摘要:

J O U R N A L OF THE CHEMICAL SOCIETY, ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. G e n e r a l a n d P h y s i c a l C h e m i s t r y , Apparatus for Measuring the Heat of Combustion. By F. WISCHER (Bey.,* 12, 1694-1696). Chemical Constitution of Amalgams of the Alkali-Metals. By BERTHELOT (Compt. rend., 89, 465).-The solution of the potas- sium-amalgam Eg2& in four times its weight of mercury, absorbs -8.0 kilogram-degrees of heat, and in twenty times its weight, -9.0 ki1.-degs. The solution of the sodium-amalgam NaHg,,, in 3 parts of mercury, absorbs -2% ki1.-degs., and in 18 parts, -2.9. It may thus be concluded that the solution of definite amalgams in different quantities of mercury, like the solution of salts in water, absorbs a constant amount of heat.Only one amalgam of potassium and one of sodium is known in the crystallised form, but from experi- ments on the varying quantities of heat evolved by the addition of potassium or of sodium t o these amalgams, the author concludes that there are two more of each. The progressive addition of potassium to the amalgam €€g,,R, evolves nearly constant quantities of heat, until an amalgam, 8.7Hg + K, is obtained; the heat evolved then varies from 8.7 t o 5.7, and remains constant From 5.7 to 2.9. There exist, therefore, two more amalgams of potassium, the first having the composition Hg8K, and evolving in its formation -t 29.3 ki1.-degs. (Hg liquid), or + 27-1 (Hg solid), the last figure being identical with that for Hg,,K. The formula of the other amalgam, that richest in potassium, cannot be calculated with any degree of accuracy. The progressive addition of sodium t o the amalgam Hg12Na, evolves constant quantities of heat up to 8.1 Na, and is also constant from 8.1 to 3.5 Na. It is probable, * The " Berichte der deutschen chemischen Gesellschaft " will in future be ab- breviated to " Ber." VOL.XXXVlII. h2 ABSTRACTS OF CHEMICAL PAPERS. therefore, that two sodium-amalgams, Hg,Na, and Hg,Na2, may exist. c. w. w. Condition of Alkaline Phosphates in Aqueous Solution. By J. M. VAN BREMMELEN (Ber., 12, 1675--1678).--When a solution of trisodic phosphate is subjected t o dialysis, the soda diffuses rapidly, and a small quantity of disodio-hydric phosphate is formed in the dialyser. This experiment shows that trisodic phosphate undergoes partial dissociation when dissolved in water.Disodio-hydric phos- phate, dihydro-sodic phosphate, and microcosmic salt do not dissociate under these circumstances. w. c. w.J O U R N A LOFTHE CHEMICAL SOCIETY,ABSTRACTS OF CHEMICAL PAPERS PUBLISHED INBRITISH AND FOREIGN JOURNALS.G e n e r a l a n d P h y s i c a l C h e m i s t r y ,Apparatus for Measuring the Heat of Combustion. ByF. WISCHER (Bey.,* 12, 1694-1696).Chemical Constitution of Amalgams of the Alkali-Metals.By BERTHELOT (Compt. rend., 89, 465).-The solution of the potas-sium-amalgam Eg2& in four times its weight of mercury, absorbs-8.0 kilogram-degrees of heat, and in twenty times its weight,-9.0 ki1.-degs. The solution of the sodium-amalgam NaHg,,, in3 parts of mercury, absorbs -2% ki1.-degs., and in 18 parts, -2.9.It may thus be concluded that the solution of definite amalgams indifferent quantities of mercury, like the solution of salts in water,absorbs a constant amount of heat.Only one amalgam of potassiumand one of sodium is known in the crystallised form, but from experi-ments on the varying quantities of heat evolved by the addition ofpotassium or of sodium t o these amalgams, the author concludes thatthere are two more of each.The progressive addition of potassium to the amalgam €€g,,R,evolves nearly constant quantities of heat, until an amalgam, 8.7Hg +K, is obtained; the heat evolved then varies from 8.7 t o 5.7, andremains constant From 5.7 to 2.9. There exist, therefore, two moreamalgams of potassium, the first having the composition Hg8K, andevolving in its formation -t 29.3 ki1.-degs.(Hg liquid), or + 27-1(Hg solid), the last figure being identical with that for Hg,,K. Theformula of the other amalgam, that richest in potassium, cannot becalculated with any degree of accuracy. The progressive addition ofsodium t o the amalgam Hg12Na, evolves constant quantities of heatup to 8.1 Na, and is also constant from 8.1 to 3.5 Na. It is probable,* The " Berichte der deutschen chemischen Gesellschaft " will in future be ab-breviated to " Ber."VOL. XXXVlII. 2 ABSTRACTS OF CHEMICAL PAPERS.therefore, that two sodium-amalgams, Hg,Na, and Hg,Na2, mayexist. c. w. w.Condition of Alkaline Phosphates in Aqueous Solution.By J. M. VAN BREMMELEN (Ber., 12, 1675--1678).--When a solutionof trisodic phosphate is subjected t o dialysis, the soda diffuses rapidly,and a small quantity of disodio-hydric phosphate is formed in thedialyser. This experiment shows that trisodic phosphate undergoespartial dissociation when dissolved in water. Disodio-hydric phos-phate, dihydro-sodic phosphate, and microcosmic salt do not dissociateunder these circumstances. w. c. w

ISSN:0368-1769    

DOI:10.1039/CA8803800001

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

2 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Purification of Hydrogen. By A. LIONET (Compt. rend., 89, 440). -Metallic copper removes all the impurities from hydrogen, except hydrogen phosphide. hydrogen silicide, and hydrocarbons. Cuprous oxide removes all but hydrogen silicide and the hydrocarbons. Cupric oxide removes all but the hydrocarbons. The best form of cup& oxide is that precipitated by potash from a, solution of cupric Non-existence of Nascent Hydrogen. By D. TOMNASI (Chen7. News, 40, 171) .-Reduction of Potassium Perch1ovate.--It was found that when chemically pure potassium perchlorate was submitted to the action of various reducing agents, giving nascent hydrogen, it did not undergo reduction, although it is easily transformed into chloride by the action of a compound which does not set hydrogen free, viz., sodium-hydrogen sulphite.The author asks, how can it be explained that this same perchlorate which undergoes no reduction by means of nascent hydrogen, as shown by sixteen different reactions, can be reduced by the hydrogen disengaged by the action of zinc on sodium- hydrogen sulphite. Although Wurtz declares himself to be in favour of the naacent state of bodies, it appears to the author unlikely that when hydrogen is set free by a reaction, it can be in the state of iso- lated atoms. It is known that copper, even when finely divided, is but very slightly attacked by hydrochloric acid at the ordinary tempera- ture, although copper hydride is decomposed very energetically. “ How can this fact be explained,” justly remarks Wurtz, in his Atomic Theory, “ i f to the affinity of chlorine for copper be not added the affinity of the two atoms of hydrogen to form a molecule ?” This reasoning may be said to apply equally to all the reactions producing hydrogen ; for example, we know that by the action of hydrochloric acid on zinc, there neither is nor can be any hydrogen in the state of isolated atoms, as Wurtz thinks, and the special properties of nascent hydrogen can be attributed osly to the heat which accompanies hydrogen while it is being set free.It is therefore impossible to con- clude that hydrogen can be active only in the molecular state, as hun- sulphate, and dried at 100”. C. w. w.INORGANIC CKEMISTRY. 3 dreds of examples prove to us that in many cases it is not the mole- cule of hydrogen that acts, but its atom.I n conclusion it is mentioned that the recent results of Gladstone and Tribe coincide entirely with the above hypothesis. These chemists, as is known, consider the different allotropic states of hydrogen a s ordinary hydrogen in different physical conditions. Active Condition of Oxygen induced by Nascent Hydrogen. By F. HOPPE-SEYLER (Ber., 12, 1551-1555)..-Every attempt to explain the vital processes of animals and plants necessarily implies the assumption of a cause whereby the oxygen is rendered actit-e. Hydrogen is evolved in the free state only when oxygen is not present ; and most cuTiously, in presence d oxygen, nascent hydrogen leads to energetic oxidation of any oxidisable substance which may happen to be present.The author has proved the fact by two very st'riking examples. The alloy of palla- dium with hydrogen discovered by Graham, when placed in oxygel), gives rise to water, owing to combination of the hydrogen of the alloy with the oxygen. This, of course, is well known, but it is not so well known that if indigo be present it is decolorised, and then destroyed ; that a mixture of starch withpotassium iodide is first turned blue, and. that the starch is then completely oxidised ; that ammonia is oxidised to ammonium nitrite; that benzene is oxidised to phenol; and that toluene yields benzoic acid. Perhaps a still more remarkable instance is the oxidation of rock-oil by metallic sodium in presence of the small quantity of aqueous vapour which comes in contact with it.The pro- ducts appear to be acetic and caproic acid, and perhaps butyric acid; and the hard crust which forms rmnd sodium, when it is kept under rock-oil, is really a product of oxidation of the oil, and in fact may be made to yield a number of the higher members of the fatty acid series, It thus appears to be the case that when nascent hydrogen acts on oxygen, it renders the latter gas also naseent, or a t least active. Is Ozone produced during the Atmospheric Oxidation of Phosphorus ? By C. T. KISGZETT (Chem. News, 40, 96).-It is generally believed that ozone is produced during the atmospheric oxidation of phosphorus, but the author considers it to be improbable that ozone is formed by the asrial oxidation of phosphorus, considering the constitution of ozone.Moreover, as peroxide of hydrogen is the only known agent which resembles ozone in its general properties, and it is known that hydrogen peroxide is produced in various pro- cesses of slow oxidation, it would seem likely that it is this substance which is produced in connection with the oxidation of phosphorus. In addition to various objections which the author has pointed out t o viewing the active agent produced in the atmospheric oxidation of tur- pentine as ozone, there are many considerations which lead to the con- clusion that the active agent is peroxide of hydrogen. There is no known process of slow oxidation which has been esta- blished to produce ozone. In various writings on this subject observers have always relied on properties which are common to ozone and hydrogen peroxide, and have never instituted volumetric inves- D.B. This is specially the case with ferments. W. R. b 24 ABSTRACTS OF CHEMICAL PAPERS. tigations, which are alone sufficient to decide the question. On the other hand, several processes of slow oxidation are known, in which peroxide of hydrogen is formed, as for instance, those relating to ether and the t,erpenes ; and it is thought that as hydrogen peroxide is formed in each of these cases as a secondary product, clue to the action of water on a peroxide, so also the oxidation of phosphorus by air gives rise to an oxide which generates peroxide of hydrogen by contact with water. I n conclusion, the author mentions that until it has been proved that the active agent produced in the aGrial oxidation of phosphorus has the volumetric relat'ions of ozone, such very decided statements as are to be found in chemical text-books should not be made.D. B. New Method of forming Hyponitrites and Hydroxylamine. By W. ZORN (Bey., 12, 1509--1511).-This consists in the electrolysis of a nitrite, using mercury electrodes. Thorpe describes an experiment in which he passed a current from platinum electrodes through a solu- tion of potassium nitrite, and a t the negative pole only hydrogen was evolved. On using mercury electrodes, however, if the current is stopped as soon as ammonia begins to be evolved, the liquid, after neutralisation and addition of silver nitrate, gives a copious precipitate of silver hyponitrite. I n this reduction, hydroxylamine is also formed, and it is necessary to remove it from the solution by precipitation with mercuric oxide, before adding silver nitrate to precipitate the hyponitrous acid.Four Bnnsen's elements are sufficient for t'his reac- tion; it is recommended as an advantageous method of preparing hypo ni t ri t es . W. R. Experiments tending to show the Non-elementary Charac- ter Of Phosphorus. By N, [JOCKYER (Conzpt. rend., 89, 514).- Phosphorus heated in it tube with copper gives a gas exhibiting the spectrum of hydrogen ; heated done, phosphorus gives no gas. Phos- phorus a t the negative pole of a battery in a tube-apparatus (of which a drawing is given), gives a large quantity of gas which shows the spectrum Df hydrogen, and is not phosphoretted hydrogen.c. w. w. By E. J. MAU- M S N ~ (Coinpt. rend., 89, 506).--Tn the preparation of ammonium sulphide, the hydrogen sulphide which passes through the first bottle carries ammonia, with it, and colourless crystals are deposited in the connecting tube. These crystals have the composition NH,.HS. When they are added to strong aqueous ammonia at 0", colourless crystals are deposited in a few hours having the composition (NH,),HS. The author imagines the existence of two series of ammonium- compounds containing respectively excess of ammonia and excess of hydrogen sulphide, 1 mol. of one of the constituents being united with (2, - 1) molecules of the other. Members of one series may unite with members of the other series, producing compounds like HS(NH,)15.'L[(HS),NH3] = (HS)15(NH3)1,, which might be mistaken for (NH3)HS.The compounds of ammonia with hydrochloric acid present analogies Compounds of Hydracids with Ammonia. with the above compounds. c. w. w.INORGANIC CHEMISTRY. 5 Oxygen-acids of Sulphur. By E. J. MAUXEN~ (Contpt. Tend., 89, 422).-The action of iodine on barium thiosulphate gives rise to tetrathionic acid, as observed by Fordos and Gelis, but seven other acids should be produced, according to the proportions of iodine a i d thiosulphate employed. The acids, H2S201 and H2S609, have been obtained. The latter is prepared by mixing 3 mols. of barium thio- sulphate and 2 atoms of iodine. The mixture becomes colourless in three or fonr days. It is then filtered through cotton-wool, and the crystals remaining behind are washed with alcohol.They are then pure and have the composition Bas&& ; with silver nitrate, this salt gives a white precipitate, turning black, and the liquid a t the same time becomes acid. The sodium salt crystallises in large, colourless, very soluble crystals, containing a large quantity of water. Basicity of Dithionic Acid. By H. KOLBE (J. pr. Chenz. [a], 19, 485-4,Si).-As the author hams been unable to obtain an acid salt of this acid or a neutral salt containing two bases, he doubts the cor- rectness of the usually accepted view of the bibasicity of this acid, and is now inclined to the original supposition of Berzelius that it is a monobasic acid, and is represented by the formula S0,OH. In fact, that it contains the radicle SOz, but united with only one atom of hydroxyl, that is, joined with only one atom of hydrogen by one atom of oxygen.On this supposition sulphur must exist in this acid as a pentad. That the radicle sulphoxyl (SO,) may exist as a dyad in sulphuric acid, and as a monad in dithionic acid, appears to the author to be not more improbable than the tetrad and dyad atomicities of tin in stannic and stannous compounds. Behaviour of Calcium Oxide with Carbonic Anhydride. By K. BIMBAUN and M. MAHU (Ber., 12, 1547--1561).-The object of the experiments described in this paper was to ascertain at what tempera- ture calcium oxide begins to absorb carbonic, anhydride, and a t what temperature calcium carbonate begins to dissociate. If was found that the lowest temperature at which absorption takes place is the melting point of zinc, 415-3", and that the carbonate dissociates par- tially at that temperature, although dissociation begins a t a much lower one.The amount of anhydride absorbed by the oxide is about half an equivalent. W. R. c. w. w. A. J. C. Calcium Phosphite. By R. ROTHER (Pharm. J. Trans. [3], 10, 286).--Ry adding sugar to a solution of calcium hypophosphite, the latter is precipitated, a circumstance which 'is generally unknown, and hence it is highly probable that a dense syrup of the mixed hypophos- phites contains little if any calcium salt. In the presence of iron, a, precipitate is also formed ; the proportion of sugar, however, has 110 share in this change. Ferric hypophosphite, when contained in such a sugar, is said to revert easily to th.e ferrous form, and it was found that' the ferrous salt readily oxidises even in the presence of sugar, forming the dark green and very soluble ferroso-ferric hypophosphite.Ferric hypophosphite occurs in several modifications, of which the crys-6 ABSTRACTS OF CHEMICAL PAPERS. talline variety is almost insoluble in hypophosphorous acid, and hence it is this compound which deposits from the syrup. It was attempted to regenerate this sediment by reducing it to the ferrous condition by the intervention of sulphurous acid. However, the latter was de- eomposed into sulphuric acid, sulphur, and oxygen, which reacted with the hypophosphorous acid of the sediment,, and converted it into phosphorous acid. When solutions of calcium bypophosphite and aodium sulphite are mixed, calcium sulphite is precipitated, which is redissolved by hydrochloric acid, no further reaction setting in until both the hypophosphorous and sulphurous acids are entirely freed by the addition of enough hydrochloric acid.The solution, after filtering off the sulphur, yields, on the addition of ammonia, a crystalline pre- cipitate of calcium phosphite. The latter, however, contains less than half of the phosphorous acid generated, owing to the fact that hypo- phosphorous acid is monobasic, whilst phosphorous acid is dibasic, and also that a small loss of calcium is incurred as sulphate. By treating the liquid filtered from the sulphur with calcium carbonate, a much larger amount of phosphite is thrown down than with ammonia. The addition of a solution of calcium chloride to the filtrate causes a further precipitation of phosphite, which becomes more distinctly crystalline, and subsides more rapidly when a, very little ammonia has been added to the precipitate.Calcium phosphite is a white crystalline powder, which when heated in a test-tube evolves spontaneously inflammable hydrogen phosphide accompanied by slight detonations. At a, certain temperature, it sud- denly becomes incandescent, and leaves a residue qf calcium phos- phate. D. B. Zirconium Derivatives. By S. R. PAYK~LL (Ber., 12, 1719).- The moist hydrated oxide, ZrO(OH),, absorbs carbonic anhydride from the atmosphere. By treating zirconium sulphate with the hydrate, one amorphous and two crystalline basic salts were obtained, viz., Zr02.S03+zAq, 3ZrO2.4SO3+15H,O, and 6Zr02.7S03+ 19H20.The sulphate forms with pofassium sulphate basic double salts, e.g., Researches on Erbia. By LECOQ DE BOISBAUDRAN (Cow@. rend., 89, 516).--The author examined the spectrum of erbia from various sourceEi, and with one exception the spectra thus obtained exhibited identical lines of the same intensity. The exception was the erbia derived from samarskite. The principal differences were that with samarskite-erbia, the ray in the green, X == 536.3, is much more in- tense that the ray X = 540.9, whilst in the other erbias the difference is but slight; and the line in the red, h = 640.4, is as strong, or stronger, than X = 653.4; whereas i n the other erbias, the line h = 653.4 is much stronger than k = 640.4.Two specimens of erbia were taken, one nearly pure, giving the normal spectrum, the other from samarskite, and containing a large quantity of yttria. On fractionation by means of ammonia and sub- sequently by potassium or sodium sulphate, a portion was obtained from the first which gave a spcctrum resembling that of the second, K,0~60,+2(12~.0.02.50~) + 1%H,O. w. c. w.INORGANIC CHEMISTRY. 7 and a portion was obtained from the second giving ft spectrum like that, of the first. The author is continuing this research. c. w. w. Two New Elements in Erbia. By P. T. CLEVE (Compt. rend., 89, 478).-In attempting to obtain pure erbia, the author was led to suspect the existence of two other earths in the erbia obtained. The mixture was therefore fractionated, and the different fractions ex- amined spectroscopically.It was found that, in addition t o bands common to all, one band X = 6840 was strong in the residues rich in ytterbia, and want’ing in those containing yttria and erbia, whilst two others, X = 6400 and 5360, were strong in the yttria and ytterbia residues. The colour of the fraction treated for ytterbia was a violet-rose, whilst the yttria fraction had an orange tint. The metal characterised by the first band, X = 6840, the author pro- poses to name thuZium ; it would have an atomic weight of about 113 (the oxide being TmO). Pure erbia, to which must be attributed the common bands, has probably an atomic weight of 110-111. Its oxide has a clear rose colonr. The third metal, holmium, is charncterised by the bands X = 6400 and 5360 ; it should have an atomic weight less than 108 ; its oxide seems t o be yellow.c. w. w. Spectra of the Earths of the Yttria-group. By J. L. SORET (Compt. rend., 89, 521).-The author considers that the new earth, ldmiu, discovered by ClBve, is identical with an earth discovered by Delafontaine and Marignac, whose absorption-spectrum was described by himself (Compt. ren,d., April 29, 1878), and to which Delafontaine gave the name plziZ@pia. CIBre’s holmium is characterised by two bands X = 640 and X = 536, and these two belong likewise t o philip- pium, which is characterised by several other bands. Clhe’s second earth, thdia, is characterised by a red ray X = 684. The author claims to have indicated the existence of this element also ( A ~ c h .Sci., 63, 99). Marignac also showed the probable existence of this earth in the products rich in philippia and having a low equiva- lent. c. w. w. Scandium. By P. T. CLEVE (Compt. rend., 89, 419).-This metal occurs only in gadolinite (0.002 to 0.003 per cent.) and yttrotitanite (0.005 per cent.). Scandium forms but one oxide, scandia, Sc,03; the composition of which is proved by that of potassium scandium oxalate, and of the double sulphates of scandium with the sulphates of potas- sium and with ammonium. 8 to 10 grams of scandinm oxide, having a molecular weight of 106, agreeing with the number obtained by Nilson, yielded, by repeated decompositions of its nitrate, about 1 gram of a white oxide. This was converted into sulphate, and 1.451 grams of this sulphate yielded 0.5293 gram of scandium oxide.The atomic weight of the metal is therefore 44.91, and the mole- cular weight of the oxide, considered as ScO, is 45.94 (? 60.91 = 44.91 + 16), diflering greatly from the lowest number found by Nilson, viz., 105.83. The author considers that this is due to a large8 ABSTRACTS OF CHEMICAL PAPERS. admixture of ytterhia in Nilson’s scandia. The atomic weight, as determined by the decomposition of the nitrate, is 45.12. The atomic weight of scandium may therefore be takeu as 45. Scandizim oxide o r Scandin, Sc203? is a light, white, infusible powder of sp. gr. 3.8, resembling magnesia; it is scarcely soluble even in strong acids, but more so than alumina. Sulphuric acid converts it into a bulky white mass of sulphate ; hydrochloric acid dissolves the oxide more easily than nit,& acid.Scandium hydrate is a bulky white precipitate, drying up to semi- transparent fragments. It does not absorb carbonic acid from the air, is insoluble in ammonia or in potash, and does not decompose ammonium salts when heated with them. Scandium salts are colourless or white, and have an acid, astringent taste, very different from the sweet taste of the salts of the yttrium metals. The sulphate does not form distinct crystals; the nitrate, oxalate, acetate, and formate, are crystallisab!e. The chloride ex- hibits the following reactions :-It gives no spectrum when heated in it gas flame. Potash and ammonia produce bulky white precipitates, insoluble in excess ; tartaric acid prevents the precipitation by ammonia in the cold, but on heating an abundant precipitate falls.Sodium carbonate gives a precipitate, soluble in excess. Sulphuretted hydrogen produces no change ; ammonium sulphide precipitates the hydrate. Sodium orthophosphate gives a gelatinous precipitate. Oxalic acid give8 a curdy precipitate, quickly becoming crystalline ; this preci- pitate dissolves in strong acids, and cannot be completely reprecipitated. Although it appears more soluble than the oxalates of the other yttrium metals, it is found in the first precipitates in the fractional precipitation of a mixture of scandium and ytterbium by oxalic acid. Acid potassium oxalate precipitates a crystalline double salt. Sodium hyposulphite precipitates a boiling solution easily, but incompletely.Sodium acetate behaves similarly. The sulphates of potassium and sodium precipitate crystalline double salts, soluble in a saturated solution of the precipitant. The author describesin a previous paper (BUZZ. SOC. Chinz., 31, 486) the chloride, nitrate, and sulphate of scandium ; the double sulphates, the double oxalate, Sc,(C,O,),.K2C2O4.3H,O ; the acetate, the formate, and selenite, 3Sc,0,.10SeO2.4H2O. The existence of scandium was predicted by Mendelejeff, and its pro- perties described under the name of ekabor (Anmalen, Sq., 8, 1.13). The following table shows a comparison of the observed properties of scandium witlh those predicted of ekabor. SC,(SO~),.~K$~O~, S C , ( S O ~ ) , . ~ N ~ S O ~ . ~ ~ H ~ O , S C ~ ( SOi)s.(NH4)2SO4 ; 8upposed Characters of Ekabor.Atomic Weight = 44. Ekabor should have but one stable oxide, Ebz03, :t stronger base than alumina, which it should resemble in mauy respects. It should be less basic than mag- nesia. Observed Ch,aracters of Scandium. Atomic Weight = 45. Scandium forms only one oxide, Sc203, more energetic than alu- mina, and less so than magnesia.INORGANIC CHEMISTRY. 9 Ekabor oxide should resemble yttria, although less basic. The se- paration of these two earthswill be difficult, depending on differences of solubility or of basicity. Oxide of ekabor is insoluble in alkalis; it will probably not de- compose ammonium salts. The salts should be colourless, and give gelatinous preci.pitates with KHO, Na2C03, and HNaS02. The sulphate should form a double salt with K2S04, having the composition of alum, but not isomorphous with it.But few ekabor salts should crystallise well. The anhydrous chloride should be decomposed by water, giving off hydrochloric acid. The oxide is infusible a,nd so- luble with difficulty in acids after ignition. The density of the oxide would be about 3.5. Scnndia is less basic than yttria, and their separation depends on differences of solubility between their nitrates. Scandium hydrate is insoluble in alkalis ; it does not decompose ammonium chloride. The salts are colourless, and give gelatinous precipitates with KHO, Na2C03, and HNaS02. Potassium - scandium sulphate is anhydrous, but otherwise cor- responds in composition with alum. Scandium sulphate does not form distinct crystals, but the nitratc, acetate, and formatme crys- tallise well. The crystallised chloride is de- composed by heat, giving off hydrochloric acid.The oxide is an infusible powder, nearly insoluble in acids after ignition. The density of the oxide = 3.8. c. w. w. Absorption of Nitrogen Dioxide by Ferrous Salts. By J. GAY (Compt. rend., 89, 410).-Peligot assigned the formula 4FeS04.N20, to the compound of nitrogen dioxide with ferrous su1- phate. The author finds that the composition of this body depends on t'he temperature and on the pressurc of the residual nitrogen dioxide. At temperatures up to 8" and at the ordinary pressure, the com- pound formed has the formula 3FeS01.N202 ; from 8" to 25", at the atmospheric pressure, i t has the formuh 4FeSO4.N2O2 ; at tempera- tures above 25" nitrogen dioxide is rapidly given off, and the com- pound 5FeSO4.N,O, is produced.All these compounds exhibit very marked tensions of dissociation, a fact which explains their decomposition in st vacuum ; they are also decomposed by a current of hydrogen. Reducing agents, such as ferrous oxide, reduce the nitrogen dioxide, a mixture of monoxide and free nitrogen being evolved, while the temperature rises sensibly. c. w. w. Nitrosothioferrates. By J. 0. R l ~ ~ ~ (Ber. 12,1715-1717). -By the action of potassium nitrite and ammonium sulphide on a ferrous salb, Roussin (Ann. Chim. Phys. [3], 52, 285) obtained a black substance, which was afterwards examined by Porczinsky (Annden, 125, 302), Demel (Be?-., 12, 46l), and Pawel (ihid., 12, 1407). This is named by the author ammoiziunz nitrosoferrclthiofen.ate.10 ABSTRACTS OF CHEMICAL PAPERS.On the addition of an alkali ferrous oxide is precipitated, and potassium nitrosothioferrate is obtained. The free acid which is liberated when this salt is treated with hydrochloric acid, combines with alkaline sulphides to form a red salt, to which the name nitroso- ferrous potassimn sulphide is given. Salts correspondiug with each of the two first-mentioned acids have been prepared. They are all converted into nitroprussides by the action of potassium cyanide. w. c. w. Potassium and Ammonium Ferric Chromates. By C. HENSGEN (Rer., 12,1656-1658) .-These salts separate out in dark-red plates containing 4 mols. H20 [K or NH,], when a solution containing ferric chloride and ammonium or potassium dichromate, is slowly evaporated.They have the formula KzCr04.Fe2(Cr04)3.4H,0. The ammonium salt is decomposed by cold water and also by the action of heat. w. c. w. Contributions to the Chemistry of the Chrornammonium- compounds. By S. 31. JORGENSER (J. p r . Chem. [el, 20, 105-145. -1. C l ~ l o r o p u ~ p u ~ e o - c l ~ ~ o ~ ~ a i ~ ~ ~ ~ ~ Salts.-The starting point for these salts is the chloride, CI,(Cr210NH3) C1,. This is prepared by reducing violet chromic chloride in a stream of pure dry hydrogen, at a red heat, and adding it to a solution of ammonium chloride in strong ammonia (25 grams Cr,CI, reduced to Cr2C14, 90 grams NH4C1, 0.5 litre ammonia). Air is then passed through the blue liquid until oxidation is complete. Two litres of crude hydrochloric acid are added, and the mixture is boiled for some minutes, during which chloropurpureo-chromium chloride separates as a carmine-coloured powder.The crude chloride is washed with a mixture of equal volumes of hydrochloric acid and water, dissolved in very weak sulphuric acid, and filtered into a great excess of strong cold hydrochloric acid. The resulting precipitate is boiled with hydrochloric acid, and washed first with a mixture of acid and water, then with alcohol, and finally dried in the air a t the ordinary temperature. This chloride is also a bye-product in preparing ClAve’s tetramine chloride by the following process :-Ammonium dichromate is I educed by boiling with hydrochloric acid and alcohol, and after addition of ammonium chloride the liquid is evaporated to dryness.The dry residue is then dissolved in strong ammonia ; strong hydrochloric acid is added, and the crystals which are deposited on standing are washed first with a mixture of equal parts of hydrochloric acid and water until free from ammonium chloride, then with water, and finally dried. It consists of a mixture of chromium-tetramine chloride and chloropnrpureo chloride. This mixture must be protected from the action of light during the remaining operations. It is dissolved in cold water, and shaken with a solution of one part of ammonium sulphate in five parts of water. The tetramine chlorosulphate precipitates in crystals ; the filtrate containing the purpureochloride is mixed with hydrosilico- fluoric acid, and gives a precipitate of chloropurpureo-chromium silico- fluoride.After being washed, it is treated with dilute hydrochloricIN ORGANIC CHEMISTRY. 11 acid, to reconvert it into chloride ; after reprecipitation with strong acid and washing, first with dilute acid and then with alcohol, it is quite pure. The two salts may also be separated by taking advantage of the insolubility of the componnd C1,( CrJONH,) ( HgsC1,),, produced by adding mercuric chloride to the mixture. The mercury-compound atter washing is easily reconverted into the chloride by treatment with h-j-drochloric acid. Chloropurpureo-chromium chioride is a red crystalline powder, of a purer red colour than the corresponding cobalt-compound. It appears to crystallise in octohedra of sp. gr. 1.687. It dissolves in 154 parts of water a t 16", and forms a violet-red solution, which, on exposure to light, deposits chromium hydrate.When it is kept, even in the dark, or boiled, roseochromium chloride is produced. It gives the follow- ing reactions :-With sodium hypochlorite, nitrogen is evolved, and the chromium is oxidised to chromic acid. Its solution gives a preci- pitate with strong hydrochloric acid, owing to the insolubility of the chloride in acid. With hydrobromic acid, it gives a crystalline preci- pitate of the bromide, and with solid potassium iodide one of the iodide. When boiled with potassium cyanide, it turns yellow. Strong nitric acid precipitates the chloro-nitrate. Hydrosilicofluoric acid throws down the red crystalline chlorosilicofluoride. Platinic chloride precipitates, even from a very dilute solution, the chloropurpureo- chromium platinochloride.Sodium platino-bromide gives an ana- logous precipitate. Mercuric chloride gives red needles of the double salt. Precipitates are also produced by potassium mercuribromide and iodide, by sodium dithionate, potassium chromate, and dichromate, ammonium molybdate, and phosphomolybdate, and by picric and oxalic acids. I n these respects this salt closely resembles the analogous cobalt salt. On treatment with silver nitrate only four atoms of chlorine are removed, and the chloro-nitrate is formed. By rubbing the solid chloride with silver oxide and water, raseochromium hy- drate is formed. It is a, deep red alkaline liquid, which gives a yellowish-red precipitate of roseochromium bromide with strong hydrobromic acid ; this, when boiled with hydrobromic acid, changes to bromopurpureo-chromium bromide.In the chloro-chloride, the radicle chlorine is so firmly combined that hot strong sulphuric acid does not expel i t ; the product is acid chloro-sulphate. Towards reducing agents, however, the chromium series differ in behavionr from the cobalt series, for the chromium is not so easily re- duced. With snlphuretted hydrogen, or with ammonium sulphide, the purpureo-cobalt-compounds give cobalt sulphide, but the purpui-eo- chromium compounds suffer no change, except the forniation of a crystalline pnrpureopolysulphide, if the ammonium sidphide contains much free sulphur. The cobalt salts are also reduced by potassium ferrocyanide, whereas the chromium salts give a precipitate of ferro- cyanide of chloropurpureo-chromium.The latter part of this paper is occupied with detailed descriptions and analyses of numerous salts of chloropurpureo-chromium chloride, prepared by double decomposition. They have all a red or orange-red colour, and closely resemble the corresponding salts of chloropurpureo- cobalt. W. R.12 ABSTRACTS OF CHEMICAL PAPERS. Behaviour of Copper- Ammonium Chloride with Ferrous Sulphide. By W. F. K. STOCK (C'hern. News, 40, 159).--In the course of recent experiments on the accurate determination of carbon in iron and steel containing much sulphur, i t appeared desirable to ascertain definitely in what manncr the reagent used for the carbon separation acted on the iron sulphnr compound, but as the composition of that compound is unknown, it was thought best t80 experiment with a sulphide of known quality.The process used for the carbon separa- tion was McCreath's method based on treating a weighed quantity of iron or steel with a hot concentrated solution of copper ammonium chloride. From the results, it was evident that the actions of the double cop- per ammonium salt upon iron carbide and upon iron sulphide were pre- cisely analogous, and that tbe method held out no hope of separation. It only remained to find to what extent the decomposition had pro- ceeded during the exposure, which was for half an hour a t nearly boiling heat, It is shown that allowing for oxidation during washing, &c., it may safely be assumed that 80 per cent. of the original sul- phide was decomposed by the double copper salt with liberation of the corresponding amount of free sulphur. A second experiment was made with native ferric sulphide, which was very finelypowdered and exposed a t boiling heat for over an hour t20 the copper solution, but although some free sulphur was obtained, the deconiposition was far from complete.Action of the HaloTd Acids on the Sulphates of Mercury. By A. DITTE (Ann,. Qhim. Phys. [ 5 ] , l7,120--128).