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VEGETABLE PHYSIOLOGY AND AORICULTURE. 20 1 Chemistry of Vegetable Physiology and Agriculture, Physiology of Yeast and the Importance of Selected and Pure Cultures for Wine Fermentation. By HERMXNN MULLER (Bied. Cefztr., 1895, 24, 695-698 ; from Jahyesber. deut. schweiz. Versuchs. Stat. Wudensweil, 1894, 3, 73).-A comparison of the number of yeasts and fungi (given in millions per hundred grapes) on healthy and burst grapes shows an enormous increase in the latter, especially in the number of yeast-like fungi, as compared with that of wine yeast. The relation of wine yeasts to others is most favourable in dry autumns, and high-hanging grapes are bcttcr in this respect than those near the ground. The diffei~ent wine yeasts vary very much in activity. Rapid production of violent fermentation forms the best means of suppressing injurious fungi and bacteria, both by quickly utilising the oxygen present in the liquid and replacing the air by carbonic anhydride, and also by the poisonous action of carbonic anhjdride on many fungi.Too violent fermentation may be dis- advantageous, by causing frothing over, and especially by producing too high a temperatnre. Frothiiig is produced by the yeast rising to the surface and by the separation of fine particles from the liquid, which subsequently float and form a thin layer. A number of jeasta from Farimis mine districts were examined as regards their power of fermenting sugar. The bouquet of wines is produced by fermentation from substances i n the gi’apt? juice which possess no odour. Apart from the bouquet, the yeasts produce tastes and odonrs peculiar to themselves (just as202 ABSTRACTS OF OHEMICAL PAPERS.Peiticillizcm causes the characteris tic mouldy odour) , which, of course, alter the bouquet more or less. I n cultivating the jeakts, fresh, sterilised grainmust is most s u i t - able, currant, apple, and pear must are less, and artificial solutions still less suitable. Addition of ammonium chloride iucreases the pro- duc tion. By means of pure cultivations of yeast, the process of wine-making is shortened, the taste and odour are decidedly purer and free from faults ; the wine will also keep better. Cider, so made, has a greater resemblance to wine from grapes. The general employment of pure cultivations is only a matter of time. N. H.J. M. The Sugar that forms in the Auto-digestion of Yeast. By ERKST L. SALKOWSKI ( Z e i t . Biol., 1895, 32, 468--472).-M. Cremer suggests that the sugar which the present author previously described as formed on the auto-digestion of yeast, and a s being hvorotatory, does not exist, but that peptone accounts for the rotation. Renewed experiments show that no peptone or proteose is present, and that the leucine found will only account for a small part, of the rotation. The identification of the sugar is not, however, yet effected. W. D. H. Measurement of the Reducing Power of Pure Yeasts. By NASTUKOFF (Conzpt. rend., l895,121,535--536).-The author measures the reducing power of yeasts by the degree of blackening produced in a 10 per cent. solution of cane sugar, to which has been added 5 grams per litre of Gastine’s saline mixture (Compt.rend., 1889, 109, 479), the calciam sulphate heing replaced by magnesium sul- pliate and some basic bismuth nitrate being added. The same race of yeast gives practically constant results, but different races show diflerent reducing powers. Comparison of the degree of darkening with the quantity of alcohol produced, or of carbonic anhydride eyolved, shows that these two forms of protoplasmic activity have no direct connection. The liquid containing the bismuth may be placed in R tube im- mersed in a liquid containing no bismuth, but otherwise similar in composition, the two being separahed by goldbeater’s skin and mixing only by diffusion. Instead of measuring the darkeniug of the bismuth solution, advantage may be taken of the fact that the sulphide gives a yellow tint with the nitrites that are formed simultaneously, thab this coloration is not affected by boiling, and that its intensity can be measured.The five yeasts examined, showed reducing powers in the following order, the most powerful redncer being placed first : (1) wine yeast from Champagne ; (2) wine yeast from Portugal ; (3) Saccharomyces pasto.r.ianus ; (4) Saccharomyces apicdittus ; ( 5 ) bear yeast from Brussels. C. H. B. Fermentation of Cellulose. By V. OmmxsKI (Compt. rend., 1895, 121, 653-655) .--BaciLZus nmyZobactey, which has hitherto be( n regarded as the special ferment of cellulose, is really a collectiveVEGETABLE PHYSIOLOUY AND AGRICULTURE. 203 species? including a large number of different butyric ferments.None of these has, so far, shown any mayked power of decomposing pure cellulose. The special microbe of cellulose fermentation can be isolated by the method of elective cultures. Swedish filter paper and chalk arc placed in a solution of potassium phosphate, magnesium sulphate, and ammonium sulphate, with a trace of ooze of the N6va. The flasks are hermetically closed and kept a t 30-35' ; ferrnentatio!i is somewhat rapid, and the paper becomes yellowish, transparent, 2nd gelatinous, and finally dissolves, some of the chalk dissolving a t the same time. The ferment i s found on the paper, and cot in the liquid ; it is very thin, 6 to 7 p long, and 0.2--0*3 p broad, and forms very round SporeE, 1 p in diameter. Further cultivations on potato arc necessary, in order t o obtain the bacillus quite pure.Ethylic Alcohol from the Fermentation of Asphodelus ramosus and Scilla maritima. By G. RIVI~RE and BA[LHACHIq: (Compt. Tend., 1895,121, 659-662).-l'he tuberous roots of AsphodeZ1c.y ~amosw, which grows abundantly in the wild state in Algeria, were cut up and extracted with warm water by diffusion. The solution was boiled, allowed to cool, mixed with 2 percent. oE lime, allowed to remain for 48 hours, filtered, and the excess of calcium precipitated with sulphuric acid; after removal of the calcium sulphate, the " solution '' was limpid, arid slightly amber coloured. The exhausted cossettes were pulped, mixed with 2 per cent,. of sulphuric acid, boiled in order to completely saccharify the starches, filtered, mixed wit11 lime in quantity sufficient to leave an excess of 2 per cent., and allowed to remain for 48 hours.It was then filtered, neutralised with sulph- iiric acid, and, after separation of the calcium sulphate, mixed with the solution obtained in the first stage. The mixed solutions were sterilised by successive ebullitions with two days' interval, cooled, and mixed with pure yeast from the white wine of Burgundy. Fermentation begins almost immediately, and is complete in four or five days, distillation yielding a liquid with an alcoholic strength of 50' to 55'. The alcohol has the agreeable bouquet due to the yeast, and is free from the disagreeable odour t h a t has hitherto characterised alcohol from the asphodel. SciZEa maritinza, which also grows abundantly in the wild state in Algeria, when treated in a similar manner, yields an alcohol resembling wine brandy, and with the bouquet characteristic of the particular yeast.The alcohol from SciEEa has a flavour somewhat inferior to that of the alcohol from AsphodeZfcs, and contains a higher proportion of aldehyde. Both, however, are free from furfuraldehyde, and contain only slight traces of higher alcohols. Assimilation of Elementary Nitrogen by Plants. By JULIL-s STOKLASA (Landw. Johrb., 1895,24,827--863).-The results of obser- vations made with lupins (Lupinus angustifolius) grown in a field, indicated that the plants without nodules grew as well as those with nodules. The soil was a poor, loamy sand (nitrogen =. 0.023 per cent.).The total nitrogen of both plants was practically the same, but (at C. H. B. C. H. B.204 ABSTRACTS OF OHEXIClAL PAPERS. Dry pro- duce (lo plants)* the flowering period) was differently distributed. I n the plants without nodules, there was more nitrogen in the stems and leaves ; in those with nodules, the root,s were richer in nitrogen than the roots withont nodules. The average weight of the nodules was 0.74 gram when fresh, 0.117 gram when dry, and the dry matter contained 4.5 per cent. of nitrogen. Four series of pot experiments were made, iu which lnpins were grown : (1) in ignited sand, maintained in a state of sterilisation ; (2) in the same sand, with the addition of a few grams of lupin soil; (3) in sandy soil (N = 0.0065 per cent.) ; and (4) in the sandy soil, microbe seeded with lupin soil.There were 12 or 16 pots (each with one plant) in each series, but in the following table the results of 10 pots are taken together in each case. The nitrogen supplied includes in each case (I) the nitrogen of the 10 seeds sown (0.069 gram), (2) nitrogen as ammonia (0.099 pram), and as nitrates (0.100 gram), supposed to have been possibly absorbed from the air, and ( 3 ) the nitrogen of the lupin soil added (= 0.152 gram) to the 10 pots. Nitrogen. Supplied. 1 In produce. 1 Gain. 1. Ignited sand stcrdised.. . . 2. ,, ,, inoculated .. 3. Sandy soil not sterilised . . 4. ,, ,, inoculated.. . . 27'86 64 *85 66 -40 63 *85 0.265 0.459 0.191 0 '420 1.995 1.575 0 -268 2-394 2.126 0 -420 2.510 2*000 In series (1) there was thus some fixation under conditions of sterilisation, and without nodule formation, that is, without sjm- biosis, whilst in series (2), in which well formed.iiodules were pro- duced, fixation w~ much increased.I n series ( 3 ) the surface of the soil was covered with a l p ; incompletely dereloped nodules were found on the roots of four plants ;' but in the above table only plants free from nodules are included. I n series (4), in which a number of well formed nodules were produced, there was rather less fixation than in series (3). As regards the nitrogen of the sandy soil of series ( 3 ) and (4). the percentage increased from 04065 a t the commencement to Of)OY8 in series (3), and 0.0104 in series (4) at the conclusion, whilst the total soil nitrogen in each pot (14 kilos. of sand) rose from 0.91 gram to 1.372 and 1.456 gram respectively ; there was thus a gain of nitrogen due t o the bacteria and a l p .The results show that under conditions of sterilisation, nitrogen assimilation is very feeble, whilst soil inoculation increases it eight fold. I n non-sterilised soil, in which a l p and bacteria increase the nitrogen required for tho urst development of the plants, lupins without nodules assimilate nitrogen to the same extent as lupins with nodules. An examinat+ of the nodules of Lupiniis luteus showed that they contained no ammonia, and only traces of nitric acid, the latter dis-VEGETABLE PHYSIOLOQY AND AGRICULTURE. 205 period. 1 .... 2 .... 3 .... Nitrogen in nodules. Nitrogen in roots. Total. As prote'ids. As amides.As aspnragine. --- ----------- 1-64, 5 -22 3 -99 0 -35 0 -34 1'84 2 -61 1-42 1 -73 1.54 0.15 traces - - - The pure ash of the roots (4.55 per cent.), and the nodules (6.32 per cent.) had the percentage composition. K20. h'a20. CaO. MgO. Fe20,. PzO,. SOB. SiO.,. Roots.. 14.52 26-88 16.87 11.73 1.08 9.82 15.84 3.59 Nodules 20.86 2274 10.71 12.35 1.19 14.94 12.25 3-01 In order to ascertain whether the absence of light bas any effect on t h e nodules as well as on the leaves, a number of well-developed, flowering lupin plants were kept in the dark for 13 days ; by this time the plants had become yellow, and were taken u p along with similar plants, kept under ordinary conditions, and examined. The results are given in percentages of the dry substances of (1) leaves and nodules of normal plants, and (2) of the plants kept in the dark.Asysra- gine. Lecithin. Asparu- gine. Total. Protei'n. ------------ - I 1 .. 3-29 2.87 2 .. 3.47 1.80 I Nodules. I Learcs. Nitrogen. 1 I I Nitrogen. I 0.49 1-24 4-99 3-96 1.37 4-19 0.63 13-11 1 1'47 4-98 Lecitliiii. 1 -12 0 *53 The average weight of the single nodules was (1) 0.1184, (2) 0.0806 gram. The wsults of these experiments confirm the view gerierally held regarding the production of asparagirie in plants in absence of light, not only in the IeaTes b u t also in the root nodules ; they also show that in the nodules t h e living plasma wiih the bacteria does not support independent processes of nitrogen assimilation. The following amounts of oxalic acid and hexoses (reckoned as glucose) were found in the dry nodules.206 Dry produce.3.04 20.43 41 -24 58.56 ABSTRAOTS OF CHEMIOAL PAPERS. Eitrogen. i I In seeds I n produce. Gain. sown. ---- ----- ,-- 0.0176 - 0'0712 0 *0536 0.0190 - 0.603 0.5840 O'OOi6 1'258 0.5504 0.0076 '.' 0 -7 1.816 1'1084 Oxnlic acid. Hesoses. Nodules of tEe normal plants , . . . . 2.06 6.33 ,, of the plants kept dark.. . 1.06 5.89 It is concluded that assimilation takes place in the leaves, and that the amides migrate from the leaves to the root nodules, where they interact with glucose to produce proteids, these forming the nutritive medium f o r bacteria. Experiments were made on nitrogen fixation by a non-leguminous plant-buckwheat. The plants were grown in iron vessels holding 14 kilograms each; five seeds were sown in each pot.There were four series, each comprising eight ( o r four) pots, as follows:-(1) lgnited sand, with minerals ; (2) sandy soil (N = 0*0065 per cent.), not sterilised ; ( 3 and 4) same as (1) and (2) respectively, with addition of ammonium nitrate (0.5 gram to each pot). The following results were obtained. 1 L..... 2 ...... 3 ...... 4 ...... 37 4.0 16 16 The average gairf of nitrogen i n these, and a number of similar ex- periments made from 11390 to 1994, was (1) 0.138, (2) 1.378, (3) 3,385, and (4) 6.09 grams for 100 plauts. The gain in the soil itself was in series (2) from 0.0065 to 0.020 ; series (4) to 0.039 per cent. There was about the same gain in similar soil kept without vegetation. I n series (1) and (3), a trace of nitrogen was found in the sand a t t h e end of the experiment. The results obtained with series (1) indicate a gain of nitrogen under conditions of stcrilisation, but in such small quantity that it may have been derived from the combined nitrogen of the air.In series (2), the results obtained with the plants and with soils free from vegeta- ticn show that the plants must have fixed free nitrogen. In sterilised sandy soil, series (3), with ammonium nitrate, the assimi- lation was greatly increased, whilst in series (4) there was over forty times as much nitrogen assimilated (by the plants) as in steri- lised sand. Further experiments were made i n which buckwheat was grown in theignited sand, to which sterilised horn meal was added (so as t o make the percentage of nitrogen correspond with that of the soil) as well as 0.5 gram of ammonium nitrate.The gain of nitrogen in the plants was practically the same as that already obtained in series (3). It is, therefore, seen that in sterilised soil containing an excess ofVEGETABLE PHYSIOLOGY AND AGRIOULTURE. 201 nitrogenous food, the plant never derelops a s well as in non sterilised soil, in presence of alg2e and bacteria. It is concluded that nitrogen fixation by buckwheat increases with the development of the leaves and roots ; that i n sterilised soil and without combined nitrogen there will be no corsiderable fixation ; that in preseiice of nitrates in excess, if under conditions of sterilisa- tion, nitrogen assimilatioii never reaches the maximum, as compared with plants grown in non-sterilised soils, and that Hellriegel’s theory of nitrogen fixation by Leguminosae alone in symbiosis is wrong.Whilst agreeing with Frank, that free nitrogen is assimilated by the living protoplasma of the cells of green leaves and roots, the authoi. niaintains that the bacteria of the soil play a very essential part in the process. The Mineral Food of Lower Fungi. By HANS MOLISCH (Bied. Centr., 1895,24,635 ; from Bot. Centr., 1894,167). -Iron is necessary for fungi, and cannot be replaced by manganese, cobalt, or nickel. In opposition to Nageli, it is stated that magnesium is indispensable, and cannot be replaced by metals of the alkaline earths or of the zinc group (Zn, Be, Cd), cadmium being poisonous even in very dilute solutions. Caicium is not necessary for the lower fungi (or, as has recently been shown, for alg~e) ; this is the one remarkable difference as regards the requirements of fungi as compared with the higher plants ; the other nine elements (C, H, 0, N, S, P, I(, Mg, Fe) being cqually necessary for both.Physiological Studies on Hops. By J. BEHREKS (Bied. C’entv., 1895,24,635; from Bot. Cenfy., l894,178).-The rhizome differs from the above-ground sprouts in colour, absence of leaves, and also in being much thicker, its fleshy consistence indicating its character as reservoir. It is produced only by external influences. The percentage composition of the dry rhizome branches (free from sand), cut in the spring, is as follows. N. H. J. 11. N. H. J. H. Directly lnvert Non-protei’n reducing sugar Ether K.Protei’ds. (as asparagine). sugar. (as cane). extract. Ash. 3.46 14.28 5.5 7 9.62 8.58 2.08 7.08 N. H. J. M. Formation of Indigo in Plants of the Order Indigofera. By C’. J. VAN LOOKEREN and P. J. VAN DER VEEN (Landw. Versuchs-Xtat., 1895, 46, 249-258 ; compare Abstr., 1895, i, 96).-The extract of the leaves of the indigofera shows an alkaline reaction with litmus and with rosolic acid, an acid reaction with phenolphthaleh. When the leaves are “ fermented ” with dilute (0.5 to 1 per cent.) acids, solutions are obtained which yield indigo under the influence of atmospheric oxygen and behave similarly to the solutions obtained by reducing cjrdinary indigo, precipitating with dilute acid, extracting with chloroform, and taking up the residue with water. Such a solution cannot bc obtained from pure indigotin.Indigotin-white, together with jndirubin-white, and other products formed from indican under the influence of enzymes in absence of air,2@8 ABSTRACTS OF CHEMICAL PAPERS. behave differently, as regards solubility in water and chloroform and in the readiness with which they are oxidised, from indigo-white, either in t,he pure state or mixed with indifferent substances. Indigo-blue containing so-called " indigo-brown " is slightly soluble in preseiice of free alkali, whilst if indigo-red is present it is also soluble in alcohol ; this explains why acid extracts contain indigo-white in solution. N. H. J. M. Occurrence of Carotene. By SCHROTTER-KRISTELLI (Bied. Centr., 1895, 24, 709-710; from Bot. Centr., 1895, 61, 33).-The yellow dye was found dissolved in oil, i n the outer cell layers of the seed covering of Afzelia Cuanzensis.The Fellow,. yellowish-red, and vermilion dyes, known under various names, which occur in plants and animals, mostly belong to a homoIogous series for which the mme Zipoxanthin series is proposed. The dyes are always united to fatty substances, are insoluble in water, are not fluorescent, give a blue colour when treated with sulphuric acid, absorb the violet rays of the spectrum, and are readily decomposed by light and heat,. I n plants, an entirely different grdup of yellow dyes occurs. These are dissolved in the sap, and give a red or brown colour with sulph- uric acid. The lipoxanthin colours are terpene-like substances, which absorb oxygen without being destroyed as long as the protoplasm has sufficient vigour.It is probable that by continued reducing action, cholesterol yields yellow, and finally green, colouring matters (chlorophyll) ; whilst, by oxidation, chlorophyll would yield yellow dyes, and finally cholesterol. X. H. J. If. The Nitrogenous Constituents of Young Green Plants of Vicia Sativa. By ERNST SCHULZE (Landw. Versuchs.-Stat., 1895,46, 383-397) .-In the course of an investigation on the composition of etiolated seedlings of the vetch, Vicia satica, as compared with normal green plants, Prianischnikow (Abstr., 1895, ii, 12b) identified aspara- gine with certainty, whilst the other compounds were not obtained in sufficient quantity for separation. The author has now succeeded in identifying leucin in six-weeks old plants.Amidovaleric acid and phenylalanin, which occur along with leucine in etiolated seedlings, could not be detected in the green plants. As regards organic bases, both betaine and cholinc were separated, whilst the results of both the author's and Prianischnikow's experiments make it probable that guanidine is present in small amount. I n nine-weeks old plants, asparagine and xanthine substances (nuclein bases) were found, but not vernin ; betaine and a very small quantity of a base which seemed to be choline were also found. Betaine seems not to belong to those constituents of seeds which are consumed during germination. Choline occiirs in etoliated plants in greater amount than in the ungerminated seeds, and is probably produced in the decomposition of lecithin in absence of light.Guanidine is doubtless present in much smaller quantity in green than in etiolated plants. N. H. J. M,VEGETABLE PEYSIOLOQY AND AGRICULTURE. 209 The Seeds of Nephelium Lappaceum and the Fats con- tained therein. By MAX BACZEWSKI (Moitatsh., 1895, 16, 866-880). -The percentage composition of the ground seed of Nephelium lappacezm is as follows. Water, 5.87; fat, soluble in ether and petroleum, 35.07 ; ether extractive matter, insoluble in petroleum, 3.00; ash, 1.95; albumin, 8.89; crude fibre, 6.90; starch, 25.63; sugar, 1-25. The fats consist of the triglycerides of arachic and oleic acids, together with a very small quantity of the triglyceride of stearic acid. G. T. M. Chemical Composition of Capsicum. By BELA VON BITT~ (Laizdw.Versuchs-Stut., 1895, 46, 309-327 ; compare Abstr., 1893, ii, 546).-The oil extracted by ether from the seeds of capsicum becomes green when kept in a vacuum over sulphnric acid. Its sp. gr. = 0.91095 a t 15” ; iodine number, 119.5 ; Kottsdorfer number = 187.2. The mean of two determinations of free fatty acids (mainly palmitic, with some stearic and ole’ic acids) in the oil was 2.75 per cent., or 0.64 and 0.70 per cent. in the fresh arid dried seeds respectively. Tbe glycerides cal- culated as olein (which was the chief constituent) amounted t o 24.06 per cent. in the dry seeds. When the oil is long exposed t o air, an intense green colonr is produced owing to the presence of a small quantity of chlorophyll. In separating the frea fatty acids from the glycerides by extracting once or twice with light petroieum, it mas noticed that the acids had il sharp, burning taste, due to the presence of an active substance which was separated in small quantity.This forms white crystals, very readily soluble in chloroform and ether, rather soluble in light petroleum, sparingly soluble in absolute alcohol, and insoluble in water. It has an acid reaction, dissolves in alkaline solutions, but is precipitated by carbonic anhydride. It has an extremely burning taste, and when heated, gives off vaponrs which violently attack the mucous membrane. The average amount of lecithin in the dried seeds was found to be 1.82 per cent., when determined directly by Schulze and Steiger’s method. Fresh analyses of the seeds were made, as before, by Henneberg’s method, but the results do not differ much from those previously ob- tained (Zoc.cit.), except in the case of the nitrogeen-free extract (29.64) and the crude fibre (21.23 per cent. on dry matter). The crude fibre was redetermined by Schiilze’s method (Landzu. Versuchs.-Stat., 39, 283) ; the average result was 30.50 per cent. The nitrogen-free extract then amounts to 20.19 per cent., consisting in part only of carbo- hydrates. There seems to be only a trace of a true carbohydrate (either dextrose or a substance which, when hydrolysed, gives dextrose) ; pentoses are present. in greater amount, whilst galactose, mannose, starch, and cane sugar, &c., could not be detected. By means of 1.5 per cent. aqueous potash, a new carbohydrate, termed capsicum seed mucilage, was extracted from the seeds.It is insoluble in water, merely swelling. With iodine, a green coloration is produced which rapidly becomes blue, Zinc chloride and potassium It contains C = 76.35, H = 11.35 per cent.210 ABSTRACTS OF CHEMICAL PAPERS. iodide give no reaction. After boiling with acids, it readily reduces Febling.’~ solutioii. It contains pentose a r d probably galactose groups. New analyses of tlie placenta are given, and also the averages OE these and the earlier results (Zoc. cit.). The pure ash of the placenta has the following percentage composition. K,O. Nn20. CaO. MgO. Fe,O,. P,O+ SO,. SiO.,. C1. 66.06 4.44 4.70 3.97 0.88 8.75 8.32 3.72 t S 9 Alumina and manganese were found in traces in the ash. R. H.J. 11. Constituents of the Tissues of Fungi. By ERNST WINTERSTEIN (Zeit. ph?/sioZ. Chcm., 1895, 21, 134-151 ; compare Abstr., 1894, ii, 425 ; 1895, i, 80, 199, 323, and 493 ; also Gilson, Abstr., 1895, i, 323, ii, 323 and 408).-This paper is mainly a r&szsmc‘ of work published elsewhere. J. J. S. Constituents of the Cell Membranes of various Cryptogams. By ERNST WINTERSTEIN (Zeit. physiol. Chem., 1895, 21, 152-154 ; compare Schulze, Abstc., 1894, ii, 250).-For his investigation, the author has used two species of fern, Aspidium $Zia mas. and risplenium $lix fem., and several species of moss belonging to t h e Bryacem family. Ccllulose preparations were made from the cell membranes, and then the products obtained by hydrolysis with sulphnric acid were investigated ; from each preparation a syrup mas obtained, which consisted mainly of d-glucose mixed with a small quantity of mannose.Prote‘ids of Cotton Seecs. By THOMAS B. OSBORNE and CLAI~K G. VOORHEES (J. Arne).. Chem. SOC., 1894, 16, 778--785).-This is mainly an account oE preliminary cxpcriments. The ail-free cotton seed meal was first extracted with water, and the solution, after dialysis, yielded 0.75 per cent. of proteose-like matter, When further extracted with 10-20 per cent. solution of common salt, tho meal yielded a larger amount of globulin (15.83 per cent.), which in properties and composition is remarkably similar to the vegetable vitellin of flax, hemp, 8;c.; no other globulins soluble in sodium chloride solution could be isolated. The authors term the globulin which is soluble in salt “ edestin,” tsince it occurs i n so many im- portant food stuffs.The meal was further treated with aqueous potash, and yielded other protejid matter, which, however, could not be obtained in a pure state. The residue, after treatment wit11 potash, also contains a notable quantity of nitrogen. J. J. S. J. J. S . Injury to Plants by Nitrogen acids. By F. JOSEF KOXIG and EMIL HASELHOFF (Bied. Centr., 1895, 24, 610-611 ; from Landlo J d w b . , 1894, 23, 1031 ).-Esperiments made on young trees showed that 1 part of hyponitrous acid (calculatcd as N,04) in 20,000 payts of air (or 0.05 gram in 1 cubic metre) is iiijurious. As air contailis U.00003 gram of nitrous acid per cubic metre, the air to be injuriousVEGETABLE PHYSIOLOGY AND AGRICULTURE.211 must contain 2,000 times as much as is generally present. The limit, wit>hin which nitrogen acitls become injurious is between those OF hydrogen chloride (1 : 15,000 v01. according to Christel) and sul- phurous acid (1 : 54,000 vul. nccording to Freitng). The effects produced on leaves by nitrogen ucids are similar t o those of sulphurous and lijdrachloric acids-brown or yellow spots 01- edges. N. H. J. M. Effect of Strychnine on Plant Development. By R. OTTO (Bied. Centr., 1895, 24, ill ; from Naturw. TtTochenscl~r., 1894, No. 52, 6'25).--The addition of strychnine phosphate to four weeks old beans, grown in sand and i n humus soil respectively, greatly retarded the growth of the plants growing in sand. The plants flowered, but did not, produce normal f r u i t .In soil, t'he plants were slightly retarded, had an almost normal colour, and produced a quantity of normal fruit. More than 10.5 grams of strychnine salt was added to 2 kilo- %rams of soil duiaing the eight weeks the experiment lasted. On extracting the soils with water, no stqchnine was found, the poisoit having been destroged by the soil. I n soils which were saturated with a solutioc of strychnine from the commencement, the germina- tion oE beans was considerably delayed ; two plants in soil, however, developed comparatively normally, whilst those in sand decayed. N. H. J. &I. Black Siberian Lupins. By BERNHARD SCHULZE (Bied. Centr., 1895, 24, 614-615 ; from L). Land&, 1895, No. 30, 175),-BIack lupins are said to be unusually poor in alkaloi'ds, so that it is not necessary to destroy the alkalo2da before feeding. A number of samples of imported black lupins were found to contain in nearly every case more alkaloids than are found in the native yellow, whitc.and blue lupins, and complete analyses of black and yellow lupins, t h e results OF which are given, show that the black are not better than the German varieties either as regards nutritive qualities or amount of alkaloids. Black lupins are very rich in alkaloilds, and probably contain the poison which causes the disease known as lupi- nose. N. H. J. M. Effect of Different Manures on the Compositidn and Com- bustibility of Tobacco. By HARRY J. PATTERSON (Bied. Celz.fr., 1895, 24, 662-663 ; from Agric. Science, 1894, 8,329).-The experiments were made in five of the chief tobacco growing districts of Maryland.The amount of total as11 depends chiefly on the soil, and only slightly on manuring, b u t i t was found that potassium chloride raised the percent,age of ash most. The amounts of lime and magnesia are i n - fluenced by manuring, but still more by the character of the soil, whilst the amount of chlorine ia more intliienced by manuring. Tobacco which burns well generdlly contains much sand and silica ; the combustibility increases with the amount of lime and magnesia, but there seems to he no relation between combustibility and amount of phosphoric acid or of crude fibre. The quality of tobacco is largely influenced by the character of tho previous growth. I n Maryland, land growing pines is found moat suitable; chestnut land comes312 ABSTRAOTS OF CHEMICAL PAPERS.next, whilst land on which oaks and hickory are growing is un- suitaLle for tobacco, and is planted first mitli rlndropogou rirgi?ziczlm, followed by pines. The effect of these plants on the cultivation of tobacco is explaiiied by its requirements as regards potash and chlorine. The relation between chlorine and potash in the red pine is 1 : 1.3, in Andropoqon 1 : 2.5, in chestnut 1 : 14*4t in oak 1 : 50.0, and in hickory 1 : 63.0. The beneficial plants withdraw much chlo- rine from the soil, the others much potash. Composition of Rice imported into France. Bg BALLAND (Conzpt. rend., 1895, 121, 56 1 4 6 4 ) .-Decorticated rice from tho principal localities (Burmah, Carolina, India, Japan, Java, Piedmont, Saigon [Cochin China]) shows percentage compositions varying between the extremes quoted below.N. H. J. 31. Nitrogenous Cellu. Water. matter. Fat. Amyloi’ds. lose. Ash. Maximum.. , . 16-00 8.82 0.75 81-55 0.42 0.58 Minimum . . .. 10.20 5.50 0.15 75-60 0.18 0.42 Crude rice contains a higher proportion of nitrogenous and fatty substances and ash, the limits being as follows. Nitrogenous Water. matter. Fat. Amyloi’ds. Cellulose. Ash. Minimum.. , . 11.20 6.18 1.85 73.85 0.93 1.20 Maximum.. . . 13.30 9.05 2-50 75.60 2.38 2.20 In refined rice, the acidity lies between 0.032 and 0.062, and the sugar between 0.15 and 0.50, the values in the case of crude rice being 0*043-0*087 and 0 . 5 6 4 9 0 respectively. There is no con- nection between the size of the grains and the proportion of nitro- genous matter.Rice has more value as a food than is commonly supposed. The Cochin China rice, although the grains are small, contains as much nitrogenous matter and phosphatic ash as some wheats, and rather more fat. The process of decorticating, especially by machinery, greatly reduces the proportion of fat, nitrogenous matter, and ash, and the loss is still higher if the grains are polished, Are Nitrates indispensable for the Growth of Plants ? By OTTO PITSCH and J. VAN HAARST (Landzo. Versuchs-Stat., 1895, 46, 357-370 ; compare Abstr., 1693, ii, 385).-The experiments now described were silzlilar to the earlier oaes ; the nitrifying bacteria were destroyed, and the nitrates present in the soil extracted with water.In 1892, wheat was grown in soil containing 0.105 per cent, of nitrogen, and in the same soil, with addition of ammonium sulphate (corresponding with 1.05 gram and 0.513 gram of nitrogen) and of sodium nitrate (1.05 gram of nitrogen) respectively. The total yield (grains and straw) with the larger amount of ammonium snlphate was less than where no nitrogen was applied ; with the smaller amount of ammonium salt, the yield was about the same as without any applica- tion, whilst with nitrate, the yield was largely increased. I n 1893, experiments mere made with oats. The application of nitrates again C. H. B.VEQETABLE PHYSIOLdGY AND AGRICULTURE, 213 gare a much higher yield than the ammonium salts. The npplica- tion of both potassinw and sodium chlorides in conjunction with ammonium salts resulted in n considerably increased production oE dry matter as compared with that obtained under the influence of ammonium salts alone ; moreover, the yield wils practically the sam3 with the larger and smaller amounts of ammonium salts, whereqs without ths chlorides, considerably less total produce was obtaincd with the larger than with the smaller amount of ammonium salt.Similar results were obtained (again with oats) in 1893. The ques- tion how the sodium and potassinm chlorides act has not been studied, but results obtained by Pagnoul (Abstr., 1895, ii, 130) indicate some interaction in the soil beneficial to the plants. N. H. J. M. Assimilation of the Nutritive Matters of the Soil by Plants. By F. JOSEF K ~ N I G and EMIL HASELHOFF ( f l i e d .Celitr., 1895, 24, 687-691 ; from Landzo. Jcthrb., 1894, 23, 1009).-Two artificial soils were made, i n which the constituents mere partly in a physically com- bined (absorbed), and partly in a chemically combined, state. The percentage composition was as follows. Sand. Clay. Humus. Fe2( Al,(liO)G. Si(HO)+ Zeolite. A. 84-1 10.0 2.5 2.5 0-7 0-2 0.0 13. 82.0 10.0 2.5 3.0 0.3 0.2 2.0 The absorptive powers of the two mixtures were tested by Zalomrtnoff and Pillitz’s process, with nutritive solntions of different strengths. In the case of mixture A, it greater absolute as well as percentage amount was nbsoi.bed from stronger than from weaker solntions. In the second mixture B, the absorptive power for lime, magnesia, ancl pvtash was increased by the presence of zeolite, and the double strength of the nutritive solution caused greater absorption only in the case of lime.Generally + to 4 of the lime, 0 to Q of the magnesia, and Q to 3 the potash applied were absorbed. Soda and sulphuric acid were only absorbed in traces, whilst the phosphoric acid was corn pletel y absorbed. Vegetation experiments were made, in which barley followed by horse beans were grown in the artificial soils, with and without application of further nutritive matter. The nutritive substances were applied (1) entirely in a soluble form (2, 3, and 4) in both soluble and insoluble form in varying proportions, and (5) in an in- soluble form. It was found that whilst the gramineous plant (barley) gave a yield in nearly direct relation to the amount of soluble nutritive matter applied, the yield of Iegumir,ous plant (horse bean) was rathei- in relation to the total amount of nutritive matter than amount O F soluble matter.Lime seems to influence the growth of leguminous plants niore than potash under otherwise similar nutritive con- di tions. The actual amounts of nutritive matter in the soluble and insolublc foisms which were taken up by the plants are giren in tables. N. H. J. M. VOL. LXX. ii. 16214 ABSTHACTS OF CHEMICAL PAPERS. Composition of Native and Cultivated Soils. Effect of Continuous Cultivation on t h e i r Fertility. BY HARRY SXYDJX (Mi)z?zesota Stat. Bull., 1893, No. 30).-Aualysis of about 150 Ninne- sota soils, bolh cultivated and uncultivated, were made, t h e surface soils being smnplecl to a depth of about 9 inches, or until a change of colour was noticed.The most, important soils are the deep black soils of the Red River Valley, containing 0.35 to 0.4 per cent. of nitrogen which, by continuous cultivation for 12 or 15 years, has been reduced t o 0.2-0.3 per cent. Small spots of alkali soils sometimes occur ; these are most benefited by deep ploughing, drainage, and the application of stable manure. ‘I Gumbo ’’ soils are heavy soils con- sisting of very fine particles less than 0.01 inch in size, and free from true sand. By the continuous, exclusive growth of grain crops for 10--15 years, the amount of humus in the soil is reduced to one-third or one-half, t,he soil, from loss of organic matter, losing its power of retaining wt-tter, and t!ius becoming subject to drying out.Soils rich in humus contain more avaiiable phosphoric acid than poor soils, and produce more carbonic anhydride, which acts as ,a solvent on the mineral matter, and thus aids thc roots in taking up food. I n order to keep up the supply of organic matter in the soil, a system of rotation and application of stable manure is recommended. Artificial manures mill then be unnecessary. I n some cases where, fbr instance, the surface soil is rich in nitrogen and phosphates, the corresponding suhoil rich in potash and lime, the good qualities of both surface and subsoil would be utilised by a rotation of crops. Citrate Solubility of the Phosphoric acid of Basic Slag. By WILHELM HOFFMEISTER (Lnndw. Versuchs-Stat., 1895, 46, 399- 405).--The results of the experiments described indicate that the citrate solubility of the phosphoric acid depend8 on the amount of lime and silica present, and on the fineness, both as regards the total amount of fine meal, and also the degree of fineness.Fineness is rendered more easy to obtain mechanically by the presence of large amounts of lime and silica. The value of basic slag depends essentially on the greater or less possibility of the produc- tiou of tetrabasic calcium phosphate i u the fused substance, and on its fineness. N. H. J. M. They are rich in potash. N. H. J. M. Phosphate Manuring. By VON IAIEBENBERG (Bied. Centr., 1895, 24,663-664 ; from Mitteil. Ver. Ford. ‘Versuchwesens Oesteweich, 1894, 9, 125--128).-The object oE the experiments, which will be con- tinued for some years, is to ascertain whether yearly applications of soluble phosphates may with advantage be substituted by one rery heavy application of a cheap, but sparingly soluble phosphate. The dry surface and subsoil contained respectively N = 0.1166 and 0.0969 ; P,O, = 0.188 and 0.183; K20 = 0.364 and 0.423; CaC03 = 3.139 and 2.239 per cent. Two plots of 100 square metres were manured as follows :-(1) No manure ; (2) sodium nitrate, 200 kilos. ; (3) same as ( d ) , with soluble phosphoric acid, 50 kilos., as Spodium superphos- phate (q mme as (?), with phosphoric acid, 500 kilos., as RedondaANALYTICAL CHEMISTRY. 215 phosphate. The crop was winter rje. The application of nitrate d o n e gave n very satisfactory increase, whilst phosphoric acid in both forms gave a still greater increatse. The superphosphate gave ratlier more straw an2 less grain than the Redonda phosphate ; but, 011 the whole, the eEect of both manures may be considered equal. N. H. J. ar. Pigeon Manure. By BERXHARD SCHULXE ( B i d Centy., 1895, 24, 590-591; from Der Landwirt, 1895. No. 51, 301).--The value of‘ pigeon manure depends on the amount of water and sand which it contains, and on the very variable amounts of nitrogen, phosphoric acid, and potash. The following percentage results were obtained from 40 samples. Water. pu’. P,O,. K20. 3.80-40.00 1.47-5.04 1-00-2.77 0.71-2‘57 Averages.. 21.0 2.53 1.79 1 a46 As much as 43.3 per cent. of sand was found. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA8967005201

