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VEGETABLE PHYSIOLOQT AND AQRIOULTURE. 313 Chemistry of Vegetable Physiology and Agriculture. Reducing and Qxidising Properties of Brtcteria. By W. HEBAEUS (Bied. Centr., 1887, 783-784).-The author prepared pure cultivations of the various bacteria (Bacilli and Micrococci) which occur in river water, in spring water and in soil, and ah0 of the mould fungi (Macor and AspergiZZus J l a u z ~ s ) . Besides ash con- stituents, the nutrient liquids contained either ammonium carbonate or calcium nitrate or carbamide. There were found (besides those bacteria that would not grow in artificial liquids) two species which reduced nitric acid to nitrous acid and ammonia, and converted carbamide into ammonium carbonate ; one species which made use of nitric acid without reducing it to nitrous wid and which changed cwbstmide into ammonium salts ; one species which behaved similarly with nitric acid, but which did not change carbamide into ammouium compounds ; one species which gave no indications of action on nitro- genous substances ; one species which left nitric acid unaltered but changed carbamide into ammonium salts ; and lastly two mould fungi which gave no indications of action on nitrogenous substances.No Hpecies of bacteria were found which had an oxidising action; but some micro-organisms were obtained from soil infusion and from putrefying urine which converted the nitrogenous matter of Loth rtmmoniacal and urine solutions, and of diluted meat-infusion into nitrous acid. Further an examination for oxidising properties was made with various known species of bacteria ; namely, the hay bacillus, H~crococGus prodigiosus, Finkler's bacteria ; also with the pathogenic ones, namely, those of anthrax and typhus, Tetragonus and others.In solutions coutaining sugar and the ash constituents, almost all of them were devoid of any perceptible growth ; whiIst in urine diluted with four times its bulk of water, Hicrococcus prodigioszcs, root-shaped bacteria, the spirillum of cheese, Finkler's bacteria, those of typhus and anthrax and Staph yZococcus citrezcs, succeeded in forming nitrous acid. Hay bacillus, ~!3'taphyZococcus aureus, and the bacteria of green pus and of pneumonia produced a thick turbidity but no nitrous acid. Brieger's bacteria had a feeble oxidising action, and the experiments with Miller's bacteria gave a negative result.Spring Sap of the Birch and Hornbeam. By R. HORNBERGER (Bied. Centr., 1887, 821-825).--The titap waR drawn from fhe horn- beam at two spots, the one 0.7 m. the other 4.1 m. above the ground ; from the birch at 0'5 m. and 3.5 m. above the ground, and the hours of collectioa were 10 A.M. sDd 6 F.M. from April 13 to May 4. The sap of both trees contains lsevulose with some dextrose, nitrogen and mdic acid and salts ; the highest percenksge of sugar is found in the sap collected at the upper boring, and the total quantity is also greater, moreover the morning sap irJ always richer in sugar than the evening, and if the upper opening is closed, then the sugar obtained below is in H. H. R.314 ABSTRACTS OF CIIEMICAL PAPERS. greater quantity ; there appears also to be a diminution in gmms per litre as the season progresses. Comparing the two saps, the horn- beam is poorer in sugar than the birch, the highest yield being 4-72 grams per litre (15.59 in the birch), and this was only obtained at the upper boring and at the commencement of the observation; ever afterwards t,he quantity decreased : the higher percentage of fiugar in the morning sap was found in both t'rees.Nearly all sugar disappeared before the hornbeam ceased to blossom, whilst it still appeared up to the end of the blossoming of the birch. Xaiic acid is in larger quantities in both saps at the later periods, and there is no difference by day or nighh, but it is present in double the quantity in the birch sap, which contains least sugar.The total nitrogen in the birch sap at; 3.5 m. height is twice as much as at the lower level, and the hornbeam is much poorer in nitrogen than the other tree; but little of the nitrogen appears as albuminoi'ds, but the albumino'ids do increase during blossoming period ; the greater portion appearing as amido-acids and in other forms, even as am- monia. The mineral constituents were found to increase during the period of observation; the upper boring yielded a sap richer in minerals than the lower, and the sap is also richest when collected in the evening. With the hornbeam, this is not the cass; if any difference is observable i t is that the lower sap is the richest. Potash increases in the birch sap as time goes on, the evening sap being richer in it than the morning:, the upper than the lower; the same holds good foi* lime and magnesia.Phosphoric acid increases at the lower boring as the season progresses, but it decreases at the upper ; also the evening is richer in this compound than the morning sap, but i t is always in larger quantities at this boring. In the hornbeam, this is different, for there is not much variation between the two yields either as time goea on or as the examination is made at evening or morning. The bases in the birch sap are largely in excess of the mineral acid present, only & to being thus combined, and with the hornbeam there is a similar condition of affairs, only that the difference between the amounts of bases and acid is hardly so great. The author considers that the malic acid found in the sap of both trees is present as a bye-product.E. W. P. Citric Acid in O x y ~ o ~ ~ u s Palustris. By P. KOSSOVI~ (Chern. Cen.tr., 1887, 1157, from J. Rzcss. Chem. SOC., 1887, 278-274).-The amount of citric acid found in three different samples of cranberry, Orycoeczcspulustris, was 2*0,2+44, and 2.8 per cent. of the total weight of the berries. As these occur very largely in many districts of the interior and the north of Russia, the author proposes to use their juice for industrial purposes, for instance in dyeing, instead of the con- centrated lemon-juice imported from Italy. J. W. L. Organic Constituents of the Beetroot Juice. By E. 0. V. LIPPMAXN (Ber., 20, 3201--,3209).--Durin (BdZ. Assoc. Chem., 1, No. 5) observed a thick froth, having an odour of butyric acid, to be formed on the surface of the bye-products from the preparation ofVEGETABLE PHYSIOLOGY AND AGRICULTURE.315 siig:sr when being evaporated down. The author has examined the froth and found that besides the potassium salts of fatty acids, it con- tains dextran and phytosterin (Hesse, Abstr., 1878, 850). Beetroot was extracted with a mixture of ether and alcohol, the ether evaporated and the residue dissolved in alcohol and treated with platinum chloride ; the precipitate so obtained when purified and decomposed with hydrogen sulphide yielded lecithin. This when boiled with baryta-water yielded oleic acid, glycerol, phosphoric acid, and beta'in. A second experiment gave a lecithin which yielded no betajine, but choline.Betnine and choline are readily separated by means of the hydro- chlorides ; betaine hydrochloride forms stable crystals, whilst choline hydrochloride is very deliquescent. Beetroot contains also other compounds containing phosphorus which are related to the nuclejins ; the products of decomposition of these compounds-the xnnthine compounds-are almost all conhained in the molasses, Chemico-physiological Study of Algae. By 0. LOEW and T. BOKORNY (J. pr. Chem. [ 21, 36, 272-291).--Algze (Zygrzemacere) superficially dried with blotting-paper contain 85-90 per cent. H,O ; when dried at 100" their composition is-fat 6 to 9 per cent., albumin 28 to 32 per cent., cellulose and starch 60 to 66 per cent. The fat ig situated chiefly in the chlorophyll region, but is not visible in drops under ordinary circumstances ; lecithin is probably present.The q uantity of starch varies very considerably according t o circum- stances ; during copulation its amount decreases and glucose i s formed, which otherwise very seldom accumulates iu appreciable quantities. The gum is situated in the membrane, the tannin, how- ever, in the substance of the plant. Cholesterin and succinic acid (0.4 per cent.) are also found in algae, but the xanthines, leucine and aspayagine are not present. For %ygnemacem, nitrates are a more suitable source of nitrogen than ammonia, but this does not apply to all algze, as some thrive very well in presence of ammoniacal salts. Potassium nitrate is far less suitable than sodium nitrate. Sphog?yroe when placed in dilute solu- tions of the former died after four weekg' time, probably from over- production of starch.Potassium chloride and potassium dihydrogen phosphate do not, however, act injuriously. Some organic compounds (aspartic acid, succinic acid, hexa- methyleneamine, &c.) act nutritiously, especially in the light, but lnalic and conmalinic acids cause death Algae live for weeks in solutions of urethane without injury ; in solutions of carbamide they die after a few days, and in a few hours when placed in solutions of guanidine. On the other hand, hydantoin and creatine act beneficially, so that the injurious action of a compound is increased when, by entrance of amido-groups, its alkalinity is increased, but lessened whcn, by entrance of acid radicles, its alkaline character is dimi- nished.Ammonia and many organic bases (ethylamine, quinoline, quinine, The formula, of lecithin is probably CI4H,,O,PN. (Compare Scheibler, AnnuZen, 148, 77.) N. H. M.316 ABSTRACTS OF CHEMICAL PAPERS. &c.) cause granulation in the protoplasm of Xpirogym, and death results, probably owing to polymerisation of the active albumin ; their hydrochlorides act similarly, but in a less degree; it is probable, however, that ammonia salts do not act banefully when added in such quantity that the production of albumin and consumption of am- monia keep pace with the supply of the latter. Many other sub- stances (nitrous acid, hydrocyanic acid, potassium chlorate, &c.) cause death more or less quickly, but numerous salts (sodium phosphite, bypophosphite, t hiosulphate, barium chloride, potassium ferrocganide, &c.) have no harmful action.Algm kept in the dark lose their starch more rapidly when the tem- perature is increased ; a supply of peptones, however, decreases the rapidity of the absorption. Starch is not produced by SpirogyrE when the alga3 are placed in a solution containing 0.1 per cent. of sugar ; Vaucheria, though it produces no starch when placed in a 5 per cent. sagar solution, forms a little when placed in a 20 per cent. solution, 8 p i r o g g m deprived of its starch lived i n the dark for three weeks in a 0.1 per cent. solution of methylal, but no starch was formed. At the end of this time it was exposed to the light in water containing car- bonic anhydride, whereupon starch was produced ; a second portion of the same plant died in about three days under similar conditions, but without the addition of methylal.Vuucheria placed in 0-2 per cent. methylal solution sent off numerous shoots, whilst in water alone the mowth was quite inconsiderable ; a 1 per cent. methylal solntion can be borne by Vaucheria for several days, but in a 0.05 per cent. solution of formaldehyde death soon ensues. It follows, therefore, that methylal serves as nourishment for algae, although starch is not formed from it, but it seems that a carbo- hydrate is first formed which is suitable for the production of cellu- lose, and the authors conclude that Baeyer's theory of the formation of starch is the correct one, not! only from the result of their own experiments, but because it is snpported by other facts, especially by the rapid growth of bacteria in solutions containing compounds of met hy 1.E. WOLLNY (Bied. Centr., 1887, 721-723).-The author has experi- mented on this subject, employing flower pots with closed bottoms and of about 4 litres capacity. These were filled with a soil rich in humus, containing in different pots amounts of water varying from 10 to 100 per cent. of the qnantity the soil could hold when fully saturated. The plants experimented on were peas, rye, rape, and a grass mixture. Additions of water were made from time to time to make up for evaporation and preserve a constant degree of moist- ness. At the end of the experiments the crops were weighed. The following results were obtained :--1. A proper supply of water is by jar the most.potent factor in producing a good crop. 2. Up to a certain limit, increase of water gives increased yields, but beyond that limit further increase of water produces a continuous diminution in yield, which falls almost to zero when complete saturation of the soil is reached. 3. Within the limit mentioned, different plants are F. S. I(. Effects of Atmospheric Deposits on Plants and Soil. BYVEGETABLE PHYSIOLOGY AND AGRICULTURE. 31 7 affected in different degrees by the amount of water. 4. The most favourable amount of water is different at different stages of growth. The observations that have been made up to date lead to the con- clusion that the maximnm yield is obtained within a limit lying between 40 and 80 per cent.of the amount of water the soil can hold when fully saturated. In the case of each particular plant, the amount of water giving the best yield is higher, the more fertile the soil, the more the climate favours the development of the organs of transpiration, and the closer together the plants are situated. As re- gards the duration of growth, the smaller the water supply the shorter this period is, and in a drought the plants are more liable to die before they are perfectly developed, and to become prematurely ripe the closer they are together. The chemical composition of the grain is also affected by the supply of water ; analysis shows that dryness of soil favours the development of a compact, g.lassy grain rich in nitrogen, whilst in moist situations the grain is less compact in texture, more mealy, and proportionally poor in nitrogen.H. H. R. Testing Soil by the Growth of Oats. By A. ATTERBERG (Bied. Centr., 1887, 723-728) .-At the Calmar experimental station in Sweden, a soil suspected of having a deficiency of nitrogen and magnesia was examined as follows:-Portions of it placed in tin vessels were sown with black bearded oats, which were manured in some cases with nitrogen, in others with magnesia, and in others no manure was applied. P a r t of the plants were cut when the panicle had emerged from the sheath, and the rest when the oats were fully ripe. The results were determined as regards (1) the oats cut green, (2) the ripe straw, and (3) the ripe grain. Where magnesia had been applied, the results were negative.From the comparison of the oats manured with nitrogenous manures with the unmanured crop the following inferences are drawn :-(1.) Liberal nitrogenous manuring considerably increased, not only the weight o € the crop, but also the amount of nitrogen both in the ripe and unripe plant. (2.) This was accompanied by a material diminutioli in the amounts of potash and silica. (3.) The amounts of lime and ma,gnesia were less affected. (2) and ( 3 ) are attributed to the fa(+, that the soil, which was very poor in nitrogen, was not rich enough in available potash and phosphates to properly meet the demands of the luxurious vegetation induced by the nitrogenous manuring, but was rich enough, however, in lime and magnesia. This suggested experiments with potash and phosphates in addition to nitrogen as manuring agents, and these experiments showed- 1.That manuring with phosphates produced an increase of phos- phoric acid throughout the plant, whilst, notwithstanding that the crop had not increased, the amount of nitrogen diminished in the cases of the plants cut green and of the ripe straw. 2. That manur- ing with potash was accompanied by a material increase of crop, and that here not only was the aniount of potash raised, but dso the amounts of nitrogen and phosphoric acid were considerably lowered in both the plants cut green, the ripe straw, and the ripe grain. VOTA. LIV.318 ABSTRACTS OF CHEMICAL PAPERS. The author also conducted some sand culture experiments on tho same kind of oats by Hellriegel’s method, and found equally remark- able relations among the constituents.In the first set, varyiiig quantities of nitrogenous manures were applied, and the results showed that the smaller the application of nitrogen, the smaller is the amount of i t in the plant and the greater is the amount of phosphoric acid, of magnesia, and in most cases of potash and lime. In the second set, varying quantities of phosphates were applied, and the results showed that the smaller the application of phosphates the smaller is the amount in the plant, and the greater is the amount of nitrogen and of potash. In the grain, the amounts of potash and magnesia are more constant, and the amount of magnesia appears t o follow that of the phosphoric acid. In the third set, varying quantities of potash were applied, and the results showed that the smaller the application of potash, the smaller is the amount of it in the plant, whilst the amounts of nitrogen, phosphoric acid, and magnesia rise regularly.This did not hold in cases where the growth of the plant was checked, for here the com- position was that of the unripe plant. In the fourth set, varying quantities of magnesia were applied, and the results showed that the smaller the application of magnesia, the greater is the amount of nitrogen and phosphoric acid, ak least in the unripe plant and in the straw; the amount of lime also increases regularly. The author sums up thus:-In the case of a plant-food, if the quantity available for the plant diminishes, then diminishing amounts of it are taken up and assimilated, and the quantity in the plant also sinks.This is accompanied by a feebler development of the plant, and consequently by a smaller crop ; thus the other foods are in excess relatively to the food present in a minimum degree, and so are taken up and assimilated in increasing quantities. Influence of Lime as a Soil Constituent on the Develop- ment of Plants. By E. W. HILGARD (Bied. Centr., 1887, 738- 739).-1n general, the effect of a large proportion of lime is to encourage a low, compact growth and increased fruitfulness, whilst a deficiency of lime in a soil, otherwise of good composition, produces a thin growth and diminished fruitfulness. The droughty territories of Arizona, California, and Oregon show this on a large scale in the low and compact forms of their trees, which are less due to the parching sun than to the high proportion of lime, all the greater there for the want of a liberal rainfall to dissolve it away.H. H. R. H. H. R. Injury to Vegetation by Sulphurous Acid. By L. JUST (Bied. Centr., 1887, 790).-The injury which some mangolds planted near a cellulose factory had suffered, proved on chemical investigation to have been due to the sulphurous acid in the gases from the factory. The figures obtained show that the amount of sulphuric anhydride in the diseased plants is abnormal, and is higher than in the uninjured ones. H. H. R.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 319 Manuring Hops. By C. KRAGS (Bied. Cmtr., 1887, 785--786).- In general the manure should contain three plant-foods, phosphoric acid, potash, and nitrogen, and contain some organic substance, which by its decay will slowly render those foods available.Guano made from fseces in moderate dressings is preferable to the potash- ammonia-superphosphate formerly recommended ; it acts better even than mixtures of sodium nitrate and superphosphate containing the Bame amounts of plant-food. Rape-cake meal would appear t o be suitable on the above grounds, and in France it has been found to give good results. These manures are like fqrmyard manure both in chemical nature and physical effects, and, as with farmyard manure, care must be taken to avoid over manuring. Although nitrogen is of the greatest importance to the hop, as it is to other plants, y.et it is possible to give too much of it, and so cause injury. If nitro- genous manures are employed alone on the poorer soils, the yield will not be a full one, and even on the better soils the crops will in time fall off.Potash and phosphates should only be employed without nitrogen when a trial has proved that there is enough nitrogen stored up i n the soil, and that nitrogenous manuring will not increase the yield without injuring the quality. In good situations, artificial manure in addition to farmyard manure is tho best means of realising the profit which the locality affords. H. H. R. Manuring Sugar Beets with Basic Slag. By E. v. PROSKOWITZ (Bied. Centr., 1887, 739-742).-The trial WRS made in Kwassitz on an alluvial soil in low marshy country. The plots were 100 square metres (0.025 acre) in area. The manures employed were a basic slag and a superphosphate.The slag contained 20.5 per cent. of phos- phoric anhydride, only 0.04 per cent. being soluble in citrate solution. Its state of division was one of medium fineness. The snperphos- phate contained a total of 17.3 per cent. of phosphoric anhydride, 12-44 per cent. being soluble in water. The nnmanured plots all snifered from root decay. The best matured roots (as indicated by their having the smallest proportion of leaves to roots) were on the plots manured with superphosphate. The author concludes that in that particular neighbourhood, on heavy clay land, the basic slag was less efiectual than the customary quantity of superphosphate, and that the time of applying it had no decided influence. H. H. R. Comparison of the Different Properties and Character of Manure made with Straw and with Turf Litter.By M. FLEISCHER (Bied. Centr., 1887, 808-814).-As regards the value of straw or peat, alone as manure, it appears that straw contains most potash, lime, and phosphoric acid, whilst peat moss litter contains most nitrogen, and when mixed with manure the peat manure con- tains more easily soluble nitrogen than the straw manure ; the reten- tion of soluble nitrogen (ammoniacal compounds) by peat therefore renders it somewhat more valuable than straw. Field experiments show that peat makes the better manure, especially on light land,320 ABSTRACTS OF CHEMICAL PAPERS. because of its retentive capacity for soluble nitrogen? consequently the after effects are greater than when straw is employed.On heavy lands, however, the question is not yet decided. Behaviour of Various Plants towards Nitrogenous Manures. By E. WOLFF and C. KREUZHAGE ( X e d . Centr., 1887, 793-808).- The object in view was not to estimate the capability of plants to absorb nitrogen from the air either directly or indirectly, but rather to collect facts to prove that various plants are differently influenced by nitrogenous manures. To this end plants were sown in artificial soils, the base being sand, in some cases calcined, in others in the ordinary state, and the experiments extended over some years. Some plants received no added nitrogen, whilst others received increasing quantities. Full details of the weight of the crops harvested, the manures, &c., are given.The Field of straw crops (oats, &c.) is greatly increased by the addition of Chili saltpetre, but Leguminosae, beans, lupines, clover, &c., are not increased in yield even when the amount of added nitrogen is trebled. Beans, &c., remove from the soil more nitrogen than i s contained in the original seed and the manure, whilst the opposite is the case with oats, &c. E. W. P. E. W. P.VEGETABLE PHYSIOLOQT AND AQRIOULTURE. 313Chemistry of Vegetable Physiology and Agriculture.Reducing and Qxidising Properties of Brtcteria. By W.HEBAEUS (Bied. Centr., 1887, 783-784).-The author prepared purecultivations of the various bacteria (Bacilli and Micrococci) whichoccur in river water, in spring water and in soil, and ah0 of themould fungi (Macor and AspergiZZus J l a u z ~ s ) .Besides ash con-stituents, the nutrient liquids contained either ammonium carbonateor calcium nitrate or carbamide. There were found (besides thosebacteria that would not grow in artificial liquids) two species whichreduced nitric acid to nitrous acid and ammonia, and convertedcarbamide into ammonium carbonate ; one species which made useof nitric acid without reducing it to nitrous wid and which changedcwbstmide into ammonium salts ; one species which behaved similarlywith nitric acid, but which did not change carbamide into ammouiumcompounds ; one species which gave no indications of action on nitro-genous substances ; one species which left nitric acid unaltered butchanged carbamide into ammonium salts ; and lastly two mould fungiwhich gave no indications of action on nitrogenous substances.NoHpecies of bacteria were found which had an oxidising action; butsome micro-organisms were obtained from soil infusion and fromputrefying urine which converted the nitrogenous matter of Lothrtmmoniacal and urine solutions, and of diluted meat-infusion intonitrous acid.Further an examination for oxidising properties was made withvarious known species of bacteria ; namely, the hay bacillus,H~crococGus prodigiosus, Finkler's bacteria ; also with the pathogenicones, namely, those of anthrax and typhus, Tetragonus and others.In solutions coutaining sugar and the ash constituents, almost all ofthem were devoid of any perceptible growth ; whiIst in urine dilutedwith four times its bulk of water, Hicrococcus prodigioszcs, root-shapedbacteria, the spirillum of cheese, Finkler's bacteria, those of typhusand anthrax and Staph yZococcus citrezcs, succeeded in forming nitrousacid.Hay bacillus, ~!3'taphyZococcus aureus, and the bacteria of greenpus and of pneumonia produced a thick turbidity but no nitrous acid.Brieger's bacteria had a feeble oxidising action, and the experimentswith Miller's bacteria gave a negative result.Spring Sap of the Birch and Hornbeam. By R. HORNBERGER(Bied. Centr., 1887, 821-825).--The titap waR drawn from fhe horn-beam at two spots, the one 0.7 m. the other 4.1 m. above the ground ;from the birch at 0'5 m. and 3.5 m. above the ground, and the hoursof collectioa were 10 A.M.sDd 6 F.M. from April 13 to May 4. Thesap of both trees contains lsevulose with some dextrose, nitrogen andmdic acid and salts ; the highest percenksge of sugar is found in thesap collected at the upper boring, and the total quantity is also greater,moreover the morning sap irJ always richer in sugar than the evening,and if the upper opening is closed, then the sugar obtained below is inH. H. R314 ABSTRACTS OF CIIEMICAL PAPERS.greater quantity ; there appears also to be a diminution in gmms perlitre as the season progresses. Comparing the two saps, the horn-beam is poorer in sugar than the birch, the highest yield being4-72 grams per litre (15.59 in the birch), and this was only obtainedat the upper boring and at the commencement of the observation;ever afterwards t,he quantity decreased : the higher percentage offiugar in the morning sap was found in both t'rees.Nearly allsugar disappeared before the hornbeam ceased to blossom, whilst itstill appeared up to the end of the blossoming of the birch. Xaiicacid is in larger quantities in both saps at the later periods, and thereis no difference by day or nighh, but it is present in double thequantity in the birch sap, which contains least sugar. The totalnitrogen in the birch sap at; 3.5 m. height is twice as much as at thelower level, and the hornbeam is much poorer in nitrogen than theother tree; but little of the nitrogen appears as albuminoi'ds, but thealbumino'ids do increase during blossoming period ; the greaterportion appearing as amido-acids and in other forms, even as am-monia. The mineral constituents were found to increase during theperiod of observation; the upper boring yielded a sap richer inminerals than the lower, and the sap is also richest when collected inthe evening.With the hornbeam, this is not the cass; if any differenceis observable i t is that the lower sap is the richest. Potash increasesin the birch sap as time goes on, the evening sap being richer in itthan the morning:, the upper than the lower; the same holds goodfoi* lime and magnesia. Phosphoric acid increases at the lowerboring as the season progresses, but it decreases at the upper ; alsothe evening is richer in this compound than the morning sap, but i tis always in larger quantities at this boring.In the hornbeam, thisis different, for there is not much variation between the two yieldseither as time goea on or as the examination is made at evening ormorning.The bases in the birch sap are largely in excess of the mineral acidpresent, only & to being thus combined, and with the hornbeamthere is a similar condition of affairs, only that the differencebetween the amounts of bases and acid is hardly so great. The authorconsiders that the malic acid found in the sap of both trees is presentas a bye-product. E. W. P.Citric Acid in O x y ~ o ~ ~ u s Palustris. By P. KOSSOVI~ (Chern.Cen.tr., 1887, 1157, from J. Rzcss. Chem. SOC., 1887, 278-274).-Theamount of citric acid found in three different samples of cranberry,Orycoeczcspulustris, was 2*0,2+44, and 2.8 per cent.of the total weightof the berries. As these occur very largely in many districts of theinterior and the north of Russia, the author proposes to use theirjuice for industrial purposes, for instance in dyeing, instead of the con-centrated lemon-juice imported from Italy. J. W. L.Organic Constituents of the Beetroot Juice. By E. 0. V.LIPPMAXN (Ber., 20, 3201--,3209).--Durin (BdZ. Assoc. Chem., 1,No. 5) observed a thick froth, having an odour of butyric acid, to beformed on the surface of the bye-products from the preparation oVEGETABLE PHYSIOLOGY AND AGRICULTURE. 315siig:sr when being evaporated down. The author has examined thefroth and found that besides the potassium salts of fatty acids, it con-tains dextran and phytosterin (Hesse, Abstr., 1878, 850).Beetroot was extracted with a mixture of ether and alcohol, theether evaporated and the residue dissolved in alcohol and treatedwith platinum chloride ; the precipitate so obtained when purified anddecomposed with hydrogen sulphide yielded lecithin.This whenboiled with baryta-water yielded oleic acid, glycerol, phosphoric acid,and beta'in.A second experiment gave a lecithin which yielded no betajine, butcholine.Betnine and choline are readily separated by means of the hydro-chlorides ; betaine hydrochloride forms stable crystals, whilst cholinehydrochloride is very deliquescent.Beetroot contains also other compounds containing phosphoruswhich are related to the nuclejins ; the products of decomposition ofthese compounds-the xnnthine compounds-are almost all conhainedin the molasses,Chemico-physiological Study of Algae.By 0. LOEW andT. BOKORNY (J. pr. Chem. [ 21, 36, 272-291).--Algze (Zygrzemacere)superficially dried with blotting-paper contain 85-90 per cent. H,O ;when dried at 100" their composition is-fat 6 to 9 per cent., albumin28 to 32 per cent., cellulose and starch 60 to 66 per cent. The fat igsituated chiefly in the chlorophyll region, but is not visible in dropsunder ordinary circumstances ; lecithin is probably present. Theq uantity of starch varies very considerably according t o circum-stances ; during copulation its amount decreases and glucose i sformed, which otherwise very seldom accumulates iu appreciablequantities. The gum is situated in the membrane, the tannin, how-ever, in the substance of the plant.Cholesterin and succinic acid(0.4 per cent.) are also found in algae, but the xanthines, leucine andaspayagine are not present.For %ygnemacem, nitrates are a more suitable source of nitrogenthan ammonia, but this does not apply to all algze, as some thrive verywell in presence of ammoniacal salts. Potassium nitrate is far lesssuitable than sodium nitrate. Sphog?yroe when placed in dilute solu-tions of the former died after four weekg' time, probably from over-production of starch. Potassium chloride and potassium dihydrogenphosphate do not, however, act injuriously.Some organic compounds (aspartic acid, succinic acid, hexa-methyleneamine, &c.) act nutritiously, especially in the light, butlnalic and conmalinic acids cause death Algae live for weeks insolutions of urethane without injury ; in solutions of carbamide theydie after a few days, and in a few hours when placed in solutions ofguanidine.On the other hand, hydantoin and creatine act beneficially,so that the injurious action of a compound is increased when, byentrance of amido-groups, its alkalinity is increased, but lessenedwhcn, by entrance of acid radicles, its alkaline character is dimi-nished.Ammonia and many organic bases (ethylamine, quinoline, quinine,The formula, of lecithin is probably CI4H,,O,PN.(Compare Scheibler, AnnuZen, 148, 77.)N. H. M316 ABSTRACTS OF CHEMICAL PAPERS.&c.) cause granulation in the protoplasm of Xpirogym, and deathresults, probably owing to polymerisation of the active albumin ; theirhydrochlorides act similarly, but in a less degree; it is probable,however, that ammonia salts do not act banefully when added in suchquantity that the production of albumin and consumption of am-monia keep pace with the supply of the latter.Many other sub-stances (nitrous acid, hydrocyanic acid, potassium chlorate, &c.) causedeath more or less quickly, but numerous salts (sodium phosphite,bypophosphite, t hiosulphate, barium chloride, potassium ferrocganide,&c.) have no harmful action.Algm kept in the dark lose their starch more rapidly when the tem-perature is increased ; a supply of peptones, however, decreases therapidity of the absorption. Starch is not produced by SpirogyrEwhen the alga3 are placed in a solution containing 0.1 per cent.ofsugar ; Vaucheria, though it produces no starch when placed in a 5 percent. sagar solution, forms a little when placed in a 20 per cent. solution,8 p i r o g g m deprived of its starch lived i n the dark for three weeks in a0.1 per cent. solution of methylal, but no starch was formed. At theend of this time it was exposed to the light in water containing car-bonic anhydride, whereupon starch was produced ; a second portion ofthe same plant died in about three days under similar conditions, butwithout the addition of methylal. Vuucheria placed in 0-2 per cent.methylal solution sent off numerous shoots, whilst in water alone themowth was quite inconsiderable ; a 1 per cent.methylal solntion canbe borne by Vaucheria for several days, but in a 0.05 per cent. solutionof formaldehyde death soon ensues.It follows, therefore, that methylal serves as nourishment for algae,although starch is not formed from it, but it seems that a carbo-hydrate is first formed which is suitable for the production of cellu-lose, and the authors conclude that Baeyer's theory of the formationof starch is the correct one, not! only from the result of their ownexperiments, but because it is snpported by other facts, especiallyby the rapid growth of bacteria in solutions containing compounds ofmet hy 1.E. WOLLNY (Bied. Centr., 1887, 721-723).-The author has experi-mented on this subject, employing flower pots with closed bottomsand of about 4 litres capacity.These were filled with a soil rich inhumus, containing in different pots amounts of water varying from10 to 100 per cent. of the qnantity the soil could hold when fullysaturated. The plants experimented on were peas, rye, rape, and agrass mixture. Additions of water were made from time to time tomake up for evaporation and preserve a constant degree of moist-ness. At the end of the experiments the crops were weighed. Thefollowing results were obtained :--1. A proper supply of water is byjar the most. potent factor in producing a good crop. 2. Up to acertain limit, increase of water gives increased yields, but beyondthat limit further increase of water produces a continuous diminutionin yield, which falls almost to zero when complete saturation of thesoil is reached.3. Within the limit mentioned, different plants areF. S. I(.Effects of Atmospheric Deposits on Plants and Soil. BVEGETABLE PHYSIOLOGY AND AGRICULTURE. 31 7affected in different degrees by the amount of water. 4. The mostfavourable amount of water is different at different stages of growth.The observations that have been made up to date lead to the con-clusion that the maximnm yield is obtained within a limit lyingbetween 40 and 80 per cent. of the amount of water the soil canhold when fully saturated. In the case of each particular plant, theamount of water giving the best yield is higher, the more fertile thesoil, the more the climate favours the development of the organs oftranspiration, and the closer together the plants are situated.As re-gards the duration of growth, the smaller the water supply the shorterthis period is, and in a drought the plants are more liable to diebefore they are perfectly developed, and to become prematurely ripethe closer they are together. The chemical composition of the grainis also affected by the supply of water ; analysis shows that drynessof soil favours the development of a compact, g.lassy grain rich innitrogen, whilst in moist situations the grain is less compact intexture, more mealy, and proportionally poor in nitrogen.H. H. R.Testing Soil by the Growth of Oats. By A. ATTERBERG(Bied. Centr., 1887, 723-728) .-At the Calmar experimental stationin Sweden, a soil suspected of having a deficiency of nitrogen andmagnesia was examined as follows:-Portions of it placed in tinvessels were sown with black bearded oats, which were manured insome cases with nitrogen, in others with magnesia, and in others nomanure was applied.P a r t of the plants were cut when the paniclehad emerged from the sheath, and the rest when the oats were fullyripe. The results were determined as regards (1) the oats cut green,(2) the ripe straw, and (3) the ripe grain.Where magnesia had been applied, the results were negative. Fromthe comparison of the oats manured with nitrogenous manures withthe unmanured crop the following inferences are drawn :-(1.) Liberalnitrogenous manuring considerably increased, not only the weight o €the crop, but also the amount of nitrogen both in the ripe andunripe plant.(2.) This was accompanied by a material diminutioliin the amounts of potash and silica. (3.) The amounts of lime andma,gnesia were less affected. (2) and ( 3 ) are attributed to the fa(+,that the soil, which was very poor in nitrogen, was not rich enoughin available potash and phosphates to properly meet the demands ofthe luxurious vegetation induced by the nitrogenous manuring, butwas rich enough, however, in lime and magnesia.This suggested experiments with potash and phosphates in additionto nitrogen as manuring agents, and these experiments showed-1. That manuring with phosphates produced an increase of phos-phoric acid throughout the plant, whilst, notwithstanding that thecrop had not increased, the amount of nitrogen diminished in thecases of the plants cut green and of the ripe straw.2. That manur-ing with potash was accompanied by a material increase of crop, andthat here not only was the aniount of potash raised, but dso theamounts of nitrogen and phosphoric acid were considerably loweredin both the plants cut green, the ripe straw, and the ripe grain.VOTA. LIV318 ABSTRACTS OF CHEMICAL PAPERS.The author also conducted some sand culture experiments on thosame kind of oats by Hellriegel’s method, and found equally remark-able relations among the constituents.In the first set, varyiiig quantities of nitrogenous manures wereapplied, and the results showed that the smaller the application ofnitrogen, the smaller is the amount of i t in the plant and the greateris the amount of phosphoric acid, of magnesia, and in most cases ofpotash and lime.In the second set, varying quantities of phosphates were applied,and the results showed that the smaller the application of phosphatesthe smaller is the amount in the plant, and the greater is the amountof nitrogen and of potash.In the grain, the amounts of potash andmagnesia are more constant, and the amount of magnesia appears t ofollow that of the phosphoric acid.In the third set, varying quantities of potash were applied, and theresults showed that the smaller the application of potash, the smalleris the amount of it in the plant, whilst the amounts of nitrogen,phosphoric acid, and magnesia rise regularly.This did not hold incases where the growth of the plant was checked, for here the com-position was that of the unripe plant.In the fourth set, varying quantities of magnesia were applied, andthe results showed that the smaller the application of magnesia, thegreater is the amount of nitrogen and phosphoric acid, ak least in theunripe plant and in the straw; the amount of lime also increasesregularly.The author sums up thus:-In the case of a plant-food, if thequantity available for the plant diminishes, then diminishing amountsof it are taken up and assimilated, and the quantity in the plant alsosinks. This is accompanied by a feebler development of the plant,and consequently by a smaller crop ; thus the other foods are in excessrelatively to the food present in a minimum degree, and so are takenup and assimilated in increasing quantities.Influence of Lime as a Soil Constituent on the Develop-ment of Plants.By E. W. HILGARD (Bied. Centr., 1887, 738-739).-1n general, the effect of a large proportion of lime is toencourage a low, compact growth and increased fruitfulness, whilst adeficiency of lime in a soil, otherwise of good composition, produces athin growth and diminished fruitfulness. The droughty territories ofArizona, California, and Oregon show this on a large scale in the lowand compact forms of their trees, which are less due to the parchingsun than to the high proportion of lime, all the greater there for thewant of a liberal rainfall to dissolve it away.H.H. R.H. H. R.Injury to Vegetation by Sulphurous Acid. By L. JUST (Bied.Centr., 1887, 790).-The injury which some mangolds planted near acellulose factory had suffered, proved on chemical investigation tohave been due to the sulphurous acid in the gases from the factory.The figures obtained show that the amount of sulphuric anhydridein the diseased plants is abnormal, and is higher than in the uninjuredones. H. H. RVEGETABLE PHYSIOLOGY AND AGRICULTURE. 319Manuring Hops. By C. KRAGS (Bied. Cmtr., 1887, 785--786).-In general the manure should contain three plant-foods, phosphoricacid, potash, and nitrogen, and contain some organic substance,which by its decay will slowly render those foods available.Guanomade from fseces in moderate dressings is preferable to the potash-ammonia-superphosphate formerly recommended ; it acts better eventhan mixtures of sodium nitrate and superphosphate containing theBame amounts of plant-food. Rape-cake meal would appear t o besuitable on the above grounds, and in France it has been found togive good results. These manures are like fqrmyard manure both inchemical nature and physical effects, and, as with farmyard manure,care must be taken to avoid over manuring. Although nitrogen isof the greatest importance to the hop, as it is to other plants, y.et itis possible to give too much of it, and so cause injury. If nitro-genous manures are employed alone on the poorer soils, the yield willnot be a full one, and even on the better soils the crops will in timefall off.Potash and phosphates should only be employed withoutnitrogen when a trial has proved that there is enough nitrogen stored upi n the soil, and that nitrogenous manuring will not increase the yieldwithout injuring the quality.In good situations, artificial manure in addition to farmyard manureis tho best means of realising the profit which the locality affords.H. H. R.Manuring Sugar Beets with Basic Slag. By E. v. PROSKOWITZ(Bied. Centr., 1887, 739-742).-The trial WRS made in Kwassitz onan alluvial soil in low marshy country. The plots were 100 squaremetres (0.025 acre) in area. The manures employed were a basic slagand a superphosphate. The slag contained 20.5 per cent.of phos-phoric anhydride, only 0.04 per cent. being soluble in citrate solution.Its state of division was one of medium fineness. The snperphos-phate contained a total of 17.3 per cent. of phosphoric anhydride,12-44 per cent. being soluble in water.The nnmanured plots all snifered from root decay. The bestmatured roots (as indicated by their having the smallest proportionof leaves to roots) were on the plots manured with superphosphate.The author concludes that in that particular neighbourhood, on heavyclay land, the basic slag was less efiectual than the customary quantityof superphosphate, and that the time of applying it had no decidedinfluence. H. H. R.Comparison of the Different Properties and Character ofManure made with Straw and with Turf Litter. By M.FLEISCHER (Bied. Centr., 1887, 808-814).-As regards the value ofstraw or peat, alone as manure, it appears that straw contains mostpotash, lime, and phosphoric acid, whilst peat moss litter containsmost nitrogen, and when mixed with manure the peat manure con-tains more easily soluble nitrogen than the straw manure ; the reten-tion of soluble nitrogen (ammoniacal compounds) by peat thereforerenders it somewhat more valuable than straw. Field experimentsshow that peat makes the better manure, especially on light land320 ABSTRACTS OF CHEMICAL PAPERS.because of its retentive capacity for soluble nitrogen? consequentlythe after effects are greater than when straw is employed. On heavylands, however, the question is not yet decided.Behaviour of Various Plants towards Nitrogenous Manures.By E. WOLFF and C. KREUZHAGE ( X e d . Centr., 1887, 793-808).-The object in view was not to estimate the capability of plants toabsorb nitrogen from the air either directly or indirectly, but ratherto collect facts to prove that various plants are differently influencedby nitrogenous manures. To this end plants were sown in artificialsoils, the base being sand, in some cases calcined, in others in theordinary state, and the experiments extended over some years. Someplants received no added nitrogen, whilst others received increasingquantities. Full details of the weight of the crops harvested, themanures, &c., are given. The Field of straw crops (oats, &c.) isgreatly increased by the addition of Chili saltpetre, but Leguminosae,beans, lupines, clover, &c., are not increased in yield even when theamount of added nitrogen is trebled. Beans, &c., remove from thesoil more nitrogen than i s contained in the original seed and themanure, whilst the opposite is the case with oats, &c.E. W. P.E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8885400313

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

320 ABSTRACTS OF CHEMICAL PAPERS. An s l y t i c a1 Chemistry. Gas Receiver for Absorption Analyses. By F. A. WTLBER (Amer. Chem. J., 9, 418--420).-A peculiar form of eudiometer intended for the analysis of the gases obtained from potable waters. Use of Asbestos for Assisting the Subsidence of Suspended Matter. By W. FRESENIUS (Zeit. anaE. Chem., 27, 32-33).-1n cases where, owing to the presence of very finely divided suspended matter, as in experiments on artificial digestion, it is difficult to get clear filtration, the subsidence of the solid particles may be greatly assisted by vigorously shaking with fibrous asbestos. Determination of Sulphur, Chlorine, Bromine and Iodine in Organic Compounds. By P. CLASON (Ber., 20, 3065-3066),- This method consists in burning the substances in air charged with nitric acid.The nitric acid is contained in rolls of platinum gauze 5 cm. long and 1 cm. in diameter, filled with very small glass beads; these rolls absorb the acid readily, and it does not run out when the rolls are placed horizontally. The combustion tube is connected at one end to the air supply, then come two nitric acid rolls, a roll with- out nitric acid, boat containing the substance, two rolls without nitric acid placed a small distance apart, aft.er an interval two more nitric acid rolls, and lastly a roll without acid ; the end of the tube is drawn out, bent downwards, and dips into a flask containing water, or, in the M. J. S.ANALYTICAL CHENISTRY. 32 1 case of chlorine and bromine combustions, a solution of silver nitrate. The combustion is conducted in the usual manner, the empty rolls in the front part of the tube being first heated to redness, and the sub- stance and acid rolls then so heated that a steady stream of nitrous fumes issues from the exit tube.A. J. G. Comparative Value of Borne Proposed Tests for Nitric Acid. By P. WALDEN (Chem. Centr., 1887, 1180-1181, from J. Buss. Chem. Soc., 1887,27$-295).-Brucine gives a feeble coloration with solutioiis of potassium nitrate, 1 : 500000, and of potassium nitrite, 1 : llOO000. Diphenylamine is equally delicate. The author does not recommend phenol or toluidine. For nitrous acid, diamidobenzoic acid, meta- phenplenediamine, naphthylamine and amidobenzeneorthosulphonic acid are recommended, their delicacy being 1 : 5000000.The colour reaction with naphthol is not characteristic for nitric and nitrous acids nor for chlorine ; iti is much less delicate than the brucine and diphenylamine tests. Nitric and nitrous acids in presence of other oxidising agents can be detected in the following way :-Concentrated sulphnric acid and the solution in question are added to an alcoholic solution of &naphthol. The solution is coloured red, yellowish, or cinnamon, and shows fluorescence, which is not caused by the other oxidising agents. The delicacy is one in 300,000. These reagents can only be used as group reagents, the colours being produced by any energetic oxidising agent. If nitric and nitrous acids are both present, the former can be detected by the compounds mentioned with tolu- idine.The nitrous acid is then destroyed by an excess of carbamide and sulphuric acid, and the nitric acid which has remained unchanged can be detected by means of brucine or diphenylamine. In water analysis, where there are no other cjxidising agents present, brucine, diphenyl- amine, and metaphenylenediamine are to be preferred to zinc iodide and starch-paste. The author finally recommends a solution of diphenyl- amine in concentrated snlphuric acid as ft reagent for chromic acid, which produces quickly a fugitive blue colour even with a dilution of one part potassium dicbromate in 700,000. Presence of Sodium Phosphate in Glacial Phosphoric Acid. By A. BETTENDORFF (Zeit. and. Chem., 2 7, 24-26) .-The phosphoric acid in sticks found in commerce frequently contains sodium phos- phate, which communicates hardness t o the otherwise soft glassy acid.It can be detected by dissolving the solid in fuming hydrochloric acid, wheu the sodium remains undissolved as chloride. A quantity of sodium pyrophosphate (ignited to destroy organic matter) dissolved in hydrochloric acid of 1-19 sp. gr., left 98.5 per cent. of its sodium as chloride. One part of sodium chloride requires 1348 parts of this acid at 12" for its solution. This fnrnishes a direct method of pre- paring phosphoric acid from sodium phosphate. Estimation of Phosphoric Acid in Basic Slag. By G. KEKNEPOHL (Chem. Zeit , 11, 1089--1091).-The author confirms the opinion expressed by Klein (Abstr., 1886, 83.5), that there is little or no iron phosphide in bmic slag. The phosphoric acid in basic slag J.W. L. M. J. S. Y 2322 ABSTRACTS OF CHEMICAL PAPERS. may be accurately defermined in the following manner: 10 grams of the finely powdered slap (moistened with alcohol to prevent adherence) placed in a 500 C.C. flask, is heated with 40 C.C. of hydrochloric acid, gp. gr. 1.12, and 4Ll C.C. of water, for at least a half an hour on a water-bath; if much ferrous salt is present, it is well to add a little nitric acid or bromine before heating. An aliquot part of the filtered solution is mixed with ammonium nitrate and molybdate solution, without previons removal of the dica. The solution, after heating at about 80" for 15 minutes, is fikered, and the precipitate washed with water containing 3 per cent. of nitric acid (to remove adhering iron salts), redissolved in 2.5 per cent.ammonia, and then precipitated with magnesia mixture. The presence of silica does not interfere, owing to the ready solubility of ammonium silicomolybdate in the washing water. D. A. L. Estimation of Arsenic in Pyrites. By H. FRESENIIJS (Zeit. anaE. Chem., 27, 34?-35).-To ascertain whether by fusion the whole of the arsenic could be obhained in alkaline solution, about 10 grams of pyrites was intimately mixed with two parts of sodium carbonate and one part of potassium nitrate. The mixture was fused and thoroughly exhausted by boiling with sodium carbonate solution. The filtrate was neutralised with hydrochloric acid, mixed with ferric chloride, and precipitated by calcium carbonate. The precipitate was distilled with ferrous chloride and hydrochloric acid as long as arsenic passed over.The undissolved residue from the fusion was also dissolved in hydrochloric acid and distilled with ferrous chloride. In the latter distillate, about 9 per cent. of the whole qnnntity of arsenic was found. The method therefore presents no advanta*ges over direct distillation in a current of chlorine, or distillation wit'h ferrous chloride, after dissolving in hydrochloric acid with addit,ion of potassium c h lor at e . M. J. S. Estimation of Oxygen, Cmbonic Anhydride and Carbonic Oxide. By 6. SINIBALDI (BUZZ. Soc. Chim., 48, 244--246).-An apparatus somewhat resembling Elliott's gas analysis apparatus in principle, but not intelligible without the diagram. C. H. B. Apparatus for Direct Determination of Carbonic Anhydride.By 0. OSTERSETZER (Zeit. anal. Chem., 27, 27-30).--6 conical flask of 70 C.C. capacity is closed with a caoutchouc stopper bored with two holes. This is the inlet for washed air. Below the stopper the diameter of this tnbe is reduced so tha,t when raised it is loose in the hole. Near its lower end it has a glass hook on which is hung the glass bucket containing the carbonate. At the elid it is dmwn out' to a point which is turned up- wards. The other hole carries a Welter's safety bulb tube joined to a Geissler's drying tube. Into the upper end of the Geissler's tube is ground a small cylinder for holding pumice saturated with copper sulphate, arid the potash bulbs for absorbing the carbonic anhydride are directly connected to the Through one passes a tube bent at a right angle.Both of these contain sulphuric acid.ANALYTICAL CHEMISTRY. 323 upper end of tahis. To use the apparatus, the inlet tube is raised, and the bucket containing the subsfance is hung on its hook. A small excess of highly dilute acid is placed in the flask, and all the connec- tions are made. The tube cai=rying the bucket is then pushed down into the acid, its wider portion immediately making it fit tight in the stopper. Purified air is gently aspirated through during the decom- position, and finally the flask is shaken and gently warmed. &I. J. S. Analysis of German Silver. By F. OETTEL (Zeit. anal. Chem., 27, 15--18).-This alloy consists of copper, nickel, and zinc, but may also contain tin, lead, iron, cobalt, and manganese.The copper can with certainty be separated from zinc by one precipitation by hydrogen sulphide from a sulphuric acid solution, although not from a nitric acid solution. The solution of 0.5 gram of the alloy in nitric acid (which is consequently free from tin), is evaporated with sulphuric acid, which removes lead. It is then diluted to 100 c.c., acidified with 2 C.C. of strong hydrochloric acid, and precipitated by hydrogen sul- phide. It is heated to boiling and re-cooled before filtering, and the precipitate is washed with dilute aqueous hydrogen sulphide, adding a little hydrochloric acid at first. The filtrate is evaporated to remove hydrochloric acid, diluted, neutralised with potash, mixed with a few drops of sodium acetate, and saturated in the cold with hydrogen sulphide; zinc sulphide separates in a palverulent form, easily filtered and washed.The hydrogen sulphide is removed from the filtrate by boiling, the iron is oxidised by bromine (not by nitric acid), and precipitated by ammonia. The concentrated filtrate is made strongly alkaline with ammonia and electrolysed. Nickel and cobalt are deposited together on the platinum cylinder, whilst the manganese separates as hydrated peroxide, Pre- cipitation of the nickel by an alkali is only to be trusted when per- formed in platinum vessels. The copper and lead can also be deter- mined electrolytically. By electrolysing a nitric acid solution of the nitrates with four small Daniel1 cells, the copper from 0.5 gram of the alloy can be completely deposited in three hours, the lead at the same time separating as peroxide which can be weighed.If a sulphuric acid solution is electrolysed, the copper separates as a red mud, which can be filtered off after stopping the current, leaving the other metals for determination as above. M. J. S. Separation of Aluminium and Beryllium. By A. ZIMMERMANN (Zeit. anal. Chem., 27, 61--63).-0f all the processes hitherto pro- posed that based on the precipitation of beryllia, when its solution i n potash is boiled, seems to be the best. A very pure potash (purified by alcohol and heated till free from organic matter) is requisite. The solution of 0.3 gram of substance must not exceed 300 c.c., or alumina will be precipitated with the beryllia. After 15 to 20 minutes’ boiling in a platinum basin much hot water is added, and the beryllia is filtered off and washed.When the two earths are present in about equal quantities, but not otherwise, they may be completely separated by neutralising with It is free from potassium.324 ABSTRACTS OF CHEMICAL PAPERS. sodium carbonate and boiling with thiosulphate until no more sul- phurous acid is given off; 15 to 20 hours’ boiling is sometimes neces- sary. The alumina is precipitated together with sulphur. M. J. S. Determination of Alumina in Preaence of Iron and Phos- phoric Acid. By L. BLUM (Zeit. anal. Chem., 27, 19-24).-1n the technical analysis of such a mixture, it is usual to determine iron and phosphoric acid in two portions of the solution, to precipitate a third by ammonia, and estimate the alumina from the difference.The iron is best determined by precipitation as sulphide after adding tartaric acid. Permanganate gives higher results, owing probably to the presence of organic matter. The author draws attention to the risk of error in the precipitation of alumina by ammonia. An excess of ammonia re-dissolves the precipitate. The common practice is therefore to boil until the odour of ammonia becomes exceedingly faint. When, however, ammonium chloride is present, the detechion of ammonia in the steam by the sense of smell is compatible with an acid condition of the liquid caused by dissociation of the ammonium chloride, and in such a case part of the alumina will be re-dissolved. Presence of ammonium chloride, however, diminishes the solubility of alumina in ammonia, and by using only a small excess of ammonia, and boiling for only a short time, then filtering and washing rapidly, and only with hot water, no loss will be incurred.M. 5. S. Determination of Traces of Bismuth and Antimony in Com- mercial Copper. By P. JUNGFER (Zeit. anal. Chem., 27, 63-65). -On adding sodium carbonate to a nitric acid solution of copper containing bismuth, the latter is precipitated first. After vigorous stirring and remaining for an hour or two, the precipitate can be filtered off, dissolved in a little hydrochloric acid, and the bismuth precipitated as oxychloride by diluting. I f on dissolving the copper in nitric acid a residue remains, this should be fused with sodium sarbonate and sulphur, and tested for bismuth by Hampe’s method (ibid., 13, 184). The separation of arsenic and a.ntimony from coppep by conversion into iodides (Flajolot), is only satisfactory in the case of arsenic, but the addition of potassium fluoride greatly facilitates the washing out of the antimony from the cuprous iodide, owing seemingly to the formation of the highly soluble potassium antimonious fluoride.To the solution of 10 grams of copper in 50 C.C. of nitric acid of 1-4 sp. gr., after dilution to 200 or 300 C.C. with cold water, 0.15 gram of potassium fluoride is added, and then 26.2 grams of potassium iodide in small portions alternately with sulphurous acid. Excess of iodide is to be avoided. The liguid is then heated until the precipitate has completely subsided. The precipitate is washed with hot water containing sulphuric acid. After removing the excess of sulphiirous acid from the filtrate by iodine, hydrogen sulphide is passed in.The precipitate is dissolved in hydrochloric acid with addition of potassium chlorate, and after adding tartaric acid and ammonia, the copper, lead, and bismnth are thrown down by the cautious addition ofANALYTICAL CHElCiISTR Y. 325 dilute hydrogen snlphide, leaving +he arsenic and antimony in the filtrate to be separated by the usual methods. M. J. S. Estimation of Dissolved Carbonic Anhydride in Water. By L. VIGNON (Compt. rend., 105, 1122--1124).-50 C.C. of recently dis- tilled water or of a well-boiled sample of the water to be tested is mixed with 10 drops of a saturated alcoholic solution of phenolphtha- leih and a standard solution of lime water is added until a pink colour is developed.50 C.C. of the water to be tested is treated in precisely the same way, the standard solutiozl being added until the intensity of the coloration is the same in both tubes. Towards the end of the titration, a little time must elapse between successive additions of the calcium hy- droxide. The difference between the volume of alkali required in the two cases gives the amount of free carbonic anhydride. Chlorides, sulphates, and nitrates of calcium or magnesium do not affect the result, but if the water contains magnesium carbonate, or alkaline salts the acids of which form insoluble compounds with calcium, a sufficient quantity of neutral calcium chloride should be added to convert the magnesium and the alkalis into chlorides.If the second liquid becomes so turbid that comparison of the tints is dificult, some calcium carbonate may be added to the liquid in the first tube. This method will estimate 1 C.C. of carbonic anhydride dissolved in 1000 C.C. of water. C. H. B. Estimation of Ash in Organic Substances. By A. KOBRICH (Chem. Zeiit., 11, 1159).-5 or 1.0 grams of the substance is sub- mitted to a preliminary burning in a platinum dish, the latter being prefFrred to a crucible, as the chance of loss by creeping over the side is less. I f the substance burns readily, the ignition is completed in the dish; if otherwise, the char is pulverised, transferred to a pla- tinum crucible, and the ignition completed in a current of oxygen ; the operation proceeds quietly without any spluttering, as is the case when ammonium nitmte is used.When particles of carbon are enclosed by the fusion of the nsh, it is recommended to dissolve the mass in water ; the particles of carbon rise to the surface, and after careful evaporation are easily oxidised by igniting. D. A. L. Thiophen Reaction with Nitrous Sulphuric Acid. By C. LIEBERMANN (Bw., 20, 3231-32344 .-This reaction was mentioned in 1883 (Ber., 16, 1473), but seems to have been overlooked, as one practically identical with it, has just been given by Claisen and Manasse (Bey., 20, 2197). Two or three drops of sulphuric acid con- taining nitrous acid are shaken for some time with 1 C.C. of the benzene under examination, when the acid gradually acquires a corn flower-blue colour.If much thiophen is present, the reaction occurs almost at once ; with 2 to 3 per cent. of thiophen, i t appears after a few minutes, whilst with very small quantities some 10 to 15 minutee is required for its complete development. As little as 0.25 milli-326 ABSTRACTS OF CHEMICAL PAPERS. gram of thiophen can be detected by this test. The colouring matter is precipitated on dilution with water as a deep-brown, flocculent substance, soluble in sulphuric acid, with deep-blue colour, insoluble in water. It seems to have the constitution OHON< atmospheric oxygen is absorbed in its formation; hence the necessity of the continued shaking. C4BH‘2>0. C4SHa ’ A. J. G. Examination of Cane-sugar for Sulphurous Acid. By DAVIDSEN (Chem. Centr., 1887, 1180, from Deut.Zuckerind, 12, 939). -The sugar is dissolved in a few C.C. of cold very dilute starch solu- tion. To this a few drops of iodic acid are cautiously added, so that the liquids do not mix. A blue ring appearing at the junction shows the presence of sulphurous acid (or t,hiosulphuric acid). This method can also be used as a quantitative one by titration with iodine. J. W. L. Detection and Direct Estimation of Starch in Liquids con- taining Dextrin. BS G. BURKHARD (Chsm. Zeit., 11, 1158).-The liquid containing starch and dextrin is well mixed with just suficient alcohol to produce a slight turbidity; it is then warmed until the turbidity disappears. Tannin solution is now added to this weak alco- holic solution, and when cold the starch precipitate is collected.For qualitative purposes, the precipitate can be simply tested on the filter with dilute iodine solution. For quantitative work, the tannin is washed from the precipitate by means of alcohol ; the filter and pre- cipitate are then transferred to a Lintner’s pressure flask, and mixed with 20 C.C. of water and 1 C.C. of normal sulphuric acid. After heating for four hours at below 1Eo, the contents of the flask are neutralised with 1 C.C. of normal soda, filtered, and the sugar determined by Fehling’s solution, using Allihn’s tables for converting the quantity of reduced copper formed into sugar, and multiplying this figure by 0.9 to find the amount of starch present. Detection and Estimation of Aldehydes in Commercial Alcohols. Ry U. GAYON (Compt.rend., 105, 1182-1183) .-The author ntilises the well-known fact that aldehydes and ketones pro- duce a red coloration in solutions of magenta which have been deco- lorised by sulphurous acid. In order to prepare the reagent, a solution of 1 gram of magenta in 1000 C.C. of water is mixed with 20 C.C. of a solution of sodium hydrogen sulphite of 30” B. After about an hour, when the liquid has become nearly colourless, 10 C.C. of pure concentrated hydrochloric acid is added. The reagent is preserved in small, well-closed bottles, and becomes more sensitive on keeping. The alcohol to be examined is mixed with water until its strength is approximately 50°, and 2 C.C. of tbe diluted liquid is mixed with 1 C.C. of the reagent. A rose-violet colour appears in a few minutes, the reaction being sufficiently delicate to detect one part of aldehyde in 500,000 parts of alcohol.D. A. L. The order of mixing is important.ANALYTICAL OHENISTRY. 327 Quantitative estimations are made by comparing the depth of tint produced by the alcohol under examination with that produced by nlco hol containing a known proportion of ordinary aldehyde, the results being expressed in terms of the latter. By N. v. LORENZ (Zeit. anal. Chew., 27, 8-14) .-Goldenberg's method (ibid., 22, 270), as modified by the author, is carried out as follows:- 15 grams of the finely ground substance (argol or lees) is boiled with ?SO C.C. of water and 6 grams of potassium carbonate for 20 minutes with stirring, in a basin of at least 700 C.C. capacity over a free flame.After cooling, it is made up to 500 C.C. I f the substance is calcium tartrate only 7.5 grams is taken, and is made up to 250 C.C. It is filtered, and 100 C.C. of the filtrate is evaporated on the water-bath as far as i8 possible without any salt depositing. While still hot, it is mixed with 5 C.C. of glacial acetic acid, and 5ts soon as effervescence has ceased 100 C.C. of absolute or 95 per cent. alcohol is added. I t is vigorously stirred for two minutes, allowed to remain for 15 minutes, but not longer, then the potassium hydrogen tartrate is collected by suction through a filter of 50 C.C. capacity, on which it is washed once with 50 c.c., and twice with 25 C.C. of absolute alcohol. Without drying, it is thrown with its filter into the precipitating basin, boiled with 200 C.C.of water, and titrated hot with 3/3/10 normal soda, boiling for five minutes, when the end is approached. A neutral decoction of litmus is used, the preparation of which is minutely described. The original solution obtained by boiling the substance with potassium carbonate must be alkaline. If, owing t o the pre- sence of much calcium sulphate, this is not the case, a fresh portion must be boiled with 12 grams of carbonate. Direct experiments show that considerable variations in the quantity of potassium carbonate used do not affect the result. On the other hand, the quantity of acetic acid prescribed must be adhered to. The 200 C.C. of alcoholic tiltrate retains in solution about 0.01 77 gram of potassium hydrogen tartrate, corresponding with 0.59 per cent., but this loss is to a great extent compensated for by neglecting the volume of the insoluble matter, although in the case of lees an additional 5 C.C.of water should be added in making up to partially allow for this. Points of Difference between Linseed Oil and Linseed-oil Varnish. By FINKENER (Ohem. Zeit., 11, 905-906) .-In columns 15 mm. thick, the oil appears yellow, the varnish brown, by transmitted light. When smeared on a plate, the oil remains greasy for 24 hours, whilst the varnish becomes sticky, or even solidifies. The following test will distinguish a pure linseed oil from an oil containing 25 per cent. of the varnish. 12 C.C. of the oil under examination is shaken with 1 C.C. of a 20 per cent. solution of ammonia mixed with 5 C.C.of the test solution (composed of 100 grams of lead acetate, 150 C.C. of water. and 32 grams of glycerol), and heated at 10G" for three minutes; linseed oil forms two liquid layers, the lower one clear as water; whereas linseed-oil varnish sets to a salve-like mass. So-called bleached linseed-oil varnish is paler yellow than linseed oil, neverthe- C. H. B. Analysis of Materials containing Tartaric Acid. M. J. S.328 ABSTRACTS OF CHEMICAL PAPERS. less it resembles the latter in other points. With solvents, saponifying and oxidising agents, the behaviour of the oil is not readily dis- tinguishable from that of the varnish. Apparatus for the Estimation of Urea. By P. CAZENEUVE and HUGOUNENQ (BdE. SOC. China., 48, 82--86).-This apparatus consists OC a copper oil-bath, provided with a thermometer and thermoreguln- tor, and bronze tubes fitted with screw-caps, coated internally with platinum by electrolysis, and capable of withstanding a pressure of 60 atmos.25 to 30 C.C. of the liquid to be examined is agitated with unwashed bone-black, which decolorises and neutralises it, and 10 C.C. of the filtered liquid is diluted with 20 C.C. of water, heated in one of the tubes at 180" for half an hour, and the ammonia formed is estimated by titration with normal sulphuric acid, using methyl-orange or phenolphthalein as indicator. The results of the test analyses given are very satisfactory. Hugounenq has previously shown that tyrosine, leucine, peptones, &c., give no ammonia when heated with water at 180-190". C. H. B. Note by Abstractor.-Phenolphthale'in is useless as an indicator in presence of ammonium salts or for the titration of ammonia.-G.H. B. D. A. L. Volatile Alkaloyds. By 0. DE CONINCK (Compt. remd., 105, 1180- 1182).-A summary of the methods available for distinguishing the volatile alkaloids from one another. Details of the application of these methods will be given in a subsequent paper. C. H. B.320 ABSTRACTS OF CHEMICAL PAPERS.An s l y t i c a1 Chemistry.Gas Receiver for Absorption Analyses. By F. A. WTLBER(Amer. Chem. J., 9, 418--420).-A peculiar form of eudiometerintended for the analysis of the gases obtained from potable waters.Use of Asbestos for Assisting the Subsidence of SuspendedMatter. By W. FRESENIUS (Zeit. anaE. Chem., 27, 32-33).-1ncases where, owing to the presence of very finely divided suspendedmatter, as in experiments on artificial digestion, it is difficult to getclear filtration, the subsidence of the solid particles may be greatlyassisted by vigorously shaking with fibrous asbestos.Determination of Sulphur, Chlorine, Bromine and Iodinein Organic Compounds.By P. CLASON (Ber., 20, 3065-3066),-This method consists in burning the substances in air charged withnitric acid. The nitric acid is contained in rolls of platinum gauze5 cm. long and 1 cm. in diameter, filled with very small glass beads;these rolls absorb the acid readily, and it does not run out when therolls are placed horizontally. The combustion tube is connected atone end to the air supply, then come two nitric acid rolls, a roll with-out nitric acid, boat containing the substance, two rolls without nitricacid placed a small distance apart, aft.er an interval two more nitricacid rolls, and lastly a roll without acid ; the end of the tube is drawnout, bent downwards, and dips into a flask containing water, or, in theM.J. SANALYTICAL CHENISTRY. 32 1case of chlorine and bromine combustions, a solution of silver nitrate.The combustion is conducted in the usual manner, the empty rolls inthe front part of the tube being first heated to redness, and the sub-stance and acid rolls then so heated that a steady stream of nitrousfumes issues from the exit tube. A. J. G.Comparative Value of Borne Proposed Tests for Nitric Acid.By P. WALDEN (Chem. Centr., 1887, 1180-1181, from J.Buss. Chem.Soc., 1887,27$-295).-Brucine gives a feeble coloration with solutioiisof potassium nitrate, 1 : 500000, and of potassium nitrite, 1 : llOO000.Diphenylamine is equally delicate. The author does not recommendphenol or toluidine. For nitrous acid, diamidobenzoic acid, meta-phenplenediamine, naphthylamine and amidobenzeneorthosulphonicacid are recommended, their delicacy being 1 : 5000000. The colourreaction with naphthol is not characteristic for nitric and nitrousacids nor for chlorine ; iti is much less delicate than the brucine anddiphenylamine tests. Nitric and nitrous acids in presence of otheroxidising agents can be detected in the following way :-Concentratedsulphnric acid and the solution in question are added to an alcoholicsolution of &naphthol.The solution is coloured red, yellowish, orcinnamon, and shows fluorescence, which is not caused by the otheroxidising agents. The delicacy is one in 300,000. These reagentscan only be used as group reagents, the colours being produced by anyenergetic oxidising agent. If nitric and nitrous acids are both present,the former can be detected by the compounds mentioned with tolu-idine. The nitrous acid is then destroyed by an excess of carbamide andsulphuric acid, and the nitric acid which has remained unchanged canbe detected by means of brucine or diphenylamine. In water analysis,where there are no other cjxidising agents present, brucine, diphenyl-amine, and metaphenylenediamine are to be preferred to zinc iodide andstarch-paste.The author finally recommends a solution of diphenyl-amine in concentrated snlphuric acid as ft reagent for chromic acid,which produces quickly a fugitive blue colour even with a dilution ofone part potassium dicbromate in 700,000.Presence of Sodium Phosphate in Glacial Phosphoric Acid.By A. BETTENDORFF (Zeit. and. Chem., 2 7, 24-26) .-The phosphoricacid in sticks found in commerce frequently contains sodium phos-phate, which communicates hardness t o the otherwise soft glassy acid.It can be detected by dissolving the solid in fuming hydrochloric acid,wheu the sodium remains undissolved as chloride. A quantity ofsodium pyrophosphate (ignited to destroy organic matter) dissolvedin hydrochloric acid of 1-19 sp. gr., left 98.5 per cent.of its sodium aschloride. One part of sodium chloride requires 1348 parts of thisacid at 12" for its solution. This fnrnishes a direct method of pre-paring phosphoric acid from sodium phosphate.Estimation of Phosphoric Acid in Basic Slag. By G.KEKNEPOHL (Chem. Zeit , 11, 1089--1091).-The author confirms theopinion expressed by Klein (Abstr., 1886, 83.5), that there is little orno iron phosphide in bmic slag. The phosphoric acid in basic slagJ. W. L.M. J. S.Y 322 ABSTRACTS OF CHEMICAL PAPERS.may be accurately defermined in the following manner: 10 grams ofthe finely powdered slap (moistened with alcohol to prevent adherence)placed in a 500 C.C. flask, is heated with 40 C.C. of hydrochloricacid, gp.gr. 1.12, and 4Ll C.C. of water, for at least a half an hour on awater-bath; if much ferrous salt is present, it is well to add a littlenitric acid or bromine before heating. An aliquot part of the filteredsolution is mixed with ammonium nitrate and molybdate solution,without previons removal of the dica. The solution, after heatingat about 80" for 15 minutes, is fikered, and the precipitate washedwith water containing 3 per cent. of nitric acid (to remove adheringiron salts), redissolved in 2.5 per cent. ammonia, and then precipitatedwith magnesia mixture. The presence of silica does not interfere,owing to the ready solubility of ammonium silicomolybdate in thewashing water. D. A. L.Estimation of Arsenic in Pyrites. By H. FRESENIIJS (Zeit.anaE.Chem., 27, 34?-35).-To ascertain whether by fusion the wholeof the arsenic could be obhained in alkaline solution, about 10 gramsof pyrites was intimately mixed with two parts of sodium carbonateand one part of potassium nitrate. The mixture was fused andthoroughly exhausted by boiling with sodium carbonate solution.The filtrate was neutralised with hydrochloric acid, mixed with ferricchloride, and precipitated by calcium carbonate. The precipitate wasdistilled with ferrous chloride and hydrochloric acid as long asarsenic passed over. The undissolved residue from the fusion wasalso dissolved in hydrochloric acid and distilled with ferrous chloride.In the latter distillate, about 9 per cent. of the whole qnnntity ofarsenic was found.The method therefore presents no advanta*gesover direct distillation in a current of chlorine, or distillation wit'hferrous chloride, after dissolving in hydrochloric acid with addit,ion ofpotassium c h lor at e . M. J. S.Estimation of Oxygen, Cmbonic Anhydride and CarbonicOxide. By 6. SINIBALDI (BUZZ. Soc. Chim., 48, 244--246).-Anapparatus somewhat resembling Elliott's gas analysis apparatus inprinciple, but not intelligible without the diagram. C. H. B.Apparatus for Direct Determination of Carbonic Anhydride.By 0. OSTERSETZER (Zeit. anal. Chem., 27, 27-30).--6 conical flaskof 70 C.C. capacity is closed with a caoutchouc stopper bored with twoholes. This is theinlet for washed air. Below the stopper the diameter of this tnbe isreduced so tha,t when raised it is loose in the hole. Near its lower endit has a glass hook on which is hung the glass bucket containing thecarbonate.At the elid it is dmwn out' to a point which is turned up-wards. The other hole carries a Welter's safety bulb tube joined toa Geissler's drying tube. Intothe upper end of the Geissler's tube is ground a small cylinder forholding pumice saturated with copper sulphate, arid the potash bulbsfor absorbing the carbonic anhydride are directly connected to theThrough one passes a tube bent at a right angle.Both of these contain sulphuric acidANALYTICAL CHEMISTRY. 323upper end of tahis. To use the apparatus, the inlet tube is raised, andthe bucket containing the subsfance is hung on its hook. A smallexcess of highly dilute acid is placed in the flask, and all the connec-tions are made.The tube cai=rying the bucket is then pushed downinto the acid, its wider portion immediately making it fit tight in thestopper. Purified air is gently aspirated through during the decom-position, and finally the flask is shaken and gently warmed.&I. J. S.Analysis of German Silver. By F. OETTEL (Zeit. anal. Chem.,27, 15--18).-This alloy consists of copper, nickel, and zinc, but mayalso contain tin, lead, iron, cobalt, and manganese. The copper canwith certainty be separated from zinc by one precipitation by hydrogensulphide from a sulphuric acid solution, although not from a nitricacid solution. The solution of 0.5 gram of the alloy in nitric acid(which is consequently free from tin), is evaporated with sulphuricacid, which removes lead.It is then diluted to 100 c.c., acidified with2 C.C. of strong hydrochloric acid, and precipitated by hydrogen sul-phide. It is heated to boiling and re-cooled before filtering, and theprecipitate is washed with dilute aqueous hydrogen sulphide, addinga little hydrochloric acid at first.The filtrate is evaporated to remove hydrochloric acid, diluted,neutralised with potash, mixed with a few drops of sodium acetate,and saturated in the cold with hydrogen sulphide; zinc sulphideseparates in a palverulent form, easily filtered and washed. Thehydrogen sulphide is removed from the filtrate by boiling, the iron isoxidised by bromine (not by nitric acid), and precipitated by ammonia.The concentrated filtrate is made strongly alkaline with ammonia andelectrolysed.Nickel and cobalt are deposited together on the platinumcylinder, whilst the manganese separates as hydrated peroxide, Pre-cipitation of the nickel by an alkali is only to be trusted when per-formed in platinum vessels. The copper and lead can also be deter-mined electrolytically. By electrolysing a nitric acid solution of thenitrates with four small Daniel1 cells, the copper from 0.5 gram of thealloy can be completely deposited in three hours, the lead at the sametime separating as peroxide which can be weighed. If a sulphuricacid solution is electrolysed, the copper separates as a red mud, whichcan be filtered off after stopping the current, leaving the other metalsfor determination as above.M. J. S.Separation of Aluminium and Beryllium. By A. ZIMMERMANN(Zeit. anal. Chem., 27, 61--63).-0f all the processes hitherto pro-posed that based on the precipitation of beryllia, when its solution i npotash is boiled, seems to be the best. A very pure potash (purified byalcohol and heated till free from organic matter) is requisite. Thesolution of 0.3 gram of substance must not exceed 300 c.c., or aluminawill be precipitated with the beryllia. After 15 to 20 minutes’ boilingin a platinum basin much hot water is added, and the beryllia isfiltered off and washed.When the two earths are present in about equal quantities, but nototherwise, they may be completely separated by neutralising withIt is free from potassium324 ABSTRACTS OF CHEMICAL PAPERS.sodium carbonate and boiling with thiosulphate until no more sul-phurous acid is given off; 15 to 20 hours’ boiling is sometimes neces-sary.The alumina is precipitated together with sulphur.M. J. S.Determination of Alumina in Preaence of Iron and Phos-phoric Acid. By L. BLUM (Zeit. anal. Chem., 27, 19-24).-1n thetechnical analysis of such a mixture, it is usual to determine ironand phosphoric acid in two portions of the solution, to precipitate athird by ammonia, and estimate the alumina from the difference. Theiron is best determined by precipitation as sulphide after addingtartaric acid. Permanganate gives higher results, owing probably tothe presence of organic matter.The author draws attention to the risk of error in the precipitationof alumina by ammonia.An excess of ammonia re-dissolves theprecipitate. The common practice is therefore to boil until the odourof ammonia becomes exceedingly faint. When, however, ammoniumchloride is present, the detechion of ammonia in the steam by thesense of smell is compatible with an acid condition of the liquidcaused by dissociation of the ammonium chloride, and in such a casepart of the alumina will be re-dissolved. Presence of ammoniumchloride, however, diminishes the solubility of alumina in ammonia,and by using only a small excess of ammonia, and boiling for onlya short time, then filtering and washing rapidly, and only with hotwater, no loss will be incurred.M. 5. S.Determination of Traces of Bismuth and Antimony in Com-mercial Copper. By P. JUNGFER (Zeit. anal. Chem., 27, 63-65).-On adding sodium carbonate to a nitric acid solution of coppercontaining bismuth, the latter is precipitated first. After vigorousstirring and remaining for an hour or two, the precipitate can befiltered off, dissolved in a little hydrochloric acid, and the bismuthprecipitated as oxychloride by diluting. I f on dissolving the copperin nitric acid a residue remains, this should be fused with sodiumsarbonate and sulphur, and tested for bismuth by Hampe’s method(ibid., 13, 184). The separation of arsenic and a.ntimony from coppepby conversion into iodides (Flajolot), is only satisfactory in the caseof arsenic, but the addition of potassium fluoride greatly facilitatesthe washing out of the antimony from the cuprous iodide, owingseemingly to the formation of the highly soluble potassium antimoniousfluoride. To the solution of 10 grams of copper in 50 C.C.of nitricacid of 1-4 sp. gr., after dilution to 200 or 300 C.C. with cold water,0.15 gram of potassium fluoride is added, and then 26.2 grams ofpotassium iodide in small portions alternately with sulphurous acid.Excess of iodide is to be avoided. The liguid is then heated until theprecipitate has completely subsided. The precipitate is washed withhot water containing sulphuric acid. After removing the excess ofsulphiirous acid from the filtrate by iodine, hydrogen sulphide is passedin. The precipitate is dissolved in hydrochloric acid with addition ofpotassium chlorate, and after adding tartaric acid and ammonia, thecopper, lead, and bismnth are thrown down by the cautious addition oANALYTICAL CHElCiISTR Y.325dilute hydrogen snlphide, leaving +he arsenic and antimony in thefiltrate to be separated by the usual methods. M. J. S.Estimation of Dissolved Carbonic Anhydride in Water. ByL. VIGNON (Compt. rend., 105, 1122--1124).-50 C.C. of recently dis-tilled water or of a well-boiled sample of the water to be tested ismixed with 10 drops of a saturated alcoholic solution of phenolphtha-leih and a standard solution of lime water is added until a pink colouris developed.50 C.C. of the water to be tested is treated in precisely the same way,the standard solutiozl being added until the intensity of the colorationis the same in both tubes.Towards the end of the titration, a littletime must elapse between successive additions of the calcium hy-droxide. The difference between the volume of alkali required in thetwo cases gives the amount of free carbonic anhydride.Chlorides, sulphates, and nitrates of calcium or magnesium do notaffect the result, but if the water contains magnesium carbonate, oralkaline salts the acids of which form insoluble compounds withcalcium, a sufficient quantity of neutral calcium chloride should beadded to convert the magnesium and the alkalis into chlorides. Ifthe second liquid becomes so turbid that comparison of the tints isdificult, some calcium carbonate may be added to the liquid in thefirst tube.This method will estimate 1 C.C.of carbonic anhydride dissolved in1000 C.C. of water. C. H. B.Estimation of Ash in Organic Substances. By A. KOBRICH(Chem. Zeiit., 11, 1159).-5 or 1.0 grams of the substance is sub-mitted to a preliminary burning in a platinum dish, the latter beingprefFrred to a crucible, as the chance of loss by creeping over the sideis less. I f the substance burns readily, the ignition is completed inthe dish; if otherwise, the char is pulverised, transferred to a pla-tinum crucible, and the ignition completed in a current of oxygen ; theoperation proceeds quietly without any spluttering, as is the casewhen ammonium nitmte is used. When particles of carbon areenclosed by the fusion of the nsh, it is recommended to dissolve themass in water ; the particles of carbon rise to the surface, and aftercareful evaporation are easily oxidised by igniting.D. A. L.Thiophen Reaction with Nitrous Sulphuric Acid. By C.LIEBERMANN (Bw., 20, 3231-32344 .-This reaction was mentioned in1883 (Ber., 16, 1473), but seems to have been overlooked, as onepractically identical with it, has just been given by Claisen andManasse (Bey., 20, 2197). Two or three drops of sulphuric acid con-taining nitrous acid are shaken for some time with 1 C.C. of thebenzene under examination, when the acid gradually acquires a cornflower-blue colour. If much thiophen is present, the reaction occursalmost at once ; with 2 to 3 per cent. of thiophen, i t appears after afew minutes, whilst with very small quantities some 10 to 15 minuteeis required for its complete development.As little as 0.25 milli326 ABSTRACTS OF CHEMICAL PAPERS.gram of thiophen can be detected by this test. The colouring matteris precipitated on dilution with water as a deep-brown, flocculentsubstance, soluble in sulphuric acid, with deep-blue colour, insolublein water. It seems to have the constitution OHON<atmospheric oxygen is absorbed in its formation; hence the necessityof the continued shaking.C4BH‘2>0.C4SHa ’A. J. G.Examination of Cane-sugar for Sulphurous Acid. ByDAVIDSEN (Chem. Centr., 1887, 1180, from Deut. Zuckerind, 12, 939).-The sugar is dissolved in a few C.C. of cold very dilute starch solu-tion.To this a few drops of iodic acid are cautiously added, so thatthe liquids do not mix. A blue ring appearing at the junction showsthe presence of sulphurous acid (or t,hiosulphuric acid). This methodcan also be used as a quantitative one by titration with iodine.J. W. L.Detection and Direct Estimation of Starch in Liquids con-taining Dextrin. BS G. BURKHARD (Chsm. Zeit., 11, 1158).-Theliquid containing starch and dextrin is well mixed with just suficientalcohol to produce a slight turbidity; it is then warmed until theturbidity disappears. Tannin solution is now added to this weak alco-holic solution, and when cold the starch precipitate is collected. Forqualitative purposes, the precipitate can be simply tested on the filterwith dilute iodine solution.For quantitative work, the tannin iswashed from the precipitate by means of alcohol ; the filter and pre-cipitate are then transferred to a Lintner’s pressure flask, and mixedwith 20 C.C. of water and 1 C.C. of normal sulphuric acid. After heatingfor four hours at below 1Eo, the contents of the flask are neutralisedwith 1 C.C. of normal soda, filtered, and the sugar determined byFehling’s solution, using Allihn’s tables for converting the quantityof reduced copper formed into sugar, and multiplying this figure by0.9 to find the amount of starch present.Detection and Estimation of Aldehydes in CommercialAlcohols. Ry U. GAYON (Compt. rend., 105, 1182-1183) .-Theauthor ntilises the well-known fact that aldehydes and ketones pro-duce a red coloration in solutions of magenta which have been deco-lorised by sulphurous acid.In order to prepare the reagent, a solution of 1 gram of magentain 1000 C.C.of water is mixed with 20 C.C. of a solution of sodiumhydrogen sulphite of 30” B. After about an hour, when the liquidhas become nearly colourless, 10 C.C. of pure concentrated hydrochloricacid is added. The reagent ispreserved in small, well-closed bottles, and becomes more sensitive onkeeping.The alcohol to be examined is mixed with water until its strengthis approximately 50°, and 2 C.C. of tbe diluted liquid is mixed with1 C.C. of the reagent. A rose-violet colour appears in a few minutes,the reaction being sufficiently delicate to detect one part of aldehydein 500,000 parts of alcohol.D.A. L.The order of mixing is importantANALYTICAL OHENISTRY. 327Quantitative estimations are made by comparing the depth of tintproduced by the alcohol under examination with that produced bynlco hol containing a known proportion of ordinary aldehyde, theresults being expressed in terms of the latter.By N. v.LORENZ (Zeit. anal. Chew., 27, 8-14) .-Goldenberg's method (ibid.,22, 270), as modified by the author, is carried out as follows:-15 grams of the finely ground substance (argol or lees) is boiled with?SO C.C. of water and 6 grams of potassium carbonate for 20 minuteswith stirring, in a basin of at least 700 C.C. capacity over a free flame.After cooling, it is made up to 500 C.C. I f the substance is calciumtartrate only 7.5 grams is taken, and is made up to 250 C.C.It isfiltered, and 100 C.C. of the filtrate is evaporated on the water-bath asfar as i8 possible without any salt depositing. While still hot, it ismixed with 5 C.C. of glacial acetic acid, and 5ts soon as effervescence hasceased 100 C.C. of absolute or 95 per cent. alcohol is added. I t isvigorously stirred for two minutes, allowed to remain for 15 minutes,but not longer, then the potassium hydrogen tartrate is collected bysuction through a filter of 50 C.C. capacity, on which it is washedonce with 50 c.c., and twice with 25 C.C. of absolute alcohol.Without drying, it is thrown with its filter into the precipitatingbasin, boiled with 200 C.C. of water, and titrated hot with 3/3/10 normalsoda, boiling for five minutes, when the end is approached.A neutraldecoction of litmus is used, the preparation of which is minutelydescribed. The original solution obtained by boiling the substancewith potassium carbonate must be alkaline. If, owing t o the pre-sence of much calcium sulphate, this is not the case, a fresh portionmust be boiled with 12 grams of carbonate. Direct experiments showthat considerable variations in the quantity of potassium carbonateused do not affect the result. On the other hand, the quantity ofacetic acid prescribed must be adhered to. The 200 C.C. of alcoholictiltrate retains in solution about 0.01 77 gram of potassium hydrogentartrate, corresponding with 0.59 per cent., but this loss is to a greatextent compensated for by neglecting the volume of the insolublematter, although in the case of lees an additional 5 C.C.of water shouldbe added in making up to partially allow for this.Points of Difference between Linseed Oil and Linseed-oilVarnish. By FINKENER (Ohem. Zeit., 11, 905-906) .-In columns15 mm. thick, the oil appears yellow, the varnish brown, by transmittedlight. When smeared on a plate, the oil remains greasy for 24 hours,whilst the varnish becomes sticky, or even solidifies. The followingtest will distinguish a pure linseed oil from an oil containing 25 per cent.of the varnish. 12 C.C. of the oil under examination is shaken with1 C.C. of a 20 per cent. solution of ammonia mixed with 5 C.C. of thetest solution (composed of 100 grams of lead acetate, 150 C.C. of water.and 32 grams of glycerol), and heated at 10G" for three minutes;linseed oil forms two liquid layers, the lower one clear as water;whereas linseed-oil varnish sets to a salve-like mass. So-calledbleached linseed-oil varnish is paler yellow than linseed oil, neverthe-C. H. B.Analysis of Materials containing Tartaric Acid.M. J. S328 ABSTRACTS OF CHEMICAL PAPERS.less it resembles the latter in other points. With solvents, saponifyingand oxidising agents, the behaviour of the oil is not readily dis-tinguishable from that of the varnish.Apparatus for the Estimation of Urea. By P. CAZENEUVE andHUGOUNENQ (BdE. SOC. China., 48, 82--86).-This apparatus consistsOC a copper oil-bath, provided with a thermometer and thermoreguln-tor, and bronze tubes fitted with screw-caps, coated internally withplatinum by electrolysis, and capable of withstanding a pressure of60 atmos.25 to 30 C.C. of the liquid to be examined is agitated with unwashedbone-black, which decolorises and neutralises it, and 10 C.C. of thefiltered liquid is diluted with 20 C.C. of water, heated in one of thetubes at 180" for half an hour, and the ammonia formed is estimatedby titration with normal sulphuric acid, using methyl-orange orphenolphthalein as indicator. The results of the test analyses givenare very satisfactory. Hugounenq has previously shown that tyrosine,leucine, peptones, &c., give no ammonia when heated with water at180-190". C. H. B.Note by Abstractor.-Phenolphthale'in is useless as an indicator inpresence of ammonium salts or for the titration of ammonia.-G. H. B.D. A. L.Volatile Alkaloyds. By 0. DE CONINCK (Compt. remd., 105, 1180-1182).-A summary of the methods available for distinguishing thevolatile alkaloids from one another. Details of the application ofthese methods will be given in a subsequent paper. C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8885400320