-1t has beenstated that dry hydrochloiic acid gas decomposes mercuric sulphate, forming mercuric chloride and free sulphurie acid, and t h a t since the chloride is more volatile than the acid, the former can be separated by sublima- tion at a suitable temperature ; and further, that hydriodic and hydro- cyanic acids act in a similar manner. The author shows that these statements are wholly incorrect.When dry hydrochloric acid is passed over mercuric sulphnte a t ordinary temperatures, no reaction ensues : on warming the sulphate, absorption takes place, with disengagement of heat and without forma- tion of water ; on heating more strongly, the product sublimes, but the crystals hare no resemblance whatever to sublimed mercuric chlo- ride. An analysis of the crjstals showed that their composition exactly corresponded with the formula HgSO, 2HCl; they are very hygrometric, dissolving in water apparently without decomposition. When volatilised they do not disengage hydrochloric acid. Hydrobromic acid gas acts in a precisely similar manner, forming the compound HgS01.2HBr.The body HgSO,.BHCl is likewise formed with great facility by gently heating a, mixture of sulphuric acid and mercuric chloride, in molecular proportions ; or by dissolving the neutral sulphate in hydro- chloric acid, and evaporating until crystals are obtained. The action of hydriodic acid is different; sulphuric acid decom- poses mercuric iodide on heatir,g, no compound o f thc formula €€gSOa.2HI being formed. In the same manner, solution of hydriodic D. B.MINERALOGICAL CHEMISTRY. 13 acid in excess, partly or wholly decomposes mercuric sulphate, but no definite combination takes place. Hydrofluoric and hydrocyanic acids are without action on mercuric sulphate. Basic mercuric sulphate, twpeth wahzeral, acts with regard to hydro- chloric acid in a manner analogous to mercuric sulphate, but it ab- sorbs 6 molecules of HCl for every molecule of sulphate, forming the compound HgS04.2Hg0.6HC1 ; the latter on being heated strongly, breaks up into the mercuric compound and mercuric chloride, Hg3S06.6HC1 = HgS04.2HCl + 2HgC12 + ‘2H20. thus :.- A precisely similar compound is formed by the action of either gaseous or liquid hydrobromic acid on tnrpeth mineral.A New Salt of an Iridammonium. By K. BIRNBAUV (Bey., 12, 1544--1547).-By boiling the double salt of iridic sulphite and sodium sulphite with hydrochloric acid, an acid salt is formed pre- sumably of the formula Irz( S03)3.3NaHS03. When its solution is saturated with gaseous ammonia, a compound crystallises out in red crusts, having the formula Ir2Naa( S03)G(NH3),.10H20.The author assigns to it the constitutional formula- SO3 : Ir(NH3)3 NH4 Na so,< 1 SO3 : Ir(N%)s J. W. + 3 >s03.0H2c), and supposes the SO3 group t o be i n combination with an irid- ammonium of the formula (NH&Ir2. W. R.2 ABSTRACTS OF CHEMICAL PAPERS.Inorganic Chemistry.Purification of Hydrogen. By A. LIONET (Compt. rend., 89,440). -Metallic copper removes all the impurities from hydrogen,except hydrogen phosphide. hydrogen silicide, and hydrocarbons.Cuprous oxide removes all but hydrogen silicide and the hydrocarbons.Cupric oxide removes all but the hydrocarbons. The best form ofcup& oxide is that precipitated by potash from a, solution of cupricNon-existence of Nascent Hydrogen. By D. TOMNASI (Chen7.News, 40, 171) .-Reduction of Potassium Perch1ovate.--It was foundthat when chemically pure potassium perchlorate was submitted to theaction of various reducing agents, giving nascent hydrogen, it didnot undergo reduction, although it is easily transformed into chlorideby the action of a compound which does not set hydrogen free, viz.,sodium-hydrogen sulphite.The author asks, how can it be explainedthat this same perchlorate which undergoes no reduction by means ofnascent hydrogen, as shown by sixteen different reactions, can bereduced by the hydrogen disengaged by the action of zinc on sodium-hydrogen sulphite. Although Wurtz declares himself to be in favourof the naacent state of bodies, it appears to the author unlikely thatwhen hydrogen is set free by a reaction, it can be in the state of iso-lated atoms.It is known that copper, even when finely divided, is butvery slightly attacked by hydrochloric acid at the ordinary tempera-ture, although copper hydride is decomposed very energetically.“ How can this fact be explained,” justly remarks Wurtz, in his AtomicTheory, “ i f to the affinity of chlorine for copper be not added theaffinity of the two atoms of hydrogen to form a molecule ?” Thisreasoning may be said to apply equally to all the reactions producinghydrogen ; for example, we know that by the action of hydrochloricacid on zinc, there neither is nor can be any hydrogen in the state ofisolated atoms, as Wurtz thinks, and the special properties of nascenthydrogen can be attributed osly to the heat which accompanieshydrogen while it is being set free.It is therefore impossible to con-clude that hydrogen can be active only in the molecular state, as hun-sulphate, and dried at 100”. C. w. wINORGANIC CKEMISTRY. 3dreds of examples prove to us that in many cases it is not the mole-cule of hydrogen that acts, but its atom.I n conclusion it is mentioned that the recent results of Gladstoneand Tribe coincide entirely with the above hypothesis. These chemists,as is known, consider the different allotropic states of hydrogen a sordinary hydrogen in different physical conditions.Active Condition of Oxygen induced by Nascent Hydrogen.By F. HOPPE-SEYLER (Ber., 12, 1551-1555)..-Every attempt toexplain the vital processes of animals and plants necessarily impliesthe assumption of a cause whereby the oxygen is rendered actit-e.Hydrogen is evolved in the free state only when oxygen is not present ;and most cuTiously, in presence d oxygen, nascent hydrogen leads toenergetic oxidation of any oxidisable substance which may happen tobe present. The author hasproved the fact by two very st'riking examples.The alloy of palla-dium with hydrogen discovered by Graham, when placed in oxygel),gives rise to water, owing to combination of the hydrogen of the alloywith the oxygen. This, of course, is well known, but it is not so wellknown that if indigo be present it is decolorised, and then destroyed ;that a mixture of starch withpotassium iodide is first turned blue, and.that the starch is then completely oxidised ; that ammonia is oxidisedto ammonium nitrite; that benzene is oxidised to phenol; and thattoluene yields benzoic acid.Perhaps a still more remarkable instanceis the oxidation of rock-oil by metallic sodium in presence of the smallquantity of aqueous vapour which comes in contact with it. The pro-ducts appear to be acetic and caproic acid, and perhaps butyric acid;and the hard crust which forms rmnd sodium, when it is kept underrock-oil, is really a product of oxidation of the oil, and in fact may bemade to yield a number of the higher members of the fatty acid series,It thus appears to be the case that when nascent hydrogen acts onoxygen, it renders the latter gas also naseent, or a t least active.Is Ozone produced during the Atmospheric Oxidation ofPhosphorus ? By C.T. KISGZETT (Chem. News, 40, 96).-It isgenerally believed that ozone is produced during the atmosphericoxidation of phosphorus, but the author considers it to be improbablethat ozone is formed by the asrial oxidation of phosphorus, consideringthe constitution of ozone. Moreover, as peroxide of hydrogen is theonly known agent which resembles ozone in its general properties,and it is known that hydrogen peroxide is produced in various pro-cesses of slow oxidation, it would seem likely that it is this substancewhich is produced in connection with the oxidation of phosphorus. Inaddition to various objections which the author has pointed out t oviewing the active agent produced in the atmospheric oxidation of tur-pentine as ozone, there are many considerations which lead to the con-clusion that the active agent is peroxide of hydrogen.There is no known process of slow oxidation which has been esta-blished to produce ozone.In various writings on this subjectobservers have always relied on properties which are common to ozoneand hydrogen peroxide, and have never instituted volumetric inves-D. B.This is specially the case with ferments.W. R.b 4 ABSTRACTS OF CHEMICAL PAPERS.tigations, which are alone sufficient to decide the question. On theother hand, several processes of slow oxidation are known, in whichperoxide of hydrogen is formed, as for instance, those relating to etherand the t,erpenes ; and it is thought that as hydrogen peroxide is formedin each of these cases as a secondary product, clue to the action of wateron a peroxide, so also the oxidation of phosphorus by air gives rise toan oxide which generates peroxide of hydrogen by contact with water.I n conclusion, the author mentions that until it has been provedthat the active agent produced in the aGrial oxidation of phosphorushas the volumetric relat'ions of ozone, such very decided statements asare to be found in chemical text-books should not be made.D. B.New Method of forming Hyponitrites and Hydroxylamine.By W. ZORN (Bey., 12, 1509--1511).-This consists in the electrolysisof a nitrite, using mercury electrodes. Thorpe describes an experimentin which he passed a current from platinum electrodes through a solu-tion of potassium nitrite, and a t the negative pole only hydrogen wasevolved.On using mercury electrodes, however, if the current isstopped as soon as ammonia begins to be evolved, the liquid, afterneutralisation and addition of silver nitrate, gives a copious precipitateof silver hyponitrite. I n this reduction, hydroxylamine is also formed,and it is necessary to remove it from the solution by precipitationwith mercuric oxide, before adding silver nitrate to precipitate thehyponitrous acid. Four Bnnsen's elements are sufficient for t'his reac-tion; it is recommended as an advantageous method of preparinghypo ni t ri t es . W. R.Experiments tending to show the Non-elementary Charac-ter Of Phosphorus.By N, [JOCKYER (Conzpt. rend., 89, 514).-Phosphorus heated in it tube with copper gives a gas exhibiting thespectrum of hydrogen ; heated done, phosphorus gives no gas. Phos-phorus a t the negative pole of a battery in a tube-apparatus (of whicha drawing is given), gives a large quantity of gas which shows thespectrum Df hydrogen, and is not phosphoretted hydrogen. c. w. w.By E. J. MAU-M S N ~ (Coinpt. rend., 89, 506).--Tn the preparation of ammoniumsulphide, the hydrogen sulphide which passes through the first bottlecarries ammonia, with it, and colourless crystals are deposited in theconnecting tube. These crystals have the composition NH,.HS. Whenthey are added to strong aqueous ammonia at 0", colourless crystalsare deposited in a few hours having the composition (NH,),HS.The author imagines the existence of two series of ammonium-compounds containing respectively excess of ammonia and excess ofhydrogen sulphide, 1 mol.of one of the constituents being unitedwith (2, - 1) molecules of the other. Members of one series mayunite with members of the other series, producing compounds likeHS(NH,)15.'L[(HS),NH3] = (HS)15(NH3)1,, which might be mistakenfor (NH3)HS.The compounds of ammonia with hydrochloric acid present analogiesCompounds of Hydracids with Ammonia.with the above compounds. c. w. wINORGANIC CHEMISTRY. 5Oxygen-acids of Sulphur. By E. J. MAUXEN~ (Contpt. Tend.,89, 422).-The action of iodine on barium thiosulphate gives rise totetrathionic acid, as observed by Fordos and Gelis, but seven otheracids should be produced, according to the proportions of iodine a i dthiosulphate employed.The acids, H2S201 and H2S609, have beenobtained. The latter is prepared by mixing 3 mols. of barium thio-sulphate and 2 atoms of iodine. The mixture becomes colourless inthree or fonr days. It is then filtered through cotton-wool, and thecrystals remaining behind are washed with alcohol. They are thenpure and have the composition Bas&& ; with silver nitrate, this saltgives a white precipitate, turning black, and the liquid a t the sametime becomes acid. The sodium salt crystallises in large, colourless,very soluble crystals, containing a large quantity of water.Basicity of Dithionic Acid. By H. KOLBE (J. pr. Chenz. [a],19, 485-4,Si).-As the author hams been unable to obtain an acid saltof this acid or a neutral salt containing two bases, he doubts the cor-rectness of the usually accepted view of the bibasicity of this acid,and is now inclined to the original supposition of Berzelius that it isa monobasic acid, and is represented by the formula S0,OH.In fact,that it contains the radicle SOz, but united with only one atom ofhydroxyl, that is, joined with only one atom of hydrogen by one atomof oxygen. On this supposition sulphur must exist in this acid as apentad.That the radicle sulphoxyl (SO,) may exist as a dyad in sulphuricacid, and as a monad in dithionic acid, appears to the author to be notmore improbable than the tetrad and dyad atomicities of tin in stannicand stannous compounds.Behaviour of Calcium Oxide with Carbonic Anhydride.ByK. BIMBAUN and M. MAHU (Ber., 12, 1547--1561).-The object of theexperiments described in this paper was to ascertain at what tempera-ture calcium oxide begins to absorb carbonic, anhydride, and a t whattemperature calcium carbonate begins to dissociate. If was foundthat the lowest temperature at which absorption takes place is themelting point of zinc, 415-3", and that the carbonate dissociates par-tially at that temperature, although dissociation begins a t a muchlower one. The amount of anhydride absorbed by the oxide is abouthalf an equivalent. W. R.c. w. w.A. J. C.Calcium Phosphite. By R. ROTHER (Pharm. J. Trans. [3], 10,286).--Ry adding sugar to a solution of calcium hypophosphite, thelatter is precipitated, a circumstance which 'is generally unknown, andhence it is highly probable that a dense syrup of the mixed hypophos-phites contains little if any calcium salt.In the presence of iron, a,precipitate is also formed ; the proportion of sugar, however, has 110share in this change. Ferric hypophosphite, when contained in sucha sugar, is said to revert easily to th.e ferrous form, and it was foundthat' the ferrous salt readily oxidises even in the presence of sugar,forming the dark green and very soluble ferroso-ferric hypophosphite.Ferric hypophosphite occurs in several modifications, of which the crys6 ABSTRACTS OF CHEMICAL PAPERS.talline variety is almost insoluble in hypophosphorous acid, and henceit is this compound which deposits from the syrup.It was attemptedto regenerate this sediment by reducing it to the ferrous condition bythe intervention of sulphurous acid. However, the latter was de-eomposed into sulphuric acid, sulphur, and oxygen, which reactedwith the hypophosphorous acid of the sediment,, and converted itinto phosphorous acid. When solutions of calcium bypophosphite andaodium sulphite are mixed, calcium sulphite is precipitated, which isredissolved by hydrochloric acid, no further reaction setting in untilboth the hypophosphorous and sulphurous acids are entirely freed bythe addition of enough hydrochloric acid. The solution, after filteringoff the sulphur, yields, on the addition of ammonia, a crystalline pre-cipitate of calcium phosphite.The latter, however, contains less thanhalf of the phosphorous acid generated, owing to the fact that hypo-phosphorous acid is monobasic, whilst phosphorous acid is dibasic, andalso that a small loss of calcium is incurred as sulphate. By treatingthe liquid filtered from the sulphur with calcium carbonate, a muchlarger amount of phosphite is thrown down than with ammonia. Theaddition of a solution of calcium chloride to the filtrate causes a furtherprecipitation of phosphite, which becomes more distinctly crystalline,and subsides more rapidly when a, very little ammonia has been addedto the precipitate.Calcium phosphite is a white crystalline powder, which when heatedin a test-tube evolves spontaneously inflammable hydrogen phosphideaccompanied by slight detonations.At a, certain temperature, it sud-denly becomes incandescent, and leaves a residue qf calcium phos-phate. D. B.Zirconium Derivatives. By S. R. PAYK~LL (Ber., 12, 1719).-The moist hydrated oxide, ZrO(OH),, absorbs carbonic anhydridefrom the atmosphere. By treating zirconium sulphate with thehydrate, one amorphous and two crystalline basic salts were obtained,viz., Zr02.S03+zAq, 3ZrO2.4SO3+15H,O, and 6Zr02.7S03+ 19H20.The sulphate forms with pofassium sulphate basic double salts, e.g.,Researches on Erbia. By LECOQ DE BOISBAUDRAN (Cow@. rend.,89, 516).--The author examined the spectrum of erbia from varioussourceEi, and with one exception the spectra thus obtained exhibitedidentical lines of the same intensity.The exception was the erbiaderived from samarskite. The principal differences were that withsamarskite-erbia, the ray in the green, X == 536.3, is much more in-tense that the ray X = 540.9, whilst in the other erbias the differenceis but slight; and the line in the red, h = 640.4, is as strong, orstronger, than X = 653.4; whereas i n the other erbias, the lineh = 653.4 is much stronger than k = 640.4.Two specimens of erbia were taken, one nearly pure, giving thenormal spectrum, the other from samarskite, and containing a largequantity of yttria. On fractionation by means of ammonia and sub-sequently by potassium or sodium sulphate, a portion was obtainedfrom the first which gave a spcctrum resembling that of the second,K,0~60,+2(12~.0.02.50~) + 1%H,O.w. c. wINORGANIC CHEMISTRY. 7and a portion was obtained from the second giving ft spectrum likethat, of the first.The author is continuing this research. c. w. w.Two New Elements in Erbia. By P. T. CLEVE (Compt. rend.,89, 478).-In attempting to obtain pure erbia, the author was led tosuspect the existence of two other earths in the erbia obtained. Themixture was therefore fractionated, and the different fractions ex-amined spectroscopically. It was found that, in addition t o bandscommon to all, one band X = 6840 was strong in the residues rich inytterbia, and want’ing in those containing yttria and erbia, whilst twoothers, X = 6400 and 5360, were strong in the yttria and ytterbiaresidues.The colour of the fraction treated for ytterbia was a violet-rose,whilst the yttria fraction had an orange tint.The metal characterised by the first band, X = 6840, the author pro-poses to name thuZium ; it would have an atomic weight of about 113(the oxide being TmO).Pure erbia, to which must be attributed thecommon bands, has probably an atomic weight of 110-111. Its oxidehas a clear rose colonr. The third metal, holmium, is charncterised bythe bands X = 6400 and 5360 ; it should have an atomic weight lessthan 108 ; its oxide seems t o be yellow. c. w. w.Spectra of the Earths of the Yttria-group. By J. L. SORET(Compt. rend., 89, 521).-The author considers that the new earth,ldmiu, discovered by ClBve, is identical with an earth discovered byDelafontaine and Marignac, whose absorption-spectrum was describedby himself (Compt.ren,d., April 29, 1878), and to which Delafontainegave the name plziZ@pia. CIBre’s holmium is characterised by twobands X = 640 and X = 536, and these two belong likewise t o philip-pium, which is characterised by several other bands.Clhe’s second earth, thdia, is characterised by a red ray X = 684.The author claims to have indicated the existence of this element also( A ~ c h . Sci., 63, 99). Marignac also showed the probable existence ofthis earth in the products rich in philippia and having a low equiva-lent. c. w. w.Scandium. By P. T. CLEVE (Compt. rend., 89, 419).-This metaloccurs only in gadolinite (0.002 to 0.003 per cent.) and yttrotitanite(0.005 per cent.).Scandium forms but one oxide, scandia, Sc,03; thecomposition of which is proved by that of potassium scandium oxalate,and of the double sulphates of scandium with the sulphates of potas-sium and with ammonium. 8 to 10 grams of scandinm oxide, havinga molecular weight of 106, agreeing with the number obtained byNilson, yielded, by repeated decompositions of its nitrate, about 1 gramof a white oxide. This was converted into sulphate, and 1.451 gramsof this sulphate yielded 0.5293 gram of scandium oxide.The atomic weight of the metal is therefore 44.91, and the mole-cular weight of the oxide, considered as ScO, is 45.94 (? 60.91 =44.91 + 16), diflering greatly from the lowest number found byNilson, viz., 105.83. The author considers that this is due to a larg8 ABSTRACTS OF CHEMICAL PAPERS.admixture of ytterhia in Nilson’s scandia.The atomic weight, asdetermined by the decomposition of the nitrate, is 45.12. The atomicweight of scandium may therefore be takeu as 45.Scandizim oxide o r Scandin, Sc203? is a light, white, infusible powderof sp. gr. 3.8, resembling magnesia; it is scarcely soluble even instrong acids, but more so than alumina. Sulphuric acid converts itinto a bulky white mass of sulphate ; hydrochloric acid dissolves theoxide more easily than nit,& acid.Scandium hydrate is a bulky white precipitate, drying up to semi-transparent fragments. It does not absorb carbonic acid from theair, is insoluble in ammonia or in potash, and does not decomposeammonium salts when heated with them.Scandium salts are colourless or white, and have an acid, astringenttaste, very different from the sweet taste of the salts of the yttriummetals.The sulphate does not form distinct crystals; the nitrate,oxalate, acetate, and formate, are crystallisab!e. The chloride ex-hibits the following reactions :-It gives no spectrum when heated init gas flame. Potash and ammonia produce bulky white precipitates,insoluble in excess ; tartaric acid prevents the precipitation byammonia in the cold, but on heating an abundant precipitate falls.Sodium carbonate gives a precipitate, soluble in excess. Sulphurettedhydrogen produces no change ; ammonium sulphide precipitates thehydrate. Sodium orthophosphate gives a gelatinous precipitate.Oxalicacid give8 a curdy precipitate, quickly becoming crystalline ; this preci-pitate dissolves in strong acids, and cannot be completely reprecipitated.Although it appears more soluble than the oxalates of the otheryttrium metals, it is found in the first precipitates in the fractionalprecipitation of a mixture of scandium and ytterbium by oxalic acid.Acid potassium oxalate precipitates a crystalline double salt. Sodiumhyposulphite precipitates a boiling solution easily, but incompletely.Sodium acetate behaves similarly. The sulphates of potassium andsodium precipitate crystalline double salts, soluble in a saturatedsolution of the precipitant.The author describesin a previous paper (BUZZ. SOC. Chinz., 31, 486)the chloride, nitrate, and sulphate of scandium ; the double sulphates,the double oxalate, Sc,(C,O,),.K2C2O4.3H,O ; the acetate, the formate,and selenite, 3Sc,0,.10SeO2.4H2O.The existence of scandium was predicted by Mendelejeff, and its pro-perties described under the name of ekabor (Anmalen, Sq., 8, 1.13).The following table shows a comparison of the observed properties ofscandium witlh those predicted of ekabor.SC,(SO~),.~K$~O~, S C , ( S O ~ ) , .~ N ~ S O ~ . ~ ~ H ~ O , S C ~ ( SOi)s.(NH4)2SO4 ;8upposed Characters of Ekabor.Atomic Weight = 44.Ekabor should have but onestable oxide, Ebz03, :t strongerbase than alumina, which itshould resemble in mauy respects.It should be less basic than mag-nesia.Observed Ch,aracters of Scandium.Atomic Weight = 45.Scandium forms only one oxide,Sc203, more energetic than alu-mina, and less so than magnesiaINORGANIC CHEMISTRY.9Ekabor oxide should resembleyttria, although less basic. The se-paration of these two earthswill bedifficult, depending on differencesof solubility or of basicity.Oxide of ekabor is insoluble inalkalis; it will probably not de-compose ammonium salts.The salts should be colourless,and give gelatinous preci.pitateswith KHO, Na2C03, and HNaS02.The sulphate should form adouble salt with K2S04, havingthe composition of alum, but notisomorphous with it.But few ekabor salts shouldcrystallise well.The anhydrous chloride shouldbe decomposed by water, givingoff hydrochloric acid.The oxide is infusible a,nd so-luble with difficulty in acids afterignition.The density of the oxide wouldbe about 3.5.Scnndia is less basic than yttria,and their separation depends ondifferences of solubility betweentheir nitrates.Scandium hydrate is insolublein alkalis ; it does not decomposeammonium chloride.The salts are colourless, andgive gelatinous precipitates withKHO, Na2C03, and HNaS02.Potassium - scandium sulphateis anhydrous, but otherwise cor-responds in composition withalum.Scandium sulphate does notform distinct crystals, but thenitratc, acetate, and formatme crys-tallise well.The crystallised chloride is de-composed by heat, giving offhydrochloric acid.The oxide is an infusiblepowder, nearly insoluble in acidsafter ignition.The density of the oxide = 3.8.c. w. w.Absorption of Nitrogen Dioxide by Ferrous Salts. ByJ. GAY (Compt. rend., 89, 410).-Peligot assigned the formula4FeS04.N20, to the compound of nitrogen dioxide with ferrous su1-phate. The author finds that the composition of this body depends ont'he temperature and on the pressurc of the residual nitrogen dioxide.At temperatures up to 8" and at the ordinary pressure, the com-pound formed has the formula 3FeS01.N202 ; from 8" to 25", at theatmospheric pressure, i t has the formuh 4FeSO4.N2O2 ; at tempera-tures above 25" nitrogen dioxide is rapidly given off, and the com-pound 5FeSO4.N,O, is produced.All these compounds exhibit very marked tensions of dissociation,a fact which explains their decomposition in st vacuum ; they are alsodecomposed by a current of hydrogen.Reducing agents, such as ferrous oxide, reduce the nitrogen dioxide,a mixture of monoxide and free nitrogen being evolved, while thetemperature rises sensibly.c. w. w.Nitrosothioferrates. By J. 0. R l ~ ~ ~ (Ber. 12,1715-1717).-By the action of potassium nitrite and ammonium sulphide on aferrous salb, Roussin (Ann. Chim. Phys. [3], 52, 285) obtained a blacksubstance, which was afterwards examined by Porczinsky (Annden,125, 302), Demel (Be?-., 12, 46l), and Pawel (ihid., 12, 1407). Thisis named by the author ammoiziunz nitrosoferrclthiofen.ate10 ABSTRACTS OF CHEMICAL PAPERS.On the addition of an alkali ferrous oxide is precipitated, andpotassium nitrosothioferrate is obtained.The free acid which isliberated when this salt is treated with hydrochloric acid, combineswith alkaline sulphides to form a red salt, to which the name nitroso-ferrous potassimn sulphide is given.Salts correspondiug with each of the two first-mentioned acids havebeen prepared. They are all converted into nitroprussides by the actionof potassium cyanide. w. c. w.Potassium and Ammonium Ferric Chromates. By C.HENSGEN (Rer., 12,1656-1658) .-These salts separate out in dark-redplates containing 4 mols. H20 [K or NH,], when a solution containingferric chloride and ammonium or potassium dichromate, is slowlyevaporated. They have the formula KzCr04.Fe2(Cr04)3.4H,0. Theammonium salt is decomposed by cold water and also by the action ofheat.w. c. w.Contributions to the Chemistry of the Chrornammonium-compounds. By S. 31. JORGENSER (J. p r . Chem. [el, 20, 105-145.-1. C l ~ l o r o p u ~ p u ~ e o - c l ~ ~ o ~ ~ a i ~ ~ ~ ~ ~ Salts.-The starting point for thesesalts is the chloride, CI,(Cr210NH3) C1,. This is prepared by reducingviolet chromic chloride in a stream of pure dry hydrogen, at a redheat, and adding it to a solution of ammonium chloride in strongammonia (25 grams Cr,CI, reduced to Cr2C14, 90 grams NH4C1,0.5 litre ammonia). Air is then passed through the blue liquid untiloxidation is complete. Two litres of crude hydrochloric acid areadded, and the mixture is boiled for some minutes, during whichchloropurpureo-chromium chloride separates as a carmine-colouredpowder.The crude chloride is washed with a mixture of equal volumesof hydrochloric acid and water, dissolved in very weak sulphuricacid, and filtered into a great excess of strong cold hydrochloric acid.The resulting precipitate is boiled with hydrochloric acid, and washedfirst with a mixture of acid and water, then with alcohol, andfinally dried in the air a t the ordinary temperature. This chloride isalso a bye-product in preparing ClAve’s tetramine chloride by thefollowing process :-Ammonium dichromate is I educed by boiling withhydrochloric acid and alcohol, and after addition of ammoniumchloride the liquid is evaporated to dryness. The dry residue is thendissolved in strong ammonia ; strong hydrochloric acid is added, andthe crystals which are deposited on standing are washed first with amixture of equal parts of hydrochloric acid and water until free fromammonium chloride, then with water, and finally dried.It consistsof a mixture of chromium-tetramine chloride and chloropnrpureochloride. This mixture must be protected from the action of lightduring the remaining operations. It is dissolved in cold water, andshaken with a solution of one part of ammonium sulphate in five partsof water. The tetramine chlorosulphate precipitates in crystals ;the filtrate containing the purpureochloride is mixed with hydrosilico-fluoric acid, and gives a precipitate of chloropurpureo-chromium silico-fluoride. After being washed, it is treated with dilute hydrochloriIN ORGANIC CHEMISTRY.11acid, to reconvert it into chloride ; after reprecipitation with strongacid and washing, first with dilute acid and then with alcohol, it isquite pure. The two salts may also be separated by taking advantageof the insolubility of the componnd C1,( CrJONH,) ( HgsC1,),, producedby adding mercuric chloride to the mixture. The mercury-compoundatter washing is easily reconverted into the chloride by treatmentwith h-j-drochloric acid.Chloropurpureo-chromium chioride is a red crystalline powder, of apurer red colour than the corresponding cobalt-compound. It appearsto crystallise in octohedra of sp. gr. 1.687. It dissolves in 154 partsof water a t 16", and forms a violet-red solution, which, on exposure tolight, deposits chromium hydrate.When it is kept, even in the dark,or boiled, roseochromium chloride is produced. It gives the follow-ing reactions :-With sodium hypochlorite, nitrogen is evolved, andthe chromium is oxidised to chromic acid. Its solution gives a preci-pitate with strong hydrochloric acid, owing to the insolubility of thechloride in acid. With hydrobromic acid, it gives a crystalline preci-pitate of the bromide, and with solid potassium iodide one of theiodide. When boiled with potassium cyanide, it turns yellow. Strongnitric acid precipitates the chloro-nitrate. Hydrosilicofluoric acidthrows down the red crystalline chlorosilicofluoride. Platinic chlorideprecipitates, even from a very dilute solution, the chloropurpureo-chromium platinochloride.Sodium platino-bromide gives an ana-logous precipitate. Mercuric chloride gives red needles of the doublesalt. Precipitates are also produced by potassium mercuribromideand iodide, by sodium dithionate, potassium chromate, and dichromate,ammonium molybdate, and phosphomolybdate, and by picric and oxalicacids. I n these respects this salt closely resembles the analogouscobalt salt. On treatment with silver nitrate only four atoms ofchlorine are removed, and the chloro-nitrate is formed. By rubbingthe solid chloride with silver oxide and water, raseochromium hy-drate is formed. It is a, deep red alkaline liquid, which gives ayellowish-red precipitate of roseochromium bromide with stronghydrobromic acid ; this, when boiled with hydrobromic acid, changesto bromopurpureo-chromium bromide.In the chloro-chloride, theradicle chlorine is so firmly combined that hot strong sulphuric aciddoes not expel i t ; the product is acid chloro-sulphate.Towards reducing agents, however, the chromium series differ inbehavionr from the cobalt series, for the chromium is not so easily re-duced. With snlphuretted hydrogen, or with ammonium sulphide,the purpureo-cobalt-compounds give cobalt sulphide, but the purpui-eo-chromium compounds suffer no change, except the forniation of acrystalline pnrpureopolysulphide, if the ammonium sidphide containsmuch free sulphur. The cobalt salts are also reduced by potassiumferrocyanide, whereas the chromium salts give a precipitate of ferro-cyanide of chloropurpureo-chromium.The latter part of this paper is occupied with detailed descriptionsand analyses of numerous salts of chloropurpureo-chromium chloride,prepared by double decomposition.They have all a red or orange-redcolour, and closely resemble the corresponding salts of chloropurpureo-cobalt. W. R12 ABSTRACTS OF CHEMICAL PAPERS.Behaviour of Copper- Ammonium Chloride with FerrousSulphide. By W. F. K. STOCK (C'hern. News, 40, 159).--In thecourse of recent experiments on the accurate determination of carbonin iron and steel containing much sulphur, i t appeared desirable toascertain definitely in what manncr the reagent used for the carbonseparation acted on the iron sulphnr compound, but as the compositionof that compound is unknown, it was thought best t80 experiment witha sulphide of known quality.The process used for the carbon separa-tion was McCreath's method based on treating a weighed quantity ofiron or steel with a hot concentrated solution of copper ammoniumchloride.From the results, it was evident that the actions of the double cop-per ammonium salt upon iron carbide and upon iron sulphide were pre-cisely analogous, and that tbe method held out no hope of separation.It only remained to find to what extent the decomposition had pro-ceeded during the exposure, which was for half an hour a t nearlyboiling heat, It is shown that allowing for oxidation during washing,&c., it may safely be assumed that 80 per cent. of the original sul-phide was decomposed by the double copper salt with liberation of thecorresponding amount of free sulphur.A second experiment was made with native ferric sulphide, whichwas very finelypowdered and exposed a t boiling heat for over an hourt20 the copper solution, but although some free sulphur was obtained,the deconiposition was far from complete.Action of the HaloTd Acids on the Sulphates of Mercury.By A.DITTE (Ann,. Qhim. Phys. [ 5 ] , l7,120--128).-1t has beenstatedthat dry hydrochloiic acid gas decomposes mercuric sulphate, formingmercuric chloride and free sulphurie acid, and t h a t since the chlorideis more volatile than the acid, the former can be separated by sublima-tion at a suitable temperature ; and further, that hydriodic and hydro-cyanic acids act in a similar manner. The author shows that thesestatements are wholly incorrect.When dry hydrochloric acid is passed over mercuric sulphnte a tordinary temperatures, no reaction ensues : on warming the sulphate,absorption takes place, with disengagement of heat and without forma-tion of water ; on heating more strongly, the product sublimes, butthe crystals hare no resemblance whatever to sublimed mercuric chlo-ride. An analysis of the crjstals showed that their compositionexactly corresponded with the formula HgSO, 2HCl; they are veryhygrometric, dissolving in water apparently without decomposition.When volatilised they do not disengage hydrochloric acid.Hydrobromic acid gas acts in a precisely similar manner, formingthe compound HgS01.2HBr.The body HgSO,.BHCl is likewise formed with great facility bygently heating a, mixture of sulphuric acid and mercuric chloride, inmolecular proportions ; or by dissolving the neutral sulphate in hydro-chloric acid, and evaporating until crystals are obtained.The action of hydriodic acid is different; sulphuric acid decom-poses mercuric iodide on heatir,g, no compound o f thc formula€€gSOa.2HI being formed. In the same manner, solution of hydriodicD. BMINERALOGICAL CHEMISTRY. 13acid in excess, partly or wholly decomposes mercuric sulphate, but nodefinite combination takes place.Hydrofluoric and hydrocyanic acids are without action on mercuricsulphate.Basic mercuric sulphate, twpeth wahzeral, acts with regard to hydro-chloric acid in a manner analogous to mercuric sulphate, but it ab-sorbs 6 molecules of HCl for every molecule of sulphate, forming thecompound HgS04.2Hg0.6HC1 ; the latter on being heated strongly,breaks up into the mercuric compound and mercuric chloride,Hg3S06.6HC1 = HgS04.2HCl + 2HgC12 + ‘2H20.thus :.-A precisely similar compound is formed by the action of eithergaseous or liquid hydrobromic acid on tnrpeth mineral.A New Salt of an Iridammonium. By K. BIRNBAUV (Bey.,12, 1544--1547).-By boiling the double salt of iridic sulphite andsodium sulphite with hydrochloric acid, an acid salt is formed pre-sumably of the formula Irz( S03)3.3NaHS03. When its solution issaturated with gaseous ammonia, a compound crystallises out in redcrusts, having the formula Ir2Naa( S03)G(NH3),.10H20. The authorassigns to it the constitutional formula-SO3 : Ir(NH3)3 NH4Naso,< 1SO3 : Ir(N%)sJ. W.+ 3 >s03.0H2c),and supposes the SO3 group t o be i n combination with an irid-ammonium of the formula (NH&Ir2. W. R

