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J O U R N A L OF THE CHEMICAL SOCIETY, ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. General and P h y s i c a l Chemistry. Spectroscopic Examination of the Constituents of the Atrno- sphere. By J. JANSSEN (COW@. rend., 101, 649--651).-At the Meudon Observatory, four absorption tubes, one of which is 60 metres long, have been set up, and the absorption-spectra of hydrogen, air, and oxrgen have been examined, sometimes under high pressures. In the case of hydrogen, an enormous stratum of gas must be employed before any absorption-spectrum can be observed. When oxygen is examined in the 60-metre tube under pradudly increasing pressure, mccessive groups of lines appear. The first are the lines and bands in the red, which Egoroff regards as identical with the lines A and B in the solar spectrum, but if the pressure is raised beyond 27 atmos., and the intensity of the light employed is increased, evidences of absorption are obtained between A and B, and bettween B and C, but still higher pressures are necessary before the existence of absorption- bands in these positions can be definitely established.At rery high pressures, three other bands become visible, one in the red near OC, one in the greenish-yellow near D, and one in the blue. No similar bands are known in the solar spectrum. C. H. B. Optical Properties of Malic and Tartaric Acids. By L. BELL (Amer. Chem. J., 7, 120--128).-Both tartaric and malic acids show an increase oE optical activity with a rise in temperature, or with a decrease of concentration, and in the case of I ~ ~ ~ o - n ~ a l i c and dextro- tartaric acids, the sign of polarisation is reversed i f solutions suffi- ciently strong and cold are examined.From thermic observations it seetiis that this change of rotary power cannot be accounted for either by the supposition of changes of confignration of the molecule, or nf the formation of hydrates, or of the formation of crystal mole- cules. It is, however, thought that the change is due to the formn- tion of polymerides, which are gradually decomposed by dilution or VOL. L. b2 ABSTRACTS OF CHEMICAL PAPERS. application of heat ; in dilute solutions, the changes effected by rarin- tion are but slight when compared with those in strong solutions, where one must expect the polymeride to exist in comparatively large proportion.A further proof of the formation of polymerides is the fact that the solutions show abnormal rotary dispersion-a phenomenon not possible with the solution of a single substance-and this may be gradually made normal by dilution or by heating. Tartaric and malic acids both exist in more forms than can be accounted for on any existing theory; this may possibly be explained by the observation that two molecules of a substance containing an asymmetrical carbon-atom may be symmetrically united in four different ways. H. B. Sensitiveness t o Light of Selenium and Sulphur Cells. By S. BIDWELL (Chem. News, 52, 191--193).-With regard to the action of light in diminishing the electrical resistance of selenium, and pro- ducing in it a photo-electric current, Adams and Day have observed that in such mses the structure of the selenium is so modified that it behaves apparently like an electrolyte, and hence conclude that selenium, under those conditions, conducts electrolytically.I n the present paper, the author attributes these phenomena to actual electrolysis, and bases this assertion on the following facts. It is known that in making seleaium “ cells,” the longer they are “ annealed ” (that is, heated i n contact with the metallic electrodes) the more sensitive the selenium becomes to the action of light. Again, a very sensitive selenium “ cell ” has been constructed by Fritts, in the following manner :-A film of selenium is melted on R plate of metal with which it can combine, and ultimately the other surface is coated wit,h a transparent conductor.Moreover, a piece of selenium con- tained in a good “ cell ” with.copper electrodes indicated a specific resistance = 0.9 megohm, whilst the resistance of a similar piece of selenium annealed in a glass mould out of contact with metal = 2500 megohms. The author infers that a selenide is formed during the heating with the metal, and that the sensitiveness is due to the presence of the selenide and its electrolysis by the current. To complete the chain of experimental evidence, sulphur, which has hitherto resisted numerous attempts to develop in i t the sensitiveness to light so characteristic of selenium, was mixed with silver sol- phide, and incorporated in a “ cell ” with silver electrodes ; it then exhibited remarkable sensitiveness to light, and its resistance was greatly reduced by it.Numerous experiments are described proviiig this effect to be due to the direct action of radiation, and not simply t o R rise in the temperature, by which this sulphur “cell ” is affected jn a similar manner. Electrolytically considered, the action in the sulphur ‘‘ cell ” containing silver sulphide and silver electrodes is this : when the current passes, silver is deposited upon the cathode and sulphur upon the anode, but any sulphur deposited on the anode would stop the current, an occurrence which is prevented by the silver combining w i t h the sulphur, hence the quantity of electricity passing js regulated by the quantity of sulphur disposed of in this manner. By. replacing one of the silver electrodes by a metal which does riotGENERAL AND PHYSICAL CHEMISTRY.3 combine so readily with sulphur, iron for instance, then on the above hypothesis, when iron is the anode the resistance ought to be greater than when silver is the anode, and such is the case in actual experimcnt, the resistance being 30 times greater in the former than i t is in the latter case. Other experiments show that light assists the direct combination of silver and sulphur, and it is inferred that “the electrolysis of silver sulphide may be assisted by light, and its electrolytic resistance a t the same time diminished.” I n a few experiments made with sulphur “ cells ” containing copper and copper sulphide, there was no indication of sensitiveness to light.With regard to the effect of temperature on selenium “ cells,” the auhhor has observed that whether exposed to light or not, selenium “ cells ” have a temperature of maximum resistance, which is generally a few degrees higher than the average temperature of the air. D. A. L. Dry Electric Batteries. By W. v. BEETZ (Ann. Phys. Chem. [2], 26, 13--26).-This paper contains a series of determinations of the electromotive force of certain dry forms of Dnniell’s battery, especially of those consisting of U-tubes containing in the one limb copper sulphate solution, in the other zinc sulphate solution, both being xorked u p into a paste by plaster of Paris, and then allowed to set in the tnbes. Their use as an unit in electric measurements was examined ; it was found that in some cases the difference of poten- tial remained constant, whilst.in others i t decreased very rapidly. Such batteries cannot be used in electro-therapeutics. V. H. V. New Forms of Thermopiles. By H. KAPSER (Ann. Phys. Chem. [2], 26, 9--13).--In this paper, measurements are given of the electromotive forces and resistances of various forms of thermopiles, tlhe source of heat being a gas flame burning a known number of litres of gas per honr. The electromotive force of a NoG-Rebiceck’s thermoelectric pile of 20 elements was found to be constant, for an indefinite lengt,h of time, provided that the external conditions, namely, gas pressure and temperature of the air, were unaltered ; its electromotive force also exceeded that of a Bunsen’s element. The internal resistance increased to a maximum, with a consumption of gas from 0-60 litres per hour, and from that point to 110 litres per hour it diminished ; the maximum resistance of a pile of 25 elements was 0.868 ohm.The relative advantages of a thermopile over a, Bunsen’s element in cases of small external resistance are also dis- cussed. V. H. V. Electrical Conductivity of Air under Reduced Pressure. By T. HOMPN (Ann. Phys. Chenz. [ Z ] , 26, 55--81).-Experiments on the relation of the conductivity of air to the pressure, have led to the opposed conclusions that an absolute vacuum is a perfect non-con- ductor, and a good conductor of electricity. In this paper, an elabo- rate series of experiments on the conductivity of air in discharge tubes under various degrees of pressure are described.The results show that the phenomena of conductivity of air under reduced b 24 ABSTRACTS OF CHEMICAL PAPERS. pressure are of two kinds, the one, the particulw resistance of the air, which is proportional to the distance between the electrodes, the other the actual resistance of the electrodes themselves. The former i s independent of the diameter of the air column, and its increase is nearly proportional to the pressure, whilst the latter increases very quickly with decrease of pressure, and under low pressures reaches a point at which the resistance is such that electricity, even at the highest difference of potentiaJ, cannot overcome it, These results are not in accordance with the view that a vacuum is a good conductor of electricity. V.H. V. Electrical Conductivity of Alcohol. By E. PFEIFFER (Ann. Pliys. Chenz. [el, 26, 31-44).-1n this paper a description is given of determinations of the Conductivity of absolute alcohol, and the rnrintions produced by change of condition. The lowest value for recently distilled alcohol was 0.1261 x 10-10 ohms in ternis of mercury as the unit. The relative conductivity is increased by the presence of traces of impurities, but decreased to a considerable extent by the absorption of air.; it decreases, as that of metals, with rise of temperature, until a point is reached a t which the influence of temperature is nil. The author proposes to call this point ” the point of indifference.” Comparing the temperature coe5cient, or the ratio of decrease of conductivity, with r i s e of temperature = ?!! of alcohol with that of the mehals, it is found that the former is to the latter in the ratio 0*OG87 to 0.0037.V, H. V. k0 Electrical Properties of Salt Solutions. By J. MOSER (Xonatsh. Chem., 6, 634-638) .-The author has previously investi- gated the electromotive force of cells in which the total amount of purely chemical reacttion is reduced t o a minimum, the current being conditioned by the minor molecular attractions of a salt with the water in which it is dissolved ; such, for example, is the combination From these experi- ments Helmholtz determined the relation between the E.M.F., the vapour-tension of the salt solution, and the tmn+ference-uaZues of the ions (compare Faraday lecture, Trans., 1881, 299), so that if two of these values were known the third could be calculated.By the experi- mental elimination of the third factor, the relation could be determined between the E.M.F., conditioned by difference of concentration and the vapour-tension. Then, if the theories of Helmholtz are com- patible in the two cases stated above, the transference-value should be the quotient of the E.SLF.’s, with and without a possible transference of the ions. I n the paper this point is examined and found to be in accordance with the thtiory. There is also mentioned a case of electro-neutrality of a combina- tion Zn I ZnC1, I ZnSOi I Zn, in which the solutions were of .such a. degree of concentration thatj the addition of water to either of them produced a current with concomitant transference of the ions. Attention is also drawn to the fact that the E.M.F., produced by I Zn I dilute ZnSOa I concentrated ZnSOd I Zn.GENERAL AND PHYSICAL CHEMISTRY.n differences of concentration, does not correspond with the heat changes on dilution. V. H. V. Incandescence by Ultra-red Rays. By E. LOMMEL (Ann. Phys. Chew. [2], 26, 157--158).-After alluding to the experiments of Tyndall on the incandescence of p€atiiium by the impact of the ultra- red rays transmitted through a solution of iodine in carbon bisulphide, the author shows that t h e effects of these rays can be rendered visible by means of the so-called luminous paints, inasmuch as these rays are emitted as a greenish-blue fluorescence, A solution of nigrosin in chloroform or alcohol is proposed as a substitute for iodine in carbon bisulphide as a perfectly opaque but diathermic medium.V. H. V. So-called Specific Remission, By W, RAMSAY and S. YOUSG (Ber., 18, 2855-2858) .-The authors, after alluding to their various papers on the elation between the pressure and boiling points of liquids (compare Abstr., 1885, 629, Trans., 1885, 640-657) point out the im- probability of the relation designated by Kahlbaum “specific remission ” (Abstr., 1884, 141, 900), and the sources of error iii his method of investigation. The authors’ results for the vapour-tensions of ethyl alcohol are in accordance with t’hose of Regnault, although the former mere obtained by the dynamical, the latter by the startical method, hut those of Kahlbaum are widely divergent from both, a d are mesumablv worthless.I # L In the equation -- = !!f (in which L is the latent heat of the s1 - sz d t r vapour, s1 its volume, sz the volume of the liquid, 9 the increase of d t pressure for each degree temperature, t the absolute temperature, and T the heat equivalent of the work), the authors propose to show that the values for -- are approximately constant for several liquids, L 81 - sz and further, t,hat the ratio 3 for two substances A and R a t pre i- dt T sure p1 is equal to that for t,he same substances at different pre;- Fjure p2 : that-is- for A a t p l = !?!for A at p z . dt T dt T for B atpl= *! for R atp2. dt T dt T or expressed in terms of absolute temperature, 3 at pl = 3 atp,. T B TI3 A list of substances is given for which this relation is valid.V. H. V. Modification of Bunsen’s Ice Calorimeter. By A. RL~~MCKE (Ann. Phys. Ckem. [a], 26, 159--160).-Two forms of Bunsen’s ice calorimeter are used ; in the one the heat, change is measured by the change of position of a, mercury thread along a graduated scale, whilstr, ABSTRACTS OF CHEMlCAL PAPERS. in the other the instrument is made into an inverted weight ther- mometer. Both these methods have relative advantages and dis- advantages; the latter is more exact, but requires a longer time, wlrilst the former requires an inordinately long scale. I n this paper au instrument is described, by which determinations by both methods can be conducted simultaneously. The experimental tube is closed with a caoutchouc plug, through which pass two pieces of quill tubing, each bent a t right angles and provided with stop-cocks, the limb of the one being graduated, the limb of the other being bent again a t right angles, and dipping under the surface of a weighed quantity of it iercury.Then by opening or closing the stop-cocks determinations are made both by the scale and the inverted weight-thermometer met hods. V. H. V. Phenols. By BERTHELOP (Compt. rend., 101, 687--690).- C)rthocresoZ.-Heat of solution at 11.4" = - 2.08 cal.; heat of neutralisation by Boda, first equivalent + 7.79 cal., second half- equivalent + 0.4 cal. = + 8.19 cal. Paracresol.--Heat of solution at 11.4" = - 2.13 cal.; heat of neutralisa.tion b.y soda, first equivalent + 7.64 cal., second half- equivalent + 0.43 = + 8.27 cal. The values obtained are very similar in the case of each isomeride, and they agree closely with those obtained with phenol.ThyrrzoZ.-The specimen employed was obtained from oil of thyme, and had been crystallised for thirty years When dissolved in sodium hydroxide solution, the heat developed is + 5.73 cal., a number very similar to that obtained with solid phenol and the solid cresols under the same conditions. It follows, therefore, that the heats of solution and neutralisation of thymol are practically the same as those of its homologues. Recently fused or precipitated specimens of thymol give cliff erent and non-concordant results, because thyrnol, like chloral hydrate, parts very slowly with its heat of fusion. a-Naphthol.-Solution in one equivalent of sodium hydroxide solu- tion develops + 2.S4 cal., and the addition of a second equivalent of alkali develops + 0.2 citl., giving for the algebraic sum of the heats of solution and neutralisation the value + 3.04 cal.The corresponding values for 6-ncvphthol are + 2.19 cal. and + 0.00 cal. = + 2.19 cal. Quinhydrone (green quinone), CBH40z.C6H1(0H)2.-Heat of solution of quinone a t 13" = - 3-77 cal., Werner having previously found - 4-23 cal. The mean value is - 4.00 cal. Heat of solution of quinol at 13" = 4.155 cal. Concentrated solutions of the two com- pounds were mixed, the heat developed was measured, and the amount of quinbydrone which separated was determined. Froni these data the following values were calculated :- C6H,0, diss. + C,H,(oH), dim. = C,,H,,04 diss. + 0.50 C6H,02 ,, + C,H,(OH), ,, = Cr2H,,04 cryst.+ 17.2 CsH402 cryst. + c,H,(OH), cryst. = CI,HIOOI 9 , + 9.0 One part of quinhpdrone dissolves in 300 parts of water a t 14". No thermal disturbance is produced by the addition of an alkali to anthraquinone, phenanthraquinone, phlorone, and similar compounds,GESERAL AND PHYSICAL CHEXISTRY. 7 SO that, in this respect these compounds differ from the true quinones. They are more probably analogous to acetone, allylene oxide, and similar oxy-deriva tives of hydrocarbons. A l i z a r i n when dissolved in one equivalent of sodium hydroxide solution develops + 5.15 cal ; the addition of a second equivalent of alkali develops + 0.64 cal., whilst a tbird equivalent produces no thermal disturbance. It follows that in very dilute solutions alizarin shows only one phenolic function towards alkalis.I n this respect it resembles catechol, pyrogallol, and siniilar compounds of the ortho- series, and hence it would follow that alizarin also belongs to the same series. C. H. B. Isomerism in the Benzene Series: Phenols of Complex Function. By BERTHELOT (Compt. rend., 101, 651-6.56) .-Para- nzethoxybenzoic Acid (anisic acid), MeO*Cs H ,*CO OH.-Heat of solution i n an equivalent quantity of sodium hydroxide solution = + 5.125 cal. ; hence, assuming the heat of neutralisation to be the same as that of parahydroxybenzoic acid, + 13.0 cal., the heat of solution in water is - 7.9 cal. The addition of a second equivalent of alkali causes no sensible further development of heat; hence ariisic acid has no phenolic function.This agrees with the commonly accepted con- stitution of this acid. alethy1 rS'aZicylate, HO.C,H,*COOkfe.-Heat of solution in one equivalent of alkali + 4.0 cal., in a second equivalent + 0.20 cal. The first value will differ but little from the heat of neutralisation in an aqueous solution, since the solution of one liquid in another is never accompanied by any considerable absorption of heat. The heat of neuti-alisation of this ethereal salt is therefore comparable with that. of a phenol of weak function. Phenylglycollic Acid (mandelic acid): HO*CHPh*COOH.-Heat of solution a t 18" = - 3.09 cal. The addition of half an equivalent of alkali develops + 6.74 cal., a second half-equivalent + 6.88 cal., and a third half-equivalent + 0.34 cal. It is therefore a monobasic acid without any phenolic function.VanilZin, OH*C6H,(OMe)*CH0 [4 : 3 : 11.-Heat of solution at 13.7" = - 5.20 cal. The first equivalent of alkali develops + 9.26 cal., a second cquivalent produces no thermal disturbance. Methylproto- catechuic aldehyde therefore behaves as a monhydric phenol. VuniZZic Acid, OH*C6H:3(OMe).COOH [4 : 3 : 11.-Heat of solution at 13.9" = - 5.16. The first equivalent of alkali develops + 12.64 cal., the second + 9.74 cal., and the third + 1-37 cal. This acid, therefore, behaves as a monobasic acid and a monhydric phenol, as the ordinary formula indicates. Similar experiments show that piperonal (methyleneprotocatechuic aldehyde), piperonylic acid, pjperic acid, veratric acid, anisaldehyde, anisyl alcohol, anisoil, anethoil, and salicin have no phenolic function.The first equivalent of soda develops + 5.77 cal., the second + 0-86 cal., and the third produces no thermal disturbance. Tolueneparasulphonic acid and sodium benzenesulphonate have no phenolic function. Eugenol, on the other hand, behaves as a monhydric phenol.8 ABSTRACTS OF CHEMICAL PAPERS. I n all these cases, there is complete agreement between the thermo- chemical data and the generally accepted constitution of the corn- pounds as deduced from their chemical behaviour. Acids of the Benzene Series. By BERTHELOT (Compt. rend., 101, C. H. B. 685--686).--MeZlitic Acid, C,(COOH),.-Hed of solution = + 3%i2 cal. at 20.4"; it is therefore a positive quantity, and differs in this respect from the heats of solution of the majority of highly oxidised carbon acids.The heat of neutraliaaiion by successive equivalents of sodium oxide is as follows :- 9 , ,, + 14.70 ,, z= -+ 44.30. 9 , 9 9 ,, + 12.90 ,, = + 39.13. Third ,, 9 9 ,, + 14.80 ,, } 7, 1 First equivalent (&Na20) develops + 14.80 cal. Second ,, 97 Fourth ,, ,, + 13-60 ,, Sixth ,, ,, + 12-63 ,, Fifth The mean value is + 13.90 x 6 cal., which is almost exactly the same as that of benzoic and phthalic acids. The last three equivalents of alkali develop somewhat less heat than the first three, and in bhis respect also mellitic acid is analogous to phthalic acid. Meconic Acid, C,H,O, + 3H20.-Heat of neutralisation at 12.7" - - - '3.10 cal. the first, second, third, and fourth equivalents of alkali are respec- tively + 14.4 cal., + 13.6 cal., + 8.7 cal., + 0.7 cal., and from these results, which are analogous to those obtained by Louguinine wit'h phosphoric acid, it follows that meconic acid is really bibasic, with an accessory function which is either analogous to or identical with the phenolic function.Acrylacetic Acid (tetric acid), CbH,O,.-Heat of solution a t 12.7" = - 3.9 cal., heat of neutralisation + 12.5 cal. A second equivalent of alkali produces no sensible thermal disturbance, and therefore acrylacetic acid is a monobasic acid of Bimple function. It is worthy of note that the heat of neutralisation of very niany organic acids of very varied constitution differs but little from the value + 13 cal. The quantities of heat developed by the addition of C. H. B. Liquid Atmospheric Air.By S. v. WROBLEWSHI (Ann. Phys. (?hem. [2], 26, 134--144).--In many of its properties, atmospheric air resembles a, perfectly homogeneous gas, and on compression it appears to the superficial observer to behave as a single gas, so that its critical pressure and temperature have been determined. But in this paper it is shown that the liquefaction of air is accompanied by various complex phenomena, resembling those noticed in the com- pression of a mixture of five volumes of carbonic anhydride with one of air. Thus if atmospheric air is compressed until the meniscus first formed disappears, and the pressure allowed to decrease slowly, there are produced two superposed menisci, separating heterogeneous fluids, in which the relative propqrtion of oxygen and nitrogen is different, the lower fluid containing about 213 per cent., the upper 17.5-18-5 per cent.oxygen. Secondly, the tension curves of atmo-GENERAL AND PHYSICAL CHEJIISTRT. 9 spheric air are not regular, inasmuch as on compression the tem- perature a t first sinks uniformly in proportion t o decrease of pressure, urltil a minimum point a t - l Y 8 O is reached ; on further compression the temperature begins to rise to a maximum at - 19tj0, and thence decreases. These irregularities of the tension curves show that the two constitutents of the air are not vaporised equally, and the tem- perature observed is dependent on the momentary composition of the fluid. V. H. V. Variation of Temperature of Maximum Density of Water with Pressure. By G. P.GRIMALDI (Gazzetta, 15, 297-302)- Puschl and Van der Waals have shown that if the Coefficient of compressibility of water decreases with increase of temperature, then the temperature of the maximum density of any liquid must decrease with increase of pressure. This point has been experimentally ob- served by Marshall, Smith and Ormond, and Tait. The last-named agree in assigning a decrease of one degree temperature for every increase of fifty atmospheres, whilst Van der Wads assigns a decrease of 3.24" under the same conditions. In this paper, it is pointed out that this value of Van der Waals is probably incorrect, inasmuch as it is based on wrong data of the coefficient of compressibility obtained by Grassi. V. H. V. Do Crystals grow only by Juxtaposition of New Molecules ? By L.WULFF (Zeit. Kryst. Min., 10, 374--389).-From his experi- ments the author concludes that in some cases at least this question must be answered in the negative. Rate of Decomposition of Ozone. By E. MULDER (Rec. Trav. Chim., 4, 135--146).-1n continuation of his experiments with the ozonometer described in a previous paper (Rec. Trac. Chim., 3, 137-- 157), the autbor finds that the rate of decomposition of ozone, in a mixture of ozone and oxygen, a t a given temperature, is directly pro- portional to the number of ozone molecules present, and that this rate increases rapidly with the temperature. Contact Actions in Dissociation. By D. KONOWALOW (Bey., 18, 2808-2833).- Wurtz in the course of investigation on vapour-den- sities found that in the case of amyl bromide, the time taken for ihe determination, other conditions remaining the same, affected the result.In a recent paper, the author in conjunction with Menschutkin observed that the nature of the substances with which the vapour came in contact influenced the degree of dissociation (Abstr., 1884, l l l Y ) , the phenomenon being very marked with fine asbestos. In this paper, the contact effect of various subst'ances on the degree of dis- sociafion of various amyl compounds is more fully examined, a slightly modified form of V. Meyer's vapour-density apparatus being used. Thus the contact of finely divided silica caused 53 per cent. of the rapour of tertiary amyl acetate to be dissocialed at the end of 40 minutes. Amongst other substances, the following were found to be active in inducing this dissociation : silics, barium and calcium sul- phates, animal charcoal, freshly cleaned platinum foil, glass wool and A.P.10 ABSTRACTS OF CHEJIICAL PAPERS. glass powder from broken Rupert's drops. With amyl chloride, not only the pressure, &c., to which the vapour was subjected, but also the nature of the glass of the containing vessel, affected the degree of the dissociation. As regards the former, the collected results show that the velocity of the decomposition increases with increased pressure up t o a certain point, a t or above which it is independent of the pressure. As an explanation of this contact, action phenomenon, it is asked whether it is not possible that the bombardment of the molecules on the solid matter causes the kinetic energy of the molecules to be transformed in part into the internal work required for their decomposition.However this may be, these phenomena herein de- tailed are analogous to those observed in the experiments of Faraday and Dulong, on the effect of finely divided substances in inducing the combination of hydrogen with oxygen, and other chemical changes. In an added note, the author meets the criticisms of V. Meyer and Pond, and points out the reasons for the unsuccessful repetition of the experiments described by himself and Menschutkin. Decomposition of Carbon Compounds by the Electric Spark. By A. PIZZARELLO (Gazzettn, 15, 233-238).-1n this paper, a dcscrip- tion is given of the decomposition of the vapours of various carbon compounds introduced into a Torricellian vacuum and subjected to a series of electric sparks.Thus under these conditions a given volume of methyl alcohol is tripled, owing to its resolution into car- bonic oxide and hydrogen, thus : CH,*OH = CO + 2H2 ; the presence of both these gases was indicated. Similarly ethyl ether yields carbonic oxide, acetylene and hydrogen, together with carbon deposited on the platinum wires or walls of the tube, whilst ethyl formate gives water in addition to the above- mentioned products. V. H. V. Dissociation of Salts containing Water, and Conclusions drawn therefrom as to the Constitution of the Salts. By W. M~LLER-ERZRACH (Chem. Centr., 1885, 470).-A continuation of the author's experiments in which the vapour-tension of the water in the salt is compared with that of pure water (Abstr., 1885, 952).In tlhe present paper, the following salts are investigated :-MgS04 + 7H20, relative tension at 18 = 0.34, after loss of 1 mol. H,O, relative tension = 0.009; NiSO, + 7H20 = relative tension 0.56, became inappre- ciable after loss of 1 mol. H20 ; CoSOa + 7H20 gave similar results ; FeSO, + 7H20 gave different results, according to the method of crystallisation, the normal results seemed to be relative tension at 18.5 = 0.36 ; after loss of 3 mol. H,O, inappreciable. ZnSO, + 7H20, relative tension a t 19.5" = 0.43 ; after loss of 5 mol. H,O, this fell to 0%4-0*18, and was inappreciable when a salt containing 1$ mol. H,O was arrived at. Relative tension of CuSOa + 5H20 at 17" = 0*04-0-05; of CuSO, + 3H20 = about 0.02; after long exposure over solid potash, a salt with 1% mol.H,O was left. Relative tension of MnSOa + 5H,O = 0.50 ; of MnSO, + 1&H,O = 0.003 ; of MnS0, + 1% H,O = 0 : of CaC1, + 6H10 = 0 12; of CnC12 + 4H,9 = 0.08; of CaC1, + 2H20 = 0*013-0~01i ; of CaC12 + H2O = 0 : of CoClz + V. H. V.GENERAL AKD PHYSICAL CHEJIISTRY. 11 Propionic acid. 6H,O = 0.20; of CoCI, + 4H20 = 0: of MnCl, + 4H,O = 0.18; of MnC13 + 2H20 = 0 : of NaRr + 2H20 = 0.27: of BaCl, + 2H20 = 0.035; of BaClz + H,O = 0.097. The author calls attention t o the peculiar behaviour of some ~ a l t s , in which there is a t first no loss of water, the tension then gradually rises until it attains its maximum. A. J. G. Diffusion of Fatty Alcohols and Acids. By A. WISKELMANN (A7in.Phys. Chem. [ Z ] , 26, 10t5-134).-This paper is an extension of the author's researches on the diffusion of homologous ethereal salts (Abstr., 1885, lo), and contains an account of similar experi- ments with the paraffinojid alcohols and fatty acids. Observations with formic and acetic acids show that the observed reciprocal values of the molecular path-lengths are concordant with those calculated from the results of the ethereal salts; but in the case of the higher acids the calculated and observed values are not thus concordant. In the course of the research, it was noticed that in order to obtain comparable results, i t was necessary to determine the tension of the vapour and its diffusion with equal quantities of the liquid. The following table contains the diffusion coefficients and the mean path-lengths (I X 10') i n centimetres a t 0" and 760 mm.Butyric acid. Acetic acid. Air ................ Hydrogen .......... Carbonic anhydride . . Mean path-length .... -_--- I-- ---- 0.1061 0.404 0.0713 29'7 ~- 0.8847 0 * 3333 0 * 0595 227 ---- 0.068 0 * 2639 0 * 0476 166 0'1325 0 * 0994 0'0803 0.0688 0.06R1 0.0385 0'0589 0 -0499 Isobutjric acid. -- 0 * 0'704 0'2713 0 * 0472 171 --- 0.5001 0*088 0 * 3806 0.0693 0'3153 0.0577 0.2771 0 *0483 0.2716 0.0476 0.234 0.0419 0.2351 0'0422 0.1998 0-0351 IsovaIeric acid. -- 0.0555 0*2118 0-0375 124 --- Similar determinations were made with the paraffinoid alcohols, and the deduced mean path-lengths of the molecules show considerable variation in the case of the higher alcohols, but with the lower these differences are more constant.Below are given some of the reduced results, the upper number giving that for air, the middle that for hydrogen, and the lower that for carbonic anhydride. Alcohol. Met,hyl ............ Propjl ............ Isobutpl ........... Normal b rity 1 . ...... Ferinentat,iori amyl . . Normal amyl ....... Normal hexyl.. ..... Ethyl. ............. Diffusion coefficient. Mean path -length (1 x 108). 361 259 203 168 164 137 139 11112 ABSTRACTS OF CHEMICAL PAPERS. t = 10'. t = 20". P- ~ d. c. [.ID. d. c. [ n ] ~ . 7- - --- - - -- 60 p. c. .. 1.274563'725 + 5.92" 1.26'7063.350 + 7.36' 40 ,, .. 1*211348*460 '7.63 1.2065 $8'260 8-95 30 ,, . , 1 -1535 34 -605 9- 16 1 -1495 34 '485 10 -41 20 ,, . . 1.09'75 21 -950 10.89 1 *0045 d l -890 11.99 In conclusion, the results obtained for molecular path-lengths by this diffusion method are compared with those by Meyer and Schumann's transpiration method (Abstr., 1881, 504) ; the latter gives values nearly double as great as the former.It is, how- ever, shown that the tendency of the transpiration method is to give excessive results, and the apparent discrepancy is further cleared up by mathematical reasoning. By T. THOMSEN (J. pr. Chem. [2], 32, 211-230).-0f the large number of substances which are now known to rotate the plane of polarisation of a ray of polarised light, sugar has been by far the most fnlly inves- tigated. The optical activity of such substances is expressed as the speci,fic rotation [a], which is calculated from the formula [a] V.H. V. Conditions of Equilibrium in Aqueous Solutions. -- - a'100 where a = the observed rotation, I the length of liquid I , c ' examined, and c the concentration (expressed in grams of active substance in 100 c.c.) of that liquid. If the liquid is a pure substance, c becomes 100 d, where d = sp. gr. (density compared with water at &) ; but i f , as in the present case, the liquid is a solution of the active substance, c becomes p . d where p = the percentage of active a 100 substance in the sclution, and the formula becomes [a] = ;-- The author points out. the unfortunate looseness with which this formula is often used ( p being, for instance, often confounded with c ) , and the fact that the kind of light used is often not stated, so that many determinations published are practically useless.For cane-sugar the specific rotation has been found to be [a]= = + 66.5", and this value is correct within narrow limits, whatever the temperature or concentration of the solution employed. But in the case of most other optically active substances, the specific rotary power varies, and even sometimes changes in direction with change of temperature and concentration of solution. In the case of tartaric acid, the effect of heat and concentration is very marked, and, further, the rotation is increased between three and four fold by the neutralisa- tion of the acid with an alkali. The author has taken advantage of this sensitiveness of tartaric acid in investigating the conditions of equilibrium in mixed solutions.He has observed the rotary power of 50, 40, 30, and 20 per cent. solutions of tartaric acid at the tempe- ratures lo", 20", SO", with the following results :- 1.p.d' t = 30'. d. c. - --- 1*260063'000 + 8-63 1*201548*060 10-11 1.1460 34.380 11 -44 1.0905 21'810 12 *95GENERAL AND PHYSICAL CHEBZISTKT. 