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

329 General and Physical Chemistry. Degree of Oxidation of Chromium and Manganese in Fluorescent Compounds. By L. DE BOISBAUDRAN (Compt. rend., 105, 1228-1233) .-This paper contains details of the results ob- tained by calcining, in air or in hydrogen, mixtures of pure alumina with chromic oxide ; of gallium oxide and chromic oxide ; of calcium oxide and chromic oxide ; of magnesium oxide and chromic oxide ; of alumina with small quantities of potassium and manganese oxides ; and of calcium and manganese oxides. Too large a proportion of chromium reduces and may even destroy the fluorescence. In Some cases, calcination in hydrogen reduces, in ohhers it intensifies the fluorescence, but no general conclusions are drawn as to the influence of the degree of oxidation on the phe- nomenon.C. H. B. Rotatory Dispersion. By L. GRIMBERT (J. Pharm. [ 5 ] , 16, 295- 300 ; 345-350) .-The author employed Laurent's polnrimeter and rnonobnromAkic'ii&h. "LO ahtiin rays near '507 I , a'iayer'i cm.'tkEK of the following solution was used :-Carmine No. 40 0.25 gram, ammonia 20 c.c., water to make up t o 100 C.C. With white light, this solution gives a specti-urn reduced to a very narrow band coincid- ing with the C line. On taking the rotative power of an active sub- stance in this light and also in the sodium light, two different values are obtained, [ a ] n and The ratio [a]~/[a]~ gives the dispersive power. Usually tubes of 200 mm. length were ernploj-ed ; sometimes 100 mrn. tubes were used, as, for example, when the deviation was over 2 0 " ~ 8accharose.-Both water and alcohol were ernplored as solvents.The rotative power varies neither with the concentration nor with the solvent : [a]= = +66*45"; [.Ic = 52.85"; and [a]D/[aIc = 1.257. Lactose.-It is well known that the rotative power of lactose diminishes rapidly when first dissolved in the cold. The rotative power does not v a ~ y with the concentration. It is [ a ] D = + 52.37 and [a]. = +41.58". The ratio between the rotative power when first dissolved to that when it becomes stationary is as 8 : 5. The dispersive power is [a]D/[a-jc = 1.259, and is constant during tohe time the rotative power is passing to the minimum. I t does not vary with the concentration of the solution. Maltose.-When dissolved in the cold, the rotative power of maltose increases to a maximum.Its dispersive power is 1.262, and is con- stant during the time the rotative power is changing. The ratio between the initial and final rotative powers is as 2 : 1. The dispersive power is 1.258, and is con- stant whilst the rotative power is passing to the minimum. .Morphine ~?/dl.ochZoride.--Solntions of different degrees of concen- tration confirmed the value given by Hesse, [ a ] D = -100*67"-1-14 C. VOL. LIT. I Glucose acts like lactose.330 ABSTRACTS OF CHEMICAL PAPERS. The dispersive power [~&]D/[ct]c = 1.284, and does not vary with the concentration. Codehe.-In absolute alcohol, [a]D = -134*24', and in chloroform -114.82", but the dispersive power only varies slightly and is on the average 1.268. Brztcine.-Anhydrous brucine, dissolved in absolute alcohol and in chloroform, gave values for [a]D confirming those obtained by Oude- mans.The dispersive power does not vary with the nature of the solvent, and is = 1.357, the highest hitherto observed. Quinine.-The hydrate, dissolved in absolute alcohol, and in chloroform ; the basic hydrochlode dissolved in water; and the normal sulphate dissolved in water, and in 90" alcohol, all give the same dis- persive power of 1.313, the variation in the solvent and in the acid combined with the base producing no change in this respect. Cinchonine.-The basic sulphate was observed when dissolved in water, absolute alcohol, and chloroform. Although the nature of the solvent has considerable effect on the rotative power of the salt, the dispersive power remains constant and equal to 1.268.Strychnine.-Two samples of different character were recrystallised from alcohol, and dissolved both in 80" alcohol and in chlorofornr. Notwithstanding considerable differences in the rotative power of the two samples in both solvents, the dispersive power was constant and equal to 1313. Camphor.-This substance was recrystallised from alcohol and fused. It was dissolved in alcohol of various strengths, in chloroform, and in dry ether. The rotative power varies with the nature of the solvent ; its dispersive power is sensibly constant. In alcoholic solu- tion, the rotative power increases with concentration of the alcohol. I n dry ether, the rotative power does not vary with the concentration of the solution. I n chloroform, as well as in alcohol, the dispersive power remains eonstant, notwithstanding that the rotative power increases with the concentration.Its dis- persive power averages 1.323. I t doeH not vary, like the rotative power, with the nature of the solvent. Cho2esferin.-This was observed in ether and chloroform. Essence of Te're'benthine.-A laevorotatory sample gave- [a]= = - 30.46, [a], = - 28.37, and [ a ] D / [ ~ ] c = 1.241. The results obtained with the foregoing substances show that the dispersive power remains constant whatever be the concentration of the solution ; that the dispersive power of those substances whose rotative power varies with t,he temperature, remains constant all through that variation ; that for the same snbstance it scarcely varies with the nature of the solvent; that each substance has its own proper dispersive power which seems to bear no relation to the chemical constitution of the substance, although it may be noted that the sugars have all the same value.Distribution of Electromotive Force in the Cells of Batteries. By J. MIESLER (LZ rcwtsk., 8: 626--631).--The author has extended the work of Moser (this vol., p. 209) to the butteries of Grove, J. T.GENERAL AND PHYSICAL CHEMISTRY. 931 Bunsen, Grenet, Smee, Lalande, and Leclanchh. In every case, the total electromotive force of the battery under examination was found to be equal to the sum of the electromotive forces between the different parts of the cell. Electrochemical Studies. By W. OSTWALD (Zeit. physikd. Chem., 1,74436 and 97-109) .-From his former experiments (J.pr. Chem., 1884-1886), the author has drawn the conclusion thaf the molecular conductivity increases for monobasic acids with increasing dilution, teuding to a maxinium value which it was thought would prove to be the same for all acids. On careful repetition of these experiments, the latter view is found to be incorrect, as the maxima observed for a dilution of 1024 litres diffep for 15 different acids by as much as 12 per cent. That this difference does not affect the proportionality between the maximum conductivity and the rate of chemical action of these acids is proved by experiment, the latter being in fact proportional to the relative observed maximum con- ductivity. A difficulty, however, obviously arises in determining the value af this maximum for feeble acids of low conductivity. To overcome this, Kohlrausch's law that the conductivity of a neutral salt may be represented as a sum of two constants, one of which depends on the nature of the acid and the other on that of the base, is resorted to.It is shown by the determination of the con- ductivities of a number of sodium salts of acids of kuown conductivity that a constant difference exists between the two. The same holds good for lithium and potassium salts, which also differ in Conductivity from the sodium salts by a constant fixed quantity. The molecular con- ductivities of different salts having the same base, differ very largely amongst themselves, and altoget'her contradict the opinion of Arrhenius and Bouty that the molecular conductivities of dilute salt solutions are the same. The numbers prove, however, that it is possible to represent the conductivity of an acid by that of one of its salts, plus some constant.The determination of these constants is reserved for tt future paper. Another interesting result is that there is an almost constant in- crease in the molecular conductivity of the sodium salts of the mono- basic acids, with an increase in the dilution of from 32 to 1024 litree, varying between 10 and 13 units. The poorer conductors give the smaller value, so that the increase appears to depend partly on the conductivity. For bibasic acids it has about double the above value, and is nearly three times as great for tribasic. Polyvalent bases act similarly to polyvalent acids although not quite so regularly.It would seem, in fact, that if m is the molecular conductivity, and the dilntion, dnzldv is of the form ?al x n3 x const., where n1 is the valency of the acid, and nz that of the base. According to this mode of testing, dithionic acid appears to he truly bibasic. G. T. M. H. C. Pyrometer. By J. MENSCHING and V. MEYER (Zeit. phpi7caZ. Chem., 1, 145--158).-The advantage of the instrument presently to be described is that i t affords a quick as well as an exact measure- ment of temperature. The principle of the method is to determine Z Y332 ABSTRACTS OF CHEMICAL PAPERS. the temperature from the measurement of the volumes of gas con- tained in the instrument at the temperature of the laboratory and at the higher temperature that is required.Part of the instrument is at a low temperature, but error from this cause is obviated by means of a compensator. The instrument consists of a vapour-density vessel, *a platinum cylinder 200 mm. high and 36 mm. in diameter. To the middle of one end of the cylinder is connected a platinum tube 350 mm. long and 4 mm. in diameter. Close by the side of this tube runs a pla- tinum capillary tube with very thick wz11Is, which passes through the circular end of the vapour-density vessel and goes down to within 3 mm. of the bottom. The end of the capillary tube is bent round through a right angle. The compensator is composed of a platinum tube connected at one extremity with a capillary tube, so that it is of exactly the same shape and size as the part of the instrument outside the cylinder.The instrument was heated by Perrot's gas-oven, by means of which a temperature of about 1500" can be produced. lncandescent platinum, as Deville and Troost have shown, is per- meable by hydrogen but not by air. The platinum cylinder was there- fore surrounded by a Berlin porcelain tube which is impermeable to all gases. In making an experiment, the platinurn cylinder was filled with nitrogen by an india-rubber tube attached to the capillary tube, and communicating with a series of drying tubes connected with a gas- ometer. The quantities of gas contained in the whole instrument and the compensator at the higher temperature T were measured, and the difference reduced to volume at temperatiire 0" and normal pressure. Then V being a similar quantity for the temperature of the laboratory, T is given by- T = (V - v>/(Va - V,), when a , y are the coefficients of cubical expansion of platinum and nitrogeu.c. s. Specific Heat of Tellurium. By C. FABRE (C~olnpt. rend., 105, 1249-1251) .-Tellurium was precipitated by means of sulphurous acid, washed with water saturated with nitrogen, and dried in a current oE nitrogen. The mean of three determinations of the specific heat is 0.05252. The same tellurium was volatilised in a current of sul- phurous anhydride, and was thus obtained as a black sublimate with a crystalline fracture, different in appearance from the product obtained by distillation in hydrogen. Determinations of the specific heat, gave 0.05182. Crystallised tellurium was prepared by the decomposition of alkaline tellurides, washed with water saturated with nitrogen, distilled in al current of hydrogen, fused, and allomred to cool slowly.It had a crystalline fracture. Two determinations of the specific heat gave as the mean 0.048315. From these results, it follows that the various forms of tellurium have sensib!y the same specific heats at temperatures near 100"GENERAL AND PHYSICAL CHEMISTRY. 333 Possibly differences may appear at higher temperatures, and especially near the point oE transformation of amorphous tellurium into the crystalline variety. C. H. B. Constancy in the Heat produced by the Reaction of certain Salts on eash other. By S. U. PICKERING (Chem. News, 57, 75-77). -The author shows that the constancy in the heat evolved i n the reaction of silver nitrate on metallic chlorides in solntion, observed by R'ichards (Chem.News, 5 7, 16), is an inevitable consequence of the heat of neutralisation of hydrochloric and nitric acids being independent of the nature of the alkali, the number 16165 cal. being merely the heat of precipitation of sil vcr chloride. Similarly, the heat measured by Fay on adding barium chloride t o sulphates is the heat of precipitation of barium sulphate, 5580 cal. In this case, however, it is constant only when dyad metals are concerned, since it is only with these that the difference between the heat of neutralisa- tion of the hydrate with sulphuric and hydrochloric acids is a constant quantity. The quantities determined by Fay have already been deter- mined by Thomsen.s. u. P. Heat Equivalents of Benzoyl Compounds. By F. STOHMANN, P. Rowrz, and W. HERZBERG (J. p r . Chern. [ S ] , 36, 353--370).-The anthors, continuing their previous work (Abstr., 1887, 878), have determined the heat of combustion (in free oxygen) of the following benzoyl-compounds :- Glyceryl benzoate, C:,H, (C7Hj0.,)3.. ............... Mannityl benzoate, C,H,(C7H,0,)6 ................ Benzophenone, COPh, ........................... Acetophenone, COMePh (solid) .................. Methyl salicylate, OH.C6H,.C0031e .............. ,, .. (liquid).. ................ Ethyl .. OH*C,H,.COOEt ............. PrOpyl .. OH-C6H,-COOPr .............. Isclbutpl .. OH*C,jH,*COOBufl.. ............ Methyl parahydroxgbenzonte, OH*C6H4 .COOilIe Ethyl parahpdrosybenzoate, OH.C,H,.COOEt (solid) (solid) Propyl 9 , OH.C,&*COOPr (solid) Heat equiv.er gram-mol -_I_ 2'720536 5361915 1557556 10014Qo 1003440 898776 105 1748 1206120 1366270 889200 10433 10 1201117 ~~ Heat of formation. 225464 461085 9444 26600 24560 129224 139252 147880 160730 138800 147690 - Comparing the differences of the heat equivalents sf the benzoates, salicylates, and parahydroxybenzoates, the authors calculate the heat of combustion for salicylic acid to be 72:3600 cal., that of para- hydroxybenzoic acid 715839 cal. Thus, whilst the substitution of a hydrogen in benzoic acid t o form salicylic acid decreases the heat- value 46833 cal., a similar substitution to form the para-acid decreases it 54628. The latter number is very close to that found in the formation of phenols from benzene, and it therefore appears that the334 ABSTRACTS OF CHEMICAL PAPERS.para-acid more closely corresponds with the phenols than the ortho- acid does. GZyceryZ hengoate was prepared by the action of glycerol and soda on benzoic chloride. It forms long, silky needles melting at 72.4". XannityZ benzoate forms colourless scales melting a t 124--125". L. T. T. Boiling Points and Specific Volumes of the Normal Fatty Ethers. By P DOBRINER (AnnuZen, 243, 1-22).-The author's experiments lead him to the following results. In the case of meta- meric ethers, the boiling point falls as the difference in the number of carbon-atoms in the two alcohol radicles diminishes. Methyl ethers have the highest boiling points. I n a series of homologous ethers containing one alcohol radicle in common, the difference between the boiling points diminishes as the ca.rbon-atoms increase in number.Methyl ethers form an exception to this rule, as the difference between the boiling points of the methyl and ethyl ethers in such an homo- logous series is smaller than the difference between the ethyl arid propyl ethers. The boiling points of amyl and hexyl ethers can be calculated approximately, as the difference between the boiling points of homo- logous amyl and hexyl ethers is equal to one-third of the difference between butyl and heptyl ethers. The difference between butyl and amyl ethers is a little larger, and the difference between hexyl and heptyl ethers is a, little less. The difference between the boiling points of methyl and ethyl compounds is smaller than the difference between ethyl and props1 compounds when the alcohol radicles are directly attached to an oxygen-atom (for instance, in the case of the methyl, ethyl, and propyl salts of the adipic acids), but the case is reversed if the alcohol radicles are directly united to carbon-atoms.SpeciJic Gruvity.-In the case of metnmeric ethers, the highest specific gravity is exhibited by the ether with the highest boiling point, and the lowest specific gravity by that of the lowest boiling point. In an homologous series, the specific gravity a t 0" increases wit.h the carbon-atom, bdt the specific gravity at the boiling point diminishes as the compounds increase in carbon. Speczjk Yoluwe.-The specific volume of an ether is approximately identical with that of an ethereal salt, the radicles of which contain the same number uf carbon atoms.The specific volumes of the ethers are larger than the specific volumes of the metameric alcohols. In a series of metmneric ethers, the methyl ether has the smallest co- Specific Volumes of Normal Alcoholic Iodides. By P. DOBRINER (Anlzalen, 243, 23-31).-The specific volumes of the fol- lowiug iodides were determined :- efficient of expansion. w. c. w. CHJ, 64.1 CzHfjI, 85.7 C3H71, 106.8 CIHJ, 128.5 C5Rl1I, 151.2 C,Hl,I, 175.5 CTHJ, 198.6GESEBAL AND PHYSICAL CHEXISTRY. 335 The specific! volume of an iodide C,H,n+lI is the same as that of an acid of the formula C,H2, + I-COOH. w. c. w. Boiling Points and Specific Volumes of Phenols and their Ethers.By J. PINETTE ( A n d e n , 243; 32-63) .-In homologous ethers of the same phenol, the difference in the boiling points of the methyl and ethyl ethers is about 5" less than the difference between those of the ethyl and prop.yl ethers. I n ascending hhe series from the ethyl ethers, the difference gradually diminishes. The difEerence between phenol and thymol ethers of the same alcohol radicle decreases with an increase of carbon in the alcohol radicle. Meta- and para-cresol have almost the same boiling point, this is also true of their metameric ethers. Orthocresol boils about ll", and its ethers about 6" lower than the corresponding meta- and para-compounds. The boiling points of propyl, butyl, and octyl phenyl ethers are almost identical with the boiling points of the metameric ethers of meta- and para- cresol, and are higher than the orthocrcsol and thymol-derivatives.The diEerence between the boiling point of aphenol and its methylic ether decreases with the increasing molecular weight of the phenol. Specific VoZume.-Phenols have a smaller specific volume than the metameric ethers. The specific volumes of phenol and its ethers coincide with those OF butyl alcohol and its ethers. Meta- and para- cresols and their et,hers have approximately the same specific volumes ; they are about 1 per cent. higher than the corresponding orthocresol- derivatives. The specific volumes of the tliyniol ethers are relatively small. The author obtains the following values for the specific volumes of the isomeric xylenes :- Ortho.Meta. Pam. 137-6 139.75 139.9 Schiff found 139.9 139-7 140.2 w. P&.W.. Boiling Points and Specific Volumes. By W. LOSSEN (Anwalen, 243, 64--103).--The author has compared the boiling points of a large number of organic compounds, and agrees with Dobriner (pre- ceding page) that in an homologous series, the first difference (that is the difference between the boiling points of methyl and ethyl coni- pounds) is less than the second (namely, between ethyl and propyl) when the alcohol radicle is attached to the rest of the molecule by an oxygen-atom. When the radicle is attached to a carbon-atom, the reverse is true in the majority of cases. In many cases, the first and second differences are equal, and in a few cases the first difference is ft little less than the second.The author agrees with Horstmann (Abstr., 1886, 759) that a com- parison of molecular volumes determined a t the same temperature possesses many advantages not shared by specific volume determina- By C. SCHALL (Ber., 21, 100-101) .-Blurther modifications in the apparatus lately described by the author (Abstr., 1887, 695, 882). tions at the boiling point. w. c. w. Estimation of Vapour-densities. J. W. L.336 ABSTRACTS OF CHEMICAL PAPERS. Determination of Vapour-density at Low Pressure. Ry H. MALFATTI and P. SCHOOP (Zeit. physikaz. Chem., 1, 159--164).--ln spite of the many modifications of methods of measuring vapour- density, there is not at present a convenient method when the tension is small. Hofmann’s method requires for small tensions a cumbrous apparatus, whilst in Habermann-Dumas’ method there is the objec- tion of the additional determination of the weight of the mpour.A tubular glass vessel of 100 C.C. capacity closed at one end is care- fully cleaned and dried. Inside the tube is placed a short barometer tube. The substance is weighed in a small glass sphere having two sides drawn out into fine tubes ; one capillary tube is stopped with alloy, and the other hermetically sealed after the introduction of the substance. The end of the glass vessel is drawn out iiito a capillary tube and the air is exhausted from the vessel ; when the levels of the arms of the barometer tube remain unaltered the vessel is hermeti- cally sealed. I t is next immersed in a bath of known temperature, and the difference of level of the arms of the barometer is read off by a millimetre scale, so that the pressure is known.The vessel is im- mersed in water and the capillary point broken off. The vessel when filled is weighed. Thus, having measured the volume of a given length of the barometer tube, we have sufficient data to determine the vapour-density. In order that the barometer may contain no moistnre, it is con- structed as follows :-A tube is bent into the form of a double U-tube, and one end is passed through a cork inserted in the neck of a frac- tional distillation flask which contains a small quantity of mercury. The flask is inclined, so that the end does not touch the mercury, and heated while dry air is drawn through the tube. When the flask is placed upright, the tube is immediately filled with mercury.The proper quantity of substance to be placed in the sphere is de- termined by a preliminary calculation. For higher temperatures, the barometer is filled with an alloy of 3 parts lead and 1 part tin, which does not stick to the tube and has no perceptible tension. For higher temperatures, the author also shows that a modification of I;. Meyer’s apparatus (Ann. Phys. Chem. [S], 1880, 550) can be Viscosity of Dilute Aqueous Solutions. By S. ARRHENIUS (Zeit. physikal.. Chew., 1, 285--298).-The solution is contained in a glaes sphere of volume 0.9846 c.c., and is allowed to flow vertically through a. fine capillary tube, the bore of which suddenly enlarges at its lower end, so that the velocity of efflux is negligible.The flow of liquid may be started by turning on a tap connected with the upper part of the sphere. The sphere and the capillary tube connected t o it are immersed in a wnter-bath so that the solution may be kept at a known temperature. Since the liquid escapes with a very small velocity, the work done by the solution in falling through the height of the capil- lary tube will be entirely spent in overcoming the resistance due to viscosity, provided no energy is consumed in setting up vortex-motion as the liquid passes from the capillary tube into its enlarged end. In any case, the energy so spent will be less than if all the kinetic energy employed. c. s.GENERAL AND PHYSICAL OHEMILSTHP. 337 of the liquid passiiig into the enlargement were employed in setting up vortex-motion.But on this hypothesis the energy spent niay be cal- culated by a formula given by Hagenbach (Ann. Phys. Chem., 109, 385), and was found t o be negligible with the dimensions of the ap- paratus used by the author. Thus a correction, which has been cal- culated by various experimenters on hypotheses never completely satisfied, is entirely avoided, By placing the capillary tube vertical, the small particles which are seen to form are carried away and not left adhering to the sides of the tube. Hence the coefficient of rela- tive viscosity, y, will be given by TI = (st)/(ST), when s is the specific gravit,y of the sohtion, t the time of efflux of the volume contained in the sphere, and S, T similar quantities for water. The results of numerous experiments show that the relative vis- cosity of a dilute aqueous solution of two different substances is equal to Ax BY, where 2, y are the volume percentages of the two sub- stances, and A and B two functions of the temperature which remain constant for the same temperature and the same substance.There does not appear to be any connection between A and the viscosity of the corresponding substance. The constant A diminishes as the tem- perature increases in the case of non-conductors, so that the values of the relative viscosity tend to a common limit, unity. The viscosity of water is increased by the addition of a small quantity of a non-con- ductor. Those normal solutions which have greater conductivity have in general less relative viscosity, but there does not Reem to be any Dissociation of Hydrated Salts.By P. C. F. FROWEIN (Zeit. yhysikal. Chew., 1, 5-14 and 362--364).-The relation which must exist between the heat of combination of the water in hydrated salts and the maximum vapour- tension has been thermodynamically cal- culated, but hitherto has not been experimentally established in a satisfactory manner. This is the aim, therefore, the author has in view. The thermodynamical relation given by Van’t Hoff, d . ZK,/dT = g/2‘1’’, is transiormed, in order to be applicable to calorimetric work, into d . lF/clT = Q/fL”, where T is the absolute temperature, Q the amount of heat evolved by the absorption of 18 kilos. OH, by the dehydrated salt, and F the ratio of the maximum tensions of salt and water. By iutegration of the above on the assumption that Q remains consCant between small limits of temperature- simple law connecting conductivity and viscosity. c.s. Q=- 2TIT2 $ %* Ti - T, F2 This equation does not, however, give numbers agreeing with Thomsen’s observed values for the heat of combination in the cases of cusoc + 5 0 8 2 ; BaC& + 20H2; SrCl, + 60H2; MgSO, -+ 70H2, and ZnSOa + 70H2, if the values for F1F2 are calculated from the num- bers given by Pareau and Wiedemann for the vapour-tensions. Attributing this to errors in the vapour-tension determinations, arising partly from the very small differences in pressure which have to be observed, the author bas redetermined these by means of an338 ABSTRACTS OF CHEMICAL PAPERS. apparatus in which olive oil is used in the manometer in place of mercury.The numbers thus obtained for FIF, give values of Q w%ich agree well with those observed by Thomsen for all the before- mentioned salts, with the exception of SrC1, + GOH,. The tension of NazHPOa + 120H2 has also been redetermined, and the calculated value for Q brought into agreement with the observed, a result which the former determinations by Debray and Muller-Erzbach had not rendered possible. H. C. Nature of Chemical Afflnity. By W. OSTWALII (Zeit. pkysikal. Chem,., 1, 61--62).-1n a former paper (Abstr., 1886, 294), the author has pointed out that chemical affinit’y depends not only on the nature and the relative distance of the atoms from one another, but also on the direction in which it acts. The difference in the molecular con- ductivities of the two nitrosalicylic acids, [COOH : OI-: : NOz = 1 : 2 : 3 and 1 : 2 : 51, is here offered as proof that although in each clhe relative positions of the NO, and OH to the COOH-group is the same, yet the former acid is the stronger of the two, the closer group- ing of the radicles being more favourable to their combined action.H. C. Thermodynamical Expression of the Influence of Tempe- rature on the Rate of Chemical Change. By F. URECH (Bey., 21, 56).-A continuation of the author’s investigations (Abstr., 1887, 768). Instead of Van’t Hoff’s expression, log c = -A/T + BT + C the equation log c = -A’/T + B‘, corresponding with the thermo- dynamical formula log c = --p/RT + B’, has been applied, and is fnund to give remlts agreeing generally with the author’s observed values for the rates of inversion of saccharose with hydrochloric acid of different strengths.H. C. Action of Sulphurow Acid on Periodic Acid and Rate of the Change. By F. SELMONS (Ber., 21, 230--24l).-The action of sul- phurous acid on periodic acid takes place for all proportions of the two acids, the products varying, however, with the amounts employed. A separation of iodine takes place only within the limits represented by the equati~ris- 4H,SO3 i- HIO, = 4H,so4 + HI $H2SU3 + 4HIO4 = 4H2S04 + 4HIO3, namely, when more than one and less than 4 mols. HI04 enter into reaction with 4 mols. H2S03, the production of iodine being in fact due to the action of the hydriodic on the iodic acid. With dilute solutions, the rate of change of the reactions involving the production of iodine from sulphurous and periodic acids can be measured, using starch solution as an indicator.This reaction is similar to that studied by Landolt (Abstr., 1886, 658) on the action of sulphurous acid on iodic acid, and depends on the concentration of the solutions when the proportion between the two acids is kept constant,, on the molecular weights for unit concentration, and on the temperature. If C, is the concentration of the sulphurous, Cp that ofGENERAL AND PH Y STCAL CHEMJ STKY. 339 the periodic acid, then the time t = k,/(C,C,)", where calculated from - _ If the two consecutive observations, x = - sulphurous acid be keDt constant in amount, and the periodic acid log t - log t l log (C,Cp), - log (CsCp)' alldwed to vary, t = k/lCf,, where k is constant and y cafculated from two consecutive observation H.C, log t' - log t" log c"p - log Influence of Molecular Contiguity on the Chemical Equi- librium of Homogeneous Gaseous Systems. By SARRAU and VIEILLE (Compt. rend., 105, 122-2-1224) .-The combustion of organic compounds which do not contain sufficient oxygen for complete oxida- tion results in the production of a condition of equilibrium between the gaseous products, some of which are completely oxidised, as car- bonic anhydride and water, whilst in others, such as carbonic oxide, hydrogen, and methane, oxidat ion is incomplete. Experiment shows that the conditions of final equilibrium change with an increase in the weight of substance exploded in the same space, that is to say, wit.h an increase in the pressure produced by the products.Two principal reactions are concerned in the progressive alteration of equilibrium. The first CO + H,O = CO, + H,, usually occurs ; the second, 2CO + 2HqO = CO, + CH4, takes place when the first has reduced the pro- portion of water vapour and increased the proportion of free hydrogen to a certain extent, or when the explosive contains so little oxygen that water is formed in relatively very small quantity. The first reaction was observed to take place by Noble and Abel in their ex- periments with gunpowder. The autbors find that it also takes place in the explosion of cotton powder and of picrates. The results obtained with cotton powder, C2aH,,N1104,, are as follows :- S P d > V nf 0.023 gas.Methane. 0.010 33CO + 15C0, + 8H, + 11N2 + 21H,O 0.00 0.200 2iCO + 21C0, + 14& + 11N, + 15H,O 0.300 26CO + 22C0, + 15H, + 11N, + 14H,O The temperature of final equilibrium is about 3000°, the pressure varying between 100 and 4000 atmospheres. The formation of methane, which occurs only to a very limited extent in the case of cotton powder, becomes more marked with such compounds as the 1omTer nitrated derivatives, picrates, and picric acid. The results with the last compound were as follows :-- 30CO + 18C02 4- I l H , + 11NZ + 18HaO 0.00 0.006 0.016 Density of gas. 0.10 11C0, + 84CO + 24N, + C& + 16H2 4- 6H,O 0.30 20C02 + 69CO + 24N, + 7CH4 + 7H-z + 3HzO 0.50 25C02 + 61CO + 24Nz + 9iCH4 + 4Hz +' H,O+QC. The pressures varied from 1000 to 7500 atmos.The reactions which tend to reduce the proportion of carbonic oxide are exothermic340 ABSTRACTS OF CHEMICAL PAPERS. In the case of the first reaction, the development of heat is not great, and there is no alteration in the volume of the gas ; but i n the second case there is 5t considerable development of heat, and the volume of the gases taking part in the change is reduced to one-half. The alterations in the conditions of equilibrium tend towards the develop- ment of the maximum quantity of heat, and the two reactions concur in making the pressure increase in a greater ratio than the weight of the explosive charge. Influence of Neutral Salts on the Rate of Hydrolysis of Ethyl Acetate. By S . ARRHENIUS (Zeit. physikal. Chern., 1, 110-133).- In Warder and Reicher's equation for the rate of saponification, C.H. B. - _ dC = kCCI, where t is the time, C the concentration of the base, d t and C1 that of the salt, k is a quantity which the author proposes to call the specific rate of saponification. This quantit'y is independent of the amounts of base and salt which act on one another, but most probably varies for different concentrations. In the present case, the influence of the presence of neutral salts on k was studied. This influence is as a rule small, and Ic remains nearly constant; salts of the halogens and nitrates lower, whilst sulphates and hyposulphitea raise the value of k. Theinfluence of potassium iodide is greater than that of potassium bromide, which is greater than that of potassium chloride, the three being very nea.rly in the ratio 3 : 3 : 1. Quite abnormal is the influence of ammonia and ammonium salts, the action being very greet and varying very distinctly with the amount of salt in solution. k in fact here depends on the amount of dissolved salt, 8, according to the equation 3c = The rate of hydrolysis is practically in all cases proportional to the conductivity.The lorn conductivity of a weak base such as ammonia, on which other dissolved electrolytes can exercise such a large relative influence, probably explains its abnormal behaviour. A 1 + a s + bS2 H. C. Formation and Decomposition of Ethereal Salts : Decom- position of Liquid Tertiary Amy1 Acetate. By D. KONOWALOFF (Zeit. physikaZ. Chem., 1, 63-67) .-Menschutkin (Abstr., 1883, 178, 309) has observed that the rate of decomposition of liquid tertiary amyl acetate at 180" increases until about 50 per cent.of the acetate employed is decomposed, then diminishes, and finally ceases when the decomposition has reached 97.42 per cent. The author shows that the cause of this is the action of the liberated acetic acid on the acetate, and finds that the addition of acetic acid brings about the decomposition of the acetate. By heating amyl acetate with varying amounts of acetic acid for one hour at 159", he shows that the amount decomposed is dependent on the amount of acetic acid added. This is expressed. by the equation d:c/dt = k (100 - F) (m + 2 g p ) , where z is the percentage of acetate decomposed in the time t, p the quantity of acetic acid added, 2g the ratio of the molecular weights of the acetate aud acetic acid, and k a constant.All other acids have anQENERAL ASD PHYSICAL CHE3JISTRY. 342 action similar to this of acetic acid although in different degree, propionic and butyric acids being far less active. The action of the haloyd hydrogen acids was also studied, but in these cases the gaseous acid was passed into the liquid acetate at the ordinary t,emperature. The action is violent, a considerable develop- ment of heat takes place, and a tertiary amyl halrjid salt and acetic acid are formed. I n the action of hydrogen chloride two stages may be distinguished, the acetate being first decomposed into amylene and acetic acid, and the amylene then combining with the hydrogen chloride. This reaction the author proposes to employ to determine the heat-change represented by C5Hll*C2H302 = C,H,, + C,H40,.The comparative ease with which the halogen acids act on tertiary amyl acetate explains the formation of amyl chloride instead of acetate when dimethyl ethyl carbinol is treated with acetic chloride. Chemical Decomposition produced by Pressure. By W. SPRING and J. H. VAN'T HOFF (Zeit. physiknl. Chem., 1, 227-230).- The results of numerous experiments show that in many cases sub- stances which exert no action on each other at atmospheric pressure under ordinary circumstances, can be made to combine more or less completely if they are subjected to a pressure sufficient t o cause R perceptible condensation. The researches hitherto made relate to compounds, the volume of which is smaller than that of their con- stituents.I t is therefore a question of some int,erest and importance to examine whether the temperature of conversion can be lowered in the case of copper calcium acetate, for which the volume is greater than t h a t of its constituents. In the first experiment the acetate Enely powdered at a temperature of 16" Was submitted to a pressure of 6000 atmospheres. The powder was thus reduced to a crystalline mass resembling marble, kut presenting no sign of chemical decomposition. Next a screw press (Bull. Acc. Belg., 49, 344) was employed; at a tem- perature of 40" there were very marked results; three-fourths of the mass being liquefied. On removing the pressure, it became solid again, but the sides of the containing vessel were covered with a coat- ing of copper, and it was possible to pick small leaves of copper out of the mass.The dark blue of the acetate had changed for the most part to green interspersed with white points, showing that the mass had been decomposed into acetate of copper and acetate of calcium. The result, was entirely due to the change of volume, since the thermal effect of compression was less than a rise of 1". When the tempera- ture was raised to 50", the piston sank without resistance through the mass. The first experiment, which bad given a nugatory result, was now repeated in order to discover whether sufficient pressure had been used, or the result had escaped observation. A press worked by a lever was used, and this time it was found that the piston sank 1.25 mm.in an hour, or, roughly, that the whole could be decomposed in about 110 hours. Lastly, potassium sulphate under the same con- ditions gave no perceptible diminution of volume. Thus, the higher the pressure and temperature, the more quickly is the acetate decom- posed. Since the progress of chemical action depends on the time, it H. C.842 ABSTRACT8 OF CHEMICAL PAPERS. seems that i t is not sufficient to say that the molecules of a subshnce assume the arrangement which corresponds- with the given volume directly it is reached, for a substance can be compressed without altering its state, if the pressure does not last too long. c. s. Crystallisation of Mixtures. By 0. LEHMANN (Zeit. physikal. Chem., 1, 15-26 arid 49-60).-The author discusses the different cases in which mixed crystals have been formed, and the possibi1it.y of obtaining such from non-isomorphous forms.He repeats the ex- periments of Herrmann (Ahstr., 1886, 972), on t,he crystallisation of ethyl quinonedihydroparadicarboxylate with ethyl succinomccinate with similar results. He also investigates the mixed ciytals of ethyl dihy d ro x yquino neparadicarbox y Iat e with e thy1 te trah ydrox ybenzene- p~radicarboxylate, and of each of these with each of the two foregoing. These substances, although having a somewhat analogous chemical constitution, differ pretty widely in crystalline form. They give, however, well-defined mixed crystals of form and colour intermediate between those of the t w o substances of which they are formed.Constitution of Solutions. By F. R ~ O R F F (Bw., 21, 4-11). -Numerous experimenters have found that the solution of a double salt difyuses as if it were a solution of a mixture of its component parts; for this and other reasons, it is generally stated that double salts do not exist as such in solution. On dialysing solutions of the following double salts, R2S0,,NiSOa + 6H,O; K2SOa,MnS04 + 6H@; (NH4)2S04,MnS04 + 6H,O; K,SO,,Cr,(SO,), + 24B20 ; 2KC1,CuC12 + 2H,O ; 2NH4C1,CuCl, + 2H20; 2KC1,2nCl2 + H,O; KCl,MgCI, + 6H,O; 2NaC1,CdC12 + 3Hz0 ; BaC12,CdC12 + 4H20, i t was found that the ratio of the metals i n the dialysate was entirely different from that in the original liquid ; the componeiit parts, therefore, do not form a molecular compound, but exist in solution independently of each other.On the other hand, the following double salts, KCN,AgCN ; 2KCN,Hg( CN),; 2KCN,C;d(CN)z; &KCN,Ni(CN),; GKCN,Cu,(CN),; 2NaCl,PtCla + 6H20 ; 3NazC,04,1-’e2(C204)3 + GH20 ; 3KzC,0,,Fez(C,04), + H20 ; 3KzC,04,Cr2(C204)3 + 6Hz0 ; are not decomposed, but must exist in solution and diffuse as such, inasmnch as the ratio of the metals is found to be the same in the dialysatc as in the original liquid. Several simultaneous experiment’s were made with each salt, and a membrane prepared from the cuticle of the caecum of an ox was found to be most suitable, a parchment membrane not being sufficiently homogeneous. F. S. I(. Absorption of Gases by Petroleum. By S. GNIEWOSZ and A. WALFISZ (Zeit. physilcal. Chew,., 1, 7O--T2).-The statement that a layer of petroleum will protect an aqueous solution from the action of the air has led the authors to examine the absorption of oxygen and other gases by Russian petroleum.The following table contains the rceults :- H. C.INORQANIC CEIEMISTRY. 343 ---- H2 .............. N2 .............. 0 2 .............. NzO ............ C,H, ............ cu2 ............. co. ............. CH4 ............ Absorption coeficients for petroleum at 20°. 0 '0382 0.117 0 '202 2.11 0 - 142 1 *17 0 '123 0 -131 10" 0 -0692 0 *135 0.229 2 *49 0 -164 1.31 0'134 0.144 Ratio. 1 . 2 1 .15 1.13 1 *18 1.15 1.12 1.09 1.10 Water at 20". 0.0193 0'0140 0 *0%4 0.670 0.149 0.901 0 '0231 c1.03.50 The ratio is given on account of E. Wiedemann's statement that the changes which the absorption coefficients of different gases undergo with change of temperature is about the same for all gases ; the values for water are given for the sake of comparison.It will be seen that the absorption of oxygen is greater for petroleum than for water, BO that the protective action above spoken of must be a doubtful one. H. C. Lecture Experiments with Nitrogen Chloride. By V. MEYEK (Ber., 21, 26--28).-An experiment is described by which the explo- sion of nitrogen chloride can be shown, without danger, by allowing turpentine to come into contact with a few drops of the chloride swimming on the surface of the electrolysed ammonium chloride solu- tion contained in an inverted flask, the whole apparatus being placed under a thick glass case. F. S. I(.329General and Physical Chemistry.Degree of Oxidation of Chromium and Manganese inFluorescent Compounds.By L. DE BOISBAUDRAN (Compt. rend.,105, 1228-1233) .-This paper contains details of the results ob-tained by calcining, in air or in hydrogen, mixtures of pure aluminawith chromic oxide ; of gallium oxide and chromic oxide ; of calciumoxide and chromic oxide ; of magnesium oxide and chromic oxide ;of alumina with small quantities of potassium and manganese oxides ;and of calcium and manganese oxides.Too large a proportion of chromium reduces and may even destroythe fluorescence. In Some cases, calcination in hydrogen reduces, inohhers it intensifies the fluorescence, but no general conclusions aredrawn as to the influence of the degree of oxidation on the phe-nomenon.C. H. B.Rotatory Dispersion. By L. GRIMBERT (J. Pharm. [ 5 ] , 16, 295-300 ; 345-350) .-The author employed Laurent's polnrimeter andrnonobnromAkic'ii&h. "LO ahtiin rays near '507 I , a'iayer'i cm.'tkEKof the following solution was used :-Carmine No. 40 0.25 gram,ammonia 20 c.c., water to make up t o 100 C.C. With white light, thissolution gives a specti-urn reduced to a very narrow band coincid-ing with the C line. On taking the rotative power of an active sub-stance in this light and also in the sodium light, two different valuesare obtained, [ a ] n and The ratio [a]~/[a]~ gives the dispersivepower. Usually tubes of 200 mm. length were ernploj-ed ; sometimes100 mrn. tubes were used, as, for example, when the deviation wasover 2 0 " ~8accharose.-Both water and alcohol were ernplored as solvents.The rotative power varies neither with the concentration nor with thesolvent : [a]= = +66*45"; [.Ic = 52.85"; and [a]D/[aIc = 1.257.Lactose.-It is well known that the rotative power of lactosediminishes rapidly when first dissolved in the cold.The rotativepower does not v a ~ y with the concentration. It is [ a ] D = + 52.37and [a]. = +41.58". The ratio between the rotative power whenfirst dissolved to that when it becomes stationary is as 8 : 5. Thedispersive power is [a]D/[a-jc = 1.259, and is constant during tohetime the rotative power is passing to the minimum. I t does notvary with the concentration of the solution.Maltose.-When dissolved in the cold, the rotative power of maltoseincreases to a maximum.Its dispersive power is 1.262, and is con-stant during the time the rotative power is changing.The ratio between the initial and finalrotative powers is as 2 : 1. The dispersive power is 1.258, and is con-stant whilst the rotative power is passing to the minimum..Morphine ~?/dl.ochZoride.--Solntions of different degrees of concen-tration confirmed the value given by Hesse, [ a ] D = -100*67"-1-14 C.VOL. LIT. IGlucose acts like lactose330 ABSTRACTS OF CHEMICAL PAPERS.The dispersive power [~&]D/[ct]c = 1.284, and does not vary with theconcentration.Codehe.-In absolute alcohol, [a]D = -134*24', and in chloroform-114.82", but the dispersive power only varies slightly and is on theaverage 1.268.Brztcine.-Anhydrous brucine, dissolved in absolute alcohol and inchloroform, gave values for [a]D confirming those obtained by Oude-mans.The dispersive power does not vary with the nature of thesolvent, and is = 1.357, the highest hitherto observed.Quinine.-The hydrate, dissolved in absolute alcohol, and inchloroform ; the basic hydrochlode dissolved in water; and the normalsulphate dissolved in water, and in 90" alcohol, all give the same dis-persive power of 1.313, the variation in the solvent and in the acidcombined with the base producing no change in this respect.Cinchonine.-The basic sulphate was observed when dissolved inwater, absolute alcohol, and chloroform. Although the nature of thesolvent has considerable effect on the rotative power of the salt, thedispersive power remains constant and equal to 1.268.Strychnine.-Two samples of different character were recrystallisedfrom alcohol, and dissolved both in 80" alcohol and in chlorofornr.Notwithstanding considerable differences in the rotative power of thetwo samples in both solvents, the dispersive power was constant andequal to 1313.Camphor.-This substance was recrystallised from alcohol andfused.It was dissolved in alcohol of various strengths, in chloroform,and in dry ether. The rotative power varies with the nature of thesolvent ; its dispersive power is sensibly constant. In alcoholic solu-tion, the rotative power increases with concentration of the alcohol.I n dry ether, the rotative power does not vary with the concentrationof the solution.I n chloroform, as well as in alcohol, the dispersivepower remains eonstant, notwithstanding that the rotative powerincreases with the concentration.Its dis-persive power averages 1.323. I t doeH not vary, like the rotativepower, with the nature of the solvent.Cho2esferin.-This was observed in ether and chloroform.Essence of Te're'benthine.-A laevorotatory sample gave-[a]= = - 30.46, [a], = - 28.37, and [ a ] D / [ ~ ] c = 1.241.The results obtained with the foregoing substances show that thedispersive power remains constant whatever be the concentration ofthe solution ; that the dispersive power of those substances whoserotative power varies with t,he temperature, remains constant allthrough that variation ; that for the same snbstance it scarcely varieswith the nature of the solvent; that each substance has its ownproper dispersive power which seems to bear no relation to thechemical constitution of the substance, although it may be noted thatthe sugars have all the same value.Distribution of Electromotive Force in the Cells of Batteries.By J.MIESLER (LZ rcwtsk., 8: 626--631).--The author has extendedthe work of Moser (this vol., p. 209) to the butteries of Grove,J. TGENERAL AND PHYSICAL CHEMISTRY. 931Bunsen, Grenet, Smee, Lalande, and Leclanchh. In every case, thetotal electromotive force of the battery under examination was foundto be equal to the sum of the electromotive forces between thedifferent parts of the cell.Electrochemical Studies.By W. OSTWALD (Zeit. physikd.Chem., 1,74436 and 97-109) .-From his former experiments (J. pr.Chem., 1884-1886), the author has drawn the conclusion thaf themolecular conductivity increases for monobasic acids with increasingdilution, teuding to a maxinium value which it was thought wouldprove to be the same for all acids. On careful repetition of theseexperiments, the latter view is found to be incorrect, as the maximaobserved for a dilution of 1024 litres diffep for 15 different acidsby as much as 12 per cent. That this difference does not affect theproportionality between the maximum conductivity and the rate ofchemical action of these acids is proved by experiment, the latterbeing in fact proportional to the relative observed maximum con-ductivity. A difficulty, however, obviously arises in determining thevalue af this maximum for feeble acids of low conductivity.To overcome this, Kohlrausch's law that the conductivity of aneutral salt may be represented as a sum of two constants, one ofwhich depends on the nature of the acid and the other on that of thebase, is resorted to.It is shown by the determination of the con-ductivities of a number of sodium salts of acids of kuown conductivitythat a constant difference exists between the two. The same holdsgood for lithium and potassium salts, which also differ in Conductivityfrom the sodium salts by a constant fixed quantity. The molecular con-ductivities of different salts having the same base, differ very largelyamongst themselves, and altoget'her contradict the opinion ofArrhenius and Bouty that the molecular conductivities of dilute saltsolutions are the same.The numbers prove, however, that it ispossible to represent the conductivity of an acid by that of one of itssalts, plus some constant. The determination of these constants isreserved for tt future paper.Another interesting result is that there is an almost constant in-crease in the molecular conductivity of the sodium salts of the mono-basic acids, with an increase in the dilution of from 32 to 1024 litree,varying between 10 and 13 units. The poorer conductors give thesmaller value, so that the increase appears to depend partly on theconductivity. For bibasic acids it has about double the above value,and is nearly three times as great for tribasic.Polyvalent bases actsimilarly to polyvalent acids although not quite so regularly. Itwould seem, in fact, that if m is the molecular conductivity, and thedilntion, dnzldv is of the form ?al x n3 x const., where n1 is the valencyof the acid, and nz that of the base. According to this mode of testing,dithionic acid appears to he truly bibasic.G. T. M.H. C.Pyrometer. By J. MENSCHING and V. MEYER (Zeit. phpi7caZ.Chem., 1, 145--158).-The advantage of the instrument presently tobe described is that i t affords a quick as well as an exact measure-ment of temperature. The principle of the method is to determineZ 332 ABSTRACTS OF CHEMICAL PAPERS.the temperature from the measurement of the volumes of gas con-tained in the instrument at the temperature of the laboratory and atthe higher temperature that is required.Part of the instrument is ata low temperature, but error from this cause is obviated by means of acompensator.The instrument consists of a vapour-density vessel, *a platinumcylinder 200 mm. high and 36 mm. in diameter. To the middle ofone end of the cylinder is connected a platinum tube 350 mm. longand 4 mm. in diameter. Close by the side of this tube runs a pla-tinum capillary tube with very thick wz11Is, which passes throughthe circular end of the vapour-density vessel and goes down to within3 mm. of the bottom. The end of the capillary tube is bent roundthrough a right angle. The compensator is composed of a platinumtube connected at one extremity with a capillary tube, so that it is ofexactly the same shape and size as the part of the instrument outsidethe cylinder.The instrument was heated by Perrot's gas-oven, bymeans of which a temperature of about 1500" can be produced.lncandescent platinum, as Deville and Troost have shown, is per-meable by hydrogen but not by air. The platinum cylinder was there-fore surrounded by a Berlin porcelain tube which is impermeable toall gases.In making an experiment, the platinurn cylinder was filled withnitrogen by an india-rubber tube attached to the capillary tube, andcommunicating with a series of drying tubes connected with a gas-ometer. The quantities of gas contained in the whole instrumentand the compensator at the higher temperature T were measured,and the difference reduced to volume at temperatiire 0" and normalpressure.Then V being a similar quantity for the temperature ofthe laboratory, T is given by-T = (V - v>/(Va - V,),when a , y are the coefficients of cubical expansion of platinum andnitrogeu. c. s.Specific Heat of Tellurium. By C. FABRE (C~olnpt. rend., 105,1249-1251) .-Tellurium was precipitated by means of sulphurousacid, washed with water saturated with nitrogen, and dried in a currentoE nitrogen. The mean of three determinations of the specific heatis 0.05252. The same tellurium was volatilised in a current of sul-phurous anhydride, and was thus obtained as a black sublimate witha crystalline fracture, different in appearance from the product obtainedby distillation in hydrogen. Determinations of the specific heat, gave0.05182.Crystallised tellurium was prepared by the decomposition of alkalinetellurides, washed with water saturated with nitrogen, distilled in alcurrent of hydrogen, fused, and allomred to cool slowly.It had acrystalline fracture. Two determinations of the specific heat gave asthe mean 0.048315.From these results, it follows that the various forms of telluriumhave sensib!y the same specific heats at temperatures near 100GENERAL AND PHYSICAL CHEMISTRY. 333Possibly differences may appear at higher temperatures, and especiallynear the point oE transformation of amorphous tellurium into thecrystalline variety.C. H. B.Constancy in the Heat produced by the Reaction of certainSalts on eash other. By S. U. PICKERING (Chem. News, 57, 75-77).-The author shows that the constancy in the heat evolved i n thereaction of silver nitrate on metallic chlorides in solntion, observedby R'ichards (Chem. News, 5 7, 16), is an inevitable consequence ofthe heat of neutralisation of hydrochloric and nitric acids beingindependent of the nature of the alkali, the number 16165 cal. beingmerely the heat of precipitation of sil vcr chloride. Similarly, theheat measured by Fay on adding barium chloride t o sulphates is theheat of precipitation of barium sulphate, 5580 cal. In this case,however, it is constant only when dyad metals are concerned, since itis only with these that the difference between the heat of neutralisa-tion of the hydrate with sulphuric and hydrochloric acids is a constantquantity.The quantities determined by Fay have already been deter-mined by Thomsen. s. u. P.Heat Equivalents of Benzoyl Compounds. By F. STOHMANN,P. Rowrz, and W. HERZBERG (J. p r . Chern. [ S ] , 36, 353--370).-Theanthors, continuing their previous work (Abstr., 1887, 878), havedetermined the heat of combustion (in free oxygen) of the followingbenzoyl-compounds :-Glyceryl benzoate, C:,H, (C7Hj0.,)3.. ...............Mannityl benzoate, C,H,(C7H,0,)6 ................Benzophenone, COPh, ...........................Acetophenone, COMePh (solid) ..................Methyl salicylate, OH.C6H,.C0031e .............. ,, .. (liquid)..................Ethyl .. OH*C,H,.COOEt .............PrOpyl .. OH-C6H,-COOPr ..............Isclbutpl .. OH*C,jH,*COOBufl.. ............Methyl parahydroxgbenzonte, OH*C6H4 .COOilIeEthyl parahpdrosybenzoate, OH.C,H,.COOEt (solid)(solid)Propyl 9 , OH.C,&*COOPr (solid)Heat equiv.er gram-mol-_I_2'7205365361915155755610014Qo1003440898776105 17481206120136627088920010433 101201117~~Heat offormation.22546446108594442660024560129224139252147880160730138800147690-Comparing the differences of the heat equivalents sf the benzoates,salicylates, and parahydroxybenzoates, the authors calculate the heatof combustion for salicylic acid to be 72:3600 cal., that of para-hydroxybenzoic acid 715839 cal.Thus, whilst the substitution of ahydrogen in benzoic acid t o form salicylic acid decreases the heat-value 46833 cal., a similar substitution to form the para-acid decreasesit 54628. The latter number is very close to that found in theformation of phenols from benzene, and it therefore appears that th334 ABSTRACTS OF CHEMICAL PAPERS.para-acid more closely corresponds with the phenols than the ortho-acid does.GZyceryZ hengoate was prepared by the action of glycerol and soda onbenzoic chloride. It forms long, silky needles melting at 72.4".XannityZ benzoate forms colourless scales melting a t 124--125".L. T. T.Boiling Points and Specific Volumes of the Normal FattyEthers. By P DOBRINER (AnnuZen, 243, 1-22).-The author'sexperiments lead him to the following results. In the case of meta-meric ethers, the boiling point falls as the difference in the number ofcarbon-atoms in the two alcohol radicles diminishes.Methyl ethershave the highest boiling points. I n a series of homologous etherscontaining one alcohol radicle in common, the difference between theboiling points diminishes as the ca.rbon-atoms increase in number.Methyl ethers form an exception to this rule, as the difference betweenthe boiling points of the methyl and ethyl ethers in such an homo-logous series is smaller than the difference between the ethyl aridpropyl ethers.The boiling points of amyl and hexyl ethers can be calculatedapproximately, as the difference between the boiling points of homo-logous amyl and hexyl ethers is equal to one-third of the differencebetween butyl and heptyl ethers.The difference between butyl andamyl ethers is a little larger, and the difference between hexyl andheptyl ethers is a, little less.The difference between the boiling points of methyl and ethylcompounds is smaller than the difference between ethyl and props1compounds when the alcohol radicles are directly attached to anoxygen-atom (for instance, in the case of the methyl, ethyl, andpropyl salts of the adipic acids), but the case is reversed if thealcohol radicles are directly united to carbon-atoms.SpeciJic Gruvity.-In the case of metnmeric ethers, the highestspecific gravity is exhibited by the ether with the highest boilingpoint, and the lowest specific gravity by that of the lowest boilingpoint. In an homologous series, the specific gravity a t 0" increaseswit.h the carbon-atom, bdt the specific gravity at the boiling pointdiminishes as the compounds increase in carbon.Speczjk Yoluwe.-The specific volume of an ether is approximatelyidentical with that of an ethereal salt, the radicles of which containthe same number uf carbon atoms.The specific volumes of the ethersare larger than the specific volumes of the metameric alcohols. In aseries of metmneric ethers, the methyl ether has the smallest co-Specific Volumes of Normal Alcoholic Iodides. By P.DOBRINER (Anlzalen, 243, 23-31).-The specific volumes of the fol-lowiug iodides were determined :-efficient of expansion. w. c.w.CHJ, 64.1CzHfjI, 85.7C3H71, 106.8CIHJ, 128.5C5Rl1I, 151.2C,Hl,I, 175.5CTHJ, 198.GESEBAL AND PHYSICAL CHEXISTRY. 335The specific! volume of an iodide C,H,n+lI is the same as thatof an acid of the formula C,H2, + I-COOH. w. c. w.Boiling Points and Specific Volumes of Phenols and theirEthers. By J. PINETTE ( A n d e n , 243; 32-63) .-In homologous ethersof the same phenol, the difference in the boiling points of the methyl andethyl ethers is about 5" less than the difference between those of theethyl and prop.yl ethers. I n ascending hhe series from the ethyl ethers,the difference gradually diminishes. The difEerence between phenoland thymol ethers of the same alcohol radicle decreases with anincrease of carbon in the alcohol radicle.Meta- and para-cresol havealmost the same boiling point, this is also true of their metamericethers. Orthocresol boils about ll", and its ethers about 6" lowerthan the corresponding meta- and para-compounds. The boilingpoints of propyl, butyl, and octyl phenyl ethers are almost identicalwith the boiling points of the metameric ethers of meta- and para-cresol, and are higher than the orthocrcsol and thymol-derivatives.The diEerence between the boiling point of aphenol and its methylicether decreases with the increasing molecular weight of the phenol.Specific VoZume.-Phenols have a smaller specific volume than themetameric ethers. The specific volumes of phenol and its etherscoincide with those OF butyl alcohol and its ethers. Meta- and para-cresols and their et,hers have approximately the same specific volumes ;they are about 1 per cent.higher than the corresponding orthocresol-derivatives. The specific volumes of the tliyniol ethers are relativelysmall.The author obtains the following values for the specific volumes ofthe isomeric xylenes :-Ortho. Meta. Pam.137-6 139.75 139.9Schiff found 139.9 139-7 140.2 w. P&.W..Boiling Points and Specific Volumes. By W. LOSSEN (Anwalen,243, 64--103).--The author has compared the boiling points of alarge number of organic compounds, and agrees with Dobriner (pre-ceding page) that in an homologous series, the first difference (thatis the difference between the boiling points of methyl and ethyl coni-pounds) is less than the second (namely, between ethyl and propyl)when the alcohol radicle is attached to the rest of the molecule by anoxygen-atom.When the radicle is attached to a carbon-atom, thereverse is true in the majority of cases. In many cases, the first andsecond differences are equal, and in a few cases the first difference isft little less than the second.The author agrees with Horstmann (Abstr., 1886, 759) that a com-parison of molecular volumes determined a t the same temperaturepossesses many advantages not shared by specific volume determina-By C. SCHALL (Ber., 21,100-101) .-Blurther modifications in the apparatus lately describedby the author (Abstr., 1887, 695, 882).tions at the boiling point. w. c. w.Estimation of Vapour-densities.J. W. L336 ABSTRACTS OF CHEMICAL PAPERS.Determination of Vapour-density at Low Pressure.Ry H.MALFATTI and P. SCHOOP (Zeit. physikaz. Chem., 1, 159--164).--lnspite of the many modifications of methods of measuring vapour-density, there is not at present a convenient method when the tensionis small. Hofmann’s method requires for small tensions a cumbrousapparatus, whilst in Habermann-Dumas’ method there is the objec-tion of the additional determination of the weight of the mpour.A tubular glass vessel of 100 C.C. capacity closed at one end is care-fully cleaned and dried. Inside the tube is placed a short barometertube. The substance is weighed in a small glass sphere having twosides drawn out into fine tubes ; one capillary tube is stopped withalloy, and the other hermetically sealed after the introduction of thesubstance.The end of the glass vessel is drawn out iiito a capillarytube and the air is exhausted from the vessel ; when the levels of thearms of the barometer tube remain unaltered the vessel is hermeti-cally sealed. I t is next immersed in a bath of known temperature,and the difference of level of the arms of the barometer is read off bya millimetre scale, so that the pressure is known. The vessel is im-mersed in water and the capillary point broken off. The vessel whenfilled is weighed. Thus, having measured the volume of a givenlength of the barometer tube, we have sufficient data to determinethe vapour-density.In order that the barometer may contain no moistnre, it is con-structed as follows :-A tube is bent into the form of a double U-tube,and one end is passed through a cork inserted in the neck of a frac-tional distillation flask which contains a small quantity of mercury.The flask is inclined, so that the end does not touch the mercury, andheated while dry air is drawn through the tube. When the flask isplaced upright, the tube is immediately filled with mercury.The proper quantity of substance to be placed in the sphere is de-termined by a preliminary calculation.For higher temperatures, thebarometer is filled with an alloy of 3 parts lead and 1 part tin, whichdoes not stick to the tube and has no perceptible tension.For higher temperatures, the author also shows that a modificationof I;. Meyer’s apparatus (Ann.Phys. Chem. [S], 1880, 550) can beViscosity of Dilute Aqueous Solutions. By S. ARRHENIUS (Zeit.physikal.. Chew., 1, 285--298).-The solution is contained in a glaessphere of volume 0.9846 c.c., and is allowed to flow vertically througha. fine capillary tube, the bore of which suddenly enlarges at its lowerend, so that the velocity of efflux is negligible. The flow of liquidmay be started by turning on a tap connected with the upper part ofthe sphere. The sphere and the capillary tube connected t o it areimmersed in a wnter-bath so that the solution may be kept at a knowntemperature. Since the liquid escapes with a very small velocity, thework done by the solution in falling through the height of the capil-lary tube will be entirely spent in overcoming the resistance due toviscosity, provided no energy is consumed in setting up vortex-motionas the liquid passes from the capillary tube into its enlarged end.Inany case, the energy so spent will be less than if all the kinetic energyemployed. c. sGENERAL AND PHYSICAL OHEMILSTHP. 337of the liquid passiiig into the enlargement were employed in setting upvortex-motion. But on this hypothesis the energy spent niay be cal-culated by a formula given by Hagenbach (Ann. Phys. Chem., 109,385), and was found t o be negligible with the dimensions of the ap-paratus used by the author. Thus a correction, which has been cal-culated by various experimenters on hypotheses never completelysatisfied, is entirely avoided, By placing the capillary tube vertical,the small particles which are seen to form are carried away and notleft adhering to the sides of the tube.Hence the coefficient of rela-tive viscosity, y, will be given by TI = (st)/(ST), when s is the specificgravit,y of the sohtion, t the time of efflux of the volume contained inthe sphere, and S, T similar quantities for water.The results of numerous experiments show that the relative vis-cosity of a dilute aqueous solution of two different substances isequal to Ax BY, where 2, y are the volume percentages of the two sub-stances, and A and B two functions of the temperature which remainconstant for the same temperature and the same substance. There doesnot appear to be any connection between A and the viscosity of thecorresponding substance.The constant A diminishes as the tem-perature increases in the case of non-conductors, so that the values ofthe relative viscosity tend to a common limit, unity. The viscosity ofwater is increased by the addition of a small quantity of a non-con-ductor. Those normal solutions which have greater conductivity havein general less relative viscosity, but there does not Reem to be anyDissociation of Hydrated Salts. By P. C. F. FROWEIN (Zeit.yhysikal. Chew., 1, 5-14 and 362--364).-The relation which mustexist between the heat of combination of the water in hydrated saltsand the maximum vapour- tension has been thermodynamically cal-culated, but hitherto has not been experimentally established in asatisfactory manner.This is the aim, therefore, the author has inview.The thermodynamical relation given by Van’t Hoff, d . ZK,/dT =g/2‘1’’, is transiormed, in order to be applicable to calorimetric work,into d . lF/clT = Q/fL”, where T is the absolute temperature, Q theamount of heat evolved by the absorption of 18 kilos. OH, by thedehydrated salt, and F the ratio of the maximum tensions of salt andwater. By iutegration of the above on the assumption that Q remainsconsCant between small limits of temperature-simple law connecting conductivity and viscosity. c. s.Q=- 2TIT2 $ %*Ti - T, F2This equation does not, however, give numbers agreeing withThomsen’s observed values for the heat of combination in the cases of cusoc + 5 0 8 2 ; BaC& + 20H2; SrCl, + 60H2; MgSO, -+ 70H2, andZnSOa + 70H2, if the values for F1F2 are calculated from the num-bers given by Pareau and Wiedemann for the vapour-tensions.Attributing this to errors in the vapour-tension determinations,arising partly from the very small differences in pressure which haveto be observed, the author bas redetermined these by means of a338 ABSTRACTS OF CHEMICAL PAPERS.apparatus in which olive oil is used in the manometer in place ofmercury.The numbers thus obtained for FIF, give values of Qw%ich agree well with those observed by Thomsen for all the before-mentioned salts, with the exception of SrC1, + GOH,. The tensionof NazHPOa + 120H2 has also been redetermined, and the calculatedvalue for Q brought into agreement with the observed, a result whichthe former determinations by Debray and Muller-Erzbach had notrendered possible.H. C.Nature of Chemical Afflnity. By W. OSTWALII (Zeit. pkysikal.Chem,., 1, 61--62).-1n a former paper (Abstr., 1886, 294), the authorhas pointed out that chemical affinit’y depends not only on the natureand the relative distance of the atoms from one another, but also onthe direction in which it acts. The difference in the molecular con-ductivities of the two nitrosalicylic acids, [COOH : OI-: : NOz =1 : 2 : 3 and 1 : 2 : 51, is here offered as proof that although in eachclhe relative positions of the NO, and OH to the COOH-group is thesame, yet the former acid is the stronger of the two, the closer group-ing of the radicles being more favourable to their combined action.H.C.Thermodynamical Expression of the Influence of Tempe-rature on the Rate of Chemical Change. By F. URECH (Bey., 21,56).-A continuation of the author’s investigations (Abstr., 1887,768). Instead of Van’t Hoff’s expression, log c = -A/T + BT + Cthe equation log c = -A’/T + B‘, corresponding with the thermo-dynamical formula log c = --p/RT + B’, has been applied, and isfnund to give remlts agreeing generally with the author’s observedvalues for the rates of inversion of saccharose with hydrochloric acidof different strengths. H. C.Action of Sulphurow Acid on Periodic Acid and Rate of theChange. By F. SELMONS (Ber., 21, 230--24l).-The action of sul-phurous acid on periodic acid takes place for all proportions of the twoacids, the products varying, however, with the amounts employed.A separation of iodine takes place only within the limits representedby the equati~ris-4H,SO3 i- HIO, = 4H,so4 + HI$H2SU3 + 4HIO4 = 4H2S04 + 4HIO3,namely, when more than one and less than 4 mols.HI04 enter intoreaction with 4 mols. H2S03, the production of iodine being in factdue to the action of the hydriodic on the iodic acid.With dilute solutions, the rate of change of the reactions involvingthe production of iodine from sulphurous and periodic acids can bemeasured, using starch solution as an indicator. This reaction issimilar to that studied by Landolt (Abstr., 1886, 658) on the actionof sulphurous acid on iodic acid, and depends on the concentration ofthe solutions when the proportion between the two acids is keptconstant,, on the molecular weights for unit concentration, and on thetemperature.If C, is the concentration of the sulphurous, Cp that oGENERAL AND PH Y STCAL CHEMJ STKY. 339the periodic acid, then the time t = k,/(C,C,)", where calculated from - _If the two consecutive observations, x = -sulphurous acid be keDt constant in amount, and the periodic acidlog t - log t llog (C,Cp), - log (CsCp)'alldwed to vary, t = k/lCf,, where k is constant and y cafculated fromtwo consecutive observation H. C, log t' - log t"log c"p - logInfluence of Molecular Contiguity on the Chemical Equi-librium of Homogeneous Gaseous Systems. By SARRAU andVIEILLE (Compt. rend., 105, 122-2-1224) .-The combustion of organiccompounds which do not contain sufficient oxygen for complete oxida-tion results in the production of a condition of equilibrium betweenthe gaseous products, some of which are completely oxidised, as car-bonic anhydride and water, whilst in others, such as carbonic oxide,hydrogen, and methane, oxidat ion is incomplete.Experiment showsthat the conditions of final equilibrium change with an increase in theweight of substance exploded in the same space, that is to say, wit.han increase in the pressure produced by the products. Two principalreactions are concerned in the progressive alteration of equilibrium.The first CO + H,O = CO, + H,, usually occurs ; the second, 2CO +2HqO = CO, + CH4, takes place when the first has reduced the pro-portion of water vapour and increased the proportion of free hydrogento a certain extent, or when the explosive contains so little oxygenthat water is formed in relatively very small quantity.The firstreaction was observed to take place by Noble and Abel in their ex-periments with gunpowder. The autbors find that it also takes placein the explosion of cotton powder and of picrates. The resultsobtained with cotton powder, C2aH,,N1104,, are as follows :-S P d > V nf0.023gas. Methane.0.010 33CO + 15C0, + 8H, + 11N2 + 21H,O 0.000.200 2iCO + 21C0, + 14& + 11N, + 15H,O0.300 26CO + 22C0, + 15H, + 11N, + 14H,OThe temperature of final equilibrium is about 3000°, the pressurevarying between 100 and 4000 atmospheres. The formation ofmethane, which occurs only to a very limited extent in the case ofcotton powder, becomes more marked with such compounds as the1omTer nitrated derivatives, picrates, and picric acid.The resultswith the last compound were as follows :--30CO + 18C02 4- I l H , + 11NZ + 18HaO 0.000.0060.016Densityof gas.0.10 11C0, + 84CO + 24N, + C& + 16H2 4- 6H,O0.30 20C02 + 69CO + 24N, + 7CH4 + 7H-z + 3HzO0.50 25C02 + 61CO + 24Nz + 9iCH4 + 4Hz +' H,O+QC.The pressures varied from 1000 to 7500 atmos. The reactionswhich tend to reduce the proportion of carbonic oxide are exothermi340 ABSTRACTS OF CHEMICAL PAPERS.In the case of the first reaction, the development of heat is not great,and there is no alteration in the volume of the gas ; but i n the secondcase there is 5t considerable development of heat, and the volume ofthe gases taking part in the change is reduced to one-half.Thealterations in the conditions of equilibrium tend towards the develop-ment of the maximum quantity of heat, and the two reactions concurin making the pressure increase in a greater ratio than the weight ofthe explosive charge.Influence of Neutral Salts on the Rate of Hydrolysis of EthylAcetate. By S . ARRHENIUS (Zeit. physikal. Chern., 1, 110-133).-In Warder and Reicher's equation for the rate of saponification,C. H. B.- _ dC = kCCI, where t is the time, C the concentration of the base,d tand C1 that of the salt, k is a quantity which the author proposes tocall the specific rate of saponification.This quantit'y is independentof the amounts of base and salt which act on one another, but mostprobably varies for different concentrations. In the present case, theinfluence of the presence of neutral salts on k was studied. Thisinfluence is as a rule small, and Ic remains nearly constant; salts ofthe halogens and nitrates lower, whilst sulphates and hyposulphitearaise the value of k. Theinfluence of potassium iodide is greater thanthat of potassium bromide, which is greater than that of potassiumchloride, the three being very nea.rly in the ratio 3 : 3 : 1.Quite abnormal is the influence of ammonia and ammonium salts,the action being very greet and varying very distinctly with theamount of salt in solution. k in fact here depends on the amount ofdissolved salt, 8, according to the equation 3c =The rate of hydrolysis is practically in all cases proportional tothe conductivity.The lorn conductivity of a weak base such asammonia, on which other dissolved electrolytes can exercise such alarge relative influence, probably explains its abnormal behaviour.A1 + a s + bS2H. C.Formation and Decomposition of Ethereal Salts : Decom-position of Liquid Tertiary Amy1 Acetate. By D. KONOWALOFF(Zeit. physikaZ. Chem., 1, 63-67) .-Menschutkin (Abstr., 1883, 178,309) has observed that the rate of decomposition of liquid tertiaryamyl acetate at 180" increases until about 50 per cent. of the acetateemployed is decomposed, then diminishes, and finally ceases when thedecomposition has reached 97.42 per cent.The author shows thatthe cause of this is the action of the liberated acetic acid on theacetate, and finds that the addition of acetic acid brings about thedecomposition of the acetate. By heating amyl acetate with varyingamounts of acetic acid for one hour at 159", he shows that the amountdecomposed is dependent on the amount of acetic acid added. Thisis expressed. by the equation d:c/dt = k (100 - F) (m + 2 g p ) , wherez is the percentage of acetate decomposed in the time t, p the quantityof acetic acid added, 2g the ratio of the molecular weights of theacetate aud acetic acid, and k a constant. All other acids have aQENERAL ASD PHYSICAL CHE3JISTRY. 342action similar to this of acetic acid although in different degree,propionic and butyric acids being far less active.The action of the haloyd hydrogen acids was also studied, but inthese cases the gaseous acid was passed into the liquid acetate at theordinary t,emperature.The action is violent, a considerable develop-ment of heat takes place, and a tertiary amyl halrjid salt and aceticacid are formed. I n the action of hydrogen chloride two stages maybe distinguished, the acetate being first decomposed into amylene andacetic acid, and the amylene then combining with the hydrogenchloride. This reaction the author proposes to employ to determinethe heat-change represented by C5Hll*C2H302 = C,H,, + C,H40,. Thecomparative ease with which the halogen acids act on tertiary amylacetate explains the formation of amyl chloride instead of acetatewhen dimethyl ethyl carbinol is treated with acetic chloride.Chemical Decomposition produced by Pressure.By W.SPRING and J. H. VAN'T HOFF (Zeit. physiknl. Chem., 1, 227-230).-The results of numerous experiments show that in many cases sub-stances which exert no action on each other at atmospheric pressureunder ordinary circumstances, can be made to combine more or lesscompletely if they are subjected to a pressure sufficient t o cause Rperceptible condensation. The researches hitherto made relate tocompounds, the volume of which is smaller than that of their con-stituents. I t is therefore a question of some int,erest and importanceto examine whether the temperature of conversion can be lowered inthe case of copper calcium acetate, for which the volume is greater thant h a t of its constituents.In the first experiment the acetate Enely powdered at a temperatureof 16" Was submitted to a pressure of 6000 atmospheres.Thepowder was thus reduced to a crystalline mass resembling marble,kut presenting no sign of chemical decomposition. Next ascrew press (Bull. Acc. Belg., 49, 344) was employed; at a tem-perature of 40" there were very marked results; three-fourths ofthe mass being liquefied. On removing the pressure, it became solidagain, but the sides of the containing vessel were covered with a coat-ing of copper, and it was possible to pick small leaves of copper out ofthe mass. The dark blue of the acetate had changed for the mostpart to green interspersed with white points, showing that the masshad been decomposed into acetate of copper and acetate of calcium.The result, was entirely due to the change of volume, since the thermaleffect of compression was less than a rise of 1".When the tempera-ture was raised to 50", the piston sank without resistance throughthe mass. The first experiment, which bad given a nugatory result,was now repeated in order to discover whether sufficient pressurehad been used, or the result had escaped observation. A press workedby a lever was used, and this time it was found that the piston sank1.25 mm. in an hour, or, roughly, that the whole could be decomposedin about 110 hours. Lastly, potassium sulphate under the same con-ditions gave no perceptible diminution of volume.Thus, the higherthe pressure and temperature, the more quickly is the acetate decom-posed. Since the progress of chemical action depends on the time, itH. C842 ABSTRACT8 OF CHEMICAL PAPERS.seems that i t is not sufficient to say that the molecules of a subshnceassume the arrangement which corresponds- with the given volumedirectly it is reached, for a substance can be compressed withoutaltering its state, if the pressure does not last too long. c. s.Crystallisation of Mixtures. By 0. LEHMANN (Zeit. physikal.Chem., 1, 15-26 arid 49-60).-The author discusses the differentcases in which mixed crystals have been formed, and the possibi1it.yof obtaining such from non-isomorphous forms. He repeats the ex-periments of Herrmann (Ahstr., 1886, 972), on t,he crystallisation ofethyl quinonedihydroparadicarboxylate with ethyl succinomccinatewith similar results. He also investigates the mixed ciytals of ethyldihy d ro x yquino neparadicarbox y Iat e with e thy1 te trah ydrox ybenzene-p~radicarboxylate, and of each of these with each of the two foregoing.These substances, although having a somewhat analogous chemicalconstitution, differ pretty widely in crystalline form. They give,however, well-defined mixed crystals of form and colour intermediatebetween those of the t w o substances of which they are formed.Constitution of Solutions. By F. R ~ O R F F (Bw., 21, 4-11).-Numerous experimenters have found that the solution of a doublesalt difyuses as if it were a solution of a mixture of its componentparts; for this and other reasons, it is generally stated that doublesalts do not exist as such in solution.On dialysing solutions of the following double salts, R2S0,,NiSOa + 6H,O; K2SOa,MnS04 + 6H@; (NH4)2S04,MnS04 + 6H,O;K,SO,,Cr,(SO,), + 24B20 ; 2KC1,CuC12 + 2H,O ; 2NH4C1,CuCl, +2H20; 2KC1,2nCl2 + H,O; KCl,MgCI, + 6H,O; 2NaC1,CdC12 +3Hz0 ; BaC12,CdC12 + 4H20, i t was found that the ratio of the metalsi n the dialysate was entirely different from that in the original liquid ;the componeiit parts, therefore, do not form a molecular compound,but exist in solution independently of each other. On the otherhand, the following double salts, KCN,AgCN ; 2KCN,Hg( CN),;2KCN,C;d(CN)z; &KCN,Ni(CN),; GKCN,Cu,(CN),; 2NaCl,PtCla +6H20 ; 3NazC,04,1-’e2(C204)3 + GH20 ; 3KzC,0,,Fez(C,04), + H20 ;3KzC,04,Cr2(C204)3 + 6Hz0 ; are not decomposed, but must exist insolution and diffuse as such, inasmnch as the ratio of the metals isfound to be the same in the dialysatc as in the original liquid.Several simultaneous experiment’s were made with each salt, and amembrane prepared from the cuticle of the caecum of an ox wasfound to be most suitable, a parchment membrane not being sufficientlyhomogeneous. F. S. I(.Absorption of Gases by Petroleum. By S. GNIEWOSZ andA. WALFISZ (Zeit. physilcal. Chew,., 1, 7O--T2).-The statement thata layer of petroleum will protect an aqueous solution from the actionof the air has led the authors to examine the absorption of oxygenand other gases by Russian petroleum. The following table containsthe rceults :-H. CINORQANIC CEIEMISTRY. 343----H2 ..............N2 ..............0 2 ..............NzO ............C,H, ............cu2 .............co. .............CH4 ............Absorption coeficients forpetroleum at20°.0 '03820.1170 '2022.110 - 1421 *170 '1230 -13110"0 -06920 *1350.2292 *490 -1641.310'1340.144Ratio.1 . 21 .151.131 *181.151.121.091.10Water at 20".0.01930'01400 *0%40.6700.1490.9010 '0231c1.03.50The ratio is given on account of E. Wiedemann's statement that thechanges which the absorption coefficients of different gases undergowith change of temperature is about the same for all gases ; the valuesfor water are given for the sake of comparison. It will be seen thatthe absorption of oxygen is greater for petroleum than for water, BOthat the protective action above spoken of must be a doubtful one.H. C.Lecture Experiments with Nitrogen Chloride. By V. MEYEK(Ber., 21, 26--28).-An experiment is described by which the explo-sion of nitrogen chloride can be shown, without danger, by allowingturpentine to come into contact with a few drops of the chlorideswimming on the surface of the electrolysed ammonium chloride solu-tion contained in an inverted flask, the whole apparatus being placedunder a thick glass case. F. S. I(