ISSN:0368-1769    

DOI:10.1039/CA8803800002

出版商:RSC    

年代:1880

数据来源: RSC

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MINERALOGICAL CHEMISTRY. 13 M i n e r a l o g i c a l C h e m i s t r y . Cobalt-glance. By P. GROTH (Jahrb. f. Min., 1878, 864-865). -In addition to the forms already known to occur on cobalt-glance, the author has observed two dyakisdodecahedrons, two trapezohedrons, and one triakisoctohedron. On cobalt-glance from Tunaberg, Sweden, he observed the following. combinations, viz. :- v m02 (1.) 9 . o . mom . 30+. - (2.) . 0. $0.2. +o+. 'L m 0 2 * 0 . 2 20% . - 2 - . o . 2 m02 20" (3.) 2 2 Crystals from Skutterud, near Modurn, in Norway, exhibited the following forms in combination, viz. : s2 . 0 . 20. 2 C. A. B. Cobalt-speis. By P. GROTH (Jahrb. f. Nin., 1878, 865).-Hitherto it has been considered doubtful whether the crystals of this mineral were holohedral or hemihedral, but the author has succeeded in prov-14 ABSTRACTS OF CHEMICAL PAPERS. ing the occurrence of pentagon dodecahedrons, and consequently the isomorphism of cobalt-speis and iron pyrites.On one crystal of cobalt- speis from Wolkenstein - and m* were observed. A large crystal from Schneeberg exhibited the following forms in combina- tion, viz. : mom. 0 . COO . 202 . m03 - and a dyskisdodecahedron, which couId not be more nearly determined. Sulphide of Silver (Silber-kies). By A. WEISBACH ( J ~ h r b . f. Xin., 1878,866) .-Argyropyrites ( Ag3Fe7S11) occupy an intermediate position, chemically speaking, between sternbergite (Ag,Fe6Sg) and argentopyrites (Ag3Fe9Su), and the same fact is observed in regard to its physical properties. Argentopyrites crystallises in the rhomhic system, the crystals from Marienberg being but small, whilst those from Freiberg attained a length of 3 mm.The prisms were terminated either by the basal terminal plane, which was macrodiagonally striated, or else log an obtuse pyramid, the Freiberg crystals being characterised also by a very distinet basal cleavage. The crystals exhibiting the obtuse pyramids in combination were probably “ penetration trillings.” mO5 2 2 ’ C. A. B. C. A. B. Bismuth Minerals from Norberg’s Mine, Wermland. By H. SJOGREX (Ber., 12, 1723).-Bismuth occurs in Wermland : lst, native, mixed with galena and pyrites; 2nd, as bjelkite, 2PbS.Bi2S,; and 3rd, as the new mineral gdenobismuthite, PbS.Bi,S,, W. C. W. Polysynthetical Twin-crystals of Oriental Spinelle. By J. STRGVER (Jahrb..f. Min,., 1878, 865-866).-This paper can only be thoroughly understood by reference to the drawings given. The author concludes that there are three groups of polysynthetical spinelle crystals, viz. : (1.) Those with one twin-axis in common. (2.) Those in which the twin-axes are not parallel to each other, but in which the “ twin-face ” is common to all, for instance, 8 form composed of three individuals having a face of cm0 in common, as twin-plane, and two of their twin-axes parallel to that face. Trillings were also observed resembling a tetrahedron, owing to the predomi- nation of an individual having a tetrahedral development. Some- times groups composed of four individuals were observed, having all the twin-axes parallel with the Qwin-planes (m0).(3.) Those in which there is no parallelism in the twin-axes, nor a twin-plane corn- mon to all the forms. C. A. B. Manganite. By P. GROTH (Jahrb. f. M k , 1878, 863--864).-The finest crystals of this mineral are found a,t Weld, and are characterised by the great number of forms occurring in combination. According to Haidinger, the hemihedry of this mineral is peculiar t o the pyramid 9 PZ, a fact which appears all the more singular when the great number of pyramids observed on manganite is taken into considera-MINERALOGICAL CHEMISTRY. 15 tion, and also that, in the case of the isomorphous mineral goethite, no such occurrence is observed. The author, on the contrary, did not observe a single instance of hemihedry, or even twins according to the law “ the twin-plane mP&,” although he examined one of the finest collections of Ilfeld manganite crystals.The results of his investiga- tion are briefly as follows :-1. Manganite must be considered as a holohedral mineral, hemihedral combinations being very rare. 2. Man- ganite crystals can be divided into four types, the first two being characterised by an almost entire absence of twins, according to the law “ the twin-plane a face of P& ” and the occurrence of intermediate forms, whilst the last two types are characterised by the crystals occurring nearly always as twins according to the above-mentioned law, and a more sharply-defined distinction of the types from each other. The following table will show this more clearly:- A. Long prismatic Type I. Prisms, and basal terminal plane pre- dominating. Type 11.Prisms, with macropyramids as termi- nals. (Type 111. Twins, with somewhat numerous I forms in combination, the basal terminal plane and obtuse macrodomes predominating. Short prismatic< Type IV. Twins, with very numerous forms I in combination, macropyramids predominat- From the above table it seems probable that an intimate connection exists between the twin formation and the number of forms occurring in combination. Occurrence of Manganese in Nordmark’s Mine, Wermland. By A. SJOGREN (Ber., 12, 1723).-1n this locality manganese is found as manganosite, MnO ; pyrochroite, MnOH,O ; hausmannite and manganese-spar, together with brucite, heavy spar, hornblende, and c ing. The third and fourth types are the rarest.C. A. B. garne t. w. c. w. Vanadinite. By T. NORVSTROM (Ber., 12, 1723).-Vandanite has been fouxd in the Undenas manganese dioxide mine in West Goth- land. A mineral has also been discovered a t Fahlun, containing 5 per cent. of selenium. w. c. w. Titanates from Smgland. By C. W. BLOMSTRAKP (Ber., 12, 1721 -1 723).-The following minerals were found a t Slattgkra, Alsheda, occurring in coarse granite :-1. Polycrase. 2. Titanqerous imn ore, remarkable on account of the water it contained ; and 3. A new mineral abhedite, which appears to occupy an intermediate position as regards composition between yttrotitanite and gr oothite. In this compound titanium dioxide plays the part of a base. w. c. w. Pseudomorphs of Calcite after Aragonite. By G. TOM RATH (Jahrb. f. A f i n ., 1878, 863).-The crystals in question came from Schemnitz, and were from 10 to 20 cm. in length and from 4 to 6 cm.16 ABSTRACTS OF CHEMICAL PAPERS. in breadth: they were terminated apparently by a brachydome, the space originally filled by aragode being taken up by calcite. One specimen, 7 cm. long, 4 cm. broad, and from 2 to 3 cm. thick, con- sisted of the outter shell of an aragonite crystal, which was built lip out of an aggregate of small, well-developed calcite crystals, exhibiting the following forms in combination, viz. : R3. - +R.mR, the crystals not occupying any regular position with regard to the original arago- nite crystal. C. A, B. Crystal-system of Leucite. By J. HIRSCHWALD (Jahrb. f. Miia., 1878, 867).-Hirschwald stated in a former paper that leucite might be considered as a mineral crystallising in the regular system, with a polysymmetrical development in the sense of the quadratic system.From further investigations he arrives a t the conclusion that a dif- ference in opinion aboui; the practical relationships of leacite is possible in the two following cases only, viz. :--1. Is the polysynthetical twin- formation a complete dodecahedra1 one, or does it only represent the faces of the pyramid ? 2. Have the imbedded crystals the interfacial angles (winkelwerthern) of 202, or have the apparently regular forms, without exception, the angles of the acuter lateral edge of the eight- sided pyramid ? Hirschwald considers that he has found a complete answer to these questions in the results of his investigations, and states that the imbedded leucite crystals have undoubtedly the interfacial angles of 202, whilst the optical properties prove a complete dodeca- hedral twin-formation.C. A. B. Composition of Eclogite. By E. R. RIESS (Jahrb.f. Mi%., 1878, 877) .-Eclogite is a non-felspathic crystalline rock which, in its simplest forms, consists of omphazite and garnet, whilst the varieties of this rock are produced by the occurrence of quartz, hornblende, cyanite, zoisite, or mica. The accessory minerals are zircon, apatite, titanite, epidote, iron-pyrites, magnetic iron-pyrites, and magnetite. Omphazite occurs as'an angite in short, thin prisms of a grass-green colour ; the rare smaragdite as a green hornblendic mineral. The garnet often contains numerous enclosures of zircon, quartz, &c., and is occasionally decomposed. Zircon occurs enclosed in large amount (in reddish-brown grains or greyish-yellow prisms, exhibiting P with mP and mPm, also twins, parallel to a face of Pm) i n the garnet and omphazite.The true eclogite is found imbedded in the strata of the crvstalline slates. and is often intimatelv associated with hornblendic .I d plagioclase garnet-rocks, but not with those containing omphaaite. C. A. B. Thaumasite. By G. LINDSTROM (Bey., 12, 1723).-This new mineral, having" the composition CaOSiOz + CaC03 + CaS04 + 14H20, is found in the Areskutan mountains in Jutland. w. c. w. Manganese-nodules from the Bed of the Pacific Ocean. By C. W. GEMBEL ( J u h ~ b . f. Mirz., 1878, 869--870).-These nodules were collected a t a depth of 2740 fathoms, between Japan and the Sandwich Islands, by the " Challenger" Expedition, They were either round or long in shape, with a dull, dirty-brown coloured surface, andMINERALOGICAL CHEMISTRY. 17 enclosed fragments of pumice-stone, and more rarely teeth of shai-ks or fragments of mussels, A microscopical examination showed that organic life had nothing t o do with their formation, which was due to a, mechanical concretion of inorganic matter ; a kind of oolitic forma- tion on a large scale.The pumice-stone was most probably the result of submarine eruptions; it was trachytic in character, and there was evidence to show that it had lain for a considerable space of time in muddy water, which penetrated it eventually, and left behind a depo- sition of manganese oxide.The author believes that the nodules in question derived some of their constituents from submarine springs, whilst their form can be accounted for by the action of the waves. An analysis gave the following results :- Fe,O,%. MnOz. HzO. SiO,. A1,0,. Na20. 27.460 23.600 17.819 16.030 10*210 2.3.58 c1. CaO. TiO,. so3. &O. MgO . 0.941 0.920 0.660 0.494 0.396 0.181 cop p20,. CuO. NiOCoO. BaO. 0.047 0.023 0.023 0 012 0.009 = 101.173 The minute quantity of carbonic acid is striking, and it wonld appear from the above analysis that an energetic oxidation takes place at great depths. The occurrence of these manganese-nodules a t the bottom of the sea is of great geological interest, as similar manganese- nodules are common in various sedimentary formations.C. A. B. Occurrence of Lithium in Rocks, Sea Water, Mineral Waters, and Saline Deposits. By L. DI~ULAFAIT (Ann. Chim. Y ~ J s . [ 51, 16, 377-391).--P~imary Rocks (Granite, Syenite, Gneiss). -The anthor has examined one hundred and thirty-nine specimens from different localities in Europe and Africa, and detected lithium in all of them, although in very different proportions. Mother Waters of SaZt-wmrshes.-The author found these to be so rich in lithia, that by simply dipping a platinum wire into the water and holding it, in the flame, the lithium spectrum obtained was as intense as that of sodium. Lithium could always be detected in the waters of from 15-25' B., as a t that concentration almost all the gypsum is deposited ; the crystals of gypsum themselves, however, contained only excessively minute traces of lithium.The sedimentary deposits forming the bottom of the basins invariably contained it. Lithium was found also in all sedimentary deposits left by the spontaneous evaporation of sea water. Xea Water.-Bunsen succeeded in 'detecting lithium in 40 C.C. of sea water, but the author found that on evaporating 1 C.C. of the water of the Mediterranean to dryness, treating the residue with alcohol, and evaporating the alcoholic solution, the second residue gave a very dis- tinct lithium spectrum. As lithium was shown to be a constituent of all the primitive rocks, it appeared highly probable that it would be found in all sea waters. The author has detected if in the waters of VOL. XXXVIII.c18 ABSTRACTS OF CHEMICAL PAPERS. the Red Sea, the Indian Ocean, the Chinese Sea,, the Atlantic Ocean, the Antarctic Ocean, and the Northern Ocean. Neither Forchhammer nor Credner, in his Traife' de Geblogie, mentions lithium as a constituent of sea water. The author applies tlhe results of his experiments to test his theory, that deposits of gypsum of all ayes have a purely sedimentary origin. This theory has been opposed by geologists, especially as applied t o gypsums of tlhe tertiary formation. Gypsunz of the Tei-ticrry Period.-Paris.-Samples of the pure crys- tals from the quarries of Montmartre and Pantlin were found to be quite free from lithium, although in every case the yellow calcareous deposit adherinq to the crystals or embedded in their cavities con- tained it in such quantity, that *0002 gram was amply sufficient to give the characteristic spectrum. -4ix mid Provenee.-In these localities the gypsum occurs in beds, separated by thin layers of marl.I n certain spots, large honey-yellow crystals of gypsum occur, imbedded in a yellowish deposit. In all cases the pure gypsum was free from lithium, whilst the yellow marl contained it in considerable quantity. Similar results were obtained on examining the gypsum from Camoins and Dauphin, near Mar- seilles, from Vauclnse, and from different parts of Italy. The waters fkom the S O I O I L ~ were found to contain lithium in considerable quantity. Gypstim of the Secondary Formation.-Forty-eight samples froin the Alpine district, eleven from Languedoc, seven from the Pyrenees, three from Lorraine, and four from Wurtemberq, all belonging t o the triassic formation, were examined, with rcsults similar to those ob- tained with the gypsums of the tertiarr periods.The samples of pure gypsum were free from lithium, or contained o d y traces ; whilst the associated earthy deposits were invariably rich in this element. These investigations show a complete analogy between the triassic gypsum deposits, those of the tertiary formation, and those from the salt, marshes of the modern period : whence the conclusion that the former two classes of deposits w e ~ e formed under the same conditions as those we now see causing the formation of gypsum in the salt marshes. ikfhzeral Waters of the Prhnnry Formation,.-A characteristic group of these waters is found in France in the Pyrenees district.The fol- lowing were examined, and in ever7 case lithium was found t o be a constituent :-Luchon, Cauterets, Bardges, Saint-Sauveur, LabassBre, Visbs, Bonnes, Ax, Amelie. XaZi n. e Waters. -T hose of All e var d, B alar uc, Bonrbonne, C apvern, Contrexeville, Digne, GrBonlx, Mi&, Montbrun, Montmirail, Pougues, Saint Gervais, SaliBs, Salins, Uriage, Vittel, Haurmem Meskou tin (Algiers), La Reine (near Oran),' Baden (Switzerland), Birmenstooff (Swit,zerland), Lo&che (Switzerland), Wildegg (Switzerland), Pullna, Hornbourg, Kissingen, Kreusnach, Naucheim, and Soultzmatt, were examined, and lithium found in all ; in some cases in such quantity that it could be detected in the evaporation residue of a single drop of the water.This fact, taken in conjunction with the previous expe- riments, strengthens the author's theory that saline waters are mine-MINERALOGICAL CHEMISTRY. 19 ralised at the expense of saliferous deposits left by the evaporation of ancient seas. J. M. H. M. Note on the Silesian Basalts and their Mineral Consti- tuents. By P. TRIPRE (Jahrb. f. Min., 1878, 876--877).-0f these basalts from Upper and Lower Silesia, fifteen were plagioclase basalts, two were nepheline basalts, and one from Wickenstein, near Querbach, was nephelinite. The microscopical characteristics of these basalts were briefly as follows, viz. :-A colourless glass-zone (which was itself surrounded by a glassy wreath of felt-like augite-microlites) surrounded the quartz inclosures, this observation agreeing with that of Lehmann on the inclosures of the basalts of the Lower Ehine.Some of the interfused quartz-fragments were converted into tridymite. The orthoclase was not surrounded by glass substance or augite. Lamellar enstatite occurs aiternately with lamellar diallagite in the olivine nodules of the Griiditaberg, the lamellze being parallel to the macropinaco’id of the enstatite. The acicuhr and tabular inclosures in these minerals the author considers to be negative forms of enstntite and diallagite, filled with opal. The phillipsite from Sirgwitz was monosymmetrical, and exhibited a complicated polysynthetical twin- formation. The basalt of Steuberwitz contains simple augite crystals, and those with a polysynthetical twin-formation.The olivine from Thomasdorf was changed into magnesium carbonate, whilst the nephelinite from Wickenstein contains augites having a zonal struc- t ure . C. A. B. Basaltic Lavas of the Eifel. By E. HUSSAK (Jahrb. f. M ~ w , 1878, 871).-The author made a thorough examinat’ion of the above- mentioned basalts, and arrived a t the following conclusions, viz. :- (1.) There are no fe1sp:ikhic basaltic lams in the Upper Eifel, but only nepheline or lencite-hasaltic lavas, which diff er-considerably from the non-melted, mound-forming basalts. (2.) The olivine from the Eifel lava is always fresh ; it is not present, however; in the lava from Dockweiler. (3.) The lava from the Bifel contains biotite, in contra- distinction to the basalt of the Eifel. (4.) Melilite occurs in con- siderable quantity in some of the lavas, especially in that from Bongs- berg, where it can be microscopically detected.(5.) Hauyn is only present in the lava from Scharteberg. (6.) Perowskite occurs as a characteristic of the lava from Scharteberg, but it is also present in lnvas of the Laacher See district (the three last-named minerals do not occur in the basalts of the Eifel). (7.) The chemical analyses of the lnvas agree very well with the results of the microscopical examina- tions. (8.) The tufa of the Kolenberg, near Anel, was found to be tme palagonite-tufa, containing, however, leucite and mqnetite. (9.) The microscopical examination of this tufa fully confirms Rosen- busch’s theory of the formation of the palagonite-tufa. (10.) Mits- cherlich’s analysis of t’his palagonite-tufa agrees fully with its micro- scopical analysis.(1 1 .) The so-called basalt-rock from Luxenberg, near Weierhof, in the Eifel, proves to be a true garnetiferous picrite, the first which has been observed on the left bank of the Rhine. (12.) The garnets in this picrite exhibited a zonal structure, were par- c 220 ABSTRACTS OF CHEMICAL PAPERS. tially double-refracting, and very probably were the variety called me1 anite. C. A. B. The Meteorite of Vavilovka. By B. PRENDEL (Jahrb. .f. Jfh~., 1878, 868).--Numerous meteorites fell on the 7th of June, 1876, near the village of Vavilovka, in Cherson, Russia, accompanied by a sound resembling thunder. A specimen examined by the author exhibited the characteristic black rind, which was 0.6-1 mm.in thickness, also irregular stripes here and there. A polished surface showed the mass of the meteorite to consist of numerous angular whitish specks. The nietallic constituents were particles of nickel-iron disseminated throughout the whole mass, and grains of magnetic-pyrites not, how- ever, magnetic. Sp. gr. = 3.51. Chemical composition as follows, v1z. :- Si02. MgO . 8190,. CaO. 53.8 I 18.54 8.75 2.07 1-14 9.41 5-26 0.70 = 99.68 Alkalis. Fe,08. Magnetic pyrites. Nickel. The meteorite belongs to the chondrites. C. A. B. The Meteorite of Grosnaja. BY G. TSCHERMAK (Jahrb. f. d f k , 1878, 868-869).-Two specimens which fell on the 28th of June, 1861, at the above locality on the Terek, Caucasus, were examined by the author. They were encrusted with a moderately thick fused sur- face (schmelz-rinde), and were black-grey in colour. The ground niass was massive, black, and opaque, and enclosed numerous light- coloured particles consisting of olivine, enstatite, bronzite, and magnetic iron-pyrites.The bronzite, olivine, and a mineral resembling augite were found together forming nodules in the ground mass, whilst specks of the magnetic iron-pyrites were observed in the inclosures and also in the ground mass. The bronzite-nodules exhibited an incrustation or rind, and the magnetic iron-pyrites occurred zonally on the enclosed minerals. An analysis of the meteorite furnished the following results :- SiO,. Al,O,. FeO. CaO. MgO. 33.78 3.44 28.66 3.22 23.55 Magnetic K,O. Na,O. C. H. iron pyrites. 0.30 0.63 0.68 0.17 5.37 = 100*00 Sp.gr. = 3.55. carbon. C. A. B. The Grosnaja meteorite is a chondrite one, poor in Chalybeate Springs of Carlstad. By A. ALM~N (Ber., 12, 1724 -1 725) .-These springs are exceptionally rich in ferrous carbonate. Tot,al solids. FeCO,. No. 1 contains in 10,000 parts . . . . 1.348 0.593 9, 2 7 9 9 9 .. .. 1.653 0.669 w. c. w.ORGANIC CHEMISTRY. 21 Water of the River Vartry. By J. FLETCHER (Chern. NWS, 40, 171).-This water shows on analysis very little chlorine, 0401155 per litre or 0,8025 grain per gallon. I t is of great softness, the hardness being only 3" on Clark's scale, and yielding a total sdid residue vary- ing, as the result of many experiments, from 4 to 6 grains per gallon. The results of tlie author's experiments shorn that the water is of qwat purity, chemically considered, but strongly impregnated with peat, having a very decided action on lead when flowing through pipes of that material, although without action on it when at rest, but rather leaving an organic deposit.D. 13.MINERALOGICAL CHEMISTRY. 13M i n e r a l o g i c a l C h e m i s t r y .Cobalt-glance. By P. GROTH (Jahrb. f. Min., 1878, 864-865).-In addition to the forms already known to occur on cobalt-glance,the author has observed two dyakisdodecahedrons, two trapezohedrons,and one triakisoctohedron. On cobalt-glance from Tunaberg, Sweden,he observed the following. combinations, viz. :- v m02(1.) 9 . o . mom . 30+. - (2.) . 0. $0.2. +o+. 'Lm 0 2 * 0 . 2 20% . - 2 - . o . 2 m02 20"(3.) 2 2Crystals from Skutterud, near Modurn, in Norway, exhibited thefollowing forms in combination, viz.: s2 . 0 . 20. 2 C. A. B.Cobalt-speis. By P. GROTH (Jahrb. f. Nin., 1878, 865).-Hithertoit has been considered doubtful whether the crystals of this mineralwere holohedral or hemihedral, but the author has succeeded in prov14 ABSTRACTS OF CHEMICAL PAPERS.ing the occurrence of pentagon dodecahedrons, and consequently theisomorphism of cobalt-speis and iron pyrites. On one crystal of cobalt-speis from Wolkenstein - and m* were observed. A largecrystal from Schneeberg exhibited the following forms in combina-tion, viz. : mom. 0 . COO . 202 . m03 - and a dyskisdodecahedron,which couId not be more nearly determined.Sulphide of Silver (Silber-kies).By A. WEISBACH ( J ~ h r b . f.Xin., 1878,866) .-Argyropyrites ( Ag3Fe7S11) occupy an intermediateposition, chemically speaking, between sternbergite (Ag,Fe6Sg) andargentopyrites (Ag3Fe9Su), and the same fact is observed in regard toits physical properties.Argentopyrites crystallises in the rhomhic system, the crystals fromMarienberg being but small, whilst those from Freiberg attained alength of 3 mm. The prisms were terminated either by the basalterminal plane, which was macrodiagonally striated, or else log anobtuse pyramid, the Freiberg crystals being characterised also by avery distinet basal cleavage.The crystals exhibiting the obtuse pyramids in combination wereprobably “ penetration trillings.”mO522 ’C. A. B.C. A. B.Bismuth Minerals from Norberg’s Mine, Wermland.By H.SJOGREX (Ber., 12, 1723).-Bismuth occurs in Wermland : lst, native,mixed with galena and pyrites; 2nd, as bjelkite, 2PbS.Bi2S,; and3rd, as the new mineral gdenobismuthite, PbS.Bi,S,, W. C. W.Polysynthetical Twin-crystals of Oriental Spinelle. By J.STRGVER (Jahrb. .f. Min,., 1878, 865-866).-This paper can onlybe thoroughly understood by reference to the drawings given. Theauthor concludes that there are three groups of polysyntheticalspinelle crystals, viz. : (1.) Those with one twin-axis in common.(2.) Those in which the twin-axes are not parallel to each other,but in which the “ twin-face ” is common to all, for instance, 8 formcomposed of three individuals having a face of cm0 in common, astwin-plane, and two of their twin-axes parallel to that face.Trillingswere also observed resembling a tetrahedron, owing to the predomi-nation of an individual having a tetrahedral development. Some-times groups composed of four individuals were observed, having allthe twin-axes parallel with the Qwin-planes (m0). (3.) Those inwhich there is no parallelism in the twin-axes, nor a twin-plane corn-mon to all the forms. C. A. B.Manganite. By P. GROTH (Jahrb. f. M k , 1878, 863--864).-Thefinest crystals of this mineral are found a,t Weld, and are characterisedby the great number of forms occurring in combination. Accordingto Haidinger, the hemihedry of this mineral is peculiar t o the pyramid9 PZ, a fact which appears all the more singular when the greatnumber of pyramids observed on manganite is taken into consideraMINERALOGICAL CHEMISTRY.15tion, and also that, in the case of the isomorphous mineral goethite,no such occurrence is observed. The author, on the contrary, did notobserve a single instance of hemihedry, or even twins according to thelaw “ the twin-plane mP&,” although he examined one of the finestcollections of Ilfeld manganite crystals. The results of his investiga-tion are briefly as follows :-1. Manganite must be considered as aholohedral mineral, hemihedral combinations being very rare. 2. Man-ganite crystals can be divided into four types, the first two beingcharacterised by an almost entire absence of twins, according to the law“ the twin-plane a face of P& ” and the occurrence of intermediateforms, whilst the last two types are characterised by the crystalsoccurring nearly always as twins according to the above-mentionedlaw, and a more sharply-defined distinction of the types from eachother.The following table will show this more clearly:-A. Long prismaticType I.Prisms, and basal terminal plane pre-dominating.Type 11. Prisms, with macropyramids as termi-nals.(Type 111. Twins, with somewhat numerousI forms in combination, the basal terminalplane and obtuse macrodomes predominating.Short prismatic< Type IV. Twins, with very numerous forms I in combination, macropyramids predominat-From the above table it seems probable that an intimate connectionexists between the twin formation and the number of forms occurringin combination.Occurrence of Manganese in Nordmark’s Mine, Wermland.By A.SJOGREN (Ber., 12, 1723).-1n this locality manganese is foundas manganosite, MnO ; pyrochroite, MnOH,O ; hausmannite andmanganese-spar, together with brucite, heavy spar, hornblende, andcing.The third and fourth types are the rarest.C. A. B.garne t. w. c. w.Vanadinite. By T. NORVSTROM (Ber., 12, 1723).-Vandanite hasbeen fouxd in the Undenas manganese dioxide mine in West Goth-land. A mineral has also been discovered a t Fahlun, containing 5 percent. of selenium. w. c. w.Titanates from Smgland. By C. W. BLOMSTRAKP (Ber., 12, 1721-1 723).-The following minerals were found a t Slattgkra, Alsheda,occurring in coarse granite :-1. Polycrase.2. Titanqerous imn ore,remarkable on account of the water it contained ; and 3. A new mineralabhedite, which appears to occupy an intermediate position as regardscomposition between yttrotitanite and gr oothite. In this compoundtitanium dioxide plays the part of a base. w. c. w.Pseudomorphs of Calcite after Aragonite. By G. TOM RATH(Jahrb. f. A f i n . , 1878, 863).-The crystals in question came fromSchemnitz, and were from 10 to 20 cm. in length and from 4 to 6 cm16 ABSTRACTS OF CHEMICAL PAPERS.in breadth: they were terminated apparently by a brachydome, thespace originally filled by aragode being taken up by calcite. Onespecimen, 7 cm. long, 4 cm. broad, and from 2 to 3 cm. thick, con-sisted of the outter shell of an aragonite crystal, which was built lipout of an aggregate of small, well-developed calcite crystals, exhibitingthe following forms in combination, viz.: R3. - +R.mR, the crystalsnot occupying any regular position with regard to the original arago-nite crystal. C. A, B.Crystal-system of Leucite. By J. HIRSCHWALD (Jahrb. f. Miia.,1878, 867).-Hirschwald stated in a former paper that leucite mightbe considered as a mineral crystallising in the regular system, with apolysymmetrical development in the sense of the quadratic system.From further investigations he arrives a t the conclusion that a dif-ference in opinion aboui; the practical relationships of leacite is possiblein the two following cases only, viz. :--1. Is the polysynthetical twin-formation a complete dodecahedra1 one, or does it only represent thefaces of the pyramid ? 2.Have the imbedded crystals the interfacialangles (winkelwerthern) of 202, or have the apparently regular forms,without exception, the angles of the acuter lateral edge of the eight-sided pyramid ? Hirschwald considers that he has found a completeanswer to these questions in the results of his investigations, and statesthat the imbedded leucite crystals have undoubtedly the interfacialangles of 202, whilst the optical properties prove a complete dodeca-hedral twin-formation. C. A. B.Composition of Eclogite. By E. R. RIESS (Jahrb.f. Mi%., 1878,877) .-Eclogite is a non-felspathic crystalline rock which, in itssimplest forms, consists of omphazite and garnet, whilst the varietiesof this rock are produced by the occurrence of quartz, hornblende,cyanite, zoisite, or mica.The accessory minerals are zircon, apatite,titanite, epidote, iron-pyrites, magnetic iron-pyrites, and magnetite.Omphazite occurs as'an angite in short, thin prisms of a grass-greencolour ; the rare smaragdite as a green hornblendic mineral. Thegarnet often contains numerous enclosures of zircon, quartz, &c., andis occasionally decomposed. Zircon occurs enclosed in large amount(in reddish-brown grains or greyish-yellow prisms, exhibiting P withmP and mPm, also twins, parallel to a face of Pm) i n the garnet andomphazite. The true eclogite is found imbedded in the strata of thecrvstalline slates. and is often intimatelv associated with hornblendic .I d plagioclase garnet-rocks, but not with those containing omphaaite.C.A. B.Thaumasite. By G. LINDSTROM (Bey., 12, 1723).-This newmineral, having" the composition CaOSiOz + CaC03 + CaS04 + 14H20,is found in the Areskutan mountains in Jutland. w. c. w.Manganese-nodules from the Bed of the Pacific Ocean.By C. W. GEMBEL ( J u h ~ b . f. Mirz., 1878, 869--870).-These noduleswere collected a t a depth of 2740 fathoms, between Japan and theSandwich Islands, by the " Challenger" Expedition, They were eitherround or long in shape, with a dull, dirty-brown coloured surface, anMINERALOGICAL CHEMISTRY. 17enclosed fragments of pumice-stone, and more rarely teeth of shai-ksor fragments of mussels, A microscopical examination showed thatorganic life had nothing t o do with their formation, which was due toa, mechanical concretion of inorganic matter ; a kind of oolitic forma-tion on a large scale.The pumice-stone was most probably the result ofsubmarine eruptions; it was trachytic in character, and there wasevidence to show that it had lain for a considerable space of time inmuddy water, which penetrated it eventually, and left behind a depo-sition of manganese oxide. The author believes that the nodules inquestion derived some of their constituents from submarine springs,whilst their form can be accounted for by the action of the waves. Ananalysis gave the following results :-Fe,O,%. MnOz. HzO. SiO,. A1,0,. Na20.27.460 23.600 17.819 16.030 10*210 2.3.58c1.CaO. TiO,. so3. &O. MgO .0.941 0.920 0.660 0.494 0.396 0.181cop p20,. CuO. NiOCoO. BaO.0.047 0.023 0.023 0 012 0.009 = 101.173The minute quantity of carbonic acid is striking, and it wonldappear from the above analysis that an energetic oxidation takes placeat great depths. The occurrence of these manganese-nodules a t thebottom of the sea is of great geological interest, as similar manganese-nodules are common in various sedimentary formations.C. A. B.Occurrence of Lithium in Rocks, Sea Water, MineralWaters, and Saline Deposits. By L. DI~ULAFAIT (Ann. Chim.Y ~ J s . [ 51, 16, 377-391).--P~imary Rocks (Granite, Syenite, Gneiss).-The anthor has examined one hundred and thirty-nine specimensfrom different localities in Europe and Africa, and detected lithium inall of them, although in very different proportions.Mother Waters of SaZt-wmrshes.-The author found these to be sorich in lithia, that by simply dipping a platinum wire into the waterand holding it, in the flame, the lithium spectrum obtained was asintense as that of sodium.Lithium could always be detected in thewaters of from 15-25' B., as a t that concentration almost all thegypsum is deposited ; the crystals of gypsum themselves, however,contained only excessively minute traces of lithium. The sedimentarydeposits forming the bottom of the basins invariably contained it.Lithium was found also in all sedimentary deposits left by thespontaneous evaporation of sea water.Xea Water.-Bunsen succeeded in 'detecting lithium in 40 C.C.of seawater, but the author found that on evaporating 1 C.C. of the water ofthe Mediterranean to dryness, treating the residue with alcohol, andevaporating the alcoholic solution, the second residue gave a very dis-tinct lithium spectrum. As lithium was shown to be a constituent ofall the primitive rocks, it appeared highly probable that it would befound in all sea waters. The author has detected if in the waters ofVOL. XXXVIII. 18 ABSTRACTS OF CHEMICAL PAPERS.the Red Sea, the Indian Ocean, the Chinese Sea,, the Atlantic Ocean,the Antarctic Ocean, and the Northern Ocean. Neither Forchhammernor Credner, in his Traife' de Geblogie, mentions lithium as a constituentof sea water.The author applies tlhe results of his experiments to test his theory,that deposits of gypsum of all ayes have a purely sedimentary origin.This theory has been opposed by geologists, especially as applied t ogypsums of tlhe tertiary formation.Gypsunz of the Tei-ticrry Period.-Paris.-Samples of the pure crys-tals from the quarries of Montmartre and Pantlin were found to bequite free from lithium, although in every case the yellow calcareousdeposit adherinq to the crystals or embedded in their cavities con-tained it in such quantity, that *0002 gram was amply sufficient togive the characteristic spectrum.-4ix mid Provenee.-In these localities the gypsum occurs in beds,separated by thin layers of marl.I n certain spots, large honey-yellowcrystals of gypsum occur, imbedded in a yellowish deposit.In allcases the pure gypsum was free from lithium, whilst the yellow marlcontained it in considerable quantity. Similar results were obtainedon examining the gypsum from Camoins and Dauphin, near Mar-seilles, from Vauclnse, and from different parts of Italy. The watersfkom the S O I O I L ~ were found to contain lithium in considerablequantity.Gypstim of the Secondary Formation.-Forty-eight samples froin theAlpine district, eleven from Languedoc, seven from the Pyrenees,three from Lorraine, and four from Wurtemberq, all belonging t o thetriassic formation, were examined, with rcsults similar to those ob-tained with the gypsums of the tertiarr periods. The samples of puregypsum were free from lithium, or contained o d y traces ; whilst theassociated earthy deposits were invariably rich in this element.These investigations show a complete analogy between the triassicgypsum deposits, those of the tertiary formation, and those from thesalt, marshes of the modern period : whence the conclusion that theformer two classes of deposits w e ~ e formed under the same conditionsas those we now see causing the formation of gypsum in the saltmarshes.ikfhzeral Waters of the Prhnnry Formation,.-A characteristic groupof these waters is found in France in the Pyrenees district.The fol-lowing were examined, and in ever7 case lithium was found t o be aconstituent :-Luchon, Cauterets, Bardges, Saint-Sauveur, LabassBre,Visbs, Bonnes, Ax, Amelie.XaZi n. e Waters. -T hose of All e var d, B alar uc, Bonrbonne, C apvern,Contrexeville, Digne, GrBonlx, Mi&, Montbrun, Montmirail, Pougues,Saint Gervais, SaliBs, Salins, Uriage, Vittel, Haurmem Meskou tin(Algiers), La Reine (near Oran),' Baden (Switzerland), Birmenstooff(Swit,zerland), Lo&che (Switzerland), Wildegg (Switzerland), Pullna,Hornbourg, Kissingen, Kreusnach, Naucheim, and Soultzmatt, wereexamined, and lithium found in all ; in some cases in such quantitythat it could be detected in the evaporation residue of a single drop ofthe water.This fact, taken in conjunction with the previous expe-riments, strengthens the author's theory that saline waters are mineMINERALOGICAL CHEMISTRY. 19ralised at the expense of saliferous deposits left by the evaporation ofancient seas.J. M. H. M.Note on the Silesian Basalts and their Mineral Consti-tuents. By P. TRIPRE (Jahrb. f. Min., 1878, 876--877).-0f thesebasalts from Upper and Lower Silesia, fifteen were plagioclase basalts,two were nepheline basalts, and one from Wickenstein, near Querbach,was nephelinite. The microscopical characteristics of these basaltswere briefly as follows, viz. :-A colourless glass-zone (which wasitself surrounded by a glassy wreath of felt-like augite-microlites)surrounded the quartz inclosures, this observation agreeing with thatof Lehmann on the inclosures of the basalts of the Lower Ehine.Some of the interfused quartz-fragments were converted into tridymite.The orthoclase was not surrounded by glass substance or augite.Lamellar enstatite occurs aiternately with lamellar diallagite in theolivine nodules of the Griiditaberg, the lamellze being parallel to themacropinaco’id of the enstatite.The acicuhr and tabular inclosuresin these minerals the author considers to be negative forms of enstntiteand diallagite, filled with opal. The phillipsite from Sirgwitz wasmonosymmetrical, and exhibited a complicated polysynthetical twin-formation. The basalt of Steuberwitz contains simple augite crystals,and those with a polysynthetical twin-formation. The olivine fromThomasdorf was changed into magnesium carbonate, whilst thenephelinite from Wickenstein contains augites having a zonal struc-t ure . C. A. B.Basaltic Lavas of the Eifel. By E. HUSSAK (Jahrb. f. M ~ w ,1878, 871).-The author made a thorough examinat’ion of the above-mentioned basalts, and arrived a t the following conclusions, viz.:-(1.) There are no fe1sp:ikhic basaltic lams in the Upper Eifel, butonly nepheline or lencite-hasaltic lavas, which diff er-considerably fromthe non-melted, mound-forming basalts. (2.) The olivine from theEifel lava is always fresh ; it is not present, however; in the lava fromDockweiler. (3.) The lava from the Bifel contains biotite, in contra-distinction to the basalt of the Eifel. (4.) Melilite occurs in con-siderable quantity in some of the lavas, especially in that from Bongs-berg, where it can be microscopically detected. (5.) Hauyn is onlypresent in the lava from Scharteberg. (6.) Perowskite occurs as acharacteristic of the lava from Scharteberg, but it is also present inlnvas of the Laacher See district (the three last-named minerals do notoccur in the basalts of the Eifel).(7.) The chemical analyses of thelnvas agree very well with the results of the microscopical examina-tions. (8.) The tufa of the Kolenberg, near Anel, was found to betme palagonite-tufa, containing, however, leucite and mqnetite.(9.) The microscopical examination of this tufa fully confirms Rosen-busch’s theory of the formation of the palagonite-tufa. (10.) Mits-cherlich’s analysis of t’his palagonite-tufa agrees fully with its micro-scopical analysis. (1 1 .) The so-called basalt-rock from Luxenberg,near Weierhof, in the Eifel, proves to be a true garnetiferous picrite,the first which has been observed on the left bank of the Rhine.(12.) The garnets in this picrite exhibited a zonal structure, were par-c 20 ABSTRACTS OF CHEMICAL PAPERS.tially double-refracting, and very probably were the variety calledme1 anite.C. A. B.The Meteorite of Vavilovka. By B. PRENDEL (Jahrb. .f. Jfh~.,1878, 868).--Numerous meteorites fell on the 7th of June, 1876, nearthe village of Vavilovka, in Cherson, Russia, accompanied by a soundresembling thunder. A specimen examined by the author exhibitedthe characteristic black rind, which was 0.6-1 mm. in thickness, alsoirregular stripes here and there. A polished surface showed the massof the meteorite to consist of numerous angular whitish specks. Thenietallic constituents were particles of nickel-iron disseminatedthroughout the whole mass, and grains of magnetic-pyrites not, how-ever, magnetic.Sp. gr. = 3.51. Chemical composition as follows,v1z. :-Si02. MgO . 8190,. CaO.53.8 I 18.54 8.75 2.071-14 9.41 5-26 0.70 = 99.68Alkalis. Fe,08. Magnetic pyrites. Nickel.The meteorite belongs to the chondrites. C. A. B.The Meteorite of Grosnaja. BY G. TSCHERMAK (Jahrb. f. d f k ,1878, 868-869).-Two specimens which fell on the 28th of June,1861, at the above locality on the Terek, Caucasus, were examined bythe author. They were encrusted with a moderately thick fused sur-face (schmelz-rinde), and were black-grey in colour. The groundniass was massive, black, and opaque, and enclosed numerous light-coloured particles consisting of olivine, enstatite, bronzite, and magneticiron-pyrites. The bronzite, olivine, and a mineral resembling augitewere found together forming nodules in the ground mass, whilst specksof the magnetic iron-pyrites were observed in the inclosures and alsoin the ground mass. The bronzite-nodules exhibited an incrustationor rind, and the magnetic iron-pyrites occurred zonally on the enclosedminerals. An analysis of the meteorite furnished the followingresults :-SiO,. Al,O,. FeO. CaO. MgO.33.78 3.44 28.66 3.22 23.55MagneticK,O. Na,O. C. H. iron pyrites.0.30 0.63 0.68 0.17 5.37 = 100*00Sp. gr. = 3.55.carbon. C. A. B.The Grosnaja meteorite is a chondrite one, poor inChalybeate Springs of Carlstad. By A. ALM~N (Ber., 12, 1724-1 725) .-These springs are exceptionally rich in ferrous carbonate.Tot,al solids. FeCO,.No. 1 contains in 10,000 parts . . . . 1.348 0.5939, 2 7 9 9 9 .. .. 1.653 0.669 w. c. wORGANIC CHEMISTRY. 21Water of the River Vartry. By J. FLETCHER (Chern. NWS, 40,171).-This water shows on analysis very little chlorine, 0401155 perlitre or 0,8025 grain per gallon. I t is of great softness, the hardnessbeing only 3" on Clark's scale, and yielding a total sdid residue vary-ing, as the result of many experiments, from 4 to 6 grains per gallon.The results of tlie author's experiments shorn that the water is ofqwat purity, chemically considered, but strongly impregnated withpeat, having a very decided action on lead when flowing through pipesof that material, although without action on it when at rest, but ratherleaving an organic deposit. D. 13