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 215 A n a l y t i c a1 Chemist rg. New Method of Quantitative Spectrum Analysis. By -According to Lambert-, i f a ray of monochromatic light is passed through a. layer of thickness m, and its luminosity is reduced l / n t h by a layer of unit thickness, the original luminosity J becomes J’ = J / n t n , Assuming that the reduction in iunxinosity is the same for a layer of solution of thickness m and concentration c as for a layer of thickness c and concentration m, and t,hat the luminosity is reduced l/YLth by ~t layer of thickness 1 and coiicsntration 1, then J‘ = J/nme. Placing ?Z?’~C = x we get log x = mc log n, or if x = 10, a condition that can be realised by so arranging the experiment that the luminosity of the light used is reduced to 1110th of its original valuc by absorption in the solution, GEEHARD K R ~ S S and H.KRGss (Zeit. niiorg. Chenz., 1895, 10, 31-43). 1 c = -, m log ?L It is evident that n is a constant for one and the same substance, and represents what may be termed the specific absorptive power of that substance. The constant k may be taken to represent the qnnutity l / l o g 12, and, therefore, c = k/m. If k has been determined by observation with a solution of known concentration, it will only be necessary to determine the thickness of the layer, m, of a similar solution oE unknown concentration, required to reduce the luminosity to l/lOth of its original value, in order to find, c, the concentration. The authors describe a new spectrocolorimeter with the aid of which a comparison of solutions of dift’erent concentration can be effected.H. C. 16-2216 ABSTRACTS OF CHEMICAL PAPERS. Separation of Minerals Gf High Specific Gravity. By SAPIIUM, L. PENFTELD (Amer. J. Sci., 1895, [ 3 ] , 50, 446--448).-A description is given of a better form of apparatus than thnt previously described by Penfield and Kreider (Abstr., 1894, ii, 456), to be used in the separa- tion of minerals by aid of Retgers' double silver and thallium nitrate (Abstr., 1893, ii, 294). The tabe b, containing athe heavy liquid and the material to be separated, fits into the cap c, and has its lower end closed by the stopper a ; the whole is placed in a tnbe d in hot water. As the liquid is diluted, the successively lighter portions of the material are collected from the cap c.For dealing with large quantities of material, the larger cap c' is used. With larger amounts of thal- lium nitrate (than TINO, : AgNO, = 1 : l), the density and melting point increase until, for the pure salt, sp. gr. = 4.94 and m. p. = about 250'. As Rekgers' liquid acts on mineral sulphides, it cannot be used for their separation. The specific gravity of the separated fragments is conreni- ently determined by weighing in water i n a small tube suspended from the balance arm. L. J. S. New Reagent for Bromine and Iodine. By J. H. RA-STLE (Amer. Chem. J., 1895, 17, 706-~08).-Dichlorobenzenesulphonamide liberates bromine and iodine from metallic bromides and iodides, and cau be used either in the solid state or in carbon bisnlphide solution ; it is recommended as a reagent instead of chlorine water, but, like this, excess must be.avoided, otherwise iodine trichloride will be formed. It is possible to recogiise the presence of iodine in solutions containing 0*0000127 and 0.00000635 gram, tcgether with 0.04 and 0*00036 gram bromine respectively. J. B. T. Quantitative Separation of Bromine and Chlorine. By STEFAN BUGARSZKY (Zeit. anorg. Chem., 1895, 10, 387--397).-The mixture of chloride and bromide is treated with from 50 to lU0 C.C. of one-tenth normal potassium hydrogen iodate (according to the amount of bromine present), then with 10 C.C. of sulphuric acid (20 per cent. by volume), and the whole made up with water to 200 C.C. and boiled in a &-litre flask until the volume is reduced to 60-80 c.c., whereby the liberated bromine and iodine are evolved.The residae in the flask is made up to 100 C.C. Half of this, diluted to 100 c c., is treated with a little potassium iodide and titrated with l/lOth normal sodium thiosulphate. The amount of bromine is then calculated from the quantity of iodic acid used up by the oxidation. The remaining half of the 100 C.C. is treated with sulphurous acid t o reduce the iodic acid, the hydrogeu iodide decomposed by sodiumANALYTICAL CLEEXISTRP. 217 nitrite, the solution then boiled until all the iodine is expelled, and the chlorine estimated by Volhnrd’s method. The results are fairly accurate. Instead oE dotermining the chlorine separately, the total amount ot chlorine and bromiue can be estimated by Volhnrd’s method, and then the bromine estimated by the above method. Estimation of Sulphurous Anhydride and Sulphuric acid in the Products of Combustion of Coal Gas.By MAXIMILIANO DNNNSTEDT and CZSAR L4,HltEHs (Zek anal. ohem., 1896, 35, 1--10).- The authors have repeated the work of Uno Collan (Abstr., 1895, ii, 3S8), with the following modification. A flask of 11 litres capacity was fitted with a cork, through which passed three tubes. One of these, reaching to the bottom, was recurved and furnished with a jet for burning the gas ; a second served for the admission of purified air ; and the third was connected wit.li a long Liebig’s condenser sloping upwards. To the upper end of the condenser there was attached a Drehschmidt’s absorption apparatus, with a Bunsen pump for aspi- r,itiug a current of air through the whole system.It was assumed that the sulphuric acid formed would be retained in t,he flask and condenser, the sulphurous anhydride alone passing into the absorption apparatus. The results obtained were much more concordant than those of Collan, but the amount of sulphurous anhydride calculated from the chromic acid reduced was only (on the average) YO per cent., whilst that Pound gravimetricdly in the absorbing liquid was 92.5 per cent. of the whole. Sevcu flasks moistened with water, were then interposed between the condenser and the absorption apparatus. Sulphuric acid, to an average amount of 0.5 pzr cent., condensed in each of these flasks. The irregularities in the results seeming to b3 counected with variations in the air supply, the experiment was made of varying the relation of the sulphur to the oxygen by replacing the air by pure oxygen in one series of experiments, and in another increasing the sulphur by vaporising into the gas a, known quantity of carbon hisulptiide.With the oxygen atmosphere as much as 3 7 per cent. of the sulphur R ~ S directly burnt to snlphuric acid, whilst the addition of the carbon bisulphide caused an increase in the proportion escaping as sulphurous anhydride. These facts are regarded as indicating that although sulphurous anhydride is the chief direct product of the combustion, it neverthe- less, when diffused through an excess of atmospheric air, continues to oxidise until i t is wholly converted into sulphuric acid. The inju- rious effects i n rooms where coal gas is burnt are therefore in no way diiuinished by the fact that t h e sulphuric acid is formed at a distance from the flame, instead of in the flame itself.E. C. R. 31. J. S. Estimation of Nitrogen in Peruvian Guano. By HEIBER (Landu;. Verszichs-Stat., 1895, 46,407-408) .--The nitrogen in several silmples of guano was determiued by the Jodlbauer method, and by the washing out process. The guano was mixed with 2 parts cf gjpsum, and the acid (containing 40 grams of phenol per libre) added gradually, keeping well cooled ; zinc dust was gradually added in si~isll quantities. Loss of nitric oxide and of nitrophenol waa thus218 ABSTECAOTS OF OHEMIOAL PAPERS. avoided. When all the zinc dcst ( 3 grams) had been added, the whole was kept for a long time, after which 20 C.C.of strong siilpli- uric acid and mercury (2 gmms) were added, and the decomposition proceeded with. I n the washing out method, ihe separation of the soluble and insoluble portions was carried out in the usual manner with 5 grams of guano. The filtrate was made up to 500 c.c., OF which 100 C.C. mas treated with canstic soda, iron dust,, and zinc dust, and distilled after some hours. The results, unlike those obtained by Haselhoff (Abstr., 1895, ii, 138), sliowed that the Jodlbauer method gave the higher percentages, owing probably to the fact that such compounds as guanine and uric, acid are not decomposed by dilute soda. N. H. J. M. Kjeldahl’s Method and Platinochlorides. By W. VAP; L)AM (Rec. Trav. Chirn., 1895, 14, 217--226).-DBlepine (Abstr., 1895, ii, 290) has shown that the percentage of nitrogen in certain platino- chlorides, as estimated by Kjeldahl’s method, falls considerably below the theoretical value.The author confirms this, and shows that by prolonging the heating and applying Gunning’s modification of the method, the results are not. improved. When Wilfarth’s modification is emplojed (addition of a drop of mercury), the platinochlorides of several amines were found to yield satisfactory values for the per- centage of nitrogen. Even under these circumstances, however, ammonium platinochloride yields low results. The last-mentioned compound gives theoretical values, as do the platinochlorides of all the amines tried, when a little zinc-dust is added to the concentrated sulphuric acid during the heating therewith.Ethylamice aurochloride and ethylamine mercurochloride give good results, both by Gunning’s modification, and also by that of Wilfarth. The author has demonstrated that the whole of the nitro- gen is evolved as such when ammonium platinochloride is heated with concentrated sulphuric acid for five hours. By PIETRO SPICA (Chem. Cents-., 1895, i, 562 ; from Boll. Fama., 1895, 2).-After a portion of the material has been qualitatively tested by Mitscherlich’s process, the remainder is treated as follows. It is put into a flask which is connected with a carbonic acid apparatus ; the flask, after the air has been expelled, is gently heated on a sand bath, and the rolatile products are Fassed through three Peligot tubes charged with a neutral solution of silver nitrate.To see whether all the phosphorus has passed over, the tubes are replaced by fresh ones ; six to eight honrs heating generally suffices to expel all the phosphorus. The silver solution is oxidised, and, after precipitating the silver, the phosphoric acid is estimated by means of molybdate solution. l’lie residue in the flask may still contain phosphorus in an incompIete state of oxidation, and capable of yielding hydrogen phosphide, Zinc is therefore added, and also dilute sulphuric acid a little at a time, so as to keep up a feeble current of hydrogen for about six days. All this time, a current of carbonic anhydride is also parsed; A. R. L. Toxicological Estimation of Phosphorus.ANALYTICAL CHEMISTHI’. 2 1‘3 the gases are passed through Peligot tubes charged with silver nitrate solntion, and should any precipitate form i t is treated as before.L. DE K. Testing for Arsenic in the Presence of Selenium. By L. DAWTDOW (Chem. CeTztY., 1895, i, 811 ; from Chem. Zed. Rep., 19, 70). -The presence of selenium interferes with Marsh’s test, and also with Bettendorf’s stannous chloride test, and if present in l a ~ g c quantities, the first may fail altogether. The author recommen(ls precipitating both arsenic and selenium by means of hydrogen sulpll- ide, and then acting on the mixed sulphicles with ammonium carbonatc. Decomposition of Silicates by Boric acid. By PAUL J A m A s C I i (Bey., 1695, 28, 2822-2823) .-Silicates may readily be brought, into condition f o r analysia by fusion with boric acid.The boric acid is removed by repea,tedly evaporating the solution with hydrochloric acid and methylic alcohol. Estimation of Argon. By TH. SCHLOESIKO, jun. (Conipt. md., 1895, 121, 525-528) .-The author describes an arrangement of a n ordinally mercury pump for passing a comparatively small, measured volume of nitrogen, containinw argon, repeatedly through a tube con- taining heated magnesium. %he last traces of argon are swept out of the tubes at the close of the operation by means of carbonic: anhydride, and, before measuring the gas, any traces of nitrogen or of combustible gases are removed by sparking with oxygen in prcs- cnce of potash, the excess of oxygen being afterwards absorbed by phosphorus (compare this vol., ii, 16G). Estimation of Calcium and Magnesium Carbonates in Soil.By ROBERT MAUZELIUS and ALBERT VESTERBERG (Bied. Centr., 1895, 24, 583-584 ; from Bedogorelse f. verksamhefen rid ULtwaa LnnJt- bruksinst. iir, 2894. Upsala, 1895, 62-71) .-Extraction of calciu IIA and magnesium carbonates with hydrochloric acid, and precipitation gives too high results. Carbonic anhydride was determined iu 16 loamy soils (0.05 to 18.13 per cent. of CO,) with a modified Hresenius’ apparatus, and also the amount of lime and magnesia extracted by 0-9 to 1 per cent. hydrochloric acid. The carbonic anhydride represented by the lime and magnesia so determined, exceeded that actually found by 0.25 to 0.85 per cent. The results show that the amounts of readily decomposed zeolithic lime cotli- pounds in soils are too great to be neglected, especially in the case of soils p o o ~ in lime.I n exact estimations, the carbonic anhydride should also be determined. By increasing the strength of the acid to 4 per cent., much mom lime and magnesia were dissolved. Volumetric Estimation of Lead. By ALLERJON S. CUSHMAN and J. HAYES-CAMPBELL ( J . Amel.. Chem. SOC., 1895, 17, 901-904).- Various methods for the volumetric estimation of lead have hee~i The arsenical solution may then be further tested. L. DE K. A. H. C. H. B. N. H. J. M.220 ABSTRACTS OF CHEJIICAL PAPERS. tried. A modified form of Schwsrtz-Diehle's method (Abstr., IS&), 756) is suggested. After the lead clwornate has been filtered ojY, t l i 2 excess of dichromate in solution is titrated by means of il staitdardised solution of ferrous ammonium sulphate, using potassi urn ferrricyanide as an indicator, under exactly the same conditions as olserved in standardising dichromate solutions.The results obtained are a trifle low. Low's metbod (J. A12d Chem., 6, 12) gave too high rtsults. Knight's niodification of Hempel's method (ibid., 6, 11) did not yield concordant resulls. Electrolytic Separations. By EDGAR I?. Sm1.H and DASIEL I;. WALLACE (J. Anzer. Cl~em. Soc., 1895, 17, 612--615).-&Iercury may be electrolytically separated from cadmium ; gold from cobalt, nrsenic, copper, zinc, and nickel ; silver from zinc, nickel and cobalt, be operating a t 65" in preseiice of potassium cyanide. With a current of 0.02--0.08 ampkre for mercury, 0.1 for gold, nncl 0.04 for silver, the deposition of the metal is general1.y compIete J.J. S. in 3-3; hours. L. DE K. Separation of Manganese from Zinc in Ammoniacal Solu- tion by means of Hydrogen Peroxide under Pressure. By PAUL JANNASCH and E. VON CLOEDT (Zed. anwg. Chent., 1895, 10, 405-407).--8 weighed qiiantity of manganese and zinc salts is dissolved in water (20 c.c.) and glacial acetic acid (10 c.c.), and poured into a cold mixture oE 5 to G per cent. hydrogen peroxide (30 c.c.), concentrated ammonia (60 c.c.) and watcr (20 c.c.). The mixture is allowed to remain for 1+ hours in a thick walled glass flask closed with tt rubber bung and capable of withstanding pressure, and is then heated for l& hours at the temperature of boiling water. The precipitated hydrated manganese dioxide is washed with amrnonin and then with hot water; fire to seven washings are usually snffi- cimt to remove all traces of zinc.The filtrate containing the zinc is evaporated to dryness on {he water bath, and then for a short time a t 120--130° to remove the last trace of ammonium acetate. The residue is dissolved in water and dilute hydrochloric acid, and the zinc precipitated with sodiuni hydrogen carbonate. Separation of Iron from Beryllium. By ELIZABETH A. ATKIN- SON and EDGAR I!'. SMITH (J. Amer. Chem. Xoc., 1895, 17, 688-689). -The authors adopt the process ictroduced by ron Knorre (Abstr., 1893, ii, 500) and separate the iron from berjllium b j means of nitroso-/I-naphthol. The iron solution containing about 0.1 gram of the metal is diluted to about 200 C.C. and 125 C.C.of a solution of the reagent in50 per cent. acetic acid is added and the mixture is left for 24 hours. The iron precipitate is then collected and washed, fir& with 50 per cent. acetic acid and then with water until free from soluble matter. Owing to the slightly explosive nature of the com- pound, it is, after drying, mixed with an equal bulk of powdered oxalic acid and gradually heated until the carbon is burnt off! and the iron converted into oxide. The test-analyses show tbe accuracy E. C. R. of the process. L. DE I(,ALNALY TICAL CHEMISTRY. 221 Separation of Arsenic from Iron and Manganese. By PAUL J a x s s s c ~ and H. KAM~IERER ( X e d . nnory. c/ie?)z., 1895, 10, 408-414 ; see also Abstr., 1895, ii, 423).--Separation of i ~ o n jwnz useizic.Am- inonium iron alum (0.5-0.6 gram), aiid arsenious anhydride (0.25-0.3 gram) arc dissolved in 3 C.C. of a mixture of equal volumes of con- ceutrated hydrochloric and nitric acids and a little water, and craporated to dryness ; the residue is dissolved in water and hjdro- gen peroxide, and poured into a mixture of sodium hydroxide (5. grams) water (50 c.c.) and hydrogen peroxide (30 c.c.). The iiiixture is heated to boiling, diluted to 250-300 C.C. a i d filtered. The iron precipitate is redissolved in dilute nitric acid and ,z littJe hydrogen peroxide, and again precipitated with amnioniacal hydro- gcu peroxide. The filtrates are evaporated in order to expel the am- inonia, acidified with nitric acid, allowed to cool, and the arsenic precipitated with ammonia and inagnesium chloride and weighed as Ng2As207.Sepayation of 1 ~ o u fTont Nickel, Zinc, and Coppeq-, in Hyd~ochloric acid Solution.-Ammonium iron alum, and nickel ammonium sulpliate (0.5 gram of each) are dissolved in waster (25 c.c.) and concentrated hydrochloric acid (6.7 c.c.), and poured into a mixture of ammonia, hydrogen peroxide, and water. The mixture is heated on the water bath, and the iron precipitate washed aud redissolved in dilute hydrochloric acid containing hydrogen peroxide, and then again precipitated. The filtrates are evaporated to expel tlie ammonia, 1 gram of hydroxylamine added, and the nickel precipitated with excess of sodium hydroxide. The separation of iron from zinc, and iron from copper is carried out in a similar manner. The preceding separations are more easily effected when acetic mid is used instead of hydrochloric acid, since in the evaporationof the filtrates, the am- monium acetate is more easily volatilised.Manganese and amenic are separated in a similar way. E. C . R. Chromium Estimations. By JOHN E. STEAD (Chem. Cent?.., 1895, i, 623-624 ; from Joum. I ~ o n and Steet Inst.).-The author has improved Galbraith's process for tlie testing of chrome steel. The sample is dissolved in dilute sulphuric acid, filtered, the solution diluted t J about 300 c.c., arid heated to boiling. Strong solution of potassium permanganate is now added until the red colour is per- manent for 10 minutes, then 80 C.C. of 10 per cent. hydrochloric acid, and the liquid heated until decolorised; 150 C.C. of water is added, about 100 C.C.boiled o e to expel the chlorine, and the chi-omium is then titrated. The residue insoluble in dilute sulphuric acid is mixed with 0.5 gram of a mixtuye of 200 parts of calcium oxide, 50 parts of potassium carbonate and 50 parts of sodium car- bonate and heated to intense redness for half an hour; the chromium is afterwards titrsted in hjdrochloric acid solution with ferrous sulphate and potassium dichromate. Another process consists in dissolving 2 grams of the sample in hydrochloric acid ; without filtering, the liquid is nearly neutralised with a 2 per cent. solution of Eodium hydroxide, and after diluting to 300 c.c., 10 C.C. of rt 5 per cent. solution of digodium hydrogen pliosphrtte and 30 grams of sodium thiosulphate is added.After2.22 ABSTRACTS OF CHEMICAL PAPERS. boiling to expel the sulphurous acid, 20 C.C. cf a saturated solution of sodium acetate is added and the boiling continued f o r 5 minutes ; the precipitated chromium phosphate is then washed with a 2 pel cent. solution of ammonium nitrate, dried, calcined, and fused with the above lime mixture. The melt, dissolved in YO C.C. of hydro- chloric acid 2nd 150 C.C. of water, is boiled for 10 minutes and titrated. The process may be used in presence of vanadium. I n this case, the chromium must be titrated by means of ferrous snlphate and potassium permanganate in presence of sulphuric acid. Separation of Chromium from Manganese, Iron, and Mu- minium. By PAUL JANNASCH arid E. VON CLOFJDT (Zeit. anorg. Chem., 1895, 10, 398-404) .-Sepa~atioiz of Manganese and Chromium- Manganese ammonium sulphate and ammonium chrome-a1 um (0.35- 0.4 gram) are dissolved in water (50 c.c.) and concentrated nitric acid (5 c.c.,), and the solution poured into at mixture of 3 per cent.hydrogen peroxide (40 c.c.) and soda (1 : 5 , 40 c.c ). The mixtuie is heated to boiling, and the precipitate of hydrated manganese di- oxide washed with dilute ammonia containing hydrogen peroxide, is dissolved in nitric acid containing hydrogen peroxide, and again subjected to the above method of precipitation. The precipi- tate, which contains traccs o€ soda, is redissolved and precipitated with ammoniacal hydrogen pcroxidc, then dried, and heated to a constant weight. The filtrates, which contain the chromium as sodium chromate, are concentrated and treated with hydrochloric acid and alcohol, whereby the chromate is converted inio chromium chloride ; and the solution, freed from alcohol, is diluted, treated with hydroxplamine chloride (0.3 gram) and carefully precipitated wit Lb ammonia.Manganese and chromium are more readily separated by treating their mixed salts under pressure with ammoniacal hydrogen per- oxide, whereby only one precipitation is necessary. The solution of the salts mixed with 6 per cent. hydrogen peroxide (80 c.c.) and concentrated ammoiiia (30 c.c.) is allowed to remain R short time i n n thick-walled glass flask closed with an india-rubber stopper, and is heated for 1-2 hours a t the temperature of boiling water; the flask is then opened, and the precipitate washed and treated as pre- viouvly described.It is most essential to use 6 per cent. hydrogen peroxide, as, if weaker solutions are employed, the precipitate con- tains chromium. Iron and chromium are easily separated in the same way. Aluminium and chromium are separated in a similar way, b u t pressure is not necessary. 5-6 per cent. hydrogen peroxide is used, and aftcr the mi.utnre has been allowed to remain 1-2 hours in the cold, it is heated until all b u t the last traces of’ ammonia are removed, Yhe precipitate of aluminium hydroxide must be washed with great care. E. C. R. L. DE K. Warning against the Use of Fluoriferous Hydrogen Peroxide in Eatimating Titanium. By WILLIAM F. HILLEBRAND ( J . Amer. Chem. Soc., 1895, 17, 718-719).-1n estimating ti tank acid coloi*o-ASALYTICAL CHEMISTRY 223 metrically, the hydrogen peroxide employed must be free fiom fluorine compounds, as even a minute nrnouiit mill weaken the yel'ow coloration, or even entirely preveri t its formation.L. DE K. Electrolytic Estimation of Ruthenium. By EDGAR F. SJIiTH and HARRY B. HARRIS (J. 9me7-. Chenz. SOG., 1895, 17, 652-G54).- The authors have found that ruthenium may be conveniently c?e- posited by electrolysis best in presence of acid sodium phosphate. Sodium acetnte may also be used, but the deposit is then inclined to be spongy. The platinum dish in which tho decomposition is carried out must be coated inside with copper. If the amount of ruthenium does not much exceed 0.05 gram, a current of 0*01-0.05 ampare acting for about six hours will suffice.Ruthenium may be thns separated from iridium. L. DE I(. Testing Ethereal Oils. By EDUARD HIRSCHSOHN (Chenz. G'enty., 1895, i, 695-696 ; from Pliarnz. Zeit. RZISS., 34, 97-102, 113-119). -Two kinds of oil of thyme exist; when distilling samples of the first group, tlhe first two distillates measure over 70 per cent., of which nearly 13 per cent. is soluble in 2-4 vols. of 70 per cent. alcohol, whilst the second group yields 62 per cent. of the first two distillates, 12-31 per cent. of which is soluble. The different fractions give different colour reactions, showing that the commercial oils vary in constitution. Oil of patchouli should dissolve in an equal balk of 90 per cent :~lcohol; if not, adulteration with copaiba may be suspected. Oils of rosemary of French, Italian, and Spanish origin all give the iodol reaction.When distilling the French samples, the first two fractions amounted to 62--68 per cent., and the last fractions to 20- 27 per cent.; the first fraction is soluble in 3 vols. of 90 per cent. alcohol, and the last fractions give, with bromoform and acetic acid, Of Italian samples, the first, distillate amounts to 46 per cent. soluble in 10 vols. of 80 per cent. alcohol ; the first two disbillates amount to 78 per cent. The first distillntesof the Spanish oils are more soluble in 80 or 70 pcr cent. alcohol. strong reaction. L. DE I(. Estimation of Simple Cyanides in the Presence of Com- pound Cyanides and certain other Substances. By J. E. CLENSELL (Chem. News, 1895, 72, 227--229).-The iodine method is t,ot seriously interfered with by ferrocyanides, ferricyanides, or thio- cyanates, but with the silver nitrate method the first salts render ths results somewhat too high ; the second salts have the reverse effect, and the third salts render the end reaction obscure, In the presence of zinc, neither method is trustworthy, so that the total cyanide and zinc must then be determined.The zinc is determined by adding a known excess of standard ferrocyanide, acidifying and titratiag the unexhausted iesidue with permanganate ; in the absence of sub- stancer;l which react with iodine, the total cyanide may be estimated in neutral or neutralised solutions containing both simple cyanides224 ABSTRACTS OF CHENIOAL PAPERS. and zinc double cyanide by adding excess of ferrocyanide, and titrat- i n g with standard iodine. Technical Analysis of Cyanide Working Solutions.By WILLIAM BETTEL (Chem. Xeuw, 1895, 72, 286--287).-The methods apply to the &Arthur-Forrest working solutions contaiiiing zinc. Free cyariide is estimated by titrating 50 C.C. with silreia nitrate, to faint opalescence or precipitate ; this mill indicate (if sufficient ferro- cyanide is presentl to form a flocculent precipitate of zinc ferrocyanide) the free cyanide and cyanide equal to 7.0 per cent. of the potassium zinc cyanide present. Hydrocyanic acid is estimated in 50 C.C. by adding sodium or potassium hydrogen carbonate and titrating as foi- free cyanide. Double cyanides are estimated by adding excess OF caustic soda to 50 C.C. of the solution, then a few drops of 10 per cent.potassium iodide, and titrating with silver nitrate to opnl- escence. On deducting the free cyanide and hydrocyanic numbers, t'he result is potassium cyanide duo to double cyanide, the quantity of which may be obtained by multiplying by 0.9493 and adding '7.9 for every 92.1 parts of potassium zinc cyanide indicated. Estimation of Rosin Oil in Mineral Oil. By J. KLIMOST (Chem. Centy., 1895, i, 563 ; from Chenz. Rer. Fett Haw-Id., 1895, 10, 4--5).--The author applies his bromine process (Abstr., 1895, ii, 91). Rosin oils give an average turpentine number (Zoc. cit.) of 51 ; mineral lubricating oils of only about five. The amount of rosin oil may, therefore, be estimated by the aid of the equations 51~j100 +5y/100 = a and z+y = 100, in which a represents the tfirpentinc number of the sample, z the percentage of rosin oil, and y the amount of mineral oil.L. DK K. L). A. L. D. A. L. Estimation of Total Solids and Alcohol in Wine by an Optical Method. By E. RIEGLER (Zeit. anal. Cheni., 1696, 35, 27--31).-The refractive index of a wine may be regarded a s cousisting .of three parts-a, that due to the water ; b, that due to the solids ; c, that due to the alcohol. The presence of each gram of alcohol in 100 C.C. of the wine causes an increase of 0.00068 in the index of refraction. I n the wine freed from alcohol, each gram of solids raises the index by 0.00145 (extremes observed are 0*00137 aiid 0.00150). A quantity of the wine (25 c.c.), measured in a flask, is evaporated on the water bath to about 8 c.c., returned to the flask, and made up with distilled water to the original volume.'l'he refractive index (u+b) of the resulting solution, thai of the original wine (N): and that of distilled water ( a ) are then deter- niined after the three liquids have been brought to exactly the same temperature by plunging them into a vessel of water of the temperature of the workroom. Pulfrich's refractometer (Zeit. anal. Ckem., 28, 81) gives results to the 5th decimal place with ease and rapidity. Then N-*k) gives grams of alcohol, and 0.00068 grams of solids per 100 C.C. of wine. From the exami- (a + b ) - a 0.00145ANALYTICAL CHEMISTRY. 223 nation of a single sample of beer, the constants seem to be the same for bear as for wine. M. J. S. The Cyano-cupric Estimation of Glucose.By ALFRED TV. GERRAXD (Pharnz. J. Trajis., 1895, [ 3 ] , 25, 913).--The author has improved the formula for his cyano-cupric test for glucose, and now adopts the following. To 10 C.C. of Fehling’s solntion, heated t o hoil- ing in a porcelaiii dish, a 5 per cent. solution of potassium cyanide i s gradually added until only a very faint blue colourremains. Another 10 C.C. of Fehling’s solution is now added, and while the mixture is kept boiling, the solution of sugar or urine is run in slowIg from n burette until the blue colour disappears. The volume of liquid required will contain 0.05 gram of glucose. Analysis of Urine. Estimation of small Quantities of Sugar by means of Nylander‘s Bismuth Solution. By GEORG BUCHNER (Chem. Centr., 1895, i, 303 ; from &Iiii~cl~. med.Wochschr., 41, 991),-- The bismuth solution should be added to the urine in the proportion of 1-10. Ammonium carbonate in large quantity, albumin, rhubarb, senna, salol, nntipyrine, turpentine, or other drugs likely to yield compounds with glycuronic acid, must be absent. The test will dis- tinctly show the presence of 0.025 per cent. of sugar by the grey colour of the phosphatic precipitate. The author has, llowever, noticed urines which give this reaction, although, when examined by the phenylhydrazine test, they mere found to contain no sugar. The reaction with the bismuth was here probably caused by the presence of uroerythrin which occurs in abnormsl quantity in the urine of persons suffering from fever, rheumatism, liver complaints, or diar- rhoea, and also often contains an increased anioant of uric acid, creatinine, and colouring matters.The greyish colour of the phos- phatic precipitate can only be taken as an indication of the presence of sugar when R pure white deposit is obtained after boiling with Estimation of Sugar in Preserved Fruits. By Jos. MATRHOFER (Chem. Centr., 1895, i, 898-899 ; from Forsch.-Rer. Lebensm. u. Hyg., 1895, 75--79).-The author states that the oficial method for the detection of glucose in jams is not trustworthy, and proposes a modification. The sugar mixture is inverted and titratecl with Fehling’s solution, and the result. calculated as cane sugar, from which the polarisation is then calculated. If glucose is present, the calculated polarisation will be more than the observed, and 5 per cent.R. R. aqueous potash. L. DE K. of this substance may thus be detected. L. DE I(. Estimation of Cane Sugar in Malt. By ED. JALOW’ETZ (Clie7n. Centr., 1895, i, 934 ; from Zeit. angzu. Chem., 1895, 208-209).-The actual polarisation of the solution is first observed in the 20.cm. tube of Laurent’s apparatus; 75 C.C. is then heated with 5 C.C. of’ hydrochloric acid (sp. gr. 1.88) in a narrow necked 100 C.C. flask at 69-71O for 10 minutes. After inrersion, 1 gram of animal charcoal is added, the liquid cooled to 20°, then made up to the mark, and226 ABSTRACTS OF OEEhlICAL PAPERS filtered. dilution. found by dividing the difference in the two polarisations by 1.78%. The filtrate is again polarised, and due StlloM-iinCe made for The amount of cane sngaia in 100 C.C.of malt infusion is L. DE K. Estimation of Formaldehyde. Bey M. KLAR (&if. anal. Chem., 1896, 35, 116-117 ; from Plznrrn. Zed., 40, 61Z).-Formaldehyde may be estimated by tresbment with an aqueous solution of aniline, when methylenenniliue, C6HS*N:CH2, is precipitated, and may be collected, dried a t 40°, and weighed. A more expeditious method consists in titrating the excess of aniline in the filtrate, using Congo- red as indicator. For such a formaldehyde solution a s that of the German Pharmacopmia, 400 C.C. of aniline solution (3 grams of aniline per litrej is placed in a flask, and 1 C.C. of the formaldehyde soiution added by drops with shaking. The mixture is made np t o 500 c.c , and, :ifter Rome time, filtered.The excess of aniline is then esti- mated in 50 c.c., taking as the end point that a t which the red colour acquires a h-ong, bluish tone, remaining unaltered on the further addition of a small quantity of acid. The original aniline solution is similarly titrated. One C.C. of N/10 acid corresponds with 0.003 gram of formaldehyde. M. J. S. Estimation of Benzoyl and Acetyl Groups. By RICHARD MEYER and HEINRICH MEYKK (Bcr., 1895, 28, 2965--2969).-About 0.5 p a m of the substance is placed in a round-bottomed flask of 250 C.C. capacity, 30-50 C.C. of alcohol is added, and then caustic potash in excess, the whole being heated in a reflnx apparatus until the hydrolysis is complete. Tbe contents of the flask are then acidified with a strong solution of phosphoric acid, and distilled with steam ; after 1-14 litre has passed over, each successive 150 C.C.or so of the distillate is titrated until it is found to contain no more acid. The bulk of the distillate is meanwhile treated with a drop of rosolic acid and a measured excess of N/10 soda, rapidly concentrated in a platinum, silver, or nickel dish over a spirit burner to a volume of 100-150 c.c., and the excess of alkali determined by titration with N/10 acid in boiliug solution. The results obtained are a little high, 0.5-1.0 C.C. more alkali being used than is theoretically neces- sary, owing to the absorption of acid during evaporation. The caustic potash and phosphoric acid used must not contain either nitrous 01- nitric acid ; a little potassium chloride in the potash does not matter when phosphoric acid is used, but it would be prejudicial were snl- phuric acid used instead, as hydrochloric acid would then be set free from it.Acetyl groups can be estimated in the same wny, but more easily ; the distil- lation, which can be stopped when the distillate is no longer acid t o litmus paper, does not take so long ; phenolphthaleyn should be used as an indicator in the titration. C. F. R. The above applies to the estimation of benzoyl groups. Separation of Solid and Liquid Fatty acids. By LEONARD DE KONINGH ( J . Amer. Chem. Xoc., 1895, 17, 740-741).-Twitchell tibid., 290) has attempted to show that Muter’s process for the separa-ANALYTICAL 0 HE MISTRY. 28’7 tion of solid and liquid fatty acids is erroneous on account of the slight solubility of the lead salts of the solid fatty acids in ether and tllcir probable greater solubility in ether cmtaininq Iead oleate. Thc: iodine figure of the liquid acids is also said to be erroneous, chiefly OR account of a supposed oxidation which occurs vhen applying this method.The author thinks that, when present in fair propor- tion, the separation of the liquid from the solid fatty acids by the lead ether method is fairly complete ; the iodine figures of the isolated Patty acids are also trustworthy, and the danger of oxidation is By E. RIEGLEI: (‘Zeit. airal. Chem., 1896, 35, ;31--34).-An alkaline solution of uric acid boiled with Fehling’s solution throws down cnprous oxide, the average amount of copper in the precipitate being 0.8 gram for 1 gram of iiric acid.The extreme values in 10 experiments ware 0.7818 and 0.8333 gram. To estimate uric acid in urine, it is first separated in the form of ammonium mate as follows. 200 C.C. of urine is mixed with 10 C.C. of a saturated solnt,ion of sodium carbonate, and after half an hour, the precipitate of phosphates is filtered off, and washed with about 50 C.C. O E hot water. The filtrate, mixed with 20 C.C. of a stturated solution of ammonium chloride, is stirred well, and left for five hours. Tlie precipitate is then collected on a small filter, washed witJi 50 C.C. of water, and then rinsed through the pierced filter with 50 C.C. of water into a 300 C.C. beaker; 60 C.C. of Fehling’s solution (30 C.C. of copper sulphate solut#ion containing 69.2 grams of the crystsl- lised s d t per litre, and 30 C.C.of alkaline tartrate solution containing 346 grams of sodium potassium tartrate, and 250 grams of potassium hydroxide per litre) is added, and the mixture boiled gently for five mi uutes. After thorough subsidence, the liquid is filtered through a sinnll (9 em.) close filter, and the precipitate thoroughly washed with hot water. It is then dissolved from the filter by20 C.C. of hot nitric acid of 1.2 sp. gr., and the filter washed with about 60 C.C. of water. l’hc solution is neutralised with powdered dry sodium carbonate, until a slight turbidity is produced ; the turbidity is cleared up with a, few drops of dilute sulphuric acid, and the whole made up to 100 C.C. 25 c c. of the liquid is then mixed with 1 grani of potassium iodide, and after 10 minutes, starch paste is added ; the liberated iodine is then titrated by thiosulphate solution, made by diluting 126 C.C.of N/10 solution to 500 C.C. 1 C.C. of this solution corresponds with greatly exaggerated. r,, Di<: K. Estimation of Uric acid by Fehling’s Solution. 0.002 gram of uric acid. ?,I. J. S. Detection of Salicylic acid in Beer. Ry R. J. L. SCHOEW (Ned. Tydschr. Pharrn, Pc., 7, 67--71).-The process generally etuployed is to agitate the acidified sample with a mixture of 2 parts of ether and 1 part of light petroleum, as ether alone also dissolves colouring matters. The :tuthor found, however, that when applying the wall known ferric chloride test, the salic~lic acid reaction was occasionally obtained with samples which were undoubtedly free from adulteration, thi8 reaction being due to maltol, a substance recently isolated by Brand (Abstr., 1894, i, 270) from roasted malt.Maltol228 ADSTRACTS OF GEEMIGAL PAPERS. does not, however, give any pnrticixlar reachion with Millm’s reagent, whereas salicylic acid gives a dwk red coloration. I n beer analysis, this test should be emplojed, as well as the ferric chloride test. By ARTHUIC BoRx-rR;iGI:R (Zeit. anal. CILena., 1896, 35, 35--38).--The proportion in ber- gamot oil of the linalol acetate, which is its essential odoriferous con- stituent (Abstr., 1892,868), being fairly constant, namely, 34-43 per cmt. according to Schimmel and Co., 37.6-39.9 par cent. according to the author, an estim:ition of its amount by saponification serves to detect the presence of oil of turpentine, the most usual adulterant of bergamot oil. About 2 grams of the oil is cohobated for 1-2 hours with 20 C.C.of N/2 alcoholic potash, and titrated back with N/B siilphuric acid and phenol ph thale’in. The oil evaporated on the wnter-bat,h should not leave more than 6 per cent. of residue. This residne contlitins 1-2 per cent. of saponi- fiable substance?, the amount of which should be deducted when estimating the linalol acetate. A large percentage of non-volatile saponifiable substance mould poizit to tho addition of a fatty oil. Colophony would be indicated by a high residue containing free acids (abietic, &c.), the gennine oil containing only traccs either of colo- phony or of free acid. Estimation of Fat in Milk. By H. WELLER (Chenz. Cent?.., 1895, i, 898 ; from Fwsch. Ber. ub. Lebensm., 1895, SO-83).-10 C.C. of the sample is poured into a weighed cylindrical aluminium tube containing about 3 grams of cotton wool, previously extracted with ether. The exact quantity of milk is found by reweighing the tube. After drying in a special drying apparatus, the total solids are obtained. After e x t r a c h g the f a t in a suitable extractor, the residue i s again dried and reweighed. The loss representls the fat, but after evaporating the ether, the fat may be also directly weighed. r,. 1)E K. Examination of Oil of Bergamot. If. J. S. L. DE I(. Rapid Estimation of Fats in Milk : a new Lactobutyrometer By Awroxxo LONGI (Gazzetta, 1895, 25, i, 441-451) -The author describes and sketches ft new simple form of lactobutyrorneter, which he has used with excellent results for some years past. W. J . P. Examination of Lard for Impurities. By DAVID WESSOS ( J . Amer. Chena. SOC., 1895, 17, 723--735).-The author has investi- gated most of the published physical and chemical methods for the analysis of lard, and concludes that, unless the origin of the sample is known, no method gives satisfactory results, partictilady if the amount of adulteration is small. If cotton-seed oil is suspected, the only trustworthy test is the one based on the iodine absorption of the liquid f&ty acids, but i t must 5s remembered that American lard differs greatly from the European ,w cle, and has a much higher iodine absorption. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA8967005215

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

General and P h y s i c a l Chemistry. The Atomic Refraction of Oxygen. By FKANCESCO AN~~ERLXNI (Gazzetta, 1895, 25, ii, 127-162).--The author has determined the refraction equivalents of a. number of oxygen compounds of dift'erent types, for the hydrogen lines a, @, and -{, and gives the refraction and dispersion constants; the results for the ray Ha are summarised in the appended table. The methods of preparation a.nd the criteria of purity of the several substances are given. 1)ipropionyl .......... Dibu tyryl ............ Iaodivaleryl .......... y-Valerolactone ....... y-Isocaprolactone ...... Pyrotartarict anhydride. a Propionic anhydride.. .. Isovaleric anhydride. ... Propo'in .............. Butyroyn ............. Isoraleroin ............ Diphenjlmethane ..... Succinic anhydride .....Male'ic anhydride ...... Lact.ide ............. Beiizoic anhydride.. , . , . Benzile ............... Coumarin .............. Phenolphthsleln ....... Dimethylfumaric anhy- dride. .............. Terebic acid. .......... TripLenplmethane.. .... ) l .......... ), .......... 7 ) ....... 1 J ........ 1 7 .... 1 ) .... ................. .................. ,, ............. t . 26 -3' 5 *6 20 '0 24 -5 6 '2 22 '4 16'9 16 '2 14 -9 13 -7 23 -3 23 -9 26 -7 23 *2 16 -6 16 5' 17 -4 16 -8 20.4 19 -20 9.9 20 *8 14 -9 13 -0 7 . 0 7 -3 7 -7 5 *5 19 *4 24 -4 18 *4 p PHo. - f d Observed. -- 101 '53 101 '78 133 -2 168 -28 162 -9 41 '03 40 -97 48 *6 48 -55 41 -54 51 -80 51 -82 82 -66 82 '57 52 -59 68 -4 82 '8 95 -21 34 -10 33 -09 51 -86 52 -12 109 * 23 108.14 107.55 73 .O '73 -0 159 '4 51 -0 58 *o 138 '1 2alculated -- 100 -8 100 -8 131 *2 161 -6 161 -6 41 -6 41 *6 49.2 49 -2 42 -4 52 *6 52 *6 83 -0 03 -0 51 *8 67 *O 82 *2 95 '0 34 -8 34 -6 52 -8 52.8 107 -0 104 -2 104.2 68 -6 68 -6 151 -6 49 -8 58 -4- 137 -4 Observed, 60.28 60 *78 79 -7s 97 -70 97 -49 24 '64 24 '59 29 -18 29 '14 24.81 31 *39 31 '41 49 '85 49 '98 31.62 41 -06 49 '6 54 '92 20 -37 20 '28 31 '10 31 -69 63 *04 63 '40 63 '56 43 *18 42 '91 91-82 30 -83 35 '8 81 -37 -- Calculated.-- 60 -18 60 -18 78 -42 96 -66 96 '66 21 -64 21 -64 35 -20 29-20 24 -90 31.54 31 -54 49 -78 49 -78 31 *28 40.4 49 *52 55 -28 20 -35 20 *04l 31 *041 31 *04 62 -06 60 -48 60 '48 39 90 39-70 87 -26 29.16 35 -50 79 *78 Maleic, dimethylfumaric, and benzoic anhydrides, benzile, coumarin, and triphenylmethane were examined in benzene, lactide and terebic acid in acetone, succinic anhydride in acetic acid, and phenolphthalein VOL.LXI. ii. 17230 ABSTRAOTS OF CBEMIOAL PAPERS. in alcoholic solution; the other substances mentioned in the table were examined in the pure liquid state. Dipropionyl, dibutyryl, and isodivaleryl have been shown to be really diethylacetylenic dipropion- ate, dipropylacetglenic dibutymte, and dii~obutylacetylenic cliisovaler- ate respectively (Klinger and Schmitz, Abstr., 1891, 890 ; Anderlini, this vd., i, 202) ; the molecular refractions a m therefore calculated in accordance with these facts. The difference between the observed und Calculated values of the molecular refraction are usually too great to be ascribed to experi- mental error, showing that the refraction constants are intimately affected by small changes in constitution, which cannot, yet be accurately valued owing to the lack of experimental data.W, J. P. Modified form of Polarimeter for Chemical Purposes. By HANS HEINRICH LAKDOLT (Ber., 1896, 28, 3102--3104).-The author describes a form of apparatus which facilitates the examination of rotatory liquids at temperatures extending over a wide range, the substance being introduced into a brass tube enclosed in a jacket con- structed of sheet brass ; a verhical, tubular limb of small bore allows for the contraction or expansion of the contents of the brass tube, the inner surface of which is gilded. Moreover, a simple lever replaces the micrometer screw for the purpose of controlling the analyser, and, by employing a Lippich polariser, the length of the instrument is reduced, owing to the fact that a 2-decimeter tube is sufficiently long for most purposes, coiisequent on the accuracy with which the neutral tint may be observed. Cause of Birotation.By EDMUND 0. YON LIPPMXNN (Ber., 1896, 29, 203-204).-The author, in bis book, Chemie der Z?cc/ce?wrlen, suggested stereochemical changes as the cause of birotat ion before either Lobry de Brnyn and van Ekenstein (this vol., i, l l S ) , or Trey (ibid., ii, 139). M. 0. F. C. F. B. Loss of Energy of a Battery during Electrolysis. BY HANS JAEN (Zeit. physiknl. Chem., 1895, 18, 399-425) .-By the direct measurement of the heat developed in the battery, and the calculation of that dereloped in the circuit, the author obtains the total heat development per unit current, (I) without, (11) with, polarisation. The difference is the energy necessary for the decomposition of the corresponding quantity of the electrolyte, from which t>hat necessary for the decomposition of the milligram equivalent is obtained, and che value of the polarisation is deduced.The last two values are given (for Oo) in the accompanying table, under the headings w and p , dp/dt being the heat coefficient (in volts) of the polarisation between 0" arid 40°, at which temperatures the experiments were performed. The values for the polarisation are, i n all cases, markedly higher than those obtained by other methods. The difference between the heat value thus obtained and the heat of formation of the electrolyte must equal the heat produced in the decomposition cell.Owing to the Peltier effect, the quantities of heat produced a t the two elec- trodes differ, and from the difierences actnally obtained the PeltierGENERAL -4ND PHYSICAL CHEMISTRY. 231 Copper sulphate .............. Zinc sulphltte.. ............... Cadniirim salphate ............ Copper nitrate.. .............. Lead nitrite* ................ Silvci. nitnite* ................ 79 -86 126 -88 111 -15 81 -81 I 1-756 2.790 2 a 4 4 4 1 0788 2 *267 1 -330 - 0 '00608 - 0 a0524 - O'OO315 -0*00465 - 0 * 00460 -0 00382 et€ect is determiued, in the case of copper 1 copper sulphate, zinc I zinc sulphate and cadmium I cadmium sulphate junctions, the values so derived agreeing satisfactorily with those calculated from the thermo- electromotive forces of tlie junctions.Next is calculated the cathodic, and hence the anodic polarisation, the values for the latter being somewhat greater for sulphates than for nitrakes. The heat of ionisation of the metal is also readily obtained, arid the values agree well, as would be expected, with the heats of solution of the metals in dilute nitric or hjdrochloric acid. L. 31. J. Electrical Conductivity of Salts dissolved in Glycerol. By CARLO CA'LTANKO (Real. Accad. Lincei, 1893, ii, 112-1 19).-1u con- tinuation of his work on the electrical conductivity of salts dissolved in water, alcohol, and ether (Real. Accad. Torino, 1893), the author has determined the conductivities of solutions of ammonium, sodium, zinc, barium, and ferric chlorides, and potassium bromide and iodide, in glycerol containing 2.5 per cent.of water, at various temperatures between 0" and 84'. The conductivity of the various salts is, in general, greater than that of the corresponding ethereal solutioiis, but, less than that of the alcoholic ones ; the conductivity of t h c aqueous, alcoholic, and glycerol solutions increases more slowly than the concentration, but that of the ethereal solutions increases more rapidly than the coucentration. As the concentration decreases, the molecular conductivity of the salts in aqueous solution increases, and in ethereal solution decreases ; that of the chlwides increases, whilst that of the bromides and iodides decreases, in alcoholic solution, and in glycerol, tlie molecular conduc- tivity of the chlorides increases whilst the concentration decreases.The temperature coefficients are usually greater for aqueous than for nIco11olic solutions ; in et.her, they are of appinoximately the same order as iu water, but arc3 negative in sign, whilst, in glycerol, the temperature coefficients have very high values. A table of the conductivities of the glycerol used a t various tem- peratures is givan, showing that it obeys the rule enunciated by Bartoli, which states t h -it those carbon compounds which become most viscous on cooliiig are those whose couductivity increases most rapidly as the temperatx1.e rises. At lS0, the conductivity of the glj-cei-ol was found to be of the ordei. of lo-''. W. J. P. * These vducs are calculated froin those of copper nitrate by aid of the knowii E.M.F. of Cu-Ag and Cu-Pb ct41~.17---2232 ABSTRACTS OF CHEMICAL PAPERS. Absorption of Acid and Alkali from Solutions by Platinum Black. By CARL KELLXER ( A m . Plqs. Cltem., 1895, [2], 57, 79-90). -Kohlrausch obserred that the conductivity of solutions of cei-tain acids and bases decreases slowly m hen determined in vessels coctain- ing platiniseci electrodes, and that, if the solution is removed froin the vessels, the electrodes washed several times with distilled water, and the conductivity then redetermined, it will be found to have returned to its original value. Neutral salt solutions do not exhibit this behavioui-. The author has examined solutions of a number of acids and bases, and finds that the peculiarity here spoken of is due to an absorption of some of the acid or alkali by the platinum black of the platinised electrodes.The acid or alkali abscjrbed is given up again to distilled water, as is shown b j the gradual rise i n the conduc- tivity of water placed in the resistance vessels after the acid or alkali has bee11 removed. T t is only i n this way that the absorption bg the electrodes can be determined, as the absoliite quantities absorbed are too minnte to be detected by the ordinary chemical tests. Pro duction of very Low Temperatures and Liquefaction of Gases. By C. LIXDE ( A m . Phys. Chew., 1895, [2], 57, 328-332).- Tlie gas at the temperature tl is brought in the compressor from the pressure p , to the pressure p,, arid then, after cooling by a water jacket, passes into the inner tube of the cooling apparatus, from which i t issues through a throstle valve, the temperature under- going, on expansion of the gas, a reduction of' t2-t3.I n the cool- ing apparatus, it has met, at the temperature tJ, with the ~evei-se current of expanded gas passing through the outer tube of the apparatus. Temperature equilibrium is here established, and the gas, after traversing tlic outer tube of the cooling apparatus, returns to the compressor again with the pressurep, and temperature t+ In this may, by successive compressions and expansions, the gas may be cooled until, on expansion, i t parbIy liquefies, and with an apparatus of this kind liquid air has been obtained. Tlie author claims that the apparatus recently described by Dewar for liquefying air, is identical with the above (compare, 'however, Dewar, Pmc., 1895, 221).Dependence of the Specific Heat of Water on the Tempera- ture. By KOKRAD D I E T E R ~ C I ( A m . Phys. ohem., 1895, L2], 57, 333--338).-1f two quantities of water at different tempeiatures are mixed, and CI,, is the mean specific heat of water between the higher temperature and that of the mixture, and C,,, the mean specitic heat between the lower temperature aud that OE the mixture, then CI,,,~ = aC,,,. The specific heat has here no simple physical meaning, but is made up of the specific heat c at constant yoluure and the heat of expaiisiou 8, and the equation may, therefore, be giren in the form H. C. H. C. ChUb + ahid = a(cNM f s 7 W L ) .From the experiments of Baumgartner-Pf aundler, Atiinclihausen- WiiIlner, Velten, and Liidin, the author has calculated the syecifioGENERAL AND PHYSIOAL CHERIISTRY. 233 heat a t constant volume c as a function of the temperature, and so obtnined the equation Ck = co (1 - x t - /3P), in which a = 0.00062, fi = 0*0000049, and co = 0.9996. The specitic heat of water a t constant pressure and at 0' is taken as unity. From the a.bove i t will be seen that the specific heat at constant volume decreases with rising temperature ; F, on the other hand, increases with the temperature, and t h e sutn of the two quant,ities which gives the specific heat a i constaiit pressure first decreases aiid then rises with increasing temperature. H. c'. The Thermal Expansion of Salt Solutions.By S. DE LANXOY (Zeit. phpilid. Chem., 1895, 18,448472).--The dilatometric method is employed in preference to other methods, reasons for its adoption being given. The various correotioiis applied to the results are stated, and the possible error of the determinations estimated as 0.000088. This is probably of the order of the actual probable error, for, although above the mean value in the experimental work, it is apparently not un t' re yue n tly rea ched . The t her monie t em employed were corn pa red with an air thermometer, and the various corrections for the exterior cooled portion of tbe tube, the alterations of the zero-point, &c., are applied to the readings. The dilstometers are stated to have been cali- brated, but no mention is made of the met,hod of calibration rrnployed.The experimental observations are reproduced by the unsatisfactory method of two expansion f o r m n k of the form 1 + at + pt2, the one available below, the other above 40°, but in some cases one formula suffices for the complete range. The observed results and those given by the expansion formulae appear to agree satisfactorily, but nre not compared in the paper, where comparisons are given only between the calculated values and those obtained froin curves. The solutions examined were those of ammonium nitrate, po tassinrn ferrocyanide, potassium bromide, amrnoniuni sulphate, zinc sulpliate, sodium nitrate, lead nitrate, strontium nitrate, and magnesium snlphate at various concentrations, and complete tables are given showing tho composi- tion of the solntion, the expansions observed, the expansion formulse, densitj, and temperature of maximum density which, however, most probably has 110 real significance. The author postpones the discussion of the results.L. M. J. Normal Boiling Tube. By GEORC; W. A. KAHLBALAI (Ber., 1695, 29, i1-73).-11he boiling column described by the author consists of an outer tube, which is fitted into the distilling vessel, and an inner tube, which communicates at its lower extremity with the condenser. The thermometer, which is placed in the inner tube, is thus sur- rounded by a double envelope of vaponr, and is also screened from projected particles of liquid. 31. 0. F. Boiling Point and the Genesis of the Elements. Bg CHARLES T. BLANSHARD (Chem.ivews, 1895, 72, 299--YOl).-The differences in the boiling I'oints of elements i n various groups are compaiaed with234 ABSTRAOTS OF CHEMICAL PAPERS. the differeuces in boiling p0int.s in various homologous series of carbon compounds. From the results, the author concludes that the ele- ments of groups I to IV am less highly evolved t,han the other elements. D. A. r,. Phenomena observed at the Critical Point. By GIULIO ZAMJ~IAS~ (Real. Accad. Lincei, 1892, ii, 425--431).--The gaseous and liquid forms of a substance are supposed to have the same specific volumes at the critical temperature; this assumption was made by van der Waals i n dealing with the continuit? of the liquid and gaseous states. Cailletet fouud, however, that in tlie case of carbonic: anhydride.the meniscus disappeared before the specific volumes of the liquid and gas became quite equal. Tbe author has investigated the critical point of ether in the following manner. Ether is sealed in an annular tube containing mercury, in such a way that the mercury in the two arms is surmounted by unequal heights of ether ; on very gradually and regularly raising the temperature of the tube to the critical tern- perature of ether, the mercury in the two arms of the tube should attain the same level n t the instant the meniscus disappears. This, however, is not t'he case ; the meniscus vanishes at about 1 9 3 O , whilst the level nf the mercury only beconies the same in the two arms at 196'. The temperature at which the meniscus disappears is, moreover, not constant; this may be clearly seen by heating a tube of which the two arms contain very different heighbs of ether, the meniscus may becaused to vanish several times in the one arm without the other meniscus being affected. The author coilcludes that the temperature at which the meuiscns disappears is not constant for the same sub- Rtance, but depends on the quantit'y of liqiiid employed.Disappearance of the Meniscus at the Critical Point. By GIULIO ZAMBIASI (Real. Acccrd. Lincei, 1893, i, 21-27> .-The author has devised (see preceding abstract) a method by which it may be shown that the temperature of disappearance of the meniscus between a liquid and i t s vaponr enclosed in a tube varies for the same sub- stance. The temperature of disappearance rises as the ratio of the volume of liquid to that of the vapour decrezses ; the highest tem- perature a t which the meniscus can be made to disappear is the critical tempemtare, and the substance is then in the cyitical state, The meniscus disappearrj at the critical temperature only when the substance has the critical volume, but vanishes below tlie critical temperature if the total volume is less than the critical volume and greater than the volume which the whole mass would occupy in the liquid state at the same temperature.To raise a substance to the critical state, it is necessary to heat such a quantity that. at the critical temperature it will have the crit,ical volume. By using the annular form of tube described by the author, furnished with a regulator of the volume, the substance is in the critical state when the meniscus between the liquid and vapour disappears at the same instant as the level of the mercury in the two arms becomes the 6ame.The space occupied by the substance is then the critical voiumc, and the tem- perature and pressure are also the critical oiim. W. J. 1'. JV. J. P.GENERAL AND PHYSIOAL OHEMISTRY. 233 Gas and Vapour Density Determinations by means of a Pressure Balance. Bg MAX TOEPLHR (Ann. Phys. Chem., 1895, [Zj, 57, 311--323).-A method is described for determining the density of :I gas from the difference in pressure in two capillary tubes opec to the atmosphere, one of which is filled with the gas in question and the other with air. H. C. Extension of the Laws of Gay-Lussac and Avogadro to Homogeneous Liquids and Solid Substances.By ISIDOR TRAUBE (Ber., 1895, 28, 3292-3302).-1n a numbel. of previous communica- tions (Abstr., 1895, ii, 70, 308; this vol., ii, 152), the ant.hor has shown that, for homogeneous liqnids, the molecular volume where ZnC is the sum of the products of the numbers of atoms nl, t ~ ~ , %, &c., and the atomic volumes C,, C2, C3, &c., and the constant 25-9 is what has been termed the molecular dilatation, and is thc same for all substances. For the same pressure and temperature, the molecular volumes of the gases are the same, or V = constant. But, when a gas is under a high pressure or near its point of condensatmion, as van der Wads has shown, the volume proper of the molecule can no longer be regarded as small in comparison with the intermediate spaces, aa is the case with a perfect gas.Avogadro’s lam for the same tern- peratiure and external presrure then becomes V - 1) = const. where b is a simple function of the true molecular volume, the value of which, for tile perfect gas, becomes zero. A comparison of this formula with that given above shows that the two, if not identical, woiild, a t any rate, become so on sufficient condensation of the gas. The quantity ZnC denotes the true volume of the molecule in the narrow 8ense of the term, and the value of h should, according to theory, be four times the molecular volume ; bnt, as van der Waals has pointed out, as the condensation of the gas increases the value of b diminishes, and, therefore, for liquids, this relationship cannot hold, as the assumption 2) > b is no longer hue.It may, therefore, be main- tained that for liquids the constant b is nothing more than the true molecular volume, or ZILC‘. The constant V - ZnC! acquires, accord- ingly, a new meaning, and may be termed the “ molecular co-volume,” so that the observed molecular rolnine of any compound may be regarded as thc sum of t w o quantities, the true molecnlar volume, or volume occupied by the moiecule, and the molecnlar co-volume. T t will be seen from the above that Avogadro’s law may be applied to both gases and liquidc in the form of the general statement, that, under like condit,ions of temperature and pressure, the volumes in which the molecules are free to move are the same, or the molecular co-volumes are equal.If Avopdro’s law applies to the molecular co-volumes of liquids, the same should be true of Gay-Lussac’s law, and the molecular co- volumes of different liquids should expand by equal amounts for the same rise in temperature. To test this conclusion, the author has236 ABSTRACTS OF CHEMICAL PAPERS. calculated the molecular co-volumes at 0' and 100" for a number of the psraffinoid hydrocarbons and for the ethereal salts of some of the fatty acids, these compounds being selected as the disturbing influence of molecular association in the liqnid state is thus avoided. The , is found to be coefficient of expansion, x. = - cov.0 100 approximately the same in all cases, and its mean value is 0 00366 or 1/273. It therefore appears that the molecular co-volumes nf the liquids increase by 1/273 of their value for each degree rise of tem- perature, and, consequently, t h a t the expansion of liquids like that of gases is proportional to the absolute temperature.The molecular co-volume a t any temperature is 24.5 (1 + 0.00366 t ) , or 0.090 T, the units being grams and cubic centimeters, t temperature in Centigrade degrees, and T the absolute temperature. As the laws of Avogadro and Gay-Lussac bold for liquids, that of Boyle must, in consequence, be aIso true, but the present data we insufficient EOP direct proof. Thc author shows that there is reason to believe that in the above form these laws may be extended t o solid substances, and that the molecular co-volnmes are the same in both the liquid and solid states. The passage from the solid to the liquid state is then unattended by any change in the molecular co-volume, but, in passing from the liquid to the gaseous condition, the molecular co-volume decreases, the decrease being the greater the higher the temperature.There will, therefore, be for every substance a particular temperature at which the molecnlar co-volumes of the liquid nnd the gas are the same. This is obviously the critical temperature. H. C. Degree of Dissociation a.t Zero Temperature. BY R. W. WOOD (Zeit. phpikal. Chem., 1895, 18, 521-523).-The values for the dissociation obtained by the freezing point method are usually lower than those obtained from the conductivity, and Wilderrnann has suggested that tbe differences are due to the fact that the couduc- tivity is usually determined a t a higher temperature, about 18" to 23".The author, therefore, determined the conductivity of solutions of potassium chloride at Oo, and the values then obtained for the dissociation, although in almost complete accord with the numbers obtained by Kohlrausch at 18", are considerably higher than those obtained from the freezing point by Wildermann. The autVbor con- siders it most probable that, as yet, the freezing point depressiaiw in very dilute solutions are not accurately known. Determination of Molecular Weights. 111. By ERNST BECK- MA", GOTTHOLD FUCHS, and VJCTOR GERNHARDT (Zeit. physikaE. Chem., 1895, 18, 473-513 ; compare Abstr., 1895, ii, l54,382).--According to Arrhenius' formula, the constant for the boiling point elevation is obtained by the equation I; = 0.0198 T / w , where to is the laoent heat of raporisation of the solveljt.This constant is, however, fre- quentJy unknown, but may be calculated from Clausius' formuIa w = 1*98 TL . dp/dt x l/JIp, the letters having their usual significance. Also, by Trouton's rules, which nas found to be valid by liuginin 1 COV.l,Kl - COV.0 L. M. J .GENERAL AND PHYSICAL CHEMISTRY. 237 and by Schiff (Abstr., 1895, ii, 154), the latent heat is given by the expression TIM x constaut, the d u e of the constant varying in different series of compounds. These expressions were tested by the authors foy a large number of liquids, the molecular elevation of the boiling point being determined directly and calculated from vatpour pressure alteration experiments, as well as by Trouton’s rule.The latent heat of vaporisation of the liquid was d s o calculated, both Ily the boiling point and vapour pressure determinations. The following liquids were investigated : benzene, cymene, carbon bisulphide, chloro- form, niethylic iodide, ethylic iodide, ethylic byomide, nitroethane, propionitrile, etbylenic dibroniide, ethplenic dichloride ; water, methylic, ethylic, propylic, isopropylin, isonmylic, and terhiai-y amy lic alcohols ; ether, methylal, rnethylic and ethylic formate and acetate, isoamylic acetate, paraldehyde, acetone, methyl propyl ketone, ca 111- phor, nienthone, menthol, and glycerol. In most cases, Trouton’s rule gives approximate results, whilst the ca.lculated latent heats agree with one another aud with the direct determinations as well as the latter agree among themselves.The values f o r the latent heat of water obtained by the two methods were 548.8 and 536.8. L. iU. J. Boiling Points of Solutions of Salts in Methylic and Ethylic Alcohols. By J. WOELE’ER (Am. Phys. Chew., 1895, [2], 57,91-211). -The author 1x1s determined the boiling points of dilute solutions of the iodides arid acetates of sodium and potassium, the chlorides of lithium and calcium, and the nitrates of silver and calcium in methylic and ethylic alcohols. The molecular weights of the dissolved sub- stances were in each case calcnlated from the results by means of the forniula where I - is the latent heat of vaporisation of the alcohol, Tits boiling point in absolute temperature, d l ’ the raising of the boiling point by the dissolved snbstance, and g the percentage of the dissolved sub- stance contained in the solution.The calculated molecular weights were found to 5e al~r~ost inviiriably loiver than the true values. -They illcrease, however, with rising concenti*ation, b u t , iii the case of the methylic alcohol solutions, suffer a subsequent ‘ decrease when the concentration I-eaches a certain value. The maxiinurn for the methylic alcohol solutions OCCUI’S when the niolecular concentriition is 0.302 per litre, or, in the case of calcium nitrate, about double this valoe. The dissociation calculated from the raising of the boiling point, in the case of the etliylic alcohol solutions, only agrees with that determined from the conductivity ill the case of the very dilute solutions.In the more coiiceiitrated solutions, the dissociation calculated from the boil- ing points is srnaller than that calculated from t.he conductivities. A better agreemerit is obtained w i t h the solutions i n methylic alcohol. The author’s results are not in ngreemtnt with Ostwald’s law of dilu- tion. H. C.238 ABSTRACTS OF CHEMICAL PAPERE. Use of Bromoform in Crgoscopy. By G. AMPOLA and C MANUELLT (Gnzzeffa, 1895, 25, ii, !)l-lOl).-Bromoform behaves somewhat similarly to benzzrne and pnraxylene (compare Patern6 and Montemartini, Abstr., 2895, ii, 207) when used as the solvent in molecular weight determinations by the cryoscopic method. Ac- cording to Raoul t’s law, the molecular depression of the freezing point of bromoform should be L56.86; the menu of a number of determinations made with paraldehyde, benzene, naphthalene, parn- xylene, thiophen, aniline, dimethylaniline, and quinoline give the value as 144.The substances named in the above list may be said to behave normally towards this solvent ; ethylic oxalate gives depres- sions which are too low, whilst isobutyric and acetic acids, the only two acids studied, give molecular depressions of about half the normal values just as they do in benzeno and paraxylene. The behavionr of phenols and alcobols i n bromoform is also very similar to their behaviour in benzene and paraxylene; phenol and thymol give low molecular depres-ions, which decrease rapidly as the con- centration increases, until, in a 9 per cent. solution, the molecular depression with phenol is only 53%.The molecular depressions with ethylic and benzylic alcohols and trimethylcarbinol are low eveti in 0.5 per cent. solutions, and decrease as the concentration increases until, in a 15.8 per cerit. solution, the molecular depression with ethylic alcohol is only 16.2. It is noteworthy that chloroform depresses the freezing point of bromoform normall?. W. J. P. Laws of Connection between the Conditions of a Chemical Change and its Amount. 111. Further Researches on the Reaction of Hydrogen Dioxide and Hydrogen Iodide. By A. VERNOB UAKCOURT and W I L L I A M Essoiv (Phil. Trnris., 189S, 186, 81 7 - 895. Bakerinn Lecture). -The investigations commenced nearly 30 years ago by the authors (Trans., 1867, 20, 460) on the reactions which take place between hydrogen dioxide and hydrogen iodide as R case of gradual chemical cha’nge, ha\-e been continued at intervals, and the results obtained are commuriiciLted in this paper.The vessel employed in nialiiug the observations consisted of a tall, glass cylinder, 12 x 3 inches, round which, about Sh inches from tbe top, a fine line had been etched. The cylinder was closet1 by il caoutchouc stopper, through whicli passed (1) an inverted funnel tube in the centre, (2) a thermometer, (3) a short tube, 1 x 4 inclr, giving access to the interior. Into the cylinder were poured water, and measured quantities of solntions of all tlie reacting siib- stances except hydrogen dioxide ; the temperat,ure was brought to the desired degree ; mid more water was added until the upper surface of the liquid coincided wit11 the line round the cylinder.Then a measure of hydrogen dioxide was brought i u . Large bubbles of carbonic anhgdritle were sent through the liquid to act as R stirrer, the bubbles issuing at the bottom of the inverted funnel. Whenever the liquid, in which iodine was being slowly formed, showed the blue colour of iodised starch, drops of uniform size of a concentrated solu- tion of sodium thiosulphate were brought in one at a time through the short tube. As soon as the sniall portion of thiosulphate, dis-GENERAL AND PHYSICAL CHEMISTRY. 239 solved in each drop, was exhausted, the iodine liberated by the peroxide was no longer removed, the liquid became blue, and the moment of change was noted. Thus were observed the successive intervals required for the performance of a known fraction of the total change, and from these the rate of change was inferred.Such observations furnish the means of measuring the time reqnired for a definite amount of chemical change under known conditions. The time required varies, because one condition is continually varying, namely, the amount of dioxide in the liquid. If y is the amount of dioxide at a time t, ?J' a t a timo t', the relation connecting these quantities is y' = ye-w' - 9, in which a is the fraction of the dioxide which disappears in it unit of time. Each observation furnishes a value of a, and the mean of the values obtained in this way from a set of observatioiis is taken as the true value under the conditions of each experiment.The substances used in most of t'he observations were (1) a solntion containing hydrogeii dioxide, made by dissolving sodium dioxide in a slight excess of dilute sulphuric acid; (2) a solution of potassium iodide or hydrogen iodide; (3) dilute sulphuric acid; of the last named, a relatively large quantity being generally taken. l'he quan- tities of each subst'ance are stated as the number of millionth-gram molecules per c.c. The first series of observations welie made in order to ascertain the influence on the rate of change of variations in the amount of eulph- uric acid. If i denotes the number of millionth-gram molecules of iodide and s the number of millionth-gram molecules of sulphnric acid in 1 c.c., the following three formuk hold for the solutions examined at 30' a = i (4730 + 18(s - 190.5)]10-n, a = i { 161.30 + 26*5(s - 762) ) I F , the first formnla holding from s = 190 to s = 514, the second from s = 514 to s = 762, and the third frow .s = 762 to s = 1143.It appears from this that the increment in the rate of change due to each unit-substitntion of sulphuric acid for water is constant until a certaiu ratio of acid to water is I eaclied ; a t this point, the increment suddenly rises and remains constant until another ratio of acid to water is reached, after which it again rises and then remains constant as far HS the experiments procceded. These results accord with the view that when a drop of sulphuric acid is mixed with a relatively lwge volume of water, the liquid consists of a mixture of water with whatever hydrate of the mid contains the largest number of mole- cules of water.If the addition OF acid is contiiiued, the proportion of t h i s first hydrate increases and the proportion of water diminishes, until a point is reached a t which the liquid consists of the hydrate. After this point, a new order of events begins ; a second hydrate is formed with ft larger proportion of acid, its amount increasing and that of the first hydrnte decreasing, until the liqnid consists of the = i(10550 + 2 2 . 5 ( ~ - 514))10-',240 ABSTRAOTS OF CEEBIIOAL PAPERS. second hydrate. Then begins the formation of a third hydrate, and so on. Sets of observations at the lower temperatures of 36' and 20°, also show that the value of the increment of rate, caused by successive yeplacements of water by sulphuric acid, changes abruptly a t certain points.The results are consistent with tolie supposition that, at the three temperatures of the authors' experiments, the compositioii of the two hydrates indicated is the same. Their composition is prob- ably not far removed from H,S04,106H20 and H2S04,71H20, and it may hare some significance that these numbers are to one another in the ratio of 3 : 2. The rise of temperature of 14' augments the incre- ment of thc rate of change per unit, of sulphuric acid in the ratio 2.62 : 1, whichever hydrate is being formed. Separate investigations were made with the object of ascertaining the effect of the first additions of very small quantities of acid. The fimt small addition of sulphuric acid causes a much greater incre- ment of the rate than subsequent small additions, and it is only when thc proportion of acid reaches a certain limit that tlie first minimum and constant value of the coefficieiit of s appears The influence of hydrogen chloride on the rate of change was next investigated. Puttiny i for the naiiiber of millionth-gram molecules of hydrogen iodide, and c f o r the nnmbcr of millionth-gram molecules of hjdi-ogen chloride, the eqnation which represents the variation of the rate with the amount of hydrogen chloride, at 30' and over the range of the observations, which were extended from c = 71 to c = 355, is a = i (2800 + 16.8 ( c - 71.1) j10-6.Comparing the influence on the rate of the preseiice of sulphuric acid and hydrogen chloride respcctivcly, it, will bc seen that, molecule for molecule, the two acids arc nearly equivalent, instead of one molecule uf sulphuric acid being eqnivalent to two molecules of hydrogen chloride as in combining with \lases. An addition of hydrogen iodide, like an addition of hydrogen chloride or sulphuric acid, causes an incrrment in the rate.It is necessary in this case to separate the effect of the hydrogen iodide as one of the substances which is undergoing change from that of the hydrogen iodide as an acid; and when this is done, the numbers found are in arithmetical progressiou, and correspond with the pre- vious series representing the accelerating effects of sulphui*ic acid and hydrogen chlotide. The effect of an addition of sodium hjdrogen carbonate was also invcstigated, atrd here again the results obtained were similar to those given by the other substunccs examined.Instead of varying the conditions of the change by taking more or less of some of the ingi.edieiits of thc solution, i t was possible to make a variation by snbstituting salts with the same metal or acid radicle, one for another, in the proportion of their molecular masses. The effect of snbstituting sodium for potassium iodide molecules is to increase the rate ; a substitution of sodium for hydrogen chloride caiises a decrease. The influence of sodium chloride on the rate, andGENERAL AND PHYSICAL CHEJIISTRY. 24 1 doubtless that of other salts, is far greatel- in presence of sodium hydrogen carbonate than it is in presence of hydrogen chloride. A substitution o€ iodide for chloride, in molecular proportion, causes a retardation ; but, absolutely, each salt accelerates.The results obtained throughout do not seem t o show any effect of progressive dilution beyond the neceaaary consequence that every addition of water diminishes proportionally the mass of each acid or salt in unit roluine. If the hypothesis OF ionic dissociation is accepted, i t seems to follow that the acids and salts which have beell the subject of these experiments arc either (1) so near complete dis- sociat,ion i t 1 solutions of normal strength that no great increase i11 the proportion of ions to molecules is caused by further dilution, or (2) that not8 much dissociation has yet taken place in solutions of less than centinormal stxength, or (3) that the ions interact at tho same rate, and accelerate chemical change in thc same degree, as the molecules from which they are formed.In order to study the effect of varying the temperature, the rates a t different ternpei-atures were compared when the change takes place with the same amounts of each substance in urlit volume. A solution containing sulphuric acid and hydrogen iodide was selected for the Purpose, and to facilitate the investigatioil of the law of connection between a and t, a calculation was riiade, by interpolation from the results, of the rates a t degrees of tern- perature expressed in whole numbers and with successive dif- ferences of 5". The observations extended from 0" to 50°, and the table is giren of the values of a, their logarithms to the base 10, and the successive differences of the logarithms, A loga.These last numbers continually diminish as the temperature increases, and as a first approximation may be assumed to be in arithmetical pro- gression ; so that we may put A log a, = a - bz. This formula, how- ever, although convenient for calculating the rates at different tern- peratures ranging from 0' to 50" would fail for higher degrees of tem perature. A function of x, the successive differences of whicb closely resemble the successive differences of log a, is uz = log ( c + x), when c is considerably larger than z. Assnmiug that log a, = m log (" - x, + log a , , the values of W L aud c may be found from the experimental numbers. If the value of z is taken as 5, that of c is found to be 54.52, or siilce 51L: = t, + log a,, 272.6 + t 2 72-6 log at = m log 272.6 + t 272-6 This equation implies that DO chemical change will take place when t = -273.6, a temperature a t once recognised as practically iden- tical with that of the absolute zero.Thus, within the limits of ex- perimeutal error, it may be assnmed that the zero of chemicalchange OL'242 ABSTRAOTS OF OtlEMTOAL PAPERS. coincides with the zero of absolute teitiperature. If we call the absolute temperature n t the freezing point To, the equation of connec- tion of the amount of chemical change wit'h temperature may be written i n thc form The form of this equation shows that the relatioil between the amonnt of chemical change at a giveu temperature and the absolute temperature is independent of the units i u which each of these quan- tities is measured.I t is fiirther shown in the paper that the number 712, which remains constant in ,z series of experiments at different temperatures with the same kind of solution, varies with the nature of the main ingredient of the solution, but not with the amount of that ingredient. If a and a' are two rates corresponding with two temperatures very near to each other a ' - - a T ' - T U T = 111. which implies that the increase of each unih of chemical change per unit increment of each unit of temperature is constant at all tem- peratures. A large number of experimental confirmations of t h i s law of the connection between chemical change and temperature are given in the paper. It is convenient to express the relation in the form log a - log u, = m(1og T - log To).This mode of stating the law has the advantage that the graphic representat,ion is a straight line. H. C. Stability of Imides of Dibasic Acids. By AiwuRo MIoLArI (Real. Accnd. Lincei, 1894, i, 515-521 j.-The imides of the dibasic acids are soluble in water, and are slowly decomposed by dilute hydrochloric acid a t the ordinary temperature, so that they lend themselves readily to determinations of the velocity of reaction. The reaction is of the second order, and is therefore represented by the usual expression Ac = x / t ( A - z), the units being cubic centimetres and minutes. The determinations were made at 2.5' in 190 C.C. of N/190 solutions of the itnide to which 10 C.C. of N/lO caustic soda was added ; from this mixed N/200 solution, samples were drawn at de6nite intervals and the acid determiued by titi*ation. The velocity constants, Ac, for succinimide, pyroiartarirnide, and glutarimide are 0.002382, 0.001374, and 0.2511 respectively.It is seen that, by ilitroducirig ti methyl group into succinimide, and so getting pyrotartarimide, the resistance to hydrolysis is greatly increased ; by lengthening the inethjlene chain by one -CH, group, as in glutarimide, the velocity ot' decomposition becomes a hundred times greater than with the original succinimide. W. J. P. Stability of Substituted Succinimides. By ARTUHO MIOLATJ and E. LOSGO ( R e a l . Accad. Lin(:ei, 1894, i, 597-605).-Using tlieGENERAL AND PHYSICAL CHEMISTRY. 243 method previously described (see preceding abstract), the authors have determined the velocities of hydrolysis of a number of snccin- >NR, where R is an alkylic imides of the constitution I radicle ; the velocity constants Ac are tabulated below.CH2*C0 CH2*C 0 H . . .................. Et. .................. Me. ................. CHB.CH2.CHZ. ........ 1 dc. I -I 0 -00238 0 '05500 0 * 08500 0.2L'iOO It. C,II,*C H,. .......... C,H,Me (psr'i). ..... CH2:C K*C'H,. ........ C,H,* .............. 0 -276 0.282 1 -1 20 2 -270 ~ _ _ _ _ _ The substances are arranged in order of stability, and, as will be seen, are yery much more readily hjdrolpsed than the unsubstituted succinimide. W. J. P. Reaction Velocity of Intramolecular Changes in Stereo- isomeric Oximes. By HEIXRICH LEY (Zeit.physikal. Chem., 1895, 18, 576--398).-The first change studied was that from the sgn- aldoxime acetate to the corresponding nitrile and acetic acid. The observations were made at temperatures varying from 25O to 70" in the case of the acetates of t hiophen-synaldoxime, anis-syn-aldoximc, benz-syn-aldoxime, parachlor-, Imrabrorn-, aud pariodo-benz-syn- aldoximes, the compounds being enumerated in the order of magnitude of the reaction constants, which vary from 0.00041 to 0.000'7 a t 25O, and 0.00196 to 0.012 a t 50°, the reaction being of the first order. The results are also shown by curves, in which R specific influence of the thiophen group is evident, the curve for its derivative falling apart from the rest. The temperature iiifluerice agrees fairly satis- factorily with van't Hoff's formula, KL = KO .e The iicxt change considered was the intramolecular change from the syn-aldoxime tJo the anti-aldoxime in alcoholic hydrogen chloride solution. This was done in the case of the benzaldoxime, anisald- oxirne, and p-chloraldoxime acetates, at temperaturea varying from 10' to 40°. The constant was greatest for benzaldoxime, C,p = 0.0148, and least for anisaldoxime, Cleo = 0.0075, whilst the tempera- tare change is as indicated theoretically. In this case, the thiophep derivative could not be examined, as, under the conditions of the experiments, the nitrile is produced. Action of Unorganised Ferments. By GUSTAV TAMMAN (Zeit. physikal. Chem., 1895, 18, 426-442).-The enzymes dieer from inorganic hydrolytic agents in exerting a special, and not a general, action, and also in their loss of activity during the progress of the action.Hence, of two reactions with equal initial velocities, that caused by an enzyme progresses more slowly than that caused by an acid, &c. For the study of this loss of activity, the decomposition of salicin by emulsin was investigated. T, - To T, . To * a- L. M. J.244 ABSTRACTS OF CHE311CAL PAPER$. Other corditions being bimilar, the quantity of salicin decomposed iu a given timewas found to be dependent on, and could be employed as a measure of, the quantity of emulsin present. Emulsiii was then dissolved in water, and, from time to time, equal quantities were with- drawn, and the quantity of the active enzyme measured by salicin, as indicated above. At temperatures above 50°, the loss of activity of the emulsin appears to he due to a unimoleculilr reaction, since the value l / t . log lOO/(lOO - x) remains approximately coI1stant, where 100 - x is the percentage of active enzyme found in the solution after a given time t ; at temperatures below 50°, however, this expres- sion did not lead to a constant. value. The loss of activity of solid emulsin was also determined a t teniperatures between SO" and 108O, the reaction being again of the first order. The reaction velocity for the decomposition of saliciii diminishes, thereforc, but the measurement of the initial velocities a t 25' and 40' &Free well with those calculated from the initial velocity a t 0'. The decornposition cannot be com- plete, but must tend towards a definite limit, which is a function of the original quantities of both saliciii and emnlsin, varying, from 0 to 1 when t,he quantity of ferment varies from 0 to 8, and the validity of this deduction is proved experimentally. L. 31. J. Molecular Symmetry and Asymmetry. By ALBERf LADENBURG (Be,.., 1895, 28, 3104-3105 ; compare Abstr., 1895, ii, 489).-A reply to Groth (this vol., ii, 159). BAUM (Be,.., 1896, 29, 69--71).-The form of apparatus in general use is a modification of the condenser originally described by Weigel in the year 1771. Liebig simply refewed to it (Handbuck Chem., 1843) as R known form, having man? advantages. Modification of Mohr's Balance, and a Simple Apparatus for Measuring the Volumes of Solids. By GIOVANNI GUGLIELMO (Real. Accad. Lincei, 1894, ii, 299-303).-The author describes n modification of Mohr's balance for determining densities. The volume of a solid can be determined within 0.01 C.C. by measuring with a burette the volume of water which i t displaces from a beaker, the edge of which is ground. and which is furnished with a glass or platinum poiliter, terminating iu the plane of the edge of the beaker. M. 0. F. The so-called Liebig's Condenser. By GEORG W. A. KAHL- M. 0. F. W. J. P.

