . . . - 13.9 54.99,, amyl sulphate . . . . -- 5.0 73.97The methyl compound is thus intermediate between the ethyl and theamyl compounds. Determinations of the sp. gr. of these salts a340 ABSTRACTS OF CHEMICAL PAPERS.19.6" gave potassium methyl suIpha,te = 2.097 ; potassium ethylsulphate = 1.843 ; and potassium amyl sulphate = 1.144. Thespecific gravities of these salts are thus regularly in the inverse orderof their molecular weight.V. H. V.Laws of Solution. By H. LE CHATELIER (Compt. rend., 100,50-5'2). -A mathematical application of the laws of chemical eqni-librium (this vol., p. 117) to the case of the dissolut'ion of salts inwater. C. H. B.Saturation of Salt Solution. By W. W. J. NICOL (Phil. Nag,[ 5 ] , 17, 537--550).-1n a, former paper (Abstr., 1884, 253), theauthor put forward the theory that the saturation of a salt solutionobtains when the sum of the attraction of the individual salt mole-cules for one another is equal to the sum of the attraction of the waterfor the salt molecules. In this connection, it is presumable that ttheattraction of the het'erogeneous molecules of water end salt respec-tively is one cause of the contraction attending the solution of thesalt, whilst conversely the attraction of the honiogeneous molecules ofthe salt has an opposite effect.If then this theory were a correctrepresentation of the phenomena in question, larger molecular volumesare due to an attraction of a weaker kind between homogeneous mole-cules of salt, and a greater solubility would t,hus result. Fromexperiments on the chlorides and nitrates of potassium and sodium, itis to be concluded that the more soluble a salt is in any liquid, themore nearly will its molecular volume in the solid state and in a stateof solution approximate. Instances are adduced to show that dimi-nished molecular volume is attended with diminished solubility, andthis, whether the composition of the salt remains unchanged or not.Experiments are also detailed regarding the saturation of two saltsdissolved simultaneously, which tend to show (1) that each saltdissolves independently of the other, and (2) that each salt increasesthe solubility of the other, not by any tendency to form homogeneougcombinations, but rather by a mechanical interposition of the mole-cules of the two salt's with those of water.V. H. V.Reciprocal Solution of Liquids. By W. ALEX~EFF (BUZZ. SOC.Chim., 42, 329).-With liquids between which no chemical reactionoccurs, the solubility of the liquid possessing the greater cohesion ishigher in the liquid having the less cohesion, than the solubility of theliquid of less cohesion in that of greater cohesion. Where, however,there is a tendencj to chemical reaction, this rule does not apply.Thus a t 0" the fiolubility of paraldehyde in water is greater than thatof water in paraldehyde, but a t higher temperatures where the com-pound is decomposed, the inverse of this occurs, and constitutes aparticular case of the law.With liquids having a tendency to com-bine, as well as to dissolve, there are two limits to reciprocal action.At temperatures above which the liquids mix in all proportions, ahomogeneous liquid is formed as a, result of " solubilit,y," but a t lowertemperatures a compound is produced tbrough the agency of " affinity.''W. R. DGENERAL AND PHYSICAL CHEMISTRY. 34 1Lines of no Chemical Change. By E. J. MILLS and TV. M.MACKEY (Phil.Mug. [ 5 ] , 16,429-433).-1f zinc is acted on by dilutedsulphuric acid of a percentage strength expressed by y, a quantity ofhydrogen gas will be given off which may be represented by z, andwill vary with y, so that one may be represented inathemstically as alinear function of the other, thus :-y = a + btl: + cx2.From three experiments made under conditions described in thepaper, the values of the constants a, b, and c are calculated ; then x inthe equation is put = 0, and a should then represent a certain per-centage strength of the sulphuric acid with which the zinc will not beacted upon, the temperature being the same as in the three deter-mining experiments. The results laid down as a curve, in which theordinates represent the strength of the acids, whilst the abscissa?represent the temperature, gave a line of " no chemical action " whichup to 35.25" forms a hyperbolic curve ; higher temperatures furnish :Isecond hyperbola tending to symmetry with the first, and touching i tat a point corresponding with the percentage strength of 79.62.Anexperiment was made with acid of 76.55" per cent. at the correspondingtamperature, and R very slight, though distinct, evolution of gas tookplace. The reaction between diluted sulphuric acid and zinc is thusshown to be very complicated ; for with strengths of 58.77 t o 79-69per cent. there are two temperatures of no chemical change, andbetween 54.47 and 57.77 there are four such temperatures. R. R.Rate of the Chemical Absorption of Gases.By J. J. HOOD(Phil. Mug. [ 51, 17, 352-367) .-The object of the invnstigationsrecorded i n this paper was to obtain an estimate of the rates of interdif-fusion in atmospheres of air and of hydrogen respectively, of hydrogensulphjde, carbonic anhydride, chloriue, and sulphurous anhydride.The results were obtained by observing the rapidity with which theseveral gases were taken up by chemical absorbents. It was foundthat the rate a t which each gas is absorbed is less when i t is mixedwith air than when it is mixed with hydrogen. In both atmospheres,hydrogen sulpliide is absorbed more rapidly than carbonic anhydride,and sulphurous anhydride than chlorine; yet these last are eachabsorbed much more rapidly than either of the former, especially i uan atmosphere of air. When hydrogen is used, hydrogen sulpltideand chlorine are absorbed with nearly equal rapidity.Correction of the Numerical Results given in a formerPaper on Compressed Gas Manometers.By E. H. AMAGAT(Compt. rend., 99, 1153-1154).R. R.Combination of Gases. By J. J. THOMSON ( P l d Mag. [5], 18,233--267).-Accordkg to the doctrine of Clausius and Williamsoii,the individual atoms forming the molecules of a compound gas arecontinually changing partners ; its consequences can thus be developedby mathematical analysis. I n this memoir, an attempt is made inthis direction, particularly as regards the effects producible by time342 ABSTRACTS OF CHENICAL PAPERS.pressure, temperature, and the relative masses of trhe substancesundergoing chemical change. In order to form a definite meutalpresentation of these phenomena, it is here assumed that the con-stituent atoms consist of one or more vortex rings. In a former work,the author has shown that when two vortex rings of equal strengthin approximately parallel planes, perpendicular to the lines joiningthe centres, are moving in the same direction, and the conditions aresuch that the hinder ring overta,kes the one in front, they coalesce,the lines of vortex core remaining approximately constant.Such aunion or pairing together of vortex rings may take place in the com-bination of atoms, whether of the same or different kinds, to formmolecules. If, under these circumstances, the paired vortex rings aresubjected to some distnrbing influence, their radii will be changed bydifferent amounts ; the velocities of translation will thus becomedifferent and separation will occur.In the case of a permanenthomogeneous molecule, it is necessary that the mean time duringwhich an atom is paired with another atom, of the same or differentkind, which is here called the paired time, should be large as com-pared with the time during which it is alone, and free from otheratoms, which is here called the free time. An external disturbancewill diminish this ratio, and provided it be of sufficient magnitude,the value of the ratio will be so much diminished that the substancewill no longer exhibit the properties of a homogeneous chemicalentity, but of its constituent elements.Further, if the value of theratio of the free to the paired times be very small, the gas possessingthis characteristic will not readily enter into chemical reactions ;nitrogen may be ail exampie of this kind. It is thus evident thatthe energy of a gas, and therefore the temperature, depends on themean radius of the vortices which form its constituent atoms, andconversely the mean radius is a function of the temperature. Unless,then, the atoms do not remain long together after the coaIescence ofthe vortices, chemical combination will not readily take place.This theory of the vortex rings offers a more particular explanationof the combination of the constituent atoms in a molecule, or underaltered conditions, of their reverse decomposition.For if in such acoalescence as described above, there are forces which tend to makethe velocity of the front less than that of the hinder ring, the twowill tend to combine more closely ; if the converse phenomenon takesplace, the two rings will tend to move further apart, the result ofwhich will be decomposition. These doctrines are illustrated bymathematical analysis, and the case is supposed of the dissociation ofmolecules of a gas containing two atoms, under such a condition thatthe initial violence of the chemical change is moderated. If f beproportional to the mean paired time of the atmorris and 7 proportionalto the mean free time, let m be the molecules at any given time, n. theatoms at the same time; then if the gas be in a closed vessel, n+2mwill be constant and equal to N, the number of atoms if all themolecules were dissociated.Then T will be inversely proportional ton, let it equal2. I n the time at the number of molecules split up isequal to mEt/f, the number of pairs of atoms which combine in theGENERAL AND PHYSICAL CHEMISTRY. 343Same time Et = d t / t = ?b2it/7 ; so that if 6nz is the increase in thenumber of molecules in the time at, then 6?n = n2Et - - - n Et or dqiz -7 t at - na m d n - 2m 2n2; similarly - - - - - When things have got (I). - _ - -7 f 6t T2f n + 2m = N, then n + - ?z2 = N ; if the dissociation is slight, so that7the number of atoms is small as compared with that of the molecules,then 2f?L' = N. This last equation can be represented in terms ofthe density of the mixed gas ; for if A be the vapour-density of thedissociated gas, D the density of the gas not dissociated, thenN -n D-A o r - = -.If p be the pressure of the -- A 2 - ND - n X - T + - N Agas, p = ClY where C is a constant, and substituting for n and .m inequation (11), then ( D - A ) ~ = 7 'LD A. In accordance withthis equation, the author compares the calculated with the observedvalues for the vapour-density of iodine partially dissociated at 1250" ;the difference between them might be accounted for by experimentalerrors. Similar but more complex mathematical reasoning is appliedto cases of decomposition and subsequent recombination such as that ofphosphorus trichloride and chlorine, or of the compound of methyl oxideand hydrochloric acid investigated by Priedel (BUZZ. Xoc. China., 1875,160 ; 1876, 241), and the observed and calcnlated values are found tobe in accordance. As a still more complex case, the combination ofhydrogen with chlorine, is investigaced, which presents five systemsof particles, the atoms and molecules of hydrogen, the atoms andmolecules of chlorine, and the molecules of hydrochloric acid, and anequation deduced to find the quantity of hydrochloric acid producedwhen hydrogen and chlorine are mixed in any proportions. Althoughthis particular case has not been investigated, yet the analogousinstance of the combination of hydrogen wihh iodine has beenexamined by Lemoine, whose results agree with those caluulated bythe author's theory. Cases are also examined in which gases A, B, C,mixed in a closed vessel and exploded, can form the combinationsAB and AC respectively, but B and C cannot combine ; such are thecombinations by explosion of oxygen with carboric oxide and hydrogen.From the equation deduced, it follows that the ratio of the quantityof water formed to the quantity of carbonic anhydride bears a con-stant ratio to that between the quantities of hydrogen and carbonicoxide left unalhered. This & priori deduction agrees with the expe-rimental deduction of Horstmann. Similar principles may be appliedto other cases of gaseous combination, and much of the reasoningwould seem to be applicable to liquids, although the want of know-ledge of t.he molecular composition of liquids presents difficulties inthe reasoning of such cases on direct dynamical principles.fCp ( 2 1V. H. V344 ABSTRACTS OF CHEMICAL PAPERS.The Numerics of the Elements. By E. J. MILLS (Phil. Mag.[ 5 ] , 18, 393-399).-In this paper it is shown that the " numerics "or numbers representing the atomic weights of the elements can bedetermined by t'he equation y =p15-13(0*9376)", in which y is theatomic weight, p and x: are factors. Tables are given in aThich thecalculated values are compared with those given in the treatises ofClarke and Meyer and Seubert. These results are opposed toProut's theory of integral multiples, for this could only hold good inthe few cases in which IZ: = 0 or E . V. H. V.The Periodic Law. By T. CARNELLEY (Phil. Mag. [ 5 ] , 18, 1-22).--ln this paper, certain relations between the melting and boilingpoints and heat of formation of the halogen compounds of the ele-ments are given in illustration of the periodic law. The generalresults may be summed up as follows :-(i) If in a series of binarynormal compounds one element is common to all, the melting points,boiling points, and heats of formation are periodic functions of theatomic weight of the other element ; (ii) the influence of the halogenon these physical properties increases with the number of atoms inthe compound ; (iii) in normal halogen compounds, the influence ofeither of the elements on the melting or boiling point increases withthe atomic weight of the one, but decreases with the at'oniic weightof the other element. The numerical relations existing between themelting points and boiling points of the halogen compounds of theelements, are detailed a t length in the original memoir, and serve asa means of calculating or even predicting these points within certainlimits, and of applying the results obtained for the classificatioiiand determination of the atomic weights of the metals. Numerous v examples are given of the application of these several processes.V. H. V

ISSN:0368-1769    

DOI:10.1039/CA8854800317

出版商:RSC    

年代:1885

数据来源: RSC

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344 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c C h e m i s t ry.Hydrogen Peroxide. By HANR~OT (Compt. rend., 100, 57-60and 172-1 75) .-A 5-10 volume solution of hydrogen peroxide, thatis, a solution capable of giving off 5 to 10 times its own volumeof free oxygen, can be boiled without sensible decomposition, butwhen the strength reaches 12 vols. decomposition commences. If,however, the hydrogen peroxide is very pure, decomposition is so slowthat t h e solution can be concentrated on a water-bath until it attainsa strength of 15 vols.When a dilute solution of hydrogen peroxide is partially frozen byplacing i t in a mixture of ice and salt, the portion which remainsliquid contains a much higher proportion of the peroxide, whilst thebulk of the solid portion is practically pure ice.If, however, the iceis slowly melted, the liquid which first forms is very rich in hydrogenperoxide, and this ~a-ould seem to indicate the existence of a hydratINORGANIC CHEJITSTRY. 345melting between -13" and -15". By successive freezings the per-oxide can be concentrated until it has a strength equal to 70 vols.,but beyond this point it no longer freezes a t -13". By using methylchloride as a ref rigerator, however, the hydrogen peroxide can befrozen a t -15", and concentration can be carried to 140 vols. or evenfarther, but the process becomes tedious and troublesome. The maindifficulty in this method of concentration is the separation of themother-liquor from the crystals of ice.Dilute solutions of hydrogen peroxide are best prepared by theaction of hgdrofluoric acid on barium peroxide carefully freed fromsoluble salts.The peroxide solution thus obtained is made distinctlyalkaline by adding baryta-water, and barium peroxide arid any ironor manganese are thus precipitated. The solution is then acidifiedwith sulphuric acid, and the hydrogen peroxide concentrated first ona water-bath and then by successive freezings. The advantage ofthis method is that the hydrogen peroxide is obtained in a high stateof purity, and therefore is much less liable t o decompose in the pro-cess of concentration.If a solution of hydrogen peroxide is distilled under a pressure of30 mm. of mercury, the amount of peroxide which passes over isgreater the higher the concentration of the solution.If commercialhydrogen peroxide (10-1 2 vols.) is distilled in a vacuum, practicallyno hydrogen peroxide passes over until the liquid in the retort isreduced to about one-fifth its original volume. At this point, thefractionating bulbs are removed, and the distillation continued in avacuum until the liquid in the retort begins to decompose. Morewater is then added, and distillation continued. The strength of thedistillate obtaiiied in this way corresponds with 5-8 vols., and it isconcentrated in a vacuum nntil decomposition commences. By con-centration under a pressure of 30 mm., a 267 vol. solution can beobtained. Hydrogen peroxide undergoes no decomposition whateverwhen distilled, provided the concentration of the solution in the retortis no higher than that corresponding with 150 vols.Estimation of Hydrogen, Peroxide.-The volume of oxygen evolvedwhen the solution is boiled gives no exact measure of the amount ofhydrogen peroxide present, for a considerable proportion of the lattervolatilises without decomposition.When the hydrogen peroxide isdecomposed by manganese dioxide, a certain quantity always escapesdecomposition, but the error is constant, and corresponds with0.3 vol.Even if a solutionis made alkaline with baryta and boiled, the vapour of hydrogen per-oxide reddens litmus. It is evident t h a t Thenard's rte.rLtraZ hydrogenperoxide must have contained a small quantity of baryta, and henceits instability. The vapour of hydrogen peroxide has a distinct odour,recalling that of nitric acid.Hydrogen peroxide conducts electricitybetter than pure water, and can be electrolysed without addition ofacid, large quantities of oxygen being given off at the positive elec-trode. A t the same time, a small quantity of a mixture of oxygen andhydrogen, in proportions varying with the duration of the experiment,is given off at the negative pole. The current decomposes hydrogenIf this correction is made, the results are exact.Pure hydrogen peroxide has an acid reaction346 ABSTRACTS OF CHEMICAL PAPERS.peroxide into oxygen and water. It; cannot be a,dmitted that thehydrogen peroxide is reduced by hydrogen liberated from the waterat the negative pole, for if the solution is acidified, hydrogen isevolved a t the negative pole and the peroxide is not reduced.C.H. B.Iodic Anhydride. By K. WEHSARG (Ber., 17, 2896-2897).-Theauthor passed mixtures of iodine and oxygen through tubes, containingplatinised asbestos and heated a t 200°, 250°, and 300" respectively,but no combination took place. No better results were obtained whensimilar mixtures were heated with spongy platinum in a Hofmannvaponr-density apparatus a t 192" (? by dimethylaniline vapour), or inclosed tubes a t 200°, 250°, or 300". It therefore appears, that althoughthe heat of formation of iodic anhydride is positive (Thomsen givesI, + O5 = 44.860 cal.), iodine does not combine directly with oxygen,even in the presence of spongy platinum or platinised asbestos.L.T. T.Allotropic Transformation of Sulphur at very Low Tempera-tures. By J. M. R U Y ~ (Chenz. Centr., 1884, 449).-Fused sulphurwas exposed for several days to a temperature varying between-339.5" and -11.2". A change of colour was noticed at the edgessoon after solidification had taken place, whilst the mass remainedunaltered for some days ; small yellow spots then appeared, whichgradually became larger and brighter in colour until after twelve daysthe whole mass had changed into the rhombic modification. A secondexperiment in which the temperature varied between -338.4" and-4%" gave similar results.The Temperature of Allotropic Transformation of Sulphur.By L. T. REICHER (Chem. Celztr., 1ES4, 450).-The author finds thatthe temperature of the allotropic transformation of sulphur is 95.6".Below this temperature, monoclinic sulphur suffers a diminution involume, above it rhombic sulphur experiences an increase in volume,whilst at the temperature of change both modifications have a, con-stant volume.In these experiments, the pressure was equal to fouratmospheres. At a pressure of 15 atmospheres, the temperature oftransformation was raised to 96.2", indicating a difference of 0.05" forone atmosphere pressure.Preparation of Hydrogen Sulphide. By H. N. DRAPER (Chew,.News, 50, 292) .-Two two-necked Woulff's bottles are each fittedwith corks, and a long and a short glass tube bent at right angles.One of the bottles contains ammonium sulphide, which more thancovers the end of the long tube, the other contains dilute sulphuricacid (1 of acid to 4 of water) to a somewhat greater height.Theammonium sulphide bottle is connected by means of its short tubewith the long tube of the other bottle. For use, a gentle current ofair is forced through the ammonium sulphide, it passes through thesulphuric acid bottle, and escapes from its short tube mixed withhydrogen sulphide. No free ammonia passes the acid liquid, nor isthere any sulphur deposited in it. When not in use, there is noA. K. M.A. K. MINORGANIC CHEMISTRY. 347escape of hydrogen sulphide, and the introduction of a stop-cockbetween the bottles prevents the diffusion of the ammonium sulphidevapour into the acid. The author considers that forcing the vapour offuming hydrochloric acid into sodium sulphide solution may probablygive a good result.Purification of Sulphuretted Hydrogen from Arsenic. By0, v.D. PFORPTEN ( B e y . , 17, 2897-2903).-The author recommendgpassing the impure gas over potassium polysulphide, heated at350-360". A glass tube about 30 cm. long is filled with pieces ofliver of sulphur and heated by means of an air-bath, in the ends ofwhich are holes just large enough to push the tube through. Thetemperature of the air-bath is kept at 350-360". The previouslydried sulphuretted hydrogen is passed through this tube, and finallythrough a wash-bottle containing a solution of sodium carbonate.Sulphuretted hydrogen, prepared from crude mnterials containingarsenic, is entirely freed from arseniuretted hydrogen by this process,and may be used with safety in forensic investigations.The authorbelieves the result obtained to be due t o the reaction 3AsH, + 3K,S3=2AsS,Ks + 3HZS. L. T. T.D. A. L.Spontaneous Oxidation of Sulphur. By E. POLLACCI (Chem.Centr., 1884, 484).-It has long been known that when sulphur ismixed with water and exposed to the air at a temperature of 35-40',oxidation takes place with formation of snlphuric acid. The a,uthorconcludes from his experiments that the oxidation is due t o atmo-spheric oxygen, and not to the decouiposition of water as is sometimesstated. It is found that water free from air may remain for monthsin contact with sulphur without the formation of an appreciablequantity of sulphuric acid.Nascent oxygen effects the oxidationmuch more readily than ordinary oxygen, whilst ozone is proba,blythe active constituent of the air. A. I(. M.Electrolytic Preparation of Nitrogen Chloride. By F. MARECK(Chern. Cenntr., 1884, 481-482). - The following phenomenon wasobserved whilst pa,seing an electric current through a coneenhatedsolution of ammonium chloride covered with a thin layer of turpen-tine. On passing a strong current through the solution so as toproduce a rapid series of detonations, and then quickly removing theplatinum electrode, this was found to be covered with a slight greycoatling, but if the current be allowed to pass for 8-10 minutes andthe platinum then removed, a dense soot-like deposit is found, which,however, gradually vanishes, like condensed moisture (from thebreath) from polished steel, and during this vaporisation a distinctodour of ammonia is observable. When dipped intso dilute acid, theprecipitate vanishes almost instlantaneously. If mercury be pouredupon the coated platinum it spreads as i t does on zinc when wettedwith acid.A. K. M.Crystallisation of Phosphoric Acid. By P. L. HUSKISSON(Pharm. J. Trans. [3], 14, 644--645).-Solutions of phosphoric aci348 ABSTRACTS OF CHEMICAL PAPERS.of sp. gr. less than 1.660 cannot be crystallised by any means a tordinary temperatures ; whilst solutions of higher sp. gr. under similarconditions can only be crystallised by the introduction of a crystal oforthophospiioric acid. Phosphoric acid of sp.gr. 1*800, however,crystallises when exposed in a vacuum over sulphuric acid. Thecrystals obtained in this manner mill not start cryst~allisation insolutions of lower sp. gr. than 1.800, and on the other hand thecrystals from the weaker solutions will not induce crystallisation inthe stronger acid. D. A. L.Saturation of Phosphoric Acid by Bases. By A. JOLT(Compt. rend., 100, 55--57).-The author has previously pointedout (Abstr., 1852, 926,) that when “ helianthin,” or Poirrier’sOrange No. 3, is used as an indicator, one molecule of phosphoric acidis neutralised by one equivalent of an alkali. If, however, phenol-phthale’in is used as an indicator, two equivalents of alkali are requiredto neutralise a molecule of phosphoric acid. This is a striking ex-ample of the fact that the ‘‘ neutrality ” of a saIt formed by the unionof a strong acid with a strong base, depends on the nature of theiridicator employed.The difference in the behaviour of these indicators may be em-ployed as a means of estimating the amount of phosphoric acid and ofa monobasic acid, such as hydrochloric acid, which is neutralised byone equivalent of alkali when they exist together in the same solution,for instance, in the solution obtained by the action of water on thechlorides of phosphorus.A given volume of the liquid is titrated withhelianthin as indicator, and then an equal volume is titrated withphenolphthaleb as indicator. If x and y represent respectively thevolumes of alkali require to neutralise the phosphoric and hydro-chloric acids separately, and V the total volume of alkali required bythe mixed acids when helianthin is the indicator, then-v = x + y ,and if V’ repressnts the volume of alkali required when phenol-phthalein is the indicator, then-V’ = 2x + y,and from these two equations the amounts of phosphoric and hydro-chloric acid can be readily calculated.Atomic Weights of Carbon, Phosphorus, Tin, and Zinc.By J.D. VAN DER PLAATS (Compt. rerid., 100, 52--55).--Ca~-bon.-Ceylon graphite, purified by the usual methods ; carbon from sugar,purified by heating in chlorine; and carbon from Schleicher andSchiill’s purified filter-paper, were burnt io oxFgen gas and the car-bonic anhydride weighed, the necessary corrections being made forthe ash and hydrogen contained in the carbon.The mean of six deter-minations is C = 12.0028, the extremes being 12.0010 and 12.0053.Phosphorus.-Three methods were employed, namely :-( 1 .) Theprecipitation of silver from a solution of silver sulphate by phosphoruswhich had been twice distilled in nitrogen; (2) the analysis of silverC. H. BINORGANIC CHEMISTRY. 349phosphate ; and (3) the oxidation of ordinary phosphorus in oxygenunder low pressure. The mean of two determinations by each methodgives P = 30.975.Tin.-Purified tin was converted into stannic oxide by the actionof nitric acid ; and stannic oxide, obtained by fractional precipitation ofa solution of stannous chloride by exposing it to the air, was reduced ina current of hydrogen.Three determinations by the first method giveSn = 118.08, and four determinations by the second method giveSn = 118.07.In all the above calculations 0 = 16 and Ag = 107.93.Zinc.-Zinc obtained by reducing the oxide in hydrogen or byelectrolysis of the snlphate, was dissolved in dilute sulphuric acid, andthe volume of the liberated hydrogen determined. The meau of thethree determinations is Zn = 65.18.The author points out that the value of the relation 0 : H is stilluncertain by 0.5 per cent.Preparation of Sodium Sulphide. By A. DAMOISEAU (J.Phurm. [5], 10, 351--353).-The best yield is obtained when 45 partsof soda in solution are saturated with sulphuretted hydrogen, thesolution being allowed to become warm; a solution of 55 parts ofcaustic soda is then added, and the whole allowed to crystallise.Molecular Modifications of Silver Bromide.By DE PITTEC'RS(Ckem. Centr., 1884, 411-412).-The knowledge of the molecularmodifications of silver bromide has been very much extended by thegelatin process of photography. The different modifications, a1 thoughapparent to the eye, become more sharply distinguishable by theirunequal sensitiveness to light. The following table exhibits the dif-ferences which exist in the appearance and behaviour of various silverbromide films :-C. H. B.H. B.By transmitted light. By reflected light.[slate-blue . . . . Most fresh collodion emul-Iy n g e * { bluish-white . . sions.Older bromide of silvercollodion. Wet plates.Very sensitive wet collo-orange yellowish-white Very old bromide of silvertrans par en tSemi-bluish-white ..reddish- dim.collodion.yellowish-white Very sensitive ditto,greenish-yellow Bromide of silver gelatinof medi urn sensitiveness. 1 greenor violet- Very sensitive ditto.1[. . . . Very slightly sensitive bro-mide of silver collodion.AlmostopaqueLVOL. XLVITI.yielding indistinct pic-tures, and those affectedby the red end of thespectrum.2 350 ABSTRACTS OF CHEMICAL PAPERS.The most sensitive varieties of silver bromide consist of coarsegrains, and, therefore, yield inferior negatives.Combination of Silver Chloride, Bromide, and Iodide withColouring Matters. By M. CAREY LEA (Chem. News, 51, 30-31).-A considerable number of colouring matters combine with silverhaloiid salts. The colou~ing matters most frequentJy impart to thesesilver salts their own shade or something approaching it, ; but this isnot always the case, for sometimes the colour of the silver salt differsconsiderably from that of the colouring matter ; and, moreover, eachof the three haloiid salts may be coloured differently by one 2nd thesame dye.For example, silver bromide, precipitated from the nitratei n presence of aniline-purple is coloured purple ; with cardinal-red i t iscoloured bright flesh or salmon colour ; with naphthalene-yellow, lightyellow ; with eosin, pinkish or salmon colour. Different specimensof the same dye sometimes give different colours, for example, bluish-green and purple silver bromide have been obtained from differentsamples of methyl-green.The author refers to the use of these factsin photography, and points out that they are in many cases opposedto Vogel's theory, that sensitive films stained with these colouringmatters gain sensitiveness for those rays of the spectrum which theuncombined colouring matter absorbs.Purification of Mercury by Distillation in a Vacuum. ByJ. W. CLARK (Phil. Hag. [5], 17, 24-27).-Mercury is distilled inthe Torricellinn vacuum, and condensing, feeds at the top the baro-metric column, while the metal runs out at, the same rate from theupturned lower end of the tube. The paper is accompanied by aplate representing the apparatus.Solubility of Mercuric Iodide in Water and Alcohol.ByE. HOURGOIN (BUZZ. Xoc. Chim., 42, 620-622).-1 litre of dist'illedwater at 17.5" dissolves 0.0403 gram mercuric iodide ; the solution istinged brown with sulphuretted hydrogen and deposits mercuric snl-phide after a lapse of time. At 22", water dissolves 0.0536 gram perlitre. The iodide is much more soluble in alcohol ; absolute alcoholdissolves 11.18 grams per litre ; 80 per cent. alcohol, 2.857 grams perlitre ; and 9 per cent. alcohol, 0.086 gram per litre at 18".By A. v. WELSBACH (Honatsh. Chem., 5, 508-522).-A detailed description of the methods and operations employedin extracting cerium, didymium, and lanthanum from cerite.Double Sulphide of Aluminium and Potassium. By D.GRATAMA (Chem. Centr., 1884, 452).-St. Claire-Deville deecribed adouble sulphide of aluminium and potassium, which was obtained bypassing sulphur vapour over a strongly ignited mixture of carbonwith pot,ash-alnm ; the product decomposed water with violence.Theauthor has repeated this experiment and obtained a substance whichis spontaneously inflammable, yields no gas with pure water, and onlya slight evolution of hydrogen sulphide when treated with hydro-P. F. F.D. A. L.R. R.J. K. C.The Rare Earths.P. P. BINORGANIC CHENISTRT. 351chloric acid. The filtered solution contained no aluminium, showingthat no double sulphide had been formed. The experiment has beenrepeat,ed at higher temperatures, but in no case was the compoundsought for obtained.Tricobalt Tetroxide. By A. GORGEU (Compt.rend., 100, 175-1?7).-Tricobalt tetroxide is obtained i n the same way as artificialhausmannite (Abstr., 1883, 859), by the action of moist air on cobaltchloride a t a red heat. Measurable crystals separate in rings on thesides of the crucible above the fused salt, and are washed with water.They are free froin chloride, and approach more nearly in compositionto Co304, the lower the temperature a t which they have been formed.The percentage of oxygen is usually about 24-24-5 instead of 26.5.There is litile doubt, however, that the crystals have the true form ofCo304. When this oxide is heated bo bright redness, it graduallyloses oxygen, and is converted into the monoxide COO, the decom-position being perfectly contiiiuous. When the monoxide is heatedin presence of air, it absorbs oxygen up to a dnll red heat, but athigher temperatures the oxygen is again partially expelled.The crystals of Co,O, are qusdratic octahedra, without modificn-tions, but the angles are very different from those of hausmaunite(Zoc.cit.), and hence it follows that trimanganese tetroxide and tri-cobalt tetroxide are not isomorphous.A. K. &I.C. H. B.Basic Salts. By J. HABERMANN (Moiaatsh. Chem., 5,432-450).-This is an account of the results of the investigation of basic com-pounds, of which a short notice has already appeared (Abstr., 1884,151). Basic sulphates, chlorides, and nitrates, of the metals copper,nickel, cobalt, zinc, and cadmium, have been prepared.These compounds are obtained by adding dilute ammonia to a boil-ing solution of the normal salt of the metal, as long as any pre-cipitate is obtained ; in this manner, the following compounds havebeen produced :-Basic copper suZphate, 7Cu0,2803 + 6H20, is a finelygranular bluish-green powder; insoluble in cold water ; when heatedto dull redness it forms a black compound of the formula 'iCuO,ZSO,.Basic copper rtitrate, 4Cu0,N,05 + 3H20, is a light blue granularnon-crystalline powder; it is insoluble in water, but is convertedinto a dark powder when boiled with it.Basic copper chloride,Cu@l2,3Cu0 + 3QH20, is a bluish-green powder, not acted on bywater. It seems to be identical with the compound obtained byReindel from copper sulphate, sodium chloride, and ammonia,aiid has a composition similar to that of some specimens ofatacamite, analysed by nebray and Kraut (Gwzelin-Kraut, 3, 644).Basic: ~ ~ i c l c e l sulphate, 7Ni0,S03, 7H20 + 3H20, is a yellowish-greenpowder, sparingly soluble in water; it has an nlkaliiie reaction,and absorbs carbonic anhydride from the air.Basic nickel nitrate,3Ni0,2N205 + 5B20, is a light whitish-green powder, completelyjnsolnble in either cold or hot water. The basic chloride has nohbeen obtained in a pure state. Basic cobalt sulphate, 5C00,S03, isobtained as a blue flocculent precipitate, which loses water com-pletely at 288--292", forming a brownish-black powder. B&c2 b 352 ABSTRACTS OF CHEMICAL PAPERS.cobaZt nitrate, 4Coo,N2o5 + 6H20, forms a blue precipitate, whichabsorbs oxggeii to form a green compound. Basic cobalt chloride,CoCl2,3Co0 + 34H20, is a peach-coloured precipitate, which ishygroscopic, but insoluble in hot and cold water.Basic zincsuZphate, 4Zn0,Sr),,3H20 + 2H,O, is a white crystalline powdei-,which loses 2H20 a t 100'. The remainder of the water is ex-pelled at a, considerably higher temperature. Back zinc nitrate,5Zn0,N205 + 5$H20, and the chloride, 2ZnCI2,9ZnO + 12H20, areboth white crystalline compounds.The following basic cadmium compounds form white crystallineprecipitates : the szclphnte has the formula BCdO,SO, + H20 ; thenitrate, 12CdO,N205 + 11H20 ; the chloride, CdCI2,CdO + H,O.P. P. B.Hydrates of Chromic Chloride. By L. GODEFROY (Compt. rend.,100, 105--108).-A mixture of 7 parts ethyl alcohol with 3 partspotassium dichromate is saturated with chlorine gas (Abstr., 1884,l2t;6), the solution filtered through cotton-wool, and the filtrate dis-tilled until it separates into two layers.On cooling, the green lowerlayer solidifies to a mass of crystals which are purified by recrystalli-sation from a small quantity of water. The crystals thus obtainedare thin lozenge-shaped lamella? which readily give off some of theirwater, but can be preserved in a closed vessel. They have the com-position Cr2C1, + 12Hz0.The hydrate, CrzC16 + 20H,O, is obtained by placing a saturatedsolution of the preceding salt in a dry vacuum for several days at at*emperature below +6". It forms brilliant gl-een triclinic needles asmuch as 3 cm.in length. These crystals readily give off some of theirwater; above 6" or 7" they melt slowly i n their water of crystallisa-tion. When placed over sulphuric acid, the crystals lose 8H20 andbecome opaque and friable.The hydrate, cr?,c16 + 8H20, is a pale-green powder obtained by keep-ing the duodecahydrate in a dry vacuum until it ceases to lose weight.All these hydrates are extremely soluble in water, and they alsodiwolve readily in alcohol o r ethyl acetate, forming green solutionswhich show no dichroism. That they are true hydrates of chromicchloride, and not oxychlorides or hydrochlorides of chromic oxide isshown by the fact that they readily form double chlorides with alkalinechlorides.Dilute aqueous solutions of these salts slowly become bluish-violetin colour a t the ordinary temperature, and the change is instantaneousa t about 70-80".Concentrated solutions do not alter i n this way,even after prolonged boiling. It seems probable that the chromicchloride is converted into an oxychloride with liberation of hydro-chloric acid, and that decomposition ceases when a certain quantity ofhydrochloric acid has been set free. This supposition is supported bythe fact that the change is entirely prevented by the presence of 2.5per cent. of free hydrochloric acid.By M. MihCER (J. pr. Chew. [2], 30, 252-279).--Numei.ous methods have been described for the preparation ofthis colou~, in which the presence of both stannic and stannous chlo-C. H. B.Purple of CassiusINORGANIC CHEMISTRY.353rides appears to be essential : the results, however, are very uncertain,and the varying composition azld appearance of the products obtainedhave led to widely differing views as to the constitution of this purple.It has long been a disputed point as to whether the gold is present asmetal or suboxide. Acting on the supposition that the former view w a scorrect, the author concluded that the finely divided metallic gold mightgive colour to other substances besides stannic oxide, and he thereforetried experiments with the object of confirming this view. Mag-nesium oxide in fine pulp was mixed with a solution of gold chloride :the resulting mixture of magnesia and gold oxide was washed freefrom chloride, dried, and ignited in n platinum crucible.A beautifulintensely purple powder was the result, perfectly homogeneous andsurpassing in brilliancy any of the tin purples. By varying thequantity of gold all shades from a pale roge to a deep carmine tintcan be obtained, 0 1 per cent, of gold being sufficient to colour themagnesium oxide pink. In this case, the colour is obviously due fafinely divided metallic gold, as similar results are obtained by ignitingthe mixture in a sheam of hydrogen, and the purple colour is destroyedby igniting at a temperature sufficiently high to melt gold.Similar results were obtained by using lime instead of magnesia,but the lime required much more gold to give the same tint as thatobtained in the magnesia purples.Endeavours were next made fo colour barium sulphate by suspend-ing the latter in gold chloride solution, and reducing the gold byvarious reagents, drying and igniting the resulting product.It wasfound that barium sulphate could thus be easily made to yield purplesof various degrees of intensity, although not equal to those obtainedfrom magnesia. Reduction of the gold solution with grape-sugargave the best results. Purples of this kind were also obtained withcalcium carbonate and phosphate, but an unsatisfactory result wasobtained with silica. Zinc and lead oxides also yielded purples withgold chloride. The best result of all wa8, however, procluced byalumina: this purple is many times more intense in colour than themagnesia purple, and was prepared at first in the same way, thestarting point being the precipitated hydrate: as however by thisprocess the whole of the gold cannot be removed from solution, it isbest as in the case of barium sulphate to reduce the gold by niearis ofan alkaline solution of grape-sugar : the solution is kept in constttntmotion and heated up to it point at which the colour is a brightwarlet: if the operation is not stopped a t this point a brownish-redis obtained, which on drying and igniting yields a purple of no bril-liancy.Stannic oxide treated in this way also yields fine purples :the best proportions for obtaining a 10 per cent. stannic oxide purpleare as follows :-A quantity of stannic chloride equivalent to 9 gramsSn02 is dissolved in 200 C.C. of water, potassium carbonate addedto alkaline reaction, then 1 gram of gold as chloride, and the grape-sugar added, and the whole diluted to 300 litres and warmed until thecolour has assumed its most brilliant tole.The stnnnic oxide purplesare at their best inferior to magnesia or alumina purples.The author finds that an alkaline solution of glycerol is an excellentreagent for reducing gold : the reduction takes place at the ordinar354 ABSTRACTS OF CHEMICAL PAPERS.temperature, and the gold is deposited in a n exceedingly finc state ofdivision. The above experiments show that gold is able to colour notonly stannic oxide, but a large number of other bodies of variouschemical constitution, whether bases, acids, or salts. The colourcannot therefore be due to any chemical combination, but simply tothe presence of finely divided metallic gold.Atomic Weight of Bismuth.By R. SCHNEIDER (J. pr. Chem. 12 1,30, 237-251).-Lagerhjelm’s determination of the atomic weight ofbismuth, which up to 1851 was accepted as correct, was based on theconversion of the nietal into (1) sulphide ; (2) oxide ; and (3) snlphate :the second of these methods he considered the most trustworthy,and from five experiments the number 213 was deduced as the atomicweight of bismuth. Following a remark of Gmelin’s, the author in1851 revised Lagerhjelm’s experiments, selecting the conversion ofmetal into oxide as the safest method, and as st mean of eight deter-minations found the atomic weight to be 208 (0 = 16). In 1859,however, Dumas by estimating the amount of chlorine in bismuthchloride, calculated tbat the atomic weight of bismuth was 210.Thatt>his number is too high follows from several considerations. Dumashimself acknowledged the difficuky of rendering soluble the whole ofthe chlorine present by means of soda solution as, after repeatedtreatment with the latter reagent, small quantities of chlorine werestill left in the insoluble residue. The strongly hygroscopic characterof bismuth chloride renders it also unsuitable for atomic-weightdeterminations : the least contact with the atmosphere causes it toabsorb moisture, so that on distillation small quantities of oxychlorideare formed which are very difficult to get rid of, and by lowering thepercentage of chlorine give a number for the atomic weight of bismuthwhich is too high ; the same error was found by Cooke to have vitiatedDumas’ estimation of the atomic weight of antimony.Marignac has lately made a fresh investigation of this question.Bythe reduction of bismuth trioxide in a stream of hydrogen, he ob-tained the number 208.6, but considered this as rather too high,because a s~nall quantity of suboxide was formed which could not beentirely reduced to metal. By the conversion of the oxide into snlphatehe obtained as the mean of six experiments 208.16 as the atomic weightof bismuth, a number which agrees very closely with that obtained bythe author.J. K. C.This number has also been lately confirmed by Lowe.J. I(. C.Nitric Peroxide in Bismuth Subnitrate.By HAGER (Arch.Pha;m. [3], 22, 741, aud Pharm. Centr., 321.-Bismuth subnitrateoften has the odour of nitric peroxide. Hager explains theformation of t h i s impurity as follows :-Free nitric acid under theinfluence of sunlight decotqposes into oxygen and nitric peroxide. Iflight and air be not cart?fully excluded from moist bismuth subnitrate,a little nitric acid becomes free and is decomposed as above. To pre-Tent this decomposition, the subnitrate should be preserved from lightand air in well-stoppered glass vessels. To renovate such subnitrate,i t is placed in thin layers on porcelain and heated at 30-35” for notnlore than 20 minutes. J. TINORGANIC CHEMISTRY. 355Atomic Weight O f PlatinUm. By w. HA4LBERSTADT (Ber., 17,2969-2975) .-The author has made a series of careful determina-tions of the atomic weight of platinum.The compounds employedwere platinic bromide, and potassium and ammonium platinochloridesand platinobromides. The estimations of the platinum were carriedout by Senbert's method of the reduction of the salt in a currentof hydrogen, and also by Classen's method of electroiytic depositionThe author also attempted to employ the estimation of the chlorineand bromine by the various methods in use, but abandoned thisattempt as these methods did not prove accurate enough for an investi-gation of this kind. I n the analysis of the potassium platinochloride,the potassium chloride or bromide was also estimated. 300 gramsof platinum were employed in the investigation, and this was carefullypurified by the Bunsen-Schneider process, The platinic bromide wasprepared by the method of v.Meyer and H. Zublin (Abstr., 1880,443). During the preparation, the author obtained hydrogen platino-bromide in the form of monoclinic crystals easily soluble in water,alcohol, ether, chloroform, and glacial acetic acid, insoluble in carbondisulphide. Platinz'c bromide was not obtained in a crystalline con-dition, but formed a, dark brown non-hygroscopic powder sparinglysoluble in water; 100 grams of an aqueous solution saturated a t 20"contained 0.41 gram PtBr,. The anwnonium platinobromide wasobtained by the addition of the calculated quantity of ammoniumbromide to a dilute aqueous solution of hydrogen platinobromide orto an aqueous solution of platinic bromide.It forms small carmine-redoctahedra. 100 grams of an aqueous solution saturated at 20" con-tain 0.59 gram of the dry salt. The potassium platinobromide em-ployed was prepared in exactly similar ways and crystallised in redoctahedra: 100 grams of an aqueous solution saturated at 20" con-tained 2.02 grams of the dry salt.Altogether 97 determinations of the atomic weight were made:namely, 10 with plat inic bromide, 32 with ammonium platinobromide,18 with potassium platinobrornide, 18 with ammonium pla,tinochloride,and 19 with potassium platinochloride. The results obtained were asfollows :-By decomposition by ignition in a current of hydrogen,the atomic weight deduced from 39 platinum estimations =19454246; from the ratio KBr or KC1 : Pt (18 estimations) =194.77061 ; by decomposition by electrolysis, the atomic weight de-duced from 38 platinum estimations = 194.36073 ; and from the ratioKBr or KC1 : Pt (19 estimations) = 194 62987.The mean of all the results obtained gives the atomic weight ofplatinum as 194.57592, which agrees very closely with the number194.46 found by Seubert (Abstr., 1861, 514).L. T. T.New Rhodium Salt. By WTLM (Bull. SOC. Chiqn,, 42, 327).-I n the preparation of the salts described by Claw (Rh2C16,NH,C1 +3H,O and Rh2C1,,3NH4C1 + 2H,O), in presence of excess of aquaregia, the compound Rh2C1,,8NH,C1 + 7H20 is precipitated incrimson hexahedral plates. It is decomposed by water, yielding oneor other of the former salts. After all the rhodium has been precipi-tated, the mother-liquor still contains a substance which often accom35 6 ABSTRACTS OF CHEMICAL PAPERS.panies rhodium, and is probably the cause of anomalies in the reactionof rhodium salts. W. R. D.New Compounds of Iridium. By C. VINCENT (Compt. rend.,100,112-114) .-When moderately concentrated and boiling solutionsof iridium tetrachloride and mono-, di-, or tri-methylamine hydro-chloride are mixed, and the liquid allowed to cool, double chloridesseparate in crystals, and can easily be purified by recrystallisation.These iridiochlorides have the general formula IrCl4,2&C1, whereAm stands for the amine.Monorneth y lamine iridiochloride forms small hexagonal tables of avery dark reddish-brown colour.Dimethy larnine iridiochloride crystallises in rhombic octahedra of a,rich reddish-brown colour. The crystals cleave parallel with theface m, and the ratio of the axes D : d : h = 1.9689 : 1 : 1.9540.Trimeth y lamiue iridiochloride forms large reddish- brown regularoctahedra. The ease with which t{his compound crystallises may boused as a means of separating iridium from the traces of rhodiumwhich i t frequently retains.All three compounds are decomposed by heat with intumescence,and a residue of iridium and carbon is left. The carbon burnsrapidly when heated in the air, and leaves a bulky very brilliantresidue of perfectly pure iridium. C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8854800344