ISSN:0368-1769    

DOI:10.1039/CA8803800013

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

ORGANIC CHEMISTRY. 210 r g a n i c C h e m i s t r y.Specific Gravities of Solid Organic Compounds. By H.SCHRODER (Ber., 12, 1611--1618).--The* author has determined thespecific gravity and molecular volumes of the following compounds :-Sp. gr.1.5591.281Malic acid . . . . . . . . . . . . . . . . . .Dimethyloxarnide .. .. .. ......Die thyloxamide . . . . . . . . . . . . . .Salicylic acid . . . . . . . . . . . . . . . .Metahydroxybenzoic acid. . . . . .Parahydroxybenzoic acid,. . . . .Phthalic anhydride . . . . . , . . . .1.4731-2471.2311.542 Protocatechuic acid1.7031.6851-3551.236Gallic acid . . . . . . . . . . . . . . . . . .Mandelic acid.. . . . . . . . . . . . . . . { 1.3671.385Methylparahydroxybenzoic acid 1.376 i' 1,364Phenylacetic acid .. . . . . . . . . . .1.2491.246 Cinnamic acidCumi * 'Benzoic anhydride, . . . . . . . . . . ,. . . . . . . . . .i 1.169. . . . . . . . . . . . , .Volume.85.990.5123.7122.892-993.193.793.594.556.956.7181.3183.2183.699.9-10O~c;99%100.9112.2111.2110.0111.5109.8110.5111.5118.6118.8140.3141.22 ABSTRACTS OF CHEMICAL PAPERS.sp. tT-1.296 { 1.2883 Orcinol . . . . . . . . . . . . . . . . . . . .Benzamide . . . . . . . . . . . . . . . . . . { ;:EAmidobenzoic acid . . . . . . . . . . { ;:;gOrthonitrobenzoic acid. . . . . . . .Metanitrobenzoic acid . . . . . . . . / ;:;;;1.216 { 1.205 Ace t anilide . . . . . . . . . . . . . . . . . .Benzanilide. . . . . . . . .. .. . . . ... . .1.2271.216 Aniline hydrochloride . . . , . . . .Thiocarbanilide . . . . . . . . . . . . . .Aniline nitrate . .. . . . . . . . . . . . .Aniline sulphate. . . . . . . . . . . . . .Naphthalene . . . . . . . . . . . . . . . .il": 1.201{ ;:;2Nitronaphthalene . . . . . . . . . . . . { ::;;;Ammonium benzoate. . . . . . . . . . { ?;;*1.3771.145a-Xaphthol . . . . . . . . . . . . . . . . . .&Naphthol. . . . . . . . ... . . . . . . . .1.2941.217Calcium benzoate . . , . . . . . . . . .Volume.109.7110.790.091.290-591.2106.0106.1111:6112.0111.0112.0149.2150.8171.5173-9105%106.5107.8114.8115.0206.311 1.9129.0131.0117.8118.2110.0110.3230.6234.1The molecular volumes of the majority of the above compounds aremultiples of 5.91, which in a former communication ( B e y ., 12, 566)was shown to be true for some benzene derivatives.I n the case of some isomerides, the " stere " appears to v a q a littlefrom 5.91, as shown by the following :-Volume. " Stere." __ .. .. .. . . .. .. .. . . 82.6-43.1 5-91 { Pyrocatechol Qainol .. .. .. .. .. 81.6-82.1 5.83* {4.{5. {Parahydroxgbenzoic acid 93.5-94.5 57153-5T Metahydroxybenzoic acid 93.7 -Orthohydroxybenzoic acid 93.9-93.1 5.8Orthonitrophenol.. .. .... 135.8-96.3 - G.0---?3%5Paranitrophenol . . . . . . . . 94.5-94.7Mandelic acid . , . . . . . . . . 111.2-112*2Anisic acid . . . , . . . . . . . . 109*8-110.5Isonaphthol . . . . . . . . . . . . 118.2a-Naphthol .. . . . . , . . . . . 11 7.85.915T1 's2*ORGANIC CHEMISTRY. 23The members of the following six groups are isosteric : (1.) Malicand tartaric acids. (2.) Benzoic and paraoxybenzoic acids. (3.) Re-sorcinol and pyrogallol. (4.) Phenylacetic and anisic acids. (5.)Protocatechuic and gallic acids. (6.) Benzamide and benzamic acids.In former communications, the author has shown that the element’scarbon, hydrogen, oxygen, and nitrogen occupy in the solid state thespace of one “ stere.”The determinations given above offer further support of this state-ment, thus : oxamide, dimethyloxnmide, and diethyloxarriide haverrloiecular volumes differing by CiH:, or 6 steres. I n naphthalene andisonaphthol we have difference of 0: = 1 stere, and in benzoic andorthonitrobenzoic acids we have the difference N:Oi - Hi = 2 steres.Some other examples are given.Prom this rule, i t follows that the benzene nucleus possesses onestere more than the sum of those of the elementary atoms containedin it. Thus : benzoic acid, C6H,.C00H = 16 x x1.Paranitro-phenol, C,H,.NO,O = 16 x 5.91, phthalic anhydride, C,HL03 = 16 x m. Orthonitroberizoic acid, C,H,.NO,.CO, = 18 X m. Phenyl-acetic acid = 19 x 5.8. lso-naphthol, C6H,.C4H,0 = 20 x 5- Cinnamic acid, C,H5.C,H2.COOH= 20 x 5-91. P. P. B.Naphthalene, C,H,.C,H, = 19 x m.-Formation of Hydrocyanic Acid in the Electric Arc. Bg J.DEWAR (Chem. News, 39, %3’L).-From the statements made by Plucker,ingstr6m, and Thalhn, that the so-called carbon lines are invariablyassociated with the formation of acetylene, the author made experi-ments with a view to extract this substance from the electric arc,which shows this spectrum a t the positive pole when the electric cnr-rent is powerful and occasionally intermittent. The carbons wereused in the form of tubes so that air could be drawn through them,and so that any gas might be passed up one tube and drawn downthe other and then examined.A Siemens and a De IRlkritens magneto-machine were employed.I n the first experiment a current of air was drawn down the nega-tive pole and passed through solutions of potash and potassiumiodide arid starch.No nitrates were indicated, but the potash solutioncontained sulphides.I n the second experiment in which hydrogen was led in by theposi-tive pole and withdrawn by the negative, acetylene was found by theammoniacal sub-chloride of copper-test, whilst water through which thegases were passed gave distinct evidence of hydrocyanic acid.Thehydrogen flame burning alone gave no evideiice of these substances.Air drawn through the negative pole gave considerable quantitiesof hydrocyanic acid, but when drawn through the positive pole alarger proportion was found, whilst the same carbons used with DeMhritens’ magneto-machine gave no result.I f the carbons are not purified, hydrogen sulphide is always foundalong with the other compound.The author concludes that the high temperature of the positive poleis required t o produce the hydrocjanic acid, which is in all probabilit24 ABSTRACTS O F CHEMICAL PAPERS.formed by the free nitrogen reacting on the acetylene thus : C,H, +2N = 2HCN, and that the hydrogen to form the acetylene is obtainedfrom the decomposition of aqueous vapour and from the combinedhydrogen in the carbons.Oxidation of Alcohols by Electrolysis.By A. RENARD (Ann.Chiw~. Phys. [ 51, 16, 289-33$).-I. Electrolysis of Alcohols in pwsenceof W a t e r A c i d d a t e d hj Sulphuric Acid. Methyl Alcolw1.-The purestmethyl alcohol of commerce, after being carefully freed from traces ofacetone and methyl ethers, was acidified with about 5 per cent. ofdilute sulphuric acid (1 : 4), placed in a flask holding from 100-200c.c., and submitted to the action of a current from 4 Bunsen cells ofabout a litre and a half capacity.Hydrogen was evolved at the nega-tive pole, and at the positive pole a gas was very slowly given off( a t the rate of 25-30 C.C. in 24 hours) : it contained CO,, 23.9 ; CO,SO.0; 0, 26.1. At the end of 48 hours the yellowish liquid was dis-tilled. The distillate was found to contain methyl formnte and methylaZ.Methyl aldehyde was never found as a product of the electrolysis,being no doubt oxidised to formic acid as soon as formed, or reactingwith the methyl alcohol to form methylal. The methylal is one of thechief products of the reaction, and may be prepared quite easily bythis method. The residue of the distillation of the electrolysed liquidcontained hydrogen methyl sulphnte. To show that this was pro-duced by the electrolysis, a mixture of the alcohol with dilute sul-phuric acid was prepared and divided into two parts, one beingallowed to rest, and the other submitted to electrolysis.The latterwas found to contain hydrogen methyl sulphate, whilst the former wasquite free from it.Ethyl AZcohol.-The electzolysis of ethyl alcohol has already beenattempted by various chemists, amongst others by tliche, D'Almeidaand Bontan, and Jaillard. The only products hitherto recognised,besides chloracetic acid and compound ammonias resulting from thehydrochloric and nitric acids employed for acidification, are aldehydeand acetic acid.The author's experiments were conducted in the same manner asthose with methyl alcohol. An abundant evolution of hydrogenoccurred at the negative pole; but a t the positive pole no gas wasdisengaged, all the oxygen being absorbed by the oxidation of thealcohol. The process was arrested at the end of 48 hours, and theliquid on being distilled yielded (besides alcohol) ethyZ fomzate, a littlealdehyde, and a large proportion of ethyl acetate ; small quantities ofm e t a l were likewise obtained, and a new substance which the authorconsiders to be ethylidewe monethylate, CH,.CH(HO).EtO, i.e., acetal,in which C2H5 is replaced by H. This substance when separated,and purified by fractional distillation, boiled a t 88-90" C., and onanalysis gave numbers corresponding with the formula C,H,,O,.Theresidue from the distillation of the electrolysed mixture containedhydrogen ethyl sulphate, the formation of which was proved, as in theprevious case, to be really due to the electrolysis.Under certain con-ditions, more than 60 per cent. of the sulphuric acid employed foracidification is transformed into the sulphate.W. TORGANIC CHEMISTRY. 25If the electrolysis of methyl or ethyl alcohol be continued for severaldays, a point is reached at which the liquid appears to containnothingbut formic or acet]ic acid; on still prolonging the operation, almostpure oxygen is disengaged a t the positive pole, in volume almostexactly half that of the hydrogen, and the liquid is found still tocontain a little hydrogen methyl or ethyl sulphate, the decompositionof which is very slow.Electrolysis of Hydrogen X r t l y Z XuIphate.-lOO C.C.of a solutioncontaining 20 grams of this ethereal salt, prepared by decomposingbarium methyl sulphate with sulphuric acid, was submitted to theaction of the current from 4 Bunsen cells. Hydrogen was disengageda t the negative pole, aiid oxygen containing 5 or 6 per cent. of theoxides of carbon a t the positive pole, about 23 volumes of oxygenbeing evolved for every 100 volumes hydrogen. After 48 hours theliquid was distilled, and the distillate was found to contain formicacid and a solid polymeride of methaldehyde, ti-ioxy methyleyhe, C3H603,which was obtained as a white, amorphous, insoluble residue byevaporation of the solution over sulphuric acid in a bell-jar. Similarrcsults were obtained by the electrolysis of a more dilute (5 per cent).)solution of hydrogen methyl sulphate, and also of a similar solutioncontaining a, little free sulphuric acid.From this, it would seem thatmethaldehyde is first produced, a part being a t once transformed intothe polymeric modification, whilst the other is oxidised to formic acid.No trioxymethylene is produced by electrolysis of methyl alcohol,because the methaldehyde as fast as it is formed, reacts on the methylalcohol to produce niethylal.Electrolysis of Hydmgen Ethyl Xu@hate.--This compound was sub-mitted to electrolysis in a manner similar to the corresponding methylcompound, and gave acetic acid and a little formic acid. No aldehydewas found in the distillate, but the odour of aldehyde was perceptibleduring the progress OE the electrolysis.Electrolysis of G7ycerol.-Glycerol diluted with two-thirds of itsvolume of water, acidulated with one-tenth of sulphuric acid, was sub-mitted to the action of the current from 5 Bunsen cells.Hydrogen wasdisengaged a t the negative pole, and at the positive pole a gaseous mix-ture containing CO,, 2.9 ; CO, 32.8 ; 0,64.3 volumes. After 48 hoursthe process mas arrested, the liquid saturated with calcium carbonate,filtered, and submitted t o distillation without boiling at a low pressurei n an atmosphere of carbonic anhydride. On spontaneous evaporationover sulphuric acid, the distillate left a white amorphous residue,which gave on analysis numbers agreeing with the formula CzH2xOx,and which proved to be identical with triozymethyZene, C,H,03. Theyield o€ this substance is very small, 130 C.C.of the distillate givingabout half a gram of the dry substance. Submitted to electrolysis,trioxymethylene gives rise to formic acid, and a gaseous mixture corl-baining, in 100 volumes, C02, 5 ; CO, 15 ; and 0 , W . By treating a solu-tion of trioxymetliylene with sulphuretted hydrogen, a white precipitateis obtained, of the formula, (C3H6S20)2H20. It differs therefore fromthe body C3H6S3, which Hoffmann obtained by acting on trioxy-methylene with a mixture of hydrochloric and hydrosulphuric acids.The oxysulphide obtained by the author melts at 80--82O, and solidifie26 ABSTRACTS OF CHEMICAL PAPERS.on cooling to a hard, white, opaque mass, like wax. It is soluble inhot water, insoluble in alcohol and ether, and boils a t 180-185" C.By treating the trioxymethylene with ammonia, the author obtainedthe hezamethyZenanzine of Butlerow, CsH12KT4, but was unable to obtainfrom it the hydrochloride C6Hl3NICI, described by that chemist.The residue from the distillation of the electrolysed glycerol containedcalcium format'e, acetate, and glycerate.Besides these substances thereis formed by electrolysis of glycerol a small quantity of a glucose isomericwith ordinary glucose, and which is probably a polymeride of trioxy-methylene. It is found in the alcohol used to precipitate the limesalts from the distillation residue of the electrol-ysed liquid. This alco-holic solution also contains the lime salt of a new acid, identical wit,hthat formed in the electrolysis of mnnnitol.The pure glucose isobtained in the form of a yellow-brown syrup, which may be dried a tGO" in a current of hydrogen. At 80-100" it blackens, loses water,and gives out, the odour of caramel. Its alcoholic solution yields aprecipitate with barium hydrate, the composition of which agrees withthe formuh (CsHI20,),( BaO),. The glucose reduces silver uitrate,with formation of a mirror, and precipitates cuprous oxide fromFehling's solution on heating. It is oxidised to oxalic acid when heatedwith dilute nitric acid. Slightly heated with soda its solution darkensstrongly. It is very soluble in water and alcohol, is not precipitatedby lead subacetate, but forms an abundant precipitate with ammoniacnllead acetate.It appears to be incapable of fermentation by beer yeast.When the electrolysid of glycerol is prolonged f o r several days, thetrioxymethylene and glucose disappear., the liquid becomes stronglycharged with oxalic acid, and this, as well as the formic and acdticacids, is finally resolved into carbonic anhydride and carbonic oxide,so that the solution a t last contains nothing but sulphuric acid.E'lectrolysis of Glycol.-Hydrogen was evolved at the negative pole,and a t the positive pole a gaseous mixture containing CO,, 5.00;C0, 57.15; 0, 37.85. The current was interrupted a t the end of36 hours. The liquid, saturated wiLh calcium carbonate and distilled,gave a distillate containing trioxymethylene, whilst the residue i n theretort contained calcium formate and calcium glycollate, some unalteredglycol, and a glucose identical with that obtained by the electrolysisof glycerol.3Lectrolysis of MunnitoZ.-Hydrogen was evolved a t the negative pole,and a t the positive pole a gaseous mixture contaiuing CO,, 22.1;CO, 55.0 ; 0,22*9.The liquid treated as in the glycol experiment, gavetrioxymethylene, calcium formate, and the calcium salt of a new acid.This calcium salt, when separated from fhe accompanying calciumformate, purified, and analysed, gave numbers corresporldixlg with theformula C6H6Ca08 + 2H20. It is very soluble in water, and itis not precipitated either by lime water, or by lead acetate or sub-acetate. It reduces silver nitrate almost instantaneously, withoutheating, and in the dark ; if the mixture be heated slightly a metallicmirror is obtained.At 120" C., the wlcium salt loses 6-7 per centl.cf water, and at 150" it swells up, and begins to decompose. Theacid, obtained from the calcium salt by decomposition with oxalic acid,is a syrupy product, forming very soluble, gummy salts, with bariunlORGANIC CHEMISTRY. 27lead, and magnesium. The author assigns the formula C6H808 tothis acid, and suggests that it may be an aldehyde of saccharic acid,C6HI0O8, bearing the same relation to the latter that glyoxylic (01- gly-oxalic) acid, C2H2O3, does $0 glycollic acid, CLH403. A glucose iden-tical with that obtained from glycerol, and probably also with themannitose of Gorup-Besanez, was also formed during the electrolysis,togetLer with a considerable quantity of oxalic acid, but no saccharicacid or msnnitic acid could be detected.Electrolysis of Glucose.-Hydrogen was evolved a t the negative pole,and at the positive pole EL gaseous mixture containing C 0 2 , 22 8 ;CO, 18.2 ; 0, 59.0.The electrolysed liquid contained trioxymethylene,formic acid, and saccharic acid.Electroh~sis of Alcohols when the Electrodes are sepamted by n PorousPartition.-In these experiments, the liquids to be electrolped werecontained in a porous cell, into which the positive electrode was intro-duced, the porous cell being surrounded with acidulated water, intowhich the negative electrode was plunged. The alcohols experimentedwith were methyl alcohol, ethyl alcohol, and glycerol.The productswere the same as in the experiment in wbich no porous partition wasemployed.Electrolysis of Acetic Acid.-25 C.C. of glacial acetic acid was mixedwith 40 C.C. of water, acidulated with one-tenth of sulphuvic acid, andsubmitted to the action of the ciirrent from 4 Bunsen cells. At theend of three hours the gaseous mixture evolved a t the positive polecontained CO,, 41 3 ; CO, 11.4; 0, 47.3. After 24 hours the gasevolved consisted of COz, 45.4 ; CO, 9.2 ; 0, 45.4. The proportion ofcarbonic anhydride was still greater a t the end of 36 hours. After48 hours the liquid was examined, and found to contain formic acid,but no oxalic acid.Electrolysis of Oxalic Acid.-The sole products in this case were car-bonic anhydride and carbonic oxide.The gaseous mixture evolved a tthe positive pole contained about 50 per cent. C 0 2 , and 10 per cent. CO,the rest being oxygen. At the ecd of 48 hours all the oxalic acid haddisappeared.Electrolysu of Forinic Acid.-The sole products were carbonic anhy-dride and carbonic oxide. If concenkrated formic acid is used, car-bonic anhydride is the only product.E’lectrol!isis of Alcohols in presence of Phosphoric Acid.-Experimentswere made with solutions of methyl alcohol, ethyl alcohol, glycerol,and glycol, acidulated with phosphoric instead of sulphuric acid. Alarger proportion of phosphoric acid than of sulphuric acid was foundnecessary, in order to secure the decomposition of the alcohols, but theproducts were exactly the same, and in about the same proportions aswhen sulphuric acid was used, except that in the case of methyl andethyl alcohols no hydrogen methyl or ethyl phosphate was formed.Action of Ozune o n the Alcohols.-The action of ozonised oxygen onthe alcohols is very slow ; for example, when a stream of this gas ispassed through solutions of glycerol, glucose, or mannitol, the escapinggas is still strongly odorous, and the liquid contains only very smallquantities of acetic or formic acid, even after many days’ action.Carbon dioxide and carbon monoxide are also formed.Contrary t28 ABSTRACTS OF CHEMICAL PAPERS.expectation, ozone was found to act much more quickly on the alcoholsof low atomicity, such as methyl and et,hyl alcohols, than on the poly-atomic alcohols, glycol, .glycerol, mannitol, and glucose.The action ofelectrolytic oxygen i s similar to that of ozone in this respect.Action qf Hydrogen Peroxide on t h e AZcoho1s.-Hydrogen peroxideappears to have no actioa on the alcohols, whether in acid, neutral, oralkaline solutions, dilute or concentrated, even after the lapse ofseveral days.The author concludes that the products obtained in the electrolyticexperiments above described are riot due to direct electrolysis of thealcohols, but are simply due to the action on the alcohols of the oxygen,resulting from the electrolysis of the acidnlated water. He suggestst,he electrolytic method as a convenient one for effecting the oxidationof organic bodies at a low temperature, and in a manner permitt'ingthe examination of intermediate products.J. M. H. M.Two New Hydrofluoboric Acids and Ethylene FluoboricAcid. By F. LANDOLPH (Bey., 12,1583-1586).-When boric fluorideact's on amylene, the latter is polymerised, and a fluoboric acid,Bo20iH43HYl, is obtained. It is a clear yellow liquid boiling a t 160",is easily decomposed by water, forming boric acid. A second fluoboricacid, Bo209H1(LHF1, is obtained when boric fluoride acts on anethol a thigh temperatures. It is a heavy, transparent liquid, boiling at 130".Like the above it fumes in contact with air, and is decomposed bywater.Ethylene fluoboric acid, C2H~HF1.Bo02, is formed by the action ofboric fluoride on ethylene at 25-30" in sunlight. It is a clear, mobile,fuming liquid (b.p. 124-125"), of sp. gr. 1.0478 at 23". It burnswith a green flame. Water decomposes this compound, forming boricacid, and a volatile compound (b. p. 10-15'), which does not burnwith a green flame, and is supposed to be ethyl fluoride.Sulphates of Mono- and Poly-hydric Alcohols and Carbo-hydrates. By P. CLAESSOX (Bey., 12, 1719--1721).-Mefhyl sulphateis best prepared by the decomposition a t 130-140" of hydrogenmethyl sulphate obtained by the action of' sulphuric monochlorideon methyl alcohol.P. P. B.Ethyl s u l p h f e is an oily liquid insoluble in water (b. p. 208").The polyhydric alcohols when treated with sulphuric monochlorideyield the corresponding hydrogen sulphates.Dextrose, dextrin, starch, and cellulose, form with sulphuric mono-chloride cZezt~-osechZorz'd e-tet ram@ honk acid, C4H5 ( S 0,OH) 4.C HC 1. C HO ,which cryst allises in large prisms. Corresponding compounds couldnot be obtained with levulose and galactose. w. c. w.Changes of Ammonium Isethionate at High Temperatures.By 3'. CARL (Bey., 12, 1604-1607) .-Ammonium isethionate heateda t 210-220" loses 12 per cent. of its weight, forming a body whichcrystallises from alcohol in leaflets, having a pearly lustre (m. p.196--198).-Seyberth (Bey., 7, 391) has observed the same change,but gives 190-193" as the melting point of the compound producedORGANIC CHEMISTRY. 29which he describes as an amide of the formula C,H7KSOs. Theauthor finds this compound has the formula C4H16S2N207, and explainsSeyberth's results by the suppositiori that his product contained smallquantities of another substance, which is formed simultaneously.Byboiling with baryta-water, this compound does not form barium ise-thionate as it. would if it mere an amide, but a barium salt is formedcrystallising in prismatic tables united to globular masses, having thecomposition C,U1,S2BaO7 + H,O. This salt differs from barium ise-thionate in its action on polarised light, as also i n its solubility i nalcohol. The author regards the new product as ammonium di-isethionate, NH,SO,.( CH,),.O. (CH,).,SO,NH.+Besides ammonium di-isethionate another bod7 is produced, which ismore soluble in alcohol, and has the composition C4H,,S,NO7. Itowes its existence to the evolution of ammonia observed whenammonium isethionate is heated.That it is not anacid salt is shownby the fact that when treated with alcoholic ammonia, and the solutionevaporated on the water-bath, the solution has still an acid reaction.For this reason the author attributes to this compound the formulaNH4SO,.(CH2),.S03.(CHz),.OH. P. P. B.By M. BEES LAUER ( J . pr. Chenz.[ S ] , 20, 188--193).--Von Richter (Ber., 10, 677) observed that drysodium acetate has no action on epichlorhydrin, but that in presenceof absolute alcohol, ethyl acetate and epihydrin alcohol (glycide) areformed. The author confirms von Gegerfelt's statement (BuZl. Xoc.Chim., 23, l60), that epihydrin acetate, C3H50Ac, is produced by theaction of potassium acetate on epichlorhydrin.The best mode ofpreparing this acetate is to heat equivalent proportions of epichlor-hydrin and potassium acetate in a flask provided with an uprightcondenser at 110-115° for several hours, and then raise the tem-perature slowly to 150". By extracting the product with ether,epihydriiz acetate (To. p. 164-168") is obtained, and also a liquid boilingatl 258-261 O , which Gegerfelt regarded as glycerol- triacetin, butwhich is really a polymeride of epihydrin acetate,Epihydrin acetate is a mobile liquid (sp. gr. 1,129 a t 20°), soluble inalcohol and ether. It precipitates metallic silver from an ammoniacnlsolution of silver nitrate. By the action of potash on epihydrin acetatediluted with ethyl acetate, glycerol is produced, but if soda is usedinstead of potash e p i l z y d h atcohol, C3H50.0H, is obtained.Thealcohol boils a t 160°, and is soluble in water, alcohol, and ether.When heated with water glycerol is formed.Diglycid, ( C,H,O.@H),, results from the saponification of the poly-Sugar from Populin. By E. 0. v. LIPPMANN (Bey., 12, 1648-1649). When the glucoside populin, CJ&208 + 2H20, is decom-posed by dilute acids, it splits up into benzoic acid, saliretin, ClaH,,O,,Partial Synthesis of Milk-sugar, and a Contribution to theSynthesis of Cane-sugar. By X. UEMOLE (Compt. rend., 89, 481).Epichlorhydrin-Derivatives.meric modification of epihydrin acetate. w. c. w.and grape sugar. w. c. w30 ABSTRACTS OF CHEMICAL PAPERS.-Schutzenberger (Ann. Chim. Phys., 21, 235), by the action of aceticanhydride on glucose, obtained an acetyl-derivative of a body formedby the union of 2 mols.of glucose with elimination of water, for whichthe author proposes the name of diylucose. Schutzcnberpr consideredthis body identical with octacetyl-saccharose. The solnhili ties cf thesetwo ethers in alcohol are, however, different ; and octacet~yl-saccharosehas a specific rotatory power [a],, = 38.36, whilst that of octacetyl-diglucose is [a]= = 54.62 ; moreover, the saccharose-derivative yieldssacchsrose by saponification, whereas the diglucose-compound yieldsdiglucose.When milk-sugar is heated with a dilute acid, it is converted byassimilation of water into galactose and lactoglucose. When themixture of these bodies, obtained in the-above manner, is dried andheated with acetic anhydride, it is converted into a pitch-like ether,having all the properties of octacteyl-lactose, and giving milk-sugar bytreatment with alkalis.When 2 mols. of glucose, like OF unlike, are in presence of a dehy-drating agent, they are converted into their anhydrides ; and by theaction of these anhydrides on acetic anhydride, an ether of a diglucoseis formed, just as ethylene oxide takes up acetic anhydride to form anReaction of Tungstates in presence of Mannitol. By KLRIN(Compt.Tend., 89, 484).-The action of tungstates on mannitolresembles that of borax. A solution of 12 grams mannitol and4 grams sodium tungstate, made up to 100 c.c., gives %deviation of + 40’. The solution has an alkaline reaction; boiling effects nochange.A solution of 10 grams of mannitol and 4 grams of sodium paratung-state, 5Na,0.12W0,.25H20, made LIP to 100 c.c,, has no rotatory powerin the cold,.but after boiling produces a deviation of + 36’.Thesolution, which is originally neutral, becomes strongly acid onboiling.Barium metatungstate, BaW40,5.9H,0, added to a solution ofmannitol, produces no deviation, even after boiling. The barium saltis not decomposed by the solution of mannitol, although it is by wateralone.If baryta-water be added t o the above solution when boiling, theliquid, after filtering, has a; rotatory power of + 25’; this effect is notether of diglycol. c. w. w.produced in the cold. c. w. w.Decomposition of Ethylamine Hydrochloride by Heat.ByM. FILETI and A. RICCINI (RPT., 12, 1508).-When this salt is beatedto a temperature somewhat lower than that a t which lead melts, amixture of ammonia and mono- and di-ethplamine (separated in neutralsolution by means of potassium nitrite), ethyl chloride and ethylene isevolved, whilst the residue consists of ammonium chloride, diethyl-amine hydrochloride, and some undecomposed ethylairline hydrochlo-ride. The reaction is thus analogous to the decomposition of phenyl-ethylamine by heat, except that a further decomposition into ammoniaanti ethyl chloride takes place. W. RORGANIC CHEMISTRY. 31Cyanethine. By E. v. METER (J. pr. Chem. [2], 19, 484-485).-Cyanethine appears to be a tertiary base. When heated with mode-rateIy dilute sulphuric or hydrochloric acid a t 180-200", it is trans-form€ d into a crystalline base, C9H14N20, which forms easily solubleand Enely crystallising salts.The investigation is being continued.A. J. C.A Double Function of the Monobasic Acids. By LOIR (Apm.Chirn. Phzp. [5], 18, 125-1 38).-In reference to Gerhardt's paper onthe anhydrides (illid. [3], 37, 333), the author considers that if theanhydrides are classed as ethers, that under certain circumstances theacids may act as alcohols, and if such be the case they must also havethe properties of aldehydes. This becomes evident on examination ofthe formula for acetic acid, which may be written thus : OH.CH,.COH.Considered as an alcohol it, is CJ&O(HO), the Ct,H,0 containing analdehyde grouping ClH2.COH.The fbllowing experiments are adducedin support of this vieF.By the action of reducing agents on aldehydes, atcohols are obtained,and when acids are treated with hydriodic acid, Berthelot has shownthat the hydrides of the alcohol radicles are formed.Bntyric acid (b. p. 155-160') when heated with a concentratedsolution of sodium hydrogen sulphite a t O", yields long transparentneedles ; these melt a t 20" without the evolution of sulphurous anhy-dride, whilst butyric acid floats on the top of the solution. On col-lecting the crystals, dissolving in water, and distilling with sulphuricacid, sulphnrc>us anhydride is evolved, and biityric acid distils over.R n tyric acid decolorises potassium permanganate, and reduces ammo-niated silver solutions.That acetic anhydride possesses the functions of an aldehyde as wellas an ether has been shown by the author (this Journal, Abst., 1879,621).Acetobenzoic anhydride, however, exists in two isomeric modifica-tions, according as it is prepared from sodium benzoate and aceticchloride, in which case the author calls it acetyb henzoic tcnhydride, orfrom sodium acetate, and benzoic chloride, when it is called benzoyl-acetic nrrhydr-ide.The two bodies have the same chemical properties,except in their reaction with hydrochloric acid.Beizzoy Z- acetic cilzhydride when heated in hydrochloric acid gas boils atISO", and acetic chloride comes over, leaving benzoicacid as a crystal-line rpsidue.AcetyZ-benzoic anhydride when treated in a similar manner boils at160', and benzoic chloride distils over.With chlorine similar results are obtained, the residue in the firstcase being chlorobenzoic acid, and in the second chzoracetic acid.These two isomeric bodies may be considered as ethereal salts;benzoyl acetic anhydride being the acetic salt of benzoic acid whichacts as an alcohol, whilst acetyl benzoic anhydride is the benzoic saltof acetic acid acting as an alcohol.Renzoic chloride at 0" forms a crystalline compound with sodinlnhydrogen sulphite.Since glyoxal and glyoxyli: acid are obtained from alcohol by theValeric acid has similar properties.The same holds good for butyric anhydride32 ABSTRACTS OF CHEMICAL PAPERS.action of nitric acid, they may be considered as derivatives of aldehydeand acetic acid.As glyoxal, COH.COH, contains the aldehyde-grouptwice, its mode of formation depends on the previous formation of analcohol aldehyde ; arid as me have acetic acid (alcohol), OH.CH,.COH,yielding glyoxylic acid, 0H.CO. COH, containing the acid and aldehydegroups, i t requires the same conditions.A table showing the relations of the derivatives of alcohol and aceticacids is given. L. T. 0's.Existence of Double Salts in Solution. By P. H. B. INGEF-HOES (Ber., 12, 1678--1684).--Bariurn formio?citrats, Ba.NO,.CHO, +2Hz0, is prepared by dissolving barium nitrate i n an almost satu-rated warm solution of barium formate. Crystals of barium nitrateare first deposited, and then the double salt separates out.Solutlionsof barium formio-nitrate and aceto-nitrate and calcium acetochloridewhen dialysed, diffuse like mixtures of simple salts ; this shows thatthese salts dissociate in dilute solutions. w. c. w.Oxidising Action of Cupric Oxide ; Transformation of AceticAcid into Glycollic Acid. By P. CASENEUVE (Compt. rend., 89,525).-It is known that formic acid is oxidised by cupric oxide tocarbonic acid, and similarly, if carbonic acid be regarded as the acidof methylene glycol, it might he expected that acetic acid, the homo-logue of formic acid, would be oxidised to glycollic acid.Cupric acetate was heated in a sealed tube with water a t 200" foran hour. The tube contained crystallised cuprous oxide, and a liquidwhich deposited crystals o i glycollate of copper.A small quantityof carbonic anhydride was also formed. The reaction is probablyexpressed by the equation, 2Cu(C2H302), + 2H,O = C2H403 +The carbonic anhydride is due to a secondary reaction by whichpropionic acid is also formed: 2Cu(CaH30,), + H,O = CO? 1-C,H,O, + CuzO + 2CzH402 : this reaction takes place to a very limitedand variable extent.CUZO + 3CzHi02.c. w. w.Action of Nitric Acid on Epichlorhydrin. By V. V. RICHTER( J . yr. Chem. [2], 20, 193-195) .-When epichlorhydrin is treatedwith 3 or 4 parts of warm nitric acid (sp. gr. 1.38) an energetic reac-tion takes place. On pouring the acid liquid into water and extractingwith ether, monochZoroZactic acid is obtsined. To r2move the chloro-nitrohydrin and oxalic acid with which it is mixed, it is dissolved inwater, again extracted with ether and converted into the calcium salt.The acid crystallises in flat prisms (m.p. 77"), which are deliquescentEthyl Nitracetate. By FORCRAND (J. pr. Chem. [el, 19, 487-488).-This is obtained by the action of silver nitrite on ethyl bromacetate.The product is distilled, and the portion which pawes over at 130"(with slight decomposition) is essentially ethyZ rzitranetate, a liquid ofsp. gr. 1.133 at 0' (b. p. 151-153"). By the action of zinc and hydro-and dissolve readily in alcohol, ether, and water. w. c. wORGANIC CHEMISTRY. 33chloric acid it was converted into amido-acetic hydrochloride, whencethe silver salt was obt(ained in iridescent crystals which blacken onexposure t o the light.Preparation of Nitrated Fatty Acids.By J. LBIWKOWITSCH (J. pr.Chem. [2], 20, 159-173).-Nitro-products could not be obtained bythe action of the strongest nitric acid (sp. gr. 1-53) o r of a mixture ofiiitric and sulphuric acids on caproic and stearic acids.EthyZ nityoacetate, CH,(NO,).COOEt, is formed by digesting ethyliodacetate with silver nitrite at 100' ; towards the end of the processthe mixture is heated up to 130". On treating the product with abso-lute ether, a pale-yellow liquid, insoluble in water, is obtained, whichboils between 150" and 160" with decomposition.E t h y l nitropropionate, prepared by the action of silver nitrite onethyl 6-iodopropionate (which is most readily obtained by heating analcoholic solution of 6-iodopropionic acid with a small quantity of sul-phuric acid), is a colourless mobile liquid (b.p. 161-165"). Theethyl salt dissolves in a dilute solution of potash ; by acidifying theliquid with sulphuric acid and extracting with ether, crystals of nitro-propionic acid were in one instanoe obtained, but the operation gene-i d l y yields a thick liquid which dries up to a hard glassy mass whenexposed over sulphuric acid.P-Nitropropionic acid is easily obtained by adding about 2 equivalentsof silver nitrite to 1 of P-iodopropionic acid dissolved in water. (Thebest results are gained bg working with not more than 5 grams ofiodopropionic acid for each operation.) The solution of silver nitro-propionate which is formed is decomposed by hydrochloric acid andextracted with ether.After evapora'ting the ethereal soltition, a thickliquid remains which solidifies forming a white deliquescent crystallinemass. By recrystallisation from chloroform, the nitro-acid is obtainedin pearly-white scales which melt a t G6" and decompose a t 160". Theacid is soluble in water, alcohol, and ether ; its salts are also soluble inwater, but undergo decomposition. By reduction with tin and hydro-chloric acid, /3-nitropropionic acid is converted into /3-alrcizine 1zydro-chloride. w. c . w.A. J. C.Derivatives of Thiacetic Acid. By S. GABRIEL (Ber., 12, 1639-1641).-Phe~z2/Zene-dithiacetic acid, C,H,(S.CH,.COOH),, is preparedby the action of chloracetic acid (2 mols.) on a warm alkaline solutionof thioresorcinol (1 mol.).On acidifying t'he mixture with hydro-chloric acid, the acid separat'es out as an oily liquid, which soonsolidifies to a crystalline mass. The crystals melt a t 127", forming aturbid liquid which becomes clear at 1.50".Toluene-dithiacetic acid, C6H,Me(S.CH,.COOH),, obtained by asimilar reaction, crystallises in needles (m. p. 151*5"), soluble in hotwater.PhenyZene-dioxyacetic acid, C,H4(0.CH2.COO€I)2, produced b, theaction of chloracetic acid on an alkaline solution of resorcinol, fornispale-yellow crystals (m. p- 193"). Dibro.lno~lL~n~le.1Le-dioxllacetic acid,separates out as a white powder when bromine vapour is passed intothe aqueous solution of this acid. It is deposited from a hot alcoholicVOL.YXXVIII. 34 ABSTRACTS OF CHEMICAL PAPERS.solution in white, silky needles (m. p. 250"). Benzyl-thiacetic acid,C6H,.CH,.S.CH2.COOH, crystallises in flat plates (m. p. 59"). Theantide, C6H3.CH2.S.CH2.CONH2, is obtained in rectangular plates(m. p. 97"), by the action of ammonia a t 100" on ethyl benzyl-thi-acetate (b. p. 275-290"). w. c. w.Lauric Acid and its Conversion into Undecylic Acid. By F.KRAFFT (Bey., 12, 1664-166€) .-Lauric acid is best prepared fromcommercial bay oil (01. Zaurin w~girinos). For this purpuse the oil issaponified by boiling with a solution of potash for several hours ; thepotash soap is decomposed by warm hydrochloric acid, and the mixtureof acids thus set free is distilled under greatly diminished pressure.The first portion of the distillate subjected to repeated redistillationunder diminished pressure yields pure lauric acid (m.p, 435", b.p.222-5" under 100 mm. pressure).The ketone, C,,H2,0, obtained by the dry distillation of a mixtureof barium laurate and acetate under diminished pressure, melts a t 28"and boils a t 263". On oxidation with chromic mixture this substanceyields acetic acid and an oily liquid consisting of a mixture of unde-cylic acid and unaltered ketone. The undecylic acid is converted intoits barium salt, which is treated with ether to remove the ketone.This acid crystallises in scales, which melt a t 28.5" and boil at 213'under 100 mm. pressure. w. c. w.Tridecylic, Pentadecoic, and Margaric Acids. By F. KRAFFT(Ber., 12, 1668-1 675) .-Myristic acid, prepared by the saponificationof Muscata butter and purified by distillation under diminished pres-sure, melts a t 53.5" and boils at 248" under 100 mm.pressure.The ketone, CI,Hl,O, obtained by the dry distillation under dimi-nished pressure of a mixture of barium acetate and myristate, meltsak 39", boils at 294", and on oxidation yields acetic and tridecoicacids.The latter acid, purified by redistillation and conversion into itsbarium salt, melts at 40.5" and boils a t 2Z6" under 100 mm. pressure.By a similar process pentndecoic acid, C15H3002, can be obtainedfrom palmitic acid (m.p. 62" and b. p. 268.5" under 100 mm. pressure).The ketone melts a t 48" and boils a t 320". Pentadecoic acid meltsat 51", and boils a t 257" under 100 mm.pressure.Mnrywic a,cid, prepared synthetically from stearic acid (b. p. 387"under 100 mm. pressure), is identical with the margaric acid obtainedby Heintz (Pogg. Ann., 102, 257) by the saponification of cetylcyanide. The acid melts a t 59.8" (uncorr.), and boils at 277" under100 mm. pressure.The discovery of tridecoic and pentadecoic acids makes the list offatty acids complete as far as stearic acid. w. c. w.Hydroxethylrnethylacetic Acid. By W. v. MILLER (Bey., 12,1544).-To show that Neubauer's angelic acid resulted from ethyl-methylacetic acid, which, together with isobutylformic acid, is a productof the oxidation of amyl alcohol obtained by fermentation, the autlioORGANIC CHEMISTRY. 35prepared ethylmethylacetic acid by Sauer's process, and oxidised itwith potassium permanganate.The product was 'a-hydroxethyl-methylacetic acid, CEtMe(OH).COOH (m. p. 68'). On didilling thisacid with sulphuric acid no methylcrotonic acid was formed.W. R.Hydraxisobutylformic Acid. By W. V. h'lraLEin (Ber, 12, 1542-1543).--From a careful comparison of the copper salts, the authorconcludes that the dimethacrylic acid, prepared by him by oxidising6-hydroxisobutylformic acid, CMe,( OH).CH,.COOH, is identicalwith an acid obtained by A. and M. Sajtzeff, by oxidising syntheti-cally prepared ally1 dimethyl carbinol. The P-hydroxisobutylformicacid, of which the formula is given above, is an intermediate productbetween isobutplformic acid and its ultimate product of oxidationwith potassium permanganate, viz., dimethacrylic acid.W. R.Synthesis of Ketonic Acids. By P. HOFFERTCHTER ( J . pr. Chem.[a], 2Q, 195--20O).-FrichZoru,cetic cyanide, prepared by the action ofsilver cyanide on trichloracetic bromide, is a colourless liquid (b. p.117-119"), soluble in ether. It refracts light powerfully, and has asp. gr. 1.559 a t 15". It is decomposed by water with formation ofhydrocyanic and trichloracetic acids. On exposure to moist air, adeliquescent white crystalline substance is formed. A solid poly-meride, which is produced in small quantities in the preparation of theliquid trichloracetic cyanide, crystallises in rhombic plates (m. p. 140"),soluble in alcohol and in ether. It is decomposed on boiling withwater.Trichloracety Zcarboxy Zic acid is formed when the liquid cyanide istreated with dilute hydrochloric acid (sp.gr. 1.16) a t 50". It isseparated from trichloracetic acid by recrystallisation of the sodiumsalts. Sodium trichloracetylcarboxy late cry stsllises in prisms contain-ing 2 mols. HzO, which are less soluble than the tabular crystals ofsodium trichloracetate. The acid forms small prisms (m. p. 89O),soluble in water. By the action of fuming hydrochloric acid on tri-chloracetic cyanide, a white cr,ystalline amide is produced, whichappears t o have the composition C,C1,05H8N2. w. c. w.Maleic Acid from Dichloracetic Acid. By S. TANATAR (Ber.,12, 1563-1566) .-Ethyl dichloracetate dissolved in alcohol is notacted on by molecular silver a t the boiling point of alcohol ; if, how-ever, ethyl dichloracetate is heated with molecular silver a t 210" insealed tubes, silver chloride is formed, and a small quantity of anethereal salt boiling about 210", which on saponification with baryta-water yields barium mnleate.Sodium acts energetically on dry ethyl dichloracetate ; if the reactionis modified by use of anhydrous ether, there is found amongst the pro-ducts of decomposition, an ethereal sait distilling between 100-120",which is more soluble in water than the ethyl dichloracetate; it issoluble in warm baryta-water.On standing, this solution decomposeswith formation of barium carbonate. The nature of this product isas yet unexplained. P. P. B.d 36 ABSTRACTS O F CHEMICAL PAPERS.Occurrence of Tricarballylic and Aconitic Acidk in Beet-Juice.By E. 0. VON. LIPPMANN (Ber., 12,1649-1651) .-Tricarbally-lic acid is not found in fresh beetroot, but the author confirms hisprevious observation (Ber., 11, 707, this Journal, 1878, Abst., 662) as tothe occurrence of 6he calcium salt of this acid in the vacuum pans ofthe beet-sugar manufactory. Aconitic acid, detected by Behr in thejuice of the sugar-cane (Ber., 10, 351, this Journai, 1877, 2, 182) isBy G. STEIN (Ber., 12,1603) .-According to Lucas and Trommsdorf (Annct7en, 8, 237) theacid contained in this plant is malic, whilst Reess and Will (Centyal-blirtt f . AgricuZticrchei~zie, 10, 230) suppose it t o contain formic, pro-pionic, and butjric acids, and finally Hager asserts that it containscitric and malic acids.The author has extracted some of this acid,and from the characters of its salts concludes that i t is citric acid.The acid has also been cjhtained crystallising in rhombic prisms, andthe analysis of its lead salt shows it to be citric acid.Derivatives of Triethyl citrate. B y J. CONEX ( B e y . , 12, 1653-1655).-T~-lethyZ citpate, C,H,OH( COOEt),, prepared by the action ofhydrochloric acid on a mixture of citric acid and alcohol, is a thickcolourless liquid, sp. gr. 1.1369 at 20° compared with water a t 4",b. p. 261" under 300 rnm. pressure.Tetrethyl c i t m f e , C,I-I,OEt(COOEt),, is formed when the product ofthe action of sodium on triethyI citrate (diluted with dry ether) isheated with ethyl iodide atl 100".This citrate is a pale-yellow oil,sp. gr: 1.1022 a t 20", boiling a t 290" with decomposition.A liquid having the composition C,H,(COOEt),, and of sp. gr.1.1064, is produced by hesting a mixture of phosphorons chloride andethyl citrate a t 100".also present in beet-j uice. w c. w.The Acid of Drosera Intermedia.P. P. 13.This substance decomposes on dist3illation. w. c. w.Action of Phosphorus PentachIoride and Hydriodic Acid onSaccharic Acid. By H. m LA MOTTE ( B e y . , 12, 1571--1573).-Theresults published by C. J. Bell (t.his Journal, Abst., 1879, 917) arethe same as those published by the author in his Dissertation (Halle,1878). The author also points out that chlorornucic acid obtainedfrom saccharic or mucic acid always crystallises with 2 mols.of waterof crystallisation, C6H4C1,O~2H,O.Saccharic acid when heated with hydriodic acid and amorphousphosphorus in sealed tubes a t 140-150", yields a small quantity of anacid, m. p. 148-149", the analysis of whkh, and its properties, as alsothose of its salts, show it to be adipic acid. P. P. B.Ccmstitution of Deoxalic Acid. By J. K L E r x (J. pr. Chem. [2],20, 146-159).-By acting on ethyl oxalato with sodium-amalgam,Liiwig, in 1861, obtained a substance of the formula C1lHlsOs, whichhe regarded as the triethyl salt of deoxalic acid, C5H,0e, and by heat-i n g this with dilute sulphuric acid, he converted it into ethyl racemate,with evohtion of carbonic anhydridc. Brunner, in 1870, contendeORGANlC CHEMISTRY.37that the original reduction-product of ethyl oxalate has the formulaClrH200g, and is the triethyl salt of an acid of the formula CeH60g,which, however, he could not isolate, owing to its decomposition intoracemic and glyoxylic acids. The author has confirmed Lowig's resultsin the following manner :-Et"nyl deoxalate prepared by the action ofsodium-amalgam on ethyl oxalate melts a t 85", and has all the pro-perties attributed to it by Lowig. The barium salt was prepared bytitrating the ethyl salt with standard baryta-water. Bot'h the titra-tion and the ai~alysis of the barium salt point to the correctness ofLowig's formula. The calcium salt has the formula ( C5H308)2Ca3.The free acid, prepared from the barium salt by means of sulphuricacid, forms very deliquescent crystals, and from several analysesappears to have the formula C,H,O,.HI,Q.Treated with acetic or with benzoic chloride, it farms monacetyl-and benzoyl-deoxalic acid, and with acetic anhydride, or with benzoicchloride, a t a higher temperature, a diacetyl or dibenzoyl acid.Itlappears therefore to contain two alcoholic hydroxyls. The amount ofcarbonic anhydride erolved on bailing the acid with dilute; sulphuricacid was estimated, and agreed with the equation C,H,O,.Et, =C,H,O,.Et, + CO,, ethyl racemat'e being formed a t the same time.The ethyl raceniate gave an acid agreeing with the ordinary racemicacid in all its properties.On heating deoxalic acid with hydriodic acid no reduction tookplace, but it was converted into racemic acid, and a t a still highertemperature, succinic acid .was produced.The tricarboxylic acid,of which debxalic acid is a hydroxylic derivatire, was not isolated inthis reaction. W. R.Synthesis of the Closed Benzene Ring. By V. v. RICHTER( J . p. Chena. [el, 19, 205--208.-In order to accomplish the synthesisof benzene by means of diethylene-diketone the author subjected thesuccinates of potassium, sodium, magnesium, calcium, and lead to drydistillation. The distillate contained quinol, and benzene was obtainedby the action of zinc dust on the distillate, but diethylene-diketane hasnot yet been isolated.Xo benzene derivatives were formed by distilling ethylene succinatewith zinc dust. w. c. w.Derivatives of Isodurene. By M.BBTECEFELDT (AnnaZen, 198,380--388).--The isodurene used in .these experiments was prepared bythe method described by Jannasch (Ber., 8, 355), viz., by the actionof sodium on a mixture of monobromomesitylene and methyl iodidediluted with a small quantity of benzene. Tsodurene boils at 195-19 7". Isodz~renesu~~~iorLic acid obtained by treating the hydrocarbonwith fuming sulphuric acid crystallises in plates which meltin their water of crystallisation at 100". Lead isodurenesulpl~ate,(CGHMe4S03),Pb + 3H20, forms needle-shaped crystals, so also dothe salts of barium (anhydrous), cdciuin (3H20), and potassium(lH,O). The copper s d t crystallises in pale bluish-green needles,which are anhydrous. The siZuer suZt forms trandparent rhombicplates ; the strontium salt is deposited in lustrous plates containin38 ABSTRACTS OF CHEMICAL PAPERS.9 mols.HzO. The sodium sa7t crystallises in shining rhombic platescontaining 6 mol. H,O. The cohalt snlt crystallises in pale red four-sided plates which contain 74 mols. HzO.When isodurene is boiled with dilute nitric acid (1 : 4) for two days,a mixture of a- and 6-isoduric acids (CloH1202) is formed, togetherwith a polybasic acid, which does not melt a t 300", and also severalnitro-products. The a- and @-acids can be separated by recrystallisa-tion from hot water, or by fractional crystallisation of their calciumsalts.a-Isoduric acid melts a t 215" and at a higher temperature sublimes,forming long glistening needles. It is very sparingly soluble inwater, but dissolves in alcohol, ether, and hot benzene. Prom a diluteethereal solution, the acid is deposited in clear monoclinic crystalswhich refract light powerfully.The a-acid can be distilled in acurrent of steam. Ibs salts are crystalline and are soluble i n water.( CI0H110&Ca + 5E20, ( CloHllOz)~Sr + 5H@, and ( CloHl102)2Ba + 4H2Oform needle-shaped crystals.P-lsoduric acid is much more soluble in water, ether, chloroform,benzene, alcohol, and light petroleum than the a-acid. It crystallisesin needles which melt at liL0-123°, The oaZciurn salt forms glisten-ing needle-shaped crysbals containing 2 mols. H.0.Monobromisodurene boils at 252-254", and crystallises in nacreousBehaviour of Cymene in the Animal Organism. By JACOBSEB( B e y ., 12, 1512--1518).-As cImene has been prepared from normalpropyl iodide and parahromotJoluene, and as the author has shown thatthe hydrocarbon produced from parabromocumene and methyl iodide isnot cymene, but an isomeride,.no doubt would remain regarding thecoristitution of cymene were it not for two reactiions. The first of these,noticed by Kraut and aonfirmed by the author, is that cymene is pro-duced by the action of zinc dust on cymyl alcohol, and the second isthe oxidation of cymerie in the organism to cuminic acid, observed byNencki and Zieglen. Bobh of hhese results are unfavourable to thetheory that cymene contains a normal props1 group. In the present,paper, the author gives an aocount of a repetibion of Kencki aiidZiegler's experiments.The cymene was administered to a.dog, and its urine, after evapo-ration, was acidified and shaken with ether. After distillating off theether, the residue gal-e a copious precipitate with hydrochloric acid,which was found to consist for the most part of cuminuric acid,CI,Hl,NO,. The filtrate from this precipitate gave a, distillate contain-in; a little paraxylylic acid, showing that the cymene administered tothe dog had contained a little pseudocumene.Cuminuric acid melts a t 168", and volatilisea without decomposi-tion. It is almost insoluble in cold, but comparatively easily solublein warm water ; it dissolves with the greatest readiness in alcohol ;ether, however, dissolves it with difficulty. From water it crystal-lises-(l), on addition of an acid, in nacreous scales; and (2), onslow evaporation, in large iridescent rhombic plates, without water ofcrystallisation ; and from alcohol, on evaporation, in radiated crystals.plates.TV. c. wORGANIC CHEMISTRY. 