ISSN:0368-1769    

DOI:10.1039/CA8967005229

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

244 ABSTRACTS OF CHE311CAL PAPER$. I n o r g a n i c C h e m i s t r y. Ratio of the Atomic Weights of Oxygen and Hydrogen. By JIJLIUS THOMSEN (Zeit. nnorg. Chem., 1895, 11, 14-30; see also Abstr., 1894, ii, 277).-The method employed consisted in determin- ing the weight of hydrogen evolved by dissolving a known weight of pure aluminium in sodium hydroxide in a specially constructed appa-I S 0 2GhNIC C K EM IST Ec T . 245 ratus ; the weight of hydrogen being determined by the difference in weight before and after the dissolution of the aluminium. Also, in a similar apparatus, by determining the increase in weight brought about by burning the evolved hydrogen in pure oxygen. Drawings and a full description of the apparatus employed are given in tke original paper. The mean of 21 experiments, in which altogether 162.3705 grams of aluminium were used and 18.1778 grams oE hydro- gen evolved, gave hydrogenlaluminium = 0~11190+0*000015, and the mean of 11 experiments in which 86,9358 grams of aluminium was used and 77.1876 grams of oxygen, gave oxygen/aluminium = 0.88i87 0.00001S. Whence 0 : H = 15.8690+ 0.0022.Or when 0 = 16, the atomic weight of hydrogen is 1.008255, mid the mole- cular weight of water is 18.0165. These results agree very closely with the recent determinations by other experimenters. Origin of Atmospheric Oxygen. By THOMAS L. PHIPSOX E. C. R. (Cowzpt. Tend., 121, 719-721).--See this vol., ii, 265. Decomposition of some Trinitrides. By ALBERTO PERATOXER and GIUSEPPE ODDO (Gazzettn, 1895, 25, ii, 'L3--81).-The molecular weight of argon, 40, approximating to that of a triatomic polymeride of nitrogen, the authors have made a number of experiments on the gas obtained by the decomposition of azoimide and its derivatives, and find that argon is in no case obtained.During the electrolysis of sodium azoimide solutions, nitrogen and hydrogen are a t first evolved in the proportion of 3 : 1, but as the quantity of salt decreases, oxygen and nitrogen collect at the positive pole, although not iii quantities equivalent to the hydrogen separated at the negative pole, owing to oxidatioii of the nitrogen to nitric acid. The same Eehaviour is observed in the electrolysis of aqueous azoimide ; ammonia, but no hydrazine, is found in tohe residual solu- tion. The irregularities observed by Hittorf during the electrolysis of trinitrides are due to the occurrence of secondary reactions such as are here indicated.The nitrogen obtained on exploding silver trinitride by heat in a special apparatus, and that evolved during the hydrolysis of paranitrotriazobenzene mere also examined. The densi- ties of the various samples of gas obtained in these experiments were determined and the gas was sparked after mixing with oxygen ; in no case, however, was argon detected or evidence obtained of the existence of the polymeride N3-N3, corresponding with the azoirnide radicle. W. J. P. Argon. 13y RAFFAELO NASINI (Gazzetfa, 1895, 25, i, 37-46).- The author contends that i€ the ratio of the two specific heats of an elementary gas such as argon approximates to 1.67, this fact can only be wed as confirmatory evidence of the probable monatomicity of the molecules, but cannot be accepted as authoritative and conclusive evidence, if no other facts pointing to the same conclusion are forth- coming.The values of k for all the polyatomic gases are consider- ably less than 1.67, but the values for the diatomic gases are not all the same, indieating that the approximation to sphericity of the VOL. LXX. ii. 18246 ABSTRACTS OF CHEMICAL PAPERS. molecules, or tbe magnitudes o€ the interm~lecular movements, or both, have different values for different gases; i t is thus quite possible that the molecules of argon are diatomic, but so nesrly spherical, and possessed of so little internal movement that the value of X: is almost that of a monatomic gas.If argon is monatomic, it has an atomic weight of about 40, aud finds no place in the recog- nised periodic classification ; if, as seems more probable, it is diatomic and has an atomic weight of about 20, between those OE fluorine and sodium, it finds a suitable place in the periodic system as the first member of a new series of elements lying between the series of the halogens and of the alkali metals. By ARTHUR 31. EDWARDS (Chern. Xetus, 1896, 73, 13).-The siliceous shells oE Bacilliariacece, XpongidE, and Radiolarice, in infusorial earth and soundings are observed to dissolve in fresh spring water, probably from its containing ammonia. W. J. P. Solubility of Silica. D. A. L. Italian and other Cements. By GIUSEPPE ODDO and E. MAN- ZELLA (Cazeffa, 1895, 25, ii, 101--113).--The authors have made analyses and resistance tests of a number of hydraulic, Roman and Portland cements of Italian, German, and French origin; the per- centage compositions of the Italian cements are not rery different from those of the other samples examined.The mean composition of the slowly setting cements in percentages is 61.14 CaO, 1.05 MgO, 20.94 Si02, 9.26 A1203, and 1.5 Fe203, whilst that of. the rapidly setting samples is 57.67 CaO, 0.90 MgO, 21.97 SiO?, 9-91 A1,0,. and 1-46 Fe203. The molexdar compositions of the slowly mid rapidly setting cements are respectively = 2.481 2.183 CaO + 0.052 MgO 0.070 SiO, + 0.182 Al,03 + U.019 h’e203 and = 2.227. 2.060 CaO + 0.045 MgO 0.0732 SiO, + 0.194 A1203 + 0.019 h1e2O, The ratios of numerator to denominator are the molecular ratios of basic to acid radicles present, and are considerably lower than the ralncs found by Le Chatelier.W. J. P. The Setting of Cements. By GIUSEPPE ODDO and E. MANZELLA (Gazzetta, 1895, 25, ii, 113-127 ; compare preceding abstract).- Although no noteworthy difference in composition exists bet ween Italian and other cements, there is a very appreciable difference be- tween the behaviour of the two classes of cements towards potassium carbonate. Samples of powdered cements, before and after setting, were extracted for definitc times with potassium carbonate solution, using a special form of mechanical agitator, samples of the solution being drawn off at definite iutervals, and the total and caustic alka- linity determined.The caustic alkali extracted from the French and German samples of un set cements practically reached a maximum within the first half hour; after setting, however, a much largerINORQANIC CHEMISTRY. 247 quantity of caustic alkali was extracted and the quantity increased continually as the time of extractiou was increased to 9 hours. It is concluded that before the setting of these cements they contain but small quantities of free lime and readily decomposable polysalts ; the quantity of these salts, which are slowly and continuously decom- posed by potassium carbonate, is much greater after the setting. Most of the Italian cements contain considerable quantities of lime before setting, and i t is concluded that the setting is due to hydra- tion of the salts present, for the amount of caust,ic alkali extracted by the potassiud carbonate solution is riot appreciably greaker, and sometimes less, after setting, and frequently decreases as the time of extraction is increased.W. J. P. Manufacture and Commercial Separation of Beryllium. By HENRY N. WARREN (Chew,. News, 1895, 72, 310-31 l).-Pul- veriaecl and lixiviated emerald is fused for 3 hours in a blast furnace, with four times its weight of sodium carbonate ; the solidified mass is decomposed by superheated steam, and then by hydrochloric acid ; evaporated t o dryness, extracted with water, and the silica sepa- rated. The solution, freed from iron and chromium by the acetate method, is first treated with excess of sodium carbonate, and the pre- cipitate heated with excess of suiphurons acid, when the alumina and glucina pass into solution ; on boiling, the alumina is precipitated in a granular form, that, can be readily washed ; excess of ammonium carbonate is then added to the solution, which is well boiled.The precipitate of beryllium carbonate thus obtaiocd is ignited with lamp- black out of contact with the air, and then submitted to the action of bromine vapour at a full red heat in clay retorts. Beryllium bromide distils over, and is reduced electroljbically. D. A. L. Sulphur and Carbon in Zinc. By ROBERT FUNK (Ber., 1895, 28, 3129-3132 ; compare Abstr., 1895, ii, 390).-The purified zinc of commerce usually contains traces of sulphur and carbon, which are not, however, dissolved in the metal, and may, therefore, be removed from the fused zinc by filtration through asbestos; the odour of the gas evolved by the action of zinc on sulphuric acid is due to the presence of hydrogen sulphide.(Compare this vol., ii, 874). M. 0. I?. Orthoplumbates of the Alkaline Earths. By GEORG KASSNEH (Arch. Pharm., 1895, 233, 501-507) .-Calcium orthoplumbate, C%PbO, + 4H20 (Abstr., 2895, ii, 14) loses 3H20 at 2.W--250°, and is converted into a mixture of cabiz~rn metapktntbate, CaPbO,, and hydroxide, although at a higher temperature (500') these two substances condense again to the orthoplumbate. Calcium metaplnmbate, on ignition, is converted into the orthoplumbate, lead monoxide, and oxygen. Anhydrous calcium metaplumbate is a choco- late brown powder, which, after long contact with water, absorbs 2H20, and asmmes a, lighter hue.Calcium diplumbate (loc. cit.), CaH2Pb206, loses half its water at 18-224s ABSTRACTS OF CHEMICAL PAPERS. 310°, and the remainder at 3SO -490Q. cctlciz~m tetraplumbate, Ca,H, Pb,O,,, is a loose yellowish powder. The intermediate product, Jx. W. Metaplumbates of the Alkaline Earths. Bg BRUNO GRhZKER and M. HOHNEL (Arch. Phnynz., 1895, 233, 512--521).-Calcium metsplumbate (preceding abstract) may he prepared by digesting the orthoplumbate Fpith sodium peroxide and water; it is R white powder, cry~t~allising in microscopic cubes, The analyses point to its containing 4&0. stituting caustic alkali for the alkali peroxide. Silver metupliirnbate, obtained by digesting calcium metaplumbate with aqueous silver nitrate a t the ordinary temperature, is a dark gray, silky powder, crystallising in microscopic cubes.The crude product contains silver oxide, which can be dissolved out with am- monia ; the product thus purified is of a cleay gray colour, and its composition corresponds with the formula AgzPb03. The barium and strontium salts cannot be prepared by the above methods. JN. W. A less pure product may be obtained by sub Thallous Fluoroxymolgbdate and Fluoroxyhypomolybdate. By FRANCESCO MAURO (Real. Accad. Lincei, 1893, ii, 382-384 ; com- pare Abstr., 1893, i, 124) .-Delafontaine first prepared thallous fluor- oxymolybate, 2TIF,MoO2F2, by dissolving thallous oxide and molybdic anhydride in dilute hydrofluoric acid, but made the erroneous state- ment that it contains water of crystallisation ; it is sparingly soluble in water and forms long, orthorhombic crystals which lose their transparency after R time ; a : b : c = 0.85521 : 1 : 1.02474.Thallous$uoroxyh yponaolybdate, 2T1 F,MoOF,, is prepared by electro- lysing a solution of molybdic anhydride in hydrofluoric acid, covered with a layer of petroleum, and adding thallous oxide until the solu- tion is decolorised. The deposited salt crystallises in uitreous, green, orthorhombic plates or prisms ; a : b : c = 0.86595 : 1 : 1.02952. Monothallous $zcoroaymolybufe, TIF,MoO,F,, which is deposited on concentrating a hydroflnoric acid solution of thallous fluoroxp- molybdate over sulphuric acid, crystallises in lustrous, yellow, mono- clinic plates which begin to decompose at 240' ; It was found by Scacchi (Real.Accad. Lincei, 1893, ii, 401) to be iso- morphous with monammonium fluoroxymolybdate. By MAURICE FRANqors (Compt. rend., 1895, 121, 768-770).-&1ercuric iodide dissolves somewhat, readily in hot phenol and separates in the yellow modifi- cation, which only slowly changes into the red form. Boiling phenol decomposes mercurous iodide into the mercuric salt, which dissolves, and mercury which remains undissolved. The decomposition is however limited, and equilibrium is established when the phenol contains 2.75 parts of mercuric iodide in 100. A solution containing a higher proportion of mercuric iodide will attack mercury wibh formation of the mercurous salt, this action continuing in a : b : c = 0.61985 : 1 : 1.39755. /3 = 86" 7'.W. J. P. Action of Phenol on Mercurous Iodide.INORGANIC CHEMISTRY. 249 presence of excess of mercury, until the proportion of mercuric iodide in solution is reduced to 2.75 parts in 100". illercurous iodide is o d y very slightly soluble in boiling phenol i n preseiice of sufficient mercuric iodide to prevent decomposition, but the mercurous iodide which has been heated to 100Oin piesence of phenol is converted into very distinct though microscopic crystals. (Compare this vol. i, 22). C. H. B. Probable New Element in Terbia. By PAUL LECOQ DE BOIS- EAUDRAN (Compt. rend., 1895,121, i09).-A deep red- brown terbia when dissolved in hydrochloric acid showed only a faint absorption spectrum of dysprosium, and a nebulous band at X487.7 which does not coincide with any known band, but seenis to belong to a new element which the author distinguishes as Zo".C. H. B. Manganese Silicide. By VIGOUROUX (Compt. rend., 2895, 121, 771-773).-Manqanese silicide, SiRfn,, is obtained (1) by heating silicon with nine times its weight of manganese in the electric furnace and treating the product first with water, then with dilute hydrochloric acid, and finally, and rapidly, with dilute hydrofluoric acid, or (2) by heating in the electric furnace a mixture of 1 part of silica, 3 parts of manganoso-manganic oxide, and 1 part of sugar- carbon, and treating the product as above, 01- better, (3) by heating silicon with 4 or 5 times its weight of manganoso-manganic oxide in a porcelain dish in an atmosphere of dry hydrogen up to the softening point of porcelain.It has a metallic lustre and ft steel-grey colour, is very hard and very brittle, and perfectly crystallised ; sp. gr. = 6.6 a t 15'. It does not alter when exposed to air, and melts at the temperature of the reverberatory furnace. Fluorine attacks it a t the ordinary tempera- tiire, chlorine at. about 500°, and iodine and bromine a t higher temperatures; oxygen and air attack it a t a red heat. Dry hydrogen fluoride decomposes it readily, especially if gently heated, hydrogen chloride below a red heat, and hydrogen iodide a t a higher temperature; water is without action at 100°, but a t a red heat decomposes the silicide, with liberation of hydrogen. Dilute acids attack i t readily, and concentrated acids, especially hydrofluoric acid, are violent in their action ; aqueous potash is without effect, but the solid substance attacks the finely powdered silicide when heated with it, and fused alkali carbonates or mixtures of carbonate and nitrate oxidise it readily.C. H. B. Electro-dissolution and its Uses. By HENRY N. WARREN (Chew. News, 1696, 73, 37-38).-When iron containing boron, silicon, sulphur, phosphorous or carbon is the positive electrode, platinum being the negative in a bath of sulphuric acid, the iron dissolves, whilst the impurities are wholly or partly precipitated With impure copper in a hydrochloric acid bath, the copper is pre- cipitated on the platinum, whilst the impurities-arsenic, iron250 ABSTRACTS OF CHEMICAL PAPERS. zinc, &c., remain in solution. ferric acetate may be prepared by electro-dissolution.Stannic nitrate, potassium ferrate, and D. A. L. Hydrolytic Decomposition of Ferric Chloride. By UBALDO ANTONY and G. GIGLIO (Gnzzetta, 1895, 25, ii, l-l2).-Freshly pre- pared and perfectly neutral ferric chloride solutions were made by digesting precipitated ferric hydroxide with dilute hydrochloric acid in the cold, filtering from the excess of ferric hydroxide, and subsequently adding the requisite quantity of hydrochloric acid to give a pure solu- tion of Feel,. Those which contain less than 1.1 per cent. of the salt appear colourless in a 40 centimetre tube, but after several hours become yellow, the colour increasing in intensity during 48 hours after preparation. Dilute solutions, which have been preserved for some days, only slowly give a blue colour with ferrocyanide, whilst a solu- tion containing only 0.00083 per cent.of ferric chloride gives no colour with ferrocjanide. From these results, and from the behaviour of the solutions towards sodium chloride and hydrogen sulphide, it is concluded that the ferric chloride reacts with the water, being con- verted in infinitely dilute solutions, or those containing less than 0.00083 per cent., into colloidal ferric hydroxide, which is not acted on by potassium ferrocyanide ; i t is further shown by colorimetric measurements that the velocity of the reactions does not stand in simple relation t o the concentration of the solution, so that it must be assumed that the hydrolysis leads to the formation of intermediate products, like FeCI,( OH) and FeC1( OH),.In the more concentrated solutions, a stable equilibrium is set up between these basic corn- pounds and the other constituents of the solution ; this equilibrium is destroyed by the addition of ferrocyanide, which only reacts with the ferric chloride, thus causing the hydroxy-chlorides to be acted on by the acid present, again yielding ferric chloride. W. J. P. Salts of Ferric acid. By LUDWIG MOESER (Arch. Phann., 1895, 233, 521-527) .-Potassium ferrate is best prepared by gradually adding bromine (50 grams) to ferric hydroxide (80-90 grams) sus- pended in a cooled concentrated caustic potash (50 grams in 80 grams of water) ; more potash is then added, and the mixture warmed and kept at 50-60' foil half an hour. The cooled ferrate is drained on a tile, and the excess of alkali removed by alcohol; the potassium bromide is then removed by dissolving the product in a little water and repre- cipitsting it with alcohol.Potassium femate is a reddish-black powder, very soluble in water, forming a deep red solution. When igxiited, it loses oxygen, and i8 converted into the green ferrite, which, unlike it, is very deliquescent, and rapidly oxidises to pot,assium and ferric hydroxides when exposed to a.ir. Pctassium ferrate is converted by alkali sulphides into a green substance, possibly a sulphoferrate. Barium ferrate is obtained as a dark crimson, amorphous powder by precipitating potassium ferrctte with barium chloride. It is also prepared by boiling fresbly precipitated ferric hydroxide with baryta water and an appropriate oxidising agent, such as barium hypochlorite.Barium ferrate, on ignition, is decomposed into barium ferrite, water,BIINERALOQlCAL OHEMISTRY. 251 and oxygen, and is violently acted on by acids, evolving oxygm, and yielding barium and ferric hydroxides; if nitric or sulphuric acid is used, the oxygen contains much ozone. Barium ferrate may be reconverted into an alkali ferrate hy digestion with the alkali carbonate, and in this way mbidiicrn arid c a s i z m fewates may be obtained. JN. W. Platosombnodiamine Compounds. By ALFOKSO COSSA (Real. Accud. Lincei, 1894, ii, 360-362) .-On heating aqueous platosodiarnine chloride with hydrochloric acid for some hours, platososemidiamine chloride separates ; on adding potassium platinosochloride to the filtrate, the undecomposed platosodiamine chloride is immediately de- posited as Mapus’ green salt, and after filtering and concentrating the solut,ion, platosomonodiamine plat inosochloride, ZPt(NH,)3C12,PtC12, separates in uniaxial, red laminae of somewhat metallic lustre. It is dissolved by ammonia, with formation of platosodiamiiie chloride, and with nitric acid yields chEm.oplatinonaonodinmi~ze nitrate, which is colourless, and very insoluble in water. Plat~somonodiamine chloride is best prepared by adding the equiva- lent proportion of platosodiamine chloride to the platinosochloride ; 011 concentrating the solution, Magnus’ green salt separates, and on evaporating t,he filtrate a residue of plntosomonodiarnine chloride is obtained ; this crystallises in colonrless, monoclinic prisms, and is rery soluble in water. W. J. P.

ISSN:0368-1769    

DOI:10.1039/CA8967005244

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

BIINERALOQlCAL OHEMISTRY. 251 Mineralogical Chemistry. Platinum, Pickeringite, and Magnesia zinc alum from N.S.W. By GEORGE W. CARD (Records Geol. Survey, N.S. W., 1895,4,130-154). --Platinum as grains from the alluvial gold works of Fifield, Forbes, gave, ou analysis by J. C. H. Mingaye, Pt. Ir. Rh. Pd. Osmiridium. Fe. c u . 75.90 1.30 1.30 trace 9.30 10-15 0.41 Au. Pb. Insoluble. Tot,al. nil trace 1.12 99-48 Pickeringite, occurring as silky, acicular crystals at Mt. Victoria, gave HZO. A120,. FeP03. FeO. (3110. MgO. K20. 3i.23 10.65 1-27 trace nil 2.38 0.74 Ns,O. SO,. Ineol. (sand). Total. trace 30.28 17-89 100.44 The magnesia is too low for pickeringite.252 ABSTRACTS OF CHEMICAL PAPERS. Nagnesia zinc alum, from New England, gave &O,. FeO. ZnO. CnO. MgO. Xa,O. K20.SO.,. P,O,. Insol. H,O[diff.]. 9.36 trace 3-34 trace 5.78 0.60 trace 34.62 0.28 2.51 [43*51] L. J. S. Analyses of Gold, Meerschaum, Amber, and Magnetite from Servia. By SIMA 31. LOZAXI~ (LOSASITSCH) ( A m . Ge'ol. Ye'nins. Bdkan., 1893, 4, (2), 81-8G).-Gold from Slatina gave, An 89-39 ; Ag 9.20 ; sand, traces ; = 98.59. Meerschaum from Zlatibor gave Si02. 3IgO. FeO. Loss on ignition. Total. 53.89 22-83 0.88 2220 59-86 Amber from VranjeS, KraljeT-o, of hardness 2-2.5, sp. gr. 1.081, Analjses, mainly technical, are given of various ores and coals ; the gave C, 73-16 ; H, 10.13 ; 0,11*71 = 100.00. followirig is of magnetite from Ven6ac. Loss on Insol. Fa,O,. FeO. Cr,O,. A1,0,. XgO. ignition. Total. 11.63 60.34 79.2 4-49 4-43? 5-44 5.46 99.T7 L. J. S Analyses of Austrian Minerals, &c.By COSRALJ vos JOHN and C. F. EICELEITER (Jahrab. k. li. geol. Reichsamt., TtTren, 1895,45,1-2s). --Numei*ous analyses, mainly technical, are given of coals, ores and impure minerals, rocks, mineral waters, and some artificial alloys. L. J. S. Vanadiferous Coal from Peru. By Tociwo 1- MECA (Beyg- ZLnd h 2 i f t . Zeit., 1895, 361 ; from Boleth de illincis, 1894, December 31).- This coal, from Ytiuli, resembling anthracite in appear:tnce, was examined for platinum, but with a negative result. One sample gave 1.2 per cent. of a greenish-yellow ash, which contained 3 8 per cent. of vanadic acid; the blue sulphuric acid solution con- tained, besides vanadium, sinall quantities of alumina, lime, and mag- nesia, and a little nickel. Molybdic and tnngstic acids were itot found.L. J. S. Burmite, a New Amber-like Resin from Upper Burma. By OWO HELM (Records G'eol. Survey, India, 1892, 25, 180-181 ; 1893, 26, 61-64 ; and Schrvten Ges. Uanzig, 1894, 8, 63-66).-This ncw fossil resin is semi-transparent, and varies in colour from pale yellow to reddish and dirty brown, whilst some specimens are ruby-red and transparent ; it shows a fine blue fluorescence. The shiny conchoidal fracture has a greasy touch. The darker, clouded specimens, of slightly higher specific gravity, enclose particles of organic matter and veins of calcite. A brown, weathered crust is usually present. The hard- ness of 2.5-3 is slightly higher than that of Baltic amber (succi- nite) ; sp. gr. 1*030-1.095. By dry distillation, it decomposes with- out fusion, yielding white aromatic fumes, a brow4sh-yellow oil, and a little watery liquid, the latter containing forniic acid and piobably pyrogallol.Analysis gaveAILNERALOOICAL CHENISTRY. 253 C. 11. 0. S. Total. 80.05 11.50 8-43 0.02 100~00 The ash in a pure piece amounted to 0.2 per ceut., and consisted of calcium sulphate and carbonate and ferric oxide ; an impure speci- men gave 4% per cent. of ash. J t is very resistant to solvents ; oil of turpentine dissolving 18.3 per cent., other solvents much less ; it is gradually dissolved by concentrated sulphuric acid, yielding a red- brown solution. Burniite is distinguished from the Baltic succinite by the absence of succinic acid ; from the Sicilian simetite by its resistance to solvents; aud from the Auckland mnbrite by its low percentage of oxygen and smaller solubility in carbon bisulp hide. The name burmite was first proposed by F.Noetling (Records Geol. Survey, India, 1893, 26, 31), wlio describes the mode of occurrence and niining of the mineral near Maingkhwan, in the Hukong Valley. Composition and Constitution of Cubanite (Cupropyrite) . By R. SCHNEIDER (J. pi.. Chem., 1895, [2], 52, 355-559).-The author's analyses of this mineral arc in accord with the empirical formula CuFe,S,, and agree with those of Scheidhauer (Am. Phys. Chem., 1845, 64, 280). Cu,S,FeS, FeS,FeS)FeSz, the mineral inay be regarded as the analogue of sterabergite, Ag,S,FeS,FeS,FeSj) FeS,, and of a number o€ sulpho-salts, which the author has from time to time described, of the general form X"S,X"S,X"S,X"S)ZivS2 where X is a bivalent group 01- element, and Z a quadrivalent, group or element.Several examples are quoted. Artificial Precious Opal. By GIGSE PPG C E S ~ R O ( J d ~ b . $. Ku., 1895, ii, Ref. 8 ; froin Bull. AcaE. Belg., 1893, [3], 26, 721-730),- A glass flask, which had contained hydrofluosilicic acid f o r several years, was coated with a white, translucent, opal-like deposit ; this showed a play of colours, and had tae conipositiou 3Si0,.H20. Sodium and calcium silicofluorides were also formed by the action of the acid on the glass. Emery from Naxos. By GUSTAV TSCHEKMAK (T~ch. Xin. Xitth., 1894, 14, 311--342).-The emery of Naxos, an island in the Grecian Archipelago, occurs as lenticular masses in the granular limestone associated with gneiss and schist; it consists, as seen in thin sections, principally of corundum and magnetite, with a little secondary haematite and limonite, and some margarite, t,ourmaline, niuscovi te, chloritoid, diaspore, and, less frequently, kyanite, staurolite, biotite, rutile, spinel, idocrase, and pyrites.There is a more or less banded structure marked out by layers of the iron ore. The corundum is mostly as rounded grains, but sometimes as crystals when surrounded by magnetite, and it is rich in enclosures, principally of magnetite. Analyses by E. Ludwig gave I for qualityA from Kremnd, and IT for quality B from Ilenidi. L. J. S. If the rational forniuls be A. G. B. L. J. S.254 ABSTRACTS OF CHEMICAL PAPERS. SiO,. B203. A1,0,. Fez03. MgO.CaO. Na,O. K,O. I. 5.64 1.15 57.67 3 - 3 6 0.83 0.43 n.d. 0.31 11. 5.45 0-SS 56.52 34.65 0.43 0.90 0.60 0.40 LOSS On TiO,. COP ignition. Total. I. n.d. - 0.70 100.09 11. n.d. n.d. 0.42 100.25 From these analyses is calculated Corundum. I. 52.4 32.1 11.5 - Magnetite. Tourmaline. Cliloritoid. Muscovite. Margarite. Calcite. - 2 2 1 11. 50 33 9 4 3 The emery of each deposit is described iu detail. The sp. gr. varies from 3.71 to 4.07. L. J. S. Magnetite from the Madras Presidency, containing Manga- nese and Aluminium. By THOMAS H. HOLJ~AND (Recwds Geol. Survey. India, 1893, 26,164--1€5).-A granular specimen of magne- tite, with a distinctreddish streak, and sp. gr. 5.045, from the Kodhr mines, Vizagapatam district, gave, on analysis, - Moieture H,O 1 ~ ~ 0 1 . below 105'.on ignition. in HCI. AI20,. Fe30,. Mn,O,. Total. 0.14 2.18 0.11 2-52 91.62 3.00 99.57 L. J. S. Artificial Haematite and Magnetite. By WILHELM M ~ L L E R (Zeit. deutscli. geol. Ges., 1893, 45, 63-68).--The residue obtained on reducing nitrobenzene to aniline by means of iron and hydrochloric acid is allowed to stand in heaps before being Bmelted at Laar, near Ruhrort. Owing to the energetic oxidation of the ferrous chloride, there is a considerable rise i n temperature, sometimes to glowing, and the substance becomes a dark, hard, compact mass of iron oxides, the numerous cavities being lined with well-developed crystals (to 1 cm. diani.) of hEmatite and small octahedra of magnetite. Although the hEmatite crystals have all been formed under the same conditions (which are very similar to those in volcanic sublimations, as at Vesn- Tius), they vary considerably in habit, being tabular, rhombohedral, pyramidal, or.prismatic. Analyses of the crystals by Loscher gave Fez03 87.38, FeO 12.45 = 99.83; and Fe,Os 86.45, FeO 11.78 = 98.23 per cent. ; this indicates an intergrowth of magnetite with the hwnatite, as is also shown by the fact that the crystals are somewhat magnetic. The magnetite gave Fe203 71.18, FeO 28.72 = 99.90 per cent. L. J. S. Analyses of Magnesite, Dolomite, Mica, and Magnetite from Servia. By A. STANOJEVI~ (Ann. Gebl. PeiZins. Balkan,., 1893, 4, (2), 86-88).-Magnesite (I) and dolomite (11) from Avala gave Si02. FeO. CaO. MgO. COB. Total. I. 0-17 0.66 - 46-60 52.21 99.64 11. 4.37 3.97 24.12 22.25 4390 100.61IMINERALOOIC A L CHEMIT STRT.255 White mica from near Vranja gave SiOz. A1,0,. Fe,O,. MgO. KzO. HzO. Total. Sp. gr. 48.93 34.60 3.22 0.63 8.76 5.17 100.68 2.7 Iron ore of sp. gr. 5.01, from Snvo Rudiste (Kopaonik), gave Insol. CuO. MgO. FeP03. FeO. CO,. Total. 1-59 4.03 0-80 6i.37 27-63 0.11 101.53 Analyses of other Servittn ores are given. Iglesiasite, Tarnowitaite, and Hemimorphite from Silesia. By HERMANN TRAUBE (Zeit. deutsch. geol. Ges., 1894, 46, 57-67).- Iglesiasite occurs on smithsonite at Radzionkau, in comb-like aggrega,- tions ; analysis gave PbO. ZnO. C02[diff.]. ZnCO,. Sp. gr. L. J. S. 78.65 3.41 C17.941 5-47 6.187 The crystals are flattened i n the direction of the vertical ( e ) axis ; Turuowitzite : ,Qnalgses of specimens from Tarnowitz gave Colourless.., . .. . . 54.09 0.26 2.24 - [43-391 2.61 Green ... . . . .. . . 52-70 0.25 4-26 - [42*71] 3-09 Reddish-brown ... 51.93 035 4.76 0.34 [42.62] 3-70 Yellowish.. . . . . .. 53.43 trace 3.58 - C42.991 4.29 No connection can be traced between the composition and the colour. The crystals used in the last analysis have the habit of arago- nite rather than of witherite. Hemimorphite, from Scharley, was analjsed 011 account of the un- usual dark brownish-red colour ; lead has not before been recorded in this mineral. SiO,. ZnO. PbO. H,O. Total. Sp. gr. 2&81 66-23 2.17 7.39 99.65 3.627 u : b : c = 0.59906 : 1 : 0.72465. 2EN, = 17" 7'. CaO. SrO. PbO. ZnO. CO,[diff.]. PbCOH. Crystallographic determinations are given of the above, and of good crystals of hemimorphite from Radzionkau, and of cerussite from Tarnuwitz.L. J. S. Spodiosite from Nordmark. By G UsrAF NORDENSKIOLD ( J d r b . Miu., 1895, ii, Ref. 18; from GeoZ. 3'0s.. FCrh., 1893, 15, 460-466). -Spodiosite occurs as large, orthorhombic crystals, with chondrodite, amphibole, magnetite, and calcite in serpentine veins at Nordmark, Sweden. The freshest portion of the much decomposed mineral gave on analysis P,05. Si02. CaO. A1,09. Fe20,. MgO. F. H,O. (less 0 for F). Total L-- v-- 29.62 8-74 45%4 2-83 8.56 2-94 3-76 100.60256 ABSTRACTS OF CHEMICAL PAPERS. As the SiO, and MgO belong to the serpentine, the formula becomes mCa,P,O, + nCaF?, where In = 8 and n = 3, this being analogous Celegtite from Bourke, N.S.W. By GEORGE W. CARD (Records Geol. Szcrvey, N.S.W., 1893, 3, 201-20:3).-.& soft mass of sp.gz-. 3.73 consisting of an aggregation of small crystals, gave, on analysis by J. C. H. Mingaye, SrSO,. CaSO,. BaSO,. %On. Fe,O, (Al,O,). JIgO. NaC1. H20. Total. 93.57 0.99 tyace 3.22 1.52 0.33 trace 0.70 100.33 L. J. S. A supposed Sulphocarbonate of Lead. By P. T. HAMMOXD (Becords Geol. Survey, N.S. W., 1895, 4, 163--166).-White to colour- less, brittle, orthorhombic crystals, with an imperfect cleavage, and an adamantine to resinous lustre, found on cerussite from Broken Hill, N.S.W., gare, on analysis by J. C. H. Mingaye, PbO. so3. co-. Totai. 74.11 22.27 3.32 99.70 i4.11 25.00 1-33, 103.45 There is an absence of water ; sp. gr. 6.2.2-6.33. The crjstals diffei- in niany points from leadhillite, and are probably anglesite, containing admixed cerussite, the latter possibly being due to the alteration of the former.L. J. S. to apatite. L. J. s. Zinciferous Melanterite, Seelandite and Zinkmanganerz?’ By AUGUST BRUNLECHNER (Jahrb. naturhist. Lmzdea-JItjseums, Klagen- flirt, 1893, Heft 22, 186--194).-Numerous minerals recently found in Carinthia are shortly described. X e l a n t e d e (zinc(feroz6s) as small stalactites incnzsting dolomitic limestone from Raibl, gave, on analysis, FeO. ZnO. SO,. HCO. Total. 20.69 6.01 28.95 44.35 100.00 Seelandite : Colourless, white, or yellowisli-white needles, occurring as an efflorescence on siderite from Lolling, gave 3IgO. Al,Op SO,. H20. Total. 4.07 10.54 34.03 51.22 99.86 thus corresponding with the formula Mgdl,(S04), + 27H20.[This is near to pickeringite ; seelandite is a new name (see “ Carinthia,” ii, 1891, No. a).] ‘‘ Zinli~nanyanerz ” : This “ new species ” occurs as a thin, dull, compact layer of reddish-brown or bIackish-brown to steel-grey colour, i n hemimorphite druses, or coating hydrozincite a t Bleiberg. Streak, dark reddish-brown ; fracture, even t o flat, conchoidal. Given as a zinc manganite containing water. Analyses of an impure limonite and a bituminons dolomitic lime- stone are also given. L. J. s.MISERALOOICAL CHEJIISTRY, 257 Kentrolite from Jakobsberg. By G LWAF NOR D LSSKIOLD (Jahd,. f. illin., 1895, ii, Ref.: 241 ; from Cieol. Fiir. F&*h., 1894, 16, 153- '158) .-Small, dark reddish-brown to black, orthorhombic crystals on inesite from Jakobsberg, Sweden, gave, on analysis, SiOi. PbO.Mn203. Fe?O,. 16 50 19 1 L. J . S. Action of Water on Apophyllite. By GIORGIO SPEZIA (Juhi*b..f. nfi??., 1895, ii, Ref., 242 ; from Atti Accad. Xci., Torino, 1895, 30, 455-465).-Water under a pressure of 1750 atmospheres at the ordinary temperature had no action on apophyllite from Poonah ; under a pressure of 500 atmospheres at 93-107" there was no marked a,ction ; but water at 190-211', and under the normal pressure for that temperature, strongly corroded the niineral in 13 days, producing beautiful etch-figures. Glass behaves in a similar manner. L. J. S. Lepidomelane, Actinolite, Andradite, Grossular, Horn- blende, Clinochlore, Talc, Diallage, Damourite, Sericite, Cookeite, Cobaltiferous Lollingite, Bismuthite, Strontianite, and Native Iron from Canada.By G. CHR~STTAN HOFFMANS (Report Geol. ,Survey, Canada, 1895,6, R., 1-93) .-Lepidonzelane (I), brilliant, black plates in a granular mispickel at Marmora, Hastings Co., Ontario. Actinolite (11), light greenish-grey, finely fibrous, from Westmeath, Renfrew Co., Ontario. Aizdradite (111), massive, black, in thin splinters dark purple-red, from Cawood, Quebec ; (IV), clove-brown, massive, from Fraser River, B.C. G?-OSSZ~~UP. (V), massive, honey-yellow, from Litchfield, Quebec. Hornblende (VI), finely fibrous, radiated, blackish-green, from Fraser River, R.C. Analyses I to VI by F. G. Wait. I. 11. 111. IV. v. TI. SiOz ............ 32.79 56.70 36.09 34.52 36.80 38.79 Al,O,. ........... 14.34 1.62 32-69 4.09 20.5% 11-51 Fe203.. ..........4.52 3-06 12.33 25.82 2-38 16-88 FeO.. ........... 26-32 7.19 3.30 2-66 0.56 15.96 MnO.. .......... 0.29 0.30 0.48 0.94 0.50 0.62 Ni 0. - 0.54 - - CaO.. ........... 1.45 10.62 34-46 31.49 37-41 11-57 MgO ............ 4.68 17.20 0.94 0.59 1-51 2.86 ............. - 1-36 K20 7.24 0.24 - - - 0.71 Na,O ............ 2-00 0.64 - - TiO, - - ............ 0.92 - H20 (at loo").. .. 1-38 0.64 0.04 0.03 0.07 0.09 - 0.83 H20 (above 100'). 3.68 2.05 - - 99.61 100.80 100.33 100.14 99.76 101.18 - - ............ - - ------ -- - Sp. gr.. ......... 3.19 2.941 3.690 3.706 3.623 3.404 CZinocl'tZore (VII), white or faint bluish-white, scaly, from a scapo-258 ABSTRACTS OF CHEMICAL PAPERS. lite-serpentine rock at Buckingham, Quebec, ; sp. gr. 2.631. (VIIIj, dark green, broadly foliated, froin Ragot, Renfrew Co., Ontario.Both analyses by R. A. A. Johnston. Si02. AI,O,. Fe,O,. FeO. Cr20,. MgO. K,O. HzO. Total. VII. 25.65 18-96 - - - 37.49 - 1-5-22 100.32 VITI. 27.23 19.44 2.17 4.91 0.99 32-67 0.08 12.04 99.53 Talc (IX), pale yellowish-green, foliated, from Grimsthorpe, Ontario ; water at loo", 0.32 per cent,. ; above looo, 5.42. Analysis by Wait . DialZage (X), thin-foliated, light greenish-grey, in serpentine, from Melbourne, Q oebec. Damourite (XI), scaly, yellowish-green, in a ferruginous dolomite, from Kicking Horse Valley, B.C. Over sulphuric acid, 0.68 per cent. of water was lost ; at looo, 0.03 ; 011 ignition, 5.54, = 6-25 per cent. Sericite (XTI), small, yellowish-white scales, forming 6 1.64 per cent. of a sericite-schist from Wait-a-bit Creek, Columbia River, B.C.Analysis was made on th? portion of the rock insoluble in hydrochloric acid, the soluble portion consisting mainly of carbonates. Cookeite (XIII), white or pale green, and foliated ; occurs as thin bands in the sericite-schist above mentioned. Analyses X to XI11 by Johnston. SiO ?....... Fe203 ..... FeO ....... Cr,O, ...... NiO ....... CaO ...... 31gO ...... K,O ....... Nit,O ...... Li,O ....... cszo ....... HzO ....... F .......... c1 ......... A1203 ...... Less 0 foi. F Sp. gr. ..... IX. 60.45 0.2 i 0.78 2-04 0.50 0.16 29-84 - - - -- - 5-74 - - -- 99.78 2 65 - X. 50.66 4.47 0.70 2.75 1.43 21.81 17.45 - . - - -- - 0.69 - 99-93 - 3.238 xr. 44-28 33.60 0.62 - - - - 3.03 9.8 7 0.40 - - 6.25 0.59 0.51 99.13 0.36 2.857 -- XIT. 46-05 38.36 0.97 - - - 2-43 0.47 6-19 2-98 0.3 % 0.03 2.48 - - 100.27 - - 100.40 0.01 - Cobaltiferous Lollingite, massive, steel-grey, with pyrrhotite, from Analysis by Johnston gave, after deducting 1.69 Galway, Ontario.per cent. of quartz, AS, S. Fe. co. Ni . Total. Sp. gr. 70.85 0.81 24.67 2.88 0.79 100.00 7-028MINERALOGICAL CHEMISTRY. 259 Bismuthite, massive and foliated, lead-grey, from a granite vein Bi. s. Fe. Pb. cu. Total. Sp. gr. 79.28 18.46 0.74 1.68 0.48 100.64 6 . i S l Strontiunife, radially crystalline, pale yellowish-green to white, as cop 81.0. CaO. Insol. Total. Sp. gr. 30.54 65.43 338 0.17 99.52 3.704 Nutice iron occurs as small spherules, very similar to those pre- viously described by the author (Abstr., 1895, ii, 20) in kaolin and limonite in a pegmatite vein at Cameron, Ontario.Analysis by John- ston gave Fe. M n . Xi. 8. P. Organicmatter. Insol. Total. Sp. 6'. L-,-J 90.45 0.75 trace not det. 7.26 98.46 7.237 a t Jonquihre, Quebec. Analysis by Johnston gave veins in limestone at Nepean, Ontario. Analysis by Johnston gave Copper and cobalt are absent. On dissolving in hydrochloric acid, there is a strong smell of phosphine. The insoluble concretionary nuclei contain 88.77 per cent. of silica, with some AlZO3, Fe,03, and CaO. The report also contains nunierous analyses of ores, waters, &c. L. J. S. Xiphonite, a New Amphibole [Hornblende] from Etna. By GaETANo PLATANIA (Jahrb. j'. Min., 1895, ii, Ref., 236-237 ; from Atti Tend. Accad. Sci., kc., di Acireale, 1893, N. Ser., 5,55-62).-This occurs as small, light yellow to honey-yellow, transparent, monosymmetric crystals in the drusy cavities of a slaggj lava.I t is supposed, together with the accompanying haematite, to have been formed by sublimation. On account of the feeble pleochroism, the light colour, and the special mode of occurrence, it is considered to be a distinct variety of horn- blende. L. J. s. Chemical Composition and Constitution of Vesuvians [Idocrase] and Wiluite. By PAUL JANNASCH and P. WEINGARTEN (Zeit. anorg. Chem., 1895, ii, 40-48 ; see also Abstr., 1895, ii, 319).- The paper contains the results of the complete analysis of (I) idocrase from Vesuvius, free from fluorine, of (11) idocrase from the same locality, containing fluorine, and (111) of idocrase from the Matterhorn. SiOp.TiO,. Fe,O,. A120,. FeO. CsO. MnO. MgO. K20. I. 36-38 4 25 2-77 12.29 2-14 35.56 0.37 2.94 0.43 11. 37.15 0.50 3-28 15.73 1.94 35.49 0.52 2-64 0.38 111. 37.09 2~1~5 3.59 15.56 0.83 35.24 0.18 2.24 0.72 N&,O. H,O. F. Total. I. 0.95 2.68 - 100.78 11. 0.67 1.97 1-63 101.9,? 111. 0-53 '2.71 - 100*84260 ABSTRACTS OF OHERIICAL PAPERS. The results obtained agree with the former determinations, and arc Si,O ,, (A1 Fe" ' ) 2( Ca,Mg,Mn ,Fe" ,K,Na) ( H, F) ?. i u accordance with the composition A complete analysis of wiluite gave Si02. TiO,. B,03. Fe,O,. A1,0,. BeO. CaO. MnO. MgO. 36.01 1.30 2-81 2.18 12.23 1-49 35-81 0.15 6.05 Na,O. F1. H20. Total. 0.45 0.22 1-34 100.04 from which the formula, (Si ,Ti)803(Al, Fe"',B)l( Ca,Mn,Mg,Fe",Nn) ,o(H,F)2, is deduced. E. C.R. Origin and Composition of Onyx Marbles. By GBORGE P. MERRILL (Sniithsonian Report, U.S. National Museum, for 1893-4, 1895, 539-585) .-Certain travertines and cave deposits oE calcium carbonate, which are characterised by being banded and translucent, are the so-called onyx marbles or oriental alabasters ; they are here shown (by their sp. gr.) to consist, in almost all cases, of calcite, and not of aragonite. The true onyx marbles are superficial deposits from hot springs, and, according to the view taken by the author, deposi- tion has taken place slowly a t the bottom of pools of water; cave marbles (that is, stalactites, &c.), on the other band, are cold-water deposits, and are of greater puritry, The former rarely contain less than 90 per cent. of calcium carbonate; iron oxide and carbonate being the next prominent constituents, these being the main cause of the wide range in colour.The pale and green colonrs are associated with ferrous carbonate, and the red-browns with ferric oxide, which latter has been produced by the oxidation of the carbonate along cracks and joints ; for example, a green marble with 4.27 per cent. FeCO,, contained in the brown-red (osidised) portions 1.22 per cent. FeCO, and 3.53 per cent. Fe203. Some of the colour variations may be partly due to manganese; and in some amber-brown and yellow marbles (and one rose coloured) they are due to organic matter; they are rarely due to mechanical enclosures, such as clay. Of the 16 analyses given, I is a white onyx marble, from Lower California ; 11, milk-white from Persia, also with 0.24 C%(PO,), ; 111, lightl green, from Mexico; IV, red-brown, from Arizona; V, dark amber, from California, containing organic matter, and 1.59 SrC03 and 0.21 BaC03.,911. gr. CaCO,. MgC03. FeC03. MnC03. Fe203. SiO,. CaSO,. H20. Total. I. 2.78 96.86 0.24 2.79 - 0.61 0.06 - not det. 100.56 11. 2.75 90.93 0.75 1.37 4.34 - - 2.30 - 99-93 111. 2.75 89.36 3.00 5.24 0 29 - - 1.34 0.57 99.80 IV. 2.67 93.82 0.53 4.06 - 173 0.05 - not det. 100.19 0.37 99.75 V. 2.70 95.48 2.20 - These marbles are holocrysfalline ; sometimes granular, but more - - - -NINERALOQICAL OHEMISTRY. 261 often fibrous or radially colnmnar in structure. The specific gravity varies from 2.64 to 2.79, and the hardness from 3 to 3.5 ; only in one case was the sp.gr. as high as 2.87 with H = 4, this being the only aragonite in the whole series examined. L. J . S. Hislopite. By THOMAS H. HOLLAXD ( R e c o d s Geol. Szcwey, Indin,, 1893, 26, 166--171).-Cnlcite from the Deccan traps, containing paf ches of botryoidal “ green earth,” and small, bright crystals of Iieiilandite, ga~7e, on analysis, Insoluble in Moisture. acetic acid. Fe203 + &03. CaO. GOn. Total. Sp. gr. 4.03 23.48 0-25 40.48 30.98 99.22 2,546 The iron, aluminium, and a little calcium are due t o the slight solubility of the enclosures in the acid. A specimen from Nagpur, of sp. gr. 2.659, contained 4.615 per cent. of moisture and enclosnres. The calcite varies from clear and colourless to green and opaque, owing to the unequal distribution of the enclosures ; and the sp.gr. decreases as the amount of the enclosures increases. The “green earth ” has a sp. gr. of 2-62 ; i t is of indefinite composition, and possibly consists of glauconite and celadouite. L. J. S. Alteration of Diabase and Granite. Formation of Clay. By PHILIP HOLLAND and EDNIJND DICKSON (Proc. IiverpooE Geol. Soc., 1893, 7, 108-117).-1, Analysis of the fresh rock of a diabase dyke in the granite, at St. Helier, Jersey ; 11, the brown, ochreous, clayey matter into which I is weathered. 111, unaltered granite from thc same locality ; IV, the weathered, friable rock ; V, clay derived from the same. SiO, ......... 43.56 44.93 70.23 71.22 48.44 I. IT. 111. IV. v. TiO, ......... Fen03.. ....... FeO. ......... MnO ......... CaO ......... MgO .........KzO ......... NazO. ........ coz.. ........ Hz0 .......... A1203 ......... 1.03 14-58 3-84 7-00 0.39 10.78 9.95 1-02 1.86 1.93 3.85 13.37- 2.37 2.36 - 0.98 0.07 0.28 0.18 0.20 1.84 0.94 0.44 6-40 0.50 0.68 0.84 3-13 4-10 2.03 4.19 4.25 12-55 0.70 2.10 - - - 27-24 5 -04 0.38 0.38 2.93 7.43 0.35 7 9 1 - - ---- - ---- 99.79 99.85 99.95 100.34 100.10 Sp. Gr. ...... 2.923 2.592 2.65 2.60 - By the prolonged action of carbonic anhydride and water under pressure on such rocks, some calcium, magnesium, and iron went into solution. These alterations are discnsfied in connection with the formation of clay. L. J. S. VOL. LXX. ii. 192 62 ABSTRAOTS OF UHEMIUAL PAPERS. Amount of Silica and Quartz in Granites. By STANISLAUS ZALMKI (Tsch. Min. Mittlz., 1894, 14, 343--359).-The percentages of silica and quartz (the latter being separated by means of a heavy solution) of various granites are given as Si02. Quartz. 74.44 Nigg (Kincardine) . . . . . . . . 69.84 13.0 65-33 Baveno (Italy) . , . . . . . . . . . 41.38 Dannemol e (Sweden) . . . . . 61.06 15.2 54.08 Haiigo (Finland) .,. . . . . . . 71.42 29.5 59.46 The third column gives the calculated silica percentage of the rock after deducting the quartz, and as these figures differ considerably from the silica percentage of syenite (which has 58-60), it is considered that granite is not syenite plus quartz. Fuller’s Earth from Wingen, N.S.W. By GEORGE W. CARD (Records Geol. Survey, N.S. W., 1894,4,30-32).-A yellowish-green, unctuous clay from this locality gave the following analysis, by Mingaye. Under water, it softens and disintegrates ; when heated, it becomes colonrless, finally fusing to a green glass. 56.4 L; J. S. H20 H20 (corn- (moisture). bined). SO2. A1203 Fe&. CaO. MgO. K20. N%O. Total. 13.73 6.45 50.61 19.35 3-55 1.37 3.24 0.92 0.47 99-69 There is a trace of P,05 ; FeO, MnO, and SO3 are absent. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA8967005251

出版商:RSC    

年代:1896

数据来源: RSC

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2 62 ABSTRAOTS OF UHEMIUAL PAPERS. P h y s i o 1 o g i c a 1 C h e mi s tory . Mehbolism Experiment on Sheep with a Pettenkofer Respiration Apparatus. By FRANZ LEHMANN (EayeT. Stat. Record, 1595, 7, 235-236; from Landw. Jahrb., 1895, 24, Suppl. 1, 117- Ilg).-ProteYn, fat, starch, and cellulose were compared as producers of fat and Iean meat respectively. Two sheep were fed with a ration rather more than sufficient for maintenance. After the production of Iean and fati had been determined, the constituents to be tested were added in separate periods, between each of which the basal ration intervened. The amounts given in each period were as follows (in grams). Prcte'in. Fat. Crude fibre. N-free extract, 1. Basal .. . . . . 96.9 15.2 84.7 287.7 2. Starch . .. . . 95.2 15.1 89% '369.0 %.Cellulose . . 100.2 16.7 156% 320.3 4. Protein . . . . 178.5 16.0 88.5 312-7 5. Fat .. . . .. . . 103.0 49.7 86.2 295.0 The basal ration resulted in a very slight production of lean meatPHYSIOLOQIOAL CHEMISTRY. 263 and much fat. The addition of Btarch and cellulose gave rise (equally) to a considerable increase in lean, but cellulose was much inferior to starch in fat production. The addition of protein produced the greatest increase in lean, whilst fat produced fat alone, being without effect on the production of lean. N. H. J. M. Normal Occurrence of Iodine in the Body. By EUGEN BAUMANN ( Z e i t . plysiol. Chem., 1895, 21, 319-330).-In the course of investi- gations on the active physiological substance of the thyroid gland, a substance was obtained, to which the name thyroiodin is applied.The glands, when boiled for some days with 10 per cent. sulphuric acid, yield a liquid which deposits a flocculent precipitate ; this, after extraction with alcohol, is regarded as the active substance. It may be it deriva- tive of aucleic acid : i t contains 0.54 per cent. of phosphorus, but it cannot he obtained fiaoni the thymus gland, nor from pure nucleic acid; the most remarkable point about it is that it coutains iodine in organic iinion in considerable amount. W. D. H. A Dermoid Cyst. By VICTOR LIEBLEIN (Zez't. physiol. Chem., 1895, 21, 285--287).--The contents of an ovarian cyst of dermoid nature contained 83-87 per cent. of water. The quantity of ethereal extract was large, and it contained cholesterol ; isocholesterol and cetylic alcohol were not detected, although the latter is stated to have been found in a dermoid cyst by Sotnitschewsky, ibid., 1880, 4, 345.W. D. H. A rapid Method of Desiccating and Sterilising Serum. By CHARLES JAMES MARTIN ( J . Yuthol. aizd Bucte~iol., 1896, 3, 507- 509) .--The simple apparatus used is figured. The method consists essentially in filtering the serum through a Pasteur-Chamberland filter into a bottle connected with a water pump ; the whole is kept at 40°, and the serum, which comes through in bubbles, dries as quickly as it filters. W. D. H. Excretion of Oxalic acid. Bg JAMES CRAUFURD DUNLOP ( J . Pathol. and Bacteriol., 1896, 3, 389--429).-Oxalic acid is a constant constituent of the urine of men eating ordinary diet; in the urine, excess of calcium salts tends to precipitate the acid, but in normal urine this is prevented by acid sodium phosphate, and possibly by other substances.The precipitation is most liable to occur if the percentage of oxalic acid in the urine is high, and, in fact, actually occurs in about one in every three specimens; the precipitated cnlcium oxalate is in the form of octahedra. The daily excretion of oxalic acid averages 0.017 gram. Alcohol is an efficient precipitant of the oxalate? and may be used in both qualitative a d quantitative analysis. Oxalic acid is not a pro- duct of metabolism, but is absorbed directly from the food, and is excreted as such; increased acidity of the gastric contents aids absorption. Oxaluria is not a special morbid condition, but is essen- tially a hyperacid dyspepsia.W. D. H. 19-2264 ABSTRAUTS OF OHEMTCAL PAPERS, Experimental Anaemia in Dogs. By RALPH STOCKMAW (J. Fathol. and Bacferiol., 1896, 3, 385--388).-1n one dog, anemia was prodaced by bleeding ; in another, by giving food containing insuffi- cient iron. not!] factors are probably conceri;ed in actual chlorouis, as, in both dogs, examination of the blood from day to day, and of the organs after death, show many siniilnrities to that disease. The animals, liowerer, possess a power of regenerating the corpuscles, a power which in chlorosis is extremely limited by some superadded condition. W. D. H. By JOHN HILL ABRAar ( J . PatAoZ. and Bncteriot., 1896, 3, 430--432).-The present experiments confirm Becker’s (Deut.med. Woch., 1895, No. 19) original statement. that acetonuria follows antesthesia in two-thirds of the cases, the anwthetic used making no difference ; if acetomria is present before, anzstbesia increases it. The probable source of acetone is protei’d destruction. The practical outcome is that, except i n cases of urgency, anEsthetics should not be administered to diabetic patients. Haematoporphyrinuria. By ARCHIBALD E. GARROD and F. Gom- LAND HOPKINS (J. Pnthol. and Bacteriol., 1896, 3,434448) .-Normal urine contains a little haematoporphyrin, but the amount is consider- ably increased by various conditions, especially by taking sulphonal. Three suchcases are recorded in the present paper, whichgives a clinical history of each case with chemical and spectroscopic examinations of the blood and urine.The causation of this condition is nok yet fully explained. and the principal new point that comes out in the present research is that urinary haematoporphyrin does not imply excessive blood destruction ; there is, at any rate, no corresponding increased excretion of iron. The best way to obtain the pigment from t h e urine is to add sodium hydroxide, and then extract the pigment from the washed precipitate of phosphates, or to saturate the urine with ammonium chloride, and extract the pigment from the uratos with a, mineral acid. W. D. H. Poisoning of Cattle by Potassium Nitrate. By N. S. MAYO (Exper. S t a t . Record, 1895, 7, 2.50 ; from Kaiisns Stat. Bull., No. 49, :j-ll>.-A number of cattle fed on dried cornstalks having died, the stalks were examined and were found to contain, both outside and inside, a quantity of potassium nitrate.The com had grown on very rich soil formerly used a s a, hog lob. I n direct experiments with potassium nitrate on animals, a, heifer (about 500 lbs.) drenched with a solution of nitrate (300 grams) died within 24 hours ; a cow (1,200 Ibs.) was killed by 500 grams, and an adult rabbit by 5 grams of potaFsium nitrate. The symptoms are described in the original paper. N. H. J. M. By L. BROCINER (Compt. rend., 1895, 121, 773-’774).-Experiments previously made by the author (Annales d’Hygiene, 1887, [ 3 ] , 17, 454) show that 100 vols. of blood dissolve about 80 vols. of acetylene ; the solution shows no charactor- istic spectrum, and is reduced by ammonium hjdrosulphide as readi1.y Acetonuria. W. D. H. Poisonous Effects of Acetylene.VEGETABLE PELYSIOLOGY AND AGRICULTURE. 265 as ordinary arterial blood. In a vacuum, part of the acetylene is evolved at the ordinary temperature and part at 60". If the blood is allowed t,o putrefy, the volume of acetylene given off at the ordinary temperature remains practically the same, but the quantity liberated at GOo decreases as putrefaction advances. If any compound of acetylene and hemoglobin is formed, it is very unstable, and is not analogous to carboxyhemoglobin. The poisonous action of acetylene is very feeble, and animals can breathe large quantities of the gas for several hours without injurious effect., provided the proportion of oxygen is kept up to the normal amount, and the products of re- spiration are not allowed to accumulate (compare this vol., ii, ZOO). C. H. B.