ISSN:0368-1769    

DOI:10.1039/CA8885400329

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

INORQANIC CEIEMISTRY. 343 I n o r g a n i c Chemistry. Specific Gravity of Sulphuric Acid Solutions. By D. MEN- DELEEFF (Zed. physika2. Chem., 1, 273-284) .-The composition of the solutions is expressible by the formula H2SOa i- d 3 . , O ; p denotes t,he percentage of HzS04 in the solution, taking S = 32, 0 = 16, and s is its specific gravity. A table of the value of s derived from the researches of seven experimenters is given for different values of m. Plotting a curve, abscissz representing the values of p , ordinates those of dsldp, it appears that tlie curve consists of a number of straight lines, the discontinuities corresponding with the known hydrates. Since ds/dp is alinear function of p , an integration shows that s is arational function of p of the second degree, the constants remaining un- changed between two consecutive discontinuities or two consecutive hydrates.Thus for the values rn = 0, 1, 2, 6, 150, there are discontinuities in the values of dsldp, the first being the most considerable. The data344 ABSTRACTS OF CHEMICAL PAPERS. given are not sufficient to determine the positions of the discontinuities for m = 6 and m = 150 with accuracy. Formulae are given for daldp and s in terms of p for the intervals through which these quantities are continuous, and it is shown that ds/dp = a linear function of p is probably not an approximation but an exact law. The same law obtains in the case of alcohol solutions. c. s. Pyrosul3hites. By W. MEYSZTOWICZ (Zeit. physikal. Chew,., 1, 73) .-The failure of an attempt to prepare pyrosulphites of polyvalent metals leads the author t o draw an analogy between pyrosulphurons and dichromic acids, concluding that in each the position of the hydrogen-atoms is such that they cannot be simultaneously replaced by a, bivalent element.H. C. Action of Water on Lead Pipes. By E. REICHARDT (Arch. Pharm. [3], 25, 858--877).-1n the vast majority of cases where lead pipes are used for domestic water supply, no injurious results follow, but in some few cases highly dangerous lead poisoning has been experienced. When lead is alternately in contact with air and water, it is rapidly attacked, and the water becomes impregnated. This solvent action is doubtless due to the oxygen of the air ; b u t when the lead i8 always in contact with water only, whether under pressure or not, the presence or absence of dissolved oxygen a.ppcars to have no effect on the amount of lead dissolved.The author examined two different water supplies which caused lead poisoning. where lead service pipes were employed, and compared these with several other waters which did not take up lead under similar conditions. The cont'aminated waters were found to contain free carbonic anhydride, that is more than was required to form bicarbonates with the bases present as carbonates, and when this free anhydride was expelled, as by boiling, or neutralised, the water no longer acted on lead. The uncon- taminated waters did not contain this excess of anhydride, but on adding excess of the anhydride the waters became capable of dissolving lead (compare (Miiller, this vol., p.225). J. T. Tungsten Compounds. By W. FEIT (Ber., 21, 133--137).-By the reduction of R fused mixture of sodium and potassium tungstates with tin, t,he author obtains the compounds 3R2W4012 + 2Na2W,09 and 5K2W4012 + 2Na4W6Ol5, prepared by v. Knorre (Abstr., 1883, 650, 651), and also a compound which probably has the formula K2W4O,, + Na2W5ClI5. The author has endeavoured to prepare corresponding compounds of lithium. By reducing a fused mixture of sodium tangstate and lithium tungstate with tin, three com- pounds are obtained, a deep blue lithium compound (probably Li,W6015) and two sodium coinpounds, one of which seems to be the compound Na,W,O IH. A homogeneous product, Li2W5OI5 + 3K2W4OI2, crystnllising in violet needles, is obtained by reducing a mixture of potassic tungstate (one mol.), and lithium tungstate (one mol.).As the proportion of base and acid (3 : 7 or 5 : 12) in the para- fnngstates of the light metals can scarcely be proved by analysis, theMINERALOGICAL CHENISTRY. 345 difference being too small, the author intends t o prepare the salts of some metals of a high atomic weight. J. W. L. Boiling Point and Molecular Formula of Stannous Chloride. By H. BILTZ and V. MEPER (Her., 21, 22-24).-The boiling point of stannous chloride is found to be 606*1", as a mean of two series of experiments. The vapour-density of this salt diminishes only very gradually with an increase of temperature, so that it must be heated hundreds of degrees above its boiling point in order to obtain numbers agreeing with the molecular formula SnC1,.The determinatioiis made at tern- ' peratnres less than 100" above the boiling point show that the view of V. and C. Meyer, that at low temperatures the molecular formula is Sn2Cl,, cannot be upheld ; for although at relatively low tempera- tures values are obtained which are greater than those corresponding to SnCl,, no constant results could be obtained which would lead to the doubled formula. F. S. K. New Source of Germanium. By G. K R ~ ~ S S (Ber., 21,131-133). -The author finds that germanium is contained in euxenite to the amount of 0.1 per cent., and that i t replaces titanium in this mineral. He intends to examine other minerals, such as rutile, yttrotitiinite, wohlerite, &c., for germanium. J. W.1;. Atomic Weight of Gold. By G. KtlFss (Ber., 21, 126-130).- A controversial paper i n reply to Thorpe and Laurie (Trans., 1887, 563, 866).INORQANIC CEIEMISTRY. 343I n o r g a n i c Chemistry.Specific Gravity of Sulphuric Acid Solutions. By D. MEN-DELEEFF (Zed. physika2. Chem., 1, 273-284) .-The composition of thesolutions is expressible by the formula H2SOa i- d 3 . , O ; p denotest,he percentage of HzS04 in the solution, taking S = 32, 0 = 16, ands is its specific gravity. A table of the value of s derived from theresearches of seven experimenters is given for different values of m.Plotting a curve, abscissz representing the values of p , ordinates thoseof dsldp, it appears that tlie curve consists of a number of straightlines, the discontinuities corresponding with the known hydrates. Sinceds/dp is alinear function of p , an integration shows that s is arationalfunction of p of the second degree, the constants remaining un-changed between two consecutive discontinuities or two consecutivehydrates.Thus for the values rn = 0, 1, 2, 6, 150, there are discontinuities inthe values of dsldp, the first being the most considerable.The dat344 ABSTRACTS OF CHEMICAL PAPERS.given are not sufficient to determine the positions of the discontinuitiesfor m = 6 and m = 150 with accuracy. Formulae are given for daldpand s in terms of p for the intervals through which these quantitiesare continuous, and it is shown that ds/dp = a linear function of p isprobably not an approximation but an exact law.The same lawobtains in the case of alcohol solutions. c. s.Pyrosul3hites. By W. MEYSZTOWICZ (Zeit. physikal. Chew,., 1,73) .-The failure of an attempt to prepare pyrosulphites of polyvalentmetals leads the author t o draw an analogy between pyrosulphuronsand dichromic acids, concluding that in each the position of thehydrogen-atoms is such that they cannot be simultaneously replacedby a, bivalent element. H. C.Action of Water on Lead Pipes. By E. REICHARDT (Arch.Pharm. [3], 25, 858--877).-1n the vast majority of cases where leadpipes are used for domestic water supply, no injurious results follow, butin some few cases highly dangerous lead poisoning has been experienced.When lead is alternately in contact with air and water, it is rapidlyattacked, and the water becomes impregnated. This solvent action isdoubtless due to the oxygen of the air ; b u t when the lead i8 alwaysin contact with water only, whether under pressure or not, thepresence or absence of dissolved oxygen a.ppcars to have no effect onthe amount of lead dissolved.The author examined two differentwater supplies which caused lead poisoning. where lead service pipeswere employed, and compared these with several other waters whichdid not take up lead under similar conditions. The cont'aminatedwaters were found to contain free carbonic anhydride, that is morethan was required to form bicarbonates with the bases present ascarbonates, and when this free anhydride was expelled, as by boiling,or neutralised, the water no longer acted on lead.The uncon-taminated waters did not contain this excess of anhydride, but onadding excess of the anhydride the waters became capable of dissolvinglead (compare (Miiller, this vol., p. 225). J. T.Tungsten Compounds. By W. FEIT (Ber., 21, 133--137).-Bythe reduction of R fused mixture of sodium and potassium tungstateswith tin, t,he author obtains the compounds 3R2W4012 + 2Na2W,09and 5K2W4012 + 2Na4W6Ol5, prepared by v. Knorre (Abstr., 1883,650, 651), and also a compound which probably has the formulaK2W4O,, + Na2W5ClI5. The author has endeavoured to preparecorresponding compounds of lithium. By reducing a fused mixtureof sodium tangstate and lithium tungstate with tin, three com-pounds are obtained, a deep blue lithium compound (probablyLi,W6015) and two sodium coinpounds, one of which seems to be thecompound Na,W,O IH.A homogeneous product, Li2W5OI5 + 3K2W4OI2,crystnllising in violet needles, is obtained by reducing a mixture ofpotassic tungstate (one mol.), and lithium tungstate (one mol.).As the proportion of base and acid (3 : 7 or 5 : 12) in the para-fnngstates of the light metals can scarcely be proved by analysis, thMINERALOGICAL CHENISTRY. 345difference being too small, the author intends t o prepare the salts ofsome metals of a high atomic weight. J. W. L.Boiling Point and Molecular Formula of Stannous Chloride.By H. BILTZ and V. MEPER (Her., 21, 22-24).-The boiling point ofstannous chloride is found to be 606*1", as a mean of two series ofexperiments.The vapour-density of this salt diminishes only very gradually withan increase of temperature, so that it must be heated hundreds ofdegrees above its boiling point in order to obtain numbers agreeingwith the molecular formula SnC1,. The determinatioiis made at tern-' peratnres less than 100" above the boiling point show that the viewof V. and C. Meyer, that at low temperatures the molecular formulais Sn2Cl,, cannot be upheld ; for although at relatively low tempera-tures values are obtained which are greater than those correspondingto SnCl,, no constant results could be obtained which would lead tothe doubled formula. F. S. K.New Source of Germanium. By G. K R ~ ~ S S (Ber., 21,131-133).-The author finds that germanium is contained in euxenite to theamount of 0.1 per cent., and that i t replaces titanium in this mineral.He intends to examine other minerals, such as rutile, yttrotitiinite,wohlerite, &c., for germanium. J. W. 1;.Atomic Weight of Gold. By G. KtlFss (Ber., 21, 126-130).-A controversial paper i n reply to Thorpe and Laurie (Trans., 1887,563, 866)

ISSN:0368-1769    

DOI:10.1039/CA8885400343

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

MINERALOGICAL CHENISTRY. 345 Mineral o g i c a1 C h emi s t r y. An English Coal. By SCHEURER-KESTNER and MEUNIER-DOLFCS (Compt. rend., 105, 1251--1255).-The coal was obtained from Glamorganshire. It gave 88 per cent. of coke and 3 to 4 per cent. of ash, the composition being as follows:-C 90.27, H 4.39, S 0.69, N 0.49: 0 4.16. The composition of the volatile portion was C ‘22.53, H 34-96, 0 + N + S 42.51. The heat of combustion as actually de- termined (8864 cal.) diaers considerably from that calculated by meme of any of the usual formulaj. C. H. B. Afti’ficial ’Pyrodhroite. B y A. DE BCHULTEN (Compt. renL,lD5, 1265-1267) .-300 grams of pure potassium hydroxide was dissolved in 500 C.C. of water, boiled for some time in a flask through whicli a current of hydrogen or coal gas was passing, and a recently boiled solution of 15 to 1’7 grams of crystallised manganous chloride i n 1.5 C.C.of water WAS iritroduced by means of a, funnel with a stopcock. The flask was then heated to about 160°, when the whole of the mao- gnnous hydroxide dissolved. As the liquid cools, it deposits crys- VOL. LJV. 2 a346 ABSTRACTS OF CHEMICAL PAPERS. tallised manganous hydroxide, and becomes almost solid. The crystals are washed with recently boiled water, alcohol, and ether, and dried at a gentle heat in a current of hydrogen. If sodium hydroxide is used, t,he precipitate does riot dissolve even in concentrated solutions a t 200°, but it becomes crystalline. Crystallised manganous hydroxide dissolves readily in hydrochloric acid and in a solution of ammonium chloride.When heated to redness in the air, it forms manganoso- manganic oxide, which retains the form of the original crystals. When heated in hydrogen, it yields manganous oxide, which is green when hot and grey when cold. Manganous hydroxide under these conditions crystallises in flat- tened, transparent, regular, hexagonal prisms, with a reddish tint. The crystals are uniaxial, and the axis is negative, as in pyrochroite. Crystallised cadmium hydroxide likewise has a negative axis, but magnesium hydroxide, natural or artificial, has a- positive axis. When the manganous hydroxide is pure, it alters very slowly in presence of air. but if it contains even a small quantity of alkali, it oxidises very quickly . C. H. B. Mineralogical Notes. By G.I?. KUNZ (Anter. J. Sci., 34, 477- 480) .-1. Rhodochroisite from Colorado.-Rhodochroisite, in rich, red, transparent rhombohedra, has been found in the John Reed Mine a t Alicante, Lake Co., Colorado. This is the first locality that has yielded crptals of such size (12 mm. across) and transparency. The sp. gr. is 3.69, and the hardness 3.5. Analysis gave the following results:- MnO. FeO. CaO. MgO. cog. Total. ’%%!a %“ti nil ’trace ‘(3bV6’) l i ~ f i ~ 2. Hollow Quartz Crystals from Arizona.-These crystals are found about 3 miles south-west of the town of Pinal, Pinal Co., Arizona. They occur in sandstone, penetrated in many places bey spherules of obsidian. The crystals are mere walls surrounding hollow spaces much larger than the area of the wall itself. 3. Hydrophane from Colorado.-A white, opaque variety of hydro- phane in rounded lumps, 5 to 25 mm.in diameter, has recently been brought from Colorado. It is remarkable for its power of absorbing water. When water is allowed to slowly drop on it,, it first, becomes white and chalky, and then gradually perfectly transparent. It was found by weighing that this mineral absorbs more than an equal volume of water 4. A Remai*kable Nugget of Xiluey.-One of the most remarkable nuggets of silver known was found in limestone a t the Greenwood Mines in the State of Michoacan, Mexico. It weighed 606+ oz., and in its original state weighed 12 lbs. more. It consists of almost pure silver, and is entirely worn except in cavities where the form of some of the crystals is still visible.B. H. B. Bismuthospherite from Willimwntic and Portland, Con- necticut. By H. L. WELLS (Amer. J. Xci., 34, 271-274).-The author has exa)mined two specimens of basic bismuth carbonate, the composition of which appears to be identical with that of Weisbach’sJIINERALOQICAL CHEMISTRY. 347 bisinuthosphserite. The composition of that mineral has been con- sidered doubtful by A. H. Chester (Abstr., 1887, 783), because no water was included in the analysis. In the Connecticut specimens, the percentage of water did not exceed 0.94. Since a part of the water found was probably hygroscopic moisture, and since the determina- tions were made by weighing the water in a calcium chloride tube, a method apt to give slightly high results, these two specimens of bismuth carbonate must be regarded as anhydrous. The analyses agree closely with the formnla Bi203,C02.The existence of bismutho- sphzerite must thus be considered as established. B. H. B. Natural Borates and Borosilicates. By J. E. WHTTFIELD (Amer. J. Sci., 34, 281--287).-The author has repeated the analyses of some natural bomtes, in order to correct ei’rors due t o defective analytical methods. The boric acid was determined by the method devised by I!’. A. Gooch (Abstr., 1887, 299). CoZemanite from Death Valley, California, gave on analysis tlhe following results :- R2O. W3. CaO. MgO. Total. 21.87 50.70 2‘7.31 0.10 99.98 These results correspond with the formula 2Ca0,3B20,,5H2O. The same formula mas calculated by J. T. Evans (Abstr., 1885, 958), from his analysis, in which the boric acid was determined by differ- ence.Priceite from Curry Co., Oregon, gave the following composi- tion :- HBO. B2°3. CaO. Total. 19.42 48-44 32-15 100.01 Pandermite from Panderma, in the Black Sea, gave on analysis HQO. 33203. CaO. Total. the following results :- 19.40 48.63 38.1 6 100.19 It will thus be seen that priceite and pandermite are identical in composition. The difference is solely in the physical character of the minerals, priceite being soft and friable, and pandermite hard and compact (compare Abstr., 1885, 1117). ZJZeaite from Rhode’s Marsh, Esmeralda Co., Nevada, gave on analy- sis the following figures :- SiOa. 01. B20,. SO,. CaO. Na20. K20. H20. Total. 0.04 2.38 43-20 0.28 14.52 10.20 0.44 29.46 100.52 The analysis being corrected f o r impurities, the formula NaCaB50g LzLdwigite from Moravitza, in the Banat, gave on analysis the follow- + 6H20 is deduced. ing results :- 2 n 2348 ABSTRACTS OF CHEMICAL PAPERS.B20+ Fe20,. FeO. MgO. MnO. H20. Total. 12-04 37.93 15-78 30.57 0-16 3-62 100*10 Tschermak obtained 16-09 per cent. of boric acid, but gives no DatoZite from Bergen Hill, New Jersey, gave- water. SiO,. FeO. CaO. RZO,. H20. Total. 35.74 0.31 35.14 22.60 6.14 99.93 The formula is thus B203,Hz0,2Ca0,2Si02. Uanbzwite from Russell, St. Lawrence Co., New York, gave- SiO,. B203 CaO. Fe,03 + A1203. Ign. Total. 49.70 25.80 23-26 1.02 0.20 99-98 Axinite from Cornwall (I), and from Bonrg d’oisans, Dauphin6 (11), gave on analysis the following results :- SiO,. d1203. Fe203. FeO. CaO. MnO. MgO.B20,. HT,0. Tot,al. I. 42.10 17-40 3.06 5.84 20.53 4.63 0.66 4-64 1-80 100.66 11. 41-53 37-90 3.90 442 21.66 5.79 0.74 4.62 2-16 100.32 The formula is BR””R”4H2( SiO,),O. B. H. B. Pseudomorphs in the Lead Mines of the Puy de Dome. By F. GONNAED (Compt. rend., 105, 1267--1869).-The enveloping pseudomorphs or perimorphoses consist of bhin coatings of one mineral on the crystals of another. In the lead mines of the Puy de Dome, enveloping psmdomorphs of pyromorphite on cerussite or galena are frequently observed. Sometimes the mineral inside bas undergone alteration, owing to the fact that the envelope has not protected it from the air, &c. Not unfrequently, when the layer of pyromorphite is of appreciable thickness, it is distinctly crystalline, and the hexagonal prisms can readily be recognised.It is obvious that an envelope of this character is not a true pseudornorph. Another mineral found in the form of enveloping pseudomorphs is siderite, One specimen showed the unusual form of hexagonal prisms surmounted by rhombohedrons. Calcite does not occur associated with it, and hence it cannot be regarded as a pseudomorph after that mineral. The nature of the original mineral was not determined. The form is, however, possible for any substance crystallising in the rhombic system, and hence this is a case of siderite occurring as a pseudomorph under a form in which it might crystallise itself. Pseudomorphs of pyrites on calcite were also found, the envelope of pyrites being crystalline, and showing combinations of the cube with the pentagonal dodecahedron.Crystalline Compounds prepared by Ebelmen. By E. MALLARD (Compt. rend., 105, 1260-1265) .-Artificial phenacite, SiO,,BBeO, obtained by fusing beryllia and silica with borax, forms C. H. B.MINERALOGICAL CKEMISTRY. 349 small, regular, hexagonal prisms with very brilliant faces, the optical sign being positive. Bei-yllium chrornite, Be0,Cr203, prepared by fusing chromic oxide wiQh beryliia and boric anhydride, is a deep green powder, which polarises strongly under the microscope, and consists of minute crys- tals of a form identical with that of the variety of cymophane known as alexandrite. It is therefore analogous t o the corresponding alum- inium compound, the artificial cymophane likewise obtained by Ebelmen. Crystallised niobic anhydride forms small, rhombic prisms with two perpendicular cleavages, h' and g', the angle wtm being 140" 50', and the horizontal parameters 0.355 : 1.The form seems to be pseudo- cubic ; the acute positive bisectrix is perpendicular to h', the plane of the axes beingp. Tantalic anhydride was obtained in rhombic prisms with the faces g' h' well developed, and the subordinate faces m, g2, g3, g5, the angle rnm being about 143". I t follows that niobic and tantalic anhydrides are isomorphous. Crystnllised beryllia has the parameters a : h = 1 : 1.6305, the optical sign being positive. In crystallised zinc oxide, the parameters are a : It = 1 : 1.6034, and the optical sign is likewise positive. It follows that these two oxides are isomorphous, notwithstanding the difference in their specific volumes.Alurninium borate, Bz0,,3Al20, which Ebalmen annlysed but did not describe, crystallises in rhombic needles, the dominant face being m truncated by 9' and 71,' ; angle mm = 92" 21' ; acute positive bisec- trix parallel with the vertical, the plane of the axes being parallel with 9'. The compound 3B,O3,2Fe2O3,9Mg0, which Ebelmen analysed, forms black, opaque prisms, which have very brilliant faces, and probably belong to the rhombic system. The principal faces are m and h', the angle mm being 90" 32'. An analogous compound containing chro- mium in place of iron forms a dark brown powder consisting of small prisms, which when examined by polarised light seem to belong to the rhombic system. Ebelmen prepared crystallised tribasic borates, B,o3,3RO, which on his assumption that boric acid is analogous to silicic acid, are analogous to peridote, the oxygen ratio being 1 : 1; and likewise crysfallised sesquibasic borates, which on the same assumption are analogous to enstatite.The tribasic borates actually obtained were the magnesium, manganese, and cobalt compounds. They are isomorphous, and belong t o the rhombic system, the parameters being as follows :- Bz0,3MgO . . . . 0.6412 : 1 : 0.5494 rnnt = 114" 40' B2O3,3CoO .. .. 0.6461: 1 : ? rnm = 114 15 B203,3Mn0 . . . . 0.6511 : 1 : 0.5351 mm= 113 52 The faces m are faces of cleavage, and the acute positive bisectrix is parallel with the vertical, the plane of the axes being g'. The principal indices of refraction for 1) are respectively 1.6748, 1.6537, 1.6527.The sesquibasic borates obtained are the magnesium, manganese,350 ABSTRACTS OF CHEXICAL PAPERS. 66 *58 21-26 0.07 1 e l 8 10 *26 0 -76 0 -16 .-. and zinc compounds. They are isomorphous, and belong t o the tri- clinic system, the parameters of the mangauese compound being 1.8373 : 1 : 2.012, and xy = 76" 26', xx 123" 58', yz 92" 6', g'h' 75.01, ph' 124" 2Y', pg' 83" 16'. All have easy nacreous cleavage along p , and a less easy vitreous cleavage along t. The nacreous cleavage is almost always perpendicular to an opt'ical axis. Triclinie Felapars with Twinning Striations on the Brachy- pinacoid. By S. L. PENFIELD and F. L. SPERRY (Amer. J. Sci., 34, 390--393).-The authors gve the results of a careful study, in connect'ion with the chemical c_omposition of the felspars, of the stria- tions due to twinning on cnPm exhibited by very inany cleavage specimens of plagioclase felspar, in additionJo the ordinary striations on the basal plane.These striations on 00Pm have been shown by G. v. Rath (Abstr., 1878, 713) to have resulted from twinning according to the pericline law. The two individuals are united by a plane deviating slightly from the basal plane, passing through the macro-axis, and so inclined that the four plaFe angles it makes with the prisms w'P and mP' and the pinacoid mPm are all equal. This is the so-called rhombic section. Owing to the variations in the axial angles of anorthite felspars, the direction of the rhombic section changes consjderably. The direction above the line parallel to the edge OP : mPm being regarded as positive, and that below as nega- tive, the direction of the rhombic section in felspars of the albite- anorthite group was found by Tschermak to be as follows :- C.H. B. 66-83 20.88 0'25 1.46 10.36 0.70 0.27 --- Na?O CaO per cent. per cent. Albite, NazA1,Si,0,6 . . Ab +22" 11.8 0.0 Oliaoclase.. ......... Ab3Anl + 4 66.06 21.57 0'18 1-80 9.57 1.01 - -- Anvdesine ........... AbiAni - 2 Labradorite ......... Ab,An3 - 9 Anorthite, Ca2AI4Si4OlG An - 18 99'71 2.627 9.20 1 : g . a 8.7 5.2 5.7 10.4 2.8 15.3 0.0 20.1 99.92 100.78 2.628 2.622 9-70 15.17 1 : 9 ' 0 1 : 4 ' 1 Si02 ............... Al,O, .............. F+03 .............. CaO ............... Na,O .............. K20 ............... Ignition ............ Total ..............- $p. gr. .............. Ratio An : Ab ...... Anorthite per cent. .. Rhombic section . . , . Extinction on caPco,, 2.610 2.632 2-63; 5'87 'I -25 8 -94 + 12' 14O 13' 15 15 16 1 : 16.0 1 : 13.0 1 : 9 . 6 66 -34 20 9 2 1 *85 9 '44 0 -98 0 '38 - 65 -73 21 -32 0 -12 1 -95 9 *66 0 -95 0 -19 63 "76 22 '67 0 -41 3-05 6 *89 3.60 0.40MINERALOGICAL CHEMISTRY. 351 Tn order to show the relation between the direction of the striations and the chemical composition of the feispars, the authors made analyses of cleavage specimens from six different localities, namely : 1, Brauchville, Connecticut ; 2, Hittero, Norway ; 3, Haddam, Con- necticut ; 4, Mineral Hill, Pennsylvania ; 5, Danbury, Connecticut ; 6, Pierjepont, New York. All the specimpns show distinct striations on wPw, and a,ll satisfy Tschermak's formula as mixtures of Na,AI,Si,O,, and Ca,A1,Si4016.The analytical results are given on the preceding page. Judging from" the above, it will be safe to predict that where the striations on 03Pm make an angle of about +12", the felspar will be a mixture of albite with 5 to 10 per cent. of anorthite. The authors have been unable to find many specimens of felspars more basic than oligoclase exhibiting striation on wPw. The analysis of a. specimen of labradorite from Labrador gave results i n very satis- factory accord, both as regards the direction of the rhombic section and the extinction angle on mPm, with the table given by Tschermak. Althoiigh the variation in the angles of plagioclase crystals is con- siderable, the change in position of the rhombic section from +22" to -18" is so great that the direction of the striations will clearly indi- cate what pgsition any plagioclase holds in the albite-anorthitgseries.B. H. B. So-called Indicolite from Harlem. By R. B. RIGGS (Amer. J. Sci., 34,406).-A peculiarly bright blue niineral found at Harlem, New Pork, was supposed to be the rare variety of tourmaline known as indicolite. An analysis made by the author showed relations very different from those in tourmaline, the analytical results being as follows :- iSiOz. B203. Al,03. MgO. Na20. K20. Ignition. Total. 34.82 4.07 55.30 0.57 1-76 1-04 2.96 100.52 The molecular ratios, deduced from the analysis, are closely expressed by the formula 3H,0,(Na,K)20,10A120,,10Si02,B203, a new borosilicate.A microscopic study of this blue mineral shows that the angle of extinction is very small. The mineral is undoubtedly biaxial with remarkable pleochroism (ultramarine, reddish-violet, colourless). Its structure is subfibrous, so as t o render the angle of prismatic cleavage somewhat obscure. It is thus certain that the blue mineral is not indicolite, but in all probability a new borosilicate. B. H. B. Remarkable Crystals of Pyroxene from New York. By G. H. WILLJAMS (Amer. J. Sci., 34, 275--276j.-Some yellowish-grey crystals of pyroxene occurring in the crystalline limestone of Orange Ca., New York, have a peculiar tabular habit produced by the unusual development of the basal pinacoid. A remarkably fine group of these crystals, in the collection of the Johns Hopkins University, exhibits great singularity of form. It consists of six simple tabular crystals, and of two larger ones, which are at the same time twins and hemi- morphic.The upper portion shows the usual forms: OP, -P, P, 2P, mP, M ~ O O , The largest of these crystals measures 3 by 3 i cm.352 ABSTRACTS OF CHEMICAL PAPERS. mPm. Below, however, towards the front, there are only the forms 2P and Pm, indicating that the crystal is hemirnorphic in the direc- tion of the vertical axis. The lower back quarter of the crystal is exactlylike the lower front quayter, but in a reversed position, so that the lower half of the crystal is a twin. The second crystal is essen- tialIy the same as the one just described. B. H. B. Blue Clay from Farrnington, Maine.By F. C. ROBINSON (Amer. J. Xci., 34, 407--408).-An analysis of blue clay from Far- mington, Maine, gave the following results :- Si02. Al,O,. FeO. CaO. NaaO. H20. Total. 63.69 17.02 10.18 0.97 4.02 4-05 99.93 An approximate mechanical analysis gave the following per- centages :- Coarse sand. Fine sand. Fine clay. Water. 3.73 22.97 69.25 4.05 The sand consisted principally of felspar, with traces of quartz and mica. The clay is used for brickmaking. B. H. B. Meteorite from St. Croix Go., Wisconsin. By D. FISHER (Amer. J. Sci., 34, 381--383).-The mass of meteoric iron described was ploughed up in 1884 on R farm in Hammond Township. I t weighed 53 Ibs., and measured 8 by 8 inches across the face, with an average thickness of 5 inches. The character of the meteorite renders it probable that its fall did not precede the date of its discovery by many months.An analysis of the meteorite gave tohe following results :- Fe. Ni. co. P. Si02. Total. SP. gr- 89.78 7.65 1.32 0.51 0.56 99.82 7.60-7.70 with traces of carbon, copper, and tin. 5 to 10 mm. in size. Widmanstatten figures quickly appear. ment. tion at New Haven. Troilite is present in nodules On the application of dilute nitric acid, the These are cubical in arrange- The meteorite now forms part of the Yale University collec- B. H. B. The Rockwood Meteorite. By J. E. WHITFIELD (Amer. J. Xci., 34, 387-390).-This meteorite was found in March, 1887, i n a field 43$ miles west of Rockwood, Tennessee. Three pieces were found. The smallest measured 4 by 3 by 29 inches, and weighed 3 Ibs.104 oz.; the next measured 73 by 6$ by 28 inches, and weighed 5 lbs. 13+ 02. ; and the largest measured 142 by 10 by 84 inches, and weighed 85 lbs. Cut slices show irregu- larly shaped stony fragments, with metallic grains distributed through the mass. An analysis of the metallic portion gave 87.59 per cent. of iron, 12.09 per cent. of nickel, with traces of cobalt and copper, but The mass is very brittle.MINERALOGICAL CHEMISTRY. 353 neither phosphorus nor sulphur. gave the following results :- SiOP A1,0,. FeO. CaO. MgO. Fe. Xi. C1. P. 8. Total. 41-92 9-27 22.94 9.09 8.76 3.75 1.74 0.18 0-65 1-58 99.88 An analysis of the stony portion This meteorite appears to be a lithosiderite poor in metal, the The stony metallic portion not exceeding 16 per cent.of the mass. part is probably anorthite and enstatite. €3. H. B. The Powder Mill Creek Meteorite. By G. F. KUNZ (Amer. J. Xci., 34, 47647i).-This meteorite is identical with the Rockwood meteorite (see preceding Abstract), and has been called from the Powder Mill Creek, because it fell in Cumberland Co.; Roane Co. in which Rockwood is situated being adjacent to this. The author is the possessor of a piece weighing 2000 grams. It resembles very closely the Hainholz, W estphalia, and the Taney Co., Missouri, meteorites. Chloride of iron (lawrencite) is present in considerable quantities. Under the microscope, clear crystals of anorthite and olivine were seen in the ground-mass of metallic iron. B. H. B. Its sp. gr. is 4.745. Some American Meteorites. By G .F. KUNZ (Arner. J. Xci., 34, 467477).-1. The Taney Go., Xissouri, Meteorite.-This is supposed to have fallen in 1857 at a spot near Miney in Taney Co., 11 miles south-east of Forsyth. It was taken 60 miles to a farm in Limestone Valley, Arkansas, on the supposition that it was of value. In June, 1887, it came into the author's possession. It measures 34 by 35 by 29 cm. It is similar to the Hainholz, West.phalia, iron, and belongs to the logronite group of Meunieia and the syssidhres of Daubrhe. Two large crystals of olivine are present, and at one corner of the mass there is a large inclosure of augite. The surface of the meteorite is deeply pitted, and exhibits traces of a black crust. An analysis of the metallic portion gave- Fe. Ni. c o . P. Total. 89.41 10.41 0-29 0.16 100.27 Its weight is 89.796 kilos.The analysis af the stony portion gave- SiO,. AI,O,. FeO. CaO. MgO. NiS. FeS. Total. 45.88 7.89 19-73 6.02 17-96 1.67 0.54 99.69 Further analyses of the finely ground stony portion show that the insoluble portion is enstatite only, and that the soluble portion is a lime-iron silicate containing 1 7 per cent. of alumina,. The fragments described by C. U. Shepard (Anzer. J. Sci., 30, 1860, 205) as the Forsyth iron, and by J. L. Smith (ibid., 40, 1865, 213) a,s the Newton Co., Arkansas, meteorite, are undoubtedly parts of the same meteorite which originally fell near Miney, in Taney Co. 2. The! Chnttooga Co., Georgia, Meteorite.-This mass was found on March 27th, 1887. In all, 12.5 kilos. were found. It is one of the354 ABSTRACTS OF CHEMICAL PAPE1ZS. caillike group of Meunier, and has a sp.gr. of 7.615. the following results :- Analysis gAve Fe. Ni. co. P. Total. 94-60 4.9 7 0.21 0.21 99.99 This iron does not bear the slighest resemblance to either of the Whitfield Co., Georgia, irons, found i n the vicinity. It is a white iron, whilst the Walker Co., Alabama, iron has a bluish tinge and was found 100 miles due east. 3. Meteoric Iron *from Wuldron Ridge, Claiborm Co., Tennessee.- This was found in March, 1887, and supposed to be iron ore. The meteorite is one of the caillite group of Meunier. On the largest piece, weighing 15 lbs., the octahedral structure is very marked. The smaller pieces, weighing collectively several pounds, show considerable weathering. The iron separates readily at the cleavage plates, between which are thin leaves of schreibersite.Troilite and graphite were also observed. It thus appears that this meteorite is identical with the Cosby Creek, Cocke Go., the Sevier Go., the Greenbrier Co., and the Jennies Creek meteorites, which, although inde- pendently described, have been shown by Huntington to be parts of one meteorite. B. H. B. Phosphatic Mineral Water. By BOURGOIN and CHASTAING ( J . Ph.arm. [ 51, 16, 337--.341).-At Viry (Seine-et-Oise) is a spring found in a gallery cut in clay. The temperature of the water is constant at 4" even in summer, the yield is about 14 litres per minute, and though quite limpid at first a deposit is quickly formed. A litre of water was found to contain- Carbonic anhydride ...........Tricalcium p hos phat.e ........ Calcium hydrogen carboilate.. .. ,, sulphate ............ Magnesium hydrogen carbonate Calcium nitrate .............. Sodium chloride .............. Potassium chloride. . . . . . . . . . . . Lit hi nm .................... Silica ...................... Organic matter .............. 0.17096 or 86.49 C.C. 0.17901 0.21740 0-03MO 0-04100 0.05 364 044130 traces sensible quantity 0.01 980 0~00200 0.76151 In an open flask, beautiful, lamellar crystals form after some days, which seem to be composed of calcium phosphate, and the water, originally acid, becomes sensibly neutral. Composition of Certain Colliery Waters. By P. P. BEDSON (J. SOC. Chem. Ind., 6, 712--715).--The author gives the results, expressed in grams per litre, of the analyses of two colliery waters:- J.T.ORGANIC CHENISTRY. 355 FeSO,. BaC1,. CaCI2. MgCI,. LiC1. NrtC1. CaS04. I. - 1.372 21.053 3.127 0.358 59.265 - L------J 11. 1.080 - 20-021 2.770 53.530 0-620 CaC03. MgCO,. Total.' I. - - 85.180 11. 0.134 0,021 78.1 76 I. Water from the Redheugh Colliery. This water drains from the Brockwell seam and adjacent rock. Temperature 13". 11. Water from the Wardley Colliery. This water is remarkable not only from its mineral constituents but also from the fact that it contains a large amouiit of gas dissolved in it. The analysis of the gas showed it to have the following composi- tion :- co,. CH4. N. 81.14 5-20 13.29 D. €3.MINERALOGICAL CHENISTRY. 345Mineral o g i c a1 C h emi s t r y.An English Coal. By SCHEURER-KESTNER and MEUNIER-DOLFCS(Compt.rend., 105, 1251--1255).-The coal was obtained fromGlamorganshire. It gave 88 per cent. of coke and 3 to 4 per cent. ofash, the composition being as follows:-C 90.27, H 4.39, S 0.69,N 0.49: 0 4.16. The composition of the volatile portion was C ‘22.53,H 34-96, 0 + N + S 42.51. The heat of combustion as actually de-termined (8864 cal.) diaers considerably from that calculated bymeme of any of the usual formulaj. C. H. B.Afti’ficial ’Pyrodhroite. B y A. DE BCHULTEN (Compt. renL,lD5,1265-1267) .-300 grams of pure potassium hydroxide was dissolvedin 500 C.C. of water, boiled for some time in a flask through whicli acurrent of hydrogen or coal gas was passing, and a recently boiledsolution of 15 to 1’7 grams of crystallised manganous chloride i n 1.5 C.C.of water WAS iritroduced by means of a, funnel with a stopcock.Theflask was then heated to about 160°, when the whole of the mao-gnnous hydroxide dissolved. As the liquid cools, it deposits crys-VOL. LJV. 2 346 ABSTRACTS OF CHEMICAL PAPERS.tallised manganous hydroxide, and becomes almost solid. The crystalsare washed with recently boiled water, alcohol, and ether, and driedat a gentle heat in a current of hydrogen. If sodium hydroxide isused, t,he precipitate does riot dissolve even in concentrated solutionsa t 200°, but it becomes crystalline. Crystallised manganous hydroxidedissolves readily in hydrochloric acid and in a solution of ammoniumchloride. When heated to redness in the air, it forms manganoso-manganic oxide, which retains the form of the original crystals. Whenheated in hydrogen, it yields manganous oxide, which is green whenhot and grey when cold.Manganous hydroxide under these conditions crystallises in flat-tened, transparent, regular, hexagonal prisms, with a reddish tint.The crystals are uniaxial, and the axis is negative, as in pyrochroite.Crystallised cadmium hydroxide likewise has a negative axis, butmagnesium hydroxide, natural or artificial, has a- positive axis.Whenthe manganous hydroxide is pure, it alters very slowly in presence ofair. but if it contains even a small quantity of alkali, it oxidises veryquickly . C. H. B.Mineralogical Notes. By G. I?. KUNZ (Anter. J. Sci., 34, 477-480) .-1. Rhodochroisite from Colorado.-Rhodochroisite, in rich, red,transparent rhombohedra, has been found in the John Reed Mine a tAlicante, Lake Co., Colorado.This is the first locality that has yieldedcrptals of such size (12 mm. across) and transparency. The sp. gr.is 3.69, and the hardness 3.5. Analysis gave the following results:-MnO. FeO. CaO. MgO. cog. Total.’%%!a %“ti nil ’trace ‘(3bV6’) l i ~ f i ~2. Hollow Quartz Crystals from Arizona.-These crystals are foundabout 3 miles south-west of the town of Pinal, Pinal Co., Arizona.They occur in sandstone, penetrated in many places bey spherules ofobsidian. The crystals are mere walls surrounding hollow spacesmuch larger than the area of the wall itself.3. Hydrophane from Colorado.-A white, opaque variety of hydro-phane in rounded lumps, 5 to 25 mm.in diameter, has recently beenbrought from Colorado. It is remarkable for its power of absorbingwater. When water is allowed to slowly drop on it,, it first, becomes whiteand chalky, and then gradually perfectly transparent. It was found byweighing that this mineral absorbs more than an equal volume of water4. A Remai*kable Nugget of Xiluey.-One of the most remarkablenuggets of silver known was found in limestone a t the GreenwoodMines in the State of Michoacan, Mexico. It weighed 606+ oz., andin its original state weighed 12 lbs. more. It consists of almost puresilver, and is entirely worn except in cavities where the form of someof the crystals is still visible. B. H. B.Bismuthospherite from Willimwntic and Portland, Con-necticut.By H. L. WELLS (Amer. J. Xci., 34, 271-274).-Theauthor has exa)mined two specimens of basic bismuth carbonate, thecomposition of which appears to be identical with that of Weisbach’JIINERALOQICAL CHEMISTRY. 347bisinuthosphserite. The composition of that mineral has been con-sidered doubtful by A. H. Chester (Abstr., 1887, 783), because nowater was included in the analysis. In the Connecticut specimens, thepercentage of water did not exceed 0.94. Since a part of the waterfound was probably hygroscopic moisture, and since the determina-tions were made by weighing the water in a calcium chloride tube,a method apt to give slightly high results, these two specimens ofbismuth carbonate must be regarded as anhydrous.The analysesagree closely with the formnla Bi203,C02. The existence of bismutho-sphzerite must thus be considered as established. B. H. B.Natural Borates and Borosilicates. By J. E. WHTTFIELD (Amer.J. Sci., 34, 281--287).-The author has repeated the analyses ofsome natural bomtes, in order to correct ei’rors due t o defectiveanalytical methods. The boric acid was determined by the methoddevised by I!’. A. Gooch (Abstr., 1887, 299).CoZemanite from Death Valley, California, gave on analysis tlhefollowing results :-R2O. W3. CaO. MgO. Total.21.87 50.70 2‘7.31 0.10 99.98These results correspond with the formula 2Ca0,3B20,,5H2O. Thesame formula mas calculated by J. T. Evans (Abstr., 1885, 958),from his analysis, in which the boric acid was determined by differ-ence.Priceite from Curry Co., Oregon, gave the following composi-tion :-HBO.B2°3. CaO. Total.19.42 48-44 32-15 100.01Pandermite from Panderma, in the Black Sea, gave on analysisHQO. 33203. CaO. Total.the following results :-19.40 48.63 38.1 6 100.19It will thus be seen that priceite and pandermite are identical incomposition. The difference is solely in the physical character of theminerals, priceite being soft and friable, and pandermite hard andcompact (compare Abstr., 1885, 1117).ZJZeaite from Rhode’s Marsh, Esmeralda Co., Nevada, gave on analy-sis the following figures :-SiOa. 01. B20,. SO,. CaO. Na20. K20. H20. Total.0.04 2.38 43-20 0.28 14.52 10.20 0.44 29.46 100.52The analysis being corrected f o r impurities, the formula NaCaB50gLzLdwigite from Moravitza, in the Banat, gave on analysis the follow-+ 6H20 is deduced.ing results :-2 n 348 ABSTRACTS OF CHEMICAL PAPERS.B20+ Fe20,.FeO. MgO. MnO. H20. Total.12-04 37.93 15-78 30.57 0-16 3-62 100*10Tschermak obtained 16-09 per cent. of boric acid, but gives noDatoZite from Bergen Hill, New Jersey, gave-water.SiO,. FeO. CaO. RZO,. H20. Total.35.74 0.31 35.14 22.60 6.14 99.93The formula is thus B203,Hz0,2Ca0,2Si02.Uanbzwite from Russell, St. Lawrence Co., New York, gave-SiO,. B203 CaO. Fe,03 + A1203. Ign. Total.49.70 25.80 23-26 1.02 0.20 99-98Axinite from Cornwall (I), and from Bonrg d’oisans, Dauphin6 (11),gave on analysis the following results :-SiO,. d1203. Fe203.FeO. CaO. MnO. MgO. B20,. HT,0. Tot,al.I. 42.10 17-40 3.06 5.84 20.53 4.63 0.66 4-64 1-80 100.6611. 41-53 37-90 3.90 442 21.66 5.79 0.74 4.62 2-16 100.32The formula is BR””R”4H2( SiO,),O. B. H. B.Pseudomorphs in the Lead Mines of the Puy de Dome.By F. GONNAED (Compt. rend., 105, 1267--1869).-The envelopingpseudomorphs or perimorphoses consist of bhin coatings of one mineralon the crystals of another. In the lead mines of the Puy de Dome,enveloping psmdomorphs of pyromorphite on cerussite or galena arefrequently observed. Sometimes the mineral inside bas undergonealteration, owing to the fact that the envelope has not protected it fromthe air, &c. Not unfrequently, when the layer of pyromorphite is ofappreciable thickness, it is distinctly crystalline, and the hexagonalprisms can readily be recognised.It is obvious that an envelope of thischaracter is not a true pseudornorph.Another mineral found in the form of enveloping pseudomorphs issiderite, One specimen showed the unusual form of hexagonal prismssurmounted by rhombohedrons. Calcite does not occur associated withit, and hence it cannot be regarded as a pseudomorph after that mineral.The nature of the original mineral was not determined. The form is,however, possible for any substance crystallising in the rhombic system,and hence this is a case of siderite occurring as a pseudomorph under aform in which it might crystallise itself.Pseudomorphs of pyrites on calcite were also found, the envelopeof pyrites being crystalline, and showing combinations of the cubewith the pentagonal dodecahedron.Crystalline Compounds prepared by Ebelmen.By E.MALLARD (Compt. rend., 105, 1260-1265) .-Artificial phenacite,SiO,,BBeO, obtained by fusing beryllia and silica with borax, formsC. H. BMINERALOGICAL CKEMISTRY. 349small, regular, hexagonal prisms with very brilliant faces, the opticalsign being positive.Bei-yllium chrornite, Be0,Cr203, prepared by fusing chromic oxidewiQh beryliia and boric anhydride, is a deep green powder, whichpolarises strongly under the microscope, and consists of minute crys-tals of a form identical with that of the variety of cymophane knownas alexandrite. It is therefore analogous t o the corresponding alum-inium compound, the artificial cymophane likewise obtained byEbelmen.Crystallised niobic anhydride forms small, rhombic prisms with twoperpendicular cleavages, h' and g', the angle wtm being 140" 50', andthe horizontal parameters 0.355 : 1. The form seems to be pseudo-cubic ; the acute positive bisectrix is perpendicular to h', the planeof the axes beingp.Tantalic anhydride was obtained in rhombic prisms with the facesg' h' well developed, and the subordinate faces m, g2, g3, g5, the anglernm being about 143".I t follows that niobic and tantalic anhydridesare isomorphous.Crystnllised beryllia has the parameters a : h = 1 : 1.6305, theoptical sign being positive. In crystallised zinc oxide, the parametersare a : It = 1 : 1.6034, and the optical sign is likewise positive.Itfollows that these two oxides are isomorphous, notwithstanding thedifference in their specific volumes.Alurninium borate, Bz0,,3Al20, which Ebalmen annlysed but did notdescribe, crystallises in rhombic needles, the dominant face being mtruncated by 9' and 71,' ; angle mm = 92" 21' ; acute positive bisec-trix parallel with the vertical, the plane of the axes being parallelwith 9'.The compound 3B,O3,2Fe2O3,9Mg0, which Ebelmen analysed, formsblack, opaque prisms, which have very brilliant faces, and probablybelong to the rhombic system. The principal faces are m and h', theangle mm being 90" 32'. An analogous compound containing chro-mium in place of iron forms a dark brown powder consisting of smallprisms, which when examined by polarised light seem to belong to therhombic system.Ebelmen prepared crystallised tribasic borates, B,o3,3RO, which onhis assumption that boric acid is analogous to silicic acid, are analogousto peridote, the oxygen ratio being 1 : 1; and likewise crysfallisedsesquibasic borates, which on the same assumption are analogous toenstatite.The tribasic borates actually obtained were the magnesium,manganese, and cobalt compounds. They are isomorphous, and belongt o the rhombic system, the parameters being as follows :-Bz0,3MgO . . . . 0.6412 : 1 : 0.5494 rnnt = 114" 40'B2O3,3CoO .. .. 0.6461: 1 : ? rnm = 114 15B203,3Mn0 . . . . 0.6511 : 1 : 0.5351 mm= 113 52The faces m are faces of cleavage, and the acute positive bisectrixis parallel with the vertical, the plane of the axes being g'.Theprincipal indices of refraction for 1) are respectively 1.6748, 1.6537,1.6527.The sesquibasic borates obtained are the magnesium, manganese350 ABSTRACTS OF CHEXICAL PAPERS.66 *5821-260.071 e l 810 *260 -760 -16.-.and zinc compounds. They are isomorphous, and belong t o the tri-clinic system, the parameters of the mangauese compound being1.8373 : 1 : 2.012, and xy = 76" 26', xx 123" 58', yz 92" 6', g'h' 75.01,ph' 124" 2Y', pg' 83" 16'. All have easy nacreous cleavage along p ,and a less easy vitreous cleavage along t. The nacreous cleavage isalmost always perpendicular to an opt'ical axis.Triclinie Felapars with Twinning Striations on the Brachy-pinacoid. By S. L. PENFIELD and F.L. SPERRY (Amer. J. Sci.,34, 390--393).-The authors gve the results of a careful study, inconnect'ion with the chemical c_omposition of the felspars, of the stria-tions due to twinning on cnPm exhibited by very inany cleavagespecimens of plagioclase felspar, in additionJo the ordinary striationson the basal plane. These striations on 00Pm have been shown byG. v. Rath (Abstr., 1878, 713) to have resulted from twinningaccording to the pericline law. The two individuals are united by aplane deviating slightly from the basal plane, passing through themacro-axis, and so inclined that the four plaFe angles it makes withthe prisms w'P and mP' and the pinacoid mPm are all equal. Thisis the so-called rhombic section. Owing to the variations in theaxial angles of anorthite felspars, the direction of the rhombic sectionchanges consjderably.The direction above the line parallel to theedge OP : mPm being regarded as positive, and that below as nega-tive, the direction of the rhombic section in felspars of the albite-anorthite group was found by Tschermak to be as follows :-C. H. B.66-8320.880'251.4610.360.700.27---Na?O CaOper cent. per cent.Albite, NazA1,Si,0,6 . . Ab +22" 11.8 0.0Oliaoclase.. ......... Ab3Anl + 466.0621.570'181-809.571.01 - --Anvdesine ........... AbiAni - 2Labradorite ......... Ab,An3 - 9Anorthite, Ca2AI4Si4OlG An - 1899'712.6279.201 : g . a8.7 5.25.7 10.42.8 15.30.0 20.199.92 100.782.628 2.6229-70 15.171 : 9 ' 0 1 : 4 ' 1Si02 ...............Al,O, ..............F+03 ..............CaO ...............Na,O ..............K20 ...............Ignition ............Total ..............-$p. gr. ..............Ratio An : Ab ......Anorthite per cent. ..Rhombic section . . , .Extinction on caPco,,2.610 2.632 2-63;5'87 'I -25 8 -94 + 12' 14O 13'15 15 161 : 16.0 1 : 13.0 1 : 9 . 666 -3420 9 21 *859 '440 -980 '38-65 -7321 -320 -121 -959 *660 -950 -1963 "7622 '670 -413-056 *893.600.4MINERALOGICAL CHEMISTRY. 351Tn order to show the relation between the direction of the striationsand the chemical composition of the feispars, the authors madeanalyses of cleavage specimens from six different localities, namely :1, Brauchville, Connecticut ; 2, Hittero, Norway ; 3, Haddam, Con-necticut ; 4, Mineral Hill, Pennsylvania ; 5, Danbury, Connecticut ;6, Pierjepont, New York.All the specimpns show distinct striationson wPw, and a,ll satisfy Tschermak's formula as mixtures ofNa,AI,Si,O,, and Ca,A1,Si4016. The analytical results are given onthe preceding page.Judging from" the above, it will be safe to predict that where thestriations on 03Pm make an angle of about +12", the felspar will bea mixture of albite with 5 to 10 per cent. of anorthite.The authors have been unable to find many specimens of felsparsmore basic than oligoclase exhibiting striation on wPw. The analysisof a. specimen of labradorite from Labrador gave results i n very satis-factory accord, both as regards the direction of the rhombic sectionand the extinction angle on mPm, with the table given by Tschermak.Althoiigh the variation in the angles of plagioclase crystals is con-siderable, the change in position of the rhombic section from +22" to-18" is so great that the direction of the striations will clearly indi-cate what pgsition any plagioclase holds in the albite-anorthitgseries.B.H. B.So-called Indicolite from Harlem. By R. B. RIGGS (Amer.J. Sci., 34,406).-A peculiarly bright blue niineral found at Harlem,New Pork, was supposed to be the rare variety of tourmaline known asindicolite. An analysis made by the author showed relations verydifferent from those in tourmaline, the analytical results being asfollows :-iSiOz.B203. Al,03. MgO. Na20. K20. Ignition. Total.34.82 4.07 55.30 0.57 1-76 1-04 2.96 100.52The molecular ratios, deduced from the analysis, are closelyexpressed by the formula 3H,0,(Na,K)20,10A120,,10Si02,B203, a newborosilicate. A microscopic study of this blue mineral shows thatthe angle of extinction is very small. The mineral is undoubtedlybiaxial with remarkable pleochroism (ultramarine, reddish-violet,colourless). Its structure is subfibrous, so as t o render the angle ofprismatic cleavage somewhat obscure. It is thus certain that the bluemineral is not indicolite, but in all probability a new borosilicate.B. H. B.Remarkable Crystals of Pyroxene from New York. ByG. H. WILLJAMS (Amer. J. Sci., 34, 275--276j.-Some yellowish-greycrystals of pyroxene occurring in the crystalline limestone of OrangeCa., New York, have a peculiar tabular habit produced by the unusualdevelopment of the basal pinacoid.A remarkably fine group of thesecrystals, in the collection of the Johns Hopkins University, exhibitsgreat singularity of form. It consists of six simple tabular crystals,and of two larger ones, which are at the same time twins and hemi-morphic. Theupper portion shows the usual forms: OP, -P, P, 2P, mP, M ~ O O ,The largest of these crystals measures 3 by 3 i cm352 ABSTRACTS OF CHEMICAL PAPERS.mPm. Below, however, towards the front, there are only the forms2P and Pm, indicating that the crystal is hemirnorphic in the direc-tion of the vertical axis. The lower back quarter of the crystal isexactlylike the lower front quayter, but in a reversed position, so thatthe lower half of the crystal is a twin.The second crystal is essen-tialIy the same as the one just described. B. H. B.Blue Clay from Farrnington, Maine. By F. C. ROBINSON(Amer. J. Xci., 34, 407--408).-An analysis of blue clay from Far-mington, Maine, gave the following results :-Si02. Al,O,. FeO. CaO. NaaO. H20. Total.63.69 17.02 10.18 0.97 4.02 4-05 99.93An approximate mechanical analysis gave the following per-centages :-Coarse sand. Fine sand. Fine clay. Water.3.73 22.97 69.25 4.05The sand consisted principally of felspar, with traces of quartz andmica. The clay is used for brickmaking. B. H. B.Meteorite from St. Croix Go., Wisconsin. By D.FISHER(Amer. J. Sci., 34, 381--383).-The mass of meteoric iron describedwas ploughed up in 1884 on R farm in Hammond Township. I tweighed 53 Ibs., and measured 8 by 8 inches across the face, with anaverage thickness of 5 inches. The character of the meteoriterenders it probable that its fall did not precede the date of itsdiscovery by many months. An analysis of the meteorite gave tohefollowing results :-Fe. Ni. co. P. Si02. Total. SP. gr-89.78 7.65 1.32 0.51 0.56 99.82 7.60-7.70with traces of carbon, copper, and tin.5 to 10 mm. in size.Widmanstatten figures quickly appear.ment.tion at New Haven.Troilite is present in nodulesOn the application of dilute nitric acid, theThese are cubical in arrange-The meteorite now forms part of the Yale University collec-B.H. B.The Rockwood Meteorite. By J. E. WHITFIELD (Amer. J. Xci.,34, 387-390).-This meteorite was found in March, 1887, i n a field43$ miles west of Rockwood, Tennessee. Three pieces were found.The smallest measured 4 by 3 by 29 inches, and weighed 3 Ibs.104 oz.; the next measured 73 by 6$ by 28 inches, and weighed5 lbs. 13+ 02. ; and the largest measured 142 by 10 by 84 inches, andweighed 85 lbs. Cut slices show irregu-larly shaped stony fragments, with metallic grains distributed throughthe mass. An analysis of the metallic portion gave 87.59 per cent. ofiron, 12.09 per cent. of nickel, with traces of cobalt and copper, butThe mass is very brittleMINERALOGICAL CHEMISTRY. 353neither phosphorus nor sulphur.gave the following results :-SiOP A1,0,.FeO. CaO. MgO. Fe. Xi. C1. P. 8. Total.41-92 9-27 22.94 9.09 8.76 3.75 1.74 0.18 0-65 1-58 99.88An analysis of the stony portionThis meteorite appears to be a lithosiderite poor in metal, theThe stony metallic portion not exceeding 16 per cent. of the mass.part is probably anorthite and enstatite. €3. H. B.The Powder Mill Creek Meteorite. By G. F. KUNZ (Amer. J.Xci., 34, 47647i).-This meteorite is identical with the Rockwoodmeteorite (see preceding Abstract), and has been called from thePowder Mill Creek, because it fell in Cumberland Co.; Roane Co.in which Rockwood is situated being adjacent to this. The author isthe possessor of a piece weighing 2000 grams. It resembles veryclosely the Hainholz, W estphalia, and the Taney Co., Missouri,meteorites.Chloride of iron (lawrencite) ispresent in considerable quantities. Under the microscope, clearcrystals of anorthite and olivine were seen in the ground-mass ofmetallic iron. B. H. B.Its sp. gr. is 4.745.Some American Meteorites. By G . F. KUNZ (Arner. J. Xci., 34,467477).-1. The Taney Go., Xissouri, Meteorite.-This is supposedto have fallen in 1857 at a spot near Miney in Taney Co., 11 milessouth-east of Forsyth. It was taken 60 miles to a farm in LimestoneValley, Arkansas, on the supposition that it was of value. In June,1887, it came into the author's possession. It measures 34 by 35 by29 cm. It is similar to the Hainholz,West.phalia, iron, and belongs to the logronite group of Meunieia andthe syssidhres of Daubrhe.Two large crystals of olivine are present,and at one corner of the mass there is a large inclosure of augite.The surface of the meteorite is deeply pitted, and exhibits traces of ablack crust. An analysis of the metallic portion gave-Fe. Ni. c o . P. Total.89.41 10.41 0-29 0.16 100.27Its weight is 89.796 kilos.The analysis af the stony portion gave-SiO,. AI,O,. FeO. CaO. MgO. NiS. FeS. Total.45.88 7.89 19-73 6.02 17-96 1.67 0.54 99.69Further analyses of the finely ground stony portion show that theinsoluble portion is enstatite only, and that the soluble portion is alime-iron silicate containing 1 7 per cent. of alumina,. The fragmentsdescribed by C. U. Shepard (Anzer. J. Sci., 30, 1860, 205) as theForsyth iron, and by J. L.Smith (ibid., 40, 1865, 213) a,s theNewton Co., Arkansas, meteorite, are undoubtedly parts of the samemeteorite which originally fell near Miney, in Taney Co.2. The! Chnttooga Co., Georgia, Meteorite.-This mass was found onMarch 27th, 1887. In all, 12.5 kilos. were found. It is one of th354 ABSTRACTS OF CHEMICAL PAPE1ZS.caillike group of Meunier, and has a sp. gr. of 7.615.the following results :-Analysis gAveFe. Ni. co. P. Total.94-60 4.9 7 0.21 0.21 99.99This iron does not bear the slighest resemblance to either of theWhitfield Co., Georgia, irons, found i n the vicinity. It is a whiteiron, whilst the Walker Co., Alabama, iron has a bluish tinge and wasfound 100 miles due east.3. Meteoric Iron *from Wuldron Ridge, Claiborm Co., Tennessee.-This was found in March, 1887, and supposed to be iron ore.Themeteorite is one of the caillite group of Meunier. On the largestpiece, weighing 15 lbs., the octahedral structure is very marked. Thesmaller pieces, weighing collectively several pounds, show considerableweathering. The iron separates readily at the cleavage plates,between which are thin leaves of schreibersite. Troilite and graphitewere also observed. It thus appears that this meteorite is identicalwith the Cosby Creek, Cocke Go., the Sevier Go., the GreenbrierCo., and the Jennies Creek meteorites, which, although inde-pendently described, have been shown by Huntington to be parts ofone meteorite. B. H. B.Phosphatic Mineral Water. By BOURGOIN and CHASTAING ( J .Ph.arm. [ 51, 16, 337--.341).-At Viry (Seine-et-Oise) is a springfound in a gallery cut in clay. The temperature of the water isconstant at 4" even in summer, the yield is about 14 litres per minute,and though quite limpid at first a deposit is quickly formed.A litre of water was found to contain-Carbonic anhydride ...........Tricalcium p hos phat.e ........Calcium hydrogen carboilate.. ..,, sulphate ............Magnesium hydrogen carbonateCalcium nitrate ..............Sodium chloride ..............Potassium chloride. . . . . . . . . . . .Lit hi nm ....................Silica ......................Organic matter ..............0.17096 or 86.49 C.C.0.179010.217400-03MO0-041000.05 364044130tracessensible quantity0.01 9800~002000.76151In an open flask, beautiful, lamellar crystals form after some days,which seem to be composed of calcium phosphate, and the water,originally acid, becomes sensibly neutral.Composition of Certain Colliery Waters. By P. P. BEDSON(J. SOC. Chem. Ind., 6, 712--715).--The author gives the results,expressed in grams per litre, of the analyses of two colliery waters:-J. TORGANIC CHENISTRY. 355FeSO,. BaC1,. CaCI2. MgCI,. LiC1. NrtC1. CaS04.I. - 1.372 21.053 3.127 0.358 59.265 -L------J11. 1.080 - 20-021 2.770 53.530 0-620CaC03. MgCO,. Total.'I. - - 85.18011. 0.134 0,021 78.1 76I. Water from the Redheugh Colliery. This water drains from theBrockwell seam and adjacent rock. Temperature 13". 11. Waterfrom the Wardley Colliery. This water is remarkable not only fromits mineral constituents but also from the fact that it contains a largeamouiit of gas dissolved in it.The analysis of the gas showed it to have the following composi-tion :- co,. CH4. N.81.14 5-20 13.29 D. €3