39The barium saZt, ( C,,H,4N03)2.H,0, dissolves wiih some difficulty,and crystallises from its hot solution in long right-angled plates orin flat needles, arranged in a fan-shaped form. The caZczuwz srclt,( C,2H2,N0,)2.3H20, crystallises in thin needles, and is also solublewith difficulty. The unmmiurn and potassium salts are very easilysoluble, and crystallise in needles. The two latter salts give pre-cipitates with salts of zinc, manganese, cadmium, magnesinm, ferrousand ferric salts, copper, lead, and silver ; with mercuric chloride, itgives no precipitate, and with mercuric nitrate, a flocculent insolubleprecipitate.This cuminuric acid probably differs from that which Cahours pre-pared from cuminic chloride and glycolyl silver.I n order further t o confirm the relations of this acid, it was decom-posed by heating with liydrochloric acid ; it split up into glycocine andcuminic acid, melting a t 116-117", and agreeing in all its propertieswith that described by others.It thus appears that cuminic acid isreally a product of oxidation of cymene in the animal organism, butto remove all doubt, and further to connect cumiiiic and cuminuricacids, the latter acid was synthetically prepared from cymyl alcoholand glycocol silver. The product was identical in all respects withthat separated from the uriue.If, then, there is conclusive proof that cumene contains normalpropyl and that cuminic acid contains isopropyl, then the preparationof cumene from cymyl alcohol with zinc dust involves the trans-iormation of isopropyl into normal propyl, and, on the other hand, theformation of cuminic acid from cymene implies the opposite change.In conclusion, the author draws attention to the fact that in hisexperiments, the chief product was cuminuric acid, whilst in those ofNencki and Ziegler, cuminic acid was formed.He also found thelatter acid, but in very small amount. W. R.Products of Distillation of Gum-ammoniac Resin withZinc-dust.. By G. .L. CIAMICIA4N (Bey., 12, 1658--1664).--The oilyliquid which is obtained by the distillation of gum-ammoninc resinwith zinc-dust consists of a mixture of para- and metaxylenes (b.p.136-138"), meta-ethyltoluene (b. p. 160"), methyl ortho-ethylphenate(G. p. 180-200"~, and a hydrocarbon having the composition C,3H,n0,which yields on oxidation henzoic, acetic, and perhaps propionic acids.No naphthalene derivatives are formed. Ortho-ethylphenol obtaiuedby the saponification of the methyl ether is a thick, colourless oil(b. p. 220"), which remains liquid when cooled down in a freezingmixture. On fusion with potash, it is decomposed with production ofCondensation-products of Aldehydes with Primary AromaticBases. By 0. PISCHER (Bey., 12, L693-1694),-Although the authorwas unable to obtain dia?)iidotri~henyZmethane by decomposing tetra-inethyldiamidotriphenylmethane with concentrated hydrochloric acid,he has succeeded in preparing it by the action of zinc chloride on amixture of aniline and benzaldebyde.This base is a crystalline sub-stance and is soluble in light petroleum. By the action of methylsalicylic acid. w. c. w40 ABSTRACTS OF CHEMICAL PAPERS.iodide, at 130", on the solution of the base in methyl alcohol, Letra-methyldiamidotriphenylmethane methiodide is produced. w. c. w.Condensation-products of Tertiary Aromatic Bases. By0. FISCHER (Ber., 12, 1685-.1693).-A good mode of preparingtetrn7neth~ldinmic7otr~?tenylmetliaite consists in digesting on a water-bath a mixture of benzaldehyde (I mol.) and dimethylaniline (2 mols.)m ith a quantity of solid zinc cliloride, equal in weight to the dimethyl-aniline taken, until scarcely any dimethylaniline separates out on theaddition of an alkali to a small quantity of the product.If the massgrows very thick during the operation, sufficient water should beadded to reduce it to a pasty consistency. The solution obtained bytreating the crude product with boiling water deposits the base in astate of comparative purity. The IydrochZoride, Cz3H,,N22HC1, crys-talliges out in colourless hygroscopic needles, when ether is added t o asolution of the base tiissolved in strong hydrochloric acid mixed withalcohol. The methiodide, C,,H2JY22MeI, is deposited from concentratedaqueous solutions in plates, and from dilute solutions in needles,which melt a t 218-222" with decomposition izto methiodide andthe original base.T e t rai72ethyldiai7aidotri23T2 en y lcarbinol, C,,H,,N,.H,O, the base con-tained in benzaldehyde green, is obtained in colourless needles byrecrjstallising from light petroleum the precipitate formed by theaction of an alkali on the salts produced by the oxidation of the leuco-base.The crystals melt at 120°, and form ethers when recrystallisedfrom alcohol. The etlryZ ether, best prepared by heating the carbinolwith alcohol at llO', melts a t 162".The zimochloride, C,3H24N, + ZnC1, + HzO, crystallises in dark-green glistening needles or scales freely soluble in water. Thesulyhate, CZsHz4N2 + HzS04, forms beetle-green needles, containing1 mol. of water.The metliiodide, C23H2,0C&N2(MeI)2 + 2H20, crys-tallises in colourless needles, which begin to decompose a t 100".The constitution of benzaldehyde green (Ber., 12, 796 ; and thisJournal, 1879, Abst., 787) is represented by one of the followingformids :-C6H4NMe CH,.Ph( CsH,.NiWe2)C<&:>NMe, or Ph(C,H,.NMe,)C( 1Tet rcnmeth y Idinmidoprop y Ztr+ 1~ eny 1 me€hane, obtained from cumic alde -hjde and dimethylaniline, crystallises in long colourless needles (m. p.118"). It bears close resemblance to the leuco-base of benzaldehydegreen, yielding on oxidation 8 bluish-green colouring matter.Dimethylaniline and methylal yield tetramethyldiamidodiphenyl-methane (m. p. 91"), which has been previously described by Han-hart (Bey., 12, 681 ; this Joarnal, 1879, Ahst., 714.Doebner (Ber.,12, SlO), and by Michler arid Moro (ibid., 12, 1170). The compoundwhich Pauly ( A n n a l e n , 187, 198) obtained by the action of benzoORGANIC CHEMISTRY. 41phenone chloride on dimethylaniline has the composition C21H21N, andnot. C2,H,,N as given by the discoverer.Dimethylaniline-phthale'in, C2.1HllN202, is prepared by the action ofzinc chloride on a mixture of phthalic chloride and dimethylaniline.The excess of dimethylaniline is removed from the resulting productby treatment wit<h hot water, apd the residue is dissolved in diluteacetic acid. The precipitate which is thrown down on the additionof an alkali to this acid liquid is dried and dissolved in a small quantityof benzene.When light petroleum is poured into this solution, theimpurities separate out, together with a portion of the phthalein. Onevaporating the filtrate, the phthale'in slowly crystallises out, and ispurified by recrystallisation from benzene. The pure substance formscolourless rhombohedrons, which melt, at 188". A green colonringmatter is produced as a bye-product in the preparation of dimethyl-aniline-phthalejin ; its formation increases with the temperature a tSome New Colouring Matters. By P. GREIFF (Bey., 12,which the process is conducted. w. c. w.1610-1611) .-By the action of chloranil on dimethylaniline, a deepbluish-violet colouring matter is obtained ; it is insoluble in water, butdissolves in alcohol and acetic acid. Methyldiphenylamine gives acolouring matter of a deeper blue.These reactions take place a t theordinary temperature, and give good yields. Quinone gives similarproducts. Chloranilic acid and the s-ulpho-acids of chloranil reactdifferently. Phenanthraquinone gives under similar circumstancesbluish-violet bodies, having strongly marked dichroism. The additionof zinc chloride in all these reactions is advantageous. P. P. B.Action of Hydrocyanic Acid on Diazo-compounds. ByS. GABRIEL (Bey., 12, 1637--1639).-A substance, having the com-position C8&N4, separates out in orange-colonred crystals when a coldaqueous solution of diazobenzenesulphate or nitrate is allowed to dropslowly into a well-cooled solution of potassium cyanide. The crystalsare dissolved in a small quantity of warm alcohol, and warm water isadded to the solution.When .the mixture cools, large prisms (m. p.69") are deposited, which decompose, forming a brown resin, if left incontact with the mother-liquor for several hours. The compound isalso decomposed by boiling in water, hy drocyanic acid being evolved,and a resinous bodyformed.By the action of potassium cyanide on bromodiazobenzene nitrate(from bromaniline, m. p. 61) an unstable crystalline product (m. p.127.5") is obtained, which appears to have the composition C8H,BrN4.By a similar reaction, the compound CgH8N4 may be prepared fromtoluene. It is deposited from an alcoholic solution in reddish-yellowplates or needles, which melt at 77-5", but decompose if heated a t 60"for some time.w-. c. w.Formula of Quinhydrone. By H. WICHELHAUS (Bey., 12,1500-1505).-The question considered in this paper is which one of the fol-lowing formulae for qninbydrone is the correct one :-HO.CJ&. O .O. C6H4. OH = C,?H,,O42 ABSTRACTS OF CHEMICAL PAPERS.proposed by Graebe, or H0.C6H,0.0C6H,0.0C,H~.oH = C20H1006,siiggested by the author.Nietzki's argument in favour of the former formula is, that asquinone is reduced to quinol in theoretical proportion by sulphurousacid, quinhydrone should also be acted on in the same manner. I nsupport of this view, he has adduced a series of experiments, in whichquinhydrone was reduced by such a qnantitg of sulphurous acid as tolead to the formula C,,H,,,Oa.The author has repeated these experiments, and has fonnd that theyare untrustworthy, owing to the fugitive blue colour produced by iodinein pyesence of quinhydrone during titration of excess of sulphurousavid.He next brings forward in support of his own views, the factthat ~nethylquinhydrone, prepared by melting ab 100" a mixture ofmethylquinol with quinone, gives numbers which, though differingliut slightly from those required for Graebe's formula, still agreebetter with the formula proposed by him; also, t!liat during the re-action between methylquinol and qninone, hydrogen i s set free, whichreduces the latter, giving rise to a considerable formation of quinol ;and, lastly, that on decomposing methylquinhydrone with sulphurousacid, the resulting quinol bears to the methylquinol the.proportion of1 : 2.5. This agrees closely with the proportion calculated forC20Hl,06, viz., 1 : 2-26, but not with that for C,,H,,OA, viz., 1 : 1-13.In further support of his views, the author calls attention t o thefact that dimethyl- and diethyl-quinone have no action c?n quinol, forhydroxyl is not present in their molecules. When substituted quinolsact on quinone, unsubstituted quinhydrone is invariably focmed, whilsta reduction takes place owing to the liberated hydrogen.I n a similar manner the formation of chloroquinol by treatment ofquinone with hydrochloric acid is explicable by the followingequations :-C&02 + 2HC1 = C~HGOZ -k GI,; and c12 -k c6&02 =An analogous reaction takes place with hydrobromic acid.C*HSG102 + HC1.Theresulting monobromoquinol has the formula C6H5Br02; it may besublimed in small quantities, melts at 110-112", and is soluble inchloroform, benzene, and hot water: During its purification by crys-tallisation from light petroleum, a product, agreeing fairly with theformula CGH4Br20, is obtained less soluble Ghan the former ; it crys-tallises in white needles grouped in stars, and melts a t 185-186".W.R.Constitution of. Phenylhalogenpropionic Acids. By E. ERLEN-NEYEIR (Bsr., 12, 1607-1610). The author criticises the views heldby Glaser (Annalen, 154, 167) and Fittig (ibid., 195, 170) on theconstitution of the phenylhalogenpropionic acids and phenyllacticacids prepared by them, and concludes that these acids have the fol-lowing constitutions :-C6H,.CHX. CH,.COOH ; C6H5. CH (OH). CH,. CO OH, andCGHs.CH(OH) .CHX.COOH. P. P. BORGANIC CHEMISTRY. 43Monobromocinnamic Acids and Phenylfumaric Acid. ByF. BAKISCH ( J . p. Chenz. [23, 20, 173-188).-By the action ofalcoholic potash on dibromohy drocinnamic acid, Glaser (AnmZei-L, 143,330) obtained two isomeric monobromocinnamic acids, which wereseparated by recrystallising their ammonium salts. /?-Bromostjrene,PhCBr : CH, (b. p. 117"), is former1 as a bye-product in this opera-tion from the decomposition of a portion of the monobromocinnamicacid (m. p. 131"), PhCBr : CH.COOH.Glaser prefixes a to the acid crystallising in needles (m. p. 131"),and calls the isonleride which forms crystalline plates (m.p. 120°)the &acid.The author proposes to reverse this nomenclature. sincea-derivatives have a lower melting point, and enter inore readily intoreactions than PLcompounds. Both a- and 13-monobrornocinnamic acidwhen treated with alcoholic potash yield the same phenylpropionic acid,PhC i C.CO0H. When hydrochloric acid is passed through theiralcoholic solutions, they both yicld the same ethyl 6-bromocinnamate(13. p. 290"). The a-acid during the act of etherification is transformedinto the 6-acid.P'henyIfuinaYic acid, CloH804, or COOH.CPh : CH.COOH, is ob-tained by heating at 150" a mixture of potassium c-janide, alcohol, andethyl-P-bromocinnamate, and builing the product with alcoholicpotash. On the addition of hydrochloric acid, a resinous substanceseparates out, the supernatant liquid is concentrated by evaporationand extracted with ether, whrn the new acid is obtained in whitecrystals (m.p. 161"), freely soluble in alcohol, ether, and hot water.The potassium, sodium, ammonium, calcium, and barium salts of thisacid dissolve readily in water. TV. c. w.Formation of Para-hydroxybenzoic Acid from Sodium Phe-nate. BJ- H. OST (J. p ~ . Cl~em. [2] 20, 208).--Very small quantitiesof para-hydroxybenzoic acid and traces of a-phenol-dicarboxylic acidare formed by the action of carbonic anhydride on sodium phenate.The presence of these acids can be detected in the filtrate after theConstitution of Ellagic Acid. By H. SCEIFF (Ber., 12, 1533-1537) .-Gallic acid, when boiled with, arsenic anhydride, forms digallicacid by union of twosmolecules.If the mass is dried and heated tolC;O", the arsenic acid is reduced and ellagic acid is formed :-The question is, are the two benzene-groups in ellagic acid uniteddirectly, o r by means of oxygen ? The ease with which that acid isformed from gallic acid seems to point to a~ negative answer ; but, onthe other hand, no attempt to convert ellagic into gallic acid has beensuccessful. Assuming that direct union subsists, the author suggeststhe following formulax-precipitation of the salicylic acid. IT. c. w.2C14H1009 + As205 = 2C,4H,O, + 4HzO + AS~O~.2C6H,( OH),.COOH = C6H( OH),(COOH) .CsH (o'H),.COOH.2 mols. of ellagic acid. EIlagic acid dried in air.Ellagic anhydride cannot be etherified, does not combine with hydro-gen, and cannot be reconverted into gallic or tannic acids; it forms 44 ABSTRACTS OF CHEMICAL PAPERS.tetracetyl derivative.The author supposes it to have one of the fallow-ing formule : - - coo-\c,H(oH), /o\/o\ I I O \ ICO-C,H(OH), orCO-C6H(OII), CO--CGH(OH)2.The two molecules of water are not expelled a t the same temperature,but it has recently been shown that the temperature a t which thesecond is expelled is much lower than was formerly supposed. Theseformuh sufficiently represent the neutral and basic salts formed byellagic acid. W. R.New Organic Acid occurring in Agaricus Integer. By W.THORNEX (Ber., 12, 163,%1637).--Prom 19 to 20 per cent. of mannitolcan be extracted from Agaricus integer by treatment with boilingalcohol.An acid having the composition C,,HsoO, is contained in thealcoholic mother-liquors. I n order to isolate it, the alcoholic solutionis evaporated to dryness on a water-bath, the residue is exhausted firstwith water to remove any mannitol which may be present, and thenwith hydrochloric acid. It is finally dissolved in a solution of soda towhich one-third of its volume of alcohol has been added. After eva-porating off the alcohol, the acid is precipitated by boiling with dilutehydrochloric acid. The pure acid is deposited from an alcoholic solu-tion in white needles (m. p. 70') soluble in ether, benzene, toluene,carbon bisulphide, chloroform, boiling alcohol, a d 'boiling glacial aceticacid. The potassium, sodium, and ammonium salts are sparingly solublein cold water, but dissolve in warm dilute alcohol.Ba(C15H2,0,)2 andPb( C,,H2,0,)2, and also \the calcium, magnesium, and silver salts arewhite insoluble compounds. The lead salt melts a t 114". w. c. w.Kynuric Acid. By M. KRETSCHY (Ber., 12, 1673-167.5).-Kynuric acid is completely r-olved into its elements by fusion withpotash. Chinoline is formed when this acid is heated at 240" withstrong hydrochloric acid, and also when it is distilled with zinc-dust. w. c. w.Aromatic Thiocarbamides. By C. FEUERLEIN (Ber., 12,1602-1603) .-The preparation of phenylcyanamide from monophenyl thio-carbamide has been described in a, former communication (this Journal,Abst., 1879, 804). NPh), +3H20 ; when placed over sulphuric acid, it forms a syrupy mass, whichon standing becomes crystalline, forming phenylcyanamide.Theplatinum, (NH : C : NPhHCl),PtCI,, and the silver compounds,(NH : C : N(Phj),Ag, have been obtained. Monophenyl thiocarb-amide is converted into monophenylguanidine, NH,.C (NH),Ph, by theaction of alcoholic ammonia. This compound when heated burns with-out previously melting, and is decomposed by exposure to the air o rover sulphuric acid into phenylcyansmide.By C. LIEBERMANN and A. L.~x'GE(Ber., 12, 1588--1595).-0ne of the authors has already describedFrom analysis, its formula, is (NH : CI'. P. B.Formulze of ThiohydantoinsORGANIC CHEMlSTRY. 45the preparation of diphenylthiohgdanto’in (this Journal, Abst., 1879,651), which when decomposed with alcoholic potash mas supposed toyield diphenyl thiocarbarnide, potassium sulphide, and potassium glg-collate.Further investigation has shown that this decompositionyields thioglycollic acid, a reaction also observed by Andreasch ( B e y . ,12, 1385). This decomposition is expressed thus : C,,H,?N,SO +KOH + H20 = C,,H,,N20 + C2H,KS02. Diphenyl-bhiohydanto‘inis similarly decomposed by alcoholic ammonia a t 150”, forming anilineand thioglycollic acid, thus: C,,HI2N2SO + 3NH, + 4HzO =The supposition that thioglycollic acid owes its formation to asecondary reaction, is found t o be untenable, since glycollic acid cannotbe converted into this thio-acid either by boiling with potassium hydro-gen sulphide or with diphenylthiocarbamide and alcoholic potash.Further, the product C,HiNSO, obtained from diphenylthiocarbamide(Zoc.cit.) is also resolved by alcoholic potash and baryta-water intocarbanilide, carbonic anhydride, and thioglycollic acid. These resultsshow that the formula, CS 1 , attributed to diphenylthio-hydanto’in is incorrect. Rather must it be regarded as analogous toJager’s phenjlcarbodiimido-thiacetj c acid,2C,H,N + CzHSSO2NHA + C03(NH4)2.,B Ph-CH,‘flPh-CO,COOH.CH,S.C(NHPh) N H(J. pr. Chem. [2], 16, 17), and therefore its formula isS.K,C\NPh.&OPhN : C’Its formation may then be explained as follows :-(1.) CS(NHPh), + C1C2H302 = CIC(NHPh),.S.CHz.COOH.(2.) ClC(NHPh),S.CH.zCOOH - IECl - HZO =S.H,CPhN : c/‘NPh .This view of the constitution of the tjhiohydantoin is supported bythe investigations of Wallach (this Journal, 36, 312), Wallach andBleibtreu (Ber., 12, 1061), Bernthsen (AnsaaZen, 197, 341), and theinvestigation on thiocarbamide of Claus (Ber., 7, 236 and 841).In this light thiohydantoin will have the formnla-NH,.C S < ;%> C 0,and the product obtained by Lange from diphenylthiohydantoin (Zoc.cit.) is a derivative of monothiocarbaniIic acid, having the formula0 : CS<,,~>CO. This is analogous to Volhard’s C,H,NS02(J.yy. Chem., 9, 8 ) , which may be written 0 : CS<:%>CO. . InC46 ABSTRACTS OF CHEMICAL PAPERS.an analogous manner Nencki's compounds (J. pr. Chern. [el, 16,l) hasthe constitution S : CS<NH >CO, and to the carbaminethiaceticacid of the same aut,hor, the formula 0 : C(NH,)S.CH,COOH maybe attributed.These new formulae also explain why it is so difficult to remove thesulphur from thiohydant(iins, a fact which has been point,ed out byVolharci (Anwalen, 166, 384), Mulder (Ber., 8, l264), Maly (A.n.nalen,168, 133), and noticed by the aut'hors in the case of diphenylthiohy-dantoin. P.P. B.CH,Action of Potassium Pyrosulphate son Indigo-white. ByA. BAEYER (Ber., 12,1600-1609) .-According to Baumann, the intli-can contained in urine is riot a glucoside, but the potassium salt of asulphonic acid of indoxyl (Zeit. .f. Physiol. Chem., 1, 60 ; Die Synthe-1isclze.n Processe <w ThierIcorpe~-, Berlin, 1878, 6 ; R. Baumann and L.Brieger, Zeit. f. Physiol. CJzem., 3, 254 ; and Baumann and Tiemann,this Journal, Abst., 1879, 936).A body possessing the same proper-ties as the above-mentioned indican is obtained by heating 1 part ofindigo, 1 of ferrous sulphate, 2 of potagh, 2 of water, and 3- 4 of potas-sium pyrosizlphate'in sealed tubes for 12 hours a t 60". From this, theauthor concludes that the indican froni urine is potassium hydrin-cligotin-sulphonate, 4216HloN2( O.SO,K),. Baumann's analyses confirmthis observation. P. P. B.Action of Chlorine on Dibenzyl. By R. 'KADE ( J . p. Cliern. [g],19, 461-467) .-Pa~adiclaZorodibeizzyl, CsH,C1.CH2.CHz.C,H,C1 (m. p.112'), is formed by passing chlorine over the crystalline productobtained by melting together iodine and dibenayl, and continuing theaction until hydrochloric acid begins to be evolved.The resultingthick cherry-coloured oil is ,distilled, and the crystals of para,dicliloro-dibenzyl deposited from the oily djstiIlate are purified by crystallisationfrom alcohol. It forms &in fine laminae, closely resembling naph-thalene, and is casily soluble in alcohol, ether, and chloroform.It can be sublimed, giving an odour of bitter almonds when heated,and be distilled without decomposition. It yields parachlorobenzoicacid by oxidation with chromic mixture.The oily body which is formed a t the same time is probably mono-chlorodibenzyl .Quite a different reaction takes place when chlorine is passed into amixture of pzdreimised dibenayl with iodine. In this case toluylenewith unaltered dibenzyl is produced.Toluylene is also formed t,o someextent by the action of chlorine on the vapour of dibenzyl, and bypassing chlorine into melted dibenzyl until it hegins to turn brown,and then . distilling, the whole is transformed into toluylene. Con-tinuing the action until hydrochloric acid is again given off, dichloro-toluylene, CliHl0Cl2 (m. p. 170") is obtained. It crystallises in silkywhite needles or laminae, and easily dissolves in alcohol and ether.'I'olu-ylene is also formed from dibenzyl by the action of potassiumchlarate and hydrochloric acid. It can be distilled and sublimed likORGANIC CHEMISTRY. 47benzoic acid.chloride. A. J. C.Its alcoholic solution gives a red coloration with ferricDerivatives of 7-Dichloronaphthalene, &Nitronaphthalene-sulphonic Acid.By P. T. CLEVE (Ber., 12, 1714).--~-Trichloro-naphthalene (m. p. 65') was prepared by the action of phosphoruspentachloride on 7-dichloronaphthalene (m. p. 48"). The salts of8-nitronaphthnlenesnlphonic acid are crystalline. The chloride of thisacid melts a t 169", the smide a t 216", and the ethyl salt at 108". vv. c. w.Action of Chlorine on C hloronaphthalene : Nitro-derivativesof a- and p-Dichloronaphthalene. By 0. WIDMARN (Ber., 12,1714-1715) .-a-Monochloronaplithalene combines with chlorine toform C,,H,CI, (m. p. 67"), and CI,H,Cl.C1, (m. p. 131*5"), whilst13-monochloronaphthalene forms a liquid trichloronaphthalene, and atetrachloride, C,oH,Cl.Cl~ (m. p. 81°), which when treated with potashgives a t8richloronaphthaleiie, melting a t 140".By the action of chlo-rine on an acetic acid solution of a-monochloronaphthalene, an aceto-chloride, C,,H,C12. C1,Ohc (m. p. 195") is produced. a-Dichloronaph-thalene yields only one nitro-derivative, viz., the trinitro (m. p. 178"),but the P-componnd forms a mono- and a dinitro-derivative, which melta t 92" and 158' respectively. w. c. w.On the Quinone occurring in Agaricus Atrotomentosus.By W. THORNER (Bcr., 12, 1630--1635).--The spectrum of the redalcoholic solution of the quinone extracted from Agnl-lcus LEtrotomen-toszu by means of ether is chsracterised by a deep red band betweenB and D.A crpt,alline ammonium salt separates out as a dirty green-colouredpowder, when strong ammonia is added to a hot alcoholic solution ofthe quinone.It, dissolves in dilute alcohol and in water, forming aviolet solution, which produces coloured precipitates with manymetallic salts, viz., a flesh-coloured crystalline precipitate with bariumchloride ; dirty pink flocculent precipitate with calcium chloride ;brownish-green with lead acetate ; black with ferric chloride ; darkgreen with mercuric chloride ; brownish-black with alum ; reddish-brown with copper sulphate ; brown with platinum chloride ; dirtygreen with silver nitrate ; and a beautiful green crystalline precipitatewith magnesium sulphete.The conipound obtained by the action of benzoic anhydride on theyuiiione forms yellow needle-shaped ci-ystttls, which melt a t 285" withdecomposition. By heating the quinone with dilute nitric acid, oxalicand nitric acids and also a nitro-product are formed.The latter bodyis a yellow powder (m. p. 255-260") soluble in alcohol and chloro-form.By the reduction of the quinone with hydriodic acid, or by zinc andhydrochloric acid, two bodies are produced, viz., a yellow powder,insoluble in the usual solvents, but easily converted into qninone byalkalis, arid a white crystalline compound (m. p. 162-164'), solublein alcohol and ether48 ABSTRACTS OF CHEMICAL PAPERS.When heated with zinc-dust,, a large volume of gas is evolved, hutno solid hydrocarbons were formed in appreciable quantity. Fromthese results, the author concludes that this substance is ruethyldihy-droxynaphtlioquinone, CloH,Me( 0,) (OH),.The mother-liquor from the quinone contains an acid (m.p. 54"),which dissolves in benzene, toluene, ether, chloroform, carbon bisul-phide, glacial acetic a,cid, and petroleum ether. I t s barium, calcium,lead, and silver salts are insoluble in water. w. c. w.Action of Ammonia and Amines on Quinones. By T. ZINCKEBey., 12, 1641--1647).--Phe,zantl~reneqz~ino~~i~7~ide, C14H80.NH (m. p.159') is obtained in yellow, needle-shaped crystals, by passing gaseousammonia into a warm alcoholic solution of the quinone, or by dissolv-ing the quinone in warm concentrated alcoholic ammonia, C,2HR02 +NH, = C14H8.0.NH + H,O. The b i d e is decQrnposed by boilingwith alcohol, the quinone being regenerated. It combines with acidsto produce red-coloured compounds, which are destroyed by water,with production of the quinone.When heated with acetic or benzoicanhydride, the imide loses a molecule of water, giving rise to a crystal-line compound (m. p. 247") which is sparingly soluble in hot benzene.By the prolonged action of alcoholic ammonia on phenanthrenequinone,the imide which is first formed disappears. and a mixture of a basicsubstance soluble in acetic acid, and a ceutral compound insoluble inacetic acid, is produced. The latter cornpound sublimes in lustrousyellow needles, which have the composition CZ,H,,N2. A second basicsubstance, very soluble in alcohol, is also formed. It is probably iden-tical with voii Sommaruga's base (IUer., 12, 982). A yellow crystallinecompound, probably CldH8.0.NMe, separates out, when phenanthrenequinone is treated with an alcoholic solution of methylamine.Thecrystals are insoluble in atlcohol, but dissolve in hot benzene. Theyform a blue compound with strong hydrochloric acid.The mother-liquor froin the yellow compound contnins a strongbase, c16Hl*Na which appears t o be formed according to the followingequation: CldH.,02 + 2MeNHz = C,J&(NMe)2 + 2H20. This sub-stance crystallises in colourless prisms (m. p. 186"), and formswell crystallised salts, viz., the hydrocldoride Cl&Il~N,HCl, colour-less prisms, soluble in water, insoluble in alcohol ; the nitrate, fineneedles, sparingly soluble in water and in alcohol ; the sulphate, needlessparingly soluble in alcohol ; the oanlate, transparent prisms, solublein hot dilute nlcohol. hTaylit7ioquii~o?ae forms with ammonia a brownarnorpbous product, but with primary amines it yields crystallineclerivatives, according to the equation :-2C,,H,02 + NHZR' = C,,H,(O),NR' 4- CmH,(OH),.Naphtho- Amine.New compound. Naphthoquinol,quinone.The compound C,,H,.O,.NPh is obtained by adding an excess ofaniline to a hot alcoholic solution of naphthoquinone. The precipitatewhich is thrown down on the addition of water to the mixture istreated with acetic acid to xemove excess of aniline, and is thenrccrjstallised from alcohol, when the pure substance separates oiit iORGANIC CHEMISTRY. 49lustrous red needles, which melt at 191", and sublime a t a higher tern-perature. The crystals dissolve in hot benzene, alcohol, and ether ;they yield with sulphuric acid a red solution, and with alcoholic potasha purple colour.By the action of zinc and hydrochloric acid, or of sulphurous acid,the compound is split up into naphthoquinol and aniline.With paratoluidine, naphthoquinone forms a beautiful red compound,crystallising in needles (m.p. 200"). The methylamine compoundcrystallises in bright red needles, which melt a t 225", and the ethyl-amine compound fornis orange-coloured needles (m. p. 140").A crystalline substance is also produced by the action of diphenyl-amine on naphthoquinone, in presence of hydrochloric acid.Benzoquinone differs from naph thoquinone in its behaviour toamines, e.y., 2C6H402 + 2Ph.NH2 = C6H402(??BPh)2 + CsH*(OH)2. w. c. w.Amidoanthraquinone from Anthraquinone-monosulphonicAcid. By H.It. v. PERGER (BET., 12, 1566--1571).-Anthraquinone-monosulphonic acid, or its ammonium salt, when heated with ammoniain sealed tubes a t 19@", yields a red crystalline product, which is solublein concentrated hydrochloric acid, and on addition of water is throwndown again as an oraiige or red flocculent precipitate. By repeatedsublimation in a current of carbonic anhydride, and crystallisationfrom alcohol and benzene, this compound is obtained pure. Analysisshows it to be monamidoant8hraquinone, C1,H702.NH2 (m. p. 302") ; andits formation may be expressed thus : C,IH,02S03NH, + (NH,), =C,,Hi02.NH2 + (NH4),SOs. Bourcart (Bey., 12, 1418) describes acompcmnd obtained in the same way, which melts a t 301", and to whichhe attributes the formula CI,H,02.NH2.0H; such an amidoanthraquinolshould be soluble in alkalis, which is not the case with this compound.The views of t,he author are further supported by the behaviour of thiscompound with nitrous acid ; first a yellow crystalline body is obtained(m.p. 23S0), which on boiling with alcohol yields authraquinone ; andon boiling with water, a-monoxyanthraquinone is obtained.Heated with acetic anhydride_ amidoanthraquinone yields the yellowacetoxy-derivative, C,,H,O,NHAc ; i t is soluble in alcohol and ether.It melts a t 257", the melting-point of Bourcart's (Zoc._cit.) acetoxy-derivative, to which he attributes the formula C14HS03NAc3.I n conclusion, the author states that attempts made to prepare mono-nitrosnthrayuinone according to Bottger and Petersen's method(Annaleib, 166, 147) have given negative results.Y. P. B.Decomposition of Hydroxyanthraquinone by Potash. By C.LIEBERMANN and J. DEHNST (Ber., 12, 1597).-Amongst the productsobtained by the fusion of anthraquinonemonosulphonic acid with potash,the authors found small quantities of paraoxybenzoic acid. Thisowes its existence to the decomposition of monhydroxyanthraquinone,which may, therefore, have the constitutional formula-P. P. B.e VOL. XXXVIIL 50 ABSTRACTS OF CHEMICAL PAPERS.Constitution of Camphor-compounds. By M. BALLO (Be?.., 12,1597-1600) .-In another communication (Awnaten, 197, 321) theauthor has given his reasons for regarding camphor as a tertiary alco-hol, having the constitution 1 1 .Thisview is sup-ported by the fact that when camphor is oxidised by boiling chromicmixture, acetic, carbonic, and adipie acids are formed, thus :H C : C(CH,)-CHZ(0H)C : C(C,H,)-CH,the central nucleus of the camphor forming adipic acid,the methyl group, carbonic acid, whilst the propyl group forms carbonicacid and acetic acid.The author regards camphrene, C9€€,IU, as a homologue of camphor,since it also yields adipic acid when oxidised (Kachler, Ann,aZen, 164,90), and has the properties of an alcohol.Essence of Marjoram. By BRUPLANTS (J. Pharm. [4], 30, 33-3?5).-Essence of marjoram, obtained by distilling the flowery tops of0rignlzzl.m Mncyjoyaaa in a current of steam, is a yellowish liquid, whenfreshly prepared (sp.gr. 0.911 a t 15"), but becomes brown on stand-ing. It has a pungent smell, and a hot, peppery, and slightIy bittertaste. It is dextrorotatory, and has an acid reaction. When distilled,it begins to boil a t 185", but the temperature rnpidlyrises to 200°, andremains constant between 215 to 220", a resinous mass being left inthe retort.By repeatedly fractioning the oil which passes over a t 185--190", aportion is obtained, boiling between 160-162", consisbing principallyof a terpene.The fraction boiling a t 215-2.20" yields no portion having a constantboiling point, nor does it deposit crystals when cooled to - 2.5". Itsvapour-density and analysis correspond with either laurel camphor orborneol. When distilled with phosphoric anhydride, it yields a mix-ture of cymene and a terpene (b.p. 160--170"). When treated withacetic anhydride, it forms a compound (b. p. 230-235'), which withalcoholic potash yields terpene and potassic acetate. Chi-omicmixture oxidises it with the formation of acetic and formic acids, andlaurel camphor.Essence of marjoram is therefore composed of a dextrorotary hydro-carbon, 5 per cent. ; a mixture of dextrorotatory camphor and borneol,85 per cent. ; resin, 10 per cent.(C H2) 4( coo H) 2,P. P. B.L. T. 0's.Essences of Lavender and Spike. By BRUYLANTS (J. P~Kw-H?.[ 4 ] , 30, 139--141).-Essence of lavender when freshly preparedis a colourless liquid, which becomes yellow on standing; i t smellsof lavender, and its taste is hot, camphorous, and slightly bitter.It is lEvorotatory, has an acid reaction, and sp.gr. 0.87.5 a t 1.5'. Itbegins to boil a t 185", the temperature quickly rises t o 190", and thegreater portion distils over between 195-215". The first portion ofthe distillate consists of a mixture of acetic and formic acids, but con-tains no vnleric acid. By repeated fractionation, a laevorotatory terORGANIC CHEMISTRY. 51perene (b. p. 162") is separated, capable of forming a crystallinehydrochloride. The essence also contains a mixture of camphor andborneol : this mixture Forms an acetate (b. p. 230°), which is decom-posed by potash, yielding a terpene and potassium acetate. When it isdistilled with phosphoric anhydride, a hydrocarbon is obtained, con-sisting for the most part of terpene, and containing also some cymeneEssence of lavender consists of terpene, 25 ; borneol (+), and cam-phor (+), 65 ; resin, 10 per cent.Essertce of Spike.-This essence obtained from Lavnndula aspicoZatyolia is a colourless liquid, which in time thickens and darkens incolour. It has an acid reaction, and sp.gr. 09081 a t 1 5 O . Itsodour resembles that of lavender. I t s composition is almost identicalwith that of essence of lavender, but as it contains more hydrocarbon,it begins to boil a t 170-175". Its composition isas follows:-Terpene, 35; borneol and camphor, 55; resin, 10 percent. L. T 0's.It is ltmorotatory.Limited Oxidation of the Essential Oils. Part V. TheAtmospheric Oxidation of Turpentine.By C. T. KINGZETT(Chew. News, 39, 279).-The author has shown in his previous papersthat when so-called essential oils are exposed to the atmosphere, per-oxide of hydrogen is indirectly produced. In turpentine oil, i t appearsas if a camphoric peroxide, CloHla04, is first formed, and that in con-tact with water t3his is decomposed, yielding hydrogen peroxide andcamphoric acid, thus : Cl0Hl4O4 + 2H,O = CloHl,Oa + H202.Similarly, berpene, CIoHl,, and menthene, CloHl, give rise to per-oxide of hydrogen, whilst hydrocarbons of the formula CI,H,, do not.As all terpenes and menthene yield cymene, CloHI4, and as cymeneitself yields hydrogen peroxide, the author believes that there is somerelation between Che formation of this body and that of hydrogen per-oxide, and this opinion is strengthened by the fact t,hat the hydro-carbon from oil of cloves, CI5H2p, yields neither cymene nor hydrogenperoxide.The product of oxidation which is formed by exposing turpentineto tlie action of the air, and which in contact with water forms hydro-gen peroxide, may be produced in such quantities that when the tur-pentine oil containing it is heated a little above the boiling point,decomposition occurs v1 ith almost explosive violence. The atmo-spheric oxidation of turpentine is now carried out, on the large scale, inthe manufacture of? the disinfectant called " sanitas."Different essential oils and varieties of turpentine absorb oxygenwith different degrees of rapidity, and when oxidation has once com-menced, the oil absorbs oxygen with increasing rapidity in proportionas the oxidation increases, up to a certain point.As to the differencesin this respect in different oils, the author gitres the following resultsdeduced from experiment by exposing the various oils under similarconditions to light and air. Assunling that the amount of oxygenabsorbed by Russian oil of turpentine (which absorbs the largestamount) be represented by 100, then Swedish oil of turpentine absorbs100.e 52 ABSTRACTS OF CHEMICAL PAPERS.An oil obtained from Switzerland. ................... 89.4American oil of turpentine.. ........................ 78-9Oil of eucalyptus.. ................................ 75.0Adulterated Swedish turpentine ....................52.6'' Scotch distilled American turpentine ". ............. 42.1The two last-mentioned oils were presumed to be adulterated with so-called pine-oil of commerce. When these oils are placed in cylinders,the mouths of which are covered with papers saturated with a mix-ture of potassic iodide and starch, the papers become coloured in theorder given above, owing to the formation of different quantities ofhjdrogen peroxide in the vicinity of each.When the aqueous solution obtained by blowing air through a mix-ture of turpentine and water (" snnitas "), is evaporated to drynesson a steam-bath, the hydrogen peroxide contained in i t is decomposed,the acetic acid is expelled, and there remains a dark coloured matter,which when hot is viscid, and has a sugar-like odour, b u t on coolingsets to an adhesive but firm mass; when treated with sulphuric:acid it gives a colour reaction somewhat resembling that bearingPettenkofer's name.This adhesive mass, which was slightly volatileat looo, after drying gave numbers corresponding with the formulaC10H1803. It has remarkable antiseptic properties, t'o which thesimilar properties of " sanitas " are largely due.About 95 per cent. of this adhesive matter is soluble ~JI water,forming a yellowish-brown solution, from which charcoal failed toremove the colour, although it absorbed a considerable proportion ofthe substance itself. This solution on evaporation to dryness left atransparent varnish-like substance, semi-fluid wlien hot, and volatile a t100".The 5 per cent.of the original adhesive substance which was in-soluble in water did not give the vivid reaction with sulphuric acidwhich the soluble poktion did; this insoluble matter is soluble inpresence of an oily substance which the original aqueous solutioncontained, and which was expelled on evaporation.On submitting the soluble portion to distillation, it melted, boiled,and a small quantity of an almost colourless oil passed over, which oncooling became a colourless, soft crystalline mass ; this was followedby a permanent oil, which became darker as the distillation pro-ceeded ; towards the end, the vapour in the retort had a green colour,~ i i d a pitch was left. None of these products have as yet been furtherexamined.On acidulating the solution of the soluble portion, CI0Hl8O3, withdilute sulphuric acid, it becomes milky, and on standing, a slightlycoloured oily body separates in considerable quantity.The authorhopes that a study of this substance will throw light not only on theconstitution of the soluble substance, but also on that of the terpenefias a class.The aqueous solution (" sanitas ") obtained by oxidising Russianturpentine, when neutralised with soda, darkens very much in colour,and on evaporation of the mixture a t loo", a dark soft resin-like residueis left. On treating this with dilute sulphuric acid, it yields it darkProm analysis, the formula ClOH1803 was calculatedORGANIC CHEMISTRY. 53oily mass : the clear acid solution is filtered and.subjected to distilla-tion ; as it becomes hot more oil separates out, and an acid distillatepasses over, together with 20 or 30 C.C. of a slightly yellow oil with anodour resembling that of mixed cymene and eucalyptus. At the endof the distillation a quantityof tarry-looking matter remains in theretort floating on the acid solution. The acidity of the distillate wasfound t o be due to acetic acid, which amounted to about 0.25 graniper litre of the aqueous solution (“sanit;tr~”), and no other volatileacid could be detected. The author anticipates that the further studyof those compounds will be attended with very important and interest-ing results, inasmuch as they have the advantage of having beenproduced by the mildest possible oxidation. W.T.Fusion of Rhamnetin with Potash. By L. SMORATVSRI. (Ber.,12, 1595-1596).-According to Stein ( 2 e i t . f . Chenz. [Z], 5, 183, 56S),rhamnetin when fused with potash yields phloroglucinol and querceticacid. The aubhor finds that by fusion with potash or soda, rham-netin is decomposed into phloroglucinol and protocatechuic acid ; a tthe same time, sniall quantities of a substance are formed which, likequercetic acid, gives a deep red coloration with alkalis. This last-named body could not, however, be obtained in quantities sufficient foranalysis. P. P. B.Chlorophyll.. By F. HOPPE-SEYLER (Ber., 12, 1555-1.556).-When grass-blades, after treatment with ether to remove wax, arecohobated with alcohol, two crpstalline cdouring matters are dissolved,one of which, named erythrophyll by Bougarel, ci*ystallises out first ingreenish-white quadratic tables, whilst the other is more soluble inhot alcohol, and may be purified by optallisation from ether, fromwhich i t is deposited in microscopic needles and scales, dark green byreflected, and brown by transmitted light.The crystals of the latterbody are of the consistence of soft wax ; it dissolves with difficnlty incold alcohol, easily in hot alcohol, and readily in ether and chloroform.The ethereal and alcoholic solutions of this substance have the knownred fluorescence of chlorophyll, and absorb the light between B and Cof the spectrum with such intensity, that 1 milligram dissolved in alitre of water gives distinct absorption-bands in a thickness of 3.5cm., with a Browning’s spectroscope.Several analyses show it tohave the composition: .C, 73.4 ; H, 9.7 ; N, 5.62 ; 0, 9.57 ; P, 1.37 ;Mg, 0.34 p.c. The presence of phosphorus and magnesium may be dueto impurities, and the author proposes to investigate this more closely,He has named this substance chZorophyZlan, and remarks in conclusion,th:rt i t is now possible to estimate the amount of chlorophyll in plantsapproximateIy by means of its power-of absorbing light.Characin. By T. L. PHIPSON (Chein. News, 40,86) .-Amongst theorganic substances present in fresh water IS a new and interesting pro-duct, to which algae in general owe their peculiar odour, and commu-nicate this odour to the water in which they abound. The author hasobtained this substance in minute quantities only at present from.Pnlnzella crue”lzta, Vauckeria terrestris, and from several OscillariE.ItW. R54 ABSTRACTS OF CHEMICAL PAPERS.is appazvently more developed in the genus Chnra, and C. fcetida millprobably yield it in larger quantity than the plants already mentioned.Characin is R kind of camphor, which is extracted from the aboveplants in the following manner.The PaZnLelZa or Oscillaria which is to be treated must be previouslydried by exposure to the air, a t a temperature not exceeding summerheat, for about 24 hours; it is then covered with cold water in acapsule, which must itself bc covered with a sheet of glass, and in thecourse of about 36 hours more (with PaZmeZZa cruenta) thin films ofcharacin will be observed floating on the water.The latter is thendecanted off into a long tube, together with the films, and shaken upwith ether. On evaporation a product is obtained which is quite white,devoid of crystnllisation, and more or less unctuous in appearance.Up to the present time, the author has not obtained this substancein sufficient quantity to ascertain more of its properties. D. B.Phthalei'n of Haematoxylin. By E. A. LETTS (Bey., 12, 1651-1653) .-H~matoiiyli?L-phthalei'n, CIOH30011, is prepared by heatinghacmatoxylin wioh rather more than half its equivalent of phthalicanhydride a t 150-170" for five hours. The alcoholic solution of thecrude product is poured into water, when a brown flocculent precipi-tate separates out, which is filtered, washed, and dried in a vacuum.The phthalein conld not be obtained in the crystalline state ; when thealcoholic solution is evaporated, it leaves a gummy residue insolublein water, but soluble in ammonia and soda, with a purple colonr.Hacmatoxylin fornis white crystalline potassium, sodium, and bariumcompounds. w.c. w.Collidine from Aldehyde. By A. WISCHNEGRADSKY (Ber., 12,1506--1508).-Thc object of this research was to ascertain by oxida-tion whether collidine, CsHIIN, is trimethyl-pyridine, C5H2NMeS,ethyl-methyl-pyridine, C,H,NMeEt, o r propyl-pyridine, C5H4NC3H7.The collidine was oxidised with chromic acid in presence of sulphuricacid, and yielded an acid crystallising in white slender prisms, solublewith difficult'y in cold, but easily soluble in hot water.Its formulawas C8H7NO4, and as it yielded picoline on distillation with lime, it isprobably methyl-dicarbopyridenic acid. From this research, theauthor believes that collidine may be viewed as trimethyl-pyridine.W. R.Piperidine Salts : Quinine Sulphate, hnd Selenate. By T.HJORTDAHL (Ber., 12, 1730-1731 j.-The hydrochlorides and golddouble salts of piperidine and methylpiperidine are isomorphous.Quinine sulphate and selenate are also isomorphous ; the relationbetween the axes of the latter substance is a : b : c = 0%04 : 1 : 0.3110. w. c. *w.Aspidospermine. By G. FRAUDE ( B e y . , l2,1560--1562).--Someaccount of this alkaloid has already been given by the author (thisJournal, 1879, Abst., 470).The bark containing it is that of Aspido-sperrna querbracho bZanco (Schlectendahl). Further analyses showaspidospermine to have the composition C22N30N202. Concerning itORGANIC CHEMISTRY. 55preparation, the author finds that the liquors obtained after a precipi-tatJion of the alkaloid by means of sodium carbonate yield a furtherquantity by treatment with phosphotungstic acid. This precipitate istreated with baryta-water, and the solution thus obtained with car-bonic acid to precipitate the barium ; the alkalo'id is then extracted bymeans of alcohol from the residue left on evaporation. One part ofaspidospermine is soluble in 600U parts of water a t 14" ; this solutionhas a bitter taste. It is also soluble in 48 parts of alcohol (99 percent.) at 14", and in 106 parts of pure ether a t the same tempera-ture.A small quantity of aspidospermine treated with a few drops ofconcentrated sulphuric acid, and then with a little lea,d peroxide, givesa cherry-red coloration, which has a violet shade if the alkalo'id is notquite pure.Iodic anhydride and sulphuric acid produce the same reaction,whilst pot,assium dichromate and sulphuric acid give a brown zoneslowly changing to an olive-green.Chlorine reacts on aspidosperminesuspended in water, producing a white flocculent mass, which is notdissolved by hydrochloric acid ; this compound begins to decompose at145". Bromine acts similariy.Aspidospernzii~e sulphate, ( C22H,~,0,),H4S04, is obtained byevaporation and drying a t 120" as a hard, transparent, resinous mass.The ?yhochZoride, 3( C2,H,,N202 + 4HC1, has similar properties to thesulphate. Bg treating solutions of the base with potassium chromatethe chi-onzate is obtained as a yellow precipitate, which on exposureto the air becomes green. The perchlorate is obtained by addingaqueous perchloric acid t o a not too dilute solution of the base.Hydrochloric acid solutions of the base are precipitated by potassiummercuric iodide in yellow flocks; by potassium sulphocyanide, as awhite flocculent precipitate ; by iodine dissolved in potassium iodide, asbrown flocks ; by picric acid, as a yellow precipitate; and by tannin,as a white precipitate. Further, these solutions reduce Fehling'ssolution when boiled with it.According to Penzoldt ( B e r l . Klilz. Tochenschrift, 1879, 14), thebark of Aspidospermu querbracho bZanco has important medicinal pro-perties. P. P. B.Oxidation of Cholic Acid. By H. TAPPEINER (Ber., 12, 1627-1629) .-The author obtained stearic acid as an oxidation-product ofcholic acid ( B e y . , 11, 2258), but, Latschinoff denies that this acid isformed (Ber., 10, 2059, and 12, 10%). The discrepancy between theseresults is explained by the fact that the author employed a mixture ofpotassium dichromate and sulphuric acid as the oxidising agent, wbiktLatschinoff used potassium permanganate.A weak solution of the oxidising mixture must be used when it isdesired to isolate the fatty acids obtained by the oxidation of a smaZZqzmi~tit!j of cholic acid.A crystalline barium saZt, (C12H13C7)2Ba3 + 6H20, is formed byheating a saturated solution of cholic acid in baryta-water in sealedtubes at 120". It crystallises in long white prisms, which are verysparingly soluble in water56 ABSTRACTS OF CHEMICAL PAPERS.To prepare pyrochoZesteric acid on the large scale, a solution ofcholesteric acid in glycerol is heated a t 198" for a week ; the glycerateis then saponified, and after removing the volatile prodiicts by distilla-tion, the pyrocholesteric acid is extracted from the residue by meansof ether. w. c. w.Oxidation-products of Cholic Acid. By P. LATSCHINOFF (Ber.,12, 1518-152S).-By oxidation of cholic acid, the author did notobtain cholesteric acid, nor fatty acids, as Tappeiner did, but an acidtermed choloidic acid, to which Redtenbacher gave the formulaC16H2407. This acid, which he prepared by oxidising cholic acid withnitric acid of sp. gr. 1-37, evaporating the oxidised product to dryness,and separating the acid first with alcohol, and then as soluble bariumsalt', after repeated crystallisation from alcohol, gave numbers agree-ing with the formula C1,H,,O4 ; it is thus isomeric with camphoricacid, and the author has therefore named it cholecany?m..ic acid.The properties of cholecamphoric acid are as follows :--It is solublein water and in ether with difficulty ; easily in alcohol, more easilywhen aqueous, also in acetone, and in acetic acid. From ft boilingaqueous solution, i t is deposited in such a thick mass of interlacedhair-like crystals, that it presents the appearance of a jelly. It has a,bitter, acid, somewhat astringent taste. when heated, it loses water,varying in quantity, but approximating to +H,O. It does not melt,but begins to blacken a t 270". Its solution is dextrorotatory. It is adibasic acid, forming soluble salts wit'h metals of the alkalis andalkaline earths, and insoluble salts with the heavy metals. The authoradduces numerous analyses of the salts to confirm the formula of theacid, and indicates the acid potassium salt, Cl0HI5KO4, as a proof of itsdi basic character.Cholecamphoric acid may be regarded as a product of hydration ofcholic acid, thus: C20H2806 + 2lLO = 2CloHl,O4.Such bodies, and many resembling them, for example cholesterinand cholic acid, may be regarded as compounds of condensed valery-lenes, and may be connected with the terpenes. Thus cholesterin mayprovisionally be given the formula (C,H,),H,O, and cholic acid(C,H,),O,.+H,O. This view is supported by the oxidation of cholicacid into cholecamphoric acid, and also by the results of oxidisingcholesterin, the product being trioxycholesterin, analogous to betu-lin. W. R