ISSN:0368-1769    

DOI:10.1039/CA8967005262

出版商:RSC    

年代:1896

数据来源: RSC

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VEGETABLE PELYSIOLOGY AND AGRICULTURE. 265 Chemistry of Vegetable Physiology and Agriculture. Growth of Cholera Bacilli in Sunlight. By F. F. WESBROOK (J. Pathol. and Bacteriol., 1896, 3, 352--358).--Direct sunlight de- stroys cholera bacilli if they are in contact with air, but aids by its heating power the growth of those not in free contact with air. W. D. H. Origin of Atmospheric Oxygen. By THOMAS L. PHIPSOX (Cornpt. rend., 1895, 121, 719-721) .-Plants such as Convolvulw arvensis, grow readily in an atmosphere of moist nitrogen co3taining a certain quantity of carbonic anhydride, and eventually the atmo- sphere may contain more oxygen than is present in the air. The lower plants, such as P~otocowus, Conferva, CTl.ua, &c., behave simi- larly, and, for a given weight, liberate much more oxygen in a given time than plants of higher organisation. These facts support the .author's view that originally the earth's atmosphere consisted mainly of nitrogen, together with some carbonic anhydride, and that the presence of oxygen is due to the decomposition of the carbonic anhy- dride by plants.They also indicate that plants are essentially anaB- robic, although the gradual increase in the proportion of oxygen in the air may have led to the gradual modificat,ion of the anagrobic cells and their conversion into asrobic cells like those of fungi. Metabolism and Respiration of Sprouting Potato Tubers. By E. ZIEGENUEIN (Bied. Cedr., 1895, 24, 784 ; from D. Landwirt, 1895, No. 33).-Observations made with sprouts of Lupinus Zuteus showed that the albumin decomposes at about the same rate in ab- sence, as in presence of oxygen.Free nitrogen was not evolved during 24 hours. The conditions of light only essentially influence the decomposition of proteids, so far as light increases the production of carbonic anhydride in sprouting potato tubers, but hinders the growth of the shoots. The temperature optimum for the normal respiration of Tuyaxacum oficixalis is 40' (the same as that found by Clnusen for Trilicum, Lupinus, and Syringa flowers), for sprouts of Abies excelsa, C. H. B.266 ABSTRACTS OF OHEMICAL PAPERS. and seedlings of Ticia jaba 35", and for potato tubers 45". Above these temperatures, the energy of respiration diminishes slowly until the maxinium is reached (about 10' higher than the optimum), but very rapidly at still higher temperatures.Assimilation of Lecithin by Plants. By JULIUS STOKLASA (Sitzungsber. k. d k a d . Wissens. Wien., 1895, 104 ; Abth. I, 1-ll).- Lecithin occurs in soil in quantities varying with the amount of organic matt,er. This and the importance of lecithin in the produc- tion of chlorophyll lend interest to the question of its assimilation by plants. Water-culture experiments were made in which oat sprouts were grown in nutritive solut'ions (1) free from phosphorus, (2) contain- ing calcium phosphate, and ( 3 ) containing lecithin. I n the case of lecithin, the solution had to be frequently changed owing to the de- composition of the lecithin into glycerol phosphate, choline, and fatty acids. In the lecithin cultures, the nutrition was not sufficient, but the lecithin was no doubt assimilated.Without pbosphorus, the plants produced no seed, and ceased growing after 96 days. The following table shows the average amounts of dry produce, the total phosphoric acid and the lecithin in the produce grown in solutions containing (1) calcium phosphate, (2) lecithin, and (3) no phosphorus. N. H. J. M. The plants grew best in presence of calcium phosphate. I Dry produce. 1 Roots. I Stems, &c. I Grain. I Total. 0 -120 0 - 0605 0 -0882 0 -0037 - The results of the experiments show clearly the assimilation and utilisation of lecithin by the oats. Assimilation of phosphorus in an organic form by plants had not been proved before. N. H. J. M. Effects of Chlorides, Bromides, and Fluorides on Algae.Bg M. WYPLEL [ ? WYPFEL] (Bied. Centr., 1895, 24, 785; from Bot. Centr., 1895, 62, 216 ; compare Abstr., 1895, ii, 175).-Different Alga vary in their power of resisting the action of solutions of salts, the higher Algae being more sensitive than the lower. Spirogyra is the most sensitive, then L!?dogonium Vaucheria, Stichococcus, Oscil- laria, Pleurococcus, and Protococcus in the order given. As regards chlorides, the ammonium salt is the most injurious, then manganese, aluminium, and barium chlorides. Even Protococcus dies i n 2-4 per cent. solutions of these salts. Magnesium chloride is the least injurious; the sodium and strontium salts are less active than potassium chloride. Of bromides, the ammonium salt is again the most injurious, then potassium and sodium salts.Sodium, potassium, and ammo- nium fluorides are injurious even in 1/8th per cent. solutions.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 267 Sodium and calcium nitrates are more favourable to Algae than potassium nitrate. The effect of the chlorides, &c., is to retard growth and hinder division of cells. The amount of starch is dimin- ished, the cell membrane thickened, and the colour of the chlorophyll changed and finally destroyed. Weak solutions are injurious after prolonged contact. Effect of Copper Salts on the Growth of thevine andon Soil. By BERLESE and LIVIO SOSTEGNI ( B e d . Ueiitr., 1895, 24, 768 -769 ; from Bot. Cedi.., 1895, 63, 270).-When copper bicarbonate is added to a nutritive solution in which vines are growing, the copper is taken up in traces by the roots. Vine leaves are more sensitive to soluble copper salts than the Yeronospora mycelium, and t.he leaf is only protected from Peronospora as long as soluble copper compounds are present on the surface.The mycelium will develop on portions of leaves not reached by the copper solutions. When the roots of a vine were allowed to grow in 1 per cent. aqueous copper sulphate, copper could only be detected in the roots. I n the case of branches immersed in copper sulphate solution, only the walls of the fibrovsscnlar bundles were attacked at first, after which the solution penetrated further mechanically. Contrary to Millardet, i t was found that only the collenchyma, and never the cuticula, took up copper. In the absorption of copper sulphate by soil, lime takes the pre- dominant part, alkalis, magnesia, iron, and alumina being dissolved.Humic acid and silicates do not combine with copper. The copper remains in the soil as oxyhydrate of the basic sulphate, or as a double salt of copper and calcium. The basic sulphate being readily decom- posed by carbonic anhydride, dissolves, and is absorbed by plants. Injurious Action of Cobalt and of Barium on Plants. By EMIL HASELHOFE’ (Landzo. Jahrb., 1895, 24, 959-961 ; 962-9671.- By means of water-culture experiments, i t was shown that, like nickel (Abstr., 1894, ii, 208j, cobalt is injurious to vegetation; 1 to 2 parts per million being sufficient to destroy the plants. As regards barium, experiments with maize and with beans showed that very small amounts injure vegetation.The ashes of plants so treated contained small amounts of baryta. It is possible that in- creased application of lime would, to some extent, hinder the taking up of baryta by the plant. Pectase. By GABRIEL BERTRAND and ALFRED MALL~VRE (Compt. rend., 1895, 121, 726-728) .-Pectase is of very common occurrence in plants (compare Abstr., 1895, i, 312), and was found by the authors in 40 species of plants containing chlorophyll, five of which belonged to the cryptogams. It is found in the roots, stems, leaves, flowers, and fruit. The time required for the plant juice to coagulate a 2 per cent. solution of pectin varies from less than a minute, in the case of potatoes, clover, lucern, and others, to two hours in the case of carrots, and 48 hours in the case of ripe tomatoes.The activity of the ferment varies not only with different plants, but also with N. H. J. M. N. H. J. M. N. H. J. M.268 ABSTRACTS OF OHEMICAL PAPERS. different organs of the same plant, and as a rule is most abundant in the leaves, and especially the leaves of rapidly growing plants. It can be prepared froin the leaves of lucern or clover i n vigorous growth; these are bruised and pressed, and the juice is saturated with chloroform and allowed to I-emain for 24 hours in a well-closed flask in the dark. It is then filtered, the limpid filtrate mixed with twice its volume of alcohol of go", and the white precipitate thus formed is suspended iu a small quantity of water. After 12 hours, it i+ filtered, and the filtrate allowed to ruu into a large excess of alcohol ; the precipitated pectase, when dried in a vacuum, forms a white, non- hygroscopic solid, very solnble in water.Laccase in Fungi. B.y EM~LE E. BOURQUELOT and GABRIEL BERTRAND (Cornpi. rend., 1895, 121, 783-786) .-Examination of 200 different species of fungi belonging to different genera shows that the great majority contain laccase, and in certain cases the presence of laccase coincides with the existence of a distinct odour, and in others with the existence of constituents that become coloured when ex- posed to air. Whilst in some genera or sub-genera such as Russula, Lactarius, and Psalliota, almost all the species contain laccase; in others, such as Marasmius, Hygrophorus, Cortinarius, and Amanita, few or none contain the ferment.Further, the proportion of laccase varies in different parts of the same plant, aud mag be absent in the young plant, but present at a later stage of development (compare Abstr., 1895, i, 386). Amount of Substances soluble in Water in Plants. By E. GAIN (Exper. #tat. Record, 1895, 7, 187-188 ; from Bull. SOC. Bot., F?*ance, 1895, 41, 53-67).-The amounts of soluble matter in plants grown in dry and in wet soil were determined by macerating the powdered substances with hot water and determining the dry matter in the extracts. The results show that plants grown in wet soils contain more soluble matter than when grown in dry soils, and that the parts of the plant above-ground contain more soluble matter than the roots. In comparing analyses of most plants, it is very important t o consider the different conditions under which they were grown.C. H. B. C. H. B. N. H. J-. M. Sulla, (Heydoarum coronarium). By I;. GRANDEAU (Expw. Stat. Record, 1895, 7, 206-207; from J. Agr. Prat., 1895, 59, 812-814 and 850-854) .-Perennial, white sulla is considered suit- able for meadows on thin, poor, dry soils, and is said to thrive, even on pure schists. There are also a native Algerian biennial variety, aud a red variety. The stems and leaves of red sulla were analysed with the following results (per cent. in fresh mbstance). Water. Prote'id. Fibre. N-free extract. Fat. Ash. P205. '&O. 85-00 2-38 4-63 5.75 0.27 1.97 0.117 0-116 The fresh roots had the following percentage collposition. Organic Water. matter. N. Ash. &O.CaO. RlgO. P205. 78-50 19.49 0.22 2.01 0.10 0.32 0.11 0.06VEGETABLE PHYSIOLOGY AND AGRICULTURE. 269 Oats. Slruw. Grtlin. ---- 25-3 7'4 115.6 56 3 123'd 62.2 112.6 54.6 The plant withdraws less potash Zrom the soil (72 lbs. per acre) than most other leguminous plants. Owing to the immense quantity of nitrogen in the crop (224 Ibs. per acre), presumably obtained largely from the air, sulla seems well suited as a crop for green manuring on laud not irrigated in somi-arid regions. The nutritive value is about the same as that of red clover. Importance of Potash as Plant Food. By C. VON FEILITZKS ( B i e d . Ceizt~., 1895, 24, 732-733 ; from Svensli. illossX.ult.-foreiaing. tidwkr., 1SY4, 283-287; 1895, 211-214).-In a number of zinc cylinders filled with peaty soil, well limed in 1888 and 1892, and yearly manured with (2) basic slag alone, (3) kainite and (4) fel- spar, respectively, oats, clover (two years), rye, and peas were successively grown ; there was also a shorh experiment (1) without manure.Oats and rye had, in addition, a dressing of sodium nitrate. The following amounts of produce were obtained (in grams). N. H. J. If. Clover (green). 1890. 1891. 0 3 -0 318 71.0 589 70.3 349 I 97'4 1.. .. 2 . . .. 3 . . . . 4.. .. Straw. 23.5 102.5 120.0 92-8 Grain. 7.0 63.7 100.0 58.2 Rye. I 1 Straw. -- 16 '0 52'1) 98 -6 54 -6 Grain. 2 . 0 19 -0 40 -0 20 *3 I I The importance of potash for peaty soils was also shown by the results of field experiments in various parts of Sweden. Both insufi- cient and excessive potash manuring should be avoided, as potash is not so readily absorbed by the soil as phosphoric acid.Thus, the drainage from the peaty soils of Jonkoping generally contain 0*3-0*5 gram (on one occasion 1.2 gram) of potash per bectolitre ; 2-26 grams of lime ; only traces of phosphoric acid. Application of Phosphates and Superphosphates to Acid Soils. By G. YAGEOT (Ried. Cesztr., 1895, 24, 743-744; and by L. GRANDEAU (itid., 744) ; from JOUY. Agric. Ps-at., 1895, 2, 334-337 and 337-338 respectively).-Pageot found t h a t the soil contained P,O, 0.035, K,O 0.042, NhO 0.060, CaO 0.879, MgO 0.110, SOs O*OC;8, and N 0.193 per ceut. Whilst basic slag and crude phosphate had 110 appreciable effect, superphosphate converted the worthless, sterile soil i n three years into a fertile arable soil which yielded 30 to 35 hecto- litres of wheat per hectare.Grandeau suggests that the farourable effect of superphosphate compared with the other phospbates may be due to the sulphuric acid it contains. Sulphur in an assimilable form is essential, and nothing is known as to the availability of the sulphate in the soil in question. N. H. J. M. Investigations [on Manures] at Halle. By MAX MARCKER (Bied. N. H. J. M. Cewtr., 1895, 24, '734-743 ; froni Ber. Versuchs-Stat. Hallc a. S., 1895,270 ABSTRACTS OF UHEMIUAL PAPERS. 49 pp.) .-Application of Crude Potassium Sa.1t.s to Beetroot.-Whilst in extremely wet or dry seasons the application of potash has no certain quantitative effect, in moderately dry years t h e effect will always be considerable.It is only in very special cases- that potash can act injuriously on the production of sugar. Experiments on 2CIanuring Beetroot with Potctssiurn a d Sodium Nitlates.-Experiments were made in order to decide whether it is the nitrogen of sodium nitrate, or the soda which causes diminished sugar production in beetroot. Tbe results showed that with small applications of sodium and potassium nitrates respectively, the roots manured with potassium nitrate contained rather less sugar than those manured with sodium nitrate, and that with large applications there was slight diminution in the amount of sugar in both potash and soda plants; so that sugar production may be diminished by potassium as well a9 by sodium nitrate. Experiments with Phosphates.-Potassium metaphosphate, a pro- duct of the Stassfurt industry, containing 53.6 per cent.of phosphoric acid, gave good results with barley; it is probably rapidly changed into orthophosphoric acid, either in the soil or in the plant. The phosphates of the sludge of sugar works gave very poor results with it first crop, owing to the amount of free lime present; with a second crop, however, very good results were obtained, and it is thought that a heavy dressing would render phosphate manuring unnecessary for two years. Bone meal, as compared with bone superphosphate, has comparatively little effect in the second year. As a nitrogenous manure bone meal may give, according to the conditions, very good results. As regards basic slag, the best results are obtained with products rich in citrate-soliible phosphates, not only with the first but with subse- quent crops.Stable Manure a d its Constituents.-The effect of sodium nitrate was compared with (1) urine, (2) feces, (3) mixture of faeces and urine, and (4) stable manure. The nitrogen of urine gave very satis- factory results, an average of 89.2 per cent. of the effect of the nitrogen as sodium nitrate. The nitrogen of faces gave only a very Blight increase o€ produce, ;ibout 11 per cent, of the effect of an equal amount of nitric oitrogen. The effect of the mixture of faeces and urine was about the same as when used singly, whilst stable manure showed an average effect of 34-25 per cent. of an equal amount of nitric nitrogen. As regards losses of nitrogen in animal excrement, the results of experiments showed that whilst faeces and urine lost over half the total nitrogen (in five months), the addition of peat litter alone reduced the loss to 20.11 per cent.With a small quantity of phosphoric acid (as well as peat litter), the loss was 21-78 per cent,. ; with four times the amount of phosphoric acid, 7.82 per cent. ; with small and larger amounts of sulphnric acid (2 and 4 per cent. of t h e dry matter of t h e peat), the losses were 5.68 and 5-64 per cent. ; whilst with lime (10 per cent. added to the peat) 16.5 per cent. of the total nitrogen was lost. The best of the mixtures is therefore peat and sulphuric acid (2 per cent.). Nitrification was most active under the influence of lime, 29.82 of the total nitrogen being nitrified in the five monthsANALYTICIAL CHEMISTRY. 271 of the experiment (28.76 in the first two months). The next largest amount of nitric nitrogen was produced under the influence of the greater amount of phosphoric acid, namely, in five months, 22.11. and in two months 4.08 per cent. of the total. With suIphuric acid (4 per cent.), there mas, after five months, only 1.52 per cent. of the total nitrogen in the form of nitric acid; whilst with 2 per cent., 16.41 per cent. of the nitrogen was nitrified. In the original substance alone, 3.37 per cent. of the nitrogen was nitrified ; with the addition of peat, 1949 per cent. was nitrified. I n the original paper, the per- centage amounts of albuminoi'd, ammonia, nitric and amide nitrogen in the original mixtures, and, after two and five months respectively, are given iu a table. E$ect of Kainite and Carnallite on the yield and composition of Grass. -By potash manuring, the vegetation of meadows becomes less nitrogenous, although the total nitrogen is greater. With carnnllite, at least as much nitrogen was taken up as when kainite was employed. Under the influence of potash, the first crop is rendered distinctly poorer in phosphates, whilst the second crop is much richer than without potash manure. The first cutting of grass manured with potash is much richer, and the second crop poorer, in potash than when no potash is applied. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA8967005265