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

35 6 ABSTRACTS OF CHEMICAL PAPERS.M i n e ra 1 o g i c a 1 C h e mi s t r y.Occurrence of Gold in Brazil. By 0. A. DERBT (Amer. J. Sci.[3), 28, 440--44’7).-Two peculiar modes of occurrence of gold aredescribed. A specimen in the National Museum at Rio de Janeiro,from Ponte Grande, Sabark, province of Minas Geraes, shows filmsof gold resting on the surface of a secondary mineral, limonite;the conditions are such that. the author thinks, they cannot be ac-counted for except on the hypothesis of natural deposition fromsolution. The districts of Campanha and Ssto Gongalo, in southernhlinas Geraes, afford an example of extensive auriferous deposits indecomposed gneiss, in which the almost complete absence of veins andof the other usual concomitants of gold is remarkable.B.H. B.Ozokerite. By F. S. SMITH (Chem. News, 51, 35).-A combustionof an unpurified sample of ozokerite found in some clay fields in SouthAmboy, New Jersey, gave the following figures per cent. :-C, 86.46 jH, 12 83. The hydrocarbons probably belong to the C,H, series.D. A. L.Genesis of the Specular Iron Ores of Cuba. By J. P.KIMBALL (Amer. J. ScL [3), 28, 416-429).-The Juragua hills arethe culmination of the foot-hills of the Sierra Maestra, between thebays of Santiago and Guantanamo. They are distinguished from thMINERALOGICAL CHEMISTRY. 357massive body of the Sierra by their isolation as four distinct ranges.The second range affords the best type of ore bodies. The dioriteof these hills is in contact with the syenite, and the contact seemsto have become the seat of great chemical activity.The large massesof iron ore are secondary products from the decomposition of basiceruptive rock, now represented by the epidotic diorite that has pene-trated the syenite of' the Sierra Maestra. The best of the iron orebodies are replacements of coralline limestone. Proof of this replace-ment is afforded by fragments of the ore still retaining the structureof coral. Collateral proof is to be found in the presence of isolatedmasses of marble without stratification, but with marked prismaticcleavage.The larger ore bodies present all the numerous physical types ofspecular oxide, besides a variety of phases from unequal distributionof iron pyrites and of magnetic and manganic oxides, and from anunequal degree of hydration.Earthy admixtures are of a chloritic andepidotic type, and thus essentially basic. The composition of theore is shown by the following percentages from commercial sam-plings :-Moisture, 0.24 to 0.81 ; silica and insoluble, 5 to 10.5;phosphorus, OmO03 to 0.065; sulphur, 0.045 to 0.248; and iron, 61to 68.5.Besides the iron ore bodies, above described as repZacew&ents, anotherclass of deposits of ferric oxide are described as concentrations. Theseare partially altered dioritic masses characterised by a notable butunequal concentration of ferric oxide in situ. The outcropping por-tions of such masses are often no less rich in specular oxide than thereplacements of coralline, from which they are readily distinguishedby their superior hardness and density, as well as by their metasomaticassociation with unaltered diorite.B. H. B.Bauxite from Langsdorf. By J. LANG (Ber., 17, 2892-2894).The bauxite found in this neighbourhood varies considerably i ncolour (from bright red to brownish-red), cheniical composition,density, &c. The following are the results of the aiialysis oftwo specimens. (I.) Brownish-red specimen. (11.) Light red speci-men.SiO2. Al,O,. Fe20,. FeO. CaO. MgO. KzO. Na,O.I. 5-18 50.85 14.36 0.35 0-41 0.11 0.09 0.17TI. 10.27 49.02 12.90 - 0.N trace 0.11 0.20H20. HzO.at looo. on ignition. GO,. P,O,. Total.I. 1.35 2 7-03 trace 0.48 103.3411. 0.93 25-88 0.26 0.38 100.57A microscopic examination showed the presence of crystals of mag-netic iron-ore, augite, silicic acid, and silicates, and of amorphous redlmmatite, and (probably) aluminium hydroxide.From the analysesand mineralogical character of this substance, the author considers itto be a product of the weathering of basalt. L. T. 1'358 ABSTRACTS OF CHEMICAL PAPERS.Hemihedrism of Cuprite. Ry H. A. M~ERS (Phil. Mug. [ 5 ] , 18,127-150).-Among certain specimens of cuprite from Wheal Phmnix,Cornwall, a mode of hemihedrism was observed whose existence hasbeen considered possible on theoretical grounds, but has only beenpreviously observed in ammonium chloride. This mode, described asthe trapezohedral or gyroidal, is formed by the combination of thecube, octahedron, and dodecahedron. The following were the observa-tions of the angles :-(100) : x = 47" 30' [18 edges] ; (010) : z = 53" 43' [lS edges] ;(001) : z = 63" 58' [ l S edges] ; (111) : x = 9" 23' [ll edges].I f the alternate faces of t'he complete 48-faced figure he sup-pressed, two half forms are obtained, for which the cube and dodeca-liedral planes are no longer symmetrical; such two half forms areexantromorphous.V. H. V.Erosion of Limestone. By A. L. EWING (Amer. J. Sci. [3], 29,29-31) .-In attempting to determine the amount and rate of chemi-cal erosion taking place in the Limestone Valley of Center Co., Penn-sylvania, the nature of the problem precludes the idea of even a closeapproximation to accuracy. The author claims, however, that hisdeterminations form a more trustworthy basis than mere estimates.The method pursued was as follows :-The amount of water flowingfrom a given hydrographic basin in the region under question wasdetermined from the cross section and velocity of the stream drainingit.The amount of solids in the water was determined by evaporation.These data, with the area of the basin, formed the basis of calcu-lation.The region selected was that of the Spring basin, which forms aconsiderable portion of the limestone valley of Center Co. The author'scalculations show that 25,456,560 kilos. of solids are removed perannum. As the limestone area drained by Spring Creek is about100 square miles, this gives 255.654 kilos. of solids as the amount re-moved per annum per square mile.This is equivalent to 282 tons.Making a correction for the water carried off by Spring Creek, whichfalls upon the mountains bordering the valley, it still leaves 275 tonsper square mile as the amount annually removed in solution.B. H. B.Colemanite. BJ- A. W. JACKSON (Anter. J. Sci. [3], 28, 447-418; comp. this vol., p. 224).-This mineral has recently beendetermined by J. T. Evans, whose analysis gives the formula2Ca0,3B2O, + 5H20. It differs from pandermite in containing 5 mols.instead of 3 mols. of water, but its main interest lies in its morpho-logical relations. The crystals are small and colourless ; the examina-tion in the polariscope showed them to be monoclinic. The plane ofthe optic axis is normal to the clinopinacoid, and makes an angle of$313" 25' with the chief axes.With a primitive form having a : b : c =0.774843 : 1 : 0.540998, and /3 ==: 69" 50'45'', the authordetermined thefollowiDg forms : WPC, m ~ & , OP, m ~ 3 , WP$, WP+;, WP, ~ P Z , PA,BP&, SPfi, 6P&, 4 P 3 , ZPC, PS, ,-P&, P, 2P, - P, -3P, - $#Q-P,ZPZ, 3P$, 4P2, $Pp, ZPi, 3P3, - 3P3, .3P3,4P&, -3P3. The crystalsare all very complex. One of them has 24 different forms upon itMIKERALOGICAL CHEMISTRY. 359The primitive prism mP is always largely developed, and determinesthe columnar habit of the crystals.Herderite from Oxford Co., Maine. By W. E. HIDDEN and J. B.MACKINTOSH (Amer. J. Sci. [3], 27, 135--138).-The specimens ofthe mineral described were originally thought to be topaz, but theauthors noticed that the basal cleavage was absent, axid that thehardness was 5 instead of 8.The crystals are implanted on quartzor on muscovite, and have an average diameter of about 3 mm. Theyare apparently rhombic, well-formed, and rich in planes. Streakwhite. Crystals very brittle with conchoidal fractnre. Sp. gr. = 3.Phosphoric anhydride mas found t o be present in large quantity.These results prove that the mineral is herderite, or a new mineralspecies. As no quantitative analysis of herderite has ever beenpublished, the authors made an analysis in order to determine itsformula.CaO. BeO. P205. F. Total. Less 0. Total.33-21 15-76 $431 11.32 104.60 4.76 99-84B. H. B.The results obtained were as follows :-Corresponding with the formula-3Ca0,P206 + 3Be0,P205 + CaFz + G1F2,OP, 3(+CaO+BeO)P205 + (&Ca&Be)F2.These results are interesting, since it is the first time that# beryllinmhas been found in any mineral in any other form than as a silicate o raluminate.The mineral is probably identical with the herderite ofHaidinger, described as an alwrruina lime phosphate fluoride. Shouldit prove otherwise, the authors suggest the name of gbucinite asappropriate (comp. Abstr., 1884, 827, and 1102).Saltpetre Deposit. By SACC (Bied. Centr., 1884, 784-785).-Near Anan6, in Bolivia, a, deposit occurs having the composition: potas-sium nitrate 60.7 ; sodium chloride and water 30.7 ; organic matter 8%per cent. with traces of borax. The soil under the deposit is brown, andwhen moistened an odour of ammonium carbonate and sulphhgdrate isnoticed ; the analyses show it,s composition to be :-residue after igni-tion (sand, calcium, magnesium, and iron phosphahs) 74.2 per cent.;borax and salts 15.5 ; organic matter, water, and ammonium salts 10.3.The author thinks that the nitrate has been formed by the oxidationof the ammonium salts in presence of the sodium and potassium derivedfrom the underlying shale. The potassium nitmte has risen bycapillarity to the sarface, whilst the more deliquescent sodium nitmtehas been washed away to the hotter and drier regions of the coast,there forming Chili saltpetre deposits. As many fossil bones arefound here, it is possible that these saltpetre deposits are all due tothe decomposition of the remains of antediluvian animals.A New Tantalite Locality.By C. A. SCHAEFFER (Amer. J . Sci.[3], 28, 430).-At the Ettn tin mine, Dakota, crystals occur of itrblack mineral, believed by Blake (Amer. J. Sci. [3], 26, 235) to bewolframite. A careful examination of all the specimens received byR. TI. B.E. W. P360 AESTRACTS OF CHEMICAL PAPERS.the author has resulted in finding no wolframite, b u t a considerablequantity of tantalite, which gave on analysis the following results :-Ta,05. Sn02. FeO. MnO. Total. Sp. gr.79.01 0.39 8.33 12-13 99.86 7-72B. H. B.Columbite in the Black Hills of Dakota. By W. P. BLAKE(Amer. J. Sci. [33, 28, 340-341).-At the Etta and Ingersoll mines,Dakota, columbite associated with cassiterite, albite, and mica occursin granite dykes traversing the mica schists and sandstones.At theTngersoll mine, an enormous mass of nearly pure columbite withinclusions of quartz was found protruding from a matrix of albiteand quartz. The mass weighed about one ton. Thin tabular crystalsoccurred at the lower end, where it was enclosed in quartz. Thehabit of the Ingersoll crystals is thin and tabular, with acute, wedge-like prismatic edges, the plane wPZ being nearly obliterated by theextension of wP3 and mP ; whilst a t the Etta mine the seplanes aresubordinate to cnP2 and mP2. The plane UP is narrow in thecrystals from both localities, and is flanked by a series of bevellingplanes, +P2 being especially prominent.Several cavities in the large mass were filled with a yellow powder,consisting chiefly of hydrous uranium oxide.The blowpipe reactions of the lngersoll columbite are peculiar inthe amount of manganese indicated.Sand and Kaolin from Quartzite.By J. I3. DANA (Amer. J. 8ci.[3], 28, 448-452; 29, 57-58). From observations made(Amer. J. Xci. [ S ] , 28, 203) on the quartzose rocks of Minas Geraes,Brazil, 0. A. Derby inferred that the flexibility attributed to themis not an original characteristic, but only a surface character, a phaseof weathering or decay brought about, by percolating waters. Factsfrom the quartzite regions of Massachusetts, Connecticut, andVermont fully sustain these observations, and appear to throw lighton the nature of the change. The conclusion from the facts describedby the author is, that the kaolin is derived from the felspar of afelspathic quartzite. The quartzite contained much felspar, and onlytraces of iron pyrites and mica, and was easily permeable by water,hence its fitness for making deposits of pure white clay.It isalso evident that the quartz, sand, and friable part of thc quartziteare produced by the removal of finely disseminated felspar ; whilst thebuhrstones have been found where the felspar is disseminated in largishpieces through the quartzite. A very common source of the destruc-tion of the quartzite is the oxidation of its iron pyrites. One peculiarresult of this oxidation is a pseudo-breccia; this is a quartzitedivided up by a succession of cracks, with limonite colouring the rockalongside of the cracks, and also deposited in them.Within some ofthe dark limonite-coloured bands, cavities occur containing a coatlingof limonite. They have generally a lining of minute qunrt'zcryst,als coating the limonite, showing that the quartz was depositedaFter the limonite. The quartz penetrates the limonite-colouredbands to such an extent thab it is prvbable that they were alsoB. H. BMINERALOGICAL CHEMISTRY. 361produced during the formation of the limonite, and a t the ordinarytern peratwe.The only fact as yet observed which seems to bear on the origin ofthese eridently recent quartz deposits, is that t,he quartzite massshows by the occurrence in it of a few large ragged cavities, and alsoof many minute holes, that the rock probably contained grains andlarger pieces of felspar.If so, alkaline silicated solutions, derivedfrom the action of carbonated waters on the felspar, may have beenthe source of the crystals. This supposition is reasonable, but morefacts are needed to sustain it. B. H. B.Siliceous Earth from Morris Co., New Jersey. By J. W.MCKELVEY (Chenz. News, 51, 35).-This sample of infusorial earthwas greyish-white in colour, and on ignition becomes perfectly white.It contains small fragments of leaves and twigs. Its density is 1.11 ;on analysis it gave, per cent. : SO,, 80.66 ; d1,03, 384 ; CnO, 0.58 ;loss on ignition, 14-01. The deposit from which it was obtained is3 acres in extent. It is peaty for 1 foot from surface, then infusorialearth for 3 feet, followed by 7 feet of white clay, resting on a driftof gravel and cobble-stone.The clay is mixed throughout withinfusorial earth. The deposit is thin near the edges, and the upper15 inches of the 3-feet layer is more porous than the rest.D. A. L.Chrysotile from Shipton, Canada. By E. G. SMITH (,4.mer. J.Xci. [3], 29, 32-33) .-The fibrous serpentine, or chrysotile fromShipton occurs in narrow veins traversing the solid serpentine. Themineral has a fine silky lustre, and varies in colour from deep greento pale yellow. Two specimens mere analysed: I, dark green,sp. gr. 2.142; IT, pale yellow, density 2.286. The results were asfollows :-SiO,. FeO. MgO. H,O. TotaI.I. 41.837 2.234 41.990 14.282 100.34311. 42.043 3.663 39.540 14.309 99.555These results clearly establish the identity of this mineral with thechrysotile from other localities.Nephrite from Jordansmuhl in Silesia.By H. TRAUBE (Jahrb.f. Min., BeiEage iii, 412-427).--Nephrite has recently been found insitu, with granulite and serpentine a t Jordansmiihl. The structureand colour of the nephrite are extremelyvariable. The colour is, as arule, a dark-green ; the compact varieties have mostly a fine olive-green colour and great transparency. The nephrite encloses magnetite,compact epiclote, and zoisite. The chemical composition is tolerablpuniform, the differences being confined to the percentage of iron.The Jordansmuhl nephrite differs in microscopic structure from allother occurrences, and proves Arzruni’s theory, that every occurrenceof nephrite has a special microscopic structure.If the composition,manner of formation, and geological occurrence are regarded apartfrom the structure, two varieties of the Jordansmuhl nephrite may beB. H. B362 ABSTRACTS OF CHEMICAL PAPERS.assumed ; the pyroxene-nephrite, (Analysis I) closely connected withthe granulite, and the primary nephrite (Analysis 11) occurring in theserpentine.SiO,. A1203. FeO. MnO. CaO. MgO.I. 56.93 1-01 499 0-71 14.54 19.2111. 39.21 1.16 2.40 0.80 14.08 20.81I. 1.93 99.32 2.98211. 1-81 100.27 3.043H,O. Total. Density.B. H. B.The Santa Catharina Meteorite. By 0. A. DERBY (Amer. J.Sci. [ 3 ] , 29, 33--35).--An ochreous crust is mentioned by Daub&as occurring on some of the specimens of the Santa Catharinameteorite now in the National Museum of Rio de Janeiro.Thiscrust he took to be of secondary or terrestrial origin, and to becomposed of limonite with imprisoned fragments of the disintegratedgranite upon which the mass was stated to have rested. This crust,however, proves to be an essential part of the meteorite, and appearsto indicate the existence of a new group of meteorites intermediatebetween the holosiderites and the syssiderites of Daubree. Themeteorite presents a mixture of metallic and siliceous elements com-bined in a way that has not hitherto been noticed, and the stonyportion also presents a new type of structure in which olivine andplagioclase predominate. The partial vitrification of the stony por-tions affords evidence of the meteoric origin of the mass. Theauthor is collecting material for a more extended memoir.B. H. B.Mineral Spring Romerbrunnen ” at Echzell Wetterau.By C. PISTOR (Ber., 17, 2894-2896).-This spring rises, at anelevation of 450 feet above the level of the North Sea, on the westernslope of the Vogelsgebirg, in a stratum of peat (1.75 feet thick),overlying late diluvial deposits. Analysis of the water yielded thefollowing results in parts per 1000 :-Si02 GO2. N20,. N203. A1203. FeC03. MgC03.0.090 2.7910 trace trace 0.0450 0.0205 0.5611OrganicCaCO,. CaSO,. NaC1. KC1. MgCI,. batter. NH3.1.0590 0.1240 1.6275 0.0642 0.1780 0.0230 traceThe temperature of the water issuing from the spring was 12.3”.L. 1’. T