13 t 5 20°. For each temperature, the variation curve for different degrees of concentration between 20 and 50 per cent,. forms a straight line, and the following formula may therefore be deduced :- t = 25'. [.IF = 14.154 - 0.16&~1 = - 2.286 + 01644q. 50 p. (2.. . . 40 ,, ... 30 ,, ... 20 ,, ... I.]? =: 15.050 - 0.1535~ = - 0.300 + 0.1535~. 5.93" '7 -58 9'22 10.87 [a]?= 15.784 - 0.1429~ = + 1.494 + 0 1 4 2 9 ~ . 7 -38' 8.91 10 * 45 11.98 The second set of formula are obtained from the first bp taking p = 100 -q, where q = the percentage of water in the solution.It should be noticed, that whilst the variation for concentration, within the above limits, is constant. the increase of specific rotation for a given pise of temperatare diminishes with increasing temperature. Taking this into account and using the above formulae, the author has calmlated the following more complete table :- 8.03' 9.51 10.99 12.47 Spec& Rotation [a]= of Tartaric Acid. p . 1 t = 10". --I-- t = 15". 6-67' 8.26 9 -85 11 *44 I-- -- t = 30". --- 8 -64' 10.07 11-50 12 -93 [.IF= 14.615 - 0.158813 = - 1.265 + 0.1588q. These results lie between those obtained by Krecke (Arch. Ne'er- landaise, 7, 102) and those by Arndtsen (Ann. Chini. Phys. [ 3 ] , 54, 411).The author finds that a solution of tartaric acid (50 per cent.) may be kept for months withont undergoing any optical change. Determinations of the rotary power of varying mixtures of tartaric and citric acids and water, tartaric and acetic acids and water, and tartaric and sulphuric acids and water were made. The results obtained lead to the conclusion that the two acids present appropriate water in the proportion in which they aye present, or, in other words, that the solution consists of a mixture of solutions of the two acids of equal strength. Thus, for instance, if 30 grams tartaric acid and 20 grams citric acid are dissolved iii 50 grams water, the tartaric acid will appropriake 30 grams, the citric 20 grams of this water, and the specific rotation of the tartaric acid will be that of a 50 per cent.1 4 ABSTkACTS OF CHEMICAL PAPERS.solution. Tn the case of sulphuric acid and tartaric acid, the former appears to be present in the shape of its hexahydrate, HsSO,. These results seem to show that from such observations, it will be possible to determine the state of hydration in which various substdances exist in solution. L. T. T. Molecular Movements. By G. KRGSS (Ber., 18, 2586-2591).- Although the kinetic theory of gases gives some account of the trans- lation of molecules through space, yet no satisfactory hypothesis has been brought forward to illustrate either the rotation of the molecules about their own axes, or the interatomic movements within the mole- cules. These two last the author classifies under the title of ‘‘ inner molecular movements.” Prom the undulatory theory of light, deduc- tions can be drawn regarding these molecular movements, inas- much as the vibration of the ether, which fills the intramolecular s p c e , is conditioned within that space by the velocity and amplitude of the molecular vibrations. Thus if X be the wave-length of a ray emitted by a substance, v the velocity of light, the number of vibra- tions, n, which a molecule sends forth by rnovements of it as a whole and of its parts, can be determined by the equation n =: x’ The phenomena of emission and of absorption spectra thus throws Some light on the least and most extensive form of this inner molecular movement. I n this paper, this latter point is discussed, together with its relation to the interatomic attraction, which is conditioned by the chemical constitution of the molecule ; inasmuch as vibrations of the particles of a body are capable of being excited only by vibrations of a like period in the external ether, so from the wave-lengths of those rays of light, which are absorbed to the greatest degree by the solution of any substance, the numher of the vibrations of the mole- cules within the liquid can be calculated from the equation above. These positions of greatest absorption for derivatives of indigo and fluoresce’in have previously been determined by the author (Abstr., 1883, 1042), and from the observations, resiilts are obtained for the maximum number of vibrations for billionths of a second.In a table are given the results for indigo, its paraffino’id-, bromo-, nitro-, and amido-derivatives, for rosolic acid and its tetrabromo-derivative? and for fluorescein and its potassiom, bromo-, nitro-, and paraffino’id-derivatives.From the numbers given, it follows that the molecule of a com- pound emits fewer vibrations per second, the greater the number of hydrogen-atoms, or! in the case of analogous replacements of the hydrogen-atoms, the zncrease or dewease of molecular vibrations i s pro- portiond to the number of hydrogen-atoms thus replaced. The results are in accordance with those deduced by Kellstab from experiments v. H. v. on the transpirability of homologous compounds. Simple Burner for Monochromatic Light. By NOACK (Chem. Centr., 1885, 497-498) .-Consists of a hydrogen evolving apparatus, jnto the cork of which is inserted the stem of a Bunsen burner made of glass, and a wire for lowering or raising a block of metallic zinc.The salt for producing the required light is dissolved in the acid. J. K. C.INORGAVLC CHEJIISTRY, 15 An Aspirator. By A. GAwAr,ovsKI (Chern. Centr., 1885, 465).- A description of an aspirator, consisting of two vessels, revolving on an axis, and so constructed that it can be used as an aspirator or respirator. P. P. B. New Apparatus for Chemical Laboratories. By A. KALEC- SINSZEY (Chem. Centr., 1885, 545--546).-To expel sulphuric acid in the course of analysis, the author employs a wide glass tube sealed at the lower and upper extremities, the upper end being driven inwards to receive a platinum crucible fitted in with asbestos, and having a smdl open tube inserted laterally.Through this tube sulphiaric acid is passed into the apparatus ; the tube is connected with ,z suitable condenser, heat applied, and the liquid contents of the platinum crucible speedily evaporate. The author also describes a simple appa- ratus for obtaining an air blast by means of air and water dropping into a large flask. J. K. C. By C. M. STUART (Chew. News, 5 2, 208) .--9 modification of the glass hood described by Hempel (Ber., 18, 143i), so arranged as t o be placed on every working bench. A Gas Regulator constructed without Metal. By H. SCRIFF (Rer., 18, 2833-2841).-The arrangement cannot well be described without a figure. Improved Method of Ventilating Laboratories.J O U R N A LOFTHE CHEMICAL SOCIETY,ABSTRACTS OF CHEMICAL PAPERS PUBLISHED INBRITISH AND FOREIGN JOURNALS.General and P h y s i c a l Chemistry.Spectroscopic Examination of the Constituents of the Atrno-sphere.By J. JANSSEN (COW@. rend., 101, 649--651).-At theMeudon Observatory, four absorption tubes, one of which is 60 metreslong, have been set up, and the absorption-spectra of hydrogen, air,and oxrgen have been examined, sometimes under high pressures.In the case of hydrogen, an enormous stratum of gas must be employedbefore any absorption-spectrum can be observed. When oxygen isexamined in the 60-metre tube under pradudly increasing pressure,mccessive groups of lines appear. The first are the lines and bandsin the red, which Egoroff regards as identical with the lines A and Bin the solar spectrum, but if the pressure is raised beyond 27 atmos.,and the intensity of the light employed is increased, evidences ofabsorption are obtained between A and B, and bettween B and C, butstill higher pressures are necessary before the existence of absorption-bands in these positions can be definitely established.At rery highpressures, three other bands become visible, one in the red near OC, onein the greenish-yellow near D, and one in the blue. No similarbands are known in the solar spectrum. C. H. B.Optical Properties of Malic and Tartaric Acids. By L. BELL(Amer. Chem. J., 7, 120--128).-Both tartaric and malic acids showan increase oE optical activity with a rise in temperature, or with adecrease of concentration, and in the case of I ~ ~ ~ o - n ~ a l i c and dextro-tartaric acids, the sign of polarisation is reversed i f solutions suffi-ciently strong and cold are examined.From thermic observationsit seetiis that this change of rotary power cannot be accounted foreither by the supposition of changes of confignration of the molecule,or nf the formation of hydrates, or of the formation of crystal mole-cules. It is, however, thought that the change is due to the formn-tion of polymerides, which are gradually decomposed by dilution orVOL. L. 2 ABSTRACTS OF CHEMICAL PAPERS.application of heat ; in dilute solutions, the changes effected by rarin-tion are but slight when compared with those in strong solutions,where one must expect the polymeride to exist in comparatively largeproportion. A further proof of the formation of polymerides is the factthat the solutions show abnormal rotary dispersion-a phenomenonnot possible with the solution of a single substance-and this may begradually made normal by dilution or by heating.Tartaric and malic acids both exist in more forms than can beaccounted for on any existing theory; this may possibly be explainedby the observation that two molecules of a substance containing anasymmetrical carbon-atom may be symmetrically united in fourdifferent ways.H. B.Sensitiveness t o Light of Selenium and Sulphur Cells. ByS. BIDWELL (Chem. News, 52, 191--193).-With regard to the actionof light in diminishing the electrical resistance of selenium, and pro-ducing in it a photo-electric current, Adams and Day have observedthat in such mses the structure of the selenium is so modified that itbehaves apparently like an electrolyte, and hence conclude thatselenium, under those conditions, conducts electrolytically.I n the present paper, the author attributes these phenomena to actualelectrolysis, and bases this assertion on the following facts.It is known that in making seleaium “ cells,” the longer they are“ annealed ” (that is, heated i n contact with the metallic electrodes)the more sensitive the selenium becomes to the action of light.Again,a very sensitive selenium “ cell ” has been constructed by Fritts, in thefollowing manner :-A film of selenium is melted on R plate of metalwith which it can combine, and ultimately the other surface is coatedwit,h a transparent conductor.Moreover, a piece of selenium con-tained in a good “ cell ” with.copper electrodes indicated a specificresistance = 0.9 megohm, whilst the resistance of a similar piece ofselenium annealed in a glass mould out of contact with metal= 2500 megohms. The author infers that a selenide is formed duringthe heating with the metal, and that the sensitiveness is due to thepresence of the selenide and its electrolysis by the current. Tocomplete the chain of experimental evidence, sulphur, which hashitherto resisted numerous attempts to develop in i t the sensitivenessto light so characteristic of selenium, was mixed with silver sol-phide, and incorporated in a “ cell ” with silver electrodes ; it thenexhibited remarkable sensitiveness to light, and its resistance wasgreatly reduced by it.Numerous experiments are described proviiigthis effect to be due to the direct action of radiation, and not simplyt o R rise in the temperature, by which this sulphur “cell ” is affectedjn a similar manner. Electrolytically considered, the action in thesulphur ‘‘ cell ” containing silver sulphide and silver electrodes is this :when the current passes, silver is deposited upon the cathode andsulphur upon the anode, but any sulphur deposited on the anodewould stop the current, an occurrence which is prevented by the silvercombining w i t h the sulphur, hence the quantity of electricity passingjs regulated by the quantity of sulphur disposed of in this manner.By.replacing one of the silver electrodes by a metal which does rioGENERAL AND PHYSICAL CHEMISTRY. 3combine so readily with sulphur, iron for instance, then on theabove hypothesis, when iron is the anode the resistance ought tobe greater than when silver is the anode, and such is the case inactual experimcnt, the resistance being 30 times greater in theformer than i t is in the latter case. Other experiments show thatlight assists the direct combination of silver and sulphur, and it isinferred that “the electrolysis of silver sulphide may be assisted bylight, and its electrolytic resistance a t the same time diminished.”I n a few experiments made with sulphur “ cells ” containing copperand copper sulphide, there was no indication of sensitiveness to light.With regard to the effect of temperature on selenium “ cells,”the auhhor has observed that whether exposed to light or not,selenium “ cells ” have a temperature of maximum resistance, whichis generally a few degrees higher than the average temperature of theair.D. A. L.Dry Electric Batteries. By W. v. BEETZ (Ann. Phys. Chem. [2],26, 13--26).-This paper contains a series of determinations of theelectromotive force of certain dry forms of Dnniell’s battery,especially of those consisting of U-tubes containing in the one limbcopper sulphate solution, in the other zinc sulphate solution, bothbeing xorked u p into a paste by plaster of Paris, and then allowedto set in the tnbes.Their use as an unit in electric measurementswas examined ; it was found that in some cases the difference of poten-tial remained constant, whilst. in others i t decreased very rapidly.Such batteries cannot be used in electro-therapeutics.V. H. V.New Forms of Thermopiles. By H. KAPSER (Ann. Phys. Chem.[2], 26, 9--13).--In this paper, measurements are given of theelectromotive forces and resistances of various forms of thermopiles,tlhe source of heat being a gas flame burning a known number oflitres of gas per honr. The electromotive force of a NoG-Rebiceck’sthermoelectric pile of 20 elements was found to be constant, for anindefinite lengt,h of time, provided that the external conditions,namely, gas pressure and temperature of the air, were unaltered ; itselectromotive force also exceeded that of a Bunsen’s element.Theinternal resistance increased to a maximum, with a consumption ofgas from 0-60 litres per hour, and from that point to 110 litres perhour it diminished ; the maximum resistance of a pile of 25 elementswas 0.868 ohm. The relative advantages of a thermopile over a,Bunsen’s element in cases of small external resistance are also dis-cussed. V. H. V.Electrical Conductivity of Air under Reduced Pressure. By T. HOMPN (Ann. Phys. Chenz. [ Z ] , 26, 55--81).-Experiments on therelation of the conductivity of air to the pressure, have led to theopposed conclusions that an absolute vacuum is a perfect non-con-ductor, and a good conductor of electricity.In this paper, an elabo-rate series of experiments on the conductivity of air in dischargetubes under various degrees of pressure are described. The resultsshow that the phenomena of conductivity of air under reducedb 4 ABSTRACTS OF CHEMICAL PAPERS.pressure are of two kinds, the one, the particulw resistance of the air,which is proportional to the distance between the electrodes, theother the actual resistance of the electrodes themselves. The formeri s independent of the diameter of the air column, and its increase isnearly proportional to the pressure, whilst the latter increases veryquickly with decrease of pressure, and under low pressures reachesa point at which the resistance is such that electricity, even at thehighest difference of potentiaJ, cannot overcome it, These results arenot in accordance with the view that a vacuum is a good conductorof electricity. V.H. V.Electrical Conductivity of Alcohol. By E. PFEIFFER (Ann.Pliys. Chenz. [el, 26, 31-44).-1n this paper a description is givenof determinations of the Conductivity of absolute alcohol, and thernrintions produced by change of condition. The lowest value forrecently distilled alcohol was 0.1261 x 10-10 ohms in ternis ofmercury as the unit. The relative conductivity is increased by thepresence of traces of impurities, but decreased to a considerableextent by the absorption of air.; it decreases, as that of metals, withrise of temperature, until a point is reached a t which the influence oftemperature is nil.The author proposes to call this point ” the pointof indifference.” Comparing the temperature coe5cient, or the ratioof decrease of conductivity, with r i s e of temperature = ?!! of alcoholwith that of the mehals, it is found that the former is to the latter inthe ratio 0*OG87 to 0.0037. V, H. V.k0Electrical Properties of Salt Solutions. By J. MOSER(Xonatsh. Chem., 6, 634-638) .-The author has previously investi-gated the electromotive force of cells in which the total amount ofpurely chemical reacttion is reduced t o a minimum, the current beingconditioned by the minor molecular attractions of a salt with thewater in which it is dissolved ; such, for example, is the combinationFrom these experi-ments Helmholtz determined the relation between the E.M.F., thevapour-tension of the salt solution, and the tmn+ference-uaZues of theions (compare Faraday lecture, Trans., 1881, 299), so that if two ofthese values were known the third could be calculated. By the experi-mental elimination of the third factor, the relation could be determinedbetween the E.M.F., conditioned by difference of concentration andthe vapour-tension.Then, if the theories of Helmholtz are com-patible in the two cases stated above, the transference-value should bethe quotient of the E.SLF.’s, with and without a possible transferenceof the ions.I n the paper this point is examined and found to be in accordancewith the thtiory.There is also mentioned a case of electro-neutrality of a combina-tion Zn I ZnC1, I ZnSOi I Zn, in which the solutions were of .such a.degree of concentration thatj the addition of water to either of themproduced a current with concomitant transference of the ions.Attention is also drawn to the fact that the E.M.F., produced byI Zn I dilute ZnSOa I concentrated ZnSOd I ZnGENERAL AND PHYSICAL CHEMISTRY.ndifferences of concentration, does not correspond with the heat changeson dilution. V. H. V.Incandescence by Ultra-red Rays. By E. LOMMEL (Ann. Phys.Chew. [2], 26, 157--158).-After alluding to the experiments ofTyndall on the incandescence of p€atiiium by the impact of the ultra-red rays transmitted through a solution of iodine in carbon bisulphide,the author shows that t h e effects of these rays can be rendered visibleby means of the so-called luminous paints, inasmuch as these rays areemitted as a greenish-blue fluorescence, A solution of nigrosin inchloroform or alcohol is proposed as a substitute for iodine in carbonbisulphide as a perfectly opaque but diathermic medium.V.H. V.So-called Specific Remission, By W, RAMSAY and S. YOUSG(Ber., 18, 2855-2858) .-The authors, after alluding to their variouspapers on the elation between the pressure and boiling points of liquids(compare Abstr., 1885, 629, Trans., 1885, 640-657) point out the im-probability of the relation designated by Kahlbaum “specific remission ”(Abstr., 1884, 141, 900), and the sources of error iii his method ofinvestigation. The authors’ results for the vapour-tensions of ethylalcohol are in accordance with t’hose of Regnault, although theformer mere obtained by the dynamical, the latter by the starticalmethod, hut those of Kahlbaum are widely divergent from both, a dare mesumablv worthless.I # L In the equation -- = !!f (in which L is the latent heat of thes1 - sz d t rvapour, s1 its volume, sz the volume of the liquid, 9 the increase ofd tpressure for each degree temperature, t the absolute temperature, andT the heat equivalent of the work), the authors propose to show thatthe values for -- are approximately constant for several liquids, L81 - szand further, t,hat the ratio 3 for two substances A and R a t pre i- dt Tsure p1 is equal to that for t,he same substances at different pre;-Fjure p2 : that-is-for A a t p l = !?!for A at p z .dt T dt Tfor B atpl= *! for R atp2.dt T dt Tor expressed in terms of absolute temperature, 3 at pl = 3 atp,.T B TI3A list of substances is given for which this relation is valid.V.H. V.Modification of Bunsen’s Ice Calorimeter. By A. RL~~MCKE(Ann. Phys. Ckem. [a], 26, 159--160).-Two forms of Bunsen’s icecalorimeter are used ; in the one the heat, change is measured by thechange of position of a, mercury thread along a graduated scale, whilsr, ABSTRACTS OF CHEMlCAL PAPERS.in the other the instrument is made into an inverted weight ther-mometer. Both these methods have relative advantages and dis-advantages; the latter is more exact, but requires a longer time,wlrilst the former requires an inordinately long scale.I n this paperau instrument is described, by which determinations by both methodscan be conducted simultaneously. The experimental tube is closedwith a caoutchouc plug, through which pass two pieces of quill tubing,each bent a t right angles and provided with stop-cocks, the limb ofthe one being graduated, the limb of the other being bent again a tright angles, and dipping under the surface of a weighed quantity ofit iercury. Then by opening or closing the stop-cocks determinationsare made both by the scale and the inverted weight-thermometermet hods. V. H. V.Phenols. By BERTHELOP (Compt. rend., 101, 687--690).-C)rthocresoZ.-Heat of solution at 11.4" = - 2.08 cal.; heat ofneutralisation by Boda, first equivalent + 7.79 cal., second half-equivalent + 0.4 cal. = + 8.19 cal.Paracresol.--Heat of solution at 11.4" = - 2.13 cal.; heat ofneutralisa.tion b.y soda, first equivalent + 7.64 cal., second half-equivalent + 0.43 = + 8.27 cal.The values obtained are very similar in the case of each isomeride,and they agree closely with those obtained with phenol.ThyrrzoZ.-The specimen employed was obtained from oil of thyme,and had been crystallised for thirty years When dissolved in sodiumhydroxide solution, the heat developed is + 5.73 cal., a number verysimilar to that obtained with solid phenol and the solid cresols underthe same conditions.It follows, therefore, that the heats of solutionand neutralisation of thymol are practically the same as those of itshomologues. Recently fused or precipitated specimens of thymol givecliff erent and non-concordant results, because thyrnol, like chloralhydrate, parts very slowly with its heat of fusion.a-Naphthol.-Solution in one equivalent of sodium hydroxide solu-tion develops + 2.S4 cal., and the addition of a second equivalent ofalkali develops + 0.2 citl., giving for the algebraic sum of the heats ofsolution and neutralisation the value + 3.04 cal.The correspondingvalues for 6-ncvphthol are + 2.19 cal. and + 0.00 cal. = + 2.19 cal.Quinhydrone (green quinone), CBH40z.C6H1(0H)2.-Heat of solutionof quinone a t 13" = - 3-77 cal., Werner having previously found - 4-23 cal. The mean value is - 4.00 cal. Heat of solution ofquinol at 13" = 4.155 cal. Concentrated solutions of the two com-pounds were mixed, the heat developed was measured, and the amountof quinbydrone which separated was determined. Froni these datathe following values were calculated :-C6H,0, diss. + C,H,(oH), dim.= C,,H,,04 diss. + 0.50C6H,02 ,, + C,H,(OH), ,, = Cr2H,,04 cryst. + 17.2CsH402 cryst. + c,H,(OH), cryst. = CI,HIOOI 9 , + 9.0One part of quinhpdrone dissolves in 300 parts of water a t 14".No thermal disturbance is produced by the addition of an alkali toanthraquinone, phenanthraquinone, phlorone, and similar compoundsGESERAL AND PHYSICAL CHEXISTRY. 7SO that, in this respect these compounds differ from the true quinones.They are more probably analogous to acetone, allylene oxide, andsimilar oxy-deriva tives of hydrocarbons.A l i z a r i n when dissolved in one equivalent of sodium hydroxidesolution develops + 5.15 cal ; the addition of a second equivalent ofalkali develops + 0.64 cal., whilst a tbird equivalent produces nothermal disturbance.It follows that in very dilute solutions alizarinshows only one phenolic function towards alkalis. I n this respect itresembles catechol, pyrogallol, and siniilar compounds of the ortho-series, and hence it would follow that alizarin also belongs to thesame series. C. H. B.Isomerism in the Benzene Series: Phenols of ComplexFunction. By BERTHELOT (Compt. rend., 101, 651-6.56) .-Para-nzethoxybenzoic Acid (anisic acid), MeO*Cs H ,*CO OH.-Heat of solutioni n an equivalent quantity of sodium hydroxide solution = + 5.125 cal. ;hence, assuming the heat of neutralisation to be the same as that ofparahydroxybenzoic acid, + 13.0 cal., the heat of solution in water is - 7.9 cal.The addition of a second equivalent of alkali causesno sensible further development of heat; hence ariisic acid has nophenolic function. This agrees with the commonly accepted con-stitution of this acid.alethy1 rS'aZicylate, HO.C,H,*COOkfe.-Heat of solution in oneequivalent of alkali + 4.0 cal., in a second equivalent + 0.20 cal.The first value will differ but little from the heat of neutralisation inan aqueous solution, since the solution of one liquid in another isnever accompanied by any considerable absorption of heat. The heatof neuti-alisation of this ethereal salt is therefore comparable with that.of a phenol of weak function.Phenylglycollic Acid (mandelic acid): HO*CHPh*COOH.-Heat ofsolution a t 18" = - 3.09 cal.The addition of half an equivalent ofalkali develops + 6.74 cal., a second half-equivalent + 6.88 cal.,and a third half-equivalent + 0.34 cal. It is therefore a monobasicacid without any phenolic function.VanilZin, OH*C6H,(OMe)*CH0 [4 : 3 : 11.-Heat of solution at13.7" = - 5.20 cal. The first equivalent of alkali develops + 9.26 cal.,a second cquivalent produces no thermal disturbance. Methylproto-catechuic aldehyde therefore behaves as a monhydric phenol.VuniZZic Acid, OH*C6H:3(OMe).COOH [4 : 3 : 11.-Heat of solution at13.9" = - 5.16. The first equivalent of alkali develops + 12.64cal., the second + 9.74 cal., and the third + 1-37 cal.This acid,therefore, behaves as a monobasic acid and a monhydric phenol, asthe ordinary formula indicates.Similar experiments show that piperonal (methyleneprotocatechuicaldehyde), piperonylic acid, pjperic acid, veratric acid, anisaldehyde,anisyl alcohol, anisoil, anethoil, and salicin have no phenolic function.Thefirst equivalent of soda develops + 5.77 cal., the second + 0-86 cal.,and the third produces no thermal disturbance.Tolueneparasulphonic acid and sodium benzenesulphonate have nophenolic function.Eugenol, on the other hand, behaves as a monhydric phenol8 ABSTRACTS OF CHEMICAL PAPERS.I n all these cases, there is complete agreement between the thermo-chemical data and the generally accepted constitution of the corn-pounds as deduced from their chemical behaviour.Acids of the Benzene Series.By BERTHELOT (Compt. rend., 101,C. H. B.685--686).--MeZlitic Acid, C,(COOH),.-Hed of solution = + 3%i2cal. at 20.4"; it is therefore a positive quantity, and differs in thisrespect from the heats of solution of the majority of highly oxidisedcarbon acids. The heat of neutraliaaiion by successive equivalents ofsodium oxide is as follows :-9 , ,, + 14.70 ,, z= -+ 44.30.9 , 9 9 ,, + 12.90 ,, = + 39.13.Third ,, 9 9 ,, + 14.80 ,, }7, 1First equivalent (&Na20) develops + 14.80 cal.Second ,,97 Fourth ,, ,, + 13-60 ,,Sixth ,, ,, + 12-63 ,,FifthThe mean value is + 13.90 x 6 cal., which is almost exactly thesame as that of benzoic and phthalic acids. The last three equivalentsof alkali develop somewhat less heat than the first three, and in bhisrespect also mellitic acid is analogous to phthalic acid.Meconic Acid, C,H,O, + 3H20.-Heat of neutralisation at 12.7" - - - '3.10 cal.the first, second, third, and fourth equivalents of alkali are respec-tively + 14.4 cal., + 13.6 cal., + 8.7 cal., + 0.7 cal., and from theseresults, which are analogous to those obtained by Louguinine wit'hphosphoric acid, it follows that meconic acid is really bibasic, with anaccessory function which is either analogous to or identical with thephenolic function.Acrylacetic Acid (tetric acid), CbH,O,.-Heat of solution a t 12.7"= - 3.9 cal., heat of neutralisation + 12.5 cal.A second equivalentof alkali produces no sensible thermal disturbance, and thereforeacrylacetic acid is a monobasic acid of Bimple function.It is worthy of note that the heat of neutralisation of very nianyorganic acids of very varied constitution differs but little from thevalue + 13 cal.The quantities of heat developed by the addition ofC. H.B.Liquid Atmospheric Air. By S. v. WROBLEWSHI (Ann. Phys.(?hem. [2], 26, 134--144).--In many of its properties, atmosphericair resembles a, perfectly homogeneous gas, and on compression itappears to the superficial observer to behave as a single gas, so thatits critical pressure and temperature have been determined. But inthis paper it is shown that the liquefaction of air is accompanied byvarious complex phenomena, resembling those noticed in the com-pression of a mixture of five volumes of carbonic anhydride with oneof air.Thus if atmospheric air is compressed until the meniscusfirst formed disappears, and the pressure allowed to decrease slowly,there are produced two superposed menisci, separating heterogeneousfluids, in which the relative propqrtion of oxygen and nitrogen isdifferent, the lower fluid containing about 213 per cent., the upper17.5-18-5 per cent. oxygen. Secondly, the tension curves of atmoGENERAL AND PHYSICAL CHEJIISTRT. 9spheric air are not regular, inasmuch as on compression the tem-perature a t first sinks uniformly in proportion t o decrease of pressure,urltil a minimum point a t - l Y 8 O is reached ; on further compressionthe temperature begins to rise to a maximum at - 19tj0, and thencedecreases.These irregularities of the tension curves show that thetwo constitutents of the air are not vaporised equally, and the tem-perature observed is dependent on the momentary composition ofthe fluid. V. H. V.Variation of Temperature of Maximum Density of Waterwith Pressure. By G. P. GRIMALDI (Gazzetta, 15, 297-302)-Puschl and Van der Waals have shown that if the Coefficient ofcompressibility of water decreases with increase of temperature, thenthe temperature of the maximum density of any liquid must decreasewith increase of pressure. This point has been experimentally ob-served by Marshall, Smith and Ormond, and Tait. The last-namedagree in assigning a decrease of one degree temperature for everyincrease of fifty atmospheres, whilst Van der Wads assigns a decreaseof 3.24" under the same conditions.In this paper, it is pointed outthat this value of Van der Waals is probably incorrect, inasmuch asit is based on wrong data of the coefficient of compressibility obtainedby Grassi. V. H. V.Do Crystals grow only by Juxtaposition of New Molecules ?By L. WULFF (Zeit. Kryst. Min., 10, 374--389).-From his experi-ments the author concludes that in some cases at least this questionmust be answered in the negative.Rate of Decomposition of Ozone. By E. MULDER (Rec. Trav.Chim., 4, 135--146).-1n continuation of his experiments with theozonometer described in a previous paper (Rec. Trac. Chim., 3, 137--157), the autbor finds that the rate of decomposition of ozone, in amixture of ozone and oxygen, a t a given temperature, is directly pro-portional to the number of ozone molecules present, and that this rateincreases rapidly with the temperature.Contact Actions in Dissociation.By D. KONOWALOW (Bey., 18,2808-2833).- Wurtz in the course of investigation on vapour-den-sities found that in the case of amyl bromide, the time taken for ihedetermination, other conditions remaining the same, affected theresult. In a recent paper, the author in conjunction with Menschutkinobserved that the nature of the substances with which the vapourcame in contact influenced the degree of dissociation (Abstr., 1884,l l l Y ) , the phenomenon being very marked with fine asbestos. Inthis paper, the contact effect of various subst'ances on the degree of dis-sociafion of various amyl compounds is more fully examined, a slightlymodified form of V.Meyer's vapour-density apparatus being used.Thus the contact of finely divided silica caused 53 per cent. of therapour of tertiary amyl acetate to be dissocialed at the end of 40minutes. Amongst other substances, the following were found to beactive in inducing this dissociation : silics, barium and calcium sul-phates, animal charcoal, freshly cleaned platinum foil, glass wool andA. P10 ABSTRACTS OF CHEJIICAL PAPERS.glass powder from broken Rupert's drops. With amyl chloride, notonly the pressure, &c., to which the vapour was subjected, but also thenature of the glass of the containing vessel, affected the degree of thedissociation. As regards the former, the collected results show thatthe velocity of the decomposition increases with increased pressure upt o a certain point, a t or above which it is independent of the pressure.As an explanation of this contact, action phenomenon, it is askedwhether it is not possible that the bombardment of the moleculeson the solid matter causes the kinetic energy of the molecules tobe transformed in part into the internal work required for theirdecomposition. However this may be, these phenomena herein de-tailed are analogous to those observed in the experiments of Faradayand Dulong, on the effect of finely divided substances in inducing thecombination of hydrogen with oxygen, and other chemical changes.In an added note, the author meets the criticisms of V.Meyer andPond, and points out the reasons for the unsuccessful repetition ofthe experiments described by himself and Menschutkin.Decomposition of Carbon Compounds by the Electric Spark.By A. PIZZARELLO (Gazzettn, 15, 233-238).