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

269 0 rg a n i c C h e m i s t r y . Sodium Nitrosoferrocyanide. By KARL A. HOFUANX (Zeit. anory. Chem., 1896, 11, 2 7 8 4 8 7 ) .-The salt, FeC5N60zNaiH,10Hz0, is obtained by treating an aqueous solution of sodium nitrosoferr+ cyanide with eodiuni hydroxide. On adding alcohol to the reddish- yellow solution thus obtained, a yellow syrup is precipitabed; i t is dissolved in water and again precipitated with alcohol, and then allowed to crystallise in :t vacuum over sulphuric acid. Care must be taken to exclude carbonic anhydride, nnd to maintain tIie tempera- ture below 15", for in the presence of carbonic anhydride, sodiiim nitrosoferrocyanide is re-formed, and at temperatures above 15' decorn- position takes place with forinntion of sodium ferrocyanide, ferric hydroxide, and sodium nitrite.It crystallises in beautiful, yellowish- red, monosymmetric tablets vesy similar to those of potassium ferri- cyanide ; It is very easily soluble in water, gives t~ dark red coloration with ammonium sulphide, nnd when dried at l l O o , yields a yellow powder which is conipletely soluble in watel-. The silrer saZt, I"eC,N,02Ag,H,2R20, is obtained by adding a solutiou of the sodium P a ! t to a solution of silver nitrate containing ammoniuni nitrate. Nethylic 1Litrosof~rrocyaiziiEe, He( CN),NOMeH,,2H20, is obtained by treating an ice-cold mixture of sodium nitrosoferrocyanide and methylic alcohol with hydrogen chloride, and concentrating the aolu- tiou in a vacuum over potassium hydroxide and sulphuric acid. It crjstallises i n red nodules, is easily soluble in water and dilute sodium hydroxide with a reddish-yellow coloration, and gives a characteristic bluish-violet coloration with ammonium sulphide. The efhylic c o w pound, obtained in a similar way, crystallises in small, lustrous, bright red plates vvit.h 3H20, and gives the nitrosoferrocyanide reac- tions with alkali carbonates and ammonium sulphide.The propyZic. compowd, with :3H20, crystallises iu bright red aggregates, which quickly turn green on exposure to air. From the formation of the above compounds, the author concludes that the nitrosoferrocyanide ccntains an oximido-group as expressed in the fomiula = 98-100'. It loses its water of crystallisation at 90". Fe(CN),H,:NOH. E. C. It. Composition of the Ohio and Canadian Sulphur Petroleums.By CHARLES 3'. MABERY (Amer. Chem. J., 1893, 17, 713--748).--The constituents were separated by distillation in an apparatus somewhat ~*esemltling that used in Warren's classical research, but the fractiona- Lion mas eEected under reduced pressure, the latter being regulated by means of an adjustable artificial leak. Ohio petroleum is intermediate i n properties bet ween Caucasian and Pennsylvanian oils, and co!itains the folloaing pasaffinoYd hydrocarbons: Two butanes (b. p. = Oo and 7--5O), pentme and isopentane, hexanes, aid hep tanes, together VOL. LXL i. X2 7n ABSTRACTS OF CHEMICAL PAPERS. with octane and nonane. These form less than one-tenth of the oil, and correspond with those present in Pennsyt\.anian oils, of which they form about one-fifth (see next abstract). Composition of the Ohio and Canadian Sulphur Petroleums.By CIIAI~LES 3'. MALIERY (Ainei.. Chem. J., 1896, 18, 43-79 ; compare Abstr., 1894, i, 266, and preceding abstract).-The principal features of the Ohio sulphur petroleum are : (1) Tbe crude oil is heavier than the Pennsylvanian, and lighter than the Russian oil. I n the qunnti- ties of the higher distillates, and in its general properties it moiw neorly resembles the latter than the former. (2) It diffe1.s from other petroleums in tphe large amounts of sulphur compounds, which affect its general properties. ( 3 ) I t resembles the Pennsylvania oif i n containing, below 150°, members of the seiies C,,H,,, + 2, although in much smaller quantities. The presence of the two isomeric series, CItH2,! + 2, in the Ohio oil confirm the observations of Warren on the Pennsglvania petroleum.(4) The aromatic hydiaocarhons are pre- sent in niinute quantities, apparently much smaller than i n other petroleums. Benzene, toluene, and meta- and para-xylene have been identified. The herdiydro-series, C,lH2)1, is represented by hexahy- droisoxylene, and very probably by higher members. Hexahydro- benzene and hexabydrotoluene are not present. ( 5 ) By the forma- tion of characteristic nitro-products, and from the results o€ irwomine absorption, the presence in the crude oil of unsaturated hydrocarbons, C,,H?,,, seems to be indicated. The characteristic qualities of the Canadian petroleums are summa- rised as follows : (1) In its high specific gravity and in the proportions which distil at different temperatures, Canadian petroleum approaches rile Russian oil more nearly than it approaches the Ohio petroleum, but the specific g~avity of the distillates is lower thau that of the Russian distillates.As indicated by its lower specific gravity, Oil Springs oii is ejsentially different from the Petrolia oil. This is especially evident in the lower. percentage of sulphur, the larger quantities of the distil- lates, the higher specific gravity of these distillates, and the higher bromine absorption. (2) Petrolia oil is composed pl.incipally, below l+iOo, of members of the series C>zHz>t + 2, although in niuch smaller quantities even than in Ohio oil (sic). Another serie.3 is present cap- able of forming nitro-products resembling the nitro-componnds of the series C,,H2,t -1.?, or the nnsaturaied hydrocarbons CZlrHll (sic). (13) Benzene, toluene, and para- and meta-qlene are present i? niinute proportions. The hextihydro-series is represented by hexahy- cli-oisoxylene, and probably by higher members. (4) The piaesence of Iiydrocarbons capable of formiug additive prodnets is indicated by the behavionr of the distillates towards bromine, as well as the forma- tion of unsaturated liydrocarbons i n the distillates above 200' or 250°, due to cracking. (5) As in Ohio oil, the sulphur compounds have a tendency to collect i n the bigher fractions. The paper concludes with s'ome remarks on the origin of petroleum, niid i t is shown that the liinertone petroleums in general contain a higher perccutage (up to 0.35 per cent.) of nitrogen than ot,hei* petro- leums do.A. G. B- A. L.0 RQAXIC CHEMISTRY. 271 Combustion of Acetylene. By HEXR~ L. LE C H A ~ L L E I Z (Co?ILpt. Tend., 1895, 121, 1144--1147).-The combustion of acetylene was inyestigated by the methods previously employed by the author and JIallard with other gases. Mixtures of acetylene and air containing less than 7.74 per cent. of the former burn completely to carbonic anhydride and water, with a yellowish flame of low illuminating power. With proportions of acetylene between 7.74 and 17.37 pey cent., the flame is pale blue with a feeble yellowish aureole, and liydrogen and carbonic oxide are amongst the products of combustion, the relative proportions of these gases being represented by the same formula of equilibrium as in the cas9 of other combnstible gases.Wit11 more thnii 17.37 per cent. of acetylene, the reactions are incomplete, and free carbon and unburnt acetylene aru present in the gases from the flame as well as hydrogen and caisbonic oxide, the flame being red and smoky. The lower and upper limits of combus- tibility are, with oxygen, 2.8 and 93 per cent. of acetylene respectively, and with ail- 2% and 65 per cent. In a tube 40 mm. in diameter, the velocity of propagation of the flame is 0.1 metre per second with 2.9 per cent. of acetylenc, b u t increases rapidly with the proportion of tzcetjleiie until the latter i q 8 per cent., when the velocity is 5 metres per second, and afterwards it increases slowly to a maximum of 6 metres per second wikh 9 to 10 per cent.of acetylene, and beyond this limit it decreases rapidly. The temperature of i p i t i o n is only 480°, and hence explosivc mixtures of acetylene can be ignited i n glass tubes heated with a spirit lamp. The calculated temperature of combustion with 7-74! per cent. of acetylene is 2420°, with 12.2 per cent. 2260°, and with 17.37 per cent. 2100O. When burnt with its owi volume of oxjgen, the tkrnperature of the flame should be 4000°. c:. 11. 13. Homolinalol. By PEI~DXXAXD TIEMASS and R. SCHMIDT (Her., 1896, 29,691-69s ; compare Abstr., 1895, i, 646).-HomoEinalol, is obtained by slowly adding a mixture of allylic iodide and methyl- heptenone to granulated zinc i n a flask surrounded by a freezing mixture ; after remaining at low temperatures during three days, the product is distilled in an atmosphere of steam, hoinolinalol being separated from the distillato by converting i t into the aceinto, it liquid which boils a t lll-ll?o under a pressure of 15 mni.Homo- liualol boils a t 102-104° under rt pressure of 14 mm., and h a s nn odour wliich suggests linalol; the sp. gr. = 0.8618 at 20°, and the refractive index nn == 1,46534 at the Fame temperature, whence the molecular refraction 31: = 53.92. When hornolinalol is rapidly heated with csmphoik or succinic anhydride, i t yields the h9dl.o- carbon C,lH,R, which hoils a t 182-185', has the sp. gr. 0.8415 at 16", and the refractive index H D = 1.47292, whence the moleculztr refrac- tion M = 50.00. Agitation with 10 per cent.. sulphuric acid converts hornolinalol into a co32pind which boils at 135---136° under a pressure of 11 mm.Oxidation with potaesiuni permanaauafe foliowed by chromic anhgdride and sulphuric acid gives Fise to n . 22 72 ABSTRACTS OF CHEMICAL PAYERS. acetone and a small quantity of leoulinic acid, along with an acid which is probably methy1hydroxyadip;c acid, C 0 OH*CH2* C H,* C Me (0 H) C El2* C 0 0 H. XI. 0. F. Compounds of Sugars with Ethylene Mercaptan, Trimethyl- ene Mercaptan, and Benzyl Mercmptan. By WILLIAM T. LAWRENCE (Ber., 1896, 29, 547-558 ; compare Abstr., 1894, i, 269).-GZzscose- efhyEenemercaptaZ, C6H1205:S2CtE4, is obtained by agitating ethylene mercaptan with a solutioii of g2;lucose in hydrochloric acid (sp. gr. 1-19) ; it has a bitter taatt?, and crystallises from alcohol in colourless, slender needles me'lting at, 143' (uncorr.).Three parts of boiling watei- dissolve the mercaptal, which is soluble in 12 parts of water at common temperatures, separating from a 10 per cent. solution in pyramids ; the specific rottttory power [ x ] ~ = -10.81" in aqueous solution a t 20". The mercaptal is indifferent toward., dilute acids, but is readilg decomposed by bromine, which gives rise to dictbyl- enic tetrasnlphide and glucose. Mannose-ethylenemercaptal melts at 153-154' (nncorr.), an? has the specific rotatory power [aID = + 12.88" a t 20". GaZactose-ethNle~ze,nel.- captal melts at 149' (uncorr.), atid does not crystallise readily; arabi- ~ioseethylenemercaptal melts at 154' (uncorr.), and dissolves in 8 parts of water.Rhaniizose-eth~i,2eneme~c~~t~l crystallises from alcohol in slender, colourless needles, and melts a t 169' (uncorr.) ; ;vylosc- ethylenemercaptal resembles the derivatives of gluc:)se and rhamnose. Glucose-trimethylenemercaptal, C, H1?05:S2C3HG, crystallises from alcoltol in slender needles, which taste bitter and melt at 130'; i t dissolves in 14 parts of boiiing wster and 15 parts of boiling alcohol, beiiig soluble in 9 parts of' water at the ordinary temperature. Arahi- .ttoseti.imethyZe?~eme~ca~tal crystallises in long needles, liac, a bitter taste, and melts a t 150" (iincorr.) ; galactose-ti.intetltyleiteme,.cuptnl and xylose-triniethylenemercaptnl are colourless syrups. Glucose-br?tzyl?iie,.captal, CsHl,O,( SCH2PI~)2, crptallises from 50 per cent. alcohol i n slender, white iieedles, and melts a t 133' (uncorr.) ; i t has a bitter taste, and dissolves in 8 parts of boiling alcohol, but requires 50 parts of boiling water.GaZactose-b~~izyl?ner.ca~taE melts at 130' (uncorr.), and dissolves in 6 parts of hot alcoIio1; rhamnose- benzylmercaptal crystallises in plates, and melts at 1'26'. Ayabiirose- benzylmercaytul crystallises from 50 per cent. alcohol in very long needles, and melts at 144" ; xl/lose-beizz~lmerca~tnl is a syrup. 111. 0. F. Crystallised &Mannose. By W. ALRERDA VAN EKESSTEIN (Rec. Trav. Chim., 1895, 14,329).-Tlic author has obtained d-mannose crys- tnllised in the form of prisms, which are only slightly hygroscopic ; its aqueous solution shows niult;rotation, at first being lzevogyrate, but afterwards dextrogjrate.J. J. S. Crystallised Anhydrous Rhamnose. By EMIL FISCHER (Ber., 1896, 29,324-325).--Tiinret (Compt. rend., 1896,122,86) has over- looked the fact that the xnthor has already prepared this substance by heating ordinary rliamnosc 011 tlic water bath and crystallisingORGANIC CHEMISTRY. 273 the product from acetone (Abstr., 1895, i, 440). I n 10 per cent. aqueous solution at ZOO, the specific rotation is [a]= = + 31.5 one minute after the substance has been dissolved ; after half an hour, it is only + 1 8 O , and it sinks eventua.lly to the value generally ascribed to rhamnose. C. F. B. Volemitol, a new Saccharine Matter. By EMrr,E E. BOURQCELOT (J. Phnrnz., 1895, [6], 2, 385-390).-To prepare volemitol (Abstr., 1895, i, 639), 500 grams of the dried fungus Laderius ro2emiis is digested for 20 minutes, on a water bath, with t w o litres of 85" alcohol, or, i f the fresh fungus is used, 95" alcohol is employed ; the hot alcohol is decanted, the digestion repeated with 1.5 litze of fi-esh alcohol and the residue pressed.The combined liquors are filtered when cold, the alcohol distilled off, and the residue concentrated to a syrup which is extracted with 95O alcohol ; from this solution, volemitol is very slowly deposited. It is purified by dissolving it in boiling 80" alcohol, using 8 parts of solvent to 1 of volemitol, filtering, warming, allowing to crystallise, drying with the air pump, and washing first with 95' alcohol, then with ether, and finally drying at 60'. Volcniitol forms little spherical accumuiatioiis of minute, fine, white, soluble needles, the melting point, specific rotation, &c., for a pure sample are given in the abstract referred to.It contains no water of crystailisa- tjon, and decomposes when heated above 200°, evolving water and an odour of caramel. It is faintly sweet, is very soluble in water, b u t only slightly so in alcohol ; the solubility, in the latter case, however, being increased by the presence of certain oTganic compounds. It does not reduce Fehling's solution even after treatment with boiling dilute sulphuric acid, nor is i t fermented by yeast. It prevents the precipitation of copper oxide by alcohol, b u t prodnces a blue pre- cipitate in ammoniacal copper sulphate. The author has not obtained any nitro-derivative, and when digested a t the boiling point €or 12 hour with anhydrous sodium acetate, and acetic anhydride, it yields a crystalline compound having the properties of mannitol hexacetate, but, unlike mannitol, when digested only 20 minutes, no crystalline prodiict is obtained.With acetaldehyde and benzaldehyde, it forms acetals, which crystallise in silky needles. The ethylir: acetai is very soluble in boiling 73" alcohol; it melts at 190" and is Ievo- rotatorj-. D. A. L. Dextrins obtained by the Hydrolysis of Starch. By K. 13iir;o~ (PJEuger's Archie, 1895, 62, 131-155) .-The author has obtained amylodextrin by adding pure potato starch in small quantities to an equal weight of potash dissolved iu water. The mixture is warmed on the water bath, and finally, for about 10 minutes, over a free flame ; the amylodextrin may then be precipitated by alcohol, aud if the directions are carefully followed, it is obtained in the form of a, colourless powder which can easily be filtered off.It is best purified by repeated solution in hot water and precipitation by absolute alcohol, when it is obtained in the form of a white solid which, when quite free from alcohol, is not affected by exposure to air. It, is only sparingly solable in water, even when hotb, and yields an opalescent2 74 ABSTRACTS OF CHESCOAL PAPERS. solution, from which after a time, a portion of the dextrin separates. With iodine solution, i t gives a blue coloration, and does not reduce Pehling’s solution, even on boiling with it for some time. The author has also obtained nmylodextrin from starch by digesting it at 60° for 10-15 minutes with a chloroform solution of diastase.If‘ the digestion is continued for too long a time, erythrndextrin is obtained together with amylodextrin, Attempts t o separate the two dextrins by means of fractioiial precipitation with bnyyta solution proved useless, the metehod of dialysis is also too slow for the sepa- ration of the two, but may be used for the det,ection of erythrodextrin in a sample of amyIodexti*in. Bgth ainjlodextrins were partially prc- cipitated by barium hydroxide soliltion and the precipitate analyscd. The precipitate obtained from the amylodextrin from potato starch bad the composition : Dext.rin : Ba(OH), = 100 : 23-25, which agrees well with the formula (C,H,,Oj),,Ba(OH),.Amylodextrin obtaineci from starch by means of dilnte sulphuric acid has the same properties as that obtained by means of potash OL’ diastase ; but all thiwe diifer materially from the amylodextrin described by Lintner and Dull (Abstr., 1894, i, 5), especially as regards tlieir solubility in hot water. The author considem his com- pound to be pure amylodextrin, and thinks that the substance described by Lintner and Dull is merely a mixture of his amylodextriii with erythrodextrin. A half per cent. solution of amylodestrin in water is immediately gclatinised when treated with a 20 pep cent. sodiunr hydroxide solution. The gelatiaised mass beconies liquid on warming, but again solidifies on cooling, and is readily soluble in cold water. Potassium hydroxide does not act in the same way.Bqth.r.odextri?i was prepared by treating starch paste with diastase at 60-70° until i t gave a clear red coloration with iodine. After destroying the diastase by boiling and evaporating, the eqthro- dextrin was precipitated by means of alcohol, and freed from achroodextrin by treatment with excess of ba,rium hydroxide, where- by the barium compound of erythrodextrin was thrown down while the achroodextrin remained in solution. The erythrodextrin was also pieepared by slightly modified methods, b u t in all cases i t forms a mow-white powder, which is not altered when exposed to air. It is readily soluble in water, yields a brownish-red coloration with iodine solution, and does not reduce alkaline copper sulphate solution at the ordinary temperature.The solution was precipitated with an insufficient qnantity of barium hydroxide, when a compound wag obtained, probably having the formula ( CGHto05)5,Ba(OH)2, 01’ (CcH,oOa)G,Ba(OH),. The rotatory power in all cases is about [a]= = 190, evexi when the erythrodextrin is mixed with achroodextrin. Achroodextrin was obtained by treating starch paste with diastase at 60--70° until i t remained colourless wheii treated with iodine. Af-tei- boiling to destroy the diastase, i t was precipitated by 96 per cent. alcohol. It forms a snow-white powder readily soluble in water and is not pPecipitated from its aqueous solution by barium hydroxide, but can be precipitated in +,his way from an alcoholic solution, yielding a compound (C6H,o05)r,Ba( OH),. I t s specific rotatory powel.i s [all> = + 1‘19---184O, and i t readily reduces Fehling’R solution.ORGANIC CIIEBIISTRY, 275 Attempts to further pii*ify the nclri+oodexti*in (1) by treatment with phenylhydrazine, (2) b y paytial oxidittion with alkaline coppel. sulphate solution, ( 3 ) by Landwehr’s iron precipitation method proved fruitless, but the author thinks that it is quite possible eithw by fractional p*ecipitatioii with barium hydi*oxide in a 10 per cent. alcoholic solution, 01’ by dialysis, or by a combination of both methods, to prcpare an achroodextrin with constant properties 2nd fin all^ to make a, molecular weight detenniiistion. J. .J. S. Reduction Products of Methylbutylnitrarnine. By A s c r n ~ r 1.: P. N. FI~.~SCIIIMOX~~ and H. VAN l+:itr (Rcc.Tmv. Chim., 1695, 14, 317-326 ; compare Abstr., 1885, 9G3).--A mixture of methylbutyl-. amine and n~ethylbntylhydrazine was obtained by redueiug methyl- butylnitramine with zinc dust and acetic acid. The two are best separated by twatment with etbylic oxalate, since the liydrazine yields o.ualmethylbutylhydrazic~e and the tlmine methylbuf~-Ioxamic acid. O~~~n??)~ethyZbztfyZh~~d,.a=idL., C,0,(NH*NMe*C4H-I,)2, is a oolourless, ctytalline substance ; i t melts at 156O, and is moderately soluble i n boiling alcohol. When boiled with aqueous potash and then distilled, it yields methy Zbulylhydrctziite, which boils at 50-5-51” under 38 mni. pressnre; it is a colourless liquid, of sp. gr. = 0.8092 at 15O, and is miscible in all proportions with water, alcohol, and ether.Its fqdro- cftloride is extremely hygroscopic, and therefore difficult to prepare, and its pZatiitochZoride does not crystallise readily. When an ethereal solution of the liydrazine is treated with yellow mercuric oxide, it yields ?IrethyEbutyltctrnzone; this distils at 119-120O under 18 mm. pressure, and is a colourless liquid of sp. gr. = 0*8708 at 1 5 O . It is only sparingly soluble in water, has an alkaline reaction, and does not reduce Fehling’s solution. The mother liquoi*s from the oxal- methylbutjlhydrazide were treated with nitrous acid, in oyder to convert any of the hydrazine into methylbntylamine, and, zfter dilution with water, were distilled. ~ e f h ~ l ~ u t y z ~ r n ~ n e is a colourless liquid with a slight ainiiioniacal odour, and is readily soluble in water, alcohol, and ether.It has ft sp. p. = 0.7375 at ljo, boils at 90.5-91*5° under i64 inm. pressure, and does not reduce Fehling’s solution. The authors contradict Zublin’s statement (Abstr., 1878, 284) t h a t normal butylamine reduces Behling’s solution. The hyd?-ochZo?ide, NHMe*C4HT,,HCI, CSJS- tallises in small platcs, melts at 170-171°, is extremely hygroscopic, and is soluble in water, alcohol, and chloroform. The platiizo- chZo.r*ide is readily soluble in water, sparingly in alcohol, and melts at 2 0 3 O , at the same time undergoing decomposition. 2ClethyZbzit?lZnif?.osnminc is n yellow liquid, only slightly soluble in water, but miscible with alcohol and ether ; its sp. gr. = 0.936 at 15O, and it boils at 89-85’ under 15 mm. pressure, and a t 199-201° under 767 mni. pressurc.J. J. S. Action of Fused Potash on Methylnitramine and Dimethyl- nitramine. By H. VAN ERP (Rpc. Trav. Chim., 1894, 14, 327-328,276 ABSTRACTS OF CHEMICAL PAPERS. and Ber., 1896, 29, 474-476) .-When diniethyliiitra,nine is fused with potash, i t yields potassium nitrite and ethylamine, which was recognised by conversion into dinitromonomethylaniliue. Methyl- nitramine, when treated in a similar manner, yields a mixture of hydrogen a\cd ammonia, together with formic and nitrous acids. These results are at variance with the statements of Thiele and Lachmann (Abstr., 1895, i, 587), according to whom the nitramines yield nitric acid and methylamine and dimethylamine respectively. A. H. Dimethylglyoxime. By EXRICO RIMIXI (Gnzzefta, 1895, 25, on reduction ii, 266--2GI).-The glyoxime peroxides, with tin and hycirochIoric acid, yield furfurrtzinic derivatives, whilst, on reduction with zinc dust and acetic acid, they give syn-dioximes.I)imethy?gIyoxime peroxide, when treated with zinc dust and acetic acid, yields the dimethylglyoxime obtained By Fittig (Abstr., 1889, 490) by the action of hydroxylamine on diacetyl. This glyoxime is therefore a syn-glyoxirne, as is also indicated by the readiness with which it yie!ds dimethylazoxazole (Wolff, Abstr., 1895, i, 182). NO*ON W. J. P. Action of Hydroxylamine Hydrochloride on Glyoxal. By ARTURO MJOLATI (Gazxetta, 1895, 25, ii, 213---217).-0n preparing glyoxirne by the action of hydroxylamine on glyoxal in acid solution, the crude product contains c1 certain proportion of an explosive substance, which is obtained pure by evaporating a concen- trated solution of hydroxylamine hydrochloride and glyoxal until cr~stallisation begins, and then neutralising exactly with sodium carbonate ; the crystalline precipitate is extracted with ether t o i*emove glyoxime, and crystallised from boiling water, when colourless needles are obtained of the composition C&N@3, melting and decomposing a t 176'.When heated on it spatula, i t explodes like guncotton, leaving no residue, and is sparingly soluble in cold water, alcohol, or ether; i t is readily soluble in acids, alkalis, or alkali carbonates, but is precipitated unaltered on c;trefully neutrs- lising the solution. I t is slowly decomposed when boiled with acetic anhydride o r chloride.It Fields a beruoyl derivative, which was not nnalysed ; its hyd?*ochZoi*ide, C4H5N303,ECl, crystal Iises in needles melting a t the same temperature as the base, and the ptafiizochloride is very soluble in water and explodes on heating. The base probably has the constitution CHhN / C ( N o H ) > ~ ~ ~ ~ ~ : ~ and is ~ o t formed by the action of hydroxylamine on glyoxal in neutral or alkaline solutions, therefore glyoxime should be capable of being prepared under such conditions. W. J. P. Action of Balogens on Formaldehyde. By Asm6 BI~OCHET (Conzpt. rend., 1895, 121, 1156-1159),-Dry chlorine has no action on tarioxymethylene in diffused daylight a t the ordiiiaiy temperature, but, on gently heating, hydrogen chloride and carbonic oxide areORGANIC OHEMISTRY.277 given off. I n direct sunlight, carbonic chloride is also formed, but i t is a secondary product, resulting from the action of excess of chlorine on carbonic oxide, and the quantity produced is greater the more rapid the current of chlorine. A mixture of 1 gram of trioxymethylene and 1 C.C. of bromine at the ordinary temperature forms a dry powder, which, when allowed to remain at the ordinary temperature in the dark or in diffused day- light, gradually liquefies and acquires a blood-red colour. I n sun- light, these changes are much more rapid, but in both cases 5t gas is liberated which contains a high proportion of carbonic oxide. A t looo, the solid mixture liquefies at once, but gas is only very slowly liberated, and it contains a lower proportion of carbonic oxide with some carbouic anhydride.In all these cases, some carbonic bromide is formed, probably as a result of the action of bromine on the car- bonic oxide. I n all cases, the action of chlorine or bromine on formaldehyde pro- duces carbonic oxide: and this 1-esult explains the occnrrence of carbonic oxide in the products of the action of halogens on methylic alcohol (Abstr., 1895, i, 637). When methylic alcohol is burnt with ft limited quantity of oxygen, from 5 t o 10 per cent. is converted into formaldehyde, and from 3 t o 5 per cent. into carbonic oxide, whilst the rest is completely burut to carbonic anhydride and water. C. H. B. Tetrinic [Tetric] acid. By PAVL C. FREER [and, in palat, E. It. MILLER] (Arne?.. Chem.J., 1895, 17, 779-726).-‘l’he aiithor’s results are not in accordancs with those of Nef (see Abstr., 1892, 140). The product of bromination of ethylic methylacetoacetate or its sodium derivative is not a single substance, and contains nnaltercd ethylic methylacetoacetate, and etbylic a- and -1-monobromo- and dibromo- methylacetoacetates. It niay be partially resolved by distillation, the diff ereiit fractions yielding, under the same conditions, different pro- portions of tetric acid. On oxidising the mixture by cold alkalinc permanganate, a small quantity of oxalic acid is obtained, together with chloracetic acid and much acetic acid, the first two obviously being produced by the oxidation of the -/-broino-derivative, and the latter from the P-derivative.The total amount of yderivative pre- sent in a specimen prepared by the author i s estimated at 6 per cent., a specimen prepared from Kahlbaum’s ethylic met’tiylacetoacetate containing much less. The isomeric ethylic bromomethylacetoacetates may be partially separated by means of alkalis, in which the a-derivative is insoluble ; after treatment in this maniior, the a-derivative yielded no tetric acid, the presence of hydrobromic acid being necessary to effkct an initial change to the y-derivative, which alone affords tetric acid wlien distilled or heated. Ethylic broinomethylacetoa.cetate, on being heated a t 100’ for some time, yields 87.4 per cent. of the theoretical quantity of tetric acid, and a small quantity of hydrogen bromide may be detected in the libel-ated gases. As different samples of apparently pnre etliylic methylacetoacet ate278 ABSTRACTS OF CHEMICAL PAPERS.differ in behariour when brominated, i t is possible tliat there exist to,aetlicr the geometric isoinerides (1) wonld give a -pderivative which would readily evolve ethylic bromide and yield tetric acid ; (2) would merely change gradually by m ol ecu lar re- arrangement . With E. X. MIJ,LEK --Contrary to Demarqay's account, silver tetrate is fairly soluble in water, and is used fur the preparation of ethylic tetrate, the vapour density of which, at 1 7 4 O , agrees with the formula C5H,0JEt. 'l'he bc?~izo?/Z derivative of t.etric acid, obtained by the action of benzoic chloride 011 sodium tetrate, separates fi*om acetone in long, Iustrous needles, melting a t 128"' and is partiallydecom- posed by boiling alcohol, ethylic benzoate beiug formed. Its molecular weight i n boiling benzene is normal.Tetric chloride, coutrary to the statements of Wolff (this vol., i, $877, is capable of existence, and has a normal rapour density ; it dissolves slowly in alkalis, thus evincing its lactonic character. As i n the case of ethylic: tetrate, a liqriid and zl solici modification have been obtained. a. IJ. Action of Inorganic acidic Metallic Oxides on Organic acids. By A n ~ n v n ROSESHEIM [and, in part, LCDWI(; COHS] (Zeit. (rnorg. Chenz., 1896, 11, 1175-222 ; see also Abstr., 1893, i, 626).-1. Altcrni- 72ium Oxdates [with Luuwic CoHs].--When a solution of oxalic acid is saturated with an excess of alumina and the filtrate evaporated on the water bsth, a clear, pale yellow syrup is obtained, which con- tains the compound AI2Os,3C2Os.Jt cannot be obtained in crystals, gives no precipitate when treated with alcohol or ettier, solidifies to a homogeneous, white mass when cooled to -15*, and melts again at -5'. It gives no reaction with vanadic acid, showing that i t con- tains no free oxalic acid, gives an acid reaction towards indicators, and when boiled with ammonia is decomposed, with formation of 8 complex ammotiium salt and precipitation of about half the aluminium as hydroxide. With chlorides of the metals, it forms well-characterised compounds containing alumina. The barizcnt salt, AL2Ba3(C204), + 6H20, cry stallises in silky, lustrous needles, and is pai*tially decom- posed on recrystallisation.A dozcblc salt, of the composition Al,K,(C,O,)G + 5Hz0, is obtained by treating a boiling solution of acid potassium oxalate with excess of alumina ; it crystallises in large, colourless, prismatic needles, gives most of the reactions for aluminium, except that only part of the alnminfum is precipitated by boiling with ammonia. With calcium chloride, it yields a compound containiug aluminium, and calcium oxalate is not precipitated. The corresponding sodium and ammo- nium salts, with 94 and 5+ H20 respectively, are obtained in a similar msnner. The salts are likewise obtained by treating the above aluminium oxalate with the corresponding chlorides. They give up their water of crystallisation when heated a t 80---90*, and do not reduce rauadic acid.ORGANIC CHEMISTRY, %79 A ~ ( ~ l f , of the composition 2~~,o,~1,o3,3C2o,,.~H,O, is obtained by saturating a boiling solution of acid potassium oxalate with excess of dumina, concentrating the solution in p~escnce of excess of alnmina over a bare flame, and, after rapid filtmtion, eraporating it to crys- tallisstion ; it.forms rhombic scales, and decomposes 0x1 recrystallisa- tion. The sodium saEt with 8H,O separates in nodules or 1-hombic crystals, and emoresces rapidly on exposure to ail.. The nmnioniw~ salt was not obtained, as the solution on concentmtion gives 08 ammonia and the salt 3(NH4)20,A120~,6C~03,5~Hz0, then separates. These salts contain one-OH group, as shown by the fact that the lash -& mol. of water is only given off at 130'.They dissolve vanaclic acid with it yellow coloration, have a neutral reaction, and give crystal- line precipitates of double aluinirrium oxalates tv hen treated with chlorides of the alkaline earths. When dissolved in water, they decompose accordiiig to the equation 30H*Al,( 00C.COOH)5 = 3Al(OOC*COOR), + AI(OH),, and can therefore only be obtained i n the presence of an excess of alumina. The salt 2K20,A1203,4C203,3H20 is obtained by slowly adding potassium hydroxide (1 rnol.) to a solution of acid potassium oxalate (5 mols.) saturated with alumina. It crystallises in rhombic scales, and is easily soluble in cold arid warm water, but these solutions a t once decompose with separation of alumina. The sodimi salt with 6 and 7H20 crystallises in small plates.The am7noi~iitm salt crptallises with 2H,O. These salts give similar reactions t o the preceding, and contain lH20 more intimately combined. Salts more basic than tlie above cannot be obtained. When a solution containing the con- stituents in the proportion 2~R2O,A1,O3,5C20, is treated with 2 or 3 mols. of potassium hydroxide, alumina is precipitated, and the pre- ceding salts, together with normal oxalates, are obtained. The saEt K20,A1203,4C,0,,7~H,0 is obtained by adding to a, filtered solutioii of oxalic acid ( 3 mols.), saturated with alumina, a concen- trated solution of normal potassium oxalate (1 mol.) evaporating to a syrup, and then stirring well with a giass rod. The salt crystallises in microscopic tablets, and can be recrystallised without decom- position.The sodium and ammonizm salts are similar, and crystal- lise with 104 and 5 H,O respectively. These salts give a faintly acid reaction: do not react with vanadic acid, and give crystalline double aluminium oxalates when treated with chlorides of the alkaline eartlis. Only part of tlie aluminium is precipitated by boiling with ammonia. 11. Alkali Chromium 0xalate.-When a boiling solution of oxalic acid is saturated with an excess of freshly precipitated chi*ornium hydroxide, a deep bluish-red syrup is obtained which will r,ot erystaliise, is completely eoluble in alcohol and ether, and contains the coastitueats in the ratio ~r20,,3c,03. Neither the oxalic acid nor tbe chramiurn hgdroxicle can be detected by the ordinary methods. With chlorides of the alkaline earths, the compound gives beautifully crystalline salts containing chromium.With ammonia, no precipitate is obtained, and by prolonged boiling with excess of caustic alkali, a roluminous green precipitate i s obtained. The Bu~izrnz salt, Cr,Ba3(C204),,8H20, crystallises in bright green needles280 ABSTRACTS OF CHEJIICAL PAPERS. having a red fluorescence, and has been previously obtained by Werner. The salts of the composition 3R20,Cr203,6C203, are obtained in a similar way to the preceding aluminium compounds, and are blue to bluish-red. The potassium salt crystallises with 6H20 in monoclinic scales, the sodium salt with 9H20 in tablets, and the ammonium salt with 6H20 in leaflets. The salts of the composition 2-ijR20,Cr,03,5C203 cannot be pre- pared. A green syiwp containing the constituents in the right pro- portions is obtained in a similar manner to that described for t h e preparation of the aluminium compounds, but this syrup quickly de- composes with separation of chromium oxide, and then the preceding blne salts crystallise out.I n one experiment, by cooling the green syrul) to - Z O O , green needles were obtained, but they decomposed so rapidly that an analysis was not possible. The salt, 2K20,Cr203,4C203,Hz0, is obtained in a similar manner to the correspondinc aluminium salt; it crystallises in deep green, micro- scopic needles. The sodium salt has also been obtained crystalline. The ammonium salt could not be obtained crystalline, but formed a gummy mass containing chromium oxide. The stilt, K2(?,Cr2O3,4C2O3,1OH2O, is obtained in a similar manner to the corresponding aluminium salt ; it crystallises in beautiful deep red prisms.111. Alkali Fewk 0ralates.-The author has examined the iron corn- pounds obtained in a similar manner to the preceding. By the action of oxalic acid on freshly prepared ferric hydroxide, a deep yellow syrup is obtained, containing the constituents in the ratio Fe203 : 3C203. Alkali iron oralates of the series 3 : 1 : 6 are obtained by saturating solutions of the acid alkali oxalates with ferric hydroxide. The salts of the composition 2$RZO,Fe20,,5C2O3, like the preceding chromium compounds, cannot be obtained crystalline, although the analysis of the solution indicates their presence. The salts of the series f: : 1 : 4 could not be prepared, and attempts to obtain them yielded green salts of the series 3 : 1 : 6, together with a brownish-red precipit,ate cf Fariable composition con tainiug all three constituents.The salt K2O,Fe2O3,4CZO3,5H20, obtained in a similar manner to the aluminium salt, crystallises in bright brown crystals, and is decomposed when recrystallised, with formation of the green salt (3 : 1 : 6 ) and sepe- ration of ferric hydroxide. The salt, K20,E’e203,4M00,,2Cz03,10H20, is obtained in beautiful bright yellow crystals by saturating a solution of the salt 3K2O,Fe2Os,6C2O3,6H2O with molyhdic acid. IV. Of the five types of compounds described, all the aluminium conipounds, four of the chromium compounds, and three of the iron compounds are capable of existence, that, is, the number of the complex acids varies with the basicity of the tervalent metal.The normal tribasic salts of the type M”’(OOC*COOR)3 are the most stable, and are easily obtained from the sesquioxides of iron, aluminium, and chromium, and also, though less easily, from the oxides of manganese and cobalt. By the addition of oxalic acid gIoups to the sesqnioxides, acids are formed, which are strongerOtlQXNIC CEIEMISTRY. 231 and more capable OF foi*miug salts according as moi'e hydroxjl groups of the scsquioxide are replaced by oxalic acid groups, and also according to the less b s i c character of the sesquioxide. E. C . R. Derivatives of Tartaric and Parapyruvic acids. By EDUARD MULDER (nec. Trnv. Chim., 1895,14, 281-306 ; compare Abstr., 1893, i, 685, and 1395, i, 449).-The author has continued his investi,ant,ions on the products respectively soluble and insoluble in aceiic acid, which rcsult from the action of et'hylic chloride on ethylic disodium tartrate.On treatment with baryta water, R mixture of two substances was obtained. One of these, the crystalline barium compound, is shown to be barium oxalate, BaCzOJ + 2H,O ; i t loses l$HzO at 120°, and the remaining 4Hz0 at 1'20-1-1.0". The other substance, t h e mamcllated compound, when freed from barium oxalate, yields racemic acid, and a second crystalline acid, the constitution of which has not yet, been determined. Tltese three acids, oxalic, raceniic, and the acid of unknown constitution, are regarded 2s decomposition products of tartryl tart ark acid. The author recommends slight modifications in the preparation of ethylic tartrates, and also in the manner of treatment of ethylic disodium tartrate with ethylic cbloride.Barium pampyruvate has the composition, (C3€I,303)zBa, + H?O ; parapyruvic acid itself is unstable, and readily loses carbonic anhydr- ide and water. J. J. S. Stereoisomeric Dimethyltricarballylic acids. By NICOLAI D. ZtiLiNsKY and N. TSCHERSOSWITOYF (Be?.., 1896, 29, 333-339).- Ethylic c.yanodimethylcarhallylate, CO@st*C(CN)(CH~e*COOEt), (compare Harthe, Abstr., 1888, 937, and Ann. CItim. Phys., 1892, [6], 27, %I), was prepar3d by the action of ethylic cyanacetnte on ethylic a-bromopropionate in the presence of sodium ethoxide, the fraction boiling at 190-210" (for the most part at 195-197") being used for the further experiments. When heated mit(h dilute sulph- uric acid ( 1 : l ) , it yields three acids, all of which have the com- position, C8H1206, that is, COOH*CH(CHl\Ie*COOH)z ; one of these is fairly insoluble in water, and melts at 203--204°; by fractional crystallisation of the motlrcr liquor from this acid, the other two, melting respectively at 175-176O and 248-149", were obtained.A11 three, when warmed with acetic chloride, yield crystallised isomeric anhydrides, CsHloOd, melting respectively at 111-1 13O, 129-1303, and 117-119', and these re-unite with water, reforming the ori- ginal acids. But the acids also yield anhydrides, transparent, and Fiscid in character, when they are heated done at 200-210°, and these, with water, regenerate the original acids, with the exception of the anhydride of the acid melting a t 203-20P0, which yields the acid melting 2t 148-149'. Further, the second and third acids ai-a both tratlsformed into the first (melting a t 203-204') when heated with hydrochloric acid a t 190-200".The isonierism of these three acids is, doubtless, of stereochemical nature. C. F. B.282 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Arnides and Acid Chlorides. Bp ALB1:R.r Corsox (Ccmpt. Tend., 1895, 121, 1 t53--1156),-When di*y f-iydrogen chloride is passed into a mixture of a nitrile and an acid cooled at. about O", an airiide and an acid chloridz are formed, RCN + R'COOH + 2HC1 = RCO*NH,,HCl + R'COCI. Acetonitrile and acetic acid yield acetarnide and acetic chloride ; acetonitrile and propionic acid yield acetamide and propionic chloride ; acetic acid and propionitrile yield propionamide and acetic chloride. Formic acid, under similar conditions, decomposes in a d iffercnt manner.The well-known efficiency of hydrogen chloride in promoting the formation of ethereal snits is probably dut) to its tendency to convert. acids into acid chlo- rides i n presence of any substance which will combine with water. Acid chlorides are formed still more easily if the acid in the above reaction is replaced by the anhydride. C. H. B. Method of Decomposition of some Arnides and Imides. By WILLIAM ~ C H S S E R DE CONIXCK (Compt. rend!., 1893,121, 893-894).- 'I'he author has investigated the behariour of various amides and imides with a solution of sodium hypochlorite, prepared by precipi- tating a solution of 50 parts of fresh bleaching powder in 500 parts of water, with a solution of 100 parts o€ sodium carbonate ill 300 parts of water.Formamide is decomposed slightly at the ordinary temperatuw, and more rapidly on heating. Acetsinide is not decomposed, even when moderately hexted. Propionamide begins to decompose in the cold, and the change becomes very rapid on heating ; butyramidc also decomposes on heating. Oxamide and succinarnidc behave like pi-opionamide. Glycocine, amidopropionic acid (alanine), and aspa- ragine decompose when gently heated; but hippuric acid is not decomposed unless strongly heated. Succinimide decomposes very rapidly, e w n at the ordina1.y temperature. I n all cases the gas liberated has the negative properties of nitrogen.By J. TOPIN ( A m . Cl~inz. Phys., [7], 5 , 99--132).-Basic acetamide hydrobvonzide. (C2tl,NO),,HBr, is obtt&ecl. when a solut,ion of acetsmide in equal parts of alcohol and et,her is treated with pure, dry, gaseous hgdrogcn bromide. It is necessary to pass the gas in a slow stream, and to keep the vessel containing the solution of acetamide cool bey means of cold water, The hydrobromide crystallises in colourless, odourless, fragile needles, which have an acid taste and reaction. It melts a t 139.5", and shortly afterwards decomposes, is readily soIuble in water, sparingiy in alco- hol, and insoliible in ether, and is decomposed by alkalis. C. H. B. New Salts of Amides. The author was not able to prepare acetnmide hydriodide.Acefaniide pZuti?zocliZo&le, (C~HsNO)2,H,PtC16, obtained from aqueous solutions of acetamide and platinic chloride, is an orange-yellow crystalline powder, which is very sparirigly soluble in >\Fate", even less so in alcohol. and melts and decompmes at 225'. Acetamitle hydwyex ozalate, C'2H6N0,2C2H,0J, is best obtained by adding acetainide (1 rnol.) in concentrated aqueous solution t o oxalic acid (2 mots.), also in aqueous solution ; i t is also formed when theORGANIC CHEMISTRY. 283 two compounds, in molecnlar prol)ortion, arc mixed i n aqueons or- alcoholic solntio!i. I t crystwllises in colourless It,r.i+ms or plates, an& melts a t 129'. Another oxaZaCt~, C2H5X07C2H,04, was obtained by the author on adding the amide (2 iirols.) to oxalic acid (1 mol.) ; it lorms small,.colourless, brilliant prisms, whicli are rend ily solnble in water and in alcohol, and redden hlue litmus. The acid t a h u t e , C,H5N0,C,H60,, is be3t obtained by treatring ncctamide i n alcoholic solution with an excess of tartaric acid. It- cqstallises in colourless plates, melts a t 130.,5', is extremely soluble i u water, more sparingly in alcohol, and has an acid reaction. I t is decomposed on heating, and also, like all the other salts of amides, on t re t m en t with a1 k a1 i s. The uo~rnnl tartmte, (C2H,N0)2,C4H,0,, is obtained when 2 inols. of the amide a m taken for each iiiolecule of acid. I t forrris short, brilliant crystals, with sinall facets ; on heating, it turns brown a t 190°, and decomposes at abont 225O. rlcetamide picmte, C2H3X0,C6H3X3O7, may easily be prepared by the action of picric acid on acetnmide in alcoholic solution, or by dissolving the aniide in fused picric acid.The salt is moderately soluble i n a'lcohol, somewhat more sparingly in water. When care- fnlly heated, i t melts at 117.5'. It crystalliscs in small prisms, of a brilliant yellow colour. 2\;ormcd ozumide tartrule, ( C2H,N20L),,C4H,06, crystnllises in small, orthorhombic pIates : i t dissolves readily in wacer, more sparingly in alcohol ; it has acid propert,ies, and in aqueous solution is dextro- rotatory, pi.actica1l.y to t h e same extent as the normal acetamide tartrate (compare Wyrouboff, Abstr., 1894, ii, 177). Xtzsic ncetmzilide hydr*obronzidr, 2C8H,N0,HBr, may be prepared in much the same way as the acetaniide hydrobromide.It crystal- lises in small, colourless needles, which ;we readily soluble in water and i n alcohol, but almost insoluble in ether. Acetaizilide pZut iizochloride, ( C,FI,N O),, H,P tCl,, cry s tall i ses i n orange-yellow needles, u-hich are only very sparingly soluble in water and in alcohol. Acetaizilide picrate, CBH9K0,C6H3X3O7, crystall ises in yellow prisms. It is but sparingly soluble in water and in alcoliol, aud decomposes when gently heated. The crystallograpliic pi*opert,ies of most of tlie salts are given in detail. J. J, S. Synthesis of Complex Amides. By Ar,k<Ert.i. COLSOS ( C ~ m p t . rrud., legs, 121, 88ri-8.27).-Cya.iao~~o~u~a~i~ehyde acetute, OAlc*C E (CN) *C HMe,, is a stable compound which boils, without decomposing, a t 189" under ordinary pressure, and is insoluble in water (compare Abstr., 1S95, ii, 257).AcetyZZnctyZacefa?,zide, KHAc*CO*CHMe*OAc, constitntes the frac- tion which boils a t abont 178", when the product of the action of acetic cliloi-ide on the lactic nitrile (Zoc. cit.) is distilled under a pres-284 ABSTRACTS OF OHEMIOAL PAPERS. sure o l 15 mm. It forms white, hygroscopic crystals which, when dry, melt at 73". When dissolved i n warm water, i t forms a crystal- line hydrate containing 1 mol. H,O. It has none of the properties of cyanides, and yields no ammonia with aqueous potash i n the cold. When heated i n sealed tubes with water a t 150°, it splits up into ammonium acetate and acetic and lactic acids. Diacefgldilactnmide, NH(CO*CHMe*OAc),, is obtained by the action of water a t Oo on the crystalline product, OBc*CKMe*CN + HCl, obtained by the action o€ dry hydt-ogcn chloride on cooled cyaniso- bataldehyde acetate. It forms white, nacreous needles which meIt at l l O c , and, when heated with water at 150°, yields 3 mols.of acid. When dissolved i n benzene, it forms crystals of the compound XH(C5H7O3)2 -+- c6I3[6, but when dissolved in acetic acid, its molecular weight is found to be 230 (calc. 245). The formation of these amides is probably analogous to that of amides from nitriles bay the action of water; the change is determined by the presence of a small quantity of hydi*ochloric acid, and takes place according to the equation, R*CN + &*OH = .It* C 0 *N H Lie. C. H. B. Biuret Reactions.By Hwo SCHIFF (Ber., 1896, 29, 298-303). ---Bint.et is best prepared by heatiag the liquid carbamide hydro- chloride a t 130°, and then separating the biuret from the potassium cyanate which is formed on treating the prodnct with weak alcoholic potash. The following metallic derivative? have been examined and analjsed. The potash compoand, C,H,N,O,,KO K, crystallises in needles, and is decomposed by water and by tlie carbonic anhydride of the air. The compound with soda, C,H,N,O2,NaOH, has similar properties. Mercuric oxide forms two compowds, C2H5NJOr,Hg0 and Hg(C,H,NJ0,),,2Hg0, both of which are obtained by adding mercuric nitrate t o an aqueous solution of binret. Biuret unites with the so!uble copper salts, forming liglit blue, crystalline compounds such as CnE04,2C2H5N302, CuG12,2C2H5N3O2, which are partially deconiposed by water.The violet compound formed in the well kiiown binret reaction is best prepared by adding copper acetate solution to biuret, and then prezipitatitig with alcoholic potash. It forms long, carmine-red needles, wbich may be preserved under weak alcoholic potash ; this compound has the composition 2C2H,N,O,,2~0H,Cii(OH),, the metals being prohably united with the nitrogen of the amido-groups. Nickel salts behave towards biuret i n the same manner as the copper salts, pale green compounds being piduced, which form yellow solutioris in aqueous potash. Cobalt salts also combine with biuret, but the products do not give a characteristic coloration wit)h potnsh. The biuret reaction with potash and a, copper 01' nickel salt, appears to be given by all such diamides as contain two -CO*NH, groups uuiteci togethey, 019 with a single atom of carbon oi* nitrogen, or with several -CO.NH groups in an open chain.Thus maloilaruide and oxalyldiureide, NH,*CO*NH*NH*CO*NH2, give tlie reaction, whilst succinamide does not. A. H.ORQAXIC CHEMISTRT. 285 Oximes of a-Halogenised Aldehydes, Ketones, and Acids : Oximido-acetic acids. By ARrHnR R. HANTZSCH and WILHELN WILD (AnimZer:, 1896, 289, 2XG--309).--The authors have found that, hydroxylsmine converts a-halngenised aldehydes and a-halogen- ised ketones of the type RCHX*CO*R' into glyoxines of the general formula 1t.C (NO H) C (NO H ) K', whilst a- f-ialogenised acids yield a-oximido-acids of the type R.C(NOH)*COOH.Thus methylglyoxime has been obtained by the action of liydroxylamine on chloracetone, whilst dichlorethylic ether and amidothiazole have given rise to gly- oxime ; mono- and di-chloracetic acids yield oximidoaceLic acid, whilst a-oximidopyopionic and a-oximidobutyric acids are obtained froni a- brorno propion ic and a- bromobutyric nci d respectively. Oxil?tidoacefic-acetic acid, COOH*CH:N*O*CH,*COOH (" oximido- essigacetsiiare ") is produced along with oximidoacetic acid when hydroxylamine acts on chloracetic acid ; it crystallises from water in needles, arid melts at lSl0, yielding hydrogen cyanide. This acid iq indifferent towards acetic anhydride and acetic chloride, but phos- phorus yenta,chloride converts it into the oily chloride; neither ammo- nincd silver nor Fehling's solution is reduced by the acid when boiled with it.Tlie aiiimoniurn salt is a crystalline precipitate, and the barium salt, containing 1H20, separates in small needles ; the siEue?* salt is crystalline, and the umide crystallises in leaflets and melts a n d decomposes a t 2 1 4 O . When the acid is reduced with hydriodic achid, glycocine is produced, and hot alkalis give rise to carbonic anhydride, hydrogen cyanide, and glycollic acid ; it i s indifferent towards boiling mineral acids, but at 140°, it/ is decomposed by 35 per cent. sulphuric acid into carbonic anhydride, ammonia, formic acid, and glycollic: acid, (compare Wolff , this vol., i, SS), COOH.CIlrle:N*O*CH.,*COO~, is obtained by heating oxinlidopropionic and chloracetic acids with aqueous potash a t 50-60Ofor three hours ; it melts and decomposes at 130-132O.The acid is indifferent towards amrnonincal silver and Fehling's solution, and is not, attacked by boiling alkalis and concentrated hydrochloric acid ; the siEver salt c-rystallises f roni hot water, and coloured precipitates are formed with copper and lead acetates, and ferric chloride. A~iiidopropionic acid is obtained on reducing the acid with hydriodic acid. * Normal benzaZdon:iiizido-acetic acid, CHPh:N*O*CH,*COOH, is ob- tained by heating moleculsr proportions of the potassium derivative of benz-antialdoxime and potassium chloracetate in aqueous solution ; i t crystallises from hot water in long needles, and melts at 98". It is indifferent towards Fehling's solution and boiling concentrated hydro- chloric acid ; alkalis convert it into benzonitrile and glycollic acid, whilst hydriodic acid at, 100" gives rise to benzaldehyde, ammonia, and glycollic acid.The potassium salt contains 1H20, and crystallises from water, whilst the tin salt separates in long needles ; tho ethy& salt crvstallises in lone: needles, and melts a t 59O. Ozi~nitlopro~llionic-acet i c acid from benzspnaldoxime a.nd chloracetic acid ; it crystaIlises in long needles, and melts at 183O, decomposing vigorously at this temperature. VOL. LXX. i. Y2% ABSTRACTS OF CHEMICAL PAPERS. Reduction with hydriodic acid gives rise t o benzddehyde and glyco- cine ; i t is readily oxidised by ferric chloride and Fehling's solution, yielding benzaldehyde, which is also formed under the influence of canstic potash and boiling hydroclrloric acid.Hydroxylamidoacetic acid (Ti-auhe, this vol., i, 9) is obtained along with benzaldehyde when isobenzddcximidoacetic acid is treated wit,h boiling hydrochloric acid. M. 0. F. Action of Hydroxylamine on Ethylic Succinate. By GIORGIO EBRERA (Gazzetta, 1895, 25, ii, 263-266).-By the action of hpdroxyl- smine on ethylic succinate, Hantzscli and Urhahn (Abstr., 1895, i, 393) were unable to prepare pure succinylhydroxamic acid, but got ;I product which, on scetylat<ion, yielded what they supposed to be a tetracetylsuccinyl hydroxamic acid ; this, however, the author finds to be the succinylacetoxylamine which he has recently described (this vol., i, 209). The behaviour of ethylic succinate towards hydroxyl- amine is, therefore, exactly similar to that of methylic phthalate ( t h i s VOL, i, 222).Synthesis in the Pentamethylene Series. By NICOLAI D. ZELINSKY and It. REDSKY (Bey., 1896, 29, 403-405).-Dimethyl- a4ipic acid, when distilled with calcium hydroxide, yields dinzethyl- ketopenfameth!/Zene ; this boils at 145--14'i0, and does not combine with sodium hydroqen sulphite. The yield is 32 per cent. of the acid employed. When reduced by means of sodium in moist ethereal solution, a corresponding aZcohoZ is formed; it boils a t 154' (744 mm.), and has a sp. gr. = 0.9224 Oo/Oo. The yield is 75 per cent. of the ketone. By the action of hydriodic acid (sp. gr. = 1.96) at looo, an oily iodide is formed, and this, by the fiirther actioii of hydriodic acid at 22O0, is converted into 1 : 3-dimethykenta- inethylens boiling a t 93' (743 mm.), the sp.gr. = 0.7543 at 2Oo/4O, tlie refractive index ?a = 1.4130 a t 20°, and the molecular refractive power = 32.38, which agrees with the t,heoretical value for a saturated hydrocarbon. The compound has an odour of petroleum, is imme- diately coloured by bromine vapour, and quickiy dissolves in fuming (yellow) nitric acid ; this readily distinguishes i t from the synthetical hexamethylene hydrocarbons which, at tbe ordinary temperature, are extremely stable towards nitric acid either alone or with sulphuric acid. J. B. T. 7V. J. P. Syntheses in the Camphor and Terpene Series. By EMIL KNOEVENAGEL (AnnaZen, 1895, 289, 131-172 ; compare Abstr., 1895, i, 48, also Baeyer, Abstr., 1893, i, 2,58).---'l'he author has synthesised numerous meta-alkyl derivatives of hydrogenised toluene by reducing certain cycloYcl ketones which have been already described (Zoc.cit.) ; c4irninatiou of water from the phenols obtained in this way has given rise to dihvdrotoluene derivatives. The carbon atoms are numbered J 2 3 8 9 as indicated by the expression ' C*C<, c'c(c*q>6, and reference is 6 5 nude to A2-ketotetrahydrobenzeiie derivatives as cyclohexenones.ORGIANlO CHEMISTRY. 287 Tetrahyc~romsfac,resol (methyl-1-cycEohexeIlo1-j) is obtained by re- ducing methyl-1-cyclohexenone-5 with sodium and alcohol ; i t is a colourless, viscous oil, which boils a t 175-176', and is volatile in alcohol vnpour. and in steam. The sp.-gr. = 0.9320 at 15", and the refractive index ?hD = 1.4695 at 15", whence the molecular refraction R r== 33.48.The substance is unsaturated, and gives rise to a liquid dibromide. The acetyl derivatiTe boils a t 1$%---1&9", and the wetliane, C14H,i02N, obtained from phenylic isocyanate, melts at 90" ; tile chloride is obtained by the action of phosphorus pentachloride, and decomposes slightly when boiled in a vacuum. Tetrahydro-1 : 3 : 5-zylemd (dimethyl-1 : 3-cyclohexenol-5) is obtained froat dimethyl-1 : 3-cyclohexenone-5, and boils a t 187" under atmo- spheric pressure, and a t 8.3" under a pressure of 15 mni. ; the sp. gr. = 09056 at 15" and 09007 at 20.5". The refractive index ?zD = 1,4539 a t 20*5", whence the molecular refraction R = 37-88. The dibrorizide crjstallises in colourless needles, and melts at 14$O ; the acetyl derivative is a limpid, colourless liquid, which boils a t 195---196". The uretlzane melts at 10To, and the chloride is a highly refractive oil, which boils at 80-85" under pressure of 25 mm.; the bronrids becomes brown and resinous in air, and the iodide boils at 110-115" under a pressure of 25 mni. Te tmhydTo-1 : 3 : 5-ca rz-acrol (methyl- 1-isopropg 1- 3- c yclohezenob-5) is a colourless, viscous oil having the odour of peppermint ; it boils at 1 1 2 O , 125", and 1503 under pressures of 14 mm., '22 mm., and 65 mm. respectively, and under atmospheric pressure, i t boils at 2.24'. The sp. gr. == 0.9090 at 15", and the refractive index nD = 1.4664 a t 15", whence the molecular refraction €3 == 47.02. The acetyl derivative is n colourless liquid having an agreeable odour, and boils at 228' ; tbe methyl ether boils at 122" under a pressure of 40 nini.The chloride, C,,,K,,CI, obtained from tetrahydrocarvawol by the action of phos- phorus pentachloride, is a colourless, highly refractive oil, which boils at 99-100" under a pressure of 22 rnm. ; the bromide boils at 1S3" under a pressure of 24 rum. Meta-isobutyltetrahydrometacresol (methyl-1-isobutyl-3-cyclo~exenol-5) is obtaiiied by reducing methyl-1-isobutyl-3-cyclohexenone-5 with sodium and alcohol ; i t boils a t 119' and 127-129" under pressure.; of 10 rum. and 20 mm. respectively. At 21*5", the sp. gr. = 0 8909. ' and the refractive index nD = 1.4614, whence the moleculai* 1-efraction R = 51'77. The acetyl derivative bods at 132-134" under a pressure of 18 mm., and the methyl ether at 112" under ;I pressure of 9 mm.; the isopropyl ether boils at 116' under a pressure of 10 nim. dilletahe~:yltetrahydrometacresol (naethyl-1-hex~1-3-cycEohe~~aol- 5 ) boils a t 14.7-149" under a pressure of 20 mm., and has the sp. gr. = 0.8840 a t 21*5O, a n d the refractive index ?LD = 1.4617 at 'Ll*5O, whence the molecular yefraction R = 60.92. The ncetyl derivative boils a t 154-156' under a pressure of %2 mm., and the methyl ether at 135-136" under a pressure of 10 mm. ; the isopropyl ether has a disagreeable odour, and boils at 138-139' under a pressure of' 10 rnm. When the bromide of tetrahydrornetacresol is distilled with 10 parts Y 2288 ABSTRACTS OF CHEMICAL PAPERS. of quinoline, dibydrotoluene is produced (compare Baeyer, Annulen, 155, 271), and it is also obtained by treating tetrahydrometacyesol 14th phosphoric anliydridc. It boils at 106-10'7°, and has sp.gr, = 0.8088 a t 15', and 0.8017 a t 18.3', and the refr:tctii-e index i i D = 1.4460 at 18*3", whence the ~~olecilli~1* refraction R = 31.20. DZh2/d~o)~2Ctan.yle?ie is obtained from tetrahydro-1 : 3 : 5-xylenol by the action of phosphoric anh-ydride and by distilling the bromide with quii?oIine; it is also produced when tlte hpdrochloride of tetra- hydro-xylidine (Abstr., 1895, i, 52) is subjected to dry distillation, and by 1-educing syrrimetrical chlorodihyclro-xylene (Zoc. cit., 86). Dihydrometnxyiene is a. limpid, coloui.less liquid, which boils a t 123' ; a t 15' and 20.5' the sp.gr. = 0.7989 and 0.7948 respectively, whilst the refractive index i i D = 1.4416 a t 20.5', and therefore the niolecular refraction H, = 35.92. Alcoholic sulphuric acid (4 parts of alcohol and 1 of acid) develops a reddish-violet coloration, which subsequently becomes blue ; when half the propoi*tion of alcohol is employed, the liquid acquires a yellow tint, which changes to reddish- yellow, and finally becomes blue. These phenomena are attended with marked changcs in the absorption spectm. W:ill:ich 11xs obtained ketone isomeric with dimethyl-1 : 3-cyclohexenone-5, wliicli yields dihydrometnxylene under the influence of zinc chloride iAn.izalen, 258, 327), but the substance boils a t 132-134'; both hydrocarbons, however, are converted into triuitrometaxjlene (m.I). 