ISSN:0368-1769    

DOI:10.1039/CA8854800356

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

ORGANIC CHEMISTRY. 363Organic C h e m i s t r y .Reactions of Aluminium Salts with Organic Compounds.By GUSTAVSON (Bull. 80c. Chim., 42, 325--327).-The reactions ofhaloid aliiminium salts with organic compounds may be divided intotwo classes, the first, in which combination occurs, and the second,where double decomposition is effected. To this latter class belongthose reactions where, by means of the correspording halo'id salt ofaluminium, the chlorine or bromine of certain simple compounds,(CCl,, C2C16, &c.), which do not contain oxygen, is replaced by anotherhalogen. If t'he organic compound contains hydrogen in addition to thehalogen, a halogen hydride is evolved, while the elements that remainform an unsaturated radical which at once combines with the alum-inium salt', unless some indifferent liquid is added in the first place,when substitution of the halogen takes place.I n those reactionswhere combination occurs, either the aluminium salt combines directlywith the organic compound, or decomposition is in the first placeeffected, resulting in the Formation of an unsaturated radical, whichthen combines with the aluminium salt. The compounds studied bythe author contained either hydrocarbon radicals or oxygen inaddition to carbon and hydrogen. As instances of the first set ofcompounds, benzenoid hydrocarbons and olefines may be taken ; thesecombine directly with haloid aluminium salts, provided a halogenhydride he present. The compounds formed enter into reaction withother substances with great facility.Ethylene combines with alum-inium bromide, producing a compound of the formula A1,Br6,C8&,and similar reactions occur with saturated hydrocarbons, whilst a tthe same time simplei= saturated hydrocarbons are formed. Theorganic radicle which remains conjugated with the aluminium saltcombines with other substances, and, in fact, appears to act in pre-cisely a similar manner to the Free aluminium salt. The reactions ofhaloid aluminium salts with the chlorides and bromides of thesaturated alcohols resemble those with the saturated hydrocarbons.These salts also combine with compounds which contain oxygen.Thus aluminium chloride combines with sulphurous anhydride andalso with compound ethers. In these cases, saturated compounds aredecomposed, forming an unsaturated radical, which combines with thealuminium salt.For instance, the chlorides of the fatty acids, whenacted on by aluminium chloride, evolve hydrogen chloride and anunsaturated radical containing oxygen is produced, and remainscombined with the aluminium chloride, Al,CI, + 4C2H,OC1 = 4HC1 +&CI6,C8H8O4. The author considers that mineral salts perform animportant function in the living organism by combining with organicmatter to form unstable compounds, which readily enter into reactionwith other bodies, aiid enable the organism to harmonise with changesin the environment. W. R. D.Chloroform Hydrate. By G. CHANCEL and F. PARMENTIER(Comnpt. r e d , 100, 27-30).-If a, mixture of chloroform and wate364 ABSTRACTS OF CHEMICAL PAPERS.is cooled a t 0" with frequent agitation, the hydrate, CHCI3,18H,O,separates in colourless lamellae resembling crystals of potassiumchlorate. The crystals are lighter than chloroform but heavier thanits aqueous solution.They melt a t 1%", and form a milky liquidwhich soon separates into chloroform and water.Sometimes the hydrate will not crystallise unless some previouslyformed crystals are dropped into the cooled mixture of chloroform andwater. If the mixture is cooled below 0" with frequent agitation,the crystals which separate are not chloroform hydrate, but ice mixedwith very small proportions of chloroform. This result is due to thefact that the heat of formation of chlorofol-m hydrate is less than thelatent heat of water. The heat of formation of the hydrate fromliquid water and liquid chloroform is 22.9 cal., and is the same as itsheat of fusion, but its heat of formation from ice and solid chloroform isnegative, arid combination would therefore be endothermic.The amount of chloroform in tbe hydrate was determined by heat-ing i t with aqueous or alcoholic potash in sealed tubes at loo", andprecipitating the chlorine as silver chloride.By RIESEL (BUZZ.XOC. Chim.,42, 319).-When the nitroparaffins are prepared by the action ofsilver nitrite on iodo-derivatives, secondary products are formed ; thesehave been examined by the author. They appear to be isomerides of thenitroparaffins and alcoholic nitrites. In the cases of nitroethane andnitropropane, compounds are formed which boil a t 29.5" and 55"respectively.When the latter compound is treated with hydrogenchloride, ammonium chloride is formed, together with a crystallinesubstance, which, from its chemical behaviour, appears to be thehydrochloride of a base, (CHO),C : NH,HCl. The nitrate of this basewas also prepared. A similar compound is formed by the action ofhydrogen chloride on the new isomeride of nitromethane, but was notobtained pure. W. R. D.Alkaline Ferrocyanides and their Compounds with Ammo-nium Chloride. By A. ~ ' I A R D and G. BI~MONT (Compt. rend., 100,108-11 0 ; seealso thisTol., p. 233) .-When dry potassium ferrocyanidsis heated to incipient fusion in a vacuum, no gas is evolved, but a partof the salt is converted into potassium cyanide, which can be dissolvedout by alcohol, and Williamson's salt, which is left in somewhat bulkycrystals, 2K,FeCys = FeK2FeCys + 6KCy.The ferrous potassium salt decomposes a t a red heat into potassiumcyanide, cyanogen, and pure crystalline iron ; thus, FeK,FeCy, = Fez+ 2KCy + 2CN.The complete decomposition of the potassiumfemocyanide is represented by the equation K$eCys = Fe +4KCy + 2CN.If a solution of potassium ferrocyanide is allowed to drop into a,solution of ammonium chloride, boiling out of contact with the air,decomposition takes place in accordance with the equation 2KFeCy,+6NH4C1 = FeK,FeCy, + 6NH4Cy + 6KC1. When equal bulks ofgranular ammonium chloride and potassium ferrocyanide are treatedwith twice their volume of water at 25", with frequent agitation, aC.H. B.Constitution of NitroparafflnsORGANIC CHEMISTRY. 365crystdline mass is formed, and if this is dried by means of a filter-pump and redissolved in water a t 35-49", the solution on coolingdeposits large, brilliant, refractive, yellowish crystals of the composi-tion (NH4),KFeCy,,ZNH4C1. When equal parts of potassium fzrro-cyanide and ammonium chloride are dissolved at loo", the solution oncooling deposits ammonium chloride and pale yellow rhombohedraof the composition NH4KH2FeCyG,2NH4C1. Ammonium ferrocyanidecan only be obtained by saturating hydroferrocyanic acid withammonia and precipitating with alcohol. When dissolved, it decom-poses, yielding, amongst other products, ammonium cyanide.Ifammonium ferrocyanide, or better, sodium ferrocyanide, is treatedwith ammonium chloride, Bunsen's salt, (NH4)4PeCy6,2NH4C1, isobtained. This salts splits up into ammonium cyanide and ferrouschloride, a reaction which shows that the iron in ferrocyanides has a,ferrous function. C. H. 33.Action of Chlorine on Ethyl Thiocyanate. By J. W. JAMES( J . pr. Chem., 30 [el, 316--:<17).-When chlorine is passed throughcooled ethyl thiocyanate, crystals of cyanuric chloride separate, and aliquid is formed which boils between 130-140" with partial decom-position, and consists of dichlorefhyl sulphochloride.By MILLER (Bull. Xoc. Chim., 42,328).-The author recommends the following process for the prepara-tion of canarine.One part of potassium thiocyanate is dissolved intwo parts of water, and to this liquid is added one-tenth part ofBerthollet's salt and one part of hydrochloric acid. The reaction com-mences at once, and a€ter it has subsided, the vessel is cooled bywater, and one-tenth part of Berthollet's salt and one part of hydro-chloric acid are again added. The temperature should not be allowedto fall below 80". The crude canarine is washed with water andpurified by dissolving it in potash, from which solution the potassiumderivative of canarine is precipitated by adding alcohol. The pre-cipitate is washed with alcohol and decomposed with hydrochloricacid, when canarine is obtained as a brown-red powder of somewhatmetallic appearance ; it is insoluble in water, alcohol, and ether, butsoluble in alkalis When dissolved in concentrated sulphuric acid,sulphurous anhydride is evolved ; this distinguishes canarine frompseudosulphocyanogen.Canarine forms soluble salts with the alkali-metals, and coloured precipitates with other metals. It is the onlycolouring matter by which vegetable fibres can be dyed without theuse of a mordanb. W. R. D.J. K. C.Preparation of Canarine.Dichlorether. By I(. NATTEREE (Monatsh. Chem., 5,491-507).-As the constitution of dichlorethor is represented by the formulaCHLC1.CHCl.OEt, the author anticipated being able to resolve it bylieat into monochloraldehyde and ethyl chloride ; t'he result of heatingthis compound in sealed tubes at 18~", is, however, to resolve it into ethylchloride and a black pitch-like mass.This decomposition, the authorconsiders, may be attributed to the action of a small quantity of watercontained in the dichlorether, since the compound is not decomposedVOL. XLVIII. 2 366 ABSTRACTS O F CHEMICAL PAPERS.when its vapours nre passed throuzh tubes heated at 200". Dichlor-ether heated a t 110-120" with sodium oxalate, yields a distillate con-taining monochloraldehyde, monochloracetal, and hydrochloric acid,and a residue consisting of a dark liquid and sodium chloride.Monochloraldehy de appears t o unite with alcohol, forming thicknon-crystallisable liquids consisting of alcoholates, the composition ofwhich has not been determined ; a solution of monochloraldehyde inalcohol yields monochloracetal, when allowed to remain for sometime.The alcoliolates and monochloracetal are converted intodichloibetjher by hydrochloric acid.Dichlorether is decomposed by alkalis ; €he action of baryta-wateron i t has been especially studied, the author expecting to obtainhydroxyaldehyde, thus : CH,Cl.CHCL.OEt + Ba( OH), = BaC1, +EtOH + OH.CH2.CH0. Although barium chloride and ethyl alcoholare formed, hydroxyaldehyde is not found amongst the products ofthis reaction, but two organic compounds are produced, whose composi-tion has not been determined ; it is possible that they owe their origint o the production of hydroxyaldehyde in some phase of the reaction.Dichlorether is acted on by aqneous ammonia, monochloraldehydeammonia, ethyl alcohol, and ammonium chloride being formed, thus :CH,Cl.CHCl.OEt + H,O + 2NH, = CH,Cl.CH(OH).NH, + EtOH + NH4C1.Alcoholic ammonia, heated with monochloraldehyde-am-monia, yields a n amorphous basic compound. P. P. Iu.Reactions of Dichlorether. By J. WPLICENUS (Annnten, 226,261-281) .-A complicated reaction takes place when metallic zinc isbrought into contact with dichlorether, the chief products of whichare zinc chloride, hydrochloric acid, ethyl chloride, ethyl alcohol,monochloraldehyde, and the condensation-product C8H,6CI,03, whichhas been described by Abeljanz (this Journal, 1873, 154).I n the presence of water, a more simple reaction takes place, whichresults in the formation of ethyl ether, acetaldehyde, ethyl alcohol,and monochhaldehyde.Small quantities of crotonaldehyde, chlor-acetal, @-hydroxychlorether, OH.CH,. CHCl.OEt, and the condensation-product, CH,.CICH(OEtj,O, are also formed. The reaction may berepresented by the equations :-Zn + C,H3C1?.0Et + H2r) = ZnC1, + C2H60 + C2R40, and2Zn + SC,H,Cl,.OEt + 2H20=2ZnCI, + 2C2H60 + 2C,H3C10 + Et,O. w. c. w.Action of Benzoic Peroxide on Amylene. By E. LIPPXANN(Monntsh. Chem., 5, 559-566) .-Benzoic peroxide and amylene donot react a t the boiling poiut of the latter, even in closed vesselsunder 2 atmos. pressure. I n sealed tubes at 100" (equal t o about10 atmos. pressure), a reaction occurs of so violent a nature, that onlysmall quantities can be operated on at a time. The products of thereaction are benzoic acid, small quantities of benzoic anhydride,pentane, and carbonic anhydride, and an oil of pleasant etbel-ealodour, lighter than water ; it cannot be distilled without decomposi-tion, even in a vacuum.This oil appf'ars to be a mixture ofbenzoates, as ou saponification with alcoholic potash i t yields potasORGASIC CHEMISTRY. 367sium benzoate and a clear yellow oil, of which about one-half consists ofan amylene oxide, CloH20Ol boiling at 198-203" (uncorr.). It is lighterthan water, has an odour resembling that of oil of rue, and does notcombine with sodium hydrogen sulphite nor reduce ammoniacal silversolution. Further experiments are required to phow whether i t isidentical with the amylene oxide obtained by Eltekoff by the action oflead oxide and water on diamylene bromide. The amylene employedin these experiments was a mixture of isomeric hydrocarbons boilingat 35-40".A. J. G.Trichloromethylsulphonic Chloride and the Derivatives ofMethylsulphmic Acid. By G . MCGOWAN ( J . pr. Chenz. [2Jl 30,280-;304).-Continuing his former work on this subject (Abstr.,1884, 1126), the author has studied the reactions of methyl-sulphonic and dichloromethylsulphonic chlorides and their respectiveacids.Metbylsulphonic acid, chloride, and amide, were prepared asdescribed hy Carius (Annalen, 114, 14S), and also the anilide; thelatter crystallises in large plates, very soluble in alcohol. The chlorideis not affected by sulphuretted hydrogen. All attempts to convert itinto the cyanide by means of potassium cyanide failed, and the authorwas also unsuccessful in chlorinating methylsulphonic acid or itschloride. Trichloromethylsulphonic acid dissolves iron with evolutionof hjdrogen, forming the ferrous salt; tin and zinc reduce the acid.The chloride cannot be obtained from the acid or any of its salts byheating with phosphorus pentachloride. Potassium cyanide, as Loewhas shown, converts the chloride in aqueous or alcoholic solution intothe potassium salts of trichloromethylsulphinic and dichlorhydroxy -methylsulphinic acids.From the salt of the lather acid, dichlor-hydroxymethylsulphonic chloride may be obtained by treatment withphosphorus pentachloride. The corresponding anilide was also preparedand ana lysed.Sulphuretted hydrogen has no action on trichloromethylsulphonicchloride when dissolved in benzene.With aniline also, the reactionproceeds according to the solvent : in alcohol and benzene, the corre-sponding anilide is formed, whilst in ether the products are anilineand chloraniline sulphate. Methylamine, like ammonia, evolvesnitrogen when broiight into contact with trichloromethylsulphonicch 1 or ide.Dichloromet hylsulphonic acid, prepared by the a4ion of zinc ontrichloromethylsnlph~rli~ acid, differs from the lat,ter in easily yieldingcliloride with phosphorus pentachloride, which is further convertedinto its corresponding amide by ammonia. The action of sulphurettedIipdrogen and sulphurous anhyhide on this chloride could not beproperly studied for want of material.New Anhydride of Mannitol.By SOKOLOBOFF (Bull. SOC. C I L . ~ ~ . ,42, .327).--Ry reducing mannitol dichlorhydrin with sodiiimamalgam, a crystalline arid a viscous substance are obtained. Bothdissolve easily i n water and alcohol, but are insoluble in ether. Thecrystalline compound melts at 119" and Soils under diminishedJ. K. C.2 C 368 ABSTRACTS OF' CHEMICAL PAPERS.pressure without decomposition ; i t has the formula C6Hl0O4, andfrom its physical properties appears to be an isomeride of the isoman-nide of Fauconnier and of the mannide of Berthelot. W. R. D.Raffinose (Melitose P) from Molasses. By B. TOLLENS (Bey., 18,26--28).-The author has examined a sugar crystallising in needlesobtained from a sample of molasses from cane-sugar purified by thestrontium hydroxide process.This sugar after purification crystal-lises in white needles of the formula Cl2HZLOll + 3Hz0. In thehydrated condition, i t melts a t loo", but if previously dried at 60--80", it remains solid a t 130". A 9.5986 per cent. solution whenpolnriscopically examined shows a specific rotation [?ID = 102.5-103". No birotation is observable. When t'his solution 1s heatedwith a little sulphuric acid, the specific rotation is reduced to 4.5'.The original. sugar does not reduce Fehling's solution, but aftertreatment with acid becomes strongly reducing. When treated withnitric acid, it yields a substance melting a t 210--214", and moresoluble than mucic acid.This sugar appears to be identical with the raffinose obtained byLoiseau from molasses, and by Ritthausen from cotton-seed cake, andis probably identical with melitose obtained from eucalyptus-manna.Ritthausen considered his sugar to be identical with melitose (A bstr.,1884, 12861, but the author points out that the rotation found byBerthelot for melitose was o d y about 85"; it is very likely that,Berthelot's melitose wm impure.This sugar has a highx rotation than cane-sugar, and is probablythe cause of the high rotation of some sugars which in the trade aresaid to contain plus-sugar.Action of Heat on Starch Granules.By S. SCHUBERT(Nonaish. Chem., 5, 472-487) .-This paper contains an accountof the result of the investigation 0' the changes which dry starchundergoes when heated a t temperatures varyinq from 260-190" ; anaccount is given of the change in form and structnre which thegranules gradually undergo under these conditions ; this the authorregards as due not only to a loss of water on the part of the granules,b u t also to the different physical and chemical behaviour of theindividual layers of the granule.The microscopic examination of thegranules heated at 160" sElows the presence of gas bubbles in thecentre of the staimch-granule, which increase in size when the tem-perature is raised to 175", a t the same time the layers become moredistinct ; when the temperature is raised to 190°, the granule appearst o be composed of a series of scales, which, by the loss of intermediatesubstance, seem to be separated from one another.In the con-version of starch into a soluble variety by beating it with glycerol,the author considers that the glycerol acts simply as a regulator oftemperature, Starch, which by heating has been converted into a sub-stance entirely soluble in hot water, is partially dissolved when treatedwith cold water, the dextrin and soluble starch produced from thegranulose being dissolved, whilst the insoluble matter is representedby an organised residue, consisting chiefly of cellulose, and havingL. T. TORGANIC CIIEXISTRY. 369the original form of the grain : this residue is soluble in hot water,and its solutions are dextrogyrate : the specific rotation being, how-ever, less than that of soluble starch. P. P. B.Action of Certain Substances on Dextrin.By W. K. J.SCHOOR (Chem. Centr., 1884, 455).-Whilst estimating glucose in itvery impure commercial product containing starc h, dextrin, andglucose, the amount of cuprous oxide separated was found to varywith the concentrafion of the liquid and the duration of heating :this was therefore effected on a water-bath below 100". On addinga solution of salt to the mixture of dextrin and Fehling's solution,and then heating, a powerful reduction takes place, and is increased bythe further addition of salt ; hydrogen sodium carbmate produces thesame effect. Glycerol, which alone has no reducing action onFehling's solution, also effects a reduction when added to a solution ofdextrin, and the action is even more marked when otie of the abovesalts is employed together with glycerol.In this case, the dextrinappears to be completely converted into dextrose. The change takesplace a t the ordinary temperature. A. K. &I.Optical Activity of Cellulose. Observations on a RecentCommunication by M. B6champ. By A. LEVALLOIS (C0?7?j9ft.rend., 99, 1122).Rotatory Power of Solutions of Cellulose in Schweizer'sReagent. By A. B~CHAMP (Compt. rend., 100, 117--119).-Themolecular rotatory power of cellulose, as determined by dissolvingpurified cotton in Schweizer's solution, is not constant but shows verywide variations. The author is of opinion that the cellulose is notsimply dissolved by the reagent, but undergoes progressive molecularalterations which terminate in a constant molecular state in whichthe substance retains certain characteristics of cellulose, but has othei.properties peculiar to the particular molecular condition.C.€3. B.Cutose. By E. FREXY and URBAIN (Comnpt. rend., 100, 19-24).-The substance of this paper has already appeared elsewhere (com-pare Abstr , 1884, 859). c. H. R.Trimethylamine and Pyrroline from Coal Gas. By G.WILLtAMS (Chenz. News, 51, 15--16).-1n a previous communication(Jow. Gas Lightim, 41, 913, 960) it was shown that ammonia andanother ~olatile base are produced when coal-gas is passed overhydrogenised palladised piimice heated much below redness. T tiepailadised pumice is charged with hydrogen by passing coal-gas overit when heated ah 100". Finding t h a t zinc-dust treated in a similarmanner can replace the palladium, more extensive experiments harebeen made.A globular flask is fitted with a cork, and two tubes, oneof which reaches nearly to the bottom, its lower end being protectedby fine copper gauze, this tube serves for admission of gas. Th+:flask is filled up to the neck with zinc-dust which is hydrogenised at alow temperature, and while the gas is passing, it is gradually heate370 ABSTRACTS OF CHEMICAL PAPERS.more strongly ; between 95-208", best of all a t about 117", hydrogensulphide, ammonia, pyrroline, and trimet hylamine are recognisableamong the products. The yield of these substances is extremelyirre-gular, in one experiment 100 feet of gas yielded 1.7 grains NMe3 and15.0 NH4Cl; in another, 101 feet gave O a - 5 grain NMe3 and 6.2NH4C1; the total amount obtained in six experiments, using morethan 260 feet of gas, was 7.2 grains NMe3 and 25.2 NH,Cl.In asimilar manner, using hydrogen prepared from zinc and snlphuric acidinstead of coal-gas, ammonia and methylamine were obtained fromhydrocyanic acid. A sample of zinc-dust treated with dilute sulphuricacid, washed and dried, did not act in the manner described.Formation of Tetramethylammonium Nitrate. By E.DUVILLIEK and H, MALBOT (Compt. rend., 100, 177--178).-Whenmethyl nitrate (1 mol.) is mixed with concentrated aqueous ammonia(1 mol.), and the mixture allowed to remain with periodica'l agitation,the whole of tlhe methyl nitrate disappears after about six weeks, andthe liquid contains the different amines in the following proportionsapproximately :-Ammonia = 10, monomethylamine = 13, dimethyl-and trimethyl-amines = 1, tetramethylammonium hydroxide = 6.The volatile amines were expelled by boiling the liquid with excessof potash, and were separated by Duviilier and Buisne's method (Ann.Chim.Phys. [ 5],22,319). The tetrainethylammonium hydroxide wasextracted from the residual liquid. When methyl nitrate and concen-trated aqueous ammonia are heated in the same proportions in sealedtubes a t loo", the same products are obtained in the same proportions.The action of methyl nitrate on. aqueous ammonia differs from itsaction on alcoholic ammonia (Abst'r., 1880, 545), in that tetmmetliyl-ammonium hydroxide is formed in considerable quantity in the firstcase, but only in very small quantity in the second.In both cases,dimethylamine and trimethylamine are formed in very small pro-portions,The action of aqueous a,mmonia on methyl nitrate resembles theaction of ammonia gas on a solution of methyl nitrate in wood spirit(crlbstr., 1884, 577).D. A. L.C. H. B.Action of Zinc Organo-metallic Compounds on Aldehydes.By E. WAGNER (Bull. SOC. Chinz., 42, SSO).-The reaction of zincethyl with saturated and unsaturated paraEno'id and benzeno'id alde-hydes yields secondary alcohnls. Zinc methyl probably behaves in asiinilar way. With zinc propyl, the result is not so simple, for thepropyl group is also decomposed, yielding propylene and hydrogen ;the latter reduces the aldehyde to a primary alcohol.In fact, as theiriolecular weight oE the zinc-compound becomes greater, the reaction isrendered more complicated and difficult to effect. By acting with zincethyl on acetaldehyde, valeraldehyde, cenanthaldehyde, acraldehyde,and benzaldehyde respectiveiy, the following secondary alcohols wereobtained :-Methyl ethyl e a r b i d , ethyl isobutyl carbinol, ethyl heayl car-binol, ethyl vinyl carbinol, and ethyl phenyl carbinol. The reaction of zincpropyl with oenanthaldehyde results in the formation of a mixture ofpyopgZ heayZ carbind with primary heptyl alcohol, and with acetaldehydORGANIC OHEMISTRY. 371in the production of methyZpropyZ carbinoZ and etJ$ alcohol. In thesereactions, the rate of chemical change depends on the relative numberof carbon and hydrogen atoms in the molecule, and also on the mole-cular weights of the reacting bodies.It is greater with unsaturatedthan with saturated aldehydes, and is inversely proportional to themolecular weights of the compounds reacting. Thus with zinc ethyland acraldehyde, the change is instantaneous, with acetaldehyde it iscomplete in two or three dnsys, with benzaldehydc in about nine days,with valeraldehyde in about a month, whilst with cenanthaldehyde thereaction is not completed until nearly two months. With zinc propyland acetaldehyde, the completion of the change occupies from six toeight days. The method is recommended as a general one for pre-paring secondary alcohols.Action of Metals on Chloral Hydrate.By M. 8. COTTON(Bull. Xoc. Chim., 42, 622-685).--Zinc foil scarcely attacks anaqueous solntiori of chloral hydrate at the ordinary temperature, butat 80" or 100" a rapid action sets in with formation of hydrogen,methane, and zinc oxychloride. Zitic dust acts more energeticallyand at the ordinary temperature, the same products being formedtogether with chlorinated methanes, and the reaction proceedingalmost on the same lines as the reduction of chioroform by zinc.The action of iron on chloral hydrate depends on the temperatureand the state of division of the metal ; besides methane and chloro-methnnes, other products are formed the nature of which is stillunder investigation. J. K. C.Crystallised Anhydrous Zinc Acetate. By J. PETER and0.DE ROCHEFONTAINE (flull. Soc. Chim., 42,573-574).-Zinc acetatedried a t 150" is boiled with pure glacial acetic acid. The filteredsolution kept in a well-corked flask deposits crystals of anhydrouszinc acetate on cooling. J. K. C.Compound of Ethyl Acetate with Calcium Chloride. ByJ. -4. LE CANU (C0112pt. rend., 100, 110--112).--liebig pointed outthat ethyl acetate combines with calcium chloride, but the compuundformed lias not previously been nnalysed.When pure, dry ethyl acetate boiling at 76-77" is poured on topowdered calcium chloride, the mixture soldifies with developmentof heat,. The product is dissolved in an excess of ethyl acetate at40--50", and the solution filtered and allowed to cool, when sl~ot'tslender needles of the composition 2CzH30,Et, CaCl, are deposited.This compound is rapidly decomposed by moist air, and when dis-solved in water, the ethyl acetate is liberated.It dissolves readily illabsolute alcohol. If a current of dry ammonia gas is passed into asolution of the compound in ethyl acetate, the calcium chloride it;completely precipitatpd.If magnesium chloride is dissolved in ethyl acetate at 70-80°,crystals resenrblirig the calcium compound are deposited on cooling.Calcium iodide dissolves still more readily in ethyl acetate with greatdevelopment of heat and formation of a very thick liquid.W. R. D.c. €€. B372 ABSTRACTS OF CHEMICAL PAPERS.Haloi'd Substitution Derivatives of Propionic Acid. ByL. HENRY (Compt. rend., 100, 114-11 7).-/3- Chloropropionic acid,CH,Cl.CH,.COOH, obtained by the decomposition of its chloride byexposure to air, forms large thin white lamella? which are somewhathygroscopic.It melts at 37-38', and boils with slight decompositionat 203-205", under a pressure of 764 mm. Unlike its isomeride, itis neither corrosive nor caustic.p- Chloropropionic chloride, CH2CI.CH2.COCl, obtained by the actionof phosphorus trichloride on the preceding compound, is a colourlessliquid with a strong suffocating odour; it reacts violently withwater, alcohol, and ammonia. It boils a t 143-lG", under a pressureof 763 mm. ; vapour-density 442 ; sp. gr. a t 13"= 1.3307.E t h y l p-7~ onochloropropionata, CH,Cl. CH2. C OOE t, prepared by theaction of the acid on ethyl alcohol in presence of sulphuric acid, orbetter by the action of the acid chloride on alcohol, resembles thecorresponding acetate, but has a less powerful odour.It boils a t162-163" under a pressure of 765 mm. ; vnponr-density 4.94 ; sp. gr.at 8'= 1.11GO. Unlike the corresponding acetate, i t has very littleaction on an alcoholic solution of sodium iodide. It differs in the sameway from propyl chloracetate which resembles it in phyqical properties,and is obtained in a similar manner. This latter compound boils at161-162" under a pressure of 765 mm. ; sp. gr. a t 8 O = 1.1096.Methyl 6-chloroprqionute, CH2C1.CH, C(_)OMe, boils at 155-157".Monochlorethyl /3-cl~loropr~~ionr~te, CH,C1.CH2.CO0.C2H4Cl, obtainedby the action of /3-chloropropionic chloride on glycol-monochlorhydrin,is a colourless liquid with little odour.It is insoluble in water andboils a t 210-215'; sp. gr. a t 8"= 1 282. Unlike its lower homologue,it has little action on sodium iodide in alcoholic solution.ac-l~onochZoropropio?iic chloride, CHMeCl.COC1, obtained by theaction of phosphorus trichloride on a-chloropropionic acid, boils a t109-110", under n pressure of 744 mm. ; sp. gr. a t 7.5" = 1.2394;vapour-density 4.38. Monochloracetic chloride boils at 107-108".The a-chloropropionic derivatives closely resemble in volatility thecorresponding acetic compounds.Methyl P-iodopropionate boils without decomposition a t 188", undera pressure of 756 mm. ; sp. gr. a t yo= 1.8408. Ethyl /3-iodoprr,yiortnteboils with slight decomposition a t 198-200", under a pressure of754 mm.; sp- gr.at 8 O = 1-707. Both compounds are colonrlessliquids which become brown on exposure t o light. They are in-soluble in water, and have an agreeable ethereal odour, which doesnot affect the eyes. In this respect, they differ from the correspondingacetic compounds. They are obtained by the action of 13-iodopro-pionic acid on the alcohol in presence of sulphuric acid.Propyl iodoace!ate, CH,I.COOPr, obtained by the action of propylchloracetate on sodium iodide in alcoholic solution, resembles themetameric ethyl iodopropionate in its physical properties (boiling a t198", under 756 mm. pressure ; sp. gr. a t 7" = 1.6i94). It differs fromit by the fact that its vapour produces lachrymation.p-IodopropionamidP, CHJ CH,.CONH2, obtained by the action ofaqueous animonia on methyl ,fj-iodopropionate a t the ordinary tem-perature, forms colourless tabular crystals which become yellow wheORGANIC CHEMISTRY.373exposed to light. They melt a t 1OO--10lo, and dissolve readily inwater, yielding a solution which can be precipitated with silver nitrate.Iodacetamide, obtained by the action of alcoholic ammonia on methyliodacetate under the same conditions, forms small needles whichmelt at 157-158". C. H. B.a-Ethylamidopropionic Acid. By E. DUVILLTER (Compt. rend.,99, 1120-1121). - a-Ethylamidopropionic acid is obtained by theaction of a-bromopropionic acid on ethylamine. It crystallises froman aqueous solution in large monoclinic crystals with a rhombohedra1appearance, containing 4H,O, which is gradually given off a t theordinary temperature over sulphuric acid. At 25", a-ethylamidopro-pionic acid dissolves in rather less than twice its weight of water,and in about 50 times its weight of alcohol.It is somewhat moresoluble in boiling alcohol, from which it separates in nacreous plateson cooling. When carefully heated, the acid volatilises withoutmelting and without decomposition. It forms a hydrochloride whichcrystallises in slender needles and is extremely soluble in water andin alcohol. The platinochloride is also extremely soluble in bothwater and alcohol, but after some time is deposited from an aqueoussolution in very deliquescent slender needles. The addition of ethert o the alcoholic solution precipitates the platinochloride i n the form ofan oil.The aurochloride forms large anhydrous golden-yellow pris-matic crystals. The copper salt of a-ethylamidopropionic acid isobtained by adding cupric hydroxide to an aqueous solution of the acid.It forms small deep blue anhydrous prisms, which give a pale bluepowder. This salt is soluble in water and in alcohol, yielding bluesolutions. C. H. B.Residue obtained by the Distillation of Castor-oil in aVacuum. By 3'. KHAFFT and T. BRUNNER (Be]"., 17, 2985-2987).