-1n this paper, a dcscrip-tion is given of the decomposition of the vapours of various carboncompounds introduced into a Torricellian vacuum and subjected toa series of electric sparks. Thus under these conditions a givenvolume of methyl alcohol is tripled, owing to its resolution into car-bonic oxide and hydrogen, thus : CH,*OH = CO + 2H2 ; the presenceof both these gases was indicated.Similarly ethyl ether yields carbonic oxide, acetylene and hydrogen,together with carbon deposited on the platinum wires or walls of thetube, whilst ethyl formate gives water in addition to the above-mentioned products.V. H. V.Dissociation of Salts containing Water, and Conclusionsdrawn therefrom as to the Constitution of the Salts. By W.M~LLER-ERZRACH (Chem. Centr., 1885, 470).-A continuation of theauthor's experiments in which the vapour-tension of the water in thesalt is compared with that of pure water (Abstr., 1885, 952). In tlhepresent paper, the following salts are investigated :-MgS04 + 7H20,relative tension at 18 = 0.34, after loss of 1 mol. H,O, relative tension= 0.009; NiSO, + 7H20 = relative tension 0.56, became inappre-ciable after loss of 1 mol. H20 ; CoSOa + 7H20 gave similar results ;FeSO, + 7H20 gave different results, according to the method ofcrystallisation, the normal results seemed to be relative tension at18.5 = 0.36 ; after loss of 3 mol.H,O, inappreciable. ZnSO, + 7H20,relative tension a t 19.5" = 0.43 ; after loss of 5 mol. H,O, this fell to0%4-0*18, and was inappreciable when a salt containing 1$ mol.H,O was arrived at. Relative tension of CuSOa + 5H20 at 17" =0*04-0-05; of CuSO, + 3H20 = about 0.02; after long exposureover solid potash, a salt with 1% mol. H,O was left. Relative tensionof MnSOa + 5H,O = 0.50 ; of MnSO, + 1&H,O = 0.003 ; of MnS0, +1% H,O = 0 : of CaC1, + 6H10 = 0 12; of CnC12 + 4H,9 = 0.08;of CaC1, + 2H20 = 0*013-0~01i ; of CaC12 + H2O = 0 : of CoClz +V. H. VGENERAL AKD PHYSICAL CHEJIISTRY.11Propionicacid.6H,O = 0.20; of CoCI, + 4H20 = 0: of MnCl, + 4H,O = 0.18; ofMnC13 + 2H20 = 0 : of NaRr + 2H20 = 0.27: of BaCl, + 2H20 =0.035; of BaClz + H,O = 0.097. The author calls attention t o thepeculiar behaviour of some ~ a l t s , in which there is a t first no loss ofwater, the tension then gradually rises until it attains its maximum.A. J. G.Diffusion of Fatty Alcohols and Acids. By A. WISKELMANN(A7in. Phys. Chem. [ Z ] , 26, 10t5-134).-This paper is an extensionof the author's researches on the diffusion of homologous etherealsalts (Abstr., 1885, lo), and contains an account of similar experi-ments with the paraffinojid alcohols and fatty acids. Observationswith formic and acetic acids show that the observed reciprocal valuesof the molecular path-lengths are concordant with those calculatedfrom the results of the ethereal salts; but in the case of the higheracids the calculated and observed values are not thus concordant.Inthe course of the research, it was noticed that in order to obtaincomparable results, i t was necessary to determine the tension of thevapour and its diffusion with equal quantities of the liquid.The following table contains the diffusion coefficients and the meanpath-lengths (I X 10') i n centimetres a t 0" and 760 mm.Butyricacid.Aceticacid.Air ................Hydrogen ..........Carbonic anhydride . .Mean path-length ....-_---I-- ----0.10610.4040.071329'7~-0.88470 * 33330 * 0595227----0.0680 * 26390 * 04761660'13250 * 09940'08030.06880.06R10.03850'05890 -0499Isobutjricacid.--0 * 0'7040'27130 * 0472171---0.5001 0*0880 * 3806 0.06930'3153 0.05770.2771 0 *04830.2716 0.04760.234 0.04190.2351 0'04220.1998 0-0351IsovaIericacid.--0.05550*21180-0375124---Similar determinations were made with the paraffinoid alcohols,and the deduced mean path-lengths of the molecules show considerablevariation in the case of the higher alcohols, but with the lower thesedifferences are more constant. Below are given some of the reducedresults, the upper number giving that for air, the middle that forhydrogen, and the lower that for carbonic anhydride.Alcohol.Met,hyl ............Propjl ............Isobutpl ...........Normal b rity 1 .......Ferinentat,iori amyl . .Normal amyl .......Normal hexyl.. .....Ethyl. .............Diffusion coefficient.Mean path -length(1 x 108).3612592031681641371391112 ABSTRACTS OF CHEMICAL PAPERS.t = 10'. t = 20".P- ~d. c. [.ID. d. c. [ n ] ~ .7- - --- - - --60 p. c. .. 1.274563'725 + 5.92" 1.26'7063.350 + 7.36'40 ,, .. 1*211348*460 '7.63 1.2065 $8'260 8-9530 ,, . , 1 -1535 34 -605 9- 16 1 -1495 34 '485 10 -4120 ,, . . 1.09'75 21 -950 10.89 1 *0045 d l -890 11.99In conclusion, the results obtained for molecular path-lengthsby this diffusion method are compared with those by Meyer andSchumann's transpiration method (Abstr., 1881, 504) ; the lattergives values nearly double as great as the former. It is, how-ever, shown that the tendency of the transpiration method is to giveexcessive results, and the apparent discrepancy is further cleared upby mathematical reasoning.By T.THOMSEN (J.pr. Chem. [2], 32, 211-230).-0f the large number ofsubstances which are now known to rotate the plane of polarisationof a ray of polarised light, sugar has been by far the most fnlly inves-tigated. The optical activity of such substances is expressed asthe speci,fic rotation [a], which is calculated from the formula [a]V. H. V.Conditions of Equilibrium in Aqueous Solutions.-- - a'100 where a = the observed rotation, I the length of liquidI , c 'examined, and c the concentration (expressed in grams of activesubstance in 100 c.c.) of that liquid.If the liquid is a pure substance,c becomes 100 d, where d = sp. gr. (density compared with waterat &) ; but i f , as in the present case, the liquid is a solution of theactive substance, c becomes p . d where p = the percentage of activea 100 substance in the sclution, and the formula becomes [a] = ;--The author points out. the unfortunate looseness with which thisformula is often used ( p being, for instance, often confounded with c ) ,and the fact that the kind of light used is often not stated, so thatmany determinations published are practically useless.For cane-sugar the specific rotation has been found to be [a]== + 66.5", and this value is correct within narrow limits, whateverthe temperature or concentration of the solution employed.But inthe case of most other optically active substances, the specific rotarypower varies, and even sometimes changes in direction with changeof temperature and concentration of solution. In the case of tartaricacid, the effect of heat and concentration is very marked, and, further,the rotation is increased between three and four fold by the neutralisa-tion of the acid with an alkali. The author has taken advantage ofthis sensitiveness of tartaric acid in investigating the conditions ofequilibrium in mixed solutions. He has observed the rotary power of50, 40, 30, and 20 per cent. solutions of tartaric acid at the tempe-ratures lo", 20", SO", with the following results :-1.p.d't = 30'.d. c. - ---1*260063'000 + 8-631*201548*060 10-111.1460 34.380 11 -441.0905 21'810 12 *9GENERAL AND PHYSICAL CHEBZISTKT.13t 5 20°.For each temperature, the variation curve for different degrees ofconcentration between 20 and 50 per cent,. forms a straight line, andthe following formula may therefore be deduced :-t = 25'.[.IF = 14.154 - 0.16&~1 = - 2.286 + 01644q.50 p. (2.. . .40 ,, ...30 ,, ...20 ,, ...I.]? =: 15.050 - 0.1535~ = - 0.300 + 0.1535~.5.93"'7 -589'2210.87[a]?= 15.784 - 0.1429~ = + 1.494 + 0 1 4 2 9 ~ .7 -38'8.9110 * 4511.98The second set of formula are obtained from the first bp takingp = 100 -q, where q = the percentage of water in the solution. Itshould be noticed, that whilst the variation for concentration, withinthe above limits, is constant.the increase of specific rotation for agiven pise of temperatare diminishes with increasing temperature.Taking this into account and using the above formulae, the authorhas calmlated the following more complete table :-8.03'9.5110.9912.47Spec& Rotation [a]= of Tartaric Acid.p . 1 t = 10".--I--t = 15".6-67'8.269 -8511 *44I-- -- t = 30". ---8 -64'10.0711-5012 -93[.IF= 14.615 - 0.158813 = - 1.265 + 0.1588q.These results lie between those obtained by Krecke (Arch. Ne'er-landaise, 7, 102) and those by Arndtsen (Ann. Chini. Phys. [ 3 ] ,54, 411).The author finds that a solution of tartaric acid (50 per cent.) maybe kept for months withont undergoing any optical change.Determinations of the rotary power of varying mixtures of tartaricand citric acids and water, tartaric and acetic acids and water, andtartaric and sulphuric acids and water were made.The resultsobtained lead to the conclusion that the two acids present appropriatewater in the proportion in which they aye present, or, in other words,that the solution consists of a mixture of solutions of the two acidsof equal strength. Thus, for instance, if 30 grams tartaric acid and20 grams citric acid are dissolved iii 50 grams water, the tartaricacid will appropriake 30 grams, the citric 20 grams of this water, andthe specific rotation of the tartaric acid will be that of a 50 per cent1 4 ABSTkACTS OF CHEMICAL PAPERS.solution. Tn the case of sulphuric acid and tartaric acid, the formerappears to be present in the shape of its hexahydrate, HsSO,.Theseresults seem to show that from such observations, it will be possibleto determine the state of hydration in which various substdances existin solution. L. T. T.Molecular Movements. By G. KRGSS (Ber., 18, 2586-2591).-Although the kinetic theory of gases gives some account of the trans-lation of molecules through space, yet no satisfactory hypothesis hasbeen brought forward to illustrate either the rotation of the moleculesabout their own axes, or the interatomic movements within the mole-cules. These two last the author classifies under the title of ‘‘ innermolecular movements.” Prom the undulatory theory of light, deduc-tions can be drawn regarding these molecular movements, inas-much as the vibration of the ether, which fills the intramoleculars p c e , is conditioned within that space by the velocity and amplitudeof the molecular vibrations.Thus if X be the wave-length of a rayemitted by a substance, v the velocity of light, the number of vibra-tions, n, which a molecule sends forth by rnovements of it as awhole and of its parts, can be determined by the equation n =: x’The phenomena of emission and of absorption spectra thus throws Somelight on the least and most extensive form of this inner molecularmovement. I n this paper, this latter point is discussed, together withits relation to the interatomic attraction, which is conditioned by thechemical constitution of the molecule ; inasmuch as vibrations of theparticles of a body are capable of being excited only by vibrationsof a like period in the external ether, so from the wave-lengths ofthose rays of light, which are absorbed to the greatest degree by thesolution of any substance, the numher of the vibrations of the mole-cules within the liquid can be calculated from the equation above.These positions of greatest absorption for derivatives of indigo andfluoresce’in have previously been determined by the author (Abstr., 1883,1042), and from the observations, resiilts are obtained for the maximumnumber of vibrations for billionths of a second. In a table are given theresults for indigo, its paraffino’id-, bromo-, nitro-, and amido-derivatives,for rosolic acid and its tetrabromo-derivative? and for fluorescein andits potassiom, bromo-, nitro-, and paraffino’id-derivatives.From the numbers given, it follows that the molecule of a com-pound emits fewer vibrations per second, the greater the number ofhydrogen-atoms, or! in the case of analogous replacements of thehydrogen-atoms, the zncrease or dewease of molecular vibrations i s pro-portiond to the number of hydrogen-atoms thus replaced. The resultsare in accordance with those deduced by Kellstab from experiments v. H. v. on the transpirability of homologous compounds.Simple Burner for Monochromatic Light. By NOACK (Chem.Centr., 1885, 497-498) .-Consists of a hydrogen evolving apparatus,jnto the cork of which is inserted the stem of a Bunsen burner madeof glass, and a wire for lowering or raising a block of metallic zinc.The salt for producing the required light is dissolved in the acid.J. K. CINORGAVLC CHEJIISTRY, 15An Aspirator. By A. GAwAr,ovsKI (Chern. Centr., 1885, 465).-A description of an aspirator, consisting of two vessels, revolving onan axis, and so constructed that it can be used as an aspirator orrespirator. P. P. B.New Apparatus for Chemical Laboratories. By A. KALEC-SINSZEY (Chem. Centr., 1885, 545--546).-To expel sulphuric acid inthe course of analysis, the author employs a wide glass tube sealed atthe lower and upper extremities, the upper end being driven inwardsto receive a platinum crucible fitted in with asbestos, and having asmdl open tube inserted laterally. Through this tube sulphiaric acidis passed into the apparatus ; the tube is connected with ,z suitablecondenser, heat applied, and the liquid contents of the platinumcrucible speedily evaporate. The author also describes a simple appa-ratus for obtaining an air blast by means of air and water droppinginto a large flask. J. K. C.By C. M.STUART (Chew. News, 5 2, 208) .--9 modification of the glass hooddescribed by Hempel (Ber., 18, 143i), so arranged as t o be placed onevery working bench.A Gas Regulator constructed without Metal. By H. SCRIFF(Rer., 18, 2833-2841).-The arrangement cannot well be describedwithout a figure.Improved Method of Ventilating Laboratories

ISSN:0368-1769    

DOI:10.1039/CA8865000001

出版商:RSC    

年代:1886

数据来源: RSC

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INORGAVLC CHEJIISTRY, 15 I n o r g a n i c C h e mi s t r y. Source of Hydrogen Occluded by Zinc-dust. By G . WILLIAMS (Chem. News, 52, 205--207).-1n continuation of the experiments on the occlusion of hydrogen by zinc-dust (comp. Abstr., 1885, 369, 634), i t is now shown that when 6.749 grams (1 c.c.) of commercial zinc-dust was exposed for a long time in a hard glass retort t.0 the greatest heat of a Bunsen burner, it yielded as much as 47.4 C.C. of hjdro- gen. When the zinc-dust was moistened with boiling water and dried at loo", its weight increased by about 0.1742 gram OIL 6.479 grams, and on heating 6.479 grams of this dried dust in the manner described above, 89.4 C.C. of hydrogen were obtained ; whilst zinc-dust, which had been exposed in a moist atmosphere until it ceased to gain in weight, then dried arid heahed as in the other experiments, gave as much as 362.8 C.C.of hydrogen per 6.479 grams of zinc-dust. Hence zinc-dust t'akes up water and decomposes it, and gives up its hydrogen on heating ; in another experiment it was proved that zinc-dust absorbs hydrogen (9 C.C. per 6.479 grams) a t ordinary temperatures, when surrounded by i t in a moist condition. The author's previous conclusions (Zoc. cit.), therefore, are confirmed. D. A. L.16 ABSTRACTS OF' CHEMICAL PAPERS. Genesis of Sulphur Crystals in Square Tables. Bg C. BRAME ( Compt. rend., 101, 639-642) .-A description of peculiar crystals obtained by condensing sulphur vapour on glass plates. Iodide of Nitrogen. Ry F. RASCHTG (AnnuZen, 230, 212-221). -The author accounts for the discordant results of the analyses of iodide of nitrogen by Gladstone (this Journal, 1851,34), Stahlschmidt, (Pogg.Ann., 119, 421), and Bunsen (Annulen, 84, 1) by the fact that the precipitate obtained by adding ammonia to a sollition of iodine, is decomposed by washing with water. Sesqui-iod amine, NH,,NI, or NH,I,NHI,, is first precipitated, but it is converted during the process of washing into NHT, and NI,. The latter compound dissolves in potassium cyanide, forming cyanoqen iodide :-NT, + 3KCN + 3HzO = 3CNI + NH, + 3KOH. The iodide of nitrogen prepared from a solution of iodine differs in its properties from the io'dide obtained by the action of ammonia on finely divided iodine. The latter compound is much more explosive t'han khe former, as it is capable of exploding when moist.The composition of this substance has not yet been ascertained. w. c. w. Behaviour of Carbonic Anhydride towards Hydrogen at a, High Temperature. By A. NAUMANN arid C. PTSTOR (Bey., 18, 27'24-2727 ; comp. this vol., p. 1036).-Hydrogen has no reducing action on carbonic anhydride at 900". Reactions with Carbonic Anhydride, Carbon Bisulphide, and Sulphurous Anhydride. By A. EILOART (Chem. News, 52, 183--184).-When a mixture of carbonic anhydride and carbon bisul- phide vapour is passed over copper heated to redness, almost pure carbonic oxide is abundantly evolved with simultaneous formation of copper snlphide, Cu2S. Carbon bisulphide alone is decomposed when passed over copper heated below redness, and if copper, coated with carbon from the decomposition of carbon bisulphide, is heated in a stream of carbonic anhydride, only a limited and small quantity of carbonic oxide is slowly produced. Hence the mixture of gases is necessary for the above reaction, and decomposition and combination evidently go on a t the same time.Without copper the mixture of gas is not decomposed in this manner, for instance, when passed over heated pumice. Sulphurous anhydride and carbon bisulphide, when passed over copper or pumice heated even below redness, give rise to cbarbonic anhydride, and as a secondary product carbonic oxide. When sulphurous anhydride is passed over strongly heated carbon, freed as far as possible from air and hydrogen, sulphur is deposited and carbonic anhydride formed. D.A. L. Absorbents for Carbon Bisulphide Vapour. By A. EILOART (Chem. News, 52, 184).-To test the efficiency of various absorbents €or carbon bisdphide vapour, air saturated with this vapour was passed through certain substances, a t the rate of 1 litre per hour. Caoutcliin, powdered roll sulphur, bromine dissolved i n pot'assium bromide, and linseed oil are imperfect absorbents, iodine and potassiumINORGANIC CHEMISTRY. 17 tri-iodide absorb completely a large proportion of carbon bisulphide vapour, but soon get saturated. When these substances are used, a guard tube (filled with paraffin) must be attached to arrest iodine yapour. The carbon bisulphide can be removed from the saturated iodine solution by simple exposure to the air. Large quantities of gas cannot be conveniently treated in this manner.For analytical purposes, the volume of gas t o be analysed is treated with linseed oil in a Crum's tube ; used in this way, linseed oil is the best, as it absorbs the carbon Eisulphide immediately without dissolving the carbonic anhydride. Artificial Formation of Twin Crystals of Potassium Sulphate and Chromate by Increase of Temperahme. By H. BAUMHAUER (Zeit. Kryst. dlin., 10, 405).-The observation made by Mallard, that in twin crystals of potassium sulphate new twin-lamelle are formed by heating, is confirmed by the author. Perfectly simple crystals (:an, by heating, be converted into complicated twin crystals. In the same way, plates of potassium chromate, cut parallel to the basal plane, after slight heating, exhibit a great number of twin lamellae.B. H. B. Action of Sodium Thiosulphate on Metallic Salts. By P. JOCHUM (Chem. Centr., 16, 642-644) .-By treating solutions of sul- phate or chloride or acetate of copper, lead, cadmium, silver, gold, platinum, zinc, manganese, cobalt, or nickel, with solution of sodium t hiosulphate, the author has obtained a series of double thiosulphates, of which an account is given in this paper. D. A. L. P. P. B. Action of Carbonic Oxide on Lead and Silver Chlorides. By A. G. BLOXAM (Chem. News, 52, 183).--Contrary to the statement of Gobel ( J . pr. Chem., 6,388), who describes a method of preparing carbonyl chloride founded on the supposed reaation between carbonic oxide and these chlorides, the author finds that neither lead nor silver chloride is attacked by heating in a current of dry carbonic oxide.When heated in a current of moist nitrogen, lead chloride loses weight with evolution of hydrogen chloride. Alteration of Mercurous Iodide by Exposure to Light. By - YVON (J. Pharm. [ S ] , 11, 148-149) .-Crystallised mercurous iodide, exposed to the light for eight years, in a flask closed by a sheet of paper, had become almost black. Analysis shows the altered iodide to contain 60.72 per cent. of mercury, instead of 61.16 per cent. Chromic Phosphate. By C. L. BLOXAM (Chem. News, 52, 194- 195) .-The precipitate produced by boiling solutions of chromic salts with sodium phosphate and acetic acid has been found by the author t o consist of normal chromic phosphate, mixed with slight excess of chromic oxide, Crz03, and retaining about 5 mols.H,O a t 100". D. A. L. D. A. L. J. T . Molybdenum-derivatives. By C. BARKALD (Chenz. Cerbtr., 1885, 424-425).-Some time ago, Werther showed ( J . pr. C72em., 83, 198) that hydrogen peroxide caused a jellow coloration in acid solutions of VOL. L. C18 ABSTRACTS OF CHEMICAL PAPERS. molybdic acid. The same reaction takes place with the oxides, sul- phides, and salts of molybdenum, but after a, time gas is evolved, and the colour disappears. The reaction forms a good test for molybdenum, and serves to detect it in the presence of chromates, as the blue coloration caused by hydrogen peroxide with chromates may be ex- tracted by agitation with ether, whilst the yellow molybdic coloration remains in the aqueous liquid. The test is, however, much less delicate with molydic compounds than with chromates, and is quite masked by the presence of vanadium or titanium compounds.The normal molybdates and polymolybdates when added to hy- drogen peroxide CRU~F: a brown coloration and strong evolution of oxygen. But when commercial ammonium molybdate, Am6Mo,O2( + H20, or analogous salts (for instance, Rammelsberg's seven-thirds salts) are employed, scarcely any evolution of gas takes place, and the deep yellow solutions yield crystalline lemon-yellow compounds by spontaneous evaporation. The ammonia compound, 18Mo03,14NH3,8HZ02 + 18H20, crystallises in lemon-yellow prisms which do not change on ex. posure to the air. Acids deepen the yellow colour of the solution, alkalis discharge it. If zinc is added to the acidified solution, becoxes darker and finally green.Potassium ferrocyanide and thio- cpanate give the .same reactions as with ordinary molybdates ; lead nitrate gives a white precipitate, soluble in nitric acid, insoluble in, b u t becoming dark-coloured by ammonia. Silver and mercurous nitrites both give white precipitates ; barium chloride, a white compound, 19M00,,8Ba0,2H202 + 13H20 ; ferrons sulphate, a dark yellow voluminous precipitate. Silver nitrate gives a pale yellow amorphous precipitate, 32MoOj,13Agz0,2H202. Ferric sulphate yields an amorphous lemon-coloured powder, Fe,03,6Mo03, 16H,O. When fused with molybdic acid the ammonia compound yields a violet-blue powder of the formula Mo,O,. The crystals of the ammonia compound are highly refractive, and have a sp.gr. of 2 * 9 i 5 ; the sp. gr. of their solution saturated a t 17.4" is 1.486. The analogous potassium molybdate, K6M07024 + 4HL0, yields, with the peroxide, the derivative 16hf0~O,6K,0,4H,0~ + 13H,O ; no corresponding sodium salt could be obtained. The author has also made experiments on the use of the electmlytic method for the quantitative estimation of molybdenum, but finds the results unsatisfactory. L. T. T. Vanadic Anbydride. By A. DITTE (Cf371Zpt. rend., 101, 698-702). -When ammonium vanadate is heated in a closed crucible out of contact with air, the vanadic acid is reduced by the evolved gases, and yields a dark coloured mixture of the two oxides, VZ04 and V,OB, in which the latter predominates. If this product is oxidised with nitric acid, the solution evaporated to dryness, and the residue gently heated, pure vanadic anhydride is left in the form of a reddish-yellow ochreous powder. When this powder is exposed to the air, i t absorbs water and becomes red, forming first the hydrate V205,H20, and after- warcis the hydrate V2O5;2HI1O, The latter compouud, if placed in anINORGANIC CHEMISTRY.19 atmosphere saturated with aqueous vapour, absorbs more water and forms the hydrate V,05,8H,0, but this loses 6 mols. H,O when ex- posed to the air. The amount of water absorbed by the vanadic anhgdride depends on the tension of the aqueous oapour in the sur- rounding atmosphere. When the anhydride or one of the red hydrates is brought in contact with a small quantity of water, it instantly forms a viscous, almost gelatinous mass, which dissolves completely on adding more water, forming a deep blood-red, limpid solution.No precipitate is formed when this solution is boiled, or i f it is mixed with alcohol in the cold, but the addition of a small quantity of nitric acid produces a flocculent reddish precipitate soluble in excess of acid with production of a straw-coloured solution. If this solution is evaporated in a vacuum over potash, it leaves a reddish, velvety mass of hydrated vanadic acid, readily soluble in water with production of the original blood-red solution. If the blood-red solution is mixed with excess of potassium chloride, the whole of the vanadic anhydride is precipitated in reddish flocks, which are not altered by boiling, and are insoluble in water coutaining potassium chloride, but dissolve slightly in pure water, forming a yellow solution, whilst the precipitate, which settles very slowl~, becomes orange coloured.When a cold solution of ammonium vanadate is mixed with a small quantity of nitric acid, a reddish turbidity is produced, which dis- appears on adding more acid, but if the solution is boiled, the greater part of the vanadium is precipitated. This precipitat'e, after washing, and drying by exposure to air, has the composition V205,2H20, but differs from the hydrate described above, in that it does not alter in contact with water, and is only very slightly soluble even at 100". If the product of the calcination of ammonium vanadate is heated in a current of dry air a t 440" for several hours, it is converted into a pale yellow vanadic anhydride with a slight greenish tinge. This variety corresponds with the slightly soluble hydrates, and can also be obtained by heating these hydrates a t 350-440", but is then red- dish-yellow. It does not absorb moisture from the air, and dissolves only very slightly in water, forming a yellow solution.When ammonium vanadate is heated in contact with the air until the residue fuses, the product is not pure vanadic anhydride, hut contains a compound of this oxide with the lower oxide, V,O,. If, however, the product obtained by the action of nitric acid on the mixed oxides formed by heating amnionium vanadate in a closed vessel, is heated to fusion and allowed to cool, it solidifies in dark brownish-red needles, which have a greasy lustre and are transparent in thin plates.This variety of the anhydride does not form a hydrate even if left in contact with water f o r several months, and a saturated solution of it contains only 0.05 gram per litre. From these observations, it follows that vanadic anhydride exists in three distinct modifications, which may be regarded as analogous to the polymeric varieties of phosphoric anhydride, described by Haute- feuille and Perrey. C. H. B. c 220 ABSTRACTS OF CHEMICAL PAPERS. Action of Hydrogen Peroxide on Antimony Sulphides. Bp F. RASCHIG (Rer., 18, 2743 - 2745).-When freshly precipitated antimony sulphide, from 30 grams of tartar emetic, is treated with 500 C.C. of concentrated ammonia, and 900 C.C. of a 2+ per cent.solution of hydrogen peroxide, about is converted into antimonic acid which forms a flaky precipitate. The solution contains am- monium sulphate and antimoniate ; the latter salt is precipitated by the addition of alcohol, and when dried at the ordinary tetnperature, has the composition NH4SbOs + 3H20, and is therefore identical with Frbmy’s hydrogen ammonium metantimoniate, H,(NH,),Sb,O, + 5H,O. The reaction above described is fresh evidence of the non-existence of an antimonic acid corresponding v i t h orthophosphoric acid. N. H. M. Equilibrium in the Reaction of Hydrochloric Acid on Antimony Trisulphide, and of Hydrogen Sulphide on a Solution of Antimony Trichloride. By J. LANG (Ber.? 18, 2714- 2724) .-Experiments made by the author confirm the result obtained by De Clermont and Frommel (Abstr., 1879, 13), that water de- composes antimony trisulphide ; the decomposition continues as long as water is present.Hydrochloric acid of all degrees of strength acts on antimony sul- phide. In presence of an excess of the sulphide, the action continues until the strength of the hydrochloric acid diminishes to a certain point, this point depending on the amount of hydrogen sulphide present iu the solution. The equilibrium will then be disturbed if the pressure on the hydrogen sulphide over the solubion be increased ; this causes a reversal of the reaction which is shown by the separation of antimony sulphide. On the other hand, if the hydrogen sulphide be removed from the solution as it is formed, the action of the hydro- chloric acid will continue until ail the antimony sulphide is dis- solved.N. H. M.INORGAVLC CHEJIISTRY, 15I n o r g a n i c C h e mi s t r y.Source of Hydrogen Occluded by Zinc-dust. By G . WILLIAMS(Chem. News, 52, 205--207).-1n continuation of the experimentson the occlusion of hydrogen by zinc-dust (comp. Abstr., 1885, 369,634), i t is now shown that when 6.749 grams (1 c.c.) of commercialzinc-dust was exposed for a long time in a hard glass retort t.0 thegreatest heat of a Bunsen burner, it yielded as much as 47.4 C.C. of hjdro-gen. When the zinc-dust was moistened with boiling water and driedat loo", its weight increased by about 0.1742 gram OIL 6.479 grams, andon heating 6.479 grams of this dried dust in the manner describedabove, 89.4 C.C.of hydrogen were obtained ; whilst zinc-dust, whichhad been exposed in a moist atmosphere until it ceased to gain inweight, then dried arid heahed as in the other experiments, gave asmuch as 362.8 C.C. of hydrogen per 6.479 grams of zinc-dust. Hencezinc-dust t'akes up water and decomposes it, and gives up its hydrogenon heating ; in another experiment it was proved that zinc-dust absorbshydrogen (9 C.C. per 6.479 grams) a t ordinary temperatures, whensurrounded by i t in a moist condition. The author's previousconclusions (Zoc. cit.), therefore, are confirmed. D. A. L16 ABSTRACTS OF' CHEMICAL PAPERS.Genesis of Sulphur Crystals in Square Tables. Bg C. BRAME( Compt. rend., 101, 639-642) .-A description of peculiar crystalsobtained by condensing sulphur vapour on glass plates.Iodide of Nitrogen. Ry F.RASCHTG (AnnuZen, 230, 212-221).-The author accounts for the discordant results of the analyses ofiodide of nitrogen by Gladstone (this Journal, 1851,34), Stahlschmidt,(Pogg. Ann., 119, 421), and Bunsen (Annulen, 84, 1) by the fact thatthe precipitate obtained by adding ammonia to a sollition of iodine,is decomposed by washing with water. Sesqui-iod amine, NH,,NI,or NH,I,NHI,, is first precipitated, but it is converted duringthe process of washing into NHT, and NI,. The latter compounddissolves in potassium cyanide, forming cyanoqen iodide :-NT, +3KCN + 3HzO = 3CNI + NH, + 3KOH. The iodide of nitrogenprepared from a solution of iodine differs in its properties from theio'dide obtained by the action of ammonia on finely divided iodine.The latter compound is much more explosive t'han khe former, as it iscapable of exploding when moist.The composition of this substancehas not yet been ascertained. w. c. w.Behaviour of Carbonic Anhydride towards Hydrogen at a,High Temperature. By A. NAUMANN arid C. PTSTOR (Bey., 18,27'24-2727 ; comp. this vol., p. 1036).-Hydrogen has no reducingaction on carbonic anhydride at 900".Reactions with Carbonic Anhydride, Carbon Bisulphide,and Sulphurous Anhydride. By A. EILOART (Chem. News, 52,183--184).-When a mixture of carbonic anhydride and carbon bisul-phide vapour is passed over copper heated to redness, almost purecarbonic oxide is abundantly evolved with simultaneous formation ofcopper snlphide, Cu2S.Carbon bisulphide alone is decomposedwhen passed over copper heated below redness, and if copper, coatedwith carbon from the decomposition of carbon bisulphide, is heated ina stream of carbonic anhydride, only a limited and small quantity ofcarbonic oxide is slowly produced. Hence the mixture of gases isnecessary for the above reaction, and decomposition and combinationevidently go on a t the same time. Without copper the mixture ofgas is not decomposed in this manner, for instance, when passed overheated pumice. Sulphurous anhydride and carbon bisulphide, whenpassed over copper or pumice heated even below redness, give rise tocbarbonic anhydride, and as a secondary product carbonic oxide.When sulphurous anhydride is passed over strongly heated carbon,freed as far as possible from air and hydrogen, sulphur is depositedand carbonic anhydride formed.D. A. L.Absorbents for Carbon Bisulphide Vapour. By A. EILOART(Chem. News, 52, 184).