ISSN:0368-1769    

DOI:10.1039/CA8803800021

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 57 Chemistry of Vegetable Physiology and Agriculture. Influence of Light on the Growth of Plants. By C. KRAUS (Bied. Cendr., 1879, 351).-The alterations of growth produced in plants by absence of light are of two kinds, one part of an organ or plant exhibiting an excessive, whilst another exhibits a diminished growth. This is easily verified in the case of dicotyledonous plants, where the internodes are subject to an increased and the leaves to a diminished growth when the plant is placed in the dark. Similar phenomena are observed in the case of monocotyledons and cryp- togams. Methyl alcohol when applied to the roots of plants causes them to die off, and has the same effect a3 light in promoting the formation of chlorophyll in tbe cells.Under the influence of methyl alcohol, young plants live longer in the dark, and their weight58 ABSTRACTS OF CHEMICAL PAPERS. when dried is greater than in the case of plants which have not been placed under the same influence. J. K. C. Action of Ozone on the Colouring Matters of Plants. By A. R. LEEDS (Chem. News, 40, 86).-In the first trial, in which many varieties of flowers were exposed during nirieteen hours to the action of a currentf of 152 litres of air, containing in all 228 mgrms. of ozone, the bleaching effected was extremely imperfect,. When 1,200 litres of air were passed over various flowers (total ozone 1.8 grams), they were partly or wholly bleached at the end of five days. A piece of calico with a pattern in bright green and black was completely bleached during the same interval, the green having disappeared completely, and the stain of the mordant only remaining where the black had been.From these and other results, it is concluded that the colouring mat,ters of both leaves and flowers of the species (Lantana, Puchsia, Petunia, Rosa, Verbena, Pelargonium, Bouvcr,rdia, Eiiphorbia, &c.) es- perimented with were partly or wholly destroyed by ozone; but a considerable percentage of ozone is required t o produce this result, or if such small amounts as are obtained in the customary methods of ozonising air by phosphorus are employed (1 to 3 mgrms. per litre), a large volume of ozonised air must be used, and a considerable interval elapse before bleaching is effected. Distribution and Functions of Asparagine in the Vegetable Kingdom.By J. BORODIN (Bied. Centr., 1879, 35’i-SGO) .-Aspara- gine, according to Pfeffer, occurs only in a few plants, and in these only a t the time of germination. The author finds, however, that asparagine is present a t the time of budding in most plants, and also when they are in bloom. It appears to be a decomposition-product of albumin, and is formed when there is a lack of carbohydrates in the plant. When these, however, reappear, the asparagine is reconverted by their agency into albumin. From his researches, the author con- cludes that in $he early processes of growth there is a lack of these carbohydrates, and theref9re asparagine is formed a t these periods, being afterwards converted into albumin. Mineral Constituents in Hyacinths. By A.E. ROJEN and KRELAGE (Bied. Centr., 1879, 360-366).-The hyacinths were planted according to size, a t the ratle of 42? 90, and 196 plants to the square metre. The results of the examination of their mineral constituents may be seen from the following table. D. B. J. K. C. Miueral constituents in grams in each plant. 196 t; sq. metre. 90 to sq. metre. 42 to sq. Getre. Blossoms .... 0.042 0.230 0.303 Stem ...... 0.027 0.036 0.106 Leaves ...... 0.082 0-245 0.632 Bulb.. ...... 0.146 0.355 1.380 Roots ...... 0.022 0.022 0.311. Total.. .... 0.319 0.888 2.732 - - -VEGETABLE PHYSIOLOGY AND AGRICULTURE. 59 From this table, it is a t once evident that the mineral constituents increase very rapidly with t’he size of the plant, and also that the quantity extracted from the soil is by no means small.From one hectare alone, when planted with 42 hyacinths to the square meter, would be extracted in one season 1,147 kilos. of mineral substance. The following table shows the diffeyence in quantity of mineral matter in the bulbs when taken out of the ground just after the blossoming period and at the end of summer:- 196 to sq. metre. 90 to sq. metre. 42 to sq. melre. Bulbs dug out just after blossoming ........ 0.146 0.355 1.380 At the end of summer.. 0.557 0.987 2.3 14 J. K. C. Experiments with Various Sorts of Beet. By J. LANEK and C. PORTELE (Bied. Centr., 1879, 368--370).--The authors bring for- ward an account of the results obtained by growing various kinds of beet. They find that the ’‘ mammoth ” variety yielded the largest crop, whilst, the “ imperial” contained the largest percentage (10.7) of sugar.Formation of Nitric Acid in the Soil. By HkwErB, E. REJCHARDT, and HERTZ (Bied. Ceiztr., 1879, 327).-According to a former paper of Hunefeld’s, nitric acid is produced when the higher oxides of manganese are brought into contact with air, water, and magnesium carbonate. To confirm this statement, Reichardt and Hertz performed the following experiments. Hydrated oxide of manganese, together with various oxides and earths, such as magne- sium and calcium carbonates, alumina, and oxide of iron, were placed with a little water in a large flask, which was then closed and shaken a t intervals, care being taken to ascertain that no nitric acid was present at the beginning of the experiments.No nitric or nitrous acid was obtained when the manganese was used in conjunction with calcium carbouate or oxide of iron and alumina, but when mixed with magnesia or alkaline carbonates, nitric acid was recognised in the pro- duct. Pyrolusite gave the strongest reactions, and it was found that 50 grams put in a litre flask with 500 C.C. of water after sta’nding for eight days and frequent agitation yielded 045.5 gram of nitric acid. J. K. C. J. K. C . Calcium Carbonate in Water filtered through Dry Soil. By F. H. STORER and S. LEWIS ( B i e d . Cei~tr., 1879, 32b--331).-The authors find that a soil which has been ignited a t a temperature just sufficient to destroy the organic matter yields calcium carbonate when treated with pure water, even after it has just cooled.They have arrived, therefore, at the conclusion that when ignited at a low tem- perature, a soil has tlie power of still retaining ca,rbonic acid. When a dried soil is treated with water containing. carbonic acid, part of the latter is retained by the soil. This, according to Storer, is merely a mechanical result, and is due to the adhesion of the gas to the solid particles of the soil. J. K. C.60 ABSTRACTS OF CHEMICAL PAPERS. Mill Waste for Manure. By FRIEDBURG (Bied. Centr., 1879, 386).-This waste, consisting chiefly of dust and chaff from rye, was found on analysis to contain the following percentages of consti- tuents :-Phosphoric acid, 0.96 ; nitrogen, 1.80 ; water, 5-80 ; organic substance, 62.84 ; ash, 31.36. J. K. C.Analyses of Marl. By J. KONIG ( B i d Cent?.., 1870, 385).-The following are the results of the analysis of 85 samples from West- phalia :-The calcium carbonate varied from 1-36 to 94.83 per cent. ; magnesium carbonate was present in 21 samples, and in quantity from 0.38 to 27.39 per cent. Phosphoric acid varying in amount from 0.029 to 1.55 per cent. was found in 23 samples. Lastly potassium was estimated in 28 samples, and varied from 0.08 to 2.43 per cent. J. K. C. Influence of the Physical Condition of Superphosphate on its Value. By P. WAGNER (Bied. C'entr., 1879, 336--339).-The soluble phosphoric acid in superphosphate on corning into contact with the lime of the soil is converted into an insoluble form, and consequently does not penetrate into the soil; this is especially the case with a soil which contains much limestone, the author finding in one experiment that 93 per cent.of the soluble phosphoric acid had, after three hours' contact with a calcareous soil, become insoluble; the more quickly this conversion takes place, the less is the penetrating power of the phosphoric acid, and the more necessary it becomes to have the superphosphate in as fine a state of division as possible, and well mixed with the soil. J. K. C. The Shells of Crabs, Oysters, Mussels, &c., as Manure. By F. H. STORER and J. A. HKXSHAW ( R i d Cent?.., 1879, 331-336). -The authors have made several analyses of the shells of these animals, with a view to ascertain their value as manure. They find that the shells of oysters and mussels are composed almost entirely of carbonate of lime, and contain very little available phosphorus, nitro- gen, or potash, with the single exception of the common small mussel ( M y t h s borealis) , 1000 kilos.of which contain 2.8 kilos. of nitrogen. On the other hand the shells of crabs and crawfish are tolerably rich in fertilising materials, the king-crab (Linzulus americnm~s) containing as much as 12.5 per cent. of nitrogen, the agricultiiral value of which being, however, probably less than that of the nitrogen i n guano, On the whole, the shells of oysters and mussels may be used with advan- tage as a lime manure, especially after burning, whereby the small percentqes of phosphorus and potash are increased, and in those countries where they are cheaper than calcined limestone.J. I(. C.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 57Chemistry of Vegetable Physiology and Agriculture.Influence of Light on the Growth of Plants. By C. KRAUS(Bied. Cendr., 1879, 351).-The alterations of growth produced inplants by absence of light are of two kinds, one part of an organ orplant exhibiting an excessive, whilst another exhibits a diminishedgrowth. This is easily verified in the case of dicotyledonous plants,where the internodes are subject to an increased and the leavesto a diminished growth when the plant is placed in the dark. Similarphenomena are observed in the case of monocotyledons and cryp-togams. Methyl alcohol when applied to the roots of plants causesthem to die off, and has the same effect a3 light in promoting theformation of chlorophyll in tbe cells.Under the influence ofmethyl alcohol, young plants live longer in the dark, and their weigh58 ABSTRACTS OF CHEMICAL PAPERS.when dried is greater than in the case of plants which have not beenplaced under the same influence. J. K. C.Action of Ozone on the Colouring Matters of Plants. ByA. R. LEEDS (Chem. News, 40, 86).-In the first trial, in which manyvarieties of flowers were exposed during nirieteen hours to the actionof a currentf of 152 litres of air, containing in all 228 mgrms. of ozone,the bleaching effected was extremely imperfect,. When 1,200 litres ofair were passed over various flowers (total ozone 1.8 grams), theywere partly or wholly bleached at the end of five days. A piece ofcalico with a pattern in bright green and black was completelybleached during the same interval, the green having disappearedcompletely, and the stain of the mordant only remaining where theblack had been.From these and other results, it is concluded that the colouringmat,ters of both leaves and flowers of the species (Lantana, Puchsia,Petunia, Rosa, Verbena, Pelargonium, Bouvcr,rdia, Eiiphorbia, &c.) es-perimented with were partly or wholly destroyed by ozone; but aconsiderable percentage of ozone is required t o produce this result,or if such small amounts as are obtained in the customary methods ofozonising air by phosphorus are employed (1 to 3 mgrms.per litre), alarge volume of ozonised air must be used, and a considerable intervalelapse before bleaching is effected.Distribution and Functions of Asparagine in the VegetableKingdom.By J. BORODIN (Bied. Centr., 1879, 35’i-SGO) .-Aspara-gine, according to Pfeffer, occurs only in a few plants, and in theseonly a t the time of germination. The author finds, however, thatasparagine is present a t the time of budding in most plants, and alsowhen they are in bloom. It appears to be a decomposition-product ofalbumin, and is formed when there is a lack of carbohydrates in theplant. When these, however, reappear, the asparagine is reconvertedby their agency into albumin. From his researches, the author con-cludes that in $he early processes of growth there is a lack of thesecarbohydrates, and theref9re asparagine is formed a t these periods,being afterwards converted into albumin.Mineral Constituents in Hyacinths. By A.E. ROJEN andKRELAGE (Bied. Centr., 1879, 360-366).-The hyacinths were plantedaccording to size, a t the ratle of 42? 90, and 196 plants to the squaremetre. The results of the examination of their mineral constituentsmay be seen from the following table.D. B.J. K. C.Miueral constituents in grams in each plant.196 t; sq. metre. 90 to sq. metre. 42 to sq. Getre.Blossoms .... 0.042 0.230 0.303Stem ...... 0.027 0.036 0.106Leaves ...... 0.082 0-245 0.632Bulb.. ...... 0.146 0.355 1.380Roots ...... 0.022 0.022 0.311.Total.. .... 0.319 0.888 2.732- - VEGETABLE PHYSIOLOGY AND AGRICULTURE. 59From this table, it is a t once evident that the mineral constituentsincrease very rapidly with t’he size of the plant, and also that thequantity extracted from the soil is by no means small.From onehectare alone, when planted with 42 hyacinths to the square meter,would be extracted in one season 1,147 kilos. of mineral substance.The following table shows the diffeyence in quantity of mineralmatter in the bulbs when taken out of the ground just after theblossoming period and at the end of summer:-196 to sq. metre. 90 to sq. metre. 42 to sq. melre.Bulbs dug out just afterblossoming ........ 0.146 0.355 1.380At the end of summer.. 0.557 0.987 2.3 14J. K. C.Experiments with Various Sorts of Beet. By J. LANEK andC. PORTELE (Bied. Centr., 1879, 368--370).--The authors bring for-ward an account of the results obtained by growing various kinds ofbeet.They find that the ’‘ mammoth ” variety yielded the largest crop,whilst, the “ imperial” contained the largest percentage (10.7) of sugar.Formation of Nitric Acid in the Soil. By HkwErB, E.REJCHARDT, and HERTZ (Bied. Ceiztr., 1879, 327).-According to aformer paper of Hunefeld’s, nitric acid is produced when the higheroxides of manganese are brought into contact with air, water, andmagnesium carbonate. To confirm this statement, Reichardt andHertz performed the following experiments. Hydrated oxide ofmanganese, together with various oxides and earths, such as magne-sium and calcium carbonates, alumina, and oxide of iron, were placedwith a little water in a large flask, which was then closed andshaken a t intervals, care being taken to ascertain that no nitric acidwas present at the beginning of the experiments.No nitric or nitrousacid was obtained when the manganese was used in conjunction withcalcium carbouate or oxide of iron and alumina, but when mixed withmagnesia or alkaline carbonates, nitric acid was recognised in the pro-duct. Pyrolusite gave the strongest reactions, and it was found that50 grams put in a litre flask with 500 C.C. of water after sta’nding foreight days and frequent agitation yielded 045.5 gram of nitric acid.J. K. C.J. K. C .Calcium Carbonate in Water filtered through Dry Soil.By F. H. STORER and S. LEWIS ( B i e d . Cei~tr., 1879, 32b--331).-Theauthors find that a soil which has been ignited a t a temperature justsufficient to destroy the organic matter yields calcium carbonate whentreated with pure water, even after it has just cooled.They havearrived, therefore, at the conclusion that when ignited at a low tem-perature, a soil has tlie power of still retaining ca,rbonic acid. Whena dried soil is treated with water containing. carbonic acid, part of thelatter is retained by the soil. This, according to Storer, is merely amechanical result, and is due to the adhesion of the gas to the solidparticles of the soil. J. K. C60 ABSTRACTS OF CHEMICAL PAPERS.Mill Waste for Manure. By FRIEDBURG (Bied. Centr., 1879,386).-This waste, consisting chiefly of dust and chaff from rye, wasfound on analysis to contain the following percentages of consti-tuents :-Phosphoric acid, 0.96 ; nitrogen, 1.80 ; water, 5-80 ; organicsubstance, 62.84 ; ash, 31.36.J. K. C.Analyses of Marl. By J. KONIG ( B i d Cent?.., 1870, 385).-Thefollowing are the results of the analysis of 85 samples from West-phalia :-The calcium carbonate varied from 1-36 to 94.83 per cent. ;magnesium carbonate was present in 21 samples, and in quantity from0.38 to 27.39 per cent. Phosphoric acid varying in amount from0.029 to 1.55 per cent. was found in 23 samples. Lastly potassiumwas estimated in 28 samples, and varied from 0.08 to 2.43 per cent.J. K. C.Influence of the Physical Condition of Superphosphate onits Value. By P. WAGNER (Bied. C'entr., 1879, 336--339).-Thesoluble phosphoric acid in superphosphate on corning into contactwith the lime of the soil is converted into an insoluble form, andconsequently does not penetrate into the soil; this is especially thecase with a soil which contains much limestone, the author finding in oneexperiment that 93 per cent.of the soluble phosphoric acid had, afterthree hours' contact with a calcareous soil, become insoluble; themore quickly this conversion takes place, the less is the penetratingpower of the phosphoric acid, and the more necessary it becomes tohave the superphosphate in as fine a state of division as possible, andwell mixed with the soil. J. K. C.The Shells of Crabs, Oysters, Mussels, &c., as Manure. ByF. H. STORER and J. A. HKXSHAW ( R i d Cent?.., 1879, 331-336).-The authors have made several analyses of the shells of theseanimals, with a view to ascertain their value as manure. They findthat the shells of oysters and mussels are composed almost entirely ofcarbonate of lime, and contain very little available phosphorus, nitro-gen, or potash, with the single exception of the common small mussel( M y t h s borealis) , 1000 kilos. of which contain 2.8 kilos. of nitrogen.On the other hand the shells of crabs and crawfish are tolerably rich infertilising materials, the king-crab (Linzulus americnm~s) containingas much as 12.5 per cent. of nitrogen, the agricultiiral value of whichbeing, however, probably less than that of the nitrogen i n guano, Onthe whole, the shells of oysters and mussels may be used with advan-tage as a lime manure, especially after burning, whereby the smallpercentqes of phosphorus and potash are increased, and in thosecountries where they are cheaper than calcined limestone.J. I(. C

ISSN:0368-1769    

DOI:10.1039/CA880380057b

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 61A n a l y t i c a 1 C h e m i s t r y .Specific Gravity of Liquids. By L. SIEBOLD (Analyst, 1879,189).-From experiments carried out by the author, i t is clearlyshown that hydrometers afford reliable indications of the specificgravity of liquids, no matter whether their gravity is due to substancedissolved or in suspension. L. T. 0's.Analyses of Organic Compounds containing Fluorine andBoron. By $4. LANDOLPH (Ber., 12, 1586--1588).-1n the determina-tion of carbon and hydrogen in such compounds, the author recom-mends the use of fused lead chromate, which is placed before thecopper oxide and only heated gently, as otherwise the boric acid isvolatilised. To determine the fluorine and boron, the compound isdecomposed by a solution of calcium chloride.The fluorine is thusseparated as calcium fluoride, and the boric acid remaining in solutionis determined as magnesium borate. P. P. B.Direct Separation of Manganese from Iron. By F. BEILSTEINand L. JAWEIN (Bey., 12, 1528--1531).-The author describes twoprocesses, both of which are preferable t o the ordinary method ofseparating the iron as basic acetate. The first depends on the factthat all the manganese is precipitated as peroxide or sesquioxide froma solution of manganocyanide of potassium, on addition of iodine,whereas no precipitate is produced in potassiuni ferrocyanide byiodine. The details are as follows : The solution of ferric and man-ganous salt is poured into excess of concentratcd solution of potassiumcyanide. A minute insoluble residue always remains, which containsonly iron ; it is removed by filtration.Iodine is then added until allthe cyanide has been decomposed, and the slight excess is removed byaddition of a few drops of soda. The precipitated oxide of manganeseis filtered off, washed, and dissolved in hydrochloric acid, and esti-mated as sulphide. The only disadvantage of the process is the,largeamount, of iodine required (about 30 grams), but as it can be nearlyall recovered by addition of crude nitric acid to the filtrate fromthe manganese precipitate, this inconvenience is removed.The second process depends on the conversion of salts of manganeseinto peroxide by boiling with strong nitric acid and potassiumchlorate. The salts are dissolved in nitric acid, sp.gr. 1.35, and afterthe solution has been heated to boiling, potassium chlorate is addeduntil all manganese is precipitated. The liquor is then diluted andfiltered. Tbe precipitate contains iron, but by dissolving it in hydro-chloric acid and repeating the process, it contains only an infinitesimaltrace of iron. Both of these processes arenpplicable to the estimationof manganese in cast-iron and steel."1878, Trans., 269) ,-W. R.W. R.* The second of these procesees has been suggested by Hanmy (this Journal62 ABSTRACTS O F CHEMICAL PAPERS.Estimation of Organic Nitrogen in Natural Waters. By IT.PELLET (Compt. swzd., 89, 523). -The ammonia is estimated byBoussingault's process; the nitric acid, i n three litres of water, bySchloesing's method ; and the total nitrogen by evaporating threelitres of water to dryness, with addition of a small quantity of magne-fiia, mixing with a small quantity of starch, and heating with soda-lime in the ordinary way. The starch converts the nitric acid intoammonia, if the nitric acid does not exceed 0.23 gram of potassiumnitrate.c. w. w.Notes on Some Analyses of Waters. By T. L. PHIPSOK (Chem.News, 40, l).-The author considers that a very long experience isnecessary for a chemist to decide whether a water is fit for drinkingpurposes or not;; other questions such a s its effect in attacking anddissolving lead, or corroding iron pipes or boiler plates have often tobe decided by the chemist.For deciding the questions as to the adaptability of water for drink-ing purposes, mnch stress has been laid upon the proportion of organicmatter, but this is a mistake, because some waters containing as muchas 6 or 8 grains per gallon may be drnnk with impunity, whilst otherscontaining much less are known to be exceedingly injurious, if notfatal.Four or five grains of crenate of ammonia per gallon is not at; allhurtful, whilst putrid organic matter, nnrnerous Bacteria and Micro-coccus and minute white fnngoid growths are sources of imminentdanger.He gives the following as examples of water which he has ana-(1.) Well near Sleaford (Lincolnshire). -Water not quite clear,slightly alkaline with decided saline taste, and well a6rated with airand carbonic acid ; contains some minute green alge ; total residue,169 grains per gallon, which is composed of :-lysed :--Organicmatter. NaCJ.Na,CO, Na2S04. X2S04. MgC1, Si02. Fe203. CaC03.2-0 76.0 44.0 35.0 2.0 1.5 1.0 0.5 7.0Total, 169 grains. There were traces of phosphoric acid and ofbromine.(2.) St. Anme's Well, Bztxton (Derbyshire), contains mineralmatter 18 grains, organic matter 2.0; total, 20 grains per gallon.The mineral matter is composed chiefly of calcium carbonate andsodium chloride, with a little caleium sulphate and traces of iron,silica, czesium, and strontium, but no lithium o r rubidium. Thewater is beautifully dear and tasteless, and is said to have a constanttemperature of 80" to 82" F., sp. gr. at GOo 1.003. The fact thatthis water cures g o d is owing probably to its great purity, and to itsbeing drunk warm and in large quantities.( 3 .) Well o n Wirnbledon Common (Surrey), contains mineralmatter 26 grains, organic matter and nitric acid 6 grains; total, 3ANALYTICAL CHEMISTRY. 63grains per gallon. The mineral matter is composed principally ofcalcium carbonate and sulphate, with a small proportion of alkalinesalts. It iswell aarated, and contains no phosphoric acid. A single dropof a very dilute solution of potassium permanganate gave a rose tintto 200 C.C. of the water, which persisted for several hours. This is anexample of a good well water.(4.) Well in the Lotuer Bagshot Sand, near Esher (Surrey).-Thewell is 40 feet deep, and is sitxated about 40 feet from a small ceme-tery.The water is beautifully bright,, clear, and odourless. Itattacks and dissolves lead easily, and shows decided indications ofnitrates and ranch chlorides. It contains nitric acid and organicmatter 7.0 grains, sodium chloride 14.0, sulphates, carbonates, &c., 37.8 ;total, 58.8 grains per gallon. A very deceitful water; certainly im-pregnated and likely to get worse, sp. gr. 1.0032. A spring muchfarther from the little cemetery gave nitric acid and organic matter3 grains, mineral matter 21 grains ; total, 24 grains per gallon. Thiswater dissolves lead easily.(5.) A Yellow Water (South of EngZand), supposed to be ferrugi-nous, remains clear even on boiling, but gives off a strong marshyodour. Total residue, 2.1 grains per gallon, consists principally ofthe ulmates of lime and ammonia, a little carbonate of lime, and tracesof chlorides, &c.(6.) Well at Midland Bank, Birmingham, contains mineral matter(after calcination) 58.71 grains ; total residue, 81.62 grains per gallon.This water contains a very large amoiint of nitrates and ammonia.Itis a bad water for household use, and it is said to corrode metals.(7.) Welt in, an Brt9ciul Mcc.liure Mawufactory near 8oufhanyton.-The water contains free sulphuric acid 1500 grains, phosphates, cal-cium sulphate, alkaline salts, &c., 18.20 grains.(8.) Welt at Albuny B~l,rracl~s, London.-Organic matter and nitricacid 8 grains, mineral matter ‘72 grains per gallon. Supposed to havecaused an outbreak of typhoid.(9.) Wdl near Huntingdon, contained calcium sulphate 35-89 grains,calcium carbonate 15.37, sodium chloride 16.00, organic matter andnitric acid 5.00, silica, magnesia, oxide of iron, &c., 8.74.(10.) Water f~orn n Scul1er.y Pwnp in Bolton Street, Piccadi1ly.-Total residue, 1024 grains per gallon.It contained abundance ofphosphates, resembIFd dilute urine, and was said to have caused sicknessand diarrhcea.(11.) We& at Putney, X.W.-The total residue varies from 38 to120 grains, and some containing from 38 to 48 grains, of which 7 or 8grains are composed of organic matter and nitric acid, have been usedfor many years for drinking purposes without having produced anybad effects. Others that yield 60 gmins of total residue, of which 10grains are composed of organic matter and nitric acid, have been pro-scribed by the medical authorities.Evidence is quoted from ananalysis made by the late Dr. D. Thomson to show that althoughthese waters are highly contaminated, they have not changed in com-position for 25 years.The author generalises as follows :64 ABSTRACTS OF CHEMICAL PAPERS.(1.) The depth of a well has no influence on the quantity of solid(2.) The purer a water, the more easily does it dissolve lead.(3.) Boiler deposits from all parts of the world with a few ex-ceptions, consist almost entirely (over 90 per cent.) of calcium car-bonate.residue which a water contains.(4.) The presence of phosphoric acid is always a bad indication.W. T.Rapid Estimation of Pure Sugar in Raw and Refined Com-mercial Sugars.By P. CASAMAJOK (ClLem. News, 40, 74-76 ; 97-98 ; 107 and 131).-h Payen's process, two alcoholic solutions satu-rated m7ith sugar are used, and filially absolute alcohol, t o wash out thelast traces of the sugar-saturated solutions. The first solution isobt'ained by taking alcohol of 85 per cent. and adding to this 5 percent. of strong acetic acid ; this mixture is saturated with sugar. Thisaddition of acetic acid was made in order to decompose the sucrates,which were a great nuisance to chemists in former days, but in addi-tion, it seems to make the mixture better able to remove the impuritiesof gummy sugar. This first of Payen's solutions was the one adoptedby Dumas in a process published several years ago, which, however,lias never been studied by sugar analysts: the author's process isbased on this.Dumas proposed to agitate 100 C.C. of the first, Payeneolution with 50 grams of sugar, filter, and observe the alcohometricdegree corresponding to 15'. For every per cent. of sugar less than100 the solution is said to indicate I per cent. lesd than 74. For sugarshaving 87 per cent. or more pure sugar, the results agree very closelywith those of the saccharometer, even within 0.1 per cent., but forsugars of lower grade the results obtained are not satisfactory.As nearly one-half of the raw sugars which occur in commercestand below 87 per cent., there seemed to be lit8tle use in a processwhich was declared to he inapplicable to sugars of low grade.Theauthor found, however, after tryiug the process several times, that,although the results obtained were mostly nnfavourable, it was im-possible to dismiss it entirely ; for, upon reflecting upon khe results,it was found that many questions arose which required to be solved,and on their solution the author based the hope of modifying thisprocess so as to apply i t to the analysis of cane-sugars of all grades.By employing methyl instead of ethyl alcohol, the author suc-ceeded in obtaining, with an alcohometer, results that agree veryclosely with those of the optical saccharometer, and that with cane-sugars of all classes from the highest to the lowest. After making agreat number of trials, it was found that methyl alcohol of 83.5" ofthe alcohometer (or 87 per cent..), when saturated with sugar, standsat) 77.1".This solution is the one that has given the most accurateresults. It is easily obtained by taking methyl alcohol, standingat 834" br the alcohometer, and saturating it with sugar by the pro-cess which Numa Grav suggested t o Payen. Since the solution isliable to alteration from loss of alcohol, it is best to test it beforeusing it. When the degree is lower than required, it, may he raisedby adding more alcohol. If a certain volume V of alcohol and water,whose alcohometric degree is d is to be raised to D, with stronANALYTICAL CHEMTSTRY. 65alcohol of degree A, if the volume of the latter to be added is called x,we shall hare V d + xh = (V + x)D, whence x = v(' - 'I.Thusto raise 1000 C.C. of alcohol a t 81 to 83-5 with alcohol of 92 per cent.where d = 81, D = 83.5, V = 1000, and A = 92, the volume of alcohol'Oo0 2*5 = 294.1 C.C. If the addition of 92 to be added is, x =of alcohol has been too great, the degree may be diminished by add-ing water very gradually and stirring up the mixture with an excessof sugar. To ascertain the quantity of water the above formula maybe used, but it must be notred that A = 0, and as both numerator anddenominator have become negative quantities, the signs may bechanged when x =Next in importance is the weight of commercial sugar to be takenfor 100 C.C. methyl alcohol solution saturated with sugar. At first anarbitrary quantity may be taken and the result noted, which may becorrected by the following consideration.The lowering of the alco-hometric degree depeiids on the water and the soluble impurities con-tained in the sugar. If a cert,ain weight of sugar is taken, say45 grams, the result by the alcohol process may be 91.5 per cent. ofsugar. If the same sugar is tested by the optical saccharorneter andyields 93 per cent. of sugar, it shows that the alcohol process hasgiven too low a result, and this because the solution was too dense.The first result shows in the sugar 100 - 91.5 = 8.5 of impuritiesand water, whilst, it ought to be 100 - 93 = 7. To obtain 93 thereforea weight must be taken equal t o - 4'5':7 = 37.05 grams.8.5After trjing many experiments with solutions of different strengths,it was found that each solution required a different weight.For thesaturated solution of 77.1" of the alcohometer, which is the standardsolution employed by the author, the weight is 39.6 grams for 100 C.C.of the solution. Instead of using 100 C.C. the author for a long timeused only 50 C.C. To be able to use a cylinder in which this volumewould give indications. aicohometers had to be employed of smalldiameter. For 50 C.C. of standard solution the proper weight is19.8 grams, i.e., half of the one for 100 C.C. This weight was obtainedby calculation. Using this weight with 50 C.C. of standard solu-tion, 15 conseciitive tests of raw and refined sugars were made, theresults obtained showing that the difference between the percentageof pure sugar by the saccharometer a n d that by methyl alcohol wasvery slight, the greatest deviation being 0.7.If the operations aremade a t temperatures different from 15" C. or 60" F. the correctionscan be made by using either of the tables of Gay-Lussac or those forthe instrument of Tralles. Another correction for the variation oftemperature relative to the volume of standard solution to be takenfor a, weight of sugar equal to 19.8 grams is given in t h e table-At 15" C. 20". 25". 30". 35". 40".19.8 grams 19.7 19.6 19.5 19.4 19.3A - D8.5V ( d - D):DVOL. XXXFIIT. 66 ABSTRACTS OF CHEMICAL PAPERS.The following table contains corresponding corrections for methylalcohbl of various strengths saturated with sugar :-Degrees of thealcohometer Degrees of Degree of thebefore saturation saccharometer Grams of sugarsaturation.with sugar. (Ventzke). in 100 C.C.92.5 91.8 1.7 0.4483.5 77.1 13.2 3.4382.7 76.5 - -81.5 75.0 - -Method of procedure im testi.ng.-The sugar to be tested should notbe weighed until everything is ready. The cylinder is filled with thestandard solution to a line indicating 50 c.c., and 19.8 grams of sugarare weighed out. This is transferred to a mortar and the standardsolution poured i n ; the whole is then ground until all lumps andlarge crystals are broken up. The contents of the mortar are nowfiltered into the cylinder and washed out with the filtered solution.The filtered solution is then tested with an alcohometer and a ther-mometer in succession. To the alcohometric degree, corrected fortemperature, is added the difference between 100 and the alcohomctricdegree of the standard solution. This sum represents the percentageof sugar.D. 13.Behaviour of Various Sugars with Fehling’s Solution. ByF. SOXHLET and others ( R i d Centr., 1879, 370).-Soxhlet questionsthe accuracy of the prevailing opinion, that under all circumstances5 mols. of copper are reduced in alkaline solution by one of sugar, andstates that the qnantity of copper reduced varies with the dilution of theFehling7s reagent and the amount of the latter present in excess. Inthe early part of the titration a large excess is present, as is also thecase when the oxide of copper formed is weighed, the liquid stillremaining blue. Soxhlet, in common with the rest, finds it the bestplan to keep two solutions, one of Rochelle salt and soda, and the otherof copper sulphate, a sufficient quantity of each being measured outand mixed before each experiment. When a + per cent.solution ofdextrose was used it was found that from undiluted Fehling’s solution5.05 mols. of cuprous oxide, and from diluted only 4.85 mols., are pre-cipitated by 1 mol. of sugar in titration. Similar differences are seenwhen the gravimetric method is used, 5.5 mols. and 4.85 mols. beingreduced according as the Fehling’s solution was in large excess or onlyjust, so. As the amount of sugar is an unknown quantity, the sameconditions cannot be exactly preserved during each experiment, andSoxhlet is therefore of the opinion that an accurate analysis by thegravimetric method is impossible. On the other hand, Marcker,Behrend, and Morgen hold that if certain conditions are maintainedthroughout, the analysis gives accurate results. They recommendusing the same quantity of Fehling’s solution and the same volume ofliquid in every experiment and calculating the result by means of a nempirical table.Their method is as follows :-25 C.C. of each part ofthe Fehling’s solution is mixed with a certain quantity of sugar sohANALYTICAL CHEMISTRY. 67tion coniaining not more than 0-12 gram dextrose, and the whole madeup with water to 100 C.C. and heated on a water-bath for 20 minutes.The cuprous oxide is then filtered off, washed with 300 C.C. of hotwater, and reduced in hydrogen and weighed.From the various numbers obtained, the authors have compiled thefollowing table, by means of which the amount of sugar may be calcu-lated :-Reduced Cu.mgrms.196194.7188.5182.0175.1167.9160.4Dextrose.mgrms.111.1110105100959085Reduced Cu.mgrms.152.5144.4135.8127.0'117.8108-298.3Dextrose.mgrms.80a57065605550or the amount may be calculated by the formula-u = -19.26 + 2.689 b -0.006764 P,where a is the copper and b the dextrose.The authors consider that by the use of the above table the processgives very satisfactory results.Soxhlet has also found that the quantities of cuprous oxide obtainedby reduction with milk-sugar vary in the same manner as with dex-trose, according to the strength of Fehling's solution employed, from7.4 to 7.67 mols.of copper to 1 of milk-sugar. Rodewald and Tollensmaintain, however, that accurate results are obtainable when certainprecautions are taken, the experiments being all carried out; under thesame conditions of volume. strendh, &c. : under the conditions which 0 , 2 they employ, 1 mol, of milk-sugar reduces 7.47 mols. of copper sulphate.J. K. C.Estimation of AcetyI by Means of Magnesia. By H. SCRIFF(Ber., l2,1531---1533),--This process has an advantage over the use ofsoda, inasmuch as magnesia seldom has a decomposing influence on theproducts of the reaction. Thc magnesia is prepared by precipitating thesulphate or chloride with caustic soda, excess being avoided. 5 gramsof the paste are boiled with 1 to 1.5 grams of the acetyl-deri-oativeand 80-100 C.C.of water for four to six hours in a flask with invertedcondenser. After the reaction is over, the liquid is evaporated to one-third of its volume and filtered. the magnesia is then estimated in thefiltrate by the usual process, and from its amount that of t,he acetyl canbe deduced. W. R.Test for Phenylglyoxylic Acid. By L CLAISEN (Bey., 12,1505).-Concentrated sulphuric acid, added to a solution of phenylglyoxylicacid in benzene, gives a deep red coloration, changing to intense blue-.violet. On addition of water, the colouring matter remains dissolvedin the benzene and may be obtained by evaporation. The amides andethers of this acid, as well as benzoyl cyanide, give the same reaction.f 68 ABSTRACTS OF CHEMICAL PAPERS.Metanitrophenylglyoxylic acid produces a carmine, and orthoni troben-xoyl cyanide a bluish-green colour, analogous to that produced by treat-ing isatin with benzene and mlphuric acid.W. R.Citrate of Iron and Quinine. By F. W. FLETCHER (Anahyst,1879, 191--193).--The author has applied the following modificationof Paul's method for testing quinine to the determination of thequantity and purity of the alkaloi'd in citrate of iron and quinine.20 grams of citrate of iron and quinine are dissolved in 50 C.C. ofwater, and shaken with excess of strong ammonia. The mixture istreated with 25 C.C. of ether, and shaken until the alknlo'id is dissolved ;the two liquids are separated, and the aqueous sclution shaken withether a second and third time.The ethereal washings are mixedtogether and evaporated to the consistency of a paste at the ordinarytemperature, and finally dried at 120". It is then weighed; theweight multiplied by 5 gives the percentage of alkalo'id present. Thealkaloi'd is converted into basic sulphate by adding the requihitequantity of acid. The weight of alkalo'id multiplied by 30.86 gives thenumber of C.C. of decinormal H2S04 required. The liquid is heateduntil all the substaace is dissolved, the solution allowed to cool spon-taneously, and the crystalline mass filtered through calico. Thevolume of the filtrate is taken, and to it 20 C.C. of ether and excess ofammonia are added, and the mixkure well shaken.Itl is then allowedto stand for six hours, when, at the junction of the two liquids, crys-tals of cinchonine and quinidine will be found. These are collected ona weighed filter, dried a t 120", and weighed.The crystalline residue is dried a t 100" and weighed, and the weightmultiplied by 1.18 gives its value as erystallised sulphate of quinine.Iodic Acid as a Test for Morphine. By J. C. BELL (artalyst,1879, lsl).--Todic acid is shown by the author to be most unsatisfac-tory as a distinguishing test'for morphine. Other organic bodies, suchas ipecacuanha and guaiacum, reduce iodic acid with separation ofiodine. And, moreover, the statement that, the colour is not destroyedby ammonia in the case of morphine is incorrect.L.T. 0's.L. T. 0's.Nitric Nitrogen in Guano. By R. R. TATLOCK (Ohem. Nezos, 39,268-270).-The autlior was led by experiments made some years agot o believe that a large proportion, and in some cases nearly the wholeof the nitrogen present in guano as nitrates was converted by thesoda-lime combustion psoctesfi into ammonia, and estimated as such,and the extent of this change he has since found to depend on therelative proportion of the organic matter to the nitrates present.He was surprised to find that it was the practice of chemists oflarge experience in such analyses to determine the ammonia as if thenitrates present were not decomposed ; thus a much larger percentageof that substance would be represented than what really existed.When citrates are heated with soda-lime, no ammonia is produced,but when heated with soda-lime in presence of organic matter am-monia is produced, and its quantity depends on the nature and propor-tion of the organic matter employed.The author experimented witANALYTICAL CHEMISTRY. 69potassium nitrate in presence of different quantities of starch, sugar,camphor, albumin, and wood charcoal, .and the following are some ofthe results obtained :-20 of starch- to 1 of nitrate gave 50.74 per cent; or” the nikric3 of camphor to 1 of nitrate gave . . . . . . 26.38 per cent.1+ of wood charcoal to 1 of nitrate gave.. 11.56nitrogen as ammonia.?,6 of albumin 7, 7 , . . 49-94 ,,6 of sugar 9 7 9 , . . 63.35 ,,30 of sugar ,, ,1 . . 97.40 ,,They vary somewhat, however, even with the same proportions ofthe same organic materials.The author critieises the various processes for estimating the nitricnitrogen in guanos, and concludes that Crum’a (Proc. GlasgowYhiZ.SOC., 1848, 162) is the best, the nitric acid being determined inthe nitrometer as nitric oxide. It sometimes happens, however, thata little free nitrogen is evolved a t the same time, by the action ofthe strong sulphuric acid on nitrogenous organic matters. This canbe determined by introducing a warm solution of ferrous sulphate intothe nitrometer, which absorbs only the nitric oxide present. Theauthor has not yet arrived at a satisfactory solation of the queshion.Tatlock’s results (Chenz. NPUIS, 39, 2gl) are criticised by B.J.Grosjean. He says that he published (ibid., 25, 2Q-5) some results onthis subject, in which he drew attention to the conversion of nitricnitrogen into ammonia by the soda-lime process, but this fact is statedboth in Fresenius’s “ Quantitative Analysis ” and in Church’s“ Laboratory Guide,” The author described encouraging results forthe conversion of all the nitric nitrogen into ammonia by the combus-tion of nitre with sugar and iron filings. His best results wereobtained by mixing the nitre with a caustic alkaline solution in a re-tort, adding iron filings, and distilling the mixture to IL pasty mass,which was allowed to cool, powdered, mixed with soda-lime, and acombustion made to determine the residue of the organic nitrogen.W. T.Perchloric Acid as a Test far Alkaloids.Ey G. FRAUDE(Beg-., 12, 1558-1560) .-Perc*hloric acid of sp. gr. 1.13-1.14 has noaction on quinine, quinidine, cinchonine, cinchoiiidine, morphine,code‘ine, papaverine, vcratrine, caff e‘ine, atropine, nicotine, nor conine.When boiled with brucine, it gives a dark sherry colour, with strych-nine a reddish-yellow, and with aspidospermine an intense red. Iodicanhydride and sulphuric acid give with brncine an intense orange-yellow ; morphine, deep violet, then orange brown ; and curarine,pink. These reactions are suitable as lecture experiments.W. R.Koettstorfer’s Process for Butter Analysis. By G. W. WIGNER(Ancrlyst, 1879, 183).-The author points out that for the analysis oEsamples of genuine butter this process may be used, but i n cases ofdoubt, a complete analysis should be made.L. T. 0’s70 ABSTRACTS OF CHEMICAL PAPERS.Coefficients of Expansion of Butter, Lard, Fats, &c. ByG. W. WIGNER (Analyst, 1879, 183--185).-By comparing the sp. gr.of butter and lard fat, &c., a t different temperatures, the coefficients ofexpansion have been determined.Butter fat between 100" and 212" F., has the coefiicient 0,0434 perdegree F. Between 150" and 193" the coefficient is slightly greaterthan this number, but remains the same for all other temperatures.L a d Fat and Butteri.ne.-Thc coefhients of expansion of these iwobodies are almost identical, that of lard fat being 0.0420 per degree F.Specific Gravities of Fats, Resins, &c. By H. HAGER ( P h a m .J.Trans. [3], 10, 287).-The fat is melted, dropped into a flat vesselcontaining alcohol, in such 9~ manner that the point from which thedrops are allowed to fall is not more than three centimeters distant fromthe surface of the alcohol, and that each drop is allowed to fa,ll on adifferent spot. The fat globules thus deposited are then removed to aliquid, consisting of either alcohol, water, or glycerol, o r mixtures ofthese, until after careful stirring and reduction or increase of thedensitly, by the addition of one or another of the above liquids, the fatglobules are held in equilibrium in any part of the liquid. The sp.gr. of the latter is then determined, and this of course at the sametime represents the sp. gr. of the fat.Many of the following sp. gr.'smay be used as criteria for distinguishing the various bodies investi-gated :-L. T. 0's.Sp. gr. at 15-16' C.0.938-0.940,, several months old . . . . . . . . 0.936-0.9370.924-0.9300-931-0.9320.925-0.9290.937-0*9400*936-0*9380*950-0*9520.945-0.9460.938-0.9391*016-1*0181-014-1.0150.965-9.9660.9640.967-0-9690.959-0 9520.973-0.976Butter fat, clarified by settling . . . . . . . .Artificial butter . . . . . - . . . . . . . . . . . . . .Hog's l a d , fresh . . . . . . . . . . . . . . . . . . . .Beef tallow . . . . . . . . . . . . . . . . . . . . . . . .Sheep's tallow . . . . . . . . . . . . . . . . . . . . .Beef and sheep's tallow, mixed 1 : 1 . . . .Butter of cacao, fresh . . . . . .. . . . . . . . . .Butter and beef tallow, 1 : 1 . . . . . . . . . .Expressed oil of nutmegs . . . . . . . . . . . .Ditto, extracted with CS, . . . . . . . . . . . .Ditto, crystalline . . . . . . . . . . . . . . . . . . . .Stearic acid, melted, and in drops.. . . i.Wax, yellow . . . . . . . . . . . . . . . . . . . . . . . .yellow and resin, 1 : 1 . . . . . , . . . .,, old.. . . . . . . . . . . . . . . .. . . . . 0.940--0.9427 7 very old. . . . . . . . . . . . . .7 7 crystalline . . . . . . . . . . . . . .,, African .. .. .... .. .. .. .. . . . . .. 0.960,,7 9 ,, and paraffin, 1 : 1 . . . . . . . . 0.916-0*9197 9 ,, and yellow ceresin, 2 : 1 . . 0*942-0.943Ceresin,yellow ....................... 0.985-0.928Wax, Japan . , . . . . . .. . . . . . . . . . . . . . . . 0.977-0.978,, ,, very old . . . . . . . . .. . . . , . . 0.968-0.970,, white, very old and true . . . . . . . . 0.963-0.964J J 0.916-0.925 ,, new . . . . . . . . . . . . . . . . . . . ANALYTICAL CHEMISTRY. 71Sp. gr. at 15-16' C.Wax, Japan, new, and stearicacid, 1 : 1 . .Wax, sp. g:. 0.963, and stearic acid,Ceresin, very white, pure ............ 0*905-0*9080.945sp. gr. 0.9b3, mixed, 1: 1 . . . . . . . . . . 0.975 .. whit,e ...................... 0.923-0-924Araucaria wax ......................Resin (fir. pine), yellow, transparent . .,, whitish, opaque.. ..............Shellac, lightl-coloured. ...............,, darker.. . . . . . . . . . . . . . . :. ....Dammar, old.. ......................Benzo'in, Siam ......................Guaiac resin, pure ..................Copal, East and West Indian..........,, Pennng ....................,, Borneo ....................Amber ............................Sand arac ..........................Mastic ............................Balsam of tolu, old brittle ............0.9901*083-1.0841*044-1*0471.11 5-1*1141.12'31.0751.2351*063-1*8001 -14 5-1 $1 551*165-1.1701.236-1 23 71*074-1*0941 '0.38 -1.0441.056-1.0601.231-1 *232D. B.Testing Drugs. By L. SIEBOLD (AnaZyst, 1879, 190--191).-Themethod for the detection of mineral adulteration in flour by means ofchloroform (C. Himly, Year Book of Pharmacy, 1877) may be ap-plied for the same purposc to drugs. The powdered drug is shakenwith chloroform when the mineral matter sinks to the bottom, and inthe cases of acacia, tragacanth, starches, myrrh, Rarbadoes aloes,jalap, saffron, cinchonas, nux vomica, mustard, white pepper, capsi-cum, and guarana, the drugs float on the top. By pouring the chloro-form off, the lower stratum of mineral matter may be collected andweighed.I n some cases, however, such as gamboge, scammony, opium, Socotrinealoes, liquorice root, ginger, colocynth, coussa, ipecacuanha, cinnamon,and cardamoms, a portion of the drug sinks with the mineral matter.The test may, however, be applied qualitatively, since adulterationmay be detected by a careful inspection of the sediment.L. T. 07s.Testing Malt. By W. SCHULTZE (Ried. Centr., 1879, 375-377).--Malt is usnally mashed a t from 70" to 75" C. : the author finds,however, that the yield obtained at this temperature is always smallerthan when the mashing takes place a t 60", 65", or 70". The extract is,however, much inore quickly prodiiced at the former temperature,only 20 minutes being required at 70" as against 18.5 hours at 60".No more extract is obtained after the starch has been converted intomaltose and dextrin, and it is therefore unnecessary to continue themashing longer. J. I(. C