ISSN:0368-1769    

DOI:10.1039/CA8885400345

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

ORGANIC CHENISTRY. 355 Organic C h e m i s t r y . Constitution of Nitroethane. By G. GOTTIKG (Annulen, 243, 104--131).--Hy the action of ethyl iodide on nitroethane and sodium ethoxide in sealed tubes at loo", a liquid of the composition C,HiNO is produced. It boiis a t 166-176' and is freely soluble in alcohol and ether. At a higher temperature, it decomposes, yielding pyridine and a resinous residue. Sodium iodide, sodium nitrite, and ammonium iodide, are formed as bye-products when ethyl iodide acts on sodium nitroethane. The nitrite and ammonium iodide are probably formed by secondary reactions. The primary reaction may be represented by t,he equation 9CzH,N0, + 6EtI + 6C2€3,*ONa = 6C5HiN0 + 6CzH5*OH + 9H,O + 6NaI + 3NH,*OH. By substituting methyl, propyl and isobutyl iodides for ethyl iodide in the preceding experiment a series of homologous compounds is obtained having the composition- Boiling points.CJXjNO .............. 150-160" C,H,NO .............. 166-170 CeHgNO.. ............ 175-178 C7LTIINO.. ............ 182-185 Each of the compounds is decomposed by distillation, yielding a volatile base. The formation of C,H7N0 and its homologues can be more readily explained by Geuther's assumption that nitroethane is in reality acstamidoxide, CHs*CO*NH,O, than by V. Meyer's formula CH,*CH,*NOZ. w. c. w.356 ARSTRACTS OF CHEMICAL PAPERS. Preparation of Hydrosulphides and Sulphides of Methyl and Ethyl. By P. KLASON (Ber., 20, 3407-3413).-Methyl hydrogen sulphide is prepared by diluting with ice a cold mixture of 750 C.C.of sulphuric, acid and 500 C.C. of absolute methyl alcohol, and adding the mhole to a solntion of 2.75 kilos. of crystallised sodium carbonate. The solution is concent,rated to such an extent that most of the sodiiim sulphate separates. The mother-liquor is then concen- trated, mixed with a Rolution of 500 grams of potash in 1 litre of water, previously saturated with hydrogen sulphide, and heated on a water-bath. The gases evolved are passed first through a strong aqueous solution of 50 grams of potash, and then into a solution of 350 grams of potash in 700 C.C. of water. The small amount of hydrogen sulphide contained in the latter solution is precipitated with lead acetate, and the ethyl hydrogen sulphide liberated by the addition of hydrochloric acid. It is dried wibh potash aud distilled.500 C.C. of alcohol yielded about 200 grams of methyl hydrogen sul- phide, and 40 gyams of methyl sulphide. It is a thin, colourless, refractive liquid, having a very repulsive odour ; it boils at 5.8" under 752 mm. pressure, and yields a crystalline hydrate a-ith water (com- pare Gregory, A n d e n , 15, 239 ; and Obermeyer, this vol., p. 124). Mercury methyl mercaptide, Ilg(SMe),, is best prepared by passing methyl hydrogen sulphide through an aqueous solution of mercury cyanide; it is almost insoluble, and melts at 175". The lend conz- pound, Pb(SMe),, forms microscopic, crystalline plates ; it is decom- posed by exposure to air o r light. The bismuth compound, Bi(SMe)B, crystallises in yellow, microscopic needles ; the silver compound forms a yellow, crystalline precipitate.Ethyl hFdrogen sulphide is prepared similarly to the methyl com- pound, using 1 litre of absolute alcohol, 500 C.C. of sulplruric acid, 4 kilos. of sodium carbonate, and 800 grams of potash. Copper ethyE mereaptide, CuSEt, uot Cu(SEt),, is readily obtained when the mixed solutions of copper sulphate and sodium acetate are treated with ethyl hydrogen sulphide, and forms a pale yellow, amorphous powder. It was previously stated (J.pr. Chem. [2], 15) that zinc and cadmium mercaptides are not decomposed by hydrochloric acid ; later experi- ments show that all mercaptidea with a positive metal are decomposed by hydrochloric acid. Methyl sulphide is prepared by distilling a concentrated solution of methyl sodium sulphate (from + litre of absolute methyl alcohol) with an aqueous solution of 500 grams of potash, previously half saturated with hydrogen sulphide.It boils at 37.2" under 758 mm. pressure. Ethyl sulphide may be prepared in %I similar manner, and boils at 91.9". Methyl ethyl sulphide is pre- pared by distilling a solution of methyl hydrogen sulphide (from 250 C.C. of alcohol) in potash with sodium ethyl sulphate (from 550 C.C. of alcohol) ; it boils at 66.9". By P. 'KLASON (Ber., 20, 3413-3415). - When methyl hydrogen sulphide is passed into 100 grams of sulphur chloride, (S2C1,), a product is obtained free from chlorine, probably consisting of methyl tetrasulphide, methyl trisulpbide, and sulphur. The yield is 150 grams. The yield was 160 grams. N. H. &I. Alkyl Polysulphides.ORGANG CHEMISTRY. 357 When distilled in a vacuum, methyl trisulphide passes over, and sul- phur remains.Methyl trisulphide (Cabours, Annalen, 61, 92) is a pale-yellow oil of a very disagreeable odour, boiling at 170" with slight decomposition. In a vacuum, it distils a t 62". Sp. gr. = 1.2162 at 0" ; 1.2059 at 10" ; and 1.119 at 17" (compared with water at O O ) . Paratolyl hydrogen sulphide reacts with sulphur chloride, yielding Otto's paratolyl tetrasulphide (Abstr., 1887, 954). Sulphines and the Valency of Sulphur. By H. KLINGER and A. MAASEN (AnnaZen, 243, 193-218) .-The authors have repeated Kriiger's experiments (this Journal, 1877, i, 186) on isomeric sulphine compounds, and they prove that the diethylmethylsulphine iodide, prepared by the action of methgl iodide on diethyl sulphide, is iden- tical with the product of the action of ethyl iodide on methyl ethyl sulphide.This is shown by an exa.mination of the platino-, auro-, and mercnro-chlorides, and also of the cadmio-iodide. Dirnethylef7LyZsu~hine iodide, SMe,Etl, is formed n o t only by the action of methyl iodide on ethyl methyl snlphide, but also by the action of methyl sulphide on ethyl iodide. It is a hygroscopic, crys- talline substance, soluble in alcohol, and is precipitated from the alcoholic solution by ether. It melts at 108-110". The cadmio- iodides, 2SMe,EtI,CdI,, melting with slight decomposition at 179", and SMe,EtT,CdI,, melting a t 98-99', were prepared. The merczcro- chlorides, SMe2EtCl,ZHgC1, and SMeEt,CI,GHgCI,, melt a t 118" and 200" respectively.The platiriochloride, 2C4H11SCl,PtC14, forms orange- red crystals belonging to the regular system. It is insoluble in alcohol and ether. The aurochloride, C*HIISCl,AuCI,, forms minute ,r-sv,qt.a.Lq m J j i r g at 240-244'. As the supposed existence of Kriiger's isomeric sulphines forms the sole argument in favour of the view that the four affinities of the sulphur-atom are of dissimilar nature, the author's results show that there is no longer any experimental evidence in support of this By E. FROMM (Bet-., 21,185-188).-When brom- ethylidenediethylsulphone (Abstr., 1881, 123) is heated with aqueous potash, it is converted into ethylidenediethylsulphone ; the yield, however, does not amount to that theoretically possible, and inas- much as sulphuric acid is one of the products of the reaction, it is probable that hydroxyethylidene disulphone is formed.but acting as an oxidising agent is itself reduced to ethylideriedisulphone. When ethylidenediethylsulphone, which melts a t 75-78" and not at 60°, as stated by Escales and Baumann (ibid.), is dissolved in anhydrous ether or benzene, and treated with sodium, hydrogen is evolved and a compound obtained which could not be purified; diethylsulphonedimethylmethane (Baumann, ibid.) is, however, ob- tained if mehhyl iodide is added to the solution before treatment with sodium. A like reaction occurs when an alcoholic solution of the di- sulphone is boiled with methyl iodide and alcoholic potash. Diethyl- s ul phon edimethyl m e thane when treated in benzene solution with N.H. M. hypo thesis. w. c. w. Disulphones. sodium does not evolve hydrogen. w P. w.358 ABSTRACTS O F CHEMICAL PAPJClP. Synthetical Experiments in the Sugar-group. By E. PISCHER and J. TAFEL (Bey., 20, 3384-3390; compare this vol., p. %).- Glycerosazone (Abstr., 1887, 651) is prepared by adding 15 parts of bromine to a solution of 10 park of glycerol and 35 parts of crystallised sodium carbonate in 60 parts of water a t 10'. 900 grams of glycerol can be used in one operation. The solution is treated with 5 parts of pbenylhydrazine hydrochloride. In five t80 eight days, the gl yceros- azone separates as a yellow, crystalline precipitate. The yield is 20 per cent. of the weight of glycerol. When the oxidised glycerol is treated with aqueous soda, so that the amount of free alkali amounts to 1 per cent,., and is kept for four to five days, the liquid loses the power of reducing alkaline copper solution in the cold ; when warmed, it still has the power of reducing copper solutions.The solution is neutralised with acetic acid, and heated with phenylhydrazine hydrochloride and sodium acetate for six to eight hours. The product contains two osazones, C1,H,,N,O,. The one has all the properties previously ascribed to a-acrosasone (from acrylaldehyde bromide) ; it crystallises from alcohol in pure yellow, well-formed needles, which melt a t 217" with decomposition. The other osazone is more readily soluble in ethyl acetate, from which i t crystallises in globular groups of slender needles melting at 158- 159"; it is probably identical with p-acrosazone.This method for preparing the acrosazones is more convenient than that previously described. When a solution of 5 grams of dulcitol and 12 grams of sodium car- bonate in 40 C.C. of water is treated with 5 grams of bromine, and the whole, half an hour afterwards, is warmed with 5 grams of phenyl- hydrazine and 5 grams of sodium acetate, the osazone, C18H22N404, separates in yellow flakes. This closely resembles galactosazone (Abstr., 1887, 562) except that it melts at 205-206" with decompo- sition. The name phenyldubitosazom is ascribed to the new compound. Condensation of Formaldehyde. By 0. LOEW (Bey., 21, 270- 275) .-The condensation of formaldehyde (Abstr., 1886, 609) is most readily effected by the action of strong bases, although it can be brought about by salts having an alkaline reaction, such as potassium sulphite or carbonate ; salts having a neutral reaction are, however, without action on the aldehyde.Comparative experiments a t 100" with aqueous solutions of lime and baryta containing equimolecular proportions of the two bases showed thet the former rapidly acted on the aldehyde (15 per cent. solution) with the formation of formose as chief product, whilst the action of the latter resulted in the produc- tion of formic acid, much aldehyde remaining unaltered owing to the consequent neutralisation of the base. The production of formose by the action of lime-water is accelerated by the addition of sodium chloride, which itself does not bring about the condensation of the aldehyde, but is retarded by the presence of sodium acetate, potassium nitrate, and of much copper, iron, or tin.Calcined magnesia does not react with formaldehyde either i n the cold or a t loo", but an aqueous solution of the hydroxide converts it into formose at 100". Litharge and many lead salts also effect the condensation of the N. H. M.ORGANIC CHESIISTRT. 359 aldehyde, and metallic lead act's in like manner ; it is probable, how- ever, that in this case the action is due to the presence of traces of the oxide, since the amount of the latter dissolved by shaking litharge with distilled water for some hours, adding 0.1 per cent. of the aldehyde, filtering and heating at 100" for two hours, suRced to form formose. Iron, tetrethylammonium hydroxide, and many organic bases, also bring about the condensation.When the osazone (m. p. = 123') obtained from the sugar formed by heating a 0.5 per cent. solution of formaldehyde with tin for 15 hours (ibid., 864) is heated in alcoholic solut'ion at 100" for 25 to 30 hours, the melting point is found t o have risen to 14S0, at which it remains constant. A sugar, P-formose, which directly yields an osazone, C18H22N403, crystallising in small, yellow needles melting at 148", is formed when a 0.1 per cent. solution of formaldehyde is heated for five hours with much tin. I t is a thick, sweet, non-fer- mentable syrup, does not become brown at loo", yields humous sub- stances with hydrochloric acid, arid its solution in alcoholic hydrogen chloride yields a wine-red colour with resorcinol, and a st'eel-blue colour with diphenylamine.100 C.C. of Fehling's solution are reduced by 0.073 gram of the sugar. If formaldehyde is added to an aqueous solution of magnesium hydroxide, prepared by treating a 5 to 10 per cent. solution of mag- nesium sulphate with litharge, until the mixture contains 0.3 per cent. of the aldehyde, and the whole is digested at 100" for many hours, a mixture of at least two non-fermentable sugars is obtained, one of which yields an osaxoite crystallising from benzene in yellow Solubility of Calcium and Barium Formates, Acetates, and Propionates. By E. v. KRASNICKI (Monatsh., 8, 595-606).-The solubilities of the different salts were determined by Raupenstrauch's method. The formulae deduced from these determinations are given below :- needles melting at 152".w. P. w. Calcium formate, X = 16.2478 + 0*03229(t - 0%) - Barium formate, S = 27.7744 + 0*0236743(t - 1) + Calcium acetate, S = 37.8512 - 0*2575(t - 1) + Barium acetate, S = 58.473 + 0*65067(t - 0%) - Calcium propionate, S = 41.2986 - 0*1118G(t - 0.2) + Barium propionate, S = 48.2071 + 0*371205(t - 0.6) - The solubilities of the isobutyrates, isovalerates, and methylethyl- OS0001254(t - 0.8)2 0*0063622(t - l)z - 0.000060122(t - 1)3 0.0058845(t - l)z - 0*0000475576(t - 1)3 0*005431(t - 0.8)' 0*000085065(t - 0.2)' + 04000117907(t - O.2)9 0.0015587 ( t - 0*6)2. acetates, have been given by Sedlitzky (this vol., p. 250). A. J. G.360 ABSTRACTS OF CHEMICAL PAPERS. Temperature of Conversion of Copper Calcium Acetate.By L. T. REICHER (Zeit.physikaZ. Chem., 1, 221--226).-That there is a temperature at which the crystals of this salt are converted into crystals of copper acetate and calcium acetate, is already rendered probable by the experiments of Kopp and Schuchardt. Microscopical examination confirms this supposition, for on heating the double salt up to about 80°, it separates into colourless needles of calcium acetate and green rhombic crystals of copper acetate. To determine the temperature of conversion exactly, a dilatometer was employed. The dilatometer was filled with the powdered double salt, exhausted and filled with mercury, and the change of volume at a given tempe- rature was observed. It was found that the temperature of conver- sion lies between 78" and 76.2".c. s. Preparation of p-Iodopropionic Acid. By V. NEYER (Ber., 21, 24--25).-The author describes in detail various modifications of the method previously given for the preparation of P-iodopropionic acid (Abstr., 1887, 232). I?. S. K. Analogy between Ketonic Acids and the Alkyl Sulphones of the Fatty Acids. By R. OTTO (Bey., 21, 8!)-99).-The larger portion of this paper deals wit,h the points of analogy between t h e ketonic acids and the alkyl sulphones of the fatty acids. /3-Phen?/Zsu7phonep-opionic acid, S02Ph*CH2*CH2*COOH, is prepared by neutralising p-iodopropionic acid and benzenesulphinic acid with sodium carbonate, and heating the product until no more water is given off. It forms shining, monosymmetrical or asymmetrical plates, is sparingly soluble in cold water, somewhat more soluble in ether, and melts a t 123-124".The alkali salts are described. The ethyl salt is a thick oil of a yellow colour, readily soluble in alcohol and ether, insoluble in water. The free acid is very stable ; i t does not react with the halogens, is not attacked by potash a t 180°, but is totally decomposed a t 280" ; it is speedily reduced by sodium amalgam, the group PhSOz yielding a sulphinate. J. W. L. Isodibrornosuccinic Acid. By R. DEMUTH and V. MEYER (Ber., 21, 264--270).-A repetition of Reilstein and Wiegand's expe- riments ou isodibromosuccinic acid (Abstr., 1882, 1051) shows that bromofumaric acid and not pyrnvic acid is formed with the evolution of some carbonic anhydride when the barium salt is treated with moist silver oxide in the dark.Bromofurnaric acid is also formed when the acid is heated with water for 10 hours in a reflux appa- ratus (Kekul6, AnnuZen, Suppl. 2, go), and racemic acid is obtained when the silver salt of the acid is boiled with water. Hence the un- symmetrical formula COOH*CH2-CBr,-COOH can no longer be ascribed to this acid. Attempts to prepare an acid of this formula by the oxidation of ma-dibromobutyric acid, EtCBr,-COOH, by displacing the oxygen of the carbonyl-group in acetoxalic acid by bromine, and by treating ethyl sodiomnlonate with ethyl tribromacetate and saponi- fying the product led t o no result, the crystalline compound formedORQANIC CHEMISTRY. 361 in the last experiment being free from bromine, whilst ethyl tricar- bintetracarboxylate, when treated with 1 mol.of bromine at 140" (compare Abetr., 1883, 46), yields a compound which on hydrolysis with concentrated hydrobromic acid yields carbonic anhydride and a crystalline compound free from bromine, and not symmetrical dibro- mosuccinic acid. w. P. w. Ethyl Oxalacetate. By W. WISLICENUS (Ber., 20, 5392-3394 ; mmpare Abstr., 1887, 234) .-Ethyl oxalacetate is prepared by shaking a solution of ethyl oxalate in four parts of ether with sodium ethoxide, previously freed from alcohol by heating in a current of hydrogen at 200". The product is treated with ethyl acetate when the sodium compound separates; the yield is 70 per cent. of the theoretical. Ethyl oxalacetate boils at 131-132" under 24 mm. pressure, and reacts with ammonia and with aniline, yielding crystal- line compounds.The phenylhydrazine-deriuative, Cl1H1,N2Oa, crystal- ljses in plates melting at 76-78". When an alcoholic solution of the ethyl salt is treated with carbamide, the compound C9H,,N205 + EtOH separates in colourless crystals. The hydroxy lumirte-derivalive is a n oil. Nitrous acid reacts with ethyl oxalacetate in the cold, with for- mation of a crystalline isonitroso-derivative. Ethyl Methgloxalacetate. By W. WISLICENUS and E. ARNOLD (Ber., 20, 3394--3396).-EthyZ methyEoxalacetate, C9H1305Na, is pre- pared by the action of sodium ethoxide and ethyl propionate on ethyl oxalate dissolved in ether. It forms a colourless oil, boiling at 137-138" under 23 mm. pressure, insoluble in water, readily soluble in alcohol, ether, and alkali ; the alcoholic solution gives an intense red coloration with ferric chloride. When boiled with alcoholic potash, it is converted into oxalic and propionic acids.Boiling dilute sulphuric acid decomposes it with formation of propionyl- formic acid (Claisen and Moritz, Trans., 1880, 691). The phenyl- hy draxine-derivutiue of propion ylformic acid, CH,Me*C ( N2HP h).C 0 OH, crystallises from dilute aloohol in plates melting at 144-145" ; when warmed with sulphuric acid and alcohol, and precipitated with water, scatolecarboxylic acid, CsH4< NH >C*COOH, is obtained ; this melts at 164-165", decomposing into scatole and carbonic anhydride, and differs from Salkowski's compound (Abstr., 1885, 568) i n its crystalline form and in being mme sparingly soluble. N. H.M. CMe N. H. M. Cryoscopic Studies on Racemic Acids and Racematee. By F. M. RAOULT (Zeit.physdkaZ. Chem. 1, 186--189).-1n the case of solu- tions contlaizling not more than 5 per cent. of acid, observation shows that equal quantities of dextrotartaric acid and racemic acid produce the same lowering of the freezing point, and it is inferred that the racemic acid is completely decomposed. For solutions of greater con- centration, this will not be the case; part only will be decomposed. The fall of temperature produced by each unit of mass of this part will be known by observation. For the other, the fall caused by each VOL. LIT. 2 b362 ABSTRACTS OF CHEMICAL PAPERS. unit may be calculated from the law that the molecular fall of the freezing point is equal to 19 for all organic acids.The actual fall of temperature caused by the whole amount of racemic acid can be ob- served, and a simple equation will then give the amount of racemic acid decomposed. Thus i t was found that out of 14.229 grams of racemic acid dissolved in 100 grams of water, 0,880 gram remained undecomposed. In the case of the compounds, C,H,O,(NH,>Na + 4H20 and 2[C4H4O6(NH4)Na + H20j, the fall of temperature is the same for Organic Fluorine Compounds. Bey 0. WALLACH and F. HEUSLER (Annalen, 243, 219--244).-In the preparation of fluor- benzene (Abstr., 1887, 130), phenol and diphenyl ether, Ph20, are obtained as bye-products. Fluorbenzene can be obtained as a, crystalline mass by exposure to the temperature produced by ether and solid carbonic anhydride.The index of refraction for Frauenhofer's line C is 1.4635 ; A0 = 0.00017. Parq5horonitrobenxene melts a t 26.5". PuraJlzcoraniline can be solidified by means of solid carbonic anhydride. The acetyl-derivative, CcH4F-NHAc, me1 ts at 1 50-151". F~uorbenzeneparadiazcrpirperidide, CsHaF*Nz*C,H,,, is an unstable crystalline substance. Parad$luorobenzene, C&JFz, is liquid at the ordinary temperature. Its sp. gr. is about 1.11, and it boils between 57" and 89". ParuJluorochZorobenzene, C6HdFC!, prepared from parafluoraniline by means of Sandmeyer's method, boils at 130-131". Its sp. gr. a t 15" is 1.226. Para$uorobromobenzene melts between -15" and - 20", and boils at 152-153". Sp. gr. 1.593 at 15". ParaJluoriodobenzene is prepared by the action of hydriodic acid on fresh1.y prepared pure fluorbenzenediaaopiperidide.It boils a t 18%-184", and is decomposed by strong nitric acid, yielding iodine and fluornitrobenzene. Para- fluorphenol boils a t 186-188". Pseudocumenediazopiperidide. c6~zMe3*752*c,NH,,,, is deposited from alcohol in thick prisms and melts at 50". It is decomposed by hydro- fluoric acid, yielding Jluoropseudocunzene, C6HOMe3E', which melts at 27" and boils a t 174-175". Chloropseudocurnene melts a t 70-71" and boils a t 213-215". The bromo-derivative melts a t 72" and boils a t 233-235'. Iodopseudocumene melts a t 37" and boils at 256-258". Psendocumenol melts a t 71" and boils a t 234-235". DiJluorodiphenyl, Ci2HBFZr is crystalline, and dissolves freely in alcohol and ether. It melts at 88-69" and boils a t 256255".Although Sandmeyer's method of converting amido-compounds into chloro- and bromo-substitution pro- ducts yields admirable results, it is not to be recommended in the case of fluorides ; the decomposition of diazoamido-compounds by hydrofluoric acid almost inrariably yields better results in the latter ca8e. A comparison of the boiling points and specific gravity of the pre- ceding compounds shows that (1) the substitution of hydrogen by fluorine increases the specific gravity, and has very slight influence on the boiling point ; (2) the difference in boiling point between cor- responding iodine and bromine substitution products, and between solutions of the same strength up to about 13 per cent. c. s.ORGANIC CHEMISTRY. 363 bromine- and chlorine-derivatives is much smaller than the difference between chlorine and fluorine substitution products.T b anthors conclude that the boiling point of liquid fluorine is much lower than that of chlorine, and that it is probably near the boiling point of hydrogen. Numerous experiments show that fluorine unites more- firmly with carbon than chlorine, bromine, or iodine do. w. c. w. Dichro'ins. By H. BRUNNER and P. CHUIT (Ber., 21, 249-236).- Further experiments have confirmed the view put forward by Brunner and Eramer (Abstr., 1884, 1354) thaat compounds andogous to Liebermann's colouring matters (this Journal, 1874, 693) are formed only from paranitrosophenol and those polyhydric phenols in which two hydroxyl-groups are in the meta-position relatively to one another.These compounds are now termed dz'chrozm from their fluorescent and dichroic properties, and are divided into two p u p s termed a- and /iI-dichroins respectively. The a-dichroins contain the group C6N( 0-C,),, and comprise the colouring matters, CleHI5NO3, derived from phenol (Abstia., 2884, 1341), ClsH15N06 and C,,H&,Ol0 from resorcinol (Abstr., 1885, 525), and C,,H,,NO, from orcinol (ibid.) ; whilst the p-dichro'ins contain the group (36.N< O>C, and comprise the colour- ing matter, ClIHlINO3, derived from orcinol (&id.), together with azo- resorcinol, azoresorufin (Abstr., 1884, 1333), and nzoresorufyl ether, C4s€€mN4013 (Bw., 18, 586), the last three compounds being termed /3-resoreinol-, di-p-resorcinol-, and tetra-/3-resorcinol-dichroyn respec- tively.In the majority of reactions by which dichroi'ns are formed, other colouring matters are also obtained differing from them in con- taining more oxygen and being destitute of fluarescence ; these are termed oxychro'ius. Acetyl-o,-yhe~oldichroi'n, OAc*C&K,*NO(OPh)2., prepared by heating a-phenoldichrojin (1 part) with acetic anhydride (3 parts) and an- hydrous sodium acetate (2 parts) at 140" for an hour, is a brown, amorphous mass soluble in ether, alcohol, &c. AcetyZphenoZoxychroin, OAc.C6H4.x( OPh),, was also prepared. OrcinoZdichrozn has the formula C6H2( OH),Me*N( O*C6H3Me.0H), ; its acetyl-derivative, C2,Hl,( OAc)4NOB, is a brown, amorphous mass soluble in ether, alcohol, &c. T h y moZdichrozn was prepared by Liebermann's method (this Journal, 1875, 167), and when freed from unattacked thymol has the composi- tion O[N(C6H2MePr.OH),],.It sublimes at 140" with partial de- composition forming violet-coloured vapours, and is a dark-violet, amorphous mass, soliible in alcohol, ether, chloroform, and benzene yielding red solutions showing pale-green fluorescence. The acetyl- derivative, Cm€€48( OAc)~N~O~, is a brown, amorphous mass, Bolnble in alcohol, ether, &c. In the purification of thymoldichro'in by steam dis- tillation, thymoquinone passes over with the steam. Experiments show, however, that it is not a decomposition-prodnct of thymoldichroiri, and to explain its formation the authors point out that nitrosothymol, unlike nitroso-phenol, -resorcinol, and -orcinol, seems to act as a quinoneoxime in the formation of its dichroin, and regard it as probable 0 2 b X364 ABSTRACTS OF CHEMICAL PAPERS.that in addition to this reaction a second also occurs in which a portion of the thymol reacts with thymoquinoneoxime to form amidothymol and thymoquinone (compare Sutkowski, Abstr., 1887, 41). w. P. w. Formation of Secondary Aromatio Amines. By A. PICTET (Bey., 20, 3422-3424) .-Ethglacetanilide is prepared by adding 75 grams of finely-powdered acetanilide to a cold solution of 31 grams of oaustic potash in 300 grams of 95 per cent. alcohol ; after a short time the flask containing the mixture is fitted with a reflux condenser, 65 grams of ethyl bromide is added, and the whole slightly warmed on a water-bafh. When the reaction becomes less violent, the mix- ture is heated for one to two hours, allowed t o become cool, and filtered.The advantages of this method over Hepp's (Ber., 10, 327) are that it does not involve the use of large amounts of sodium, and that the product is more easily purified. The yield of ethylaniline (41 per cent. of the theoretical) is, however, not so good as that obtained by Hepp's method. In She case of formanilide, the yield is almost theoretical. N. H. M. Action of Sulphur on Dimethylaniline and Methylaniline. By R. M~~HLAU and C. W. KROHN (Ber., 21, 59--67).-Wheii di- methylaniline is boiled with sulphui- for 12 hours and distilled, an oil boiling at 210-345" is obtained. When this is treated with hydro- chloric acid, it is separated into an oil of indifferent character which soon solidifies, and a mixture of several basic compounds.From the latter, Hofmann's methenylarnidophenyl mercaptan (Abstr., 1887,823, 1039), aniline, and methylaniline were separated. The indifferent ) crystalline substance has the formula C,H,NS2 (P N/ C6HdLCN \CH,-SS/ ' melts at 88-89", and boils above 360". When boiled with sulphur, it is converted into methenylaniidophenyl mercaptan, and seems there- fore t o be the primary product. When treated with nitric acid. the compound C,HTNS, is changed into the base CeH,NS, probably By the action of sulphur on methylmiline, the same compounds are obtained. The authors think that at first 8 deoomposition of 2 mols. of methylaniline into dimethylaniline and aniline must have &ken place, the dimethylaniline so formed then redcfing with sulphur t18 described above.J. W. L. Action of Thiocarbonyl Chloride on Secondary Amines. By 0. BILLETER and A. STROHL (Bey., 21,108-110).-~~~~y~7~~yI- thiocarbumine chloride, CSC1-NPliPr, crystallises from light pehroleurn in thick, colourless prisms melting at 36". It is more stable in damp air than the corresponding methyl and ethyl compounds. D@opyZ- thiocarbadide, CS(NPhPr),, forms colourless plates melting at 103.5". Meihylpmp y 1 thwcarbami lide, NPhMe-C S-NPhPr, prepared either from methyl chloride and propylnniline or from propyl chlo- ride and methylaniline, forms colourless prisms melting at 56*50rORGANIC (IHEMISTRF. 365 E~hyl~ro~ylfhiocczrbanilide, NPhPr*CS-NPhEt, is prepared like the last-named compound and melts at 66.3".All these derivatives dis- solve easily in concentrated acetic, hydrochloric, and sulphuric acids without change, whereas by warming with concentrated sulphurio acid or heating at 1.50" with hydrochloric acid the secondary base is readily eliminated. Alcohols and phenols, the corresponding sulphur compoande, and also their metallic salts, react readily with the tfriocarbamine chlo- rides already described, with formation of the corresponding thio- and dithio-earbamic noids. Of thie series, the following were pre- pared :-EthyE ethylphenyIthiocarbamTate, NEtPh*CS*OEt, prepared by t h s action of ethyl phenylcarbamine chloride on sodium ethoxicie in ethereal solution, distils at 143%" under a pressure of 12 mm. Sp. gr. 1.066 a t 15". Jt solidifies by prolonged cooling to a colourless, crys- talline mass which melts at 18".Pheny I et~?l~henlllthiocarbamnte, NEtPh*CS*OPh, forms colourless needles and melts at 69.2". Pheuyl ethylphenyldif7b.iocarbamate, NPhEWSSPh, crjstallises in compact, colourless needles, and melts at 127.8". E t h y l efkylphenyldithiocar6- amate melts at 66.4". A trisubstituted thiocarbamide is formed by the action of ethyl phenylthiocarbamine chloride, aniline, $e., and can be isolated bj- stopping the reaction after the mass first solidifies. It is decomposed if the reaction proceeds too far into thiocarbanilide and aniline hydrochloride. A small quantity of a dithiobiuret is also foi-med. The dithiobiurets are readily obtained by the further action of thiocarbarnine chloride on the tertiary carbarnides first formed.Di,neEhylt~~henyId~ithiobizL.~et, C2S2N3Ph3Me2, prepared from methyl- phenylt hiocarbamine chloride and methylthiocarbanilide, forms yellow needles melting at 202.5". It is sparingly soluble in alcohol and ether, readily so in cbloroform. Diethyltripheny Idithiobiwet, C2S2W3Ph3Et2, prepared from ethyl- phenylthiocarbamine chloride and et hylthiocarbanilide, cPystallises in lemon-yellow needles melting at 158". It is more readily soluble than the methyl oompound. Methy let h y 1 trip heny ldithio biuret, ( a), NE t Ph. C (NP h) S C S-NMeP h, prepared from methylphenylcarbamine chloride and ethylthiocarh- anilide, forms small, pale yellow needles melting a t 157.5". It is soluble in chloroform, sparingly soluble in alcohol and ether. (b.) N Me Fh*C (NPh) *S .C S-NEtPh, .prepared from e thy 1 ph enylcarbamine ohloride and methylthiocarbanilide, forms small, light-yellow needles like those of the ( a ) compound, and melts at 156.5'.Dipropy 1 trip hen y ldit hiobiuret, C2S2N3Pr2 Ph3, prepared from propyl- phenglcarbamine chloride and propylthiocarbanilide, forms shining, yellow needles melting at 153.7". Iti.iphelzyldithiobiuret, C2S2N3MePrPh (a), prepared crystallises in shining yellow pyramids, melting point 110"; ( b ) pre- pared from propylphenylcarbamine chloride and methylthiocarbani- lide, forms yellow pyramids similar to the (a)-derivative, and melts E thy lprop y 1 triph en y 1 dit hio biuret, C2S2N3E t PrP hS, (a) prepared from ethplphenylthiocarbaruine chloride and propy lthiocarbanilide, crystal- It is soluble in chloroform.from Meth methy yl'pro? phenylcarbamine chloride and propylthiocarbanilide, at 111".366 ABSTRACTS OF CIHEMICAL PAPERS. lises in pale yellow needles melting at 165.8". Very sparinglyqoluble in alcohol ; ( b ) prepared from propylphenyltl-iiocarbamine chloride and ethyl thiocarbanilide, crystallises in yellow needles melting at 165'. Pr~lIZthiocarbaniZide, CSN,H.Pr-Ph,, prepared from propylaniline and phenyl isothiocyanate, consists of colourless, shining needles which melt at 104.8O.. I t is readily soluble in alcohol, and is decom- posed by hydrochloric acid info its components. Constitution of Mixed Azo-compounds. By V. MEYER (Ber., 21, ll-l8).-The author had independently arrived at views on the constitution of the mixed azo-compounds identical with those brought forward by Japp and Klingemann (Proc., 1887, 140).Compounds of Phenylhydrazine with Ketone Alcohols. By H. LAUBMANW (Annalen, 243, 244--248).-BenzoyZcarbinolphenyl- hydrazone, N,HPh : CPh*CH,*OH, crystallises in needles, melts at 112", and dissolves freely in alcohol and ether. It is converted into an ainorphous product, probably hydroxyphenylindole, by the action of zinc chloride at 150". The hydrazone is converted into the osazone, N,HPh : CPh*CH : N,HPh, by treatment with phenylhydrazine and sodium acetate in alcoholic solution. The osaxone melts at 152" and is soluble in ether, benzene, and in hot alcohol. The oscczone of acetol is identical with the product v. Pechmnnn (Abstr., 1887, 1103) obtained by the action of phenylhydrazine on nihrosoacetone.w. c. w. J. W. L. Action of Phenylhydrazine on Dioximes. By M. POLOKOWSKY (Ber., 21, 182-184) .-When glyoxime in alcoholic solution is treated with an equimolecular proportion of phenylhydrazine, an additive compound, < ~~~~~~] >NH,*N HPh, is obtained. This crystallises from alcohol in white scales, melts at 110", and is readily soluble in alcohol, less so in ether, and insoluble in water. Concentrated aqueous soda dissolves it, and the solution when heated yields phenyl- hydrazine ; a like decomposition is also produced by concentrated su lphuric acid. Under similar conditions diphenylglyoxime yields an additive com- pound, C20H20N402, which crystallises in needles, melts at 149-150", and closely resembles the preceding derivative in its properties.P-Naphthaquinonedioxime, in like manner, forms an additive com- pound, C,H,sN402. This crystallises from alcohol in tufts of long Aldines and Amidoacetophenone. By E. BRATTN and V. MEYER (Her., 21, 19--21).-When isonitrosoacetophenonc is reduced in hydrochloric acid solution, it is completely transformed into the hydrochloride of an amidoacetophenone, COPh*CH,.NH,. This salt crystallises from water in large, hard, colourless crystals, and is very stable ; it caa be recrystallised from hot water, and forms a crystal- line platinochloride. The freshly precipitated base redissolves in acids, needles, begins to fase at 105", and melts at 138". w. P. w.ORGANIC CHEMISTRY. 367 but when purified by mashing or recrystallising from alcohol, it becomes orange-coloured, and completely loses its basic properties, being converted into a coloured crystalline substance, which resembles isoindole very closely, and with which it is probably identical.A /CPh CPh\N, is readily obtained from the monoxime \CPh CPh/ ketine, N of benzil. F. S. K. Formation of Phenylhydrazile Acids from the Anhydrides of Bibasic Acids. By R. ANSCH~~TZ (Ber., 21, 88-89).-By the action of phenyl hydrazine on the chloroform or ethereal solutions of the bibasic anhydrides, the corresponding phenylhydrazile acids are obtained. The following anhydrides react in this way: male'ic, SUC- cinic, citraconic, itaconic, camphoric, phthalic, diphenylmale'ic, phthalic, diphenylmale'ic, and diphenylsuccinic (compare Hotte, Abstr., 1887, 669). J. W.L. Formation of Orthosulphaminecarboxylie Acids. By C. FAHLBERG and R. LIST (Ber., 21, 242--'248).-The products of the oxidation of orthotoluenesulphonamide under different conditions were examined, and the results show that when the oxidation is carried on in alkaline solutions by potassium ferricyanide (Abstr., 1886, S04), by potassium manganate, and by potassium perman- ganate, orthosulphaminebenzoic acid is formed ; that when it is carried on in neutral solutions by permanganate, benzoic sulphinide is the chief product, a small quantity of orthosulphaminebenzoic acid being also formed, probably by the action of the alkali produced by the decomposition of the permanganate, since the yield was much dimi- nished by adding acid from time to time to neutralise the alkali formed ; and that when i t is carried on by permanganate in solutions rendered acid either by hydrochloric acid, or by a current of carbonic anhydride, orthmulphobenzoic acid and potassium nitrate are formed.Benzoic sulphinide is to be regarded as .the primary product of the oxidation, since on evaporation with hydrochloric acid it is converted into orthnsulphobenzoic acid and ammonia, and on evaporation with potassium hydroxide into orthosulphaminebenzoic acid. Ammonia, alkaline carbonates, and the oxides of the alkaline earths cannot be employed for this purpose; moreover, in the case of barium oxide, the barium salt of the sulphinide is obtained (compare this vol., p. 282). Orthoparad~isulphnminebenzoic acid, [ COOH : SO,NH, : S0,NH2 = 1 : B : 41, is obtained either by oxidising orthoparatoluenedisulphon- rtmide with alkaline potassium manganate, or by evaporating sulphaminebenzoic sulphinide with potassium hydroxide. It crystal- lises in slender, satiny, microscopic needles, melts at 182-183", is completely decomposed a t 250-260", and is very soluble in water and alcohol, sparingly soluble in ether.The salts of the alkalis and alkaline earths are readily soluble, and those of the metals are sparingly soluble in water. The barium salt, with 5 mols. H,O, erystallises in large, colonrless, monoclinic prisms, the comer salt, with 2 mols. H,O, in bright-blue, silky needles, and the silver salt in anhydrous, white needles. The ethyl salt is identical with that pre-368 ABSTRACTS OF CHEMICAL PAPERS. pared from dianiphaminebenzoic acid (Abstr., 1881, 816).For par- poses of comparison, the corresponding salts of disulphaminebenzaic snlphinide were prepared ; the barium sdt, with .3+ rnols. HzO, crystal- lises in granular aggregates of needles, and the copper salt, with 4 mola. H,O, in blue, microscopic needles; the silver salt is anhy- drous and indistinctly crystalline. w. P. w. Derivatives of Phenyldibromisobutyric Acid. Ry A. KORNER (Ber., 21, 276--277).-When a-methylcinnamic acid (m. p. = 78") dissolved in carbon bisulphide is treated with bromine, phenyl dibromisobzctyric acid, CHPhBr*CMeBr.COOH, melting at 137", is obtained. This, when warmed with alcoholic potash, yields browm- phen ylcrolonic acid, CPhBr CMeGOOH, which crystallises from water in matted needles, and melts at 184".If phenyldibrom- isobatyric acid is boiled with water, phenylbrornh ydroxyisobutyrio acid is formed, melting at 148". In both cases, the yield of the acid is small, the chief product being phenykbromopopylene, C9H',Br ; this is a colourless liquid, of pleasant odour, and boils at 226" with decomposi- tion. When treated with alcoholic potash, it is converted into phenyl- allylerze, CPh i CMe; this is a pale-yellow liquid of unpleasant odour, boils at 185", and yields with bromine a liquid dibrotnide, which boils at 250-255" with the evolntion of much hydrogen bromide, and a solid fetrabronde, which crystallises in lustrous plates and melts at 75". On treatment with an aqueous solution of mercuric chloride, phenylallylene forms a, white, amorphous componnd, which when heated with hydrochloric acid yields not phenylallylene but phenyl ethyl ketone, COEtPh. w.P. w. Parisobutylorthobydroxybenzoie Acid. By L. P. DOBRZYCKE (J. p r . Chem. [a!, 36, 389-4UO).-Anhydrons sodium isobutyl- phenoxide was prepared by adding the exactly equivalent quantity of isobutylphenol (Liebmann, Abstr., 1882, 171) to alcoholic sodium ethoxide, evaporating off the alcohol, and drying the phenoxide at 140 -150" in a stream of hydrogen. The dry phenoxide was then treated, under pressure, with carbonic anhydride, which was rapidly absorbed with evolution of much heat, sodium isobutylphenyl carbonate being formed. When this substance was heated for some time at 130- 160" it yielded sodiunt purisobut~yEorfhohydrox.~benzoate.The free acid, C4H,~C,H,(oH).cooH, is soluble in boiling water, volatile in steam, and crystallises in long, thin, glistening, white needles. It dissolves readily in alcohol, ether, and chloroform. The aqueous solution gives an intense violet coloration with ferric chloride. The metallic salts are not well characterised. The methyl salt yields large, colourless prisms, melts at 54", and boils at 266". It is easily soluble in alcohol and ether. Cold soda converts it into a white mass probably of the formula C,H,.CaHs(ONa)*COOMe. The ethyl salt is a colourless aromatic liquid boiling at 276". The phnyl salt was pre- pared by heating the acid with phenol at 130", and adding the requi- site quantity of phosphoric chloride in small quantities. It formsORGANIC CHEMISTRY.369 long, glistening needles, sparingly solnble in cold ethyl and methyl alcohols, easily in ether, and melt,s at 68". Dilute soda does not attack it in the cold, but saponifies i t on heating. When heated in a reflux apparatus, carbonic anhydride is evolved, and phenol, isobutyl- phenol, and isobecty~~enzophenozide, C 1 7 E l 6 0 2 , are formed, The latter compound is now being investigated. When isobutylphenol is treated with phosphoric chIoride, isobaty I- ehlorobenzene is formed. The oxidation of this compound proved di5cult, potassinm chromate and sulphuric acid solution being with- out action, whilst chromic acid in acetic solution caused complete oxidation. When heated f o r a long time at 190" with dilute nitric acid, however, it yielded parachlorobenzoic acid.Liebmann's iso- butglphenol is, therefore, the para-compound, and from analogy and a, coneideration of its properties there is little doubt that the acid described above has the constitution [OH : COOE : CaH, = 1 : 2 : 4). L. T. T. ar-Methylcinnarnic Acid. By P. R,AIKOW (Rer., 20,3396-3397). -In preparing a-niethylcinnamic acid (phenylcrotonic acid) by Perkin's method, and recrystallising the product from light petroleum, two acids were obtained having the 8ame composition, The one crystnllises in plates melting a t 81-82", the other in needles melting at 74'. When the latter is often recrystallised, it iff converted into the acid of higher melting point. The relative amounts of the two acids is influenced by the temperature at which the reaction between the benzaldehyde, propionic acid, and sodium acetate takes place.At 135", 24 per cent. of the plates and 30 per cent. of the needles are obtained, whilst at 175" only the needles (56 per cent.) are formed. The two acids differ only slightly in solubility. N. H. 31. Benzeneazomalonic Acid. By R. METER (Bw., 21, 118-119). -Benzeneazomalonic acid, prepared from diazobenzene chloride and ethyl malonate, is identical with the phenylhydrazide of mesoxalic acid. J. W. L. Action of Phthalic Anhydride on Amido-acids. By L. REESE (Bsr., 21, 277- 278).-ac-Leucinphthaloic acid (this vol., p. 148) can be obtained by adding the calculated quantity of phthalyl chloride to a boiling solution of leucine in alcoholic potash, and con- tinuing the boiling of the alkaline solution for on8 minute; on cooling, the potassium salt crystallises in small, slender, concentr~cally- grouped needles, and yields the acid on treatment with dilute sul- phuric acid and extmction with ether.Pht~aaEy Zdisarcos~~~e: CI4Hl6N2O6, is formed when phthalic anhydride (5 parts) is heated at 1U--150" with sarcosine (6 parts). It crys- tallises in lustrous needles, melts at 168", and is readily soluble in water and boiling alcohol, sparingly soluble in ether, and insoluble in chloroform and light petroleum. A sodium salt could not be pre- pared, since the compound is decomposed into its constituents by the action of alkalis; a similar decomposition also occurs when it is heated with concentrated hydrochloric acid. w. P. w.3iO ABSTRACTS OF CHEMICAL PAPERS. Azotoluenesulphonic Acid.By J. V. JANOTSKY (Ber., 21, 119. 122) .-By appropiate manipulation, it is possible to directly ~u1- phonate azotoluene. Axotoluenesulphonic acid, C6H4Me*N2*C6H3Me*S03H [Me : N, : Me : SO,H = 4 : 1 : 4 : 3 I, is obtained by the action of fuming sulphuric acid on parazotoluene, care being taken that the temperature is kept below 100" ; the best result is obtained by the employment of an acid containing about 24 per cent. SO3, when the temperature produced by the reaction does not exceed 80°, It crystallises witb 5 mola. H,O in orange- red tables, sparingly soluble in cold water. The potassium (with 5 mols. H20), sodium (44 mols. H,O), calcium, barium (11 mols. H,O), lead and zinc salts are described. When nitrated, it yields a nitro- acid, N02*ClrH12N,*S03H + H20, crystallising in small, yellow needles, readily soluble in hot water; several salts were prepared.The cor- responding umido-acid crystallises in pale-yellow needles, and toge- ther with the hydrazo-acid also obtained, will be described later. A bronzo-acid, C14H,,BrN2*S0,H, was prepared, crystallising in tufts of long needles ; the potassium and calcium salts are described. Proof of the constitution assigned above to the sulphonic acid is obtained when it is treated with tin and hydrochloric acid, parntoluidine hydrochloride, and paratoluidineorthosulphonic acid [Me : S03H : NH2 = 1 : 2 : 41 being formed. Ethylindole. By A. PICTET and L. DUPARC (Ber., 20, 3415- 3422).-3'-E'thyZindole is prepared as follows :-30 grams of aniline is added to 50 grams of zinc chloride, and the whole mixed with 35 grams of lactic acid ; 200 to 300 grams of sand being added to pre- vent frothing.It is then heated in a copper retort. The oily products of several fractions are united, dissolved in ether and shaken with small amounts of dilute hydrochloric acid until no more basic sub- stance is dissolved; the ethereal solution is then distilled. It is a bright yellow oil, boiling at 282-284" (corr.), very sparingly soluble in water, readily soluble in alcohol, ether, benzene, and chloroform, bic. ; it distils readily with steam. When the alcoholic solution is treated with hydrochloric acid and a chip of pine, it gives an intense red colour. The solution in chloroform gives, on addition of a few drops of a dilute solution of bromine in chloroform, an intense violet colora- tion, resembling that of potassium permanganate. The picrate meits at 143".The basic substance formed in the preparation of ethylindole is quinaldine (compare Wallach and Wusten, Ber., 16, 2067). Propionylorthotoluidine, CsH4Me*NH.COEt [Me : NHmCOEt = 1 : 21, is readily obtained by boiling orthotoluidine with propionic acid for six hours. It crystallises from benzene in white needles an inch long, melts at 87", and is readily soluble in alcohol, ether, and glacial acetic acid, &c., sparingly soiuble in hot water. It boils at 298- 299" (corr.) under 730 mm. pressure, When oxidised with potassium permanganate, i C is converted into propionylorthamidobenzoic acid, COOH*C6fiNH*COEt. This crystallises from wetter in white, flat A.J. G. Ethylindole resembles scatole in its general behaviour.ORQ XNIC CEEMISTRT. 371 needles, melts at 117", decomposes at 180" and is readily soluble in alcohol, ether, and in hot water. The silver salt crystallises from water in small, white needles. N. H. M. Dimethylindole. By L. WOLFF (Ber., 21, 123--126).-Aniline reacts with /3-'bromolaevulinic acid, forming dimethylindole, C,,H,,N. The vapour-density shows that this is the product of the reaction and not a compound of twice this molecular formula, as the author sug- gested in a former paper (Abstr., 1887, 464-465). This indole is identical in all respects with the 2'. 3' dimethylindole obtained hy J. w. L. Isatoic Acid. By G. SCHMIDT and E. v. MEYER (J. pr. Chem., [2], 36, 370--389).-When isatoic acid is heated in closed tubes at 100" with excess of ethyl alcohol, hydrogen ethyl carboa?lEanthranilate, COOEt.C,H4*NH*COOH, is formed.It crystallises in thin, colourless needles, melts at 1 2 6 O , and is so!uble in boiling water. When heated with hydrochloric acid in closed tubes at 150," this substance yields carbonic anhydride, ethyl chloride and anthranilic acid hydrochloride. The salts of this acid are crystalline ; the silver salt, E. Fischer (Abstr., 1887, 149). C OOE t*CsH4.NH*COOAg, forms white, microscopic needles or prisms, which are soluble in alcohol and sensitive to light. When methyl alcohol is substituted for ethyl alcohol in the above reaction h ydrogew methyl carboxyawt hranil ate, CO O&fe*C6H4*NH.C 0 0 H, is formed.This crystallises in minute needles, soluble in boiling water and melting at 176". The silver salt forms small needies which are less stable than the ethyl compound, When heated with hydro- chloric acid at 120", the methyl compound dissolves, but on cooling crystallises out again unchanged. When heated at 200" with an in- different substance, such as glycerol, carbonic anhydride is evolved, and methyl anthranilate is formed. t With phenol at l8Oo, isatoic acid yields phelzyl anthranilate, NHz*CcH4*COOPh, but no carboxyl-derivative. The phenyl salt crystallises in colourless needles melting at 70". It is easily soluble in alcohol and in ether, sparingly so in boiling water. It is slightly volatile in a current of steam. When warmed with freshly psecipitaked ferrous hydrate in the presence of excess of soda, isatoic acid is reduced to anthranilic acid.-With zinc-dust and acetic acid, isatoic acid yields an thranilcarboxjlic acid, <gGSY>N*COOH. When "isitoic acid is heated with glacial acetic acid, carbonic anhydride is evolved, and a compound of the formula C35H27N606 formed. This substance is almost insoluble in the usual solvents, and only melts at a very high temperature. At 150°, it is solnble in ammonia, but crystallises out again unchanged on cooling. With hydrochloric acid at 1 90°, it yields anthrariilic acid hydrochloride. It dissolves in cold concentrated sulphuric acid with slight darkening, but is reprecipitated unchanged on the addition of water. 50 per372 ABSTRACTS OF CHEMICAL PAPERS. cent.snlphuric acid at 160" converts it into anthranilic acid. The compound is probably formed from 5 mols. of isatoic acid by the sepa- ration of 4 mols. of water. If acetic anhydride is used in place of acct'c acid, carbonic anhydride is evolved, and acetylanthranilic acid is formed. Meyep has already pointed out (Abskr., 1885, 666) that anthranil- carboxylic acid is formed from isatoic acid by sxidising as well as by reducing agents. From a careful consideration of all the experimental results obtained, the autbors conclude that isatoic acid is really identical and not isomeiic with anthranilcarboxylic acid, and that the seeming differences of properties are due to the presence in isatoic acid of small quantities of a yellow-colonred impurity. This impnrit,y, which modifies the properties of the acid, is not removed by the ordinary mckhods of purification, but is destroyed by strong oxidising O r reducing agents.Finally, the authors are inclined to think that the ethyl-compound described above is perhaps identical with that obtained by Weddige by the action of ethyl chlorocarbonate on anthranilio acid, in which case its constitution would be COOH*C6H4*NH*COOEt, and that of tha methyl-compound analogous to it. (Ber., 21, llO-l18>.-1t is easy to obtain reactions between aromatia monamines and glyoxal, if, instead of employing the latter in the free state, its compound with sodium hydrogen sulphite is used. Anili doacetanilide, NHPh*CH2*C ONI4 Ph, is prepared by hentin g aniline and glyoxal sodium hydrogen sulphite with dilute alcohol in the water-bath for 20 to 30 honrs.The melting point, 112-113", is €ound t o be rather higher than has previously been stated. Under like conditions, paratoluidine gives paratoluidoacetotoluide. When /%nsphthyla;mine is heated with glyoxal sodium hydrogen sulphite in alcoholic solution, the reaction takes another course and the sodium salt of /?.naphthoxindolesulphonie acid separates. The free acid could not be obtained. The gotassinm salt, CJ&N*SO,K(, crystal- lises in white plates, and when heated with aqueous hydrochloric or sulphuric acid at 80-90" yields p-aaphthoxindole whilst much sul- phurous anhydride is evolved. /i?-Naphthoxhadole, C,o&<CH,>CO, crystallisea in pale green needles, melts at 234', and is sparingly soluble in water, readily in alcohol, ether, and glacial acetic acid.It dissolves in potash wit,hout decomposition, and is insoluble in mineral acids, but with concentrated sulphuric acid it gives a bluish-green coloration which disappears on dilution. The isonitrmo-compound, c,&< C(N0H) NH.Co->, prepared by the action of nitrous acid, foms slender, reddish-yellow needles, and melts at 240". CloH6< co >CO, is prepared by reducing iso- nitPoso-P-nsphthoxindole in dilute, alcoholic solution by zino and L. T. T. Aotion of Glyoxal on Aromatic Amines. By 0. HINSBERG NH NH p-Naphthisatin,ORGANIC CHEMISTRY. 373 hydrochloric acid, and treating the colourless liquid so obtained with ferric chloride. It forms slender, red needles, melts a t 2 4 5 O , is moderately soluble in the ordinary solvents, and resembles isstin i n its chemical behaviour. From a-naphthylamine, the corresponding a-compounds were ob- tained in similar manner.The sodium and silver salts of a-naphth- indolesulphonic acid were prepared, but the free acid could not be obtained. a-Nuphthoxindole crystallisea in colourless needles, melts at, 245", is insoluble in aqueous soda, and gives a greenish-black coloration with ferric chloride and hydrochloric acid. The iaonitroso-compound forms yellowish-red needles, ainters, and turns black at 230", and is com- pletely fused at 260". a-Naphthisutin forms red needles, melts at 255"; the phenyl- hydrazide melts at 268-27'0". Neither of the naphthisatins give the blne coloration with sulphuric acid and benzene containing thiophen. A.J. 0. Condensation-compounds of Metanitrobenzaldehyde with Benzene and Toluene. By 0. TSCHACHER (Ber., 21, 188-191).- Meta.nitrot~i~hsszyZn.tethane, CHPh2*CsH4*N02, is formed when a solution of metanitrobenzaldehyde in benzene is shaken with half its volume of sulphuric acid ; it crystallises from light petroleum in colourless crystals, and melts at 90". When reduced in acetic acid solution with zinc-dust, it yields the amido-derivative, which crystallises from ether in short needles, melts at 120°, and forms a hydrochloride, The acety Z-derivative, CIgH15*NHAcrystallises in colourless, nacreous scales, melts at 115", and is soluble in alcohol. When metanitrotriphenylmethane in carbon bisulphide solution is freeted with the calculated quantity of bromine and exposed to sun- light, an oil, probably C19E14Br*N02, is obtained which on treatment with potassium acetate in acetic acid solution, and subsequent hydro- lysis with aqueous potash, yields metanitrotriphenyl carbinol, This crystallises from light petroleum in colourless crystals, and melts at, 75" ; when reduced, it is converted into the amido-derivative, which crvstallises from ether in colourless, stellate forms, melts a t 155", and yields an acetyl-derivative, OH*C,gH,4*NHAc, crystallising in colourless, nacreous scales and melting a t 164".Metanitrophenylditdy Zrnethane, CH(C6H4Me),*C6H,*N.02, is obtained by treating a solution of metnnitrobenzaldehyde in toluene with sulphuric acid in the cold. It crystallises from light petroleum in colourless forms, and melts at 85".w. P. w. Action of Dichlorether on PhenoL. By J. WISLICENUS and H. REINHARDT (AnnuEeB, 243, 131--165).-Dichlorefher ada on pEe~01,374 ABSTRACTS OF CHEMICAL PAPERS. forming et71 elzy Itripheno I , Hoe c6&* CH,*CH.( C6H,*0 H) *, and 0th er products. I f less than S mols. of phenol are taken, an insoluble resin is formed. The crude product is dissolved in alkali, reprecipitated by hydrochloric acid, and distilled in a current of steam to remove the excess of phenol. These three operations must be repeated several times. Ethenyltziphenol yields a triacetate soluble in ether, alcohol, chloroform, acetone, benzene, aniline, phenol, and acetic acid. The acetic acid solution is oxidised by ferric: chloride, yielding isorosolic mid, C20H1601, a dark, carmine-red, amorphous powder.Isorosolic acid yields a sulphonic acid. From an acetic acid solution of isorosolic acid, chromic acid throws down an amorphous insoluble compound containing chromium. w. c. w. Action of Dichlorether on the Dihydroxybenzenes. By J. WISLICENUS and M. SIEGFRFED (Annalerz, 243,171-192) .-Ethenyl- ti*iresorcinol, C&[ C6H,( OH),],, is formed by the act-ion of dichlorether (14 grams) on 33 grams of resorcinol dissolved in 300 grams of benzene. It is a pale-red, amorphous powder soluble in water, alkalis, alcohol, acetone, and in strong acetic acid. It is precipitated by hydrochloric acid from alkaline solutions, and after the precipitate has been dried in a vacuum, it is sparingly soluble in water, alcohol, and acetic acid.A monztcetic derivative is obtained by the action of glacial acetic acid a t 85". It is insoluble in the ordinary solvent's, and is converted into an insoluble hexacetate by the action of acetic anhydride at 200". By the action of acetic anhydride on ethenyl- triresorcinol at 170°, an amorphous hexacetate is obtained which is soluble in acetone, chloroform, benzene, and acetic acid. A chocolate- coloured, amorphous substance is formed by boiling ethenyltriresorcinol with glacial acetic acid and ferric chloride. When freshly prepared, it is soluble in alcohol, acetonet and acetic acid. It also dissolves in alkalis, yielding a cherry-red solution. It yields a pentacetate, CzOHll(A~)506. When bromine acts on ethenyltriresorcinol, two hydrogen-atoms are eliminated and six are substituted by bromine, yielding Cz,HloBr60~, a substance soluble in alcohol, ether, acetone, chloroform and acetic acid.Ethenyltricatechol is obtained as an amorphous compound by the action of dichlorether on a mixture of pyrocatechol and benzene. It is soluble in alcohol, acetone, acetic acid, and alkalis. It yields a hexacetate. On oxidation with ferric chloride, it loses two atoms of hydrogen, but the product could not be obbained in a pure state, although its pent- acetate, C20Hll( Ac),06, was prepared. Bromine converts ethenyltri- catechol into the hexabromide, CzoH,,Br506, from which the pent- acetate, C20H,Br6Ac506, was obtained. Btherzyltriquinol is prepared by the action of dichlorether on a solution of qninol in warm ethyl acetate.It is an amorphous substance, soluble in alcohol, acetone, acetic acid, and in alkalis. The hexacetate is soluble in acetone, chloroform, and acetic acid. Ethenyltriquinol yields a green colouring matter, C20H1606, when i t is treated with ferric chloride ; a bromide, C2,H,Br9O6, can also be prepared. When an excess of dichlorether acts on a solution of quinol in ethyl acetahe,ORGANIC CHEMISTRY. 375 a resin and a soluble compound are formed. ethenyltriquinol, but has the composition C16Hl,C10a. The latter resembles w. c. w. Action of Sulphur on the Salts of Aromatic Hydroxy-com- pounds. By M. LANGE (Bw., 21, 260--264).-When ,%naphthol is dissolved in aqueous soda and boiled with an excess of sulphur, the latter dissolves and dihydroxydinaphtl~yZ disulphide, S,( CloH6.0H),, is formed.This crystallises in white, opaque needles. melts at 210" (uncorr.) and is insoluble in water, sparingly soluble in ethyl alcohol, readily soluble in acetic acid, benzene, amyl alcohol, alkalis, and alkn- line sulphides. From the mother-liquors, a second compound of like composition can be separated, which crystallises in long, yellow needles, melts at 168-170", is more soluble in all solvents than dihydroxjdinaphthyl disulphide, and is also distinguished from it by its greater acidity. Bot>h compounds yield p-naph tho1 on distillation and when heated with alkalis or ammonia at 150". Dibydroxydinaph- thy1 disulphide is alone formed when P-naphthol is heated with sulphur and lead oxide at 180-200". Resorcinol, when treated in like manner, yields a compound, C6K4O2S2, provisionally termed thioresorcinol. It is a yellow powder, which carhonises before fusion, and is almost insoluble in the ordinary solvents, but readily soluble in alkalis, alkaline carbonates, and alka- Action of Fuming Sulphuric Acid on a-Naphthylamine Hydrochloride. By R.MAUZELIUS (Bey., 20, 3401-3404) .-The sulphonic acid prepared by Witt (Abstr., 1886, 554), by the action of fuming sulphuric acid on a-naph thylamine hydrochloride, is shown to be S-amidonaphthnlenesulphonic acid. The acid was prepared exactly as described by Witt (Zoc. cit.), and was purified by means of the calcium salt. The different results obtained by Witt appear to be due to the presence of some impurity. By E. BAMBERGER and W. LODTER (Ber., 21, 256-260) .-When equimolecular proportions of a-naphthabemy lamine hydrochloride and sodium nitrite are dissolved in water, the nitrite of the base, CloH7*CH2*NH2,HN02, is obtained ; this crystallises from water, in which it is sparingly soluble, in long, slender prisms, and melts and suddenly decomposes ah 148.5". a-NaphthabenzyZ abohol, CJ€,*CH2*OH, is prepared by diazotising the amine. It crystallises in long, lustrous needles, melts at 59-60', boils at 301' (corr.) under 715 mm.pressure, and is readily soluble in alcohol and ether, less soluble in hot water. On oxidation with potassium dichromate and sulphuric acid, it is converted into a-nuph- thaldehyde, CloH,*CHO. This is a thick, pale-yellow oil of slightly aromatic odour, which boils at 291.6" (cow.) without decomposition and gives the characteristic aldehyde reactions ; the pheny lhydrazide crvstallises in lustrous, bright-yellow scales and melts at 185".On treatment with nitric acid (sp. gr. = 1.47) at - 5-O", a mixture of nitraldehydes is obtained, one of which crystallises in lustrous, pale- yellow needles, melts at 136", is very sparingly soluble in cold alcohol line sulphides. w. P. w. N. H. M. m-Naphthaldehyde.376 ABSTRACTS OF CHEMlCAL PAPERS. and does not give a colour reaction with acetone and aqueous soda. 6-Naphtbaldehyde could not be obtained by distilling calcium By R. MATJZELIUS (Bw., 20, 3404-3407) .-1 : 4' Bromonaphthalenesulphonic acid (Darmstadter and Wichelhaus, Annilen, 152, ,703) is prepared by nddir?g 1 : 4' diazonaphthalenesulphonic acid to warm, strong hydro- bromic acid ; the solution is neutralised with potassium carbonate, the potassium salt recrystallised from hot water, dried and rubbed with phosphorus pentachloride ; the product is then treated with water, extracted with ether, and crystallised from glacial acetic acid.The chloride is heated with water a t 130". The impure acid melts at 126". The barium salt (with 2 mols. H,O) is sparingly soluble ; the siZver salt crystallises in pale-yellow lustrous scales. The chloride crystallises in well-formed crystals melting a t 9-4'. The amide forms yellowish needles melting at 232-233". The ethyl salt crystallises well, dissolves readily in alcohol, chloroform, and ether, &c., and melts at 51" (compare also Jolin, Verhand. d. schwed. Akad. d .Wissew., 1877, No. 7 ) . By E. BAM- BERGER and W. LODTE'R (Ber., 21, 51-56).-When an aromatic thiamide is reduced with zinc and hydrochloric acid, a benzglamine base is not the only product, a hydrocarbon is obtained a t the same time in quantities of about 1 to 2 per cent. of the thiamide employed. Symmetrical di-u-tLaphthyZetha?ze, CloH7*CH2*CH2*C10H7, is formed in the reduction of a-naphfhothiamide in alcoholic solution ; on evapora- tion, an oily resinous mass is obtained ; this is treated with soda, and the oil which separates is distilled. As soon as the naphthobenzylamine has passed over, the thermometer rises rapidly above 360" and a thick yellow oil distils, and in a short time solidifies. The dinapht hylethane thus obtained, after purification and crystallisation from alcoholic benzene, forms shining, hexagonal plates which are readily soluble in benzene and chloroform, less so in ether, and sparingly soluble in dcohol with a green 3uorescence.The crystals are greenish-yellow, and melt at 160" to a yellow oil with moss-green fluorescence. Symmetrical di-P-naphthylethane is obtained by extracting with benzene the resinous product formed in the reduction of P-naphtho- thiamide. It crystallises from benzene and chIoroform in shining silver-white, plates melting a t 253", is only sparingly soluble in ordinary solvents, most readily in chloroform and benzene, and less so in boiling alcohol and ether; the solutions have a blue-violet fluorescence. The resinous product formed in the reduction of benzothiamide contains stilbene, which can be isolated by boiling with alcoholic potash and then distilling with steam.Action of Dichlorether on Naphthol. By J. WISLICENUS and G. ZWANZIGER (Anmalen, 243,165-171) .-Ethenyltri-a-naphthol is formed by the action of dichlorether on a-naphthol. The crude product is purified by solution iu alkalis and reprecipitation by acRtic acid. It a-naphthoate with calcium formate. w. P. w. 1 : 4' Bromonaphthalenesulphonic Acid. N. H. M. Reduction of the Thiamides of Aromatic Acids. F. S. I(.ORGANIC CHEMISTRY. 377 is an amorphous, whike powder, soluble in amtic wid, alcohol, ether, acetone, and in dilute alkalis. It eorms 8 crystalline triacetyl-deriva- tive, Ca2HZlAc3O3. When ethenyltri-a-naphthol is oxidised by ferric chloride, it is converted into %t brawnisbred colouring matter of the composition C32Hm03.The action of dichlorether on /%naphthol is not analogous to its action on a-naphthol. The product, C22H,5C10, crystallises in plates melting at 174'. It resists the action of boiling Terpenes a;nd their DerivBtives. By J. W. BRGHL (Ber., 21, 145--179).-A comparative study of the chemical and physical pro- perties of the terpenes. A table containing the boiling point, rotation, density d, refractive index for the C h e N , specific refraction (n2 + 21d, and molecular refraction 7 (P being the molecular weight), of a number of the best known terpenes, has been compiled from the data of different observers. The terpenes are thuadivided into eight groups, similar to those given by Wallach (Abstr., 1881, 965), phdhndrene and terpinene coming under the heading laumne, and menthene and sesquiterpene forming an extra group. These groups are :- 1.Citrene (Kmmene) , boiling point 172-1 ?go, the differences probably dne to impnrities in the specimens examined. lhxtl-0- rotatory. Sp. gr. 0.846. Refrachive index 1.47. Specific refraction 0.328. Absorbs 2 mds. HCI, the resulting product being identical with the similar product from dipentene, aDd giving the latter and no$ citrene when the hydrogen chloride is removed by means of aniline. From this, and the formation of a tetrabromide melting at 104", the presence of two unsaturated or double bonds is probable, as also from the molecular refraction which agrees closely wihh that calcabted for such an unsaturated compoimd.2. Bpentene.-Differs from the above only in being optically inactive and yielding a tetrabromide melting at 124". 3. Pso~entene.--extrsrotato~y, differs only slightly from &he two former in physical properties. 4 XyZvestrem.-Has probably never been prepared in a state of purity, and does not appear to differ in any marked degree from the foregoing. 5. Pinene.-Boiling point 155-160". Sp. gr. 0.859. R,efractivc index 1.463. Specific refraction 0-320. The molecular refraction is that of a compound containing one double bond. This agrees with the chemical evidence, as pinene aombines with 2 mols. of bromine and I mol. HCl. 6. Laurene and Merttkerte.--Boiling p i n t 173-1 75'. Laevoro- tatory. 7. 0amphene.-Solid, melting at 47"; boils at 156-157". The hydrogen chloride derivative is very unstable and is decomposed by water at ordinary tempei-atures ; it is therefore probable that this is only a molecular compound, camphene containing no double bond, a view supported by its optical properties.8. Sesquiterpexe, Cl&.--Found in volatile oils associated with the VOL. LlV. 2 C potash and is not attacked by acetic anhydride. w. c. w. nz - 1. n z - l P n z - J Z Resembles pinene il: other respects.378 ABSTRACTS OF CHEMICAL PAPERS. terpenes. Boiling pint 250-260'. Rotation differs for different varieties. From its optical and chemical properties appears to contain two double bonds. The aa thor regards the terpenes as derivatives of paracymene. Formulae similar to those of Wallach (Zoc. cit.) are proposed for citrene, dipentene, pinene, and phellandrene, and a discussion of the various possible formulae for the ather terpenes is entered into.Specific Rotation of Dextrocamphoric Acid and its Salts. By W. HARTMANN (Ber., 21, 221-230).-The specific rot'ation of dextrocamphoric acid and its salts in solution is represented generally by [a] = a + bp or A + Bq, p being the percentage of active substance, q thatof the solvent, a the specific rotation for greatest dilution, A that for greatest concentration. The rotation of the free acid in acetic acid, acetone and alcohol varies with the nature of the solvent. The anhydride is optically inactive. The constants in the above equations were determined for solutions of the lithium, magnesium, ammonium, calcium, sodium, potassium and barium salts.By the aid of these constmts, the specific rotation of the acid in the salts was calculated, which is more than double that of the free acid, and is nearly equal for all salts for the same dilution. The molecular rotation M = [a)P/lOO, where P is the molecular weight, was also calculated for soliztions of the above salts for p = 0, 5,10, 1.5, and 20. It is found that the molecular rotation i s very nearly the same for all salts a t the same concentration. Hence also the specific rotation increases with the molecular weight. Alantic Acid and Alantole. By MARPMANN (Arch. Phnrm. [3], 25, 826-827 ; from Bred. arztl. Zeit., 5, 1887).-On distilling the Toot of InuZa heleniunt with water, a distillate is obtained containing helenin, C12H,,02, alantic anhydride, C15H2002, and alantole, C20H,0.AZantic acid crystallised from alcohol, melts a t 91", and sublimes with loss of the elements of water, hecoming alnntic anhydride ; both compounds are insoluble in water, soluble in alcohol, and with alkalis form salts soluble in water. Alaniole is an aromatic liquid which boils a t 200", is laworotatory, and has ozonising properties somewhat similar to those of the turpentine oils. Helenin, alantic acid, and alantole are antiseptics. J. T. Oxidation of 1-Quinolinesulphonic Acid, By H. Z~~RCHER (Ber., 21,180-182) .-Amidosulphobenzoic acid, [ COOH : NH, : SO,H = 1 : 2 : 31, is formed in small quantity when 1-quinolinesulphonic acid is oxidised to quinolinic acid by Fischer and Renouf's method (Abstr., 1884, 1049). The yield amounts to about 5 grams from 90 Reactions of the Opium Alkaloids.By P. C. PLUGGE (Arch. Pharrn. [3 1, 25, 793-811).-With potassium chromatle, solutions of narcotine salts, Eoth cold a ~ i d warm, give a precipitate of free narcotine. Papaverille in the cold gives a mixture of chromate and free alkaloid : but with heat free papaverine only. Narceine in cold saturated H. C. H. C. grams of quinoline. w. P. w.ORQANIC CHEXISTRY. 379 solution gives no precipitate, but if hot narceine chromate and free nnrcejine come down. Thebaine gives thebai'ne chromate. Codeine also gives the corresponding chromate, whilst morphine gives chromate and free morphine. With potassium dichromate, narcotine, papaverine and thebnhe give the corresponding dichromates, narceyne gives the dichromate and free alkaloid.Codeine in very dilute solution gives the dichro- mate ; stronger solutions afford precipitates which have not yet been examined. Morphine gives a dirty brown precipitate of variable composition. With potassium ferrocyanide, narcotine hydrochloride gives free alkalo'id or a mixture of variable composition ; the papaverine salt gives (C,H,,N04)4,H,Cfy ; the narcejine salt gives free alkaloid, the hydroferrocyanic acid becomes free ; the thebaine salt gives the com- pound (C19Hz1N0,),,H4Cfy ; the codei'ne salt solution (1 : 70) is not precipitated ; the morphine salt solution (1 - 60) is not precipitated. With potassium ferricyanide narceine gives the salt papaverine and thebai'ne give similar precipitates, narceke gives free alkalo'id, hydrogen ferricyanide also becomes free ; codeine in solution (1 : 70) gives no precipitate; morphine solution (1 : 60) becomes dark coloured and a brown deposit forms after long standing.J. T. Quinine Alkaloids. By 0. HESSE (Annnnlen, 243, 131-150).- Quinine tartrate crystallises with 2 mols. H20; it parts with one mol. H,O at 120", and the second at 140". A mixture of quinine and cinchonidine tartrates loses water more easily than quinine tar- trate, but if the mixtnre contains more than 33 per cent. of quinine tartrate, it cannot be thoroughly dried by exposure to a temperature of 120-130°. If ammonia is added to a solution of quinine disnl- phate containing not more than 10 per cent. of cinchonidine disul- phate, ether extracts from the mixture the compound C20H24N20z + 2C19H2,N20. This substance crystallises in rhombohedra, and is decomposed by boiling ether.On recry stallisation from hot dilute alcohol, crystals of the composition C20H2dN202 + 7ClgH,N20 are obtained. The compound C20H,rN202 + 2C1gHmN20 forms a normal sulphate crystallising with 18 rnols- H20, a normal tartrate containing 6 mols. H20, and zb normal chromate with 18 mols. H20. The estimation of quinine as chromate as proposed by de Vrij (Abstr., 1887, 404) is open to several objections (loc. cit.). The author confirms the existence of the compound of quinine and conchinine described by Wood and Barret (Chem. News, 45,6) and he succeeded in preparing a similar compound of quinine and hydro- conchinine, CmH2,NZO2,C,W,N2O2 + 2&H20. With cinchonidine and homocinchonidine, piperonylic acid forms salts crjstallising in needle-shaped crystals soluble in chloroform.The hydrocinchonidine salt is soluble in water and in chloroform. Quinine sulphate is converted into isoquifiine by solution in strong sulphuric acid. The new bassforms a normal sulphate which crystal- lises in small needles. It does not yield 8 precipitate with sodiurn380 ABSTRAOTS OF CHEMICAL PAPERS. tartrate. Locolecbicine is deposited from ether in needles. The sulphate, (C20HJT,02),H2SOa +- 8Ht0, is crystalline, and the platino- chloride, C,HHNgOz,HzPtC16 + 3Hz0, is amorphous. Isochacho&dine crystallises in colourless plates, freely soluble in ether and chloroform. It melts at 235". On evapo- ration, the ethereal solution leaves an amorphous residue which soon becomes crystalline, Isocinchonine is freely soluble in ether.Hydroconchinine yields a crystalline sulphonic acid, CzoH2,NZ02*SOaH + 3320. w. c, w. Optical Isomerides of Cinchonhe. By E. JLJNGFLEISGH and E. ~ G E R (Compt. rend., 105, 1255-1258). -Pure cinchonine dis- solved in four times its weight of a mixture of equal parts of water and sulphuric acid of sp. gr. 1-84, yields a colourless solution which boils at 120". After boiling for 48 hours, the liquid is amber-coloured, but does not become turbid on cooling. When diluted and made alkaline with sodium hydroxide, it yields an abundant curdy precipitate which soon changes t o a porous mass, and gradually hardens. This product contains neither cinchonine nor cinchonicine, but consids of six bases, four of these are isomerides of cinchonine, which form readily cry+ tallisable salts.Cinchmibine is insolable in ether, but crystallises from boiling alcohol in prismatic needles. It yields a succinate which forms Mky crystals slightly soluble in cold water. It is dextrogyrate, [a]= = +175*8", in an alcoholk solution of 0.75 per cent. Cinckonz&e is insoluble in ether, but crystallises from boiling alcohol in highly refractive needles. It is dedrogymte, [&ID = + 195.0°, in an alcsholic solution of 0.75 per cent The succinate crystallises in needles, and is very soluble. Cinchomigine is s o h ble in ether, from which it crystallises in prisms, and is lmvogyrate, [a]? = -60*1°, in an alcoholic solation of 1 per cent. It yields a distinctly crystalline hydrochloride slightly soluble in water.It is dextrogyrate, [a]= = -J- 53.2", in an alcoholic solution of 1 per cent. The hydrochloride forms large crystals which are very soluble ; the dihydriodide is insoluble. These four compounds increase the number of isomerides of the composition C,,H,N,O to seven. The other two bases are isomeric one with anohher, but belong to another group. They ,are products of oxidation produced with intermediate formation of a sulphonic derivative which is decomposed by water. a- Oxycinchonine, CleH&"O,, form prismatic needles insoluble in ether but soluble in dilute alcohol. I& is dextrogyrafe, [a]D = + 182.563 in an alcoholic solufion of 1 per cent. Its salts with the hydracids are only slightly soluble.P-Oxycincho&ne, CI9H,N2O2, is insoluble in ether, but dissolves in dilute alcohol, and crystallises in needles arranged in spherical groups. It is dextrogyrate, [ a ] D = + 187.14", in an alcoholic solution of 1 per cent. C i n c h n i l i n e is soluble in ether, and forms very balky crystals, Its salts with hydracids are very soluble. C. H. B.VEGETABLE PHTSIOLOGP AKD AGRICULTURE. 381 Cocaine. By A. EINHORN (Bey., 21, 47--51).-The ethereal salts of benzoylecgonine can be obtained by passing hydrogen chloride into its alcoholic solution ; the ethyl, propyl, and isobutyl salts were pre- pared in this way; they have already been described by Merck (Abstr., 1886, 163). Succinic acid is formed when anhydroecgonine or ecgonine is oxidised with potassium permanganate ; 10 grams of ecgonine hydro- chloride yield about 2.2 grams of succinic acid.Ecgonine hydro- chloride also gives succinic acid when it is boiled for some time with nitric acid ; from 2 grams of the salt, about 1 gram of succinic acid is obtained. The atomic complex, C*CH,*CH2*C, which is contained in succinic acid, must originate from the reduced pyridine-ring of the cocayne- derivative, and the formation of succinic acid shows that the side- chain is either in the a- or &position. Nitrogenous compounds are also formed in the oxidation of ecgoninc and anhydroecgonine. F. S. K. P h y s i o l o g i c a l C h e m i s t r y . Behaviour of Congo-red with Human Urine and with Acid Salts. By E. BRECKE (MoiLatsh. Chenz., 8, 632-637, compare Abstr., 1887, 986).