-To test the efficiency of various absorbents€or carbon bisdphide vapour, air saturated with this vapour waspassed through certain substances, a t the rate of 1 litre per hour.Caoutcliin, powdered roll sulphur, bromine dissolved i n pot'assiumbromide, and linseed oil are imperfect absorbents, iodine and potassiuINORGANIC CHEMISTRY. 17tri-iodide absorb completely a large proportion of carbon bisulphidevapour, but soon get saturated. When these substances are used, aguard tube (filled with paraffin) must be attached to arrest iodineyapour. The carbon bisulphide can be removed from the saturatediodine solution by simple exposure to the air.Large quantities of gascannot be conveniently treated in this manner. For analytical purposes,the volume of gas t o be analysed is treated with linseed oil in a Crum'stube ; used in this way, linseed oil is the best, as it absorbs the carbonEisulphide immediately without dissolving the carbonic anhydride.Artificial Formation of Twin Crystals of Potassium Sulphateand Chromate by Increase of Temperahme. By H. BAUMHAUER(Zeit. Kryst. dlin., 10, 405).-The observation made by Mallard, thatin twin crystals of potassium sulphate new twin-lamelle are formedby heating, is confirmed by the author. Perfectly simple crystals(:an, by heating, be converted into complicated twin crystals.In thesame way, plates of potassium chromate, cut parallel to the basalplane, after slight heating, exhibit a great number of twin lamellae.B. H. B.Action of Sodium Thiosulphate on Metallic Salts. By P.JOCHUM (Chem. Centr., 16, 642-644) .-By treating solutions of sul-phate or chloride or acetate of copper, lead, cadmium, silver, gold,platinum, zinc, manganese, cobalt, or nickel, with solution of sodiumt hiosulphate, the author has obtained a series of double thiosulphates,of which an account is given in this paper.D. A. L.P. P. B.Action of Carbonic Oxide on Lead and Silver Chlorides. ByA. G. BLOXAM (Chem. News, 52, 183).--Contrary to the statementof Gobel ( J . pr. Chem., 6,388), who describes a method of preparingcarbonyl chloride founded on the supposed reaation between carbonicoxide and these chlorides, the author finds that neither lead nor silverchloride is attacked by heating in a current of dry carbonic oxide.When heated in a current of moist nitrogen, lead chloride losesweight with evolution of hydrogen chloride.Alteration of Mercurous Iodide by Exposure to Light.By - YVON (J. Pharm. [ S ] , 11, 148-149) .-Crystallised mercurousiodide, exposed to the light for eight years, in a flask closed by asheet of paper, had become almost black. Analysis shows the alterediodide to contain 60.72 per cent. of mercury, instead of 61.16 per cent.Chromic Phosphate. By C. L. BLOXAM (Chem. News, 52, 194-195) .-The precipitate produced by boiling solutions of chromicsalts with sodium phosphate and acetic acid has been found by theauthor t o consist of normal chromic phosphate, mixed with slightexcess of chromic oxide, Crz03, and retaining about 5 mols.H,O a t100". D. A. L.D. A. L.J. T .Molybdenum-derivatives. By C. BARKALD (Chenz. Cerbtr., 1885,424-425).-Some time ago, Werther showed ( J . pr. C72em., 83, 198)that hydrogen peroxide caused a jellow coloration in acid solutions ofVOL. L. 18 ABSTRACTS OF CHEMICAL PAPERS.molybdic acid. The same reaction takes place with the oxides, sul-phides, and salts of molybdenum, but after a, time gas is evolved, andthe colour disappears. The reaction forms a good test for molybdenum,and serves to detect it in the presence of chromates, as the bluecoloration caused by hydrogen peroxide with chromates may be ex-tracted by agitation with ether, whilst the yellow molybdic colorationremains in the aqueous liquid. The test is, however, much lessdelicate with molydic compounds than with chromates, and is quitemasked by the presence of vanadium or titanium compounds.The normal molybdates and polymolybdates when added to hy-drogen peroxide CRU~F: a brown coloration and strong evolution ofoxygen.But when commercial ammonium molybdate, Am6Mo,O2( +H20, or analogous salts (for instance, Rammelsberg's seven-thirdssalts) are employed, scarcely any evolution of gas takes place, and thedeep yellow solutions yield crystalline lemon-yellow compounds byspontaneous evaporation.The ammonia compound,18Mo03,14NH3,8HZ02 + 18H20,crystallises in lemon-yellow prisms which do not change on ex.posure to the air. Acids deepen the yellow colour of the solution,alkalis discharge it. If zinc is added to the acidified solution,becoxes darker and finally green. Potassium ferrocyanide and thio-cpanate give the .same reactions as with ordinary molybdates ; leadnitrate gives a white precipitate, soluble in nitric acid, insoluble in,b u t becoming dark-coloured by ammonia. Silver and mercurousnitrites both give white precipitates ; barium chloride, a whitecompound, 19M00,,8Ba0,2H202 + 13H20 ; ferrons sulphate, a darkyellow voluminous precipitate. Silver nitrate gives a pale yellowamorphous precipitate, 32MoOj,13Agz0,2H202.Ferric sulphate yieldsan amorphous lemon-coloured powder, Fe,03,6Mo03, 16H,O. Whenfused with molybdic acid the ammonia compound yields a violet-bluepowder of the formula Mo,O,. The crystals of the ammonia compoundare highly refractive, and have a sp. gr. of 2 * 9 i 5 ; the sp. gr. oftheir solution saturated a t 17.4" is 1.486.The analogous potassium molybdate, K6M07024 + 4HL0, yields,with the peroxide, the derivative 16hf0~O,6K,0,4H,0~ + 13H,O ; nocorresponding sodium salt could be obtained.The author has also made experiments on the use of the electmlyticmethod for the quantitative estimation of molybdenum, but finds theresults unsatisfactory. L. T. T.Vanadic Anbydride. By A. DITTE (Cf371Zpt. rend., 101, 698-702).-When ammonium vanadate is heated in a closed crucible out ofcontact with air, the vanadic acid is reduced by the evolved gases,and yields a dark coloured mixture of the two oxides, VZ04 and V,OB,in which the latter predominates.If this product is oxidised withnitric acid, the solution evaporated to dryness, and the residue gentlyheated, pure vanadic anhydride is left in the form of a reddish-yellowochreous powder. When this powder is exposed to the air, i t absorbswater and becomes red, forming first the hydrate V205,H20, and after-warcis the hydrate V2O5;2HI1O, The latter compouud, if placed in aINORGANIC CHEMISTRY. 19atmosphere saturated with aqueous vapour, absorbs more water andforms the hydrate V,05,8H,0, but this loses 6 mols. H,O when ex-posed to the air.The amount of water absorbed by the vanadicanhgdride depends on the tension of the aqueous oapour in the sur-rounding atmosphere. When the anhydride or one of the red hydratesis brought in contact with a small quantity of water, it instantlyforms a viscous, almost gelatinous mass, which dissolves completelyon adding more water, forming a deep blood-red, limpid solution.No precipitate is formed when this solution is boiled, or i f it is mixedwith alcohol in the cold, but the addition of a small quantity of nitricacid produces a flocculent reddish precipitate soluble in excess ofacid with production of a straw-coloured solution. If this solution isevaporated in a vacuum over potash, it leaves a reddish, velvety massof hydrated vanadic acid, readily soluble in water with production ofthe original blood-red solution.If the blood-red solution is mixed with excess of potassium chloride,the whole of the vanadic anhydride is precipitated in reddish flocks,which are not altered by boiling, and are insoluble in water coutainingpotassium chloride, but dissolve slightly in pure water, forming ayellow solution, whilst the precipitate, which settles very slowl~,becomes orange coloured.When a cold solution of ammonium vanadate is mixed with a smallquantity of nitric acid, a reddish turbidity is produced, which dis-appears on adding more acid, but if the solution is boiled, the greaterpart of the vanadium is precipitated. This precipitat'e, after washing,and drying by exposure to air, has the composition V205,2H20, butdiffers from the hydrate described above, in that it does not alter incontact with water, and is only very slightly soluble even at 100".If the product of the calcination of ammonium vanadate is heatedin a current of dry air a t 440" for several hours, it is converted intoa pale yellow vanadic anhydride with a slight greenish tinge.Thisvariety corresponds with the slightly soluble hydrates, and can alsobe obtained by heating these hydrates a t 350-440", but is then red-dish-yellow. It does not absorb moisture from the air, and dissolvesonly very slightly in water, forming a yellow solution.When ammonium vanadate is heated in contact with the air untilthe residue fuses, the product is not pure vanadic anhydride, hutcontains a compound of this oxide with the lower oxide, V,O,.If,however, the product obtained by the action of nitric acid on themixed oxides formed by heating amnionium vanadate in a closedvessel, is heated to fusion and allowed to cool, it solidifies in darkbrownish-red needles, which have a greasy lustre and are transparentin thin plates. This variety of the anhydride does not form ahydrate even if left in contact with water f o r several months, and asaturated solution of it contains only 0.05 gram per litre.From these observations, it follows that vanadic anhydride exists inthree distinct modifications, which may be regarded as analogous tothe polymeric varieties of phosphoric anhydride, described by Haute-feuille and Perrey. C.H. B.c 20 ABSTRACTS OF CHEMICAL PAPERS.Action of Hydrogen Peroxide on Antimony Sulphides. BpF. RASCHIG (Rer., 18, 2743 - 2745).-When freshly precipitatedantimony sulphide, from 30 grams of tartar emetic, is treated with500 C.C. of concentrated ammonia, and 900 C.C. of a 2+ per cent.solution of hydrogen peroxide, about is converted into antimonicacid which forms a flaky precipitate. The solution contains am-monium sulphate and antimoniate ; the latter salt is precipitated bythe addition of alcohol, and when dried at the ordinary tetnperature,has the composition NH4SbOs + 3H20, and is therefore identical withFrbmy’s hydrogen ammonium metantimoniate, H,(NH,),Sb,O, + 5H,O.The reaction above described is fresh evidence of the non-existence ofan antimonic acid corresponding v i t h orthophosphoric acid.N. H. M.Equilibrium in the Reaction of Hydrochloric Acid onAntimony Trisulphide, and of Hydrogen Sulphide on aSolution of Antimony Trichloride. By J. LANG (Ber.? 18, 2714-2724) .-Experiments made by the author confirm the result obtainedby De Clermont and Frommel (Abstr., 1879, 13), that water de-composes antimony trisulphide ; the decomposition continues as longas water is present.Hydrochloric acid of all degrees of strength acts on antimony sul-phide. In presence of an excess of the sulphide, the action continuesuntil the strength of the hydrochloric acid diminishes to a certainpoint, this point depending on the amount of hydrogen sulphidepresent iu the solution. The equilibrium will then be disturbed ifthe pressure on the hydrogen sulphide over the solubion be increased ;this causes a reversal of the reaction which is shown by the separationof antimony sulphide. On the other hand, if the hydrogen sulphidebe removed from the solution as it is formed, the action of the hydro-chloric acid will continue until ail the antimony sulphide is dis-solved. N. H. M

ISSN:0368-1769    

DOI:10.1039/CA8865000015

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

20 ABSTRACTS OF CHEMICAL PAPERS. Mineralogic a1 C h ernis try. Absolute Hardness of Minerals. By F. PFAFF (Zeit. R ~ y s t . Min., 10, 528--531).-The author has made a series of experiments to determine the absolute hardness of minerals. An accurate chisel- shaped diamond cutter was passed with constant pressure in the same direction 100 or 1000 times over the face of the crystal, and the volume thus removed estimated by weighing the crystal before and after the experiment. A detailed description is given cf the instru- ment employed. Assuming that the hardness of two crystal planes is in inverse proportion to the volume of material removed, with t,he same load and the same number of passings to and fro of the diamond Over an equal area, the hardness of minerals can then be expressed numerically, a given substance (talc) being taken as unit.B. H. B.MiNERALOOICAL CHEMISTRY. 21 The Gold Beds of Mount Morgan, Queensland. By R. L. JACK (DingZ. polyt. J., 258, 45).--These beds are situated about 35 kilos. south-south-west of Rockhampton. The gold is distributed in hematite ironstone and in siliceous sinter. D. B. Copaline from Hiitteldorf, near Vienna. By G. Swam (Zeit. Kryst. illin., 10, 427).-In the slate of the Vienna sandstone, a fossil resin occurs in sharply angular fragments, or in sniall grains of 8 mm. diameter. Its colour varies between light greenish-yellow and brown. It is transparent to translucent. Several grains exhibit distinct fluorescence. It is brittle, fuses at 160 to 165" to a clear liquid.; at 360" it becomes brownish-black, bard, with metallic lustre, .and at a red heat it burns leaving no residue.B. H. B. Its density is less than 1.1. Pseudomorphs. By E. DOLL (Zeit. Rryst. Miw., 10, 423).-The anthor describes pseudomorphs of iron pyrites after copper pyrites, from Kapnik, and pseudomorphs of tetrahedri te after copper pyrites, from FelsobLnya. In the pseudomorphs from Kapnik and Felsiibinya described, and in the pseudomorphs of iron :pyrites after copper pyrites from Musen, numerous spherical cavities were o bserxed, around which the iron pyrites is grouped. This the author regards as a characteristic struc- ture for many pseudomorphs. Galena with Octahedral Cleavage from Wermland. By H. SJ~GREN (Zeit. K r y s t . Min., 10, 507--508).-1a a specimen of galens from Nordmarks mines in Dr.Lundstrom's collection, the usual cubical cleavage is not developed. On breaking up the specimen irregular fragments are formed of a distinctly octahedral character. The ordinary cubical cleavage is developed after two hours' heating at 200"; at 250" much more rapidly; and at 300" with still greater facility. Analysis gare the following results :- Pb. Bi. Ag. Pe. 8. Total. 85.67 0.76 0.05 0.39 13-59 100-46 B. H. B. The author is of opinion that the percentage of bismuth sulphide, which was also observed in the galena of Habach, may be the cause of the octahedral cleavage of galena. The galena, with octahedral cleavage, from Mt. Blanc, described by A. Brun (Abstr., 1883, 428), also gave on analysis 1 per cent. of bismuth sulphide. B. H.B. Tetrahedrite from the Alaska Vein, Colorado. By T. LIWEH (Zeit. Kryst. Min., 10, 488-489) .-The author has examined crystals of the new mineral from the Alaska vein, S.W. Colorado, described by Konig under the name of alaskite (Zeit. K r y s t . Min., 4, 42), in order t o prove crystallographically whether the mineral really belongs to the isomorphous rhombic group of copper-bismuth glance, lead-arsenic glance, &c. The measurements, however, showed the crystals to belong to the regular system; the mineral being evidently22 ABSTRACTS OF CHEMICAL PAPERS. tetrahedrite. A qualitative analysis showed the presence of S, Bi, Sb, Pb, Ag, Cu, Zn, the elements given by Konig in his analpis of 0 alaskite. The following forms were observed on the crystals : + %, 202 404 30 0 2 2 ' , + L , - 2 2' B.H. B. - 202 + -,03003,m0, -- - Microscopic Character of Variegated Copper Ore from New Mexico. By H. BAUMHAUER (Zeit. Kryst. Min., 10, 447-450) .-The author has examined, under the microscope, a specimen of bornite from Chloride, in New Mexico. He found that t,he compact bornite was of a crystalline character, with inclusions of copper glance. On treating these inclusions with concentrated nitric acid, it was seen that they consisted of a number of separate crystals, irregularly grouped together. I n addition to copper glance, a second mineral was observed here and there in the inclusions. This might possibly be galena. Small patches of copper pyrites also occasionally occur in the inclusions. In several places, the ore incloses small distinctly developed crystals of quartz.B. H. B. Antimonite from Czerwenitza. By H. v. FOUT~LOX (Zeit. Kryst, Min., 10, 429).-Antimonite occurs in the red trachytic mother-rock of the opals, in the form of hemispherical radiated aggregates, 1 cm. in diameter. These are frequently covered with hyalite. Several of the hemispherical aggregates of antimonite consist exclusively of an ti- monite fibres ; others, however, are found on microscopic examinatioii to consist of antimonite with interstratified hyalit'e, which the author regards as pseudomorphs after antimonite. Similar pseudomorphs are found a t the Josephis adit, in Klausenthal, near Eperies. B. H. B. Selenides from the Andes. By F. HEUSLER and H. KLIXGER (Ber., 18, 2556--2561).-Analysis of zorgite containing a con- siderable quantity of silver.The substances are not homogeneons ; analysis of the different parts gave- 45 Cu. Pb. Co. Bi. Se. Total. I . . . . 19.20 12.43 35.70 traces - 32.77 100.09 11.. , . 27-49 25-40 17.10 0.39 - 25.54 99-92 L--d 111.. .. 15.87 36.15 1.73 46.25 100.00 I V . . . . 19.16 35.77 3.45 41-62 100*00 I and I1 clear bluish-green substance of silvery lustre. I agrees with the formula Ag2Se,2PbSe,2CuSe. I11 and lV, darker samples of bluish lead colour, are essentially selenides of silver and copper (comp. Pisani, Abstr., 1880, 440). A. J. G. Refractive Indices of Fluorspar. By E. SARASTN (Zeit. K r y s t . Min., 10, 523- 524).-The author has determined the refractive indices of a fluorspar prism, with a refraction angle of 60" 4' 55".A table of the results is given for the spectrum lines, A, a, R, C, D, F, h,MISERALOGICAL CHEMISTRY. 23 H, (Cd) 9, 10, 11, 12, 17, 18, 23, 24, 25, 26, (Zn) 27, 28, 2% (A]) 3% 31, 32. B. H. B. Optical Properties and the Micro-structure of Corundrum. By A. v. LASAULX (Zeit. R ~ y s t . Min., 10, 346--365).-Corundum is without doubt an optically uniaxial mineral crystallising in the hex- agonal system. Disturbances in the regular optical behaviour depend on the nature of the growth and the structure of the corundum cryst'al. The crystals occurring in volcanic rocks appear, as a rule, to have a more uniform constitution and a more regular optical beha- vionr than those found in the older crystalline rocks. The optical disturbances appear tliroughout to be connected with the more or less distinctly developed sbructural faces parallel to R, wP2, and OR.The concentric structure in the direction of one or other of these planes determines the cleavage, which is developed in the direction of R alone, or R and OR, or mP2 and OR, or all bhree planes a t the same time, more or less perfectly. The cleavage is not dependent on the twin lamellae present, but on the other hand the latter are dependent on the presence of the structural planes which determine the cleavage. But both appear simult,aneously almost always. In this- case, struc- tural and twin planes are identical. In the direction of mP2, the plane of symmetry, a twin formation is not possible ; in bhe direction of OR it is entirely unknown, The optical disturbances hi the zone lamell= bounded by the structural planes are, however, of two kinds : -1.Optical disturbance is effected by tension in the zones of the crystal. 2. It occurs in consequence of interpolated twin lamell=. Lastly, optical disturbances also occur in corundum crystals, in con- sequence of processes of alteration, producing granular, laminated, or fibrous products in the interior of the crystals. Jn this case, how- ever, a regular interference figure is not exhibited. B. H. B. Corundum in Graphite. By H. WICHMANN (Zed. Kryst. Min., 10, 425).-On the surface of the graphite of Muhldorf, near spit^, in Lower Austria, small crystals of corundum occur. The crystals attain a thickness of 0.5-6 mm., and a length of 7-25 m u . They are of a red to blue colour, rarely grey, but always clouded with inclu- sions.The translucent crystals prove to be biaxial, with a rather large axial angle. Gahnite and Epidote from Rowe, Massachusetts. By A. G. DANA (Zeit. K7yst. Xi)! ., 10, 490 -492).-With iron pyrites, copper pyrites, and quartz, the author found at Davis' mine, Rowe, frag- ments of gahnite, which on analysis gave the following results :- Al,O,. Fe,O,. FeO. MnO. MgO. ZnO. Si02. Total. Sp. gr. 54 83 3.00 3.37 iirace 1.93 36.92 0.53 100.58 4-53 The following minerals also occur associated with the gahnite :- Ilmenite, apatite, rutile, sphalerite, garnet, calcite, green crystals of ;t triclinic felspar, and epidote. The epidote occurs in short prisms, opaque, and of a greenish-grey colour. Analysis gave the following results : - B.11. B.24 ABSTRACTS OF CHEMICAL PAPERS. SiO,. A1,03. Fe20,. MnO. MgO. CaO. Alkalis. H20. Residue. Total. 38.20 24.62 12-20 0.57 0.13 21-59 0.37 2.16 0.35 100.19 Goethite from Pitkaranta, in Finland. By M. WEIBULL (Zeit. Kryst. illin., IQ, 511-$12).-The author describes specimens of quartz aiid fluorspar w.ith..cavities lined with rock crystal and haematite, on which needles land radiated, aggregates of goethite were crystallised out. An analysis of the goethite gave 89-65 per cent. of ferric oxide, and 10.50 per cent. of water. The mineral is therefore a very pure goetliite. B. H. B. Zircon in Sbsratified Rocks. By F. SANDBERGER (Zeit. Kryst. $!in., 10, 405).-The author has observed transparent crystals of ~ r c o n in the granite of Schapbach, in the Black Forest, of Windeck, near Weinheirn, of Heidelberg, Ilmenau, of the Luisenburg, near Wunsiedel, Nabburg and Worth, near Regensburg.The crystals exhibit exclusively the combination mPm. Transparent zircons are also found in gneiss and mica-diorites, and in the porphyry of the Wagenberg, near Weinheirn, Microscopically small zircons of the same form are widely distributed in the sedimentary rocks, the mate- rial of which is mainly derived from the older rocks ; for example, iii the variegated sandstones of the Black Forest and Spessart, in car- boniferous sandstone, in the Upper Keuper sandstone, and in the sands of the Valley of the Maine. B. H. B. B. H. B. Boracite. By H. BAUMHAUER (Zeit. K ~ y s t . 3&, 10, 451-457).- The author brings forward further arguments to prove that boracite at; the ordinary temperature, in the state in which it is met with in nature, does not crystallise in the regular, but in the rhombic system.Uranothallite. By A . BREZINA (Zeit. Kryst. &!in., 10, 425-426). -Crystals of uranothallite recently obtained at Joachimsthal, gave, for the rhombic crystals, the axial ratio a : b : c = 0.954 : 1 : 0.783. The analysis gave the following results :- uop cop. CaO. FeO. HzO. Total. B. H. B. 35.45 23-13 16.28 2-48 22.44 99.78 corresponding with the formula 2CaC03 + UC20, + 10H20. B. H. B. Occurrence of Hornstone and Barytes in the Porphyry District of Teplitz. By G. LAUBE (Zeit. K~yst. A&., 10, 421).- I n a description of. a crystal of barytes from Teplitz, in Bohemia (Zeit. Kryst. Mi72., 9, 2 2 l ) , Becke stated that the crystal was deposited from the'Teplitz mineral water, which, according to the analyses of Sonnenschein, contains no barytes.This statement the author corrects by showing that barytes occurs in mineral spring fissures only where they traverse the Cenomanian hornstone-conglomerate occurring in the neighbourhood of Teplit z. From these fissures honey-yellow crystals of barytes have been long known. The Teplitz springs, however, do not contain barium. Only in the Neubad spring haveMISERALOGICAL CHEMIST kT. 25 traces of ba,rium been found. conglomerate conhaining baryt)es. This spring passes through hornstone- B. H. B. Halotrichite and Epsomite from the Falu Mine. By &I. WEIBULL (Zeit. Kryst. Min., 10, 512).-In two portions of the Falu mine, where the degree of moisture is low, and the temperature relatively high, sponge-like ma.sses occur of a recent mineral, which appears to be a mixture of epsowite and hnlotrichite.The sp. gr. of the mixtnre is 1.77. The analysis gave results corresponding with the formula- 2(MgS04 + 7%0) + (FeZnCa)(AlFe),(SO& -t 22H20. B. H. B. Turquoise from Nischapur in Persia. By E. TIETZE (Zeit. E r y s t . iklin., 10, 428) .--The mother-rock of the turquoise of Nischapur is, contrary to all former descriptions, a porphyritic trachyte. I n this, and in a breccia formed of angular fragments of the frachyte, the turquoise occurs in veins, 2 to 6 mm. thick, or in irregular patches. In the trachyte, pseudomorphs of turquoise after orthoclase occur. Turquoise is also found in shapeless fragments in the alluvium in the neighbourhood of the trachyte rocks.Berzeliite. By L. J. IGELSTROM (Zeit. Kryst. ikfin., 10, 516- 517).-The author notes the discovery of berzeliite, hitherto found only at Lingban, a t the Moss mine in Wermland. An analysis gave the following results :- B. H. B. As,O,. CaO . MgO. Mn, Pb and C1. 57.80 25.25 16.95 traces This corresponds with Dana's formula for berzeliite- (CaMgRfn) 10A~6025. B. H. B. Xanthoarsenite, a New Mineral from Oerebro. By L. J. IGELSTROM ( X e i t . Kryst. Min., 10, 518-519).-l'he new mineral occurs at a small iron mine 6 miles east of Grythytta. Its colour is sulphur-yellow to orange. In thin splinters, it is translucent. Before the blowpipe, it melts to a black glass, giving a strong odour of arsenic.As,O,. MnO. FeO. MgO. CaO. H,O. 33.26 43-60 3.11 6.08 1-93 12.02 Analrsis gave the following results :- B. H. B. Manganostibite, a New Mineral from Wermland. Ey L. J. TGELSTROM (Zeit. Kryst. Min., 10, 519).-This mineral occurs a t the Moss mine, in small, black, rhombic crystals. An analysis of 0.54 gram gave the following results :- Sba06. AszO,. MnO. FeO. CaO. MgO. Total." 24.09 7-44! 55.77 5-00 3.62 3.00 99-92 * The figures given only add up t o 98.92. B. H. B.26 ABSTRACTS OF CHEMlCAL PAPERS. Vanadates and Silver Iodide from New Mexico. By F. A. GemH and G. v. RATH (Zeit. Krysf. Min., 10, 458-474).-Quite recently new workings a t the Sierra Grande Mine, Lake Valley, Donna Anna Co., New Mexico, have yielded a number of highly interesting and rare minerals, which have been examined chemically by F.A. Genth, and crystallographically by G. v. Rath. Vanadinite, from the Sierra Bella Mine, Lake Valley, gave the following results on analysis :- C1. P,05. V,05. As205. PbO. Total.* Sp. gr. I.. . . 2.39 0-57 17-37 0.24 79.43 100.00 - 11.. . . 2.49 0.39 17.44 1.33 78.31 100.26 6.862 I1 is the analysis of vanadinite from the Sierra Grande. This corresponds with the formula Pb,Cl[ (VAsPb)0,I3 ; whilst analysis I gives a small excess of lead, probably present as cerussite. Lead Ai*sen,io-vanadate-End 1ichite.-An analysis of a supposed vanadinite from the Sierra Grande gave the following results :- SiO,. Fe203. CaO. C1. As205. V20+ PbO. C02,H,0. Total. 76-44 0.99 0.30 0.44 2.16 1-60 15.94 C2.131 100.00 The mineral has thus the composition of equal mols.of mimetite and vanadinite : Pb5C1(AsOJ3 + Pb5C1( VO,),. This mineral the authors believe to be new, and propose for it the name of endlichite, after the director of the Lake Valley mines. Desc1oizite.-Very fine red and brown crystals have recently been found a t the Sierra Grande. The mean results of three analjses of t'he red (I), and of three analyses of the black variety (11) gave the following results :- PbO. CuO. ZnO. MnO. FeO. Ae205. V,05. I1 , . . . 36-36 0.87 13.91 2.74 0.30 0.50 21.35 P205. H,O. Total. Sp. gr. I .... - 2.37 99 49 6.106 I1 . . . . 0.04 3.39 99.46 5.848 After subtracting the impurities shown by the black descloizite, itas analysis agrees vary well with that of the pure red, the composition being expressed by the following formula :- Pb,(HO) (V,As,P)O, + (Zn,Mn,Cu,Fe)z(HO)(V,As,P)O,.I . . . . 56-12 1.10 17*&1 0.49 0.15 0.20 21.65 No indunium is present in the vanadates of Lake Valley. On the ne_w descloizite crystals, thefollowi~ig form? were observed:- P, 2P2, gP3, $Pm, ZPm, COP, mP3, cnP03, m P q OP, with the rhombic axial ratio, a : b : c = 0.6367 : 1 : 0.8046. Silver iodide.-Pure silver iodide is frequently found accompanying the vanadates of the Sierra Grande. It occurs with calcite and red descloizite in yellow, indistinct crystals and crystalline masses ; and with vanadinite and black descloizite i n very small, indistinct, rounded crystals. B. H. B. * The figures giren only add 1113 t o 93.96.BIINERALOGI(I1AL CHEMISTRY.27 Minerals of the Pegmatite Vein at Moss. By W. C. BROGGER (Zeit. Z(ryst. Min., 10,494-496).--The author gives a long list of the minerals occurring in the pegmatite vein at Moss, the remarks on the new mineral atlneyodite being of special interest. This mineral is black with metallic to resinous semi-metallic lustre. H. = 6 ; sp. gr. 5.7. Analysis gave the following results :- Nb,O,. SnO?. SiO,. Zr02 UO,. Tho,. Ce oxides. Y oxides. PbO. 48.13 0.16 2.51 1-97 16.28 2.37 2.36 7.10 2.40 FeO. MnO. CaO. MgO. K,O. NasO. Also,. H20. Total. 3.38 0.20 3.35 0.15 0.16 0.32 0.28 8.19 99.51 corresponding with the foimula 2R,NbL0,(+ 5H20 + +SiO,>. The mineral, therefore, resembles samarskite, from which it differs crystallographically. The axial ratio is rhombici a : b, : c = 0.40369 : 1 : 0;3610,3.The fojms observed yere,_mPm, mPm, OP, WP, mP3, mP5,2Pm7 $Pm, Pm, P, 2P2, 2P2, 3P3,2P, B. H. B. Quartz from Burke, North Carolina. By G. v. RATH (Zeit. Kryst. ZCIin., 10, 475-487) .-A description of peculiar crystals from this locality. Opal from Nagasaki, Japan. By H. SJOGREN (Zeit. I(ryst. Min., 10, 508).-The mineral is of a yellowish-brown to chesnut-brown colour, and possesses the usual characteristics of opal. Under the microscope, 110 trace of organic structure could be detect'ed. Analyses of material dried a t 133" (I), and of undried material (11), gave the following results :- H,O. SiOs. Fe203. A1,03. MgO. Total. I . . . . 3.59 88-87 5.26 1-84 0.32 99.88 I1 . . .. 8-87 84.36 4.99 1.74 0.30 100.26 The latter analysis corresponds with the composition of menilite, H2Si30s.B. H. B. Change in Colour in Felspar due to the Action of Light. By E. ERDMANN (Zeit. K ~ y s t . Min., 10, 493).-From the pegmatite veins of the Ammeberg zinc mine, the author collected specimens of amazonite, with which he made the following experiments :-A large fragment was broken into three parts, 5 to 10 cm. long, the fresh fracture showing a pale greenish-grey colour. Of these pieces, one was packed up in black paper and kept in a dark place; the two others were exposed to the action of sunlight, one having a strip of black paper 10 mm. wide pasted on and varnished, the other having a strip of the same width varnished to exclude air and moisture, but not light. The two specimens were exposed to the action of the sun, air, and rain for 74 days.It was then found that the original pale28 -4BSTRACTS OF CHEMICAL PAPERS. green colour had become a deep emerald-green ; the portion protected by the black paper and the specimen kept in the dark room having remained unaltered. The layer of varnish had cracked, so that it could not be decided whether the change was due to air and moisture, or to light alone. A second experiment was then made. A piece of the unaltered felspar was broken up, and small pieces placed in five tubes of different colours (black, blue, yellow, pale emerald-green, and colourless). The open ends of the tubes were then sealed, without heating the felspar, and the tubes exposed to the action of light for 10 months. On opening the tubes, the felspar in the colourless tube was found to be of a deep emerald-green colour; the felspar in the green tube was less altered, still less in the yellow, and inappreciably in the blue, whilst in the black tube it was quite unaltered.The change in colour is due, therefore, to the action of light alone. B. H. B. Apophyllite from Wermland. By L. J. IGELSTROM (Zeit. Kryst. Min., 10, 517).-At the Nordmarks mines the author found, in addition to the ordinary apophyllite in crystals, concentrically radiated globnlar masses of the same mineral, 2 to 3 em. in diameter. An incomplete analysis gave the following results :- Si02. CaO. MgO. K20,Naz0,B’. H,O. Total. 52.00 23.20 1.30 7.10 16.40 100.00 B. H. B. Chemical Composition of the Amphiboles. By F. BERWERTH (Zeit. K~ysf. Mim., 10, 406-409).-1.li.emoZife.--The mean of two analyses of tremolite from St. Gottharcl gave the following results :- SiO,. d1,0,. FeO. CaO. MgO. H,O. Total. Sp. gr. 58.40 0.56 0.26 13.63 24.82 1.85 9952 3-02 Making allowance for the talc mixed with the specimen analysed, the analysis corresponds with the formula ( CaSi03) (MgSi03) (H2Si03). 2. Actindite.-The author gives the formula for pure actinolite as I 5CaSi03 9MgSi03 2HzSi03 3. Arfvedsonite, from the Nuriasornausak Mine in Greenland, gave on analysis the following results :- Si02. A1,0,. Fe,O,. FeO. CaO. K20. Na20. HzO. Total. Sp. gr. 47-08 1.44 1.70 35.65 2.32 2.88 7.14 2.08 10029 3.45 The author assumes that muscovite is mixed with the mineral analysed, and that the formula for pure mfvedsonite is 13FeSi0, CaSiO, 4Na2 Si03 2H2SiO3MINERALOGICAL CHEMISTRY.29 4. Alunzina-hornbleizd~, from Vesuvius, gave the following analj tical results :- SiOP A120,. Fe203. FeO. CaO. MgO. KJ3. 39-80 14-28 2-56 19.02 10.73 9-10 2.85 Ka20. HaO. Total. Sp. gr. 1.79 1-42 101.55 3.29 The author is of opinion that, as the amount of mica mixed with the hornblende is very small, the hornblende crystals were built up of calcium silicate and meroxene moleciiles, and assumes that at first the tendency to form meroxene predominated, but that the regular develop- ment of the merosene was disturbed by the calcium silicate coming into play. By the calcium silicate and memxene crystallising toge- ther, a hornblende crystal resulted as terminal product. 5. Alumina- hornblende (Pargasite), from the granular limestone of Pargas, had the following composition :- F.Si02. Al,03. PeO. CaO. MgO. K20. 1.66 42.97 16.42 1.32 14.99 20.14 2-85 RTa30. H20. Total. SP. gr. 1-53 0.87 102.75 3.11 Subtracting the 35.91 per cent. of mechanically mixed phlogopite, the formula, for the pure pargasite is I 8Si3A1,0,2 9SiCa204 7 Si hl g204 SiHp04 6. Glaucophune, from Zermatt, gave the following results on SiO> A1903. FeO. CaO. MgO. Na,O. H,O. Total. Sp. gr. 58.76 12.99 5.84 2.10 14.01 6.45 2.54 102.69 3 04 analysis :- The quantity of paragonite admixed could not be determined. Alterations of the Garnets in the Amphibole Schists of the Tyrol. By A. CATHREIN (Zeit. K ~ y s t . Min., 10, 433--446).