-The formation of an elastic substance resemhling caoutchouc in ap-pearance, when castor-oil is distilled in a vacuum, bas been observedby Leeds (Abstr., 1883,655), Hussy and Lecanu (Jour. Phnrm., 13, 5 i ) ,Stanek ( J .pr. Chem., 63, lStr), and Bouis ( N . Ann. Chim. Ph2s., 44,SO). The author finds that this body is di-undecylenic acid, a poly-meride of undecylenic acid, and that it is formed when undecylenicacid is heated in sealed tubes a t 300". I t melts a t 29-30', boils a t275" under a pressure of 15 mm., can be crystnllised from alcohol,and yields a silver salt of the composition C2,HBO4Ag. w. c. w.Action of Ammonia, on Ethyl Acetoacetste. By J . N. COLLIE(Alz?mZeu, 226, 294 - 322). - Et'hyl acetoacetate absorbs gaseousammonia at O", uniting with it to form a crysralline additive product,OH.CMe(NH',).CH,.COOEt, which decomposes even a t 0" into waterand the cornpound C6H,,Nc32, which has been described by Precht(Abstr., 1878, 970) and Duisberg (Abstr., 1882, 1192).It is termed'' E t h y l paramidacetoncetate " by the latter chemist. A better yield ofthe compound is obtained by passing ammonia into a mixture ofabsolute ether with ethyl acetoacet,ate, aod distilling the crystallineproduct in a vacuum374 ABSTRACTS OF CHEMICAL PAPERS.Ethyl paramidacetoacetate yields P-hydmxybutyric acid on re-duction with nascent hydrogen, and a rnonoacetic derivative,NHG.CMe: CH.COOEt (melting a t 63" and boiling at 231"), ontreatment with ace& anhydride. As it is converted into ethyl nitroso-acetoacetate by thetaction of nitrous acid, i t may be regarded as theethylic salt of P-amido-z-crotonic acid.When it is distilled under atmospheric pressure, a, large quan-tity of 8 thick oily liquid is formed, from which the ethylic salt ofhyd~oxyZutid~n~e-monocarbox~Zic acid is slowly deposited in colourlesscrystals melting a t 140" : 2C6H1,N02 = NH, + C2H60 + C,H,NO,Et.The free acid, C,H,N03 + H20, crystallises in small needles andmelts at 246".The barium salt is very soluble in water, the silver salt is an un-stable amorphous body, and the copper salt forms pale-blue microscopicanhydrous needles.The ethylic salt of ~ihy~rocollidinedicarboayZic acid, described byHantzsch (Abstr., 1883, 82), is formed when a mixture of ethylparamidoacetoacetate, paraldehyde, and a small quantity of sulphuricacid is gently heated : 2C6HllN02+C2H40=NHd + H,O + CIJ€OINOI.Ethyl paramidacetoacetate unites with two atoms of bromine, formingan unstable compound.These results leave it undecided whether ethyl paramidacetoacetateis the ethylic salt of p-amido-a-crotonic acid, NH,.CMe : CH.COOEt,or of @-imidobutyric acid, NH : CMe.CH,.COOEt.w. c. w.Butyrolactone and a-Ethylbutyrolactone. By MOEHSIN BEGCHANLAROFF ( Aimaleia, 226, 325-343).-Butjyrolactone is preparedby boiling the product of the action cf ethylene-chlorhydrin onethyl sodacetoacetate with baryta-water. After removing the excessof barytn with carbonic anhydride, the filtrate is evaporated to asyrup and exhausted with ether, in order to remove other products ofdecomposition. The residue is warmed to drive off the last traces ofether, and after the barium has been carefully precipitated as sulphate,the filtrate is repeatedly treated with ether, in order to extract thelactone.On distilling the extract, ether, water, acetic acid, andfinally the lactone pass over. The lactone, C4HSO2, boils at, 203",and remains liquid at-17". Its properties have been described bySaytzeff (J. pr. Chern., 25, 66). It is converted into a salt ofy-hydroxybutyric acid by boiling with an alkaline carbonate, or withbaryta-water.Butyrolactone is very slowly converted into yhydroxybutyric acidby water at the ordinary temperature. The change takes place morerapidly with boiling water, but as a solution of yhydroxybutyric aciditself splits up into water and the lactone when boiled, a state ofequilibrium is attaincd in 10 or 12 hours.a-EthyZbutyrolactone, C6Hlo02, is formed when the ethylic salt of ethyl-h ydroxyethylscetoacetate (the product of the action of ethylenechlor-hydrin on ethyl sodethxlscetoacetate) is decomposed by baryta-water.I t is a colourless mobile liquid which boils a t 215" and remains liquida t -17".The lactone is soluble in 10times its volume of water at O", and is less soluble i n warm water.This acid has been investigated by Saytzeff (Zoc. czt.).It sp. gr. at 16" is 1.0348ORGANIC CHEMISTRY. 375The cold solution becomes turbid when heated. I t dissolves freely iiialcohol and ether. The lactone is converted into a-eth2!l-.I-hyclroay-butyric acid on boiling with alkaline carbonates or with baryta-water.This acid forms a thick liquid which does not solidify a t --17". Thebarium salt, Bst( C6H1,0:3)2, is deposited from a hot saturated alcoholicsolution in crystals.The aqueous solution is decomposed by evapora-tion on a water-bath.The calcium salt crystallises readily ; it is freely soluble in water,sparingly solable in absolute alcohol. The crystals contain less thau1 mol. H,O, probably 6 or + H20.The crystalline silver salt, C6H,,0ag, is soluble in hot water.Ethylbutyrolactone is slowly converted into a-ethyl-~~-h~droxybutyricacid on boiling with water, and this acid readily splits up into thelactone and water, so that a state of equilibrium is soon produced. w. c. w.Action of Water and of Hydriodic Acid on Valerolactone andon Isocaprolactone. By R. F r m G and M. R~HLMANN (Annalen,226, 343--.347).-Boiling with water converts valerolactone and iso-caprolactone into hydroxyvaleric and hydroxyisocaproic acids respec-tively.The state of equilibrium is attained in the case of the formerin four hours. The conversion of the isocaprolactone into the h j -droxy-acid is less complete than that of valerolactone.A t 200", hydriodic acid in presence of amorphous phosphorus actson valerolact'one, producing normal valeric acid and a neutral oil.Mielck (Annalen, 180, 57) has shown that under these conditions iso-caprolactone undergoes a similar change. w. c. w.Condensation-products of the Lactones. By R. FITTIG (Bey. ,17, 3012--3014) .-&pro- and valero-lactones unite with sodiumethylate, forming unstable compounds which are decomposed whenheated a t 100" in a flask with a reflux condenser.On the additionof hydrochloric acid to the product, oily liquids separate whichexhibit the general properties of the lactones. They owe theirformation to the following. reactions :-22C5HI,Oz - HzO = C,,H1403and 2C,H,,02 - H20 = Cl2H,,O:+From the alka-line solutions, hydrochloric acid precipitates crystalline acids of thecomposition c1&&4 and C,,&,04 respectively. The a,cids are mono-basic. They are sparingly soluble in water, ether, and chloroform, andmelt a t 130" and 160" with decomposition , yielding carbonic anhydrideand new liquid compounds lighter than water, and distilling readilywith steam.These new compounds (C9HI6O2, boiling a t 169.5", and C11Hz,02,boiling a t 209') are also formed by boiling the lactones, C,,H,,Os aiidC12H1803, with dilute hydrochloric acid.They are not lactones, beinginsoluble in alkalis, but resemble aldehydes and ketones, for theyreduce ammoniacal silver solutions and unite with hydrogen sodiumsulphite. They are not attacked by acetic anhydride, hydroxylamine,or nascent hydrogen, but they are easily acted on by hydrobrornicacid : (1) C9H1602 + 2HBr = C9H16Br20 + H,O ; (a) C11Hz,02 +2HBr = CIIl&,Br20 + HzO.These compounds dissolve slowly in warm alkalis376 ABSTRACTS OF CHEMICAL PAPERS.The first of these bromine-compounds forms beautiful crystalsmelting a t 42", but the secocd compound has not yet been obtainedin the solid state. w. c. w.Decomposition of a-Methylprcpyl-p-hydroxybutyric Acid byHeat. By E. J. JONES ( A n n n l e n , 226, %7--294).--EthyZ rnethplpo-pylacetoacetute, prepared by the action of methyl iodide on ethylicpropylsodacetoacetate, is an oily liquid boiling about 216".It isconverted into the sodium salt of a-methylpropyl-6-hydroxybutyricacid by the action of sodium amalgam on its solution in alcohol andwater. The free acid, CSH,,U3, is a yellow oil which does not solidifya t -18". Its salts do not crystallise well. The zinc salt is less solublein hot than in cold water. The acid decomposes a t 170" into acet-aldehyde and methylpropylacetic acid. This reaction is analogous tothe decomposition of a-diethyl-p-hydroxybatyric acid by heat (Annakn,201, 62).When saponified with alcoholic potash, ethylic methylpropyl~ceto-acetate yields methyl-a-secondary yentjl ketone, bTeCO.CHMePr'l, acolourless oil boiling between 142" and 14i0, and methylpropylaceticDecomposition of Ethyl Chlorocarbonate by Zinc Chloride.By K.ULSCEI ( A n n a l e n , 226, 281-266).-Ethyl chlorocarbonate isdecomposed by zinc chloride, yielding ethyl chloride, carbonic anhy-acid boiling a t 193". w. c. w.dride, ethylene, and hydrogen chloride. w. c. w.Seleniocartamide and its Derivatives. By A. VERNEUIL (COW@.rend., 99, 1154--1157).-Ammonium seleniocyanate cannot be con-verted into seleniocarbamide, but is completely decomposed at 170".If a current of hydrogen selenide is passed into a 2 per cent.ethereal solution of cyanamide containing a small quantity of ammo-nia, the hydrogen selenide is almost completely absorbed, and aftcrsome hours seleniocarbamide begins to separate in crystals.I n twoor three days, the cyanamide is completely converted into selenio-carbamide, which can be purified by recry stallisation from water.Seleniocarba?nide, CSe(NH,),, forms white odourless needles, verysoluble in hot water, much less soluble in cold watcr, and only slightlysoluble in alcohol and ether. The solutions are decomposed by light,with separation of selenium, the decomposition taking place morereadily in presence of an alkali, but not in presence of free acid.Seleniocarbrtmide melts a t about 20U" and decomposes.I n presence of air a t the ordinary tempeiature, hFdrncids converbseleniocarbamide mi o a condensed oxygenated product, ozytriselenio-carbanaide, (CSeN,H,),O, which exists only in combination with acids.I t has no analogue in the carbamide or thiocarbamide series.Ozytri-seleniocarbamide hydrochloride, (CE+N2H4)30,2HC1, is obtained bydissolving 5 grams of seleniocarbamide in 15 times its weight of coldwater slightly acidulated with hydrochloric acid, adding 10 C.C. ofstrong hydrochloric acid, and filtering into a large vessel, so that a con-siderable surface of the liquid may be exposed to the air. The solu-tion becomes yellow and deposits the pure hydrochloride. KO changORGAY10 CHENISTRY. 377takes place in ahsence of air. When oxytriseleniocarhamide hydro-chloride is treated with alkalis or silver oxide, a metallic chloride isformed, selenium is precipitated, and the solution contains selenio-carbamide and cyanamide.The reaction takes place in accordaneewith the equation: C,N6H,,Se,0,2HC1 + BaO = BaCI, + Se +2H,O + 2CSe(NHZ), + CNFH2. The fact that only one-third of theselenium is precipitated indicates that only one-third of this elementhas been oxidised.O~~~triseleiLioccxrbarnide hydrobromide is obtained in the same way asthe hydrochloride. Both compounds form bulky crystals which aredichroic, being brown by transmitted and violet by reflected light.They are somewhat soluble in water, but are decomposed by a largeexcess of this liquid with precipitation of selenium. They decomposeat about 100" into selenium, carbonic oxide, water, ammonium cyanide,and ammonium chloride o r bromide. I f left in the liquid i n whichthey are formed, the hydrochloride and hydrobi-omide are quickly con-verted into more highly oxidised products.By H.SCHIFF (Ber., 17, 2929--2931).-1n thepreparation of aspartic acid by the action of alkalis on asparagine, theyield is very small, the chief cause being the much greater solubilityof the acid in saline solutions than in pure water. The author findsthat a very good yield is obtained if asparagine hydrochloride isboiled with exactly 1 molmdar proportion of HC1 (or 1 mol. ofasparagine with 2 mols. HCI) and 1 molecular proportion of NH,added to the product. About 10-11 per cent. solutions of hydro-chloric acid and ammonia are the best to employ, so that the resultingaspartic acid crystallises from about an 11 per cent.solution of am-monium chloride. If the saline solution is more concentrated, a muchlarger proportion of aspartic acid remains in solution.Optically Inactive Aspartic Acid. By A. MICHAEL and J. F.WING (Bey., 17, 2984) .-By heating an aqueous solutlion of the hydro-chloride of the ordinary active aspartic acid for some hours a t 170-lSO', the authors have prepared an inactive acid identical with thatobtained by Dessaignes from the ammonium salt of malic, fumaric, oruialejic acid (Compt. rend., 30, 324 : 31, 432), and further investi-C. H. B.Aspartic Acid,L. T. T.gat.ed by Wolf (Aknnlen,, 75,293) and Pasteur. (Anu. Chim. Phys. [S],34, 30). L. T. T.Two Tin Organic Compounds. By 0. W. B'ISCHER (iIfonats/l.Chem., 5, 426-431).-By careful addition of stannic chloi-ide to nbso-lute alcohol, a compound identical with that described by Kuhlmann( A n n u l e n , 33, 97 and 192) is obtained ; it may be crystallised fromether or alcohol, and is decomposed by heat.The analysis of thiscompound shows i t to have the composition SnCI,.OEf + EtOH : itis decomposed by water, forming tin ozycldoride. By acting on stannicchloride with an alcoholic: solution of sodl'um ethylate and evaporatingthe alcoholic solution, the compound Sn(OH)3Et is obtained as anamorphous mass ; it is decomposed by water with formation of stannicacid. P. I?. B378 ABSTRACTS O F CEIERlICAL PAPERS.Action of Organic Anhydrides on Pyrroline. By G. CIAMICIANand M. DENNSTEDT (Ber., 17, 2944--2961).-Many of the resultsdescribed in this paper have already been given (Abstr., 1884, 889and 1044).The authors propose the adoption of the following radicalsin the nomenclature of the-pyrroline derivatives : (C,H,(NH) .CO)'pyr7*0yL (CaH,(NH))' p y r r y l , ( CaHz(NH)) " y y r r y l e n e , and (C,H,N)"p yrro lene.T lie vapour-density of pseudacetopyrroline was taken by V. Meyer'smethod, and agreed with the fortnula (C,H,NH) .COMe. Withphenylhydrazine, pseudacetopyrroline yields white needles whichmelt at 146-1 47", and have the formula (C,H,NH) .CMe : N,HPh.This compound is soluble in benzene, sparingly so in boiling water,and turns of a dirty-green colour on keeping. Hydrochloric aciddscomposes it into its constituents. With henzaldehyde, pseudaceto-pyrroline yields pseudocinnamyZp~/rro7ine, CaH,N.CO.CH : CHPh.Thiscrystallises in yellow needles, melts at 141-142", and is sparinglysoluble in alcohol, insoluble in water. It yields a silver compound,C,H?IIU'Ag.CO.CH : CHPh, insoluble in water. Bromine forms sub-stitution, but no additive products. The monobromo-compoundmelts a t about 175-177", the dibromo-derivative a t about 225" ;but these substances were not obtained in a pure state. The authorsattempted to obtain a pyrrolinecarboxylic acid by the oxidation ofpyrrolineglyoxylic acid, C,H*N.CO.COOH (acetylpyrrolinecarboxylicacid, Abstr., 1884, ago), but without success, the acid being com-pletely decomposed. Methyl pyl"rolin,eglyoxylate, obtained by theaction of methyl iodide on the silver salt, crystallism in colonrlassplates which melt a t 70-72", and boil with partial decomposition a t285".It is easily soluble in ether, benzene, and boiling alcohol,sparingly so in water. The crystals belong to the monoclinic system,and gave 7 = + X : + Z = 92" 15/10'' and n : b : c = 1.16058: 1 : 1.47454.1Clethylp~/r~oZi~ze was obtained by Bell from methylammonium mucate(Abstr., 18i9, 525). The authors have obtained it by the action ofmethyl iodide on the sodium compound of pyrroline. There is scarcelyany action between these substances under the ordinary pressure ;but if the mixture be simply enclosed in a sealed tube, a n energeticaction very soon takes place ; the reaction should, however, be corn-plcted by heating. Dfethylpyrroline is a colourless oil boiling at 114-115" (col.in vap.) a t 747.5 mm. It has an odour resembling, butquite distinct from that of pyrroline. When heated with aceticanhydride, me thylpyrroline yields pseudacetometl~y ~ y r l . o l i n e ,This substxnce is a colourless oil, which is heavier than water andIJoils at 200-202". It is sparingly soluble in water, and does notform a silver derivative. It is thus clear that the replacement of theimidic hvdrogen in pyrroline derivatives by alkyl radicals does notprevent the formation of acetpl derivatives. All attempts to preparethis substance by the action of methyl iodide on the silver derivativeof pseudacetopyrroline proved futile, pseudacetopyrroline beingregenerated. Uipseudaceto-y y w o l i n e (pywy lene dimethiy 1 ketone),C4HzNHXCz, is obtained when pseudacetopyrroline is heated witORG-4NIC CHEXISTRY.379excess of acetic anhydride in closed tubes a t 230-250". It crys-tallises in colourless needles which melt a t 161-162'. It dissolvesin boiling potash, and, on cooling, the potassium derivative is pre-cipitated in white needles; the silver derivative is a white powder.It combines with benzaldehyde and forms d;~seudocinnamyZ~llrroline,CaH2NH (CO.CH CHPh),. This body crystallises in small needlesor plates, and melts at 238-240". It is sparingly soluble in boilingalcohol, more freely so in glacial acetic acid. It dissolves in concen-trated sulphuric acid with intensely violet coloration, and on thissolution being added to water, a white flocculent precipitate isformed.When a mixture of pyrroline, benzoic anhydride, and sodiumbenzoate is heated for about 8 hours a t 200-240", pseudobenxo-pyrrolin,e (pyrry line phenyl ketoize), C*H,NH,.COPh, is formed, butthe yield is small, a large quantity of the pyrroline becoming resinified.This substance forms white needles or scales which melt at 77".Itis easily Roluble in alcohol, sparingly in boiling water; it yields itvery unstable silver derivative. Together with this compound, thereappears to be a small quantlity of a more volatile oil formed. This isprobably benzopyrroline, but the authors have not isolated it.If 5 grams pyrroline are heated in closed tubes at 180-190" withabout 3 times its volume of glacial acetic acid and 11 grams phthalicanhydride, a substance is obtained which has the formula C12H,N0, ;it crystallises in silky yellow needles, and melts a t 240-241". It issoluble in ether, sparingly so in alcohol, and insoluble in water.Nosilver derivative could be obtained. It has the properties of an anhy-dride, and when boiled with dilute aqueous potash, dissolves to ayellow solution, which, on cooling, deposits the potassium salt inwhite scales. This salt yields an acid, C12H9N03, which is soluble inalcohol and ether, sparingly so in water, and crystallises in needlesmelting at 240-241". It is easily converted into the anhydride byheating or even by repeated evaporation on the water-bath. The acidyields a silver salt, CJ3,NO,Ag. The methyZ salt, C,,H,NMeO,, canbe obtained from the silver salt or from the acid by means of alcoholand hydrochloric acid.It crystallises in prisms melting a t 104-105°,and is soluble in alcohol and benzene, sparingly so in water. Like theacid, the ether is very readily converted into the anhydride whenheated. Measurements of the crystals showed that they belong to themonoclinic system, and gave the following numbers :-7 = + X : + Z= 107" 14' 2" and ct : b : c = 1.40305 : 1 : 1.01756.The anhydride has probably one of the two following formuh :-CO<$$F>CO or CO<!~>C(C,H~).No hydroxylamine compound could be obtained, and the authorstherefore believe the second formula to be the correct! one, and thesubstance to be pYrrolin~p~htl2alide.Formation of Parabromobenzyl Bromide by the Action ofBromine on Parabromotoluene at the Ordinary Tempe-rature. By J.SCHRAMX (Ber., 17, 2922-2925).-The investigationsof Beilstein, Kuhlberg, Jackson, and others have shown that theL. T. T350 ABSTRACTS OF CHEMICAL PAPERS.displacement of hydrogen in the side-chain of toluene and its homo-logues by bromine can only be effected a t or near the boiling point ofthe hvdrocarbon. The author h d s that with parabromotoluene nosuch high temperature is necessary. The reaction was carried out a t 0"l a ith a solution of parabromotoluene in chloroform ; with melted para-bromotoluene a t 29"; and with crnde bromotoluene (a mixture ofortho and para) a t the ordinary temperature. No iodine must beadded, and the reaction is mnch more rapid in direct sunlight than incliff used daylight.I n each case, parabromobenzyl bromide, meltinga t 61-62", was obtained, identical with that described by Jacksonand Field (Abstr., 1880, 878). The yield with pure parabromo-toluerie is almost the theoretical. The product of the reaction oftoluene a t 0" with insufficient bromine for the formation of a mono-suhstitution-derivative, was found to contain the bromide.The author believes this peculiar reaction t o be due to the repellantinfluence of the two bromine-atoms on one another already noticed byV. Meyer and others. He also points out that parabromobenzylchloride was obtained by Jtlnnasch as early as 1874 (this Journal,1875, 888). L. T. T.Pseudocumenol. By K. AUWERS (Bm., 17, 2976-2983) .-Theauthor has obtained a number of derivatives of pseudocumenol,C6HzMe3.0H [Me : Me : Me : OH = I : 3 : 4 : 61-Trinrethylorthohydroxybenzaldehyde, OE[.C,HMe,.COH [1:3 : 4 : 6 : 51,was obtained by acting on pseudocumenol, in alkaline solution, withchloroform.The solution must be kept dilute or the cumenol resini-fies. The aldehyde crystallises in pale yellow needles, which areinsoluble in cold water, soluble in alcohol, ether, chloroform, andglacial acetic acid, and melt at 105-706O. It sublimes undecomposed,and yields a mirror with an ammoniacal solution of a silver salt. Ithas the general properties of an orthaldehyde ; volatilises in a currentof steam, gives a blue coloration with ferric chloride, and an intenseyellow with ammonia.The yield of this eompound is, however,small, owing to the formation in much larger quantity of a compound,C,oHL2C120 ; the latter crystallises in prisms and plat'es, insoluble inwater and alkalis, soluble in alcohol, ether, &c. It may be heatedwith alkalis or even concentrated sulphuric acid at 100-110" withoutdecomposition, but resinifies at a higher temperature. The author isinclined t o look upon it as a dichloromethyl ether of pseudocumyl,C,H,Me,.O. CHC1,.IlilttaiLitrc)~seudocumyZ nitrate, N02.C6H&fes0.N02 [Me, : NO, : NOs= 1 : 3 : 4 : 2 : 61, is obtained by gradually adding pseudocumenol tosix times its weight of well-cooled fuming nitric acid. It crys-tallises in rhonibic prisms and tables, and melts with decomposition a t84'.It is very unstable, being decomposed by water a t 40°, and byalcohol and ether at even lower temperatures inio nitrous acid and a,resinous body which still contains nitrogen, and is probably nitropseudo-cumenol. When reduced with tin and hydrochloric acid, the nitrateyields metamidupseudocumortol, which is soluble both in acids andalkalis, and is identical with the hydroxycumidine described byLiebermann and v. Kostanecki (Abstr., 1884, 1146)ORGANIC CHEMlSTRP.Uinitropseudocumeiiol,38 1C6kfe3(N02)2.0H [Me, : (NOs), : OH = 1 : 3 : 4 : 2 : 5 : 61,was obtained from the nitrate described above by a peculiar reactionwith zmmonia. Aqueous ammonia decomposes the nitrate in thesame way as the fixed alkalis, water, &c., do, but alcoholic ammoniayields st red substance (probably an unstable ammonia cornpound),which, on neutralisation of the ammonia, yields the dinitro-compound.This substance forms groups of yellow cryatals which melt a t 110"without decomposition.It is insoluble in cold water, soluble inalcohol, ether, &c. J t is decomposed by boiling with water or alcohol,and explodes when heated above its melting point.The psendocumenol employed in this investigation was preparedfrom pseudocumidine sulphate by means of the diazo-reaction. Fromthe resin, which is always formed in considerable quantity, theauthor succeeded in isolating dipseudocumenol or hexajnethy Miphenol,H0.C6HMe3.C6HMe3.0H. This compound melts at 172" and crys-tallises in white needles which are soluble in glacial acetic acid andit1 alkalis.It is identical with the compound obtained by Hofmannby the decomposition of diazo-cumidine with alcohol (Abstr., 1884,1315). The same compound was obtained by the oxidation of pseudo-cumenol in acetic solution with potassium dichromate. The methylether was obtained by the action of caustic potash and methyl iodideon the dicumenol. It crystallises in white needles melting at 124".L. T. T.Mixed Ethers of Resoreinol. By G. SPITZ (Monatsh. Chem., 5,488490) .--The following ethers have been prepared by heatinginonomethyl resorcinol with potassium alkyl sulphates and causticpotash in sealed tubes a t 170". They are all colourless liquids ofagreeable odour, and miscible with alcohol, ether, glacial acetic acid,Ijenzene, &c., but insoluble in water ; they are volatile in steam, and(-an be distilled without decomposition :- &thy1 ethyl resorcinoi,OMe.C6H4.0Et, boils at 216" ; methyl propyl resorcinol, OMe.C6H4.0Pr,hoils at 226"; methyl isobutyZ resorcinol, 01\/Ie.C6H4.0C4H9, boils at334" ; methyl isoamyl resorcinol appears to boil a t 236".P. P. B.Colouring Matter from Paramidophenol. By NOELTING andWEINGARTNER (Bull. Xoc. Chim., 42, 339) .-The authors are inves-tigating the violet colouring matter which is formed when hydrogensulphide and ferric chloride react with paramidophenol.W. R. D.Ethglparatolytnitrosamine. By GASTIGER (BUZZ. SOC. Chim.,42, 338).-This compound has the constitution represented by theformula C6H,Me.NEtN0 [Me : NEtNO = 1 : 41.From it, the authorprepared pure ethylparatoluidine and studied the diazoamido-deri-vatives of this base. W. R. D.Xylidines. Ry NOELTING and FOREL (Bull. SOC. Chin&., 42, 332-334, aiid 338-339) .-Pure ortho-xylene when dissolved in sulphnricacid and nitrated with the theoretical quantity of nitric acid, furnishesVOL. XLVIII. 2 382 ABSTRACTS OF CHEMICAL PAPERS.two isomeric nitro-derivatives. One is crystalline, the other liquid.The former has previously been obtained by the action of fumingnitric acid on ortho-xylene, and on reduction yields crystalline ortho-xylidine ; i t melts at 29", and boils at 256". The liquid nit,ro-xylencboils at 250", and when reduced by iron and acetic acid it yields anew liquid ortho-xylidine, mixed with a small quantity of solidortho-xylidine. The new compound, which is the sixth isomeridepredicted by theory, is obtained pure by treating the mixture withacetic anhydride, and purifying the aceto-xylidine melting a t 134" byfractional crystal lisation.This, when saponified, yields the newortho-xylidine, C6H3Me2.NH2 [Me : Me : NH? = 1 : 2 : 31, in the formof a liquid boiling at 223", and having a t 15" a sp. gr. of 0.991. I tyields ort,ho-xylenol when the diazo-derivative is boiled with water,and when oxidised with the chromic mixture is converted into ortho-xyloquinone, crystallising in fine yellow needles and melting a t 55".A mixture of this xylidine with parutoluidine does not yield ros-aniline when oxidised with arsenic acid.The corresponding quinolmelts with decomposition at 221". The authors have preparedsymmetrical metaxylidine, CeH3Me2.NH2 [Me : Me : NH, = 1 : 3 : 53,by Wroblewski'R method, and by oxidising it hare obtained metsczylo-quinone. This forms yellow needles which melt a t 73"; the corre-Rponding quiuol crystallises in white needles, and melts a t 145".Symmetrical metaxylenol melts a t 68", and resembles in propertieR itssolid isomcrides. There are now six known xglenols, five of whiclIare solid and one [l : 3 : 41 liquid.Paraxyloquinone was prepared from paraxylidine ; it melts at 123",and is identical with the quinone already described by Nietzki andCarst an jen.Starting with the five known xylidines, two ortho-, one para-, andtwo meta-, the two last melting a t 134" and 1 3 5 O respectively, thramido-azo-derivatives were prepared, and their constitution deter-mined.They may be summarised as follows :-1 2 3 6 1 2 31 2 4 - 3 o r 5 1 2 4C6H3MeMe.N : N.CsH,MeMe.NH2 melts at 110.5".C6H3MeMe.N . N.C6H2MeMe.NH2 ,, 1791 3 4 5 1 3 4C6H3MeMe.N : N.C,H2MeMe.NH2 ,, 78CJ3,MeMe.N : N.C6H2MeMe.NH2 ,, 951 3 5 2 1 3 51 4 2 5 1 4 21 3 4 5 1 4 2CIH3MeMe.N N.C6H,MeMe.NH2 ,, 150C6H3MeMe.N N.C,H2MeMe.NH2 ,, 110-111"The last of these compounds was obtained from a mixture ofunsymmetrical zrylidine with paraxylidine. It has been previouslyobtained by Nietzki frorn commercial xylidine.The authors firid that when metaxylene is nitrated with snlphnricand nitric acids, in addition to ordinary nitro-xylene, the 1 : 3 : 2isomeride is also produced.The two compounds may be separated bORGANIC OKEMISTRT. 353fractional distillation, the new nitro-xylene passing over a t 222-227" ;i t s boiling point when pure is 2.25" (compare Grevingk, this vol., p. 144).By reducing the fractions obtained between these temperatures, Rxylidine is formed which is identical with that obtained by Schmitxfrom amidomesitylenic acid. After purification by conversion into theacetyl derivative (m. p. 175"), it boiled at 2145". The constitution ofthe compound is represented by the formulaC6H,Me,.NH2 [Me : Me : NH, = 1 : 3 : 21.W. R. D.New Curnidine. By N~LTING and KOHN (Bull. SOC. Chim., 42,340) .-A new cumidine was prepared by heating the hydrochloride ofsymmetrical metaxylidine with methyl alcohol.This isocumidine,which is in all probability derived from the 1 : 2 : 3 trimet#hylbenzene,melts at 69", and distils about 245". W. R. DSecondary Amines. 11. By W. GEBEARDT (Ber., 17,3033-3043).A continuation of the author's work on this subject (Abstr., 1884,1320). Methyldiphenylthiocarbamide is converted into met,hylanilineand monophenylthiocarbamide, melting at 153", by the action ofalcoholic ammonia at 1 OO", and into diorthotolylthiocarbamide andaniline by the action of orthotoluidine. The latter doubtless takesplace in two stages: phenyltolylthiocarbamide is formed in the first in-stance, and is then converted into ditolylthiocarbamide by the toluidine,NHPh.CS.NMePh + C,H,.NH, = NHPh.CS.NH.C,H, + NHMePhEthyldiphenylthiocarbamide, when boiled with aniline, is decomposedinto ethylaniline and thiocarbanilide.Phenylmethylorthotolylthio-carbamide, melting a t 121", splits up on boiling with aniline intodiphenylthiocarbamide, orthotoluidine, and methylaniline, but thecorresponding para-compound under similar treatment yields phenyl-paratolylthiocnrbamide and methylaniline.Ally Zpheny lethylthiocarbarnide, C,H,. HN. CS.NEtPh, is formed bymixing together ethylaniline and allylthiocarbamide. It is a crystal-line substance melting a t 26" and dissolving freely in the usual solvents.Symmetiical dirneth y lph eiry Zthiocarbamide, MeHN. CS.NMePh, cry+tallises in transparent prisms melting at 114", and is soluble in alcohol.~ethy~henylethyltlziocarbanzide, MeHN.CS.NEtPh, and the preced-ing compound are decomposed by boiling with aniline, yieldingdip h eny 1 t hiocarbamide.Meth ylp?Len y It hiocarbamide, prepared from methylcarbimide an daniline, crystdlises in six-sided plates which melt at 113" and dissolvefreely in alcohol.Dietl~y7aEl~~lfhiocar6amide, C3H,HN.CS.NEt,, is deposited from itssolution in alcoholor benzene, in long needle-shaped prisms melting at 55".Diethylorthotolylthiocarbamide, C,H,HflN.CS.NEt,, melting at 102",is decomposed, by boiling with aniline, into diethylamine and ortho-toluidine.Diethylsmine combines with phenyl isocyanate, forming diethy 7-yheny Zcarhamide, PhHN.CO.NEt,, a crystalline compound melting at85O, soluble in alcohol and benzene.NHPh.CS.NH.C,H, + C,H,.NH, = CS(NH.CTH,)a + PhNH2.2 d 384 ABSTRACTS OF CHEMICAL PAPERS.Di-P-na~hthyJ27henyZcarbamide, PhHN.CO.N( CloH,),, prepared bythe action of carbanil on di-p-naph thplamine, forms soft, white needle-shaped crystals melting a t 179", soluble in hot alcohol.Piperidine combines with phenyl thiocarbnmide, forming piperidy7-p l ~ e n y Zthiocarbamide, PhHN.CS.N C5HI0, which crystallises in thickneedles melting at 98".P~~eridylorthotol~lthiocarbamide, and the corresponding pnra-com-pound, are deposited from their alcoholic solutions in prisms whiclimelt respectively a t 98" and 132".Piperidylmetlhylthiocarbanzidr,MeHN.CS.N C5Hl0, crystallises in rhombic prisms soluble in alcohol,and melts a t 125". Pi~erid~il~ihenzJlcnrbarnide, P11HN.CO.N C5H,(,,formed by the action of carbanil on piperidine, crystallises in prisms,melt's a t 168", and dissolves in alcohol and benzene.Piperidylthio-carbamide, H,N.CS.N C6HI0, is prepared by evaporating a solutioiiof piperidine sulphate and potassium thiocyanate to dryness, andextractiug the residue with alcohol. I t crystallises in four- or six-sidedplates, and melts a t 92". The crystals are soluble in alcohol, water,warm acetone, and warm chloroform.Cony~p~ze.nzJZfhiocal-bamide, PhHN CS.N CBRlfi, forms silky needlesor prisms, soluble in alcohol, and melts at 88". Co.n~ilphelzyZcarbnmide,PhHN.CO.N : CsHlfi, dissolves freely in all the ordinary solvents, andis with difficulty obtained i n a pure st-ate.Hetliylphenylurethane, NMePh.COOE t, is prepared by slowly addinget,hyl chlorocarbonate to methylaniliiie largely diluted with ether..Methylaniline hydrochloride is deposited, and the urethane remains insolution : 2NHMePh + COC1.OEt = NMePh.COOEt + NHMePh,HCl.The urethane is an oily liquid boiling at 244".w. c. w.Ethenyldiphenyldiaine. By NOLTIYG and WEIITGARTNER (Bull.SOC. Chim., 42,334) .-Acetanilide hydrochloride when heated a t 250"in 8 sealed tube for one hour, yields ethe?Lyldi~henylamicline hydro-chlo?-idz, NHPh.CMe : NPh,HCl, but if heated a t 300-330" for 12-15 hours, bases of the qninoline series are obtained, together withaniline and tarry compounds. Two of the quinoline bases wereisolated, one of the formula CIIHIIN, boiling a t 265-268", the otherof the formula CizH13N, boiling at 283-285".Tarry compounds areformed when these compounds are heated with phthalic anhydride.W. R. D.Derivatives of Cumidine and Amidoazobenzene. By NOLTINGand BAUMANN (Bull. SOC. Chirn., 42, 335) .-Amidoazocumene meltingat 138" yields, on reduction, an orthodiarnine of the constitutionCGHzMeMeMe.N : N.C6HMeMe31e.NHz. Pseudocumenol, C6HzMe3.0H,from pseudocumidine, readily combines with diazo-derivatives. Pseudo-cumidine hydrochloride, when heat,ed with methyl nlcohol a t 300" in asealed tube, yields fet~~amethy7amidobenxene, C6HMel.NH2, which boilsTiear 250", and forms an acetyl-derivative melting a t 210". The samebase is obtained when mesidine hydrochloride is treated in a similarmanner.C6HMe4.NH2 [Me4 : NH2 = 1 : 3 : 4 : 5 : 21.1 2 4 5 3 1 2 4 5The new amine therefore has the constitutioORGANIC CHEMISTRY.38 -5By nitrating a solution of amidoazobenzene in sulphuric acid, anisomeride of the nitroamidoazobenzene, prepared by Nolting andBinder, is obtained. Its constitution has not yet been established. Bymethylating paradimethylsmidoazobenzene, NH2. CsH4N : N. CsH,.NMe,,the tetramethylazyline of Lippmann and Fleissner is obtained.W. R. D.Azo-derivatives. By NOLTING and BA~MANN (Bull. SOC. Chirn.,42, 340) .-By heating dimethylamidoazobenzene with sulphuric acidat 100' dimethylanzidoazobenze~aesulphonic acid is obtained ; on reduc-tion, it yields sulphauilic acid, together with dirrietlLylparapheny Eene-diamine.SOsH.C6HIN : N.C6H4.N&te2 [ sO3H : Nz : NMe, = 4 : 1 : 41,and is identical with the acid which is produced by the reaction ofparadiazop hen ylsulphonic acid with dime th y Ianiline.The sulp honkacid of paratolylazodirnethylaniline has an analogous structure, for 011reduction i t yields dimethylphenylenediamine and amidocresylsnl-phonic acid. W. R. D.Diazoamido-derivatives. B~NOLTING and BINDER (Bu71. Xoc. Chirn.,42, 336-337, and 341-342) .