180-181') 011 nitration. Uih ydronz etacy mene (112 eth y I- I.-isoprop yl- 3 -cyclohexndiene) is obtained by eliminating hydrogen bromide from the bromide of tetrahydro- 1 : 3 : 5-carvacrol, or, more conveniently, by dehjdrating this sub- stance with phosphoric anhydyide a t 120° ; i t boils a t 171-172', and has an odour recalling that o€ benzene, but like that of oi~mges, when diluted. The sp. gr. = 0.8170 at 15*5', and the refractive index n D = 1.4564 at 15.5', whence the molecular refraction It = 45*2!). Thc hydrocarbon reduces a cold solution of potassium pernianganate, and takes up four atomic proportions of bromine. Alcoholic sulphuric acid ( 4 parts of alcohol and 1 of acid) develops a wine-red coloration with d i hydrometacyniene, gradually becoming violet-red ; on e-half the proportion of alcohol gives rise to 8 jellow tint, which becomes reddish-gellow, and subsequently violet, whilst t be colonred liquids exhibit chaiaacteristic absorption spectra.The itifrosochloride of di- hj drometacymene melts a t 150'. Repeated treatment of dihydro- rnetacymene with bromine and quinoline has given rise to meta- cgruene, identical with the hydrocarbon obtained by Wallacli from tenchone (Abstr., 289& i, 380) ; metacymene, from both sources, yields a yellow trinitro-derivative, which melts a t 7'2'. is ohtnined from meta-isobntyltetrahydrometacresol by the action of phosphoric anhydride ; it is a limpid, colourless liquid, which boils a t 185O. The sp. gr. "- 0.80@9 a t 21*5O, and the refractive index BD = 1.4501 a t 21.S0, whence the molecular refraction R = 49$3 ; charac- t.ci*istic colorat ions and absorption spectra are developed mitli alco- hol and sulphuric acid.The hydrocarbon takes up four atomic pro- portions of bromine, but the product spontaneously loses hydrogen l i e ta-isobu t y l d i h y dro toluene ( nz et hy 1- 1 -isotutyl-3-c y clohexadie ize)ORQANlC CHEMISTRY. 289 bromide, and, when treated with quinoliiie, yields an oil, whicli probably contains meta-isobutyltoluene, because nitmtion gives rise t o 2 : 4 : 6-tt.irzitroisobzcty~~o~?~e?ze, which has the odour of musk, and is isomeric with Baur's " artikicial musk ; " this compound, which crystallises from alcohol and melts at 1 2 4 O , is also obtained from isobutyldihyd rotoluene. i~retahe~L.y7~i~~Lyd~~toZue.iie ~11~ethyl-l-he3Iy1-.3-cl/clohea.adiene) is pro- d u c ed w 11 en p h 0 s p h or i c anh y d r i de acts o n met ah ex y 1 t e trah y d ro ni e t a- cresol at 165'; it boils at 228-230', has the sp.gr. = 0.8216 at 21*5', and the refractive index ?iD = 1.4562 at ' 2 1 * 5 O , whence the molecular refraction R = 58.90. The hydrocarbon takes up fonr ntoniic proportions of bromine, and, on treating the prcduct with quinoline, an oil containing metahexyltoluene is obtained ; on nitra- tion, this yields 2 : 4 : 6-tri~zitrometahexyltoluene, which melts at 131°, and has a feeble odour of musk. H e taphem) heccahy drowsorcin ol ( p h m y I- 5-cycZoh exanediol- 1 : 3), is obtained by reducing , phenylitihydroresorc,inol with alcohol and sodium; i t crystallises from water in lustrous leaflets, and melts at 157'.It is iiisoluble in benzene, and sparingly soluble in chloroform and ether; i t does not dissolve more readily i n potash than in water, and crystallises unaltered from the solution. When heated with phosphoric anhydride, it yields dihydrodiphenyl, which melts a t 66--ri6-fjo, and, although extremely soluble in alcohol and etlicr, crystallises well from these solvents ; it is volatile in steam, and reducws a warm solution of potassinm permanganate. 5-methyl - 1 : 3 - diketocgclohexane-4 : 6-dicarboxylate (Abstr., 1894, i, 577) is obtained from ethylic ethylidenemdonate and ctliylic acetoacetate under the influence of sodium ethoxide. Hydro- ipis and elimination oE carbonic anhydride converts i t into rneta- ?net// yldihydro).esorciiLoZ, which crystallises from water, and melts at 125-126' ; the aqueous soliition is acidic, decomposiiig carbonates, devekps a red coloration with ferric chloride, and reduces potassiurn perxnanganate.XIetnmethyldihydroresol.cino1 is a homologue of Meding's dihydroresorcinol (Abstr., 1894, i, 177), and, like that sub- stnoce, yields a compozmd with formaldehyde ; this ciystallises from ;zlcohol i n lustrous needles, and nielts at 152-253'. The dioxilne of metarnethyldihydroresorcinol melts a t 15.5'. M. 0. F. The Cyclopentadiene of Coal Tar; the Indene of the Aliphatic Series. By GLXTA~ KRAEXER and ADOLF SPILKER (Be7*., 1896, 29, 552-S61) .-The hydrocarbon of the formula C5Hs, which tAie authors obtained from coal tar (Abstr., 1891, 205), and to which fi;tard and Lambert, having isolated the substance from the condensa- tion products of oil gas, have given the nanie pyropentylene (Abstr.., 1891, 1085), has been submitted to further investigation ; it is identi- cal with the hydrocarbon described by Roscoe (Trans., 1885, 47,669), and, - - _ as the coristitutioii is probably represented by the formula Diethylic (32HZ >CH,, the authors refer to it as the cyclopentadiene of coal tar.bZ&299 ABSTRAClTS OF OHEMICAL PAPERS. The hydrocarbon boils a t 41' (cow.) under a pressure of 760 mni., and bas the sp. gr. = 0.80475 a t 18*6"/4'; i t becomes resinous under tha iiifluence of alkalis and dilute acids, and is charred by concen- trated sulphuric wid, the action of fuming nitric acid being so vigorous a s to cause ignition.The refractive index nD = 1.4446 a t 18*6', whence tile molecular refraction M = 36.45, the value calcu- lated for two ethylene linkings being M = 36-04. Ch7orocycZopen tene, C5H&I, is obtained by saturating a solution of cyclopen tadiene in cliloroform, at low temperatures, with hydrogen chloride; i t boils at 50' under a pressure of 40 mm., and has the sp, gr. = 1.0571 a t 15'/15'. It becomes resinous spontaneously, and loses hydrogen chloride; aqueous ammonia converts it into a snb- stance resembling india-rcbber, an unsaturated alcohol, and an unsaturated bnse, C,H,NH,, which boils at 10'>--104', and forms a platinoclalol-ide. is produced by the action C HC1.Q H, CH2<CHC1*CHCI' Tric7al o roc y cl oped m e , of chlorine on the monochloro-derirative at low temperatures ; it boils a t 195-197", and has the sp.gr. = 1.3695 at 20'/4'. The substance is indifferent towards cold, concentrated sulphuric and fuming nitric acids, and is slowly attacked by bases. TetrachEorocyclo;ue~at'aiLe, C5H,C14, is obtained by leading chlorine into a solution of cyclopentadiene in chloroform at -15'; it boils at 94' and 16.3' under pressures of 15 mm. and 25 mm. respectively, and has the sp. gr. = 1.423 at 15'. Dibromocyclopentene, C5H6Br,, is produced when bromine combines with cyclopentadiene a.t temperatures approaching - 20' ; it crystal- lises in colourless prisms, and melts a t 45-46'. The sribstance decomposes spontaneously, and is attacked vigorously by bases and concentrated acids. Tetl.abromocycloyentane, c,Ef6'Br4, is obtained from the foregoing compound by the action of bromine ; it is a pale yellow liquid, having a sp.gr. = 2.5224 at 15"/4", and distils under diminished pressure without undergoing change. Dicyclopentadiene, CH< >CH, is fornied from CH yH*$lH CH CH9* CH* CH*CH, cycfopentadiene by spontaneou; change (compare Gtard and Lambert ; also Roscoe). It solidifies at 32*5', and has the sp. gr. == 0.9766 a t 33'/4* ; under pressures of 35 mm., 55 mm., and 760 mm., i t boils at 88", 95', and 170' respectively, being in part converted into cyclopentadiene at the last named temperature. The refractive index U D = 1.5050 a t 35*, whence the molecular refraction M = 68.44, the calculated value being The nitrosochloride melts at 182', and is con- rerted by piperidinc into a base, which melts at 160' ; khe ndrosate crystallises in lustrous prisms, and melts at 155'.Dicyclopenta- diene forms additive compounds with halogens, but the derivatives :we unstable; it immediately reduces a cold solution of potassium permangana te. M. 0. F. Derivatives of Metaxylene. By A. KLAGES (Ber., 1896, 29, 310--3l4).-Symmetrical chloroxylene may be prepared from sym- = 68.1.ORGANIC CHEMISTRY 291 metrical xylidine by means of Sandmeyer's reaction ; the product is identical with that previously obtained by Klages and Knoeve- nagel (Abstr., 1895, i, 86) from dimethylketotetrahydrobenzene. 5- Chlo?.ometaa.ylsne-~-szclphoizic acid forms colousless crystals me1 ting a t 52', and is not hygroscopic. When fused with potash, it yields metaxyloquinol melting a t 149-150".The sulphonic acid is accompanied by a small amount of its anhydride. The suZphonic: c h l o d e forms large, rhonibic crystals, and melts a t 56-58*, whilst the antide crystallises in colourless needles, and melts at 191-192'. Symmetrical chloroxylene is converted by fuming nitric acid and sulphuric acid into the 2 : 4 : Cj-tri?zitro-compou?~d, which melts at 218'. 4-Chlo~~o-5-~zit~~onzetaxyleize is prepared from 5-nitro-1 : 3 : 4-xylidine by sand me ye^'^ reaction. It boils at 278', melts a t 52O, and, when reduced, yields 4-chloro-1 : 3 : 5-xylitZine, which boils a t 251", and combines with the carbonic anhydride of the a i r ; its beizzoyl deri?;ntiz.e melts at 128'. This base is usually accompanied by a dichloro-1 : 3 : 5-xylidine, which crystallises in coloni*- less needles, melts at 72", boils at 265-26G0, and yields a benzo$ derivative, which me1 ts a t 1,58".4 : 5-Dichloronaeta.~yieize can readily be obtained from 4-chloro-l : 3 : 5-xylidine by means of Sandmeyer's reaction, and boils at 231-232'. 2 : 3-Dinityo-1 : 3 : 4-aceto-qlidide forms almost colourless needles melting at 226", and dissolves in warm aqueous potash, forming an unstable potassium compoucd. 2 : 5-Dinitro-1 : 3 : 4-xylidine crystallises in yellow needles meltiug at 115', which deflagrate when heated. This base can only be converted into the corresponding hydrocarbon with great difficulty. The resulting 2 : 5-dinitrometaxylene melts a t 136', and, when reduced, yields a base, the benzoyl deriuatke of which melts a t %go.4-ChZo1-o- 2 : 5-&nitmrnetazyZene, obtained by means of Sandmeyer's reaction, forms yellow crystals, melts at 61', and boils a t 290--291*. On reduction, it yields the corresponding base, which boils at 280-281" and forms a benzoyl dericatice melting at 164'. This base is readily converted, by treatment with ferric chloride and hydrochloric acid, in to 4-chloroi?2eta~:yloqz~~?2one, which crystallises in compact needles melting at 218'. The formation of this substance proves that the base from which it is obtained, and the corresponding dinitro-corn- pound, have the constitutions which have been assigned to them above. A. H. Phenylic Ethers of Nitro-compounds of Iron. Bg- KARL A. HOFNAXN and 0. FRITZ WIEDE ( Z e i t . anorg.Chem., 1896,11,288-292 ; see also Abstr., 1895, ii, 451).--Dinitrosoferrophenyl mercaptide, Fe(N0)2SP1i, which can only be obtained with difiiculty by the method previously described, is easily prepared b j adding the theoretical quantity of phenylhydrazine (7 mols.) to an alcoholic solution of pot.assium heptanitrosoferrothiosulphonic acid, Fe4(N0),S,K,H20; the mixture being well cooled w i t h ice, and allowed to remain two days. It crystallises i n brown, lustrous plates, and melts at 179'. It is also obtained on gradually adding the theoretical quantity of diazobenzene nitrate to a, solution of potassium heptaiiitrosoferrothiosulphonic acid in absolute alcohol, and cooling with ice. A determination of292 ABSTRACTS OF OHEMICAL PAPERS. the molecular weight by the cryoscopic method gave numbers agreeing with the formula [ E'e(NO),SPh],.E. C. R. Action of Carbonyl Chloride on Dimethyl- and Diethyl- metamidophenol. By FRIEDRICH VOK MEYEKBURG (Bey., 1896, 29. 501--513).--Carbonyl chloride reacts with dimethyl- and diethyl- metamidophenol in the cold to form ethereal salts of carbonic and chloro-formic acids. At higher temperatures, red and violet colour- ing matters are produced. MetadimetJryla?nidophenylic carbonate, C3(0*C,Hi*NMe2)2, is formed when an alkaline solution of metadi- methylamidophenol is shaken with a solution of carbonyl chloride in benzene. It crystallises in long, feathery needles, melts a t 1;-37-138", and boils at 265' (pressure = 15 mm.). It dissolves in moderatelj- strong acids, but is insoluble in alkalis and water; it is not affected by aqueous potash at loo", b u t is hydrolysed by alcoholic potash, &c.The salts are unstable, and readily lose a portion of their acid ; the hydrochEoride crystallises in flat needles, and melts and decomposes a t 'LOSO; the piwate melts a t lEO, whilst the platiizochloride forms golden-yellow granules, and is very unstable. 3fetadimethylamido- phe7zyZic chlo?.qfo?wznte, COC1*O*CsHa*x&fe2, is formed when dimethyl- anlidophenol in benzene solution is added to an excess of carbonjl chloride dissolved in the same golvent. It is obtained as a syrup, which decomposes when preserved, aiid has not been analysed. Wake:. decomposes it with erolutiou. of carbonic anhydride. 2lIetadieth~lamidoph~~~~li~ carbonate ciystsllises i n colourless prisms mcltiog a t 67", aiid boils at 292" (pressure = 5 mm.).The salts are IesA stable than those of the dimethyl compound. The hydrochloride melts and decomposes at 205", and the hydriodide melts at 201'. Metal7ieth217amidophenZllic chloroformate, forms a syrup which partially solidifies when preserred a t 0" for some days. illetadiethylamido- phenylic acefate is a colourless oil which boils a t 160*5' (pressure = 5 mm.). When the dialkylamidophenols are heated with carbonyl chloride at 160°, red colouring matters are formed, which are probably derivatives of triphenylmethane, and have the general formula g ~C6H3(OH)*C~CsN3(NR2)- C6H3(NR2C1)>0. These substances closely re- sernble the pyronines in colour and absorption spectrum, and tlic author proposes to call them phosgenepyyonines. The red colouring matter from diethylamidophenol forms a violet sodium saEt, the solu- tion of which is decolorised on heating, the 1-ed colouring matter being precipitated.The base of the colouring matter appears to exist i n two forms, for when the violet solution of the sodium salt is shaken with toluene, a violet solution is obtained, whereas the base precipitated by boiling from the alkaline solution dissolves in toluene, forming a reddish-yellow solution. Both solutiuns yield the original colouring matter when extracted with dilute acid. When the didkyl- nmidophenols are heated with caFbouyl chloride at loo", violet colour- ing matters are formed, the colour bases of which also appear to exist in two forms.These substances could not be analysed. A. H.ORQANlO CHEMISTRT. 233 Derivatives of Isanethoil. By CARL Hmr, and CAm GAAI; (Be,.., 1896, 29, :344-352) ,-Isanet It oil, ONe*C6H4*CH2*C H :CHz, was obtained by fractioriating essence of tarragon, and formed the chief constituent of the fraction boiling at 208-214°, which WRS about one- half of the whole. It was brominated in cooled ethereal solution, when a compound, Ohle*C6H3Br.CH,*CHB~*CH2B~, melting at 62*4O, was obtained; it was not found possible to add bromine without sub- stitution occurring at the same time, nor was it possible to introduce inore than 1 bromine atom into the C,H, group. When this brorninc derivative is oxidised with chyomic acid in acetic acid solution, it y ie i d s a, trib~onz o-lie! owe, OMe-C6 H3B r*C 043 HB r*C H2Bi*, me1 ting at 103.3O ; whereas the isomeric bromide from anethoyl, O h ~ e * C G H , ~ r g C H B r .C H ~ r ~ ~ ~ ~ , yields only a dibromo-ketone, which must hare %he formula O~Ie*C6H3Br*CO*CHBi~,cH3, for bad it been the other CHBr-group that underwent oxidation, there would be no reason why the same CHBr-group should not undergo oxidation in the case of the iso-compound, It would seem therefore that i t is alwaj-s the group next to the benzene ring which is oxiclised, the position of the bromine atoms being without influence. This ketone is oxidised by permanganate to byomanisic acid ; no acetic acid is formed. With alcoholic amrnouia at l l O o , it forms a. compound, appayently of the composition { OMe-C,H,Ur*CO*C€€( NH2)*CH2]JYH.With alcoholic potassium acetate, it yields a compound, possibly OMe*CGH3Br*CO*CH(OAc).CE12.0Ac. With socliurri ethoxide, it does not yield an ethoxy-derivative ; bromanisic acid is formed. These last experiments were performed with very small quantities of sub- stance, and great importance cannot be attached to the results. Constitution of Phenoquinone. By C. LORIXC; JACKSON and GEORGE OE'XSLAGER (Anzcr. Chein. J., 1896, 18, 1--22).--The theo- retical speculations in this paper have already appeared (Abstr., 1895, i , 513). D icltlorodianzyloxyquino?2e dium y 1 hemict cdal, C6CI2 (OH), ( OC,HI 1) .I (compare this YoI., i: 19), is pepared, in the form of its sodizem salt, by stirring together finely powdered dichlorodiphenoxyqninone (4 gz-ams) and a solutioii of sodium (1 gram) in amylic alcohol (25 c.c.) ; the salt remains dissolved, and is precipitated by the additioii of cthylic alcohol.The hemiacetal is obtained by treating the sodium halt with acetic acid; it is a white solid, insoluble in water, aud rapidly decomposes, yielding n ~ d l o v v oil. When the sodium salt is: warnled with strong hydrochloric acid, dichlo1.i,tlianzyloi~j~~~~~~ont~, C3&12( OC5H,1)20,, is deposited as a yellow oil, which ciytallises witli dlfficultg from acetic acid in irregular, yellowish-red plates ; i t melts a t 53", and is soluble in most organic solvents. Reduction with zinc dust and glacial acetic acid converts this quinone into dichlorodiamyt- ~ ~ y p " i d , C,Cl,(OC6HlJ2(OH)2, which crystallises in long, thin, whit(? plates, melts at 12&', and dissolves fi-eely in ether, benzene, chloroform, C.I?. B.294 ABSTRACTS OF CHEMIOAL PAPERS. acetone, glacial acetic acid, and carbon bisulphide, slightly in light petroleum, and not a t all in water. It 11 as found that dichlorodibenzyloxyquinone dibenzylheniincetal is white, although, on account of its great instability, no attempt mas made to analyse it. D;chlo-r.odibeiazllloxyqui.ltoize, C6C I2(OC7H,),O2, is prepared by mixing a solution of sodium (0.5 gram) in benzylic alcohol (4 c.c.) with absoliite ether (150 c.c.), a n d adding chlorodiphenoxyquinone (% grams), washing the separated mass with ether, adding it to water, and crystallising the oil, xhicb floats to the surface, from a mixture of benzene and alcohol. It forms long, slender, red plates.melts ict 1 4 2 O , and dissolves freely in alcohol, acetone, benzene, glacial acetic acid, and ethylic acetate, but not at all in ether, light petroleum, o r water. By red uctioii, the quinone yields dichlol.odibenzyloayguiizol, C6C12(OC,H,)2(0.?3)2, which crystallises in white needles, melts a t 122-123O, and is freely soluble in alcohol, ether, benzene, glacial acetic acid, and carbon bisulphide, but only slightly in light petroleum and not a t all in water. Full details of the preparation of the blue disodium salt from quinone and sodium phenoxide, and from phenoquinone and sodium 13-naphthoxide (Absty., 1895, i, 513), are given; the salt is very unstable, ignites spontaneously in the water oven, and is decomposed by water. Quinonedinaphthyllaemiacetnl, C,H,O,, (C,,H,OH),, is prepared by mixing benzene solutions of quinone (1.5 grams) and P-naphthol (3 grams) and evaporating ; it crystalliscs in thin, brown, rectangular plates, melts at 82", and dissolves freely in ether, chloroform, benzene, glacial acetic acid, and ethylic acetate, but only sparingly in light petroleum ; the sodium salt is described.Thymo¶u~n~?~e¶uinol~e~~~acetal, CloH,,02,C6ET,(OH),, from hydro- quinone and thymoquinone in ethereal solution, crystallises in dark brown, ~-ectangular prisms with a green rcflection; it melts at 136-13Cio, and dissolves easily in various solvents, nearly all of which, however, decompose it, dissolving one or other of its con- stituents. The reaction between thymoquinol and quinone produces quin- hydrone. Theauthors point out that quinhydrone has no sharp melt- ing point, but begins to decompose at 16;3O, the change being complete a t 170°, when a sublimati? of quinone, and, above that, one of quinol, is noticed in the melting tabe. A list of siibstances analogous t o phenoquinone, which have been prepared from quinones, is given, together with references to the literature of the subject. A.(3. B. a- and p-Cinnamene Nitrosite. By E. A. SoxvEn (Ber., 1896, 29, 356-360 ; compare Abstr., 1895, i, 456).-The molecular weight of the p-nitrosite agrees m7ith the formula C8H8N203, that of the a-com- pound could not be determined on account of its insolubility and instability ; when heated, it decomposes iuto phenylnitroethylene, benzonitrile, nitric oxide, carbonic anhydride, and water ; it is, there- fore, probably more complex than the p-derivative, wliicli melts with-ORGANIC CHEMISTRY.295 out decomposition. The latter is not changed by distillation with steam ; when heated 'alone, itr yields benzonitrile, nitric oxide, carboiiic anhydride, watei-, and, in traces, ammonia.. When heated with water under pressure during firc houm, both compounds jicld benzoic wid, benzonitrile, carbonic anhydride, water, ammonia, and ni trogeri ; probably the primary products are benzonitrile, caybonic anhydride, and hydroxylamine, and these interact with the result stated. By the action of nitrous acid on cinnamene, two compounds, and N02-CHPh*CH2*N0, might be formed, and by the combination OF 2 mols. of these, three substances are theoreticalIy possible ; from its decomposition products, the a-nitrosite probably has the formula NO*CHPh*CH2*N02 ?-yLcH H2*yoo?, the &compound being- O--NO*OHPh*CH2~N-- 0 N02*CHPh*CH:NOH.Both the other double molecular. compounds appear to be formed, the one, ?-r*CHPh*CH2*ry;O-? readily yields phenylnitroetbylene nitric oxide and hydrogen, the second, probably unstable, and should easily change into the p-nitrosite, the decomposition products of which were isolated. The /3-iiitrosite forms a silrer salt, and crystallises from boiling concentrated hydro- chloyic acid in colonrless, lastrous needles. Angeli states that when boiled with mineral acids, it is converted into a ketone or aldehyde. The a-nitrosite combines with aniline, forming a crystalline base, C14H,4N202 ; the hydrochloride, Cl4€1,,N2O2,HCl, is deposited in white crystals with a pale, rose-coloured reflex ; it decomposes when exposed to the air.J. B. T. By ANGELO AXGELT and EKRICO RIMINI (Gazzettn, 1895, 25, ii, 188---213).-A good yield of safrole a-nitrosite may be obtained by slowly adding dilute sulph- uric acid to potassium nitrite solution covered with a solution of safrole in light petroleum, and recry stallising the precipitate ; on boiling with alcohol, it yields the p-nitrosite, which is readily con- verted in to hydroxylamine and nitropipe,el.oiBylacetone, by boiling with dilute sulphuric acid. This ketone crystallises in colourless scales melting a t 86", and, when heated with hydroxjl- amine hydrochloride and sodium carbonatve solution, yields hon7o- p+eron,yZomamic acid, CH202:C6HJ*CH2*C 0 - N H*OH ; this crpstalliscs in minute, white needles, melting and decomposing at 166*, is very soluble in alcohol, and is converted into homopiperonylic acid and hydroxylamine on boiling with diiute sulphuric acid. On heating nitropiperonylacetone with hydroxylamine hydrochloride in presence of but little alkali, snfrole ,@-nitrosite is regenerated.That nitropiperonylacetone, which readily reduces Fehling's and ammoniacal silver nitirtte solutions, is not an aldehyde, but has the 0 --N* CHPh-C H2*NO- 0' ?-.h;O*CHPh*CH2*T-.Q is &--NO* C H Ph* C H3.N- 0' Action of Nitrous acid on Safrole. CH202:C6H3*CH2*C O*CH2*N02,296 ABSTRAXITS OF CHEMICAL PAPERS. constitution assigned above, is evident from the fact that it yields homopiperonylic acid on oxidation with potassium permanganate.On treating it with potassium nitrite and distilling the product in :L current of steam, vpiperonploniti+ile, melting at 9 4 O , is obtained, and, on treating iiitrop~peroiiylacetone with bromine in acetic acid solu- tion, bro?~opipero?ly Znit1.oacefoizc, c' H,02:C6H,h-C Hz*CO*CHz*NOz, is formed ; i t melts a t 115', is soluble in acetone or etliylic acetate, and on oxidation with alkaline permanganate yields bronzohomopiperony Zic acid, CHz02:C6H,Br*CHz.COOH ; this crystallises in lusti=ous needles melting at 190-192'. Bro?i?op~pel.cnyZorLitriEe, CH,0z:C6HzBr.CN, is obtained by distilling the product ob taiiied by heating bronio pi peyonylnitroacetone wit 11 sodium nitrite solution in a current of steam; it crystallises in minute, white needles melting a t 106*, is very soluble in benzene, acetone, or ethylic acetate, and gives a deep yellow coloration with sulphuric acid.NitropiZjPronyZnitroacetone, CH,0,:C,H2(N02)*CH,.C O*CHz*N 02, pre- pared by direct nitration, is crystalline, and nielts a t 170' ; i t gives R beautiful, blue coloration with potash, and, when the product is dis- <illed in a current of steam, a -jellow nitroyiperonylmethnne, C HzO,: C H$l e*K 02, melting a t 83O, is obtained. PipeTony Zamidoacetone, CHZOz:C6H3*CH,*C O*C H2*NH2, may be pre- pared by reducing nitropiperonylacetone with tin and hydrochloric acid ; the hydi*ochloyide, Cl,Hl,N03,HCl, crystallises in flattcneci needleP, melting and decomposing a t 198", and reduces Fehling's solution, whilst the yellow picyate, Cl,H,,N0,,C,Hz(NOz)3.0H, melts and decomposes at 160'.The free'base is not obtained by adding am- monia to its hydrochloride, but a condensation product, paradihomo- piperonplpyyazine, C H , o , : C , ~ ~ * C ~ ~ 2 ~ C ~ ~ ~ ~ ~ ~ ~ c H ~ * is formed; it crystallises in small needles, melts at 155-156', and gives a violet colorcttion with sulphuric acid. I)iazopiperonylncetone, CH20,:C6H3*CH,* COGH <.+ is cjb tained as a yellow oil, together with its decomposition product, homopiperonylic acid, by treating piperonylamidoacetone hydrochloride with sodium nitrite solution ; i t is decomposed by mineral acids with evolution of ni trogcn. W. J. P. N Synthesis of Aromatic Selenium Compounds by means of Aluminium Chloride.By PniEumr-I KRAVFT and A. KASCHAL- (Ber., 1896, 29, 42S--435).-A refutation of Chabrih's criticism (Xbstr., 1895, i, 413). The authors have obtained pure phenylic selenide by acting on selenium tetrachloride with benzene in the presence of alumiiiium chloride at a low temperature and fractionating tlie product. Diphenylic diselenide is: however., formed at the same time, and the method previously described (Abstr., 1894, i, 89) of 1prepariD.g the selenide is far more convenient. Chabri6 never ob- tained the selenide pure ; it was mixed with diselenide, and this heORGANIC CHEMISTRY, 257 mistook for hydiwselenide. was, in rcality, impure selenide. Further, what he described as selenoxide C. I?. B. Thianthrene (Diphenylene Bisulphide), C,,H,S,, and Selen- anthrene.I. By FIXIEDRICH KRAFFT and I3oiircR.r E. LYONS (Be,.., 1896, 29, 4;35--44S) .-Thianthrene, C,H,<b> CsHI, has been ob- tained by many observers and by various reactions ; it is best pi*epnred by slowly adding a benzene solution of sulphur dichloride to a cooled solution of aluminium chloride in benzene ; it melts at 158-159', and hoils at 210" under 15 nim. pi.essu1.e. DitolyZeizc bisulphide was pyepareti in a similw manner from toluene; i t melts at 117-118", and boils a t ?2S-231° under 14 nim. pressure. Tliianthrene is oxidised by boiling with nitric acid of sp. gr. 1.2 to thicc?zfh?.cne diod.ide, c,H4< So > c6H4. This melts at d29', is converted by reducing zgents into thianthrene, and sublimes at 272-274' under 13 nim. pressure, undergoing at the same tirno a molecular transformation into thianthre?zenzonosuEplrolze (diphe?tylene s d p h i d e sziZpko?Lc), C6H4<:::>c6H4, whicli me1t.s at .L79', and is converted by osidation with chromic acid in boiling acetic acid solution into the disulpbone, c6H4<so2>C6~~I.This last sub- stance yields thianthrene and sulphurous anhydride when it is lteated with sul p 1 i u 13. Phenylic sulphide can also be oxidised wacliig to the sulphoxide by boiling i t with nitric acid of sp. gr. 1.1. The snlphoxide boils at 199-200" under 10 mm., a t 210' under 15 mm,, arid a t about ;f40° under ordinary pressure, a slight decomposition taking place in the litst case. When it is gently boiled for some time in an atmosphere of carboiiic anhydride: the sulphide is regenerated; iu this respect it s so s 0 2 analogous to the selenoxide (this vol., i, 304).C. F. 13. Thianthrene and Selenanthrene, C,,H,Se,. 11. By FRIL DRIClt KRAFE'T and A. KASCHAU (J'ey., lSU6, 29, 4 4 3 4 4 5 ) .-XeZe?~a?zth ) * e m (diphenylene diselenide), c6&<s~>c6H,, is formed by gently heating diphenyvlenedisulphone (preceding ahstract) with selenium in an ntmosphere of carbonic anhydride ; a eteady evolution of sulphurous anhydride accompanies the reaction. It melts a t 18O-18lo, and boifs at, 223' under 11 mrn. pressure. When it is heated a t 60-70° with nitric acid of sp. gr. 1.4, the solution, on cooling, yields crystals, which liberate iodine from potassium iodide ard Itme a composition corre- sponding with the foriuultt C1,H,Se2,2HNO3 ; when these crystals a r e treated with aqueous soda i n the cold, and the mixture is saturated with carbonic anhjdride and then evaporated under diminLhed pressure, dcohol extracts selenanthrene dioxide, csH4<s,o>c'6H4, from the wsidae.This melts at 270', but a t the same time loses oxjgen and regenerates selenanthrene. C. F. B. S SeO2 98 ABSTRACTS OF CIHEMICAL PAPERS. Nitramines. Bg AXTOINE P. N. FRANCHIMONT and H. VAN ERP (Ziec. Trav. Chim., 1895,14,235-151; compare Abstr., 1895, i, 587).-- nIethyZf)ct~ZnitramilLe, C,H,,*N&Se.N02, obtained by heating octylic iodide (31 grams), methylnitramine (10 grams), potassinm hydroxide (10 grams), and absolute methylic aicohol (SO grams) for three days on a water bath, and purified by fractional distillation under dimin- ished pressure: forms a slightly yellow liquid, and distils a t 164.5O tinder 17.5 mm.pressure. When heated with aqueous potash at 160°, it is not appreciably acted on. i~retfLyZbenzyl~itramine, C H,Ph*NXe*NOr, after distillation in a vaxium and pressing between filter paper, forms a crystalline mass, whish melts at 22.2" and has a slightly aromatic smell. When heated at 150-160° with aqueous potash, i t is decomposed into benzalde- hyde, methylamine, nitrous acid, and small quantity of benzoic acid. llfet7t;ylorthonit~obe,~xyli~itramine cryst.allises in yellowish needles and melts a t 87". It is only sparingly soluble in ether and light petr- oleum, but readily in alcohol, chloroform, and benzene. When heated with aqueous potash for seven houm at 150°, it yields methylamine and benzoic acid.n~ethyZpa?.anitrobcnzl/lnitramine melts at 70--71", and is decomposed when heated with potash a t 140-150°, yielding the satme compounds 11s the ortho-compound. When dimethylnitrarnine itself is heated with aqueous potash, it yields me thylamine, formaldehyde, me thylic alcohol, formic acid, and nitrous acid. The authors think that the decomposition by alkali is first preceded by intramolecular change, (CH,),N*NO, - CH,-NH*CH,*NO,. This, under the influence of the alkali, yields CH,*NH, and OH*CH,-NO,, the latter being further decomposed into formaldehyde and nitrous acid (compare Bamberger, Be?.., 26, 490). Action of Sodium on Aromatic Nitriles. By C. A. ALFRED LOTTERSOSER (J. p r . Chem., 1996 [S], 53, 143-144).-The author has continued the study of the reactions between aromatic nitriles, aromatic amines and sodium.in benzene, first noticed bg Walther (Abstr., 1894, i, 503), and has prepared the following amidines: Orthotolylbenzeiiylamidine, paratolylbenzanylamidine, phenaceto- phenylamidine, orthotoluphenyIamidine, paratoluplienylamidine, u- naphthophenylamidine, p-naph thophenylamidine. B y the action of sodium on benzonitrile in benzene, a compound, which is probably ciihydrotetraphenyltriazine, has been prepared. This investigation is proceeding. A G. B. Quantitative Reduction of the Nitro-group t o the Hydroxyl- arnine-group. By HAM WISLICENUS (Ber., 1896, 29, 494-496).- Nitrobenzene is quantitatively raduced to phenglhydroxglnmine when i t is dissolved in ether, and treated with amalgamated aluminium filings, water being gradually added, aiid the mixture cooled by ice.A vigorous action occurs, which should be so regulated that the ethereal solution boils freely. Nitroacetophenone also undergoes reduction under the same conditions (compare Wislicenus and Kauf- mann, Abstr,, 1895, i, 437,63%). J. J. S. A. H.ORQANIC CHEMISTRY. 299 Chemistry of the Diazo-compounds. By EUGEN BANBERGEIi (Bey., 1896, 29, 446--473).-The author still maintains, in opposi- tion t o Hantzsch, that the metallic, normal, and iso-diazo-derivatives are struetually, and not merely geometrically, isomeric, and he denotes them respectively- by the formuhe Alph*N(iN)*OM and Alph.N:N*OM [Alph = an aromatic radicle, such as c6H,, C6Hp&fe, &c,; 31 = a metal]; for the salts of diazobenzenc with acids he adopts Hantzsch's name of alphyldiazouium salts. I n proof of the difference of structure alluded to, further experimental evidence is brought forward.The alkaline normal diazo-salts react with aliphatic alcohols in the cold, yielding diazo-ethers, Alph*N,*OMe, &c.; the iso-salts do not behave in this way. Again, the normal salts are scarcely attacked by sodium amalgam, whereas the iso-salts are readily reduced to hydrazines. But an even more striking dift'erence is seen in the behsviour of these salts with regard to acids. These liberate from the iso-sal ts the isodiazo-hydroxides, which form either oils or crystals, are colourless, or pale yellow when nitro-groups are present, and are readily dissolved by alkalis with re-formation of the iso-salt ; pura.izitroisodiaxobenzene hydroluide, NO2*C6H4-Nz*OH[, has actually been analysed, but the experimental data are to be given in a future paper.From the normal salts, on the other hand, acids a t a low temperature liberate diazo-anhydrides ; these are bright yellow, extremely unstable substances ; when placed on a porous plate, they explode spontaneously as soon as they become even approximately dry ; diazobenzene anhydride even exploded once while still in the solution at a temperature of -18", and some moist diazotoluene anhydride a t a temperature of 0" was exploded by the concussion due to the explosion, at a distance of 5 ft., of a sciali sample of the dry substance. They also readily become transformed into diazoamido-compounds.With alkalis, they re-form the colour- less normal diazo-salts, whilst with acids, they give the colourless diazonium salts. (Jn tbis connectior, it is interesting to rernembey that the colourless cthobroniide of papaverine, C20H21N01, EtBr, yields au oxide, (C,HZ,NO1Et),O, which is bright yellow ; arid also that the oxides of several metals-lead, for example-are coloured, whilst the salts of the same metals are colourless). Pa,.acl~lo?.odz'azoben~e~le anhydride, (C,H,CI*N,>,O, was the most stable of the compounds prepared ; it was even possible t o analyse it, and with it the reactions of the diazo-anhydrides were studied in greater detail. The other anhydrides prepared were those of paradi- azotolucne, diazobenzene, metachlorodiazobenzene, para- and meta- bromodiazobenzene and para- and meta-nitrodiazobenzene ; their reactions, so far as they could be studied, resembled those of the anhjdride of parachlorodiazobemcne.This yields diazo-ethers with aliphatic alcohols ; with benzene, chlorodiphenyl, C6H,C1Ph ; with aniline, yellow clitol.odiu~oanzidobenzene, CGH,CI*N2*NHPlt, melting a t ?Go, not prepared before (with ammonia, parndiazotoluene anhydride yields bistoluene diazoimide, (C6H,Me*N2),NH) ; with bromine, the cliazoperbromide ; with phenylic hydrosulphide, apparently pheajlthio- diazobenzene, C6H,Cl*N2*SPh ; with iodine, paruiodochlorobenzene, together with some chlorobenzene. c300 ABSTRAUTS OF OHEMIOAL PAPERS. The general method of preparing a diszoanhydride is fitst to obtain the normal potassium diazo-salt by slowly adding a diazotieed solution of the base to a cooled, very strong solution of potassium hydroxide in water, or mixture of the hydroxide with water; the salt is then drained with the aid of a filter pump and preserved in ik dry atmosphere free from carbonic anhydride.A concentrated aqueous solution or the salt suspended in water is then treated, a t Oo or in a freezing mixture, with 50 per cent. acetic acid, when the diazo-anhydride separates out in yellow, crystalline flakes. The normal potassium diazo-salts are very readily converted into the iso-salts; at 120--130°, the conversion is complete in 20-30 minutes, and the carbonic anbydride of the air effects the conversion a t the ordinary temperature.The presence of alkali does not f a v o u , but even retards, this transformation ; when isu-salts are obtained from normal salts by heating them with alkali, which is the usual method of preparation, it is the rise of temperature that brings about the transformation ; the alkali only acts by preventing other decompositions taking place as a result of the rise in temperature. C. F. B. Constitution of Azimides [Azoimides] I By THEODOR ZINCKE a d BRUNO HELMERT (J.pr. Chem., 1896, [2], 53,91--99).-Griess based his conclusion that the azoimides are correctly represented as derivatives of the compound c6H4< I >NH on the fact that he obtained the same azimidobonzoic acid whichever of the two nitrouramidobenzoic acids, [NO2 : NH*NHCONH2 : COOH = 1 : 2 : 41 or [NOz : NH*CONH2 : COOH = I : 2 : 51, he heated with potash solution ; furthermore, the same azimido- uramidobenmic acid was formed when the nitro-acids were reduced and diazotised (Abstr., 1883, 56).It may well be, however, that the similarity between these azimido-acids is so great that even Griess may have been unable to differentiate them. In view of this possi- bility, the aiithors decided to repeat Griess’ work, and will publish their results, but for the present they content themselves with saying that the characterisation of the azimido-acids in question is so difi- cult that their identity is hard to establish. It has been possible t o obtain two azoirnides of the general form X*CaH3N3R, which are undoubtedly isomerides, and this fact is only explicable on the sup- position that KekulB’s typical formula, CeH4<cg>N, for the azoimides is correct. The azoimide, EtO*c6H3<~p~>N [EtO : NPh = 1 : 41 is pre- pared by passing through a number of intermediate products, from metadinitrodiphenylamine (compare Nietzki, this vol., i, 164 ; the authors find that the azoimide N02*C6H,N3Ph, melts a t 1 6 7 O , not at 107’ as stated by Nietzki); it crystallises from all solvents i l l curved needles, and melts a t 99’; a saturated alcoholic solutioii yields no crjstals when in contact with the 1 : 3-compound de- N NORGANIC CHEMISTRY.30 1 scribed below, and when it does yieid crystals these melt a t 9 9 O . The methiodide melts and decomposes a t 211". The azoimide EtO*C6H,<- N>N [OEt : NPh = 1 : 31, is pre- pared from hydroxyazobenzene, through a number of intermediaries, and bas been already described by Jacobsen and Fischer (Abstr., 1892, 840) ; it crystallises from all solvents except glacial acetic acid, in lamin=, and melts at 107-108" ; a saturated alcoholic solu- tion of i t yields no crystals when in contact with the 1 : 4-derivative already described, but laminte, melting at 107--108° afterwards separate. The niethiodide melts and decomposes at 177O.A mixture of these isomerides, crystallises from alcohol, and melts at 70-75". The methylnitrazimidobsnzene, XO2*C,€T3X3*CH3, prepared from NH Eitrazimidobenzene, N~~*C,H~<-N>N, was found t o melt at 161" and t o be identical with t h a t obtained by heating chlorodinitro- benzene, [Cl : (NOz), = 4 : 1 : 31, with methylamine, reducing the dinitxomethylaniline, which is formed, and diazotising the nitr- amidomethylnniline obtained by the reduction.Since the methyl- nitrazimidobenzene prepared in this way must contain the NCH, in the para-position relatively to the nitro-group, it follows that the nitrazimidobenzene must contain the NH-group in the para-position relatively to the nitro-group. No isomeride of the nitrazimido benzene or of the methyl derivative was obtained, and the authors deem i t possible that compounds o€ the type X*CsHgN3H can exist in one form alone. A. G. B. NPh Reduction of Unsaturated Aromatic Ketones and their Con- version into Coumarane Derivatives. By CARL D. HARRIES and GEORGE J. BLJSSE (Ber., 1896, 29, 375--:@0; compare Abstr., 1895, i, 279).-Prop!ll orthohydroxystyryl ketone (propylorthocumaroketone), HO*C,H,*CH:CH*COPP, is prepared by the condensation of sdicyl- aldehyde and methyl propyl ketone in preseuce of soda ; it crystallises from dilute alcohol, is somewhat soluble in warm water, and melts at 116".At the boiling point, 1 C.C. of alcohol dissolves 1 gram of t,he ketone. The yield is 80 per cent. of the aldehyde emploJed. Tlie phe?zylhydraxone, ~O.C,H**ClrE:CH*CPi~:~~HPh, crystallises in small, yellow prisms, melts at 119", and resembles the ketone i t 1 solu- bility. P!ropyl on%ohydroqphen ylethyl ketone (propyldibydrort ho- cumaroketoiie) , HO.C,K,*CH,.CHIrfCOPrCI, is obtained by the action of sodium amalgam on the unsaturated ketone ; it is colourless, crystal- line, and melts at 74-75".The pheny Zhydrazoue crystallises in rhombic plates, meltis at 149-150", and is soluble in 7.8 parts of boiling alcohol. The ketone is coiiverted by treatment with zinc and hydrochloric acid into propyI~ih?lil~ocounaarnne, c6H4< a colourless, highlyrefrac- tive liquid, with a pleasiag odour ; i t boils a t 254-257" (760 mni.) ; the sp. gr. = 0994.6 ; it is insoluble in alkali, aild gives a red color. The yield is SO per cent. of the theoretical. C H2.7 H2 0 ---CHPra' VOL. LXX. i. z302 ABSTRACTS OF OBEMICAL PAPERS. ation with sulphuric acid. The yield is 60 per cent. of the ketone employed. Phenyl orthohydroxystyryl ketone (orthophenylcoumaroketone), HO*CsH4*CH:CH*COPh, prepared from snlicylaldehyde and nceto- phenone, is the sole product if soda (10 per cent.) is employed as the condensing agent (compare von Kostanecki and Bablich, this vol., i, 239) ; the yield is '70 per ceiit. of the aldehyde employed.The phenyl- hydrazone melts at 136', and its solutions exhibit a blue fluorescence. The tetvabromo-derivative is readily pyepared by the action of bromine in well-cooled glacial acetic acid solution ; it crystallises in yellow needles, melts a t 167-168', and decomposes when boiled with alcohol. von Kostanecki and Bablich state (loc. cit.) that the ketone is decom- posed by bromine. The benroyl-derivative is crystalline, and melts at 102'. PhenyZorthohydrozybe??z~Zcarbi~zol (phenyldiliydrocoumar.y.1 alcohol), HO*C6H4*CHz*CHPh*OH, is formed when the above ketone is reduced by means of sodium amalgam ; i t crystallises in microscopic needles, melts at 96-47', and gives a red coloration with concentrated sulph- uric acid.By the action of methylic alcoholic hydrochloric acid on the preceding compound, is formed ; it is crystalline, dihyd~ophen2/lcoumarlJne, C,H4< melts at 44-45', has a pleasing smell, does not dissolve in alkali, gives no coloration with sulphuric acid, and, at 18*, 1 gram dissolves in 7 C.C. of alcohol. The yield is 80 per cent. of the alcohol employed. Phenylchloriodopropionic acid and its Derivatives. By EMIL ERLENMETER (AnnuZen, 1896, 289, 259-284). -PhenylchEo~iodo- propionic acid, CHPhC1-CHICOOH, is formed when cinnamic acid is treated with an ethereal solution of iodine chloride containing hyd:ogen chloride ; it crystallises in colourless leaflets, becomes red at 200, and melts at 122-123O, yielding gas. Protracted treatment with cold water converts i t into phenyliodolactic acid, which is pro- duced immediately by boiling water ; aqueous potassium iodide gives rise to cinnamic acid.The methylic salt separates from petroleum in colourless crystals, and melts at 97-98', becoming red ; the ethylic salt becomes red, and melts at 69-70', ~-EthoxyyhenyZ-u-iod~~o~~onic acid, OEt.CHPh*CHI*COOH, is obtained by the action of alcoholic potash on the foregoing acid ; it cry stallises from water in long needles containing lHzO, and becomes red and melts at 138-139'. p-Methoqphenyl-a-iodopropionic acid crystdlises from water in anhydrous needles, and melts, becominq red at 164-165'. P~enyl~odo~ydrucry~~c acid, OH*GHPii*CHI*COOH, is formed when sodium cinnamate is treated with an aqueous solution of iodine chloride containing hydrogen chloride ; it crystallises from benzene in long, colourless prisms, and melts at 140-142' when it becomes red, and evolres gas.The substance decomposes i n aqueous solution when the latter is boiled for a protracted period, yielding iodine, phenylacetaldehyde, cinnamene, and cinnamic acid ; reduction of phenyliodohydracrylic acid with sodium amalgam gives rise to phenyl- The yield is 65 per cent. of the ketone. CHz* FH2 0 -CHPh' J. B. T.ORGANIC O H EM ISTRY. 303 hydracrylic acid. Boiling aqueous soda converts phenyliodohydr- acrylic acid into phenylglycidic acid, whilst hot hydrochloric acid gives rise to the conzpoimd, C~8H~~C1101, which contains phenylchlor- iodopropionio acid and cinnsmic acid in molecular proportion ; i t becomes red at 70", and melts at 110-115', when it decomposes. This substance yields cinnamic, hydrochloric, and phenyliod hydr- acrylic acids when treated with hot water, and phenjlpropionic acid is formed OR reduction with sodium amalgam, whilst potassium iodide gives rise to cinnaniic acid. New Synthesis of Phenanthrene and its Derivatives.By ROBERT PSCHORR (Ber., 1896, 29, 496-501) .-a-Phenylorthonitro- cinrtarnic acid, N02*C6H[d*CH:CPhoC00ET, is obtained by heating ortho- nitrobenzaldehyde with sodium phenylacetate, acetic anhydride, and zinc chloride. It crystallises in colourless needles, and melts at 193-195'. a-Phen2/lorthainidocinnamic acid crystallises in narrow, yellow prisms, and melts at 185-186'.I t dissolves in both acids and alkalis ; the hydrochloride melts and decomposes at 21 8", and the platiizochloride melts at 220'. The acid also exists in a colourless modification, which is formed when it is recrystallised from water and passes into the yellow form at about 1.50'. Both forms of the acid are converted into p-phenanthrenecarboxylic acid, melting at 250- 252*, when they are diazotised in sulphuric acid solution, and then treated with precipitated copper. The acid produced is identical with that previously described by Japp (Trans., 1880, 84), and yields phenanthrene when distilled. M. 0. F. a- Phenylort hamido- P-phenytlpropionic acid, NH2*C6HdgCH2*C HPh*COOH, is formed by the action of sodium amalgam on amidophenylcinnarnic acid.I t cannot be obtained in the free state, as when the alkaline solution is acidified, P-pheiLIlldihydroca~bostyril, CsH4< N =C(OH)' which melts at 169O, is formed. When the alkaline solution is treated with sodium nitrite and sulphui-ic acid, and then with precipitated copper, a syrupy acid is produced, which yields phenanthraquinone when treated with chromic anhydride and acetic acid. a-Benzoylcoumarone. By E. RAP (Gazzetta, 1895, 25, ii, 285-289) .-On adding bromacetophenone to a hot, alcoholic potash solution of salicylaldehyde and concentrating the solution, an u- bento ylcoumarone, c6H4<!E>c* c OPh, is obtained. This crystal- lises i u long needles melting at 90-91", and is very soluble in most organic solvents. It yields a hydrazone, C15HloO:N2HPb, which crystallises in minute yellow ueedles, melting at 128--129O, and an ozirne, ClJHIOO:h'OH, melting at 125-128' ; a substance melting at 126-135', is also formed by the action of hydroxylamine.C H2.S H P h A. H. W. J. P. 2 2304 ABSTRACTS OF OHEMIOAL PAPERS, Action of Some Halogen Compounds containing Oxygen on B,v HUGO ECKEh-RO'TH and KARL KLEIN (Ber., 1896, 29, 329--332).-The sodium deriva- tive of benzoicsulphinide, C,H*<co >"a, reacts with various halo- SO2 gen compounds (compare Fahlberg and List, Abstr., 1887, 835; Bey., 20, 1596). With monochloracetone, CH,Cl*C&IeO, at loo", Sodium Benzoicsulphinide (Saccharin). i t yields acetonylorthobenzoicsz~~~iinide, C6H4<S02>N*CH2*CMe0, co which melts at 143', yields a yellow phenylh?/drazone, melting a t 166O, and a monobmmo-derivative, melting at 168O, and is hpdrolyaed to orthosulphobenaoic acid, ammonia, and acetonalcohol.With brom- acetophenone, CH2Br*COPh, it reacts a t 150', in a simi1a.r way ; the pwduct, phenacylorthobei,zo~~s~~p~~inide, me1 ts at 19%*5', yields a yellow phenylhydrazon.e, melting at 168", and is hydrolysed by alco- holic potash to phe?actcylsulpha?nidobenzoic acid, which melts at 160'. C OOH*CgHt*SOz*NH*CH2* CO Ph, C. F. B. Diphenylselenone, SeO,Ph,. By FRIEDRICH KRAFE'T and ROBERT E, LYONS (Bey., 1896, 29, 424428).--Diphenylselenoxido (Abstr., 1894,89), OSePh,, is oxidised when it is boiled with aqueous perman- ganate, to diphenylselenone, which melts at 155', and boils, with slight decomposition, a t 270-271" under 9.5 mm.pressure. This substance loses oxygen when str*ongly heated, and phenylic selenide is formed. When i t is heated with snlphur to 190°, a sudden reaction occurs, phenylic diselenide being formed, and sulphurous anhydride evol red. When i t is boiled with strong hydrochloric acid, diphenylseleno- (ahloride, CI,SePh,, is formed, and chlorine is given off. It also liberates iodine from a solution of potassium iodide. The reactions of diphenylselenone are, in many points, analogous to those of iodoxy- benzene, as are those of diphenylselenoxide to those of iocloso- benzene. E i tric acid oxidises phenylic diselenide to p72enyZseleiziou.s acid, the ititrate of which, Ph*Se0,H,EKN03 [? SePh(OH),*NO,], is a well crys- tallised substance ; the hydrochloride of the correspondi np: ethylic compound was prepared long ago by Rathke ( A n d e n , 152, 219j.The substance in question has thus basic properties ; it also has acid properties, and forms a well defined silver salt. Carbazole Derivatives. By 31. LAM BER~T-ZAXARDI (Gazzettn, 7 895, 2 5, ii, 359-36 4) .- Bewoglc hZo robmnzocurbazole, C,,H,CI B i*NBz, is prepared by the action of chlorine on Jfazzara and Leonardi's benzoyl- bromocarbazole (.Qbstr., 1893, i, 349) in acetic: acid solution. It cryshllises in colourless needles meking a t 202'. and is hydrolysed by boiling potash, giving chlorobro?~zocurbuzole, C,,H,CIRrNH, wh icli crystallises in iridescent scales melting a t 197-198' ; when heated with acetic anhydride in a closed tube a t 240°, i t yields trcetylchloro- b~ontocarbuzoZc, C,?€I,Cl RrNAc, which crystallises in Iiistrous, coloup- less needles melting at 1$&-179°. C.F. B.ORGAN10 CHEMISTRT. 305 u-Be~izoyldichlo~.oi7itl.omocn~.bazole, ClqH9NOC12Bi*2, obtained by direct chlorination of benzoyldi bromocni*hzole in presence of iodine, crys- tallises in opaque, white needles melting at 267-268O; it is accom- panied by a p-isonzeride, which crystallises in small, opaque, whi te prisms melting a t 238-240", and by another substuuce melting a t p/-Carbodiphenylimide. By J. F. CARL SCHALL (J. pr. Chew., 1896, [ 21, 53, 139--142).-The authoy reviews the criticisms which Miller and Plochl (Abstr., 1895, i, 415) have passed on his work on the carbodiphenylimides, and clrtims t h a t the -/-derivative, whether freshly prepared or after long standing, contains at least one physical modification of f?-carbodipheiiylimide.The Diphenylhydroxyethylamine Bases. By EMIL E RLES- METER, jun. (Ber., 1896, 29, 295--298).-The reduction of benzoin- oxime yields a phenyl hydroxyethylamine which melts at 161', along with a second substance melting a t 129-130' (Soderbaum, this vol., i, SS), which can be resolved by crystallisation into two isomeric s u b stances, one of which crystallises in thin prisms or three-sided, pointed needles belonging to the hexagonal system, whilst the other crystallises in rectangular tablets. The same two compounds, melt- ing a t 129-130°, are also formed, but in different proportions, by the condensation of benzaldehyde with glycocirie (Abstr., 1895, i, 596).Three isomerides of phenyl hydroxyethylamine have, therefore, been described, and the relations in which they stand to one another have not yet been ascertained. The isomeride melting at 161' is converted, by means of the diazo-reaction, into isohydrobenzoin, and not iuto hydrobenzoin. A base, melting a t 128', has also been observed by Polonowska among the products of the reduction of benzilmonoxime (Abstr., 1888, 485). A. H. Reduction of Unsaturated Ketones. By CARL D. HARRIES and G. ESCHEXBACH (Ber., 1896, 29, 330-388).-Engler and Leist, who discovered benzy lideneacetone, state that it is converted into n. secondary alcohol when reduced by means of sodium amalgam in dilute alcoholic solution, but the authors only obtained resinous products uiider these conditions; if the liquid is well cooled and maintained acid by the addition of dilute acetic acid, benzylacetone and diphenyl-4 : 5-octanedione-2 : 7, 130---215', which could not be purified.w. J. P. A. G. B. COMe*CH,*C HPh*CH Ph*CH2*COMe, is formed ; it crystallises in long, colourless, transparent, tricliiiic pardlelopipeds, melts a t 161', boils at 335-340' under the ordinary pressure, and at 221-222' (10 mm.). It is not volatile with steam, does not combine with sodium hydrogen sulphite, and dissolves in concen- trated sulphuric acid with a green coloration. The yield is about 10 per cent. of the diketone arid 30 per cent. of benzylacetone ; but if alumi- nium amalgam is employed, the yield of diketone is irnproyed, and benzylacetone is only fovmed in very small quantity.Attempts to obtain a, pyrroline or pyridine derivative were unsuccessful, as, when reduced with sodium and boiling alcohol, or with sodium amalgam in alkaline306 ABSTRACTS OF CHEMIOAL PAPERS. solution, amorphous compounds are formed ; in acid solution, the diketone is not changed ; with zinc dust and alcoholic hydrochloric acid, a compound is obtained which melts at 120°, and has not been investigated. The diketone is not oxidised by sodium hypochlori te, potassium dichromate and sulphuric acid, or acetic acid; with chromic anhydride and glacial acetic acid, benzoic acid is formed. With concentrated nitric acid, two yellow, nitrogenous products are obtained, the one by gently heating, the other when the acid is boiled ; they melt at about 130' and 67-68' respectively.The diphenylhydr- U Z O R ~ is sparingly soluble, darkens at 170°, melts at 194O, aud could not be recrystallised. The dioxirne softens at ZOO', and melts at 235-237O. No monoxime or monophenylhydrazone could be obtained. By the action of sodium ethoxide on the above diketone, water is eliminated, and the resnlting closed chain compound has the formula CH2*CO-gH 3HPh -8.COMe CHPh<CRPh*CH,*CMe Or bHPh*CH%*CMe ,assuming, as appears probable, that the diketone has the formula assigned to it ; it crystal- lises in transparent plates, melts at 87', boils at 214-215O (8.5 mrn.), and at about 330-33.5' under the ordinary pressure. It is not volatile with steam, and resembles the diketone in its action towards oxidising agents.Attempts to reduce the compound by means of sodium in alcoholic solution have not yielded any definite results, and no crystalline oxime or phenylhydrazone has hitherto been obtained. Mesityl oxide resembles benzy lideneacetone in its action towards reducing agents ; the product obtained by the action of aluminium amalgam was fractionated, and the portion boiling at 210--220' con- verted into the oxime, The yield is 70-80 per cent. of the theoretical. QMe2*CH2C(NOH) CH2-fjM"e CMe2*CH2 - CMe >CH Or CMe2<Cl\le~C*CMe:NOH' which crystallises with 1H20 in long, broad prisms, melts at 156--257", has a camphor-like odour, readily volatilises at the ordinary tempera- ture, and, in small quantity, may be distilled without decomposition ; it does not reduce Fehling's solution, and, when heated with con- centrated hydrochloric acid, the ketone is regenerated. The reduc- tion product of mesibyl oxide differs from that of benzylideneacetone in stability, the hypothetical compound, COMe*CH,*CMe,*CMe,*CH2.COllle which is first formed condensing spontaneously to the above closed chain derivative. J.B. T. Synthesis of Pararosaniline and its Mono-, Di-, Tri-, and Tetra-alkylic Derivatives. By MAURICE P R u D ' H o m E (Con@. rend., 1895, 121,891-893).-When the paranitrodirtmidotriphenplmethanes are dissolved in hydrochloric acid and treated with zinc dust at the ordinarj- temperature, they yield complex hydroxylamines [GH*CaH4*NR2 : NH*OH = 1 : 41, and when the latter are heated with hydrochloric acid they yield coloured products, the hydroxjlamine group being changed into the amido-group, just as phenglhydroxyl-ORGANIO CHEMISTRY. 307 amine is converted into paramidophenol, and this notwithstanding the fact that i t is the central carbon which occupies the para-position v i t h respect to the hydroxylamine.The products have, therefore, the constitution [*C(OH)*CsH,*NR2 : NH, = 1 : 41. The intermediate leuco-bases are precipitated hy adding sodium acetate, and, after the zinc has been removed from the liquid, the colouring matters can be separated by means of alcohol. To obtain paranitro-compounds corresponding with pararosaniline and its derivatives, 1 mol. of paranitrobenzaldehyde is condensed directly with 2 mols. of aniline or dialkylanilines. The mono- and tri-alkyl-deriratives are obtained by condensing monalkylparanitr- amidohydroxydiphenyl with aniline or dialkylanilines.Similarly, the dialkylrosanilines may .contain alcohol radicles in one or two nuclei. The colonr of these derivatives becomes more violet as the number of alkylic radicles in the amido-groups increases, the substitutions having more effect in this respect if they take place in the same nucleus than if they take place in two different benzene nuclei. Desmotroposantonin and the Benzylsantonous acids. By "COLA CASTORO ( Gaxzetta, 1895, 25, ii, 348-359) .-BenzjZdesmo- $XCMe$*CHz*?H - O>co, is obtained t ~ ~ p o s a nt onin, by allowing an alcoholic solution of sodinrn ethoxide containing des- motroposantonin and benzylic chloride to remain for some days ; it crystallises in white needles melting a t 181-182O, and is soluble in ether.Its specific rotation is [a]D = + 102*G0, and it is readily hydro- lysed by boiling with potash, yielding potassium benzyldesmotropo- santonate. The isomeric bemyldesmotroposantonin, prepared in a similar manner from isodesmotroposantonin, crystallises in transparent needles melt- ing a t 81-82", has the specific rotation [ a ] D = +136.5", and is very soluble in ether. It is hydrolysed by boiling potash, giving a salt of benzylisodesmotroposantonic acid. Be nzy 1 desm ot j*oposant onous acid, C. H. B. CH2Ph*O*C= CMeG *C H,*CH*CHMe 7H:C Mw$*CH~*QH~ CH2Ph*O*C= C~~e*C*CH',*CH,*CHMe.COOH, is prepared by reducing benzyldesmotroposantonin with zinc dust and acetic acid; i t crystallises in transparent needles melting at 121-123', and has the specific rotation [aID = -39.3".The sodium salt crystallises in lustrous lamine. W. J. P. The Anhydride and Decomposition Products of Lthylic Santonite. By NICCOL~ EIZZO (Gazzetta, 1$95, 25, ii, 290-298).- On distilling ethylic dextrosautonite at 360-370", hydrogen is evolved, and after treating the distillate with water, the aqueous liquid is foiind to contain ethylic alcohol and propionic acid ; in the oily part of the distillate, ethylic propionate, dimethyldihydronaphthol, and the anhpdride, C,*H,,O, of ethylic dehydrosantonite were found. Ifr. J. P.308 ABSTRACTS OF CHEMICAL PAPERS. Conversion of Bromoprotocatechuic acid into a Dibromortho- naphthaquinonecarboxylic acid. By TH EODOR ZINCKE ( J , pr. Chem., lSY6, [Z], 53, 3 00-105) -Oxidation of bromoprotocatechuic acid by dilute nitric acid yields a compound of the formula C11H4Br204, which is probably 3 : 1'-dibromo-1 : 2-17~phthapziinone-3'-carbozylic a d , but it remains uncertain whether 3 : 4' : 1 : 2 : 2' be not the correct orientation. Nuch oxalic acid is formed during the oxidation.Towards an alkali, the new compound behaves iri part like a bromo- p-naphthaquinone, and in part like a diketone; the first reaction leads to the formation of a hydroxyparaquinone, the second to that of a dibasic acid, C11&&=& Formulae showing the probable orienta- tion of these compounds, aud of those produced by treating them with bleaching powder, are given in the paper. Action of Trichloracetic acid on Terpenes.By AL~ERT REYCELER (Ber., 1896, 29, 695-697).-When carvene and trichlor- acetic acid (2 mols.) are brought together, the compound, is formed ; it is optically inactive, crystallises in lustrous leaflets melt- ing at 104O, and yields terpin hydrate when hydrolysed. Pinene gives rise to borne01 when the hydrocarbon is in excess, but in presence of excess of trichloracetic acid, the foregoing cornpound is produced. A. G. B. (CC1,*COOH)2:CioHi,, Camphene is converted into a salt of isoborneot. Orientation in the Terpene Series. By ADOLF VON BAETRR M. 0. F. (Ber., 1896, 29, 326-329 ; compare this voi., i, 245).