-1n rocks from the Stamser Alps, the author has observed garnets altered into scspolite, epidote, oligoclase, hornblende, saussurite, and chlorite.B. H. B. B. H. B. Vesuvian Humite, Chondrodite from Nyakopparberg, and Humite from Ladugrufvan. By F. C. v. WIHGARD (Zeit. Anal. Chem., 24, 344-356).-The above minerals (with the exception of the Ladup-ufvan humite) showed no trace of alteration to serpentine. The fluorine was determined by the direct method of Fresenius, except in the case of the Vesuvian humite of type 11, and that from Ladu- grufvan, where the small quantity of material would only allow of the30 ABSTRACTS OF CHEMICAL PAPERS. use of Berzelius' process. After drying a t 110", the minerals still contained hydrogen. This was determined by igniting with lead oxide and weighing the expelled water. The following are the analytical results :- I.Vesuvian humite, type I, or hurnite of Descloiseaux. 11. Vesuvian humite, type 11, or chondrodite of Descloiseanx. 111. Vesuvian humite, type 111, or clinohnmite of Descloiseanx. IV. Chondrodite from Nyakopparberg : a, pale wine-yellow ; b, Pale win e-y ellow. Pale brownish-yellow or greyish-brown. honey-y ello w. V. Humite, type I, from Lndugrufvan. SiO,. MgO. FeO. Fe,03. MgF2. HzO. Total. 1 . . , . . . 35-49 49.47 4.32 - 9.20 1-45 99.93 11 .. . . . . 3.3'49 52.87 3.80 - 8.39 1-37' 9992 111 . . . . . . 33.40 45.65 9.63 0.82 9.25 1.41 100.16 a. 33.90 47.65 7.76 0.11 9.10 1.31 99.83 b. 31.56 37.54 18.67 2.01 9.10 1.31 100.19 V . . . . . . 35.26 50.51 3.51 - 7.70 3.07 100*05 The completely unaltered condition of the specimens, and the fact) that the water was not expelled below a red heat, negative the sup- position of v.Rath that the deficiency in the older analyses was due to water of hydration, and require the hydrogen to be regarded as existing in the form of hydroxyl, replacing fluorine isomorphouslg. The fluorine determinations (of which the above numbers are the averages deduced from numerous concordant results) do not exhibit the wide variations found by other analysts, and, in fact, with the exception of 11, in which i t is assumed that the fluorine is below the truth, of IVb, which is rejected, and of the excess of water inV, due to an obvious partial alteration, all these numbers (after calculating the iron as magnesium) lead to the identical formula IV ... { for all the three types. M. J.S. Isomorphous Silicates. By C. RAMMELSBERG (Chew,. Centr., 1885, 687--688).-The author has endeavoured, by a series of experi- ments, to add to the knowledge of the chemical nature of the members of the scapolite group. All the members of this group are perfectly isomorphous. They are called by various names, but quali- tatively their composition is the same ; they are silicates of alumina, lime, and soda. Only in one member, humboldtilite, do iron and magnesia occur to a considerable extent. There is no soda-free scapolite known, corresponding with anorthite, nor a lime-free scapolite, corre- sponding with albite, which, like the above-mentioned minerals of the felspar gronp, could be regarded as terminal members of the series. The composition of the various members of the group, however, is very different; the proportion of acid amounts to 40 to 60 per cent., that of lime varies from 24 to 4, whilst the amount ofMIXERALOGICAL CHEMISTRY.31 soda amounts to 2 to 10 per cent. With the variations in the atomic proportion of Na : Ca : A1 : Si, it appears desirable to assume Ca = 2R, A1 = 6R, and to calculate the ratio R : Si. In this way the author found that the scapolite group includes: (A) semisilicates ; (B) com- binations of normal and semi-silicates ; (C) normal silicates ; and (D) combinations of normal and quadri-silicates. He concludes that in the scapolite group only the simplest silicates occur, namely :- Normal. . . . . , . . . . Semisilicates . . . . Quadrisilicates . . . and combinations of any two of them.I n group B, which includes the majority of cases, combinations of 1 and 6 mols.,of 1 and 3 mols., of Z and 1 mol., and of 4 and 1 mol. of normal and semi-silicate, are found. The combination of normal and quadri-silicate (group D) consists of 3 and 1 mol. B. H. B. Mineralogical Notes from Bohemia. By R. RAFFELT (Zeit. Kryst. Min., 10, 42l).-In fissures and cavities in the basalt of the E ulenberg near Leitmeritz, the author found analcime, chabasite, phillipsite, and thomsonite, with aragonite and calcite. The analcime forms thin, crystalline crusts exhibiting the form 202. Chabasite occurs in yellow, twin crystals ; phillipsite also occnrs in twin crystals. On the latter are frequently planted crystals of thornsonite, with the following composition :- Si02.Al,O,. CaO. Na,O. HzO. Total. 38.44 31.48 13.60 3.53 12.93 99.98 N%SiO, ; CaSiOs ; AISi,O,. Na,Si04 ; Ca2Si04 ; A12Si3012. Na,Si,O, ; CaSi20, ; AlS&O,,, B. H. B. Empholite, a New Mineral from Horrsjoberg in Wermland. By L. J. IGELSTROM (Zeit. Kryst. Min., 10, 521).--'l'his new mineral forms white or yellowish, translucent crystals, and radiated aggregates in damourite and pyrophyllite in gneiss. The minsral crysta_llises in the rhombic system with the planes mP, d 0 3 , mP2, and mP3. The plane of the optic axes is parallel to the brachypinacoid ; the acute bisectrix is parallel to the brachydiagonal, positive ; the obtuse bisectrix is parallel to the vertical axis. In appearance the mineral resembles diaspore ; H. = 6. Analysis gave the following results :- SiO,.A1203. MgO,CaO,FeO. H,O. Total. 51-70 31.52 4-60 12.18 100.00 (Compare Abstr., 1885, 31.) By L. J. IGELSTROM (Zeit. Kryst. Min., 10, 522).- An analysis of the mineral discovered by the author in 1860, and named persbergite, shows it to be a mineral resembling falunite. The analytical results were as follows :- B. H. B. Persbergite. Si02. Al,03(Fe,03). Mg0,CaO. H20. Total. 41-20 2 7-50 18*LO 13.08 1UO.00 B. H. B.32 ABSTRACTS OF CHERlICAL PAPERS. Minerals from the Mica Diorite of Christianberg, Bohemia. By G. STARKL (Zeit. IZryst. Him, 10, 427).-The minerals examined were biotite, hornblende, plagioclase, and apatite. The three first minerals on analysis gave the following results :- Si02. Al,03. Fez03. Cr203. FeO. CaO. MgO. K20. I.. 39.53 13.45 8.06 0.14 4.99 3.38 22.52 4.13 111..65-54 21.74 trace - - 2.14 trace 3.32 N8.20. H2O. SP. gr. I .......... 1.22 1.49 2.81 I1 .......... - 1.04 2.9% I11 .......... 7.75 0.35 2.57 11.. 5.3.8:3 3.78 3.50 0.08 6-83 10.32 19.49 - Corresponding with the formula+- I. Biot,ite. ..... 2[ (HzNazK2)zSi04] + 11 [ ( FeCaMg),Si04] 11. Hornblende . 15(RSiO,) + l(R;"Si309). 111. Plagioclase . . 2(&~Al~si~o,~) + 6(Na2A1,Si6Ol6) + 1( Ca2A14Si40,6). Chemical Constitution of Staurolite. By W. FRIEDL (Zeit. K r y s t . Mi%., 10, 366-373).-Analyses of staurolite (1) from St. Gottliard and (11) from Tramnitzberg, in Moravia, gave the following + 3[ (~2FezCr2)zSi3O,z]. B. H. B. results :- Si02. A1,03. Fe203. FeO. MgO. H20. Total. I . . 28.1.5 52.17 1.70 13.84 2.54 1-63 100.03 I1 . . 28.19 52.15 1.59 14.12 2.42 1.59 100.06 Both of these analyses correspond with the formula H4( FeMg) 6( AlFe) 24SiiiOs6, O r (FeMg)6A&(AIO) m( OH),( SiO,) 11.This formula, based on analyses of rna'terial proved to be pure by microscopical examination, differs from Rammelsberg's formula for staurolite by Q mol. SiO,. And the ferric oxide, passed over by Kammelsberg, is taken into account in the new formula. An estimate of the value of the two formulst: may be formed from the foIlowing comparison of the actual and calculated results :- I, New staurolit e formula, B4 (A1 ,-$sFe) 24 (iB'e, M g) Si11066. Si02. Al,03. FezO3. FeO. MgO. HzO. Total. Calculated . . 28.38 51.87 1.68 13.93 2.58 1.55 99-99 Found ...... 28.17 52.17 1.65 13.98 2.48 1-61 100.06 11. Old staurolite formula (according t o Rammelsberg, taking into account the percentage of ferric oxide discovered by the author), Hz(~Fe,~~g)~(Al,-a,Fe) 1~Si~034.SiO,. Al,03. Fe203. PeO. MgO. H20. Total. Calculated.. 30.18 50.58 1.64 13 58 2-51 1.51 1OU.t)O Found.. .... 29.46 52.29 - 13.42 2.29 1.60 99-061lINERALOGlCXL CHEMISTRY. 33 The percentage of aluniina found by Rammelsberg exceeds the calculated amount by 1.71, whilst the silica percentage is 0-72 less than the calculated. On comparing his analysis with that of the microscopically tested material, it is evident the staurolite he employed contained some quartz. It may consequently be assumed that staurolite has the formula of a basic silicate :- (MgFe)&,( AIO),( OH),( siod 11 = &(Mg,Fe)6( A1Fe)24Si,,0,6, whichrepresents the simple oxygen ratio of 2 : 1.Pycnophyllite from Aspacg. By G. STARKL (Zeit. Krpf. Min., 10, 427--428).-The author gives the name of pycnophyllite to a compact, finely laminated substance, which fills the fissures of a talc-mica schist, south-east of Aspang. The mineral is of a preen colour, is greasy to the touch, adheres to the tongue, has a resinous lustre, H. = 2, sp. gr. 2.7!16, is easily split up parallel to one plane. Thin leaves are translucent, biaxial, negative. In composition the mineral mast resembles hygrophilite o r pini te. The analjses of specimens from two localities in the neighbourhood of Aspang gave the following results :- SiO,. d1,03. Fe&. FeO. CaO. MgQ. K20. Na20. H20. 48.88 -29.37 2.38 0.51 1.24 2.67 6.51 3.34 4.62 50.09 26.47 3.66 - 0.44 3.93 10.77 4.61 B.EI. B. Igelstromite from Delarne. By M. WEIBULL (Zeit. Kryst. Mi%., 10, 511).-This mineral, formerly desc~ibed by the author (Abstr., 1884, 409), from the Silferberg mines, has been recently found four miles further to the south-west in the Hillangs mines. The deposit cousists of magnetite with mangnnocalcite, silicates rich in man- ganese (igelstromit e, actinolite, and gnrnet), arsenical pyrites, and magnetic pyrites. An analysis of the igelstrornite gave the following resnlts :- B. H. B. - SiO?. FeO. MnO. MgO. CsC03. Total. 28-76 48.59 18.57 1.93 2.25 100.15 corresponding with the formula- 2(FeMg)2Si04 + (MnMg),Si04. B. H. R. Minerals of Vester-Silfberg. By M. WEIBIJLT, (Zeit. TG-yst. Mi?? , 10, 512-515).-The author gives a detailed description of a numb, L' of minerals occurring a t Vester-Silfberg.Manganocalcite from the Stollberg gave on analysis the following results :- CaO. MnO. FeO. MgO. C02. Insoluble. Sp. gr. 46.22 6.98 3.01 0.22 (42.86) 0.71 2.804 WmeRponding with the formula 6Catc03 + (MnFe)C03. The mineral VOL. L. d34 ABSTRACTS OF CHEMlCAL PAPERS. thus approximates closely to Breithaupt's so-called spartaite. An analysis of manganese-hisingerite, an alteration-product of igel- stromite, gave the following results : - Si02. Fe,03. Mn,03. Al,03. MgO. CaO. H20. Total. Sp. gr. 37-09 34.34 15.50 1.39 2.62 1.92 7.81 100.67 2.469 An analysis of silfbergite gaye- Si02. FeO. MnO. MgO. CaO. A1203. Ignition. Total. 49.50 30.69 8-24 8.10 2.02 0.69 0.40 99.64 corresponding wit,h the formula (FeMnMgCa)Si03.The author further mentions the occurrence of magnetite, igelstriim- ite, iron-rhodoni te, and manganese-hedenbergite (compa,re Abstr., 1884, 409). B. H. B. Manganese Minerals from Wermland. By L. J. IGELSTR~M (Zeit. Kryst. Min., 10, 519-521) .-The manganese minerals of the so-called steel ore mines of Giisborn in Wermland, axe manganese silicates, and are largely employed in steel making. The author has made several analyses of these silicates, the results being as follows :- R i 0 2 . MnO. FeO. CaO. MgO. &03. Fe,O,. Ignition. Total. 2.10 100*00 11. 47.00 31 20 10.60 5.70 2.50 - - 0.80 97.81 111. 38.63 13.00 - 19.80 - 8.20 21.90 - 101.53 I. Rhodonite ; 11. Rhodonite, with grains of magnetite; 111. A yellow manganese silicate gave the following analytical results :- I.42.37 40.63 6.80 8.10 - - - brownish and manganese garnet. Total insoluble SiO,. FeO. MnO. CaO. in acids. 38.35 14-05 29.52 10.52 92.46 Total soluble MnC03. FeC03. CaCO,. in acids. 3-70 2.01 1-36 7-07 B. H. B. Chemical Composition of Katapleite. By A. SJOGREX (Zeit. Kryst. M h . , 10, 509-510).-The mean of two new analyses of kata- plgite is as follows :- SiO,. ZrO2. FeO. CaO. Na20. H20. Total. 44-13 32.00 0.19 5.56 8.52 9-26 99.66 The author, therefore, concludes that the formula of kataplgite is (Na.J3aFe)Si03 + ZrSi20s + 2H,O. B. H. B. Two New Norwegian Minerals. By W. C. BR~GGER (Zeit. Kryst. Min., 10, 503-504).- I. Lausnite. Monosymmetrical. Axial ratio a : b : c = 1.0811 : 1 : 0.8153 ; B = 71" 24+', with the combination3IINERALOGICXL CHEMISTRY.35 mP, mP2, mPm, 0332~0, - P, - PWO. The optic axial plane is the plane of symmetry, the acute bisectrix forming with the vertical axis an angle of 20y. Cleavage perfect in the direction of the ortho- pinacoid. Colour chesnnt-brown to yellow. Slightly translucent. Analysis gave the following results :- 33.71 31.65 5.64 5.06 11-00 11.32 1-03 99.41 3.51 This very rare mineral was formerly regarded by the author its mosandrite, which it closely resembles. 2. Cuppe2enite.-A greenish-brown mineral i n thick prismatic crystals, translucent to semi-transparent. Hexagonal ; axial ratio u : c = 1 : 0.43010 ; combination, COP, P, 3P, OP. 550,. ZrO,. Fe203. MnO. CaO. Na,O. Ignition. Total. Sp. gr. Analysis gave the following results :- SiO,. B203.Y20,. (LaDi),03. Ce2@. Tho2. BaO. 14.16 (17.13) 52.55 2-97 1.23 0.79 8.15 CaO. Na,O. K20. HzO. Total. Fp. gr. 0.61 0.39 0.21 1.81 100~00 4.407 B. H. B. Barium Sulphate as a Cementing Material in Sandstone. By F. CLOWES (Clzem. News, 52, 194).--In cerhin New Red Sand- stone beds in the neighbourhood of Nottingham, known as Stapleford and Bramcote Hills, and the Hemlock St,one, the cementing material has been shown by the author to be crystalline barium sulphate. The Hemlock Stone is mushroom shaped, and whilst the- lower portion is calcareous sandstone, the upper portion is not, but contains bavium sulphate, to which fact most probably the stone owes its sha,pe. The barium sulphate occurs in some of the beds in streaks, patches, and large and small more o r less spherical masses ; the intervening ssnd being loose, weathered surfaces appear honey-combed or mammellated, and in one case yield pebble-like masses of sand held togwther by barium sulphate.D. A. L. Weathering of Sandstone. By J. STOKLASA (Landw. Versuchs-Xtaf., 1885,203-214).-The sandstone examined contained 41 per cent. of quartz, and had a sp. gr. of 2.3-2.5 at 17". The changes which this class of stoue undergoes may be thus classified : oxidation of the ferrous compounds (yellowing) ; partial solubion of carbonates ; loss of half the total calcium carbonate with relative increase of silicates and qiiartz; and final pulverisation of the mass. The analytical tables show clearly the conversion of insoluble into soluble compounds, especially in the case of the phosphates which rapidly become soluble in acetic and citric acids.E. W. P. Application of Thermochemistry to Geology. By DIEULAFAIT (Compt. rend., 101, 609-612, 644-64G, and 676--ti79).--The object of the author's investigations is to ascertain how far the main facts of geology can be explained by thermochernical laws, the inquiry being d 236 ABSTRACTS OF CHEMICAL PAPERS. limited in the present papers to the formation of minerals at the ordinary temperatures from subslances in aqueous solution. develops + 26.6 cal. From a consideration of the following reactions- 2Fe0 + 0 = Fe,O,, 2Mn0 + 0, = 2Mn02, 9 , + 21.4 9 , 2Fe0 + 2C0, = 2FeCO,, ,t + 10 0 9 ) 21In0 + 2C0, = 2MnCO3, ,, + 13.6 ,, it would follow that when oxygen and carbonic anhydride, both in ezcesc, come in contact with silicates or other minerals containing ferrous and manganous oxides, the latter will be converted into ferric oxide and manganese peroxide respectively, and no carbonates will be formed.If, however, the carbonic anhydride and oxygen come in contact with the minerals slowly and in quantity insufficient to completely trans- form both oxides, the oxygen will combine mainlv, if not entirely, with the ferrous oxide, and the carbonic anhydride, being unable to cmbine with the ferric oxide thus formed, will .unite with the manganous oxide in preference to uniting with the still un- altered ferrous oxide. The products will, therefore, be femic oxide, which is insoluble, and manganous carbonate, which is distinctly eoluble. If the two gases are dissolved in water percolating through primary rocks, the issuing water will contain manganous.carbonate in relatively much greater proportion than in the original rock, and it is easy to see that this explains the formation of manganese I minerals comparatively free fi-om iron, from rocks in which iron is present in considerable quan1,ity. Since the heat of formation of ferric oxide is so much greater than that of 'ferrous carbonate, it follows that the latter can only be formed in a reducing medium, and can only remain unchanged so long as it is protected from the action of oxygen. Naturtil ferrous carbonates may be divided into two groups : spathic 'iron, which is crgsta7listtd, and exists in the oldest rocks as well as in comparatively recent formations ; and lithoidal ferrous carbonate, which is confined t o the carhon7ferous horizon.The formations in whibh this lithoidal ferrous carbonate occurs, are of estuarine origin, and hence the ferrous carbonate has been formed in a reducing medium highly charged with carbonic anhydride. The iron in alluvial formations is invariably present as hydrated ferric oxide, which is generally supposed to have been brought up by the water springing from the underlying rocks. I f this explanation were correct, we should expect to fiiid crp*allised ferrous carbonate deposited in the caverns and fissures in these rocks, but as a matter of fact, the whole of the iron which they contain is in the state of hydrated peroxide. This would indicate' that the iron has really been derived from water percolating from above.Amongst the natural compounds of a metal, that with the greatest heat of formation should constitute the principal mineral of the parti- cular metal. If all minerals had been deposited from aqueons solutions of tolerably simple composition, it would follow from the laws of thermochemistry that there should only be one naturally occurring compound of each metal, but many minerals have been31 .NEtiALOGIdAL CHEMISTRY. 37 formed in very complex media and under extremely varied conditions, and these geological conditions have to be taken into account. All minerals may, however, be broadly divided into the folloN-ing types : those which have been formed in an oxidising medium ; those which have been formed in a reducing medium; those which have been deposited on a siliceous substratum; and those which have been deposited on a calcareous substratum.The heats of formation of the more important manganese com- pounds are manganous sulphide, MnS, 22.6 cal. ; manganous oxide, AhO, 47.4 cal.; mnnganous carbonate, MIiC0.3, 54 9 cal.; and manganese peroxide, MnOz, 58.1 cal.. These values are in complete ngrecment, with the fact that manganese peroxide is by far the most abundniit mineral of manganese, that manganous sulphide is very rare, whilst manganous oxide exists oiily in combination with the peroxide, and that manganous carbonate is a rare mineral, mainly. confined to veins and fissures, and existing only out of contact with oxygen. Tn all cases where the oxidation of the manganese is not complete this result is due to the non-permeable character of the minerals by which the manganese compound is surrounded.C. H. B. Cornpsition of Water from Uxiage (Isere), By E. PETJGOI! (J. Phurm. IS], 11, 241--245).-Berthier examined this water in 1823, and found the solid residue to be 5.76 grams per litre ; twenty p a r s later tllis became almost doubled in amount, and has smce remained constant. The following is the result of the author's analysis :- CaCO,. NaC1. KC1. CaSO,. N%S04. MgS04. N&.HAsO,. 0.388 6.000 0.402 1.145 1.255 0.609 0 002 SiOp H& Total. 0.01 4 0.010 9822 The total solid residue was 11.917 grams, the excess being due to water of crystallisation of the sulphates. The presence of minute traces of iodine and boric acid was ascertained, the latter hasriug been previously found by Dieulafait.Lefort has detected lithium,. rubi, dium, ferrous sulphide, sodium tkiosulpbate,. and organic matter. Sp. gr. 1.0084 ; dis.solved gases, nitrogen 19 c.c., carboriic anhydride, 3.2 c.c., a t 0" and i60 mm, The other coiistituents agree closely with those obtained by the auhhor. The probable origin of the water is discussed. The water is accompanied by enormous yuantitiej of gas, which is mainly composed of nitrogen and carbonic anhydride. J. T.20 ABSTRACTS OF CHEMICAL PAPERS.Mineralogic a1 C h ernis try.Absolute Hardness of Minerals. By F. PFAFF (Zeit. R ~ y s t .Min., 10, 528--531).-The author has made a series of experimentsto determine the absolute hardness of minerals. An accurate chisel-shaped diamond cutter was passed with constant pressure in the samedirection 100 or 1000 times over the face of the crystal, and thevolume thus removed estimated by weighing the crystal before andafter the experiment. A detailed description is given cf the instru-ment employed.Assuming that the hardness of two crystal planesis in inverse proportion to the volume of material removed, with t,hesame load and the same number of passings to and fro of the diamondOver an equal area, the hardness of minerals can then be expressednumerically, a given substance (talc) being taken as unit.B. H. BMiNERALOOICAL CHEMISTRY. 21The Gold Beds of Mount Morgan, Queensland. By R. L.JACK (DingZ. polyt. J., 258, 45).--These beds are situated about35 kilos. south-south-west of Rockhampton.The gold is distributedin hematite ironstone and in siliceous sinter. D. B.Copaline from Hiitteldorf, near Vienna. By G. Swam (Zeit.Kryst. illin., 10, 427).-In the slate of the Vienna sandstone, a fossilresin occurs in sharply angular fragments, or in sniall grains of8 mm. diameter. Its colour varies between light greenish-yellow andbrown. It is transparent to translucent. Several grains exhibitdistinct fluorescence. It is brittle, fusesat 160 to 165" to a clear liquid.; at 360" it becomes brownish-black,bard, with metallic lustre, .and at a red heat it burns leaving noresidue. B. H. B.Its density is less than 1.1.Pseudomorphs. By E. DOLL (Zeit. Rryst. Miw., 10, 423).-Theanthor describes pseudomorphs of iron pyrites after copper pyrites,from Kapnik, and pseudomorphs of tetrahedri te after copper pyrites,from FelsobLnya.In the pseudomorphs from Kapnik and Felsiibinya described, andin the pseudomorphs of iron :pyrites after copper pyrites from Musen,numerous spherical cavities were o bserxed, around which the ironpyrites is grouped.This the author regards as a characteristic struc-ture for many pseudomorphs.Galena with Octahedral Cleavage from Wermland. By H.SJ~GREN (Zeit. K r y s t . Min., 10, 507--508).-1a a specimen of galensfrom Nordmarks mines in Dr. Lundstrom's collection, the usualcubical cleavage is not developed. On breaking up the specimenirregular fragments are formed of a distinctly octahedral character.The ordinary cubical cleavage is developed after two hours' heatingat 200"; at 250" much more rapidly; and at 300" with still greaterfacility.Analysis gare the following results :-Pb. Bi. Ag. Pe. 8. Total.85.67 0.76 0.05 0.39 13-59 100-46B. H. B.The author is of opinion that the percentage of bismuth sulphide,which was also observed in the galena of Habach, may be the causeof the octahedral cleavage of galena. The galena, with octahedralcleavage, from Mt. Blanc, described by A. Brun (Abstr., 1883, 428),also gave on analysis 1 per cent. of bismuth sulphide.B. H. B.Tetrahedrite from the Alaska Vein, Colorado. By T.LIWEH (Zeit. Kryst. Min., 10, 488-489) .-The author has examinedcrystals of the new mineral from the Alaska vein, S.W. Colorado,described by Konig under the name of alaskite (Zeit.K r y s t . Min., 4,42), in order t o prove crystallographically whether the mineral reallybelongs to the isomorphous rhombic group of copper-bismuth glance,lead-arsenic glance, &c. The measurements, however, showed thecrystals to belong to the regular system; the mineral being evidentl22 ABSTRACTS OF CHEMICAL PAPERS.tetrahedrite. A qualitative analysis showed the presence of S, Bi,Sb, Pb, Ag, Cu, Zn, the elements given by Konig in his analpis of0 alaskite. The following forms were observed on the crystals : + %,202 404 30 02 2 ' , + L , - 2 2' B. H. B. - 202 + -,03003,m0, -- -Microscopic Character of Variegated Copper Ore from NewMexico. By H. BAUMHAUER (Zeit. Kryst. Min., 10, 447-450) .-Theauthor has examined, under the microscope, a specimen of bornitefrom Chloride, in New Mexico.He found that t,he compact bornitewas of a crystalline character, with inclusions of copper glance. Ontreating these inclusions with concentrated nitric acid, it was seenthat they consisted of a number of separate crystals, irregularlygrouped together. I n addition to copper glance, a second mineralwas observed here and there in the inclusions. This might possiblybe galena. Small patches of copper pyrites also occasionally occur inthe inclusions. In several places, the ore incloses small distinctlydeveloped crystals of quartz. B. H. B.Antimonite from Czerwenitza. By H. v. FOUT~LOX (Zeit. Kryst,Min., 10, 429).-Antimonite occurs in the red trachytic mother-rockof the opals, in the form of hemispherical radiated aggregates, 1 cm.in diameter.These are frequently covered with hyalite. Several ofthe hemispherical aggregates of antimonite consist exclusively of an ti-monite fibres ; others, however, are found on microscopic examinatioiito consist of antimonite with interstratified hyalit'e, which the authorregards as pseudomorphs after antimonite. Similar pseudomorphsare found a t the Josephis adit, in Klausenthal, near Eperies.B. H. B.Selenides from the Andes. By F. HEUSLER and H. KLIXGER(Ber., 18, 2556--2561).-Analysis of zorgite containing a con-siderable quantity of silver. The substances are not homogeneons ;analysis of the different parts gave-45 Cu. Pb. Co. Bi. Se. Total.I . . . . 19.20 12.43 35.70 traces - 32.77 100.0911.. , .27-49 25-40 17.10 0.39 - 25.54 99-92L--d111.. .. 15.87 36.15 1.73 46.25 100.00I V . . . . 19.16 35.77 3.45 41-62 100*00I and I1 clear bluish-green substance of silvery lustre. I agrees withthe formula Ag2Se,2PbSe,2CuSe. I11 and lV, darker samples ofbluish lead colour, are essentially selenides of silver and copper(comp. Pisani, Abstr., 1880, 440). A. J. G.Refractive Indices of Fluorspar. By E. SARASTN (Zeit. K r y s t .Min., 10, 523- 524).-The author has determined the refractiveindices of a fluorspar prism, with a refraction angle of 60" 4' 55". Atable of the results is given for the spectrum lines, A, a, R, C, D, F, hMISERALOGICAL CHEMISTRY. 23H, (Cd) 9, 10, 11, 12, 17, 18, 23, 24, 25, 26, (Zn) 27, 28, 2% (A]) 3%31, 32.B. H. B.Optical Properties and the Micro-structure of Corundrum.By A. v. LASAULX (Zeit. R ~ y s t . Min., 10, 346--365).-Corundum iswithout doubt an optically uniaxial mineral crystallising in the hex-agonal system. Disturbances in the regular optical behaviour dependon the nature of the growth and the structure of the corundumcryst'al. The crystals occurring in volcanic rocks appear, as a rule,to have a more uniform constitution and a more regular optical beha-vionr than those found in the older crystalline rocks. The opticaldisturbances appear tliroughout to be connected with the more orless distinctly developed sbructural faces parallel to R, wP2, and OR.The concentric structure in the direction of one or other of theseplanes determines the cleavage, which is developed in the direction ofR alone, or R and OR, or mP2 and OR, or all bhree planes a t the sametime, more or less perfectly.The cleavage is not dependent on thetwin lamellae present, but on the other hand the latter are dependenton the presence of the structural planes which determine the cleavage.But both appear simult,aneously almost always. In this- case, struc-tural and twin planes are identical. In the direction of mP2, theplane of symmetry, a twin formation is not possible ; in bhe directionof OR it is entirely unknown, The optical disturbances hi the zonelamell= bounded by the structural planes are, however, of two kinds :-1. Optical disturbance is effected by tension in the zones of thecrystal.2. It occurs in consequence of interpolated twin lamell=.Lastly, optical disturbances also occur in corundum crystals, in con-sequence of processes of alteration, producing granular, laminated,or fibrous products in the interior of the crystals. Jn this case, how-ever, a regular interference figure is not exhibited. B. H. B.Corundum in Graphite. By H. WICHMANN (Zed. Kryst. Min.,10, 425).-On the surface of the graphite of Muhldorf, near spit^,in Lower Austria, small crystals of corundum occur. The crystalsattain a thickness of 0.5-6 mm., and a length of 7-25 m u . Theyare of a red to blue colour, rarely grey, but always clouded with inclu-sions. The translucent crystals prove to be biaxial, with a ratherlarge axial angle.Gahnite and Epidote from Rowe, Massachusetts.By A. G.DANA (Zeit. K7yst. Xi)! ., 10, 490 -492).-With iron pyrites, copperpyrites, and quartz, the author found at Davis' mine, Rowe, frag-ments of gahnite, which on analysis gave the following results :-Al,O,. Fe,O,. FeO. MnO. MgO. ZnO. Si02. Total. Sp. gr.54 83 3.00 3.37 iirace 1.93 36.92 0.53 100.58 4-53The following minerals also occur associated with the gahnite :-Ilmenite, apatite, rutile, sphalerite, garnet, calcite, green crystals of;t triclinic felspar, and epidote. The epidote occurs in short prisms,opaque, and of a greenish-grey colour. Analysis gave the followingresults : -B. 11. B24 ABSTRACTS OF CHEMICAL PAPERS.SiO,. A1,03. Fe20,. MnO. MgO. CaO. Alkalis. H20. Residue. Total.38.20 24.62 12-20 0.57 0.13 21-59 0.37 2.16 0.35 100.19Goethite from Pitkaranta, in Finland.By M. WEIBULL (Zeit.Kryst. illin., IQ, 511-$12).-The author describes specimens of quartzaiid fluorspar w.ith..cavities lined with rock crystal and haematite, onwhich needles land radiated, aggregates of goethite were crystallisedout. An analysis of the goethite gave 89-65 per cent. of ferric oxide,and 10.50 per cent. of water. The mineral is therefore a very puregoetliite. B. H. B.Zircon in Sbsratified Rocks. By F. SANDBERGER (Zeit. Kryst.$!in., 10, 405).-The author has observed transparent crystals of~ r c o n in the granite of Schapbach, in the Black Forest, of Windeck,near Weinheirn, of Heidelberg, Ilmenau, of the Luisenburg, nearWunsiedel, Nabburg and Worth, near Regensburg.The crystalsexhibit exclusively the combination mPm. Transparent zircons arealso found in gneiss and mica-diorites, and in the porphyry of theWagenberg, near Weinheirn, Microscopically small zircons of thesame form are widely distributed in the sedimentary rocks, the mate-rial of which is mainly derived from the older rocks ; for example, iiithe variegated sandstones of the Black Forest and Spessart, in car-boniferous sandstone, in the Upper Keuper sandstone, and in thesands of the Valley of the Maine.B. H. B.B. H. B.Boracite. By H. BAUMHAUER (Zeit. K ~ y s t . 3&, 10, 451-457).-The author brings forward further arguments to prove that boraciteat; the ordinary temperature, in the state in which it is met with innature, does not crystallise in the regular, but in the rhombic system.Uranothallite. By A .BREZINA (Zeit. Kryst. &!in., 10, 425-426).-Crystals of uranothallite recently obtained at Joachimsthal, gave,for the rhombic crystals, the axial ratio a : b : c = 0.954 : 1 : 0.783.The analysis gave the following results :-uop cop. CaO. FeO. HzO. Total.B. H. B.35.45 23-13 16.28 2-48 22.44 99.78corresponding with the formula 2CaC03 + UC20, + 10H20.B. H. B.Occurrence of Hornstone and Barytes in the PorphyryDistrict of Teplitz. By G. LAUBE (Zeit. K~yst. A&., 10, 421).-I n a description of. a crystal of barytes from Teplitz, in Bohemia(Zeit. Kryst. Mi72., 9, 2 2 l ) , Becke stated that the crystal was depositedfrom the'Teplitz mineral water, which, according to the analyses ofSonnenschein, contains no barytes.This statement the author correctsby showing that barytes occurs in mineral spring fissures only wherethey traverse the Cenomanian hornstone-conglomerate occurring inthe neighbourhood of Teplit z. From these fissures honey-yellowcrystals of barytes have been long known. The Teplitz springs,however, do not contain barium. Only in the Neubad spring havMISERALOGICAL CHEMIST kT. 25traces of ba,rium been found.conglomerate conhaining baryt)es.This spring passes through hornstone-B. H. B.Halotrichite and Epsomite from the Falu Mine. By &I.WEIBULL (Zeit. Kryst. Min., 10, 512).-In two portions of the Falumine, where the degree of moisture is low, and the temperaturerelatively high, sponge-like ma.sses occur of a recent mineral, whichappears to be a mixture of epsowite and hnlotrichite.The sp. gr. ofthe mixtnre is 1.77. The analysis gave results corresponding withthe formula-2(MgS04 + 7%0) + (FeZnCa)(AlFe),(SO& -t 22H20.B. H. B.Turquoise from Nischapur in Persia. By E. TIETZE (Zeit.E r y s t . iklin., 10, 428) .--The mother-rock of the turquoise of Nischapuris, contrary to all former descriptions, a porphyritic trachyte. I nthis, and in a breccia formed of angular fragments of the frachyte, theturquoise occurs in veins, 2 to 6 mm. thick, or in irregular patches.In the trachyte, pseudomorphs of turquoise after orthoclase occur.Turquoise is also found in shapeless fragments in the alluvium in theneighbourhood of the trachyte rocks.Berzeliite.By L. J. IGELSTROM (Zeit. Kryst. ikfin., 10, 516-517).