- By the reaction of paradiazotoluenechloride with aniline, and of diazobenzene chloride with paratohidine,a diazo-amido-compound is obtained, which, when dissolved in benzeneand treated with bromine, forms diazotoluene bromide and tribrom-aniline. Hence the derivative has the constitution C6H4Me.NZ.NHPh.When boiled with dilute acids, it yields toluidine and phenol, togetherwith cresol and aniline, and, when reduced by stannous chloride,phenylhydrazine and paratoluidine are formed.The diazo-arnido-derivative formed when parabromo-diazobenzene chloride reacts withaniline, or yarabromaniline with diazobenzene chloride, yields brorn-aniline and phenol when boiled w i t h dilute acids. Both the foregoingcompounds have been described hy Griess. With aniline, paranitro-diazobenzene chloride forms a derivative which, under the influenceof dilute acids, yields nitraniline and phenol ; when it is heated withaniline, amidoazobenzene, nitraniline and a small quantity of para-nitramidoazobenzene are produced. The latter compound melts at203-205", and on reduction yields symmetrical diamidoazobenzene,NH,.C6H,.N2.C6H1.NH,, tbe parent base of the azyhes.Methylaniline and diazobenzene chloride f nrnish a, derivative,which, on reduction, forms phenylhydrazine and methylaniline.Diazobenzene chloride does not react with paranitraniline.Nitro-diazobenzene chloride does not react with methylaniline to form adiazamido-derivative, but yields an isomeric amidoazo-compound ofthe formula N02.CfiH4.N2.CfiH4.NHMe. When nitrodiazobenzencchloride is acted on by toluidine, a diamidoazo-compound is obtained,which reacts with orthotoluidine, forming amidoazotoluene, togetherwith a nitro-derivative, melting at 198", of the formulaThe sulpiionic acid, therefore, has the constitutionThis yields methylazyline when carefully reduced.The diamidoazo-derivative o bt,ained by acting on nitrodiaxobenzen386 ABSTRACTS OF CHEMICAL PAPERS.chloride with paranitrotoluidine reacts with aniline, forming chieflynitroamidoazobenzene.The product of the action of ethylaniline on diazobenzene chloride isEL substance of formula PhN : N.NPhEt, whilst with diaeotolnenechloride it yields C6H4MeN : N.N PhEt.These compounds are decom-posed whon boiled with dilute acids; the first yields phenol andethylaniline, the second paracresol and e thylaniline. An isomeride ofthe toluene derivative has been prepared by Gastiger, by acting ontliazobenzene chloride with methyl paratoluidine. It has the formulaPhN N.N.EtC7H7, and forms crystals which melt a t 38-39", Ityields phenyl- and ethyl-paratoluidine when heated with dilute acid,whilst on reduction it forms paratoluidine and phenylhydrazine.Themethyl derivative of this compound forms crystals which melt at alow temperature. Two nitro-derivatives have been obtained, meltingi~.pectively at 55" and 104-105". When boiled with dilute acids,all these derivatives yield ethylparatoluidine, together with paracresolin the case of the methyl derivative, metanitrophenol in that of thefirst nitro-derivative, and paranitrophenol in that of the second.4 1W. R. D.Tetramethylazyline. By NOLTING and KOHN (BUZZ. SOC. Chim.,43, 334).-By acting with dimethylaniline on the diazo-derivative ofdime thylparap henylenediamine, symmetrical tetrameth y Id iamidoazo-benzene is obtained,NMe,C6H4.Nz.C1 + PhNMe, = NMez.CgH4.N2.C6Hl.N~~ez + HCI.This compound is identical with the tetramethylazyline described byLippmann and Fleissner.New Synthesis of Pararosaniline. By J.ZIMMERMANN and A.M~~LLER (Bw., 17, 2936-2938).-lf a mixture of 20 grams paranitro-benzylidene bromide and 25 grams aniline is gradually heated, theanilide is formed. If the heating be continued to 145", an energeticreaction takes place, the temperature of the mixture rises quickly to200", and the whole has the appearance of a magenta-melt. Fromthis melt, the authors have succeeded in isolating pararosaniline. Theresidue insoluble in water dissolves readily in alcohol, and is a colour-ing matter of slightly bluer shade than pa,r:wosaniline. The authorsbelieve it to be a phenylated pararosaniline formed by the furtheraction of the excess of aniline.The authors endeavoured to prepareparanitrobenzylidene chloride in order to investigate the action ofaniline on this compound, but up to the present without success.W. R. D.L. T. T.A New Resorcinol Blue. By R. BENEDICT and P. JULIUS(Xonatsh. Chem., 5, 534--535).-By heating together 55 grams ofresorcinol with 18 grams of sodium nitrite at 130", a blue colouringmatter is obtained which dissolves in water, forming a dirty bluish-violet solution, and is soluble in alcohol and in sulphuric acid formingblue solutions. This colouring matter is reduced by zinc-dust inpresence of an alkali, forming colourless solutions which are oxidiseORGANIC CHEMISTRY.387easily by exposure to the air, with reproduction of the blue corn-pound. P. P. B.Action of Acetamide on Phenylcyanamide. By F. BERGER(Monatsh. Chem., 5, 451--471).-With the expectation of obtaininga phenylacetoxylguanidine, the author heated together a mixture of2 parts by weight of phenylcyanamide and 1 of acetamide. Thereaction which takes place is of a complex character, ammoniacalvapours, and also those having an odour of nitrile compounds beingproduced, whilst a sublimate of ammonium carbonate is formed, anda residue is left from which water dissolves out acetanilide. Theresidue, after extraction with water, yields to boiling alcohol, a mix-ture of two bases which can be separated by the different solubilitiesof their hydrochlorides in alcohol.The less soluble hydrochlorideurgstallises from alcohol in silky needles of the compositionCBHYbN1,,2HCl + 3&EtjOH ; by decomposition with caustic potash ityields the base C39H31Nll ; this crystallises in needles melting at 222".The solution of the hase in glacial acetic acid yields with bromine acompound, C39H.r9Nl,Br6, crystallking from glacial acetic acid in smallgrains composed of microscopic needles. Nitric acid converts thebase into a yellow compound which is turned to a dark red colour byalkalis. The base heated in sealed tubes with hydrochloric acid at150 yields aniline, at 200-250", aniline and ammonia.The soluble hydrochloride yields a base, C15H16N6, melting at 212-2 13" ; it is easily soluble in alcohol, ether, and glacial acetic acid, andsparingly soluble in hot benzene.Its hydrochloride, C,aHl,N6,HCl,crystallises froin alcohol in shining needles melting at 252". Besidest tiese substances, the product of the reaction of phenylcyananiide andacetamide contains a substance insoluble in the ordinary solvents, thecoiriposi tion of which has not been ascertained. P. P. B.Bl Action of Ammonia and Amines on Thiocarbamides.W. C~EBHARDT (Bey., 17, 3043-3i)46).-Alcoholic ammonia at 100converts thiocarbanilide into monophenylthiocarbamide and aniline,and it decomposes di-P-naphthylthiocarbamide into p-nsphthylamineand mononaphthylthiocarbamide melting a t 180".Amines replace the two tolyl-groups in di-orthotolylthiocarbamide ;thus with aniline the following reaction takes place : CS(NHC,H,), +l)i-parittolylthiocarbaiide does not appear to undergo an analogousdecomposition.Aniline converts me tamononi t rop heny 1 t hiocarbamideinto metanitraniline and thiocarbanilide. It also decomposes toluyl-enedithiucarbamide, C7H6 (NH.CS.NH,),, and toluylenediphenyldi-t hiocarbamide, C7H6 (NH.CS.NHPh),, forming to1 uylenediamine andt tiiocarbanilide. w. G . w.'LPhNH, = CS(NHPh), + 2CTHT.NHt.A Reaction of Aldehydes. By A. CALM (Ber., 17,2938-2941).-Amidodimethylaniline, N.H2.C6H4.N&1e2, reacts very readily withaldehydes both of the aliphatic and aromatic series. When the base ismixed with the aldehyde, either alone or in alcoholic solution, a spon388 ABSTRACTS OP CHIZMICAL PAPERS.taneous rise of temperature takes place and the condensation-productformed crystallises out.Parabeii~z~lideiteamidodimethylaniline or benzyli~eneparadimethyl-pkenylenediamine, CHPh N.C6H4.NMe2, thus obtained from benz-aldehyde and paramidodimethylaniline, forms pale-yellow glisteningscales or needles which melt at 93".It is soluble in ether and benzeneand in boiling alcohol. It is a bivalent base and yields a dihydrochh-ride, C,,H,,N,,.;'H Cl.The author has obtained similar compounds with salicylaldehyde,cuminaldehyde, anisaldehyde, &c., which will be described shortly,and he is also investigating the action of other unsymmetrical di-substituted diamines. L. T. T.Condensation-products of the Derivatives of Salicylaldehyde.By A. R6ssmG (Ber., 17, 29b8-3010).- Orthaldehydophenoxyacetic:acid, COH.C6H4.0.CH2.COOH, is prepared by gently fusing equivalentquantities of monochloracetic acid and salicylaldehyde. The productis mixed with a sufficient quantity of sodium hydroxide solution(sp. gr. 1.2-1-3) to render it strongly alkaline, and heated on a water-bath with continual stirring until the mass thickens. It is thendissolved in hot water and the solution is acidified with hydrochloricacid, when the acid is deposited in crystalline plates or occasionally aaan oil. The crystals melt a t 132" and dissolve freely in alcohol, ether,and in hot water. The concentrated aqueous solution yields precipi-tates with magnesium sulphate, copper sulphate, silver nitrate, andlead acetate. It exhibits all the charact,eristic reactions of an alde-hyd:.The et?glic salt of the acid crystallises in needles melting at114 , and is soluble in alcohol and ether. On the addition of bromineto a hot aqueous solution of aldehrdophenoxyacetic acid, the mono-bromo-derivative, C9H,BrO4, is deposited in silky needles melting at163" ; it is soluble in alcohol, ether, and chloroform.Aniline unites directly with aldehydophenoxyacetic acid to form thecompound NHPh.CH(OH).C6H4.0.CH2.COOH. This substance is notattacked by ammonia, but it combines with acids to form salts. Thehydmchboride, C,,H,,N04,HC1, crystallises in yellow needles, melts a t190-191", and is soluble in hot water and alcohol. The sulphate,C15H13NOa,H2S04, melts a t 186".The acid also combines with phenylhydrazine, yielding the compoundN,HPh CH.C6H4.0.CH2.COOH.It is a red crystalline substancewhich begins to soften a t 60" and melts completely at 105". It dis-solves freely in alcohol, ether, and in alkalis. When oxidised withpotassium permanganate, aldehgdophenoxyacetic acid yields salicyl-oxyacetic acid, C 0 OH. C6H4. 0. CH2. CO OH, a crystalline compoundmelting a t 187". The acid is soluble in alcohol, ether, and in hotwater. Neutral solutions form precipitates with lead, copper, andsilver salts. The latter, C9H6Ag?O5, is soluble in much water. Thecalcium, barium, strontium, potassium, and sodium salts of the acidare crystalline. They dissolve freely in water. Diethylic salicybowy-acetate, C,H,OsEb, is an oily liquid which is decomposed by distilla-tion.By the action of alcoholic ammimia at looo, it is converted intothe diamide melting at 158"ORGANIC CHEMISTRY. 389Ort~ocoumarozyaceticacid, COOH.CH: CH.C6H~.0.CH?.COOH,pl.c-pared by the action of acetic anhydride and anhydrous sodium acetateon aldehydophenoxyacetic acid, is deposited from a hot aqueous solu-tion in needle-shaped crystals melting a t 190". The acid is soluble inalcohol, ether, and in hot water. Its lead, silver, and magnesiumsalts are either insoIuble or sparingly soluble in water. The dihonaideof coumaroxyacetic acid is a crystalline body ; it melts a t 220°, and issoluble in alcohol and ether. It is probably converted into propiol-phenoxyacetic acid, CO0H.C i C.C,H,.O.CH,.COOH, by the action ofalcoholic potash.If an excess of sodium acetate is used in the preparation of coumaroxy-acetic acid, coumarone, C6&<-O>CH, is formed.Cournaroxyacetic CHCH * CH CO acid is converted into its anhydride, C6H,<o-cH~.CO>0, wheni t is heated for a few minutes with a concentrated solution of phosphoric:acid. The anhydride melts a t 176", and dissolves easily in alcoholand et8her. It readily absorbs bromine-vapour, yielding the dibromidewhich crystallises in orange-coloured needles melting a t 213". Abluish-green amorphous substance of the composition C9H7NO3 is pre-cipitated on the addition of water to a solution of the phenylhydr-azine-derivative of aldehydophenoxyacetic acid in warm sulphuric acid.The precipitate dissolves in alkalis, forming a cherry-coloured solution,and in alcohol with a bluish-green coloration.The same compoundis formed when equivalent quantities of orthoxybenzylidenephenyl-hydrazine and monochloracetic acid are heated a t 100".Diacet~lol.tl~occybenzyliderL(:phenyE?~ydraxine, OAc.CGH4.CH NzAcPh,i R deposited from alcoholic solutions in large prisms melting a t 133" ;it is soluble in benzene, ether, chloroform, hot alcohol, and in hot hydro-chloric acid. It is decomposed by distillation into acetic acid, phenol,acetanilide, and a reddish-yellow crystalline compound melting a t 113".The dibromide, C17H16NZ03Br2, is an unstable crystalline compound. Itis decomposed by boiling with alcohol, w i t h elimination of hydrobromicand acetic acids.The solution on cooling deposits crystals of mm-acetylvxydibromobe.nzllliden~~hen~lhydrazirae, O&. C6H213r2.CH N,HPh ;this melts a t 188" arid dissolves in chloroform and benzene. It isdecomposed by the action of hot hydrochloric acid, yielding phenyl-hydraxilie hydrochloride. It is decomposed by alkalis, forminghy dro~ydibrornobenzy lideneph eny lhydruzitw, 0 H, C sHzBrz. C H N2HPh, Hcrystalline substance melting at 148", soluble in alcohol, chloroform,benzene, ether, and dilnte alkalis. Diacetylorthozydibrmobenzylidene-p h e n y l h y d m z i n e , &%.C6H2Br,.CH N z L P h , prepared by heating themonacetic-derivative with acetic anhydride, crystallisea in whiteneedles which melt at 158". The crystals dissolve freely in alcohol,ether, benzene, and chloroform.w. c. w.Terephthalophenone. By NOLTING and KUHN (Bull. SOC. chin^.,42, 339).-This compound, C6H4(COPh)2 11 : 41, is obtained byacting on benzene with terephthalyl chloride in presence of alumi-nium chloride. It is a white crystalline solid, insoluble in water, butsoluble in alcohol and ether. The alcoholic solution is n o t attacke390 ABSTRACTS OF CHEXIOAL PAPERS.by alkalis. From these properties, the cornpound appears to have theconstitution of a &acetone, such as Ador's isophthalophenone, andnot that of a lactone like the phthalophenone of Friedel and Crafts.W. R. D.Quinones. By N~LTING and BAUMANN (Bull. SOC. Chim., 24,341).--Quinones are obtained by distilling solutions of the sulphatea ofvarious bases with chromic acid.Mesidine yields meta-xyloquinone ;cryst.allised cumidine yields para-xyloquinone ; unsymmetrical me&-xylidine yields toluquinone in small quantity, and metatoluidine thesame quinone in large quantity. W. R. D.Derivatives of Azocumia Acid. By P. ALEX~EFF (BUZZ. SOC.Chim., 42, 321).-Azocumic acid is prepared by acting with sodiumamalgam on nitrocumic acid. It forms ruby-red crystals having asp. gr. of about 9.24, and melts with decomposition a t 280". Thecrystals dissolve in alcohol, and to a less extent in ether and chloro-form, but are insoluble in benzene, light petroleum, and water. Con-centrated sulphuric acid dissolves them, and when the red liquid isheated and precipitated with water, a brown flocculent substance falb,leaving a blue liquid.Nitric acid also dissolves azocumic acid to acherry-red liquid, which becomes green when it is diluted with water.If previously heated and ammonia then added, a yellowish-red liquidwith a fine green fluorescence is obtained. The action of potassiumpermanganate on an alkaline solution gives rise to azoxyisopropyl-benzoic acid. By the action of powdered zinc or sodium amalgam onan alkaline solution of the acid, it is decolorised, with formation ofkydrazocumic acid. The metallic and ethereal salts of azocnmic acidwere also prepared. W. R. D.Melilotic Acid and Anhydride. By H. HocHsTwrm (Annaha,226, 355-363).-An aqueous solution of melilotic acid is partlycouverted int.0 the anhydride by boiling. The anhydride combineswith water very slowly a t the ordinary temperature.It does not dis-solve readily in a hot concentrat'ed solution of potassium carbonate.Melilotic acid is completely converted into the anhxdride b j the actionof hgdrobromic acid at the ordinary temperature. It is probable thatorthobromhydrocinnamic acid is first formed, which afterwards de-composes into hydrogen bromide and melilotic anhydride.Melilotic anhydride is converted into coumarin by the action ofbromine-vapour at 1'70". At the ordinary temperature, bromine actson a solution of the anhydride in carbon bisulphide, forming mono-bromomelilotic anhydride, CgH,BrO,. This compound is depositedfrom its solution in chloroform in colourless prisms, which melt at106", and do not decompose at 180".Boiling water slowly converts itinto bromomelilotic acid, C9H,Br0,. This acid crystallises in rectan-gular plates soluble in alcohol and in warm chloroform. It melts at141-142" with decomposition into wat,er and the anhydride. w. c. wORGANIC CHEMISTRY. 391Action of Hydrobromic Acid and Bromine on Coumarin,Conmarone, and Orthocoumaric Acid. By G. ERERT (Annalen,226, 347-355 ; comp. Abstr., 1883, 471) .-When hydrogen bromideis passed into a solution of coumarin in strong hydrobromic acid,crystals melting a t 42" are deposited, which rapidly decompose intohydrogen bromide and coumarin. Coumnrin dibromide is decomposedhy boiling with water ; i t splits up into coumarin and free bromine.The latter acts on the coumarin and on the dibromide, yieldinga-dibromocoumarin and @-bromocoumarin, which have been previouslydescribed by Perkin (this Journal, 1870, 368 ; 1871, 37).To convert coumarin into coumaric acid, 10 grams of coumarin areadded to a solution of 3.5 grams sodium in 60 C.C.absolute alcohol.The mixture is boiled for 1+ hours in a flask provided with a refluxcondenser. It is then diluted with water, the alcohol distilled off, andthe acid precipitated from the residue by hydrochloric acid. Coumaricacid is converted into coumarin by the action of hydrobromic aciditt 0". Bromine slowly acts on coumaric acid dissolved in carbonbisulphide, forming P-dibromocoumarin. Monobromocoumarone,CIBH6BrO, is formed by the action of alcoholic potash on the dibro-mide. It crjstallises from alcohol in colourless needles which areThiosulphonic Acids and Sulphinic Acids of Toluene.By J .PERL (Chem. Cejltr., 1884, 468) .--l)ia~nidotolueneparathiosulpho-riic w i d , C7H5(NHn),.S0,SH, is obtained by acting with ammoniummlphide on dinitrotolueneparasulphonic chloride, and decomposingthe resulting ammonium salt by hydrochloric or glacial acetic acid.It crystallises in silky- needles, and decomposes at 152". By theaction of acids, it is converted into the sulpkiuic acid, C7H,(PU'H2)2.S02H,with separation of sulphur. Diamidotolueneparasulphinic acid isconverted by nitrous acid into a voluminous brick-red compound,which is apparently the corresponding diazo-derivative. When dinitro-toluenesulphonic chloride is acted on by zinc-dust, the product treatedwith barium hydroxide, and the barium salt obtained decomposed bymeans of sulphuric acid, dinit rotolueneparasulpfiinic acid,soluble in water, and melt a t 36".w. c. w.is obtained, and may be converted into diamidotolneneparathiosnlpho-riic acid by the action of ammonium sulphide.When disulphanilic acid is submitted to the action of potassiumpermanganate, the uzotetrasdphonate, C,H,( S03K),.N2.C6H,( SO,K),,is produced, and crystallises with 3 molu. H20. The free acid has notbeen obtained, as the addition of an acid throws down a sparinglysoluble hydrogen potassium salt. The chloride melts a t 91", and theamide a t 229-230". A. K. M.Phenylhydrazine-derivatives of a- and p-Naphthaquinone.Identity of the a-Derivative with Benzeneazo-a-naphthol.Hg T.ZINCKE and H. BINDEWALD (Ber., 17, ~026-3033).-aa-Nnyhtha-quinoizehydrazide is precipitated when an aqueous solution of phenyl-hydrazine hydrochloride is added to a solution of a-naphthaquinone i392 ABSTRACTS OF CHEMICAL PAPERS.glacial aoetic acid. It is purified by solution in baryta-water, precipi-tation by hydrochloric acid, and recry stallisation from alcohol.a-Naphthaquinonehydrazide is identical with benzeneazo-a-naphthol.~-NaphthaquilLoneh:l/dl.azide melts a t 138", and closely resembles butis not identical with benzeneazo-p-naphthol. It neither combineswith acids nor bases, but it unites with bromine, forming a crystallinedibromide, Cl6Hl0Br2N2O, me1 ting between 215" and 219". Theauthors suggest the following formulae for these substances :-Ben-zeneazo-6-naphthol,C,,H,O.NzHPh [NZHPh: 0 = 1 : 21 ;p-naphthaquinonehydrazide [0 : N,HPh = 1 : 21.w. c. w.Dinaphthyldiquinone. By 0. KORN (Ber., 17, 3019-3026) .-The dinaphthyldiquinone of Stenhouse and Groves (Trans., 1878,418)yields Lossen's aa-dinaphthyl (Annulen, 144, 27) when it is heatedwith zinc-dust, and Aclol-'s diphthalylic acid (this Journal, 1873, 67)on oxidation with potassium permanganate. Hence it follows thatthe constitution of the diquinone may be represented asDinaphthyldiquinone unites with aniline, forming a, tetranilide,C,H,(NHPh),O,( NPh),, crystallising in glistening metallic plates ofa dark red colour. The crystals dissolve in glacial acetic acid, but areinsoluble in the ordinary solvents; they melt at 248-250".Thehydrochloride, C44H30N~O~(HC1)2, is freely soluble in alcohol and spa-ringly soluble in water. I n the preparation of the tetranilide, Zincke'sB-naphthaquinonedianilide (Abstr., 1882, 967) is obtained as a bye-product.I n order to distinguish between (1) a-naphthaquinol, (2) B-napti-thaqninol, and (3) 6-dinaphthyldiyuinol, the author acts on them withnitric acid of sp. gr. 1.48, when they are converted into (1) a-naph-thaquinone, (2) nitro-/3-naphthaquinone, and (3) p-dinaphthyldiqui-none, or they may be converted into their acetic derivatives:(1) diacetyl-a-naphthaquinol, forms transparent plates melting at 129",(2) tetracetyl-@-dinaphthyldiquinoI, silky needles which melt withdecomposition at ltiti", (3) diacetyl-P-naphthaquinol, transparentplates melting a t 105".Liebermann's a-dinaphthyldiquinol yields PP-dinaphthyl on distilla-tion with zinc-dust.w. c. w.Methylphenanthroline. By Z. H. SKRAUP and 0. W. FISCEER(Morzatsh. Chem., 5, 523-530) .-By heating nitrobenzene andtoluylenediamine [CH, : NH2 : NH, = 1 : 2 : 41 together with sulphurioacid and glycerol, a base is obtained which the authors style methyl-phenurithrolii~e. This compound is obtained from the product of thereaction by treating if first with caustic soda and subsequently dis-solving the resinous mass 60 obtained in hydrochloric acid. FroORGANIC CHEMISTRY. 393this solution, alcohol precipitates the hydrochloride. The hydro-chloride is next converted iuto the cliromate, from which the purebase is obtained.It melts at 95-96', boils at a temperature above:360°, and resembles phenanthroline in its general characters (Abstr.,1$83, $6). It unites with water to form a crystalline compoundhaving the formula C13HloNz + 5H20. The hydrochloride, C13HIoN2,HC1 + PH,O, is easily soluble in water, and crystallises from dilutealcohol in long transparent needles. The clwomate, (C,,H,,N,),,H,Cr,O,,forms yellow needle-shaped cr-ystals, which are sparingly soluble inwater. The pZatinochZoride, C13HloN2,HzPtC16 + 2Hz0, is obtained asa light yellow crystalline precipitate. The compound of the basewith piuric acid is ohtained as a crystalline precipitate sparinglysoluble in boiling alcohol, and melting atl 253'.Phenaqi throlinecarboxy Zic acid, C13H6Nz02, is obtained by oxidisingmethylphenanthroline with chromic acid.It melts a t 277", is almostinsoluble in hot water, and sparingly soluble in alcohol and aceticacid, but is dissolved alike by alkalis and by mineral acids.The calcium salt cryshallises in opaque needles having the formula2[(C13H7N202)2C~ + 5HzO] + C1?H6N202, and on distillation yieldsphenanthroline. The formation of phenanthroline from this acid, andthe production of methylphenanthroline from toluylenediamine, showthat the constitution of these compounds may be expressed by thefollowing formuke :-M e COOHMethylphenanthroline. Phenanthrolinecarboxylic acid.P. P. B.New Method of Preparing Phenanthroline. By Z. H.SKRAUP (Monatsh.Chern., 5, 531-533) .-As P-amidoquinolineyields phenanthroline when heated with nitrobenzene, glycerol, andsulphuric acid, its smido-group probably occupies the position 4.P. P. B.Constitution of Terebic and Teraconic Acids. By B. FROST(Annalen, 226, 363--376).-Ethyl teraconate, C5H8(COOEt),, pre-pared by saturating an alcoholic solution of teraconic acid withhydrogen chloride, is a colourless liquid boiling at 254". Teraconicacid is not acted on by nascent hydrogen, but it is converted intoterebic acid by the action of hydrobromic acid, or of hot hydrochloricor sulphuric acid. Monobromoterebic acid is produced whenbromine is added t o the aqueous or ethereal solution of teraconic acid.Monobromoteyebic acid forms coloiirless crystals which melt, at 151"with decomposition.It is soluble in ether, but is decomposed by hobwater, yielding terebilic acid. A chloroterebic acid is formed whenchlorine acts on ternconic acid in presence of water, but this substitn-tion-product is not identical with the chloroterebic acid described byWilliams (thia Jouiunal, 1874, 70) and by Roser (Abstr., 1884, 459).It forms rhombic prisms a : b : c = 0.9827 : 1 : 0.7137. The acidmelts at 168" with decomposition, and is easily decomposed by water394 ABSTRACTS OF CHEMICAL PAPERS.yielding terebilic acid, C,H,04. Nascent hydrogen from sodiumamalgam converts terebilic into terebic acid. Terebilic acid slowlydecomposes a t 250-5355, forming a crystalline lactone which melts at8' and boils at 207". It is probably identical with the terelactonewhich Geisler (Abstr., 1882, 41) obtained from dibromocaproic acid.When terebic acid is heated in sealed tubes a t 160" with a largeexcess of baryta-water, it splits up into succinic acid and acetone.This reaction can only be explained on the assumption that terebicacid has the constitution COOH.CH<~Me,.O>CO.Terebilic acid CH, -will then be represented by COOH.C<CMe2.0 CH- >GO.w. c. w.Wood-oil from Cochin China. J. MON-SOUBETRAN (J. Pharm.151, 10, 251--254).-The oil is yielded by several trees of the familyDipterocarpus. The method of extraction is described. On standing,two layers form, a clear upper one somewhat fluorescent, and a lowerone thicker and darker. The density of these oleo-resins is about,0.96-0.966.The light oil mixed with water and distilled yields about30 per cent. of an oily distillate ; distillation commences a t 242" andmay be continued up to 295' in the case of both oils. Fuming nitricacid acts very violently on the oil ; nitric acid gives a violetcoloration, sulphuric acid a red, and hydrochloric acid a reddish-violet with it. Iodine also has an energetic action. It is used as %tvarnish and lacquer and also as a substitute for copaiva.Eucalyptole. By E. JAHNS (Ber., 17, 2941-2944).-The authoi.has investigated the oil obtained by distilling the fresh leaves ofEucalyptus globulm. On rectification, the principal portion ofthis oil distilled between 170-180", the remainder consisting ofhigh-boiling terpeiies and traces of it phenolic compound.Theportion boiling at 170-180" still contained terpenes together with anoxygenated compound. This latter was isolated by the help of itshydrochloric acid compound, as recommended for cyneole by Wallachand Brass (this vol., p. 171). Thus purified eucalyptole has the formulaCloH180. It boils a t 176-177" (column in vapour), has a sp. gr. of0-923 a t 0", and is optically inactive. The authors find that thissnbstance is identical with cyneole and the chief constituent of oil ofcajeput (see Wallach, " Ethereal Oils," this vol., p. 171). They believethat the eucalyptole obtained by Cluez (Cmnpt. rend., 1870, 70,687) towhich he ascribed the formula C12H200, still contained terpenes,whilst that described by Faust and Homeyer (Ber., 7, 63) as beingfree from oxygen was probably obtained from another species ofEu calyyptus.L. T. T.Stearopten from Essence of Patchouli. By H. C. C. NAISCH(J. Pharm. [ 5 ] , 10,223-224, from Amer. J. of Pharm., 1884).-Thiscamphor is purified by solution in alcohol and then in ether, fromwhich last it crystallises in hexagonal prisms. It melts at 55-56',and has a vapour-density of 8.00 at 324". Heated with zinc chloride,it loses one molecule of water and leaves a hydrocarbon, C15H24 orCl6H26. H. B.H. BORUANIC CHEMISTRY. 395Camphoronic Acid. By J. RREDT (Annulen, 226, 249-261).-The properties of camphoronic acid have been investigated by Kachler(Ann., 159, 281) Kissling, Neugebauer, and Hjelt (Ahstr., 1880,669), who regard the substance as a lactonic acid.The authorobtained the acid from the mother-liquors from the preparation ofcamphoric acid, by precipitation as a barium salt. This salt isdecomposed by hydrochloric acid, the mixtare evaporated todryness and the residue extracted with ether to dissolve out thecamphoric acid. After removing the ether, the aqueous solution ofthe acid is nearly neutralised with milk of lime, and heated at loo",when the pure calcium salt, Ca,(CgH,106)~ + 12H20, is deposited.The author's results differ in several respects from those of hispredecessors. The barium salt, Ba,(CgH1,O6)?, is anhydrous and thesilver salt, C9H,,06Ag3, crystallises with 1 mol. H,O. Triethyl cam,-phoronate, C9H1106Et3, formed by the action of ethyl iodide on theanhydrous silver salt, boils at 301".The diethyl salt, which has beendescribed by Kachler, is decomposed by distillation into alcohol andthe monoethylic salt of anhydrocamphoronic acid.The author regards camphoronic acid as isopropyltricarballylic acid,and gives his preference to the first of the following formula :C 00 H. CH,. CPrS (C 0 0 H). CH,. C 00 H, orCOOH.CH2.CE(COOH).CHPrS.COOH ;CH,. CPrS. C HzCH2.CMe. COhe regards camphor as having the constitution I 1 1 .w. c. w.Existence of Glycyrrhizin in several Vegetable Families.By E. GUIGNET (Cow@. rend., 100, 151--153).-Glycyrrhizin existsnot only in several species of Legnminose, but also in some plants ofperfectly distinct families ; for example, it occurs in large quantity inthe rhizomes of Polypodium vuZgare, which grows abundantly in t h eneighbourhoods of Paris and Brest, and in the Vosges, also in therhizomes of P.szmipennatiJidum, var. indursum, which grows on thetemperate regions of the Andes. Both these plants are used as sub-stitutes for liquorice.The best method of extracting glycyrrhizin is to treat the dried andpowdered plant with acetic acid of 8", mix the solution with alcohol,filter, evaporate the filtrate to a syrup, and add water, which dissolvesout ammonium acetate and other impurities but leaves the glycpr-rhizin undissolved.The paper coucludes with a summary of the chemical history ofglycy rrhizin. C. H. B.Glucoside from Strychnos Nux-Vomica. By W. R. DUNSTAKand F. W. SHORT (Pharm.J. Trans. [3], 14, 1025--1026).-By per-colating the dried pulp of the fruit of Xbrychnos nux-vornica with amixture of chloroform and alcohol, by the method already described(Abstr., 1883, 689), 4 and 5 per cent. of it crystalline substance is ob-tained. It forms colonrless prismatic crystals, softening at 200°, meltin396 ABSTRACTS OF CHEMICAL PAPERS.at 215", readily soluble in water and alcohol, less so in ether, chloro-form, and benzene. Its aqueous solution is not precipitated by alkaloidreagents, nor by lead acetate or silver nitrate, neither is it affected byferric chloride. It gives no colour reaction with nitric acid oroxidising agents ; it, however, decolorises bromine solution, and isoxidised by chromic mixture. Warmed with sulphuric acid, it gives afine red colour, changing t o deep purple.It. is a glucoside, termedZogrrnin; and when treated in the usual way yields glucose and asubstance, Zoganetiw,, with similar properties to those described above.The Xtrychnos nux-vomica seeds also contain a small quantity of thisglucoside. D. A. L.Crystalline Substance from Jarnbosa, Root. By A. W.GERRARD (Pharm. J . Trans. [3], 14, 717--718j.-The root of MyrtusJanzbosa, L., yields a neutral crystalline substance, an acid, a resin,a>nd a minute quantity of an alkaloid. The crystalline substance,jambosin, CI,H5;"LT03, melts at 77", resolidifies at 60°, is white andtasteless, soluble in cold ether, alcohol, chloroform, in hot lightpetroleum and in boiling water; insoluble in cold water.Withstrong sulphuric acid, it gives a bright green colour soon changing toreddish-brown ; with nitric acid a violent action ensues, nitrous fumesare evolved, and an orange-coloured liquid is produced, in which waterfornis a precipitate. It is neither a glucoside nor an acid.D. A. L.Chebulinic Acid. By FRIDOLIN (Chern. Centr., 1884, 641) .-Theauthor has isolat8ed from the frnit of Terrninalia chebula an acid whichhe proposes to call chebulinic acid. Its percentage composition ap-proaches that of gallic acid, and in some of its properties itresembles that' acid, whilst in others it is essentially different. Itcrystallises in rhombic prisms, has a sweetish taste, is solubIe inalcohol and hot water, but only sparingly in cold water.It reducesFehling's solution, and gives a blue-black precipitate with ferricchloride. In a very dilute solution of the latter, it gives a green tint(gallic acid gives a light brown). Potassium cyanide produces noeffect, whilst with gallic acid it strikes a deep rose tint. R. R.Pipitzahoic Acid. By T. GREENISH (Pharm. J. Trans. [3], 14,698- 700) .-Microscopical examination proves that pipitzahoic acidexists as a hue secretion in the roots of Pereziafruticosa. The rootalso contains inulin. D. A. L.Colouring Matters of Ebony Wood.. By A. BELOHOUBEK(Chem. Centr., 1884, 566).