-Human urine and a solution of ammonium acetate con- taining free acetic acid give similar tints with Congo-red.The addition of mapesium sulphate, however, in no way affects the colour of the former, whilst it causes the latter to darken rapidly with the formation of a brownish-black precipitate. The acid tartrates of ammonium and potassium give with Congo-red a beautiful violet colour. The author sees no reason to change the conclusion he draws from previous experiments with Congo-red, that human urine contains no free acid. G. T. M.ORGANIC CHENISTRY. 355Organic C h e m i s t r y .Constitution of Nitroethane. By G. GOTTIKG (Annulen, 243,104--131).--Hy the action of ethyl iodide on nitroethane andsodium ethoxide in sealed tubes at loo", a liquid of the compositionC,HiNO is produced.It boiis a t 166-176' and is freely soluble inalcohol and ether. At a higher temperature, it decomposes, yieldingpyridine and a resinous residue. Sodium iodide, sodium nitrite, andammonium iodide, are formed as bye-products when ethyl iodide actson sodium nitroethane. The nitrite and ammonium iodide areprobably formed by secondary reactions. The primary reaction maybe represented by t,he equation 9CzH,N0, + 6EtI + 6C2€3,*ONa =6C5HiN0 + 6CzH5*OH + 9H,O + 6NaI + 3NH,*OH.By substituting methyl, propyl and isobutyl iodides for ethyl iodidein the preceding experiment a series of homologous compounds isobtained having the composition-Boiling points.CJXjNO .............. 150-160"C,H,NO .............. 166-170CeHgNO.. ............175-178C7LTIINO.. ............ 182-185Each of the compounds is decomposed by distillation, yielding avolatile base. The formation of C,H7N0 and its homologues can bemore readily explained by Geuther's assumption that nitroethane isin reality acstamidoxide, CHs*CO*NH,O, than by V. Meyer's formulaCH,*CH,*NOZ. w. c. w356 ARSTRACTS OF CHEMICAL PAPERS.Preparation of Hydrosulphides and Sulphides of Methyland Ethyl. By P. KLASON (Ber., 20, 3407-3413).-Methylhydrogen sulphide is prepared by diluting with ice a cold mixture of750 C.C. of sulphuric, acid and 500 C.C. of absolute methyl alcohol, andadding the mhole to a solntion of 2.75 kilos. of crystallised sodiumcarbonate. The solution is concent,rated to such an extent that mostof the sodiiim sulphate separates.The mother-liquor is then concen-trated, mixed with a Rolution of 500 grams of potash in 1 litre ofwater, previously saturated with hydrogen sulphide, and heated on awater-bath. The gases evolved are passed first through a strongaqueous solution of 50 grams of potash, and then into a solution of350 grams of potash in 700 C.C. of water. The small amount ofhydrogen sulphide contained in the latter solution is precipitatedwith lead acetate, and the ethyl hydrogen sulphide liberated by theaddition of hydrochloric acid. It is dried wibh potash aud distilled.500 C.C. of alcohol yielded about 200 grams of methyl hydrogen sul-phide, and 40 gyams of methyl sulphide. It is a thin, colourless,refractive liquid, having a very repulsive odour ; it boils at 5.8" under752 mm.pressure, and yields a crystalline hydrate a-ith water (com-pare Gregory, A n d e n , 15, 239 ; and Obermeyer, this vol., p. 124).Mercury methyl mercaptide, Ilg(SMe),, is best prepared by passingmethyl hydrogen sulphide through an aqueous solution of mercurycyanide; it is almost insoluble, and melts at 175". The lend conz-pound, Pb(SMe),, forms microscopic, crystalline plates ; it is decom-posed by exposure to air o r light. The bismuth compound, Bi(SMe)B,crystallises in yellow, microscopic needles ; the silver compound formsa yellow, crystalline precipitate.Ethyl hFdrogen sulphide is prepared similarly to the methyl com-pound, using 1 litre of absolute alcohol, 500 C.C. of sulplruric acid,4 kilos. of sodium carbonate, and 800 grams of potash.Copper ethyEmereaptide, CuSEt, uot Cu(SEt),, is readily obtained when the mixedsolutions of copper sulphate and sodium acetate are treated withethyl hydrogen sulphide, and forms a pale yellow, amorphous powder.It was previously stated (J.pr. Chem. [2], 15) that zinc and cadmiummercaptides are not decomposed by hydrochloric acid ; later experi-ments show that all mercaptidea with a positive metal are decomposedby hydrochloric acid.Methyl sulphide is prepared by distilling a concentrated solution ofmethyl sodium sulphate (from + litre of absolute methyl alcohol)with an aqueous solution of 500 grams of potash, previously halfsaturated with hydrogen sulphide. It boilsat 37.2" under 758 mm.pressure. Ethyl sulphide may be prepared in%I similar manner, and boils at 91.9". Methyl ethyl sulphide is pre-pared by distilling a solution of methyl hydrogen sulphide (from250 C.C. of alcohol) in potash with sodium ethyl sulphate (from550 C.C. of alcohol) ; it boils at 66.9".By P. 'KLASON (Ber., 20, 3413-3415). -When methyl hydrogen sulphide is passed into 100 grams of sulphurchloride, (S2C1,), a product is obtained free from chlorine, probablyconsisting of methyl tetrasulphide, methyl trisulpbide, and sulphur.The yield is 150 grams.The yield was 160 grams.N. H. &I.Alkyl PolysulphidesORGANG CHEMISTRY. 357When distilled in a vacuum, methyl trisulphide passes over, and sul-phur remains. Methyl trisulphide (Cabours, Annalen, 61, 92) is apale-yellow oil of a very disagreeable odour, boiling at 170" with slightdecomposition. In a vacuum, it distils a t 62".Sp. gr. = 1.2162at 0" ; 1.2059 at 10" ; and 1.119 at 17" (compared with water at O O ) .Paratolyl hydrogen sulphide reacts with sulphur chloride, yieldingOtto's paratolyl tetrasulphide (Abstr., 1887, 954).Sulphines and the Valency of Sulphur. By H. KLINGER andA. MAASEN (AnnaZen, 243, 193-218) .-The authors have repeatedKriiger's experiments (this Journal, 1877, i, 186) on isomeric sulphinecompounds, and they prove that the diethylmethylsulphine iodide,prepared by the action of methgl iodide on diethyl sulphide, is iden-tical with the product of the action of ethyl iodide on methyl ethylsulphide.This is shown by an exa.mination of the platino-, auro-,and mercnro-chlorides, and also of the cadmio-iodide.Dirnethylef7LyZsu~hine iodide, SMe,Etl, is formed n o t only by theaction of methyl iodide on ethyl methyl snlphide, but also by theaction of methyl sulphide on ethyl iodide. It is a hygroscopic, crys-talline substance, soluble in alcohol, and is precipitated from thealcoholic solution by ether. It melts at 108-110". The cadmio-iodides, 2SMe,EtI,CdI,, melting with slight decomposition at 179",and SMe,EtT,CdI,, melting a t 98-99', were prepared. The merczcro-chlorides, SMe2EtCl,ZHgC1, and SMeEt,CI,GHgCI,, melt a t 118" and200" respectively. The platiriochloride, 2C4H11SCl,PtC14, forms orange-red crystals belonging to the regular system.It is insoluble inalcohol and ether. The aurochloride, C*HIISCl,AuCI,, forms minute,r-sv,qt.a.Lq m J j i r g at 240-244'.As the supposed existence of Kriiger's isomeric sulphines formsthe sole argument in favour of the view that the four affinities of thesulphur-atom are of dissimilar nature, the author's results show thatthere is no longer any experimental evidence in support of thisBy E. FROMM (Bet-., 21,185-188).-When brom-ethylidenediethylsulphone (Abstr., 1881, 123) is heated with aqueouspotash, it is converted into ethylidenediethylsulphone ; the yield,however, does not amount to that theoretically possible, and inas-much as sulphuric acid is one of the products of the reaction, it isprobable that hydroxyethylidene disulphone is formed.but acting asan oxidising agent is itself reduced to ethylideriedisulphone.When ethylidenediethylsulphone, which melts a t 75-78" and notat 60°, as stated by Escales and Baumann (ibid.), is dissolved inanhydrous ether or benzene, and treated with sodium, hydrogen isevolved and a compound obtained which could not be purified;diethylsulphonedimethylmethane (Baumann, ibid.) is, however, ob-tained if mehhyl iodide is added to the solution before treatment withsodium. A like reaction occurs when an alcoholic solution of the di-sulphone is boiled with methyl iodide and alcoholic potash. Diethyl-s ul phon edimethyl m e thane when treated in benzene solution withN. H. M.hypo thesis. w. c. w.Disulphones.sodium does not evolve hydrogen. w P.w358 ABSTRACTS O F CHEMICAL PAPJClP.Synthetical Experiments in the Sugar-group. By E. PISCHERand J. TAFEL (Bey., 20, 3384-3390; compare this vol., p. %).-Glycerosazone (Abstr., 1887, 651) is prepared by adding 15 parts ofbromine to a solution of 10 park of glycerol and 35 parts of crystallisedsodium carbonate in 60 parts of water a t 10'. 900 grams of glycerolcan be used in one operation. The solution is treated with 5 parts ofpbenylhydrazine hydrochloride. In five t80 eight days, the gl yceros-azone separates as a yellow, crystalline precipitate. The yield is 20per cent. of the weight of glycerol.When the oxidised glycerol is treated with aqueous soda, so thatthe amount of free alkali amounts to 1 per cent,., and is kept for fourto five days, the liquid loses the power of reducing alkaline coppersolution in the cold ; when warmed, it still has the power of reducingcopper solutions. The solution is neutralised with acetic acid, andheated with phenylhydrazine hydrochloride and sodium acetate forsix to eight hours.The product contains two osazones, C1,H,,N,O,.The one has all the properties previously ascribed to a-acrosasone(from acrylaldehyde bromide) ; it crystallises from alcohol in pureyellow, well-formed needles, which melt a t 217" with decomposition.The other osazone is more readily soluble in ethyl acetate, from whichi t crystallises in globular groups of slender needles melting at 158-159"; it is probably identical with p-acrosazone. This method forpreparing the acrosazones is more convenient than that previouslydescribed.When a solution of 5 grams of dulcitol and 12 grams of sodium car-bonate in 40 C.C.of water is treated with 5 grams of bromine, andthe whole, half an hour afterwards, is warmed with 5 grams of phenyl-hydrazine and 5 grams of sodium acetate, the osazone, C18H22N404,separates in yellow flakes. This closely resembles galactosazone(Abstr., 1887, 562) except that it melts at 205-206" with decompo-sition. The name phenyldubitosazom is ascribed to the new compound.Condensation of Formaldehyde. By 0. LOEW (Bey., 21, 270-275) .-The condensation of formaldehyde (Abstr., 1886, 609) is mostreadily effected by the action of strong bases, although it can bebrought about by salts having an alkaline reaction, such as potassiumsulphite or carbonate ; salts having a neutral reaction are, however,without action on the aldehyde.Comparative experiments a t 100"with aqueous solutions of lime and baryta containing equimolecularproportions of the two bases showed thet the former rapidly acted onthe aldehyde (15 per cent. solution) with the formation of formose aschief product, whilst the action of the latter resulted in the produc-tion of formic acid, much aldehyde remaining unaltered owing to theconsequent neutralisation of the base. The production of formose bythe action of lime-water is accelerated by the addition of sodiumchloride, which itself does not bring about the condensation of thealdehyde, but is retarded by the presence of sodium acetate, potassiumnitrate, and of much copper, iron, or tin.Calcined magnesia doesnot react with formaldehyde either i n the cold or a t loo", but anaqueous solution of the hydroxide converts it into formose at 100".Litharge and many lead salts also effect the condensation of theN. H. MORGANIC CHESIISTRT. 359aldehyde, and metallic lead act's in like manner ; it is probable, how-ever, that in this case the action is due to the presence of traces ofthe oxide, since the amount of the latter dissolved by shaking lithargewith distilled water for some hours, adding 0.1 per cent. of thealdehyde, filtering and heating at 100" for two hours, suRced to formformose. Iron, tetrethylammonium hydroxide, and many organicbases, also bring about the condensation.When the osazone (m.p. = 123') obtained from the sugar formedby heating a 0.5 per cent. solution of formaldehyde with tin for 15hours (ibid., 864) is heated in alcoholic solut'ion at 100" for 25 to 30hours, the melting point is found t o have risen to 14S0, at which itremains constant. A sugar, P-formose, which directly yields anosazone, C18H22N403, crystallising in small, yellow needles melting at148", is formed when a 0.1 per cent. solution of formaldehyde isheated for five hours with much tin. I t is a thick, sweet, non-fer-mentable syrup, does not become brown at loo", yields humous sub-stances with hydrochloric acid, arid its solution in alcoholic hydrogenchloride yields a wine-red colour with resorcinol, and a st'eel-bluecolour with diphenylamine. 100 C.C.of Fehling's solution are reducedby 0.073 gram of the sugar.If formaldehyde is added to an aqueous solution of magnesiumhydroxide, prepared by treating a 5 to 10 per cent. solution of mag-nesium sulphate with litharge, until the mixture contains 0.3 percent. of the aldehyde, and the whole is digested at 100" for manyhours, a mixture of at least two non-fermentable sugars is obtained,one of which yields an osaxoite crystallising from benzene in yellowSolubility of Calcium and Barium Formates, Acetates, andPropionates. By E. v. KRASNICKI (Monatsh., 8, 595-606).-Thesolubilities of the different salts were determined by Raupenstrauch'smethod. The formulae deduced from these determinations are givenbelow :-needles melting at 152".w. P. w.Calcium formate, X = 16.2478 + 0*03229(t - 0%) -Barium formate, S = 27.7744 + 0*0236743(t - 1) +Calcium acetate, S = 37.8512 - 0*2575(t - 1) +Barium acetate, S = 58.473 + 0*65067(t - 0%) -Calcium propionate, S = 41.2986 - 0*1118G(t - 0.2) +Barium propionate, S = 48.2071 + 0*371205(t - 0.6) -The solubilities of the isobutyrates, isovalerates, and methylethyl-OS0001254(t - 0.8)20*0063622(t - l)z - 0.000060122(t - 1)30.0058845(t - l)z - 0*0000475576(t - 1)30*005431(t - 0.8)'0*000085065(t - 0.2)' + 04000117907(t - O.2)90.0015587 ( t - 0*6)2.acetates, have been given by Sedlitzky (this vol., p. 250).A. J. G360 ABSTRACTS OF CHEMICAL PAPERS.Temperature of Conversion of Copper Calcium Acetate.By L.T. REICHER (Zeit.physikaZ. Chem., 1, 221--226).-That there isa temperature at which the crystals of this salt are converted intocrystals of copper acetate and calcium acetate, is already renderedprobable by the experiments of Kopp and Schuchardt. Microscopicalexamination confirms this supposition, for on heating the double saltup to about 80°, it separates into colourless needles of calciumacetate and green rhombic crystals of copper acetate. To determinethe temperature of conversion exactly, a dilatometer was employed.The dilatometer was filled with the powdered double salt, exhaustedand filled with mercury, and the change of volume at a given tempe-rature was observed. It was found that the temperature of conver-sion lies between 78" and 76.2".c. s.Preparation of p-Iodopropionic Acid. By V. NEYER (Ber., 21,24--25).-The author describes in detail various modifications of themethod previously given for the preparation of P-iodopropionic acid(Abstr., 1887, 232). I?. S. K.Analogy between Ketonic Acids and the Alkyl Sulphones ofthe Fatty Acids. By R. OTTO (Bey., 21, 8!)-99).-The largerportion of this paper deals wit,h the points of analogy between t h eketonic acids and the alkyl sulphones of the fatty acids./3-Phen?/Zsu7phonep-opionic acid, S02Ph*CH2*CH2*COOH, is preparedby neutralising p-iodopropionic acid and benzenesulphinic acid withsodium carbonate, and heating the product until no more water isgiven off. It forms shining, monosymmetrical or asymmetrical plates,is sparingly soluble in cold water, somewhat more soluble in ether,and melts a t 123-124".The alkali salts are described. The ethylsalt is a thick oil of a yellow colour, readily soluble in alcohol andether, insoluble in water. The free acid is very stable ; i t does notreact with the halogens, is not attacked by potash a t 180°, but istotally decomposed a t 280" ; it is speedily reduced by sodium amalgam,the group PhSOz yielding a sulphinate. J. W. L.Isodibrornosuccinic Acid. By R. DEMUTH and V. MEYER(Ber., 21, 264--270).-A repetition of Reilstein and Wiegand's expe-riments ou isodibromosuccinic acid (Abstr., 1882, 1051) shows thatbromofumaric acid and not pyrnvic acid is formed with the evolutionof some carbonic anhydride when the barium salt is treated withmoist silver oxide in the dark.Bromofurnaric acid is also formedwhen the acid is heated with water for 10 hours in a reflux appa-ratus (Kekul6, AnnuZen, Suppl. 2, go), and racemic acid is obtainedwhen the silver salt of the acid is boiled with water. Hence the un-symmetrical formula COOH*CH2-CBr,-COOH can no longer be ascribedto this acid. Attempts to prepare an acid of this formula by theoxidation of ma-dibromobutyric acid, EtCBr,-COOH, by displacingthe oxygen of the carbonyl-group in acetoxalic acid by bromine, andby treating ethyl sodiomnlonate with ethyl tribromacetate and saponi-fying the product led t o no result, the crystalline compound formeORQANIC CHEMISTRY. 361in the last experiment being free from bromine, whilst ethyl tricar-bintetracarboxylate, when treated with 1 mol.of bromine at 140"(compare Abetr., 1883, 46), yields a compound which on hydrolysiswith concentrated hydrobromic acid yields carbonic anhydride and acrystalline compound free from bromine, and not symmetrical dibro-mosuccinic acid. w. P. w.Ethyl Oxalacetate. By W. WISLICENUS (Ber., 20, 5392-3394 ;mmpare Abstr., 1887, 234) .-Ethyl oxalacetate is prepared by shakinga solution of ethyl oxalate in four parts of ether with sodiumethoxide, previously freed from alcohol by heating in a current ofhydrogen at 200". The product is treated with ethyl acetate whenthe sodium compound separates; the yield is 70 per cent. of thetheoretical. Ethyl oxalacetate boils at 131-132" under 24 mm.pressure, and reacts with ammonia and with aniline, yielding crystal-line compounds. The phenylhydrazine-deriuative, Cl1H1,N2Oa, crystal-ljses in plates melting at 76-78".When an alcoholic solution of theethyl salt is treated with carbamide, the compound C9H,,N205 + EtOHseparates in colourless crystals. The hydroxy lumirte-derivalive is a noil. Nitrous acid reacts with ethyl oxalacetate in the cold, with for-mation of a crystalline isonitroso-derivative.Ethyl Methgloxalacetate. By W. WISLICENUS and E. ARNOLD(Ber., 20, 3394--3396).-EthyZ methyEoxalacetate, C9H1305Na, is pre-pared by the action of sodium ethoxide and ethyl propionate onethyl oxalate dissolved in ether. It forms a colourless oil, boiling at137-138" under 23 mm. pressure, insoluble in water, readily solublein alcohol, ether, and alkali ; the alcoholic solution gives an intensered coloration with ferric chloride.When boiled with alcoholicpotash, it is converted into oxalic and propionic acids. Boilingdilute sulphuric acid decomposes it with formation of propionyl-formic acid (Claisen and Moritz, Trans., 1880, 691). The phenyl-hy draxine-derivutiue of propion ylformic acid, CH,Me*C ( N2HP h).C 0 OH,crystallises from dilute aloohol in plates melting at 144-145" ; whenwarmed with sulphuric acid and alcohol, and precipitated withwater, scatolecarboxylic acid, CsH4< NH >C*COOH, is obtained ; thismelts at 164-165", decomposing into scatole and carbonic anhydride,and differs from Salkowski's compound (Abstr., 1885, 568) i n itscrystalline form and in being mme sparingly soluble.N.H. M.CMeN. H. M.Cryoscopic Studies on Racemic Acids and Racematee. ByF. M. RAOULT (Zeit.physdkaZ. Chem. 1, 186--189).-1n the case of solu-tions contlaizling not more than 5 per cent. of acid, observation showsthat equal quantities of dextrotartaric acid and racemic acid producethe same lowering of the freezing point, and it is inferred that theracemic acid is completely decomposed. For solutions of greater con-centration, this will not be the case; part only will be decomposed.The fall of temperature produced by each unit of mass of this partwill be known by observation. For the other, the fall caused by eachVOL. LIT. 2 362 ABSTRACTS OF CHEMICAL PAPERS.unit may be calculated from the law that the molecular fall of thefreezing point is equal to 19 for all organic acids. The actual fall oftemperature caused by the whole amount of racemic acid can be ob-served, and a simple equation will then give the amount of racemicacid decomposed.Thus i t was found that out of 14.229 grams ofracemic acid dissolved in 100 grams of water, 0,880 gram remainedundecomposed.In the case of the compounds, C,H,O,(NH,>Na + 4H20 and2[C4H4O6(NH4)Na + H20j, the fall of temperature is the same forOrganic Fluorine Compounds. Bey 0. WALLACH and F.HEUSLER (Annalen, 243, 219--244).-In the preparation of fluor-benzene (Abstr., 1887, 130), phenol and diphenyl ether, Ph20, areobtained as bye-products. Fluorbenzene can be obtained as a,crystalline mass by exposure to the temperature produced by etherand solid carbonic anhydride.The index of refraction forFrauenhofer's line C is 1.4635 ; A0 = 0.00017. Parq5horonitrobenxenemelts a t 26.5". PuraJlzcoraniline can be solidified by means of solidcarbonic anhydride. The acetyl-derivative, CcH4F-NHAc, me1 ts at1 50-151". F~uorbenzeneparadiazcrpirperidide, CsHaF*Nz*C,H,,, is anunstable crystalline substance. Parad$luorobenzene, C&JFz, is liquidat the ordinary temperature. Its sp. gr. is about 1.11, and it boilsbetween 57" and 89".ParuJluorochZorobenzene, C6HdFC!, prepared from parafluoranilineby means of Sandmeyer's method, boils at 130-131". Its sp. gr. a t15" is 1.226. Para$uorobromobenzene melts between -15" and - 20",and boils at 152-153".Sp. gr. 1.593 at 15". ParaJluoriodobenzeneis prepared by the action of hydriodic acid on fresh1.y prepared purefluorbenzenediaaopiperidide. It boils a t 18%-184", and is decomposedby strong nitric acid, yielding iodine and fluornitrobenzene. Para-fluorphenol boils a t 186-188".Pseudocumenediazopiperidide. c6~zMe3*752*c,NH,,,, is deposited fromalcohol in thick prisms and melts at 50". It is decomposed by hydro-fluoric acid, yielding Jluoropseudocunzene, C6HOMe3E', which melts at27" and boils a t 174-175". Chloropseudocurnene melts a t 70-71"and boils a t 213-215". The bromo-derivative melts a t 72" and boilsa t 233-235'. Iodopseudocumene melts a t 37" and boils at 256-258".Psendocumenol melts a t 71" and boils a t 234-235".DiJluorodiphenyl,Ci2HBFZr is crystalline, and dissolves freely in alcohol and ether. It meltsat 88-69" and boils a t 256255". Although Sandmeyer's method ofconverting amido-compounds into chloro- and bromo-substitution pro-ducts yields admirable results, it is not to be recommended in thecase of fluorides ; the decomposition of diazoamido-compounds byhydrofluoric acid almost inrariably yields better results in the latterca8e.A comparison of the boiling points and specific gravity of the pre-ceding compounds shows that (1) the substitution of hydrogen byfluorine increases the specific gravity, and has very slight influenceon the boiling point ; (2) the difference in boiling point between cor-responding iodine and bromine substitution products, and betweensolutions of the same strength up to about 13 per cent.c. sORGANIC CHEMISTRY. 363bromine- and chlorine-derivatives is much smaller than the differencebetween chlorine and fluorine substitution products. T b anthorsconclude that the boiling point of liquid fluorine is much lower thanthat of chlorine, and that it is probably near the boiling point ofhydrogen.Numerous experiments show that fluorine unites more- firmly withcarbon than chlorine, bromine, or iodine do. w. c. w.Dichro'ins. By H. BRUNNER and P. CHUIT (Ber., 21, 249-236).-Further experiments have confirmed the view put forward by Brunnerand Eramer (Abstr., 1884, 1354) thaat compounds andogous toLiebermann's colouring matters (this Journal, 1874, 693) are formedonly from paranitrosophenol and those polyhydric phenols in whichtwo hydroxyl-groups are in the meta-position relatively to one another.These compounds are now termed dz'chrozm from their fluorescent anddichroic properties, and are divided into two p u p s termed a- and/iI-dichroins respectively.The a-dichroins contain the group C6N( 0-C,),,and comprise the colouring matters, CleHI5NO3, derived from phenol(Abstia., 2884, 1341), ClsH15N06 and C,,H&,Ol0 from resorcinol(Abstr., 1885, 525), and C,,H,,NO, from orcinol (ibid.) ; whilst thep-dichro'ins contain the group (36.N< O>C, and comprise the colour-ing matter, ClIHlINO3, derived from orcinol (&id.), together with azo-resorcinol, azoresorufin (Abstr., 1884, 1333), and nzoresorufyl ether,C4s€€mN4013 (Bw., 18, 586), the last three compounds being termed/3-resoreinol-, di-p-resorcinol-, and tetra-/3-resorcinol-dichroyn respec-tively.In the majority of reactions by which dichroi'ns are formed,other colouring matters are also obtained differing from them in con-taining more oxygen and being destitute of fluarescence ; these aretermed oxychro'ius.Acetyl-o,-yhe~oldichroi'n, OAc*C&K,*NO(OPh)2., prepared by heatinga-phenoldichrojin (1 part) with acetic anhydride (3 parts) and an-hydrous sodium acetate (2 parts) at 140" for an hour, is a brown,amorphous mass soluble in ether, alcohol, &c. AcetyZphenoZoxychroin,OAc.C6H4.x( OPh),, was also prepared.OrcinoZdichrozn has the formula C6H2( OH),Me*N( O*C6H3Me.0H), ;its acetyl-derivative, C2,Hl,( OAc)4NOB, is a brown, amorphous masssoluble in ether, alcohol, &c.T h y moZdichrozn was prepared by Liebermann's method (this Journal,1875, 167), and when freed from unattacked thymol has the composi-tion O[N(C6H2MePr.OH),],.It sublimes at 140" with partial de-composition forming violet-coloured vapours, and is a dark-violet,amorphous mass, soliible in alcohol, ether, chloroform, and benzeneyielding red solutions showing pale-green fluorescence. The acetyl-derivative, Cm€€48( OAc)~N~O~, is a brown, amorphous mass, Bolnble inalcohol, ether, &c. In the purification of thymoldichro'in by steam dis-tillation, thymoquinone passes over with the steam. Experimentsshow, however, that it is not a decomposition-prodnct of thymoldichroiri,and to explain its formation the authors point out that nitrosothymol,unlike nitroso-phenol, -resorcinol, and -orcinol, seems to act as aquinoneoxime in the formation of its dichroin, and regard it as probable02 b 364 ABSTRACTS OF CHEMICAL PAPERS.that in addition to this reaction a second also occurs in which a portionof the thymol reacts with thymoquinoneoxime to form amidothymoland thymoquinone (compare Sutkowski, Abstr., 1887, 41).w. P. w.Formation of Secondary Aromatio Amines. By A. PICTET(Bey., 20, 3422-3424) .-Ethglacetanilide is prepared by adding 75grams of finely-powdered acetanilide to a cold solution of 31 grams ofoaustic potash in 300 grams of 95 per cent. alcohol ; after a shorttime the flask containing the mixture is fitted with a reflux condenser,65 grams of ethyl bromide is added, and the whole slightly warmedon a water-bafh.When the reaction becomes less violent, the mix-ture is heated for one to two hours, allowed t o become cool, and filtered.The advantages of this method over Hepp's (Ber., 10, 327) are thatit does not involve the use of large amounts of sodium, and that theproduct is more easily purified. The yield of ethylaniline (41 percent. of the theoretical) is, however, not so good as that obtained byHepp's method. In She case of formanilide, the yield is almosttheoretical. N. H. M.Action of Sulphur on Dimethylaniline and Methylaniline.By R. M~~HLAU and C. W. KROHN (Ber., 21, 59--67).-Wheii di-methylaniline is boiled with sulphui- for 12 hours and distilled, an oilboiling at 210-345" is obtained.When this is treated with hydro-chloric acid, it is separated into an oil of indifferent character whichsoon solidifies, and a mixture of several basic compounds. From thelatter, Hofmann's methenylarnidophenyl mercaptan (Abstr., 1887,823,1039), aniline, and methylaniline were separated. The indifferent) crystalline substance has the formula C,H,NS2 (P N/ C6HdLCN\CH,-SS/ 'melts at 88-89", and boils above 360". When boiled with sulphur, itis converted into methenylaniidophenyl mercaptan, and seems there-fore t o be the primary product. When treated with nitric acid. thecompound C,HTNS, is changed into the base CeH,NS, probablyBy the action of sulphur on methylmiline, the same compounds areobtained.The authors think that at first 8 deoomposition of 2 mols.of methylaniline into dimethylaniline and aniline must have &kenplace, the dimethylaniline so formed then redcfing with sulphur t18described above. J. W. L.Action of Thiocarbonyl Chloride on Secondary Amines.By 0. BILLETER and A. STROHL (Bey., 21,108-110).-~~~~y~7~~yI-thiocarbumine chloride, CSC1-NPliPr, crystallises from light pehroleurnin thick, colourless prisms melting at 36". It is more stable in dampair than the corresponding methyl and ethyl compounds. D@opyZ-thiocarbadide, CS(NPhPr),, forms colourless plates melting at103.5". Meihylpmp y 1 thwcarbami lide, NPhMe-C S-NPhPr, preparedeither from methyl chloride and propylnniline or from propyl chlo-ride and methylaniline, forms colourless prisms melting at 56*50ORGANIC (IHEMISTRF.365E~hyl~ro~ylfhiocczrbanilide, NPhPr*CS-NPhEt, is prepared like thelast-named compound and melts at 66.3". All these derivatives dis-solve easily in concentrated acetic, hydrochloric, and sulphuric acidswithout change, whereas by warming with concentrated sulphurioacid or heating at 1.50" with hydrochloric acid the secondary base isreadily eliminated.Alcohols and phenols, the corresponding sulphur compoande, andalso their metallic salts, react readily with the tfriocarbamine chlo-rides already described, with formation of the corresponding thio-and dithio-earbamic noids. Of thie series, the following were pre-pared :-EthyE ethylphenyIthiocarbamTate, NEtPh*CS*OEt, prepared byt h s action of ethyl phenylcarbamine chloride on sodium ethoxicie inethereal solution, distils at 143%" under a pressure of 12 mm.Sp. gr.1.066 a t 15". Jt solidifies by prolonged cooling to a colourless, crys-talline mass which melts at 18". Pheny I et~?l~henlllthiocarbamnte,NEtPh*CS*OPh, forms colourless needles and melts at 69.2". Pheuylethylphenyldif7b.iocarbamate, NPhEWSSPh, crjstallises in compact,colourless needles, and melts at 127.8". E t h y l efkylphenyldithiocar6-amate melts at 66.4". A trisubstituted thiocarbamide is formed bythe action of ethyl phenylthiocarbamine chloride, aniline, $e., andcan be isolated bj- stopping the reaction after the mass first solidifies.It is decomposed if the reaction proceeds too far into thiocarbanilideand aniline hydrochloride.A small quantity of a dithiobiuret is alsofoi-med. The dithiobiurets are readily obtained by the further actionof thiocarbarnine chloride on the tertiary carbarnides first formed.Di,neEhylt~~henyId~ithiobizL.~et, C2S2N3Ph3Me2, prepared from methyl-phenylt hiocarbamine chloride and methylthiocarbanilide, forms yellowneedles melting at 202.5". It is sparingly soluble in alcohol andether, readily so in cbloroform.Diethyltripheny Idithiobiwet, C2S2W3Ph3Et2, prepared from ethyl-phenylthiocarbamine chloride and et hylthiocarbanilide, cPystallises inlemon-yellow needles melting at 158". It is more readily soluble thanthe methyl oompound.Methy let h y 1 trip heny ldithio biuret, ( a), NE t Ph.C (NP h) S C S-NMeP h,prepared from methylphenylcarbamine chloride and ethylthiocarh-anilide, forms small, pale yellow needles melting a t 157.5". It issoluble in chloroform, sparingly soluble in alcohol and ether. (b.)N Me Fh*C (NPh) *S .C S-NEtPh, .prepared from e thy 1 ph enylcarbamineohloride and methylthiocarbanilide, forms small, light-yellow needleslike those of the ( a ) compound, and melts at 156.5'.Dipropy 1 trip hen y ldit hiobiuret, C2S2N3Pr2 Ph3, prepared from propyl-phenglcarbamine chloride and propylthiocarbanilide, forms shining,yellow needles melting at 153.7".Iti.iphelzyldithiobiuret, C2S2N3MePrPh (a), preparedcrystallises in shining yellow pyramids, melting point 110"; ( b ) pre-pared from propylphenylcarbamine chloride and methylthiocarbani-lide, forms yellow pyramids similar to the (a)-derivative, and meltsE thy lprop y 1 triph en y 1 dit hio biuret, C2S2N3E t PrP hS, (a) prepared fromethplphenylthiocarbaruine chloride and propy lthiocarbanilide, crystal-It is soluble in chloroform.from Meth methy yl'pro? phenylcarbamine chloride and propylthiocarbanilide,at 111"366 ABSTRACTS OF CIHEMICAL PAPERS.lises in pale yellow needles melting at 165.8".Very sparinglyqolublein alcohol ; ( b ) prepared from propylphenyltl-iiocarbamine chlorideand ethyl thiocarbanilide, crystallises in yellow needles melting at165'.Pr~lIZthiocarbaniZide, CSN,H.Pr-Ph,, prepared from propylanilineand phenyl isothiocyanate, consists of colourless, shining needleswhich melt at 104.8O..I t is readily soluble in alcohol, and is decom-posed by hydrochloric acid info its components.Constitution of Mixed Azo-compounds. By V. MEYER (Ber.,21, ll-l8).-The author had independently arrived at views on theconstitution of the mixed azo-compounds identical with those broughtforward by Japp and Klingemann (Proc., 1887, 140).Compounds of Phenylhydrazine with Ketone Alcohols. ByH. LAUBMANW (Annalen, 243, 244--248).-BenzoyZcarbinolphenyl-hydrazone, N,HPh : CPh*CH,*OH, crystallises in needles, melts at 112",and dissolves freely in alcohol and ether. It is converted into anainorphous product, probably hydroxyphenylindole, by the action ofzinc chloride at 150". The hydrazone is converted into the osazone,N,HPh : CPh*CH : N,HPh, by treatment with phenylhydrazine andsodium acetate in alcoholic solution.The osaxone melts at 152" andis soluble in ether, benzene, and in hot alcohol.The oscczone of acetol is identical with the product v. Pechmnnn(Abstr., 1887, 1103) obtained by the action of phenylhydrazine onnihrosoacetone. w. c. w.J. W. L.Action of Phenylhydrazine on Dioximes. By M. POLOKOWSKY(Ber., 21, 182-184) .-When glyoxime in alcoholic solution is treatedwith an equimolecular proportion of phenylhydrazine, an additivecompound, < ~~~~~~] >NH,*N HPh, is obtained. This crystallisesfrom alcohol in white scales, melts at 110", and is readily soluble inalcohol, less so in ether, and insoluble in water. Concentratedaqueous soda dissolves it, and the solution when heated yields phenyl-hydrazine ; a like decomposition is also produced by concentratedsu lphuric acid.Under similar conditions diphenylglyoxime yields an additive com-pound, C20H20N402, which crystallises in needles, melts at 149-150",and closely resembles the preceding derivative in its properties.P-Naphthaquinonedioxime, in like manner, forms an additive com-pound, C,H,sN402.This crystallises from alcohol in tufts of longAldines and Amidoacetophenone. By E. BRATTN and V. MEYER(Her., 21, 19--21).-When isonitrosoacetophenonc is reduced inhydrochloric acid solution, it is completely transformed into thehydrochloride of an amidoacetophenone, COPh*CH,.NH,. This saltcrystallises from water in large, hard, colourless crystals, and is verystable ; it caa be recrystallised from hot water, and forms a crystal-line platinochloride. The freshly precipitated base redissolves in acids,needles, begins to fase at 105", and melts at 138".w. P. wORGANIC CHEMISTRY. 367but when purified by mashing or recrystallising from alcohol, itbecomes orange-coloured, and completely loses its basic properties,being converted into a coloured crystalline substance, which resemblesisoindole very closely, and with which it is probably identical. A/CPh CPh\N, is readily obtained from the monoxime\CPh CPh/ketine, Nof benzil. F. S. K.Formation of Phenylhydrazile Acids from the Anhydrides ofBibasic Acids. By R. ANSCH~~TZ (Ber., 21, 88-89).-By theaction of phenyl hydrazine on the chloroform or ethereal solutions ofthe bibasic anhydrides, the corresponding phenylhydrazile acids areobtained. The following anhydrides react in this way: male'ic, SUC-cinic, citraconic, itaconic, camphoric, phthalic, diphenylmale'ic, phthalic,diphenylmale'ic, and diphenylsuccinic (compare Hotte, Abstr., 1887,669).J. W. L.Formation of Orthosulphaminecarboxylie Acids. By C.FAHLBERG and R. LIST (Ber., 21, 242--'248).-The products of theoxidation of orthotoluenesulphonamide under different conditionswere examined, and the results show that when the oxidation iscarried on in alkaline solutions by potassium ferricyanide (Abstr.,1886, S04), by potassium manganate, and by potassium perman-ganate, orthosulphaminebenzoic acid is formed ; that when it is carriedon in neutral solutions by permanganate, benzoic sulphinide is thechief product, a small quantity of orthosulphaminebenzoic acid beingalso formed, probably by the action of the alkali produced by thedecomposition of the permanganate, since the yield was much dimi-nished by adding acid from time to time to neutralise the alkaliformed ; and that when i t is carried on by permanganate in solutionsrendered acid either by hydrochloric acid, or by a current of carbonicanhydride, orthmulphobenzoic acid and potassium nitrate are formed.Benzoic sulphinide is to be regarded as .the primary product of theoxidation, since on evaporation with hydrochloric acid it is convertedinto orthnsulphobenzoic acid and ammonia, and on evaporation withpotassium hydroxide into orthosulphaminebenzoic acid.Ammonia,alkaline carbonates, and the oxides of the alkaline earths cannot beemployed for this purpose; moreover, in the case of barium oxide, thebarium salt of the sulphinide is obtained (compare this vol., p. 282).Orthoparad~isulphnminebenzoic acid, [ COOH : SO,NH, : S0,NH2 =1 : B : 41, is obtained either by oxidising orthoparatoluenedisulphon-rtmide with alkaline potassium manganate, or by evaporatingsulphaminebenzoic sulphinide with potassium hydroxide. It crystal-lises in slender, satiny, microscopic needles, melts at 182-183", iscompletely decomposed a t 250-260", and is very soluble in water andalcohol, sparingly soluble in ether. The salts of the alkalis andalkaline earths are readily soluble, and those of the metals aresparingly soluble in water.The barium salt, with 5 mols. H,O,erystallises in large, colonrless, monoclinic prisms, the comer salt,with 2 mols. H,O, in bright-blue, silky needles, and the silver salt inanhydrous, white needles. The ethyl salt is identical with that pre368 ABSTRACTS OF CHEMICAL PAPERS.pared from dianiphaminebenzoic acid (Abstr., 1881, 816). For par-poses of comparison, the corresponding salts of disulphaminebenzaicsnlphinide were prepared ; the barium sdt, with .3+ rnols. HzO, crystal-lises in granular aggregates of needles, and the copper salt, with4 mola. H,O, in blue, microscopic needles; the silver salt is anhy-drous and indistinctly crystalline. w. P. w.Derivatives of Phenyldibromisobutyric Acid.Ry A. KORNER(Ber., 21, 276--277).-When a-methylcinnamic acid (m. p. = 78")dissolved in carbon bisulphide is treated with bromine, phenyldibromisobzctyric acid, CHPhBr*CMeBr.COOH, melting at 137", isobtained. This, when warmed with alcoholic potash, yields browm-phen ylcrolonic acid, CPhBr CMeGOOH, which crystallises fromwater in matted needles, and melts at 184". If phenyldibrom-isobatyric acid is boiled with water, phenylbrornh ydroxyisobutyrioacid is formed, melting at 148". In both cases, the yield of the acid issmall, the chief product being phenykbromopopylene, C9H',Br ; this is acolourless liquid, of pleasant odour, and boils at 226" with decomposi-tion. When treated with alcoholic potash, it is converted into phenyl-allylerze, CPh i CMe; this is a pale-yellow liquid of unpleasant odour,boils at 185", and yields with bromine a liquid dibrotnide, which boilsat 250-255" with the evolntion of much hydrogen bromide, and asolid fetrabronde, which crystallises in lustrous plates and melts at75".On treatment with an aqueous solution of mercuric chloride,phenylallylene forms a, white, amorphous componnd,which when heated with hydrochloric acid yields not phenylallylenebut phenyl ethyl ketone, COEtPh. w. P. w.Parisobutylorthobydroxybenzoie Acid. By L. P. DOBRZYCKE(J. p r . Chem. [a!, 36, 389-4UO).-Anhydrons sodium isobutyl-phenoxide was prepared by adding the exactly equivalent quantity ofisobutylphenol (Liebmann, Abstr., 1882, 171) to alcoholic sodiumethoxide, evaporating off the alcohol, and drying the phenoxide at 140-150" in a stream of hydrogen.The dry phenoxide was then treated,under pressure, with carbonic anhydride, which was rapidly absorbedwith evolution of much heat, sodium isobutylphenyl carbonate beingformed. When this substance was heated for some time at 130-160" it yielded sodiunt purisobut~yEorfhohydrox.~benzoate. The freeacid, C4H,~C,H,(oH).cooH, is soluble in boiling water, volatile insteam, and crystallises in long, thin, glistening, white needles. Itdissolves readily in alcohol, ether, and chloroform. The aqueoussolution gives an intense violet coloration with ferric chloride. Themetallic salts are not well characterised. The methyl salt yields large,colourless prisms, melts at 54", and boils at 266".It is easily solublein alcohol and ether. Cold soda converts it into a white mass probablyof the formula C,H,.CaHs(ONa)*COOMe. The ethyl salt is acolourless aromatic liquid boiling at 276". The phnyl salt was pre-pared by heating the acid with phenol at 130", and adding the requi-site quantity of phosphoric chloride in small quantities. It formORGANIC CHEMISTRY. 369long, glistening needles, sparingly solnble in cold ethyl and methylalcohols, easily in ether, and melt,s at 68". Dilute soda does notattack it in the cold, but saponifies i t on heating. When heated in areflux apparatus, carbonic anhydride is evolved, and phenol, isobutyl-phenol, and isobecty~~enzophenozide, C 1 7 E l 6 0 2 , are formed, The lattercompound is now being investigated.When isobutylphenol is treated with phosphoric chIoride, isobaty I-ehlorobenzene is formed.The oxidation of this compound proveddi5cult, potassinm chromate and sulphuric acid solution being with-out action, whilst chromic acid in acetic solution caused completeoxidation. When heated f o r a long time at 190" with dilute nitricacid, however, it yielded parachlorobenzoic acid. Liebmann's iso-butglphenol is, therefore, the para-compound, and from analogy and a,coneideration of its properties there is little doubt that the aciddescribed above has the constitution [OH : COOE : CaH, = 1 : 2 : 4).L. T. T.ar-Methylcinnarnic Acid. By P. R,AIKOW (Rer., 20,3396-3397).-In preparing a-niethylcinnamic acid (phenylcrotonic acid) byPerkin's method, and recrystallising the product from light petroleum,two acids were obtained having the 8ame composition, The onecrystnllises in plates melting a t 81-82", the other in needles meltingat 74'.When the latter is often recrystallised, it iff converted intothe acid of higher melting point. The relative amounts of the twoacids is influenced by the temperature at which the reaction betweenthe benzaldehyde, propionic acid, and sodium acetate takes place.At 135", 24 per cent. of the plates and 30 per cent. of the needles areobtained, whilst at 175" only the needles (56 per cent.) are formed.The two acids differ only slightly in solubility. N. H. 31.Benzeneazomalonic Acid. By R. METER (Bw., 21, 118-119).-Benzeneazomalonic acid, prepared from diazobenzene chloride andethyl malonate, is identical with the phenylhydrazide of mesoxalic acid.J.W. L.Action of Phthalic Anhydride on Amido-acids. By L.REESE (Bsr., 21, 277- 278).-ac-Leucinphthaloic acid (this vol., p. 148)can be obtained by adding the calculated quantity of phthalylchloride to a boiling solution of leucine in alcoholic potash, and con-tinuing the boiling of the alkaline solution for on8 minute; oncooling, the potassium salt crystallises in small, slender, concentr~cally-grouped needles, and yields the acid on treatment with dilute sul-phuric acid and extmction with ether.Pht~aaEy Zdisarcos~~~e: CI4Hl6N2O6, is formed when phthalic anhydride(5 parts) is heated at 1U--150" with sarcosine (6 parts). It crys-tallises in lustrous needles, melts at 168", and is readily soluble inwater and boiling alcohol, sparingly soluble in ether, and insoluble inchloroform and light petroleum. A sodium salt could not be pre-pared, since the compound is decomposed into its constituents by theaction of alkalis; a similar decomposition also occurs when it isheated with concentrated hydrochloric acid.w. P. w3iO ABSTRACTS OF CHEMICAL PAPERS.Azotoluenesulphonic Acid. By J. V. JANOTSKY (Ber., 21, 119.122) .-By appropiate manipulation, it is possible to directly ~u1-phonate azotoluene.Axotoluenesulphonic acid,C6H4Me*N2*C6H3Me*S03H [Me : N, : Me : SO,H = 4 : 1 : 4 : 3 I,is obtained by the action of fuming sulphuric acid on parazotoluene,care being taken that the temperature is kept below 100" ; the bestresult is obtained by the employment of an acid containing about24 per cent.SO3, when the temperature produced by the reactiondoes not exceed 80°, It crystallises witb 5 mola. H,O in orange-red tables, sparingly soluble in cold water. The potassium (with5 mols. H20), sodium (44 mols. H,O), calcium, barium (11 mols. H,O),lead and zinc salts are described. When nitrated, it yields a nitro-acid, N02*ClrH12N,*S03H + H20, crystallising in small, yellow needles,readily soluble in hot water; several salts were prepared. The cor-responding umido-acid crystallises in pale-yellow needles, and toge-ther with the hydrazo-acid also obtained, will be described later. Abronzo-acid, C14H,,BrN2*S0,H, was prepared, crystallising in tufts oflong needles ; the potassium and calcium salts are described.Proofof the constitution assigned above to the sulphonic acid is obtainedwhen it is treated with tin and hydrochloric acid, parntoluidinehydrochloride, and paratoluidineorthosulphonic acid [Me : S03H : NH2= 1 : 2 : 41 being formed.Ethylindole. By A. PICTET and L. DUPARC (Ber., 20, 3415-3422).-3'-E'thyZindole is prepared as follows :-30 grams of anilineis added to 50 grams of zinc chloride, and the whole mixed with35 grams of lactic acid ; 200 to 300 grams of sand being added to pre-vent frothing. It is then heated in a copper retort. The oily productsof several fractions are united, dissolved in ether and shaken withsmall amounts of dilute hydrochloric acid until no more basic sub-stance is dissolved; the ethereal solution is then distilled.It is abright yellow oil, boiling at 282-284" (corr.), very sparingly soluble inwater, readily soluble in alcohol, ether, benzene, and chloroform, bic. ;it distils readily with steam. When the alcoholic solution is treatedwith hydrochloric acid and a chip of pine, it gives an intense redcolour. The solution in chloroform gives, on addition of a few dropsof a dilute solution of bromine in chloroform, an intense violet colora-tion, resembling that of potassium permanganate. The picrate meitsat 143".The basic substance formed in the preparation of ethylindole isquinaldine (compare Wallach and Wusten, Ber., 16, 2067).Propionylorthotoluidine, CsH4Me*NH.COEt [Me : NHmCOEt = 1 : 21,is readily obtained by boiling orthotoluidine with propionic acid forsix hours.It crystallises from benzene in white needles an inchlong, melts at 87", and is readily soluble in alcohol, ether, and glacialacetic acid, &c., sparingly soiuble in hot water. It boils at 298-299" (corr.) under 730 mm. pressure, When oxidised with potassiumpermanganate, i C is converted into propionylorthamidobenzoic acid,COOH*C6fiNH*COEt. This crystallises from wetter in white, flatA. J. G.Ethylindole resembles scatole in its general behaviourORQ XNIC CEEMISTRT. 371needles, melts at 117", decomposes at 180" and is readily solublein alcohol, ether, and in hot water. The silver salt crystallisesfrom water in small, white needles. N. H. M.Dimethylindole.By L. WOLFF (Ber., 21, 123--126).-Anilinereacts with /3-'bromolaevulinic acid, forming dimethylindole, C,,H,,N.The vapour-density shows that this is the product of the reaction andnot a compound of twice this molecular formula, as the author sug-gested in a former paper (Abstr., 1887, 464-465). This indole isidentical in all respects with the 2'. 3' dimethylindole obtained hyJ. w. L.Isatoic Acid. By G. SCHMIDT and E. v. MEYER (J. pr. Chem., [2],36, 370--389).-When isatoic acid is heated in closed tubes at 100"with excess of ethyl alcohol, hydrogen ethyl carboa?lEanthranilate,COOEt.C,H4*NH*COOH, is formed. It crystallises in thin, colourlessneedles, melts at 1 2 6 O , and is so!uble in boiling water. When heatedwith hydrochloric acid in closed tubes at 150," this substance yieldscarbonic anhydride, ethyl chloride and anthranilic acid hydrochloride.The salts of this acid are crystalline ; the silver salt,E.Fischer (Abstr., 1887, 149).C OOE t*CsH4.NH*COOAg,forms white, microscopic needles or prisms, which are soluble inalcohol and sensitive to light.When methyl alcohol is substituted for ethyl alcohol in the abovereaction h ydrogew methyl carboxyawt hranil ate, CO O&fe*C6H4*NH.C 0 0 H,is formed. This crystallises in minute needles, soluble in boilingwater and melting at 176". The silver salt forms small needies whichare less stable than the ethyl compound, When heated with hydro-chloric acid at 120", the methyl compound dissolves, but on coolingcrystallises out again unchanged.When heated at 200" with an in-different substance, such as glycerol, carbonic anhydride is evolved, andmethyl anthranilate is formed.t With phenol at l8Oo, isatoic acid yields phelzyl anthranilate,NHz*CcH4*COOPh, but no carboxyl-derivative. The phenyl saltcrystallises in colourless needles melting at 70". It is easily solublein alcohol and in ether, sparingly so in boiling water. It is slightlyvolatile in a current of steam.When warmed with freshly psecipitaked ferrous hydrate in thepresence of excess of soda, isatoic acid is reduced to anthranilic acid.-With zinc-dust and acetic acid, isatoic acid yields an thranilcarboxjlicacid, <gGSY>N*COOH.When "isitoic acid is heated with glacial acetic acid, carbonicanhydride is evolved, and a compound of the formula C35H27N606formed. This substance is almost insoluble in the usual solvents, andonly melts at a very high temperature.At 150°, it is solnble inammonia, but crystallises out again unchanged on cooling. Withhydrochloric acid at 1 90°, it yields anthrariilic acid hydrochloride. Itdissolves in cold concentrated sulphuric acid with slight darkening,but is reprecipitated unchanged on the addition of water. 50 pe372 ABSTRACTS OF CHEMICAL PAPERS.cent. snlphuric acid at 160" converts it into anthranilic acid. Thecompound is probably formed from 5 mols. of isatoic acid by the sepa-ration of 4 mols. of water. If acetic anhydride is used in place ofacct'c acid, carbonic anhydride is evolved, and acetylanthranilic acidis formed.Meyep has already pointed out (Abskr., 1885, 666) that anthranil-carboxylic acid is formed from isatoic acid by sxidising as well as byreducing agents.From a careful consideration of all the experimental resultsobtained, the autbors conclude that isatoic acid is really identical andnot isomeiic with anthranilcarboxylic acid, and that the seemingdifferences of properties are due to the presence in isatoic acid ofsmall quantities of a yellow-colonred impurity.This impnrit,y, whichmodifies the properties of the acid, is not removed by the ordinarymckhods of purification, but is destroyed by strong oxidising O rreducing agents.Finally, the authors are inclined to think that the ethyl-compounddescribed above is perhaps identical with that obtained by Weddige bythe action of ethyl chlorocarbonate on anthranilio acid, in which caseits constitution would be COOH*C6H4*NH*COOEt, and that of thamethyl-compound analogous to it.(Ber., 21, llO-l18>.-1t is easy to obtain reactions between aromatiamonamines and glyoxal, if, instead of employing the latter in the freestate, its compound with sodium hydrogen sulphite is used.Anili doacetanilide, NHPh*CH2*C ONI4 Ph, is prepared by hentin ganiline and glyoxal sodium hydrogen sulphite with dilute alcohol inthe water-bath for 20 to 30 honrs.The melting point, 112-113", is€ound t o be rather higher than has previously been stated. Underlike conditions, paratoluidine gives paratoluidoacetotoluide.When /%nsphthyla;mine is heated with glyoxal sodium hydrogensulphite in alcoholic solution, the reaction takes another course andthe sodium salt of /?.naphthoxindolesulphonie acid separates.The freeacid could not be obtained. The gotassinm salt, CJ&N*SO,K(, crystal-lises in white plates, and when heated with aqueous hydrochloric orsulphuric acid at 80-90" yields p-aaphthoxindole whilst much sul-phurous anhydride is evolved./i?-Naphthoxhadole, C,o&<CH,>CO, crystallisea in pale greenneedles, melts at 234', and is sparingly soluble in water, readily inalcohol, ether, and glacial acetic acid. It dissolves in potash wit,houtdecomposition, and is insoluble in mineral acids, but with concentratedsulphuric acid it gives a bluish-green coloration which disappears ondilution. The isonitrmo-compound, c,&< C(N0H) NH.Co->, prepared bythe action of nitrous acid, foms slender, reddish-yellow needles, andmelts at 240".CloH6< co >CO, is prepared by reducing iso-nitPoso-P-nsphthoxindole in dilute, alcoholic solution by zino andL.T. T.Aotion of Glyoxal on Aromatic Amines. By 0. HINSBERGNHNH p-NaphthisatinORGANIC CHEMISTRY. 373hydrochloric acid, and treating the colourless liquid so obtained withferric chloride. It forms slender, red needles, melts a t 2 4 5 O , ismoderately soluble in the ordinary solvents, and resembles isstin i nits chemical behaviour.From a-naphthylamine, the corresponding a-compounds were ob-tained in similar manner. The sodium and silver salts of a-naphth-indolesulphonic acid were prepared, but the free acid could not beobtained.a-Nuphthoxindole crystallisea in colourless needles, melts at, 245", isinsoluble in aqueous soda, and gives a greenish-black coloration withferric chloride and hydrochloric acid.The iaonitroso-compound formsyellowish-red needles, ainters, and turns black at 230", and is com-pletely fused at 260".a-Naphthisutin forms red needles, melts at 255"; the phenyl-hydrazide melts at 268-27'0". Neither of the naphthisatins givethe blne coloration with sulphuric acid and benzene containingthiophen. A. J. 0.Condensation-compounds of Metanitrobenzaldehyde withBenzene and Toluene. By 0. TSCHACHER (Ber., 21, 188-191).-Meta.nitrot~i~hsszyZn.tethane, CHPh2*CsH4*N02, is formed when a solutionof metanitrobenzaldehyde in benzene is shaken with half its volumeof sulphuric acid ; it crystallises from light petroleum in colourlesscrystals, and melts at 90".When reduced in acetic acid solution withzinc-dust, it yields the amido-derivative, which crystallises from etherin short needles, melts at 120°, and forms a hydrochloride,The acety Z-derivative, CIgH15*NHAcrystallises in colourless, nacreousscales, melts at 115", and is soluble in alcohol.When metanitrotriphenylmethane in carbon bisulphide solution isfreeted with the calculated quantity of bromine and exposed to sun-light, an oil, probably C19E14Br*N02, is obtained which on treatmentwith potassium acetate in acetic acid solution, and subsequent hydro-lysis with aqueous potash, yields metanitrotriphenyl carbinol,This crystallises from light petroleum in colourless crystals, and meltsat, 75" ; when reduced, it is converted into the amido-derivative, whichcrvstallises from ether in colourless, stellate forms, melts a t 155", andyields an acetyl-derivative, OH*C,gH,4*NHAc, crystallising in colourless,nacreous scales and melting a t 164".Metanitrophenylditdy Zrnethane, CH(C6H4Me),*C6H,*N.02, is obtainedby treating a solution of metnnitrobenzaldehyde in toluene withsulphuric acid in the cold.It crystallises from light petroleum incolourless forms, and melts at 85". w. P. w.Action of Dichlorether on PhenoL. By J. WISLICENUS and H.REINHARDT (AnnuEeB, 243, 131--165).-Dichlorefher ada on pEe~01374 ABSTRACTS OF CHEMICAL PAPERS.forming et71 elzy Itripheno I , Hoe c6&* CH,*CH.( C6H,*0 H) *, and 0th erproducts.I f less than S mols. of phenol are taken, an insoluble resinis formed. The crude product is dissolved in alkali, reprecipitated byhydrochloric acid, and distilled in a current of steam to remove theexcess of phenol. These three operations must be repeated severaltimes. Ethenyltziphenol yields a triacetate soluble in ether, alcohol,chloroform, acetone, benzene, aniline, phenol, and acetic acid. Theacetic acid solution is oxidised by ferric: chloride, yielding isorosolicmid, C20H1601, a dark, carmine-red, amorphous powder. Isorosolic acidyields a sulphonic acid. From an acetic acid solution of isorosolicacid, chromic acid throws down an amorphous insoluble compoundcontaining chromium. w.c. w.Action of Dichlorether on the Dihydroxybenzenes. ByJ. WISLICENUS and M. SIEGFRFED (Annalerz, 243,171-192) .-Ethenyl-ti*iresorcinol, C&[ C6H,( OH),],, is formed by the act-ion of dichlorether(14 grams) on 33 grams of resorcinol dissolved in 300 grams ofbenzene. It is a pale-red, amorphous powder soluble in water, alkalis,alcohol, acetone, and in strong acetic acid. It is precipitated byhydrochloric acid from alkaline solutions, and after the precipitatehas been dried in a vacuum, it is sparingly soluble in water, alcohol, andacetic acid. A monztcetic derivative is obtained by the action ofglacial acetic acid a t 85". It is insoluble in the ordinary solvent's, andis converted into an insoluble hexacetate by the action of aceticanhydride at 200".By the action of acetic anhydride on ethenyl-triresorcinol at 170°, an amorphous hexacetate is obtained which issoluble in acetone, chloroform, benzene, and acetic acid. A chocolate-coloured, amorphous substance is formed by boiling ethenyltriresorcinolwith glacial acetic acid and ferric chloride. When freshly prepared,it is soluble in alcohol, acetonet and acetic acid. It also dissolves inalkalis, yielding a cherry-red solution. It yields a pentacetate,CzOHll(A~)506. When bromine acts on ethenyltriresorcinol, twohydrogen-atoms are eliminated and six are substituted by bromine,yielding Cz,HloBr60~, a substance soluble in alcohol, ether, acetone,chloroform and acetic acid.Ethenyltricatechol is obtained as an amorphous compound by theaction of dichlorether on a mixture of pyrocatechol and benzene.It issoluble in alcohol, acetone, acetic acid, and alkalis. It yields a hexacetate.On oxidation with ferric chloride, it loses two atoms of hydrogen, butthe product could not be obbained in a pure state, although its pent-acetate, C20Hll( Ac),06, was prepared. Bromine converts ethenyltri-catechol into the hexabromide, CzoH,,Br506, from which the pent-acetate, C20H,Br6Ac506, was obtained.Btherzyltriquinol is prepared by the action of dichlorether on asolution of qninol in warm ethyl acetate. It is an amorphous substance,soluble in alcohol, acetone, acetic acid, and in alkalis. The hexacetateis soluble in acetone, chloroform, and acetic acid.Ethenyltriquinolyields a green colouring matter, C20H1606, when i t is treated withferric chloride ; a bromide, C2,H,Br9O6, can also be prepared. When anexcess of dichlorether acts on a solution of quinol in ethyl acetaheORGANIC CHEMISTRY. 375a resin and a soluble compound are formed.ethenyltriquinol, but has the composition C16Hl,C10a.The latter resemblesw. c. w.Action of Sulphur on the Salts of Aromatic Hydroxy-com-pounds. By M. LANGE (Bw., 21, 260--264).-When ,%naphthol isdissolved in aqueous soda and boiled with an excess of sulphur, thelatter dissolves and dihydroxydinaphtl~yZ disulphide, S,( CloH6.0H),, isformed. This crystallises in white, opaque needles. melts at 210"(uncorr.) and is insoluble in water, sparingly soluble in ethyl alcohol,readily soluble in acetic acid, benzene, amyl alcohol, alkalis, and alkn-line sulphides.From the mother-liquors, a second compound of likecomposition can be separated, which crystallises in long, yellowneedles, melts at 168-170", is more soluble in all solvents thandihydroxjdinaphthyl disulphide, and is also distinguished from it byits greater acidity. Bot>h compounds yield p-naph tho1 on distillationand when heated with alkalis or ammonia at 150". Dibydroxydinaph-thy1 disulphide is alone formed when P-naphthol is heated withsulphur and lead oxide at 180-200".Resorcinol, when treated in like manner, yields a compound,C6K4O2S2, provisionally termed thioresorcinol. It is a yellow powder,which carhonises before fusion, and is almost insoluble in the ordinarysolvents, but readily soluble in alkalis, alkaline carbonates, and alka-Action of Fuming Sulphuric Acid on a-NaphthylamineHydrochloride.By R. MAUZELIUS (Bey., 20, 3401-3404) .-Thesulphonic acid prepared by Witt (Abstr., 1886, 554), by the action offuming sulphuric acid on a-naph thylamine hydrochloride, is shown tobe S-amidonaphthnlenesulphonic acid. The acid was prepared exactlyas described by Witt (Zoc. cit.), and was purified by means of thecalcium salt. The different results obtained by Witt appear to be dueto the presence of some impurity.By E. BAMBERGER and W. LODTER (Ber., 21,256-260) .-When equimolecular proportions of a-naphthabemy laminehydrochloride and sodium nitrite are dissolved in water, the nitrite ofthe base, CloH7*CH2*NH2,HN02, is obtained ; this crystallises fromwater, in which it is sparingly soluble, in long, slender prisms, andmelts and suddenly decomposes ah 148.5".a-NaphthabenzyZ abohol, CJ€,*CH2*OH, is prepared by diazotisingthe amine.It crystallises in long, lustrous needles, melts at 59-60',boils at 301' (corr.) under 715 mm. pressure, and is readily solublein alcohol and ether, less soluble in hot water. On oxidation withpotassium dichromate and sulphuric acid, it is converted into a-nuph-thaldehyde, CloH,*CHO. This is a thick, pale-yellow oil of slightlyaromatic odour, which boils at 291.6" (cow.) without decompositionand gives the characteristic aldehyde reactions ; the pheny lhydrazidecrvstallises in lustrous, bright-yellow scales and melts at 185".Ontreatment with nitric acid (sp. gr. = 1.47) at - 5-O", a mixture ofnitraldehydes is obtained, one of which crystallises in lustrous, pale-yellow needles, melts at 136", is very sparingly soluble in cold alcoholline sulphides. w. P. w.N. H. M.m-Naphthaldehyde376 ABSTRACTS OF CHEMlCAL PAPERS.and does not give a colour reaction with acetone and aqueous soda.6-Naphtbaldehyde could not be obtained by distilling calciumBy R. MATJZELIUS(Bw., 20, 3404-3407) .-1 : 4' Bromonaphthalenesulphonic acid(Darmstadter and Wichelhaus, Annilen, 152, ,703) is prepared bynddir?g 1 : 4' diazonaphthalenesulphonic acid to warm, strong hydro-bromic acid ; the solution is neutralised with potassium carbonate,the potassium salt recrystallised from hot water, dried and rubbedwith phosphorus pentachloride ; the product is then treated withwater, extracted with ether, and crystallised from glacial acetic acid.The chloride is heated with water a t 130".The impure acid meltsat 126". The barium salt (with 2 mols. H,O) is sparingly soluble ;the siZver salt crystallises in pale-yellow lustrous scales. The chloridecrystallises in well-formed crystals melting a t 9-4'. The amide formsyellowish needles melting at 232-233". The ethyl salt crystalliseswell, dissolves readily in alcohol, chloroform, and ether, &c., andmelts at 51" (compare also Jolin, Verhand. d. schwed. Akad. d . Wissew.,1877, No. 7 ) .By E. BAM-BERGER and W. LODTE'R (Ber., 21, 51-56).-When an aromaticthiamide is reduced with zinc and hydrochloric acid, a benzglaminebase is not the only product, a hydrocarbon is obtained a t the sametime in quantities of about 1 to 2 per cent.of the thiamide employed.Symmetrical di-u-tLaphthyZetha?ze, CloH7*CH2*CH2*C10H7, is formed inthe reduction of a-naphfhothiamide in alcoholic solution ; on evapora-tion, an oily resinous mass is obtained ; this is treated with soda, andthe oil which separates is distilled. As soon as the naphthobenzylaminehas passed over, the thermometer rises rapidly above 360" and a thickyellow oil distils, and in a short time solidifies. The dinapht hylethanethus obtained, after purification and crystallisation from alcoholicbenzene, forms shining, hexagonal plates which are readily soluble inbenzene and chloroform, less so in ether, and sparingly soluble indcohol with a green 3uorescence.The crystals are greenish-yellow,and melt at 160" to a yellow oil with moss-green fluorescence.Symmetrical di-P-naphthylethane is obtained by extracting withbenzene the resinous product formed in the reduction of P-naphtho-thiamide. It crystallises from benzene and chIoroform in shiningsilver-white, plates melting a t 253", is only sparingly soluble inordinary solvents, most readily in chloroform and benzene, and lessso in boiling alcohol and ether; the solutions have a blue-violetfluorescence.The resinous product formed in the reduction of benzothiamidecontains stilbene, which can be isolated by boiling with alcoholic potashand then distilling with steam.Action of Dichlorether on Naphthol.By J. WISLICENUS and G.ZWANZIGER (Anmalen, 243,165-171) .-Ethenyltri-a-naphthol is formedby the action of dichlorether on a-naphthol. The crude product ispurified by solution iu alkalis and reprecipitation by acRtic acid. Ita-naphthoate with calcium formate. w. P. w.1 : 4' Bromonaphthalenesulphonic Acid.N. H. M.Reduction of the Thiamides of Aromatic Acids.F. S. I(ORGANIC CHEMISTRY. 377is an amorphous, whike powder, soluble in amtic wid, alcohol, ether,acetone, and in dilute alkalis. It eorms 8 crystalline triacetyl-deriva-tive, Ca2HZlAc3O3. When ethenyltri-a-naphthol is oxidised by ferricchloride, it is converted into %t brawnisbred colouring matter of thecomposition C32Hm03.The action of dichlorether on /%naphthol isnot analogous to its action on a-naphthol. The product, C22H,5C10,crystallises in plates melting at 174'. It resists the action of boilingTerpenes a;nd their DerivBtives. By J. W. BRGHL (Ber., 21,145--179).-A comparative study of the chemical and physical pro-perties of the terpenes. A table containing the boiling point, rotation,density d, refractive index for the C h e N , specific refraction(n2 + 21d, and molecular refraction 7 (P being the molecularweight), of a number of the best known terpenes, has been compiledfrom the data of different observers. The terpenes are thuadividedinto eight groups, similar to those given by Wallach (Abstr., 1881,965), phdhndrene and terpinene coming under the heading laumne,and menthene and sesquiterpene forming an extra group.Thesegroups are :-1. Citrene (Kmmene) , boiling point 172-1 ?go, the differencesprobably dne to impnrities in the specimens examined. lhxtl-0-rotatory. Sp. gr. 0.846. Refrachive index 1.47. Specific refraction0.328. Absorbs 2 mds. HCI, the resulting product being identicalwith the similar product from dipentene, aDd giving the latter and no$citrene when the hydrogen chloride is removed by means of aniline.From this, and the formation of a tetrabromide melting at 104", thepresence of two unsaturated or double bonds is probable, as also fromthe molecular refraction which agrees closely wihh that calcabted forsuch an unsaturated compoimd.2.Bpentene.-Differs from the above only in being opticallyinactive and yielding a tetrabromide melting at 124".3. Pso~entene.--extrsrotato~y, differs only slightly from &he twoformer in physical properties.4 XyZvestrem.-Has probably never been prepared in a state ofpurity, and does not appear to differ in any marked degree from theforegoing.5. Pinene.-Boiling point 155-160". Sp. gr. 0.859. R,efractivcindex 1.463. Specific refraction 0-320. The molecular refraction isthat of a compound containing one double bond. This agrees withthe chemical evidence, as pinene aombines with 2 mols. of bromineand I mol. HCl.6. Laurene and Merttkerte.--Boiling p i n t 173-1 75'. Laevoro-tatory.7. 0amphene.-Solid, melting at 47"; boils at 156-157". Thehydrogen chloride derivative is very unstable and is decomposed bywater at ordinary tempei-atures ; it is therefore probable that this isonly a molecular compound, camphene containing no double bond, aview supported by its optical properties.8.Sesquiterpexe, Cl&.--Found in volatile oils associated with theVOL. LlV. 2 Cpotash and is not attacked by acetic anhydride. w. c. w.nz - 1. n z - l Pn z - J ZResembles pinene il: other respects378 ABSTRACTS OF CHEMICAL PAPERS.terpenes. Boiling pint 250-260'. Rotation differs for differentvarieties. From its optical and chemical properties appears to containtwo double bonds.The aa thor regards the terpenes as derivatives of paracymene.Formulae similar to those of Wallach (Zoc. cit.) are proposed forcitrene, dipentene, pinene, and phellandrene, and a discussion of thevarious possible formulae for the ather terpenes is entered into.Specific Rotation of Dextrocamphoric Acid and its Salts.By W.HARTMANN (Ber., 21, 221-230).-The specific rot'ation ofdextrocamphoric acid and its salts in solution is represented generallyby [a] = a + bp or A + Bq, p being the percentage of activesubstance, q thatof the solvent, a the specific rotation for greatestdilution, A that for greatest concentration. The rotation of the freeacid in acetic acid, acetone and alcohol varies with the nature of thesolvent. The anhydride is optically inactive. The constants in theabove equations were determined for solutions of the lithium,magnesium, ammonium, calcium, sodium, potassium and bariumsalts.By the aid of these constmts, the specific rotation of the acidin the salts was calculated, which is more than double that of the freeacid, and is nearly equal for all salts for the same dilution. Themolecular rotation M = [a)P/lOO, where P is the molecular weight,was also calculated for soliztions of the above salts for p = 0, 5,10, 1.5,and 20. It is found that the molecular rotation i s very nearly thesame for all salts a t the same concentration. Hence also the specificrotation increases with the molecular weight.Alantic Acid and Alantole. By MARPMANN (Arch. Phnrm. [3],25, 826-827 ; from Bred. arztl. Zeit., 5, 1887).-On distilling theToot of InuZa heleniunt with water, a distillate is obtained containinghelenin, C12H,,02, alantic anhydride, C15H2002, and alantole, C20H,0.AZantic acid crystallised from alcohol, melts a t 91", and sublimeswith loss of the elements of water, hecoming alnntic anhydride ; bothcompounds are insoluble in water, soluble in alcohol, and with alkalisform salts soluble in water.Alaniole is an aromatic liquid whichboils a t 200", is laworotatory, and has ozonising properties somewhatsimilar to those of the turpentine oils. Helenin, alantic acid, andalantole are antiseptics. J. T.Oxidation of 1-Quinolinesulphonic Acid, By H. Z~~RCHER(Ber., 21,180-182) .-Amidosulphobenzoic acid, [ COOH : NH, : SO,H= 1 : 2 : 31, is formed in small quantity when 1-quinolinesulphonicacid is oxidised to quinolinic acid by Fischer and Renouf's method(Abstr., 1884, 1049).The yield amounts to about 5 grams from 90Reactions of the Opium Alkaloids. By P. C. PLUGGE (Arch.Pharrn. [3 1, 25, 793-811).-With potassium chromatle, solutions ofnarcotine salts, Eoth cold a ~ i d warm, give a precipitate of free narcotine.Papaverille in the cold gives a mixture of chromate and free alkaloid :but with heat free papaverine only. Narceine in cold saturatedH. C.H. C.grams of quinoline. w. P. wORQANIC CHEXISTRY. 379solution gives no precipitate, but if hot narceine chromate and freennrcejine come down. Thebaine gives thebai'ne chromate. Codeinealso gives the corresponding chromate, whilst morphine gives chromateand free morphine.With potassium dichromate, narcotine, papaverine and thebnhegive the corresponding dichromates, narceyne gives the dichromateand free alkaloid.Codeine in very dilute solution gives the dichro-mate ; stronger solutions afford precipitates which have not yet beenexamined. Morphine gives a dirty brown precipitate of variablecomposition.With potassium ferrocyanide, narcotine hydrochloride gives freealkalo'id or a mixture of variable composition ; the papaverine saltgives (C,H,,N04)4,H,Cfy ; the narcejine salt gives free alkaloid, thehydroferrocyanic acid becomes free ; the thebaine salt gives the com-pound (C19Hz1N0,),,H4Cfy ; the codei'ne salt solution (1 : 70) is notprecipitated ; the morphine salt solution (1 - 60) is not precipitated.With potassium ferricyanide narceine gives the saltpapaverine and thebai'ne give similar precipitates, narceke gives freealkalo'id, hydrogen ferricyanide also becomes free ; codeine in solution(1 : 70) gives no precipitate; morphine solution (1 : 60) becomesdark coloured and a brown deposit forms after long standing.J. T.Quinine Alkaloids.By 0. HESSE (Annnnlen, 243, 131-150).-Quinine tartrate crystallises with 2 mols. H20; it parts with onemol. H,O at 120", and the second at 140". A mixture of quinineand cinchonidine tartrates loses water more easily than quinine tar-trate, but if the mixtnre contains more than 33 per cent. of quininetartrate, it cannot be thoroughly dried by exposure to a temperatureof 120-130°. If ammonia is added to a solution of quinine disnl-phate containing not more than 10 per cent. of cinchonidine disul-phate, ether extracts from the mixture the compound C20H24N20z +2C19H2,N20. This substance crystallises in rhombohedra, and isdecomposed by boiling ether. On recry stallisation from hot dilutealcohol, crystals of the composition C20H2dN202 + 7ClgH,N20 areobtained. The compound C20H,rN202 + 2C1gHmN20 forms a normalsulphate crystallising with 18 rnols- H20, a normal tartrate containing6 mols. H20, and zb normal chromate with 18 mols. H20.The estimation of quinine as chromate as proposed by de Vrij(Abstr., 1887, 404) is open to several objections (loc. cit.).The author confirms the existence of the compound of quinine andconchinine described by Wood and Barret (Chem. News, 45,6) and hesucceeded in preparing a similar compound of quinine and hydro-conchinine, CmH2,NZO2,C,W,N2O2 + 2&H20.With cinchonidine and homocinchonidine, piperonylic acid formssalts crjstallising in needle-shaped crystals soluble in chloroform.The hydrocinchonidine salt is soluble in water and in chloroform.Quinine sulphate is converted into isoquifiine by solution in strongsulphuric acid. The new bassforms a normal sulphate which crystal-lises in small needles. It does not yield 8 precipitate with sodiur380 ABSTRAOTS OF CHEMICAL PAPERS.tartrate. Locolecbicine is deposited from ether in needles. Thesulphate, (C20HJT,02),H2SOa +- 8Ht0, is crystalline, and the platino-chloride, C,HHNgOz,HzPtC16 + 3Hz0, is amorphous. Isochacho&dinecrystallises in colourless plates, freely soluble in ether and chloroform.It melts at 235". On evapo-ration, the ethereal solution leaves an amorphous residue which soonbecomes crystalline,Isocinchonine is freely soluble in ether.Hydroconchinine yields a crystalline sulphonic acid,CzoH2,NZ02*SOaH + 3320. w. c, w.Optical Isomerides of Cinchonhe. By E. JLJNGFLEISGH andE. ~ G E R (Compt. rend., 105, 1255-1258). -Pure cinchonine dis-solved in four times its weight of a mixture of equal parts of water andsulphuric acid of sp. gr. 1-84, yields a colourless solution which boilsat 120". After boiling for 48 hours, the liquid is amber-coloured, butdoes not become turbid on cooling. When diluted and made alkalinewith sodium hydroxide, it yields an abundant curdy precipitate whichsoon changes t o a porous mass, and gradually hardens. This productcontains neither cinchonine nor cinchonicine, but consids of six bases,four of these are isomerides of cinchonine, which form readily cry+tallisable salts.Cinchmibine is insolable in ether, but crystallises from boilingalcohol in prismatic needles. It yields a succinate which formsMky crystals slightly soluble in cold water. It is dextrogyrate,[a]= = +175*8", in an alcoholk solution of 0.75 per cent.Cinckonz&e is insoluble in ether, but crystallises from boilingalcohol in highly refractive needles. It is dedrogymte, [&ID = + 195.0°,in an alcsholic solution of 0.75 per cent The succinate crystallisesin needles, and is very soluble.Cinchomigine is s o h ble in ether, from which it crystallises in prisms,and is lmvogyrate, [a]? = -60*1°, in an alcoholic solation of 1 percent. It yields a distinctly crystalline hydrochloride slightly solublein water.Itis dextrogyrate, [a]= = -J- 53.2", in an alcoholic solution of 1 per cent.The hydrochloride forms large crystals which are very soluble ; thedihydriodide is insoluble. These four compounds increase the numberof isomerides of the composition C,,H,N,O to seven.The other two bases are isomeric one with anohher, but belong toanother group. They ,are products of oxidation produced withintermediate formation of a sulphonic derivative which is decomposedby water.a- Oxycinchonine, CleH&"O,, form prismatic needles insoluble inether but soluble in dilute alcohol. I& is dextrogyrafe, [a]D = + 182.563in an alcoholic solufion of 1 per cent. Its salts with the hydracidsare only slightly soluble.P-Oxycincho&ne, CI9H,N2O2, is insoluble in ether, but dissolves indilute alcohol, and crystallises in needles arranged in spherical groups.It is dextrogyrate, [ a ] D = + 187.14", in an alcoholic solution of 1 percent.C i n c h n i l i n e is soluble in ether, and forms very balky crystals,Its salts with hydracids are very soluble. C. H. BVEGETABLE PHTSIOLOGP AKD AGRICULTURE. 381Cocaine. By A. EINHORN (Bey., 21, 47--51).-The ethereal saltsof benzoylecgonine can be obtained by passing hydrogen chloride intoits alcoholic solution ; the ethyl, propyl, and isobutyl salts were pre-pared in this way; they have already been described by Merck(Abstr., 1886, 163).Succinic acid is formed when anhydroecgonine or ecgonine isoxidised with potassium permanganate ; 10 grams of ecgonine hydro-chloride yield about 2.2 grams of succinic acid. Ecgonine hydro-chloride also gives succinic acid when it is boiled for some time withnitric acid ; from 2 grams of the salt, about 1 gram of succinic acid isobtained.The atomic complex, C*CH,*CH2*C, which is contained in succinicacid, must originate from the reduced pyridine-ring of the cocayne-derivative, and the formation of succinic acid shows that the side-chain is either in the a- or &position.Nitrogenous compounds are also formed in the oxidation of ecgonincand anhydroecgonine. F. S. K.P h y s i o l o g i c a l C h e m i s t r y .Behaviour of Congo-red with Human Urine and with AcidSalts. By E. BRECKE (MoiLatsh. Chenz., 8, 632-637, compare Abstr.,1887, 986).-Human urine and a solution of ammonium acetate con-taining free acetic acid give similar tints with Congo-red. Theaddition of mapesium sulphate, however, in no way affects the colourof the former, whilst it causes the latter to darken rapidly with theformation of a brownish-black precipitate. The acid tartrates ofammonium and potassium give with Congo-red a beautiful violetcolour. The author sees no reason to change the conclusion he drawsfrom previous experiments with Congo-red, that human urine containsno free acid. G. T. M