-The author notes the discovery of berzeliite, hitherto foundonly at Lingban, a t the Moss mine in Wermland. An analysis gavethe following results :-B. H. B.As,O,. CaO . MgO. Mn, Pb and C1.57.80 25.25 16.95 tracesThis corresponds with Dana's formula for berzeliite-(CaMgRfn) 10A~6025. B. H. B.Xanthoarsenite, a New Mineral from Oerebro. By L. J.IGELSTROM ( X e i t . Kryst. Min., 10, 518-519).-l'he new mineraloccurs at a small iron mine 6 miles east of Grythytta. Its colour issulphur-yellow to orange. In thin splinters, it is translucent. Beforethe blowpipe, it melts to a black glass, giving a strong odour ofarsenic.As,O,.MnO. FeO. MgO. CaO. H,O.33.26 43-60 3.11 6.08 1-93 12.02Analrsis gave the following results :-B. H. B.Manganostibite, a New Mineral from Wermland. EyL. J. TGELSTROM (Zeit. Kryst. Min., 10, 519).-This mineral occurs a tthe Moss mine, in small, black, rhombic crystals. An analysis of0.54 gram gave the following results :-Sba06. AszO,. MnO. FeO. CaO. MgO. Total."24.09 7-44! 55.77 5-00 3.62 3.00 99-92* The figures given only add up t o 98.92.B. H. B26 ABSTRACTS OF CHEMlCAL PAPERS.Vanadates and Silver Iodide from New Mexico. By F. A.GemH and G. v. RATH (Zeit. Krysf. Min., 10, 458-474).-Quiterecently new workings a t the Sierra Grande Mine, Lake Valley,Donna Anna Co., New Mexico, have yielded a number of highlyinteresting and rare minerals, which have been examined chemicallyby F.A. Genth, and crystallographically by G. v. Rath.Vanadinite, from the Sierra Bella Mine, Lake Valley, gave thefollowing results on analysis :-C1. P,05. V,05. As205. PbO. Total.* Sp. gr.I.. . . 2.39 0-57 17-37 0.24 79.43 100.00 -11.. . . 2.49 0.39 17.44 1.33 78.31 100.26 6.862I1 is the analysis of vanadinite from the Sierra Grande. Thiscorresponds with the formula Pb,Cl[ (VAsPb)0,I3 ; whilst analysis Igives a small excess of lead, probably present as cerussite.Lead Ai*sen,io-vanadate-End 1ichite.-An analysis of a supposedvanadinite from the Sierra Grande gave the following results :-SiO,. Fe203. CaO. C1. As205. V20+ PbO. C02,H,0. Total.76-44 0.99 0.30 0.44 2.16 1-60 15.94 C2.131 100.00The mineral has thus the composition of equal mols.of mimetiteand vanadinite : Pb5C1(AsOJ3 + Pb5C1( VO,),. This mineral theauthors believe to be new, and propose for it the name of endlichite,after the director of the Lake Valley mines.Desc1oizite.-Very fine red and brown crystals have recently beenfound a t the Sierra Grande. The mean results of three analjses oft'he red (I), and of three analyses of the black variety (11) gave thefollowing results :-PbO. CuO. ZnO. MnO. FeO. Ae205. V,05.I1 , . . . 36-36 0.87 13.91 2.74 0.30 0.50 21.35P205. H,O. Total. Sp. gr.I .... - 2.37 99 49 6.106I1 . . . . 0.04 3.39 99.46 5.848After subtracting the impurities shown by the black descloizite, itasanalysis agrees vary well with that of the pure red, the compositionbeing expressed by the following formula :-Pb,(HO) (V,As,P)O, + (Zn,Mn,Cu,Fe)z(HO)(V,As,P)O,.I .. . . 56-12 1.10 17*&1 0.49 0.15 0.20 21.65No indunium is present in the vanadates of Lake Valley.On the ne_w descloizite crystals, thefollowi~ig form? were observed:-P, 2P2, gP3, $Pm, ZPm, COP, mP3, cnP03, m P q OP, with therhombic axial ratio, a : b : c = 0.6367 : 1 : 0.8046.Silver iodide.-Pure silver iodide is frequently found accompanyingthe vanadates of the Sierra Grande. It occurs with calcite and reddescloizite in yellow, indistinct crystals and crystalline masses ; andwith vanadinite and black descloizite i n very small, indistinct, roundedcrystals. B. H. B.* The figures giren only add 1113 t o 93.96BIINERALOGI(I1AL CHEMISTRY.27Minerals of the Pegmatite Vein at Moss. By W. C. BROGGER(Zeit. Z(ryst. Min., 10,494-496).--The author gives a long list of theminerals occurring in the pegmatite vein at Moss, the remarks on thenew mineral atlneyodite being of special interest. This mineral isblack with metallic to resinous semi-metallic lustre. H. = 6 ; sp. gr.5.7. Analysis gave the following results :-Nb,O,. SnO?. SiO,. Zr02 UO,. Tho,. Ce oxides. Y oxides. PbO.48.13 0.16 2.51 1-97 16.28 2.37 2.36 7.10 2.40FeO. MnO. CaO. MgO. K,O. NasO. Also,. H20. Total.3.38 0.20 3.35 0.15 0.16 0.32 0.28 8.19 99.51corresponding with the foimula2R,NbL0,(+ 5H20 + +SiO,>.The mineral, therefore, resembles samarskite, from which it differscrystallographically. The axial ratio is rhombici a : b, : c =0.40369 : 1 : 0;3610,3.The fojms observed yere,_mPm, mPm, OP,WP, mP3, mP5,2Pm7 $Pm, Pm, P, 2P2, 2P2, 3P3,2P,B. H. B.Quartz from Burke, North Carolina. By G. v. RATH (Zeit.Kryst. ZCIin., 10, 475-487) .-A description of peculiar crystals fromthis locality.Opal from Nagasaki, Japan. By H. SJOGREN (Zeit. I(ryst. Min.,10, 508).-The mineral is of a yellowish-brown to chesnut-browncolour, and possesses the usual characteristics of opal. Under themicroscope, 110 trace of organic structure could be detect'ed. Analysesof material dried a t 133" (I), and of undried material (11), gave thefollowing results :-H,O. SiOs. Fe203. A1,03. MgO. Total.I . . . . 3.59 88-87 5.26 1-84 0.32 99.88I1 . . .. 8-87 84.36 4.99 1.74 0.30 100.26The latter analysis corresponds with the composition of menilite,H2Si30s. B.H. B.Change in Colour in Felspar due to the Action of Light.By E. ERDMANN (Zeit. K ~ y s t . Min., 10, 493).-From the pegmatiteveins of the Ammeberg zinc mine, the author collected specimens ofamazonite, with which he made the following experiments :-A largefragment was broken into three parts, 5 to 10 cm. long, the freshfracture showing a pale greenish-grey colour. Of these pieces, onewas packed up in black paper and kept in a dark place; the twoothers were exposed to the action of sunlight, one having a strip ofblack paper 10 mm. wide pasted on and varnished, the other havinga strip of the same width varnished to exclude air and moisture, butnot light.The two specimens were exposed to the action of the sun,air, and rain for 74 days. It was then found that the original pal28 -4BSTRACTS OF CHEMICAL PAPERS.green colour had become a deep emerald-green ; the portion protectedby the black paper and the specimen kept in the dark room havingremained unaltered. The layer of varnish had cracked, so that it couldnot be decided whether the change was due to air and moisture, or tolight alone. A second experiment was then made. A piece of theunaltered felspar was broken up, and small pieces placed in five tubesof different colours (black, blue, yellow, pale emerald-green, andcolourless). The open ends of the tubes were then sealed, withoutheating the felspar, and the tubes exposed to the action of light for10 months.On opening the tubes, the felspar in the colourless tubewas found to be of a deep emerald-green colour; the felspar inthe green tube was less altered, still less in the yellow, andinappreciably in the blue, whilst in the black tube it was quiteunaltered. The change in colour is due, therefore, to the action oflight alone. B. H. B.Apophyllite from Wermland. By L. J. IGELSTROM (Zeit. Kryst.Min., 10, 517).-At the Nordmarks mines the author found, inaddition to the ordinary apophyllite in crystals, concentrically radiatedglobnlar masses of the same mineral, 2 to 3 em. in diameter. Anincomplete analysis gave the following results :-Si02. CaO. MgO. K20,Naz0,B’. H,O. Total.52.00 23.20 1.30 7.10 16.40 100.00B. H. B.Chemical Composition of the Amphiboles.By F. BERWERTH(Zeit. K~ysf. Mim., 10, 406-409).-1. li.emoZife.--The mean of twoanalyses of tremolite from St. Gottharcl gave the following results :-SiO,. d1,0,. FeO. CaO. MgO. H,O. Total. Sp. gr.58.40 0.56 0.26 13.63 24.82 1.85 9952 3-02Making allowance for the talc mixed with the specimen analysed,the analysis corresponds with the formula( CaSi03) (MgSi03) (H2Si03).2. Actindite.-The author gives the formula for pure actinolite as I 5CaSi039MgSi032HzSi033. Arfvedsonite, from the Nuriasornausak Mine in Greenland, gaveon analysis the following results :-Si02. A1,0,. Fe,O,. FeO. CaO. K20. Na20. HzO. Total. Sp. gr.47-08 1.44 1.70 35.65 2.32 2.88 7.14 2.08 10029 3.45The author assumes that muscovite is mixed with the mineralanalysed, and that the formula for pure mfvedsonite is13FeSi0,CaSiO,4Na2 Si032H2SiOMINERALOGICAL CHEMISTRY.294. Alunzina-hornbleizd~, from Vesuvius, gave the following analj ticalresults :-SiOP A120,. Fe203. FeO. CaO. MgO. KJ3.39-80 14-28 2-56 19.02 10.73 9-10 2.85Ka20. HaO. Total. Sp. gr.1.79 1-42 101.55 3.29The author is of opinion that, as the amount of mica mixed withthe hornblende is very small, the hornblende crystals were built up ofcalcium silicate and meroxene moleciiles, and assumes that at first thetendency to form meroxene predominated, but that the regular develop-ment of the merosene was disturbed by the calcium silicate cominginto play. By the calcium silicate and memxene crystallising toge-ther, a hornblende crystal resulted as terminal product.5.Alumina- hornblende (Pargasite), from the granular limestone ofPargas, had the following composition :-F. Si02. Al,03. PeO. CaO. MgO. K20.1.66 42.97 16.42 1.32 14.99 20.14 2-85RTa30. H20. Total. SP. gr.1-53 0.87 102.75 3.11Subtracting the 35.91 per cent. of mechanically mixed phlogopite, theformula, for the pure pargasite is I 8Si3A1,0,29SiCa2047 Si hl g204SiHp046. Glaucophune, from Zermatt, gave the following results onSiO> A1903. FeO. CaO. MgO. Na,O. H,O. Total. Sp. gr.58.76 12.99 5.84 2.10 14.01 6.45 2.54 102.69 3 04analysis :-The quantity of paragonite admixed could not be determined.Alterations of the Garnets in the Amphibole Schists of theTyrol. By A. CATHREIN (Zeit.K ~ y s t . Min., 10, 433--446).-1n rocksfrom the Stamser Alps, the author has observed garnets altered intoscspolite, epidote, oligoclase, hornblende, saussurite, and chlorite.B. H. B.B. H. B.Vesuvian Humite, Chondrodite from Nyakopparberg, andHumite from Ladugrufvan. By F. C. v. WIHGARD (Zeit. Anal.Chem., 24, 344-356).-The above minerals (with the exception ofthe Ladup-ufvan humite) showed no trace of alteration to serpentine.The fluorine was determined by the direct method of Fresenius, exceptin the case of the Vesuvian humite of type 11, and that from Ladu-grufvan, where the small quantity of material would only allow of th30 ABSTRACTS OF CHEMICAL PAPERS.use of Berzelius' process. After drying a t 110", the minerals stillcontained hydrogen.This was determined by igniting with leadoxide and weighing the expelled water. The following are theanalytical results :-I. Vesuvian humite, type I, or hurnite of Descloiseaux.11. Vesuvian humite, type 11, or chondrodite of Descloiseanx.111. Vesuvian humite, type 111, or clinohnmite of Descloiseanx.IV. Chondrodite from Nyakopparberg : a, pale wine-yellow ; b,Pale win e-y ellow.Pale brownish-yellow or greyish-brown.honey-y ello w.V. Humite, type I, from Lndugrufvan.SiO,. MgO. FeO. Fe,03. MgF2. HzO. Total.1 . . , . . . 35-49 49.47 4.32 - 9.20 1-45 99.9311 .. . . . . 3.3'49 52.87 3.80 - 8.39 1-37' 9992111 . . . . . . 33.40 45.65 9.63 0.82 9.25 1.41 100.16a. 33.90 47.65 7.76 0.11 9.10 1.31 99.83b. 31.56 37.54 18.67 2.01 9.10 1.31 100.19V .. . . . . 35.26 50.51 3.51 - 7.70 3.07 100*05The completely unaltered condition of the specimens, and the fact)that the water was not expelled below a red heat, negative the sup-position of v. Rath that the deficiency in the older analyses was dueto water of hydration, and require the hydrogen to be regarded asexisting in the form of hydroxyl, replacing fluorine isomorphouslg.The fluorine determinations (of which the above numbers are theaverages deduced from numerous concordant results) do not exhibitthe wide variations found by other analysts, and, in fact, with theexception of 11, in which i t is assumed that the fluorine is below thetruth, of IVb, which is rejected, and of the excess of water inV, dueto an obvious partial alteration, all these numbers (after calculating theiron as magnesium) lead to the identical formulaIV ...{for all the three types. M. J. S.Isomorphous Silicates. By C. RAMMELSBERG (Chew,. Centr.,1885, 687--688).-The author has endeavoured, by a series of experi-ments, to add to the knowledge of the chemical nature of themembers of the scapolite group. All the members of this group areperfectly isomorphous. They are called by various names, but quali-tatively their composition is the same ; they are silicates of alumina,lime, and soda. Only in one member, humboldtilite, do iron andmagnesia occur to a considerable extent. There is no soda-free scapoliteknown, corresponding with anorthite, nor a lime-free scapolite, corre-sponding with albite, which, like the above-mentioned minerals of thefelspar gronp, could be regarded as terminal members of the series.The composition of the various members of the group, however,is very different; the proportion of acid amounts to 40 to 60per cent., that of lime varies from 24 to 4, whilst the amount oMIXERALOGICAL CHEMISTRY.31soda amounts to 2 to 10 per cent. With the variations in the atomicproportion of Na : Ca : A1 : Si, it appears desirable to assume Ca = 2R,A1 = 6R, and to calculate the ratio R : Si. In this way the authorfound that the scapolite group includes: (A) semisilicates ; (B) com-binations of normal and semi-silicates ; (C) normal silicates ; and (D)combinations of normal and quadri-silicates. He concludes that inthe scapolite group only the simplest silicates occur, namely :-Normal. .. . . , . . . .Semisilicates . . . .Quadrisilicates . . .and combinations of any two of them. I n group B, which includesthe majority of cases, combinations of 1 and 6 mols.,of 1 and 3 mols.,of Z and 1 mol., and of 4 and 1 mol. of normal and semi-silicate, arefound. The combination of normal and quadri-silicate (group D)consists of 3 and 1 mol. B. H. B.Mineralogical Notes from Bohemia. By R. RAFFELT (Zeit.Kryst. Min., 10, 42l).-In fissures and cavities in the basalt of theE ulenberg near Leitmeritz, the author found analcime, chabasite,phillipsite, and thomsonite, with aragonite and calcite. The analcimeforms thin, crystalline crusts exhibiting the form 202. Chabasiteoccurs in yellow, twin crystals ; phillipsite also occnrs in twin crystals.On the latter are frequently planted crystals of thornsonite, with thefollowing composition :-Si02.Al,O,. CaO. Na,O. HzO. Total.38.44 31.48 13.60 3.53 12.93 99.98N%SiO, ; CaSiOs ; AISi,O,.Na,Si04 ; Ca2Si04 ; A12Si3012.Na,Si,O, ; CaSi20, ; AlS&O,,,B. H. B.Empholite, a New Mineral from Horrsjoberg in Wermland.By L. J. IGELSTROM (Zeit. Kryst. Min., 10, 521).--'l'his new mineralforms white or yellowish, translucent crystals, and radiated aggregatesin damourite and pyrophyllite in gneiss. The minsral crysta_llises inthe rhombic system with the planes mP, d 0 3 , mP2, and mP3. Theplane of the optic axes is parallel to the brachypinacoid ; the acutebisectrix is parallel to the brachydiagonal, positive ; the obtusebisectrix is parallel to the vertical axis.In appearance the mineralresembles diaspore ; H. = 6. Analysis gave the following results :-SiO,. A1203. MgO,CaO,FeO. H,O. Total.51-70 31.52 4-60 12.18 100.00(Compare Abstr., 1885, 31.)By L. J. IGELSTROM (Zeit. Kryst. Min., 10, 522).-An analysis of the mineral discovered by the author in 1860, andnamed persbergite, shows it to be a mineral resembling falunite. Theanalytical results were as follows :-B. H. B.Persbergite.Si02. Al,03(Fe,03). Mg0,CaO. H20. Total.41-20 2 7-50 18*LO 13.08 1UO.00B. H. B32 ABSTRACTS OF CHERlICAL PAPERS.Minerals from the Mica Diorite of Christianberg, Bohemia.By G. STARKL (Zeit. IZryst. Him, 10, 427).-The minerals examinedwere biotite, hornblende, plagioclase, and apatite.The three firstminerals on analysis gave the following results :-Si02. Al,03. Fez03. Cr203. FeO. CaO. MgO. K20.I.. 39.53 13.45 8.06 0.14 4.99 3.38 22.52 4.13111.. 65-54 21.74 trace - - 2.14 trace 3.32N8.20. H2O. SP. gr.I .......... 1.22 1.49 2.81I1 .......... - 1.04 2.9%I11 .......... 7.75 0.35 2.5711.. 5.3.8:3 3.78 3.50 0.08 6-83 10.32 19.49 -Corresponding with the formula+-I. Biot,ite. ..... 2[ (HzNazK2)zSi04] + 11 [ ( FeCaMg),Si04]11. Hornblende . 15(RSiO,) + l(R;"Si309).111. Plagioclase . . 2(&~Al~si~o,~) + 6(Na2A1,Si6Ol6) + 1( Ca2A14Si40,6).Chemical Constitution of Staurolite. By W. FRIEDL (Zeit.K r y s t . Mi%., 10, 366-373).-Analyses of staurolite (1) from St.Gottliard and (11) from Tramnitzberg, in Moravia, gave the following+ 3[ (~2FezCr2)zSi3O,z].B. H.B.results :-Si02. A1,03. Fe203. FeO. MgO. H20. Total.I . . 28.1.5 52.17 1.70 13.84 2.54 1-63 100.03I1 . . 28.19 52.15 1.59 14.12 2.42 1.59 100.06Both of these analyses correspond with the formulaH4( FeMg) 6( AlFe) 24SiiiOs6, O r (FeMg)6A&(AIO) m( OH),( SiO,) 11.This formula, based on analyses of rna'terial proved to be pure bymicroscopical examination, differs from Rammelsberg's formula forstaurolite by Q mol. SiO,. And the ferric oxide, passed over byKammelsberg, is taken into account in the new formula. Anestimate of the value of the two formulst: may be formed from thefoIlowing comparison of the actual and calculated results :-I, New staurolit e formula, B4 (A1 ,-$sFe) 24 (iB'e, M g) Si11066.Si02.Al,03. FezO3. FeO. MgO. HzO. Total.Calculated . . 28.38 51.87 1.68 13.93 2.58 1.55 99-99Found ...... 28.17 52.17 1.65 13.98 2.48 1-61 100.0611. Old staurolite formula (according t o Rammelsberg, taking intoaccount the percentage of ferric oxide discovered by the author),Hz(~Fe,~~g)~(Al,-a,Fe) 1~Si~034.SiO,. Al,03. Fe203. PeO. MgO. H20. Total.Calculated.. 30.18 50.58 1.64 13 58 2-51 1.51 1OU.t)OFound.. .... 29.46 52.29 - 13.42 2.29 1.60 99-01lINERALOGlCXL CHEMISTRY. 33The percentage of aluniina found by Rammelsberg exceeds thecalculated amount by 1.71, whilst the silica percentage is 0-72 lessthan the calculated.On comparing his analysis with that of the microscopically testedmaterial, it is evident the staurolite he employed contained somequartz.It may consequently be assumed that staurolite has the formula ofa basic silicate :-(MgFe)&,( AIO),( OH),( siod 11 = &(Mg,Fe)6( A1Fe)24Si,,0,6,whichrepresents the simple oxygen ratio of 2 : 1.Pycnophyllite from Aspacg.By G. STARKL (Zeit. Krpf. Min.,10, 427--428).-The author gives the name of pycnophyllite to acompact, finely laminated substance, which fills the fissures of atalc-mica schist, south-east of Aspang. The mineral is of a preencolour, is greasy to the touch, adheres to the tongue, has a resinouslustre, H. = 2, sp. gr. 2.7!16, is easily split up parallel to one plane.Thin leaves are translucent, biaxial, negative. In composition themineral mast resembles hygrophilite o r pini te.The analjses ofspecimens from two localities in the neighbourhood of Aspang gavethe following results :-SiO,. d1,03. Fe&. FeO. CaO. MgQ. K20. Na20. H20.48.88 -29.37 2.38 0.51 1.24 2.67 6.51 3.34 4.6250.09 26.47 3.66 - 0.44 3.93 10.77 4.61B. EI. B.Igelstromite from Delarne. By M. WEIBULL (Zeit. Kryst. Mi%.,10, 511).-This mineral, formerly desc~ibed by the author (Abstr.,1884, 409), from the Silferberg mines, has been recently found fourmiles further to the south-west in the Hillangs mines. The depositcousists of magnetite with mangnnocalcite, silicates rich in man-ganese (igelstromit e, actinolite, and gnrnet), arsenical pyrites, andmagnetic pyrites. An analysis of the igelstrornite gave the followingresnlts :-B.H. B.-SiO?. FeO. MnO. MgO. CsC03. Total.28-76 48.59 18.57 1.93 2.25 100.15corresponding with the formula-2(FeMg)2Si04 + (MnMg),Si04.B. H. R.Minerals of Vester-Silfberg. By M. WEIBIJLT, (Zeit. TG-yst. Mi?? ,10, 512-515).-The author gives a detailed description of a numb, L'of minerals occurring a t Vester-Silfberg. Manganocalcite from theStollberg gave on analysis the following results :-CaO. MnO. FeO. MgO. C02. Insoluble. Sp. gr.46.22 6.98 3.01 0.22 (42.86) 0.71 2.804WmeRponding with the formula 6Catc03 + (MnFe)C03. The mineralVOL. L. 34 ABSTRACTS OF CHEMlCAL PAPERS.thus approximates closely to Breithaupt's so-called spartaite. Ananalysis of manganese-hisingerite, an alteration-product of igel-stromite, gave the following results : -Si02.Fe,03. Mn,03. Al,03. MgO. CaO. H20. Total. Sp. gr.37-09 34.34 15.50 1.39 2.62 1.92 7.81 100.67 2.469An analysis of silfbergite gaye-Si02. FeO. MnO. MgO. CaO. A1203. Ignition. Total.49.50 30.69 8-24 8.10 2.02 0.69 0.40 99.64corresponding wit,h the formula (FeMnMgCa)Si03.The author further mentions the occurrence of magnetite, igelstriim-ite, iron-rhodoni te, and manganese-hedenbergite (compa,re Abstr.,1884, 409). B. H. B.Manganese Minerals from Wermland. By L. J. IGELSTR~M(Zeit. Kryst. Min., 10, 519-521) .-The manganese minerals of theso-called steel ore mines of Giisborn in Wermland, axe manganesesilicates, and are largely employed in steel making. The author hasmade several analyses of these silicates, the results being asfollows :-R i 0 2 .MnO. FeO. CaO. MgO. &03. Fe,O,. Ignition. Total.2.10 100*0011. 47.00 31 20 10.60 5.70 2.50 - - 0.80 97.81111. 38.63 13.00 - 19.80 - 8.20 21.90 - 101.53I. Rhodonite ; 11. Rhodonite, with grains of magnetite; 111.A yellow manganese silicate gave the following analytical results :-I. 42.37 40.63 6.80 8.10 - - -brownish and manganese garnet.Total insolubleSiO,. FeO. MnO. CaO. in acids.38.35 14-05 29.52 10.52 92.46Total solubleMnC03. FeC03. CaCO,. in acids.3-70 2.01 1-36 7-07B. H. B.Chemical Composition of Katapleite. By A. SJOGREX (Zeit.Kryst. M h . , 10, 509-510).-The mean of two new analyses of kata-plgite is as follows :-SiO,. ZrO2. FeO. CaO. Na20. H20. Total.44-13 32.00 0.19 5.56 8.52 9-26 99.66The author, therefore, concludes that the formula of kataplgite is(Na.J3aFe)Si03 + ZrSi20s + 2H,O.B. H. B.Two New Norwegian Minerals. By W. C. BR~GGER (Zeit. Kryst.Min., 10, 503-504).- I. Lausnite. Monosymmetrical. Axial ratioa : b : c = 1.0811 : 1 : 0.8153 ; B = 71" 24+', with the combinatio3IINERALOGICXL CHEMISTRY. 35mP, mP2, mPm, 0332~0, - P, - PWO. The optic axial plane is theplane of symmetry, the acute bisectrix forming with the vertical axisan angle of 20y. Cleavage perfect in the direction of the ortho-pinacoid. Colour chesnnt-brown to yellow. Slightly translucent.Analysis gave the following results :-33.71 31.65 5.64 5.06 11-00 11.32 1-03 99.41 3.51This very rare mineral was formerly regarded by the author itsmosandrite, which it closely resembles.2.Cuppe2enite.-A greenish-brown mineral i n thick prismaticcrystals, translucent to semi-transparent. Hexagonal ; axial ratiou : c = 1 : 0.43010 ; combination, COP, P, 3P, OP.550,. ZrO,. Fe203. MnO. CaO. Na,O. Ignition. Total. Sp. gr.Analysis gave the following results :-SiO,. B203. Y20,. (LaDi),03. Ce2@. Tho2. BaO.14.16 (17.13) 52.55 2-97 1.23 0.79 8.15CaO. Na,O. K20. HzO. Total. Fp. gr.0.61 0.39 0.21 1.81 100~00 4.407B. H. B.Barium Sulphate as a Cementing Material in Sandstone.By F. CLOWES (Clzem. News, 52, 194).--In cerhin New Red Sand-stone beds in the neighbourhood of Nottingham, known as Staplefordand Bramcote Hills, and the Hemlock St,one, the cementing materialhas been shown by the author to be crystalline barium sulphate.TheHemlock Stone is mushroom shaped, and whilst the- lower portion iscalcareous sandstone, the upper portion is not, but contains baviumsulphate, to which fact most probably the stone owes its sha,pe. Thebarium sulphate occurs in some of the beds in streaks, patches, andlarge and small more o r less spherical masses ; the intervening ssndbeing loose, weathered surfaces appear honey-combed or mammellated,and in one case yield pebble-like masses of sand held togwther bybarium sulphate. D. A. L.Weathering of Sandstone. By J. STOKLASA (Landw. Versuchs-Xtaf.,1885,203-214).-The sandstone examined contained 41 per cent. ofquartz, and had a sp. gr. of 2.3-2.5 at 17". The changes which thisclass of stoue undergoes may be thus classified : oxidation of the ferrouscompounds (yellowing) ; partial solubion of carbonates ; loss of halfthe total calcium carbonate with relative increase of silicates andqiiartz; and final pulverisation of the mass.The analytical tablesshow clearly the conversion of insoluble into soluble compounds,especially in the case of the phosphates which rapidly become solublein acetic and citric acids. E. W. P.Application of Thermochemistry to Geology. By DIEULAFAIT(Compt. rend., 101, 609-612, 644-64G, and 676--ti79).--The objectof the author's investigations is to ascertain how far the main facts ofgeology can be explained by thermochernical laws, the inquiry beingd 36 ABSTRACTS OF CHEMICAL PAPERS.limited in the present papers to the formation of minerals at theordinary temperatures from subslances in aqueous solution.develops + 26.6 cal.From a consideration of the following reactions-2Fe0 + 0 = Fe,O,,2Mn0 + 0, = 2Mn02, 9 , + 21.4 9 ,2Fe0 + 2C0, = 2FeCO,, ,t + 10 0 9 )21In0 + 2C0, = 2MnCO3, ,, + 13.6 ,,it would follow that when oxygen and carbonic anhydride, both in ezcesc,come in contact with silicates or other minerals containing ferrous andmanganous oxides, the latter will be converted into ferric oxide andmanganese peroxide respectively, and no carbonates will be formed.If, however, the carbonic anhydride and oxygen come in contact withthe minerals slowly and in quantity insufficient to completely trans-form both oxides, the oxygen will combine mainlv, if not entirely,with the ferrous oxide, and the carbonic anhydride, being unableto cmbine with the ferric oxide thus formed, will .unite with themanganous oxide in preference to uniting with the still un-altered ferrous oxide.The products will, therefore, be femic oxide,which is insoluble, and manganous carbonate, which is distinctlyeoluble. If the two gases are dissolved in water percolating throughprimary rocks, the issuing water will contain manganous. carbonate inrelatively much greater proportion than in the original rock, and it iseasy to see that this explains the formation of manganese I mineralscomparatively free fi-om iron, from rocks in which iron is present inconsiderable quan1,ity.Since the heat of formation of ferric oxide is so much greater thanthat of 'ferrous carbonate, it follows that the latter can only beformed in a reducing medium, and can only remain unchanged solong as it is protected from the action of oxygen.Naturtil ferrouscarbonates may be divided into two groups : spathic 'iron, which iscrgsta7listtd, and exists in the oldest rocks as well as in comparativelyrecent formations ; and lithoidal ferrous carbonate, which is confinedt o the carhon7ferous horizon. The formations in whibh this lithoidalferrous carbonate occurs, are of estuarine origin, and hence the ferrouscarbonate has been formed in a reducing medium highly charged withcarbonic anhydride.The iron in alluvial formations is invariably present as hydratedferric oxide, which is generally supposed to have been brought up bythe water springing from the underlying rocks. I f this explanationwere correct, we should expect to fiiid crp*allised ferrous carbonatedeposited in the caverns and fissures in these rocks, but as a matter offact, the whole of the iron which they contain is in the state ofhydrated peroxide. This would indicate' that the iron has really beenderived from water percolating from above.Amongst the natural compounds of a metal, that with the greatestheat of formation should constitute the principal mineral of the parti-cular metal. If all minerals had been deposited from aqueonssolutions of tolerably simple composition, it would follow from thelaws of thermochemistry that there should only be one naturallyoccurring compound of each metal, but many minerals have bee31 .NEtiALOGIdAL CHEMISTRY. 37formed in very complex media and under extremely varied conditions,and these geological conditions have to be taken into account. Allminerals may, however, be broadly divided into the folloN-ing types :those which have been formed in an oxidising medium ; those whichhave been formed in a reducing medium; those which have beendeposited on a siliceous substratum; and those which have beendeposited on a calcareous substratum.The heats of formation of the more important manganese com-pounds are manganous sulphide, MnS, 22.6 cal. ; manganous oxide,AhO, 47.4 cal.; mnnganous carbonate, MIiC0.3, 54 9 cal.; andmanganese peroxide, MnOz, 58.1 cal.. These values are in completengrecment, with the fact that manganese peroxide is by far the mostabundniit mineral of manganese, that manganous sulphide is veryrare, whilst manganous oxide exists oiily in combination with theperoxide, and that manganous carbonate is a rare mineral, mainly.confined to veins and fissures, and existing only out of contact withoxygen. Tn all cases where the oxidation of the manganese is notcomplete this result is due to the non-permeable character of theminerals by which the manganese compound is surrounded.C. H. B.Cornpsition of Water from Uxiage (Isere), By E. PETJGOI!(J. Phurm. IS], 11, 241--245).-Berthier examined this water in 1823,and found the solid residue to be 5.76 grams per litre ; twenty p a r slater tllis became almost doubled in amount, and has smce remainedconstant. The following is the result of the author's analysis :-CaCO,. NaC1. KC1. CaSO,. N%S04. MgS04. N&.HAsO,.0.388 6.000 0.402 1.145 1.255 0.609 0 002SiOp H& Total.0.01 4 0.010 9822The total solid residue was 11.917 grams, the excess being due towater of crystallisation of the sulphates. The presence of minutetraces of iodine and boric acid was ascertained, the latter hasriug beenpreviously found by Dieulafait. Lefort has detected lithium,. rubi,dium, ferrous sulphide, sodium tkiosulpbate,. and organic matter.Sp. gr. 1.0084 ; dis.solved gases, nitrogen 19 c.c., carboriic anhydride,3.2 c.c., a t 0" and i60 mm, The other coiistituents agree closelywith those obtained by the auhhor. The probable origin of the wateris discussed. The water is accompanied by enormous yuantitiej ofgas, which is mainly composed of nitrogen and carbonic anhydride.J. T

ISSN:0368-1769    

DOI:10.1039/CA8865000020

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