ISSN:0368-1769    

DOI:10.1039/CA8803800061

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

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

ISSN:0368-1769    

DOI:10.1039/CA8803800072

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

81 G e n e r a l a n d P h y s i c a l Chemistry. Emission Spectra of Haloi'd Mercury Compounds. By B. 0. PEIRCE (Ann. Yhys. Chenz. [el, 6, 597--,599).-The emission spectra were obtained by passing the electric current through 8 Geissler tube containing a small quantity of the salt ; wken the salt is warmed with a Bunsen burner, the mercury spectrum is seen, and as bhe heat is increased bands appear which differ according t o the salt employed. The measurements were made with a Steiihcim spectroscope, the scale of which corresponded as follows with the lines of the spectrum : Si + 81, Na - 100, Hgn, - 102.9 and 103.8, Baa - 111, Hga - 114, SrP - 157, Hgp- 176, Hg6 - 138, H ~ E - 207. When mercuric chloride was used, a band appeared a t 1084 - 1 OO$. The edge of this band was sharply defined on the less refrangible side ; but when the salt was strongly heated, a continuous spectrum was observed, stretching for some distance on the more refrangible side.Mercurous chloride gives the same band, whence it is argued that mercurous chloride is dissociated. Mercuric bromide gives st band between 131 and 135; mercuric iodide a band between 168 and 172. It is remarked that the bromide band is exactly half way between that of the chloride and that of the iodide. F. D. B. Smoke of an Electric Lamp. By B. S. PROCTOR (Chenz. News, 39, 283).-Att the Newcsstle-upon-Tyne Chemical Society Mr. J. W. Swan exhibited an electric lamp on the incandescent principle, in which the current had to pass through and heat a cylinder of carbon placed between two platinum condnctors ; this arrangement was placed in a vacuum in a glass vessel, and as the current was too strong the carbon cylinder broke down.The author examined the glass which enclosed it, and found the inside covered with a sooky deposit which, under a $-inch rnicro- scopic objective, appeared nebulous, with some bright specks of plati- num here and there. The platinurn supports were also covered with the black deposit, which burned off easily on being heated to dull redness. A piece of the glass was treated with aqua regia, and platinum and iron were found in the solution. It is possible that the platinum particles were scattered about by the disruptive discharge, which fol- Thermochemical Investigation of the Oxiaes and Acids of Nitrogen. By J. THOMSEN (Bey., 12, 2062-2065).-1n order to calculate the heat of formation of the oxides of nitrogen, the following values were determined by experiment :- lowed the breaking down of the carbon cylinder.w. T. VOL. XXXVIII.82 ABSTRACTS OF CHEMICAL PAPERS. Reaction. Heat of formation. N, + H, + 0, = NFT,NO, . . . . . . . . . . 64950 units W20, + 0, = N,O, . . . . . . . . . . . . . . . . 39140 .. N,+ O..........................--18320 .. N204 + Aq ...................... 15510 .. Oxidation of an aqueous solution of N,0+ N,04Aq + 0 = + 18320. From these data, the following results were obtained. which differ considerably from Berthelot's determinations (Ann. Phys. Chem. [ 5 ] , 6, 178) :- Berthelot. Thorn Ben. N2 + 0.. . . . . . . . . . . . . N, + O2 . . . . . . .. . . . . -86600 units - 72790 ,, N, + 0 3 + Aq.. . . . . . . -51800 ,, - 36460 ,, . . . . . . . . . . . . -33650 ,, N, + 0 4 - N, + 0, -t- Aq N2 + 0, + Aq.. -14800 ,, t 180 ,, - 18320 units - - 18140 ,, . . . . . . . . - . . . . . . The following table shows in columns I and I1 the heat of forma- tion of the anhydrous nitrates ; in I by the direct union of their elements, and in I1 according to the equation + O2 + N,O1. Column I11 shows the heat of solution of these salts:- Nitrates of I. Potassium.. .. 104660 Sodium.. ..... 96430 Iithium ..... 96800 Thallium ..... 43330 Silver . . . . . . 1.3920 Barium.. .... 196100 Strontium ... 190210 Calcium . . . . . 173590 Lead . . . . . . . . 75860 Sr 4- 0, + N,O1 4- 4H20 Ca + 0, + N,O, + 4H,O Cd + 0, + NZO, + 4H,O Mg+ 0, + N,Oa + 6H2O Zn+ 0 2 + K20J + 6H20 Ni + 0, + N,O, + 6H20 CO + 0, + NZO, + 6H10 CU+ 0, + N204 + 6H,O 11. 242960 226500 227240 120300 61480 229750 223860 207240 109510 231540 218440 124870 214530 142180 124720 123330 96950 111.- 17040 - 10060 + 600 - 19940 - 10880 - 9400 - 4620 + 3950 - 7610 - 12300 - '7250 - 5040 - 4220 - 5840 - '7470 - 4 9 0 - 10710 w. c. w. Therrnochemical Research on the Carbonates. By. J. THOMSEN (Ber., 12, 2031--2032).-The heat evolved in the formation of the following anhydrous carbonates by the combination of carbonic oxide, oxygen and the metal, is given in column I ; the heat evolved by the combination of carbonic acid with the metallic oxide is showri in column 111. For the sake of comparison the heat of formation of the corresponding anhydrous sulphates from metal, oxygen and sulphurous anhydride is given in column 11.GENERAL AND PHYSICAL CHEMISTRY.53 Carbonates and sulphntes. I. 11. 111. . K, . . . . . . . . . . . . 25OCl40 273560 257510 - - Na,:!.. . . . . . . . . . . 242490 Ba . . . . . . . . . . . . 252770 266490 5.5580 Sr . . . . . . . . . . . . 251020 2598.20 53230 CR . . . . . . . . . . . . 240660 248970 42490 Mil . . . . . . . . . . . . 180690 178790 Cd . . . . . . . . . . . . 151360 150210 Y b 139690 145130 22580 - - . . . . . . . . . . . . A g 2 . . . . . . . . . . . . 92i70 96200 20060 w. c. w. Mutual Relations of Potassium and Sodium Alum in Aqueous Solution. By F. P. VENABLES (C‘hem. Kews, 40, 198-199) .-Two forms of isomorphism between these two salts may be conceived : the formation of a double alkaline alum, KNaS04.Al,(S04),.24H20 : and the isomorphous admixture of the two alums in the various crys- tals.All attrempts to prepare the double alkaline alum failed, the isomorphous displacement always being of the second kind, tlie potas- sium salt predominating, owing to its being less soluble in water than the sodium salt. Experiments T+*ere also made on the solubility of potassium alum in R solution of sodium alum of diflerent strengths and a t different temperatures, the results being that 100 grams water containing- (;r.ams sodium alum 4.8 10.0 12.1 15~4 21.1 33.7 55.6 76.7 } i.8 6.1 5.7 5.3 4.7 3.8 2.7 1.7 Will dissolve potas- sium alum L. T. 0’s. Law of Dulong and Petit applied to Perfect Gases. By H. WILLOTTE (C’onzpt. rend., $9, 540--543).-The product AC of the mole- cular weight A into the specific heat a t constant volume C is very nearly the same for all gases.In order. therefore that any two gases may be a t the same temperature, it is necessary and sufficient that the mean total energy of any molecule whatever sball have the same value in both gases, that is to say, that AB’ = A%’’ ; A and A’ being the molecular weights of the gases nnder consideration, and --, AB2 __ A’”‘, the means of the total energies of the molecules of eachgas. Tm7o or more gases are a t the same temperature, if, when placed in contact with each other they nevertheless preserve their total respective energies unchanged. It may be shown (1) by making use of the theory of Carnot, or ( 2 ) by the homogeneity as far as velocity is concerned of the equations rela- ting to the theory of percussion, that if the rule AE2 = A’B’2 holds good for any one tcniperature, it does so for all other temperatures ; tlie question is how far this can be explained from a purely mechanical point of view.It cannot be due t o the mutual collisions of the molc- cules, for Clausius has shown t h a t inter-molecular shocks exert only a disturbing influence in the theory of gases; the author therefore prefers to explain it by molecular collisions against the atoms of a material ether, a gas of exceedingly low density, having its constituent 2 2 9 284 ABSTRACTS OF CHEMICAL PAPERS. particles situated a t distances very small in relation to the dimensions of the molecules of ordinary gases ; a supposition which serves as n basis for several theories. If A represents the weizht of any molecule endued with a rapidity of translation F1, the arithmetical mean of the quantities of move- ment representing the forces of percussion due to the displacement of the molecule A, can be reprcscnted by hzAb;?dt, the sum Z being taken during anp moment of which dt is the element, X being a constant independent of the nature of the molecule under consideration.The sum of the terms calculated for unity of time is approximatelg 2Ab;ilt = AB;, where B: is a quantity equal to the mean of b;. If in any vessel there are n molecules whose mass is equal to A, and n’ whose mass is equal to A’, the arithmetical law of the forces of per- cussion acting in unity of time on the mass of ether in question will be h(nAJ3: + n’A’B’:).Again, if while n f ‘yL‘ = const., the sum just mentioned does not vary when the composition of the mixture is altered, the systems formed by the forces of percussion will not vary either ; and again the sum will remain invariable whatever be the ratio if AB; = A’B’:. ?L With a mass of molecules whose centres of gravity are Exed, bnt of which the various parts are endowed with reciprocal movements, it may be found by similar reasoning tlint in the case of equilibrium of temperature, the energies corresponding to thcse movements satisfy the relation AR; = A’B’:, whence by addition- - - *’a representing the total mean energies of the molecules. 2 ’ 2 AB2 AB2 It is thus seen why the ratio -’ is the same for all gases at any deter- minate temperatures ; further by making use of the principle of homo- geneity before mentioned, it may be easily demonstrated that if the ratio __ is the same for all gases a t any temperature arbitrarily chosen, it will hold good, o r very nearly so, for all other temperatures, the value of the ratio varying very slowly with the temperature.(lcbid., 89, 568-570). I n determining the conditions of equilibrium of t2mperature in the case of a solid body surrounded by its own vapour, t w o principal facts have to be established : (1) the influence of the colli- sions between the molecules of the solid and those of the gas ; ( 2 ) the influence of the ether. I n the first case, on account of the equality of the masses of these molecules, these collisions, far from having a disturbing effect as in the case of a mixture of two gases, are, on the contrary, sufficient of themselves to maintain an equilibrium, if all the molecules have the same mean energy, that is to say, if the B2 of the molecules of the solid is the same as the B* of the molecules of the AB2 gas.(B2 is a quantity such that ___ represents the total mean 2 energy of a molecule whose weight is A.) AB; ABZGENERAL AND PHYSICAL CHEMISTRY. 85 As far as the ether is concerned, it is obvious that the molecnles of the solid are in the same conditions as the molecules of the gas ; if B2 has the same value in both, the total mean energy being theu tlie same, the conditions of equilibrium are determined. As an illustration, if we consider two volatile solids wholly immersed in their own vapour, the two atmospheres being separated from each other by a piston moving in a liorizontnl cylinder, when the temperature of the system is in equilibrium, the gases on each side of tlie piston satisfy the equation AJ32 =; A'B'2 , and this equality holds good equally for the solids A and A', since they have the same B2 as their respective vapours. But the equality AB' = A'Bf2 is affected by the collisions of the molecules of the gases against the walls of the cylinder and piston; this disturb- ing influence obviously diminishes with the degree of expansion of the gases, so that, a t the extreme limit, when a vacuum exists on both sides of the piston, the cause of error will disappear, and, since the piston has then become useless, it may be removed.Thelaw may, therefore, be stated as follows :-Given two simple solid bodies in a vacuum but not in contact, whose atomic weights are represented by AA', the actual energy of each of these bodies when their temperature is in equilibrium should be such as t o satisfy the equation AB2 = A'W. From the preceding it follows that the product of the atomic weight of a body by its absolute caZor~lfic cn;n?ucity (Him), is constant for all simple bodies. For compound bodies, an analogous law may be de- cluced. The product __ is the same for every substance; A being a quantity proportional to the weight of the chemical molecule under consideration ; C tlie absolute calorific capacity of the latter ; and t L the number of atoms entering into the composition of the molecule.J. VS;. Variation in the Composition of the Air. By P. v. JOLLY AC Ik (A4m. P1iy.s. Chem. [ 21, 6, 520-544) .-The analpes of air which have from time to time beer1 made exhibit slight, variations in the percentage o f oxygen. These differences might be attributed to unavoidable errors in the observations ; it appeared, however, that air collected in the same place at different times had not always the same density, and conse- quently not the same composition ; experiments were therefore under- taken to clear up any uncertainty in the matter. The composition of the air was determined by two separate methods : firstly, by observing its density ; secondly, by eudiometric analysis. In the first method, the air was weighed in a glass globe holding about a litre, and the amount of oxygen which it contained calculated I)y means of the equation- zw, + (1 - X ) W , = w, where z = vol.of 0 at 0' and 760 mm. in the unit of volume of air. JVo = weight of contents of the globe when filled with pure oxygen a t 0" and 76U min. ; Wu = weight of contents of the globe when filled with pure nitrogen a t 0" and 760 mm. ; and W = weight of contents of tlle globe when filled with the air at 0" and 760 mm. It was necessary in the first place to determine the values of VC', and The oxygen used in these determinations was obtained by the86 ABSTRACTS OF CHEMICAL PAPERS. Jan. 25 ........ Peb. 9 . . . . . . . . . . E'eb. 16 ......... Mmrch 7 ........ i\la,rch 18 ...... Way 9 . . ........ May 18 . . . .. . . . decomposition o€ water by electrolysis ; the nitrogen by passing a i r over h a t e d copper gauze, which had previously been reduced by hydrogen. It was found that the copper thus reduced retained a con- siderable amount of hydrogen, which could only be renioved by heat- ing it to a red heat in a vitcuum. The weighings were conc1uctedwit:i ;tll possible precautions against error, full details of which m e given in the paper. The mean value of W, obtained from seven experiments was 1.442515 gram, tlie probable error being .OOU013, that of W, ob- tained from the same number of' ohservations was 1.269455 gram, the probable error being _+ *000024. The larger. prolnable error in the case of nit1 ogen must be nttribu ted to the greater difficulty exlncrienced in obtaining the gas in a pure state.The samples of air, the composition of which was to be determined, mere always collected a t the same place, about 2 kilometers from the city of Xunich. The following table gives the date of collection, the direction of the wiud, and the corresponding value of W. (The experr- ments were made in1875-76) :- K.E. N.W. W. ' K.W. s. E. 15. 1 *303035 1 305754 1 *305281 1 * 303099 1 '303157 1 *305014 1,305200 1 '305131 June 7 .......... June 29.. . . . . . . . . July 1 5 . . . . . . . . . . July 22 .......... Aug. 2 . . . . . . . . . . dug. 29.. . . . . . . . . Sept. 11.. . . . . . . . . Sept. 1'7.. ........ ?V. w. N. cv. s. K.E. N.E. w. s. (?) 1 '305046 1 305307 1 *305239 1'30559 4 1.30529h 1 * 305469 1.305075 1 '304931 The greatest weight, 1.305754, was observed during a north-east wind ; the least, 1.304931, during a south wind ; in both cases the wind had blown for a considerable time in the same direction.The first value of TV corresponds to 20.965 per ccnt. of oxygen ; the second to 20.477. Before passing to the eecond method, and to the experiments maclc. by its means, the weights of a litre of oxygen and of nitrogen respec- tively were obtained from the ralues of Wn aiicl TVll given above. To (lo this it was only necessary to find tlie weight of distilled water at 4" which the glass globe would contain. This weight \\as fourid to be 1009.412 grams, the weight of a liter of oxygen in the latitude of Munich (4%" 8') and a t an altitude of 515 meters above the sea level, is therefore 1.429094 gram: that of a liter.of nitrogen in the same locality 1.257614 gram. Reducing these values to the latitude and altitude of Paris, we find that in that city 1 liter of oxygen weighs 1.4293884 gram; 1 liter of nitrogen weighs 1.2578731 gram. The numbers founq by Regnault were 1.4293802 and 1.256167 respectively ; t,he differences may be due to the diffkrences in the meights used, or to the impurity of the gases used by Regnault. The composition of the air was determined eudiometricdly by first observing the pressure of a given volume of the air a t 0" in the eudi- ometer, then absorbing the oxygen by means of a red-hot copper spiral,GENERAL AND PHYSICAL CHEMISTRY. 87 ---- heated by an electric current, and finally observing the pressure of the ~emaining nitrogen, occupying the same volume a t 0”.Determined i n this manner the percentage of oxygen is not liable to an error exceeding 0.09 per cent. The following table gives the results of experiments thus made :- I-- Date. Oxygen per cent. Jnne 13 .................... )) 18 .................... ) ) 24 .................... ) ) 27 . . . . . . . . . . . . . . . . . . . . ,) 31 .................... July 3 . . .................... ,, 17 .................... ,) 19 ..................... 20 -53 20 *95 2G ‘73 20 ‘66 20 ‘69 20 %6 20 %& 20 -56 .. 27 ..................... October 12 .................. )) 1% .................. ) ) 15 .................. )) 16 .................. ) ) 21 .................. )) 27 .................. )) 31 .................. Xorember 2 ................), 10 ................ ) ) 1 3 . . . . . . . . . . . . . . . . ) ) 2 0 . . .............. ,, 23 .................. 20 ’86 20 ‘83 20 -75 20.84 20 -84 21 -01 20 -85 20 ‘91 20 ‘56 20 .G7 1 20.65 Bar. 1 Wind. I 714’03 717 -7 716 -8 ‘718 *7 718 -1 716 9 713 -1 713 .9 719.9 713 *’i 720 *9 719 9 723 -3 723.0 710 *6 i21 5 714 *Z 724 -1 718 ‘2 707 ‘0 703 ’9 N. N.E. X.E. X.E. E. S. S.W. K.E. E. N.W. E. E. E. K . cv. S. W.E. S.E. w. K.X. . These experiments, which were made in 1877, show that the p v - centage of oxygen varied from 21.01, when the north wind blew, t o 2Us.53 during the west wind. The density of the air is therefore not a constant number. Relative Space occupied by Gases. By G. ScmrDr (An,:. Phys. Chem. [el, 6, 61?-615).-1f the molecular weight of h y d r o p i = 2, and the density of the air = 1, the molecular volume of a per- iiiaient gas is ordiiiarily set down as- V = 28.8725, it is contended that this number should be 28-8384, on the supposi- tion that the air contains 20.96 per cent.in volume of oxygen, and a table is given of the densities d of the various gases and vapours, calcu- lated by means of the formula s = - where ?I?, = the moleculny F. D. B. ?I 2 2 , ’ weight. * I?. D. B. * It i E clearly shown in the preceding nbstrart of the paper by I?. v. Jolly, that the density of tlie air is :L mrisble quantity ; the d u e of V must therefore also bt: \-ariltble, and the densities of gases cannct be expressed in terms of the density of the air.-F. L). 13.S8 ABSTRACTS OF CHEMICAL PAPERS. Absolute Expansion of Liquid and Solid Bodies.By H. F. WIEBE (Ber., 12, 1761--1764).-The force of cohesion which binds together the molecular groups in liquids and solids, is measured by the expansion which these bodies andergo under the influence of heat. The absolute expansion of an atom, i e . , the coefficient of expansion of the atomic volume, bears .a relation to the number of atoms which have combined together to form a liquid or solid group of molecules. Since all bodies have the same cohesion at their boiling and also a t their melting points, if the absolute expansion is multiplied by the temperature of these fixed points (calculated from the absolute zero), multiples of the coefficients of expansion, 0.00365, are obtained, as is shown in t'he following table :- ~ - - I.Absolute expansion for 1". I-- I- --- s ............... He .............. Zn .............. Cd .............. 8 .............. Se .............. Zn .............. C:d .............. 0.003015 0 -001872 0 -000795 0 -001188 0 -003015 0 *OolS72 0 400795 0 *001188 11. B. p. C ~ C U - lsted from absolute zero. 772 975 1315 1135 m. p. 388.6 492.0 687 *O 690 *o Product of I x 11. ~- 2 -1'7688 1 32520 1 *0454.25 1.348380 1.171629 0.921024 0 *5 %61& 0 '700920 Coe5cient of expansion. m. 0.003628 x 600 0.00365 x 500 0.003485 x 300 0'003371 x 400 0903905 x 300 0*003607 x 250 0.003641 x 150 0*003505 x 200 When n equals'the atomic weight,, d the density, a: the mean coeffi- cient of expansion between the melting and boiling points, T the tem- perature of the boiling or melting point (above the absolute zero), and /3 the coefficient of expansion in the gaseous state ; then - - T = 6.~2.I n this equation nz bears a relation to the number of atoms in the liquid or solid molecule. The author has investigated homologous series of organic compounds, and obtained the following results :- aa: d --- Formic acid ........ Acetic acid.. ........ Butpic acid ........ Methyl alcohol ...... Ethyl alcohol. ....... Amy1 alcohol.. ...... I. Mean absolute expansion (between b. p. and m. p.) for 2" 11. B p. cnlcu- lated from absolute 0" 0 .O 5326 0 .om28 0 .lo235 0.05000 0.07143 0.12500 375 .o 392 -3 421 '0 341 -3 353 -3 406.8 111. Product of I x 11. I V 5.2 x 3 5.2 x 5 5.2 x 9 8.5 x 2 8.5 x 3 8 . 5 x 6 For the acids, the product of the mean absolute expansion f o r 1"INORGANIC CHEMISTRY.89 by the boiling point is equal to the constant 5.2 mnltiplied by the number of hydrogen atoms contained in the gaseous molecule, + 1. For the alcohols the constant 8.5 is multiplied by half the number of hydrogen atoms in the molecule. w. c. w. Diffusion Experiments with Acid Solutions of Mixtures of Salts. By F. HINTCBEGGER (Ber., 12, 1619-1626). --Experiments with mixtures of sulphuric acid and potassium-hydrogen sulphate, and of the latter and potassium sulphate, which were diffused into water, show that the acid diffuses more quickly than the acid salt, and the latter more quickly than the neutral salt. The same was found to be the case with oxalic acid and potassium aiid sodium oxalates ; after a time, however, this rela%ionship is reversed.Monosodic and disodic l)hosphates gave a result similar to tliat exhibited by oxalic acid. At first the monosodic phosphate diffuses more quickly, and after some time the disodic phosphate diffuses more rapidly. Hippuric acid diffuses more slowly than sodium hippurate, which is accounted for by the fact that the latter is more soluble tlian the former. P. P. B.81G e n e r a l a n d P h y s i c a l Chemistry.Emission Spectra of Haloi'd Mercury Compounds. By B. 0.PEIRCE (Ann. Yhys. Chenz. [el, 6, 597--,599).-The emission spectrawere obtained by passing the electric current through 8 Geissler tubecontaining a small quantity of the salt ; wken the salt is warmed witha Bunsen burner, the mercury spectrum is seen, and as bhe heat isincreased bands appear which differ according t o the salt employed.The measurements were made with a Steiihcim spectroscope, thescale of which corresponded as follows with the lines of the spectrum :Si + 81, Na - 100, Hgn, - 102.9 and 103.8, Baa - 111, Hga - 114,SrP - 157, Hgp- 176, Hg6 - 138, H ~ E - 207.When mercuric chloride was used, a band appeared a t 1084 - 1 OO$.The edge of this band was sharply defined on the less refrangible side ;but when the salt was strongly heated, a continuous spectrum wasobserved, stretching for some distance on the more refrangible side.Mercurous chloride gives the same band, whence it is argued thatmercurous chloride is dissociated.Mercuric bromide gives st band between 131 and 135; mercuriciodide a band between 168 and 172.It is remarked that the bromideband is exactly half way between that of the chloride and that ofthe iodide. F. D. B.Smoke of an Electric Lamp. By B. S. PROCTOR (Chenz. News,39, 283).-Att the Newcsstle-upon-Tyne Chemical Society Mr. J. W.Swan exhibited an electric lamp on the incandescent principle, inwhich the current had to pass through and heat a cylinder of carbonplaced between two platinum condnctors ; this arrangement wasplaced in a vacuum in a glass vessel, and as the current was too strongthe carbon cylinder broke down.The author examined the glass which enclosed it, and found theinside covered with a sooky deposit which, under a $-inch rnicro-scopic objective, appeared nebulous, with some bright specks of plati-num here and there. The platinurn supports were also covered with theblack deposit, which burned off easily on being heated to dull redness.A piece of the glass was treated with aqua regia, and platinum andiron were found in the solution.It is possible that the platinumparticles were scattered about by the disruptive discharge, which fol-Thermochemical Investigation of the Oxiaes and Acids ofNitrogen. By J. THOMSEN (Bey., 12, 2062-2065).-1n order tocalculate the heat of formation of the oxides of nitrogen, the followingvalues were determined by experiment :-lowed the breaking down of the carbon cylinder. w. T.VOL. XXXVIII82 ABSTRACTS OF CHEMICAL PAPERS.Reaction. Heat of formation.N, + H, + 0, = NFT,NO, .. . . . . . . . . 64950 unitsW20, + 0, = N,O, . . . . . . . . . . . . . . . . 39140 ..N,+ O..........................--18320 .. N204 + Aq ...................... 15510 ..Oxidation of an aqueous solution of N,0+ N,04Aq + 0 = + 18320.From these data, the following results were obtained. which differconsiderably from Berthelot's determinations (Ann. Phys. Chem. [ 5 ] ,6, 178) :-Berthelot. Thorn Ben.N2 + 0.. . . . . . . . . . . . .N, + O2 . . . . . . . . . . . . -86600 units - 72790 ,,N, + 0 3 + Aq.. . . . . . . -51800 ,, - 36460 ,,. . . . . . . . . . . . -33650 ,, N, + 0 4 -N, + 0, -t- AqN2 + 0, + Aq.. -14800 ,, t 180 ,,- 18320 units -- 18140 ,, . . . . . . . . -. . . . . .The following table shows in columns I and I1 the heat of forma-tion of the anhydrous nitrates ; in I by the direct union of theirelements, and in I1 according to the equation + O2 + N,O1.Column I11 shows the heat of solution of these salts:-Nitrates of I.Potassium.... 104660Sodium.. ..... 96430Iithium ..... 96800Thallium ..... 43330Silver . . . . . . 1.3920Barium.. .... 196100Strontium ... 190210Calcium . . . . . 173590Lead . . . . . . . . 75860Sr 4- 0, + N,O1 4- 4H20Ca + 0, + N,O, + 4H,OCd + 0, + NZO, + 4H,OMg+ 0, + N,Oa + 6H2OZn+ 0 2 + K20J + 6H20Ni + 0, + N,O, + 6H20CO + 0, + NZO, + 6H10CU+ 0, + N204 + 6H,O11.2429602265002272401203006148022975022386020724010951023154021844012487021453014218012472012333096950111.- 17040- 10060 + 600- 19940- 10880- 9400- 4620 + 3950- 7610- 12300- '7250- 5040- 4220- 5840- '7470- 4 9 0- 10710w.c. w.Therrnochemical Research on the Carbonates. By. J.THOMSEN (Ber., 12, 2031--2032).-The heat evolved in the formationof the following anhydrous carbonates by the combination of carbonicoxide, oxygen and the metal, is given in column I ; the heat evolvedby the combination of carbonic acid with the metallic oxide is showriin column 111. For the sake of comparison the heat of formationof the corresponding anhydrous sulphates from metal, oxygen andsulphurous anhydride is given in column 11GENERAL AND PHYSICAL CHEMISTRY. 53Carbonates andsulphntes. I. 11. 111. . K, . . . . . . . . . . . . 25OCl40 273560257510 --Na,:!... . . . . . . . . . 242490Ba . . . . . . . . . . . . 252770 266490 5.5580Sr . . . . . . . . . . . . 251020 2598.20 53230CR . . . . . . . . . . . . 240660 248970 42490Mil . . . . . . . . . . . . 180690 178790Cd . . . . . . . . . . . . 151360 150210Y b 139690 145130 22580--. . . . . . . . . . . .A g 2 . . . . . . . . . . . . 92i70 96200 20060 w. c. w.Mutual Relations of Potassium and Sodium Alum in AqueousSolution. By F. P. VENABLES (C‘hem. Kews, 40, 198-199) .-Twoforms of isomorphism between these two salts may be conceived :the formation of a double alkaline alum, KNaS04.Al,(S04),.24H20 :and the isomorphous admixture of the two alums in the various crys-tals. All attrempts to prepare the double alkaline alum failed, theisomorphous displacement always being of the second kind, tlie potas-sium salt predominating, owing to its being less soluble in water thanthe sodium salt.Experiments T+*ere also made on the solubility ofpotassium alum in R solution of sodium alum of diflerent strengthsand a t different temperatures, the results being that 100 grams watercontaining-(;r.ams sodium alum 4.8 10.0 12.1 15~4 21.1 33.7 55.6 76.7 } i.8 6.1 5.7 5.3 4.7 3.8 2.7 1.7 Will dissolve potas-sium alumL. T. 0’s.Law of Dulong and Petit applied to Perfect Gases. By H.WILLOTTE (C’onzpt. rend., $9, 540--543).-The product AC of the mole-cular weight A into the specific heat a t constant volume C is very nearlythe same for all gases. In order. therefore that any two gases may be a tthe same temperature, it is necessary and sufficient that the mean totalenergy of any molecule whatever sball have the same value in bothgases, that is to say, that AB’ = A%’’ ; A and A’ being the molecularweights of the gases nnder consideration, and --, AB2 __ A’”‘, the meansof the total energies of the molecules of eachgas. Tm7o or more gasesare a t the same temperature, if, when placed in contact with each otherthey nevertheless preserve their total respective energies unchanged.It may be shown (1) by making use of the theory of Carnot, or ( 2 ) bythe homogeneity as far as velocity is concerned of the equations rela-ting to the theory of percussion, that if the rule AE2 = A’B’2 holdsgood for any one tcniperature, it does so for all other temperatures ;tlie question is how far this can be explained from a purely mechanicalpoint of view.It cannot be due t o the mutual collisions of the molc-cules, for Clausius has shown t h a t inter-molecular shocks exert only adisturbing influence in the theory of gases; the author thereforeprefers to explain it by molecular collisions against the atoms of amaterial ether, a gas of exceedingly low density, having its constituent2 29 84 ABSTRACTS OF CHEMICAL PAPERS.particles situated a t distances very small in relation to the dimensionsof the molecules of ordinary gases ; a supposition which serves as nbasis for several theories.If A represents the weizht of any molecule endued with a rapidityof translation F1, the arithmetical mean of the quantities of move-ment representing the forces of percussion due to the displacement ofthe molecule A, can be reprcscnted by hzAb;?dt, the sum Z being takenduring anp moment of which dt is the element, X being a constantindependent of the nature of the molecule under consideration.Thesum of the terms calculated for unity of time is approximatelg2Ab;ilt = AB;, where B: is a quantity equal to the mean of b;.If in any vessel there are n molecules whose mass is equal to A, andn’ whose mass is equal to A’, the arithmetical law of the forces of per-cussion acting in unity of time on the mass of ether in question willbe h(nAJ3: + n’A’B’:). Again, if while n f ‘yL‘ = const., the sum justmentioned does not vary when the composition of the mixture isaltered, the systems formed by the forces of percussion will not varyeither ; and again the sum will remain invariable whatever be theratio if AB; = A’B’:.?LWith a mass of molecules whose centres of gravity are Exed, bnt ofwhich the various parts are endowed with reciprocal movements, itmay be found by similar reasoning tlint in the case of equilibrium oftemperature, the energies corresponding to thcse movements satisfythe relation AR; = A’B’:, whence by addition-- - *’a representing the total mean energies of the molecules.2 ’ 2AB2AB2It is thus seen why the ratio -’ is the same for all gases at any deter-minate temperatures ; further by making use of the principle of homo-geneity before mentioned, it may be easily demonstrated that ifthe ratio __ is the same for all gases a t any temperature arbitrarilychosen, it will hold good, o r very nearly so, for all other temperatures,the value of the ratio varying very slowly with the temperature.(lcbid., 89, 568-570).I n determining the conditions of equilibrium oft2mperature in the case of a solid body surrounded by its own vapour,t w o principal facts have to be established : (1) the influence of the colli-sions between the molecules of the solid and those of the gas ; ( 2 ) theinfluence of the ether. I n the first case, on account of the equality ofthe masses of these molecules, these collisions, far from having adisturbing effect as in the case of a mixture of two gases, are, on thecontrary, sufficient of themselves to maintain an equilibrium, if all themolecules have the same mean energy, that is to say, if the B2 of themolecules of the solid is the same as the B* of the molecules of theAB2 gas.(B2 is a quantity such that ___ represents the total mean2energy of a molecule whose weight is A.)AB;ABGENERAL AND PHYSICAL CHEMISTRY. 85As far as the ether is concerned, it is obvious that the molecnles of thesolid are in the same conditions as the molecules of the gas ; if B2 hasthe same value in both, the total mean energy being theu tlie same, theconditions of equilibrium are determined. As an illustration, if weconsider two volatile solids wholly immersed in their own vapour, thetwo atmospheres being separated from each other by a piston movingin a liorizontnl cylinder, when the temperature of the system is inequilibrium, the gases on each side of tlie piston satisfy the equationAJ32 =; A'B'2 , and this equality holds good equally for the solids A andA', since they have the same B2 as their respective vapours.Butthe equality AB' = A'Bf2 is affected by the collisions of the moleculesof the gases against the walls of the cylinder and piston; this disturb-ing influence obviously diminishes with the degree of expansion of thegases, so that, a t the extreme limit, when a vacuum exists on both sidesof the piston, the cause of error will disappear, and, since the pistonhas then become useless, it may be removed. Thelaw may, therefore,be stated as follows :-Given two simple solid bodies in a vacuum butnot in contact, whose atomic weights are represented by AA', theactual energy of each of these bodies when their temperature is inequilibrium should be such as t o satisfy the equation AB2 = A'W.From the preceding it follows that the product of the atomic weightof a body by its absolute caZor~lfic cn;n?ucity (Him), is constant for allsimple bodies.For compound bodies, an analogous law may be de-cluced. The product __ is the same for every substance; A beinga quantity proportional to the weight of the chemical molecule underconsideration ; C tlie absolute calorific capacity of the latter ; and t Lthe number of atoms entering into the composition of the molecule.J. VS;.Variation in the Composition of the Air. By P. v. JOLLYACIk(A4m. P1iy.s.Chem. [ 21, 6, 520-544) .-The analpes of air which havefrom time to time beer1 made exhibit slight, variations in the percentageo f oxygen. These differences might be attributed to unavoidable errorsin the observations ; it appeared, however, that air collected in the sameplace at different times had not always the same density, and conse-quently not the same composition ; experiments were therefore under-taken to clear up any uncertainty in the matter.The composition of the air was determined by two separate methods :firstly, by observing its density ; secondly, by eudiometric analysis.In the first method, the air was weighed in a glass globe holdingabout a litre, and the amount of oxygen which it contained calculatedI)y means of the equation-zw, + (1 - X ) W , = w,where z = vol.of 0 at 0' and 760 mm. in the unit of volume of air.JVo = weight of contents of the globe when filled with pure oxygena t 0" and 76U min. ; Wu = weight of contents of the globe when filledwith pure nitrogen a t 0" and 760 mm. ; and W = weight of contentsof tlle globe when filled with the air at 0" and 760 mm.It was necessary in the first place to determine the values of VC', andThe oxygen used in these determinations was obtained by th86 ABSTRACTS OF CHEMICAL PAPERS.Jan. 25 ........Peb. 9 . . . . . . . . . .E'eb. 16 .........Mmrch 7 ........i\la,rch 18 ......Way 9 . . ........May 18 . . . . . . . .decomposition o€ water by electrolysis ; the nitrogen by passing a i rover h a t e d copper gauze, which had previously been reduced byhydrogen.It was found that the copper thus reduced retained a con-siderable amount of hydrogen, which could only be renioved by heat-ing it to a red heat in a vitcuum. The weighings were conc1uctedwit:i;tll possible precautions against error, full details of which m e given inthe paper.The mean value of W, obtained from seven experiments was1.442515 gram, tlie probable error being .OOU013, that of W, ob-tained from the same number of' ohservations was 1.269455 gram, theprobable error being _+ *000024. The larger. prolnable error in the caseof nit1 ogen must be nttribu ted to the greater difficulty exlncrienced inobtaining the gas in a pure state.The samples of air, the composition of which was to be determined,mere always collected a t the same place, about 2 kilometers from thecity of Xunich.The following table gives the date of collection, thedirection of the wiud, and the corresponding value of W. (The experr-ments were made in1875-76) :-K.E.N.W.W.' K.W. s.E.15.1 *3030351 3057541 *3052811 * 3030991 '3031571 *3050141,3052001 '305131June 7 ..........June 29.. . . . . . . . .July 1 5 . . . . . . . . . .July 22 ..........Aug. 2 . . . . . . . . . .dug. 29.. . . . . . . . .Sept. 11.. . . . . . . . .Sept. 1'7.. ........?V. w.N. cv.s.K.E.N.E. w.s. (?)1 '3050461 3053071 *3052391'30559 41.30529h1 * 3054691.3050751 '304931The greatest weight, 1.305754, was observed during a north-eastwind ; the least, 1.304931, during a south wind ; in both cases the windhad blown for a considerable time in the same direction.The firstvalue of TV corresponds to 20.965 per ccnt. of oxygen ; the second to20.477.Before passing to the eecond method, and to the experiments maclc.by its means, the weights of a litre of oxygen and of nitrogen respec-tively were obtained from the ralues of Wn aiicl TVll given above. To(lo this it was only necessary to find tlie weight of distilled water at4" which the glass globe would contain. This weight \\as fourid tobe 1009.412 grams, the weight of a liter of oxygen in the latitude ofMunich (4%" 8') and a t an altitude of 515 meters above the sea level,is therefore 1.429094 gram: that of a liter.of nitrogen in the samelocality 1.257614 gram. Reducing these values to the latitude andaltitude of Paris, we find that in that city 1 liter of oxygen weighs1.4293884 gram; 1 liter of nitrogen weighs 1.2578731 gram. Thenumbers founq by Regnault were 1.4293802 and 1.256167 respectively ;t,he differences may be due to the diffkrences in the meights used, or tothe impurity of the gases used by Regnault.The composition of the air was determined eudiometricdly by firstobserving the pressure of a given volume of the air a t 0" in the eudi-ometer, then absorbing the oxygen by means of a red-hot copper spiralGENERAL AND PHYSICAL CHEMISTRY. 87----heated by an electric current, and finally observing the pressure of the~emaining nitrogen, occupying the same volume a t 0”. Determinedi n this manner the percentage of oxygen is not liable to an errorexceeding 0.09 per cent.The following table gives the results of experiments thus made :-I--Date.Oxygenper cent.Jnne 13 ....................)) 18 ....................) ) 24 ....................) ) 27 . . . . . . . . . . . . . . . . . . . .,) 31 ....................July 3 . . ....................,, 17 ....................,) 19 .....................20 -5320 *952G ‘7320 ‘6620 ‘6920 %620 %&20 -56 .. 27 .....................October 12 ..................)) 1% ..................) ) 15 ..................)) 16 ..................) ) 21 ..................)) 27 ..................)) 31 ..................Xorember 2 ................), 10 ................) ) 1 3 .. . . . . . . . . . . . . . .) ) 2 0 . . ..............,, 23 ..................20 ’8620 ‘8320 -7520.8420 -8421 -0120 -8520 ‘9120 ‘5620 .G7 1 20.65Bar. 1 Wind.I714’03717 -7716 -8‘718 *7718 -1716 9713 -1713 .9719.9713 *’i720 *9719 9723 -3723.0710 *6i21 5714 *Z724 -1718 ‘2707 ‘0703 ’9N.N.E.X.E.X.E.E.S.S.W.K.E.E.N.W.E.E.E.K . cv.S.W.E.S.E. w.K.X..These experiments, which were made in 1877, show that the p v -centage of oxygen varied from 21.01, when the north wind blew, t o2Us.53 during the west wind.The density of the air is therefore not a constant number.Relative Space occupied by Gases.By G. ScmrDr (An,:.Phys. Chem. [el, 6, 61?-615).-1f the molecular weight of h y d r o p i= 2, and the density of the air = 1, the molecular volume of a per-iiiaient gas is ordiiiarily set down as-V = 28.8725,it is contended that this number should be 28-8384, on the supposi-tion that the air contains 20.96 per cent. in volume of oxygen, and atable is given of the densities d of the various gases and vapours, calcu-lated by means of the formula s = - where ?I?, = the moleculnyF. D. B.?I 22 , ’weight. * I?. D. B.* It i E clearly shown in the preceding nbstrart of the paper by I?. v. Jolly, thatthe density of tlie air is :L mrisble quantity ; the d u e of V must therefore also bt:\-ariltble, and the densities of gases cannct be expressed in terms of the densityof the air.-F.L). 13S8 ABSTRACTS OF CHEMICAL PAPERS.Absolute Expansion of Liquid and Solid Bodies. By H.F. WIEBE (Ber., 12, 1761--1764).-The force of cohesion which bindstogether the molecular groups in liquids and solids, is measured by theexpansion which these bodies andergo under the influence of heat.The absolute expansion of an atom, i e . , the coefficient of expansion ofthe atomic volume, bears .a relation to the number of atoms whichhave combined together to form a liquid or solid group of molecules.Since all bodies have the same cohesion at their boiling and also a ttheir melting points, if the absolute expansion is multiplied by thetemperature of these fixed points (calculated from the absolute zero),multiples of the coefficients of expansion, 0.00365, are obtained, as isshown in t'he following table :-~ - -I.Absoluteexpansionfor 1".I--I- ---s ...............He ..............Zn ..............Cd ..............8 ..............Se ..............Zn ..............C:d ..............0.0030150 -0018720 -0007950 -0011880 -0030150 *OolS720 4007950 *00118811.B.p. C ~ C U -lsted fromabsolute zero.77297513151135m. p.388.6492.0687 *O690 *oProduct ofI x 11.~-2 -1'76881 325201 *0454.251.3483801.1716290.9210240 *5 %61&0 '700920Coe5cientof expansion. m.0.003628 x 6000.00365 x 5000.003485 x 3000'003371 x 4000903905 x 3000*003607 x 2500.003641 x 1500*003505 x 200When n equals'the atomic weight,, d the density, a: the mean coeffi-cient of expansion between the melting and boiling points, T the tem-perature of the boiling or melting point (above the absolute zero), and/3 the coefficient of expansion in the gaseous state ; then - - T = 6.~2.I n this equation nz bears a relation to the number of atoms in the liquidor solid molecule.The author has investigated homologous series of organic compounds,and obtained the following results :-aa:d---Formic acid ........Acetic acid.. ........Butpic acid ........Methyl alcohol ......Ethyl alcohol. .......Amy1 alcohol.. ......I.Mean absoluteexpansion (betweenb. p. and m. p.) for 2"11.B p. cnlcu-lated fromabsolute 0"0 .O 53260 .om280 .lo2350.050000.071430.12500375 .o392 -3421 '0341 -3353 -3406.8111.Productof I x 11.I V5.2 x 35.2 x 55.2 x 98.5 x 28.5 x 38 . 5 x 6For the acids, the product of the mean absolute expansion f o r 1INORGANIC CHEMISTRY. 89by the boiling point is equal to the constant 5.2 mnltiplied by thenumber of hydrogen atoms contained in the gaseous molecule, + 1.For the alcohols the constant 8.5 is multiplied by half the number ofhydrogen atoms in the molecule. w. c. w.Diffusion Experiments with Acid Solutions of Mixtures ofSalts. By F. HINTCBEGGER (Ber., 12, 1619-1626). --Experimentswith mixtures of sulphuric acid and potassium-hydrogen sulphate, andof the latter and potassium sulphate, which were diffused into water,show that the acid diffuses more quickly than the acid salt, and thelatter more quickly than the neutral salt. The same was found to bethe case with oxalic acid and potassium aiid sodium oxalates ; after atime, however, this rela%ionship is reversed. Monosodic and disodicl)hosphates gave a result similar to tliat exhibited by oxalic acid. Atfirst the monosodic phosphate diffuses more quickly, and after sometime the disodic phosphate diffuses more rapidly. Hippuric aciddiffuses more slowly than sodium hippurate, which is accounted forby the fact that the latter is more soluble tlian the former.P. P. B