-The author considers that the colouringmatters of ebony wood are due t o a, reducing action excited inoriginally colourless substances, and carried so far as the separationof carbon, as one colouring matter is insoluble in alkalis, and com-pletely combustible, yielding only carbonic anhydride.Anothercolouring matter, however, is readily soluble in alkalis, and this theauthor believes to be humic acid. R. RORGANIC CHEAIISTRY. 397Decomposition-products of Pyridine Derivatives. By A.HANTZSCH (Ber., 17, 2903-2921).-This is a continuation of theauthor's previous work (Abstr., 1884, 1045) on this subject. Whenmethglpseudolutidostyril hydrochloride is strongly heated in a carrentof hydrogen chloride, the methyl-group attached to the nitrogen-atomis replaced by hydrogen, and psmdolutidostyril, C7H90N, is formed.This compound crystallises in needles, melts at 180", and boils at303-305". I t is soluble in water, alcohol, and ether.It comhiiieshoth with acids and with bases. The potassium compound crystallisesin silvery scales, the hydrochloride in prisms, the ylutinochloride inbrownish anhydrous prisms. When this base is treated wit)h sodiumethylate and excess of methyl iodide, methylpseudolutidostyril isr*e-formed. It is thus clear that no rearrangement of the moleculecan hare taken place during the formation of pseudolutidostyril, butsimply a replacement of methyl by hydrogen. The formula of thiscompound is therefore CMe<CH-CO CH ' CMe>NH. When the hydro-chloride is mixed with ten times its weight of zinc-dust and quicklyheated in a current of hydrogen, a Zutidine, CMe< CH.CHe>N, dis-tils over. This compouod boils a t 154-155*, and shows all thecharact,eristics of a homologue of pyridine.It dissolves freely incold water, but is entirely reprecipit'ated on boiling. The ytatino-chloride crystallises in dark orange-coloured plates which areanhydrous and melt a t 216-217". The other salts are not verycharacteristic. The aurochloride crystallises with difficulty ; theTiyciyoch loride and hydrobronzide crystallise in needles ; the p i c r a t eforms bright yellow needles which melt at 176-179". The dimethyl-pyridines hitherto obtained resemble this compound in properties, buthave probably all been mixtures of isomerides. The author believesthis lutidine to be the first pure dimethylpyridine which has beenobtained.I n order to elucidate the decomposition of ethyl collidinedicar-lnoxylate methiodide described in hi8 last paper (loc.cit.). the authorprepared e t h y Z yhenyllutidinedicarbozylate, C5NPhMe,( COOEt),, bythe action of ammoniobenzaldehyde on ethyl acetoacetate. Thiscompound, however, is no longer capable of combining with methyliodide. It was therefore converted into hydrogen ethyl phennyllutidine-dicarboxylate by digestion with rather less than one molecular pro-portion of alcoholic potash. This acid salt crystallises in cubesmelting at 179-150", and is easily soluble in boiling alcohol,sparingly so in cold alcohol or ether. It forms neutral metallic salts.When subjected to distillation, carbonic anhydride is evolved, andt h j l p7~enyll~~tidinecarbox~late, C5NHYhMe,.COOEt, formed. Thiscompound is a thick liquid which boils at 316-320".It dissolves inacids, but its salts do not crystallise well ; the platinochloride melts at196". PhenyZl/ctidinecarboxylic acid, C5NHPhMe2.COOH, crystalliseswith 2 mols. H20, which it loses a t 120-130", and then melts at189-190". Its salts are described ; the platinochloride crystallisesin orange prisms with 1 mol. H,O, which it loses a t 110-115".Ethyl phenyllutidinecarboxylate was then converted into ethylVOL. XTdVIII. 2 eCH-C398 ABSTRACTS OF CHEMICAL PAPERS.phenylZ1Ltidinecarboxylate methiodide by digestion, a t loo", with itsown weight of methyl iodide. The methiodide is sparingly solubIein cold water and alcohol, and crystallises in needles which melt at205-206". When treated with potassium hydroxide, this compoundundergoes a decomposition similar to that already described (loc.cif.)for the collidine-derivative. Meth2/lcarbophen~Ibutid2/liumdehlJdrit~~,CI5Hl5O2N, thus obtained crystallises frorn benzene in rhombic plates,which sometimes contain 1 mol. C6H6, sometimes are free frombenzene; i t melts a t 160-161". It is easily soluble in benzene andalcohol, sparingly in boiling water or ether. It is decomposedwhen heated, and none of its salts could be isolated. Fuming hydro-chloric acid a t 170-180" converts it into a methylated pseudostyril ofplzeny Zpicoline, CPh<cH-co >NMe, acetic acid being formed a tthe same time. This pseudostyril is easily soluble in alcohol, less soin benzene, very sparingly in ether, and melts a t 112".It is notvolatile with steam, but dissolves pretty freely in boiling water. Itsreaction is neutral, but it yields well crystallised salts, which are,however, decomposed by water ; the platinochloride forms lightyellow microscopic needles containing 3H@. I n the formation ofthis pseudostyril, the acetic acid produced must be derived fromthe ethyl acetoacetate employed in the formation of the carboxylicether. Judging from analogy, it is clear that in the collidine com-pound previously described the acetic acid was derived from the samesource, aiid not from the aldehyde. The autbor believes the formationof these dehydrides to be a general reaction with similar pyridinederivatives obtained by the condensation of aldehydes with acetoaceticacid.Mesitene-lactone, already described by the author, stands inclose relationship to these compounds,CH: CMeMe 8 itene -lac tone. Pseudolutidostyril (mesitene-lactam) .but all attempts to convert the lactone into the styril by the action ofammonia proved futile.When oxidised by permanganate, I molecule of methylpseudoluti-dostyril requires 4 mols. of permanganate. Acetic acid, carbonicanhydride and two nitrogenous acids are produced. One of these acidsproved to be methyloxamic acid, NHMe.CO.COOH, whilst the othercould only be obtained as an impure syrup. When boiled with excessof baryta o r alkali this syrupy acid yields methylamine, and must,therefore, contain the (CO.NHMe) group.The author now finds the melting point of pure methglpseudolati-dostyril to be 90-92", and not 70°, as given in his previous commu-nication.L. T. T.Thallin Preparations. By G. VULPIUS ( A d . Pharm. [3], 22,840-845) .--hallin is a new name for tetrahydroparaquinanisoil, aderivative of paraquinanisoil. The sulphate and tartrate of thallinhave been investigated clinically. Paraquinnnisoil is produced byheating payamidoanisoil with parabromaniso'il, glycerol, and sulphuriORGANIC CHJi3fISTRY. 399acid at 140-155", as an oily liquid which, with hydrochloric acid,gives a salt soluble in water. Thallin snlphate and tartrate occuriisually in the form of a nearlywhite crystalline powder, althongh largercrystals can be easily obtained. The salts melt at 100" with slightbrowning. The sulphate is soluble in five times its weight of coldwater, and very soluble in boiling water.The aqueous golutionreadily turns brown on exposure to light. It is soluble in about 100parts alcohol ; this solution also darkens ; the coloration appears,however, to be mainly due to impurities. The solutions of thetartrate are much less sensit'ive to light. The sulphate is almostinsoluble in ether, but somewhat more soluble in chloroform. Thetartrate is much less soluble in all the above vehicles than is thesulphate. The sulphate gives the following reactions :-A solution of1 : 10,000, after a few second?, Fives a deep emerald-green liquidwith a few drops of ferric chloride; the colour is not changed bythe addition of a few drops of concentrated sulphuric acid.Reducingagents change the colour: thus sodium thiosulphate changes it toviolet, then to wine-red; oxalic acid changes it into light yellow,which becomes saff ron-yellow on heating. Other oxidising agentsproduce the green colour when carefully added, but the reaction is not,so sensitive as with ferric chloride. Picric acid gives a yellow pre-cipitate. Tannin, mercuric chloride, stannous chloride, dilute nitricacid, and hydrochloric acid produce no change in the solution.Thallin sulphate in contact with concentrated sill phuric acid show$no change in the cold ; on warming, it gives a brownish coloration ~Vapour of fuming nitric acid colours the dry sulphate carmine-red ;the colour gradually changes to brown. Thallin solution gives withfuming nitric acid, when warmed, a deep red colour, taken up bychloroform. Caustic alkalis and ammonia give a white turbidity inmoderately concentrated solutions ; the turbidity disappears on addingwater, alcohol, or ether.Diquinolines.By 0. W. FISCHER (Monatsh. Ckem., 5, 417-425).-By the aid of Skmup's reaction (Abstr., 1581, 288 and 920),the author has obtained from benzidine [NH, : NH? = 4 : 4'1 adiquimline, Cl8HI2N2, identical with that described by Weidel(Abstr., 1882, 69). From its method of formation, this must havethe two quinoline-groups united a t the 4 : 4 positions on thebenzene-rings. The author's description of the salts of this baseconfirm the observations of Weidel, except in the case of themlphates, of which two are described, namely, the acid sulphate,Cl8Hl2N2, 2H,SOJ, which crystallises in bundles of long needles, and is de-composed by water ; and the normol sulphute, C18Hl,N,,H,SOJ + 3H@,obtained by adding sulphuric acid to an alcoholic solution of the base ;it is decomposed by water, and turns brown on exposure to the air.The base combines directly with methyl iodide, yielding the methiodideC18H12N2,MeI ; this forms light-yellow crystals ; when heated with anexcess of methyl iodide, the compound C18H12N2,2MeI is formed, whichmelts above 290".Attempts made to prepare a diquinoIine by passing qninolinethrough red-hot tubes did not yield satisfactory results.J.T.P. P. 13.2 e 400 ABSTRACTS OF CHEMICAL PAPERS.Nitroparatoluquinoline. By E. FOURNEAUX (BUZZ. SOC.Cl~em.42, 337).-This substance is obtained by nitrating paratoluquinoline,dissolved in sulphuric acid, with the theoretical quantity of nitric acid.It crystallises from light petroieum in white needles, and melts a t116-116*5". The platinochloride crystallises from water in yellowneedles. On reduction, nitroparatoluqninoline yields anzidopnratolu-quinoline, crystallising in yellow needles, which melt at 132-133" ; itis dissolved by the ordinary solvents and is very soluble in toluene. Anitroparatoluquinoline identical with the preceding compound isobtained when metanitroparatoluidilre (m. p. 114') is heated withglycerol, nitrobenzene, and sulllhuric acid. This synthesis deter-mines the constitution of these derivatives, and assigns to nitro-paratoluquinoline the formula C,NN,Me.NO2 [NOz : Me = 1 : 41.Flavaniline. By 0.FISCHER and E. TAUBER (Ber., 17, 2925-2928) .-Picolinetricarboxylic acid, already shortly described (Abstr.,1884, SOO), melts a t 232O, and decomposes a t 2%". It is identicalwith the acid recently obtained from collidinedicaiTboxylic acid byR. Michael (this vol., p. 62), and when oxidised yields pyridinetetra-carboxylic acid, as shown by that investigat,or. The latter acid maybe obtained directly from flavenol by oxidation with 11 molecularproportions of permanganate in 5 per cent. aqueous solution.Towards the end of the oxidation, the action takes place exceedinglyslowly, and the mixture requires to be heated on the water-bath forsome days. Pyridinetetracarboxylic acid crystallises in needlescontaining water, which it only loses by long continued heating a t115".The hydrated acid melts at 187", the anhydrous, with decnrn-position and evolutiou of carbonic anhydride, a t 287". Michael givesthe melting point aR 188", so that probably his specimen was notdehydrated.It is thus clear that flavoline is phenyllepidine, and flavaniline andffavenol the amide and hydroxide respectively of flavoline, and thatthe last two have the constitutions C',&(NH,)&ll[e = 2' : 4' andCsH,(OH)Me = 2' : 4 respectively.W. R. D.Several metallic salts are described.L. T. T.Quinoline Dyes. By W. SPALTEHOLZ (Chem. Certtr., 1884,47'2).-The author made unsuccessful attempts to prepare the red dye formedaccording to Williams, by the action of tar quinoline and amyl iodide,the product being digested with aqueous potash.An attempt toobtaiii it by the method suggested by Hofmann (Jtthresb., 1862, 361)also yielded negative results. Amj1 iodide and quinoline w-ere heatedtogether on a water-bath, and quinoline amyliodide, C,NH,.C,HIII,obtained ; on warming this witlh an excess of potash, a reddish resinousmass is produced, readily soluble in alcohol with reddish-violet colour ;the yield, however, is very small. A red colouring matter is alsoformed in small quantity by the action of alkalis on methyl- or ethyl-quinoline iodide. When ethylqiiinolineammonium iodide, preparedfrom quinoline (from the chromate), boiling a t 232*5-233.5", andethyl iodide, is treated with aqueous alkali, a minute quantity of adye is piwduced, but if quinoline (boiling a t 231.5" at 753.5 inm.),obtained from thc pure crptallised ethiodide be employed, no dye iORGANIC CHEMISTRP.4c' 1formed. A dye can, however, be obtained from crude quinoline andethyl iodide. It crystallises in magnificent, iridescent, rhombic prismsor plates; its solutions are clecolorised by acids, whilst alkalisprecipitate the dye in amorphous flakes, This dye appears to bea condensation-product from 1 mol. quinoline ethiodide and 1 mol.quinaldine ethiodide, a compound of the same composition being prc-dnced by the action of potash on a mixture of these two substance..When dried a t 10.5", its cornposition is C,3H,sN,I + 4H20, but whendried a t 120" i t becomes anhydrous. From the above, it is concludedthat purified quinoline from coal-tar is identical with artificial quino-line.A. K. M.Conhydrine Derivatives. By A. W. HOFMANN (Bey., 18,5-23).The author has already shown (Abstr., 1883, 220) that the productobtained by Werthheini ( A n n a l e n , 127, 75) by the action of phosphoricanhydride or of hydrochloric acid on conhydrine is not conine, but amixture of two less hydrogenised bases. He has now investigatedthis product more closely, and finds that it consists of two isomericbases of the formula C,H,,N, to which he gives the names a- antiJ3-conict.ine.The decomposition of the conhydrine was effected by heating it withabout four times its weight of fuming hydrochloric acid a t 220" forfour hours.The basic product boiled between 155-175", and yieldedtwo crystalline hydrochlorides, or e of which was deliquescent and theother not. The separation of the two bases was effected by means oftheir picrates.a- Coizicezne, C,H15N, obtained from the sparingly soluble part ofthe above picrate, is a colourless liquid which boils at 158", and has anodour resembling conine. It is sparingly soluble i n water, and doesnot change on exposure to the air. It forms a hydrochloi-ide whichcrystallises in deliquesce~~t hexagonal plates. Its picrate crystallisesin yellow needles which melt a t 225", and is sparingly soluble incold alcohol, almost insoluble in water. It forms a sparingly solublecompound with mercuric chloride.Its platimchloride crysta,llises inyellow rhombic prisms, easily solnble in water. Its aurochloride formsyellow needles. a-Coniceine solidifies at, very low temperatures, andmelts at about - 16". It is a tertiarybase, and forms a methiodide, C8H15N,Mel, when treated withmethyl iodide. This, when digested with silver chloride, yields thecorresponding chloride, which forins a pZatiiiochZor;de, (C,H,,NMe),PtCI,.When treated with silver oxide, the iodide yields a strongly alkalinehydroxide. On distilling this hydroxide several volatile bases wereobtained, amongst which a-conicehe was detected.a-Conicejin may also be obtained when conine hydrochloride(1 mol.) is mixed with bromine (1 mol.), and the mixture treatedwith an alkali, a bromo-derivative, CsHl6NBr, being formed, inwhich the bromine has displaced one of the hydrogen-atoms in theimide-gronp.This conipound, when treated with sulphuric acid,yields a-conicehe according to the equation C,H,,NBr = HBr +C,H,,N. When a-conicelne is digested a t 200" witfh concentratedbydriodic acid and phosphorus, conine is re-formed. If the tenipera-Its sp. gr. is 0.893 a t 15"402 ABSTRACTS OF CHEVICAL PAPERS.ture is allowed to go much higber than this, or if conine is heated atSOP for some hours with phosphorus and hydriodic acid, an octane andammonia are formed. The boiling poiut of this octane is 118-120°, and its sp. gr. 0.712 a t 11". It is impossible to say at presentwhether this is normal octane or not. It is probable that in theabove reaction an intermediate primary amine, C,H,,NH2, is formed.By stopping the reaction before its completion, the author was able todetect traces of a primary amine, but did not obtain it in sufficientquantity to determine whether it was the expected compound,CBH1,NHlrThe easily soluble and non-crystallisable portion of the picrateprepared from the decomposition-product of conhydrine, yielded@-coniceins and another liquid base, which the author has notisolated, but which appears to be isomeric with a- and B-coniceine.The pur5cat:on of 6-coniceine is exceedingly difficult, and the authordid not succeed in obtaining i t absolutely anh.-ydrous.p-Conicezne is a clear colourless liquid, which a t low temperaturesciystallises in needles melting a t 41"; it does not change whenexposed to the air, I t boils at 168", and has the peculiar odourof conine.It forms a stable I/ ydrochloride, crystallising in colourlessprisms, easily soluble in water. Its aicyochloride crystallises in well-formed plates, and furnishes the best means of purifying the base.The platinochloride forms very soluble crystals. P-Coniceine mayalso be obtained by the action of hydriodic: acid on conhydrine. Inspite of its high boiling point, i t is very volatile. P-Conicehe is asecondary base, and when treated with methyl iodide yields a di-methylated arnnzonitcm iodide. This iodide was converted into thecorresponding chloride by digestion with silver chloride. The chlorideforms R plutinochloride, (C'&,,N&'e&PtC&, crystalhsing in easilysoluble prisms and a sparingly soluble aurochloride, (C,H,,NMe,)AuCl,.Prof, Kronecker is now studying the physiological action of a- and/!I-conicehe.He finds that the action of a-conicelne is similar to thatof conine, but that a much smaller dose is fatal. The action of the@-compound appears to be very much less powerful.If conhydrine is heated for some hours a t 180' with four times itsweight of hydriodic acid and a little phosphorus, a crystalline com-pound, C8Hl6IN,HI, is formed; if the temperature is allowed torise much higher, the principal product is octane. This compound,C,H,,IN,HT, which crystallises in sparingly soluble needles, is thehydriodide of an iodoctmine, and is formed according to the equationC,H,,NO + 2HI = C8H161N,HI + H,O.It gives up all its iodinewhen boiled with silver nitrate. When treated with silver chlorideill the cold, it is converted into the crystalline hydrochloride of theiodo-buse, which yields a platiiiochloride, ( C6H,,IN)2,HzPtC16. Whenthe iodide is boiled with excess of silver chloride, it yields the hydro-chloride of a chlorocondne, C,HI6C1N,HC1, crystahing in scales. Thislatter forms a ylatinochloride, (C8H,6C1N)2,&PtC16, crystdlising injellow soluble needles. When the iodoconine liydriodide is treatedwith reducing agents, such as tin and hydrochloric acid, conine isformed. When the iodide is treated with alkali, the free base, C,H,,TN,is liberated; this is stable at ordinary temperalures, but if heateORGANIC CHEBlISTRY.403sligh tJy above 100" it is converted into coniceke hydriodide,C8H15N,HI. I n this reaction, both a- and ,!?-conicehe appear to beformed, but sometimes the a-compound is present almost exclusively,sometimes the P-compound greatly preponderates. The a-compoundpreponderates if the iodide is treated with excess of caustic soda anddistilled by steam ; the @-product if a mixture of the iodide with limeis distilled.Phosphorus tribromide appea.rs to act on conhydrine in a similarmanner to hydriodic acid, and to produce the corresponding bromo-derivative, C8HI6BrN,HBr. L. T. T.Paraxanthine. By G. SALOMON (Chem. Cmtr., 1884, 490).-Thepreparation of this compound has been previously described (Abstr.,1883, 601). It is obtained as a loose white scaly mass of silky lustre.I t s formula appears to be C7H,NaO2, but its properties are distinctfrom those of theobromine and dioxydimethylpurine. Paraxanthineexists as such in urine, and is not produced by the action of thereagents employed.A. K. M.Alkalo'ids O f Aconitum LyCOCtOnUm. By I~RAGENDORFF andSPOHN ( J . Pharm. [ 5 ] , 10, 361 - 368; from Pharnz. Zeit. Buss.).-The roots are extracted with alcohol acidified with tartaric acid,the solution evaporated, resins and oils, &c., removed by filtrationarid shaking with ether ; and after making just alkaline with sodiumhydrogen carbonate, again extracted, first with ether and secondlywith chloroform. From the ether 1-13 percent., and from the chloro-form 0.8 per cent.of alkaloids were obtained.The first alkalojid, Eycaconitine, appears to have the compositionC,H3N2O6 + 2H20 ; it is not crystalline, neither is the aurochlorideor platinochloride. The authors conclude that it differs from thenlkalojids acolyctine and lycoctonine obtained by Hubschmann, andalso from aconitine and nt5phaline. If heated with water under pres-sure, an acid reaction is developed due to the formation of a volatileacid and a crystalline acid, Zylcoctonic acid, C,,H18N20, ; two alkaloidsremain dissolved, one Zycaconine, soluble in ether, Ihe other soluble inrhloroform, and apparently Hiibschmann's acolcytine. Lycaconitine,when heated with caustic soda solution under pressure, gives theabove-mentioned lycoctonic acid, also lycoctonine and acolyctiiie ;these alkaloids do not occur ready formed in the root, as found byHubschmann, but are produced by the action of sodium carbonate.The second alkalojid extracted by chloroform is my octonine,Cz7H,N20e -+ 5H20.When heated with water orcaustic soda, it is decomposed in a manner similar to lycaconitine.It is amorphous.H. B.Alkalo'ids of Coptis Trifolia. By J. J. SCHULTZ (J. Pliarm,.[3], 14, 273-976) .-Coarsely powdered Coptis trifolia yields 10 percent. extractive matter t o alcohol (U. S. Y.), slightly acidulated withacetic acid. It contains berberine = 0.8 per cent. berberine sulphateand 0.012 per cent. of a second alknlo'id. Berberine is only partiallyextracted from Coytl's tr;foZia by the methods usually employed for itsdetermination.D. A, L404 ABSTRACTS OF CHEMICAL PAPERS.The Alkalo'id of Macleya cordata. By J. F. EIJKMAN ( C h m .Cenfr., 1884, 727).--Macleya cordatn belongs to the Papaveracea, andgrows wild on the hills and mountains of Japan. The author hasextracted from the plant an alkalojid which he names n7acleyine. Itis crystalline, tasteless, and melts at 205". The salts are bitter, havean acid after-taste, and produce a sensation of cold. Ultimate analysisand the composition of the platinochloride lead to the formulaC20H,9N05. Va.rious vivid colorations, described in the paper, areproduced by macleyine in contact with sulphuric, nitric, and molybdicacids, or certain admixtures of them. R. R.The Poisonous Constituents of Skopolia japonica.By. J.E. EIJKMAW (Chem. Csntr., 1884, 747).-The root of ~Skopolia japonzca,one of the Solanaces, has been introduced into the European marketunder the name of " Japanese belladonna." The author has isolatedthree principles from the root : skopoletin, C12H1005, crystallising inslender needles melting at 198", and subliming a t higher temperatures :skopolezne, a crystalline rtlkalo'id ; apparently, it yields atropic acidwhen digested with baryta-water ; skopolin, C2,H300,5 + 2H20, theglucoside of skopoletin. This last siibstance ha3 not the property ofdilating the pupil possessed by skopoletin in a high degree.R. R.Formation of Ptomaines in Cholera. By A. VILLIERS (Compt.rend., 100, 91-93) .--The bodies of' two patients, sixty-three years ofage, who had died from cholera, were examined for alkalojids byStas'a method, twelve and twenty-four hours respectively after death.In both cases an alkaloid was found in notable quantity (at least 0.02gram of hydrochloride) in the intestines, and in distinct traces in thekidneys; but the liver and the blood in the heart contained a barelyappreciable quantity.This alkaloid is a liquid with a sharp taste,and a somewhat distinct odour of hawthorn. It yields a hydrochlor.idewhich is neutral to litmus, and orystallises in long, slender, trans-parent, and highly deliquescent needles. Solutions of the nlkalo'idgive the following reactions : with mercuric potassium iodide, awhite precipitate ; iodine solution, a brown precipitate, even in ROIU-tions which are so dilute that they give no precipitate with mercnrypotssaium iodide ; bromine-wa*ter, a yellow precipitate ; picric acid, ayellow precipitate ; gold chloride, a yellowish-white precipitate ;tannin or mercuric chloride, a white precipitate in concentratedsolutions ; platinum chloride, or potassium dichromate, no precipitate ;strong sulphuric acid, a pale fugitive violet coloration.Withpotassium ferricyanide and ferric chloride, the alkalojid does not givethe p toma'in e reaction immediately, but the reaction develops very6 mgrms. of the hydrochloride in 0.5 C.C. of water injected under theskin of the thigh of a guinea-pig, produced very marked periodicvariations in the contractions of: the heart, followed 45 minutesafter injection by violent trembling of the limbs, which rapidlypassed away.The animal refused nourishment and died four dajsafterwards.slo w 1sORGANIC CHEMISTRY. 40.3The presence of the alkalojid in the kidneys, althongh only in smallquantity, and its almost complete absence from the liver and blood,point to a rapid elimination by the urine.Chemical Constitution of Cartilage.-By C. F. W. RRUKENBERG( Z e i f . f. Bid., 20, 307--326).--Friedleben was amongst the firstto observe that hyaline cartilage when macerated in dilute acid forseveral days, yielded a gelatinous solut,ion in which t'he reactions ofso-called chondrin are absent, but those of glutin (gelatin) areobserved. Schultze and others attribute this to some unexplainedchanges occurring during the process of ossification.The authorrefers to his previous researches on the analogy between the process ofossification and that of new tissue formation, as throwing considerablelight on the subject. Bodecker found that on boiling cartilage withmineral acids, a substance was obtained, which he named chondroi'cicacid. Schiff, hbwever, was the first to see that the change was but astep in the transformation of albumin into carbohydrates ; he did not,however, pursue the subject, and it was neglected by other investigators.The author made four preparations of this so-called chondro'itic acid,and subjected them to searching examination with numerous reagents ;he concludes that all the end-products of the hyaline series are sugarsof different compositions, and that hyaline substances are present,not only in cartilage, but in brain matter, liver, lungs, and in manynormal and pathological fluids, and that they are evidences of a pro-cess of transformation in to pure carbohydrates.Composition of Albuminoyds.By CHICHKOFF (Ru7Z. SOC. CILim.,42, 318).--'l'he author's experiments lead hiin to the supposition thatalbuminoYds are formed by the reaction of fatty acids with sugar antiammonium nitrate, water being eliminated. When acted on byferments, albuminoids yield sugar ; their tranformation into fats nndeycertain pathological conditions indicates a relation to the paraffinojiclacids. An acid was isolated from adipocere, which had the propertiesof stearotic acid. The formation of neurine by the decomposition ofcertain a1 buminojids by living cells or micro-organisms, is explainedby the actiori of N,O from ammonium nitrate on sugw, thus:-3C6HlzO6 + ZN,O = 2CzH10NMe, + 8C02 + 2NH3 + 30H,.C.H. B.J. F.W. R. D.Diffusion of Albumin Solutions. By E. V. REGECZY ( B i d .Centr., 1884, 789).-Albumin diffuses best into a solution of sodiumchloride, and the salt solution should be concentrated. Dilute sol 11-tions of albumin diffuse best, and they should be pure ; pressure aidsthe diffusion. I n a mixture of salts and albumin, the albumin diffuscxslast, but the diffusion is more rapid when the membrane is thick.E. W. P.Comparative Experiments, with Alkali-albuminate, Acid-albumin, and Albumin. By A. ROSENBERG (Chenz. C'eutr., 1884,376-377) .-For the preparation of the albuminate, egg-albumin W;I sdialysed for two days so as to remove as much of the salts as possible,and after diluting and filtering through linen, caustic soda was adde40 ti ABSTRACTS UF CHEI\IICAL PAPERS.(14 C.C. of normal sodium hydroxide to 100 C.C. of the original solutionof albumin), and the liquid heated for some hours. On accurlttelyneutralisiog with hydrochloric acid, the albuminate was precipitated,and after thoroughly washing, was found to be almost free from ash.Neutral solutions of alkali-ad buminate obtained by dissolving t’his albu-minate in the smallest possible quantity of soda, become coagulatedon the addition of a 10 per cent. solution of sodium chloride, thecoagulation being the more rapid the stronger the solution of albn-minate, and the larger the quantity of salt added. Thus a 5 per cent.solution of albuminate does not become coagulated until after severaldays, even when the salt solution added amounts to one-tenth of itsrolume. Solutions of acid-albumin (prepared either by acidifying thealkali-albuminate with acetic or hydrochloric acid, or by dissolvingt lie albuminate itself in acids) undergo similar coagulation on theaddition of neutral salts. On dialysing serum or eKg-albumin in theirnaturally alkaline condition, the power of coagulation first disappearsin 48 hours’ time, alkali-albuminate being formed on heating;on continuing the dialysis, however, the power of coagulation isrestored, owing to the removal of alkali, whilst salts still remain ; oncontinuing the dialysis still further, the power of coagulation againdisappears, and on the seventh or eighth day boiling merely producesmore or less opalescence. The solution is now neutral and remainsso on boiling. I f this boiled solution is evaporated to dryness in avacuum, a residue is obtained, which is perfectly insoluble in water.The same results are obtained by the dialysis of albumin which hasbeen treated with C1.25 per cent. hydrochloric acid. In the undialysedblood-serum of the ox, 9-61-9.82 per cent. of soluble and 1*‘26---0*81per cent. of insoluble salts were found, whilst after exhaustivedialysis, only &% to & of the soluble, and to 2%- of the inAolublesalts were present; the latter consist almost exclusively of ferricphosphate with traces of earthy phosphates.The opalescence obtained by boiling solutions of albumin, fromwhich the salts have been almost wholly removed, was found to be dueto solid particles, the light which such solutions reflect being polarised.This opalescence the auther regards AS the first iudication of coagula-tion dependent on the presence of the minute proportion of salt,which still remains in the albumin ; highly concentrated solutions ofthis kind become coagulated in 24 hours on the addition of a smallSolubility of Fibroi’n. By LIDOFF (BUZZ. SOC. Chin?., 42, 318).-Fibrojin dissolves in oxalic, gallic, citric, and tartaric acids, as well asin pjrogallol when these are melted, and also in lactic acid whenheated with it in sealed tubes. Pibroi‘n can be precipitated bytannin, or by concentrated solutions of neutral salts from diluteaqueous solutions, whilst from its solution in oxalic acid the fibroizlis precipitated by 96 per cent. alcohol. W. R. D.By S. v. STEIN(Chem. Centr., 1884, 538).-A drop of blood is placed upon an object-glass and exposed to the air until it begins to dry at t h e edges ;quantity of sodium chloride. P. P. 3’.Method of obtaining Haemoglobin CrystalsPH1'SIOLOOICAL CHEXISTRY. 407Canada balsam is then adde;, first round the blood and then to fiIllip the space. Canadabalsam which is yellow axd not quite clear is best suited for the pur-poEe. The blood must remain for a few days exposed to the air,that is until crystallisation has ceased and the odour of the balsamvanished. The excess of balsam is then removed with the help of aknife, wetted with ether, turpentine, or oil of cloves ; the preparationis then covered with a glass, which is fixed on with asphalt orbalsam. A. I(. M.The layer of blood must not be too thick.Study of Metahaernoglobin. By A. JADERHOLM (Zeit. f. Riol., 20,419--448).--Por the purpose of obtaining metahcemoglobin crystals,the author treated dog's blood, with slight modifications, according tothe sixth process described in Preper's " Die Blutkrystalle." Thecrystals dif-fer only in size and shape from those Hammarsten obtainedby treating horse's blood with ferricyanide of potassium and snbse-quent dilution and application of cold (Zeit. Pirysiol. CYhem., 8, 186),as both forms of crystals and their solutions give the characteristicspectra of metahsmoglobin.The addition of a very small quantity of sodium carbonate (0*00053per cent.) to a solution, produces the so-called alkaline metahcemoglobinspectrum T + al + PI, 7 being always weaker than al + 8,.The bands I1 and 111 of metahaemoglobin, and al + /Il, of its alkalinesolution, correspond very nearly with a + P of oxyha?moglobin. Thespectmm r -i- al + PI of alkaline metahsmoglobin can be obtainedalso by passing pure hydrogen through a solution.If excess of sodium carbonate be avoided on the one hand, and ofhydrogen on the other, the bands I and IV of metahsmoglobin areproduced on shaking the solutions with air.The latter half of the paper is devoted to the discussion of its coil-stitution. The author explains his reason for assumirig it to be Rperoxidised oxphaemoglobin, as he did in his former paper, but nowagrees with Hiifner and Hulz in considering it to contain the sameamount of oxygen as oxyha3moglobin. J. P. L