-a-Pinonic acid (loc. cit.) is readily obtained by the oxidation of pinene at 30", i t being unnecessary to fractionate the product. If an acid solution is employed at the ordinary temperatures, small quantities of the hydro- carbon may be converted into the crystalline acid in five minutes.When a-pinonic acid is heated for 30 minutes on the water bath with 10 parts of 50 per cent. sulphuric acid, it is converted into the isomeric lactone (m. p. 63-65'), identical with the substance obtained by Wallach on oxidising terpineol, and by Tiemann and Semmler from the oxidation products of pinene (Abstr., 1895, i, 548). The author expresses the constitution of a-pinonic acid by the formula COOH*CE12*CH<~~f">CH*COMe, the isomeric lactone having the Oxidation of a-pinonic acid 0- ?Me2 CO*CH,.C:H*CH,*CH,.COMe' structure I - - with dilute nitric-acid gives rise to pink, oxalic, and terebic acids. Hydrolrypim'c acid, C9Hl4O5, is obtained by treating pinic acid with phosphorus pentachloride and bromine, converting the bromo-acid thus formed into the acetyl derivative by the action of silver acetate, and hydrolysing t.he acet.yl derivative.It crystallises from water in prisms, and melts at 193-194O. Phonic acid. By FERDIXTAKD TIEMANN and FRIEDRICH W. SEXM- LER (Bey., 1896, 29, 529-544; compare Abstr., 1895, i, 477, and von Baeyer, this vol., i, 246).-The result of oxidising pinene with potassium permanganate is entirely controlled by conditions of tempera- M. 0. F.ORGANIC CHEMISTRY. 309 ture, liquid pinonic acid being formed at 6 O , mliilst von Baeyer's a-pinonic acid is the sole product when the temperature is main- tained a t 25-40' ; the solid acid, however, slowly induces crpstal- lisation in the liquid modification, which thus yields one-half its weight of a-pinonic acid.One decimetre of freshly distilled liquid pinonic acid has a = +6', this rotation being increased to u =: 3-13" when the solid acid has been removed; the latter has a = +2O in a tube of the same length, whilst I-pinonic acid, obtained by distilling a-dihydroxydihydrocampholenic acid, has a: = -21". The semicarbuzoize of E-pinonic acid melts at 23l0, and the ozime at 125O, or at 131O after successive 1-ecrystallisations from water; the se?izicarbazo?ze of d-pinonic acid melts a t 207O, and the senzica~bazone of a-pinonic acid melts between 197' and 2 1 1 O . The formation of methoethylheptanonolide (m. p. 63-65'}, which von Baeyer obtained from a-pinonic acid (Zoc.cit.), is observed when all the modifications of pinonic acid are treated with acids, and also occurs when they are distilled slowly under atmospheric pressure. The formation of optically active pinonic acids from active pinenes would seem to indicate t h a t the oxidation process is a simple one, and the authors have shown that the change in question is not deperident on the intermediate formation of x-dihydroxjdihydro- campholenic acid; it is probable that d- and a-pinonic acids are different configurations of the same substance, and this view is sup- ported by the production of isoketocamphoric and isocaruphoronic acids when both acids are oxidised. The authors have stated that d-phonic acid is indifferent towards alkali hypobromite (Abstr., 1895, i: 478) ; action does occur slowly, however, and the Z-acid is also decomposed.The piaoduction of bro- moform does not necessarily imply the presence of ths! group *CO*CH2, because the behaviour of iretol (Abstr., 1894, i, 49) and tanacetone (Abstr., 1893, i, 107) has shown otherwise ; the authors, therefore, continue to express the constitution of pinonic acid by the formula CMe2*(?H*CK2*CooH, representing pinic acid by the ex- cHNe<CO-CH, . They attribute the formation $I Me2*$: H*CH2*C 0 OH pression COOH*CH-CH+ of pink acid, on oxidation of pinonic acid with nitric acid, to pre- liminary molecular rearrangement, and ascribe the conversion of pinonic acid into methoethylheptanonolide to the same cause. This change is iliustrated by the transformation of tanacetoketocarboxylic acid into methoethylheptanonolide, and the production of an analogous lactonio acid from tanacetogendica~*boxylic acid.11. 0. E'. Terpenes and Ethereal Oils. Pulegone. By OTTO WAr,LAcH (AnnuZen, 1896, 289, 337-361 ; compare Abstr., 1893, i, 115).--. When pulegone is heated with its own volume of anhydrous formic acid in a reflux apparatus, or with water at 250°, acetone is produced along with ;t mei%gZcycZohexenone, C7H,,0, which boils at 169O, has the sp. gr. = 0.915 at 21", and the refractive index nD = 1.4456 at the same temperature, whence the molecular refraction 31 = 32.59 ;310 ABSTRACTS OF CHEMIOAL PAPERS. the semicarbaaone melts at 180', and the oxime at 43-44', The cycloheptenamine, C7Hla*NE2, obtained by heating pulegone with ammonium formate (Eoc.cit.), is also produced when the foregoing oxime is reduced in alcoholic solution with sodium ; it boils at 151', and the carbamide and semicarbazone melt at 178" and 177" respec- tively. The formation of this primary base is attended with the pro- duction of a secondary base, NH(C7H&, which boils at 273", and: crystallises in needles (Abstr., 1894, i, 254) ; the nitrate is not very soluble. Reduction of the foregoing methylhexenone with sodium and alcohol gives rice to ?7aet7L?lEcyclohezeizol (metah ydr~x?lliexa~~d?.otoluene) C7Hi3*OH, which boils at 77" uiider a pressure of 17 mm., and at 175-176" under atmospheric pressure ; the sp. gr. = 0,914 at 1 go, and the refractive index n D = 1.4581 at the same temperature, whence the molecular refraction 2cI = 34.04.The iodide, C,HJ, is obtained fiwm the alcohol by means of iodine and amorphous phosphorus ; it boils at 100-110" under a pressure of 30 mm., and is converted by quinoline into tetrahydrotoluene, which. has been isolated from resin oil by Renard. When the methylcyclohexenone is oxidised with potas- sium permanganate, it yields an acid, which melts at 69", and closely resembles the pimelic acid obtained from menthone, which, however, melts at 84-85'. In view of the foregoing observations, the author expresses the constitution of this ketone by the formula and advocates Sernmler's formula for pulegone, The methylcyclohexenone is isomeric with Markownikoff's saberone (Abstr., 1894, i, 160), which yields the semicarbuzo.ne, melting at Pulegoneamine (Abstr., 1895, i, 153) boils at 205-210"; the carb- ainide is obtained from the lqdrochlwide, and melts at 104-105", and the phenylcarbnmide crystallises from alcohol, and melts at Pulegenic acid, CI0Hl6O2, is obtained by heating a solution of pulegone dibromide in methylic alcohol with sodium for four hours ; i t undergoes decomposition when boiled at atmospheric pressure, but boils at 155" under a pressure of 13 mm.The sp. gr. = 1.007 at 1 9 O , and the refractive index TZD = 1.48071 at the same tempera- ture. The ammo?ziunz salt is white, and the a?nide crystallises in woolly needles, and melts at 121-122' ; the nitriEe boils at 218-220", has the sp. gr. = 0,8935 at 22', and the refractive index J L ~ = 1.47047 at the same temperature. Reduction of the nitrile converts i t iuto a base, having the odour of menthylamine; the carbamide, melts at 97-99'.The hydrochloride of methylic pulegenate boils a t 113-116' under a pressure of 13 mm., and solidifies at low tem- peratures. The hydrocarbon, C9H,,, is produced when pulegenic acid is dis- 163-164'. 154-155O.ORGANIC CHEHISTRY. 311 tilled under atmospheric pressure; i t boils at 138-14,0", has t h e sp. gr. = 0.79 at 20", and the refractive index nD = 1.44 at the same temperature, whence the molecular refraction M = 41.37. Tho nitrosOchl&de melts at 74-75'. The h~drozylactone, CI0Hl6O3, obtained by oxidising pulegenic acid with potassium permanganate, melts at 129-130", and boils at 185" ilnder a pressure of 20 mm.; i t is also produced by the action of chromic acid.The ketone, CgH,,O, is formed when the hydroxy- lactone is treated with sulphuric acid, carbonic anhydride being eliminated ; it boils at 183", and has the sp. gr. 0.8925 at 21", and the- refractive index nD = 1.44506 at the same temperature. The carb- uzone and oxime melt a t 169-170" and 94" respectively. The author compares pulegenic acid with campholenic and fencho- lenic acids, and develops formula3 for the compounds just described. M. 0. F. Oil of Lemon-grass. By PHJLIPPE BARBIER and Lours BOUVEAULI (Comrzpt. rend., 1895, 121, 1159--1162).-That portion of the oil of lemon-grass which boils at 107-110" under a pressure of 10 mm. yields a, sernicarbazone, CllH19N30, which forms white Iamells, me1 t- ing a t 171", and is vevy slightly ooluble in boiling alcohol.That POP tion of the oil which boils at, 110-112" under a pressure of 10 mm. yields three isomeric semicarbazones of the composition One forms white larnelle, melting at 171", and is identical with that obtained from the lower fraction ; another cryotallises in needles, melts st 160°, and is very soluble in hot alcohol, but only moderately 80 at the. ordinary temperature ; and a third forms white needles, which melt at 135", and are very soluble in cold alcohol. When the sernicarbazone melting at 171", is boiled with dilute. sulphuric acid, i t yields paracymene and an aldehyde, which, with. semicarbazide, forms the sernicarbazone melting at 135O. Under similar conditions, the semicarbazone melting at 135", yields cgmene, and an aldehyde which can be reconverted into the original semi- cttrbazone.These results arc not caused by any stereoisomerism due to nitrogen, and i t would seem that oil of lemon-grass contains two acyclic alde- hydes, one of which, CH2:C1Sle*CH(COH)*CH2*CH:CMe2, is converted into the other, CMe,:C(COH)*CH2*CH:CMe2, by the action of dilute. sulphuric acid. The oil of lemon-grass does not contain an aldehyde of thecomposi- tion CIOHl,O (compare Abstr., 1894, i, 400-402). The Camphor Series 111: Menthones. By Emsr R E c K m x N ( A ~ ~ n a b e ? ~ , 1896, 289, 363-36'7 ; compare Abstr., 1889, 722, and- 1894, i, 240).--The author has observed that acids and bases exercise an inverting influence on limo-menthone, transforming it into a dextrorotatory modification (Zoc. cit.) ; concentrated sulphuric acid, for example, gives rise to a product which is dextrorotatory in the. same degree as the original material is hvogyrate.The oxime of the latter, however, has the specific rotatory power [ a ] D = -40.75O C ,OH 16: N*NH *C 0 *NHz. C. H. B.312 ABSTRACTS OF OBEMLCAL PAPERS. to -41.97', whilst the oximc from the dextrorotatoyg iiienthone has the specific rotatory power [ a ] D = -4.85" to -6.67'; it is found, moi'eover, that as the dextrogyrate character of the nienthone becomes intensified, hydroxylamine gives rise to a preponderating amount of the liquid oxime, until finally the product, does not yield crystals. The author endeavours to explain the mechanism of this change, basing his considerations on the formula fox* menthone. Laevo-menthone semicurbuzo?he crystallises from alcohol in small needles, melts a t 17&', and has the specific rotatory power [a],, =~1: --:3*67" in glacial acetic acid (10 per cent. solution) at 20' ; the semi- curbuzone of dextro-menthone has [a]D = -3" under ihe same condi- tions, and melts at 172', a mixture of the.two isomerides melting at 175'. M. 0. F. Menthones. By ERNST BECKMANN and H. M EHRCXNDER (Anualeit, 1896, 289, 367--391).-Oxymenthylic acid, C'OPrWH,*CH2*CHRIe*CH2*COOH (compare Manasse and Rupt., Abstr., 1894, i, 470), is obtained by oxidising menthone with chromic anhydride, and boils a t 292'; i t is also prodnced when menthol is oxidised with potassiuni perrnanga- nate, and was obtained in this way by Arth (Abstr., 1886, 892). Henthoximic acid, CloHl,Oz:NOH, obtaiued by von Baeyei.and Manasse from menthone under the influence of amylic nitrite (Abstr., 1894, i, 522), is pyoduced by the action of hydroxylamine on the foregoing acid ; the sodi?m salt is deliquescent, and the copper and siEver salts are amorphous. The ethylic salt is a colourless oil, and the acetyl derivative is crystalline, and melts at 91'. Bromine converts oxymenthylic acid into an oil, which probably has the formula C,oH,,O,Br,. The action of bromine on lavo-men- thone converts i t into a compound, CloH,,Br30, a brown oil, which fumes in moist air, and has a disagreeable odour, The conversion of I-menthoneoxime into an isorneride undey the influence of phosphorus pentachloride has been observed by Wallach (Abstr., 1894, i, 46 and 337). The same agent acting on d-menthoneoxime gives rise to an isomeric compound, wbich crystal- lises from water, and melts a t 88' ; a solution in 4 parts of alcohol has the rotatory power x, = -4.9O in a 1 decimetre tube a t 20°, and the liquid hydrochloride, under tche same conditions, has the rotatory power a = -3.67'.An oily, isomeric conrpound is formed along with the solid substance, and, under the above mentioned conditions, has the rotatory power a = -1.87'. Concentrated sulphuric acid at fOOo converts I-men thoneoxime info an isomeric compound, which melts between 68' and 83', and although this product appears to consist of a mixture of two substances, attempts to resolve it into constituents have been unsuccessful ; i t is indifferent towaids organic bases, benzoic chloride, phenplcarbamide, sodium amalgam, hydriodic acid, and zinc dust, but yields a hydro-ORGANIC CHEMISTRY.318 chloride, which melts at 91". Phosphorus pentachloride gives rise to 211 oil, which, wlien treated with aqueous soda, Fields the compound (m. p. 120") obtained by the action of phosphorus pentachloride on I-menthoneoxime (Abstr., 1894, i, 46). M. 0. F. The Menthones; Conversion into Thymol. By ERNST BECK- YAXN and H. KICKELBERG (Bey., 1896, 29, 418--421).--Dibronzo- ?)wszthoize, C,oH,,Bi-20, is obtained by adding bromine (2 mols.) to 1- or d-menthone dissolved in four parts by weight of chloroform, and, after adding ether and agitating with soda, allowing the reddish- brown oil obtained on eraporation to lose hydrogen bromide spon- trtiieously ; i t separates from alcohol in colourless crystals, and melts a t 79-80".A 3-05 per cent. solution in carbon tetrachloride has the specific rotatorypower [zJD = +199.4'. Zinc dust is without action ou dibroiiiomenthone in a.lcoholic solution, bnt in presence of glacial acetic acid, menthone is regenerated ; hydroxylamine converts i t into the ozimido-compound, OH*CloH16Br:NOH, which crystallises from light petroleum, and melts at 136-137O. When dibromomenthone is heated for five minutes with boiling quinciline (6 mols.), tbymol is produced, and the authors conclude, theleefore, that menthonc has the constitution expressed b-y the formula M. 0. F. Halogen Derivatives of Camphene and Hydrocamphene, By ERNST JCKGER and A. KLAGES (Ber., 1896, 29, 544--547).-When camphene hydrochloride is treated with glacial acetic acid, isobornylic acetate is formed ; the fact that bornylic chloride yields the- same product, is probabiy owing to initial regeneration of camphene (compare Bertram and Walbaum, Abstr., 1894, i, 204).Carnphene hydrochloride, which melts at 165O, unites with bromine forming an oil which yields bromocamphene when distilled with quinoline ; this substance, which has been described by Tnrallach (Anmiden, 230, 293), boils at 226-227', has the sp. gr. = 1.265 at 15O, the refractive index 121) = 1.52605 a t 15", and the molecular refraction 31 = 52.36. From the similarity exhibited by isobornylic chloride an4 bornylic chloride, the authors regard isoborneol and its dei*ivatires as geo- met-rically isomeric with the corresponding borneol derivatives.Isoborn ylic Chloride and Camphene Hydrochloride. By ALBERT REYCHLER (Be?.., 1896, 29, 697-699).-Both camphene and isoborneol yield isobornylic chloride when hydrogen chloride is led into the alcoholic solution ; although indifferent towards alcoholic hydrogeu chloride, phosphorus pentachloride converts borneol in to bornylic chloride, and the author, therefore, regards isobornylic chlctride and caniphene hydrochloride as identical, and stereoisomeric with bornylic chloride. Derivatives of Camphoric and Hemipinic acids. By SEBAS- TiAAN HOOGEM-ERFF and m T ~ ~ ~ ~ ~ ~ A. VAK UORP (Bec. TYUZ. Chiin., 1195, M. 0. F. M. 0. F.314 ABSTRACTS OF CHEMICAL PAPERS, 14, 252-275).-The authors have prepared a-camphoi*amic acid by a method differing but slightly from that recommended by Auwers Gad Schnell (Abstr., 1893, i, 525).I t is best purified by conversion into its hydrochloride by passing dry hydrogen chloride into all alcoholic solution of the acid; the pure hydrochloride is then decomposed by treakment with water. It cr~stallises in colour- less plates, melts at 176-177', and is fairly soIubIe in hot water, readily in acetone and alcohol, sparingIy in ether, chloroform, and benzene. Its rotatory power in alcoholic solution is [a]* = +450. Nit1*ons acid converts it into camphoric acid. The silver salt forms co]ourIess crystals; the wpper salt crystallises with 4H20 in small ssDheres. 1. a- Camphorisoimide hydrochloride, C,H,,< C(NH)> co -- O,HCl, is obtained when the a-camphoramic acid is heated with about four times its weight of acetic chloride (compare Abstr., 1893, i, 599).It is some- what unstable, and is rapidly transformed by water into a-camphor- amic acid. jellom, crystalline compound, and melts at 120-130°. When the hydrochloride is decomposed with potassium or ammonium hydr- @oxide, it is converted into a salt of cyarbolauronic acid, CN*CsH,,*CObH, This acid crystallises in orthorhombic Prisms, and melts at 151-1520 without undergoing decomposition. When rapidly distilled, i t passes over unaltered, but if kept at the boiling point for Some and when boiled with concentrated hydrochloric acid i t is hydrolysed to camphoric acid. Its alcoholic solution is optically active, [a], = +67" 30'. The methylic salt melts a t 40-4!s0, and tlhe ethylic salt at 24-27O.Cyanolauronic acid, when reduced with sodium and alcohol, yields the acid NH2*CH2*CBH~~*COOH, the pZaiinochZoride of which forms yellowish plates, and does not melt below 270'. p-Camphoramie acid is obtained, together with a small quantity of &he isomeric a-acid, on treating camphorimide with Eodium hydr- oxide (compare Noyes, Abstr., 1894, i, 339). It crystallises in prisms or plates, melts at lt3O-18l0 (Noyes 182-183O), is readily soluble in alcohol, acetone, and hot water, sparingly in ether, benzene, and chloroform ; its alcoholic solution has a, rotatory power [aID = +60°. When treated with nitrous acid, i t yields ordinary dextro-camphoric acid. (3- Camp7misoimide hydrochloride is obtained when the above acid is heated with acetic chloride, and yields a yellow, crystalline auro- chkwide.On treating the hydrochloride with aqueous ammonia and then acidifying, cy anod ihy drocampholy tic acid, CN*CEH14*C 0 OH, is formed ; this acid crysfallises in monoclinic plates, melts at 109-ill*, and has a rotatory power [&ID = + 1 8 O 12'. Methyl-P-camp horamic acid, NHMe*CO*CeH14*COOH, is obtained on treatiug camphormethyfimide (compare Abstr., 1893, i, 599) with sodium hydroxide. It crystallises with lH20 in oblong plates, loses its water at 80°, and then melts at 177-178O; it is readily soluble It forms an aurochloride, CQHI,J'?02,AuC14, which is kime it is transformed into camphorimide, C E H l , < C O > ~ ~ , co Its silver salt is only slightly sensitive to light.ORGANIC CHEMISTRY. 315 in alcohol and acetone, sparingly in benzene, and still more sparingly in ether.p-Carnpho?.inethylisoimide, obkained by the action of pliosphorus oxychl ori de on methyl-/3-camphoramic acid, crystal lises in col ourless needles, melts at 85--86.5', and boils at 255--25S0 (uncorr.) with only slight decomposition ; i t dissolves in dilute hydrochloric acid, but is quickly hydrolysed t o the methylamic acid. It yields a hydro- chloride and also an aurochloride. a-Hemipinamic acid, NN[,*CO~CGH2(OMe),*COOH [= 2 : 3 : 4 : 11, is formed, together with a small quantity of the isomeric P-acid, when hemipinic anhydride is dissolved in aqueous ammonia and then acidified with a mineral acid. It crystallises in colourless needles with 2H20, which it loses at 80°, and then melts at 160-162", at the same time undergoing decomposition and yielding hemipinimide, which melts at 220'.The acid is moderately soluble in alcohol, sparingly in acetone, and very sparingly in benzene and ether. Hot water dissolves it, but at the same time converts it into the imide. The silver salt of the a-acid is a colourless, crystalline precipi- tate. Cyanodirnethoxybenzoic acid, ~ ~ * ~ 6 H 2 ( o M e ) 2 * c o o H [ = 2 : 3 : 4 : 13, is obtained from the a-acid in exactly the same way as cyanolauronic acid from a-camphoramic acid. It crystallises in colourless needles, melts at 207-208', and is readily converted into the a-hemipinamic acid on exposure to moist air. p-Hemipinainic acid, NHz*CO*C6Rz(OMe),*COOH [= 1 : 3 : 4 : 2J, is best prepared by tritathg hemipinimido with sodium hydroxide.I t forms hexagonal plates, and, when anhydrous, melts at 142", probably yielding the irnide. A mixture of the a- and @-acids is best separated by dissolving in aqueous ammonia and adding hydrochloric acid when the @acid separates. The silver salt of the @acid crystallises in colourless needles, is soluble in hot water, and is not rapidly darkened on exposure to light. Cyanoninaethoaybenxoic acid, CN*CsH,(O&Ie)z*COOH [= 6 : 2 : 3 : 11, prepared in the same way as the isomeric acid, crystallises in slender needles which contain 2Hz0, and when anhydrous melts at The authors consider that the formation of a-amic acids on treating the anhydride of unsymmetrical dicarboxylic acids (camphoyic and hemipinic) with ammonia, and the formation of the isomeric p-amic acids on treating the corresponding imides with caustic soda ace readily accounted for on the supposition that one of the carboxylic groups of the dibasic acid has stronger acid properties than the other.81-82'. J. J. S. The Root of Rumex nepalensis. By OSWALV HESSE (Ber., 1896, 29, 325).-In consequence of an annouucement by A. G. Perkin (Trans., 1895, 1084) of his intention to investigate the substances contained in thi8 root, the author states that he has already obtained the following compounds from it, and is engaged in their examination : (1) C15H1001, yellow plates, melting a t 186-188O ; (2) Ci6H,204, orange needles, melting at 1 3 6 O ; (3) CteHleO*, greenish-yellow prisms,316 ABSTRACTS OF CHEMIClAL PAPERS.melting a t 158'. two are insoluble. The first is soluble in sodium carbonate, the otlier C. P. B. Metallic Salts with Organic Bases. By FRITZ REIZEXSTEJN (Zeit. anorg. Chew., 1896, 11, 254-263 ; see also Abstr., 1895, i, 121). --Tctmpyridine nickelous chloride, NiCI2,4C5NH5, is obtained by boil- i n g hydrated nickelous chloride, previously heated for some time at 145*, with an excess of pyridine ; the bluish-green mass thus obtained is washed with absolute alcohol and ether. It crystalliscs from pyridine in bright blue needles. PyTidine nickelous chloride, NiCl,,C5NH5, is obtained by heating the preceding compound at 115-120". Tetrapyridine cobaltous ddoride, previonsly prepared from anhy- drocs cobaltous chloride, can also be obtained by adding pyridine to an aqueous solution of cobaltous chloride ; it crystallises from the mixture in deep red crystals.Monopyridine cobaltous chloride is formed on heating the tetrapyridino compound a t 115-120°, or the dipgridine compound at 104-106° ; it is a bright blue powder. Qttirzolitte cobaltous chloride, CoCI,,C,NH,, is obtnined by heating t,be tetraquinotiuo compound a t 115-120" for one hour and then at 120-135° for one hour. Cobalt and nickel sulphate also give compounds with pyridine, which will be described later. Hydrated compounds of the above type hare not been obtained ; when the monhydrate or dihydrate of cobaltous chloride is treated with pyridine or quinoline, dipyridine or diquinoline cobaltous chloride is obtained. E;. C. R. mridine Alkyl Iodides. By ALBERT B.PRwcow (J. Amer. Chenr. Xoc., 1896, 18, 91-96).-These compounds are formed on treating pyridine with the required alkyl halo?d, the methyl com- pound being prepared by heating the mixture in a flask attached to a reflux condenser. The ethyl compound is best prepared by occasion- ally shaking the mixture in a flask a t the ordinary temperature, whilst the propyl compounds are made by heatiiig the mixture in a sealed tube at 130°. Pyridine methiodide forms flat needles, sometimes aggregated in rosettes, very soluble in water, alcohol, mehhylic alcohol, chloro- form, acetone, and glacial acetic acid, insoluble in ether, benzene, and carbon bisulphide. It is slightly deliquescent and melts a t 11 7'. Pjridine ethiodide forms colourless plates melting a t 90.5" ; it is permanent or slightly deliquescent, soluble in water, alcohol, acetone, and glacial acetic acid, from which i t ci-ystallises, and slightly soluble in etltylic acetate, insoluble in ether, benzene, carbon bisulphide, and c h lo~ofo r m .Pyric1ii)te psqopioclide forms colourless plates and me1 ts a t 52-53" ; it is deliquescent,, soluble in water, alcohol, aniylic alcohol, ethylic acetate, aiid benzene, insoluble in ether and chloroform. Pyyidiw isopopiodide forms colourless crystals, soluble in water, 95 per cent. alcohol, and ethylic acetate, but less freely in absoluteORGAXIC CHEMISTRY. 317 alcohol, amylic alcohol, or chloroform, insoluble in ether; it melts at Dipyridine Trimethylene Dibromide. By R. F. FLrNTERmNx and ALBER.~ B. PRESCOTT ( J .Arne).. Chenz. Soc., 1896, 18, 28-35).- The authors have prepared this compound, CH2(CH2.CjNH5Br)Z, by acting on pyridine (2 mols.), boiling at 116-118", with trimethylene biaomide (1 mol,), with the addition of one-fifth of the volume of abso- lute alcohol to the mixture. The compound forms completely in about a week in the cold, but is more rapidly obtained by heating in a sealed tnbe for four hours at 105-110°. The light brown, crystalline mass is drained, washed with alcohol, and once recrystallised from alcohol, then being nearly white ; a pure, white product is, however, obtained when the action takes place in the cold. It is very soluble in water, less soluble in alcohol and ethei., and but rely slightly so in chloroform. Kept in an open vessel for weeks, it shows no indication of decomposition, only getting slightly moist, The niolecLilar weight was determined by the cryoscopic method, Synthesis of Tetrahydropyridine Derivatives and their Con- version into Piperidine Derivatives. Bp ANDREAS LI PP (rln?zaZen, 1895, 289, 173-253 ; compare Abstr., 1892, 1243).-Normal aceto- butylic alcohol (hexme-2 : 6-ketoE) has been already described by the author (Abstr., 1886, 218); the anhydride, CsHl,O, which boils a t 106-107" under a pressure of 720 mm., is identical with methyl- dehydrohexone (Perkin, jun., Trans., 1887, 723).The pheny7lr ydy- cic'oite of ncetobutylic alcohol is obtained from the alcohol itself or the anhydride, and forms a yellowish, viscous oil, which becomes brown 011 exposure to the air; the oxiwe is a colourless syrup, which has no action on Fehling's solution until treated with sulphuric acid.The acetate boils at 231-232' under a pressure of 715 mm., and yields a white, crystalline conzpozmd with sodium hydrogen sulphite ; the lreizzonte is a limpid, coloiirless liquid, which decomposes when heated under atmospheric pressure. &let h yZ bewmmidobutyl ketone, C OMe*CH,*C €3,. C H2-C Hz*NHBz, is obtained by the action of benzoic chloride on h2-tetrahydropicolinc (Eoc. cit.) in presence of alkali ; it crystallises i n needles and melts a t 75-76O. When heated at 170-l8O0 with fuming hydrochloric acid, i t is resolved into benzoic acid and tetrahydropicoline. The oxinze crystallises in needles or prisms and melts at. 87". Methyl phenylamidobutyl ketone platinochloride crystallises in needles, and a t 200--'202" decomposes, evolving gas ; the picrate melts at 124-125O, and the oxirne at 68-69O, the phenylhydrazone being a jellowish, viscous oil.Reduction of the ketone in acid solution gives rise to 1-phenyltetrahydropicoline, whilst., in presence of an alkali, pl~e?~yEn~~ticlometh~Zbzitylcarbinol, which' melts at 44-45' and boils at 320-3P'L' (720 mm. pressure), is formed. The Oximes of the Cyclic Acetone Bases: Paramidotri- methylpiperidine. By CARL D. HARRIES (Bey., 1896,29,521-529). VOL. LXX. i. 2 a 114-115'. L. DE K. The crystals melt and gradually decompose a t 225-226'. using phenol as solvent. L. DE K. M. 0. F.318 ABSTIEACTS OF CHEMICAL P-4PERS. -Triacefoiza?iai.1zo~uinae, C,H,,N20, is obtained by the action of hydr- oxylamine on triacetonamiiie, altd crystallises in large, white, six- sided prisms, melting ato 152-153' ; i t forms crystalline salts with hydrochloric and sulphuric acids.Be?zz?/Zidenediacetona?ninozil,le, C,,H,,N,O, crystallises in lustrous, four-sided tablets, melting at 140-141°, and is only sparingly soluble in boiling R-ster-. VilzZlZ~incetonami?aozime, NH<Csf CHMeGH cH,?>C:NOH, crystallises iu translucent, four-sided tablets, melting at 150--151°. When reduced with alcoholic hydrogen chloride, zinc duet, and a little water, it is converted into 4-amido-2 : 2 : 6-trimeth?/~i~cridi.12e, which forms a crystalline mass, melts at 25-W, and boils at 60' (pressure = 7.5 nim.). The base has a faint odour of piperidine, and rapidly combines with tho carbonic anhydride of the air, forming a carbamatc.The hyd?-iodide of the base crystallises in fascicular gronps of white prisms, and is moderately soluble i n water; the hylrochloride is readily soluble in water ; the a z m c l d o d e crystallises in red, oblique, six-sided tablets, and is sparingly soluble in water, whilst the platiizo- chZo&Ze and picrate are also crystalline. The base forms both n wmnal and an acid oralate, the latter bziiig very hygroscopic. 4-Acetamido-2 : 2 : G-trimeth?/~ipe).i~~ne crystallises in cubes, melting at 206-207'; it is strongly basic, and foi*ms an azwochloride, melting at 235O with decomposition. e2- The diacetyl compoziitd, N A c < ~ ~ ~ CHMe*CHo -cs;>CH*NHAc, 2 is formed when the base is heated with escess of acetic anhydride at 160'; it forms small prisms, melts at 86-89', boils at 160-1'70' (pressure == 8 mm.), and has basic properties, forming a crys- talline aurochZoride.This diacetyl compound is accompanied by another basic substance, which boils at about 200' (pressure == 8 mni.), and is probably an anhydro-derivative. The base does not yield n diazo-compound with sodium nitrit'e and an acid, whilst with amylic nitrite it, yields a nitroso-derivative, the imido-group having taken part in the reaction. When heated with chloroform and alcoholic potash, no carbylamine derivatire is produced. The base reacts with carbon bisulphide, forming a thiocurbamate, C9HI8N2S2, which crystal- lises from water in prisms and melts at 187-188'. When this salt is treated with mercuric chloride, it yields the hydrochloride of a, new base.The latter crystallises in small prisms and melts at T9-803. It has not the smell or other properties of a thiocarbimide, and proh- ably has the constitution N-CS-NH-CH. C BRleGH,, / \cAle2 -CH/ A. 13. Isopipecoline. By ALIIERT LADENBURG (Her., 1896, 29,422-424). -The reasoning is given that led the autho~ to regard as isopipecoliiie what BIarckmald (this vol., i, 253) asserts to be mere17 a mixture of rl- and I-pipecoline. The author maintains that his own co~ielusioii is correct. C. F. B.ORGANIC CH.E311STRY. 319 Derivatives of Pipecolinic acid. By RICHARD WILL STAT^ E I: (Eer., 1896, 29, 389--392).-Ethylic pipecolinate, COOEt*C5NH,,,, is prepared from saif).osc~i~~ecoZi~zic w i d , which is oily ; it is a coloul.- less, highly refractive, riscici liquid, with an odour resembling that of acetamide ; it boils a t 216-217O (corr.), and a t 107' under a pressure of 20 mm., has a strongly alkaline reaction, is volatile at the ordinary tem- perature, and miscible with alcohol, water, and ether.In presence off dilate sulphuric acid, the ethylic salt slowly decomposes potassium per- mangnnate, and is extremely readily hydrolysed. H. Meyer's descrip- tion of it is incorrect, The Field is 90 percent. of the theoretical. The ncid melts at 2 6 4 O , and has a neutral reaction ; Ladeiibnrg states that it has an acid reaction, and melts at 259'. Unless diluted, niethylic iodide and ethylic yipeeolinate react with explosive violence, ethylic pipe- colinate hydriodide, etliylic methylpipeeolinate, and ethylic n-?nefhyZ- yipeeolinafe methioclide being formed ; the latter crystallises in colour- less prisms, melts ah 127-128', and, when distilled, is resolTed into its constituents.It is readily soluble in soda, and is hydrolysed, but not otherwise decomposed, when the solution is boiled ; when fused with potash, it yields dimethylamine, but the reaction proceeds with difficulty ; its stability under these conditions is in niarked contrast to the corresponding derivatives of tropinic acid, ecgonine, and nnhydroecgonine, which also contain a reduced pyridine ring (compzro this vol., i, 265). COOEt*C5NHgMe,MeAuCI,, The cruroclilo~ide of the methochloride, eiytalliscs in thin, flat, yellow plates melting a t 78'. The corres- poiicliiig salt of the ncid crystallises in golden, lustrous, tetragons! plates and'prisms, melting and decomposiug a t 227-228O.J. I%. T. 3-Nitroquinoline and 3-Amidoquinoline. Bg ADOLPI~ CLACS and LUDWIG SCHXELL . (J. p. C'henz., 1896, [2], 53, 106-l26).- Contrary to expectation, 3-nitroquinoline could not be directly nitrated to a dinitroquinoline. When dry hydrogen bromide is passed into the chloroform solution of 3-nitx-oquinoliiie, the hydrobroinide, N02*C9NH6,HBr, separates in the form of a heavy, white, crystalline powder melting at 2 4 5 O , and a t the same time losing hydrogen bro- mide, Bay shaking this salt with bromine in chloroform, the dibrowide, NO,*C,NH,,HBr,Br,, is obtained ; it foi*ms yellowish-red crystals, and is converted into 3' : 3-bromo?zit,.opzl.iizoline when heated at 170-18OC until the hydrogen bromide is almost entirely expelled.The bromonitroquinoline crg-stallises from hot water in yellowish needles, melts at 1 6 5 O , and sublimes; the methiodide crystallises from hot water in brilliant, red needles, and melts at 235O. The bromo-deriva- tive shows the same resistance to nitration t h a t is exhibited by the parent nitroquinoline ; justification for the adopted orientation is given. 3 : 3'-B~~namidopuiizoli~e is best prepared by mixing the nitro-compound with water and the calculated quantity of iron powder, so as to form a thick paste, which is then thoroughly mixed with a few drops of glacial acetic acid; after the action is over, a porous mass is left, from which the amido-compound is extracted by chloroform or ether.It crystallises i n colourless needles, melts a t380 ABSTRACTS OF CHE&lICAL PAPERS. 106', is not volatile with steam, and dissolves freely in hot watttr or alcshol ; its salts are yellow. By brominating the amido-derivat ive in chloroform, 4 : 3' : 3-dibronzamidoqe~inoli?le is obtained in the form of a hydrobromide (in, p. 210'). from the solution of which it may be precipitated by alkalis ; it crystallises in slender, lustrous needles, which are greenish in mass, and melts at 146'; evidence of the orientation is given. 3-Amidoqninoline melts at 114', not 140' (Bielstein, 0,g. Chent., 3, '752) ; the methiodide is obtained as a yellow, crystalline precipitate, and melts at 199'. By acetylising :J-amidoquinoline, 3-ncetan~iido- quinoline is formed ; it crystallises in silky, colourless, slender. needles, melts at 75', sublimes unchanged, and dissolves freely in water and alcohol, but only sparingly in benzene, light petroleum, &c.3-Benz- amidoquiitoline crystallises in brilliant, colourless lamin%, melts at 130°, and dissolves easily in hot alcohol ; i t sublimes unchanged, buk is not volatile with steam. 2 : c?-Bromumidoqziiizoline, prepared by brominrtt- ing the amidoquinoline in glacial acetic acid, crystallises in colourless laminse, me1 t s a t 67', does not sublime unchanged, and is not volatile with steam ; it dissolves easily in alcohol, but only sparingly in hot water; evidence of its Orientation is given. 2 : 3-Uromacetai~ti~oquinoline is obtained by brominating acetamidoquinoline ; the hydrobs*otllide sepa- rates first in yellow crystals, which melt at 241O; the base crystallises from hot water in brilliant, bronze coloured laminae, ancl melts at 165'.Di2j.l.omo-.3-anaidopuinoEine melts at 170°, and clibro?tio-3-ncet- nmidoquinoline at 159' ; the orientation of the second bromine atom in these two compounds is not yet ascertained. 3-Methylindazole. By SIEGSIVXD GARRIEL and ROBER'I S*ri:LzxEit (Ber., 1896, 29, 303-309).-When nitrometaxylidine, (Mez : NH, : NO, = 1 : 3 : 4 : 5), is treated with sodium nitrite in presence of dilute sulphuric acid, i t js couverted into 1 : 3-?iitrometh?/lindazole, N020C6H2&fe<& ->NH. This substance was fii8st obtained by Miiller (Diss. B e r h , 1883), who, however, ascribed to it the formula CsH,N30z.When it is reduced with tin and hydrochloric acid, it yields 4 : 1 : 3-chloranaidoi,tet7yliizd- crzoZe, which crystallises in plates with a satiny lustre, and melts a t 195', whilst the ucetyl dei*ivative melts 8.t 154'. When rednced with ammonium sulphide, on the other hand, the nitro-compound is con- rerted into 1 : .3-amidoinethylincEazo2e, NH2*C6&%Ie< I >NH, which crystallises in colourless needles, and melts and decomposes at 172O. The base dissolves both in acids and alkalis, mid forms a picrate, which melts and decomposes at 183". The dibenzoyl dericatire forms yellow crystals, and melts at 186-1873. 3-1CIethylinduzole crystallises in slender, colourless needlee, melts at 116-11 7", and boils at 293-294O (pressure = 747 mm.).The itiirosu~~ti?ze, C,R,N,O, forms yellow needles, which melt at 61', and give Liebermann's reaction. The chlorinated basea formed by the rednction of aiti*o-com- A. G. B. CH CH N - Nethylindazob picrate melts at 159-160O.ORGANIC CtiE:MISTRY. 321 pounds b y means of hydrochloric ~ e i d arid tin or stannous chloride, are USUZIIIY pnra-der.irat,i:.es. Ortho-compouuds niay, however, be formed when the para-position is occupied. It is probable that the formation of these compounds is preceded by the production of a, hydroxylamine deriiratire, and this reacts with the mid, jielding a, chloride, which then passes by iiitrmiolecular cliange into a pwa. cbloro-deri vative. A. N. Rejoinder to R. von Rothenburg : Isomerism in the Pyrazole Series. By LoDwic; KNOKR ( J .p ~ . Chert%., 1896, [ a ] , 53, 187-132). -Polemieai (compare Xhstr., 1895, i, 303, 395, 571). A. G. B. Constitution of 1- Phenylpyrasolone. B.y CARL I). HARRIES and G EORU E Low ( B e y . , 1896, 29, 513-- 5201.- i3thyZic [3-ani/idopropiom a h , NHPI~CH,*CH2*COOEt, is 1wdil.y obtained by heating ethjlic /3-iodopropionate with aniline ; i t is a, light yellow oil, which boils a t 175' (psessure = 18 nim.). Ethglic 1~if)'1?~0-P-anilid02~.opiortnfe is a n oil, which gires Liebermmu's reaction. Wf*c\n the nitroso-compmnct is dissolved i n ctller and redttcecl with nlurnitliuirl amalgam, it is coil- verted into ethylic as-/j-ph en y LittlflraxiJop?.opionntE, NH,*NPh*C H,-C H2'C 0 OE t*, which boils at, 174-175' (prcssuye = 9 inin.), and is readily soIuble i u dilute alkalis and mineral acids.The picmte crystallises in fasci- cular needles melting at 131-132°. The oxalrrte melts a t 1 0 7 O , and i s readily soluble in water. 'i'he oxalate reacts with potassium cjannte to fosni the se~tiic*nr.~)crzidc of the 7~ydrazidoaro?npou?rd ; t h i s erpstallises in cubic ciystnls nielting at 163--lt;4', and is in- so1 uhle in acids aud a1k:tlis. The phetzylthioseiliicurbnxide melts a t W lien ethylic plienylhy~rasidop~~pionRte is treated with nlcoliolic sodium ethlxide, it is couvextcd into 1 : 3-phen~lpyi.azolicloue, NPh<<NH.CO , melting at 119-12l0. The 7iydrocl~Zoride of this substance crystailises in 11itcl'eOt.ls plates melting a t 163'. 2 : 1 : 3- Ac.etllZphe?LyL~yrazoliclone w~sfallises in coloarless prisms nieltixig at 66-67O.W hell p)ienylpgt.nzolid~ne ia treated with sodium nitrite, the solution neutinlised with arunionia, and silier nitrate added, n yellow substance is oltaiiied, which, however., is not homogerit OW, bnt a mixture of the silvtr salts of 1 : 3-plieiiylpytmolone and of nitrophenyIpyi*azolone, produced by the action of riwes of nitric acid. The 1 : 3-pheny1pyraao:one obtairied from the phenylpyrazol- idone melts at 15:?O, nud forms a, hyclroehloricle, which crystallises in sleritler needles meltirtg a t 11!'. i t was found ittipossible to pre- p ave t 11 e 1 - p 11 e 11 y 1 ps ra z o 1 on e - 4- ti zo b en z en e d esc r i bed by R o th enbu 1.g (Abstr., 1894, i, 145). (4- ?) Kdm-1 : 3 y7Le?t!/~~1.""oZone is formed when phenjlpyrazolotie is dissolved in dilute nitric acid, and crystal- lises iu long, titrvad-like needles melting at, 190--19do.'2 : 1 : 3-AcefyZ- phenylpyrcrzuZc,?ie c q siallisea iu wlourless, fan4sliapcd needles melting at 62--6;j0, A. H. 71-74'. CEI,*y H, 2 u 2322 ABSTRACTS OF OH E l l JCAL PAPERS. Action of Hydrazine and Phenylhydrazine on 1 : 4-Dike- tones. -By ALKXAS~ER sbII1'II [and in part JAMES H, KAS~OSI] (Annalen, 1896, 289, 310-337).-3 : 4 : 6-117).ipJ~en?/Edih~~~op~~,~~- wine, C P I ' < ~ ~ :Cph>NH, is obtained by acting on desjlaccto- phenone with hydrirzine for one hour; it crystallises in jellow necdlcs and wben heated rapidly melts at 186-188", decomposing a t 190'. Along with t h i s substance t hrre is produccrl the ?nniLhydrnzide of desjlaretoplienone, which is also formed when the pyridaziue derivative is heated with glacial acetic acid ; it crjstnllises from alcohol in slender needles, and melts a t 168', yielding when distilled, ftr conqound which crystallises in white needles, and melts at 181'.3 : 4 : 6-Triphei?~723!/1"L'!laz~~7e, CPheCPh cw :cpll>N, --E crystallises in I U S ~ ~ O U P , white plates, and melts a t 171'; i t is easily obtained whcrl the dihydro-derivative is distilled, or oxirlised with chromic and acetic acids. The subst;ince is xlso formed during the preparation of tri- phenyldiliydrop~-ridazine, aiid may be produced by adding potassium liitrite to a solution of the latter compound i n cold glacial acetic acid. With JAMES H. TAANsox-The kydi-azone of phenacyldesoxypipe- ronoin (Abstr., 1893, i.219), C3,H2,N204, crjstallises in jellow needlw, and me1t.s a t 1f;Ci'. 1 : 3 : 4 : ti-Tet.r~tphenyIdihydropy~~idazine, obtained by the action of phenylhydrazine on desylacetophenone (Trans., 1890, 647), lias been regaiaded by Klingemarir: a s having the constitution o f an anilido- py rrol ine derivatir e, yH ' CPh>N*NHPh, becanss phenjlhydrazinc converts ccp-di benzoy 1s ti1 bene into auilidotet ra plien j l p j rrolinc (hhstr., 1892, 995) ; the author describes experimmts, however, which. are i n agreement with the pyridazine forntula. The benzoyl deri.catiw, C35H26N20, crystdlises from glac.ial acetic acid in white needles, and melts ah 139-140' ; it is indiffeierit towaids phenyl hydrnaine, alco- holic potasii, and Irydrochloric acid. An additive compoimd, C,,H,,N,O,, obtained from t~trapheiirldihydrop~ri~aaine by the action o f nikroua ncid, crystallises i n p i e ellow ow ~rt.edlcs which melt and decom- pose a t 26'2'; boiling alcoholic potash converts it into a ct)nqmand which crjstallises in rhombohedra melting a t 13:3', 2nd is identical with the substance obtained by the action o f acetic chloride on tri- p h e n y 1 d i h y d 1-0 p-pid n z in e.Tei, rap h e t I J 1 d i h y d r0pj.r i d n z i II e is in d iff er- ent towards sodium in eihylic alcoliol, but is i-educed in presence of boiling amylic alcohol, yielding two compounds which melt at '212' and 1.57' respectively ; the absence of mnilinc amotig the products has been est:-1I)lislicd. Ihiliiig dilute nitric acid converrs tetmpheItyldi- hy(1ropyt iclasine into the c o n ? ~ m t ~ i i d C2JI.2,N30i3, whicli inclts and decomposes n t 25.5".1 : 3 : 4-'1'i.;~?t(~712171)?/7."=nEe is nl)tnit?cd by t.he di*y distiltntion of I : 3 : 4 : G-teti.:~ylic~i~lctiliyd~~op~I.idnzint: ; it, ci-~stnllises from glii(*i:ll acetic! ncid in small prisms, and nic-Its n t 18.5". Tbis substance diIc's not arise from the deco.rnpwit.ittn of an xnilictopyrroline derivatirc, because neither tr.ipherijlpj rruliiie nor aniline is foiirid in the distil- , ,CPh.NH CPlr:OPhOilUANlC CHEEBIISTKY. 323 1:tte ; the gas produced during distillation, moreover, is free fwm By OTTO FIPCHER and EDUARD HEFT (Ber., 1896, 29, 351-371 ; compare t h i s vol., i, 50, and Kehi.nianli, Abstr., 1895, i , 527).---The indulines and safranines are pearlily differentiated by their behnvioiir t o w a ~ d s concenti-ated sulphuric ac+id, the former giving violet or blue COIOUTS, whilst the simple safrwniiics all dissolve with a giaeen colomtion.T tie hye-products obtained in tlm preparation of indazine arid phenylmauve’ine ( A bstr., 1895, i, 608) arc probably true indiilincs, as they dissulve witli a blue colonr in sulpli- uric acid. Objection is taken to Kehrntanii’s view tltat salts of indulines and indone (rosinduline) are derired from the orthoquin- o‘idal azonium form, whilst the induliiie bases, free from oxFgen and the indoncs, are paraquinoydal anhjdrides of amido- or hj-droxy- azonium bases, The basicity of many of these compounds must be ciiie to the imido-group and not to the pheuazine nitrogen, otherwise i t is difficult to understand the feebly basic properties of aposafranone and rosindone which form no acetntes, but contain tlie gronp NPh; tlie azonium formula also indicates tlie pt escwce of a free stmido-group in the salts of aposflfraniiie and rosinduline, but the former.do not mitt with nitrous acid, aldehydes, OY ketortes. No special significance can be attached to the formation of hydrates by the above compounds, :IS this property is common to many organic base9 ; rosaniline and rosin- dulirie hydratcs closely rcseml)le one anotlier, the former is converted into the anhydrous compouud by heatingat 40--50°, o r when extracted with ether or buwene from its aqueous soluiion. The foriiiuls of apo- safranine hydi*ocltloride and rosinduline hydroxide are, therefore, ammonia, and contains but little nitrogen.M. 0. F. Indulines and Safranines. 1 2 2 tively. I t has been TJrcviously shown (Ahstr., 1893, i, 613) khat “benzcne- induline,” C,d€I,3N3, and “ phenglinduline,” CY4Hi7N3, are formed l y t h e interaction of aposafraniiie salts and aniline ; these compouirds have now been ideutified as anili~oapu,cri,f~asti?lt?, 1 iHPh.C,H, (& H) <:&> C ,H,, 2 2 former crystallises from dilute alcohol; by the action of acids, i t 2 1 5 4 N hgdroxyapossfranone, OH*CSH,O<~> CsH4, which was previously tei nied “ benzeneindonehSdr~te.” The ?)~rtkoz~--.dei.isat.ive crystallises 9in red, stellate needles or' well developed prisms, melts a t 24G--24.13, and gives an orange solution with conceutrated sulphuric acid.Anilidoplienyl~po~afranilie is fwmed iri cottsideruble quari ti ty from aniline aud aposafranine tinder the conditions previously given, but only iu. traces if alcohol is present. Paratoluidirte and aposafranine, in the absence ctf alcohol, yield paratoluidoaposafrilnine and t o h i d o - foZyZapos*\fi.anine which, from its resemblance to the pheilyl derivative, should have a similar const'itution ; it crystallises in green, lustrous plates, and melts at 23S-240°. Paraphenylenediamine and xposafranine, in presence of alcohol, yield the compound NH,*CJ€,*NEI*CaH,( $H)<sG>c6Ht, which I 5 crystallises from benzene i n bluish-green ptsisnis, melts and decom- poses at; 2 2 7 O , and gives, with concentrated sulphuric acid, a reddislt- riulet coloration which changes to red on dilution. The If ydyochloride i s crystalline, arid, in aqueous solution, has a brownish-red colou~*.By the action of dilute sxilphupic acid a t l i O o , the base is resolved iuto par,zpheiiylenedinmirie and lrydroxPny>osafmnine. Orthophenylenediamine and aposafranine hydrochloride yield N K N - phe?zyt!$uor~ihdirtc, CGH,<--N~CGH2QN~ll>CsUI, the furmation of which is probably preceded by that of a cornpoiind isomeric with the precediirg; i t is very sparingly soluble, a n d crysialtises from ethglic benzoate in needles of a golden brohze lustre ; i n mineral acids, the soiutioii is blue, with a bluish-red fluorescence. 'l'he 1qdrot-l:loride is crystalline, and its alcoholic: solution is blue, with a red fluorescence. This s p thesis confirms the mthui 8' formulte preb iously given to the tf uoritidines, The preparation of a n il id opli eny la posa f ran in e has bc en a1 ready described (see above) ; i t is also formed from aniline and anilidonpo- s'ifraiiine, by the oxidation of azophcnine, and by the elimiiiation of t,hc ;Lmido-group from " nruidophenylinduline." The molecular weigltt in naphttinlene agrees with the above formula; the earlier determiaations were made in beiizrne solution, and the results were too low, "he nitmte crystallises in green, lustrous prisms.Amido- L viously described, but the position of the arnidwgroup JVAS not determined ; this has now been accomplished (see below). Ttic hydrocltlorid., and nitrate crystallise with 4 and l k 1 2 0 respectively. By the action of dilute sulphuric acid at 17Go on the base, amido- ~iydroxSaposiift.aniit~ (this VO~., i, r.0) is formed : the izitrate crystiil- lises in thick, greenish, lustrous prisms ; the diazo derivative yields 11ydrox.ynposaf'rnnolie wht n heated.With dilute sulphuric acid at 230--2~'~~, a n idophenyl i udulinc yields di hZld,'OL('1/Qposrf.~r?~~~~~, w 11 icli ctaystallises i n kirownish-ycltow needles, rnelts above %Oo, and dis- solves in soda with a reddish-ye~~~w coloration. With alkalis, amido- p h en y 1 i 11 d u 1 in e J i eld s I t y t l ro xy ap os H f 'ran o ue , w h ic 11 11 a s i 11 en ti !i e d a s '' eafrauo! " hf means of the methoxyderivative, wlich softens a tORGANIC CHEMISTRY. 325 210' and melts at iiC;6>, not at 240' as previously stated.A seconci base, probably cmilidosnfi.utioZ, is also formed in sniall quantity ; it crystallises in blue, lustrous prisms, and, like anilidoaposafritnone, dissolves in concentrated sulphuric acid, yjelding a dull green solution which changes successively to green and violet-i*ed when diluted. The hydrochloride is green, lu4irous, and crystalline. The constitution of amidophenylindnliue (anilidomauve'ine), as regards the position of the amido-group, is shown by the following facts : It is foivmed by the fusion of amidoazobenzene, and from azophenine and paraphenylene- diamine ; pheliosaf rauine, maure'ine, phenyl mauveine, and amido- phenylinduline hydrochlorides by the action of aniline, yield the same iriduline (m. p. 286-288O), which is the final product of the action of aniline on amidoazobenzene, pheny lamidoazobenzene, and azobenzene.The acetate of this iitduline crystallises in characteristic, flat prism9 of a coppery bronze lustre. The hydyochloyide and hydrobromide have also been prepared. The fo~mula of the induline is probably CazH3!Sc, as, in its formation from amidophenylindaline and phenylmauve'ine t Ile p rim aiy product is probably GPh: C6H3<gz> CbH3*N HPh, w h i ch 1 4 melts a t 245O, lias beeii previously described, and yields a soluble (wet ate. J. 13. T. Safranines. By GEORGE F. JAURERT (Conyt. Fend., 1895, 121 947-948 ; compare Abstr., 1895, i, 219 and 278).-The oxidation of n mixture of paraphenylenediamine and met hylmetaphenylenedi- aniinc yields the methyl derirat,ive of phenylene-red, but if meta- tolyleiiediamine is substituted for the methylmetaphenylenedinmine, > considerable quantity.It has all the characteristic properties of the safranines, dyes mordanted cotton a ponceau ped, and yields a diazo- derivative with nityoua acid. The diethyl derivative is obtained in a, similar way, and the ethjlsafranol is prepared by the action of ni trosophenol on ethylmetamidophenol. u- and p-naphthasafranols are obtained by the action of nitroso- phenol on me tahyd~*oxypheny I-a-naphthylnmine, or the P-derivative. If the sulphonic derivative of metahydpoxydipbenylamine is used, plienosafranolsulphonic acid is formed. Nomenclature of Phenazine Dyes. By GEORGE F. JALTBEI~T (Bey., 1896, 29, 414--418).---T he phenaziiie derivatives can be divided into two classes : eurhodines, with a n orthoquinonoid struc- tuye, and indulines, with a paraquinonoid structure.C. H. B. Eurhod ine. lnduline.336 ABSTRACTS OF CHEMICAL PAPERS. Et~rhodiizes.-The derivative, with an additional NH, in 3’, is to be called amidoeurhodine (“ phenylene-red ”). When the NH2 of curhodine is replaced by OH, the iiew compound is to be called mrhodoZ ; amido- and hydroxy-enrhodol have, in addition, NH, and OH respectively in 3’. Iuddines.-The 3‘-amido-derivative, amidoinduline, is the simplest possible ‘‘ safraaine.” If the NH of induline is replaced by 0, the coinpound is to be called induZouc ; amido- and hydroxy-induline (“~afraiiol’~) have, in addition, NH2 and OH respectively in 3‘. Substitution of the H of the NH-group in the middle ring is to be indicated by the vowel o ; thus, phenoindulone (“ safranone ”).I n plienylindulone some other hydrogen atom would be replaced by It is pointed orrt that in order to get a ‘‘ safranine ” dye from ail induline clerivative it is necessary that the amido-group should 50 into the para-position relatively to the a-nitrogen atom, just as, 111 order to get a parmosaniline compound from diamidotriphen?-l- methane, the third arnido-group must go to the para-position reln- tively to the methane carbon atom. Dithiazolic Derivatives. By CHARLES LAUTH ( C‘ompt. r e d , 1895, tained by Hofrnann by heating acetanilide with sulphur, contains two groups <N>C, and might, therefore, be expected to yield coloui*ing matters similar to the primulines. When treated with a mixture of nitik and sulphuric acids, it yields a mixture of two isomeric dinitro- cleriratives, one of which melts at about 210” and the other at about 290°, and this, whea reduced by stannous chloride in presence of an acid at 60-100c, yields two isomeric dilLmido-derivatives, which can be separated by the difference in their solubility in water.The less soluble of the two shows brilliant, green fluorescence in alcoholic solution ; the other is non-fluoi-escent. Both the bases and their d t s alter when their solutions are boiled, hydrogen snlphide beiug liberated. Hydrogen sulphide is also evolved when the bases are treated with an acid reducing agent. Both bases aye dyes, and impart a beautiful, yellow colonr to animal fibres, and also to unmordanted cotton. Their diazo-deriva- tives also yield a varied series of colouring matters, which d p nnmordnnted cotton ; P-naphthol-a-sulphonic acid, for example, yields a red dye with the diazo-derivative of the solnble base, and amido-x- iiaphtholdisulphoriic acid yields a blue dye with the diazo-derivative of the less soluble base. The coiours on fabrics are somewhat resis- tant to the action of acids and alkalis, but fade when exposed to light. p1 I e1131. C . F. B. 112, 11~2-1154).--The componud C6H,<N>C*C<H s S >C6€€d, ob- S C. H. R. Constitution of Tropine. By ALBERT LADENBURG (Ber., 1896, 29, 421422).-VPillstatter (this vol., i, 265) has misunderstood the author’s reasoning ; he would not otherwise maintain that tropinic acid contains ft pjridine ring with a tertiary nitrogen atom, whilstORGANIC CHEMISTRY. 327 the author has shown it to form an open chain with a secondary nitrogen atom. C. F, B. Ry RICHARD WILLSTATTER (Ber., 2896, 29, 393- 403).--Tropi.izo?ze, CHi-CO - CH,--CH, is prepared by the cautious oxidation of tropine by means of chromic anhydride in glacial acetic acid solution ; it is colourless, soon turns yellow when exposed to air, but is stable towards potassium pemnanganate ; it is readily soluble, and volatile at the ordinary temperature, and distils readily with steam if the solntion cont.ains free potash ; i t has a characteiGtic basic odour, forms flat crystals, melts at 41-42', and boils at 22P--225' (corr.). Tropine boils at, 233' (corr.). The ketone is an active base, and liberates ammonia from its salts; it forms white clouds with hydrogen chloride, and, like granatonine, gives a mirror with silver nitrate ; i t precipitates the hydroxides from copper, ferric, and aluminium salts, and with lead nitrate gives a flocculent precipitate, which becomes granular and crystalline when warmed, and dissolves readily in hot water. With phosphomolybdic acid, a greenish-yeliow, flocculent precipitate is formed; with tannin, a white one ; with potassium dichromate nncl sulphuric acid, a green coloration is obtained. The yield is 80 per ccnt. of the theoretical. The mej*cu?-ochZoyide crystallises in long, silky, lustrous needles ; the potassioiodide is at first brown and oily, but readily crystallises in prisms. The hydrochZo&de crystallises in lustrous, stellate prisms, melting and decomposing at 188-189°. The picrafe is deposited in long, lustrous, yellow needles, melting and decomposing at 280' ; i t is conveniently employed for the purification of tropinone. Tropine picidate is more readily soluble than the preceding compound, is strongly pleochroic, and gradually dect>mposes when heated. Tro- pinone platinochloride crystallises at the ordinary temperatuw in orange-red pyramids, and from hot solutions in feathery aggregates of prisms, melting and decomposing at 191-192'. The nzmv7LZoride is deposited in tabular aggregates of sulphur-yellow, microscopic prisms : it melts and decomposes at 160-170°, and, when boiled with water, deposits gold. The phenylhydrazone is oily. The methiodide forms highly refractive, crystalline aggregates, resembling those of sodium chloride, and melts and decomposes at 263-265' ; when boiled with sodium carbonate, i t is readily converted into dimethy lamine and dihydrobeozaldehyde ; the same products are obtained by treating the methiodide with silver oxide and boiling the resulting tro~~i?zone,i2etl~~Z- n inmoniunz hydroxide, which is strongly alkaline. The dihydrobenz- aldehyde appears to be identical with Einhorn's A"6-co~npound from anhjdi~ecgonine dibromide. The aurochloride of tropinone methochlode crystallises in yellow prisms, melting and decomposing at 203-206°. Tropinoize oxime crystallises from light petroleum in slender, stellate prisms, melting at 111-112'. It has both basic and feebly acidic properties, and readily reduces silver salts when warmed with them. The hiydroch7oride crystallises in prisms and melts and decomposes at 242'. The methiodide is dcposited in long, colourless, highly refiinctiro Tropinone. ,CH*-CK, \CH2*NMe'328 ABSTRACTS OF CHEMICAL PAPERS. prisms.; it melts at 236‘, but a portion decomposes previously, and is more stable than tropinone niethiodide, as it is not decomposed when boiled with alkali. The ctwochlon’de of the methochloride crystallises in slender, pale yellow prisms, melting and decomposing at 182”. The nn2nzonium hydroxide reduces silver salts, but is not decomposeci by alkali. The preceding results are in complete accord with Merling’s formula for tropine, but not with Ladenburg’s, which indicates that it is a pyimary alcohol (compare this vol., i, 65). The relationship of tropine to tropinone and tropinic acid is similar to that of borneol to camphor arid camphoric acid, and tropinone shows a striking analogy with granatonine, C,Ht&O (Tanret’s pseudopelletierine) , both in general properties and derivatives ; granatonine methiodide, fol* example, yields, by the action of alkali, dihydroacetophenone. The formula given above for tropinone corresponds with that regarded by Blerling as the more probable for tropine, but, as the position of the hydroxyl group in this is undetermined, the alternative formula, CHLCH,-CO- CH, may prove to be correct. ‘CH2*N3ie’ J. B. T. Replacement of the Hydroxyl Group in Cinchona Alkaloi’ds by Hydrogen. By W r m E m KOENIGS (Ber., 1896, YT2-374 ; com- pare this vol., i, 264).-Quinine and cinchonidine, when treated with phosphorus pentachloride, yield the compounds OMe*CgNH3*Clc,Hl5C1N and C9NH6*CloH13ClN respectively, from which, by the action of iron filings and dilute sulphuric acid at the ordinary temperature, deoxypzcii~he, OMe*C9NHj*CloHr6N, and deosycinchonidi?ze, C9NHG*CloH16N, are formed. No anhydro- bases are produced, as in the case of cinchonine. Deoxyquinine cr-j-stallises from ether or dilute alcohol Eith Z&H,O, in colourless, slender needles, melts a t about 52’, aud deliquesces over sulphuric acid; in dilute solution, it fluoresces like qninine. The salts are readily soluble, and crystailise with difficulty ; the plc6finochlor~dc darkens without melting, at 260’. The hydriodidc is cryst~lline. Deoxycinchonidine crystallises in colourless, rhombic plates, and melts at 61’. The p l n finochloride, zincochloiide, cadiniochloi-ide, and inemcri- chloride crystallise readily in needles. 30th bases give the quinine reaction with chlorine water and ammonia. Quinine and ciiichonidine are It~vorotatory, conquinine and cinchonine dextrorotatory ; all four chlorides are dex trorotatory, as are the anhydro-bases quinenine, ciiichonidenine, quinidenine, and cinchenine, but the sign of rotation of the deoxy-bases is the same as that of the alkaloids from which they are derived ; these facts accord with Pasteur’s view, that the alkaloids cbntain two asymmetric carbon atoms in the LLsecond half ” of the molecule ; t o one of these the hydroxyl group is probably linked, and, 8s the deoxy- and anhydro-bases differ in the sign of their rotation, this carbon atom must be a tertiary one. ,CH,C Hz, J. B. T.