ISSN:0368-1769    

DOI:10.1039/CA8885400355

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

VEGETABLE PHTSIOLOGP AKD AGRICULTURE. 381 Chemistry of Vegetable Physiology and Agriculture, Colour of Leaves in Relation to the Assimilation of Carbon. By T. W. ENCELMANN (Ann. Agronom., 13,477-480 ; from Bot. Zeit., 1887, 25--29).--The yellow leaves of an elder bush were studied side by side with the green leaves of the same plant by means of Engel- mann’s microspectral photometer, and by their behaviour towards aerobic bacteria. The absorption-spectrum of the living yellow cells shows that the bands I1 and I11 in the orange and the yellow-green which belong to the green colouring constituent (cyanophyll or pure chlorophyll), and 2 c 2382 ABSTRACTS OF CHEMICAL PAPERS. which are absent from the spectrum of xanthophyll, are scarcely indicated. In the spectrum of the green living cells, on the other hand, these bands are easily identified, although Reinke, working with Glan’s photometer, did not succeed in finding them. It would thus appear that the yellow cells contain little chlorophyll proper, or chlorophyllane, and it would be expected that they should lack the power of assimila- tion.By immersing equal areas cut out of the yellow and green leaves in a liquid charged with azrobic bacteria, and exposing the liquid to the light, it is easily seen that the yellow cells disengage far less oxygen in a given time than the green cells, and hence it is probable that if they contained pure xanthophyll only, the assimilating power would be nil. With reference to the plants in which the light reaches the granules of true green chlorophyll through layers of cells coloured red or purple (copper-beech, red cabbage, &c.), the author observes that they do not differ from what is observed in green plants either in the disposition of the chlorophyll granules or in their size, or the nature or intensity of their colour.Moreover, the red varieties of a plant, for example, Coleus, are quite as large and vigorous as the green speci- mens. It follows that the rad colouring matter of these plants can only absorb those rays which have little influence on assimilation. The colouring matter is always R red-purple, which has most effect in absorbing the green rays, whilst red rays pass freely, and blue and violet very well. The curve of absorption rises about the middle of the spectrum, and descends again at the other end.When the solu- tion is very concentrated a large absorption-band is seen between the wave-lengths X = 0.59,~ and X = 0.50p. Speaking generally, the absorption of light is complementary to that caused by solutions of chlorophyll. If, as was formerly believed, the maximum of assimila- tion corresponded with the yellow rays, that process would be much impeded in the red plants, for the yellow rays are enfeebled to the extent of one-third in passing through the red solution. Supply of Food Constituents at Different Periods of Plant Growth. By G. LIEBSCHER (Bied. Centr., 1887, 658-660).-As a basis for the science of manuring, the author advances a new theory. The view sometimes held, that one species of plant has a greater power than another of taking up some particular food constituent cannot be reconciled with the laws of osmosis; but the difficulties met with can be explained in another way.Each day the root should supply a, certain amount of food to the plant ; this amount varies more or less at different stages of growth, and further, these variations differ in the case of different plants ; thus one species requires R fairly uniform daily supply throughout its period of growth, whilst another requires much more at one stage than at another. From the composi- tion of various plants at different stages of growth, the author has constructed a number of cunes showing how these supplies vary. Such information affords an important clue to the proper manuring of a particular species ; thus for a plant requiring a uniform daily supply, a slowly decomposing and lasting manure is appropriate ; J.M. H. M.VEGETABLE PHYSIOLOUY AND AGRICULTURE. 38 3 whilst an easily soluble one should be given to a plant whose demand is large during a short period. Wheat Experiments in 1887. By A. LADUEEAU and MOUSSEAUX (Ann. Agronorn., 13, 538-551) .-The experiments were carried out on the poor lands of the Brie district, and had for their object to demonstrate the utility of artificial manures, and to ascertain the most productive and economical manuring for the district. The soil, limed in 1885, contained only 0.084 per cent. N, 0.085 per cent. PzOs, 0.325 per cent. K20, and 0.280 per cent. CaO. One variety of wheat (Golden Drop) was sown on all the plots, on the same day, October Ilth, 1886, at the uniform rate of 2 hectolitres per hectare ; each plot measured 3 ares.Both straw and grain were weighed on each plot, the value calculated out at the price actually realised, and compared with the expense of the various manures used. The yield varied from 950 kilos. per hectare of grain, and 1550 kilos. straw on the unmanured plot, t o 3200 kilos. grain and 5650 kilos. straw on the best plot, which was manured with 50 cubic metres farm- yard manure, and 300 kilos. of 15 per cent. superphosphate per hectare in the autumn, and top dressed with 250 kilos. sodium nitrate in the spring. The increase obtained on this plot over the unmanured plot exceeded the cost of the manures applied by 319.75 francs per hectare. A still more favourable result (although from a smaller crop) was obtained on the plot dressed with 100.5 kilos.P,O, in superphos- ph@e and 48.5 kilos. of ammoniacal nitrogen per hectare in the autumn, 69*/5 kilos. nitrogen as sodium nitrate per hectare in the spring ; on this plot, the increase obtained by the manure exceeded the cost of the latter by 389.4 francs per hectare. The results obained on all the plots justify the following conclusions :- 1. Superphosphate applied at the rate of SO kilos. per hectare pro- duces an increase of crop on these soils. 2. Ammonium sulphate applied in spring gives results greatly superior to those given by the same money value of sodium nitrate. 3. Basic cinder substituted for some of the superphosphate did not give good results. The authors are now trying basic cinder alone, and expect to get better results with it.That employed in the pre- sent series of experiments was very coarsely ground. 4. Farmyard manure alone did not even repay its cost, a result probably due to the exceptional drought of the season. The authors recommend the wheat growers of this distrtct to sell their farmyard manure to the vine growers, and with a portion of the proceeds to buy artificial manures. H. H. R, J. 31. H. M. Experimental Culture of Sugar-beet at Grignon in 1887. By P. P. DEH~RA~N (Ann. Agronom., 13,529-535).-The experiments were to decide two points, namely, the quality of the seed obtained at Grignon from previous crops of Vilmorin’s sugar-beet, and the effect of farmyard menure as compared with mineral manures on the yield of sugar.The plots sown with the Grignon seed were therefore com- pared with parallel plots sown with seed obtained direct from Vil- rnorin ; the manures tried were farmyard manure, sodium nitrate, and384 ABSTRACTS OF CHEMICAL PAPERS. ammonium sulphate ; and the quality of the roots from the rarious plots was ascertained by selecting proportionate numbers of large, medium, and small roots from each plot, and testing the juice by the hydrometer and in the saccharimeter. The chief results of the ex- periments are that the continuously unmanured plots of both series yielded very small crops of small roots poor in sugar, namely, 13900 and 10100 kilos. of roots per hectare, density of juice 6.9 and 7.2, per- centage of sugar in juice 15.8 and 14.6. The mean percentage of sugar in the juice of the roots from the Grignon seeds was 17.7, and in the juice of the roots from the Vilmorin seeds 17-1, so that it is evident a good sample of seed may be relied on by the farmer for a t any rate a second harvest.Both series of plots proved that on the light soil of Grignon, moderate dressings of farmyard manure, with or without the addition of sodium nitrate or ammonium sulphate, pro- duced considerably larger crops than the sodium nitrate or ammonium sulphate alone, and that the roots grown with the farmyard manure were by no means poor in sugar, the juice containing 18 to 19.5 per cent.; 30000 kilos. farmyard manure per hectare, or 20000 kilos. with 200 kilos. sodium nitrate, were found to be the best dressings ; a larger quantity of farmyard manure diminished the crop, and ammo- nium sulphate proved, as it generally has done at Grignon, decidedly inferior to sodium nitrate.J. M. H. M. Iron in Wine. By SANBUC (J. Pharm. [ 5 ] , 16, 344-345).-A wine from Seyne (Tar.) from an American vine, the Jacquez, was found to contain, per litre :-Alcohol, 67.54 grams; dry extract a t loo", 20.50; acidity in terms of snlphuric acid, 6.20; total ash, car- bonated, 2.60; anhydrous ferric oxide, 0.11. The iron was determined both gravimetrically and vdumetrically. The usual amount of iron in wines is equivalent to Om01-0*02 gram of ferric oxide. J. T. Nitrates in Soils and Water. By E. BR~AL (Ann. Agronom., 13, 561--568).-The author has applied the mode of detecting nitrates described in a previous memoir (Abstr., 188i, 1138) to the study of the arable, pasture, and forest soils, and the waters in the neighbour- hood of Baderi, Switzerland. A few cubic centimetres of the sulpho- phenol reagent in a stoppered bottle, and some strips of prepared filter-paper, are sufficient to show that nitrates are abundant in the arable soils, deficient in the meadow soils, and almost absent from the forest soils.He attributes the deficiency in the last two descriptions of soil to the excess of organic matter hindering nitrification, and to the rapid consumption of what nitrates are formed by the perennial Cl-ODS. The mountain streams are free from nitrates, and so is the &er of a hot mineral spring highly charged with sulphate of lime. J. M. H. MI. Sulphur and Phosphorus in Plants, Soils, and Moulds.By BERTHELOT and ANDR~ (Compt. rend., 105, 1217--1222).-Snlphur may exist in plants, soils, and moulds, in the form of sulphates directly precipitable as barium sulphate ; in the form of compounds analogous to the ethyl sulphates from which the sulphur is obtainedVEGETABLE PHYSIOLOGY AND AGRICULTURE. 385 as sulphate by hydrolysis or oxidation ; in the form of salts such as sulpbides, sulphites, and thiosulphates, which can be converted into sulphates by oxidation in solution ; and in the form of carbon-com- pounds such as taurine, cystin, albumin, &c., the sulphur in which is not converted into sulphate by oxidation in solution. In order to estimate tbe total sulphur ar phqhorus, the substance previously dried .at 100" is burnt in a current of oxygen in glass tube, the products of combustion being conducted through a column of pure anhydrous sodium or potassium carbonate.Care must be taken that the temperature does n o t rise sufficiently high to fuse the alkaline carbonates in the ash. When combustion has ceased, the current of oxygen is continued for some time in order to convert any alkaline sulphides into snlphetes. The contents of the tube are dissolved in water, acidified with hydrochloric acid, and precipitated with barium chloride. In the filtrate from the barium sulphate, the phosphoms is precipitated by means af ammonium molybdate, and is afterwards converted into magnesium pyrophosphate. The soil examined confahed 1.418 gram of sulphur per k h . , but 1 per cent.hydrochloric acid only extracted one-seventh of this, and concentrated nitric acid dissolved very lihtle more. The mould contained 6.156 grams of sulphur per kilo., of which 0.947 gram was soluble in cold dilute hydrochloric acid, and 2.0213 in concentrated boiling nitric acid. One of the specimens of the plant, Mercurialis annua, contained 10.768 grams of sulphur per kilo., 3.040 being soluble in cold dilute hydrochloric acid Another specimen contained 6.584 grams per kilo., 2.834 grams being soluble in cold 1 per cent. hydrochlmic acid and 4.554 in boiling concentrated nitric acid. The sulphur existing ac3 sulphate is in all three eases only a small proportion of the total quantity, and the sulphur convertible into sulphate by oxidation in solution, although greater, is still only a fmctim o€ the total amount.Phosphorus may exist in plants, moulds, and mils, as phosphates soluble in water or acids ; a8 ethereal compmnds yielding phosphates on hydrolysis or oxidation ; as phosphides or phosphitm, &c., which can be oxidised to phosphates in solution ; and a8 organic compounds which cannot be converked into phosphaptes in the wet way. The soil examined contained 0.641 gmm of phosphorus per kilo., 0.134 gram of which was soluble in hydrochloric acid of 1 per cent., 0.420 in hydrochloric acid of 10 per cent., 0.603 in boiling concen- trated nitric acid. The total phosphorus is much greater than that existing as phosphate, and it is not completely oxidisd by nitric acid. The mould contained 3.091 gram per kilo., 2.328 being soluble in cold dilate hydrochloric acid, and 3.085 in hot concentrated nitric acid.In this case, the proportion of phosphate is very large, and it is noteworthy that concentrated nitric acid removes the whole of the phosphorus. This last result is, however, probably abnormal. The first specimen of the plant contained 2.812 grams of phos- phorus per kilo., 1.668 gram being soluble in cold dilute hydrochloric acid. The second specimen contained 5-440 gram per kilo., 2.963 being soluble in cold dilute hydrochloric acid, and 4.154 in hot con-886 ABSTRACTS OF CHEMICAL PAPERS. centrated nitric acid. The proportion of phosphorus depends largely on the age of the plant. The last specimen contains twice as much as the mould, and nine times as much as the Foil.The proportion of soluble phosphates is greater than in the soil, and is comparable with that in the mould. From these r>sults, it is evident that sulphur and phosphorus, like nitrogen, exist i n plants, moulds, and soils, in several different forms. C. H. B.VEGETABLE PHTSIOLOGP AKD AGRICULTURE. 381Chemistry of Vegetable Physiology and Agriculture,Colour of Leaves in Relation to the Assimilation of Carbon.By T. W. ENCELMANN (Ann. Agronom., 13,477-480 ; from Bot. Zeit.,1887, 25--29).--The yellow leaves of an elder bush were studied sideby side with the green leaves of the same plant by means of Engel-mann’s microspectral photometer, and by their behaviour towardsaerobic bacteria.The absorption-spectrum of the living yellow cells shows that thebands I1 and I11 in the orange and the yellow-green which belong tothe green colouring constituent (cyanophyll or pure chlorophyll), and2 c 382 ABSTRACTS OF CHEMICAL PAPERS.which are absent from the spectrum of xanthophyll, are scarcelyindicated.In the spectrum of the green living cells, on the other hand, thesebands are easily identified, although Reinke, working with Glan’sphotometer, did not succeed in finding them.It would thus appearthat the yellow cells contain little chlorophyll proper, or chlorophyllane,and it would be expected that they should lack the power of assimila-tion. By immersing equal areas cut out of the yellow and greenleaves in a liquid charged with azrobic bacteria, and exposing theliquid to the light, it is easily seen that the yellow cells disengage farless oxygen in a given time than the green cells, and hence it isprobable that if they contained pure xanthophyll only, the assimilatingpower would be nil.With reference to the plants in which the light reaches the granulesof true green chlorophyll through layers of cells coloured red orpurple (copper-beech, red cabbage, &c.), the author observes thatthey do not differ from what is observed in green plants either in thedisposition of the chlorophyll granules or in their size, or the natureor intensity of their colour. Moreover, the red varieties of a plant, forexample, Coleus, are quite as large and vigorous as the green speci-mens.It follows that the rad colouring matter of these plants canonly absorb those rays which have little influence on assimilation.The colouring matter is always R red-purple, which has most effectin absorbing the green rays, whilst red rays pass freely, and blue andviolet very well.The curve of absorption rises about the middle ofthe spectrum, and descends again at the other end. When the solu-tion is very concentrated a large absorption-band is seen between thewave-lengths X = 0.59,~ and X = 0.50p. Speaking generally, theabsorption of light is complementary to that caused by solutions ofchlorophyll. If, as was formerly believed, the maximum of assimila-tion corresponded with the yellow rays, that process would be muchimpeded in the red plants, for the yellow rays are enfeebled to theextent of one-third in passing through the red solution.Supply of Food Constituents at Different Periods of PlantGrowth.By G. LIEBSCHER (Bied. Centr., 1887, 658-660).-As abasis for the science of manuring, the author advances a new theory.The view sometimes held, that one species of plant has a greaterpower than another of taking up some particular food constituentcannot be reconciled with the laws of osmosis; but the difficultiesmet with can be explained in another way. Each day the root shouldsupply a, certain amount of food to the plant ; this amount varies moreor less at different stages of growth, and further, these variationsdiffer in the case of different plants ; thus one species requires R fairlyuniform daily supply throughout its period of growth, whilst anotherrequires much more at one stage than at another. From the composi-tion of various plants at different stages of growth, the author hasconstructed a number of cunes showing how these supplies vary.Such information affords an important clue to the proper manuringof a particular species ; thus for a plant requiring a uniform dailysupply, a slowly decomposing and lasting manure is appropriate ;J.M. H. MVEGETABLE PHYSIOLOUY AND AGRICULTURE. 38 3whilst an easily soluble one should be given to a plant whose demandis large during a short period.Wheat Experiments in 1887. By A. LADUEEAU and MOUSSEAUX(Ann. Agronorn., 13, 538-551) .-The experiments were carried outon the poor lands of the Brie district, and had for their object todemonstrate the utility of artificial manures, and to ascertain themost productive and economical manuring for the district.The soil,limed in 1885, contained only 0.084 per cent. N, 0.085 per cent.PzOs, 0.325 per cent. K20, and 0.280 per cent. CaO.One variety of wheat (Golden Drop) was sown on all the plots, onthe same day, October Ilth, 1886, at the uniform rate of 2 hectolitresper hectare ; each plot measured 3 ares. Both straw and grain wereweighed on each plot, the value calculated out at the price actuallyrealised, and compared with the expense of the various manures used.The yield varied from 950 kilos. per hectare of grain, and 1550 kilos.straw on the unmanured plot, t o 3200 kilos. grain and 5650 kilos.straw on the best plot, which was manured with 50 cubic metres farm-yard manure, and 300 kilos.of 15 per cent. superphosphate perhectare in the autumn, and top dressed with 250 kilos. sodium nitratein the spring. The increase obtained on this plot over the unmanuredplot exceeded the cost of the manures applied by 319.75 francs perhectare. A still more favourable result (although from a smaller crop)was obtained on the plot dressed with 100.5 kilos. P,O, in superphos-ph@e and 48.5 kilos. of ammoniacal nitrogen per hectare in the autumn,69*/5 kilos. nitrogen as sodium nitrate per hectare in the spring ; onthis plot, the increase obtained by the manure exceeded the cost ofthe latter by 389.4 francs per hectare. The results obained on all theplots justify the following conclusions :-1.Superphosphate applied at the rate of SO kilos. per hectare pro-duces an increase of crop on these soils.2. Ammonium sulphate applied in spring gives results greatlysuperior to those given by the same money value of sodium nitrate.3. Basic cinder substituted for some of the superphosphate did notgive good results. The authors are now trying basic cinder alone,and expect to get better results with it. That employed in the pre-sent series of experiments was very coarsely ground.4. Farmyard manure alone did not even repay its cost, a resultprobably due to the exceptional drought of the season. The authorsrecommend the wheat growers of this distrtct to sell their farmyardmanure to the vine growers, and with a portion of the proceeds to buyartificial manures.H.H. R,J. 31. H. M.Experimental Culture of Sugar-beet at Grignon in 1887.By P. P. DEH~RA~N (Ann. Agronom., 13,529-535).-The experimentswere to decide two points, namely, the quality of the seed obtained atGrignon from previous crops of Vilmorin’s sugar-beet, and the effectof farmyard menure as compared with mineral manures on the yieldof sugar. The plots sown with the Grignon seed were therefore com-pared with parallel plots sown with seed obtained direct from Vil-rnorin ; the manures tried were farmyard manure, sodium nitrate, an384 ABSTRACTS OF CHEMICAL PAPERS.ammonium sulphate ; and the quality of the roots from the rariousplots was ascertained by selecting proportionate numbers of large,medium, and small roots from each plot, and testing the juice by thehydrometer and in the saccharimeter.The chief results of the ex-periments are that the continuously unmanured plots of both seriesyielded very small crops of small roots poor in sugar, namely, 13900and 10100 kilos. of roots per hectare, density of juice 6.9 and 7.2, per-centage of sugar in juice 15.8 and 14.6. The mean percentage ofsugar in the juice of the roots from the Grignon seeds was 17.7, andin the juice of the roots from the Vilmorin seeds 17-1, so that it isevident a good sample of seed may be relied on by the farmer for a tany rate a second harvest. Both series of plots proved that on thelight soil of Grignon, moderate dressings of farmyard manure, with orwithout the addition of sodium nitrate or ammonium sulphate, pro-duced considerably larger crops than the sodium nitrate or ammoniumsulphate alone, and that the roots grown with the farmyard manurewere by no means poor in sugar, the juice containing 18 to 19.5 percent.; 30000 kilos.farmyard manure per hectare, or 20000 kilos.with 200 kilos. sodium nitrate, were found to be the best dressings ; alarger quantity of farmyard manure diminished the crop, and ammo-nium sulphate proved, as it generally has done at Grignon, decidedlyinferior to sodium nitrate. J. M. H. M.Iron in Wine. By SANBUC (J. Pharm. [ 5 ] , 16, 344-345).-Awine from Seyne (Tar.) from an American vine, the Jacquez, wasfound to contain, per litre :-Alcohol, 67.54 grams; dry extract a t loo", 20.50; acidity in terms of snlphuric acid, 6.20; total ash, car-bonated, 2.60; anhydrous ferric oxide, 0.11.The iron was determinedboth gravimetrically and vdumetrically. The usual amount of ironin wines is equivalent to Om01-0*02 gram of ferric oxide.J. T.Nitrates in Soils and Water. By E. BR~AL (Ann. Agronom., 13,561--568).-The author has applied the mode of detecting nitratesdescribed in a previous memoir (Abstr., 188i, 1138) to the study ofthe arable, pasture, and forest soils, and the waters in the neighbour-hood of Baderi, Switzerland. A few cubic centimetres of the sulpho-phenol reagent in a stoppered bottle, and some strips of preparedfilter-paper, are sufficient to show that nitrates are abundant in thearable soils, deficient in the meadow soils, and almost absent from theforest soils.He attributes the deficiency in the last two descriptionsof soil to the excess of organic matter hindering nitrification, and tothe rapid consumption of what nitrates are formed by the perennialCl-ODS. The mountain streams are free from nitrates, and so is the&er of a hot mineral spring highly charged with sulphate of lime.J. M. H. MI.Sulphur and Phosphorus in Plants, Soils, and Moulds. ByBERTHELOT and ANDR~ (Compt. rend., 105, 1217--1222).-Snlphurmay exist in plants, soils, and moulds, in the form of sulphatesdirectly precipitable as barium sulphate ; in the form of compoundsanalogous to the ethyl sulphates from which the sulphur is obtaineVEGETABLE PHYSIOLOGY AND AGRICULTURE.385as sulphate by hydrolysis or oxidation ; in the form of salts such assulpbides, sulphites, and thiosulphates, which can be converted intosulphates by oxidation in solution ; and in the form of carbon-com-pounds such as taurine, cystin, albumin, &c., the sulphur in which isnot converted into sulphate by oxidation in solution.In order to estimate tbe total sulphur ar phqhorus, the substancepreviously dried .at 100" is burnt in a current of oxygen in glasstube, the products of combustion being conducted through a columnof pure anhydrous sodium or potassium carbonate. Care must betaken that the temperature does n o t rise sufficiently high to fuse thealkaline carbonates in the ash. When combustion has ceased, thecurrent of oxygen is continued for some time in order to convert anyalkaline sulphides into snlphetes.The contents of the tube aredissolved in water, acidified with hydrochloric acid, and precipitatedwith barium chloride. In the filtrate from the barium sulphate, thephosphoms is precipitated by means af ammonium molybdate, and isafterwards converted into magnesium pyrophosphate.The soil examined confahed 1.418 gram of sulphur per k h . , but1 per cent. hydrochloric acid only extracted one-seventh of this, andconcentrated nitric acid dissolved very lihtle more.The mould contained 6.156 grams of sulphur per kilo., of which0.947 gram was soluble in cold dilute hydrochloric acid, and 2.0213in concentrated boiling nitric acid.One of the specimens of the plant, Mercurialis annua, contained10.768 grams of sulphur per kilo., 3.040 being soluble in cold dilutehydrochloric acid Another specimen contained 6.584 grams perkilo., 2.834 grams being soluble in cold 1 per cent.hydrochlmic acidand 4.554 in boiling concentrated nitric acid.The sulphur existing ac3 sulphate is in all three eases only a smallproportion of the total quantity, and the sulphur convertible intosulphate by oxidation in solution, although greater, is still only afmctim o€ the total amount.Phosphorus may exist in plants, moulds, and mils, as phosphatessoluble in water or acids ; a8 ethereal compmnds yielding phosphateson hydrolysis or oxidation ; as phosphides or phosphitm, &c., whichcan be oxidised to phosphates in solution ; and a8 organic compoundswhich cannot be converked into phosphaptes in the wet way.The soil examined contained 0.641 gmm of phosphorus per kilo.,0.134 gram of which was soluble in hydrochloric acid of 1 per cent.,0.420 in hydrochloric acid of 10 per cent., 0.603 in boiling concen-trated nitric acid. The total phosphorus is much greater than thatexisting as phosphate, and it is not completely oxidisd by nitric acid.The mould contained 3.091 gram per kilo., 2.328 being soluble incold dilate hydrochloric acid, and 3.085 in hot concentrated nitricacid. In this case, the proportion of phosphate is very large, and it isnoteworthy that concentrated nitric acid removes the whole of thephosphorus. This last result is, however, probably abnormal.The first specimen of the plant contained 2.812 grams of phos-phorus per kilo., 1.668 gram being soluble in cold dilute hydrochloricacid. The second specimen contained 5-440 gram per kilo., 2.963being soluble in cold dilute hydrochloric acid, and 4.154 in hot con886 ABSTRACTS OF CHEMICAL PAPERS.centrated nitric acid. The proportion of phosphorus depends largelyon the age of the plant. The last specimen contains twice as muchas the mould, and nine times as much as the Foil. The proportion ofsoluble phosphates is greater than in the soil, and is comparable withthat in the mould.From these r>sults, it is evident that sulphur and phosphorus, likenitrogen, exist i n plants, moulds, and soils, in several different forms.C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8885400381

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

886 ABSTRACTS OF CHEMICAL PAPERS. A n a l y t i c a l Chemistry. Polaristrobometric Analysis. By H. LANDOLT (Ber., 21, 191- 220).-T he specific rotation of nearly all circularly polarising solutions may be expressed in terms of-(1,) The percentage q of the inactive solvent, [a] = A + Bq + Cp2. (2.) The percentage p of the active substance, [a] = a + bp + cp2. (3.) The concentration c, [a] = A, + B,c + Clc. In many cases, the third term may be neglected. The two last equations may be used for either concentration or per- centage composition, since c = p d , where d is the specific gravity of the solution. In determining from the rotation the amount of substance in solu- tion, the following cases have to be distinguished :- I. A solution may contain a single active substanee in an inactive solvent.This is the most general case, and the specific rotation is as a rule constant, that is, the angle of rotation is proportional to the concentration, as is the case for aqueous solutions of cane-sugar, milk- sugar, maltose, raffinose, dextrose, lavulose, invert sugar, and galac- tose. The specific rotation is, however, not always constant, but sometimes a linear function of the concentration, as, for instance, for solutions of nicotine and camphor in alcohol. 11. Solution of an active substance in two inactive rsolvents. The specific rotation of nearly all active substances being unequally in- fluenced by different solvents, the action of each solvent alone on the rotation has to be separately considered. These will be [ a ] = A + Bq and [all = A + Blq, the constant A being the rotation of tfhe pure active substance and the same in each case.Hence if q and q1 are the weights of two solvents contained in 100 parts of the mixture, the specific rotation will be [a], = A + Bq + Blpl. This presup- poses each solvent to act perfectly independently of the other, which, however, only happens in the case of cane-sugar, the rotation of which is the same for all solvents. In ot,her cases, the value of [a], lies irre- gularly between [ a ] and [all, as, for instance, for narcotine in 1 vol. alcohol to 2 vols. chloroform, or it attains a maximum higher than either [a] or [all, as for cinchonidine in the above solvents or cinchonidine nitrate and hydrochloride in mixtures of alcohol and water. III. Solution of two active substances in an inactive solvent.AXALYTICAL CHEMISTRY.387 Firstly, the combined weight of the two substances in 100 C.C. solution may be known. Let the specific rotation of the solution be [a], and the mixture contain x: per cent. of one constituent of the specific rota,- tion [a]x, and y = 100 - x of the other constituent of the specific rotation [a]y. Then [a]$ x + [sly (100 - o) = 100 [a], from which x and y are obtained in terms of [a], [a]2, and Instances of this are solutions of cane-sugar and raffinose and quinine and cinchoniue sulphates. Secondly, the combined weight of the two active substances may be unknown, and the analysis is then effected by measuring the rotation of the solution, and converting one or both of the constituents into another optically active substance by inversion, and again measuring the rotation.If only one con8tituent undergoes inversion, if Cpl and Cpl, the angles of rotation for unit concentration of each con- stituent be mown, p the rotation of the inverted substance, and c1 and cll the concentrations required, we have- Before inversion, @lcl + &cll = a After inversion, pkcl + q5,1c11 = a from which el and cll may be calculated. This is true for solutions of cane-sugar and invert sugar and cane-sugar and dextrin, the cane- sugar being the substance inverted. If both constituents undergo in- version, then if pI1 is the rotation of the second inverted substance- c1 - Pll" _-____ - @11a1 and cll = P1"- - @lal p116 - Pl@H p1@11 - Pll@l)l' This is true for a solution of raffinose and cane-sugar. IV.Analysis of inactive substances in solution. This would be effected by measuring the influence of certain inactive Substances on substances of known rotation, such) for instance, as the action of boric acid on tartaric acid solutions. Little has been done in this direction, and no attempt at formulating the above influence can at present be mdde. H. C. Correct Analysis of Superphosphates. By J. RUFFLE (J. SOC. Chem. Ind., 6, 491-494 and 704--705).-1n furtherance of his in- vestigations on moisture and free acid in superphosphates (this vol., p. 87), the author suggests the following method of analysing super- phosphates :-( 1.) Moisture : estimated by calcium chloride in a vacuum. (2.) Soluble phosphoric acid : estimated by direct deter- minat,ion.(3.) Insoluble phosphate : estimated by direct calculation from the amount of insoluble phosphoric acid after evaporation to dryness with hydrochloric acid and re-solution with hydrochloric acid. (4.) Calcium sulphate : estimated by determining the whole sulphuric acid present and calculating this into anhydrous calcium sulphate. (5.) Sand : estimated by evaporat,ing to dryness with hydro- chloric acid and re-solution in hydrochloric acid. (6.) Combined water and organic matters, including the uncombined calcium oxide : estimated by difference. (7.) Alkalis, magnesia : amounts as deter- mined. By this plan no more work is introduced than is practised at388 ABSTRACTS OF CEEMICAL PAPERS. the present time, whilsk the statements 1, 2, 3, 4, 5, and 7 will be true from direct dekermination, and the commercially unimportant '' combined water and organic matter" will not be attempted; hence false statements will be avoided.The author is of opinion that the calcium oxide existing as mono- calcium phosphate in arnmoniated phosphates may be wholly passed over, and the total calcium oxide, less the amoun% of the insoluble phosphate, be calcmhted out Co calcium sulphate. D. B. Separation of Zinc from Nickel and Manganese and Esti- mation of Nickel. By T. BAYLEY ( J . ISOC. Chem. Ind., 6, 499).- A good separation of zinc from nickel and from manganese may be made in a hot solution containing free phosphoric acid by precipita- tion with hydmgen sulphide. Cobalt has a tendency to go down in small quantity with the zinc.In order to precipitate nickel from solutions, the author recommends the addition of ammonium sulphide until the last drop renders the liquid alkaline; this is followed by ammo- nium benzoate, and aftelawards by a few drops of hydrochloric acid. In this solution, the nickel is completely precipitated as sulphide. The latter is heated in a porcelain dish, dissolved in nitric acid, evaporated, ignited, and weighed as sulphaite. The ignition should be effected a t a low red heat,.and the dish allowed to cool. The sulphate is then treated with sulphnric acid and submitted to a further short ignition. Success would appear ts depend on the shortness of the second igniiion. Reaction d Iron with Nitric Acid. By T. BAYLEE (J. SOC. Chew. I d , 6, 499- 500).-When an assay of " nitre '' in sulphuric acid is made in the nitrometer, an error is caused by absorption of nitric oxide when the acid contains iron.Nitric oxide, shaken with mercury and pure sulphuric acid, suffers no absorption, nor does mer- cury pass into solution in the acid unless the acid contains a small quantity of iron. On copiously diluting the acid by the addition of air-free water, and subsequently adding a solution of a ferricyanide to the cooled acid liquid, the blue reaction is readily obtained. The mercury Seem8 to take no part in the reduction of the ferric salt, since the results can be equally well obtained if pure nitric oxide is passed through a set of Geissler bulbs charged with sulphuric acid contain- ing ferric sulphate. The sulphuric acid in this case, as iii the nitro- meter, assumes a purple tint, which is characteristic of the reaction when it takes place in the acid, but not in the aqueous solution.Action of Oils on Polarised Light, By W. BISHOP (J. Pham. [ 5 ] , 16, 300--301).-Besides resin and castor oils, there are two others which very perceptibly affect polarised light. Thus in a tube of 20 cm. long colza oil gave a rotation of -1%" to -2-1", and seEame oil gave from +3*1" to 9.0". Of several other vegetable oils examined none gave as much as 1.0'. In the case of certain linseed oils, when found to have dextrorotative power, they should be examined €or sesame oil before concluding that. resin oil has been added. D. B. D. B. J. T.886 ABSTRACTS OF CHEMICAL PAPERS.A n a l y t i c a l Chemistry.Polaristrobometric Analysis.By H. LANDOLT (Ber., 21, 191-220).-T he specific rotation of nearly all circularly polarising solutionsmay be expressed in terms of-(1,) The percentage q of the inactivesolvent, [a] = A + Bq + Cp2. (2.) The percentage p of the activesubstance, [a] = a + bp + cp2. (3.) The concentration c, [a] =A, + B,c + Clc. In many cases, the third term may be neglected.The two last equations may be used for either concentration or per-centage composition, since c = p d , where d is the specific gravity ofthe solution.In determining from the rotation the amount of substance in solu-tion, the following cases have to be distinguished :-I. A solution may contain a single active substanee in an inactivesolvent. This is the most general case, and the specific rotation is asa rule constant, that is, the angle of rotation is proportional to theconcentration, as is the case for aqueous solutions of cane-sugar, milk-sugar, maltose, raffinose, dextrose, lavulose, invert sugar, and galac-tose.The specific rotation is, however, not always constant, butsometimes a linear function of the concentration, as, for instance, forsolutions of nicotine and camphor in alcohol.11. Solution of an active substance in two inactive rsolvents. Thespecific rotation of nearly all active substances being unequally in-fluenced by different solvents, the action of each solvent alone on therotation has to be separately considered. These will be [ a ] = A + Bq and [all = A + Blq, the constant A being the rotation of tfhepure active substance and the same in each case.Hence if q and q1are the weights of two solvents contained in 100 parts of the mixture,the specific rotation will be [a], = A + Bq + Blpl. This presup-poses each solvent to act perfectly independently of the other, which,however, only happens in the case of cane-sugar, the rotation of whichis the same for all solvents. In ot,her cases, the value of [a], lies irre-gularly between [ a ] and [all, as, for instance, for narcotine in 1 vol.alcohol to 2 vols. chloroform, or it attains a maximum higher thaneither [a] or [all, as for cinchonidine in the above solvents orcinchonidine nitrate and hydrochloride in mixtures of alcohol andwater.III. Solution of two active substances in an inactive solventAXALYTICAL CHEMISTRY.387Firstly, the combined weight of the two substances in 100 C.C. solutionmay be known. Let the specific rotation of the solution be [a], andthe mixture contain x: per cent. of one constituent of the specific rota,-tion [a]x, and y = 100 - x of the other constituent of the specificrotation [a]y. Then [a]$ x + [sly (100 - o) = 100 [a], from whichx and y are obtained in terms of [a], [a]2, and Instances of thisare solutions of cane-sugar and raffinose and quinine and cinchoniuesulphates. Secondly, the combined weight of the two active substancesmay be unknown, and the analysis is then effected by measuring therotation of the solution, and converting one or both of the constituentsinto another optically active substance by inversion, and againmeasuring the rotation.If only one con8tituent undergoes inversion,if Cpl and Cpl, the angles of rotation for unit concentration of each con-stituent be mown, p the rotation of the inverted substance, and c1 andcll the concentrations required, we have-Before inversion, @lcl + &cll = aAfter inversion, pkcl + q5,1c11 = afrom which el and cll may be calculated. This is true for solutions ofcane-sugar and invert sugar and cane-sugar and dextrin, the cane-sugar being the substance inverted. If both constituents undergo in-version, then if pI1 is the rotation of the second inverted substance-c1 - Pll" _-____ - @11a1 and cll = P1"- - @lalp116 - Pl@H p1@11 - Pll@l)l'This is true for a solution of raffinose and cane-sugar.IV.Analysis of inactive substances in solution. This would beeffected by measuring the influence of certain inactive Substanceson substances of known rotation, such) for instance, as the actionof boric acid on tartaric acid solutions. Little has been done inthis direction, and no attempt at formulating the above influence canat present be mdde. H. C.Correct Analysis of Superphosphates. By J. RUFFLE (J. SOC.Chem. Ind., 6, 491-494 and 704--705).-1n furtherance of his in-vestigations on moisture and free acid in superphosphates (this vol.,p. 87), the author suggests the following method of analysing super-phosphates :-( 1.) Moisture : estimated by calcium chloride in avacuum. (2.) Soluble phosphoric acid : estimated by direct deter-minat,ion. (3.) Insoluble phosphate : estimated by direct calculationfrom the amount of insoluble phosphoric acid after evaporation todryness with hydrochloric acid and re-solution with hydrochloricacid.(4.) Calcium sulphate : estimated by determining the wholesulphuric acid present and calculating this into anhydrous calciumsulphate. (5.) Sand : estimated by evaporat,ing to dryness with hydro-chloric acid and re-solution in hydrochloric acid. (6.) Combinedwater and organic matters, including the uncombined calcium oxide :estimated by difference. (7.) Alkalis, magnesia : amounts as deter-mined.By this plan no more work is introduced than is practised a388 ABSTRACTS OF CEEMICAL PAPERS.the present time, whilsk the statements 1, 2, 3, 4, 5, and 7 willbe true from direct dekermination, and the commercially unimportant'' combined water and organic matter" will not be attempted; hencefalse statements will be avoided.The author is of opinion that the calcium oxide existing as mono-calcium phosphate in arnmoniated phosphates may be wholly passedover, and the total calcium oxide, less the amoun% of the insolublephosphate, be calcmhted out Co calcium sulphate.D. B.Separation of Zinc from Nickel and Manganese and Esti-mation of Nickel. By T. BAYLEY ( J . ISOC. Chem. Ind., 6, 499).-A good separation of zinc from nickel and from manganese may bemade in a hot solution containing free phosphoric acid by precipita-tion with hydmgen sulphide. Cobalt has a tendency to go down insmall quantity with the zinc.In order to precipitate nickel fromsolutions, the author recommends the addition of ammonium sulphideuntil the last drop renders the liquid alkaline; this is followed by ammo-nium benzoate, and aftelawards by a few drops of hydrochloric acid.In this solution, the nickel is completely precipitated as sulphide. Thelatter is heated in a porcelain dish, dissolved in nitric acid, evaporated,ignited, and weighed as sulphaite. The ignition should be effected a t alow red heat,.and the dish allowed to cool. The sulphate is then treatedwith sulphnric acid and submitted to a further short ignition. Successwould appear ts depend on the shortness of the second igniiion.Reaction d Iron with Nitric Acid.By T. BAYLEE (J. SOC.Chew. I d , 6, 499- 500).-When an assay of " nitre '' in sulphuricacid is made in the nitrometer, an error is caused by absorption ofnitric oxide when the acid contains iron. Nitric oxide, shaken withmercury and pure sulphuric acid, suffers no absorption, nor does mer-cury pass into solution in the acid unless the acid contains a smallquantity of iron. On copiously diluting the acid by the addition ofair-free water, and subsequently adding a solution of a ferricyanide tothe cooled acid liquid, the blue reaction is readily obtained. Themercury Seem8 to take no part in the reduction of the ferric salt, sincethe results can be equally well obtained if pure nitric oxide is passedthrough a set of Geissler bulbs charged with sulphuric acid contain-ing ferric sulphate. The sulphuric acid in this case, as iii the nitro-meter, assumes a purple tint, which is characteristic of the reactionwhen it takes place in the acid, but not in the aqueous solution.Action of Oils on Polarised Light, By W. BISHOP (J. Pham.[ 5 ] , 16, 300--301).-Besides resin and castor oils, there are twoothers which very perceptibly affect polarised light. Thus in a tubeof 20 cm. long colza oil gave a rotation of -1%" to -2-1", andseEame oil gave from +3*1" to 9.0". Of several other vegetable oilsexamined none gave as much as 1.0'. In the case of certain linseed oils,when found to have dextrorotative power, they should be examined€or sesame oil before concluding that. resin oil has been added.D. B.D. B.J. T