ISSN:0368-1769    

DOI:10.1039/CA8854800363

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年代:1885

数据来源: RSC

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PH1'SIOLOOICAL CHEXISTRY.P h y s i o l o g i c a l C h e m i s t r y .407Influence of Variations in the Percentage Composition ofthe Air on the Intensity of Respiratory Changes. By L.F R ~ D ~ R I C Q (Compt. rend., 98, 1124--1125).-The author has investi-gated the influence of variations in the amount of carbonic anhydrideor of oxygen in the air on the intensity of respiratoiy changes, asmeasured by the amount of oxygen absorbed in the case of rabbitsand of himself.An increase in the proportion of oxygen has no effect on the ab-sorption of oxygen in the process of respiration. When an animal i408 ABSTRACTS OF CHEMICAL PAPERS.transferred from ordinary air to an atmosphere of oxygen, or one con-taining a high proportion of oxygen, there is at first an increase inthe amount of oxygen absorbed, owing to the dissolution of this gasin the plasma of the blood and lymph, but as soon as equilibrium isestablished between the tension of the oxygen in the plasma, andthat of the atmosphere in the lungs, the absorption of oxygen returnsto its noymal amouut. This result was previously arrived at bySpeck.The respiration of an atmosphere poor in oxygen produces,as is well known, more or less intense dyspnoea.Man can breathe for a long time an atmosphere which is rich inoxygen, but contains from 5 to 6 per cent. or even more carbonicanhydride. Under these conditions a peculiar kind of dyspnoea is pro-duced, charactwised by troubled, more or less convulsive, respiration,and a cephalalgy resembling headache. This dyspnma is quite dis-tinct from that caused by a deficit of oxygen, and is accompanied hyK notable increase in the amount of oxygen absorbed. I t follows thatcarbonic anhydride in small quantities acts as a powerful exciter ofreslbiratory combustion.Previous experimenters have found that' carbonic anhydride dimi-nishes the amount of oxygen absorbed, but they used large proportionsof the gas, and their results are vitiated by the direct poisonous actionof the anhydride.Differences between Pepsin and Trypsin.By E. BouRQumoT(J. Plzaim. [ 5 ] , 10, 177--187).-Pepsin is said to exercise its diges-tive action only in acid solution, whilst trypsin acts only in alkaline,neutral, or feebly acid solutions. But though the first statement istrue, the second requires modification, since 0.10 per cent.of aceticor 0.03 per cent. of hydrochloric acid may he present, without, stoppingthe digestion, and the gastric juice generally contains only 0.02 percent. The characteristic swelling which takes place when fibrin is actedon by the gastric juice, is moreover not due to the pepsin contained,but to the acid. The difference in the action of gastric juice anttpancreatic juice on milk is also due to the acidity of the former. Theproducts of the gastric and pancreatic digestion of fibrin do not diffrrexcept in the first products, which are respectively a syntonin and i tglobulin, and this difference loses its significance since Fyntonin isproduced, though somewhat slowly, by the action of hydrochloric acitlalone.The differeiwe in the action of the products of the two diges-tions on polarised light also is due, riot to any difference in the peptonesproduced, but rather to the action proceeding further in one cage thanin the other.Kuhne found ihat trypsin is destroyed by gastric juice ; if a similaraction is exerted on other ferments, such a9 that of the saliva or dias-tase, this action may be utilised to detectt pepsin. But here again tlieamount of acid present and necessary for the action of the pepsin,must be considered. The ferment of the saliva and the diastase ofmalt are not destroyed by treatment with hydrochloric acid of 0.01-0.50 per cent. :for five hours a t 18"; but the action of saliva onstarch-paste is stopped by the addition of an amount of acid sufficientto destroy the original alkaline reaction, and hence the digested liquidC.H. BPHYSIOLOGICAL CHEMISTRY. 409must first be exactly neutralised before testing its action on starch.Knowing these conditions, it is thus possible t o determine whether aliquid, digesting prote'ids, contains pepsin or trypsin.Metabolism of Five Children of Ages varying from 5 toInfluence of Meat Extract on the Temperature of the Body.By M. RUIINER (Zeif. f. Bid., 20, 265--276).-The author, from theresult of previous experiments, believed that the extractive matterof meat had no part in the production of bodily heat, but passedaway, without important change, in the urine; the experiments ofKernmerich are referred to, in which he failed to keep animals aliveon a diet of meat extract, and the fact is noted that after a meal ofmeat extract there is more carbon found in the urine than should bepresent normally.I n order to study the qnestion, the author madean experiment with a dog weighing 24 kilos., and which generallyc:onsumed daily 2 lbs. of flesh. The animal was left unfed for twoclays ; on each of the two following days 500 C.C. of solution of meatoxtract, equal to 2 lbs. flesh, was given; the following day hereceived no food. The day before the experiment he drank 200 C.C.of water, but none in the course of the experiment. The animal tookthe solution readily and lay quietly in the experimental chamber, inwhich daily estimations of respiratory products were conducted.Thevoided urine was of a fine golden-yellow, darker than the urinepassed after a diet of washed flesh. On evaporation, when t h e bulkof the water had been removed, the peculiar smell of extract of meatwas clearly perceptible; this was not the case during feeding withmeat or on the hunger days. The carbonic anhydride expired in thetwo days of hunger amounted to an average of 264.24 grams f o r64 hours, and on the two days when meat extract was supplied to863.84 grams for 24 hours ; so that the carbon of the extract did notpass in the respiration, and the body substance was plainly unchanged.Duringthe hunger days a t the commencement of the experiment, the nitrogenpassed was 4.75 grams in 24 hours ; the two days of extract feedingshowed 6-96 and 6.67 grams respectively ; it fell to 4.08 grams whenthe food was withheld.The author gives details of the processes used in fhe various experi-ments, but comes to the general conclusion that it is impossible thatthe meat extract experiences any chauge in its passage through thesystem, and that it does not in the least contribute to bodily heat ; thewaste of tissue is neither hastened nor retarded by it, and it passetiaway unaltered in its composition.Influence of Certain Amides on the Animal Organism.By H.WEISKE and B. SCHULZE (Zed. f. Biol., 20, 276--285).-Aseries of experiments on various herbivorous mammalia and geeseconvinced the authors that the considerable quantity of asparaginefrequently present in fodder is not unimportant, but can rep1:tce apart of the albumin, without the production of milk or the growth ofH.B.15 Years. By W. CBNERER (Zeit. f. BiOE., 20, 566-583).Examination of the urine showed some interesting facts.Phosphoric acid varied more irregularly.J. P41 0 ABSTRACTS OF CHEMICAL PAPERS.flesh suffering any diminution. Zuntz (Abstr., 1884, 472) reportasthe results of his experiments on rabbits, whereby this property ofasparagine is confirmed ; whilst it is shown that other amides, tyro-sine, taurine, &c., have quite a contrary effect and cause considerablewaste of albumin. Potthast (T'iiger's Archiv, 32, 280) also believesthat the combustion of asparagine in the body diminishes the wasteof tissue and acts as a true food.Schrodt, in his report of the cxpe-rimental dairy farm at Kiel (Abstr., 1884, 1396), found that the milkdid not suffer either in quality or quantity, when a part of the usualfodder was replaced by malt combings which contain much of theirnitrogen in the form of aspamgine.These experiments were made on the herbivora, because it has beenshown by Munck (Virchow's Archiu., 94, 426) that asparagine.when a,dded to the food of carnivora (a dog), act,ed as a diuretic, andcaused increased production of both nitrogen and sulphur compounds.Knieriem, however, has made experiments on a dog, with differentresults. The authors wished to determine whether this property ispeculiar to the asparagine itself, or if it possesses it in common withother related compounds.The substances taken for experiment wereamidosucciiiic acid and succinamide, the subject of experiment beinqa large gander. A larger animal, such as a sheep, wonld have requiredtoo much of the costly suhstances used, besides which, the collectionof the excrement for analysis was easier. Full details are given of thefood, its preparation and composition, and the mode of analysisadopted for the excrement. The weight, &c., of the animal wastaken daily. It was found that the addition oE the two substancesto the food caused very little difference in the quantity of nitrogenexcreted, the succinamide slightly increasing the amount, but not toan important extent. Tables accompany the paper. J. F.Digestibility of Lucerne and Clover Hay by the Horse andSheep.By E. WOLFF and others ( B i d Centr., 1884, 751-752).-The horse was 8-9 years old, the two sheep were 1 4 years old; andthey were fed with lucerne cut on May 3Otl1, and made in eight days.A second cutting (not aftermath) was made three weeks afterwards,and is designated as lucerne 2 ; the clover hay was made when thebloom was out. The horse had gentle exercise every day, and itsweight consequently remained unaltered. The coefficients of digestionare as follows :- 1 Dry 1 Organic 1 Albu-matter. matter. min.60 -7859 '2855.5456 *3354.5253 *go61-47 74-7860.93 '71.2355-22 70'3657.94 68'2254'68 60*0255-34 54.51Pat.29 *8156 -2521 -1149 -1630'7457 *61Fibre.4 -9646'0836 -3246 -8338 '6047 -78Extrac-tive.71 -2667 -9867 *2463 "7266 -5661 -2PHYSIOLOGICAL CHEMISTRY.411sheep .. .. .. ..hay * ' {horse. .. .. .. ..sheep .. .. ,. ..Red 'lover hay { horse , . . . . . . .All previous experiments have shown that meadow hay is betterdigested by the sheep than by the horse ; these experiments, however,show but little difference save i n the fat and fibre. It is evident fromthe above table that a horse can be kept in fair working condition onlucerne hay alone, but such is not the case with meadow or cloverhay. E. W. P.Digestibility of Clover and Meadow Hay by the Horseand Sheep, and the Elimination of Mineral Matter by theHorse. By E. WOLFF and others (Bied. Centr., 1884, 753-755).-In this series, two sheep were compared with one horse asregards their power of digesting clover and meadow hay, and thecoefficients are as follows :-(1882.)63.00 58.80 51-79 62.11 65-3950.02 55'07 9.81 40.50 58-2357-64 56.84 62.35 49.94 64.3052 *50 57 '02 28 -20 39 -02 64 -3663.046.1100.0100.0Again, the difference in the digestion of fat and fibre is remarkable.Examination of the excreta of two horses was made, and the followingtable shows the percentage of the ash constituents in the hay excreted.31.7 36.7 116'7 30.734.5 68.0 116.1 52.237'3 87% 102.4 26.145.7 47-4 100-7 37.3---Meadow hay-horse 1 ..>> 2horse 1 ..YJ 2 ' 0Clover-Ash.1 K20. -!-63.8 I 36.661-4 I 29*2 I57.2 1 30.053.1 28-9INa,O. 1 CaO. 1 MgO. 1 P20,.1 SO,. C1.12 -79 . 416.810'5E. W. P.Sugar in Blood : its Source and Signification. RJ- J. SEEGEN(Bied. Centr., 1884, 747). - Earlier investigations by the authorshowed that the formation of sugar was a physiological function ofthe liver, and that it was independent of the food. Later investiga-tions on dogs show that sugar is always present in blood to the extentof 0-1-0-15 per cent., and that the quantity in cardial and arterielblood is the same ; there is, however, a variation, within small limits,in the percentages existing in arterial and venous blood, whilst mesen-teric blood always contains less sugar than blood from the carotid,The blood issuing from the liver contains twice as much sugar asthat entering, the quantities being 0.230 per cent.and 0.119 percent. Passing to absolute quantities, there was produced durin412 ABSTRACTS OF CIIENICAL PAPERS.24 hours, by the livers of three dogs weighing 7, 10, and 11 kilos,,179, 233, and 433 grams sugar. respectively. As far as can be ascer-tained, the albumin is the source of sugar in cmnivora, and as thesugar is not eliminated as such, it follows that its decomposition mustbe accomplished in the circulation. E. W. P.Influence of Asparagine on the Elimitation of Albumin.By J. MUNK and C. v. VO~T (Bied Centr., 1884, 749-750.)-Weiskeand others consider that asparagine aids in preventing the loss ofalbumin from the animal system, but these two authors independently,and by different methods of experiment, come to the same conclusion,namely, that asparagine does not prevent the decomposition of albu-min in the organism, but rather assists i t ; and its after-action on theelimination of water and decomposition of albumin leave no doubtthat it cannot be considered to be a food, a t least, for the carnivora.E.W. P.Influence of Bodily Labour on the Discharge of Nitrogen.By W. NORTH (Proc. Roy. Suc., 36, ll-l7).-Parkes found thatbodily exercise caused a slight increase in the discharge of nitrogenduring and immediately after labour, alt'hough his experiments leavethe question undecided whekher this increase occurs a t the expense ofstored material independently of any concomitant or subsequent in-crease of intake. It order to decide this problem, the author carriedon a series of investigations on himself for certain intervals of time,(luring which a regulated diet of accurately known composition wastaken.During the interval, a known amount of muscular labour wasperformed. I n order to get rid of any possible surplus of nitrogen inthe body, either the diet was regulated for four or five days before1)eginning an experiment, or, better, food was abstained from on thetirst day of an experiment. The table below illustrates the resultsobtained in one of the series of experiments :-Daily. Before work. After work. Difference.Nitrogen of urine . . . . 14.15 grams 15.74 1.59,, fmes . . . . 2.48 ,, 2.15 0.33P,05 of faeces.. . . . . . . 2.54 ,, 1-85 0-69HzSOa in urine . . . . . . 2-76 ,, 3-00 0.24P,O, of urine... . . . . . 2.01 ,, 2.00 0.01The work done was a walk of 30 miles a t the rate of 4.28 miles perhour, a load of about 27 lbs being carried.The general results, while confirming those of Parkes, show thatthe disturbance produced by severe labour is more immediate and ofgreater intensity than hitherto supposed. Further, that a diminutionof the nitrogen stored in the system is followed by a retention, thatis, by a condition in which the intake is greater than the output.Thus the storage of nitrogen represents the tendency of the organismto economise its resources. Finally, unless the exertion be very severe,the elimination of phosphates is not altered, while the oiitput of sul-phates is markedly increased. V. H. VPHYSIOLOGICAL CHEXISTRY.413Iodine in Human Urine after the External Application ofIodoform. By J. GR~NDLER (Chem. Centr., 1884, 492).-In a fewcases of the application of iodoform, no iodine was found in the urine,but in all other cases in which poisoning did not occur, the iodine ispresent in the urine chiefly as potassium iodide, but to some extentalso as iodate. In cases of poisoning by iodoform, the iodine is dis-charged not so much in the form of potassium iodide, as in com-bination with organic compounds. From this it is concluded that if ameans were discovered by which the iodine could be converted, beforeits absorption, into potassium iodide, a protection against poisoningmight be secured.Occurrence of Hydroxybutyric Acid in the Urine in Casesof Diabztes Mellitus.By 0. MINKOWSKI (Chem. Cenlr., 1884, 4U6-407).-The author has proved the presence of this acid in a, case ofdiabetes mellitus, accompanied by increased excretion of ammonia.Hydroxybutyric Acid in Diabetic Urine. By 0. MIN~OWSKI(Chem. Ceizfr., 1884, 672).--Hydroxybutyric acid obtained from urineis in many respects remarkably similar to Wislicenus’ p-hydroxy-hutjric acid, but t4he two a,re not identical, as the latter is opticallyinactive. EL. R.A. K. M.P. F. F.Nitrates in Urine. By T . WEYL ( B i d Centr., I884,856).-Whennormal human urine is dist’illed with addition of sulphuric and hydro-chloric acids the distillate frequently gives the characteristic reactionsof nitric acid, and from it is obtained by oxidation a body which, whenheated with ferrous chloride and hydrochloric acid, evolves nitricoxide ; nitrates must therefore be assumed to be present until it isshown that other substances giving similar reactions occur in theurine.The author’s experiments show that under favourable conditions,nitrous acid can exist for a short time in presence of urea.J. F.Phenaceturic Acid in the Urine of Horses. By E. SACKOWSKI(Bey., l7,3010--3012).-The urine of the horse contains about 0.5 of agram of phenaceturic acid per litre. When the hippuric acid is pre-cipitated by hydrochloric acid, the phenaceturic acid remains in thesolution, from which it may be extracted by ether.Chemical Composition of Pig’s Urine. By G. SALOMON (Chem.Centr., 1884, 347-348).--The urine of the pig presents some pointsof similarity to that of man, which is not surprising considering theomnivorous habits of both.Uric acid, however, which is such anessential constituent of human urine, had not previously to theauthor’s observations been found in the urine of the pig. By employ-iiig the process of precipitation with silver nitrate, as described bySalkowski and Leube (Lehre vom Ham, 9 SS), the author obtained0.65 gram uric acid from 54 litres of pig’s urine. This quantity,although considerably less than that present in human urine, is inexcess of what is found in the case of other families, such as thew. c. w.YOL. XLYIII. a 414 ABSTRACTS OF CHEMICAL PAPERS.carnivora and herbivora. One determination showed the proportionof uric acid to urea to be as 1 : 150.The author also finds two sub-stances belonging to the xanthine-group, of which one appears to beguanine, and the other xanthine itself; creatine and an acid soliibiein ether were also found. P. F. 3'.Physiology of Uric Acid. By A. B. GARBOD (Proc. ROY. XOC.,37,148-150).Nitrogen in Fsces. By H. RIEDER (Zeit. f. BioZ., 20,378-395).-The estimation of nitrogen in the faxes of animals is of greatimportance in physiological investigations, particularly in those con -nected with the digestion of food, but as there are always preseiltresidues of the digestive fluids, mucus, epithelium of the intestines, Bc.,it is desirable that a correct idea of the probable amount of suchmatters should be obtained, in order to make allowance for them ininvestigations.It is probable that the black pitchy matter passed insmall quantities by animals after long fa'st'ing, is a fair guide t o theamount. In Voit's laboratory, several dogs were left hungry for longperiods, and it was found that for dogs averaging 26 kilos. the quan-tity of dry excrement averaged 3.2 grams per day ; this, comparedwith the animals after plentiful feeding on flesh, is remarkable, asduring that time only 11 grams of dry matter were passed; theamount passed during hunger, therefore equalled 36 per cent. of thetotal. The author reviews the experiments which have been made byother investigators, and describes some of his own. A small dog,weighing 7 kilos., kept fasting €or nine days, passed during that time11-88 grams fseces containing 7-12 per cent.nitrogen, or daily 1-32grams fseces with 0.094 gram nitrogen. When fed for a time on70 grams of air-dried starch-flour and 6.4 grams fat, and on a secondoccasion on 140 grams daily of the same food, with addition of11.3 grams of fat; the results showed that on a diet free from nitro-gen, the fieces contain more nitrogen than during the hunger period,and as much as during a flesh feeding period. The activity of theprocesses in the intestine causes greater secretion and excretion.When dogs are fed on bread or potatoes, the case is different, theamount of excrement is greater, but consists largely of undigested orlittle altered matter.The question is of great importance as regards human beings;besides quoting the experiments of Itubner and o i Pnrkes, the aut)horgives details of some of his own.A man weighing 70 kilos. rewireddaily about 600 grams of dry substance consisting of 300 grams ofstarch-flour (8624 per cent. dry substance), 1.20 grams sugar, 89 gramssuef, 12 grams cream of tartar, and 5 grams sodium bicarbonate ; fordrink, r)n the average, he received908 C.C. light white wine in mineralor carbonated water daily; the experiment lasted three days. Thesame man was the subject of another three d a p ' experiment on lessfood, namely, for each day, 90 grams starch-flour, 40 grams sugar,30 grams suet, and 11 grams baking powder, together 158.6 gramsdry matter; 1125 C.C. white wine was drunk.In a third experiment, another man was the subject ; he weighePEY SIOLOGICATi CHEMISTRY.415No. ofexperimentalseries.1 ............ 9.302 ........... 9-503 ............ 7.674 kilos., and received as food 100 grams air-dried starch-flour,30 grams sugar, 30 grams suet, and 5 grams baking powder; in allcontaining 147.2 grams dry substance ; he drank 907 C.C. of whitewine daily. The principal average daily results of these three experi-ments are thus summarised :-Faxes.Dry subs. Per cent. N. Gram N.13 *4 4 -08 0 -5415 ‘4 5 -69 0 -8713.4 5 *85 0-78.-----------The totlal nitrogen excreted in the faeces amounts therefore to a l l yabout 8 per cent. of the total passed during a non-nitrogenous diet.Rubner’s experiments show that an egg or flesh diet does not materiallyincrease the amount ; the author is therefore of opinion that thegreater part is derived from waste of the walls of the intestine, Theauthor continues his researches, as the subject requires further investi-gation.J. F.Physiological Action of some Ammonium-bases. By A.GLAIJSE and B. LUCHSINGER (Chem. Centr., 188s 444).-The authorshave investigated the action of a number of these trimethylammoniumbases, including nenrine, muscarine, amyl-, valery 1-, benayl-, andglyceryl-trimethylammonium, and also tetramethylammonium salts.The general tendency of this class of substances is to depress or evenpamlyse the action of the heart. P. F. F.Anesthetic Action of Cocaine Hydrochloride. By J. GRASSET(Compt. ren,d., 99, 1122--1123).-The injection of 0.01 gram ofcocaine hydrochloride beneath the skin of a man produces a verydistinct zone of cutaneous ana?esthesin, without any general phenomena,and without any important after-effects.The anesthesia lasts suffi-ciently long for certain surgical operations. At least 0.01-0*02 gramof the hydrochloride should be injected just below the region to heoperated on, and the operation should begin 5 or 10 minutes afterinjection. C. H. B.Hygienic Importance of Carbonic Oxide, and its Detection.By A. P. FOILKER (Chem. Cerbtr., 1884, 380--381).-The authordescribes a modification of Fodor’s method of detecting carbonicoxide. 1-2 C.C. of the blood to be tested for carbonic oxide isplaced in a shaltllow beaker, which is floated in a porcelain dish full ofwater, the beaker being kept in a vertical position by means of threeperpendicular brass wires which carry above a watch-glass containinga, little palladium chloride solution. A glass shade is inverted overthe beaker so that it stands in the dish of water, and two-thirds of2 f 416 ABSTRACTS OF CHEMICAL PAPERS.the air in the glass shade are exhausted by means of an india-rubbertube. The water in the dish is then boiled, which causes the coagula-tion of the blood in the beaker floating upon the surfaceof the water,and the carbonic oxide escapes and reduces the palladiuni chloride inthe watch-glass above. If traces only are present, the reduction doesnot take place immediately, and the apparatus should be allowed tost,and for 24 hours. I n this manner i t is possible to detect thepresence of carbonic oxide in a single drop of blood.By RAROT (J. Phurm. [ 5 ] , 10, 189-193).-Canes of poisoning of nicotine are very rare ; in the presentcase the liquid used f o r destroying insects on plants was taken inquantity. From the liquid in the stomach, 2.25 grams nicotine wereobtained, and traces were found in the bile and urine; ordinarymethods of separation were used.P. F. F.Poisoning by Nicotine.El. B