ISSN:0368-1769    

DOI:10.1039/CA8967000269

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

ANALYTIClAL CHEMISTRY. 271 A n a l y t i c a l Chemistry. Apparatus for Gas Analysis. By OTTO BLEIER (Bey., 1896, 29, 260-263; compare this vol., i, iO).-The author describes a form of the Orsat-Mueuke apparatus modified in accordance with t h e principles laid down in his previous paper. The measuring tube is connected below with a three-way cock, so that the water can be slowly run out, and be replaced by the gas to be analysed. A two- way cock is attached to the top of the measuring tube, and serves to connect the tube with the pipettes,or with the vessel from which the sample of gas is to be taken. The first two absorption pipettes are also fitted with three-way cocks. The advantages of the apparatus are that time is saved by the automatic measurement of the gas, and that the solubility of the gas in water introduces no error.An apparatus is also described which can be used for gas titration, or for complete gas analysis. The glass bulb A (see Fig., next page), of 500-600 C.C. capacity, has attached to its upper end a two-way cock, and to its lower a three-way cock, which is attached by india-rubber tubing to the measuring tube 13. An exhausted flask, C, can also be sttached to the three-way cock by means of the tube n, which also serves so empty the bulb of any liquid. For a gas titration, the bulb is Byst dried, and then the gas is introduced, either through p or n, according as it is heavier or lighter than air, and is allowed to pass through for a short time till all the air is displaced ; it is then measured at atmo- spheric temperature and pressure.If it is not necessary to meamre272 ABSTRACTS OF CHEMICAL PAPERS. the absorbent liquid (for example, water for ammonia or hydrogen chloride, sodium hydrogen carbonate for sulphurous anhydride), it is r u n in from the.cup 0, and finally run out through m into tho exhausted flask, the bulbis mashedout with water, and the wash- ings are also run into the flask. The con- tents of C are then titrated in the usual way. If it is neces- sary to measure the amount of absorbing liquid used, this is ac- complished in B, care being taken to remove all the air iu the rub- ber tube by allowing a small quantity of the liquid to flow out. through n. If the tip- paratus is to be used for absorption analy- sis, the gas is mea- sured by the replacement of water in the bulb, the absGrbing liquid is placed i n B, and the absorption is then measured by diminution of liquid in €3.After one absorption, the liquid can be removed, the measuring tube washed out, and then filled with the second ab- sorbent. J. J. S. Apparatus for Quantitative Electrolysis. By MAX GROGER (Zeit. nngzc. Cl~em., 1895, 625-626) .-The apparatus consists of a battery glass 80 mm. wide, SO mm. broad, and 120 mm. high, through one short side of which passes a horizontal platinum wire, 1 mm. thick, and 70 mm. long, from which is suspended the cathode. This consists of a carefully weighed square of platinum foil (12 grams in weight) reaching nearly to the bottom of the glass. On the opposite side to t h e long wire is fixed a short, bent wire, from which is suspended the anode, which consists of a 1 mm.thick, looped platinum wire, weighing about 16 grams : this is first bent rectangularly, the ends being finally twice bent upwards and downwards so as to form a series of loops on each side of the cathode. The galvanic current is admitted from the outside through connecting pieces attached to these wires. During the electrolysis, the glass is covered, to prevent loss by spirting, the cover being occasionaily rinsed. The principal advantage of the appa- ratus is the cheapness of the electrodes. L. DE I(. Estimation of Water in Silicates. By PAUL JAWASCH and P. WEIKGARTEN (Zeit. anmy. Chenz., 1895, 11, 37-39 ; compare Abstr.,ANA LPTICAL OHERlISTRY. 273 1895, ii, 325).-The authors have modified their process of estimating the water in silicates by heating them, mixed with dry borax, in a current of dry air, so that the sample employed may be used for the estimation of other constituents.The method is identical with that previously described, except that the mixture of silicate and borax is heated in a platinum boat; i t is essential that t,he mixing be very thorough. E. C. R. Citrate Method of determining Phosphoric acid. By F- BERGAMI (Exper. Stat. Record, 1895,7,180-181; from Journ. Franklin r72st., 1895, 140, 139--152).-The method, which is especially for insoluble phosphates, is as follows. The substance (2 grams) is boiled with a mixture of strong nitric (40 c.c.) aad hydrochloric acids (10 c.c.), diluted to 250 c.c., and aliquot parts of the solution, corre- sponding with 0.2 and 0.4 gram of substance, are mixed with 20, 50, 75, and 100 C.C.respectively of Marcker's citrate soluiion, prepared by dissolving citric acid (250 grams) in water, adding 24 per cent. ammonia (500 c.c.), and diluting with water to 1500 C.C. 25 C.C. of official magnesia mixture is then added, the whole well stirred for half an hour, and the precipitate treated as usual. The results depend largely on the amount of citrate solution cmployed. With high grade phosphates (20 to 30 per cent.), the best results are obtained by using 50 to 75 C.C. of citrate solut,ion for 0.2 gram of substance, or 75 C.C. to 100 C.C. for 0.4 gram. Slightly lower results were obtained than with the molybdate method, probably owing t o an excess of citrate.N. H. J. M. Rapid Estimation of Insoluble Phosphate. Bp VINcEm EDWARDS (Chem. News, 1896, 73, 25) .-Although not advocating the substitution of a volumetric for the gravimetric method of esti- mating insoluble phosphate, Set the following method is submitted as satisfactory. The residue, from the exhaustion oE 0.5 gram of the substance with cold and hot water, is boiled for a short time in water containing a very small quantit,y of hydrochloric acid, filtered, made up t o 300 c.c., rendered alkaline with ammonia, and then faintly acidified with acetic acid. Thesolution is then placed on a sand bath and titrated hot with standard uranium acetate of the strength 1 C.C. = 0.01 gram Ca3P208. D. A. L. Testing for Arsenic in Alloys of Tin and Lead. By LEONARD DE KONINGH (Ned.Tydschr. Phawn., 1895, 7 , 380--331).-The alloy is distilled with hydrochloric acid and ferric chloride i n a small retort., connected witah a large Peligot tube containing a little water. It is advisable to apply but a rery gentle heat at first, so that the solution may take place a t the expense of the chlorine of the ferric chloride ; the evolution of hydrogen is then hardly noticeable, and the forma- tion of arsenic hydride is reduced to a minimum. Finally, the liquid is distilled nearly to drynem ; the arsenic in the distillate may be at once precipitated by hydrogen sulphide. L. DE K.274 ABSTRACTS OF CHEMICAL PAPERS. D A C - - Apparatus for the Estimation of Sulphur in Iron. By E. J. READ (Chem. News, 1895, 72, 299). -The end of the tube D is adjusted in the flask C, so that some of the absorbing liquid is forced up among the beads by the passage of the gas, evolved from the sample in the flask A, by the action of the acid from B.The apparatus is preferably used under reduced pressure. D. A. L. Estimation of Sulphur and Carbon in Zinc. By ROBERT FUNK (Zeit. anorg. Chem., 1895, ii, 49-58 ; compare this vol., ii, 247).-The sulphur is estimated as follows. About 20 grams of the zinc is dis- solved in pure hydrochloric acid, and the gas evolved passed through a Pettenkofer’s tube (50 cm. long), contaiuing a mixture of equal volumes of a solution of zinc sulphate (2 per cent.) and am- monia (0.5 per cent.). The contents of the tube are transferred ts a glass cylinder, acidified with hydrochloric acid, and mixed with 1 C.C.of a solution of paramidodimethylaniline in hydrochloric acid (1 : SOO), and a few drops of a solution of ferric chloride (10 per cent.). If sulphur is present, a coloration of methylene-blue is produced, and this is compared with the colour produced by a known quantity of hydrogen sulphide. Jn order to remove any sulphurous acid or hydro- gen sulphide which may be present, the hydrochloric acid employed must first be boiled with a small quantity of potassium chlorate, and the excess of chlorine removed with pure zinc or alcohol. Various samples of purified zinc, when examined by this method, were found to contain from 0 to 2.5 parts of sulphur in 10,000,000 parts of zinc. The carbon is determined by burning the zinc with copper oxide. A combustion tube, closed at one end, is charged with a column, 8 cm. long, of freshly fused potassium chlornte, then with a column of granular copper oxide, followed by the zinc in a porcelain boat, and another column of copper oxide.The tube is exhausted by means of a mercury pump, and after the front column of copper oxide has been heated to redness, the zinc is volatilised. When the zinc is entirely volatilised, the potassium chlorate is cantiously heated ; the evolved oxygen is at first entirely absorbed by the metals ; when this absorp- tion ceases, which is indicated by a mercury manometer, and the pressure in the tube reaches that of the atmosphere, the gas is allowed t o pass through a Pet,tenkofer’s tube, containing st solution of barium hydroxide or basic lead acetate.The sample of zinc to be tested is first washed with hydrochloric acid, and then dried in a current of hydrogen. By the above methods 1 part of sulphiir in 10,000,000 parts of zinc aiid 1 part of carbon in 100,000 parts can be detected. The purifiedANALYTICAL CHEMISTRY. 275 zinc of commerce contains distinct traces of sulphur and minute traces of carbon. These impurities are not soluble in the metallic zinc, and can be completely sepn'rated by filtration through asbestos. E. C. R. Estimation of Sulphurous Anhydride in Carbolic Powders. By LEONARD DE KOKINGH (Ned. Tydschr. Pkcirrn., 1895, 7,329-330).- Ten grams of the sample is distilled with hydrochloric acid, and the distillate is condensed in a large Peligot tube containing a little water and a sufficiency of bromine.The distillation is continued until the bromine has been nearly decolorised by the action of the phenol 01' cresol vapours. After filtering, the liquid is precipitated by barium chloride, and the precipitate calculated into sulphurous acid. When testing carbolic powders, it must be remembered that the greater part of the sulphurous acid may have been lost either through Separation of Quartz from other varieties of Silica. By GEORG LUNGE (Zeit. angw. Chem., 1895, 593 ; 689-690).--8 reply t o Michaelis stating that aqueous sods decidedly attacks quartz, and that in any case it i s much the same thing from an analyst's point of view whether the finely divided quartz is lost by actual solution or by mechanically passing through the filter.evaporation or oxidation. L. DE I(. The author still prefers using sodium carbonate. L. DE K. Detection and Estimation of Barium Sulphate. By LEONARD DE KONINGH (Ned. Tydschr. Pltarm., gc., 1895, 7 , '257).-To test in- soluble siliceous matters for admixed barium sulphate, the author recommends heating with strong sulphuric acid, which soon dissolves the barium compound, and leaves the silicate wholly, or partially, insoluble. After decanting, or filtering through a suitable medium, the barium snlphate may be completely recovered by diluting with water, If the mixture should contain lead, recognisable by the ammonium sulphide test, this must first be removed. L. DI K. Volumetric Method for Lead Analysis. By ALFRED C. BEEBE (Chew.. News, 1896, 73, 18).-The substance is dissolved in nitric acid, with a little hydrochloric acid, if required, evaporated with sulphuric acid until white fumes of sulphuric azhydride are evolved, diluted, cooled, an equal volume of alcohol added, and, after a short time, filtered, and washed well with hot water.The precipitate is digested, with frequent and vigorous stirring, for 15 minutes, in it cold saturated solution of ammonium carbonate, filtered, the lead ear- bonate washed thoroughly with hot water, dissolved in hot dilute acetic acid, cooled and titrated with a 1 per cent. solution of potassium ferro- cyanide, using uranium acetate acidified with acetic acid as the indicator. I n this method, barium and calcium are harmless ; arsenic, iron, copper, and zinc should be eliminated in the thorough washing of the load sulphate ; whilst antimony could be removed by the use of tartaric acid in the decomposition of the substance.D. A. L.276 ABSTRAOTS OF CHEMICAL PAPERS. Estimation of Maxganese and Tin by Electrolysis. BmY CAR r. EKGFLS (Bey., 1895, 28, ~112-31s9).-Jian~anesc peroxide is deposited in a perfectly coherent form when 10 grams of arnmoniurn acetate and 1.5-2 grams of chrome alum are added to a solntion of manganese sulphate containing 0.2-0.25 gram of manganese in 150 C.C. water. The electrolysis must be carried out in a platinum vessel with a matt surface, a current density of 0.6-1 amphre, and an electromotive force of 3-4 volts being used. The deposit is washed, ignited, again washed to remove small trace9 of chromium compoiinds, and finally heated and weighed. Alcohol and ammo- nium acetate also produce good and coherent deposits of manganese peroxide.The addition of a hydroxylamine salt to an acid aolution of a manganese salt prevents the deposition of manganese peroxide, and thus enables sevei-a1 separations to be carried out. Tin can also be readiIy obtained in a coherent film by electrolysis, adding to the ~olution hydroxylamine sulphate, together with a little ammonium acetate and tartaric acid, a current density of 0-5-1 ampere and an electromotive force of 4-6 volts being used. The methods proposed for both manganese and tin appear to give excellent quantitatire results. A. H. Analysis of Chrome-iron Ore, Ferrochromium, and Chrome- steel. By SAMUEL RIDEAL and SIGMUND ROSENBT~UJT (Chem.News, 1896, 73, 1-2).-The authors review the past work on, and give a biblio- graphy of, this subject. They point out that finely powdered chrome- iron ore and ferrochromium may be decomposed by fusing with sodium peroxide, in the first case for five, in the second for ten, minutes, and in both cases allowing to cool slightly, adding more peroxide, and heating again. Before the subsequent titration, the solution Ahould firstly be boiled for 10 minutes, then acidified, and finally filtered, if necessai-y. D. A. L. Technical Analysis of Cyanide Working Solutions. By WIJ,LIAM BETTEL (Chem. News, 1895, 72,298-299 ; compare this vol., ii, 224) .-Simple or readily decomposable complex cjanides are not affected by dilute pcrmanganate in an acid solution and in the absence of organic matter, butferrocyanides and thiocyanates are rapidly oxidised.Therefore, to estimate the latter, the quantity of both is first ascer- tained by tityating 10 o r 20 C.C. of N/lOO permanganate, strongly acidified with sulphuric acid, with the cyanide solution; then the proportion of thiocyanate is determined by removing the fen-ocyanide from 50 C.C. of the cyanide solution by means of acidified ferric chloride or sulphate, and titrating with N/100 permanganate. Oxidisable o q a n i c matter in solution is estimated by digesting 50 C.C. of the solution for a n hour at 60-70" with a large excess of strongly acidified N/lUO permanganate, then cooling, and titrating back with rz standard thiocyanate solution, of a strength such that 1 C.C. = 1 C.C.N/lOO permanganate. The amount of organic matter is approxi- inately nine times the oxygen consumed in excess of that required by the ferrocyanides and thiocjanates present. The organic matter can be removed by shaking with quicklime and filtering.ANALYTICAL CHEMISTRY. 277 AZliaZinity. -With NjlO acid and phenolphthnlelii as inciicator, all the polassium cyanide, 7.9 per cent. of t’hc potassium zinc cyanide, and the potassium in potassium zinc oxide are estiiiiated ; with methyl orange as indicator, a11 the zinc in potassium zinc cyanide, the zinc and potassium in potassiuni zinc oxide, arid the hydrogen carbonates are estimated. When a caustic alkali o r n cayboilate is added to a, working cyanide solution containing zinc, the following changes ensue: K2ZnCy4 + 4KHO = ZnK202 t 4KCy and K2ZnCy4 + PNa,CO, + 2H,O = 2KCy + 2NaCy + ZnNa202 + 4XaHC0,.The hydrogen carbonates have no action on potassium or sodium zinc cyanide, which is only partially decomposed by calcium or magnesium hydroxides, so some alkalinity towards phenolphthaleln may be due to the former compounds in the presence of.potassium zinc cyanide. If lime or magnesia is added to a solution containing sodium hydrogen carbonate and potassium zinc cyanide, the zinc remains in solution as sodium zinc oxide, and the percentage of cyanide is correspondingly increased. Pervicyanide is estimated by reduction with sodium amalgam and titrating t h e resulting ferrocyanide. Szdphide is estimated by agitating with precipitated lead carbonate and titrating with permanganate ; loss above that due to ferrocyanides, thiocyanates, &c., is due to the sulphides eliminated.Ammonia is estimated by precipitating all the cyxnide compounds in 10 C.C. with silver nitrate, adding hydrochloric acid, making up to 100, shaking, filtering, distilling 10 C.C. OF the filtrate with 150 C.C. of water, and Nesslerising the distillate. Methods for dealing with urea, oxsmide, and formates are under investigation. A few specimen analyses are appended to the paper. L>. A. L. Estimation of Fuse1 Oil in Rectified Spirits by Rose’s Process. By N. GLASENAPP (Zeit. angzu. Chem., 1195, 657-663).- The author has made a thorough investigation of Rose’s chloroform process, and finds that, although it works v e ~ y well for the cruder samples of spirits, it is only by taking extraordinary precautions that trustworthy results can be obtained with the purer kinds.The author’s shaking apparatus is made of such a weight and shape that, when filled and plunged into water, it sinks down in a vertical position, so that, after some time, the contents will acquire the exact temperature desired. Even if the measuring tube is niost carefully graduated, no two apparatcs will agree, unless they arc! exactly of the same capacity. The reason of this is that, during the shaking, the air becomes saturated with chloroform vapour, and the aiiiount t h u s lost will be, of course, proportionate to the bulk of the air. Every apparatus must, therefore, be carefully calibrated. Another impor- tant item is the time allowed for the chloroform lajer t o separate ; the author advises waiting for at least o m hour.The greatest difficulty of all is to obtain a st,andsrd alcohol really free froin fuse1 oil, and it is doubtful whether such alcohol has ever, as yet, been obtained. The only plan is to keep on rectifying until the fractions give a constant result, when tested in the apparatus. It is also of the utmost importance that the spirit to be tested should be diluted to a sp. gr. of 0.96564 at VOL. LXX. ii. 20278 ABSTRACTS OF CHEMICAL PAPERS. 1 5 * 5 O , and for this purpose it is not sufficient to use n Westphal balance, but a very delicate specific gravity bottle should be used. Particular stress is lait1 on the 1icceesit.y of' thoroughly cleaning the instrument before making a new expei.iment'. A mixture of sulpliuric and Nordhausen acid is recommended f u r this purpose.L. DE K. Estimqtion of Sugar. By G. OPPERMANN (ETpei-. Sfat. R e c o d , 1895, 7, 184:; from Apoth. Zeit., 1895, 10, 216).-The method in which t h e cnprous oxide is reduced with hydrogen and weighed as copper is modified as follows. The cuprous oxide, filtered in a tube packed with asbestos, is well washed, and dissolved in moderately strong nitric acid. avoiding a great excess. The copper is precipi- tated electrolyticallj, washed, dried, and weighed. N. H. J. IT. Influence of the two Lead Acetates on the Estimation of Invert Sugar by the Fehling-Soxhlet Method. By ARTHUR BORNTR~KR (Zeif. nizgu.. Chenz., 1895, 594--596).--The author has tnbulat ed several experiment., with invert sugar solutions containing an excess either of lead acetate or of basic acetate. It appears that, when titrating in the well-known way with Fehling's solution, the presence of decided quantities of lend causes n serious decrease in the pcwxntage of sugar (compare also Abstr., i: F95, ii, 143, 296).L. DE K. Estimation of Cellulose. By GERI~ARD TJAWE (Zeit. aiz?zu. Chem., 1895, 5G1-563),-5--- 10 grams of the substance, fodder, foy instance, is moistened with 8 little water, mixed with three times its weight, of sodium hydroxide and another 20 C.C. of water, and then fused in a large, uuglazed, porcelain crucible, p r t i a l l y immersed in an oil bath. After putting on a perfprated lid, through which passes a thermo- meter, the temperature is raised to 175-18Uo, and kept so for a n hoar.The principle of t h e process is that, at this temperatui-e, the cellu- lose is not chemic~lly acted on by the alkali. After slight cooling, t-he contents are digested in dilute sulphuric acid, and, after again rendering alkaline: with soda, the whole is introduced into a large ceiitrifupl tube and thoroughly whirled. The cellulose rapidly separates, and, after pouring off the supernatant liquid, i t is once mare waslied by whirling with hot water, then washed with alcohol and ether, dried, and ceighed. Allowance must be made, as usual, for any mineral matter. If t h e sample should be rich in fat, this may with advantage be first extraceed. L. DE K. Forensic Chemistry. By GEORC DRAGEBDORFF (Arch. Phcrrm., 1895, 233, 6 12--6;-30).--The ethereal salts of guaiacol, naphthol, cresol, &c., are readily extracted from their acid aqueous solutions by light petrolcwm 01- benzene, b a t , when mixed with large quantities of organic mattel*, 3i'c' best first separated from the latter by means of alcohol.Guaincol benzoate (benzosol), when moistened with concen trdted sulphiiric acid, jields a reddish-purple colour with acetone ; withANALYTICAL CHERIISTRY. 279 ferric chloride a violet colour, striped n ith green and violet-blue ; an orange and green colonr wit11 nitric acid ; n peen, violetJ, and yellow colour with potassium nitrite ; a bright red colour with cane or grape sugar; a violet to red colour with Friihde’s reagent ; and a violet, green, and blue colour with sulphovnnadic acid.Gnaiacol salicylate yields a violet colour with ferric chloride and a bright red colour with concentrated sulphuric acid, changing to green, violet, and I-ed on the addition of nitric acid. When nioisteued with concentrated sulphuric acid, it is coloured green, blue, and r e d by potassium nit>rite, and bright red by acetone. Sulphovanadic acid gives a bluish-black colour, Friihde’s reagent, a violet, clmngincr to green. Guaincol cinnaniate dissolves i n concentrated s u lpharic acid with a yellow coloiir, changed t o orange by nitric acid, to violet and green by potassium nitrite, and to violet by acetone. Guaiacol cinnamate is less soluble in light petroleum thau the salicylate, and is further dis- tinguished from the Iattcr by its ready conversion into benzaldehyde hy alkaline pemmnganate. Guaiacol itself‘, when pui e, dissolves i n concentrdted sulphuric acid, yielding a colourless solution, which is coloured red to brown by niti4c acid.violet and green by potassium nitrite, green by potassium selennte, blue-green and violet by sulpho- vanadic acid. With Frohde’s reagent, guaiacol yields a green snd violet colour ; with alcoholic ferric chloride, n blue and emerald-green coloiir ; and with permanganate aud hydrochloric acid, a cherry-red to brown colour. It is colonred green by aqueous fewic chloride, and the spectrum of the solution shows an absorption band in the red and orange (654-610p), a slight shading a t 595 p, and a further slight absorption in the violet and indigo up to 450 p. Alphol (a-naphtliylic salicylate) dissolves in concentrated sulpliuric acid with 3, yellow coloration, changed to blue, green,aud red by nitrates and nitrites ; conversely, the reaction serves as a delicate test for thzse salts.The absorption spectrum shows a band from the violet to the green (500 p), and a band in the red (680--650 p). A mixture of alphol and concentrated sulphuric acid is coloured purple by aqueous furfuraldehyde, and cherry-red by cane bugar, the colour in the latter case being chnnged to blue by ammonia. The sulphuric acid mixture is tiirned green by ferric chloride, yellow by acetone, and fluorescent green by iodoform. Frohde’a reagent gives a green coloration with alphol, sulphovanadic acid a green colour, changed t o reddish-brown by the addition of water, and sulphuric acid with am- monium uranate green, changing t o greyish-brown on heating.Alco- holic alphol is colourecl violet by ferric chloride, and, on warming, blue by chloroform and caustic soda. Betol (/3-naphthylic salicylate) dissolved in concentrated sulphuric acid yields a characteristic colour on the addition of a crystal of chloral hSdrate, the orange coloration a t first produced changing to reddish-violet :tnd then to red with green fluorescence. The other reactions resemble those of its isomeride. [j-Naphthylic benzoate is coloured yellow by concectrated sulphuric acid, but dissolves, on warming, to a violet solution, having a green fluorescence. This solution is coloured dark brown by nitric acid, and, by potassium nitrite, violet, changing to red and blue; it is D280 ABSTRACTS OF CHEMIOAL PAPERS.coloured violet and red by ferric chloride, bluish-violet by ammonium molybdate, changing to red, green, and blue; violet by Frohde’s reagent and sulphovanaciic acid, the colour in the latter case changing to red and blue ; green to oranse by chloral hydrate, purple to violet by aqueous furfnwldehyde, violet by tho sugars, and jellow by acetone. The benzoate is coloured blue when heated with chloroform nnd ulcohplic soda. p-Naphthylic carbonate gives much the same reactions as a- and /%uaphthol. The tolylic benzoates mid salicylates give reactions of fhe same character as the corresponding salts of guaiacol. The reactions of rnrious amido-derivatives, such as paracetamidophenylic salicylate, are also described in similar det,ail.JN. W. Detection of Formaldehyde. By G. ROMTN (Ned. T!jdschr. Phamn., $c., 189.5, 7, 169--17,5).-The article of food, milk for instance, is snbmitted to distillation. Alt.hough a portion of the formaldehyde is retained by the albuminous matters, a little of it is sure to pass over with the distillate, and may then be identified as follows. A drop of the liquid is mixed on an object glass with a drop of ammonia, and evaporated to drjness ; the crystalline residue, when examined under the microscope, will be found t o consist, not of rhombohedra, but of regular c r j s tals if formaldehyde was present. It is then moistened with water, and treated with either of the follow- i ng reagents. Mercuric chloride in excess a t once gives a precipitate ; in a short time, three, four, or six-sided stars are noticed, afterwards octahedra.This test still shows a t a dilution of 1--100,000. Potassium mercuric iodide and dilute hydrochloric acid give hex- agonal, six-angled, pale-yellow stars ; this reaction is ohtained at a dilution of 1--10,000, but not when it reaches 1--100,000. Platinic chloride gives regular octahedral crystals, much resembling ammonium platinochloride, but darker in colour ; the reaction is just visible a t a dilution of 1--20,000. Phospliomolybdic acid gives right, rhombic crystals, very character- istic at a dilution of 1-10,000. Potassium bismuth iodide and dilute hydrochloric acid gives regular crystals, mostly octahedra. The yellow precipitate is formed at once, a t a dilution of 1--1,000; but only slowly when a t a dilution of Stannous chloride ancl strong hydrochloric acid give rhombic needles and crystals.The reaction is very strong in a 1 per cent. solution, and just risible when at a dilution of 1--1,000. Potassium iodide containing iodine gives rectangular plates and aggregations of the rhombic system, very distinct a t a dilution of 1-1,000, but no longer visible a t 1-10,000. When the dilution 1--10,000. Picric acid gives needles, probably rhombic. Volatility of Fatty Acids and Laws Deduced therefrom. Bg HENRY DROOP RICHNOXD (Analyst, 20, 193-198 ; 217--229).--The author has tabulated a number of results obtained by distilling the reaches 1--1,000, they only form after some time. L. DE K.ANALYTICAL CHEMISTRY. 281 mixed fatty acids of butter under rarying conditions, and mathematical equations w e given to explain the results.I t appears that in the well-known Eeichert- Wollny process only about 87 per cent. of the t,otal volatile acids is found i n the distillate. L. DE I<. Estimation of Uric acid in Urine. By MARTIN KR~~GEH (Zeit. plLysioZ. Chcni., 1895, 21, 311--318).-The following method, based on the author's previous work, is recommended. One hundred C.C. of urine is taken, and the nitrogen of the uric acid, phis that of alloxuric bases, estimated. This is done by adding to the boiling urine 10 C.C. of sodium hydrogen sulpliite solution, 10 C.C. of copper sulphate (10 per cent.) solution, and 5 C.C. of barium chloride (10 per cent'.) solution. The mixture is boiled f o r three minutes, and allowed to remain two hours ; the precipitate is then collected, washed with hot water, and it's nitrogen estimated by Kjeldahl's method.I n another specimen, the urine is first freed from uric acid by adding sodiuni carbonate until a flocculent precipitate forms, and then 5 C.C. of' 10 per cent. acetic acid is added. The nitrogen of the alloxuric bases is theii estimated, and this, subtracted from the nitrogen obtained in the first experiment, gives the uric acid nitrogen by difference. There are various safeguards introduced when this is applied to pathological urines. The results given come out very nearly the same a s those obtained by the standard Salkowski-Ludwig process. Iodine and Bromine Absorptions of Linseed Oil. By Row- LAND WILLIAMS (Aizalyst, 20, 276--277).--The author states thnt the iodine absorption of raw linseed oil is much higher than is geusrally believed.An examination of several hundred samples of undoubtedly genuine origin gave figures varying from 180 to 190 per cent. of iodine. The author attributes the low figures of other observers to the fact, which is not sufficiently appreciated, that it is absolutely necessary to use a large excess of bhe Hub1 reagent, and to let this act for a t least 18 hours. As regards the bromine absorption, the author strongly recommends the gravimetric process proposed by Hehner (Abstr., 1895, ii, 428), as the results are more trustworthy than those obtained by the volumetric method. When applying the iodine or bromine absorption process to the assay of boiled linseed oil, it must be remembered that both absorptions are considerably lessened by the boiling. Saponification in the Cold.Saponification Numbers and Reichert-Meissl Numbem. By ROBERT HENRIQUES ( X e i t . angw. Chew., 1895, i21-i24).-T1he author rccominends the following modification of the lieichert-Meissl process. Yire grams of the fat is put, into a porcelaiu dish, and dissolved in 25 C.C. of l i g h t petroleum, 25 C.C. of 4 per cent. alcoholic soda is added, and the dish is covered, and allowed to remain over night; the liquid is then evaporated to com- plete dryness on the water-bath, and the powder transfei-red to the distilling flask. After rinsing the basin with the prescribed amount of \rater, t h e process is conducted as usual. No volatile ethereal salts are formed in the cold process.The small amount of carbonic W. D. H. L. DE K.282 ABSTRAOTS OF CHEMICAL PAPERS. anhydride absorbed from t h e air does not inflnence the result. The process may also be used foi. taking the saponificaiion number ; for this purpose the f a t is dissolved in ;L stoppered flask as directed, allowed t o remain for 24 Iio'ilrs, and the excess of alkali titrated ; if the mass should have becomc somewhat too solid, the addition of some mow alcohol and pent'le warrniiig will lw found useful. Wax must be dissolved in hot, light petroleum (boiling point, 100-150") before adding the soda. I d . DE K. reizd., 1895, 121, 646--647).--No method of precipitation with soluble gelatin or a metallic salt will remove the whole of the tannin from a solution ; this can o d y be effected by means O F animal meni'cranes, such as the g u t cords used i i i Girard's process.The sensitiveness rcquired in dealing with dilute solutioiis like wines is obtained by combining Girard's process with the use of pernianga- nate. One hundred C.C. of champagne or ocher wine containing a similar quantity of tannin (01' of stronger wines previcusly diluted with a known volume of water) is allowed t)o remain in contact with 1 gram of g u t cords for about a week in a well-closed flask. The liquid is then titrated by ineans of permanganate solution, 1 C.C. oE which is equivaleiit to 0.02 milligram of pure gallotannin, indigo solution being used as tlie indicator. The difFerei:ce between t h e volumes of' permanganate solution required by a given volume of wine before and after thc removal of t h e tannin gives the quantity of =no-tannins present, in ternis of gallotannin.In champagnes, the quantity varies from 8 milligrams to 50 milligrams per litre. The g u t cords for this process are prepared by washing unoiled violin striiigs with dilute alcohol, dilute acids, and water until these solveuts no longer remove anything thatt reduces potassium permanganate. C. H. B. Titration of Alkaloids with Iodine Solution. By CARL KIPPEXBERGCB (Zeit. anal. Chem., 1€!96, 35, 10-27).-1n a, former paper (Abstr., 1895, ii, 465), it was stated that when R salt of a n alkaloi'd is mixed with a solution of iodine in potassium iodide, only the free iodine is concerned i n the formation of the alkaloid pey- iodide, Alk,HT,I,, three atoms of iodine being consumed for each molecule of alkalo'id.The author now investigates the rcaction more closely. When the iodine solution is prepared with the smallest possible quantity of potassium iodide, the results present consider- able irregularities : t h e precipitate contains free iodine in larger or smaller amount as the excess of iodine solution used is larger or smaller ; the amount of potassium iodide decomposed is sometimes larger and sometimes smaller than would correspond v i t h the equa- tion Alk,HCI + KI + I2 = Alk,HI,12 + KCI: and the amount of free iodine consumed is considerably larger than is the case when more iodide is present. By adding either a laige excess of hydriodic acid or of potassium iodide, especially when the free acid in the alka- loid solution has been nearly neutralised, the consumption of free iodine falls, in the case of strychnine, to 2 atoms.With narcotine Estimation of Tannin in Wines. By E. RIAXUEAU ( C o ~ p t .ANALYTICAL CHEMISTRY. 283 andatropine, thc ainouiit consumed is always more than 2 atoms, axid varies somewhat with the conditions. For alkalo'ids other than strychnine, i t is thei.efoi*e best to standarLlise the iodine solution ngainst lcnowii quantities of dkalo'id under circumstances as closely as possible resembling those of the titration itself; but on this sub- ject a further communication is promised. 11. J. s. Estimation of Creatinine in Urine. By RUDOLF KoLrscit (Chem. Cent?.., 1E95, i, 814-615 ; froni Ceih..inn. Med., 16, 265- 269).-The estin~at~ion of creatinine has as yct received but little appreciation on account of the very imperfect analytical methods. The author proposes a new process. Two hundred C.C. of urine is precipi- tated with 20 C.C. of a mixture of calcium chloride md milk of lime and filtered. Tnro hundred C.C. of the filtrate is acidified with acetic acid, evaporated to n thick s-pip, and the residue while still warm is exhausted four or five timcs with dcohol. The solution is diluted in a graduated flask to 110 c.c., and 100 C.C. is then used for precipi- tation with mercuric chloride solution, after first acidifying witlt acetic acid. This niercnry solution is prepared by dissolving 30 grams of mercuric chloride, 1 gram of sodium acetate, and 3 drops of acetic acid i i i 125 C.C.of absolute alcohol. After nddiug enough of this solution to precipitate all tlie creati- nine, tlie precipitate is waslied on a filter with absoltite aicoliol containing a little sodiain acetate until the washings no longer become turbid when neutralised, showing that all the urea has beeii removed. Thc creatiuine is now calculated from the amount of nitrogen contained in t lie precipitate, which is best estimated by using Kjeldahl's process. Its percentage is finally found by multiply- ing by 100/81. L. n~ K. Assay of Opium. By DAVID B. DOIT ( P 7 ~ n z . J. TNWS., 1894, [3], 24, 847).-Ten grams of powdered opium is digested with 25 C.C. o f water, 1.8 grams of barium chloride dissolved in 1'2 C.C. of watel- added, and the whole made u p to 50 c.c., mixed, and, after a short time, filtered.To half the filtrate, ~*egreseiiting 5 grams of opium, just enough sulphuric iwid to precipitate the barium is added, and to the filtrate from this, enough ammonia to neutrnlise the free :wid. Thc solution is then concentrated to 6-7 c.c., and allowed t o cool ; 1 C.C. of alcohol and I C.C. of ether are next added, then aiiiruonia in slight excess. After three I~OUIS, the pmcipitate is collected on a tared filter. dried, washed with benzene or cliloroform, dried, and weighed. I t i.; then titrated with K/lO acid, until the morphine is neutralised, as indicated by the solution reddening litmus paper. One C.C. of NjlO acid = 0*0303 gr.titi of morphiiie hjdrate. R. R. Estimation of Aconitine.By J o i n C. UMSEY (Phnr,)~. J. T~ans.: 12395, [3], 25, SSO).--A4. definite -eight oE aconitine is hydrolysed by liesting oti a watw bath f o r two houis with a known volnrtie of n standard alcoholic solution of caustic alkali in a reflux apparatus. By tiiis treatment, i t is rcsoived into aconine, and acetic and benzoic acid., the latter combining with the alkali present; the amount of tlie acicls284 ABSTRAOTS OF OHEMICAL PAPERS. can then be found by titrating the unconibiced alkali. The solution is again made alkaline, the alcohol evaporated off on a water bath, and sufficient hydrochloric acid added t,o separate the benzoic acid, which is extracted by successive washings with ether, weighed, and the quantity of alkali required for its neutralisation in the first part of the process calculated.By deducting this from the total amount, the qnantity of acetic acid is found, aud the amount of cr,ystalline aconitine is thus determined. R. R. Assay of Ipecacuanha. By RICHARD A. CnrePs (Phnrnz. J. Trans., 1805, [3], 25,1093-1094).-The author refers to Paul and Cownleg’s investigations, and mentions the presence i n ipecacnanha of a fourth nlkalo’id, noted by himself iu 1891 ; he has sought in vain for Arndt’s volatile alkaloid. He finds that the proportion of the third alkaloid to the emetine and cephaeline taken together may rary from one- twentieth to one-fourth, and thinks that ipecacuanha, like other drugs containing several alkaloids, contains them in varying proportions. I n an assay, therefore, the total alkaloids should be taken into account. Lyons’ process should be the one recognised, and only tlie Brazilian root be official, this being required to yield not less than 2.0 nor more than 2-5 per cent. of alkaloids. A table shows many difiei-ent assays and their divergent results. Ehrlich’s Diazo-reaction. By RICHARD T. HEmLETT (Brit. $fed. J., 1896, i, 136-137) .-Several modifications have been proposed in the original method of testing with sulphanilic acid and sodiuin nitrite. The reaction is invariably given by the urine in typhoid fever, although occasionally it is seen in ohher diseases also. Attention is drawn t o the fact. that the test solutions must be freshly prepared before using. The nature of the substance i n the urine that gives the reaction is uncertain, and of a large number of materials examined, morphine was the only one which gives a similar red reaction, but no green precipitate forms on standing. One part of morphine in 10,01)0 of water gives the test. Colour Reactions of Proteids with Nitrous wid and Phenols. By KARL LANDSTEINER (Chern. Centr., 1895, i, 695 ; from Centr. f. phpiol., 8, 773--774).-The colonr obtained by the action of nitrous acid and phenols on proteids is attributed by Oberrnayer to the f o r - mation of diazo-compounds. The author, however, explains the re- action as follows: By acting on the hydrochloric acid solution ot’ tyrosine, first with nitrous acid, then with alkali, and firially wit11 a- or p-naphthol, a bluish-red colour is obtained. This reaction is not caused by the amido-gyoup contained in the tyrosine,> a g para- hydroxybenzoic acid also gives the test. Proteids undoubtedly fir-t R.. R. W. D. H. yield tyrosine when the reaction is applied. L. DE I(.

ISSN:0368-1769    

DOI:10.1039/CA8967005271

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

General a n d Physical Chemistry. Relation between the Intensity of Light and its Action on Mixtures of Ferric Chloride and Oxalic acid. By GEORGES LEMOINE (Compt. rend., 1895, 121, 817--819).-The author has investigated the relation between the visual intensity of light and its action on mixed solutions of ferric chloride and oxalic acid, using n system of two large polarising prisms as a means of varying the intensity of the light incident on the small cell containing the liquid. He finds that the chemical change produced is proportional to the visual intensity of the light; that there is no sensible “period of induction,” the result being the same whether an exposure of a given total duration is intermittent or continuous ; and that on cloudless days, the visual intensity of the sunlight remains practically constant for comparatively long periods (compare Abstr., 1895, ii, 249).New Molecular Refraction Formula. By F. ZECCHINI (Gazzettcc. 1895, 25, ii, 269--284).-The author has calculated the observed and theoretical molecular refractions of a long series of compounds of different types, using the formula (n3 - ___ + 2)d. The values calculated from the set of atomic refractions given, agree well with the observed molecular refractions, but the formula is not independent of the teniperat nre. W. J. P. Relations between the Composition and Absorption-spectra of Organic Compounds. By GERHARD KRUSS (Zeit. physikd. Chem., 1895, 18, 559--562).-An addition to the late author’s pre- vious communication on this subject (Abstr., 1888, 1141). The paper contains the observations on the absorption-spectrum in the case of alizarin, purpurin, quinimrin, hystazarin, anthraflavic acid, and a number of their derivatives.L. M. J. C. H. B. n2 - 1 Anomalies in the Rotatory Dispersion of Malic acid. Bg RAE’FAELE NAS~NI and G. GEKNARI (Zeit. physikal. Chem., 1896, 19, 113-129) .-Anomalies having been previously observed in the rota- tion of this acid, the authors investigated the optical phenomena by means of a Landolt-Lippich polarimeter. The effects of temperature, concentration, and of the addition of boric acid, in aqueous solutions were investigated, and solutions were examined in methylic, ethylic, and yropylic alcohols, and in acetone. Tbe phenomena in aqueous solutiohs were very complicated ; dilute solutions were lsvorotatory arid normal ; by increase of concentration, a levorotatory, achromatic solation was first obtained, then a I~vo-maximum in the yellow, after which the more refrangible rays gare a dextrorotation, whilst for the highest, concentrations, the solutions were normally dextrorotatory, Increase of temperature had an effect analogous to dilution, whilst in the organic solven6s the dilute solutions were Isevorotatory, but tlie VOL.JJX ii. 21286 ABSTRACTS OF CEEMICAL PAPERS. concentrated solution gave dextrorotations for the more refrangible rays. It is evident that such variations are associated with great changes in the dispersion. The probable cause of these results is discussed ; the presence of two compounds of different dispersion coefficients and opposite rotatory power is suf€icient to explain the results, but the nature of the two compounds does not seem clear.The authors do not consider as probable the formation of hydrates, 01- polymerides, or the existence of " crystalline molecules " (compare Abstr., 1893, ii, 103), neither does dissociation appear entirely satis- factory. The explanation regarded as most probable is that of a specific action of the solvent in which the molecular dissymmetry is altered or destroyed, so that the compound may acquire physical pro- perties approximating to those of its ions without being actually dissociated. In the alcoholic solutions, in an analogous manner, the approximation is to the lsvorotatory etheiteal salts of malic acid (Abstr., 1895, ii, 251).L. M. J. Rotatory Dispersion of Nicotine and its Salts. By G. GEN- NART (Gazzetta, 1895, 25, ii, 252-257; also Zeit. physikal. Chew,., 1896, 19, 130--134).-1n continuation of the work of Gennari and Nasini (this vol., ii, 133), the author has examined the specific rota- tions of nicotine, and its sulphate, hydrochloride, and acetate under various conditions of concentration and solvent, for five different, wave-lengths, using Landolt's ray filters. At 20°, pure nicotine of sp. gr. = 1.01071 at 2 O o / 4 O has the specific rotations of -123.37", -162*84", -209-78", -250*71", and - 317.79", for the ray filter colours rt, D, gr, hb, and clb (compare Abstr., 1895, ii, 1) respect>ively ; the specific rotations are considei*ably lower in benzene and ethylic and methylic alcoholic solutions, and very much lower in aqueous solutions, the specific rotation diminishing as t h e dilution increases.The solutions, however, are all lrevorotatory, and the coefficients of rotatory dispersion calculated as [a],/ [a Jy for t h e various rays are the same for nicotine, both pure and in solution, The specific rotations of the various salts examined at 20" are given in the following table. I I-- I Sulphate . . . . . . , , 31 '420 + 12 '19 + 15 066 Hydrochloride. , . 18 *41P + 12 -13 + 15 *45 Acetate . . . . . . . . .I 24 -276 I + 13 -00 1 + 16 '96 (--I__- It will be seen that the salts are all dextrorotatory in aqueous solu- tion, and the rotatory dispersions are found to be less taban those of nicotine itself. A mixture of nicotine and acetic acid, in molecular proportion, is.strongly laevorotatory, but), on gradual dilution with water, the laevo- rotation decreases until the solution becomes highly dextrorotatory. This can only be explained by supposing that, as the acetic acid solu-QENERAL AND PHYSICAL CEEMISTRY. 287 tion i R diluted, more and more of tbe dextrorotatory acetate is formed, whilst the proportion of lsevorotatory base decreases. Rotatory Power of Superfused Rhamnose. By DBs~RE GERNEZ (Conipt. rend., 1895, 121, 1150--1152).--The specific rotatory power of rhamnose at 18' is -6.5" a minute after dissolution, but attains the constant value of +9.75' in less than an hour. Direct measurements of the sp. gr. and specific rotatory power of the superfused rhamnosc, (C6H1205 + H20) gave the following results.to. 0'. 16". 18". 19". 46". 70". 73". 100". Sp. gr. . . . . . . .. 1.400 1.388 1.387 1.386 1.357 1.349 1.346 1.32.5 Sp. rot. power.. 9.28' 8*6G0 8.59' 8.53' 7.57" 6-73' 6*643 5.70" The observations are accurately represented by the expression W. J. P. [z]; = 9.22' - 0.03642t + 0*0000123P. The rotatory power of the superfused rhamnose diminishes regu- larly as the temperature rises, and at 100' has only 61 per cent, of its value at 0'. Its specific rotatory power in aqueous solution is not identical with that of the superfused substance, and this difference must be taken into account in any attempts to explain multirotation. Flames and Illuminating Gases. By JOSEF M. EDER ( Z e i f . physikal. Chem., 1896, 19, 20-24) .-The author criticises various points in Bohn's com.mnnication (this vol., ii, 140), and calls atten- tion to the fact that several of the observations and conclusions had been previously recorded by himself.C. H. B. L. M. J. Luminosity of pure Inorganic Compounds and of Solid Solutions. By EILHARD WIEDENANN and GERHARD C. SCHMIDT (Zeit. physikal. Chem., 1895, 18, 529-552).-Many inorganic, as well as organic, compounds (this vol., ii, 86) become luminous when subjected to the influence of the cathode rays, frequently exhibiting also an after-luminosity, and possessing the property of again becoming Iuminoiis when heated. The effect of the cathode rays on pure compounds is first considered, and tables of the luminosity pheiomena are given. The luminosity colonr of the salts appears to be dependent on the metal, the acid only influencing the intensity of the light.In solid solutions, a small quantity of the dissolved substance may cause a great alteration of the colour and intensity, both of which are also dependent on the solvent, whilst the intensity is, in dilute solution, a direct function of the concentration. The previous heating of the conipound almost invariably influences the phenomena, either owing to chemical changes so occasioned, or to alteration of the physical state, whilst the after-luminosity is also of longer duration. At high temperatures, the luminosity still remains, but the after-effects de- crease or disappear, and the colour usually changes to a more refrangible shade, whilst a t low temperatures, the luminosity is brighter and the after-effect of longer duration.The physical modi- fication which is produced by these cathode rays appears to be usually of a fairly stable nature, being only destroyed by relatively high 21-2288 ABSTRACTS OF CHEMICAL PAPERS. temperatures (200' and above), whilst at ordinary temperatures the thermo-luminosity may last over six months, although in some cases it is lost in a week. The addition of foreign substances may cause either an increase or a decrease of luminosity, both in the case of pure compounds and of solid solutions. Experiments 0x1 phosphor- escence showed thht the phosphorescence colour is the same as that of the cathodic luminosity, and that it also is frequently destroyed by foreign substances, whilst Stokes' rule was found to be valid for all the solid solutions examined.The paper concludes with a brief theo- retical consideration of the observed facts. L. M. J. Dependence of the Dielectric Constant on Temperature ahd Pressure. By FLORIAX RATZ (Zeit. physikal. Chem., 1896,19, 94- 112) .-The dielectric constant was determined at various tempern- tures and pressures by Eernst's method (Abstr., 1894, ii, 437), in the case of benzene, toluene, carbon bisulphide, ethylic ether, chloroform, aniline, amylic alcohol, ethylic alcohol, and water. The value (D - l ) / ( D + 2)d is a function of both temperature and pressure, the temperature coefficient increasing with the dielectric constrant. The variation between the valnes of the constant obtained from the formula and the actual number is, for a temperature of 30', below 10 per cent., and the value of the above expression within 40" chamges by less than 5 per cent.The temperature coefficient is small, a i d in all cases negative, decreasing slightly as the temperature rises. No maximum f o r D is found at 4' in the case of water, and if such exists at all, it must be between 0" and 1". I n all cases, the value of D is greater than A2 obtained from refraction observations. The pressure coefficient is small and positive, so that i t follows that' the influence of temperature is greater, and that of pressure less, than the calculated effect. Details of the method, the purification of t,he compounds examined, and the experimental numbers are given in the paper. L. M. J. The Dilution Law of Electrolytes. By LUDWG STORCH (Zeit.physikaZ. Chem., 1896, 19, 13--19).-The author has obtained a Ctilu- - - tion law of the form (A?-)" = k ( e r , * where /urn and p are the molecular conductivities at infinite dilution and volume 21 respectivelv. v r 03 V.P 03 This may be expressed as x log (,u/zJ) = log (/urn - p/o) + log (&.,T-~). By the construction of curves with Kohlrausch's values for p/v, and a probable p,,,, values for tl: and (kprn2-') are obtained, and hence, by recalculation, tbe actual value of p,,,. The value for x differs for different electrolytes, but in the 12 cases considered varies only between 1.400 and 1577, and the conductivities then calculated from the formula agree very closely with the observed numbers. It is seen that the above formula for the value ~ t : = 1.5 is identicaI with that obtained by van't Hoff from Iludolphi's numbers (compare this vol., ii, 145).For very high concentrations, however, the formulae * There appear to be misprints in the formulse as printed in the Zeitschrift; the equation given is obtained by recalculation from the final form.GENERAL AND PHY SEAL CHEMISTRY. 289 are not valid; thus, from o = 0.33, 1 aud 2, the values z = 1,699 pa = 104 were obtained for potassium chloride, ihe corresponding values derived from v = 10 to 16667 being 1.435 and 122 ; the lower values for ,urn probably indicate the presence of double molecules in the more concentrated solutions. L. M. J. Specific Heats of Solutions. By Gus~av TAMMAFN (Zeit. physikal. Chem., 1895, 18, 625-644).-0bservations have shown that the heat capacity of solutions, if not too dilute, is generally smaller than that of the two components, and frequently less than that of the water alone.The heat capacity of the water has, however, been calculated without due provision for the alteration of the specific heat, owing to the change in the internal pressure. The alteration of specific heat by pressure change being given by the equation (dCldp)(T const.) = -T(d%/d!P)(p const.), that due to the solu- tion in water of any compound is given by a similar equation, where p = Ah‘; the alteration of internal pressure (see Abstr., 1895, ii, 307, and previous abstracts). If the expansion of the solution be given by v = A + at + bt?, which holds for small temperature changes, then d2v/dt2 = 2b, and is determined from Amagat’s experinient,s t o be a linear function of p , and the value is obtained at various tem- peratures.The value for the specific heat is thus obtained, and, on adding the heat capacity of the water to that of the salt in solutions of potassium chloride, bromide, iodide, nitrate, and hydroxide ; hydro- gen chloride, nitric and sulphuric acids ; sodium sulphate, nitrate, and hydroxide ; ammonia, ammonium sulphate, magnesium sulphate, and barium chloride, results are obtained iii very close approxiniation to the experimental determinations, except in the cases of sodium chloride and sulphuric acid. The changes due to alteration of AK with temperature are considered, but cause no appreciable difference. Similar reasoning is applied to the cases of neutralisation, where the heat capacity of the salt solution formed is not the sum of those of the added acid and base together with that of the water formed by neutralisation. When corrections due to the alteration of internal pressure are applied, concordant results are obtained.The changes in the specific heat of solutions due to temperature alterations are also considered, and found to be of the order indicated by the early experiments of Marignac. L. M. J. Relationship of the Heats of Vaporisation of Gases to their Densities, and also to their Boiling Points. By WILLIAM L. DUDLEY (J. Amer. Chem. Xoc., 1895, 17, 969-986).-The author has proved, by a series of experiments on snbRtances belonging to the fatty and aromatic series, that in any homologous series the beat of vaporisa- tion in a unit of volume of the vaponr under the same conditions as to temperature and pressure is proportional to the density, and also to the absolute boiling point.The characteristic of the curve is dependent on the acid radicle ; that is, the acid radicle is the basis of the structure of the molecule, and the bases in combination with it do not altcr the general mole- cnlar architecture. L. DE K.290 ABSTRACTS OF CHEMICAL PAPERS. Ethylic oxalate ..... -41.0" Ethylenic dicbloride. -36.0 Ethylenic chlorobro- inide ............ - 16.6 Ethylenic chloriodide - 15.6 Clilorobenzene.. .... -45.0 Bromobenzene.. .... -30.5 Iodobenzene ...... -28.5 The Physical Alteration of certain Sulphur Compounds at Temperatures below their Melting Points.By WALTHBRE SPRTKG (Zeit. physikal. Chem., 1895, 18, 553-558).-Experiments analogous to those undertaken with metals (Abstr., 1895, ii, 37) were made on the sulphides of silver, arsenic, antimony, bismuth, copper, tin, cadmium, lead, and zinc. The amorphous sulphides obtained by precipitation mere used, being first washed, dried, and lightly pressed into cylinders. The latter treatment was merely to bring the par- ticles into contact, the pressure being so slight that the cylinders could be easily crumbled between the fingers. One half of the cylinder was kept for comparison, the other enclosed in an exhausted glass tube and exposed for niiie days of 7-44 hours to a temperature of 265' (156" for the arsenic sulphide). The cylinder of silver sul- phide, after this treatment, was steel grey, with a metallic lustre, and with crystal faces visible on the surface.It could not be broken by the hand, and, after forcible breaking, exhibited a crystalline fracture resembling that of steel. Similar results were also obtained with the other compounds. Uncompressed powders mere also employed, which formed compact masses, with, usually, indications of a, crystalline nature. The author points out the probable importance of these results in geology, as they indicate the possible formation of ci-ystal- line rocks, he., without fusion or the aid of a solvent. L. M. J . Benzonitrile. ....... -12*g3 Diethylaniline. ..... -38.8 Paraphenetidine.. , . + 2.4 Orthonitrotoluene .. -14.S Aniso'il ............ -37.8 Ethylthiocarbimide .- 5.9 Chloropicrin ....... --G9*2 Ethylic salicylate . . + 1.3GENERAL AND PHYSICAL CHEMISTRY. 291 and if band to are the temperatures of the liquid and freezing point respectively, dt/dz = k(t, - tf) + c(t8 - Q) ; hence, when the tem- perature is constant, t' = to + i ( t 8 - t'), nud t' the observed tem- perature must be higher than to, the actual freezing point, and less than ts, the convergence temperature. In order that (is - t ) c / k may be small, c must be as small as possible, that is, the volume of the liquid should be great, and k should be large, which means that the surface of the ice should be great, and the ice, therefore, in fine needles and as large as possible, so that those determinations in which the readings are taken when the ice specks disappear are the worst possible.As the same formula applies to both pure water and the solution, the observed depression is given by to - trO = 1 + - (t' - t') (if the ralues of c and 1; are equal for solution and i D \ pure water) ; so that the apparent values bear to the true values a constant ratio at all concentrations, if not too great. In the author's experiments, the results are hence only 0.1 per cent. too small, and the greatest error due to this cause in the work of various observers appears to be about 0.0048°. The author points out also the bearing on the results of the presence of an ice cap (compare Trans., 1895, 6 , and Absti-., 1895, ii, 105). Where the convergence temperature is below the freezing point, the temperature change is given by dt/dz = c"(to - 9) + c(ts - t f ) , which, by equat,ing t.0 zero, jields t' = t, + :,(t8 - t'), so that t' lies between t, and fs.Experiments to find the value of the constants liere aud in the previous formdB are recorded, and the result, obtained that f o r a bath at -5Othe value c/c"(t8 - t ' ) would not reach 0*003", whilst for the freezing point depressions, that is, the difference of the corrections for solvent and solution, the values become still less. I n this case, also, it is pointcd out that the neces- sity of avoiding an ice cap no longer exists. L. 31, J. Method for the Determination of the Freezing Points of Concentrated Solutions. By MAX ROLOFF (Zeit. physikal. Chem., 1895, 18, 572--584).-The freezing point is determined by finding the composition of the solution which, at a determined constant tem- perature, remains in equilibrium with ice.The chief difficulty is t'he maintenance of the freezing mixtures at a sufficiently constant tern- perature, but this is overcome by the use of '' cryohydrates " jacketed by colder freezing mixtures. Experiments with hydrogen chloride included observations on 22 solutions varying in concentration froni 1.42 per cent. to 26.98 per cent. The molecular depression mas found to increase from 36.7 to 61.9, a result accounted for by the positive heat of dilution of the solution. The values are compared wit,h those obtained by Nernst, Jones, and Le Blanc and Noyes, the agreement being very close. In the case of potassium chloride solu- t ions, the molecular depression decreased from 34.3 at 0.836 per cent.to 38.6 at 24.62 pcr cent., the values being again in satisfactory292 ABSTRACTS OF CHEJHCAL PAPERS. accord with those of Jones and Kistiakowsky. From the values also the osmotic pressures are calculated by means of the expression deduced by Arrhenins, the numbers being in satisfactory accord with those obtained by Dieterici from the alteration of the vapour pres- sures. By use of the values found for the osmotic pressure, the ratios of the vslpour pressures of solvent and solution are also calculated, the numbers being in agreement with the measurements of Dieterici, Fischer, and Tamrnann, but not with those of Jchlin and Ramsay and Young. Researches with acetic acid gave a value for the molecular depression which decreased from 19.4 to 10.0, the fall below the normal value 18 being probably due to the formation of complex molecules.L. 31. J. The Freezing Points of Dilute Solutions. By WALTHER KERNST and RICHARD ABEGG (Zeit. physiknl. Chem., 1893, 18, 658--661).--A reply to Jones (this vol., ii, 155), in which the authors point o u t that the correction of 20 per cent. must be allowed if found to be theo- retieally valid. Further the variations of 5 per cent. i n their values for the sodium chloride depression are stiIl within the errors of observat,ion, and that the increase in the molecular depression of ethylic alcohol is also within the limits of observation. L. 31. J. Exceptions to the Law of Freezing BoinVDepressions. By FELICE GARELL[ (Gazzettn, 1895, 25, ii, 173-178) .-In continuation of the previous work of Garelli and Montanari (Abstr., 1&95, ii, 2d5) on the anomalous depressions of t.he freezing point of a solveut produced by a dissolved substance of similar constitution, the author has examined the behaviour of a number of organic substances in various solvents.Using paraxylene as the solvent (compare Paternb and Monte- martini, Abstr., 1895, ii, 207), normal depressions are obtained with naphthalene, pyrroline, and piperidine ; aa-dimethylpyrrolinc and xa-dimethylthiophen, however, in paraxylene, give molecular weights which are too high, just as pyrroline and thiophen do in benzene solution. Similarly, aa-dithionyl gives too high a molecular weight in diphenyl solution, whilst it behaves quite normally in freezing benzene (compare Auwers, Abstr., 1895, ii, 41).Substances which are geometrical or position isomerides do not seem to form isomorphous mixtures or solid solutions, and therefore the one depresses the freezing point of the other quite normally. Thus apiole dissolved in isoapiole, and isocrotonic acid dissolved in crotonic acid give the theoretical molecular weights ; the same is true of pyrocatechol and quinol dissolved in resorcinol. The molecular depression of the freezing point of resorcinol is found to be 65. W. J. P. Cryoscopic Behaviour of Substances of similar Constitution to the Solvent. By FELICE GARELLI (Qazzetta, 1895, 25, ii, 279- 188) .-Anomalonb cryoscopic behavionr may in any particular case be due to one of two causes. Some substances, such as alcohols, oximes, or phenols, which contain hydroxyl, tend to form complexGENERAL AND PHYSICAL CHEMISTRY.293 molecular aggregates when dissolved in hydrocarbons, and their molecular weights approximate to the theoret,ical ones only in dilute solutions ; further, when the dissolved substance and the solvent have analogous constitutions, a solid solution is formed as t,he solrent freezes out, and the results give no indication of the true molecular weight of the dissolved substance. Since both these caiises may bring about anomalies, Paternb’s criticisms (this vol., ii, 156) of Garelli and Montanari’s previous results (Abstr., 1895, ii, 205) lose considerably in force ; the fact that phenol and paraxylenol behave abnormally both in benzene and paraxylene solutions is not snrpris- ing, as phenol would tend to form solid solutions in benzene solution, whilst in paraxylene solution it would tend to form molecular aggre- gates.The kind of abnormalities observed are in agreement with this view. The observation of Ampola and Manuelli (this vol., ii, 238) t h a t chloroform has the normal molecular weight in bromoform solu- tion is not a t variance with the author’s views, for he has n o t hitherto observed the formation of solid solutions amongst aliphatic compounds (Abstr., 1894. i, 157); it may also be remarked that, chlorobenzene and bromobenzene behave quite normally in benzene solution. W. J. P. The Cryoscopic Behaviour of Substituted Phenols in Naphthalene. By KARL AUWERS [and W. R. INNES] (Zeit. physikal. Chern., 1895, 18, 595-624) .-Cryoscopic experiments on hydroxy- compounds in benzene have been previously recorded (Abstr., 1891, ii, 133 ; 1895, ii, 41), and the observations are here extended to solu- tions of such compounds in naphthalene.In order to prevent changes in the thermometric readings due t o alteration of the freez- i n g point, the thermometers were maintained between the experi- ments at a temperature of BOO, that is, close to that of the actual experiments. The molecular depression for naphthalene being uncertain (previous determinations varying from 85 to TO), i t was redetermined by experiments with benzile, benzilosazose, and ethylic ethanetetracarboxylate. The values thus obtained vary between 68.25 and 69.3, mean 68.92, agreeing well with the value 69, calculated by van% HOE’S formula, which is afterwards employed.Experiments were made with 52 homologons and substituted phenols, and the following general relations observed. (I) Ortho- substituted phenols are cryoscopically normal, para-derivatives abnormal, whilst meta-derivatives occupy an intermediate position, but approximating more towards the para-compounds. (11) A substi- tuting group in the ortho-position may hence be said to exert a “normali~ing” influence, the reverse obtaining for a group in the para-posit>ion, the extent of this influence depending on the nature of the group. In this respect, the aldehyde group CHO exerts the greatest influence ; then in order-carboxalkyl, COOR ; nitro-group ; halogens ; alkyls. (111) Other conditions being similar, the ortho- group has a stronger influence than the para- or meta-, so that, for instance, ortho-nitrophenol is normal, para-nitrophenol abnormal, and orthopara-dinit.ropheno1 normal.The cryoscopic behaviour of a com-2 94 ABSTRACTS OF OHEMICAL PAPERS. pound, therefore, unless further observations prove the rules to be not general, may be used to determine the constitution or orientation. The cause of these peculiarities is very uncertain, but the author points out some possible explanations. The abnormal valaes may be due to double molecules ; these are not formed, however, in the case of ortho-compounds owing to the hindrance to the approach of the inolecules, caused by the ortho-substituent. Or i t may be due to a difference in constitution analogous to that indicated by Armstrong (Proc., 1892, 102).New Method for the Determination of the Density of Gases. By HEKRI MOISSAN and HEXRI GAUUER (Ann. Chim. Phys., [7], 5, 568--573).-The principle made use of in this method is the same as that of the Dumas’ vaponr density method. The difference in weight between a given volume of gas, measured under given conditions of temperature and pressure, and the same volume of air measured under the same conditions is determined. L. 31. J. H 1 760 I + 0.00367t’ p = 2: x 0*001293(x - 1) x x where y = difference between the two weights expressed in grams, v = the volume of gas and of air, t = temperature and, H = pressure under which the volume is measured. Then te = density of the gas. The apparatus used is represented in the accompanying cut.,4 is the globe in which the air or gas is weighed ; i t carries a three way cock, It” and can be attached by means of an air-tight joint to the measuring vessel, B, which also has a three-way cock, R. K is a capillary tube, by which the gas to be inves- tigated is introduced into B. The measuring vessel, B, is graduated on the stem bc, and has a capacity of about 95 C.C. The pressure is brought to the atmospheric by regulating the amount of mercury in D. The globe A is exhausted, and then filled with carefully dried air. This operation is repeated some 10 times, and then the cock R ’ is turned off. B and K are completely filled with dry meivxry, and the point of K is then introduced into the vessel containing the gas t o be examined, andGESERAL AND PHYSICAL CHEMISTRT.295 about 160 C.C. of gas are introduced into B, and the cock R is then turned, so as to shnt off the measuring vessel from the rest of the apparatus, and the mercury in c and D is brought to the same 1e-i-el. The whole apparatus is then left for 6-7 hours, or still better ol-er night, to attain a constant temperature. The temperature, volume, and pressure are then read, care being taken to see that the gas is at the atmospheric pressure. The cock R" is opened for a moment, in ordcr that the air in A may assume the atmospheric pressure. A is then removed and neighed; it is afterwards exhausted, and again connected with B. The cocks R and R" are slowly opened, and the n.hole of the gas in B is made to pass into the globe, A, which is again detached, cleaned, aiid weighed.The authors have determined the n p o u r densities of pure samples of caybonic anhydride, hydrogen, oxygen, and nitrogen, and they 6nd that the numbers agree extremely well with those obtained by Regnault. J. J. S. Vapour Tension of Hydrated Salts and the Constitution of the Combined Water. By WILHELM MTLLER-ERZBACH (Zeit. q,hysikuZ. Chew., 1896, 19, 135--154).-The tension of aqueous vapour was determined, in the case of a number of hydrated salts, by finding the specific gravity of the sulphuric acid solution with which the salt remained in equilibrium, preliminary approximation being first made, The values for the vapour tension fall suddenly at defi- nite changes of hydration for most salts, so that between certain limits of hydrat,ion the vapoui- tension remains constant.The results obtained were as follows, the rnpour pressure being referred to that of water at the same tempei.ature:-Barium chloride, 1-2 aq. 0.21, 0-1 aq. 0.10 ; copper sulphate, 3-5 aq. 0.31, 1-3 aq. 0.20 ; 0-1 aq. below 0.02; zinc snlphate, 6-7 nq. 9-55, 1--6 aq. 0.50, 0.1 aq. below 0.02 ; disodium hydrogen phosphate, 7-12 aq. 0.75, 3-7' aq. 0.58, 0-2 aq. 0.06. The Dilution Law for Salt Solutions. By FKIEURICH KOHL- I:AUSCH (Zeit. physikal. Chew., 1895, 18, 662).-Van't Hoff has shown that, according to Rudolphi's experiments, the expresssion Ci3/Ci2 leads to a constant 1-alue where C'i and Cs are the concentration of ions and undissociated compound (1895, ii, 490 ; this vol., ii, 145). This expression may be written Ci/C', = const./C,+, that is the ratio of the undissociated cornpGuIid to ions is proportional to the lineal.density of the fcrmer. L. 31. J. L. Af. J. Partition of a Substance between Two Solvents. By A. A. JAI~OWKIN (Zeit. physikal. Ch~m., 1895, 18, 585-594) .-The partition coefficients were determined, in the case of solutions of iodine and bromine, in water aiid (1) carbon bisulphide, (2) bromoform, (3) carbon tetrachloride. In carbon bisulphide and water, a marked decrease of the partition ratio occurs with dilution, probably owing to the decomposition of complex molecules. A similar decrease occurs with bromoform, but with carbon tetrachloride the ratio remains almost constant. The numbers obtained with iodine for the carbon bisulph-296 ABSTRACTS OF CHEMIOAL PAPERS.ide: water ratio (685 to 600 at 18') differ considerably from those obtained by Berthelot and Jungfleisch (400). In saturated so lutiona, the partition coefficient should be equal to the ratio of the solubilities in the two solvents, and the following table shows that this is the case, the numbers being obtained by extrapolation. I I Water and I Solubility ratio. I Partition coefficient. Carbon bisulphicle. ......... Bromoform ............... Carbon tetrachloride. ....... 679 *O 569 -0 89.6 685 '0 558 '5 89 -7 On the assumption that the change in the coefficient is due to the passage from double to single molecules, the concentration of the aqueous solution is calculated from that in the other solvent, the num- bers agreeing well with the observed values.The departure from normality i n the case of solutions of carbonic anhydride is also ~011- sidered and referred to the formation of complexes a t the hight.1- concentrations. L. &I. J. The Course of Chemical Xeactions in Gases. By LUDWIG S'I'oiccH (Zed. physikal. Chem., 1896, 19, l--l2).-According to the researches of van't Hoff, the reaction velocity for the formation of water from the mixed gases does not lead to a constant, if calculated for a trimolecular equation. The author, by applying the general differential equation dC/dt = kC", obtains a constant k = 0.004725 when n = 9, in the case of moist mixed gases. For the experiments with the dry explosire mixture, the value obtained is k = 0.003091; n = 12. It has also been shown that similar experiments with other gases do not lead to the reaction order expected, and the author explains these anomalies by the heat generated during the action.Thus, in the above case, at the temperature employed (boiling point of sulphur = 440') the heat evolved per niolecular equivalent is 111,345 units at constant volume, and 112,771 a t constant pressure, so that the temperature of the water produced would be 3785" and 3108" respectively. At this temperature, however, the water molecules can- not exist, and in order that they may actlually be formed, an excess of cooling molecules must be present. If 1500-2000" be taken as the temperature at which the water remains undissociated, the true equation hence becomes (2H2 + 0 2 + 9'8 &l)i400 = (2H20 -+ 9.8 M)I!~oo~, or (2H2 + 0, + 4 7 bl)4400 = (2HZO + 4.7 M)ZOOOO at con- stant pressure, and similar equations occur with 12.9 M or 6-7 M a t constant volume, so that the value for n should be between the limits 12.8-7.7 and 15.9-9-7 respectively.Similarly, the formation of hydrogen chloride should be abnormal, and the normal values of Bunsen and Roscoe are referred chiefly to the presence of the water, whilst the normal value of Bodenstein for the decomposition of hydro- gen iodide, is owing t o the fact that the thermal change accom- panying it is very small (hbstr., 1893, ii, 369; 1S94, ii, 12). L. LM. J.GENERAT, AXIJ PHYSICAL CHEMISTRY. 297 Chemical Kinetics of Oxidation. I. Speed of Liberation of Iodine in Mixed Solutions of Potassium Chlorate, Potassium Iodide, and Hydrochloric acid.By HERMAK SCHLUSDT (Ainer. Chern. J., 17, 754-770).-Mixed solutions of potassium iodide and chlorate were heated a t 100°, in small sealed tubes, with hydrobromic, hydrochloric, nitric, or sulphuric acid, the liberated iodine being estimated by titration with sodium thiosulphate. The conclusions drawn from the results are : (1) The speed of the reaction increases with the temperature. (2) Equivalent excess of iodide or chlorate produces equal accelerations, excess of acid produces a, more marked acceleration. (3) The speed increases with the concentration. (4) For complete and rapid reduction of the chlorate, excess both of iodide and acid must be present. (5) The four common mineral acids may be arranged in the order given above, in regard to their relative influence in accelerating the action ; the order being identical with that assigned t o them by Ostwald.Chemical Kinetics of Oxidation. 11. Mathematical Theory of Oxidation Processes. By ROBEIiT B. WARDER (Anzer. Chem. J., 1896, 18, 23--43).-This paper is a review of the work which has been done in search of the mathematical law controlling the speed of oxidation of hydriodic acid in different systenis, and has special reference to the preceding paper. A. L. A. G. B. Mixer for accelerating Chemical Reactions. B y WLdDIMII: MARKOWSIROFF (Annalen, 1895, 289, 254-257).--The author describes a form of apparatus which finds application to all classes of liquids, and may be heated or cooled, as occasion requires. Essen- tially it consists of a tinned copper cylinder capable of rapid rotation o n its axis, and provided with ribs or beaters parallel to the axis. M. 0. P. Pressure Tube for Laboratory Experiments. By JOHANK WALTER (J. pr. Chenz., 1896, [2], 53, 132--139).-The object of this tube is to render i t possible to maintain an external pressure on the glass tube which is being heated equivalent to the internal pressure, a principle which has been applied by Ullmann (Ber., 23, 379). The steel tube is of Mannesman make, and is of 32 nim. diameter, and 560 mni. in length. The head piece is usually of bronze, in which case no washer is necessary, the flange being tightened by a screw working in a, stirrup, made iu n piece with a collar welded on t o the tube. Two side necks in the head-piece, provided with appropriate valves, permit of connection with a cylinder of compressed carbonic anhydride, and a manometer. In this way it is possible t o maintain a constant pressure withixi the steel tube. The author finds that, instead of the usual pressure tubing, it is possible to use soft glass tubing of 1-5-2 mm. thickness in the walls when external pressure is maintained in this way, except when corrosive liquids are being heated ; indeed, i t is frequently permissible t o omit to seal the glass tube, a cork serving when the carbonic anhydride is to be excluded and the temperature will permit. Details of the application of the tube for determining the solubility of sparingly soluble gases in298 ABSTRACTS OF CHEMICAL PAPERS. liquids, the solubility of substances at high temperat nres under pres- sure, and the vapour pressure of liquids at high temperatures, are given, and two drawings accompany the paper. A. G. B.

ISSN:0368-1769    

DOI:10.1039/CA8967005285

出版商:RSC    

年代:1896

数据来源: RSC