3s ABSTRACTS OF CHEhlICAL PAPERS. Organic Chemistry. Melting and Boiling Points of Cyanogen Bromide. By E. 3fULDER (Rec. Trav. Chim. 4 151-152).-Cyanogen bromide be- comes somewhat transparent a t 16" but melts a t about 52' it boils a t 61.3" (corr.). A. P. Normal Cyanuric Acid. By E. MULDER (Rec. Tmv. C'him. 4 91-1Ol).-In continuation of his researches on the derivatives of normal cyanic acid (Abstr. 1883 304 and Rec. Tmv. Crlziliz. 2 133) the author finds that both normal ethyl cyanurate and the crude prodact a(CN*OEt*C,H,O) (Abstr. Zoc. cit.) when saponified with aqueous soda at the ordinary temperature and then neutralised with ltydrochloric acid yield a white crystalline deposit haring the compo- sition C3N303HEtZ and probably the constitution C.3N3(OEt)2*OH or C,N,(OEt);CONH. Normal ethyl cyanurate yields isoqanuric acid on acidification with hydrochloric acid normal cy;innric aqid seeming t o be incapable of existing in the free state.The author considers that Wurtz's diethglcyanuric acid is most probably identical with that obtained by Habich and Limpricht and has the constitution c:,O,(NE!t), KK. A. P. * Additive Compounds of Normal Ethyl Cyanurate with 'Cyanogen Bromide. By E. MULDER (Eec. Trac. Claim. 4 147- 150) .-On treating normal ethyl cyanurate with excess of cyanogeii bromide an additive compound C,N30,Et,2CNBr is formed. I t I S liquid a t the ordinary temperature crystallising a few degrees lower. The author considers that i t has the constitution CBr(0Et)N C(0 Et) NC'N< CBr( OEt) --N (CN ) > When heated for several hours a t 125" until no further pressure is developed a yellow liquid is formed which by continued heating a t the same temperature in an open tube is converted into a hard and vitreous niass.On treating cyanogen bromide with excess of norms1 ethyl cyanurate a second additive compound seems to be formed having the composi- tion C3N3O3Et,CNBr. A. P. Action of Ammonia and Amines on Methyl Thiocyanurate and Cyanuric Chloride. Normal Alkyl Melamines. By A. W. H.OFMANX (Ber. 18 2755-2781).-The final product of the action of ammonia on methyl thiocyanurate is melamine but by modifying the conditions of the experiment either of the intermediate products may be produced. To obtain the primary aqnido-base C,N,( SMe)2.NH the methyl tliiocjanurate is digested with a moderate excess of strong alcoholic ammonia for about five hours a t 100".The purified base cq-stallises from boiling alcohol in rhombic plates melting at 200; it is readily soluble in hot more sparingly in cold alcohol and is not cluite insoluble in wat8er. I t s solutions give no reaction with vegetable colours and no sulphur reaction with alkaline lead salts. The base dissolves sparingly in hydrochloric acid and is reprecipitated on the addition of water. On boiling i t for a. long time with hydrochloric acid it is decomposed with production of mercaptan ammonia arid cyanuric acid. The platinochloride and aurochloride are described. The secondary amido-base C3N,(NH2),.SMe is obtained on digesting methyl thiocyanurate with alcoholic ammonia for about five hours at 160". It differs from the primary basc by its ready solubility in water and more sparing solubility i n alcohol ; it melts a t 268" dissolves readily in hydrochloric acid and yields a platino- chloride (C,H,N5S)2,H2PtC16.When boiled with hydrochloric acid it gives the same decomposition-products as the monamido-compound. The tertiary amido-buse meZumine can be obtained in nearly theoretical amount by heating methyl thiocyanurate with an excess of strong aqueous ammonia for several hours a t 180". I t s properties agree wizh those assigned to it by Liebig (Annnlen 10 el). The author has also succeeded in obtaining two plntinochlorides from it ( C3H,N6),H,PtC16 + 2H20 and C3H,N,H2PtCI (?). The amines are found to react with methyl thiocyanurate in the same way as ammonia.The primary methy lamido-base C3N3( S3Je),*NHMe i3 produced on heating methyl thiocyanurate with a 33 per cent. aqueous solution of methylamine for several hours at 100". It is readily soluble in alcohol and ether and crystallises in well-formed prisms melting a t 174-175" ; it forms crystalline salts with hydro- chloric nitric and oxalic acids mid also yields a sparingly soluble i'latinochloride and an aurochloride. Hydrochloric acid deconiposes the base a t 100" into ethyl mercaptan methylamine and cyanuric acid. The secondary methylarnido-base C,N,(NHMe),*SMe is produced simul- taneously with the primary compound. It is very readily soluble in alcohol less so in ether and is best crystallised from a large bulk of boiling water from which it separates in slender needles meltiug a t 144".I t s salts are mostly very readily soluble the nitrate crystal- lising best ; the platinochloride is very sparingly and the aurochloride moderately soluble. The base is decomposed by hydrochloric acid a t 200" and yields the same products as the primary base. The tertiayy naethy lamido-base trimethylmelamine is prepared by heating methyl thiocyanurate with 33 per cent. aqueous methylaniine tor several hours a t 180" ; or a mixture of the primary and secondary bases may first be prepared at a temperature of 130-140" and this then heated at l70-18O0 with more methylamine. Trimethylmel- amine is very readily soluble both in water and in alcohol and the author has not succeeded i n obtaining it quite pure ; its hydrochlo- ride nitrate and sulphate are also extremely soluble the oxalate more sparingly so.Like melamine i t yields two platinochlorides [ C,N,( N HMe)3]2,H2P t C Is and C3N3( NHMe),H,Pt C1,.By the action of ammonia on cyanuric chloride Liebig (Atznalen 10 45) obtained the compound C3H4N5C1 which he termed chloro- cyanamide but which the author shows to be C3N3(NHz),Cl that is an intermediate product between cyanuric chloride and melamine and it may in fact be converted into the latter by a few hours' heatinq a t 100" with strong aqueous ammonia. A nearly theoretical yield of melamine may likewise be obtained directly from cyanuric chloride. A solution of methylamine in absolute methyl alcohol like- wise reacts with cyanuric chloride with production of dimeth yZamido- cyariuric chloride C3N3( NHMe)?Cl; it is nearly insoluble in water alcohol and ether soluble with slight decomposition in boiling glacial acetic acid from which hot water precipitates it in needles melting a t 241" with decomposition.I n acid solutions the chlorine soon becomes replaced by hydroxyl. When dimethylamidocyanuric chloride is heated with a solution of methylamine in methyl alcohol for a few hours at loo" it is converted into trimethylamine; this when heated a t 150" with hydrochloric acid splits up into methy lamine and cyanuric acid. On heating dimethylamidocyan uric chloride with aqueous ammonia a t 150° the chlorine is displaced and a base produced which is without doubt diniethyhnelumine C,N,(NHMe),*NH ; its salts are soluble the sulphate crystallising in six-sided plates and the oxalate in rhom- bic crystals ; i t yields two platinochlorides C,Hl,N6,H2PtCl6 and The dimethylainidocyanuric acid C,N,(NHMe)2*OH obtained from dimethylamidocyanuric chloride (see above) by the action of an acid (or of water at ZOO") is separated from its hydrochloride as a white indistinctly crystalline precipitate which is almost insoluble in boiling water insoluble in alcohol and ether; its platinochloride has the formula ( C5 H BN50) ,HZPt C 1,.D irneth y lamidocy anuric acid forms salts both with acids aud with bases ; the hydrochloride and nitrate are crystalline and soluble without decomposition ; the sodium salt and the methyl salt (obtained from dimethylamidocyanuric chloride and sodium methylate) crystallise in prisms.The mother-liquors from the preparation of dimethylamidocyanuric chloride contain (besides methylamine hydrochloride) a crystalline substance found to be methylamidonaetiioxycyanzLric chloride MeO*C3N3C1*NHMe ; it forms acicular crystals melting at 155" is soluble in alcohol and ether also in hydrochloric and nitric acids with formation of crystal- lisable salts. It may be boiled with acids without parting with its chlorine. Attempts to obtain hexamet?ylnaelam ine C3Ns(NMe2) by heating methyl thiocyanurate with dimethylamine were without success but its hydrochloride may be obtained by heating a mixture of equal weights of dimethylamine hydrochloride and cyannric chloride as long as hydrogen chloride is evolved. The base ci.ystallises in needles melting at 171-172" ; its platinochloride and aurochloride are de- scribed. When it is heated with hydrochloric acid a t 200" it splits up into cyannric acid and dimethylamine.Methyl thioayanurate is acted on by ethylamine in the same way as by ammonia and by methylamine with formation of corresponding products. The primary et l ~ y Zir mid o- bn se C3N3( S Me) 2* NHE t cry stallises from boiling dilute alcohol in lustrous needles melting a t 114" is sparingly soluble in boiling water readily in cold alcohol ; i t yields a platinochloride of the formiila ( C,H,2N4S,)z,H,PtC16. The secondary etlr y/u)nido-base C3N3(NHEt),-SMe forms needles melting a t 83-8 &' ; its hydrochloride is crystitlline extremely soluble in water less so in alcohol aud insoluble in ether ; the nitrate is more sparingly soluble ; the oxalate forms slender very soluble needles whilst the snlp'iate does not crystallise.A plat inocliloride aurochloride and stanno- chloride have also 1 been obtaiued. The tertiirry eth!/Zitt,iido-Case triethy Zmelainine CJN3(NHEt) can be obtained both from methyl thiocy anurate and from cyanuric chloride and forms prisms melting at 73-74'. It is soluble in alcohol ether and benzene ; the platino- chloride ( C9H,N6),H2PtC1 and aurochloride are described arid also a compound with silver nitrate ( C9Hl~N&,AgN03. Triethjlmel- amine is decomposed By hydrochloric ac4d at 150' into cyanuric acid and ethylamine. Hexethylmelamine C3N3(NEt2) is formed by the action of diethyl- amine on cyanuric chloride. The platinochloride ( C,H&6)2,H,Pt~16 and aurochloride CI5H,K6,HAuCl4 are described.Hydrochloric acid a t 150" decomposes the base into diethjlamine and ojanurio acid. In order to shvw that the higher amines also react with methyl thiocyanurate this latter -substance was digested with alcoholic amyl- amine at 10U". The primary anrylamido-base,. C3N,(SMe)z*NHC5H11 obtained crystallises in clusters of silky needles melting at 96". Hydrochloric acid decomposes- itL slowly a t the ordinary tempeiature. When the reac- tion bakes place at 200" the secondary base C3N3(NC5H,),*SMe is ob- tained and forms colourless crystals melting a t 106-107' ; its platrinoch1oride has the formula (~l~H,3~,S),HzPtC16. If the reaction takes place a t 250° the tertiary base trip3iperidylnrelamip.Le Piperidine also reacts with methyl thiocyanurate.C3&( N C5&3)3 is produced and crptallises in small needles melting at 213" ; it dis- solves rcadily in acids and yields a sparingly soluble platinochloride ( c,eH,N6)2,HzPtC16. Hydrochloric acid decomposes the base a t 150" into piperidine and cyanuric acid. Tripheitylmelamiwe CJN3(NHPh) may be obtained by the action of aniline on methylthiocyanurate or cyanuric chloride and hexa- phenylmelamine C,N3(NPhZ) may likewise be obtained from dipheriyl- amine and cyanuric chloride. Alkyl Isomelamines derived from the Alkyl Cyanamides and the Constitution of Melamine and of Cganuric Acid. A. K. M. been proposed for melamine the former is the one which most simply explains the formation of melamines and of mercaptan by the action of ammonia or amiies on methyl thiocyanurate and of melamines and lrydrocliloric acid from cyanuric chloride and ammonia or nmines (sse last Abstract).The second formula on the other hand would necessitate the assumption of complicated molecular changes ; in the formation of the hexalkylmelamines by the action of a secondarp amine one alkyl group of the latter must be assumed to detach itself from one nitrogen-atom aud to attach itself to another and the - >NMe should resulting hexalkylmelamine NNe C<NMe.C(N31e) NMeG (NAIe) be split u p by the action of water into methyl cyanurate and methyl- amine ; cyanuric acid and dimethylamine are however produced. The formation of the piperidine-derivative of melamine is met by similar difficulties if the imido-formula be taken as correct whilst the nmido-formula readily explains all the reactions.Alkylmelamines corresponding with ail imido-melamine can how- ever be obtained but these yield no cyanuric acid; they split u p into ammonia and alkyl cyanurates. l'rimethytisomelamine C3N3Me3 (NH) has been previously men- tioned by the author (Eer. 3 264) and by Bauniann (Ber. 6 1372). I n order to obtain it monomethylthiocarbanride is treated with dry mercuric oxide in absolute alcohol the methylcyanamide first formed r:x pidlg polymerising to trimetl-tylisomelamine. This i s very readily soluble in water and alcohol insoluble in ether the solution exhibit- ing a distinctly alkaline reaction. It crystallises in well-formed needles melts at 179" and readily sublimes ; the platinochloride chN6H12,H2PtC16 and aurochloride C&GH,,H&.u?CI& are described.Hydrochloric acid at 100" decomposes the base into ammonia arid methyl isocyanurate ; this decomposition takes place in stages and the author has succeeded in isolating one of the two intermediate pro- ducts namely NH C3N,Me,02; it forms a n aurochloride CsHioNdOa HAu C 1 and a hydrochloride C6HloN402,HC1. Triethy~isometamine C3N3E t3( NH) has also been previously mentioned (Hofmann Ber. 1 27). It forms stellate groups of needles melts at 92" and crystallises from water with 4 mols. H20. Platino- and auro-chlorides are described. It is decomposed by acids in the same way as the trimethyl-derivative and here again the one intermediate product HN C3N,Et30 can readily be isolated.In further support of the amido-nature of melamine the author mentions its decomposition by water into ammonia and cyanuric acid the constitution of which he indicates to be HO*CeN. C(oH)>N. He points out that the formation of cyanuric acid from carbamide does not prove it t o have the constitution CO<NH,CO>NH as the constitlution of carbamide has not been definitely established (compare this Journal 1866 161). There also appears to be little ground for the assumption of the iso-nature of cyanic acid. On the contrary the formation of cyanates from potassium cyanide the conversion of xmmonium cyanate into carbamide and of cyanic acid with the elemmts of water into ammonia and carbonic anhydride run perfectly N-C( OH) NH*CO parallel with the formation and behaviour of thiocjanic acid the normal constitution of which is not doubted.The formation of alkyl isocyanurntes from cyanuric acid may be accounted for by the fact that t,he normal ethers may be readily converted into the iso-ethers (Rer. 3 272 ; Rec. Tmv. Chinz. 1 191). The production of cyanuric chloride from phosphorus pentachloride and cjaiiuric acid and the re-formation of the latter by the action of water on the chloride (Annalen 116 357) also support the view that cyanuric acid contains li-ydroxyl-groups. Phosphorus pentachloride acts in the same way on the normal methyl salt of cyanuric acid with formation of methyl chloride phosphorus oxytrichloride and cyanuric chloride. Methyl isocyanurate however gives a very different reaction when heated with phosphorus pentachloride hydrochloric acid phosphorus tri- chloride and trichioromethyl isocyanui*ate N(CH2C1)*CO>N(CH2C1) co<N(CH2Cl)*C0 being formed.A. K. M. Allyl-sulphuric Acid. By F. SZYMAKSKI (AnnuZen 230 43- 50).-The preparation of rtllyl-sulphuric acid by the action of sul- pbnric acid on allyl alcohol was first described by Cahours and Hof- Inann (Ani-,aZen 102 293). Beilstein and Wiegand (Abstr. 1885 740) have recently stated that allyl alcohol is completely carboriised by sulphuric acid. The author finds that this is not the case when the alcohol is slowly added to the acid. The best results are obtained when the acid is diluted with an equal volunie of water. The barium salt has been previously described by Cahours and Hofmann (Zoc.cit.). The stroritiurn salt forms anhydrous rhombic prisms soluble in water and in alcohol. The anhydrous calcium salt crystallises in quadratic 1,lates. The copper salt crystallises in needles with 4 mols. H,O. It is soluble in water and alcohol On saturating allyl-sulphuric acid with lead carbonate a basic salt (C,H,SO&Pb + PbO + 6H20 is obtained which is soluble in water. The magnesium saZt Mg(C3H5SOA)2 + 4H20 crystallises in trans- parent needles soluhle in water. The potassium arnmoniuni and sodium salts are hygroscopic and soluble in water. The f e w o u s salt forms quadratic plates soluble in alcohol. w. c. w. It is hygroscopic. Methylene-derivatives. By 1;. HENRY (Conzpt. rend. 101,599- GOO).-Diethoxy,izethane CH,(OEt) obt'airied by the action of diiodo- methane on sodium ethoxide is a colourless mobile limpid liquid with :L pungent taste and a peculiar agreeable odour quite different from that of acetsl.It is only slightly soluble in vc-ater and quite iiisoluble in a concentrated solution of calcium chloride. It boils a t 82-83" under a pressure of 760 mm. ; sp. gr. a t 16.7" compared with the water a t the same temperature = 0.8275 ; vapour-density 3.44. C~I~Zorobromornetl~ane CH2C1Br obtained by the action of excess of bromine on chloriodomethane is a mobile colourless liquid with au agreeable ethereal odour and a sweetish pungent taste. It is insolu- IAe in water does not decompose when exposed to light and boils at44 ABSTRACTS OF CHEMICAL PAPERS. 68-69" under a pressure of 765 mm. ; sp. gr. at 19" compared with water at the same temperature = 1.9907 ; vapour-density 4.43.R~orniodornethutze CH2RrT is obtained by the action of a limited quantity of bromine or better of iodins chloride on diiodomethane. It is a colourless liquid which becomes purple when exposed to light. It has an agreeable etherealsodour and a sweetish bitter taste is insoluble in water and boils a t 138-140" under a pressure of 754 mm. ; sp. gr. a t 16.8" compared with1 water at tihe same temperature = 2.9262; vapour-density 7.65. C. H. B. Sulphatea of some Carbohydrates. By M HONIG and S. SCHUBERT (Mm~atsli. Chern. 6 708-749).-By the action of sulphuric acid on1 cellulose a t different temperatures varying from 7" to 40° and subsequent treatment of tbe product with barium caiBbonate salts were obtained which contained the same percentage of barium but which possessed a ,greatly varying rotatory p o m r ( [ a ] j = - 3.65" to + 72.99").Further experiments made t o ascertain the influence of the quantity of acid used showed that salts varying in composition but having the same rotatory power can be formed. Prolonged action of sulpl~uric acid causes an increase of. barium in the salt as well as an increase of rotdory power. When the action is allowed to take place at a& low temperature the product coiitains salts varying more from one another than if the reaction takes place a t a higher temperature. The following salts were separated :- They form white or yellowish-white voluminous powders with varying solubilities io water; the lead and calcium salts are similar.The hydrogen su1phate.s form white amorphous very hygroscopic com- pounds which dissolve very readily in water and in alcohol ; they are insoluble in ether. The aqueous solution decomposes slowly at the ordinary temperature more quickly when boiled losing sulphnric acid. similar way ; but the action is much slower than in the case of cellulose. The products have the same general formula C6,Hlo,0,-,( SO,) as those obtained from cellulose but turn po1arised:liglit to the right. When the hydrogen sulphates are boilea with alcohol they lose all the sulphuric acid leaving modified forms of cellulose and starch respectively. N. H. M. Organic Iodides of Nitrogen. Rg; F. RASCHKG (AnnuZen 230 221-224).-RfeOhylnmiiie~ hydrochloride is completely converted into m e t h y Zdiiodamine Nl,Me when the theoretical quantity of iodine (dissolved in potassium iodide) is- added to a solution of methylamine hydrochloride and sodium hydroxide MeNH2,HC1 + 41 + 3NaOH = NLMeI + NaCl + 2NaI -!- 3H,O.Dimeth.yZiodumine,NMezI is obtained from d imethylamine by a similar reaction as a yellow precipitate. It is sparingly soluble i n alcohol and ether. I t soon decomposes and acquires a dark colour. A solution of potash changes tthe colour of the compou a d to greenish-yellow without Anhydrous starch is acted on by sulpliuric acid inORGASIC CBEMISTRI'. 45 affecting its composition. Iododimethylamine and di-iodomethylamine decompose without exploding when they are touched by a hot body. Etkyldi-bdamine and diethyliodamiiie are obtained by sirnihr reactions in the form of brick-red and orange-coloured precipitates.They rapidly decompose into iodoform and a dark blue liquid. w. c. w. Synthesis of a Ketone from (Enanthylidhe. By A. &I. &$HAL (J. Pharm. [ 5 ] 811 155-158).-AmyZ meihyl ketone C5H,*COMe is obtained by dissolving mnanthylidine in sulphnric acid diluting with water and distilling. It forms an oily liquid of pungent odour boils a t 147-148" under 759.2 mm. pressure shows the property of a ketone jieldiiig a hydrogen sodium sulpbite compound &c. and on oxidation is converted into aceticband valeric acids. .A. J. G. Action of Bromine in Alkaline Solution on Amides. By A. W. HOFMANN (Ber. 18 27~-2741).-Chloracetamide -is acted on by bromine in alkaline solution with formation of a compouud CH,CI*NH*CO*NH.C,H,CLO.This substance me1 ts at; 180" and is spar- ingly soluble ; it is decomposed by acids or alkalis into chloracetic and hydrochloric .acids,*carbonic anhydride ammonia and met haldehyde. Ethoxyacetamide when treated with an a l h a h e solution of bromine yields a compound EtO*CH~.*NH*CO*NH*C,H?O.OEt. It crystallises in cdcmrless needles which melt at 80° and is decomposes by acids and alkalis into et,hoxyacetic acid alcohal ammonia and mcth- aldehyde. When 1 mol. of phenylacetamide is acted on by 1 mol. bromine and 4 mols. of a 5 per cent. solution of alkali and then distilled in steani much benzylamine is obbained together with some bromobenzylamine which may be 4 convert,ed by (the action of sodium amalgam into benzylamine.IJy drocinnamamide is prepared. by heating ammonium hydrocinna- mate for five hours a t 220" ; it forms small thin needles which melt a t 105". When treated with bromine in -alkaline solution and then distilled with steam it yields a .mixture of phenylethylamine and a bromine-derivative C8H8Br*NH2 which boils at 252-254". To obtain pure phenylethylamine the mixed product contained in the distillate is treated with sodium amalgam. The yield is about 60 per cent. of the theoretical. .The yield is about 30 per cent. N. H. M. Action of Ethyl Acetoacetate on the. Amidines Pyrimidines By A. PINNER (Bey. 18 2845-2852).-Jn order to test the general character of this -reaction (Abstr. 1885 158 751) the author has tried to prepare the corresponding pyrimidines from various amidines and he finds that with the exception of formamidine all t h e nmidines experimented with are capable of yielding pyrimidines.When formamidine hjdrochloride (25 grams) is treatled with the calculated amouirt of ethyl azetoacetate a 10 per cent. solution of sodium carbonate added and the whole allowed to remain several weeks a substance is obtained which crystallises in long broad silky needles melting at 70-71" is readily soluble in the ordinary solvents with46 ABSTRACTS OF CHEMICAL PAPERS. the exception of water and has neither acid nor basic properties ; its composition indicates it to be ethyZ cyanoacetoacetate CHS.C(CN) CH*COOEt. Acetamidine reacts readily with ethyl acet oacetate yielding di- nl.ethyZhycZroz~~?/1.imidine CMeqN C(oal>CH ; this forms lustrous needles melts at 192" is readily soluble in water and alcohol sparingly in ether and cold benzene.EtJi yZn7p,thyZhy~rox~pyrimI'dine CiHloN,O obtained from propionamidine and ethyl acetoacetate forms ,slender white needles melting at 160" and readily solnble in water and alcohol. The hydrochloride C,HloN20,HCi crystalliees in thick prisms melts at 240-2413' with decomposition is very readily soIubIe in water and somewhat less so in alcohol. The platino- chloride forms thick yellow prisms melting a t 236" with decom- position. Succinimidine rezcts with ethyl acetoacetate wihh elimination of only one molecule of water and production of a compound N -CMe C4HJT,HZ*C4H,O2. A description is given of some more derivatives of phenylmethyl- liydroxypyrimidine (Zoc.cit.). When a solution of silver nitrate is added to a hot aqueous or alcoholis solution of the pyrimidine a clear solution is obtained from which ammonia throws down a white granular precipitate of the silver salt ; i t is extremely soluble in excess of ammonia and in nitric acid. On adding bromine to a solution of phenylmethylhydroxgp.yrimidine in chloroform four atoms of the halogen are taken up with formation of the compound CllH10N20Br4 which crjstallises in yellow lustrous needles melting a t 245' with decomposition. It dissolves slowly with decomposition when boiled with alcohol and on cooling colourless transparent needles of the composition C1,H,N2Br separate melting a t 260". Phenylmethyl- hydroxypyrirnidine is not acted on by nascent hydrogen but may be reduced by distillation with zinc-dust the pheny Znzethy Zpyri- midine CI,HI,Nz obtained melts a t 74-78' and yields a platino- chloride melting at 190" with decomposition.Chromic acid and alkaline potassium peymanganate have little action on the hydroxj- compound whilst acid permanganate oxidises i t readily with produc- tion of bcnzamide. Attempts to reduceg~henylmethy7c7~Zoropyi.imidiize CI1H9N2Cl (Abstr. 1855 159) by the action of sodium amalgam on its alcoholic solu- tion yielded phemylmethy k e t h o x ~ ~ y r i m i d i i z e CIIH9N2*OEt which how- ever is more readily obtained by boiling the chloropyrimidine with sodium nlcoholate. It forms thick colourless transparent prisms melting a t 30-31° boils a t 300-301" is insoluble in water and ihlkalis readily soluble in alcohol ether and acids. The hydro- chloride C,H,N20Et,HC1 + 2H,O crystnllises in slender white very soluble needles and when dried melts a t 148-149" ; it breaks up at about 150" into phenylmethylhydroxypyrimidine and ethyl chloride.The plutinochloride (C,H,N20Et)2,HzPtC16 melts a t 197" with decom- position. The hydriodide Cl,H9N20Et,HI( + &HzO 3) forms yellowORGANIC CHEJIISTRY. 47 prisms or long needles very sparingly soluble in cold moderately solnble in hot water ; i t meIts a t 143.5". Phenylm ethy~~lyrin2idinean~~lide F,H,N,*NHPh is obtained on heat- ing the chloropyrimidine with a,niline. The hydrochloride forms small slender needles which blacken a t 236" and melt with decompo- sition a t 240". The free base melts a t 150-153" and its nitrate at 85-87".A. K. If. Condensation of Acetoacetates with Bibasic Acids. By .R. FITTIG (Bei-. 18 2526-2527).-Ethereal acetoacetates condense readily with bibasic acids with elimination of 2 mols. HzO. With succinic acid and ethyl acetoacetate %I crystalline compound CloH1205 melting a t 75-5-76' is obtained. This is the monethyl salt of a bibasic acid C,H805 ; the free acid is crystalline melts a t 199-200° and loses carbonic anhydride a t a slightly higher temperature. From ethyl acetoacetate and sodium pyrotartrate the monethyl salt of the homologous acid C9H1005 which melts a t 194O is obtained. The investigation of these acids is proceeding. Condensation of Aldehydes with Bibasic Acids. By R. F~TTIG (Ber. 18 2523-2525) .-By the condensation of succinic acid with acetaldehyde propaldehyde isobutaldehyde valeraldehyde or cpnanthaldehyde a single lactonic acid .is formed in each case in accordance with the equation XmCHO + COOH*CH,-CH,*COOH = < ~ ~ ~ ~ 2 > C H * C O O H ; with pyrotartaric acid on the other hand A.J. G. two isomeric lactonic acids < ~ ~ ~ ~ z > CMe-COOH and < &,:%t>CH-COOH are obtained. Benzaldehyde and pyrotartaric acid give i n addition to the acid described by Penfield a second isomeric acid melting a t 123.5". These lactonic acids when heated lose carbonic anhydride arid are converted mainly into monobasic acids the isomeric lactones being obtained as bye-products. The constitution of these unsaturated acids is still uncertain except in the case of the acid C6H1,02 derived from the lactonic acid prepared from propaldehyde and succinic acid which has been shown to be identical with hydrosorbic acid. Salicylaldehyde and succinic aldehyde yield a dicozcniarin very similar in chemical behaviour to coumarin.succinic aldehyde yield two acids of the formub Anisaldehyde and MeO*CsH4*CR CH*CH,*COOH and MeO*CGH,*CH CH.C(COOH) CHC6H,*OMe respectively. No description is given of these su bstnnces. A. J. G.45 ARSTRACTS OF CHEMICAL PA1 ERS. Tartronic Acids. By A. PrNNEn (Rer. 18 2852-2854).--The author finds that no better jield of this acid is obtained by Baponi- fying trichlorolactic acid directly,with haryta water and he prefers t o use the method previously given (Abstr. 1885 759). Experiments in which other precipitants (in the place of barium chloride) were employed gave unsatisfactory results. In the preparat>im of ethyl tartronate only a part of the acid is converted into normal ethyl salt some hydrogen ethyl-derivatirn being also probably formed.The normal salt boils .at 222-225" is readily decomposed by water and is readily converted into the amide by the aktion of ammonia. The only secondary products produced in the preparation of tartronic acid which the author has been able to confirm are di- chloracetic acid and a small quantity of oxalic acid. Tartivnnmide OH*OH ( CON Ha)z forms six-sided sales melting at 195-1 96" with decomposition. I t is sparingly soluble in cold water moderately in hotr and sparingly in alcdhol. Malic Acids. By H. VAN'T HOFF jun.(Bey. 18,2713-2714; corn- yare Abstr. IF8.5 1202).-Inactive mdlic acid from monobromo- succinic acid prepared from fumaric acid and hydrobrsmic acid (identical with that examined by Anschutz &id. p. 1049) and an inactiue nialic acid obtained by the action of soda and water on tnaleic acid are shown by crystallographic measurements to be identical with .Pasteur's acid. A. K. M. N. H. M. Decomposition of Malic Acid obtained from Fumaric Acid. By G. J. W. BEEMER (Rec. Tmv. Chim. 4 180-182).-It is usually st,ated that the inactive malic aoid obtained from fumaric.acid is a distinct modification and cannot be decomposed into the lavo- and dextro-acids. :This is however not the rase as by the fractional crystallisation of its cinchonine salt it malic acid is obtained whose hydrogen ammonium salt shows a specific rotary power identical with that of the corresponding salt of the natural acid (Ber.,.13 352).Constitution of Isosaccharic Acid. By H. KTLIANI (Bey. 18 2514-2518).-In the author's last paper on this subject (Abstr. 1885 'i44) the position of m e of the hydroxyl-groups was still left unsettled ; he now shows that the dihydroxypropenyltricarboxplic acid obtained by oxidising isosaccharic acid (Zoc. cit.) yields a dihy- droxj-glutaric acid not identical with the /%V-dihydroxy-acid ; this must therefore be the a-y-acid A. P. COOH*CH( OH).CH,*CH(OH) 'COOH. From this isosaccharic acid must have the constitution COOH*C(OH) (CH2*OH)*CH,*CH( OH) *COOH. a-l- DiAydmzyg)Iutaric acid is best obtained by heating dih ydroxy- propenyltricarboxylic acid for four hours at 120" I t crystallises in colourless prisms begins to soften at 106" with loss of water and only fuses completely at a considerably higher temperature; it isORGANIC CHEMISTRY.4 9 nearly insoluble in ether readily soluble in alcohol and water. The calcium salt C5H606Ca -k 3H20 forms white nodular crystals sparinglg soluble in water. S- -Dihy droxyg Zutaric acid COO H*CH,*CH( OH) *CH( OH) *C 00 H is obtained by converting glut'aconic acid COOH-CH,*CH CH-COOH into dibromoglutaric acid by treatment with bromine and boiling the product in dilute solution for two hours and a half with calcium car- bonate. It crystallises in needles or six-sided plates melts a t 155- 156' and is sparingly soluble in alcohol very readily sduble in water.It is further distinguished from the a-yacid by the ready solubility of its calcium and cadmium salts. A. J. G. Oxidation of Benzene. By J. G. HOLDER (Arner. Chew,. J. 7 114-116).-When treated in the cold with manganese dioxide and sul- phuric acid benzene yields carbonic anhydride and a small quantity of benzoic acid ; neither formic nor phthalic acid could be detectld. By gradually adding sulphuric acid to benzene and lead dioxide i L vigorous reaction occurs and carbonic anhydride and benzoic acids i r e formed ; no succinic acid was observed. Potassium permanqanate acts very slowly ; lead dioxide and boiling dilute nitric acid yield only oxalic acid ; chromic acid yields only carbmic anhydride. H. B. Parachlorometanitrotoluene and its Reduction-products.By L. GATTERMANN and A. KAISER (Ber. 18 2599-2602).-This compound was prepared from metanitroparatoluidine hydrochloride by treatment wit8h cuprous chloride and sodium nitrite. It crystallises in yellow needles melts a t 7" to a strongly refractive golden-yellow oil of sp. gr. 1.297 at 22" (water at 62" = l) and boils at 260-261' under 745 aim. pressure. I t seems to be identical with the a-nitro. compound obtained by Wroblewsky by the direct nitration of pam- chlorotol uene. Parnc hlorometanityot oZuid ine C,H,MeC l-NH2 obtained by reduction of the nitro-compound crystallises in thin colourless tables melts at 29-30" and has an odour similar to that of naphthylamine. The hydrochloride crystallises in colourless needles the salphate in broar 1 needles or plates ; the acetyl compound crystallises in colourless needles and melts a t 96'.A. J. G. Action of Phenyl Cyanate on Polyhydric Alcohols. By H. TESMER (Ber. 18 2606-2610 compare Abstr. 1885 774) .-The author coutirrns the formula C6H90 (O*CO*NHPh) previously given for t,he quinovide of phenylcarbaniic acid. Quercyl penta~heriylcnrba.nznte C6H7( O*CO.NHPh) is prepared by heating quercite and phenyl cyanate in sealed tubes at 165" for two hours; it is an amorphous white mass melts somewhere betwetn 120-140" and is soluble in the ordinary solvents except light petro- leum. When heated with aqneous baryta a t 1-50" it is decomposed into aniline quercite and carbonic anhydride. SucchttryL pher~yZc~~bimate C6H,O,(0.CO*NHPh> + CONPh pre- VOL. L e50 ABSTRACTS OF CHEMICAL PAPERS.pared in a similar manner from saccharin crystallises in silky inter- Iitced needles melts at 230-240J with decomposition. It is sparingly soluble in benzene and alcohol soluble in ether readily soluble in aniline; aqueous baryta at 160-170" converts it in aniline and barium carbonate and saccharate. Metasaccharyl pliemylcarbamate C6H,02( O.CO*NHPh) + CONPh is obtained as an amorphous white powder which softens a t 205" melts about 210" and is soluble in most solvents. With aqueous baryta it yields aniline and barium carbonate and metasaccharate. IsosacchnryZ plienylcarbamate C6H,02(0*CO-NHPh) + COKPh also forms an amorph(lus white powder softens at 180" and melts at 181" ; with aqueous baryta it is decomposed in the same manner as the preceding compounds.Quercetyl phenylcarbama,te C2&06(0*CO*NHPh) prepared by heat- ing quercetin and phenyl cyanate at 160° is a pale yellow amorphous mass. It melts a t 'LOO-205" and is insoluble in most solvents. Aqueous baryta at 270" decomposes it into quercetin aniline and barium carbonate. Pl a v y u r p r y 1 p heny lcarbamate C J&03 ( 0 *C ONHP h ) 2 is prepared by heating flavopurpnrin and phenyl cyanate at 165" ; it crystallises in yellowish microscopic plates insoluble in most solvents ; boiling aniline dissolves it with formation of flavopurpurin and diphenyl- carbamide ; alkalis resolve it into flavopurpurin aniline and carbonic anhydride. A. J. G. Para- and Meta-phenylene Cyanate. By L. GATTEHMANN and E. WRAMPELMEYER (Ber. 18 2604-2606).-ParaphenyZene cyanate C6H4(N CO) is prepared by the actlion of carbonyl chloride on paraphenylenediamine ; it crystallises in white needles melts a t 91" boils a t 231" under 745 mm.pressure. It shows a close resemblance in reactions and properties to pbenyl cyanate giving paraphenylene- dicarbamide wit'h ammonia diphenylphenylenedicnrbamide wi tli ani- line &c. When heated with absolute alcohol it yields prrraphenylene- urethane C6H,(NH*COOEt)2 which crystallises in colourleso prisms and melts at 193". Paraphenylenecarbamide is also formed in the preparation of paraphenylene cyanate. Metaphenylene cyanate is prepared in similar manner to and closely resembles the para-compound. Resorcinol-derivatives. By G. ERRERA (Gurzetta 15 261-274). -Trinitrodi~benzo~~lresorcino7 ?J02.CsH,(0.C0.C6H,*N0,)2 obtained by the action of nitric acid (sp. gr 1.4) on dibenzoylresorcinol is a yellow amoiaphous substance melting at 123- 124" insoluble in water sparingly soluble in alcohol readily in benzene and chloroform.It is not decomposed by hydrochloric acid but is saponified completely by alcoholic potash into nitroresorcinol together with iso-dinitro- resorcinol and metlanitrobenzoic acid or the latter and benzoic acid according to the conditions of the experiment. The nitroresorcinol and metanitrobenzoic acid can be separated by treatment with acetic chloride o r by the different solubility of the copper salts or by the etherification of the acid. A. J. G.ORGANIC CHEMISTRY. 51 Trinitrodibenzoylresorcinol is reduced by tin and hydrochloric acid to amidoresorcinol and amidobeneoic acid.Mononitrodibenzoylresorcinot N02*C6H3(OEh)2 prepared either b y the action of zinc-dust on a mixture of nitrosoresorcinol (1 mol.) with benzoic chloride (2 mols.) or by the nitration of dibenzoylresor- cinol by a mixture of nitric and slslphuric acias crystallises in acicular needles melting a t 110" ; on hydrolysis it yields mononitroresorcinol and benzoic acid and on reduction benzoic acid and amidoresor- cinol . Mononitromonobenzoy I r e s o r c ~ ~ o Z N02*C6E3( OH) GBz obtained by heating a mixture of nitiwresorcinol and benzoic chloride in equi- molecular proportions crystallises in pale-yellow needles. Mononitrodiacetylrcorcino~ NOz*C6H3(OAe)2 from acetic chloride and nitroresorcinol forms long lamellar colourless crystals melting a t 90-91" ; it is converted by bromine into Weselsky's dibromonitro- resorcino1.V. H. V. Fluoresceins from Maleic Acid. By R. BUECKHARDT (Ber. 18 2864-2870) .