ISSN:0368-1769    

DOI:10.1039/CA8854800407

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

416 ABSTRACTS OF CHEMICAL PAPERS.Chemistry of Vegetable Physiology and Agriculture.Changes which Milk undergoes through the Agency ofMicro-organisms. 3 y F. HUEPPE (Chem. Centr., 1884, 315-316).-The author points out the chemicapl changes taking place in thesterilisation of milk by heat. On heating milk above 75", the actionof rennet is retarded, but this retardation can be to it certain extentcounteracted by increasing the amount of rennet. Exposure to ahigh temperature increases the dissimilarity between COW'S milk andhuman milk, and also renders it less digestible, as owing to theimpaired action of the rennet the curdling of boiled milk in thestomach is almost exclusively performed by the 'gastric acids. Thedigestibility of milk is, however, not materially diminished by tempe-ratures below loo", and it is, therefore, desirable that in preservingmilk the sterilisation should be effected at a temperature not exceeding100".This can be done by heating the milk for one hour on five con-secutive days a t 65"-75". Milk sterilised in this manner is hardlydistinguishable by its taste from fresh milk, but on standing thecasejin is gradually deposited, so that the supernatant liquid hasthe appearance of watered milk. The sterilisation can be effectedmuch more rapidly by a current of steam. On inoculating this steri-lised milk wi6h a pure cultivation of the lactic ferment, the lacticfermentation was in all cases set up. The activity of these organismsceases below 10" and above 44*8"-45*5" ; they produce lactic acidfrom milk-sugar, cane-sugar, mannite, and dextrose, and if is probable,therefore, that they do not convert milk-sugar into lactic acid andcarbonic anhydride, but that their action consists in the first instancein the hydration of the di-saccharates.The lactic acid bacteria exhibitclisstntic action, but no peptonising properties.The author has also studied the butyric acid bacilli, wliich he finds iYEGETABLE PHYSIOLOGY AND AGRICULTURE. 417the first instance curdle the milk like rennet, and, if the Initial reactionlie neutral or wealky acid, actually dissolve the curd by converting itinto peptones and other products of decomposition, amongst which isammonia, although the bacilli are unable to induce the ammoniacalfermentation of carbarnide. The spores of these bacilli are far m o ~ erefractory than the lactic acid bacilli, thus offering considerable diffi-culty to the preservation of milk.The author then treats of the orynnisms of Hue YniZk : these bacteria”multiply by fission and by means of spores, they neither curdle noracidify milk, but on the contrary render it gradually alkaline.Thecolouring matter which is produced a t the expense of the case’in, is, inthe absence of acid, not sky-blue but rather slate-grey, but becomesintensely blue on the addition of acid. These bacilli, by their actionon ammonium tartrate, produce a green colouring matter which isconverted into the above blue one by oxidation. There can be nodoubt that these bacilli are not only the invariable concomitants ofblue milk, but also the inducing cause of this phenomenon.Oidiurnlactis is a fungus which forms a thick white mycelium on the surfaceof milk, the latter remaining liquid and becoming faintly alkaline.This organism has become erroneously regarded 13s some as a lacticacid ferment ; it, only, however, indirectly furthers the production oflactic acid by removing the free acid as it is formed, and thus enablingthe lactic organisms to convert fresh quantities of sugar.Origin of Microzymae and Vibrioles in Air, Water, Soil, Bcc.P. F. F.By A. B~CHAMP (C‘ompt. rend., 100, 181).-A claim for priority.Degeneration of Brewer’s Yeast. By H. BUNGENER ( B d l . XOC.Chim., 42, 567--573).-As is well known, yeast which has beenrepeatedly employed for fermenting purposes, becomes after severalgenerations unfit for further use. Knmerous attempts to explainthis fact have been made, b u t so far without success.The presenceand growth of lactic and acetic ferments along wish the Saccham-inyces cerevisice are not sufficient to cause degeneration, as theirnumbers can be kept down at a minimum in all well-conductedbreweries. Doubtless the composition of the wort, the quantities ofsugar, extract, and salts, it contains, have a great deal to do withthis result, and this is particularly the case with the nitrogenousconstituents. Of the latter, certain of the amido-componnds whichyield the nitrogen food to the ferment, are the must important.Recent observations have shown that after each fermentation thequantity of nitrogen in the yeast.increases, as does also the fer-menting power; but after a time the fermentation finishes, leavingthe cells still suspended in the liquid, and the yeast is no longer fit touse. J. K. C.Vitality of Germs of Microbes. By E. DUCLAUX (Compt. rend.,100, 119, and 184--186).-The germs of different species of Tyro-thrix, more particularly Tyrotl~rix scaber, are not killed by at leastthree years’ exposure in a dry state to air at a tropical temperature,but are killed by exposure to sunlight at the same temperature fo418 ABSTRACTS OF CHEMICAL PAPERS.some weeks. The exact time required depends on the species and onthe nature of thefluid in which it has been cultivated.The author has also examined.various cultivations which have beenkept in flasks a t the ordinary temperature for several years, includingthose which were used by Pasteur in 1859 and 1860, and which areconsequently 25 years old. The vitality of the germs contained inthese flasks was determined by seeding various liquids with thecontents of t h e flasks. Of 27 flasks which originally contained aslightly acid aqueous aolution of yeast, without sngar, only two con-tained living germs ; of 2.5 others, 18 contained mycelinms which hadriot fructified. Fifteen flasks of aqueous yeast and sugar containedonly three living species, and 10 flasks of milk contained only twoliving species. In all the flasker which contained living germs, theliquid was slightly alkaline, whi qt in all the others it was acid.tained living germs.Five flasks containing urine 20 years old, andstrongly alkaline, contained no living germs. It would seem, there-fore, that sZight alkaJinity is mwh more favourable than acidity to thepreservation of microbes.Of the 65 flasks examined, 15, or nearly a quarter, contained livinggerms. Among these were certain known species, such as Xterigmn-hystis mipa, which, if dried in the air, are dead after the expirationof three years. The liqnids also contained several species of Tyro-thrix, still in a, vepy active condition, and several new species ofmicrobes. (3. H. B..Eight flasks containing aqueous y P ast and calcium carbonate all con-Source af the Nitrogen of the Leguminosse. By B. E.DIETZELL(Arm. Agronornipes, 10, 543--544).-T he author accepts the cogclu-sion 01 Boussingault, confirmed by Lawes, Gilbert, and Pugh, thatplants do not directly assimilate the free nitrogen of the atmosphere,Rut it still seemed to him possible that leguminous plants shouldassimilate combined nitrogen directly from the air. In order to testthis point under conditions as nearly natural as possible, he hasgrown clover and peas in pots of ordinary garden soil, in free air, butsheltered from the weather and watered with pure distilled water. Aweighed quantity of soil was used in each case, and the nitrogen ini t determined (0.415 per cent.). The nitrogen contained in the seedssown and in the matured plants was also determined. Each seriesconsisted of six pots, No.1 being without added manure, .No. 2 withksinite, No. 3 with kainite and superphosphate, No. 4 with kainite,superphosphate, and calcium carbonate, No. 5 without plants, but withkainite, superphosphate, and calcium carbonate, and No. 6 without plantsand without added manure. The results show that peas and clover donot absorb combined nitrogen from the air. In all cases except twothere was a Zoss, varying from 5.10 to 15.32 per cent. of the nitrogen inthe soil. The two exceptions were, No. 6 , the soil without plants andwithout manure, which gained 0.26 gram nitrogen, and No. 3, peasgrown with potash and phosphoric acid, in which there wrts neithergain nor loss, The author suggests that acid calcium phosphateor bibasic calcium phosphate may react upon the ammonium nitriteformed in the soil, and by converting it into calcium nitrite and am-iuoniurn phosphate may prevent its decomposition.J. M. H. MVEGETABLE PHYSIOLOOT AND AGRICULTURE. 419A New Germinator. By J. KONIG (Bied. Centr., 1884, 789).-A zinc trough, 20 cm. broad by 23 long and 4 cm. high is employed,this is divided along the length by a strip of zinc reaching to theIbottom, and on each division thus formed is laid a glass sheet 4 cm.llroad, Strips of tilter-paper, 9+ x 17 cm., are laid on the glass, sothat the ends fall over the sides of the glass into water in the bottomof the trough ; the seeds will germinatgon this moist paper.E. W. P.Influence of Light on the Germination of Seeds. By A. CIESLAR(Bied. Centr., 1884, 860).-The author finds that many seeds hithertothought to germinate in light oniy, will do so equally well in darkness.Small seeds with poor reserve of material germinate better in light,whilst t'hose with a large reserve do so equally well in darkness ; he(lid not find any seeds which grew better in darkness than in light.Yellow light accelerated, violet retarded germination, and the latterat a low temperature almost rendered growth impossible.I n whitelight, there was greaterenergy of growth, a higher percentage of budsRnd generally more activity than with colourec! lights ; the authorthinks this due in part to the transformation of light into heat.By SCH~BELER (Bied.C'entr., 1884, 791).--Ry reason of the long days in northern latitudes,plants produce larger and heavier seeds than in the more southerlylatitudes ; yet although the grain is heavier, the extra weight is notdue to nitrogenous matter, which remains unaltered.Leafy plants,such as vegetables, produce larger leaves, and blossoms which areE. w. P.Influenae of Intermittent Heat on the Germination ofSeeds. By A. v. LIEBENBERG (Bied. Centr., 1884, 756-757).-Poayratensis germinated to the amount of 80 per cent'. when exposed todaylight ; but when the pots in which the seed was sown, were placedin darkness at 22", only 2.5 per cent. germinated ; from these result,s, itappeared evident that intermittent light was more effective than hightemperatme and darkness ; to prove this, seeds were placed in frontof a window ; in the dark a t 20" ; in the dark at 28" ; and a fourth setwere alternately in the dark at 20°, and then for 5 hoursat 28".Thehest, results were obtained in this last case, when 23 per cent. germi-nated, whilst in the second only 1.5 per cent. did so. Several other seedswere tried, and all proved that variable temperatures, even in t.he dark,were better than exposure to sunlight only.J. F.Action of Long Days on Vegetation.white elsewhere are frequently violet here.E. W. P.Effects of Running Water on Plants. By B. J~NSSON (Bied.Centr., 1884, 86O).-When a plasmodium of Myxomycetes in ahealthy state is placed on filter-paper, so arranged that a portion ofthe paper is in contact with water, a movement in the direction ofthe water is perceived ; the author's experiments were made to dis-('over whether the protoplasm of other plants was similarly affected ;lie found t h a t the hyphen of the spores of mycelia were affected, butthat the movements were in the same direction as the flow of water.He placed young plants of maize in such a way that the roots dippe420 ABSTRACTS OF CHEJIICAL PAPERS.into swiftly running water ; although a t first perpendicular, after20 hours they formed a right angle, their points growing against thestream, and when their position was reversed with the points downstream, they bent until they again brought their points against it.Water Culture of Lupines.By TROSCHKE (Bied. Centr., 18t34,85O-852). -Lupines have not yet been successfully cultivated inwater ; the author has been more successful than other experimenters,but still cannot produce plants as healthy as those grown in opensoils.The roots of the water-grown p l m k do not contain thoseexcrescences which are usually present on the roots in a state ofnature. These excrescences are connected with a minute fungus, butthe manner of their growth is unknown. The author submitted aquantity of them to chemical examination, and found them quitedifferent in coniposition from the roots proper, being very rich in fat,albumin, and phosphoric acid ; the large proportion of nitrogenousmatter i s similar to that in earth-nut cake, one of the richest feedingmaterials. J. F.J. 1'.Water Culture of Lupines. By M-EISKE ( R i d Centr., 1884,790).-Lupine seeds were grown in glass vessels which w-ere more orless tightly closed, other seeds were grown on paper in basins; thesolutions contained some nitrogenous, others no nitrogenous plant foodconstituents.When the plants were dead, they were dried and thenitrogen estimated. It was found that those plants grown in non-nitrogenous liquids contained but very little nitrogen, and that thosegrown in the basins were the richest in this constituent.E. W. P.Chemical Phenomena of the Respiration of Plants. By 1'. L.PHIPSON (Chem. News, 50, 288).-In connection with the general ideathat the exposure of the green parts of plants to light is sufficient tocause them to breathe, $he author remarks that temperature is quite RSimportant an agent.For example : plants were exposed to light 011two days of nearly equal photometric intensity of daylight ; but wheiithe temperature was respectively 38" El. and 70" F., in the first casethe evolution of gas was nil, whilst in the second it was abundant.On another occasion a plant at 45" F. in bright sunlight gave no gas,whereas, after an hour a t 59" F. in much less powerful light, gas wasevolved. The plants employed in these observations are unicellularalgm ; they have no stomata, it is therefore inferred that these organsare not indispensable for the respiration of plants. A temperature of'from 60" F. to 90" F. and exposure to sunlight appear t o be themost favourable conditions for the respiration of these plants.Other observations and experiments tend to show that circulation isclosely connected with respiration, and, like it, is equally dependenton temperature as well as light.It is stated that the oxygen evolvedfrom the organisms in stagnant water comes from zoospores, and notfrom infusoria, as is sometimes supposed. I t is inferred that the respi-ration of plants is independent of chlorophyll, b u t that chlorophyll isformed by the process of respiration, inasmuch a s the brown oryellowish Protococcus pZuvinZis emits oxygen, and alga accidentallVEGETABLE PHYSIOLOGY AND AGRICELTURE. 42 1bleached by adding a minute quantity of sodium hydroxide to thewater in which they were being cultivated, after washing and againexposing to light, gave off oxygen after four hours, and the next daydeveloped green patches. The author’s experiments negative theidea that for the cultivation of plants, carbonic anhydride may bereplaced by organic acids.Evaporative Surfaces of Plants and Influence of Moisture inSoils on Plant Growth.By H. HELLRIEGEL (Bied. Centr., 1884,b34-849) .-The author’s previous experiments have convinced himthat plants so dissimilar as beans and barley have nearly the sameextent of evaporative surface, the measurement of which, althoughdifficult, should aiford much information as to the effect of moisture inthe soil. These effects have been frequently remarked. The authormade experiments with barley grown in soils containing 10, 20, 40, andti0 per cent. of water; with the higher percentages, the size of leafincreased proportionally, but) when examined under the microscopethe leaves of the plants grown with the lesser quantities of moistureshowed far larger numbers of stomata than the others, and in theformer the stomata were larger, arid the cells more developed. Thegreater quantity of matter produced by well watered plants, appearsto be due to the quick multiplication and development of the cells ;in the less watered plants, the contents of the cells appear to be moreconcentrated.Plants do not possess the power of assimilating the moistureexisting as vapour in the air ; the rainfall is therefore a most impor-tant factor in the growth of plants in dry soils; the transpirationfrom the leaves and the loss of moisture from the soil by emporationserves to balance the effect of excessive rainfall.The author hasobserved the fall for 15 years a t one station, but the conclusionsdrawn are incomplete. Soils possess this power of absorption ofmoisture from damp air ; the author’s experiments show that they donot absorb sufficient for plant-life in the abseme of other sources ofmoisture. The diffusion of rain in the soil depends very much on thephysical condition of the soil, which for this purpose may be lookecton as a mass permeated by numerous capillary tubes of smaller orlarger dimensions. One important result of the experiments was thegreat difference in the absorptive capacity of one and the same soilwhen in loose or close condition, the proportion in good garden Boilbeing in round numbers 2 : 3, and the author thinks the greatadvantage of deep cultivation consists as much in improving the powerof absorption, as in bringing fresh soil to the surface.J. F.Existence of Manganese in Plants and Animals. By E. J.MAUMENE (BulE. SOC. Chim., 42, 305--315).-Manganese occurs insmall quantity in most vegetables ; tea is particularly rich in mangan-ese (0.5-0.6 per cent.). So also is tobacco, especially the Kentuckyvariety, which contains from 1.5-1.6 per cent, Both yellow and red-cinchona bark appear to contain more than traces of manganese.Lemons, oranges, garlic, and onions do not contain this element.Human blood, as is generally known, does not contain the metal, butD. A. L422 ABSTRACTS OF CHEMlGAL PAPERS,small quantities can be detected in milk, urine, bones, and hair, andin mutton fat.The fseces often contain considerable quantities, infact the manganese taken in food appears to be eliminated prin-cipally by this excretion ; whence the author concludes that mangrtn-t'se is not essential to the support of the animal system, and for thisreason cannot be employed in medicine as a substitute for iron. I tprobably, howerer, plays an important part in the nourishment anddevelopment of certain plants. W. R. D.Influence of Temperature on the Development of Wheat.By E. RISLER (Bied. Centr., 1884, 778--779).-1t appears that wheatceases to grow when the temperature falls below + 6" : a table showsthat the highest, yields have occurred i n those years with the highestt'otal temperatures (above + 6") namely: 2215" in 1868-69, and2318" in 1873-74.E. W. P.Cultivation of Swedish and German Cereals. By G. LIEBSCHER(Beid. Centr., 1884, 775--776).-Swedish seed is to be recommendedfor rough high lying land, but the yield of such seed is much inferiort o that of German origin, except perhaps in the case of oats.E. W. P.Comparison of Barleys of Different Countries. By L. MARX(Bled. C'entr., 1884,853-855).-1n order to decide the question as towhat country produced barley richest in proteid matter, the authoranalysed more than 400 samples from different countries and fromharvests of six years. He found the mean percentages of proteidmatter to be Russia 12.76, Baden 12.38, Sweden 11.97, llannbianprovinces 11.68, Brunswick 11.449, North Germany 11.21, Bavaria10.76, Alsace 10.70, Hungary 10.62, Prance 10.55, Hesse 10.43,Wiirtemburg 10.38, Denmark 10.91 (9.91 ?), England 9-69,, andAuHtria 9.61.Some of the Bussian barley yielded 16 per cent.of protei'd matter ;the maximum in Baden wag 15 per cent., the minimum 10.60 per cent.Bohemia and England gave few samples of over 10 per cent.; 68samples of Bavarian were examined, six of which were over 12 percent., the remainder under 10 per cent.Amongst French barleys, those of Auverpe were the lowest, thoseof Champagne and Burgundy being up to the average of Bavaria.The nitrogenous contents of Hungarian varied more than any other,some containing but 9 per cent., others 12 per cent.: as a rule thickhkinned grain is poorer in nitrogen than thin skinned, but notinvariably. The quantity of phosphates in barleys varies also withinwide limits, but bears no relation to the nitrogenous contents.Chemical analysis is, in the opinion of the author, the only means ofjudging grain, if the brewer requires regular fermentation and Boundyeast. J. F.Ensilage Experiments with Various Fodders. By RIRCHNERand others (Bied. Centr., 1884, 817--822).-Experiments made inEngland are first referred to. Several silos at Merton in Norfolkconstructed with cemented sides were filled with finely chopped coarsVEGETABLE PHYSIOLOGY AND AQRICULTURE. 423gram part cut in rain, part in unsettled weather, 1-2 lbs. of wlC, percwt. were added and the whole well trodden in.In one case, afterthree weeks, the mass had shrunk one-third in bulk, a wooden coveringwas then put on, then 8 or 9 inches of clay and on that heavy stones.After 3 to 5 months the fodder was found well preserved and waseaten readily by cattle, after removal of the topmost, and lowest layers.Similar results were obtained with lucerne, red clover, and rye-grass.0 ther experiments made in Kent were equally successful. Miles(Massachusetts) in the MiZk Gazette, recommends a method for keep-ing the fodder sweet, and preventing acidification. The bacteria whichare the acid ferment, are killed by a temperature of 50-60"; heproposes to obtain that temperature by slow filling of the trenches,when the temperature advances to 70"; quick filling and stampingdown will only give about 40".Baker is reported to have used oldpetroleum barrels as silos and kept fodder therein for a long time,without injury. Thomas, who reports on these experiments, thinksthere is nothing new in them, and that they teach nothing; heconsiders it is teaching a false doctrine t o say that green fodder canbe preserved unaltered ; heating more or less must take place, whichin a plant is a s i p of decay, and fermentation must invariably set in,attended with important loss of substance.Kirchner as a result of his experiments expresses an unfavournbleopinion of ensilage with green maize ; there was a loss of 35 per cent.in weight, of which about one-third was protein, and in 8 monthsthere was a loss of 41.2 per cent.of protein. In three experiments, infeeding milch cows with acid fodder, he found that the quantity ofmilk was increased, but the quality deteriorated, there was less fat,it had the taste of hutyric acid, and the butter made from it kept badlyand had a disagreeable flavour. Schultze studied the changes whichtook place in lupines, maize, and lucerne preserved in casks for threemonths, at the end of which time a very serious loss of nitrogenoussubstance had occurred. E. Kinch, in experiments with grassperceived a similar loss (Trans., 1884, 122) ; Liebscher made experi-ments with sliced beets in deep trenches lined with cement, andcovered some with heavy stones, some with soil ; in two of them1 kilo. of borax was mixed with the roots.In six trenches, the per-ceutage of weight lost was from 7 to 19 per cent., and the addition ofborax appeared to have an injurious effect.Loss of Weight in Ensilage of Beet-leaves. By M. MARCKER( B i d Centr., 1884, 815-816).-Two quantities of leaves were storedin pits in October, and taken out in March : the loss per cent. on onelot was 16.31, on theother 16.38, the analysis showed thatpart of theprotein had changed to amides, lowering the value as fodder.These experiments convince the author that acidification of greenfodder is a wasteful operation, only to be resorted to when othermethods of preservation are not possible, as is often the case wherelarge crops of beets are grown. J. F.By P. P.DEH~RAIN (Ann. Agrononzipues, 10, 369-539) .-The experiments ofJ.F.Cultivation of Sugar-beet at Grignon in 1884424 ABSTKAC,TY OF CHEMICAL PAPERS.1884, were undertaken with the especial object of ascertaining towhat extent certain improved strains or varieties of sugar-beet wouldwithstand the impoverishing effect (as regards percentage of sugar)of heavy doses of farmyard dung and other nitrogenous manures.The variety chosen was " Vilmorin's improved ') sugar-beet, withwhich the author had previously obtained excellent results as regardsyield. The weight of roots and leaves obtained on the different plots,and the percentage of sugar contained in the juice, are set forth in theannexed table :-Manure per hectare.30,000 kilos. farmyard mauure + 300 kilos.sodium nitrate..........................20,000 kilos. farmyard manure + 400 kilos.sodium nitrate.. ........................30,000 kilos. farmjard manure + 1500 kilos.lime .................................20,000 kilos. farmyard manure + 200 kilos.sodium nitrate + 200 kilos. potassium chlo-ride ..................................20,000 kilos. farmyard manure + 50U kilos.fiesh manure.. ..........................40,000 kilos. farmyard manure.. ............40,000 kilos. farmyard manure + 200 kilos.sodium nitrate.. ........................1000 kilos. flesh manure., ..................1000 kilos. flesh manure + 1500 kilos. lime.. .500 kilos. torrefied horn.. ..................1000 kilos. new leather, torrefied ............1000 kilos. old leather, torrefied.............800 kilos. azotine.. ........................1000 kilos. .. beet manure ..................Unmanured .............................. 1000 kilos. .. phosphoguano ................Roots,kilos.43,40036,00035,90038,00033,40035,50038,20033,20030,700s3,70034,90031,30034,20034,20033,60029,700Leaves,kilos.27,40020,5001 7,00020,00014,60013,70014,20014,70012,30013,10011,10016,50016,00013 90013,200-Sugar,per cent.of juice.--18 -117 -617 -418 *919 -418 -818 *O19 -217 -819.618 *719 -819 -420 -419 *919 -0Axotine is a soluble nitrogenous manure prepared by the action ofalkalis on woollen and cotton refuse.The most suitable manure appears to be farmyard manure in con-junction with Chili saltpetre; the results of the experiments ofprevious years lead also to this conclusion.The variations in thepercentage of sugar are so small that they cannot be attributed to theaction of the different manures ; on the other hand, the experimentssh9w that a suitably chosen seed will respond liberally to largedressings of manure without any deterioration in the quality of theroots. Analyses of roots taken a t random showed also that the largeroots were as rich in sugar as the small ones,Cultivation of Various Sugar-beets. By G. LIEBSCHER (Bied.Centr., 1884, 774--775).-When manured with 18 per cent. super-phosphate and Chili saltpetre, " Little Wanzlebcner " yielded best asJ. M. H. MVEGETABLE PHYSIOLOGY AND AGRICULTURE.42 5regards total weight of roots and sugar, though “ Vilmorin blanche ”gave thc highest coefficient of purity. A t an experimental station400 feet higher, the results as regards yield were the same, but therichest roots were produced from Stroebnitzer seeds.Sugar-beet Seed as Fodder for Cattle. By H. PET~LET (Bied.Centr., 1884, 755--756).-01d sugar beet seed is recommended as avaluable substitute for linseed cake ; by its use, cattle will increase atthe rate of 1.57 kilo. daily.E. W. P.E. W. P.Adulteration of Linseed Cake and Rape Cake. By G.KLETN (Bied. Centr., 1884, 788).-Chaff and water are now beinglargely added to linseed cakes. I n rape cake, the unground seeds ofSetaria viridis and other plants have been found, all of which arealmost absolutely indigestible.Composition of the Seeds of the Cotton Tree.By SACC(Compt. rend., 99, 1160--1161).-The seeds of the cotton tree culti-vated in Bolivia have the following composition :-Case’in 6.00 ; dextrin0.20 ; sugar 2.0 ; fibrin 23-70 ; lignose 32.40 ; starch 9.60 ; oil 9.60 ; wax0.80 ; ash 8-00 ; water 8.00 = 100. They yield when gronnd, yellowflour 56.50 ; black bran 40.50 ; loss 3.00 = 100. It is evident thatthese seeds may constitute a very valuable food. A solution of theseeds may be used for removing tbe excess of lime employed in sugarrefining, the lime being precipitated in the form of an insolublecaseate.E. W. P.The aqueous solution also forms an agreeable orgeat.C. H. B.Analyses of Cotton Seeds. By P.K~NIG (Bied. Cent?.., 1884,791).American.per cent.Water. ................ 9.24Albumino’ids ........... 16.88Fat ................... 14.86Non - nitrogenous extrac-tive ................. 28.12Fibre.. ................ 27.60Ash .................. 4.30Egyptian.r----- 7Natural. Freed from cotton.per cent. per cent.10.78 11.4219-50 19.9424.76 25.5420.63 20-082G1.13 18-954.18 4-29E. W. P.Fairy Rings. By F. v. T H ~ M E N (Bied. Centr., 1884, 792).-The,qerings are produced by the growth of mycelium. which contains muchnitrogen, so that the grass receives much valuable manure. At thesame time this fungus exerts a baneful influence on the grass root8s,consequently discolored grass is frequently to be found within thering. E.W. P.Variations in Rainfall. By W. RRFMSER (Bied. Gentr., 1884,793-i94).--The author has had the opportunity o€ collating theresults of an extended series of observations made under the auspice426 ABSTRACTS OF CHEMICAL PAPERS,of the Italian Meteorological Institute at 15 Italian and 24 Germanstations, with a less number of those in other countries. He statesthat the variations in the amount of rainfall increase as the equator isapproached, and that regions lying under the shadow of mountaini'anges are more subject to alterations than plains in the same latitude.The mountains arrest the rain clouds, but the distances of thoseclouds from the earth of course affects the results. In plains, the fallis more regular.The variations are greater in cold seasons of theyear than in the warm months.Micro-organisms in Soil. By E. WOLLNY (Bied. Centr., 18M,796-814) .--The changes, physical and chemical, which take placein earth containing humus, or the orgariic remains from which it isformed, are of great interest, and have important bearings on thefertility of the soil. In well-worked porous and asrated ground, theclecomposition of organic matter under favourable conditions liberatescarbonic anhydride, water, ammonia, and a little free nitrogen, someof which combine with the inorganic substances necesssry for thegrowth of the plant. The process of decomposition is generally con-sidered as one of oxidation, and Schlosing, Muntz, and Waringtonyegard it as due t o the action of lower organisms. In well acratedsoils, little ammonia is formed; it is quickly oxidised to nitric acid ;but when the nitrifying organism is destroyed by treatment withchloroform, carbon bisulphide, or by means of heat, the ammoniaprevails, and the nitrites and nitrates are reduced.Schlosing andMiintz produced nitrification in sterilised solutions by the addition ofa mere trace of earth ; they found in the fluid small filiform bodies,from which pure cultures were obtained. This they consider to be thenitric ferment; it is widely diffused, and finds its most favourablehabitat in arable soils; it is also found in sewage water, and Iessfrequently in flowing water ; it does not appear to exist in the air, atleast it has not been obtained from that source.It is easy to understand the great influence exercised by conditionsof moisture, heat, and light on the activity and multiplication of theseorganisms.Schlosing proved in 1873 that nitrification depends onthe free access of oxygen; when the supply is restricted, nitrificationceases, and when it is withheld altogether, the nitrates alreadyformed are reduced. Moisture is also an important factor ; even atordinary temperatures dryness is hurtful to the ferment, and earth inwhich the process is in full activity is rendered perfectly sterile bybeing dried. It is not surprising that heat should greatly influencethe growth of the ferment ; at 5 O the process proceeds slowly ; at 12'i t is clearly visible; at 37" it reaches its maximum, and at, 55" i tceases.Waringtoii's experiments (Trans., 1878, 44) have shown thegreat influence of light, the organisms prospering best in darkness.The oxidation of the carbon of organic matter is caused in a similarway by organisms, and under conditions very similar to those of nitri-fication. The author has established that treatment with chloroformTapour, the addition of antiseptics such as carbolic and boric acids, o rfhymol, or heating to 130", very materially retards the production ofcarbonic anhydride. The same factors which promote nitrifkationJ. FVEGETABLE PHYSIOLOGY AND AGRICULTURE. 427influence this process ; the production of carbonic anhydride proceeds a tthe same time as nitrification, but is independent of atmospheric oxygen,deriving what is required from the soil.This appears to support theopinion that the air contained in well tilled soil is frequently changed.I t is well known that organic Rubstances used as manures decomposemore rapidly in well asrated earth, sandy or gravelly, than in close,loamy, or argillaceous soil. Warmth greatly inff uences the activity ofproduction ; the most favourable temperature is 50" to 60°, but even a t0" the process goes on slowly. Moisture is in this case as necessary asin that of nitrification ; soil containing 4 per cent. of water was foundby Fodor to yield 16 times as much carbonic anhydride as the samesoil with only 2 per cent. ; too much moisture arrests the process bydiminishing the quantity of available oxygen present.The reductionof the nitrates already formed must be considered also as a physio-logical process, dependent on the presence of organisms which do notrequire oxygen (Pasteur's anaerobes). Deprived of air, the organicmatters yield small quantities of carbonic anhydride, water, ammonia,free nitrogen, and a carbonaceous, black, turf-like mass, an acidhumus, difficult of decomposition. Recently, a ferment has beendiscovered in arable soil which is ,capable of inducing alcoholic fey-mentation. The enormous numbers of micro-organisms in soils maybe guessed from observations made a t the Observatory of Montsouris,where one gram of earth was computed to contain 750,000, and a tGennevilliers, 870,000 to 900,000 spores.As the influence of heat, moisture, &c., does not always tend in thesame direction, the author believes that the decomposition of orga tiicmatter is governed chiefly by that factor, of which a minimum ispresent.The physical conditions of soils have a very great influenceon decomposition, namely, permeability to air, the capacity to retainmoisture, and in great measure the state of the subsoil. The powerof absorbing and retaining the sun's heat is different in various soils ;a dark-coloured soil is warm during the day, and parts quickly withits heat at night. This variation can, however, he fully neucralisedby judicious admixture of humous substances.The effects of vegetatjion and of spreading manures, straw, &c., onthe surface are very important ; ground when protected by vegetationis warmer than when fallow, and variations of temperature are less ;when covered with a thin layer of straw, &c., it is a medium betweennaked and vegetation-covered soil ; if the layer is too thick, it becomescolder.I n speaking of the effects of the constant culture of food plants,the author comes to the conclusion that soils which are tilled yearafter year become poorer, no matter how richly they may be manured,and that they commence to recover their fertility when laid down ingrass for either meadow or pasture. This property of enrichment ofthe soil belongs also to leguminous plants, but it is not because, asmany assert, that these plants have the power of obtaining nit-rogenfrom the atmosphere, but is due altogether to the methods of culture.The chemical composition of soils has an important, bearing on thedecomposition of organic matter ; the presence of lime facilitates itgreatly; the contents in humus is also a factor; the production ofcarbonic anhydride does not proceed always a t as rapid a rate as a428 ABSTRACTS O F CHEMICAL PAPERS.first, and too great a quantity may hinder the activity ot' the micro-organisms.The author considers the subject one for further experi-ment, but is of opinion that no doubt should exist that all changes inthe humous matters contained in arable earths are due to micro-organisms, and that their activity is governed b7 the factor which ispresent in a minimum, and is dependent on it balance of variousimportant influences.J. F.Germination is Soil rich in Organic Matter, but free fromMicrobes. By E. DUCLAUX (Compt. rend., 100, 66-68) .-Haicotbeans and peas were sown in soil which had been previously sterilised,and then moistened with st,erilised milk, care being taken that nomicrobes were introduced along with the seeds. Under these con-ditions the seeds germinated, but after two months the milk hadundergone no alteration, and the plant when dried weighed less thanthe original seed, and in appearance resembled the plants produced byt h e germination of seeds in distilled water. The author has previouslyshown that casejin only becomes amimilable by living organisms underthe simultaneous or successive action of two diastases, rennet andcasease.It would seem, therefore, that the seeds in germinating donot secrete and diffuse through the surrounding soil either of thesediastases. Precisely similar results were obtained with soil containingsaccharose, and with soil containing starch-paste. Tho cotyledonu,therefore, secrete neither sucrase nor amylase.These results show that a seed germinating in a soil rich in organicmatter is nnable of itself to assimilate the organic matter, and isdependent on the action of microbes which convert the organicmatter into assimilable forms, and thus place it a t the disposal of theplant.Tbe fact that a germinating seed cannot assimilate starch from thesurrounding soil, seems at first sight opposed to the fact that therescrve store of starch in the seed itself is need up during thegermination of the seed and growth of the young plant.For a plantto secrete diastase in the interior of its own tissues is, however, avery differect thing to diffusing it into the surrounding soil.C. H. B.Solution of Wool-dust. By MARCKER (Bied. Centr., 1884, 785.-For every centner of wool-waste, 5-7 kilos. calcium oxide is to beslaked and mixed with the wool, thoroughly moistened with waterand mixed so a s to remove all f a t ; the heaps, 6 inches high, are to beleft covered with earth for two to three months, but they must bekept moist. Sul-phuric acid may also be used; it is more expensive, but there is thenno loss of ammonia. The mixture of wool and 50" acid is made inleaden troughs, and regularly stirred until the mass becomes thickand unworkable.E. W. P.After this time an excellent compost is formed.Peat as Manure. By SCHREINER ( B i d Cemtr., 784).-Oats weresown in boxes filled with sand, to which had been added variousmineral manures, and in some cases 5 per cent, of peat. Tbe bestcrops were obtained from minerals (no details given) and ammoniuVEGETABLE PHYSIOLOGY AND AGRICULTURE. 429sulphate and peat' ; the same results were obtained when barley, rye,Straw, Peat, and Sawdust as Litter. By H. SAGNIER (Bid.CetLtr., 1884, 783).-These three materials were employed by theParis Omnibus Company as lit,ter, and there was produced of strawmannre 25 kilos., of peat 10-11, of' sawdust 12-13 kilos. per horsedaily, and they contained 0.51, 0.68, and 0.45-0*49 per cent. N respec-tively.After use on the land as manure for two successive crops, itwas found t8hat the sawdust and peat were equally good, and both ofthem better than straw.beans, &c., were grown. E. w. P.E. W. P.Manuring Experiments with Precipitated Phosphate. ByL~~BBECKE ( B i e d . C'entr., 1884, 735).-The crops were barley afterbeet, oats after potatoes ; and the mannres Chili saltpetre, saltpetrewith superphospha,te, and with precipitated phosphate. Results : thenitrate increased the crops, and the addition of superphosphate wasof no advantage, but precipitated phosphate was a gain; the landwhere the barley was sown was clayey loam, whilst the oats grew onchalky humous soil.Sidney Guano. By M~RCKER (Bied. Cantr., 1884, 785).-This isa new guano from Sidney Island resembling Baker Island guano, andproduces 18.8 per cent. soluble phosphat'e. Gilbert's analysis is asfollows:-Water 7.38, CO, 2.64, SO, 1.63, P,05 34.41, CaO 42.96,MgO 2.03, Na,O 0.76, C1 0.87, F1 0.40, organic matter 7.29 (N=0*28).E. W. P.E. W. 3.Manuring Sugar-beet. By G. LIEBSCHER (Bied. CPntr., 1884,737-745).-1t was arranged that phosphoric acid should be triedagainst nitrogen (equal quantities of Chili saltpetre and ammoniumsulphate) and against farmyard manure in various proportions, andwell mixed v i t h one another. During growth, those plants were thestrongest which were manured with nitrogen and farmyard manure,phosphates having b u t little influence by reason of the drought. Theheaviest crop both of roots and sugar was produced by the use of 800centners farmyard manure, mixed with 72 kilos. per hectare of phos-phoric acid i n the form of 18 per cent. superphosphate. This sameresult was obtained when equal parts of nitrogen and phosphate wereused. The author then discusses the quantities of each manure whichare most heneficial from a financial point of view on his land, as wellas the value of' farmyard manure under the same circumstances.E. W. P.Parallel Experiments on Peat Compost and Chili Saltpetreas Manures for Sugar-beet. By L. KUKTZE (BieJ. Cenfr., l%4, 745--747).-The compost which is obtained by soaking up the wasteliquids from the sugar manufactory with peat contains 2.5-3.3 percent. N, and 11-5-14 per cent. K20, and it is in a good salepbleform. This compost was compared with saltpetre as a manure, bothbeing aided by guano or superphosphate. Taking the average of theVOL. XLVIII. 2 430 ABSTRACTS O F CHEMICAL PAPERS.plots, the peat compost was the best both as regards total yield and“ quotient of purity.” Several varieties of roots were sown, but allwith a similar result. E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8854800416

出版商:RSC    

年代:1885

数据来源: RSC