ISSN:0368-1769    

DOI:10.1039/CA8885400386

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

389 General and Physical Chemistry. Dispersion Equivalents. By J. H. GLADSTONE (Proc. ROY. SOC., 42,401-4 I O).-This paper is a continuation of the author's researches on dispersion equivalents. Notwithstanding the difficulties of the investigation, the following conclusions have been arrived at :- 1. That dispersion, like refraction, is primarily a question of atomic constitution. 2. That dispersion, like refraction, is modified by pro- found differences of constitution, such as change of atomicity. 3. That dispersion frequently reveals differences of constitution, at present unrecognised. The following dispersion equivalents (H - A ) have been determined :-Phosphorus (liquid), 3.0 ; sidphur (double bond), 2.6 ; sulphur (single bonds), 1.2 ; hydrogen, 0.04 ; carbon, 0.26, 0.51, and 0.66; oxygen (double bond), 0.18; oxygen (single bonds), 0.10 ; chlorine, 0-50 ; bromine, 1.22 ; iodine, 3.65 ; nitrogen, 0.10 ; CH2, 0.34 ; NOz, 0.86.The values for CHz, H, and C are worked out in the same way as the refraction equivalents. I n unsaturated compounds, the dispersion equivalent is much greater, (0.5) in ally1 compounds and olefines, and at least 0.8 in the aromatic series. Where the carbon has all four bands satisfied with carbon-atoms (with refrac- tion value 6*0), the dispersion equivalent is enormously increased. In considering the dispersion equivalents of solutions of metallic salts, it is pointed out that where the solution is dilute the values are untrustworthy, owing to the smallness of the specific dispersion, the values for potassium and sodium alone are therefore considered.The difference between the dispersion equivalents of their salts is 0.09. In determining the value for potassium itself, the halojd salt was rejected, as it was anticipated that the chlorine value might be higher than it is in organic compounds, as is the case with the refraction equivalents. Determined from the formate and acetate, with the values given above for carbon, hydrogen, and oxygen, the dispersion equivalent for potassium is 0.53 and 0.44 fcr the salts respectively. From potassium hydroxide viewed as water, wit'h a- hydrogen-atom replaced, the value 0.565 is obtained. From the nitrite, by subtracting thc value for NOz, 0.48 is obtained. From the cyanide, 0.58 ; fkom the carbonate, 0.40 ; from the oxalate, 0.59. These variations c*annot be due to experimental error, nor is i t probable that potassium has more than one dispersion equivalent, as it has only one refraction equivalent.The unceriaint,y probably lies in the value of the radiclev to which the metal is joined. H. K. T. Mathematical Analysis of the Spectra of Magnesium and Carbon. By A. GR~NWALD (Monatsh., 8, 650-71 2).-In accordance with the principle laid down by the author (Abstr., 1887, 1070), an analysis of the spectra of magnesium and carbon has been effected, the data of different observers, chiefly those of Liveing and Dewar, being used for this purpose, VOL. LlT. 2 d390 ABSTRACTS OF CHEMICAL PAPERS. The magnesium spectrum is found to show the presence of the primary subst-ance c in the same condition in which it is found in oxygen and carbon, of the primary substance h in the state in which it exists in free hydrogen, and in the more condensed state in which it is found in the water-vapour spectrum, and also of b (helium) in an uncondensed stat'e.Besides these, a number of very weak, and at, present unknown hydrogen and oxygen lines are present. The spectrum of carbon contains the primary substance c in the stahe in which it is found in oxygen and magnesium, and also the sub- stance b. This latter exists in four different conditions : in the state in which it is observed in free hydrogen; in the state in which it exists in the hydrogen of water-vapour ; and in a, more dilated chemical condition, and a more condensed condition than that in which it occurs in free hydrogen. A number of hydrogen and oxygen lines are also present, most of them very weak, but which, on multiplying their wnve-lengths by the facttor +, as in the case of those in the magnesium spectrum also, are converted into lines in the water spectrum.H. C. Compounds of the Rare Earths yielding Absorption- spectra. By G . K R ~ S S and L. NILSON (Ber., 21, 585-588).--8 rejoinder to Bailey (this vol., p. 208). Contact Electricity. By W. v. ULJANTN (Ann. Ph?y.s. Ohenz. [Z], 33, 238).-The author points out that Exner (this vol., p. 208) has misunderstood his method (Anlz. Phys. Cheni. [2], 30, 699) of deter- mining the potential difference between zinc and copper, as he appears to have assumed that the author covered a copper cylinder with a zinc one, and inserted such a fraction of a Daniell, that when the latter cylinder was removed there was no deflection of the elec- trometer.This arrangement would clearly not enable the potential difference to be me,zsured, as it would require that the envelope also should be a t the same potential, and the latter is determined by that of the walls of the room. I n the arrangement used, the two cylinders were of zinc, and were surrounded by a copper envelope, and before removing the outer cylin- der it was separated from the inner one. Then assuming the two zinc cylinders to be at the same potential, there would be no deflection if the copper envelope was at the same potential. This condition was satisfied by the introduction of a certain fraction of a Daniell in the earth connection of the envelope. It is clear that the method would not serve to determine any poten- tial difference between the zinc cylinders, as i t depends on the assump- tion that they are a t the same potential, being of the same metal, and in contact.G. W. T. Maximum Galvanic Polarisation of Platinum Electrodes in Sulphuric Acid. By C. FROMME (Ann. Phys. Chem. [Z], 33, 80- 128).-Ttre great discrepancies between the different determinations of the maximum polarisation in a voltameter containing dilute sul- phuric acid with platinum electrodes, induced the author to investigateOFXEILAL AKI) PHYSICAL CHIEXISTRY. 391 the circumstances on which the amount of polarisation depends. A priori, the polarisation might be expected to depend on the nature of the surface of the electrodes, on their dimensions, on the concentration of the acid, and on the pressure a t which the gases are liberated.The concentration of the acid in the different experiments varied from 0.18 to 65 per cent. The author finds that the manner in which the amount of polarisa- tion varies with the concentration is most complicated i n the case of very dilute solutions, for, as the concentration is gradually increased, the polarisation at first increases and reaches a maximum, and after- wards falls to a minimum ; when the anode is small, it passes through a second maximum and minimum, until it finally increases steadily with the concentration ; with a larger anode, only a single maximum and minimum are observed. In very dilute solutions, the amount of polarisation is found to depend on whether the water used is distilled in glass or in nietallic vessels, t h i s being doubtless due to the presence of small particles of glass or of metal in the distilled water.When the. cathode is small, its surface becomes blackened by the passage of the current, whilst a larger cathode is not, sensibly altered. With the more dilute solutions, and when both the electrodes were small, a yellow deposit was observed on the anode. The black deposit remains unaltered after treatment with concentrated srrlphnric acid, but it is slowly dissolved by aqua regia. J t can also be removed by revers- ing the current for some time, or i t can be scraped off. This deposit had already been observed by de Ia Rive (Arm. Phys.Chem., 41, 156 ; 45, 421) and by Poggendorff (ibid., 61, SOS), and their experiments showed that it consisted of platinum in a state of powder, mechanically detached from the cathode. I n soue of the experiments, even when the cathode i8 larger, a greyish-brown deposit was observed on the latter, but only when the water had been distilled in glass vessels, from which the author concludes that i t was due to particles of glass. It was easily dissolved by concentrated sulphuric acid. I n the case of the larger anodes, a dark yellow coloration mas observed after some time. This yellow deposit on the anodes was unaffected by treatment with hot concentrated salphuric scid or aqua regia, and it occurred whether the water had been distilled in glass or in metallic vessels.The author was unable to determine its cause, but concluded that it was not due to the presence of any impurity i n the solution. The amount of polarisation is found to depend on the size of the eledrodes ; with dilate solutions, the size of the anode is the more important, with stronger ones that of the cathode. With the solutions used containing, as previonsly stated, from 0.18 to 65 per cent. of acid, the E.M F. of polarisation varied from 1.94 to 2.43 of a Daniel1 when the cathode and anode were both large ; from 1.45 to 2.98 wben the cathode was small and the anode large ; from 1.90 to 4.18 when both cathode and anode were small ; and from 1.89 to 4-31 when the cathode was large and the anode small. Tile least variation, therefore, occurs when both the electrodes are large, and the greatest when the cathode is large and the anode small.The resistance of the voltameter when traversed b j R strong steady 2 d 2392 ABSTRACTS OF CHEMICAL PAPERS. current diminishes as the coricentration of the acid increases, and ulti- mately reaches a minimum value when the concentration is about the same as that for which the conductivity is found to be a maximum by observations with alternate currents ; after this, it increases with further increase in the concentration. When, however, the anode is small, the resistance continues to diminish up to the highest limits of concentration used in the experiments. Electromotive Forces of Metals in Cyanide Solutions. By S . P. THOMPSON (Proc. Roy. Xoc., 42, 387--389).-The electromotive forces of copper and zinc in cyanide solutions are examined in order to ascertain the cause of the possibility of depositing these two metals simultaneouslv. It is found that, with higher concentration, the E.M.F.of copper increases more than that of zinc ; moreover, in a cold dilute solution of potassic cyanide the E.M .F. of zinc is higher than that of copper, whilst, in a boiling saturated solution the E.M.F. of copper is greater than that of zinc: hence it is possible to construct a bat- twy consisting of one metal, copper, and one electrolyte, a solution of potassic cyanide, the anode being kept hot and the cathode cold. Tables are given showing the E.M.F.’s of various metals compared with carbon in cyanide solutions of various strengths. Maxima are frequently found a t intermediate stages of concentration.I n a mixed solution of copper and zinc cyanides, there is a neutral condition, in which the E.M.F.’s of zinc and copper are equal, depending on the relative amounts of metal, the concentration of the solution, and the temperature. The E.M.F. of the copper is the most sensitive, espe- cially to variations in the concentration of the solution. A t the cathode, the concentration is determined, on the one hand, by the rapidity with which the metal is deposited, that is, by the current- dmsity ; on the other, by the rapidity of diffusion ; hence there will be a certain current-density a t which the solution will be maintained in the neutral condition and the metals be deposited equally. G. W. T. H. I(. T. Resolution of the Electromotive Forces of Galvanis Ele- ments.By J. MIESLER (Monatsh., 8, 713--720).-1n continuation of his work on this subject (this vol., p. 330), the author has examined Marik-Davy, de la Rue, and Niaudet cells, and in each the sum of tjhe potential differences i n the various parts of the cell is found to be equal to the total E.M.F. Accumulators were examined, and for these the above was also found to be true. On discharging an accu- mulator and measuring the potential differences a t different intervals, as the total E.M.F. decreased to about one-h2lf of its original value, the potential difference between the negative plate and acid also tfirninished, but tha,t between the positive plate and acid remained the mnie. After the cell had been short circuited for some time, the exact opposite Lad, however, taken place, for the potential difference between the negative plate and acid was still the same, whilst that between the positive plate and acid had decreased.An attempt mechnnicdly to construct an accumulator that should give the same 1,oteutial differences as a charged accumulator failed. H. C.GENERAL AND PHYSICAL CHEMISTRY. 393 Thermal Alteration in a Daniell Cell and in an Accu- mulator. By G. MEYER (Ann. Phys. Chem. [2], 33, 265-289).- Investigations have been made on the thermal changes in a Daniel1 cell by Lindig (Ann. Phys. Chem., 123, l), Voller (ibid., 149, 394), and v. Helmholtz ( B e y . , 18, 22), and the latter has shown that in a zinc sulphate cell the temperature-coefficient depends on the degree of concentration of the solution.The object of this paper is to determine more fully on what circumstances the temperature-coeffi- cient depends, in the case both of sulphuric and zinc sulphate cells, and to determine whether the temperature-coefficient of the cell is equal to the sum of the temperature-coefficients at each contact of uiilike sixbstances. In order to ensure their purity, the metals used were obtained by electrolytic deposition from copper sulphate a n d zinc sulphate, and the copper sulphate, zinc sulphate, and sulphuric acid were chemi- cally pure. The metals and liquids composing the cell were con- tained in a glass tube of special construction, and the liquids were separated by parchment-paper ; the dissolved. air being got rid of by use of an air-pump.The measurements of the E.M.F. were always made with a quadrant electrometer, so that there was no polarisation, and the electrometer reading was taken directly after the zinc was introduced into the liquid, to prevent a coating of hydrogen being formed, a t the higher temperatures, by the action of the sulphuri(: acid on the amalgamated zinc. The results obtaiiied with tbe cells were as follows :-The E.M.F. of a Daniell cell with sulphnric acid increases with the temperature, and the value of the tempe- rature-coefficient depends on the degree of concentration of the liquids in the cell, increasing with an increase in the concentration of the sulphuric acid, until the solution contains about 30 per cent. of the acid, when it attains a maximnm value, and diminishes when the concentration is increased beyond this point.The temperature-co- efficient increases con t8inuously without attaining a maximum as tho concentration of the copper sulphate is increased. In t,he case of a zinc sulphate cell, the E.M.F. diminishes as the temperature rises, and when the concentration of the zinc sulphate is increased from a low degree the temperatnre-coefficient falls t o zero, and as the concentration is further increased this ha3 a continually in- creasing negative value. The effect on the temperature-coefficient of varying the concentration of the copper sulphate solution is the same as in the case of the sulphuric acid cell. In the accumulator, the temperature-coefficient was found to increase with increased concentration of the sulphuric acid, but the author has not yet, been able to determine whether the degree of concentration has any effect on the E.M.F., as the latter begins to diminish as soon as the charging current is discontinued, at first rapidly, and then slowly, but not slowly enough to enable any conclusions to be drawn from the measurements of E.M.F., each of which occupied about six minutes.During the experiments on the accumulator, whilst evolution of gas WRS observed from the lead plates when it mas placed under the air- pump to free the sulphuric acid from dissolved air, i t was found394 ABSTRACTS OF CHEMICAL PAPERS. by depositing lead by means of zinc from a solution of lead acetate, and heating it in a vacuum, that finely divided lead absorbs about 0.206 of its volume of hydrogen.The absorption of air by the accu- mulator plates would be too small to have an appreciable effect on the E.M.F. The author, however, found it impossible to obtain any trustworthy results from a cell containing platinum instead of copper, owing to the dependence of the E.M.F. on the amount of air absorbed by the platinum. G. W. T. Determination of the Specific Inductive Capacities of Con- ducting Liquids. By E. COHN and L. ARONS (Ann. Phys. Chem. [2], 33, 13-3I).-In a previous memoir (ibid. [a], 28, 454), theauthors gave a means of determining the specific inductive capacity of a con- ducting liquid founded on the result obtained by, them that the dielectric polarisation and conduction are mutually independent. Jn the former experiments, the highest conductivity did not exceed 4.5 x in terms of mercury, und the values of the sp.ind. cap. were found to be of much the same magnitude as for good insulators, being in every case less than 5. In the present paper, liquids of higher conductivity are considered, and this made it necessary to devise a new method, as the former one, depending on observatious of the rate of leakage of an electrostatic charge, would have required the observations of intervals of time considerably lest3 than the millionth of a second. The method used for the present inquiry is a modification of Silow's (this Journal, 1876, ii, 267), founded on the principle that when a system of conductors immersed in a homogeneous medium is maintained at a constant potential, the work done against electrical forces, in effecting a given change of configuration, is proportional t o the sp.ind. cap. of the medium. The needle and one pair of quadrants of an electrometer mere joined to one extremity of the secondary of an induction coil, and the remaining pair to the other extremity. Readings were then taken alternately with the liquid and with air only in the electrometer. By this means measurements could be obtained for liquids having a Conductivity as high as 16 x lo-'', or about 3400 times the highest conductivity in the former series. Calling K the sp. ind. cap., and k the conductivity, it was fonnd that for distilled water I( = 76, whilst kvaried from 3.4 x lo-'' to 16 x 10-lo, so that an increase of conductivity to about five times its original value had no perceptible effect on the sp.ind. cap. For ethyl alcohol con4 taining 2 per cent. of water, K = 26.5, and when, by the addition of traces of ammonium chloride, the conductivit'y was increased from 2.3 x to 12 x lO-'O, the value of K remained sensibly constant. For amyl alcohol the values obtained were K = 15 and k = 0.16 x lo-''. When successive quantities of ethyl alcohol were added to pure xylene, both K and JG increased, but the latter at first much more rapidly than the former, the change of k from lees than to 0.03 being accompanied only by a change of K from 2.36 to 3-08. For these substances, Maxwell's law connecting sp. ind. cap.GEXERAL AND YHTSICAL CHEMISTRII'. 355 Oil of turpentine from Pinus silvestris, lzvo- rotatory Oil of turpentine from Pims maritima, l ~ v o - rotatory Oil of turpentine from Pinus AustraEis, dex- trorotatoly Oil of citron ... . . . . . . . . . . . , . , . . . . . . . . . . . and index of refraction does not hold even approximately, the deviation from the law being very much greater than even in the case of glass and the fatty oils. The author suggests that it would be of interest to investigate the sp. ind. caps. of aqueous and alcoholic solutions of various salts to as high a degree of concentration as possible, and also to determine the same constant for as many well- defined chemical compounds as possible, in order to see if it may not be possible to find some law connecting the sp. ind. cap. of it substance with its chemical constitution. G. W.T. 1 '50'70 1-4689 1 -5026 1 *4561 1 *5046 1.4685 1 '4990 1 -4706 Conductivity and Specific Inductive Capacity. By E. COHN and L. ARONS (Ann. Phys. Clrem. [a], 33, 31--32).-h this note the authors state that the numbers 2.23 and 4.43 given by them in the paper referred to (ibid. [2], 28, 454) as the specific inductive capacities of xylene and castfor oil respectively are, according to their later researches, too small, and should be 2.36 and 4.82 respectively. G. W. T. Specific Inductive Capacity of Liquids. By F. TOMASZEWSKI (Ann. Y h y s . Chew. [2], 33, 33-42).-The principal object of t h i s investigation was to obtain measurements of the specific inductive capacities of certain liquids in order t o determine, if possible, some relation between the value of this constant and the chemical constitu- tion of the liquid, which curiously enough was one of the desiderata suggested by Cohn and Arons (preceding Abstracts).There were two questions which presented themselves for solution : (1) The influence of the number of atoms in a molecule, requiring determinations for isomeric, homologous, and nietameric compounds. (2) The effect of introducing a, fresh element into the molecule, requiring determinations for non-homologous compounds. The experiments were carried out by Silow's method slightly modi- fied, and the charges were obtained from a battery of 40 zinc-copper- water cells. The principal results obtained are given below, K being the specific inductive capacity, and p the index OP refraction for infinite wave- length.Isomeric Compozcnds, C,,H,,. I J K . 1396 Benzene (free from thiophen) .............. Paraxylene ............................. .............................. Toluene. Cumene ................................ ABSTRACTS OF CHEDIICAL PAPERS. 1.4892 1 * 4’757 1 5175 1 ‘4713 1 * 5436 not determined. 1 ‘5627 1 - 4838 . Ho rno 1 o g o u d Compounds. A r o mat ic Hydrocarbons . The specific inductive capacities of isomeric compounds are, thew- fore, not equal. Where M is the molecular weight and d the density, it was found that the quantity M(n - l)/d, or the molecular refraction, was sensibly constant for the isomeric series, as also were the quantities M(K - l ) / d and M( J K - l ) / d . The specific inductive capacity of homologous compounds is seen from the second table to increase with the number of atoms.Maxwell’s relation d = ,/I( is only approxi- mately true, as is clear from the tables given. G. W. T. Electric Discharge through Gases. By A. SCHIJSTER (Proc. ROY. Xoc., 42,371-379).-A glass vessel is divided into two compartments by means of a, metal plate nearly reachiiig to the sides and connected to earth. I n one compartment charged gold leaves mere placed, in the other electrodes through which discharges were passed from an induction coil. No effect was observed a t the atmospheric pressure, but at 43 mm. prcssure the leaves slowly collapsed. In another experiment, sparks from a Voss machine were passed a t the atmo- spheric pressure between points or spheres in the ueighbourhood of charged balls. When the electrodes were similar, whether points 01’ spheres, the balls collapsed when electrified positively, but when one electrode is a sphere a.nd the other a point, the balls collapse if their electrification is of opposite sign to that of the point.Finally, the author observes that in a partial vacuum incompletely divided into two compartments by a metal screen connected to earth, a continuous discharge between electrodes in one compartment renders i t possible t o send a current between electrodes in the other compartment with an indefinitely small electromotive force. In one case, a current of 0.008 ampere through the main electrodes enabled an E.M.F. of one-fourth volt to send a current through the auxiliary electrodes. The intensity of the auxiliary current is greater the greater the main discharge and the reduckion of pressure ; it increases less rapidly than the electromotive force causing it.Anything which facilitates gaseous diffusion increases the strength of the auxiliary current. In explanatmion of these facts, the author considers that the two atoms of a gas molecule are charged with opposite electricities, and are held together by molecdar forces. When this union is ruptured by the main discharge, the atoms diffuse across to the auxiliary electrodes, and give up their electricities to them. The rupture oE the molecule is supposed to take place a t the negative pole, The diurnalGENERAL AND PHYSICAL CHEMISTRY. 397 variations of terrestrial magnetism are supposed to be due to currents produced by tidal or other regular motions, such feeble currents being rendered possible by the more powerful discharges which take place in the upper regions of the atmosphere.H. K. T. Conduction of Electricity through Gases. By F. NARR (Ann. Phys. Chem. [2], 33,295-301).-Hittorf (Awn. Phys. Chem., 7, 595) found that a pair of gold leaves attached to a stick of shellac, enclosed in a tube of hydrogen containing phosphoric acid to ensure perfect dryness, retained their charge after the lapse of four days, from which he concluded that dry hydrogen does not conduct electricity. Nahrwold (ibid., 5, 460), by a different method of experimenting, came to the conclusion that the particles of a gas cannot receive an electrostatic charge, and that the loss of charge of a conductor exposed to the air is due entirely to the presence of floating particles of dust.The author considers that Nahrwold’s experiments only show that dust is the chief factor in causing leakage in a conductor exposed to the air. He refers to some former experiments (ihid. [2], 5, 145; 8, 266; 11, 155 ; 16, 558 ; 22, 550) made by him with a charged sphere sue- pended within an insulated conducting envelope containing different gascs of varions densities, carefully freed from dust. Whilst he confirmed Hittorf’s result as to the charge being retained €or a long time, he found that there is an instantaneous small loss of cbarge, depending on t’he nature of the gas and on its density. This instan- taneous loss increases as the density is diminished, and a further instantaneous loss takes place when the envelope is connected to the earth, followed by a gradual and continuous loss of charge.The author attributes this sudden loss to a transference of electricity to the gaseous molecules, and the slow dispersion to an electrical connection between the sphere and the envelope. He has now repeated the experiments with a double metallic envelope containing gas. ‘The envelopes were in the form of cylinders open a t one end, and closed at the other, the closed ends being hemispherical. The open ends were closed by a, sheet of glass covered with lac varnish, arid the cylinders were cemented to it with their axes coinciding. The author then found a similar increased loss on connecting the outer envelope with the earth, from which he concludes that the gas between tlie two cylinders acted as a conductor, putting the inner one in connec- tion with the outer, and so with the earth.The instantaneous loss of charge was found to increase when the density of either the inner OF the outer portion of gas was diminished, which agreed with the former resultq, but t,he slow dispersion of the charge appeared to be sensibly independent of the density of the gas, as vlould be expected to be the case if the dispersion takes place by a convection of electricity by the gaseons particles, on-ing to the enormous number in contact with the surface of the envelope a t any moment;. Electrical Conductivity of Solutions of Neutral Salts. By G. JXGER (Honatsh., 8, 721-724) .-The electrical conductivities of some salts of heavy metals have been measured in solutions con- G.W. T.398 ABSTRACTS OF CHEBIIOAL PAPERS. taining proportions varying from g5 to i$m of the gram-molecular weights per litre. The salts thus examined were lead nitrate and acetate ; silver nitzate, sidphate, and acetate ; zinc sulphate, bromide, and iodide, and copper sulphate and acetate. Dividing the observed conduct,ivity by the proportion of the molecular weight in each case, the relative conductivity of the molecular weight of the salt for different dilutions is obtained. This plotted against the dilution values gives curves approximating to straight lines, a1 thoug h in no case could the conductivity be represented as of the form L = am + /3rn2. All the curves, with the exception of that for zinc bromide, appear to tend towards maxima in different directions ; this is taken as supporting the view that each salt has ite own definite molecular conductivity.H. C. Comparative Properties of the Electrical Conductivities of Salt Solutions. By G. JAGER (Monatsh., 8, 725--733).--ln a former paper (this vol., p. 217), the author proved that if L and L1 are the molecular conductivities of two different salt solutions, 6 the diameter of the molecule of the solvent, and d, d’, d,, d’l, those of the ions, From this it follows that as 6 is L, increased, the value ot L/L, will more nearly approximate to unity, or that as the size of the molecules of the ~olvent increase all molecular conductivities approach more nearly to the same value. A rise of temperature increasing the sphere of action of the molecule in accordance with the coefficient of expansion of the liquid, where this last is small and only small changes of temperature are dealt with, 6 may be looked on as constant, and the above ratio as independent of temperature.To test the above, a determination was made of the Conductivities of solutions of sodium and potassium chlorides containing $ to -L 9 2 gram- equivalent per litre in water, and in water containing ’LO to 60 per cent. alcohol, glycerol, and sugar, in each of which cases the conductivity of the solvent may be neglected. Dividing the inolecular conduc- tivity of potassium chloride by that of sodium chloride in each case, it was found, as was expected, that water gave the highest values for the ratio, and that in the other cases the ratio decreased and approxi- mated more to unity as the quantity of dissolved alcohol, glycerol, or sugar increased, or, as may be assumed, the diameter of the molecule of the solvent increased.That temperature would have no effect on &he value of the ratio may be taken as proved by the result of Kohlrausch’s experiments, “ that the resistances of the ions in water are all altered in the same proportion by change of temperature.” Also, as a consequence of Kohlrausch‘s theory, L/Ll = ( y + u)!(uI + .I) where u, u, ul, and zll are the molecular velocities ol the ions, it follows that if two salts have one ion in common, say, u = ul, then L/Ll approximates to unity as u increases, or the greater the rnolecular conductivities of two salts containing a common ion, the less will the ratio of the two conductivities differ from unity.This is also found to hold good when tested by the results of Kohlrausch’s own experimeuts. H. C. c- ’ - - 4- I/@, + q2 + I/(& + 6’iz’GENERAL AND PHYSICAL CHEMISTRY. 399 The Electrical Conductivity of Solutions of some Fatty Acids in Water and in Alcohols. By K. HARTWIG (Ann. Phys. Chem. [2], 33, 58-80) .-The author points out that corriparatively few investigations have been made int,o the conductivity of other than aqueous solutions, Of those known to the author, Mateucci (Ann. CAim. Phys., 66, 237) was the first who made experiments on alcoholic solutions, but Wiedemann has thrown doubt upon his con- clusion that aqueous and alcoholic solutions of the same substance of the same specific weight collduct equally well.Oberbeck (Ann. Phys. Chew., 155, 595) measured the resistances of aqueous and alcoholic solutions of cadmium bromide and cupric chloride, and fouiid that the conductivity was increased by each of these salts in a manner dependent on the salt and on the solvent. Guglielmo (Atti B. Accad. Torino, 17) determined the conductivity of an alcoholic solution of potassium hpdroxide, that of the aqueous solution having been previously determined by F. Kohlrausch. Vinccntini (Mem. R. Accad. Torino [ 2],36,22) investigated the conductivity of alcoholic solutions of some chlorides, and found that there is no simple relation between the solubility and the conductivity. Bartoli (Z’Orosi, 7, 3) showed that paraffin and naphthalene can be made into conductors by the addition of amylic alcohol and phenol.The same autlior (R. Acad. Lincei, 1, 550) investigated the conductivity of various mixtures of organic compounds ; and Lens (Mem. Ac. Sci. St. P&tershouyg, 7, 3U) made some researches in the conductivity of aqueous and alcoholic solutions, in the course of which he completely demonstrated the falseness of Matcucci’s conclusions. The author selected the fatty acid8 for his experiments, as being very soluble in several media. The measurements were made by the Wheatstone bridge method, with a telephone as indicator. The substances experimented on were solutions of formic, acetic, and butyric acids in water, and in methyl, ethyl, and amyl alcohols. The measurements were made immediately after the solutions were made, and as none of them occupied more than an hour, i t was found that the results were not sensibly affected by the etheritication which always takes place when organic acids and alcohols are mixed.With the exception of two of the solutions of formic acid, the author finds that the conductivity reaches a maximum a t a certain concentration, and that t h i s maximum is reached the sooner the worse the conductivity of the acid. The table below gives the percentage of acid for which each solution has the rnaximum conductivity :- Solution. ~~ ~ Acids. Formic acid. 1 Acetic acid. 1 Butyric acid. Water ................. Methyl alcohol ......... Ethyl alcohol .......... Amy1 alcohol.. ......... 30 100 100 - 16.6 30 -0 49‘0 54 -0 12.0 1’7’3 21.6 26 -0400 ABSTRACTS OF CHEMICAL PAPERS.Thus the greater the quantity of carbon present in the acid the sooner is the maximum conductivity attained, and the greater the quantity of carbon present in the solvent the later is the maximum att’aiiied, the conductivity being diminished by an increase of the quantity of carbon present either in the acid or in the solvent. The author attributes the anomalous behaviour of formic acid with regard to electrical conductivity, together with similar anomalies which it exhibits with respect to its other physical properties, to the absence of the group methyl from its composition. G. W. T. Electric Leakage. By J. J. THOMSON and H. F. NEWALL (PTOC. ROY. Xoc., 42, 410--429).-The liquid experimented on is contained in a cylindrical, metallic vessel, connected to earth, in which a metal cylinder is suspended by means of a silk thread ; this can be connected either with a battery or with ft quadrant electrometer.The inner cylinder, after being charged, is connect,ed with the electrometer, and readings taken every fire seconds. Curves are plotted showing (1) the decrease of potential with time; (2) the ratios of successive potential values. The liquids examined were benzene, olive oil, carbon bisulphide and pal-affin oil, and were filtered many times before use. With the first three, no deviation from Ohm’s law could be detected. With paraffin oil, the couductivity is slightly greater with large than wit8h small differences of potential. These results, where the E.M.F.’s were 20-100 volts, differ from those of Quincke (Abstr., 1886, 9S9), who finds that with E.M.F.’s sufficient to produce a spark the conduction does not even approximate to Ohm’s law.With carbon bisulphide, great dis- crepancies were found in the first results; these were traced to differences in time of charginp, and later experiments proved that electric absorption took place. The effect was greatest after redistilling the carbon bisulphide, but a t times it was totally absent. The con- ductivity of all the liquids was increased by rise of temperature, so tthat in this respect they resemble electrolytes. The Influence of Magnetic Forces on the Nature of the Heat Conductivity of Bismuth. By A . v. ETTINGSHAUSEN (Awn,. Phys. CltenL. [2], 33, 129--136).-The author points out that Righi (Abstr,, 1887, 1009) and Leduc (Compt.Tend., 104, 1783; 105, 250) have made some experiments, from which they conclude that the thermal conductivity of bismuth in a magnetic field is diminished to an equal extent with the electrical conductivity, supposing the magnetic! lines of force to cut the stream lines for heat o r electricity respectively at right angles. Nernst (Am,. Phys. Ohem. [ a ] , 31, 760) was unable to detect any change in the thermal conductivity. The author, after some experiments made with great care, finds that the. thermal conductivity is diminished, b u t to a much less degree than the electrical conductivity. The decrease in the thermal con- ductivity is greater when the bismuth is impure, but still much less than that of the electrical conductivity. H.K. T. G. W. T. Constancy of the Heat Produced by the Reaction of Silver Nitrate with Solutions of Metallic Chlorides. By T. W.QICNERAL AND PHPSTCAL CHEMISTRY. 401 RICHARDS (Chem. News, 57, 16-1 7) .-Tn these experiments, all necessary precautions are observed to obtain comparable conditions : 250 C.C. of the silver nitrate solution (equal to 4 grams silver nitrate) and 250 C.C. of the salt solution (containing a gram or so of the salt in excess of that required to precipitate all the silver) are poured simultaneously into the platinum calorimeter (Berthelot’s), and the rise in temperature noted. The average rise in 20 experi- ments amounts to 16.165 cal. and all the results are practically identical ; the experiments included sodium, potassium, ammonium, barium, cupric, zinc, manganous, nickelous, ferrous, aluminic, ferric, and chromic chlorides and hydrochloric acid.Taking the following equation as representing the reaction, the author concludes from these results that the amount of heat is constant no matter what R m or n may be. (>,Cln + AgN03 + Aq) = AgCl + [+Rm(NOs)n = Aq]. (Compare Pickering, this vol. p. 333.) D. A. L. Relation between the Heats of Formation of Chlorides and Sulphates in Aqueous Solution. By I. W. FAY (Chem. News, 57, 36--37).-The author conducted a series of experiments with barium chloride and soluble sulphates exactly similar to Richard’s experiments with silver nitrate and chlorides (see preceding Abstract). There is not that general regularity observed in the case of the sulphates as with the nitrates, although the rise for allied bases is quite close ; the sesqui- oxide salts give a greater rise of temperature than the protoxide salts do, and with the double salts a still larger quantity of heat is evolved, whilst sulphuric acid gives most of all.The sulphates in- cluded in the experiments were sodium, potassium, ammonium, magnesium, zinc, cadmium, copper, nickel, cobalt, ferrous and fewic, and aluminium potassium alum, potassium chrome-alum, ammonium fwrous sulphate, and sulphuric acid. The results are tabulated in the original paper. (Compare Pickering, this vol., p. 333.) D. A. 1;. Alteration in the Volumes and Density of Liquids by the Absorption of Gases. By K. ANGSTROM (Ann. Phys. Chern. [ a ] , 33, %3--233).--The author has already given an account of in- vestigations on expansion of water through the absorption of gases (Abstr., 1882, 687).Since this appeared, experiments of the same nature have been made both for water and ethyl alcohol, by Bliimcke (Abstr., 1885, 215; 1887, 435), but they do not agree witth those made by the author or by Mackenzie and Nichols (Abstr., 1878,365) and Nichols and Wheeler (Phil. Mag., 5, 11, 113), probably became Bliimcke’s method did not allow of several iaequisite corrections being made ; for example, for the compression of the areometer, and for the refraction of light at the surface of the containing vessel. A summary of the results of the author’s previous experiments and of the first series described in the present paper are given in the table below, in which &, Bg, B3, are coefficients oE expansion due to absorption.402 ABSTRACTS OF CHEMICAL PAPERS.0.00160 0.00106 0~001,70 OmO0157 0.00152 0-00184 Means = - Chloroform ....... Xitrobenzene ...... Water ............ Benzene .......... Met,hyl alcohol .... Etbyl alcohol ..... Ether ............ 1.18 1.28 1.23 1.35 1.18 1'2'7 1.17 1'28 1.22 1.34 (1'09) 1.30 1.20 1-30 - - --- Carbonic acid 6,. -- 0 *00188 0 * 001R8 0 -001 30 0 '00200 0 *00184 0 *00185 0 *00200 Air 6,. -- 0 a 00205 0.00143 0 *00216 0 .Oc1201 0 * 00203 0 * 00240 - This shows that, except for etber, the ratios 6*/E, and &/a3 are sensibly constant. Experiments on the successive absorption of two or more gases gave the result that the coeecient of expansion due to absorption is independent of any previous absorption of gas, the total expmsion being equal t o the sum of the expansions due to the absorption of the different gases.The results obtained enable the change in tbe specific weight of a liquid due to the absorption of gas to be calculated, which is of practical importance for specific weight determinations, but the effect in such cases is so small that it need only be taken into account when the most extreme accuracy is desired. The author considers the constancy of the ratios ;5,/6, and 6,/6, to be the most important of his result-s from a theoretical point of view, as it. shows that the dilatation depends on the gas, and that the relations between the co- efficients of dilatation due to absorption are independent of the nature of the liquid; froni this he concludes that Ostwald's hypothesi8 (Stiichiornetrie, p.356), founded on the values of the coefficient of dilatation due to absorption obtained by the author and by Sarraii, namely, that "the volume of the absorbed gas is almost exactly reduced to the volume of its molecules," is 6 priori extremelyaim- probable. G. W. T. Differential Tonometer. By G, J. W. BREMER (Rec. TTUV. Chim,., 6, 122 -136).-An apparatus for measuring the difference between the vapour-tension of a saline solution and the vapour-t'ension of water by allowing the vapours to act on the opposite ends of a column of olive oil. It consists essentially of small flasks con- nected with vertical tubes about 150 mm. high communicating with one another by means of a horizontal tube at the bottom.The particular apparatus described consists of four such flasks. The flasks should have exactly the same cubical contents, which may be adjusted by introducing pieces of glass rod, and should contain equal volumes of the solutions. After introduction of the liquids the flasks are cooled to O", rendered partially vacuous, and oil allowed to enter from the bottom horizontal tube until it rises to about half the height of the vertical tube. The exact pressure of the a i r in the flasks is observed, and the flasks and their contents are heated to differentGENERAL AXD PHYSICAL CREXISTRY. 403 teniperatnres and the differences between the levels of the oil in the tubes are observed. Determinations of the vapour- tensions of aqueous ~olutions of calcium chloride of different shengths show that if the salt is regarded as existing in the liquid in the anhydrous condition, the reduction of the vaponr-tension increases more rapidly than the amount of calcium chloride present, but if the solution is supposed to contain the hydrate CaCl, + GHaO, the reduction of the vapour-tension is proportional to the amount of salt present, as Wullner has pre- vionsly stated.C. H. B. Dynamical Method of Determining Vapour-pressure. By G. TAMMANN (Ann. Phys. Chem. [2], 33, 322-337).-The author on recalculating some tables given by Regnault (Ann. Chim. Phys. [3], 15, 158) for the vnpour-pressure of pure water determined by the dynamical and statical methods respectively, found that the close agreement of the results was only apparent, and that there were really some considerabe discrepancies which could not be accounted for.The author now describes a number of experiments carried out principally with a view to testing the dynamical method, following Regnault with some modifications in details. He concludes that the method is not capable of giving good results. In the case of un- saturated solutions, when the current of air is passed over thf: surface of the solution, the upper layers become more concentrRted than the lower, through the evaporation being en tirely superficial, and if the current of air is led through the solution errors are introduced, as it is impossible to prevent variation of pressure and the scattering of drops of the solution upon the interior of the glass vessels.The author attempted to use it with saturated solutions, using filter-paper soaked in the solution, then partly dried, and introduced into a U-tube through which the current of dry air was allowed to pass, but then he was met by the difEcu1t.y t h a t on taking the tube out of the bat>h used to maintain the required temperature, drops of water condensed on the inner surface of the tube, and dissolving some of the salt adhering to it gave rise t o unsaturated solutions. The author liext tried the method with hydrated salts i n crystals. Here, however, the results were found to depend on the velocity of the stream of air, which appeared to be due to the water-vapour given off dissolving a portion of the crystals arid forming hydrates containing less water, which would give a lower vapour-pressure.From some of the results obtained during the last series of experi- ments, combined with Pape’s result (Ann. Phys. Chem., 124, 389) that rates of evaporation from the different surfaces of irregular crystals are not the same, tbe author draws the conclusion that the yapour-pressure at the surface of a crystal is not the maximum value of vapour-pressure due to the crystal. The vapour-pressure at the surface depends on the nature of the surface, and is considerably less when the surface is uninjured than when i t is broken or otherwise changed. G. W. T.40 4 ABSTRACTS OF CHEMICAL PAPERS. Compressibility of Rock Salt. By I?. BRAUN (Ann. Phys. Chm. [a], 33, 239--240).-The author in a recent note (this vol., p.214), whilst giving the preference to Rontyen and Schneider's value 5 x for the cubic compressibility of rock salt over the value 1 . 4 ~ 1 0 - ~ found by him, as his own determination was a com- paratively rough one, pointed out that according to Voigt's measure- ments of elasticity the value would be 1 . 6 ~ 10". The author has since seen a later paper by Voigt (Ann. Phys. Chem. [a], 15, 497) i n which he corrects his former result, as in obtaining it he made use of a torsion formula which he has since found to be incorrect. Voigt's later measurements would give the value 4.2 x lo+, which, considering the difficulty of the piihometer method, agrees fairly wit,h that obtained by Rontgen and Schneider. By P. SABATIER (Con@. rend., 106, 63--66).-The conversion of metaphos- phoric acid into orthophosphoric acid involves the introduction of an acid function of medium activity and an acid function of feeble activity, in addition to the original energetic function.Only the latter affects methyl-orange ; the secoud feebler function affects phenolphthaleh, the third can only be qualitatively recognized by means of the blue C4B. The acidity of the liquid h to methyl-orange remaitis constant, whilst its acidity to phenolphthaleh c# increases, and affords a measure of the progress of the transformation. When conversion into orthophosphoric acid is complete 4 = 2h, and a t any stage of the change 2h - @ gives the amount of metaphosphoric acid y still remaining unaltered. The metaphosphoric acid was obtained by dissolving phosphoric anhydride gradually in cold water, and also by strongly heating the ortho-acid, and dissolving the residue in water.Both preparations behaved in the same manner. These solutions were heated at different temperatures for definite intervals of time. At a given temperature, log y is proportional to the time. Tke velocity of the change at each instant, is proportional t o the mass of transformable substance present in the system, and hence log y = - x log a + log b, and therefore y = ba-x, where b is the value of y at the commencement, and a is a constant which is a function of the temperature and the concentration, and increases with both, but the exact law of increase has still to be determined. By J. H. VAN"!? HOFF (Rec. Truv. Chem., 6, 3 6 4 2 ; 91-94; 137--139).-The par- ticular reaction considered is the conversion of mixtures of sodium and magnesium sulphates into astraknnite, N%Mg(S04)2 + 4H20, a t temperatures below 21.6".It is found that in order to separate sodium sulphate from the mother-liquors from sea-water, which con- tain a large proportion of magnesium chloride; it is necessary to cool the liquid below 5", and hence it would appear that the syst.em MgCl, + Na2SOa is stable below 5", but at higher temperatures the reciprocal sys tem is formed. If a solution containing sodium sulphate and magnesium chloride G. W. T. Rate of Transformation of Metaphosphoric Acid. C, H. B. Point of Transition and Point of Fusion.GENERAL AND PHYSICAL CHEMISTRY. 405 in equivalent proportions is placed in a dilatometer, no anomalous expansion is observed at 5", but if 2 mols.of sodium sulphate arc present for each molecule of the magnesium salt, there is a very con- siderable expansion if the liquid is heated above 5", and a cnnsider- able contraction if it is cooled below this temperature. This par- ticular temperature is in fact the point of transition between the two systems, but the author has previously observed that magnesium chloride cannot exist in presence of sodium sidphate a t temperatures below 5"' because the tension of the water of crystallisation of the latter salt is less than the vapour-tension of the saturated solution of the two salts. The slow evaporation at a low temperature of a solution containing sodium cbloride and sodium and magnesium sulphates i n equivalent proportions yields a mixture of the three salts, but if evaporation t.akes place at a higher temperature cubical crystals of sodiuni chloride are obtained, together with rosettes of ast,rakanite, which is formed by the union of the two sulphates with elimination of water.In presence of sodium chloride, formation of astrakanite takes place a t tj", and the reverse change at lower temperatures, whilst in absence of sodium chloride astrakanite is forrned at 21.6' (Alistr., 1886, 968). The reduction of the point of transition from 21.6" to 5" by the presence of sodium chloride, corresponds with the reduction which this salt produces in the freezing point of its solution. The double acetate, CuCa(C2H30?)4 + 8H20, decomposes at 75" into the simple salts Ca(CzH302)2 + H,O and Cu(C&f,O,), + HzO, with elimination of 6 mols.H20, and the change is accompanied by a distinct contraction ; at lower temperatures, the double salt is formed, nnd expansion takes place. The volume changes are analogoiis to those which accompany the solidificat.ion of water, and it was to be expected that the effect of pressure would be analogous in the two cases. A t the author's request, Spring has subjected the double acetate to high pressures at varying temperatures, and finds that under a pres- sure of 6000 atmospheres decomposition takes place at 40". Under the same pressure at 16", there is no appreciable decompositiori if the duration of the experiment is short, but if pressure is prolonged, evidence of decomposition is readily recognisable.Under a pressure of 2000 atmospheres, decomposition takes place distinctly at 50" (com- paye this vol., p. 341). Van't Hoff points out that determinations of the minimum pressure required to produce reactions of t!his kind, together wit,h measurements of the resulting changes in volume, will make it possible to express in kilogram-metres the absorption of energy involved in the reaction, and conversely the liberation of energy resulting from the reverse change. C. H. B. The Position of Atoms in Space. By J. WISLICENUS (Rer., 21, 581-585) .--&sen has challenged Van't Hoff and Wislicenus to state their views on units of affinity from the standpoint of their geometric t,heory, and he affirms that the question of the position of ;he units of affinity in space must be answered not after, but before, VOL.LIV. 2 e406 ABSTRACTS OF CHEZIIICAI, PAPERS. the question of tlie popitions of atoms in space. and above all that R definition of “ unit of affinity ” must be given (this vol., p. 218). The Nuthor admits that his views quite bar the conclusion that atoms are material points, and- it is impossible, therefore, to consider them as configurations in space in which the several chemical units of action of polyvalent, elements can he localised. Rut this conclnsion is admissible when the so-called atoms are considered, not as atoms in the strict sense of the word, but as simple groups of primitive atoms, similar to the compound radicles but less complex ; and therefore tlie position of the elementary atoms in the molecule must be determined brfore Lossen’s demand can be taken into earnest consideration.The author has shown that the determination of the arrangement in space of the atoms in a molecule is within the domain of experi- ment, and he points out that the study of the confignration of the molecule is the only way to solve successfully the question of the distribution in space of its spheres of action-the so-called units of affinity. Only by studying the properties of molecules cau inductive conclusions be drawn as to the properties of atoms. The author’s views are stated as follows :-It is more probable that the atoms are configurations in space composed of atoms of primiiive elements than that they are simply points of energy ; the most likely assumption is, therefore, that the atoms are comparalole with the compound radicles, and, as in the latter, their units of affinity are located in certain parts from which they exercise their action.It is possible, in time, to succeed in obtaining definite ideas not only of the form of elementary atoms, but also of the relative posi- tions of their spheres of action. It is not impossible that tlie atom of carbon resembles more or less in form a regular tetrahedron, and that the causes of those actions, which are evidenced by the units of afflnitly, are concentrated in the angles of this tetrahedric configuration, perhaps for analogous reasons, and similarly to the electric action of a charged metallic tetrahedron. The real carriers of energy would finally be the primitive atoms, exactly as the chemical energy of compound radicles is the resultant of the energy of the elementary atoms.The Atomic Weights of the Elements. By A. RAZAROFF (J. Russ. Chem. Soc., 1887, 61--73).-The author finds that the variation in the numbers expressing the atomic weights of the elements, nrranged according to the periodic system, is analogous to the changes in the properties of the elements and their compounds. When the most probable numbers for t h e atomic weights of the elements are arranged according to the periodic law, amd, either in the horizontal or in the vertical series, the atomic weight of an element is divided by the atomic weight of the element with the next lower atomic weight, products are obtained which decrease regularly with increase in tbe atomic weights compared.In the horizontal series, the maximum is found t o correspond with the relation of 2 = y8 = 1.2955, the L1 7.01 F. S. K. minimum to Bi -- = - 207’5 = 1.0054. This decrease, however, is not Pb 206.39GEKERAL AKD PHYSICAL CHEMISTRY. 407 con tjinuous, the products alt ernately decreasing and increasing, as is seen from the following examples :- - S = 1.0529, - c1 = 1.1060, &c. J? S This relation is best represented graphically, the order of atomic weights standing as abscissz, and the aforesaid quotients as ordinates : in this way a curve of zigzag form is obtained. This relation is expresqed by the author in the form of a law, namely, that “ t h e increase in the atomic weights of the elernent,~ proceeds with a variable int’ensity, the smaller coefficient of change vsrying with the larger in such a way that both regularly decrease.” Another regularity is observed in the vertical groups, for example, with the coefficients in the second group :- Ca Z Sr !!% = 26366, - = 1.6671, $ = 1.6257, - =; 1,3456, Ba %! = 1-2795, -- = 1,2252.sr Cd Be J% La zn This change the author expresses by the law : “ In the vertical series in the periodic system, the relation of two neighbouring atomic weights decreases with increasing atomic weight, but this decrease is alternately larger and smaller.” Neither of these functions extends to the whole periodic system, as there are many elements whose atomic weights are not yet determined wikh fiufficient accuracy. Yet it is possible, from the Gata which are to hand, to state the following general law : “ The magnitude of the atomic weight of each clement is determined by the magnitude of the atomic weights of the elements next to i t in the periodic system both horizontally and vertically.” The author further analyses the exceptions to the said rules, and expresses the opinion that several of them are due to the atomic weights not being determined with sufficient accuracy, but it is difficult to say how far he is right in correcting several of the better determined numbers (he assumes for TI 202 instead of 203.7 !).Not- withstanding the apparently complicated character of the relation pointed out, the author thinks i t possible that when the fundamental data are more exactly determined, it mzhy be possible to calculate the atomic weight of an element with greater accuracy than is the case at present.B. B. Raoult’s Method of Determining Molecular Weights.” By V, MEYER (Bey., 21, 536-539). In iuvedigating some derivatives of bemil, two series of isomeric compounds were obtained ; both series have the same constitution, in the ordinary gense of the word, and are j e t distinct from one another and yield dif-ferent derivatives. The * Raoult’s papers on this method are Abstr., 1883, 7, 278, 952 ; 1884, 254, 701, 8C8, ‘352, 1248 j 1885, 122, 858 ; 1886, 197, 763. Compare also this vol., p. 361. Z e 2408 ABSTRACTS OF CHEMICAL PAPERS. Ph*C : R I Ph*C : R isomerism of the two series is expressed by the formulse Ph*C : R and I . R : C-Ph. By means of a modification of Raoult's method for determining molecular weight by measuisinq the amount by which the solidifying point of a solvent is lowered by a known weight of a, dissolved sub- stance, it is shown that the molecular weight of the compounds of the t w o series in question is identical.The method eniployed, which only involves the use of an ordinary thermometer divided into 0.1" and a simple apparatus, will be described. Application in Chemical Laboratories of Raoult's Method for Determining Molecular Weights. By K. AUWERS (Ber., 21, 7'01-71 9).-The use of Raoult's method for determiniiig molecular weights by V. Meyer (preceding Abstract) led t o a consideration of the conditions necessary for its successful appiicntion. The exception which many solutions, notably those of inorganic salts in water, show to the law put forward by Raoult (Ahstr., 1886, 763), renders this law useless for practical purposes, and the relation N = T,'A, where M is the rnolpoular weight,, T the molecular depression, and A the depression caused by 1 gram of substance in 100 grams of solution, is used.It is recommended to first determine the value of T, which will be constant for the series of compounds under consideration, by taking members of the series of known molecular weight. Ameasurement of A then suffices to determine M in subsequent cases. 9 great objection is the impossibility of working with relatively small amounts of material, for although the above relation does not hold for concentrated solutions, the solutions must not be too dilute, and some discrimination is necessary in adjusting the strength to give the depression which should be measured in each case.With regard to the solvents used, i t is of course a condition that no chemical action should take place between the one selected and the substance under examination. The selection of a suitable solvent is a matter of great importance. Water is generally objectionable on account of its tendency to form hydrates and its non-solvent action on most organic compounds. As i t is necessary also, according to Raoult, that the depression measured should not be less than 0.5", a6 the relation does not hold when it is allowed to sink below that value, a relatively large quantity of material is necessary for each determination. Benzene gives better results, but cannot be used in the case of alcohols, phenols, or acids, and introduces an element of uncertainty in dealing with substances allied to these. By fa.r the best solvent, and the one that can be used with the greatest range of substances, is glacial aceticacid.The errors in this case are srnall, and the measurement of a depression of about 0.3" suffices. A great advantage also is that this solvent admits of working a t ordinary temperatures. It is, however, found necessary, owing to its N. H. M.GENERAL AND PHYSICAL CHEMISTRY. 409 hygroscopic nature, to conduct the experiments in a closed space, and an apparatus has been devised and is described by means of which this is easily rendered possible. A thermometer divided to one-tenth of a degree was used, and this was found to give sufficiently accurate result,s.Experiments are detailed cvit,h naphthalene and picric acid, acetanilide and benzil, and the isomeric diacetyl-compounds of /3-dip hen y lg ly oxinie. In conclusion. the author recommends the use of Raoult's method in those cases where rapour-density determinations are not possible. H. C. Isonitroso-compounds. By E. BECKMANN (Ber., 21, 766-769). --The application to the ketoximes of Raoult's method for the deter- mination of the molecular weight by the lowering of the freezing point, has led to the important result that the molecular weights are twice as large as has hitherto been assumed. The compounds experi- mented with were acetoxime and camphoroximc ; the solvent being benzene. With benzaldoxime and anisaldoxime, results were obtained point- ing to molecular weights about one and a half times as great as those previously adopted ; these results are, however, doubtless due to partial dissociation of the double molecule.Desiccation of Gases. By J. D. VAN DER PLAATS (Rec. Tyav. China., 6, 45--59).-An extended historical summary of the various methods which lave been proposed f o r hhe desiccation of gases, together with an account of experiments made by the author. Anhydrous calcium chloride is more efficient than calcium chloride containing 2 mols. H20, but the difference diminishes at low tempera- tures. Calcium oxide absorbs moisture more sIowly than anhydrous calcium chloride, and leaves twice as much water in the air as calcium chloride containing 3 mols. H20. Fused potash acts rapidly and much more completely than anhydrous calcium chloride, but less rapidly and less completely than concentrated sulphuric acid.Potash solution of sp. gr. 1.25 loses R considerable quantity of water it a current of air is passed through it for some time. A. J. G. Ammonia is almost completely dried by fused potash. Calcium chloride is a convenient but not very efficient desiccating agent. If the solution has been evaporated at B O O , it always contains calcium oxide, which cannot be neutralised even by the prolonged action of carbonic anhydride or hyarogen chloride so long as the salt remains dry. Phosphoric anhydride is the best of all desiccating agents at present known, but it is inconveniently light and bulky. Not unfrequently it contains phosphorous anhydride, but this can be removed by Stas's method of distilling it in dry air.Concentrated sulphuric acid is cheap and convenient, allows the speed of the gaseous current to be watched, and dries gases almost perfectly. It gives off no vapours, and when cooled its efficiency is increased. I t must not contain sulphuric anhydride, and the presence of 6 to 8 per cent. of water is desirable i n order to ensure absence of. the anhydride in the gas which is passed through the acid. Some-410 ABSTRAOTS OF CHEMICAL PAPERS. times the acid contains sulphurous anhydride, but this is readily removed by a current of dry air or by boiling the acid. Solphuric a::id will dissolve carbonic anhydride, but this gas is removed in a few minutes by passing a current of air into the liquid.The distribu- tion of sulphuric acid with a view to expose a large surface is best effected by means of broken glass. Pumice should be boiled with sulphuric acid containing a lithle nitric acid in order to remove chlorides and fluorides and metallic oxides which might absorb oxygen. Sulphuric acid, especially if cooled, is practically as efjicient as phosphoric anhydride, and the errors due to its employment are certainly not greater than those arising from the use of india-rubber connections or from neglect to remove, by heating, the layer of moist gas condensed on the surfaces of the glass vessels. India-rubber cannot, be completely dried on a sand-bath, but should be kept over sulphuric acid in the dark €or a lorig time, Tubing with walls 5 mm.thick allows air and aqueous vapour to pass extremely slowly, and its power of absorbing carbonic anhydride is a t a minimum. Drying tubes, &c., which have to be weighed should be kept under a. bell-jar cont,aining vessels filled with the same desiccating agent a s the tubes themselves contain. c. H. €3. Delicate Themnometer for Lecture Purposes. By S. YOUNG (Chem. News, 56,26l).--For this purpose the author recommends an air thermometer of the form commonly employed to show the expansion of air with rise of temperature, but using a volatile liquid suqh as ether in place of mercury or sulphuric acid ; to make the column of liquid visi- ble a t a distance, a little absolute alcohol coloured with aniline red i R added. The apparatus employed by the author had the following dimen- sions : the cylindei- a t the bottom containing the air confined by ether was 17 mm.in diameter and 130 mm. long, t,he narrow t.ube extended 700 mm. above this cylinder and had a diameter of 2.8 mm., above this there was a reservoir large enough to hold the ether when the tempe- lature got beyond the range of the thermometer. The total rise of column for 10" in the thermometer described was 510 mm. ; for 1" between 0" and 1" the rise = 40 mm., whilst between 9" and 10" it = 82 mm. D. A. L. Lecture Experiment for Demonstrating the Valency of Metals. By B. LEP.SIUS (Ber., 21, 556--561).-The method which Nilson and Petterson have recently described for determining the atomic weights of the rare earths can be employed for demonstrating the valency of metals.A quant.ity of the pure metal, proportional to its atomic weight, is heated in gaseous hydrogen chloride, the volume of liberated hydrogen being proportional to the valency of the metal. For various reasons many of the metals offer great difficulties in carrying out this experiment, and the author rwommends thalliuin, zinc, and aluminium as the most suitable examples. The hydrogen chloride, which must; be perfectly dry, is obtained by acting on solid publimed ammonium chloride wifh concentrated snlphuric acid in a Norblad's apparatus ; it is passed through a combustion tube which contains weighed portions of the above-named metals (twice theINORGANIO CHEMISTRT. 411 atomic weight) placed a t intervals of 10 cm. from one another.The li berat,ed hydrogen is collected in a graduated three-limbed glass apparatus filled with a 5 per cent. solution of potash and provided with a mercury seal. By heating the metals successively, the hydro- gen evolved from each can be collected separately and the volumes compared directly. F. S. K.389General and Physical Chemistry.Dispersion Equivalents. By J. H. GLADSTONE (Proc. ROY. SOC.,42,401-4 I O).-This paper is a continuation of the author's researcheson dispersion equivalents. Notwithstanding the difficulties of theinvestigation, the following conclusions have been arrived at :-1. That dispersion, like refraction, is primarily a question of atomicconstitution. 2. That dispersion, like refraction, is modified by pro-found differences of constitution, such as change of atomicity.3.That dispersion frequently reveals differences of constitution, atpresent unrecognised. The following dispersion equivalents (H - A )have been determined :-Phosphorus (liquid), 3.0 ; sidphur (doublebond), 2.6 ; sulphur (single bonds), 1.2 ; hydrogen, 0.04 ; carbon,0.26, 0.51, and 0.66; oxygen (double bond), 0.18; oxygen (singlebonds), 0.10 ; chlorine, 0-50 ; bromine, 1.22 ; iodine, 3.65 ; nitrogen,0.10 ; CH2, 0.34 ; NOz, 0.86. The values for CHz, H, and C are workedout in the same way as the refraction equivalents. I n unsaturatedcompounds, the dispersion equivalent is much greater, (0.5) in ally1compounds and olefines, and at least 0.8 in the aromatic series. Wherethe carbon has all four bands satisfied with carbon-atoms (with refrac-tion value 6*0), the dispersion equivalent is enormously increased.In considering the dispersion equivalents of solutions of metallicsalts, it is pointed out that where the solution is dilute the values areuntrustworthy, owing to the smallness of the specific dispersion, thevalues for potassium and sodium alone are therefore considered.Thedifference between the dispersion equivalents of their salts is 0.09.In determining the value for potassium itself, the halojd salt wasrejected, as it was anticipated that the chlorine value might be higherthan it is in organic compounds, as is the case with the refractionequivalents. Determined from the formate and acetate, with thevalues given above for carbon, hydrogen, and oxygen, the dispersionequivalent for potassium is 0.53 and 0.44 fcr the salts respectively.From potassium hydroxide viewed as water, wit'h a- hydrogen-atomreplaced, the value 0.565 is obtained.From the nitrite, by subtractingthc value for NOz, 0.48 is obtained. From the cyanide, 0.58 ; fkomthe carbonate, 0.40 ; from the oxalate, 0.59. These variations c*annotbe due to experimental error, nor is i t probable that potassium hasmore than one dispersion equivalent, as it has only one refractionequivalent. The unceriaint,y probably lies in the value of the radiclevto which the metal is joined. H. K. T.Mathematical Analysis of the Spectra of Magnesium andCarbon. By A. GR~NWALD (Monatsh., 8, 650-71 2).-In accordancewith the principle laid down by the author (Abstr., 1887, 1070), ananalysis of the spectra of magnesium and carbon has been effected,the data of different observers, chiefly those of Liveing and Dewar,being used for this purpose,VOL.LlT. 2 390 ABSTRACTS OF CHEMICAL PAPERS.The magnesium spectrum is found to show the presence of theprimary subst-ance c in the same condition in which it is found inoxygen and carbon, of the primary substance h in the state in whichit exists in free hydrogen, and in the more condensed state in whichit is found in the water-vapour spectrum, and also of b (helium) in anuncondensed stat'e. Besides these, a number of very weak, and at,present unknown hydrogen and oxygen lines are present.The spectrum of carbon contains the primary substance c in thestahe in which it is found in oxygen and magnesium, and also the sub-stance b.This latter exists in four different conditions : in the statein which it is observed in free hydrogen; in the state in which itexists in the hydrogen of water-vapour ; and in a, more dilated chemicalcondition, and a more condensed condition than that in which it occursin free hydrogen. A number of hydrogen and oxygen lines arealso present, most of them very weak, but which, on multiplyingtheir wnve-lengths by the facttor +, as in the case of those in themagnesium spectrum also, are converted into lines in the waterspectrum. H. C.Compounds of the Rare Earths yielding Absorption-spectra. By G . K R ~ S S and L. NILSON (Ber., 21, 585-588).--8rejoinder to Bailey (this vol., p.208).Contact Electricity. By W. v. ULJANTN (Ann. Ph?y.s. Ohenz. [Z],33, 238).-The author points out that Exner (this vol., p. 208) hasmisunderstood his method (Anlz. Phys. Cheni. [2], 30, 699) of deter-mining the potential difference between zinc and copper, as he appearsto have assumed that the author covered a copper cylinder with azinc one, and inserted such a fraction of a Daniell, that when thelatter cylinder was removed there was no deflection of the elec-trometer. This arrangement would clearly not enable the potentialdifference to be me,zsured, as it would require that the envelope alsoshould be a t the same potential, and the latter is determined by thatof the walls of the room.I n the arrangement used, the two cylinders were of zinc, and weresurrounded by a copper envelope, and before removing the outer cylin-der it was separated from the inner one.Then assuming the twozinc cylinders to be at the same potential, there would be no deflectionif the copper envelope was at the same potential. This conditionwas satisfied by the introduction of a certain fraction of a Daniell inthe earth connection of the envelope.It is clear that the method would not serve to determine any poten-tial difference between the zinc cylinders, as i t depends on the assump-tion that they are a t the same potential, being of the same metal, andin contact. G. W. T.Maximum Galvanic Polarisation of Platinum Electrodes inSulphuric Acid. By C. FROMME (Ann. Phys.Chem. [Z], 33, 80-128).-Ttre great discrepancies between the different determinationsof the maximum polarisation in a voltameter containing dilute sul-phuric acid with platinum electrodes, induced the author to investigatOFXEILAL AKI) PHYSICAL CHIEXISTRY. 391the circumstances on which the amount of polarisation depends.A priori, the polarisation might be expected to depend on the nature ofthe surface of the electrodes, on their dimensions, on the concentrationof the acid, and on the pressure a t which the gases are liberated.The concentration of the acid in the different experiments variedfrom 0.18 to 65 per cent.The author finds that the manner in which the amount of polarisa-tion varies with the concentration is most complicated i n the case ofvery dilute solutions, for, as the concentration is gradually increased,the polarisation at first increases and reaches a maximum, and after-wards falls to a minimum ; when the anode is small, it passes througha second maximum and minimum, until it finally increases steadilywith the concentration ; with a larger anode, only a single maximumand minimum are observed.In very dilute solutions, the amount of polarisation is found todepend on whether the water used is distilled in glass or in nietallicvessels, t h i s being doubtless due to the presence of small particles ofglass or of metal in the distilled water.When the. cathode is small, its surface becomes blackened by thepassage of the current, whilst a larger cathode is not, sensibly altered.With the more dilute solutions, and when both the electrodes weresmall, a yellow deposit was observed on the anode.The black depositremains unaltered after treatment with concentrated srrlphnric acid, butit is slowly dissolved by aqua regia. J t can also be removed by revers-ing the current for some time, or i t can be scraped off. This deposithad already been observed by de Ia Rive (Arm. Phys. Chem., 41, 156 ;45, 421) and by Poggendorff (ibid., 61, SOS), and their experimentsshowed that it consisted of platinum in a state of powder, mechanicallydetached from the cathode. I n soue of the experiments, even whenthe cathode i8 larger, a greyish-brown deposit was observed on thelatter, but only when the water had been distilled in glass vessels,from which the author concludes that i t was due to particles of glass.It was easily dissolved by concentrated sulphuric acid.I n the case of the larger anodes, a dark yellow coloration masobserved after some time.This yellow deposit on the anodes wasunaffected by treatment with hot concentrated salphuric scid or aquaregia, and it occurred whether the water had been distilled in glass orin metallic vessels. The author was unable to determine its cause,but concluded that it was not due to the presence of any impurity i nthe solution. The amount of polarisation is found to depend on thesize of the eledrodes ; with dilate solutions, the size of the anode isthe more important, with stronger ones that of the cathode.With the solutions used containing, as previonsly stated, from 0.18to 65 per cent.of acid, the E.M F. of polarisation varied from 1.94 to2.43 of a Daniel1 when the cathode and anode were both large ; from1.45 to 2.98 wben the cathode was small and the anode large ; from1.90 to 4.18 when both cathode and anode were small ; and from 1.89to 4-31 when the cathode was large and the anode small. Tile leastvariation, therefore, occurs when both the electrodes are large, andthe greatest when the cathode is large and the anode small.The resistance of the voltameter when traversed b j R strong steady2 d 392 ABSTRACTS OF CHEMICAL PAPERS.current diminishes as the coricentration of the acid increases, and ulti-mately reaches a minimum value when the concentration is aboutthe same as that for which the conductivity is found to be a maximumby observations with alternate currents ; after this, it increases withfurther increase in the concentration.When, however, the anode issmall, the resistance continues to diminish up to the highest limits ofconcentration used in the experiments.Electromotive Forces of Metals in Cyanide Solutions. ByS . P. THOMPSON (Proc. Roy. Xoc., 42, 387--389).-The electromotiveforces of copper and zinc in cyanide solutions are examined in orderto ascertain the cause of the possibility of depositing these two metalssimultaneouslv. It is found that, with higher concentration, theE.M.F. of copper increases more than that of zinc ; moreover, in a colddilute solution of potassic cyanide the E.M .F.of zinc is higher than thatof copper, whilst, in a boiling saturated solution the E.M.F. of copperis greater than that of zinc: hence it is possible to construct a bat-twy consisting of one metal, copper, and one electrolyte, a solution ofpotassic cyanide, the anode being kept hot and the cathode cold.Tables are given showing the E.M.F.’s of various metals comparedwith carbon in cyanide solutions of various strengths. Maxima arefrequently found a t intermediate stages of concentration. I n a mixedsolution of copper and zinc cyanides, there is a neutral condition, inwhich the E.M.F.’s of zinc and copper are equal, depending on therelative amounts of metal, the concentration of the solution, and thetemperature. The E.M.F. of the copper is the most sensitive, espe-cially to variations in the concentration of the solution.A t thecathode, the concentration is determined, on the one hand, by therapidity with which the metal is deposited, that is, by the current-dmsity ; on the other, by the rapidity of diffusion ; hence there willbe a certain current-density a t which the solution will be maintainedin the neutral condition and the metals be deposited equally.G. W. T.H. I(. T.Resolution of the Electromotive Forces of Galvanis Ele-ments. By J. MIESLER (Monatsh., 8, 713--720).-1n continuationof his work on this subject (this vol., p. 330), the author has examinedMarik-Davy, de la Rue, and Niaudet cells, and in each the sum oftjhe potential differences i n the various parts of the cell is found tobe equal to the total E.M.F.Accumulators were examined, and forthese the above was also found to be true. On discharging an accu-mulator and measuring the potential differences a t different intervals,as the total E.M.F. decreased to about one-h2lf of its original value,the potential difference between the negative plate and acid alsotfirninished, but tha,t between the positive plate and acid remained themnie. After the cell had been short circuited for some time, theexact opposite Lad, however, taken place, for the potential differencebetween the negative plate and acid was still the same, whilst thatbetween the positive plate and acid had decreased. An attemptmechnnicdly to construct an accumulator that should give the same1,oteutial differences as a charged accumulator failed.H. CGENERAL AND PHYSICAL CHEMISTRY. 393Thermal Alteration in a Daniell Cell and in an Accu-mulator. By G. MEYER (Ann. Phys. Chem. [2], 33, 265-289).-Investigations have been made on the thermal changes in a Daniel1cell by Lindig (Ann. Phys. Chem., 123, l), Voller (ibid., 149, 394),and v. Helmholtz ( B e y . , 18, 22), and the latter has shown that in azinc sulphate cell the temperature-coefficient depends on the degreeof concentration of the solution. The object of this paper is todetermine more fully on what circumstances the temperature-coeffi-cient depends, in the case both of sulphuric and zinc sulphate cells,and to determine whether the temperature-coefficient of the cell isequal to the sum of the temperature-coefficients at each contact ofuiilike sixbstances.In order to ensure their purity, the metals used were obtained byelectrolytic deposition from copper sulphate a n d zinc sulphate, andthe copper sulphate, zinc sulphate, and sulphuric acid were chemi-cally pure.The metals and liquids composing the cell were con-tained in a glass tube of special construction, and the liquids wereseparated by parchment-paper ; the dissolved. air being got rid of byuse of an air-pump. The measurements of the E.M.F. were alwaysmade with a quadrant electrometer, so that there was no polarisation,and the electrometer reading was taken directly after the zinc wasintroduced into the liquid, to prevent a coating of hydrogen beingformed, a t the higher temperatures, by the action of the sulphuri(:acid on the amalgamated zinc.The results obtaiiied with tbe cellswere as follows :-The E.M.F. of a Daniell cell with sulphnricacid increases with the temperature, and the value of the tempe-rature-coefficient depends on the degree of concentration of the liquidsin the cell, increasing with an increase in the concentration of thesulphuric acid, until the solution contains about 30 per cent. ofthe acid, when it attains a maximnm value, and diminishes when theconcentration is increased beyond this point. The temperature-co-efficient increases con t8inuously without attaining a maximum as thoconcentration of the copper sulphate is increased.In t,he case of a zinc sulphate cell, the E.M.F.diminishes as thetemperature rises, and when the concentration of the zinc sulphate isincreased from a low degree the temperatnre-coefficient falls t o zero,and as the concentration is further increased this ha3 a continually in-creasing negative value. The effect on the temperature-coefficient ofvarying the concentration of the copper sulphate solution is the sameas in the case of the sulphuric acid cell.In the accumulator, the temperature-coefficient was found to increasewith increased concentration of the sulphuric acid, but the authorhas not yet, been able to determine whether the degree of concentrationhas any effect on the E.M.F., as the latter begins to diminish as soonas the charging current is discontinued, at first rapidly, and thenslowly, but not slowly enough to enable any conclusions to be drawnfrom the measurements of E.M.F., each of which occupied aboutsix minutes.During the experiments on the accumulator, whilst evolution of gasWRS observed from the lead plates when it mas placed under the air-pump to free the sulphuric acid from dissolved air, i t was foun394 ABSTRACTS OF CHEMICAL PAPERS.by depositing lead by means of zinc from a solution of lead acetate,and heating it in a vacuum, that finely divided lead absorbs about0.206 of its volume of hydrogen. The absorption of air by the accu-mulator plates would be too small to have an appreciable effect on theE.M.F.The author, however, found it impossible to obtain any trustworthyresults from a cell containing platinum instead of copper, owing tothe dependence of the E.M.F.on the amount of air absorbed by theplatinum. G. W. T.Determination of the Specific Inductive Capacities of Con-ducting Liquids. By E. COHN and L. ARONS (Ann. Phys. Chem. [2],33, 13-3I).-In a previous memoir (ibid. [a], 28, 454), theauthorsgave a means of determining the specific inductive capacity of a con-ducting liquid founded on the result obtained by, them that thedielectric polarisation and conduction are mutually independent.Jn the former experiments, the highest conductivity did not exceed4.5 x in terms of mercury, und the values of the sp. ind.cap. were found to be of much the same magnitude as for goodinsulators, being in every case less than 5.In the present paper,liquids of higher conductivity are considered, and this made itnecessary to devise a new method, as the former one, depending onobservatious of the rate of leakage of an electrostatic charge, wouldhave required the observations of intervals of time considerably lest3than the millionth of a second.The method used for the present inquiry is a modification ofSilow's (this Journal, 1876, ii, 267), founded on the principle thatwhen a system of conductors immersed in a homogeneous medium ismaintained at a constant potential, the work done against electricalforces, in effecting a given change of configuration, is proportional t othe sp. ind. cap. of the medium. The needle and one pair ofquadrants of an electrometer mere joined to one extremity of thesecondary of an induction coil, and the remaining pair to the otherextremity.Readings were then taken alternately with the liquid andwith air only in the electrometer. By this means measurementscould be obtained for liquids having a Conductivity as high as 16 x lo-'',or about 3400 times the highest conductivity in the former series.Calling K the sp. ind. cap., and k the conductivity, it was fonnd that fordistilled water I( = 76, whilst kvaried from 3.4 x lo-'' to 16 x 10-lo,so that an increase of conductivity to about five times its original valuehad no perceptible effect on the sp. ind. cap. For ethyl alcohol con4taining 2 per cent. of water, K = 26.5, and when, by the addition oftraces of ammonium chloride, the conductivit'y was increased from2.3 x to 12 x lO-'O, the value of K remained sensibly constant.For amyl alcohol the values obtained were K = 15 andk = 0.16 x lo-''.When successive quantities of ethyl alcohol wereadded to pure xylene, both K and JG increased, but the latter at firstmuch more rapidly than the former, the change of k from lees thanto 0.03 being accompanied only by a change of K from 2.36 to3-08.For these substances, Maxwell's law connecting sp. ind. capGEXERAL AND YHTSICAL CHEMISTRII'. 355Oil of turpentine from Pinus silvestris, lzvo-rotatoryOil of turpentine from Pims maritima, l ~ v o -rotatoryOil of turpentine from Pinus AustraEis, dex-trorotatolyOil of citron .. . . . . . . . . . . . . , . , . . . . . . . .. . .and index of refraction does not hold even approximately, thedeviation from the law being very much greater than even in thecase of glass and the fatty oils. The author suggests that it would beof interest to investigate the sp. ind. caps. of aqueous and alcoholicsolutions of various salts to as high a degree of concentration aspossible, and also to determine the same constant for as many well-defined chemical compounds as possible, in order to see if it may notbe possible to find some law connecting the sp. ind. cap. of it substancewith its chemical constitution. G. W. T.1 '50'70 1-46891 -5026 1 *45611 *5046 1.46851 '4990 1 -4706Conductivity and Specific Inductive Capacity. By E. COHNand L. ARONS (Ann. Phys. Clrem. [a], 33, 31--32).-h this note theauthors state that the numbers 2.23 and 4.43 given by them in thepaper referred to (ibid.[2], 28, 454) as the specific inductive capacitiesof xylene and castfor oil respectively are, according to their laterresearches, too small, and should be 2.36 and 4.82 respectively.G. W. T.Specific Inductive Capacity of Liquids. By F. TOMASZEWSKI(Ann. Y h y s . Chew. [2], 33, 33-42).-The principal object of t h i sinvestigation was to obtain measurements of the specific inductivecapacities of certain liquids in order t o determine, if possible, somerelation between the value of this constant and the chemical constitu-tion of the liquid, which curiously enough was one of the desideratasuggested by Cohn and Arons (preceding Abstracts).There were two questions which presented themselves for solution :(1) The influence of the number of atoms in a molecule, requiringdeterminations for isomeric, homologous, and nietameric compounds.(2) The effect of introducing a, fresh element into the molecule,requiring determinations for non-homologous compounds.The experiments were carried out by Silow's method slightly modi-fied, and the charges were obtained from a battery of 40 zinc-copper-water cells.The principal results obtained are given below, K being the specificinductive capacity, and p the index OP refraction for infinite wave-length.Isomeric Compozcnds, C,,H,,.IJ K .396Benzene (free from thiophen) ..............Paraxylene ............................. .............................. Toluene.Cumene ................................ABSTRACTS OF CHEDIICAL PAPERS.1.4892 1 * 4’7571 5175 1 ‘47131 * 5436 not determined.1 ‘5627 1 - 4838.Ho rno 1 o g o u d Compounds.A r o mat ic Hydrocarbons .The specific inductive capacities of isomeric compounds are, thew-fore, not equal.Where M is the molecular weight and d the density, it was foundthat the quantity M(n - l)/d, or the molecular refraction, wassensibly constant for the isomeric series, as also were the quantitiesM(K - l ) / d and M( J K - l ) / d . The specific inductive capacity ofhomologous compounds is seen from the second table to increase withthe number of atoms. Maxwell’s relation d = ,/I( is only approxi-mately true, as is clear from the tables given.G. W. T.Electric Discharge through Gases. By A. SCHIJSTER (Proc. ROY.Xoc., 42,371-379).-A glass vessel is divided into two compartmentsby means of a, metal plate nearly reachiiig to the sides and connectedto earth. I n one compartment charged gold leaves mere placed, inthe other electrodes through which discharges were passed from aninduction coil. No effect was observed a t the atmospheric pressure,but at 43 mm. prcssure the leaves slowly collapsed. In anotherexperiment, sparks from a Voss machine were passed a t the atmo-spheric pressure between points or spheres in the ueighbourhood ofcharged balls. When the electrodes were similar, whether points 01’spheres, the balls collapsed when electrified positively, but when oneelectrode is a sphere a.nd the other a point, the balls collapse if theirelectrification is of opposite sign to that of the point.Finally, theauthor observes that in a partial vacuum incompletely divided intotwo compartments by a metal screen connected to earth, a continuousdischarge between electrodes in one compartment renders i t possiblet o send a current between electrodes in the other compartment withan indefinitely small electromotive force. In one case, a current of0.008 ampere through the main electrodes enabled an E.M.F. ofone-fourth volt to send a current through the auxiliary electrodes.The intensity of the auxiliary current is greater the greater the maindischarge and the reduckion of pressure ; it increases less rapidly thanthe electromotive force causing it. Anything which facilitates gaseousdiffusion increases the strength of the auxiliary current.In explanatmion of these facts, the author considers that the two atomsof a gas molecule are charged with opposite electricities, and are heldtogether by molecdar forces.When this union is ruptured by themain discharge, the atoms diffuse across to the auxiliary electrodes,and give up their electricities to them. The rupture oE the moleculeis supposed to take place a t the negative pole, The diurnaGENERAL AND PHYSICAL CHEMISTRY. 397variations of terrestrial magnetism are supposed to be due to currentsproduced by tidal or other regular motions, such feeble currents beingrendered possible by the more powerful discharges which take placein the upper regions of the atmosphere.H. K. T.Conduction of Electricity through Gases. By F. NARR (Ann.Phys. Chem. [2], 33,295-301).-Hittorf (Awn. Phys. Chem., 7, 595)found that a pair of gold leaves attached to a stick of shellac, enclosedin a tube of hydrogen containing phosphoric acid to ensure perfectdryness, retained their charge after the lapse of four days, from whichhe concluded that dry hydrogen does not conduct electricity.Nahrwold (ibid., 5, 460), by a different method of experimenting,came to the conclusion that the particles of a gas cannot receive anelectrostatic charge, and that the loss of charge of a conductorexposed to the air is due entirely to the presence of floating particlesof dust. The author considers that Nahrwold’s experiments onlyshow that dust is the chief factor in causing leakage in a conductorexposed to the air.He refers to some former experiments (ihid.[2], 5, 145; 8, 266;11, 155 ; 16, 558 ; 22, 550) made by him with a charged sphere sue-pended within an insulated conducting envelope containing differentgascs of varions densities, carefully freed from dust. Whilst heconfirmed Hittorf’s result as to the charge being retained €or a longtime, he found that there is an instantaneous small loss of cbarge,depending on t’he nature of the gas and on its density. This instan-taneous loss increases as the density is diminished, and a furtherinstantaneous loss takes place when the envelope is connected to theearth, followed by a gradual and continuous loss of charge.Theauthor attributes this sudden loss to a transference of electricity to thegaseous molecules, and the slow dispersion to an electrical connectionbetween the sphere and the envelope. He has now repeated theexperiments with a double metallic envelope containing gas. ‘Theenvelopes were in the form of cylinders open a t one end, and closedat the other, the closed ends being hemispherical. The open endswere closed by a, sheet of glass covered with lac varnish, arid thecylinders were cemented to it with their axes coinciding. The authorthen found a similar increased loss on connecting the outer envelopewith the earth, from which he concludes that the gas between tlietwo cylinders acted as a conductor, putting the inner one in connec-tion with the outer, and so with the earth.The instantaneous loss ofcharge was found to increase when the density of either the inner OFthe outer portion of gas was diminished, which agreed with theformer resultq, but t,he slow dispersion of the charge appeared to besensibly independent of the density of the gas, as vlould be expectedto be the case if the dispersion takes place by a convection ofelectricity by the gaseons particles, on-ing to the enormous numberin contact with the surface of the envelope a t any moment;.Electrical Conductivity of Solutions of Neutral Salts. ByG. JXGER (Honatsh., 8, 721-724) .-The electrical conductivities ofsome salts of heavy metals have been measured in solutions con-G. W. T398 ABSTRACTS OF CHEBIIOAL PAPERS.taining proportions varying from g5 to i$m of the gram-molecularweights per litre.The salts thus examined were lead nitrate andacetate ; silver nitzate, sidphate, and acetate ; zinc sulphate, bromide,and iodide, and copper sulphate and acetate. Dividing the observedconduct,ivity by the proportion of the molecular weight in each case,the relative conductivity of the molecular weight of the salt fordifferent dilutions is obtained. This plotted against the dilutionvalues gives curves approximating to straight lines, a1 thoug h in nocase could the conductivity be represented as of the form L = am +/3rn2. All the curves, with the exception of that for zinc bromide,appear to tend towards maxima in different directions ; this is takenas supporting the view that each salt has ite own definite molecularconductivity.H. C.Comparative Properties of the Electrical Conductivities ofSalt Solutions. By G. JAGER (Monatsh., 8, 725--733).--ln a formerpaper (this vol., p. 217), the author proved that if L and L1 are themolecular conductivities of two different salt solutions, 6 the diameterof the molecule of the solvent, and d, d’, d,, d’l, those of the ions,From this it follows that as 6 is L,increased, the value ot L/L, will more nearly approximate to unity, orthat as the size of the molecules of the ~olvent increase all molecularconductivities approach more nearly to the same value. A rise oftemperature increasing the sphere of action of the molecule inaccordance with the coefficient of expansion of the liquid, where thislast is small and only small changes of temperature are dealt with,6 may be looked on as constant, and the above ratio as independent oftemperature.To test the above, a determination was made of the Conductivities ofsolutions of sodium and potassium chlorides containing $ to -L 9 2 gram-equivalent per litre in water, and in water containing ’LO to 60 per cent.alcohol, glycerol, and sugar, in each of which cases the conductivityof the solvent may be neglected.Dividing the inolecular conduc-tivity of potassium chloride by that of sodium chloride in each case, itwas found, as was expected, that water gave the highest values forthe ratio, and that in the other cases the ratio decreased and approxi-mated more to unity as the quantity of dissolved alcohol, glycerol, orsugar increased, or, as may be assumed, the diameter of the moleculeof the solvent increased.That temperature would have no effecton &he value of the ratio may be taken as proved by the result ofKohlrausch’s experiments, “ that the resistances of the ions in waterare all altered in the same proportion by change of temperature.”Also, as a consequence of Kohlrausch‘s theory, L/Ll =( y + u)!(uI + .I) where u, u, ul, and zll are the molecular velocitiesol the ions, it follows that if two salts have one ion in common, say,u = ul, then L/Ll approximates to unity as u increases, or the greaterthe rnolecular conductivities of two salts containing a common ion, theless will the ratio of the two conductivities differ from unity.This isalso found to hold good when tested by the results of Kohlrausch’sown experimeuts. H. C.c- ’ - - 4-I/@, + q2 + I/(& + 6’izGENERAL AND PHYSICAL CHEMISTRY. 399The Electrical Conductivity of Solutions of some FattyAcids in Water and in Alcohols. By K. HARTWIG (Ann. Phys.Chem. [2], 33, 58-80) .-The author points out that corriparativelyfew investigations have been made int,o the conductivity of otherthan aqueous solutions, Of those known to the author, Mateucci(Ann. CAim. Phys., 66, 237) was the first who made experiments onalcoholic solutions, but Wiedemann has thrown doubt upon his con-clusion that aqueous and alcoholic solutions of the same substanceof the same specific weight collduct equally well.Oberbeck (Ann.Phys. Chew., 155, 595) measured the resistances of aqueous andalcoholic solutions of cadmium bromide and cupric chloride, and fouiidthat the conductivity was increased by each of these salts in a mannerdependent on the salt and on the solvent. Guglielmo (Atti B. Accad.Torino, 17) determined the conductivity of an alcoholic solution ofpotassium hpdroxide, that of the aqueous solution having beenpreviously determined by F. Kohlrausch. Vinccntini (Mem. R. Accad.Torino [ 2],36,22) investigated the conductivity of alcoholic solutionsof some chlorides, and found that there is no simple relation betweenthe solubility and the conductivity. Bartoli (Z’Orosi, 7, 3) showedthat paraffin and naphthalene can be made into conductors by theaddition of amylic alcohol and phenol.The same autlior (R. Acad.Lincei, 1, 550) investigated the conductivity of various mixtures oforganic compounds ; and Lens (Mem. Ac. Sci. St. P&tershouyg, 7, 3U)made some researches in the conductivity of aqueous and alcoholicsolutions, in the course of which he completely demonstrated thefalseness of Matcucci’s conclusions. The author selected the fattyacid8 for his experiments, as being very soluble in several media.The measurements were made by the Wheatstone bridge method,with a telephone as indicator. The substances experimented on weresolutions of formic, acetic, and butyric acids in water, and in methyl,ethyl, and amyl alcohols. The measurements were made immediatelyafter the solutions were made, and as none of them occupied morethan an hour, i t was found that the results were not sensibly affectedby the etheritication which always takes place when organic acids andalcohols are mixed.With the exception of two of the solutions of formic acid, theauthor finds that the conductivity reaches a maximum a t a certainconcentration, and that t h i s maximum is reached the sooner the worsethe conductivity of the acid.The table below gives the percentage of acid for which eachsolution has the rnaximum conductivity :-Solution.~~ ~Acids.Formic acid.1 Acetic acid. 1 Butyric acid.Water .................Methyl alcohol .........Ethyl alcohol ..........Amy1 alcohol.. .........30100100 -16.630 -049‘054 -012.01’7’321.626 -400 ABSTRACTS OF CHEMICAL PAPERS.Thus the greater the quantity of carbon present in the acid thesooner is the maximum conductivity attained, and the greater thequantity of carbon present in the solvent the later is the maximumatt’aiiied, the conductivity being diminished by an increase of thequantity of carbon present either in the acid or in the solvent.The author attributes the anomalous behaviour of formic acid withregard to electrical conductivity, together with similar anomalieswhich it exhibits with respect to its other physical properties, to theabsence of the group methyl from its composition.G. W. T.Electric Leakage. By J. J. THOMSON and H. F. NEWALL (PTOC. ROY.Xoc., 42, 410--429).-The liquid experimented on is contained in acylindrical, metallic vessel, connected to earth, in which a metal cylinderis suspended by means of a silk thread ; this can be connected eitherwith a battery or with ft quadrant electrometer.The inner cylinder,after being charged, is connect,ed with the electrometer, and readingstaken every fire seconds. Curves are plotted showing (1) the decreaseof potential with time; (2) the ratios of successive potential values.The liquids examined were benzene, olive oil, carbon bisulphide andpal-affin oil, and were filtered many times before use. With the firstthree, no deviation from Ohm’s law could be detected. With paraffinoil, the couductivity is slightly greater with large than wit8h smalldifferences of potential.These results, where the E.M.F.’s were 20-100volts, differ from those of Quincke (Abstr., 1886, 9S9), who finds thatwith E.M.F.’s sufficient to produce a spark the conduction does noteven approximate to Ohm’s law. With carbon bisulphide, great dis-crepancies were found in the first results; these were traced todifferences in time of charginp, and later experiments proved thatelectric absorption took place. The effect was greatest after redistillingthe carbon bisulphide, but a t times it was totally absent. The con-ductivity of all the liquids was increased by rise of temperature, sotthat in this respect they resemble electrolytes.The Influence of Magnetic Forces on the Nature of theHeat Conductivity of Bismuth. By A . v. ETTINGSHAUSEN (Awn,.Phys.CltenL. [2], 33, 129--136).-The author points out that Righi(Abstr,, 1887, 1009) and Leduc (Compt. Tend., 104, 1783; 105, 250)have made some experiments, from which they conclude that thethermal conductivity of bismuth in a magnetic field is diminished toan equal extent with the electrical conductivity, supposing themagnetic! lines of force to cut the stream lines for heat o r electricityrespectively at right angles. Nernst (Am,. Phys. Ohem. [ a ] , 31,760) was unable to detect any change in the thermal conductivity.The author, after some experiments made with great care, finds thatthe. thermal conductivity is diminished, b u t to a much less degreethan the electrical conductivity. The decrease in the thermal con-ductivity is greater when the bismuth is impure, but still much lessthan that of the electrical conductivity.H.K. T.G. W. T.Constancy of the Heat Produced by the Reaction of SilverNitrate with Solutions of Metallic Chlorides. By T. WQICNERAL AND PHPSTCAL CHEMISTRY. 401RICHARDS (Chem. News, 57, 16-1 7) .-Tn these experiments, allnecessary precautions are observed to obtain comparable conditions :250 C.C. of the silver nitrate solution (equal to 4 grams silvernitrate) and 250 C.C. of the salt solution (containing a gram or so ofthe salt in excess of that required to precipitate all the silver) arepoured simultaneously into the platinum calorimeter (Berthelot’s),and the rise in temperature noted. The average rise in 20 experi-ments amounts to 16.165 cal.and all the results are practicallyidentical ; the experiments included sodium, potassium, ammonium,barium, cupric, zinc, manganous, nickelous, ferrous, aluminic, ferric,and chromic chlorides and hydrochloric acid. Taking the followingequation as representing the reaction, the author concludes from theseresults that the amount of heat is constant no matter what R m or nmay be. (>,Cln + AgN03 + Aq) = AgCl + [+Rm(NOs)n = Aq].(Compare Pickering, this vol. p. 333.) D. A. L.Relation between the Heats of Formation of Chlorides andSulphates in Aqueous Solution. By I. W. FAY (Chem. News, 57,36--37).-The author conducted a series of experiments with bariumchloride and soluble sulphates exactly similar to Richard’s experimentswith silver nitrate and chlorides (see preceding Abstract).There is notthat general regularity observed in the case of the sulphates as with thenitrates, although the rise for allied bases is quite close ; the sesqui-oxide salts give a greater rise of temperature than the protoxidesalts do, and with the double salts a still larger quantity of heat isevolved, whilst sulphuric acid gives most of all. The sulphates in-cluded in the experiments were sodium, potassium, ammonium,magnesium, zinc, cadmium, copper, nickel, cobalt, ferrous and fewic,and aluminium potassium alum, potassium chrome-alum, ammoniumfwrous sulphate, and sulphuric acid. The results are tabulated inthe original paper. (Compare Pickering, this vol., p. 333.)D. A. 1;.Alteration in the Volumes and Density of Liquids by theAbsorption of Gases.By K. ANGSTROM (Ann. Phys. Chern. [ a ] ,33, %3--233).--The author has already given an account of in-vestigations on expansion of water through the absorption of gases(Abstr., 1882, 687). Since this appeared, experiments of the samenature have been made both for water and ethyl alcohol, by Bliimcke(Abstr., 1885, 215; 1887, 435), but they do not agree witth thosemade by the author or by Mackenzie and Nichols (Abstr., 1878,365)and Nichols and Wheeler (Phil. Mag., 5, 11, 113), probably becameBliimcke’s method did not allow of several iaequisite corrections beingmade ; for example, for the compression of the areometer, and for therefraction of light at the surface of the containing vessel.A summary of the results of the author’s previous experiments andof the first series described in the present paper are given in thetable below, in which &, Bg, B3, are coefficients oE expansion due toabsorption402 ABSTRACTS OF CHEMICAL PAPERS.0.001600.001060~001,70OmO01570.001520-00184Means =-Chloroform .......Xitrobenzene ......Water ............Benzene ..........Met,hyl alcohol ....Etbyl alcohol .....Ether ............1.18 1.281.23 1.351.18 1'2'71.17 1'281.22 1.34(1'09) 1.301.20 1-30- ----Carbonicacid 6,.--0 *001880 * 001R80 -001 300 '002000 *001840 *001850 *00200Air 6,.--0 a 002050.001430 *002160 .Oc12010 * 002030 * 00240-This shows that, except for etber, the ratios 6*/E, and &/a3 aresensibly constant.Experiments on the successive absorption of twoor more gases gave the result that the coeecient of expansion due toabsorption is independent of any previous absorption of gas, thetotal expmsion being equal t o the sum of the expansions due to theabsorption of the different gases.The results obtained enable the change in tbe specific weight of aliquid due to the absorption of gas to be calculated, which is ofpractical importance for specific weight determinations, but the effectin such cases is so small that it need only be taken into account whenthe most extreme accuracy is desired. The author considers theconstancy of the ratios ;5,/6, and 6,/6, to be the most important ofhis result-s from a theoretical point of view, as it.shows that thedilatation depends on the gas, and that the relations between the co-efficients of dilatation due to absorption are independent of the natureof the liquid; froni this he concludes that Ostwald's hypothesi8(Stiichiornetrie, p. 356), founded on the values of the coefficient ofdilatation due to absorption obtained by the author and by Sarraii,namely, that "the volume of the absorbed gas is almost exactlyreduced to the volume of its molecules," is 6 priori extremelyaim-probable. G. W. T.Differential Tonometer. By G, J. W. BREMER (Rec. TTUV. Chim,.,6, 122 -136).-An apparatus for measuring the difference betweenthe vapour-tension of a saline solution and the vapour-t'ensionof water by allowing the vapours to act on the opposite endsof a column of olive oil.It consists essentially of small flasks con-nected with vertical tubes about 150 mm. high communicating withone another by means of a horizontal tube at the bottom. Theparticular apparatus described consists of four such flasks. The flasksshould have exactly the same cubical contents, which may be adjustedby introducing pieces of glass rod, and should contain equal volumesof the solutions. After introduction of the liquids the flasks arecooled to O", rendered partially vacuous, and oil allowed to enter fromthe bottom horizontal tube until it rises to about half the height ofthe vertical tube. The exact pressure of the a i r in the flasks isobserved, and the flasks and their contents are heated to differenGENERAL AXD PHYSICAL CREXISTRY.403teniperatnres and the differences between the levels of the oil in thetubes are observed.Determinations of the vapour- tensions of aqueous ~olutions ofcalcium chloride of different shengths show that if the salt isregarded as existing in the liquid in the anhydrous condition, thereduction of the vaponr-tension increases more rapidly than theamount of calcium chloride present, but if the solution is supposed tocontain the hydrate CaCl, + GHaO, the reduction of the vapour-tensionis proportional to the amount of salt present, as Wullner has pre-vionsly stated. C. H. B.Dynamical Method of Determining Vapour-pressure. ByG. TAMMANN (Ann. Phys. Chem. [2], 33, 322-337).-The author onrecalculating some tables given by Regnault (Ann. Chim.Phys. [3],15, 158) for the vnpour-pressure of pure water determined by thedynamical and statical methods respectively, found that the closeagreement of the results was only apparent, and that there werereally some considerabe discrepancies which could not be accountedfor. The author now describes a number of experiments carried outprincipally with a view to testing the dynamical method, followingRegnault with some modifications in details. He concludes that themethod is not capable of giving good results. In the case of un-saturated solutions, when the current of air is passed over thf: surfaceof the solution, the upper layers become more concentrRted than thelower, through the evaporation being en tirely superficial, and if thecurrent of air is led through the solution errors are introduced, asit is impossible to prevent variation of pressure and the scattering ofdrops of the solution upon the interior of the glass vessels.Theauthor attempted to use it with saturated solutions, using filter-papersoaked in the solution, then partly dried, and introduced into aU-tube through which the current of dry air was allowed to pass,but then he was met by the difEcu1t.y t h a t on taking the tube out ofthe bat>h used to maintain the required temperature, drops of watercondensed on the inner surface of the tube, and dissolving some ofthe salt adhering to it gave rise t o unsaturated solutions. Theauthor liext tried the method with hydrated salts i n crystals.Here,however, the results were found to depend on the velocity of thestream of air, which appeared to be due to the water-vapour given offdissolving a portion of the crystals arid forming hydrates containingless water, which would give a lower vapour-pressure.From some of the results obtained during the last series of experi-ments, combined with Pape’s result (Ann. Phys. Chem., 124, 389)that rates of evaporation from the different surfaces of irregularcrystals are not the same, tbe author draws the conclusion that theyapour-pressure at the surface of a crystal is not the maximum valueof vapour-pressure due to the crystal. The vapour-pressure at thesurface depends on the nature of the surface, and is considerably lesswhen the surface is uninjured than when i t is broken or otherwisechanged. G.W. T40 4 ABSTRACTS OF CHEMICAL PAPERS.Compressibility of Rock Salt. By I?. BRAUN (Ann. Phys. Chm. [a], 33, 239--240).-The author in a recent note (this vol., p. 214),whilst giving the preference to Rontyen and Schneider's value5 x for the cubic compressibility of rock salt over the value1 . 4 ~ 1 0 - ~ found by him, as his own determination was a com-paratively rough one, pointed out that according to Voigt's measure-ments of elasticity the value would be 1 . 6 ~ 10". The author hassince seen a later paper by Voigt (Ann. Phys. Chem. [a], 15, 497)i n which he corrects his former result, as in obtaining it he madeuse of a torsion formula which he has since found to be incorrect.Voigt's later measurements would give the value 4.2 x lo+, which,considering the difficulty of the piihometer method, agrees fairly wit,hthat obtained by Rontgen and Schneider.By P.SABATIER (Con@.rend., 106, 63--66).-The conversion of metaphos-phoric acid into orthophosphoric acid involves the introduction of anacid function of medium activity and an acid function of feebleactivity, in addition to the original energetic function. Only thelatter affects methyl-orange ; the secoud feebler function affectsphenolphthaleh, the third can only be qualitatively recognized bymeans of the blue C4B. The acidity of the liquid h to methyl-orangeremaitis constant, whilst its acidity to phenolphthaleh c# increases,and affords a measure of the progress of the transformation.Whenconversion into orthophosphoric acid is complete 4 = 2h, and a t anystage of the change 2h - @ gives the amount of metaphosphoric acidy still remaining unaltered.The metaphosphoric acid was obtained by dissolving phosphoricanhydride gradually in cold water, and also by strongly heating theortho-acid, and dissolving the residue in water. Both preparationsbehaved in the same manner.These solutions were heated at different temperatures for definiteintervals of time. At a given temperature, log y is proportional tothe time. Tke velocity of the change at each instant, is proportionalt o the mass of transformable substance present in the system, andhence log y = - x log a + log b, and therefore y = ba-x, where bis the value of y at the commencement, and a is a constant which is afunction of the temperature and the concentration, and increases withboth, but the exact law of increase has still to be determined.By J.H. VAN"!?HOFF (Rec. Truv. Chem., 6, 3 6 4 2 ; 91-94; 137--139).-The par-ticular reaction considered is the conversion of mixtures of sodiumand magnesium sulphates into astraknnite, N%Mg(S04)2 + 4H20, a ttemperatures below 21.6". It is found that in order to separatesodium sulphate from the mother-liquors from sea-water, which con-tain a large proportion of magnesium chloride; it is necessary to coolthe liquid below 5", and hence it would appear that the syst.emMgCl, + Na2SOa is stable below 5", but at higher temperatures thereciprocal sys tem is formed.If a solution containing sodium sulphate and magnesium chlorideG. W.T.Rate of Transformation of Metaphosphoric Acid.C, H. B.Point of Transition and Point of FusionGENERAL AND PHYSICAL CHEMISTRY. 405in equivalent proportions is placed in a dilatometer, no anomalousexpansion is observed at 5", but if 2 mols. of sodium sulphate arcpresent for each molecule of the magnesium salt, there is a very con-siderable expansion if the liquid is heated above 5", and a cnnsider-able contraction if it is cooled below this temperature. This par-ticular temperature is in fact the point of transition between thetwo systems, but the author has previously observed that magnesiumchloride cannot exist in presence of sodium sidphate a t temperaturesbelow 5"' because the tension of the water of crystallisation of thelatter salt is less than the vapour-tension of the saturated solution ofthe two salts.The slow evaporation at a low temperature of a solution containingsodium cbloride and sodium and magnesium sulphates i n equivalentproportions yields a mixture of the three salts, but if evaporation t.akesplace at a higher temperature cubical crystals of sodiuni chloride areobtained, together with rosettes of ast,rakanite, which is formed bythe union of the two sulphates with elimination of water.Inpresence of sodium chloride, formation of astrakanite takes place a ttj", and the reverse change at lower temperatures, whilst in absenceof sodium chloride astrakanite is forrned at 21.6' (Alistr., 1886, 968).The reduction of the point of transition from 21.6" to 5" by thepresence of sodium chloride, corresponds with the reduction whichthis salt produces in the freezing point of its solution.The double acetate, CuCa(C2H30?)4 + 8H20, decomposes at 75"into the simple salts Ca(CzH302)2 + H,O and Cu(C&f,O,), + HzO,with elimination of 6 mols.H20, and the change is accompanied by adistinct contraction ; at lower temperatures, the double salt is formed,nnd expansion takes place. The volume changes are analogoiis tothose which accompany the solidificat.ion of water, and it was to beexpected that the effect of pressure would be analogous in the twocases.A t the author's request, Spring has subjected the double acetate tohigh pressures at varying temperatures, and finds that under a pres-sure of 6000 atmospheres decomposition takes place at 40".Under thesame pressure at 16", there is no appreciable decompositiori if theduration of the experiment is short, but if pressure is prolonged,evidence of decomposition is readily recognisable. Under a pressureof 2000 atmospheres, decomposition takes place distinctly at 50" (com-paye this vol., p. 341).Van't Hoff points out that determinations of the minimum pressurerequired to produce reactions of t!his kind, together wit,h measurementsof the resulting changes in volume, will make it possible to expressin kilogram-metres the absorption of energy involved in the reaction,and conversely the liberation of energy resulting from the reversechange.C. H. B.The Position of Atoms in Space. By J. WISLICENUS (Rer., 21,581-585) .--&sen has challenged Van't Hoff and Wislicenus tostate their views on units of affinity from the standpoint of theirgeometric t,heory, and he affirms that the question of the position of;he units of affinity in space must be answered not after, but before,VOL. LIV. 2 406 ABSTRACTS OF CHEZIIICAI, PAPERS.the question of tlie popitions of atoms in space. and above all that Rdefinition of “ unit of affinity ” must be given (this vol., p. 218).The Nuthor admits that his views quite bar the conclusion thatatoms are material points, and- it is impossible, therefore, to considerthem as configurations in space in which the several chemical units ofaction of polyvalent, elements can he localised.Rut this conclnsionis admissible when the so-called atoms are considered, not as atoms inthe strict sense of the word, but as simple groups of primitive atoms,similar to the compound radicles but less complex ; and therefore tlieposition of the elementary atoms in the molecule must be determinedbrfore Lossen’s demand can be taken into earnest consideration.The author has shown that the determination of the arrangementin space of the atoms in a molecule is within the domain of experi-ment, and he points out that the study of the confignration of themolecule is the only way to solve successfully the question of thedistribution in space of its spheres of action-the so-called units ofaffinity.Only by studying the properties of molecules cau inductiveconclusions be drawn as to the properties of atoms.The author’s views are stated as follows :-It is more probable thatthe atoms are configurations in space composed of atoms of primiiiveelements than that they are simply points of energy ; the most likelyassumption is, therefore, that the atoms are comparalole with thecompound radicles, and, as in the latter, their units of affinity arelocated in certain parts from which they exercise their action.It is possible, in time, to succeed in obtaining definite ideas notonly of the form of elementary atoms, but also of the relative posi-tions of their spheres of action.It is not impossible that tlie atom of carbon resembles more or lessin form a regular tetrahedron, and that the causes of those actions,which are evidenced by the units of afflnitly, are concentrated in theangles of this tetrahedric configuration, perhaps for analogous reasons,and similarly to the electric action of a charged metallic tetrahedron.The real carriers of energy would finally be the primitive atoms,exactly as the chemical energy of compound radicles is the resultantof the energy of the elementary atoms.The Atomic Weights of the Elements.By A. RAZAROFF (J.Russ. Chem. Soc., 1887, 61--73).-The author finds that the variationin the numbers expressing the atomic weights of the elements,nrranged according to the periodic system, is analogous to the changesin the properties of the elements and their compounds.When themost probable numbers for t h e atomic weights of the elements arearranged according to the periodic law, amd, either in the horizontalor in the vertical series, the atomic weight of an element is divided bythe atomic weight of the element with the next lower atomic weight,products are obtained which decrease regularly with increase in tbeatomic weights compared. In the horizontal series, the maximum isfound t o correspond with the relation of 2 = y8 = 1.2955, theL1 7.01F. S. K.minimum to Bi -- = - 207’5 = 1.0054. This decrease, however, is notPb 206.3GEKERAL AKD PHYSICAL CHEMISTRY. 407con tjinuous, the products alt ernately decreasing and increasing, as isseen from the following examples :-- S = 1.0529, - c1 = 1.1060, &c.J? SThis relation is best represented graphically, the order of atomicweights standing as abscissz, and the aforesaid quotients as ordinates :in this way a curve of zigzag form is obtained.This relation isexpresqed by the author in the form of a law, namely, that “ t h eincrease in the atomic weights of the elernent,~ proceeds with avariable int’ensity, the smaller coefficient of change vsrying with thelarger in such a way that both regularly decrease.”Another regularity is observed in the vertical groups, for example,with the coefficients in the second group :-Ca Z Sr !!% = 26366, - = 1.6671, $ = 1.6257, - =; 1,3456,Ba %! = 1-2795, -- = 1,2252.sr CdBe J% La znThis change the author expresses by the law : “ In the verticalseries in the periodic system, the relation of two neighbouring atomicweights decreases with increasing atomic weight, but this decrease isalternately larger and smaller.” Neither of these functions extends tothe whole periodic system, as there are many elements whose atomicweights are not yet determined wikh fiufficient accuracy.Yet it ispossible, from the Gata which are to hand, to state the followinggeneral law : “ The magnitude of the atomic weight of each clementis determined by the magnitude of the atomic weights of the elementsnext to i t in the periodic system both horizontally and vertically.”The author further analyses the exceptions to the said rules, andexpresses the opinion that several of them are due to the atomicweights not being determined with sufficient accuracy, but it isdifficult to say how far he is right in correcting several of the betterdetermined numbers (he assumes for TI 202 instead of 203.7 !).Not-withstanding the apparently complicated character of the relationpointed out, the author thinks i t possible that when the fundamentaldata are more exactly determined, it mzhy be possible to calculate theatomic weight of an element with greater accuracy than is the case atpresent. B. B.Raoult’s Method of Determining Molecular Weights.” By V,MEYER (Bey., 21, 536-539). In iuvedigating some derivatives ofbemil, two series of isomeric compounds were obtained ; both serieshave the same constitution, in the ordinary gense of the word, and arej e t distinct from one another and yield dif-ferent derivatives.The* Raoult’s papers on this method are Abstr., 1883, 7, 278, 952 ; 1884, 254, 701,8C8, ‘352, 1248 j 1885, 122, 858 ; 1886, 197, 763. Compare also this vol., p. 361.Z e 408 ABSTRACTS OF CHEMICAL PAPERS.Ph*C : RIPh*C : Risomerism of the two series is expressed by the formulsePh*C : Rand I .R : C-Ph.By means of a modification of Raoult's method for determiningmolecular weight by measuisinq the amount by which the solidifyingpoint of a solvent is lowered by a known weight of a, dissolved sub-stance, it is shown that the molecular weight of the compounds of thet w o series in question is identical. The method eniployed, which onlyinvolves the use of an ordinary thermometer divided into 0.1" and asimple apparatus, will be described.Application in Chemical Laboratories of Raoult's Methodfor Determining Molecular Weights.By K. AUWERS (Ber., 21,7'01-71 9).-The use of Raoult's method for determiniiig molecularweights by V. Meyer (preceding Abstract) led t o a consideration ofthe conditions necessary for its successful appiicntion. The exceptionwhich many solutions, notably those of inorganic salts in water, showto the law put forward by Raoult (Ahstr., 1886, 763), renders thislaw useless for practical purposes, and the relation N = T,'A, whereM is the rnolpoular weight,, T the molecular depression, and A thedepression caused by 1 gram of substance in 100 grams of solution, isused. It is recommended to first determine the value of T, which willbe constant for the series of compounds under consideration, by takingmembers of the series of known molecular weight.Ameasurement ofA then suffices to determine M in subsequent cases.9 great objection is the impossibility of working with relativelysmall amounts of material, for although the above relation does nothold for concentrated solutions, the solutions must not be too dilute,and some discrimination is necessary in adjusting the strength to givethe depression which should be measured in each case. With regardto the solvents used, i t is of course a condition that no chemicalaction should take place between the one selected and the substanceunder examination. The selection of a suitable solvent is a matter ofgreat importance.Water is generally objectionable on account of its tendency to formhydrates and its non-solvent action on most organic compounds.Asi t is necessary also, according to Raoult, that the depression measuredshould not be less than 0.5", a6 the relation does not hold when it isallowed to sink below that value, a relatively large quantity ofmaterial is necessary for each determination. Benzene gives betterresults, but cannot be used in the case of alcohols, phenols, or acids,and introduces an element of uncertainty in dealing with substancesallied to these.By fa.r the best solvent, and the one that can be used with the greatestrange of substances, is glacial aceticacid. The errors in this case aresrnall, and the measurement of a depression of about 0.3" suffices.A great advantage also is that this solvent admits of working a tordinary temperatures.It is, however, found necessary, owing to itsN. H. MGENERAL AND PHYSICAL CHEMISTRY. 409hygroscopic nature, to conduct the experiments in a closed space, andan apparatus has been devised and is described by means of which thisis easily rendered possible. A thermometer divided to one-tenth of adegree was used, and this was found to give sufficiently accurateresult,s. Experiments are detailed cvit,h naphthalene and picric acid,acetanilide and benzil, and the isomeric diacetyl-compounds of/3-dip hen y lg ly oxinie.In conclusion. the author recommends the use of Raoult's method inthose cases where rapour-density determinations are not possible.H.C.Isonitroso-compounds. By E. BECKMANN (Ber., 21, 766-769).--The application to the ketoximes of Raoult's method for the deter-mination of the molecular weight by the lowering of the freezingpoint, has led to the important result that the molecular weights aretwice as large as has hitherto been assumed. The compounds experi-mented with were acetoxime and camphoroximc ; the solvent beingbenzene.With benzaldoxime and anisaldoxime, results were obtained point-ing to molecular weights about one and a half times as great as thosepreviously adopted ; these results are, however, doubtless due topartial dissociation of the double molecule.Desiccation of Gases. By J. D. VAN DER PLAATS (Rec. Tyav.China., 6, 45--59).-An extended historical summary of the variousmethods which lave been proposed f o r hhe desiccation of gases,together with an account of experiments made by the author.Anhydrous calcium chloride is more efficient than calcium chloridecontaining 2 mols. H20, but the difference diminishes at low tempera-tures. Calcium oxide absorbs moisture more sIowly than anhydrouscalcium chloride, and leaves twice as much water in the air as calciumchloride containing 3 mols. H20. Fused potash acts rapidly andmuch more completely than anhydrous calcium chloride, but lessrapidly and less completely than concentrated sulphuric acid. Potashsolution of sp. gr. 1.25 loses R considerable quantity of water it acurrent of air is passed through it for some time.A. J. G.Ammonia is almost completely dried by fused potash.Calcium chloride is a convenient but not very efficient desiccatingagent. If the solution has been evaporated at B O O , it always containscalcium oxide, which cannot be neutralised even by the prolongedaction of carbonic anhydride or hyarogen chloride so long as the saltremains dry.Phosphoric anhydride is the best of all desiccating agents at presentknown, but it is inconveniently light and bulky. Not unfrequently itcontains phosphorous anhydride, but this can be removed by Stas'smethod of distilling it in dry air.Concentrated sulphuric acid is cheap and convenient, allows thespeed of the gaseous current to be watched, and dries gases almostperfectly. It gives off no vapours, and when cooled its efficiency isincreased. I t must not contain sulphuric anhydride, and the presenceof 6 to 8 per cent. of water is desirable i n order to ensure absence of.the anhydride in the gas which is passed through the acid. Some410 ABSTRAOTS OF CHEMICAL PAPERS.times the acid contains sulphurous anhydride, but this is readilyremoved by a current of dry air or by boiling the acid. Solphurica::id will dissolve carbonic anhydride, but this gas is removed in afew minutes by passing a current of air into the liquid. The distribu-tion of sulphuric acid with a view to expose a large surface is besteffected by means of broken glass. Pumice should be boiled withsulphuric acid containing a lithle nitric acid in order to removechlorides and fluorides and metallic oxides which might absorb oxygen.Sulphuric acid, especially if cooled, is practically as efjicient asphosphoric anhydride, and the errors due to its employment arecertainly not greater than those arising from the use of india-rubberconnections or from neglect to remove, by heating, the layer of moistgas condensed on the surfaces of the glass vessels.India-rubber cannot, be completely dried on a sand-bath, but shouldbe kept over sulphuric acid in the dark €or a lorig time, Tubing withwalls 5 mm. thick allows air and aqueous vapour to pass extremelyslowly, and its power of absorbing carbonic anhydride is a t a minimum.Drying tubes, &c., which have to be weighed should be kept undera. bell-jar cont,aining vessels filled with the same desiccating agent a sthe tubes themselves contain. c. H. €3.Delicate Themnometer for Lecture Purposes. By S. YOUNG(Chem. News, 56,26l).--For this purpose the author recommends an airthermometer of the form commonly employed to show the expansion ofair with rise of temperature, but using a volatile liquid suqh as ether inplace of mercury or sulphuric acid ; to make the column of liquid visi-ble a t a distance, a little absolute alcohol coloured with aniline red i Radded. The apparatus employed by the author had the following dimen-sions : the cylindei- a t the bottom containing the air confined by etherwas 17 mm. in diameter and 130 mm. long, t,he narrow t.ube extended700 mm. above this cylinder and had a diameter of 2.8 mm., above thisthere was a reservoir large enough to hold the ether when the tempe-lature got beyond the range of the thermometer. The total rise ofcolumn for 10" in the thermometer described was 510 mm. ; for 1"between 0" and 1" the rise = 40 mm., whilst between 9" and 10" it =82 mm. D. A. L.Lecture Experiment for Demonstrating the Valency ofMetals. By B. LEP.SIUS (Ber., 21, 556--561).-The method whichNilson and Petterson have recently described for determining theatomic weights of the rare earths can be employed for demonstratingthe valency of metals. A quant.ity of the pure metal, proportional toits atomic weight, is heated in gaseous hydrogen chloride, the volumeof liberated hydrogen being proportional to the valency of the metal.For various reasons many of the metals offer great difficulties incarrying out this experiment, and the author rwommends thalliuin,zinc, and aluminium as the most suitable examples. The hydrogenchloride, which must; be perfectly dry, is obtained by acting on solidpublimed ammonium chloride wifh concentrated snlphuric acid in aNorblad's apparatus ; it is passed through a combustion tube whichcontains weighed portions of the above-named metals (twice thINORGANIO CHEMISTRT. 411atomic weight) placed a t intervals of 10 cm. from one another. Theli berat,ed hydrogen is collected in a graduated three-limbed glassapparatus filled with a 5 per cent. solution of potash and providedwith a mercury seal. By heating the metals successively, the hydro-gen evolved from each can be collected separately and the volumescompared directly. F. S. K