ISSN:0368-1769    

DOI:10.1039/CA8803800081

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 89 I n o r g a n i c Chemistry. Allotropie Modifications of Hydrogen, By J. THOXPEN (BeT-., 12, 203O).-The author points out that ‘l’ominasi’s statement (Acr~tl. Illi’lun), that the heat of fcrmation of potassium chlorate is 9,760, and that of potassiuni chloride 104,476 units, and consequently 104,476 - 9,760, i.e., 94,716 heat-units, are alisorl~ecl in the conversion of potassium chlorate into chloride, contains no less than three errors. The heat of formation of potassium clilorate is 95,840, and not 9,760, the latter number representing the lieat evolved in the convcrsion of potassium chlorate into chloride in the dry way. Instead of 94,716 heat-units being sbsosbod in the reduction of the chlorate to the chlo- ride, a liberation of 15,370 heat-units takes place.It is obvious that the theoretical speculations based on these incorrect data are valueless. A New Method for Prepaxing Hydriodic and Hydrobromic Acids. By G. BRUYLAN‘TS (Be?.., 12, 2Wl-2062) .-Hjdriodic acid can be easily prepared by heating a solution of iodine (2u grams) in copaiba oil (60 grams) in a retort connected with an upright condenser. The gas is purified by passing it through a drying tube. When the evolution of gas slackens, fresh iodine is brought into the retort, and the process is continued until about 1.50 grams of iodine have been used. In the preparation of hydrobromic acid by this method, the bromine must be slowly dropped into the retort containing the oil, and the gas should be purified by passing through three drying towers.w. c. w. w. c. w.90 ABSTRACTS OF CHEMICAL PAPERS. Influence of Volume and Temperature in the Preparation of Ozone. A New Ozoniser.-By A. R .LEEDS (A~WUZA~L, 198, 30- 42) .-A solution of potassium dicbromate (not necessarily saturated) mixed with sulphuric acid is placed in a suitable vessel, within which a bell-jar can be placed, and pieces of phosphorus are partly immersed in the liquid. It is better, however, to connect three such jars and draw the air through them by means of an aspirator. For this purpose, the necks of the jars are cernented into brass caps, which are screwed to it bar capable of being raised and lowered as in a gnlvanic battery ; the stoppers are replaced by corks covered with paraffin, through each of which pass three glass tubes, one ending just below the stopper, another just above the liquid, and the third bent into a horizontal ring at the end.The first two tubes are connected so as to allow a current of air to be drawn through the apparatus ; the third is for lowering or mising the phosphorus. The pieces of phosphorus are melted .in watch-gla$ses to give them w more convenient shape, and are placed on glass plates in glass cells in the liquid. A flexible tube for con- veying the ozone from the generators was made of “ cei-ite” (“ kerite-” schlauch), and found to answer rery well. The maximum amonnt of ozone obtained was a little over 2.5 mgrms. per litre of air ; but a s the generator may be connected with the aspirator and allowed to work for any length of time, the s~ipply is unlimited.A Possible Cause of Variation of the Proportion of Oxygen in the Air. BF E. W. ~\~ORT,EY (Chew. News, 40, 184-186, and 1 !49-20l).-Looniis has proposed the theory that certain great and siidden depressions in the temperature of the atmosphere are caused hy the velatical descent of currents of air from cold elevated regions. If such is the case, then the air at the surface of the earthduring such depressions may contain a smaller amount of oxygen than the a;c-erage. Jolly concludes from his experiments that the air a t the equator is poorer in oxygen than that a t tjEie polar regions, owing to the amount of oxygen consumed in oxidation being greater than that liberated by reduction. Facts, however, do not confirm these conclusions, no dif- ference in the composition of the atrnosplicre of the two regions having hithertc been detected.According to the author’s views, based on Loomis’ theory, air col- lected at the centre of an area covered by a descending current would, a t a given moment, be a sample fresh from the upper atmosphere; whilst a sample collected on one side of this centre would consist of a mixture of s w f m e and wpper air, but still containing a deficiency of oxygen. Although the author has not yet succeeded in making these experiments, he has, while laying plans for the ~ o r k , conducted espe- yiments on ordinary air, to ascertain what light can be thrown 011 the changes in composition of the atmosphere. The apparatus used was constructed on McLeod’s modification of Frankland and Ward’s appa- ratus, with important modifications, so as to reduce all causes of error to a minimum.The samples were collected in the open country, in glass vessels. and preserved over mercury freed from carbonic anhydride, and exploclcvl A temperature of 24” gives the best results. G. T. A.INORGANIC CHEMISTRY. 9J with pure hydrogen. Some samples were collected in stoppered and c;ipped bottles, which were inverted, and the caps filled with water. Analyses of air were made daily from 28th December, 1878, to Gtlh April, 1879, during ivhich period some very marked and sudden de- pressions of temperature occurred, which were accompanied by a decrease in the quantity of oxygen. The deficiency, however, as might have been expected, was not proportional to the decrease i n tempe- rature (see also p.85 of this volume). By G. WOLFRBX (AmnZe/r, 198, 95--98).-IGimmerer ( J . pi.. Chem., 90, 190) has desribed a method according to which perbroinic acid may be obtained br the action of d ~ y bromine on clry perchloric acid, the latter being prepared i\ t the tlime by the decomposition of potassium perclilorate by sulphuric acid. The author has repcated this experiment, and finds tliat the :icid thus obtained, corresponding in all respects with that described hy Kammerer, is nothing more than a mixture of percliloric and sulphuric acids. The apparent absorption of the bromine by tlie perchloric acid is explained by the fact that perchloric acid, when heated with an excess of sulphuric acid, is decomposed into oxygen mid chlorine, and it is this latter which takes u p tlie bromine i n the above experiment, forming bromide of chlorine : this is volatilised, together with the excess of bromine, during the subsequent concen- tration of the liquid. L.T. 0's. Preparation of Perbromic Acid. T. C. Researches on Nitrous Acid and Nitrogen Tetroxide. By G. LUNGE (Dingl. yoZyt. J., 233, 155-165; cornp. this Journal, Abst., 18'79, 770).-8econd Pa7-t.- Oti the Re7at;ow of the Acids OJ hTitrogetl to ,Sulplm-ic ileitZ.-Our knowledge of this relation is not by any weans complete. It is well known that nitrous acid, either in the liqnicl or gaseous form, o r jmduced nascent from the union of nitrogen dioxide with oxygen, is clissolved by sulphuric acid of about. 1.7 sp. gr. ; but the heliaviour of nitrogen tetroxide towards snlphuric acid is not accu- rately known.The author has shown that it is dissolved by sulpliuric i~cid, forming nitrosulphuric and nitric acids ; but according to Weber and Winkler, nitlogen tetroxide is dissolved as such by sulphuric acid of 66" B., producing a reddish-yellow solution, which, when heated, gives off nitrogen tetroxicle with violcrit ebullition, and leaves a liquid Iiaviug the properties of nitrosulphuric acid. Winklcr stated that 28 072 grams of sulphuric acid a t 60"B. absorbed 7.307 grams of nitrogen tetroxide, but that on heating gently, the latter was eiitirely expelled. Weber describes the effects of nitrogen tetroxide on sulphui*ic acid of different specific gravities, but only qualitativel~ : thns, sulphuric acid at, a sp. gr. of 1.7 absorbs nitrogen tetroxide without becoming coloured: liecce i t was assunied that the latter was decomposed; a t a sp.gr. of 1.55 the sulphuric acid becomes yellow, and hence it was supposed that the greater part of the nitrogen tetroxide was simply dissolved. Acid of 1-49 sp. gr. takes a greenish-yellow colour; acid of 1.41 sp. gr. takes an intense green d o u r ; acid of 1.31 sp. gr. becomes blue and liberates nitrogen dioxicle, which escapes with violent ebullitioii on gently heating. The p e l 192 ABSTRACTS OF CHEMICAL PAPERS. and blue colours were supposed to be due to the formation of nitrous wid, the nitrogen tetroxide having been decomposed into that sub- stance and nitrogen dioxide. As these results are very important to vitriol manufacturers, the author studied them more accurately, and, its far as possible, quantitatively.The nitrogen tetroside, prepared from d r g fused lead nitrate, was measured oif from a burette, and mixed with pure sulphuric acid, which had been diluted to different strengths with water, and the effects of heat upon these mixtures were also noted. The following are given as examples of the mctliod employed and of the results obtained by the author in carrying out the expel-iments :- 100 C.C. sulphuric acid of 1-84 sp. gr., t o which was added 2 C.C. = 3 grams liquid nitrogen tetroxide, gave a colourless solution with :L very feeble odour, recaJling that of ozone. The amount of nitrogen dioxide evolved from 1 C.C. of this solution in the nitro- meter was determined, and also the amount required to decolorise 10 C.C.seniinormal potassium permangmate solution. From the results, the author calculates that his nitrogen tetroxide contained of pure nitrogen tttroxide 93 per cent., and of nitric acid 7 per cent. ; but lie argues, as in reality the nitrogen tetroxide does not exist, as such in the sulpliuric acid, but has undergone a decomposition, one part of tlie tetroxide having been converted into nitric acid a t the expense of the oxjgen of the other part, whilst the part which has been robbed of its oxygen remains as nitrous acid in combinatlion with tlie sul- phuric acid; then assuming that this lower oxide takes the oxygen from, and decolorises the potassium permanganate, this would wive 46.5 per cent. as nitrous acid, and 53.5 per cent. as nitric acid.?'he other calculations are niade on this supposition, that is, it8 is first assumed that all the nitrogen tetroxide remains as such, and the defi- ciency in the theoretical amount of oxygen required is calculated as nitric acid; but if, on the contrary, tho amount of oxygen required be less than that found by the permangnnate process, then he assumes that no nitric acid is present, but that nitrous acid must have been originally present as an impurity. (I.) The acid was heated to 2tiUo, and kept at that temperature for one hour ; any free nitrogen tetroside, if it were present, must have been thus expelled. When the ttmperature rose t o 20Uo, R little red vspour was evolved, and the liquid acquired a golden-yellow colour ; b u t on cooling, it again became colourless.On analysis the author calculated that 77.9 per cent. of the nitrogen present existed as N,O,, and 21.1 per cent. as HNO,; there is, con- sequently, he si;tys, a large amount of the nitric acid driven off and anobher part changed into nitrous acid. (11.) On continuing t o heat for one hour longer, a further change took place of the bame kind, and 94..5 per cent. of the nitrogen re- maining existed as Nz03, in combiliation with the sulphuric acid jorming nitrosulphnric acid ; whilst 5.rj per cent. remained as HNO;;, n~ld 18 per cent. of the nitrogen originally present having been ex- pelled by the heating. (111.) Another experiment was made by adding pure nitric t o pu:.eTN ORGANIC CHEMISTRY. 93 sulphuric acid, and analysing the resulting mixture, but no change was found to have taken place.(1V.) On boiling the mixture for half-an-hour, however, red fumes were given off, and the whole of the nitrogen present was converted into nitrous acid, which was found in combination with the sulphuric acid. That nitric acid is thus broken up has also been demonstrated in another way by Winkler, who collected the oxygen which was evolved from the decomposition. The author did not find the same result as Winkler with sulphuric acid of 66OB. above mentioned, and he explains this by assuming that, Winkler employed so much nitrogen tetroxide that it left it hrgt. excess beFond that which could combine with the sulphuric acid as nitrous acid : hence the sudden and violent ebullition and liberation of nitrogen tetroxide on heating the mixtuye.2 C.C. nitrogen tetroxide added to sulphuric acid of 1.805 sp. gr. was hroken up into practically the same proportions of nitrous and nitric acids as in the first experiment, with acid of 1.54 sp. gr. Other experiments are described in which sulphuric acid of 1.75 sp. gr. was mixed with nitrogen tetroxide and then heated ( a ) , so that the vapour evolved might a t once escape, and ( b ) where a long tube was attached to the flask in which the mixture was heated, so that the vayoar might condense and flow back again to the acid in the flask. In ( a ) nitrous acid, but no nitric acid mas found, whilst in ( b ) nitric acid was present but no nitrous acid ; this is explained by the fact, that it requires concentrated sulphuric acid to combine with and retain the nitrous acid ; and in ( a ) the acid became concentrated by evaporation, whilst in ( b ) it remained of about the same sti.eugth, arid was unable to retain the nitrous acid.Again, when the mixture was heated on a water-bath a t about 95", no such changes occurred. As Winkler found, that on heating his mixture of acid of 60°B. with nitrggen tetroxide, the latter was evolved, he presumed that i t existed as a mechanical mixture with the acid. This the author denies, stating that had Winkler examined the acid a,fter boiling, he would have found that it contained nitric acid, and that the nitrogen tetroxide had really undergone decomposition ; and further, that ho must have heated it considerably above the temperature of boiling water, otherwise no change would have resulted, and no red fumes would have been liberated.When the amount of nitrogen tetroxirle added is in excess of that required to form nitrnsulphuric acid, the author is uncertain from analysis whether it exists in the acid in the form of nitrous acid or of nitrogen tetroxide. W. T. Norwegium. By T. DAHLL (Rer., 12, 15'3 1-1 732) .-The prepam- tion of this metal from the ore has already been described (this Journal, Abs., 1879, 890). It melts a t 254', and its atomic weight is 145.552 (RO), or 218.928 (TC2G3). It can be separated from bismuth, which it closely resembles, by the solubility of its oxide in alkalis and a1 kaline carbonates. w. c. w.94 ABSTRACTS OF CHEMICAL PAPERS. Constitution of Antirnonic Acid. By P. CONRAD (C'henz.News, 40, 197--198).-With a view t o decide the constitution of antimonic wid, specimens of it were prepared from the pure metal by seven different methods, and carefully analysed. The antimony was determined as snlphide, with the usual precau- tions, whilst the water mas determined, tint by exposure over sulphu- yic acid, and iheii by heating in a slow stream of nitrogen, and collecting the wder in a weighed calcium chloride tube. The sub- stance was weighed after heating, and any discrepancy between the loss of weight by the substance and the water expelled, was regarded as due to the reduction of the oxide. The loss of water takes place verg gradually. The acid dried over sulphnric acid a t the ordinary temperature has the constitution Sb,05.3H,0, whereas the acid dried in a current of dry air a t the ordinary temperature is represcnted by SbL0,..5H,0.At loo", this loses 3 mols. H20, Sb,05.H,0 being formed ; and between 100" and 200" one more mol. H,O is expelled, leaving Sb,0,.H20. Contrary to the statement of Daubrawa (Amrden, 186, l l O ) , the anhydrous pentoxide is not formed at 2 i 5 " , and even a t 300" the pro- duct still contains + a mol. H,O. This is driven off only a t a, red heat when the oxide begins to decompose. There seems to be reason t o believe in the existence of three anti- moriic acids, corresponding with three acids of pliosphorus- Orthonntimonic acid, H3Sb04 = 3H,0.Sb205. Pyroantimonic acid (nietaritimonic acid, Fremy) H4Sb,O7 = Meta-antimonic acid (antimonic acid, Fremy) HSbO, = 2HzO.Sb205.H20.SbZOj. The gradual formation by heat of the second and third acids from the first is similar to the formation of the corresponding acids of phos- ph oras. L. T. 07s. Salts of Plumbic Acid. By 0. SEIDET, ( J . pr. C h L . [ 2 ] 20, 200-20r5') .--The author has repeated Fremy's research on plumbic acid ( A ~ L ~ L . PJys. Chew [3], 12, 490), partly confirming his results. Potassium pZumbate, R,Pb03 + 3H,O, crystal lises in quadratic pym- mids ; n : c = 1 : 12216. The crystals are efflorcscent and are not isomorphous with potassium stannate. The sodium salt has not been obtained in a state of purity. Potassium plumbate does not produce a precipitate in alkaline solutions of tin and aluminium, but impure ylumbates are thrown down on boiling a solution of the potassium salt with lime, baryta, and magnesia.The precipitate which separates out when an alkaline solution of lead oxide is added to potassium plumbate is the hydrated sesquioxide, and not Pb30d, as stated by Fremy. The precipitate is conlpletely soluble in hydrochloric acid ; when treated with nitric or acetic acid, or with a hot solution of potash, lead di-oxide remains undissolved. By F. S E m m m (Ber., 12, 20@-2068).-When a piece of platinum is heated to redness in IL w. c. w. Volatility of Platinum in Chlorine.MINERALOGlCAL CHEMISTRY. 95 glass 01- porcelain tube, through which a current of chlorine ispassed, crystals of the metal are deposited o c the sides of the tube. A suhli- mate of platinurn is also obtained by exposing a porcelain flask con- taining platinous chloride to a bright red heat.The author discusses the bearing of these experiments on the abnormal densitv of chlorine a t high teGperatures ob'served by V. and C. RIeyer (Be1-.~"12~ 1426). w. c. w. Note.-In a recent communication (Ber., 12, 2202), V. Ncyer states that, under the conditions in which his experiments were con- ducted, platinum does not volatilise. He also points out that Seel- heim's explanation cannot account for the abnormal vaponr-density of iodine: since in these determinations iodine and not platinum iodide was employed. w. c. w.INORGANIC CHEMISTRY. 89I n o r g a n i c Chemistry.Allotropie Modifications of Hydrogen, By J. THOXPEN (BeT-.,12, 203O).-The author points out that ‘l’ominasi’s statement (Acr~tl.Illi’lun), that the heat of fcrmation of potassium chlorate is 9,760,and that of potassiuni chloride 104,476 units, and consequently104,476 - 9,760, i.e., 94,716 heat-units, are alisorl~ecl in the conversionof potassium chlorate into chloride, contains no less than three errors.The heat of formation of potassium clilorate is 95,840, and not 9,760,the latter number representing the lieat evolved in the convcrsion ofpotassium chlorate into chloride in the dry way.Instead of 94,716heat-units being sbsosbod in the reduction of the chlorate to the chlo-ride, a liberation of 15,370 heat-units takes place. It is obvious thatthe theoretical speculations based on these incorrect data are valueless.A New Method for Prepaxing Hydriodic and HydrobromicAcids. By G.BRUYLAN‘TS (Be?.., 12, 2Wl-2062) .-Hjdriodic acidcan be easily prepared by heating a solution of iodine (2u grams) incopaiba oil (60 grams) in a retort connected with an upright condenser.The gas is purified by passing it through a drying tube. When theevolution of gas slackens, fresh iodine is brought into the retort, andthe process is continued until about 1.50 grams of iodine have beenused.In the preparation of hydrobromic acid by this method, the brominemust be slowly dropped into the retort containing the oil, and the gasshould be purified by passing through three drying towers.w. c. w.w. c. w90 ABSTRACTS OF CHEMICAL PAPERS.Influence of Volume and Temperature in the Preparationof Ozone. A New Ozoniser.-By A. R .LEEDS (A~WUZA~L, 198, 30-42) .-A solution of potassium dicbromate (not necessarily saturated)mixed with sulphuric acid is placed in a suitable vessel, within which abell-jar can be placed, and pieces of phosphorus are partly immersed inthe liquid. It is better, however, to connect three such jars and drawthe air through them by means of an aspirator.For this purpose, thenecks of the jars are cernented into brass caps, which are screwed to itbar capable of being raised and lowered as in a gnlvanic battery ; thestoppers are replaced by corks covered with paraffin, through each ofwhich pass three glass tubes, one ending just below the stopper,another just above the liquid, and the third bent into a horizontal ringat the end. The first two tubes are connected so as to allow a currentof air to be drawn through the apparatus ; the third is for lowering ormising the phosphorus.The pieces of phosphorus are melted .inwatch-gla$ses to give them w more convenient shape, and are placedon glass plates in glass cells in the liquid. A flexible tube for con-veying the ozone from the generators was made of “ cei-ite” (“ kerite-”schlauch), and found to answer rery well.The maximum amonntof ozone obtained was a little over 2.5 mgrms. per litre of air ; but a sthe generator may be connected with the aspirator and allowed towork for any length of time, the s~ipply is unlimited.A Possible Cause of Variation of the Proportion of Oxygenin the Air. BF E. W. ~\~ORT,EY (Chew. News, 40, 184-186, and1 !49-20l).-Looniis has proposed the theory that certain great andsiidden depressions in the temperature of the atmosphere are causedhy the velatical descent of currents of air from cold elevated regions.If such is the case, then the air at the surface of the earthduring suchdepressions may contain a smaller amount of oxygen than the a;c-erage.Jolly concludes from his experiments that the air a t the equator ispoorer in oxygen than that a t tjEie polar regions, owing to the amountof oxygen consumed in oxidation being greater than that liberated byreduction. Facts, however, do not confirm these conclusions, no dif-ference in the composition of the atrnosplicre of the two regions havinghithertc been detected.According to the author’s views, based on Loomis’ theory, air col-lected at the centre of an area covered by a descending current would,a t a given moment, be a sample fresh from the upper atmosphere;whilst a sample collected on one side of this centre would consist of amixture of s w f m e and wpper air, but still containing a deficiency ofoxygen.Although the author has not yet succeeded in making theseexperiments, he has, while laying plans for the ~ o r k , conducted espe-yiments on ordinary air, to ascertain what light can be thrown 011 thechanges in composition of the atmosphere. The apparatus used wasconstructed on McLeod’s modification of Frankland and Ward’s appa-ratus, with important modifications, so as to reduce all causes of errorto a minimum.The samples were collected in the open country, in glass vessels. andpreserved over mercury freed from carbonic anhydride, and exploclcvlA temperature of 24” gives the best results.G.T. AINORGANIC CHEMISTRY. 9Jwith pure hydrogen. Some samples were collected in stoppered andc;ipped bottles, which were inverted, and the caps filled with water.Analyses of air were made daily from 28th December, 1878, to GtlhApril, 1879, during ivhich period some very marked and sudden de-pressions of temperature occurred, which were accompanied by adecrease in the quantity of oxygen. The deficiency, however, as mighthave been expected, was not proportional to the decrease i n tempe-rature (see also p. 85 of this volume).By G. WOLFRBX (AmnZe/r,198, 95--98).-IGimmerer ( J . pi..Chem., 90, 190) has desribed amethod according to which perbroinic acid may be obtained br theaction of d ~ y bromine on clry perchloric acid, the latter being preparedi\ t the tlime by the decomposition of potassium perclilorate by sulphuricacid. The author has repcated this experiment, and finds tliat the:icid thus obtained, corresponding in all respects with that describedhy Kammerer, is nothing more than a mixture of percliloric andsulphuric acids. The apparent absorption of the bromine by tlieperchloric acid is explained by the fact that perchloric acid, whenheated with an excess of sulphuric acid, is decomposed into oxygenmid chlorine, and it is this latter which takes u p tlie bromine i n theabove experiment, forming bromide of chlorine : this is volatilised,together with the excess of bromine, during the subsequent concen-tration of the liquid.L.T. 0's.Preparation of Perbromic Acid.T. C.Researches on Nitrous Acid and Nitrogen Tetroxide. By G.LUNGE (Dingl. yoZyt. J., 233, 155-165; cornp. this Journal, Abst.,18'79, 770).-8econd Pa7-t.- Oti the Re7at;ow of the Acids OJ hTitrogetl to,Sulplm-ic ileitZ.-Our knowledge of this relation is not by any weanscomplete. It is well known that nitrous acid, either in the liqnicl orgaseous form, o r jmduced nascent from the union of nitrogen dioxidewith oxygen, is clissolved by sulphuric acid of about. 1.7 sp. gr. ; butthe heliaviour of nitrogen tetroxide towards snlphuric acid is not accu-rately known. The author has shown that it is dissolved by sulpliurici~cid, forming nitrosulphuric and nitric acids ; but according to Weberand Winkler, nitlogen tetroxide is dissolved as such by sulphuric acidof 66" B., producing a reddish-yellow solution, which, when heated,gives off nitrogen tetroxicle with violcrit ebullition, and leaves a liquidIiaviug the properties of nitrosulphuric acid.Winklcr stated that28 072 grams of sulphuric acid a t 60"B. absorbed 7.307 grams ofnitrogen tetroxide, but that on heating gently, the latter was eiitirelyexpelled. Weber describes the effects of nitrogen tetroxide onsulphui*ic acid of different specific gravities, but only qualitativel~ :thns, sulphuric acid at, a sp. gr. of 1.7 absorbs nitrogen tetroxidewithout becoming coloured: liecce i t was assunied that the latterwas decomposed; a t a sp.gr. of 1.55 the sulphuric acid becomesyellow, and hence it was supposed that the greater part of thenitrogen tetroxide was simply dissolved. Acid of 1-49 sp. gr. takes agreenish-yellow colour; acid of 1.41 sp. gr. takes an intense greend o u r ; acid of 1.31 sp. gr. becomes blue and liberates nitrogen dioxicle,which escapes with violent ebullitioii on gently heating. The p e l 92 ABSTRACTS OF CHEMICAL PAPERS.and blue colours were supposed to be due to the formation of nitrouswid, the nitrogen tetroxide having been decomposed into that sub-stance and nitrogen dioxide. As these results are very important tovitriol manufacturers, the author studied them more accurately, and,its far as possible, quantitatively.The nitrogen tetroside, preparedfrom d r g fused lead nitrate, was measured oif from a burette, andmixed with pure sulphuric acid, which had been diluted to differentstrengths with water, and the effects of heat upon these mixtureswere also noted.The following are given as examples of the mctliod employed and ofthe results obtained by the author in carrying out the expel-iments :-100 C.C. sulphuric acid of 1-84 sp. gr., t o which was added 2 C.C.= 3 grams liquid nitrogen tetroxide, gave a colourless solution with:L very feeble odour, recaJling that of ozone. The amount ofnitrogen dioxide evolved from 1 C.C. of this solution in the nitro-meter was determined, and also the amount required to decolorise10 C.C. seniinormal potassium permangmate solution.From theresults, the author calculates that his nitrogen tetroxide contained ofpure nitrogen tttroxide 93 per cent., and of nitric acid 7 per cent. ; butlie argues, as in reality the nitrogen tetroxide does not exist, as such inthe sulpliuric acid, but has undergone a decomposition, one part oftlie tetroxide having been converted into nitric acid a t the expense ofthe oxjgen of the other part, whilst the part which has been robbedof its oxygen remains as nitrous acid in combinatlion with tlie sul-phuric acid; then assuming that this lower oxide takes the oxygenfrom, and decolorises the potassium permanganate, this would wive46.5 per cent. as nitrous acid, and 53.5 per cent. as nitric acid. ?'heother calculations are niade on this supposition, that is, it8 is firstassumed that all the nitrogen tetroxide remains as such, and the defi-ciency in the theoretical amount of oxygen required is calculated asnitric acid; but if, on the contrary, tho amount of oxygen requiredbe less than that found by the permangnnate process, then he assumesthat no nitric acid is present, but that nitrous acid must have beenoriginally present as an impurity.(I.) The acid was heated to 2tiUo, and kept at that temperature for onehour ; any free nitrogen tetroside, if it were present, must have beenthus expelled.When the ttmperature rose t o 20Uo, R little red vspourwas evolved, and the liquid acquired a golden-yellow colour ; b u t oncooling, it again became colourless.On analysis the author calculated that 77.9 per cent.of the nitrogenpresent existed as N,O,, and 21.1 per cent. as HNO,; there is, con-sequently, he si;tys, a large amount of the nitric acid driven off andanobher part changed into nitrous acid.(11.) On continuing t o heat for one hour longer, a further changetook place of the bame kind, and 94..5 per cent. of the nitrogen re-maining existed as Nz03, in combiliation with the sulphuric acidjorming nitrosulphnric acid ; whilst 5.rj per cent. remained as HNO;;,n~ld 18 per cent. of the nitrogen originally present having been ex-pelled by the heating.(111.) Another experiment was made by adding pure nitric t o pu:.TN ORGANIC CHEMISTRY. 93sulphuric acid, and analysing the resulting mixture, but no change wasfound to have taken place.(1V.) On boiling the mixture for half-an-hour, however, red fumeswere given off, and the whole of the nitrogen present was convertedinto nitrous acid, which was found in combination with the sulphuricacid.That nitric acid is thus broken up has also been demonstrated inanother way by Winkler, who collected the oxygen which was evolvedfrom the decomposition.The author did not find the same result as Winkler with sulphuricacid of 66OB.above mentioned, and he explains this by assuming that,Winkler employed so much nitrogen tetroxide that it left it hrgt.excess beFond that which could combine with the sulphuric acid asnitrous acid : hence the sudden and violent ebullition and liberation ofnitrogen tetroxide on heating the mixtuye.2 C.C.nitrogen tetroxide added to sulphuric acid of 1.805 sp. gr. washroken up into practically the same proportions of nitrous and nitricacids as in the first experiment, with acid of 1.54 sp. gr.Other experiments are described in which sulphuric acid of1.75 sp. gr. was mixed with nitrogen tetroxide and then heated ( a ) , sothat the vapour evolved might a t once escape, and ( b ) where a longtube was attached to the flask in which the mixture was heated, sothat the vayoar might condense and flow back again to the acid inthe flask. In ( a ) nitrous acid, but no nitric acid mas found, whilst in ( b )nitric acid was present but no nitrous acid ; this is explained by the fact,that it requires concentrated sulphuric acid to combine with andretain the nitrous acid ; and in ( a ) the acid became concentrated byevaporation, whilst in ( b ) it remained of about the same sti.eugth, aridwas unable to retain the nitrous acid.Again, when the mixture was heated on a water-bath a t about 95",no such changes occurred.As Winkler found, that on heating his mixture of acid of 60°B.with nitrggen tetroxide, the latter was evolved, he presumed that i texisted as a mechanical mixture with the acid.This the author denies,stating that had Winkler examined the acid a,fter boiling, he wouldhave found that it contained nitric acid, and that the nitrogentetroxide had really undergone decomposition ; and further, that homust have heated it considerably above the temperature of boilingwater, otherwise no change would have resulted, and no red fumeswould have been liberated.When the amount of nitrogen tetroxirle added is in excess of thatrequired to form nitrnsulphuric acid, the author is uncertain fromanalysis whether it exists in the acid in the form of nitrous acid orof nitrogen tetroxide.W. T.Norwegium. By T. DAHLL (Rer., 12, 15'3 1-1 732) .-The prepam-tion of this metal from the ore has already been described (thisJournal, Abs., 1879, 890). It melts a t 254', and its atomic weight is145.552 (RO), or 218.928 (TC2G3). It can be separated from bismuth,which it closely resembles, by the solubility of its oxide in alkalis anda1 kaline carbonates. w. c. w94 ABSTRACTS OF CHEMICAL PAPERS.Constitution of Antirnonic Acid.By P. CONRAD (C'henz. News,40, 197--198).-With a view t o decide the constitution of antimonicwid, specimens of it were prepared from the pure metal by sevendifferent methods, and carefully analysed.The antimony was determined as snlphide, with the usual precau-tions, whilst the water mas determined, tint by exposure over sulphu-yic acid, and iheii by heating in a slow stream of nitrogen, andcollecting the wder in a weighed calcium chloride tube. The sub-stance was weighed after heating, and any discrepancy between theloss of weight by the substance and the water expelled, was regardedas due to the reduction of the oxide. The loss of water takes placeverg gradually.The acid dried over sulphnric acid a t the ordinary temperature hasthe constitution Sb,05.3H,0, whereas the acid dried in a current ofdry air a t the ordinary temperature is represcnted by SbL0,..5H,0.At loo", this loses 3 mols.H20, Sb,05.H,0 being formed ; and between100" and 200" one more mol. H,O is expelled, leaving Sb,0,.H20.Contrary to the statement of Daubrawa (Amrden, 186, l l O ) , theanhydrous pentoxide is not formed at 2 i 5 " , and even a t 300" the pro-duct still contains + a mol. H,O. This is driven off only a t a, red heatwhen the oxide begins to decompose.There seems to be reason t o believe in the existence of three anti-moriic acids, corresponding with three acids of pliosphorus-Orthonntimonic acid, H3Sb04 = 3H,0.Sb205.Pyroantimonic acid (nietaritimonic acid, Fremy) H4Sb,O7 =Meta-antimonic acid (antimonic acid, Fremy) HSbO, =2HzO.Sb205.H20.SbZOj.The gradual formation by heat of the second and third acids fromthe first is similar to the formation of the corresponding acids of phos-ph oras.L. T. 07s.Salts of Plumbic Acid. By 0. SEIDET, ( J . pr. C h L . [ 2 ] 20,200-20r5') .--The author has repeated Fremy's research on plumbicacid ( A ~ L ~ L . PJys. Chew [3], 12, 490), partly confirming his results.Potassium pZumbate, R,Pb03 + 3H,O, crystal lises in quadratic pym-mids ; n : c = 1 : 12216. The crystals are efflorcscent and are notisomorphous with potassium stannate. The sodium salt has not beenobtained in a state of purity. Potassium plumbate does not producea precipitate in alkaline solutions of tin and aluminium, but impureylumbates are thrown down on boiling a solution of the potassium saltwith lime, baryta, and magnesia.The precipitate which separates out when an alkaline solution oflead oxide is added to potassium plumbate is the hydrated sesquioxide,and not Pb30d, as stated by Fremy. The precipitate is conlpletelysoluble in hydrochloric acid ; when treated with nitric or acetic acid,or with a hot solution of potash, lead di-oxide remains undissolved.By F. S E m m m (Ber., 12,20@-2068).-When a piece of platinum is heated to redness in ILw. c. w.Volatility of Platinum in ChlorineMINERALOGlCAL CHEMISTRY. 95glass 01- porcelain tube, through which a current of chlorine ispassed,crystals of the metal are deposited o c the sides of the tube. A suhli-mate of platinurn is also obtained by exposing a porcelain flask con-taining platinous chloride to a bright red heat. The author discussesthe bearing of these experiments on the abnormal densitv of chlorinea t high teGperatures ob'served by V. and C. RIeyer (Be1-.~"12~ 1426). w. c. w.Note.-In a recent communication (Ber., 12, 2202), V. Ncyerstates that, under the conditions in which his experiments were con-ducted, platinum does not volatilise. He also points out that Seel-heim's explanation cannot account for the abnormal vaponr-density ofiodine: since in these determinations iodine and not platinum iodidewas employed. w. c. w

ISSN:0368-1769    

DOI:10.1039/CA8803800089

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

MINERALOGlCAL CHEMISTRY. M i n e r a l o g i c a l C h e m i s t r y . 95 Rock Salt from Saltville. Ry B. E. SLOAN (Chenz. News, 40, 187).-Some specimens of dark brownish-red rock salt obtained from the salt wells a t Saltville, Washington Co., Virginia, gnve the follow- ing results on analysis :- NaC1. KC1. CaS04.2H20. Fe,O,. SiOz. 89.2 1 trace 4-86 0.84 4.53 The presence of strontium, barium, OP lithium could not be de- tected. L. T. 0’s. Livingstonite. By F. P. VENABLES (Chem. News, 40, 186--187).- Owing to doubts as to the purity of the samples of this mineral analysed by BBrcena, and consequently as to the accuracy of the formula assigned to it by him, the author has a t his request examined purer specimens, and the numbers obtained give t,he formula HgS.2Sb,S3 instead of 4Sb,S3 + HgS + FeS2.Calcium sulphatc mas present in considerable quantities, but as it occurs only as a matrix, it may be eliminated from the results of analysis. This is the most strongly acid sulphantimonite yet known. Magnetite. By E. C. SMITH (Chern. ATews, 40, 189).--This mineral occurs in Henry Co., Virginia, in loose crystals coated wit,h ferric oxide, which can easily be washed off, when they present the ordinary black colour and general appearance of magnetic iron ore. Hardness = 6 ; sp. *gr. 4.98. The crystals are strongly magnetic, and are curiously distorted on the surface by step-like projections and depressions, giving them the appearance of rhornbic octohedrons, but with irregularly varying inclinations of the general surfaces. The analysis of the cleansed crystals show them.t o consist of pure mag- netite. L. T. 0’s. L. T. 0’s.96 ABSTRACTS OF CHEMICAL PAPERS. Crystalline Form of Sardinian Anglesite. By Q. SET,T,A (Gazzetfcr,, 9, 344-353b.-Anglesite7 which is found so frequently and in such fine crystals in the mines of Monteponi and elsewhere in t,he island of Sardinia, formed the subject of a monograph by Lang, and since then this mineral has been studied by other crystallographers, espcciallp Hessenbcrg, Zepharowich, and Kreuner. Although the number of forms already described is considerable, a table of no less t)han 44 being given in the paper, a careful examination of numerous fine crystals has enabled the author to increase it greatly. DetaJls of the measurements of 38 specimens are given, b u t many of these symbols cannot be considered as definitely established until they have been carefully compared with the results of former workers in this field. I n the second part of the memoir the aukhor proposes to discuss the relation between the different forms and the size of the crystals, as well as to give descriptions of other forms of angleqite.C. E. G. Composition of Amblygonite. By S. L. PENFIELD (CAem. News, 40, 208--20!~).-Brush and Dana (Am. JOUY. Sci. [3], 16, 42) have shown that triploidite, (Mn,Fe) 3Pz08 + (Mn,Fe)( OH),, is isomor- phous with wagnerite, hIgJ’,O, + I\IgF2, and similar in composition to triplite, (Mn,Pe)3P208 + (ililn,Fe)F,, and consequently argue that the OH-group plays the same part in triploidite as fluorine does in the other two minerals. Ir, amhlypnite the author shows that hydroxyl and fluol-ine are also isornorphous. The results of the analyses give the ratios of P : A1 : (Li,Na) : (OH,F) = 1 : 1 : 1 : 1, corresponding with the formula A1,P20, +2(Li,Na) (OH,F), or- 381,P,O, AL(OH,F)t3 S(Li,Na),POi + { 2 (Li,Na) (OH,F) Owing to a difference in the optical properties of some specimens, Des Cloizeaux separates the mineral into two varieties, but the varia- tion is so slight as hardly t o afford sufficient ground for the dis- tinc ti on.Details of the method of analysis are given. Uranium Minerals from North Carolina. L. T. 0’s. Ey F. A. GENTH (Cjbeqn. News, 40, 210--212).-These minerals, fonlrd in the Flat Rock Mine, Mitchell Co., North Carolina, are as follows :- UranotiZ occui-s as a pale yellow coating on gummite, and is amor- phous, massive, and compact.Hardness = 2.5 ; sp. gr. 3.84 ; lustre dull. In colour it varies from a straw-yellow t o lemon-yellow ; its streak is of a pale straw yellow, it is opaque, and has an uneven fracture. The analysis agrees with the formula Ca3( 0,),Si6O2,.18H,O, rather than Ca3( Oz),Si5O,,.l5H2O given by Rammelsberg. Guwm&e.-This orange-coloured knineral occurs in compact, amor- phous, nodular masses. Hardness 3 ; sp. gr. 4.84; lustre resinous ; and streak orange-yellow. It is opaque, and has it subcoochoidal fracture. It is soluble in acetic acid. Various opinions have been held concerning the constitution of this mineral, and the a,nthor, with Patera, mainhiins that it is principally lead uranate.Gummite is the result of the alteration of uraniiiite, and that fromMINERALOGICAL CHEMISTRY. 97 North Carolina is a mechanical mixture, since uranotil penetrates the mass throughout. From the author’s analyses it is found to consist of- Uranium hydrate, H2(UO2)O2 + H,O .... 40.10 per centa Uranotil, Cat(U02)6Si6021 + 18H20 .... 33.38 ,, Lead uranate, Pb(U02)203 + 6ILO.. . . . . 22.66 ,, Barium uranate, Ba(U02)203 + 6H20.. . . 4.26 ,, Gummite from Johann Georgenstadt has probably the follomirrg composition calculatea from Kersten’s analyses :- Uranium hydrate, H2(U02)02 + H20.. . . Uranotil, Ch(U02)qSi6021 + 18H20 . . . . 30.54 .. Phosphuranylite, (U02)3P208 + 6H20.. . . 8.73 .. Calcium uranate, Ca,(UO,),O, f 6H20 . . 52-99 ), 6.32 per cent. Phosyhurany 7ite exhibits under the microscope rectangular pcnrly The analysis shows that it may scales, having a deep brown colour. be expressed by 5: formula similar t o that of troegerite.Phosphuranylite = (U02)3P208 + 6H20 Troegerite . . . . = (U02)3A~208 + 12H,O The analyses of pittinite and eliasite admit of no calculation, as they appear bo contain too many foreign substances. A saniple supposed to be uranite was found to contain lime and’not a trace of copper, and therefore consists of aufunite. L. T. 0’s. By N. PELLEGRINI (G17Z- zetta,* 9, 293).-This specimen of chrysocolla, from Cerro Blanco in Chili, was bright green on the outside, farther in it was a beautif111 deep green, and in the centre a dark greenish-blue approaching t o brown. These were mechanically separated and analysed :- Outside.Second layer. Centre. H,O.. . . . . . . . . 7.296 24-007 26.1 48 SiO,. . . . . . . . . . 16.621 26.685 95.938 CUO.. . . . . . . . . 63.306 39.891 31.913 Analyses of Chryaocolla from Chili. . . . . . . 4.957 { +:::!!} 9.227 FeO . . . . . . . . . . - 1.824 - CaO.. . . . . . . . . 3.081 2.307 3.992 Loss.. . . . . . . . . 2.739 0.372 2.782 100*000 100*000 100~000 - -. L__ C. E. G. Volcanic Ash from Cotopaxi. By J. R. SANTOS (Chem. New.?, 40, 186).-This ash, which fell during a recent eruption at Bahia de Caraguez, a distance of 120 miles from Cotopaxi, consisted of a fine brown powder containing glassy granules mixed with ferric oxide. Its specific gravity = 2.743 and its analysis gave- * The Qazzetta chimica italiana will in future be abbreviated to Qazzetta.+ This is perhaps 3*415.-C. E. G. TOL. XXXVIII. F,98 ABSTRACTS OF CHEMICAL PAPERS. SiO,. A120,. Peso3. PbO. CaO. MgO. 56.661 19.398 7.523 0.575 6.229 trace 6.123 2.425 0.8G2 NtlaO. K20. 8 2 0 . Discarding the iron and water, the above numbers lead to tlic for- The quantity of lead contained in this mula (K,Na,CaPb)A1,Si501~. ash is interesting, as is also its state of combination, namely, silicate. L. T. 0’s.MINERALOGlCAL CHEMISTRY.M i n e r a l o g i c a l C h e m i s t r y .95Rock Salt from Saltville. Ry B. E. SLOAN (Chenz. News, 40,187).-Some specimens of dark brownish-red rock salt obtained fromthe salt wells a t Saltville, Washington Co., Virginia, gnve the follow-ing results on analysis :-NaC1. KC1. CaS04.2H20.Fe,O,. SiOz.89.2 1 trace 4-86 0.84 4.53The presence of strontium, barium, OP lithium could not be de-tected. L. T. 0’s.Livingstonite. By F. P. VENABLES (Chem. News, 40, 186--187).-Owing to doubts as to the purity of the samples of this mineralanalysed by BBrcena, and consequently as to the accuracy of the formulaassigned to it by him, the author has a t his request examined purerspecimens, and the numbers obtained give t,he formula HgS.2Sb,S3instead of 4Sb,S3 + HgS + FeS2. Calcium sulphatc mas present inconsiderable quantities, but as it occurs only as a matrix, it may beeliminated from the results of analysis. This is the most stronglyacid sulphantimonite yet known.Magnetite. By E. C. SMITH (Chern. ATews, 40, 189).--Thismineral occurs in Henry Co., Virginia, in loose crystals coated wit,hferric oxide, which can easily be washed off, when they present theordinary black colour and general appearance of magnetic iron ore.Hardness = 6 ; sp.*gr. 4.98. The crystals are strongly magnetic,and are curiously distorted on the surface by step-like projectionsand depressions, giving them the appearance of rhornbic octohedrons,but with irregularly varying inclinations of the general surfaces. Theanalysis of the cleansed crystals show them. t o consist of pure mag-netite. L. T. 0’s.L. T. 0’s96 ABSTRACTS OF CHEMICAL PAPERS.Crystalline Form of Sardinian Anglesite. By Q. SET,T,A(Gazzetfcr,, 9, 344-353b.-Anglesite7 which is found so frequently andin such fine crystals in the mines of Monteponi and elsewhere in t,heisland of Sardinia, formed the subject of a monograph by Lang, andsince then this mineral has been studied by other crystallographers,espcciallp Hessenbcrg, Zepharowich, and Kreuner.Although thenumber of forms already described is considerable, a table of no lesst)han 44 being given in the paper, a careful examination of numerousfine crystals has enabled the author to increase it greatly. DetaJls ofthe measurements of 38 specimens are given, b u t many of thesesymbols cannot be considered as definitely established until theyhave been carefully compared with the results of former workers inthis field. I n the second part of the memoir the aukhor proposes todiscuss the relation between the different forms and the size of thecrystals, as well as to give descriptions of other forms of angleqite.C.E. G.Composition of Amblygonite. By S. L. PENFIELD (CAem.News, 40, 208--20!~).-Brush and Dana (Am. JOUY. Sci. [3], 16, 42)have shown that triploidite, (Mn,Fe) 3Pz08 + (Mn,Fe)( OH),, is isomor-phous with wagnerite, hIgJ’,O, + I\IgF2, and similar in compositionto triplite, (Mn,Pe)3P208 + (ililn,Fe)F,, and consequently argue that theOH-group plays the same part in triploidite as fluorine does in theother two minerals. Ir, amhlypnite the author shows that hydroxyland fluol-ine are also isornorphous. The results of the analyses givethe ratios of P : A1 : (Li,Na) : (OH,F) = 1 : 1 : 1 : 1, correspondingwith the formula A1,P20, +2(Li,Na) (OH,F), or-381,P,O, AL(OH,F)t3S(Li,Na),POi + { 2 (Li,Na) (OH,F)Owing to a difference in the optical properties of some specimens,Des Cloizeaux separates the mineral into two varieties, but the varia-tion is so slight as hardly t o afford sufficient ground for the dis-tinc ti on.Details of the method of analysis are given.Uranium Minerals from North Carolina.L.T. 0’s.Ey F. A. GENTH(Cjbeqn. News, 40, 210--212).-These minerals, fonlrd in the FlatRock Mine, Mitchell Co., North Carolina, are as follows :-UranotiZ occui-s as a pale yellow coating on gummite, and is amor-phous, massive, and compact. Hardness = 2.5 ; sp. gr. 3.84 ; lustredull. In colour it varies from a straw-yellow t o lemon-yellow ; itsstreak is of a pale straw yellow, it is opaque, and has an uneven fracture.The analysis agrees with the formula Ca3( 0,),Si6O2,.18H,O, ratherthan Ca3( Oz),Si5O,,.l5H2O given by Rammelsberg.Guwm&e.-This orange-coloured knineral occurs in compact, amor-phous, nodular masses.Hardness 3 ; sp. gr. 4.84; lustre resinous ;and streak orange-yellow. It is opaque, and has it subcoochoidalfracture. It is soluble in acetic acid. Various opinions havebeen held concerning the constitution of this mineral, and thea,nthor, with Patera, mainhiins that it is principally lead uranate.Gummite is the result of the alteration of uraniiiite, and that froMINERALOGICAL CHEMISTRY. 97North Carolina is a mechanical mixture, since uranotil penetrates themass throughout. From the author’s analyses it is found to consistof-Uranium hydrate, H2(UO2)O2 + H,O ....40.10 per centaUranotil, Cat(U02)6Si6021 + 18H20 .... 33.38 ,,Lead uranate, Pb(U02)203 + 6ILO.. . . . . 22.66 ,,Barium uranate, Ba(U02)203 + 6H20.. . . 4.26 ,,Gummite from Johann Georgenstadt has probably the follomirrgcomposition calculatea from Kersten’s analyses :-Uranium hydrate, H2(U02)02 + H20.. . .Uranotil, Ch(U02)qSi6021 + 18H20 . . . . 30.54 .. Phosphuranylite, (U02)3P208 + 6H20.. . . 8.73 .. Calcium uranate, Ca,(UO,),O, f 6H20 . . 52-99 ),6.32 per cent.Phosyhurany 7ite exhibits under the microscope rectangular pcnrlyThe analysis shows that it may scales, having a deep brown colour.be expressed by 5: formula similar t o that of troegerite.Phosphuranylite = (U02)3P208 + 6H20Troegerite .. . . = (U02)3A~208 + 12H,OThe analyses of pittinite and eliasite admit of no calculation, as theyappear bo contain too many foreign substances. A saniple supposedto be uranite was found to contain lime and’not a trace of copper, andtherefore consists of aufunite. L. T. 0’s.By N. PELLEGRINI (G17Z-zetta,* 9, 293).-This specimen of chrysocolla, from Cerro Blanco inChili, was bright green on the outside, farther in it was a beautif111deep green, and in the centre a dark greenish-blue approaching t obrown. These were mechanically separated and analysed :-Outside. Second layer. Centre.H,O.. . . . . . . . . 7.296 24-007 26.1 48SiO,. . . . . . . . . . 16.621 26.685 95.938CUO.. . . . . . . . . 63.306 39.891 31.913Analyses of Chryaocolla from Chili.. . . . . . 4.957 { +:::!!} 9.227FeO . . . . . . . . . . - 1.824 -CaO.. . . . . . . . . 3.081 2.307 3.992Loss.. . . . . . . . . 2.739 0.372 2.782100*000 100*000 100~000- -. L__C. E. G.Volcanic Ash from Cotopaxi. By J. R. SANTOS (Chem. New.?,40, 186).-This ash, which fell during a recent eruption at Bahia deCaraguez, a distance of 120 miles from Cotopaxi, consisted of a finebrown powder containing glassy granules mixed with ferric oxide.Its specific gravity = 2.743 and its analysis gave-* The Qazzetta chimica italiana will in future be abbreviated to Qazzetta. + This is perhaps 3*415.-C. E. G.TOL. XXXVIII. F98 ABSTRACTS OF CHEMICAL PAPERS.SiO,. A120,. Peso3. PbO. CaO. MgO.56.661 19.398 7.523 0.575 6.229 trace6.123 2.425 0.8G2NtlaO. K20. 8 2 0 .Discarding the iron and water, the above numbers lead to tlic for-The quantity of lead contained in this mula (K,Na,CaPb)A1,Si501~.ash is interesting, as is also its state of combination, namely, silicate.L. T. 0’s

ISSN:0368-1769    

DOI:10.1039/CA8803800095

出版商:RSC    

年代:1880

数据来源: RSC