ISSN:0368-1769    

DOI:10.1039/CA8885400389

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

INORGANIO CHEMISTRT. 411 In o r g an i c C h e m i s t r y. The Composition of Water by Volume. By A. SCOTT (Proc. no!/. SOC., 42, 396--400).--The ratio by volume in which oxygen and hydrogen combine at 0" and 760 mm. is redetermined. The apparatus is so arranged that both gases are measured in the same vessel, a separate vessel being used for exploding. After explosion, the residue was analysed by exploding with oxygen or hydrogen and the impurity (nitrogen and carbonic anhydride) determined. The oxygen was obtained from potassic chlorate and from mercuric: oxide prepared from the nitrate, the hydrogen was obtained by electrolysis. The ratio obtained is 1.994:1, which with 15.9627 for the density of oxygeri, gives 16.01 as the atomic weight of oxygen. The Weldon-Pechiney Process for the Manufacture of Chlorine from Magnesium Chloride.By J. DXWAR ( J . SOC. Cheni. Ind.¶ 6, 775 -790). -This process, which was patented in June, 1884 (Eng. Pat. 9306), has recently been worked at Salindres on an experimental plant designed for the daily production of 1 ton of chlorine, and may be briefly descrihed as follows:-The raw material employed is hydrochloric acid, the operations being (1) dissolving magnesium oxide in hydrochloric acid ; (2) preparing magnesium oxychloride ; (3) crushing, breaking, and sifting the oxy- chloride ; (4) drying the oxychloride ; and (5) decomposing the oxy- chloride. T'he magnesium oxide to be dissolved in hydrochloric acid is a portion of that which results from the fifth operation. The hydrochloric acid also results in part from the fifth operation and the remainder from the decomposition of salt.The solution obtained is evaporated down to the point at which it will contain not more than about six equivalents of water, and is then converted into oxychloride by mixing one equivalent of magnesium chloride with one and a third equivalents of magnesium oxide. This operation lasts only about 20 minutes, b u t during this time the whole mass becomes very hard and during solidification diseugirges much heat. The product is then in the form of solid pieces of different size9 along with a small quantity of powder. It is necessary to reduce this material to frag- ments, of which the largest shall not exceed the size ofa walnut, and further to clear them of dust which might, when in the decomposing furtiace, prevent free passage oE air through the mass ; this is egected by crushing it between cylinders bristling with diamond poiuts, and H. K.T.412 ABSTRACTS OF CHEMICAL PAPERS. then passing itl through a rotating sieve. The oxychloride is then dried, this operat,icn being necessary, as in the decomposition a larger quantity of free chlorine arid a smaller amount of hydrogen chloride are produced if the material contains less water, and the decomposi- tion is performed a t a higher temperature, both conditions being realised by drying previous to decomposition. The dried oxpchloride is then decomposed in a special apparatus consisting of a series of furnaces provided with decomposing chambers heated by a movable regenerative burner, the oxychloride being decomposed in a current of air.The author’s theory of the decomposition which goes on in the furnace is that in the first stage there is a rapid evolution of steam, the steam decomposing a portion of the magnesium chloride with formation of hxdrogen chloride which passes ofT ,with the rapour of wate;.. Anhydrous magnesium chloride and magnesium oxide remain, and this mixture then undergoes decomposition into magnesium oxide and chlorine by the action on i t of atmospheric oxygen. The products are drawn off from the furnace by means of a diminished pressure steadily maintained, an aspirator being employed which acts through an ordinary hydrochloric acid condensing tower, a number of sand- stone boubonnes and a glass tube refrigerator, the lattcr being in immediate connection with the decomposing furnace.The hydro- chloric acid is condensed in these apparatus, whilst the mixture of a,ir and chlorine passes on through the aspirator and is employed for the manufacture of chlorate: for this purpose, it is driven into special apparatus, wherein the chlorine acts on calcium hydroxide and gradually transforms it into a mixture of calcium chlorate and calcium chloride. D. B. Nitrogen Chloride. By L. GATTERMANK (Rw., 21, 751-757).- The composition of nitrogen chloride has not yet been satisfactorily determined ; weighed quantities of t,he chloride hare never been analysed, but merely the ratio of nitrogen to chlorine determined i n an unknown amount of the chloride, and, as is well known, the results obtained by different observers are by no means in accordance.In the present research, the experiments were carried on as far as possible iu the glass case devised by V. Meyer (Bey., 21, 26). The nitrogen chloride was prepared in bhe usual manner by the action of chlorine on a solution of ammonium chloride. 30 sign of the formation of the chloride was visible until more than half the chlorine was absorbed, when the formation of minute drops was noticeable in the layer of liquid drawn up by capillary attraction on the sides of the flask ; this soon spread and formed a thin film on the surface of tbe liquid, and this film i n turn gradually separated into larger drops, the heavier of which sank, but were again brought to the surface by the nitrogen bubbles formed in the slight decomposition which goes on. When no more drops are formed, the chloride by careful shaking was made to fall into a small leaden capsule provided with a handle.I t was then poured, with the aid of a funnel, into a thin- walled separating funnel, the ammonium chloride solution removed by a pipette, and the nitrogen chloride repeatedly washed by shaking with water until the washings no longer gavea, chlorine reaction. ToINORGANIC CBEMISTRY. 413 assist the removal of dissolved chlorine from the oil, air was repeatedly blown through it by means of a glass tube, so that the oil was dis- seminated through the liquid in small drops. The successful carry- ing out of these operations shows that nitrogen chloride is by no means so readily exploded as has usually been supposed.The purified oil was next transferred t o a thin glass flask (an operation attended with much danger owing to the fkiction of the stopcock of' the separating funuel), dried by agitation with a small, clean piece of fused calcium chloride, and poured into the weighing glass-a weighed cylindrical vessel of about 1 C.C. capacity, provided with a stopper not quite air- tight. The weighing was effected in the usual manner, save that a glass screen was again employed. The weighed substance was then decomposed by aqueous ammonia, and the chlorine estimated as silver chloride. The results showed that the product of the action of chlorine on ammonium chloride is invariably a mixture of several chlorinated ammonias, and t h a t the product was richer in chlorine the longer the oil was in contact with chlorine, but under no condi- tions was the trichloride obtaiued directly.After washing out the ammonium chloride as described above, the separat'ing funnel containing the crude product covered with a few drops of water was placed hnrizontaliy, and a moderately strong stream of chlorine passed through for half an hour. The oil so obtained, after washing and drying, was analysed, and proTed to be pure nitro- gen trichloride. Nitrogen chloride explodes on exposure to a strong light-either bright sunshine or magnesium light, although not so readily in the latter case. As in the author's experiments, no explosions occurred for which a cause could not be assigned, it seems very probable that the so-called spontaneous explosions experienced by other observers may be attributed to the action of light.About 4. gram of nitrogen chloride was heated in a thin-walled tube immersed in a beaker filied with liquid vaselin. Up to 90" nochange was observed, but about 9.5" a violent explosion suddenly occurred. As has been noticed before in the explosion of nitrogen chloride, the main force of the explosion was exerted in a downward direction. A. J. G. Pyrophosphates. By G. v. KNORRE and E. OPPELT (Ber., 21, 76+-773).-Pahl has stated (this Journal, 1875, 375, 774) that he obtained an acid calcium pyrophosphste by the action of oxalic acid on normal calcium pgrophosphate : although closely foliowing his directions, the authors have failed to obt8ain any such salt, pyrophos- phoric acid being formed, nor is any acid pyrophosphate formed by the action of pyrophosphoric acid on the normal salt.By adding calcium chloride to a moderately concentrated solution of dihydrogen disodium pyrophosphate, a white, crystalline precipitate is obtained of the formula 2CaH2P,O,,CaJ',O7 + GH20, this can be recrystallised from hot water in which it is very sparingly soluble. When this is boiled for a long time with hot water, it is decomposed, and the residue, after thorough washing, has the composition CaH,P,O,,Ca,P,O, + 3H,O.414 ABSTRACTS OF CHEMICAL PAPERS. From concentrated solutions of strontium chloride and dihydrogen sodium pyrophosphate, a, slight flocculent precipitate of the composi- tion 2Sr2P,O7,H2SrPZO7 + 6H20 is obtained ; from diluhe soluhns, a crptnlline precipitate separates of the formula 3Sr,P207,SrH2Pa07 + 2Hz0, whilst if the solution is heated to boiling, the salt 3Sr2P2O7,SrHZP2O, + H,O is formed.when mixed in the cold yield the white crystalline salt Solutions of barium chloride and dihydrogen sodium pyrophosphate Ba2P,0,,BaH2P207 + 3H20. A. J. G. Action of Arsenious Trisulphide on Iodine. By R. SCHNEIDER ( J . p r . Chenz. [Z], 36, 498--515).-A solution of iodine in carbon bisulphide is without action on natural arsenious trisulphide (orpi- ment), but reacts with that precipitated by hydrogen sulphide, form- ing arsenious iodide and sulphur. At'tempts to prepare the compound As,S3,2As13 by heating a mixture of iodine and arsenious trisulphide in the ratio AszS, : 61, were not successful. The mixture fused at a low temperature to a homogeneous mass of a brown colour, which dissolved almost entirely in carbon bisulphide ; on evaporation of the solvent nothing but arsenious iodide and sulphur crystallised out.On distilling a mixture of arsenious trisulphide and iodine in the ratio As,S, : 61 until two-thirds of the material had passed over, the distil- late was found to contain 58.63 per cent. of free iodine, 40 per cent. of arsenious iodide, and 1.37 per cent. of sulphur; the residue con- sisted of 55.32 per cent. of arsenious trisulphide and 44.04 per cent. of arsenious iodide. When in place of the former, a mixture of arsenious iodide and sulphur in the ratio of 2As13 : 3s was employed, and the distillation continued until half the material had passed over, the distillate contained 69.44 per cent.of free iodine, 28 per cent. of arsenious iodide, and 2.56 per cent. of sulphnr. These experiments show t h a t whilst a mixture of arsenious trisulphide and iodine is converted a t moderate temperatures into arsenious iodide and sulphur, these products again react a t higher temperatures, reproducing their generators. If the distillate, rich in iodine, is sealed up in a glass tnbe, which is slightly iiiclined so that the distillate occupies the higher portion of the tube, and gently heated in a water-bath to a temperature of about 72", a dark-brown liquid which solidifies on cool- ing trickles to the bottom of the tube. By repeated liquations in sealed tubes this dark-brown mass becomes perfectly homogeneous, crystsllising in hard, brittle plates of a greyish-black colour, and dull lustre.The pure substance melts a t 72", and is represented by the formula ST6,2As2T3, On pulverising, it forms a reddish-brown powder which by exposure to the air rapidly loses iodine, whilst the residue, consisting of a mixture of arsenious iodide and sulphur, assumes a bright-red colour. On fusing a, mixture of arsenious trisulphide with iodine in the ratio As,S, : 41, the iodine reacts with only two-thirds of the arsenious trisulphide present. When, as not infrequently happens, the arsenious trisulphide contains a(rsenious acid, there remains behind, after fusionIN0 RGANIC CHEMISTRY. 415 with iodine and treatment with carbon bisulphide, an insoluble pale- yellow powder of the formula 2As,S,,3(As13,AsL03). This substance can also be prepared by heating a mixture of arsenious trisnlphide (1 part) and arsenious iodide (0.2 part) with a large excess (8 to 10 parts) of arsenious iodide, or by heating a mixture oE arsenious iodide (4 rnols.) with arsenious trisulphide (1 mol.) with free access of air.Under the microscope, the compound appears to be indistinctly crystal- line. On gently heating it, arsenious iodide first sublimes, then arsenious acid, and lastly arsenious trisulphide. The compound is completely dissolved by solutions of potash and ammonia, and is readily decomposed by the common mineral acids and by boiling water. G. T. &l. Silicon. By H. W. WARREN (Chenz. News, 57,54).-The following is a new method of preparing silicon. Small bars of " silicoa-eisen " are suspeiided in dilute sulphuric acid from the positive pole of a battery of two ferric chloride cells and are in contact with a platinum plate forming the negative pole.The iron dissolves and leaves a residue of' graphite, silica, and amorphous silicon, which is heated to redness in a stream of carbonic anhydride, and then to a f u l l red heat in a closed iron tube with some ziuc; the zinc button obta,ined in this manner is dissolved in hydrochloric acid, when crystalline silicon remains undissolved ; by heating the amorphous silicon nl a full white heat with aluminium instead of zinc, graphitoYda1 silicon is obtained. When an alloy of aluminium and silver is heated to an intense white heat with potassium silicofluoride, small quantities of silicon are pro- duced in the form of a, bright reddish-brown powder.Silver Suboxide and the Action of Potassium Permanganate on Silver. By C. FEIEDHEIX (Bey., 21, 307--318j.--The tiirst part of this paper is devoted to a criticism of v. (3. Pfordten's latest com- munication on t h i s subject (this voJ., p. 221), and, in particular, atten- tion is drawn to the fact that he no longer insists that the substance in question is silver suboxide, but only that it is not metallic silver. Referring t o the statement that silver is dissolved Fy water acidified with sulphiiric acid and exposed to the air, the author again states that the metal could not be detected in the solutions a t the end of each experiment (compare Abstr., 1887,lOig). The action of per- manganate has been studied under new conditions in an appxratas so contrived that a solution of permanganate acidified with dilute sulphuric acid placed in one bulb could by means of a connecting tube be brought, in contact with a silver mirror in a second bulb after the bulbs and contents had been heated a t 56" and a t 100" respectively for 4 to 5 hours, whilst the apparatus was connected to a Topler- Hagen's mercury pump, and then allowed to cool.Various strengths of permanganate were used, and in one experiment spongy silver was employed, but the results in every case showed that the permanqanate acted at once on the silver and completely dissolved it. Experiments with the acidified permangnnnte solution per se showed that, on boil- ing, a decomposition occurred with the separation of a n ochre-yellow or black oxide of manganese according to the concentration of the D.A. L.416 ABSTRACTS OF GHEMCCAL PAPERS. solution, and that this decomposition also occurred, aIbl2ough to a much smaller extent when the soiution was heated at 40-50” for 4 to 5 hours in a vacuum. On this account, v. d. Pfordten’s experiment of treating silver with a boilinq acidified permangallate solution in a, current of carbonic anhydride was not repeated, but i n its stead the experiment in a vacuum was modified to the extent of filling the cold vacuous apparatus with pure carbonic anhydride (free from air) under pressure; cannection was then made between the bulbs, with the result that tlhe silver dissolved as before. In reply to other objections to the author’8 views (Zoo.cit.) raised by v. d. Pfordten, it is pointed g u t that, the complete dissolution of the latter’s preparation (before ignition) in nitric acid does not disprove the presence of organic matter, since many organic substances are completely soluble in nitric acid. Again, the statement that no case is known in which impurity i n the silver hinders amalgamation is met by an experiment in which an intiinate mixture of finely divided silver and magnesia, obtained by adding calcined magnesia to a neutral solution of silver nitrate and igniting the precipitate, was shaken contiuuonsly with mercury for eight hours with the result that 1.149 gram of silver was dissolved and OS322 gram remained in the residue ; hence v. d. Pfordten’s argizrnent, based on the fact that his substance underwent no change when shaken with mercury, is open to criticism.Finally, the change of colour from black to grey occur- ring when the so-called suboxide is treated with sulphuric acid or solutions of indifferent salts (Zler., 20, 1470, 3379) is paralleled by a similar change under like conditions in the colour of metallic silver precipitated from an amrnoniacsl solution of silver chloride by zinc, or from neutral silver solutions by other metals (Vogel, Ber. Bed. Akad., 1862, 289). On these grounds, and without contesting the question of the existence of silver suboxide, the author maintains that v. d. Pfordteu’s substance is not this compound, but a mixture of finely divided silver with more or less silver oxide or organic matter.Lead Slags. By M. W. ILES (Clzem. News, 67,&7,18-19,37- 38, 43-45, 57-58) .-This commnnication contains the results ob- tained, and observations made in a very extensive investigation into the character and compotjition of lead slags. The sp. gr. of lead slags varies from 3.3 to 4.16, the best slags having a density of 3.4 to 3.65. Iron, barium, aiid lead cause high sp. gr. ; aluminum, silica, and lime low gravities. All good slags are ns a rule more or less perfectly crys- talline ; slow cooling favours crystallisation, sudden cooling impedes crystallisation or even stops it altogether, hence the crusts of pots of slag are devoid of crystalline structure. Well-crystallised slags have definite fusing points, and are more brittle than the imperfectly cry>- talline slags, and are only partially soluble in strong acids ; the form of cq-stallisation serving as an important indication of the quality of a, lead slag.Slags cooled by pouring into water are zmorphous, hare their fusing point, lowered, resemble obsidian in appearance, and when pulverised are completely dissolved by hydrochloric acid. The author takes advantage of this property i n taking and preparing samples for analysis ; the crust of the pot of slag is thrown aside, a steel bar is w. P. w.IXOROANIC CHEMISTRY. 4 f i thrust about 2 inches deep into the molten slag and then plunged into water. The outside rims of pots of slag are subject to rapid cooling. The colonr of lead slags is almost alwap black or a dark shade. Lustrous black and the darkest slags contain most iron, this element, however, sometimes imparts a reddish tint, sometimes a slight greenish cast ; lime tends to lighten the colour, giving the slag a stony or earthy appearmce ; large quantities of manganese give a reddish to amethyst- irie hue, and when associated with 20 per cent. or more of’ lime, the slag has very often w resinous colour.Zinc in the presence of alumina, manganese, and much silica produces a porcelain or obsidian- like slag, whilst some very siliceous slags have a greenish cast. The lustre of load slags is rarely pearly, often resinous, submetallic splendent, and pitchy ; most are vitreous with the exception of high iron and high lime slags. Both very viscid and very fluid slags are undesirable, inasmuch as the former retain globules of matte and metal, whilst the latter do not come sufficiently in contact with the ore, especially if it is in somewhat coarse lumps.Silica is the great cause of viscosity, whilst iron and manganese increase the fluidity of a slag, but fluidity due wholly to iron is liable to cause an iron crust, and so occasion loss. Lime may or may not make a fluid slag, most high lime slags, how- ever, fom smoothly. Fusibility is a very important property of a slag, and is increased by iron, manganese, lime, and by alumina if the silica is low, and rarely or never by manganese and zinc. It is diminished by silica and by alumina in presence of much silica. Refractory slaps arise either from insufficient temperature or from injudicious com bi- nation of the charges.Ths closer certain recognised types are approached, the greater will be both the fusibility and fluidity of a slag. Increasing the number of elements in a slag generally makes it more fusible, hence mixing different ores is advantageous ; this remark, however, does not apply to zinc, aluminium, and magnesium : the latter element for some unaccountable reason occasions great loss of silver. All lead slags are magnetic, the author attributiug this property to the presence of iron silicates and sulphides. The brittleness of these slags depends on the number, kind, and amount of the bases present; generally silica causes toughness, and bases brittleness, although the latter is not always true. Slags with less thau 34 per cent. of silica are usually brittle, whilst those containing as much as 35 to 40 per cent.are tough, unless there is little iron and much lime (22 to 30 per cent.j. Whenever there is much matte produced or when zinc is present i n the ore, i t is best not to have very brittle slags. Brittle slags are generally free from both silver and lead. Lead slags consist mainly of iron and calcium silicates, manganese, however, is frequently present, so are also zinc, aluminium, bwium, and magnesium, but the last four are to be avoided as much as possible. Incidental con- stituents of lead slags are silver, lead, potassium, sodium, phos- phorus, sulphur, sometimes copper, nickel, and cobalt ; whilst Leadvdle sl;zgs frequent17 contain vanadium I n abnormal slags, quartz, ferric oxide, and quicklime are sometixries found.Delicate needles con- taining lead and sulphnr are observed in the blistered cavities in the crust of pots of slags.418 ABSTRACTS OF CHEMICAL PAPERS. Tho author does not approve of decomposing the slags by fusion with sodium carbonate anti nitrate in a platinum crucible, bnt if sucli a method is resorted to, the pulrerised slag should he first treated with hydrochloric acid, evaporated to dryness, more hydrochloric acid added, filtered, and then fused with sodium carbonate; or, better, fuse the slag directly with potash in a silver crucible, or if silver is also to be determined, in a platinum crucible heavily plated with gold. The method generally followed by the author is to take the sample in the way already noted, pulverise and moisten about half a gram with water, add concentrated hydroch1or:c acid, and digest with a few drops of nitric acid, the silica, can then be separated perfectly free from iron in the usual manner.Iron is determined by permangn- nate, calcium as oxalate or volumetrically, manganese by the hromine or zinc oxi’Ge methods, other constituents by the iisual methods. The succem of srnelting siliceous ores depends on the economic use of lime, iron, and manganese as fluxes, whilst the life or campaign of a furnace is greatly influenced by the judicious seIection of slags; such inconveniences as the accumnlation of silica, or iron, charcoal, coke, zinc, or lead crusts may be eliminated by the use of suitable slags for some time. Slags must of course be varied to suit the impurities in the ores to be dealt with, but from the author% experience and the careful and complete analyses of TOO slag samples, theresults of which are given in a table, it is concluded that certain definite “slag tFpes,” or slags having some well-defined composition and a distinct crysballine form exist, and t h a t thenearer slags in general approach to any of these types the more effectual they are.Taking the importanfi constitnents lime, iron and manganese, and silica, it i s observed that tlie best slags range within the following. limits per cent. : SiO, 31 to 36, Fe + Mn 28 to 30, CaO 14 to 25 : wliilst the slags doing the best work and ensuring the longest campaigns do not vary beyond SiOz 31 to 34, Ye + Mn 84 to 27, CaO 14 to 25. The limits SiO, 26 to 41, Fe + Mn 18 to 35, CaO 5 to 35, would include all lead slags.The seven types laid down by the author include pract(ica1ly every known slag which is well adapted for melting argentiferous lead, and are composed as follows as pegards tlie most: important con- stituents :- T-~pes. A . B . C . . D . E . F . Gt. CaO .......... 6 10 12 16 20 24 28 FeO + MnO ... 52 45 50 34 40 33 2’7 Si0 2..n... ...... 3fL! 35 28 34 30 33 35 Type A. Crystallises im reekangular plates ; but is not adapted to Lad mclting as tihe ison is too high, the lime too low. Type B. Forms generally sniall, rhombic plates more or less thickened and characterised by well-defined striations. This type of slag will keep the furnaces in good condition, it gives large yields, but is liable to cause large losses of lead and silver ; it is not a, bad slag in localities where limestone is dear.Type C. Is black and distinctly crystalline, and has the formula 6Fe0,3Si02 + 2Ca0,Si02 assigned it. It is highly recom-ISORGANIC CHENISTRT. 41 9 mended where iron flus is abundant, and the ores carry much zinc. Type D. Can be represented by the formula 5Fe0,4SiOt + 3Ca0,2Si02; it crjstallises in more or less translucent, flat- tened prisms often wifh an abrupt arrow-shaped termination. It is well adapted to the treatment of siliceous and very impure ores. Type E. Corresponds to the formula 6Fe0.3Si02 + 4C~0,2SiO, ; i t crystallises in monoclinic prisms. This is an excellent slag and verp economical where the fluxes are easily obtained. Type F. This is a black, lustrous, distinctly resinous slag.The crystals are rectangular prisms, remarkably translncent and even transparent when there is a little manganese present; the crystals are frequently indented. It is the best slag. known for the treatment of very siliceous ores! and has been foand successful with ores containing large quauti'tities of batryta, alumina, and zinc. Gcne~ally slags intermediate or differing widely in com- position from the above types, having botryoidal, pectolitic or wavellitic crystalline forms, OF those whicth are devoid of crystalline structure, may be considered abnormal and untrust- worthy for smelting purposes. Hexagonal c r j s t d s indicahe too high a percentage of lime. Xlender-needles result from fluxing highly siliceous ores with lime, and ape accompanied by great loss of silver, bnt they contain no lead.The proportion of lime seems to exert some.influence on the crystal- line structure of slags. The use of cliarcoal increases the tonnage, but generally with an increased loss of silvey. These results show that certain ratios should existr between the silt% and the bases of a slag, and that lime exerts a, great cleansing influence on slags; but the problem why one slag is good and another of similar composition bad still remains to be answered. The author points out that loss of silver is due neither to the dissemination of globules of matte nor to the influence of manganese. It is very friable. Type G. Crystallises in cubes. D. A. L. Crystallised Halogen Salts of Mercury. By W. SIEVERS (Bey., 21, 647-652) .-Mercuric bromide is obtained in tetragonal plates when an excess of bromine is added with aqitation to a slightly acid fiolution of mercuric nitmte of sp.gr. 1.197 ; hypobromous acid being formed in the reaction as noticed by Spiller (Chem. News, 6, 249). The chloride prepared in like manner forms slender needles. Mercuric iodide is obtained in red, tetragonal plates by adding to a boiling solution of mercuric nitrate rather more iodine than it can dissolve, and boiling for some time with constant replacement of the evaporated wat,er. A niixt'ure of mercuric and mercurous chlorides is obtained by the action of chlorine on a solution of mercurous nitrate ; this is washed with hot water to remove t'he mercuric salt, and the amorphous mer- curous chloride crystallised from mercurous nitrate solution, when i t forms yellowish-white, tetragonal plates.Crptallised mercurous420 ABSTRACTS OF CHEMICAL PAPERS. bromide and iodide have been already prepared by this method by Stroman (this vol., p. 111). Ferric and Aluminium Phosphates. By P. HAU'CEFEUILT~E and J. MARGOTTET (Conyt. rend., 106, 135-1 38) .-Glacial phosphoric acid a t 100" dissolves 15 per cent. of ferric oxide or 8 per cent. of alumina, and if the solutions are kept at this temperature they deposit distinct crystals which are readily decomposed by water. They have the composition FeZ0,3PzO5 + 6H20 or A1,O3,3Pz?, + 6H,O. The ferric compound forms pinkish, rhombic plates, derived from a mono- clinic prism ; the aluminium compound forms colourless, prismatic crystals with longitudinal extinction.If the solution is heated rapidly to 150-200", and is kept a t this temperature, the crystals contain only 4 mols. H,O, and are not readily attacked by water or alcohol. The iron salt forms pinkish, nacreous, rectangular lamell=, which act strongly on polarised light ; the aluminium salt foyms birefractive needles grouped in bundles. Above 200°, the solution deposits crystals a t a temperature which is lower the greater the proportion of basic oxide present. I n all cases they have the composition Fe2O3,3PzO5 or Al,0,,3Pz05, but the form of the iron salt depends on the temperature a t which crystal- lisation takes plnce. At 200-250", it forms short, channelled, rhombic prisms ; from 253" t'o incipient redness, fusiform, triclinic crystals ; at a red heat, long, monoclinic prisms, sometimes with an almost square orthogonal section, and usually terminated by a rhombic face at an acute angle with the edge of the prism.A t 200", the aluminium phosphate separates in tetrabedrn with curved faces, without sensible action on polarised light ; a t 250°, the crystals are octahedra, frequently modified by faces OE the cube. This form i s stable up to a red heat. If the phosphate crystallises a t a red heat, or is obtained by the action of phosphoric acid on corundum, it separates in cubes which are not modified, but are frequently macled. From these results, it seems that the atihydrous aluminium phosphate always crystallises in the regular system, but the exact form depends on the temperature.These differences are comparable with the differences observed in the case of ferric and silicon phosphates. C. H. B. Volume and Carbon Contents of the Gas Evolved during Solution of Iron in Acids. By H. BACKSTROM and G. PAIJKULL (Zeit. and. Chem., 26, 683-689).-That different kinds of iron evolve different volumes of gas when dissolved in acid was ascer- tained by Bergman i n 1781, and these differences were connected by Vandermonde, Berthollet, and Monge, with the differences in the amount of carbon present. The autbors have determined the total volume of gas, and the quantity of carbon in it, from 14 samples of iron containing carbon (totalj rangiug from 0.11 t o 4.24 per cent. As a general rule, the more highly carburetted the iron, the smaller is the volume and the greater the carbon-contents of the gas evolved, but the relation is not a quantitative one in either case.No definite fraction of the A. J. G.INORGANIC CHEXISTRT. 421 combined carbon is evolved as a pseous hydrocarban. Part of the carbon invariably remains dissolved in the acid as an organic sub- stance capable of reducing permznganate, so that the results of titration are too high as well as variable. Bergmnn asserted that, sulphuric and hydrochloric acids evolved equal volumes of gas, but i n a special experiment on a white cast iron containing 3.87 per cent. of carbon, a volume of gas larger, and containing more carbon, wa8 obtained with hydrochloric acid than with sulphuric acid of corre- sponding strength. It is well known that hardened steel leaves less residue than unhardened when dissolved in acids.Cold hammered steel behaves like hardened steel. The latest view of the constitution of steel is that it contains a, true carbide of iron forming a mass of cellular texture, the pores of which are filled with pure iron. According to Osmond and Werth, the so-called cement-carbon ( Cement-KohZenstof, carbone d e r e m i t ) is that which exists in the carbide in combination with iron, whilst the hardening-carbon (~~rt2tl2gb’-RohZerzsto~, carbone de trempe) exists in solution in the iron disseminated in the cellular iiuclci. The latter may therefore be expected t o be converted more or less into gaseous hydrocarbons, whilst the former would more or less remain undissolved on treakment with acid. It is found that hardened steel gives both a larger volume of gas, and one richer in carbon than the same steel before hardening.It seems as though almost the whole of the hardening carbon is evolved as gas. The effect of cold hammering is, however, both as to volume of gas and amount of carbon, exactly the reverse. By C. N. DRAPER ( C k e m . News, 56, 25l).-A specimen of cast iron, weighing 557.31 grams, and measuring 85 mm. x 52 mm. x 20 mm., was broken from a rail which had been exposed to the alternate action of sea-water s n d the atmosphere €or about 50 years. The lateral surEaces were slightly coated with oxide, and the upper surface consisted, to a depth of 7 mm., of a brownish-grey, graphitoydal substance, amounting to 67.59 grams, and containing 23.6 per cent.of carbon along with much unoxidised iron, presumably existing as FeC3. The graphi- toidal substance was easily removed from the specimen with a knife, leaving a clean, bright, metallic surface exposed. This operation was accompanied by a distinct rise in temperature. Influence of Phosphorus on Iron. By L. SCXNEIDER (DingZ. polyt. J., 266, 378--382).-According to Cheever, the variable effect of phosphorus on iron is explained by assuming that the phosphorus is present in the metal in two forms, as ‘‘ phosphate ” and “ phosphide,” which influence the properties of iron in different ways. This assump- tion is based on the analytical results obtained in a series of experi- ments in which the iron was treated with a cold smmoniacal solution of cupric chloride, the residue being digested with an alkaline solution of ammonium oxalate, or shaken for five minutes with a 1 per cent.solution of hydmcbloric acid, and the phosphoric acid determined in the solution. Cheever assumes that the srnall amount of phosphide M. J. S. Action of Sea-water on Cast Iron. D. A. L. VOL. LIT. 2 f422 ABSTRACTS OF CKEhCICAL PAPERS. existing in the metal completely resists the action of cupric chloride, and that the complete solution of all phosphates formed from phosphides a t a red heat is effected either by a treatment with a 1 per cent. solution of hydrochloric acid for five minutes, or by the action of an ammoniacal solution of ammonium oxalate. The author criticises Cheever's method of examination, and the conclusions deduced therefrom.He shows that iron phosphide in iron is affected by cupric chloride in the cold, and i f the solutlion is quite neutral the phosphoric acid obtained by the oxidation of the phosphide remains in the residue, from which it may be subsequently extracted with ease by weak acids. Vapour-density of Ferric Chloride at Various Temperatures. By W. GR~NEWALD and V. MEYER (Bey., 21, 687--701).-1n these experiments, sublimed ferric chloride was used. The estimations were made in a slightly modified form of V. Meyer's apparatus, in which the bulb, 45 mm. in diameter, was reduced to a length of only 125 mm., whilst the whole apparatus was 670 mm. high; by this means, the whole of the bulb acquired the temperature of the bath. For greater convenience in filling with nitrogen, a thin tube was fused into the bottom of the bulb, bent so as to follow the shape of the bulb and stem until the side tubes were nearly reached, then bent at.right angles to connect with the nitrogen supply. A new device of Meyer and Biltz for the introduction of the substance is also described :-On the stem, opposite to, but just below the delivery tube, a short side tube is fused; through this passes a glass rod whose end projects across the stem ; the joint between rod and side tube being made with well-fitting caoutchouc tubing. The little bottle containing the substance rests on the end of the rod; when the bulb has attained the required temperature, the rod is slightly withdrawn, and the bottle falls into the bulb. Four determinations at 448" (in sulphur vapour) gave a density of 10.487, whilst that required by the formula FezCl6 is 11.2. After the estimation, the contents of the bulb did not give the slightest reaction for ferrous salt.Experiments at, a lower temperature were out of the question, as even in tliese the vaporisation was rather slow. A t 518" (in vapour of phosphorus pentasulphide), three experi- ments gave a vapour-density of 9.569 ; about & of the iron was found to be in the ferrous condition after the estimation. A t 606" (in vapour of zinc chloride), in a smaller apparatus, six experiments gave a mean vapour-density of 8.383; about & of the iron was in the ferrous state at the close. The determination8 at higher temperatures were effected in platinum apparatus heated in a Perrot's gas furnace.The mean of three estimations at about 750" gave a vapour-density of 5.406, whilst about f of the ii-on was found to be in the ferrous state at the close of the experiments. At about 1050", the numbers obtained for the density were 5.3 and 4.9 ; + and +- of the iron being respectively found in the ferrous state. The results a t 1300" were pra,ctically identical with those at 1Vrio". As it seemed probable that the lower results in the higher temperature experiments might be due to the action of the D. B.INORGAYIG CHEMISTRY. 423 plntinnm on the ferric chloride, experiments were made in platinum apparatus at about 600°, but the results obtained were in agreement with those previonsly got in glass. With regard to the amounts of ferrous salt observed at the end of the experiments, it must be remembered that this does not show the amount of dissociation that occurred at the temperature of the experi- ment, inasmuch as recombination occurs on cooling.Experiments in a chlorine atmosphere at the temperaiure of boiling sulphur and boiling phosphorus pentasulphide respectively, gave practically the same results as those in an atmosphere of nitrogen. From these results, it follows that ferric chloride does not at amy temperature show a vapour-density sufficiently high for the molecular formula Fe,C16, whilst at 750" and 1077" numbers were obtained not far removed from 5.6, the calculated vapour-density for the molecular formula FeCl,. A. J. G. Use of Hydrogen Sulphide to Purify Nickel and Cobalt. By H . BAUBLG-NY (Compt.r e d , 106, 132--135).-The only possible method of separating nickel and cobalt by means of hydrogen sulpliide is to saturate the solution of the sulphates with the gas at O", and heat to 100". Nickel sulphide is precipitated, but cobalt sulphate is not decomposed. The precipitate, however, always contains a notable proportion of cobalt even when the quantity of free acid is almost siifficieot to prevent the precipitation of the nickel. Dellf's method of precipitating cobalt as sulphide from the acetate by mixing a solution of the nitrates or sulphates with a quantity of sodium acetate not quite sufficient to convert all the cobalt into acetate, is not satisfactory, since a considerable proportion of the nickel is pre- cipitaied at, the same time. Alloy of Titanium, Silicon, and Aluminium. By L.L ~ V Y (Compt. rend., 106, 66-68).-10 grams of titanium, 35 grams of aluminium, 35 grams each of fused sodium and potassium chlorides, were heated iu a Perrot's furnace in a porcelain crucible enclosed in a crucible brasqued with charcoal and rutile, a current of dry hydrogen being passed into the inner crucible. The product was treated with water and then with dilute acid, and a residue was obtained consisting of lustrous, steel-grey lamellae, with angles of 90°, very brittle, and good conductors of heat, sp. gr. at 16" = 3.11. They do not alter in air or nitrogen oxides at the ordina.rg temperature, but tarnish when heated, and bwn if heated in oxygen. They are not attacked by vapours of sulphur, selenium, phosphorus, or arsenic, but burn in chlorine or in vapour of iodine or bromine, especially the former.Liquid bromine, however, is without, action. Superheated steam and cold fuming nitric acid have no action, but hot nitric acid att8acks the crystals hlightly. Hydrochloric and sulphuric acids act somewhat in the cold and more readily when hea,ted. The crystals burn when heated in hydrogen chloride, and dissolve readily in aqua regia, but are not dissolved by hydrobromic and h-j-driodic acids, 019 by mixtures of these acids with nitric acid. Sulphuric acid and calcium fluoride have little action, and potash only partially iiissolv3s C. H. B. 2 f 2424 ABS'I'RhCTS OF CHEMICAL PAPERS. the crystals in the cold, but dissolution is complete on heating, with evolution of hydrogen.The crystals have the composition A1 71-06 ; Ti 26.65; Si 2.19; loss (? C) 0.10, which agrees with the formula (Ti Si)AI4, and hence i t is probable that they are mixtures of the isomorphous compounds, TiAl, and SiAI,. If zinc or magnesium is substituted for aluminium, no crystals are obtained. C. H. B. Tktanium Trioxide. By A. CLASSEN (Bey., 21, 370-372) .-The action of hydrogen peroxide on titanium dioxide (compare Piccini, Abstr., 1882, 808 ; 1883, 1054 ; Weller, Abstr., 1883, 295) has been studied by the author, who recommends the following method for obtaining the product:-Pure titanium chloride is added drop b7 drop to dilute alcohol, and the clear and very dilute solution is treated with a large excess of hydrogen peroxide. Ammonia, ammo- nium carbonate, or aqueous potash is added to the solution with the production of a yellow or, iiz the case of ammonia: of a reddish-yellow liquid, which after some time yields a yellow precipitate.This is allowed to subside, the clear solutlion siphoned off, and the precipitate repeatedly washed by decantation ; the compound, however, tends to retain waicr and salts in considerable quant,ities. When dried on a tile, it approximates to the composition-Ti03 + 3Hz0. w. P. w. Antimony Pentachloride. By R. ANSCH~~TZ and P. N. EVANS (Proc. Roy. Xoc., 42, 379-387; compare Trans., 1886, 379).-The authors find that, contrary to the statement of Daubrawa (this Journal, 1877, ii, 406), SbOC1, is not formed when water is added to antimony pentachloride, nor is any hydrogen chloride evolved.The antimony pentachloride is best dissolved in chloroform, and the calculated amount of water added. Under these circumstances a, crystalline substance, SbCl,,H*O, soluble in chloroform, is obtained, melting a t 87-92'. It is very hygroscopic, and diljquesces to tt clear liquid, which crystallises over sulphuric acid in broad crystals, described by Daubrawa as the oxychloride. When distilled, it gives SbCl,,SbCI, and a waxy residue. A chloroform solution of antimony pentachloride, when heated with water in a sealed tube, gives antimony hichloride and pbosgene gas. Yhosgene gas is also produced by heating a chloroform solution of the monohydrate at 100". Antimony pentachloride tetrahydrate can be produced in the same way as the monohydrate. It is a crystalline mass, insoluble in chlo- roform.By adding anhydrous oxalic acid to a chloroform solution of antimony pentachloride, the authors obtain a substance, Sb2C18C204, probably C,O,( O*SbCl&. It crystallises from chloroform in tables melting a t 148*5-149", and is decomposed by water with liberation of oxalic acid. The difference in behaviour with carbon compounds bet'ween phos- ptrorus pentachloride and antimony pentachloride is attributed t o t iie property of the latter of combining with water instead of decom- posing it. H. H. 1'.INORGANIC CHEIIISTRY. 425 Dittmar and McArthur’s empirical factora. -_ 0.30627 0-7tiOl6 Redetermination of the Atomic Weight of Platinum. By W. DITTMAR and J. MCARTHUR (J. Xoc. Chem. Ind., 6, 799-803).- The value Pt = 194.8 which Seubert (Abstr., 1881, 514) deduced from his analyses of platinochlorides, is too low ; his own analyses, if properly interpreted, show that the true value lies, by a considerable fraction of a, unit, higher.According to the authors’ andysis of potassium platinochloride, the true “ Pt,” although probably a shade below, lies dose t o 195.5. Taking “ P t ” as meaning the numbev which must be substituted for Pt in the calculation of the mtios ‘LKC1 : PtC16K2 ; 2EC1 : Pt, &c., in order to obtain the correct facto~s f o r reducing analytically obtained platinochloride t o potassium chloride, &c., even the number 195.5 is too low, 196 ailording in general a better approximation. But Pt if taken in this sense is no constant at all. Those factors must be dekermined directly bg standard experiments.The results of the authord own standard experiments are given and contrasted with the theoreticaIly calcu- lated ratios in the subjoined table. The entries “ Ta ” refer to Tat- lock’s methods; those “ F” to the authors’ form of E’inkener’s method described in detail in the original paper, and those marked “ N ” to the usual platinum process for the determination of ammonia :- . 4 ;L; (1) ( 2 ) 0 T& T& F N N - ZKC1 : PtC16K2 . . . . . . . 2KCl : Pt . . . . . . . . . . . 2KC1 : Pt . . . . . . . .. . . 2NH4C1 : PtC16(NH4)a. ZNH,Cl : Pt . . . . . . . , . Theoretical factors. 0 ’30707 0 -30665 0 *30633 0 3’6571 0 -76307 0.76112 0.76571 0’76307 0-76112 0 *24123 0 -24084 0 ’24057 0.54934 0 -54‘737 0 -545% Values calculated for Symbols. Pt -194.81 195.5 1 196 I--- l-I- ----- Notes.(1) Refers to the potassium chloride in - the substance, (2) t o that in the p1atinochlo;ide precipitate, and ( 3 ) and (4) to the ammonium chloride to be determined, not to that contained in the platinochloride precipitate. D. B. Hydroxylamine Platinum Bases. By H. ALEXANDER (Chem. Centr., 1887, 1254c-l255).--As the platinum bases mentioned below are all explosive, the platinum and chlorine cannot be determined by heating the compound. The platinum was determined by moistening a quantity of the substance with concentrated sulphuric acid in a platinum capsule, evaporatiri g off the acid and finally dispelling any remaining acid by the addition of ammonium carbonate. The chlorine was determined by distilling the compound with snlphuric acid, and passing the resulting hydrogen chloride into a solution of silver nitrale.426 ABSTRACTS O F CHEMICAL PAPERS.Platoso-dih.ydro~lamin,e hydrochloride, P t ( NH30*NH30C1) 2, which Lossen has already described, is obtained by the action of potassio- platinous chloride on hydroxylamine hydrochloride. Strong bases precipitate 13latoso-dihydroxylamine hydroxide, Pt ( OH),,4NH30, from solutions of the chloride. The oxalate, PtC2O4,4NHaO, is prepared from neutral potassium oxalate and the chloride ; an acid salt does not seem to exist. Platino-dih ydroxylarnine sulphate, PtS04,4NH30 + H20, can be prepared from this oxalate by the action of weak sulphuric acid; the sulphate is more easily prepared from the free base and sulphnric acid.Platoso-dihydroxyEami.rie hydrochloride platinous chloride is prepared by the addition of platinous hydrochloride to the chloride. P latoso- hydroxy lamin e h y dyoc hloride, Pt (N H30 Cl), , is formed by the action of hydrochloric acid, on either platino-dihydroxylamine hydrate when warm, or on the corresponding chloride. The cornpound formed by the action of ammonia on platinous hydrochloride and on platoso- hydroxylamine hydrochloride, which has been described by Jorgensen, the author regards as platoso- hydroxylamine ammonium chloride, Pt(NH30-NH,C1),. The double salt, Pt(NH30.NH3C1)~,PtCl,, is obtained from platinous hydrochloride and plat oso- hy droxylamine ammonium chloride, as well as from the above-named mixed chlorides and potassio-platinous chloride.Free hydroxylamine acting on platinons chloride gives rise to the compound OH.PtC1,4NH30 + 2H20, which explodes at 140- 150". Another compound which may be regarded as platinum nitrogen chloride, PtNC1, together with the double salt, 2(0H-PtCl,4NH30) + Pt(OH)2,2NH30, or 2[Pt(OH),,4NH30] + PtC1, + 2NH30. were also obtained. Free hydroxylamine acting on platinous hydrochloride gives rise to a compound corresponding approximately with the formula PtC1,,4NH30, and by its action on potassio-platinous chloride t o it base Pt(OH)2,2NH30, which has not been obtained quite pure as yet. A phosphate was obtained, but no nitrate. J. P. L. Ruthenium Oxides. By H. DEBRAY and A. JOLY (Compt. rend., 106, 100-106) .-The authors prepared crystallised ruthenium d i - oxide by heating the amorphous oxide in a vacuum or by heating the metal in oxygen.It forms quadratic prisms with the faces m, h', a', and b'. The ratios being b : h : : 1000 : 692.43, and hence is iso- morphous with cassiterite and rutile. The faces in the zone rn h' are often striated as in those minerals, and very frequently the crystals are macled after the cassiterite and rutile types. When heatNed to bright redness in a muffle, ruthenium absorbs oxygen, but after some time absorption takes place very slowly, and the metal is never fully oxidised to the dioxide. If, however, the product is powdered and again heated, the dioxide is obtained crystalline, with an indigo-blue colour. The authors were unable to obtain the sesqui- oxide in the manner described by Claus.When ruthenium is heated in oxygen at a temperature above theMIXERALOGICAL CHEMISTR1'. 427 melting point of silver, it is entirely converted into crystalline products, and a portion volatilises and condenses in crystals. I f the current of gas is rapid, the odour of ozone or ruthenium peroxide is perceived, and a certain quantit,y of the peroxide can be condensed in a flask cooled by ice. The inside of the tube is lined with ruthenium dioxide and a small quantity of a black substance which seems to contain more oxygen than the dioxide. The products are similar to those obtained when rathenium peroxide and nitrogen are passed through a red-hot porcelain tube, and they are distributed in the same manner. The dioxide is found in the cooler parts of the tube, which indicates that the peroxide formed at about 1000" decomposes at a lower tem- perature.At temperatures above lOOO", ruthenium dioxide has a considerable tension of dissociation, and in a vacuum is partially re- duced to the metal, a small quantity of the peroxide being formed. At a bright red heat, the phenomena are similar. The authors mere unable to obtain an oxide lower than the dioxide. Ruthenium peroxide is formed at about 1 OOO", and decomqoses with explosion when cooled to 108", but can be isolated by rapid cooling. It affords another instance of a, compound which is decomposed by heat, and yet is formed at a high temperature. The crystallisation of the dioxide is a phenomenon of apparent volatilisation, and the formation of the peroxide is analogous to the formation of ozone, silicon hexachloride, silver oxide, hydrogen selenide or telluride, &c.The formation of ruthenium peroxide, like the decomposition of water, is endothermic. c. H. €3.INORGANIO CHEMISTRT. 411In o r g an i c C h e m i s t r y.The Composition of Water by Volume. By A. SCOTT (Proc. no!/. SOC., 42, 396--400).--The ratio by volume in which oxygen andhydrogen combine at 0" and 760 mm. is redetermined. The apparatusis so arranged that both gases are measured in the same vessel, aseparate vessel being used for exploding. After explosion, the residuewas analysed by exploding with oxygen or hydrogen and the impurity(nitrogen and carbonic anhydride) determined. The oxygen wasobtained from potassic chlorate and from mercuric: oxide preparedfrom the nitrate, the hydrogen was obtained by electrolysis.Theratio obtained is 1.994:1, which with 15.9627 for the density ofoxygeri, gives 16.01 as the atomic weight of oxygen.The Weldon-Pechiney Process for the Manufacture ofChlorine from Magnesium Chloride. By J. DXWAR ( J . SOC.Cheni. Ind.¶ 6, 775 -790). -This process, which was patented inJune, 1884 (Eng. Pat. 9306), has recently been worked at Salindreson an experimental plant designed for the daily production of 1 tonof chlorine, and may be briefly descrihed as follows:-The rawmaterial employed is hydrochloric acid, the operations being (1)dissolving magnesium oxide in hydrochloric acid ; (2) preparingmagnesium oxychloride ; (3) crushing, breaking, and sifting the oxy-chloride ; (4) drying the oxychloride ; and (5) decomposing the oxy-chloride.T'he magnesium oxide to be dissolved in hydrochloric acidis a portion of that which results from the fifth operation. Thehydrochloric acid also results in part from the fifth operation and theremainder from the decomposition of salt. The solution obtainedis evaporated down to the point at which it will contain not more thanabout six equivalents of water, and is then converted into oxychlorideby mixing one equivalent of magnesium chloride with one and a thirdequivalents of magnesium oxide. This operation lasts only about20 minutes, b u t during this time the whole mass becomes very hardand during solidification diseugirges much heat. The product is thenin the form of solid pieces of different size9 along with a smallquantity of powder.It is necessary to reduce this material to frag-ments, of which the largest shall not exceed the size ofa walnut, andfurther to clear them of dust which might, when in the decomposingfurtiace, prevent free passage oE air through the mass ; this is egectedby crushing it between cylinders bristling with diamond poiuts, andH. K. T412 ABSTRACTS OF CHEMICAL PAPERS.then passing itl through a rotating sieve. The oxychloride is then dried,this operat,icn being necessary, as in the decomposition a largerquantity of free chlorine arid a smaller amount of hydrogen chlorideare produced if the material contains less water, and the decomposi-tion is performed a t a higher temperature, both conditions beingrealised by drying previous to decomposition. The dried oxpchlorideis then decomposed in a special apparatus consisting of a series offurnaces provided with decomposing chambers heated by a movableregenerative burner, the oxychloride being decomposed in a currentof air. The author’s theory of the decomposition which goes on in thefurnace is that in the first stage there is a rapid evolution of steam,the steam decomposing a portion of the magnesium chloride withformation of hxdrogen chloride which passes ofT ,with the rapour ofwate;..Anhydrous magnesium chloride and magnesium oxide remain,and this mixture then undergoes decomposition into magnesium oxideand chlorine by the action on i t of atmospheric oxygen.The productsare drawn off from the furnace by means of a diminished pressuresteadily maintained, an aspirator being employed which acts throughan ordinary hydrochloric acid condensing tower, a number of sand-stone boubonnes and a glass tube refrigerator, the lattcr being inimmediate connection with the decomposing furnace. The hydro-chloric acid is condensed in these apparatus, whilst the mixture ofa,ir and chlorine passes on through the aspirator and is employedfor the manufacture of chlorate: for this purpose, it is driven intospecial apparatus, wherein the chlorine acts on calcium hydroxideand gradually transforms it into a mixture of calcium chlorate andcalcium chloride. D. B.Nitrogen Chloride. By L. GATTERMANK (Rw., 21, 751-757).-The composition of nitrogen chloride has not yet been satisfactorilydetermined ; weighed quantities of t,he chloride hare never beenanalysed, but merely the ratio of nitrogen to chlorine determined i nan unknown amount of the chloride, and, as is well known, the resultsobtained by different observers are by no means in accordance.Inthe present research, the experiments were carried on as far as possibleiu the glass case devised by V. Meyer (Bey., 21, 26).The nitrogen chloride was prepared in bhe usual manner by theaction of chlorine on a solution of ammonium chloride. 30 sign ofthe formation of the chloride was visible until more than half thechlorine was absorbed, when the formation of minute drops wasnoticeable in the layer of liquid drawn up by capillary attraction onthe sides of the flask ; this soon spread and formed a thin film on thesurface of tbe liquid, and this film i n turn gradually separated intolarger drops, the heavier of which sank, but were again brought to thesurface by the nitrogen bubbles formed in the slight decompositionwhich goes on.When no more drops are formed, the chloride bycareful shaking was made to fall into a small leaden capsule providedwith a handle. I t was then poured, with the aid of a funnel, into a thin-walled separating funnel, the ammonium chloride solution removedby a pipette, and the nitrogen chloride repeatedly washed by shakingwith water until the washings no longer gavea, chlorine reaction. TINORGANIC CBEMISTRY. 413assist the removal of dissolved chlorine from the oil, air was repeatedlyblown through it by means of a glass tube, so that the oil was dis-seminated through the liquid in small drops.The successful carry-ing out of these operations shows that nitrogen chloride is by no meansso readily exploded as has usually been supposed. The purified oilwas next transferred t o a thin glass flask (an operation attended withmuch danger owing to the fkiction of the stopcock of' the separatingfunuel), dried by agitation with a small, clean piece of fused calciumchloride, and poured into the weighing glass-a weighed cylindricalvessel of about 1 C.C. capacity, provided with a stopper not quite air-tight. The weighing was effected in the usual manner, save that aglass screen was again employed.The weighed substance was thendecomposed by aqueous ammonia, and the chlorine estimated as silverchloride. The results showed that the product of the action ofchlorine on ammonium chloride is invariably a mixture of severalchlorinated ammonias, and t h a t the product was richer in chlorinethe longer the oil was in contact with chlorine, but under no condi-tions was the trichloride obtaiued directly.After washing out the ammonium chloride as described above, theseparat'ing funnel containing the crude product covered with a fewdrops of water was placed hnrizontaliy, and a moderately strong streamof chlorine passed through for half an hour. The oil so obtained,after washing and drying, was analysed, and proTed to be pure nitro-gen trichloride.Nitrogen chloride explodes on exposure to a strong light-eitherbright sunshine or magnesium light, although not so readily in thelatter case.As in the author's experiments, no explosions occurredfor which a cause could not be assigned, it seems very probable thatthe so-called spontaneous explosions experienced by other observersmay be attributed to the action of light.About 4. gram of nitrogen chloride was heated in a thin-walled tubeimmersed in a beaker filied with liquid vaselin. Up to 90" nochangewas observed, but about 9.5" a violent explosion suddenly occurred.As has been noticed before in the explosion of nitrogen chloride, themain force of the explosion was exerted in a downward direction.A. J. G.Pyrophosphates.By G. v. KNORRE and E. OPPELT (Ber., 21,76+-773).-Pahl has stated (this Journal, 1875, 375, 774) that heobtained an acid calcium pyrophosphste by the action of oxalic acidon normal calcium pgrophosphate : although closely foliowing hisdirections, the authors have failed to obt8ain any such salt, pyrophos-phoric acid being formed, nor is any acid pyrophosphate formed by theaction of pyrophosphoric acid on the normal salt.By adding calcium chloride to a moderately concentrated solutionof dihydrogen disodium pyrophosphate, a white, crystalline precipitateis obtained of the formula 2CaH2P,O,,CaJ',O7 + GH20, this can berecrystallised from hot water in which it is very sparingly soluble.When this is boiled for a long time with hot water, it is decomposed,and the residue, after thorough washing, has the compositionCaH,P,O,,Ca,P,O, + 3H,O414 ABSTRACTS OF CHEMICAL PAPERS.From concentrated solutions of strontium chloride and dihydrogensodium pyrophosphate, a, slight flocculent precipitate of the composi-tion 2Sr2P,O7,H2SrPZO7 + 6H20 is obtained ; from diluhe soluhns, acrptnlline precipitate separates of the formula 3Sr,P207,SrH2Pa07 +2Hz0, whilst if the solution is heated to boiling, the salt3Sr2P2O7,SrHZP2O, + H,Ois formed.when mixed in the cold yield the white crystalline saltSolutions of barium chloride and dihydrogen sodium pyrophosphateBa2P,0,,BaH2P207 + 3H20.A. J. G.Action of Arsenious Trisulphide on Iodine. By R. SCHNEIDER( J . p r . Chenz. [Z], 36, 498--515).-A solution of iodine in carbonbisulphide is without action on natural arsenious trisulphide (orpi-ment), but reacts with that precipitated by hydrogen sulphide, form-ing arsenious iodide and sulphur.At'tempts to prepare the compoundAs,S3,2As13 by heating a mixture of iodine and arsenious trisulphidein the ratio AszS, : 61, were not successful. The mixture fused at alow temperature to a homogeneous mass of a brown colour, whichdissolved almost entirely in carbon bisulphide ; on evaporation of thesolvent nothing but arsenious iodide and sulphur crystallised out. Ondistilling a mixture of arsenious trisulphide and iodine in the ratioAs,S, : 61 until two-thirds of the material had passed over, the distil-late was found to contain 58.63 per cent. of free iodine, 40 per cent.of arsenious iodide, and 1.37 per cent.of sulphur; the residue con-sisted of 55.32 per cent. of arsenious trisulphide and 44.04 per cent. ofarsenious iodide. When in place of the former, a mixture of arseniousiodide and sulphur in the ratio of 2As13 : 3s was employed, and thedistillation continued until half the material had passed over, thedistillate contained 69.44 per cent. of free iodine, 28 per cent. ofarsenious iodide, and 2.56 per cent. of sulphnr. These experimentsshow t h a t whilst a mixture of arsenious trisulphide and iodine isconverted a t moderate temperatures into arsenious iodide and sulphur,these products again react a t higher temperatures, reproducing theirgenerators. If the distillate, rich in iodine, is sealed up in a glasstnbe, which is slightly iiiclined so that the distillate occupies thehigher portion of the tube, and gently heated in a water-bath to atemperature of about 72", a dark-brown liquid which solidifies on cool-ing trickles to the bottom of the tube.By repeated liquations insealed tubes this dark-brown mass becomes perfectly homogeneous,crystsllising in hard, brittle plates of a greyish-black colour, and dulllustre. The pure substance melts a t 72", and is represented by theformula ST6,2As2T3, On pulverising, it forms a reddish-brown powderwhich by exposure to the air rapidly loses iodine, whilst the residue,consisting of a mixture of arsenious iodide and sulphur, assumes abright-red colour.On fusing a, mixture of arsenious trisulphide with iodine in theratio As,S, : 41, the iodine reacts with only two-thirds of the arsenioustrisulphide present.When, as not infrequently happens, the arsenioustrisulphide contains a(rsenious acid, there remains behind, after fusioIN0 RGANIC CHEMISTRY. 415with iodine and treatment with carbon bisulphide, an insoluble pale-yellow powder of the formula 2As,S,,3(As13,AsL03). This substancecan also be prepared by heating a mixture of arsenious trisnlphide(1 part) and arsenious iodide (0.2 part) with a large excess (8 to 10parts) of arsenious iodide, or by heating a mixture oE arsenious iodide(4 rnols.) with arsenious trisulphide (1 mol.) with free access of air.Under the microscope, the compound appears to be indistinctly crystal-line. On gently heating it, arsenious iodide first sublimes, thenarsenious acid, and lastly arsenious trisulphide.The compound iscompletely dissolved by solutions of potash and ammonia, and isreadily decomposed by the common mineral acids and by boilingwater. G. T. &l.Silicon. By H. W. WARREN (Chenz. News, 57,54).-The followingis a new method of preparing silicon. Small bars of " silicoa-eisen "are suspeiided in dilute sulphuric acid from the positive pole of abattery of two ferric chloride cells and are in contact with a platinumplate forming the negative pole. The iron dissolves and leaves a residueof' graphite, silica, and amorphous silicon, which is heated to rednessin a stream of carbonic anhydride, and then to a f u l l red heat in aclosed iron tube with some ziuc; the zinc button obta,ined in thismanner is dissolved in hydrochloric acid, when crystalline siliconremains undissolved ; by heating the amorphous silicon nl a full whiteheat with aluminium instead of zinc, graphitoYda1 silicon is obtained.When an alloy of aluminium and silver is heated to an intense whiteheat with potassium silicofluoride, small quantities of silicon are pro-duced in the form of a, bright reddish-brown powder.Silver Suboxide and the Action of Potassium Permanganateon Silver.By C. FEIEDHEIX (Bey., 21, 307--318j.--The tiirst partof this paper is devoted to a criticism of v. (3. Pfordten's latest com-munication on t h i s subject (this voJ., p. 221), and, in particular, atten-tion is drawn to the fact that he no longer insists that the substancein question is silver suboxide, but only that it is not metallic silver.Referring t o the statement that silver is dissolved Fy water acidifiedwith sulphiiric acid and exposed to the air, the author again statesthat the metal could not be detected in the solutions a t the end ofeach experiment (compare Abstr., 1887,lOig).The action of per-manganate has been studied under new conditions in an appxratas socontrived that a solution of permanganate acidified with dilutesulphuric acid placed in one bulb could by means of a connecting tubebe brought, in contact with a silver mirror in a second bulb after thebulbs and contents had been heated a t 56" and a t 100" respectivelyfor 4 to 5 hours, whilst the apparatus was connected to a Topler-Hagen's mercury pump, and then allowed to cool.Various strengthsof permanganate were used, and in one experiment spongy silver wasemployed, but the results in every case showed that the permanqanateacted at once on the silver and completely dissolved it. Experimentswith the acidified permangnnnte solution per se showed that, on boil-ing, a decomposition occurred with the separation of a n ochre-yellowor black oxide of manganese according to the concentration of theD. A. L416 ABSTRACTS OF GHEMCCAL PAPERS.solution, and that this decomposition also occurred, aIbl2ough to amuch smaller extent when the soiution was heated at 40-50” for 4 to 5hours in a vacuum. On this account, v. d.Pfordten’s experiment oftreating silver with a boilinq acidified permangallate solution in a,current of carbonic anhydride was not repeated, but i n its stead theexperiment in a vacuum was modified to the extent of filling the coldvacuous apparatus with pure carbonic anhydride (free from air) underpressure; cannection was then made between the bulbs, with theresult that tlhe silver dissolved as before.In reply to other objections to the author’8 views (Zoo. cit.) raised byv. d. Pfordten, it is pointed g u t that, the complete dissolution of thelatter’s preparation (before ignition) in nitric acid does not disprovethe presence of organic matter, since many organic substances arecompletely soluble in nitric acid. Again, the statement that no caseis known in which impurity i n the silver hinders amalgamation is metby an experiment in which an intiinate mixture of finely dividedsilver and magnesia, obtained by adding calcined magnesia to aneutral solution of silver nitrate and igniting the precipitate, wasshaken contiuuonsly with mercury for eight hours with the result that1.149 gram of silver was dissolved and OS322 gram remained in theresidue ; hence v.d. Pfordten’s argizrnent, based on the fact that hissubstance underwent no change when shaken with mercury, is opento criticism. Finally, the change of colour from black to grey occur-ring when the so-called suboxide is treated with sulphuric acid orsolutions of indifferent salts (Zler., 20, 1470, 3379) is paralleled bya similar change under like conditions in the colour of metallic silverprecipitated from an amrnoniacsl solution of silver chloride by zinc,or from neutral silver solutions by other metals (Vogel, Ber.Bed.Akad., 1862, 289). On these grounds, and without contesting thequestion of the existence of silver suboxide, the author maintains thatv. d. Pfordteu’s substance is not this compound, but a mixture offinely divided silver with more or less silver oxide or organic matter.Lead Slags. By M. W. ILES (Clzem. News, 67,&7,18-19,37-38, 43-45, 57-58) .-This commnnication contains the results ob-tained, and observations made in a very extensive investigation intothe character and compotjition of lead slags. The sp. gr. of lead slagsvaries from 3.3 to 4.16, the best slags having a density of 3.4 to 3.65.Iron, barium, aiid lead cause high sp.gr. ; aluminum, silica, and limelow gravities. All good slags are ns a rule more or less perfectly crys-talline ; slow cooling favours crystallisation, sudden cooling impedescrystallisation or even stops it altogether, hence the crusts of pots ofslag are devoid of crystalline structure. Well-crystallised slags havedefinite fusing points, and are more brittle than the imperfectly cry>-talline slags, and are only partially soluble in strong acids ; the formof cq-stallisation serving as an important indication of the quality of a,lead slag. Slags cooled by pouring into water are zmorphous, haretheir fusing point, lowered, resemble obsidian in appearance, and whenpulverised are completely dissolved by hydrochloric acid.The authortakes advantage of this property i n taking and preparing samples foranalysis ; the crust of the pot of slag is thrown aside, a steel bar isw. P. wIXOROANIC CHEMISTRY. 4 f ithrust about 2 inches deep into the molten slag and then plunged intowater. The outside rims of pots of slag are subject to rapid cooling.The colonr of lead slags is almost alwap black or a dark shade.Lustrous black and the darkest slags contain most iron, this element,however, sometimes imparts a reddish tint, sometimes a slight greenishcast ; lime tends to lighten the colour, giving the slag a stony or earthyappearmce ; large quantities of manganese give a reddish to amethyst-irie hue, and when associated with 20 per cent.or more of’ lime, theslag has very often w resinous colour. Zinc in the presence ofalumina, manganese, and much silica produces a porcelain or obsidian-like slag, whilst some very siliceous slags have a greenish cast. Thelustre of load slags is rarely pearly, often resinous, submetallicsplendent, and pitchy ; most are vitreous with the exception of highiron and high lime slags.Both very viscid and very fluid slags are undesirable, inasmuch asthe former retain globules of matte and metal, whilst the latter donot come sufficiently in contact with the ore, especially if it is insomewhat coarse lumps. Silica is the great cause of viscosity, whilstiron and manganese increase the fluidity of a slag, but fluidity duewholly to iron is liable to cause an iron crust, and so occasion loss.Lime may or may not make a fluid slag, most high lime slags, how-ever, fom smoothly.Fusibility is a very important property of a slag,and is increased by iron, manganese, lime, and by alumina if the silicais low, and rarely or never by manganese and zinc. It is diminishedby silica and by alumina in presence of much silica. Refractory slapsarise either from insufficient temperature or from injudicious com bi-nation of the charges. Ths closer certain recognised types areapproached, the greater will be both the fusibility and fluidity of aslag. Increasing the number of elements in a slag generally makes itmore fusible, hence mixing different ores is advantageous ; this remark,however, does not apply to zinc, aluminium, and magnesium : the latterelement for some unaccountable reason occasions great loss of silver.All lead slags are magnetic, the author attributiug this property tothe presence of iron silicates and sulphides.The brittleness of theseslags depends on the number, kind, and amount of the bases present;generally silica causes toughness, and bases brittleness, although thelatter is not always true. Slags with less thau 34 per cent. of silicaare usually brittle, whilst those containing as much as 35 to 40 percent. are tough, unless there is little iron and much lime (22 to 30per cent.j. Whenever there is much matte produced or when zinc ispresent i n the ore, i t is best not to have very brittle slags.Brittleslags are generally free from both silver and lead. Lead slags consistmainly of iron and calcium silicates, manganese, however, is frequentlypresent, so are also zinc, aluminium, bwium, and magnesium, but thelast four are to be avoided as much as possible. Incidental con-stituents of lead slags are silver, lead, potassium, sodium, phos-phorus, sulphur, sometimes copper, nickel, and cobalt ; whilst Leadvdlesl;zgs frequent17 contain vanadium I n abnormal slags, quartz, ferricoxide, and quicklime are sometixries found. Delicate needles con-taining lead and sulphnr are observed in the blistered cavities in thecrust of pots of slags418 ABSTRACTS OF CHEMICAL PAPERS.Tho author does not approve of decomposing the slags by fusionwith sodium carbonate anti nitrate in a platinum crucible, bnt ifsucli a method is resorted to, the pulrerised slag should he first treatedwith hydrochloric acid, evaporated to dryness, more hydrochloric acidadded, filtered, and then fused with sodium carbonate; or, better,fuse the slag directly with potash in a silver crucible, or if silver isalso to be determined, in a platinum crucible heavily plated withgold.The method generally followed by the author is to take thesample in the way already noted, pulverise and moisten about half agram with water, add concentrated hydroch1or:c acid, and digest witha few drops of nitric acid, the silica, can then be separated perfectlyfree from iron in the usual manner. Iron is determined by permangn-nate, calcium as oxalate or volumetrically, manganese by the hromineor zinc oxi’Ge methods, other constituents by the iisual methods.The succem of srnelting siliceous ores depends on the economic useof lime, iron, and manganese as fluxes, whilst the life or campaign ofa furnace is greatly influenced by the judicious seIection of slags;such inconveniences as the accumnlation of silica, or iron, charcoal,coke, zinc, or lead crusts may be eliminated by the use of suitable slagsfor some time.Slags must of course be varied to suit the impuritiesin the ores to be dealt with, but from the author% experience and thecareful and complete analyses of TOO slag samples, theresults of whichare given in a table, it is concluded that certain definite “slagtFpes,” or slags having some well-defined composition and a distinctcrysballine form exist, and t h a t thenearer slags in general approach toany of these types the more effectual they are.Taking the importanficonstitnents lime, iron and manganese, and silica, it i s observed thattlie best slags range within the following. limits per cent. : SiO, 31 to 36,Fe + Mn 28 to 30, CaO 14 to 25 : wliilst the slags doing the best workand ensuring the longest campaigns do not vary beyond SiOz 31 to 34,Ye + Mn 84 to 27, CaO 14 to 25. The limits SiO, 26 to 41, Fe + Mn18 to 35, CaO 5 to 35, would include all lead slags.The seven types laid down by the author include pract(ica1ly everyknown slag which is well adapted for melting argentiferous lead,and are composed as follows as pegards tlie most: important con-stituents :-T-~pes.A . B . C . . D . E . F . Gt.CaO .......... 6 10 12 16 20 24 28FeO + MnO ... 52 45 50 34 40 33 2’7Si0 2..n... ...... 3fL! 35 28 34 30 33 35Type A. Crystallises im reekangular plates ; but is not adapted toLad mclting as tihe ison is too high, the lime too low.Type B. Forms generally sniall, rhombic plates more or lessthickened and characterised by well-defined striations. Thistype of slag will keep the furnaces in good condition, it giveslarge yields, but is liable to cause large losses of lead and silver ;it is not a, bad slag in localities where limestone is dear.Type C. Is black and distinctly crystalline, and has the formula6Fe0,3Si02 + 2Ca0,Si02 assigned it. It is highly recomISORGANIC CHENISTRT.41 9mended where iron flus is abundant, and the ores carry muchzinc.Type D. Can be represented by the formula 5Fe0,4SiOt +3Ca0,2Si02; it crjstallises in more or less translucent, flat-tened prisms often wifh an abrupt arrow-shaped termination.It is well adapted to the treatment of siliceous and very impureores.Type E. Corresponds to the formula 6Fe0.3Si02 + 4C~0,2SiO, ; i tcrystallises in monoclinic prisms. This is an excellent slag andverp economical where the fluxes are easily obtained.Type F. This is a black, lustrous, distinctly resinous slag. Thecrystals are rectangular prisms, remarkably translncent andeven transparent when there is a little manganese present; thecrystals are frequently indented.It is the best slag.known for thetreatment of very siliceous ores! and has been foand successfulwith ores containing large quauti'tities of batryta, alumina, andzinc. Gcne~ally slags intermediate or differing widely in com-position from the above types, having botryoidal, pectolitic orwavellitic crystalline forms, OF those whicth are devoid ofcrystalline structure, may be considered abnormal and untrust-worthy for smelting purposes. Hexagonal c r j s t d s indicahe toohigh a percentage of lime. Xlender-needles result from fluxinghighly siliceous ores with lime, and ape accompanied by greatloss of silver, bnt they contain no lead.The proportion of lime seems to exert some.influence on the crystal-line structure of slags. The use of cliarcoal increases the tonnage, butgenerally with an increased loss of silvey. These results show thatcertain ratios should existr between the silt% and the bases of a slag,and that lime exerts a, great cleansing influence on slags; but theproblem why one slag is good and another of similar composition badstill remains to be answered.The author points out that loss ofsilver is due neither to the dissemination of globules of matte nor tothe influence of manganese.It is very friable.Type G. Crystallises in cubes.D. A. L.Crystallised Halogen Salts of Mercury. By W. SIEVERS (Bey.,21, 647-652) .-Mercuric bromide is obtained in tetragonal plateswhen an excess of bromine is added with aqitation to a slightly acidfiolution of mercuric nitmte of sp. gr. 1.197 ; hypobromous acid beingformed in the reaction as noticed by Spiller (Chem.News, 6, 249).The chloride prepared in like manner forms slender needles. Mercuriciodide is obtained in red, tetragonal plates by adding to a boilingsolution of mercuric nitrate rather more iodine than it can dissolve,and boiling for some time with constant replacement of the evaporatedwat,er.A niixt'ure of mercuric and mercurous chlorides is obtained by theaction of chlorine on a solution of mercurous nitrate ; this is washedwith hot water to remove t'he mercuric salt, and the amorphous mer-curous chloride crystallised from mercurous nitrate solution, when i tforms yellowish-white, tetragonal plates. Crptallised mercurou420 ABSTRACTS OF CHEMICAL PAPERS.bromide and iodide have been already prepared by this method byStroman (this vol., p.111).Ferric and Aluminium Phosphates. By P. HAU'CEFEUILT~E andJ. MARGOTTET (Conyt. rend., 106, 135-1 38) .-Glacial phosphoricacid a t 100" dissolves 15 per cent. of ferric oxide or 8 per cent. ofalumina, and if the solutions are kept at this temperature they depositdistinct crystals which are readily decomposed by water. They havethe composition FeZ0,3PzO5 + 6H20 or A1,O3,3Pz?, + 6H,O. Theferric compound forms pinkish, rhombic plates, derived from a mono-clinic prism ; the aluminium compound forms colourless, prismaticcrystals with longitudinal extinction.If the solution is heated rapidly to 150-200", and is kept a t thistemperature, the crystals contain only 4 mols.H,O, and are notreadily attacked by water or alcohol. The iron salt forms pinkish,nacreous, rectangular lamell=, which act strongly on polarised light ;the aluminium salt foyms birefractive needles grouped in bundles.Above 200°, the solution deposits crystals a t a temperature whichis lower the greater the proportion of basic oxide present. I n allcases they have the composition Fe2O3,3PzO5 or Al,0,,3Pz05, but theform of the iron salt depends on the temperature a t which crystal-lisation takes plnce. At 200-250", it forms short, channelled, rhombicprisms ; from 253" t'o incipient redness, fusiform, triclinic crystals ;at a red heat, long, monoclinic prisms, sometimes with an almostsquare orthogonal section, and usually terminated by a rhombic faceat an acute angle with the edge of the prism.A t 200", the aluminium phosphate separates in tetrabedrn withcurved faces, without sensible action on polarised light ; a t 250°, thecrystals are octahedra, frequently modified by faces OE the cube.Thisform i s stable up to a red heat. If the phosphate crystallises a t ared heat, or is obtained by the action of phosphoric acid on corundum,it separates in cubes which are not modified, but are frequentlymacled. From these results, it seems that the atihydrous aluminiumphosphate always crystallises in the regular system, but the exactform depends on the temperature. These differences are comparablewith the differences observed in the case of ferric and siliconphosphates. C. H.B.Volume and Carbon Contents of the Gas Evolved duringSolution of Iron in Acids. By H. BACKSTROM and G. PAIJKULL(Zeit. and. Chem., 26, 683-689).-That different kinds of ironevolve different volumes of gas when dissolved in acid was ascer-tained by Bergman i n 1781, and these differences were connected byVandermonde, Berthollet, and Monge, with the differences in theamount of carbon present.The autbors have determined the total volume of gas, and thequantity of carbon in it, from 14 samples of iron containing carbon(totalj rangiug from 0.11 t o 4.24 per cent. As a general rule, themore highly carburetted the iron, the smaller is the volume and thegreater the carbon-contents of the gas evolved, but the relation isnot a quantitative one in either case.No definite fraction of theA. J. GINORGANIC CHEXISTRT. 421combined carbon is evolved as a pseous hydrocarban. Part of thecarbon invariably remains dissolved in the acid as an organic sub-stance capable of reducing permznganate, so that the results oftitration are too high as well as variable. Bergmnn asserted that,sulphuric and hydrochloric acids evolved equal volumes of gas, but i na special experiment on a white cast iron containing 3.87 per cent. ofcarbon, a volume of gas larger, and containing more carbon, wa8obtained with hydrochloric acid than with sulphuric acid of corre-sponding strength.It is well known that hardened steel leaves less residue thanunhardened when dissolved in acids. Cold hammered steel behaveslike hardened steel.The latest view of the constitution of steel isthat it contains a, true carbide of iron forming a mass of cellulartexture, the pores of which are filled with pure iron. According toOsmond and Werth, the so-called cement-carbon ( Cement-KohZenstof,carbone d e r e m i t ) is that which exists in the carbide in combinationwith iron, whilst the hardening-carbon (~~rt2tl2gb’-RohZerzsto~, carbonede trempe) exists in solution in the iron disseminated in the cellulariiuclci. The latter may therefore be expected t o be converted moreor less into gaseous hydrocarbons, whilst the former would more orless remain undissolved on treakment with acid. It is found thathardened steel gives both a larger volume of gas, and one richer incarbon than the same steel before hardening.It seems as thoughalmost the whole of the hardening carbon is evolved as gas. Theeffect of cold hammering is, however, both as to volume of gas andamount of carbon, exactly the reverse.By C. N. DRAPER ( C k e m .News, 56, 25l).-A specimen of cast iron, weighing 557.31 grams,and measuring 85 mm. x 52 mm. x 20 mm., was broken from arail which had been exposed to the alternate action of sea-waters n d the atmosphere €or about 50 years. The lateral surEaces wereslightly coated with oxide, and the upper surface consisted, to adepth of 7 mm., of a brownish-grey, graphitoydal substance, amountingto 67.59 grams, and containing 23.6 per cent. of carbon along withmuch unoxidised iron, presumably existing as FeC3.The graphi-toidal substance was easily removed from the specimen with a knife,leaving a clean, bright, metallic surface exposed. This operation wasaccompanied by a distinct rise in temperature.Influence of Phosphorus on Iron. By L. SCXNEIDER (DingZ.polyt. J., 266, 378--382).-According to Cheever, the variable effectof phosphorus on iron is explained by assuming that the phosphorusis present in the metal in two forms, as ‘‘ phosphate ” and “ phosphide,”which influence the properties of iron in different ways. This assump-tion is based on the analytical results obtained in a series of experi-ments in which the iron was treated with a cold smmoniacal solutionof cupric chloride, the residue being digested with an alkaline solutionof ammonium oxalate, or shaken for five minutes with a 1 per cent.solution of hydmcbloric acid, and the phosphoric acid determined inthe solution.Cheever assumes that the srnall amount of phosphideM. J. S.Action of Sea-water on Cast Iron.D. A. L.VOL. LIT. 2 422 ABSTRACTS OF CKEhCICAL PAPERS.existing in the metal completely resists the action of cupric chloride,and that the complete solution of all phosphates formed fromphosphides a t a red heat is effected either by a treatment with a1 per cent. solution of hydrochloric acid for five minutes, or by theaction of an ammoniacal solution of ammonium oxalate.The author criticises Cheever's method of examination, and theconclusions deduced therefrom. He shows that iron phosphide iniron is affected by cupric chloride in the cold, and i f the solutlion isquite neutral the phosphoric acid obtained by the oxidation of thephosphide remains in the residue, from which it may be subsequentlyextracted with ease by weak acids.Vapour-density of Ferric Chloride at Various Temperatures.By W.GR~NEWALD and V. MEYER (Bey., 21, 687--701).-1n theseexperiments, sublimed ferric chloride was used. The estimations weremade in a slightly modified form of V. Meyer's apparatus, in whichthe bulb, 45 mm. in diameter, was reduced to a length of only 125 mm.,whilst the whole apparatus was 670 mm. high; by this means, thewhole of the bulb acquired the temperature of the bath. For greaterconvenience in filling with nitrogen, a thin tube was fused into thebottom of the bulb, bent so as to follow the shape of the bulb andstem until the side tubes were nearly reached, then bent at.rightangles to connect with the nitrogen supply.A new device of Meyer and Biltz for the introduction of thesubstance is also described :-On the stem, opposite to, but just belowthe delivery tube, a short side tube is fused; through this passes aglass rod whose end projects across the stem ; the joint between rodand side tube being made with well-fitting caoutchouc tubing. Thelittle bottle containing the substance rests on the end of the rod;when the bulb has attained the required temperature, the rod isslightly withdrawn, and the bottle falls into the bulb.Four determinations at 448" (in sulphur vapour) gave a density of10.487, whilst that required by the formula FezCl6 is 11.2.After theestimation, the contents of the bulb did not give the slightest reactionfor ferrous salt. Experiments at, a lower temperature were out of thequestion, as even in tliese the vaporisation was rather slow.A t 518" (in vapour of phosphorus pentasulphide), three experi-ments gave a vapour-density of 9.569 ; about & of the iron wasfound to be in the ferrous condition after the estimation.A t 606" (in vapour of zinc chloride), in a smaller apparatus, sixexperiments gave a mean vapour-density of 8.383; about & of theiron was in the ferrous state at the close.The determination8 at higher temperatures were effected in platinumapparatus heated in a Perrot's gas furnace. The mean of threeestimations at about 750" gave a vapour-density of 5.406, whilst aboutf of the ii-on was found to be in the ferrous state at the close of theexperiments.At about 1050", the numbers obtained for the densitywere 5.3 and 4.9 ; + and +- of the iron being respectively found in theferrous state. The results a t 1300" were pra,ctically identical withthose at 1Vrio". As it seemed probable that the lower results in thehigher temperature experiments might be due to the action of theD. BINORGAYIG CHEMISTRY. 423plntinnm on the ferric chloride, experiments were made in platinumapparatus at about 600°, but the results obtained were in agreementwith those previonsly got in glass.With regard to the amounts of ferrous salt observed at the end ofthe experiments, it must be remembered that this does not show theamount of dissociation that occurred at the temperature of the experi-ment, inasmuch as recombination occurs on cooling.Experiments in a chlorine atmosphere at the temperaiure of boilingsulphur and boiling phosphorus pentasulphide respectively, gavepractically the same results as those in an atmosphere of nitrogen.From these results, it follows that ferric chloride does not at amytemperature show a vapour-density sufficiently high for the molecularformula Fe,C16, whilst at 750" and 1077" numbers were obtained notfar removed from 5.6, the calculated vapour-density for the molecularformula FeCl,.A. J. G.Use of Hydrogen Sulphide to Purify Nickel and Cobalt. ByH . BAUBLG-NY (Compt.r e d , 106, 132--135).-The only possiblemethod of separating nickel and cobalt by means of hydrogensulpliide is to saturate the solution of the sulphates with the gas at O",and heat to 100". Nickel sulphide is precipitated, but cobalt sulphateis not decomposed. The precipitate, however, always contains a notableproportion of cobalt even when the quantity of free acid is almostsiifficieot to prevent the precipitation of the nickel. Dellf's methodof precipitating cobalt as sulphide from the acetate by mixing asolution of the nitrates or sulphates with a quantity of sodiumacetate not quite sufficient to convert all the cobalt into acetate, isnot satisfactory, since a considerable proportion of the nickel is pre-cipitaied at, the same time.Alloy of Titanium, Silicon, and Aluminium.By L. L ~ V Y(Compt. rend., 106, 66-68).-10 grams of titanium, 35 grams ofaluminium, 35 grams each of fused sodium and potassium chlorides,were heated iu a Perrot's furnace in a porcelain crucible enclosed ina crucible brasqued with charcoal and rutile, a current of dryhydrogen being passed into the inner crucible. The product wastreated with water and then with dilute acid, and a residue wasobtained consisting of lustrous, steel-grey lamellae, with angles of 90°,very brittle, and good conductors of heat, sp. gr. at 16" = 3.11. Theydo not alter in air or nitrogen oxides at the ordina.rg temperature,but tarnish when heated, and bwn if heated in oxygen. They arenot attacked by vapours of sulphur, selenium, phosphorus, or arsenic,but burn in chlorine or in vapour of iodine or bromine, especially theformer.Liquid bromine, however, is without, action. Superheatedsteam and cold fuming nitric acid have no action, but hot nitric acidatt8acks the crystals hlightly. Hydrochloric and sulphuric acids actsomewhat in the cold and more readily when hea,ted. The crystalsburn when heated in hydrogen chloride, and dissolve readily in aquaregia, but are not dissolved by hydrobromic and h-j-driodic acids,019 by mixtures of these acids with nitric acid. Sulphuric acid andcalcium fluoride have little action, and potash only partially iiissolv3sC. H. B.2 f 424 ABS'I'RhCTS OF CHEMICAL PAPERS.the crystals in the cold, but dissolution is complete on heating, withevolution of hydrogen.The crystals have the composition A1 71-06 ;Ti 26.65; Si 2.19; loss (? C) 0.10, which agrees with the formula(Ti Si)AI4, and hence i t is probable that they are mixtures of theisomorphous compounds, TiAl, and SiAI,.If zinc or magnesium is substituted for aluminium, no crystals areobtained. C. H. B.Tktanium Trioxide. By A. CLASSEN (Bey., 21, 370-372) .-Theaction of hydrogen peroxide on titanium dioxide (compare Piccini,Abstr., 1882, 808 ; 1883, 1054 ; Weller, Abstr., 1883, 295) has beenstudied by the author, who recommends the following method forobtaining the product:-Pure titanium chloride is added drop b7drop to dilute alcohol, and the clear and very dilute solution istreated with a large excess of hydrogen peroxide.Ammonia, ammo-nium carbonate, or aqueous potash is added to the solution with theproduction of a yellow or, iiz the case of ammonia: of a reddish-yellowliquid, which after some time yields a yellow precipitate. This isallowed to subside, the clear solutlion siphoned off, and the precipitaterepeatedly washed by decantation ; the compound, however, tends toretain waicr and salts in considerable quant,ities. When dried on atile, it approximates to the composition-Ti03 + 3Hz0. w. P. w.Antimony Pentachloride. By R. ANSCH~~TZ and P. N. EVANS(Proc. Roy. Xoc., 42, 379-387; compare Trans., 1886, 379).-Theauthors find that, contrary to the statement of Daubrawa (this Journal,1877, ii, 406), SbOC1, is not formed when water is added to antimonypentachloride, nor is any hydrogen chloride evolved. The antimonypentachloride is best dissolved in chloroform, and the calculatedamount of water added.Under these circumstances a, crystallinesubstance, SbCl,,H*O, soluble in chloroform, is obtained, melting a t87-92'. It is very hygroscopic, and diljquesces to tt clear liquid,which crystallises over sulphuric acid in broad crystals, described byDaubrawa as the oxychloride. When distilled, it gives SbCl,,SbCI,and a waxy residue.A chloroform solution of antimony pentachloride, when heated withwater in a sealed tube, gives antimony hichloride and pbosgene gas.Yhosgene gas is also produced by heating a chloroform solution ofthe monohydrate at 100".Antimony pentachloride tetrahydrate can be produced in the sameway as the monohydrate.It is a crystalline mass, insoluble in chlo-roform. By adding anhydrous oxalic acid to a chloroform solution ofantimony pentachloride, the authors obtain a substance, Sb2C18C204,probably C,O,( O*SbCl&. It crystallises from chloroform in tablesmelting a t 148*5-149", and is decomposed by water with liberationof oxalic acid.The difference in behaviour with carbon compounds bet'ween phos-ptrorus pentachloride and antimony pentachloride is attributed t ot iie property of the latter of combining with water instead of decom-posing it. H. H. 1'INORGANIC CHEIIISTRY. 425DittmarandMcArthur’sempiricalfactora.-_0.306270-7tiOl6Redetermination of the Atomic Weight of Platinum. ByW. DITTMAR and J.MCARTHUR (J. Xoc. Chem. Ind., 6, 799-803).-The value Pt = 194.8 which Seubert (Abstr., 1881, 514) deducedfrom his analyses of platinochlorides, is too low ; his own analyses, ifproperly interpreted, show that the true value lies, by a considerablefraction of a, unit, higher. According to the authors’ andysis ofpotassium platinochloride, the true “ Pt,” although probably a shadebelow, lies dose t o 195.5. Taking “ P t ” as meaning the numbevwhich must be substituted for Pt in the calculation of the mtios‘LKC1 : PtC16K2 ; 2EC1 : Pt, &c., in order to obtain the correct facto~sf o r reducing analytically obtained platinochloride t o potassiumchloride, &c., even the number 195.5 is too low, 196 ailording ingeneral a better approximation. But Pt if taken in this sense is noconstant at all.Those factors must be dekermined directly bgstandard experiments. The results of the authord own standardexperiments are given and contrasted with the theoreticaIly calcu-lated ratios in the subjoined table. The entries “ Ta ” refer to Tat-lock’s methods; those “ F” to the authors’ form of E’inkener’smethod described in detail in the original paper, and those marked“ N ” to the usual platinum process for the determination ofammonia :-.4;L;(1)( 2 )0T&T&FNN -ZKC1 : PtC16K2 . . . . . . .2KCl : Pt . . . . . . . . . . .2KC1 : Pt . . . . . . . .. . .2NH4C1 : PtC16(NH4)a.ZNH,Cl : Pt . . . . . . . , .Theoretical factors.0 ’30707 0 -30665 0 *306330 3’6571 0 -76307 0.761120.76571 0’76307 0-761120 *24123 0 -24084 0 ’240570.54934 0 -54‘737 0 -545%Values calculated forSymbols.Pt -194.81 195.5 1 196I--- l-I- -----Notes.(1) Refers to the potassium chloride in-the substance,(2) t o that in the p1atinochlo;ide precipitate, and ( 3 ) and (4) to theammonium chloride to be determined, not to that contained in theplatinochloride precipitate. D. B.Hydroxylamine Platinum Bases. By H. ALEXANDER (Chem.Centr., 1887, 1254c-l255).--As the platinum bases mentioned beloware all explosive, the platinum and chlorine cannot be determined byheating the compound. The platinum was determined by moisteninga quantity of the substance with concentrated sulphuric acid in aplatinum capsule, evaporatiri g off the acid and finally dispelling anyremaining acid by the addition of ammonium carbonate. The chlorinewas determined by distilling the compound with snlphuric acid, andpassing the resulting hydrogen chloride into a solution of silver nitrale426 ABSTRACTS O F CHEMICAL PAPERS.Platoso-dih.ydro~lamin,e hydrochloride, P t ( NH30*NH30C1) 2, whichLossen has already described, is obtained by the action of potassio-platinous chloride on hydroxylamine hydrochloride. Strong basesprecipitate 13latoso-dihydroxylamine hydroxide, Pt ( OH),,4NH30, fromsolutions of the chloride.The oxalate, PtC2O4,4NHaO, is preparedfrom neutral potassium oxalate and the chloride ; an acid salt does notseem to exist. Platino-dih ydroxylarnine sulphate, PtS04,4NH30 + H20,can be prepared from this oxalate by the action of weak sulphuricacid; the sulphate is more easily prepared from the free base andsulphnric acid.Platoso-dihydroxyEami.rie hydrochloride platinous chloride is preparedby the addition of platinous hydrochloride to the chloride.P latoso- hydroxy lamin e h y dyoc hloride, Pt (N H30 Cl), , is formed by theaction of hydrochloric acid, on either platino-dihydroxylamine hydratewhen warm, or on the corresponding chloride.The cornpound formed by the action of ammonia on platinoushydrochloride and on platoso- hydroxylamine hydrochloride, whichhas been described by Jorgensen, the author regards as platoso-hydroxylamine ammonium chloride, Pt(NH30-NH,C1),.The double salt, Pt(NH30.NH3C1)~,PtCl,, is obtained from platinoushydrochloride and plat oso- hy droxylamine ammonium chloride, as wellas from the above-named mixed chlorides and potassio-platinouschloride.Free hydroxylamine acting on platinons chloride gives rise tothe compound OH.PtC1,4NH30 + 2H20, which explodes at 140-150". Another compound which may be regarded as platinumnitrogen chloride, PtNC1, together with the double salt,2(0H-PtCl,4NH30) + Pt(OH)2,2NH30, or 2[Pt(OH),,4NH30] +PtC1, + 2NH30.were also obtained.Free hydroxylamine acting on platinous hydrochloride gives riseto a compound corresponding approximately with the formulaPtC1,,4NH30, and by its action on potassio-platinous chloride t o it basePt(OH)2,2NH30, which has not been obtained quite pure as yet.A phosphate was obtained, but no nitrate.J. P. L.Ruthenium Oxides. By H. DEBRAY and A. JOLY (Compt. rend.,106, 100-106) .-The authors prepared crystallised ruthenium d i -oxide by heating the amorphous oxide in a vacuum or by heating themetal in oxygen. It forms quadratic prisms with the faces m, h', a',and b'. The ratios being b : h : : 1000 : 692.43, and hence is iso-morphous with cassiterite and rutile. The faces in the zone rn h' areoften striated as in those minerals, and very frequently the crystalsare macled after the cassiterite and rutile types.When heatNed to bright redness in a muffle, ruthenium absorbs oxygen,but after some time absorption takes place very slowly, and the metalis never fully oxidised to the dioxide. If, however, the product ispowdered and again heated, the dioxide is obtained crystalline, withan indigo-blue colour. The authors were unable to obtain the sesqui-oxide in the manner described by Claus.When ruthenium is heated in oxygen at a temperature above thMIXERALOGICAL CHEMISTR1'. 427melting point of silver, it is entirely converted into crystalline products,and a portion volatilises and condenses in crystals. I f the current ofgas is rapid, the odour of ozone or ruthenium peroxide is perceived,and a certain quantit,y of the peroxide can be condensed in a flaskcooled by ice. The inside of the tube is lined with ruthenium dioxideand a small quantity of a black substance which seems to containmore oxygen than the dioxide. The products are similar to thoseobtained when rathenium peroxide and nitrogen are passed through ared-hot porcelain tube, and they are distributed in the same manner.The dioxide is found in the cooler parts of the tube, which indicatesthat the peroxide formed at about 1000" decomposes at a lower tem-perature. At temperatures above lOOO", ruthenium dioxide has aconsiderable tension of dissociation, and in a vacuum is partially re-duced to the metal, a small quantity of the peroxide being formed.At a bright red heat, the phenomena are similar.The authors mere unable to obtain an oxide lower than the dioxide.Ruthenium peroxide is formed at about 1 OOO", and decomqoses withexplosion when cooled to 108", but can be isolated by rapid cooling.It affords another instance of a, compound which is decomposed byheat, and yet is formed at a high temperature. The crystallisationof the dioxide is a phenomenon of apparent volatilisation, and theformation of the peroxide is analogous to the formation of ozone,silicon hexachloride, silver oxide, hydrogen selenide or telluride, &c.The formation of ruthenium peroxide, like the decomposition ofwater, is endothermic. c. H. €3

ISSN:0368-1769    

DOI:10.1039/CA8885400411

出版商:RSC    

年代:1888

数据来源: RSC