-This is a continuation of the work published L-y Lunge and Burckbardt (Abstr. 1884 1340). CH ' 'IX is formen Dinzethy I m a l e ~ ~ u o r e s c e i i z 0 <C6H3(0Me) > C <o-co > C,H3( OMe) when a solution of rnalei'nfluoresce'in'in mkthyl alcohol is boiled witli alcoholic potash and methyl iodide and crystallises in red needles. Unsuccessfiil att.empts were made to obtain a bromine-derivative corresponding with eosin but no definite product could be obt,ained. Male'influormceh reacts with acetic chloride yielding a diacetyl-derivu- t h e C16HL006A~2 crystallising in yellowish-white needles me1 ting at 157" ; it is sparingly soluble in alcohol readily in glacial acetic acid and insoluble in water chloroform cai*bon bisulphide and benzene. CH'CH a-NuphthoZma1e~f2uoresceinn < co'o> CfC,oH,*OH) obtained on heating maleic anhydride (1 mol.) with a-naphthol (2 mols.) and zinc chloride a t 160° forms a violet powder which yields a red solution with alcohol the addition of ammonia producing an intense green-red fluorescence ; t,he solution changes on exposure to the air becoming first violet and then dirty brown.The compound is also soluble in ether glacial acetic acid chloroform ethyl acetate and methyl alcohol but is insoluble in benzene and carbon bisnlphide. It melts a t 118- 120". A second compound Cl4H,O4 is formed simultaneously with the last substance by the union of maleic anhydride (1 mol.) with a-naphthol (1 mol.).I t crystallises in small hygroscopic needles melting a t go" dissolves in the ordinary solvents with the exception of benzene toluene and carbon bisulphide ; also in hydrochloric acid water and ammonia. It forms a lead salt of the compositioti @-Naphthol yielded no fluorescent product with maleic anhydride the statement previously made (Zoc. cit.) referring to the employment of fuiuaric acid. The product of the latter reaction forms a yellow solution witli alcoh:)I which exhibits an intense moss-green fluor- escence on the addition of ammoilia. C?,Hl,Pb04. e 252 ABSTRACTS OF CHENICAL PAPERS. The reactions of several other phenols with maleic anhydride hare also been tested qualitatively. C hloro- and Ltromo-derivatives of Phloroglucinol.By K. HAZURA and R. Bmxm" (Monatsh. Chem. 6,702-707).-Heleabrorno- 1) hloroglucinol dibrornide C.16Br3(O13r)3,Br2 is obtained together with phlorobromine when a solution of 10 grams of phloroglucinol in 1 litre of water (at 40") is treated with 96 grams of bromine added 24 grams a t a time. It dissolves very readily in chloroform from which it arptallises in small yellowish-white needles melting a t 118". Sulphurous acid converts it into tribromophloroglucinol melting a t 151". When heated a t 156" it gives off a part of its bromine. Hexahyd.F.otrichloroy~loroy lucinol C6H9cl& 4- 3H20 is prepared from the above compound by the action of tin and hydrochloric acid ; it forms long white crystals which melt a t 125O.At 100" it loses its water of cry stallisa tion. TrichlorophlorogZuc~no7~ C6CI,H30s + 3H20 is prepared by the action of chlorine on a solution of phloroglucinol in glacial acetic acid. It softens when heated a t 120" amd melts at 129". At 100" it loses 3 mols. of water. N. H. M. A. K. M. Thymolphosphoric Acids. By G. DISCALZO (Gazxetta 15 278- 282).-Monothy~nolpl~osphonyZ chloride POC12*O*C6H,MePr prepared by heating a mixture of phosphorus oxychloride and thymol in equi- molecular proportions is a colourless mobile liquid boilin5 with slight decomposition a t 280-285". When heated with water it is converted into the corresponding acid PO(OH),*O*C6H3MePr a thick oily liquid sparingly soluble in wa%er soluble in alkalis decomposed completely on distillntion into thymol and metaphosphoric acid.I t s barium salt crystallises in prismatic laminae. DithymoZphosphonyZ chloride POCl (OC8H3MePr) prepared from a mixture of thymol ( 2 mols.) with phosphorus oxychloride (1 mol.) is a colourless fluorescent liquid boiling at 330-340" under a pressure of 320 mm. It is decomposed by water forming ditkymoZphosphoric acid PO( OH)(O*C6H3MePr)2. This substance is insoluble in water ; its barium salt crystallises with 5Hz0 in delicate colourless needles. V. H. V. Nitration of Parabromaniline. By H. HAGER (Bey. 18 2578). -When parabromaniline is nitrated the bromine-atom is displaced and picramide (trinitraniline) formed. Action of Isbutyric Acid on Aniline. By F. L. BARDWELL (Amer.Chem. J. 7,116-118).-Aniline and isobutyric acid do not react with each other until zinc chloride is added when isobutyranilide is formed ; the yield is increased by heating the mixture. It crystal- lises in colourless prisms and melts at 102.5". By the action of bromine-vapour on the aqueous solution a yellow precipitate is formed which when treated in alcoholic solution with charcoal yields colour- less needles of parabromisob?ctyrnnilide C6H4Br*NHCaH,0 ; itJ melts a t 128" and when heated wit11 aqueous hydrochloric acid yields para- A. J. G.ORQANIC CHEMlSTHY. 53 bromaniline ; treated with nitric and sulphuric acids it yields para- bromorthonit'raniline. H. B. Metadinitroazoxybenzene and Orthazoxytoluene. By H. KLINGER and H. PITSCHKE (Bsr. 18 2551-2556) .-Metadinitroazozy- benzene N0,.C6H4.N2(~.C6HI*N0 is obtained by treating metadinitro- benzene with a small quantity of sodium methoxide dissolved in methyl alcohol.It crystallises in long straw-yellow needles melts a t 141-142" is sparingly soluble in alcohol somewhat more soluble in ether and carbon bisulphide moderately soluble in benzene and toluene. Metndinitrohydroxyazobenxene N02*C6H,*N2*C6H3(OH) *No2 is ob- tained by heating a solution of the azoxy-compound in sulphuric acid at 140" ; it forms a yellowish-brown indistinctly crystalline mass and melts a t 172-173". It dissolves in dilute alkalis with yellowish-red colour. The silver salt C,2H,NaOa*OAg is obtained as a red crystalline precipitate. Orthazoxytoluene C6H,Me.N20*C6H4Me is prepared by the action of sodium mcthoxide on orthonitrotoluene ; it cry stallises in yellow monosymmetric tables or needles a b = 044158 1 ; @ = 68" 37' ; observed faces OP mPm o3P; melts at 59-60" and explodes when more strongly heated.When distilled with iron it yields orth- azotoluene together with a little orthotoluidine. When heated with sulphuric acid it undergoes a peculiar decomposition much orthazo- toluene being formed (44-48 per cent.) together with amorphous substances. A. J. G. Methylene-Blue Group. By A. BERNTHSEN (Annalen 230 i3 -21 1) .-A considerable portion of this research has already appeared in this Journal (Abstr. 1883 916; 1884 595 1156; 1885 259). L euco t hionine or &amid ot hiod ip hen y 1 amine NH<c6H3(NH2)>S [NI-I NH NH S = 4 1 4 61 LHs(NH2) is formed by the action of tin and hydrochloric acid on a-dinitro- diphenylamine sulphoxide Under similar treatment /%dinitro- diphenylamine sulphoxide NH<C6H'(No2) >SO yields Zeuco-isotl~io- nirze c6H4<~~>c6H,(NH2)~.On oxidation with ferric chloride isothionine NH/~6H2(NK2)>S is produced. I& is a dark crystal- line powder sparingly soluble in water and freely soluble in alcohol yielding violet-red solutions. It dissolves sparingly in warm benzene forming an orange-coloured liquid. The hydrochloride C,H,N3S,2HCl is freely soluble in water and alcohol. The aqueous soluhion is violet- red and dyes silk amethyst. The addit,ion of strong hydrochloric acid does not turn the solution blue as is the case with thionine. The salt dissolves in strong sulphuric acid with violet coloration.The composition of methylene-blue was ascertained from the analysis of the hydriodide C,H,N,SI and the hydrochloride C6H3(N02) 'N0c6H4 -54 ABST LlACTS OF CHEMICAL PAPERS. C,H,N,SCl+ 3H,O. The aqueous solution of the free base (tetra- methylthionine hydroxide) is obtained by treating a dilute solution of tJhe hydriodide lwith freshly precipitated silver oxide. On evaporat- ing the solrmbiion in a vacuum over sulphuric acid a t the ordinary tem- perature the Tree base remains as a dark amorphous mass. It dis- solves freely in alcohol and in water. The preparation and properties of leucomethylene-blue (formerly called methylene-white) have been already described (Absts. 1883 916). Pentamethylleucothionine- dimethiodide C,H,N,S,ZMeI is formed by the action of methyl iodide arid methyl alcoliol on leucomethylene blue a t 110".The com- pound is soluble in hot water but insoluble in ether. It is decom- posed by moist oxide of silver yielding the ammonium base CsH3(NMe3*OH) JZ-<C,H3(NMe,*OH)>S' On evaporating the alkaline liquid the base remains its a brittle amorphous mass soluble in alcohol and in water. It is decomposed by heat yielding methjl alcohol and pentamethylleucothionine. The consthtion of leucomethylene-blue or tetramethylparadiamidothio- dipheylamine is proved to be by the fact thad it yields on methylation the same pentamethylleuco- thioninedimethylammonium iodide which is obtained from leuco- thionine. The free base of methylene-blue is represented by the formula HO*NMe/ I CsHi---- S 'N*CsH3 (NMe) Nethylene-red is obtained as a bye-product in the preparation of methylene-blue.It is contained in the mother-liquor from which the niethylene-blue has been precipitated. The pure compound is deposited from alcohol in glistening green prisms soluble in water. The aqueous and alcoholic solutions exhibit a purple colour which disappears on the addition of an alkali. The coloiir does not re- appear on acidification. A blue colour is produced by oxidation. Reducing agents also destroy the purple colour and in this case sul- phuretted hydrogen is liberated. The hydrochloride of methylene- red has the composition CIsHI,N4S4,2HC1. On the addition of am- monia to methylene-red a yellow-coloured base is precipitated. It is soluble in alcohol and in ether.I t is precipitated from the alcoholic solution by water. When methylene-blue is treated with a dilute solution of an alkali it mixture of methylene-violet methylene-azure leucomethylene-blue and other leuco-products is formed. Methylene-violet is best ob- tained in the pure state by decomposing methylene hydriodide with silver oxide and boiling the aqueous solution of the base for several hours. The solution deposits crystals of pure methylene-violet and the mother-liquor contains methylene-azure. The precipitate of silver iodide is mixed with a considerable qnantity of leuco-bases. >.Metky lene-violet or r3osited from alcohol ORGANIC CHEMISTRY. \ CGHS- s dimet h y It hionol ine O<r?.C,tr,(NMe,) /> is in long needles soluble i n chloroform 55 de- and Sparingly soluble in hot water.The solutions have a red or violet- red colour and are fluorescent. The hydrochloride C14HI,N2S0,HC1 crystallises in long needles of a dark green colour. It is insoluble in cold dilute hydrochloric acid. The aqueous solution dyes wool or silk violet. The iodide and chromate are very slightly soluble in hot water; in other respects they resemble the corresponding salts of methylene- blue. Leucorn ethylene-violet is deposited from alcohol in white plates or scales. The solution in acids is stable but the solu- tion in alkalis absorbs oxygen with great avidity and deposits methylene-violet. The hydrochloride i H crystalline. I n order to obtain methylene-azure in a state of purity the mother-liquor from which the methylene-violet has been deposited is treated with an alka- line solution of stannous chloride.The liquid is mixed with half its volume of alcohol and left for some time in a closed vessel. The leuco-azure which is deposited as a crystalline mass is washed dissolved in dilute hydrochloric acid and oxidised by ferric chloride. On the addition of common salt rnethylene-azure is precipitated. It is dis- solved in water reprecipitated and converted into the hydriodide. This salt is more soluble in water than methylene-blue hydriodide which it closely resembles. The hydrochloride is also very soluble in water. The solution dyes silk blue. The hydrochloride dissolves in strong hydrochloric acid with a blue coloration and in strong sulphuric acid with a green colour.It is decomposed by boiling with a strong solution of potassium hydroxide with formation of dimethyl- amine. The preparation of oxythiodiphenylimide and hydroxythiodip henyl- amine has been already described (Abstr. 1885 260). The constitution of these compounds may be represented by the formulm- 0/76H3*S > and C,H4<kg> C,H,*OH. 'N*C6H4 Silk immersed in an alkaline solution of the latter compound is dyed crushed strawberry. S treating thiodiphenylamine with sulphuric acid diuted with one-fifth its weight of water at 160" for 24 hours. The product of the reaction is poured into water mixed with excess of sodium hydroxide and filtered. On the addition of hydrochloric acid t o the hot filtrate thionol hydrochloride is deposited in glistening green crystals.The free base is insoluble in cold water but dissolves freelyin acids. It is deposited from glacial acetic acid in plates. The alcoholic solu- tion is of a purple colour and the solution in strong sulphuric acid is blue. The sulphate 2ClaH,NS02,H2S04 forms green needles. The barium salt C1zH7NSO3Ba crystallises in plates exhibiting a green56 ABSTRACTS OF CHEBlICAL PAPJIRS. lustre. Silk immersed in a solution of thionol in potassium car- bonate acquires a violet colour which turns red on exposure to tlie air. Thionol is formed in small quantities by the continued action of alkalis on methyletie-blue ; it is also a product of the action of alkalis or of strong sulphuric acid on thionine. C6H3(0H)>S is formed by treating an am- Leucothionol NH< It is deposited from its On treatment with ') is formed by adding ferric chloride to amidophenol which has been saturated with snlphuretted hy- drogen. It is also produced by the prolonged boiling of thionine in water NCI2H6S(NH2)NH + H,O = NC12H6S(NH,)0 + NH3.Thionoline dissolves in hot alcohol forming a purple solution ; the C6H3(NH2)>S is soluble in acids and in alkalis. leuco-compound NH< The nitrate sulphate and hydrochloride of thionoline crystallise in needles. Strong sulphuric acid dissolves thionoline forming a blue C6H4 OH) nioniacal solution of thionol with zinc-dust. ethereal solution as a crystalline colourless mass. acetic anhydride it yields a triacetyl derivative. 'N-C6H3(NH2) CsH - Thionoline Q/ I C6H3( OH)- solution. Methylene-violet is dimethylthioDoline.w. c. w. Benzyl Compounds. By 0. BORGMANN (Chern. Centr. 1885 456-458). -This communication contains an account of several metabenzyl compounds prepared from metanitrobenzyl alcohol Home of which have already been described (Abstr. 1883 1121). Pyiniary metanitrobenzy lanaine N02*C,H1*CH2*NH is formed by treating metaiiitrobenzyl chloride with alcoholic ammonia ; it is a yellowisli oil absorbs carbonic anhydride from the air forming a solid salt and yields a sparingly soluble oxalate and platinochloride. The secondary amine NH(N02*C6H4*CH2) formed with the primary crystal- lises in yellowish rhombic leaflets melting at 87" ; its hydrochloride and platinochloride are both sparingly soluble salts. When reduced bp tin and hydrochloric acid it forms an anlido-compound the hydro- chloride of which crystallises from concentrated hydrochloric acid in long reddish needles having the composition N(NH2*C6H4*CH2)2,SHC1. The base crystallises in prisms melting at 86-87'.Z'ertiary metanitrobenzylanzine N (NO,*C,H,*CH,) is formed by digesting met anitrobenzyl chloride with aqueous ammonia ; it crystal- lises in monoclinic prisms melts at 162O is soluble in glacial acetic acid and benzene but only sparingly in alcohol is insoluble in ether and does not unite with hydrochloric acid. When reduced with tin and hydrochloric acid it yields the tertiary amido-compound which crystallises in colourless needles melts at 142O and forms a sparingly soluble platinochloride. Amidobenzyl chloride is very unstable and is formed by the reduction of the niti-o-compound with tin and hydrochloric acid.Metar~itrodibenzylnzethylamine NMe( NO2*C6H4-CH2) is formed by acting on nitrobenzyl chloride with an aqueous solution of methyl- amine ; i t melts at 81". By the action of dimethylamine metnnifro-ORGASIC CHEJlIST RT. 57 7/enz~ZdinzethyZamine N0,*C6H,*CH,*NMe is formed ; it is a yellowish oil and forms a well-defined platinochloride. MetanitrobenzyZphenyZamine Ilu'0,*CsH4.CH,*NHPh is formed by the action of aniline on nitrobenzyl chloride; it crystallises in long orange-red needles melting a t 86" ; its hydrochloride forms white leaflets is an unstable compound and does not form a platiuochloride. When reduced by tin and hydrochloric acid this base forins nzetamido- benzyZ~l~enllZai,ziize NH,.C,H',*CH,*NHPh melting a t 67".Metanitrobenzaldehyde when treated wit'h concentrated sodium hydroxide yields meta-azoxybenzoic acid ON,( C6H,*C0 OH),. P. P. B. Ethylortholuidines. By R. L. CHASE (Amer. Chem. J. 7 118- 120).-These compounds have been prepared by Reinhardt and Staedel (Abstr. 1883 578). Ethylortholuidine formed from ethyl iodide and orthotoluidine boils a t 204-206" ; its salts are exceedingly soluble in water ; the chloride platinochloride iodide acetyl- and nitroso- compounds are mentioned. Diethylorthotohidine was prepared from the monethjl-derivative and ethyl iodide it boils between 203-208" ; the hydriodide crystal- lises well from water it contains 1 mol. H,O. H. B. Consecutive Orthoxylidine and Orthoxylenol. By A. TOHL ( Ber. 18,2561-2562).-Mo~tonitrodibromortho-xylene C6H~fe,Br,.N02 [Me Br NO = 1 2 3 4 51 is obtained together with the dinitro-compound by adding 4 5 dibromortho-xylene to cold fuming nitric acid. It crystallises in colourless needles and melts a t 141".Dinitrodibromortho-xy Zene C6Me2Br2(N0,) crys tallises in small needles and melts at about 250". Uibronaort/io-xyZidine C6HMe2Br,.NH2 is prepared from the mono- nitro-derivative by heating it with iron and acetic acid. It crystallises in colourless needles melts at lOS" distils with steam is readily soluble in alcohol ether and glacial acetic acid and does not yield salts with acids. The bromine is to a great extent removed by iong treatment with tin and hydrochloric acid but complete replacement can only be effected by the action of sodium amalgam on a warm alcoholic solution.Ortho-xy Zidine C6H,Me2*NH2 [Me Me NH = 1 2 31 so obtained is a colourless oil which turns brown on long exposure to air does not solidify at - 15" and boils a t 2.21-222". The hydrochloride C6H3Me2*NH2,HC1 + H20 crystallises in large lustrous tables and sublimes readily; the nitrate and sulpbate are also described. AcetzyZide C6H3Me,-NHAc cry stallises in long slender needles and riielts at 131". Ortho-xyZemZ C6H3Me2.0H [Me OH = 1 2 31 prepared in the usual way from the xylidine crystallises in very long slender needles melts a t 75" boils at 218O and yields a blue coloration with ferric chloride in aqueous solution. The tribroino-deiivative C,Me,Br,-OH crystallises in slender needles and melts at 184".A. J. G. Paraxylidine. By E. NOLTING 0. WITT and S. FOREL (Ber. 18 2664-2668).-Crude xylidine was found to contain about 25 per cent.58 ABSTRACTS OF CEEitlICAL PAPERS. of pnraxylidine boiling a t 215" under 739 mm. pressure. Sp. gr. = 0.980 (water at 15" = 1). Nitraceto-xylide melting a t 166" is obtained by nitrating the acetyl-derivative ; it yields a nitro-zylidine which melts a t 142" and crystallises from benzene in brownish-yellow lustrous crystals readily soluble in alcohol and ether. When nitro-xylidine is reduced xylenediainine is formed ; this cryshllises from benzene in small white needles melting at 146.5-147" which when oxidised yield paraxyloquinone. Ethyl nitrite acts on nitro-xylidine with formation of the ethyl salt of nitioparaxylenol ; it is a yellow substance melting at 85"." N. H. M. The Six Isomeric Xylidines. By E. NOLYING and S. FOREL (Ber. 18 2668-2681).-A description of these compounds and some derivatives is given. When consecutive ortho-xylidine is oxidised it yields ortho-xyloquinone C6H2Mez02 [Me2 0 2 = 1 2 3 61. This compound sublimes in yellow needles which melt a t 55" ; it is rather readily soluble in alcohol ether &c. It is reduced by sulphurous acid to the quinol a white substance melting a t 221". Ortlzo-xylenol [Me2 OH - 1 2 31 is obtained from the diazo-derivative of the base; it crystnlliscs from water in white needles melts at 73" and sublimes uiichanged. The aqueous solution acquires a pale-violet colour when treated with ferric chloride. 171etaxylylquinone C6H,Me,0 [Me2 0 = 1 3 2 51 is prepared by oxidising metaxylidine ; it forms splendid yellow needles which melt a t 73".The corresponding qwin,oZ forms white needles melting a t 149". When symmetrical metaxylidine is nitrated a nitro-derivative [Me2 NH2 NO = 1 3 5 41 melting at 54" is formed; this when reduced yields metaxyleneorthodiamine melting a t 77". When the hydrochlorides of the xylidines are heated with methyl alcohol a t 300-320" amidotrimethylbenzenes are formed. Consecutive ortho-xylidine yields a liquid amidotrimeth2/lbenzene boiling a t 240' ; the acety2-derivaticve meits at 1130". Symmetrical metaxylidine yielded a crystalline isocumidine which melts a t 67-68" and boils a t 245" (uncorr.) ; the acetyl-derivative melts a t 163-164" ; the cumenol melts at 98-99".N. H. M. Arnidoazo-derivatives of the Three Xylenes. By E. NOLTING and S. FOREL (Bey. 18 2681-2686). - Amidoazometaaylene C6H3.Me2-"L*C6H2Me2.NH:! [Me Me N Me NH Me = 4 2 1 2 3 41 is prepared by the action of 69 grams of a 20-25 per cent. solution of sodium nitrite on a well-cooled mixture of 121 grams ineta- xy lidine and 157 grams metaxylidine hydrochloride. The product is extracted with ether and the resiciue left on evaporating the ether is warmed with 120 grams of metaxylidine and 10-15 grams of meta- xylidine hydrochloride at about 50". It is then boiled with dilute hydrochloric acid and the sparingly soluble hydrochloride thus obtained is washed with water alcohol aod ether. The base is liberated by means of ammonia and crystnllised from alcohol or benzene.It forms orange-yellow plates which melt at 78" is almost insoluble in water readily soluble in hot alcohol and in benzene. The 7aydrocl~Zoride forms a bright Fellow crystalline powder ; its alcoholicORQANIC UIIKJIJSTRY. 59 fiolution is peen. When reduced it yields a diamine melting at Amido-azometnxylene [Me Me N2 :Me Me NH = 6 2 1 3 5 41 crystallises in yellow plates melting at 77.5" ; it dissolves readily in alcohol and in benzene. The alcoholic solution of the hydrochloride is red. Amido-azometazyZene [N Me Ne NH = 1 2 6 41 cryst'al- lises from alcohol in yellow plates melting at 95". The solution of the hydrochloride in phenol is violet. Amido-axortho-zy Zene [Me Me N2 Me Me NH = 3 2 1 2 3 41 forms yellow plates and melts at 110.5".Amido-axortho-xylene [Me Me N Me Me NH = 6 3 1 4 5 21 forms yellow plates melting at 179" ; it is sparingly soluble in alcohol. The solution of the hydrochloride in phenol is green. Amido-azopuraxylene [Me Me N Me Me NH = 5 2 1 3 6 41 crystallises from alcohol in red plates melting at 150". The hydro- chloride is red ; its solution in phenol is violet-red. When the base is reduced a diamine melting a t 146.5-147" is formed. Experiments made by the authors show that the nmidoazoxylene described by Nietzki (Abstr. 1880 552) is a mixed amidoaso-metapara- xy7ene [Me Me K Me Me NH2 = 4 2 1 3 6 41 ; it melts at 110-111". N. H. M. 77-78'. Azo-derivatives of Carvacrol. By G. MAZZARA ( Gazzetta 15 305 -315) .-In continuation of experiments on the azo-derivatives of thymol and carvacrol (Abstr.1885 904 and 1132) the author describes the preparation of an azo-compound by heating 1 mol. of bidiazotriphenylmethane with 2 mols. carvacrol dissolved in potash. There is thus formed a purplish-red amorphous substance carvacrol- bidiazotriphenylmet hane to which is ascribed the composition [OH*CsB2MePh~N,~C,H,*CHPh*CsH4*N,C,H2MePh]20. It melts at 130" and is soluble in ether and chloroform ; its potassium-derivative is a red precipitate ; when heated with bidiazobenzene it is converted into a red crystalline substance the composition of which has not yet been definitely established. By 33. HAGER ( B e r . 18 2573-2577).-Diphenylurethane is best obtained by heating diphenyl- amine with ethyl ch lorocarbonate.Di-orthonitrophenylurethaize (N02G,H,)2N.COOEt is obtained together with the para-compound by adding diphenylurethane to nitric acid of sp. gr. 1.44 and pouring the solution into much water ; the mix- ture is separated by treatment with a little hot benzene from which the para-compound crystallises on cooling. The ortho-compound forms a brown syrupy. mass readily soluble in alcohol and seems to be miscible in all proportions with benzene. Potash convert,s it into orthonitrodi- phenylamine. When heated alone it yields a mixture of products from which a colonrless liquid boiling at 141-143" and of the formula C,HIoO was isolated. This is insoluble in water readily soluble in ether and unites with bromine to form a yellow liquid yielding on distillation an oil which gives a nitro-derivative melting a t 181-182".V. H. V. Derivatives of Diphenylurethane.60 ABSTRACTS OF CHENICAL PAPERS. Di-paralLitrophe~ylui.ethane crystallises in yellow needles melts a t 133-134" is readily soluble in benzene sparingly in alcohol and yields paranitrodiphenylamine when boiled with potash. Di-pnmmidophenylurethane ( NH,*C6H4),N*COOEt + H,O is pre- pared by reducing the nitro-compound with tin and hydrochloric acid ; it crystallises in violet needles and melts at 101" with decom- position. When treated with benzoic chloride it yields a benzoyZ- derivative (NHBZ.C~H~)~N*COOE~ crystallising in flesh-coloured needles and melting at 210" ; this is not identical with the substance to which the author had previously and erroneously assigned this formula (Abstr.1885 150). Hexabronzod~phenyluretl~ane (C,H,Br,),N*COOEt is obtained by the action of bromine on solutions of dipheriylurethane ; it crystallism in long greenish-brown needles and melts a t 184". When treated with nitric acid it yields a nitro-compound crystalliving in yellowish- bro wn needles and melting a t about 245" with decomposition New Synthesis of Vanillin. By M. ULRICH (Ber. 18 2571- 2573).-1n 1881 Meister Lucius and Briining patented a method for obtaining three isomeric mononitrometamethoxybenzaldehydes. Tiemann (Abstr. 1883 189) and Schnell (Ber. 17 1381) have stated that this method yields not mononitro- but two diiiitro-derivatives ; t'he author however finds that when metamethoxybenzaldehyde is nitrated according to the directions of the patent the three rnono- nitro-derivatives are formed.The main product of the reaction is a-nitro-metametl~oaybenznlde- hyde ; it crystallises in thick yellow prisms and melts a t 107". /?-nitro- rnetanzethoeybenzaldehyde is formed in small quantity ; it crystallises in needles and melts at 82-83" As both these acids give the indigo reaction they must be the two ortho-nitro-compounds [ COH Me NO = 1 3 2 and I 3 61 ; there is no evidence as to which is which. The third ni tro-compound crystallises in cauliflower-like masses inter- spersed with prisms melts at 97" and does not give the indigo reaction; it has the constitution [COH Me NO = 1 3 51. Ptrranitrometl~oxybenzalde7~yde [COH Me NO2 = 1 3 41 is ob- tained as follows methyl metamethoxycinnamate is nitrated a t 0" with nitric acid of sp.gr. 1.46 and the paranitro-methyl salt separated by crystadlisation from the product when it is obtained in flat white needles melting a t 163". The free pnranitro-acid irepared f r o m the methyl salt is then oxidised with aqueous potassium permanganate by which means it is converted into paranitromethoxy- benzaldehyde. This crystallises in hair-like needles me1 ts a t 62" and is soluble iu water alcohol and benzene. When treated with acetone and soda it yields a colourless solution from which after a time colourless needles melting at 84" separate. By replacing the nitro-group by hpdroxyl vaniZlin is obtained. Paramidacetophenone Ortharnidometacetyltoluene and some of their Derivatives.By J. KLINGEL (Ber. 18 2687- 2706).-Paramidacetopheiione is best prepared by boiling a mixture of 2 parts aniline 3 parts zinc chloride and 5 parts acetic anhydride A. J. G. A. J. G.ORGASIC CHEMISTRY. 61 for five hours; the product is boiled with hydrochloric acid and treated with sufficient soda solution to precipitate and redissolve the zinc hydroxide. A brown oil then appears which is sepa- rated and distilled with steam to expel aniline. The residue is extracted several times with boiling water and the united extracts evaporated down; on cooling the amide separates. The yield is 50-60 per cent. of the weight of aniline used. Several salts are described. Acetylamidacetophenone COMe*C6H4 NHAc forms small white needles which melt a t 166-167" ; it is readily soluhle in hot water and in alcohol. Hydroxyacetophenone COMe.C6H4*OH = 2 4 is prepared by acting with sodium nitrite on a well-cooled solution of the base in dilute hydrochloric acid and then slowly heating the product with water until it boils.The phenol is extracted with ether. It forms white needles melting a t 107" readily soluble in hot water alcohol and ether. When the aqueous solution is treated with ferric chloride it acquires a dark-brown colour. IocloacetoJihenone C,&I*COMe is prepared from the amide by means of the diazo-chloride; it crystallises in white plates which have an agreeable odour and melt a t 79". It dissolves readily in alcohol and ether. When oxidised it yields pariodobenzoic acid. Dimethylamid- acetophenone COMe*CsHc*NMez is obtained by the action of methyl iodide on amidacetophenone and forms yellowish plates melting at 58-59".It is readily soluble in alcohol ether and hot water. Acetopkenonea,zonaplLthoZ COMe*CGH,N NGloH6*OH is prepared by the action of the sodium compound of /%naphthol on the diazo- chloride obtained from amidacetophenone. It forms groups of slender red needles with a slightly green metallic lustre insoluble in water sparingly soluble i n ether readily in alcohol. Dilnte alkali dissolves it readily with formation of a dark-red solution. Orthar?zidonzefacetotoluene [COMe Me NH = 5 1 21 is pre- pared from toluidine in a manner similar to amidacetophenone as described above. I n appearance it is very similar to amidacetoplienone ; it melts a t 102" and boils at 280-284".It dissolves readily in hot water alcohol ether and dilute alkali and is almost insoluble in light petroleum and benzene. Several salts are described ; they resemble the salts of amidacetophenone. The acety 1-derivative melts at 143- 144" ; it is readily soluble in warm water and in alcohol. Acetocresol COMe*C7H,- OH is prepared similarly to hydroxy- acetophenone ; it crystallises in reddish prisms melting a t 104" readily soluble in alcohol ether and hot water. When treated with ferric chloride it gives a yellowish-brown coloration. Diwiethy Zamido-acetotohene COMe*C7H6*N&2 crystallises in groups of flat prisms melting a t 95'; it is readily soluble in alcohol ether and hot water almost insoluble in light petroleum. Acety Ziodotoluene COMe*C7H61 is prepared by the action of hydriodic acid on the corresponding diazo-chloride ; it forms a yellowish crystalliue mass melting at 3Y" very readily soluble in alcohol and ether sparingly soluble in light petroleum benzene and hot water.When oxidised it yields iodophthnlic acid. This crystal- lises in slender white needles which melt a t 203-204" is very sparingly soliible in boiling water and dissolves readily in glacial62 ABSTRACTS OF CHEIIICAL PAPERS. acetic acid alcohol ether and warm chloroform. The barium salt forms slender white needles very sparingly soluble in boiling water ; the calcium copper and silver salts were also prepared. When iodophtbalic acid is treated with concentrated potash solution it is partially converted into parahydroxybenzoic acid ; nascent hydrogen converts it into benzoic acid.N. H. M. Mixed Axo-compounds. By E. BAMBERGER and A. CALMAN (Rer. 18 2563-2567 ; compare Abstr. 1885 157).-A mixture of phenylazoacetophenone and ethyl phenylazobenzoylacetate is o btainecl by mixing aqueous solutions of diazobenzene chloride ethyl benzoyl- acefate and soda. Phenylazoacetophenone COPh*CH2*Nz*Ph is obtained by heating the mixtu1.e with alcoholic potash and precipitating with water ; i t crystallises in slender golden-yellow needles melts a t 128.5" and is readily soluble in hot alcohol or acetic acid. Pheny Zazobenzo y 1 acetic acid COP h* CH (N,Ph) *C 0 OH obtained from the potash salt prepared as above crystal!ises in long citron- jellow needles melts a t 141" is soluble in ether alcohol and acetic acid and yields phenylazoacetophenone when boiled for some time with dilute soda.Orthonitrophenylazoacetophenone ?J02*C6H4*N2*CH2*COPh crystal- lising in lustrous golden-yellow needles melting at 140-141" and ortlhonitropheny Zazobenz oy Zacetic acid NOz* C,H4*N2*CH( C 0 Ph) *C 0 OH crystallising in sulphur-yellow needles and melting a t 177" are formed in similar manner from orthonitrodiazobenzene chloride. When heated for some time a t the melting point the acid loses carbonic anhydride and is converted into the ketone. By the action of hydroxylamine hydrochloride on the ammonium salt the compound NO*C6H4-Na*CH( CPh NOH)*COOH is formed ; this crystallises in orange-yellow needles and melts at 142". M~tartitrotoly2i3arccxobelzxo2Jlacetic acid NO2*C6H3Me*N2* CH ( C OPh) C 0 OH prepared from metanitroparatoluidine crystallises in silky golden- yellow needles melts at 194" and is very sparingly soluble in cold alcohol or acetic acid.NOz-C6H3Me*Nz*CH2*COPh crystallises in lustrous citron-yellow needles melts at 168" and with hydroxylamine yields the ketozime NOz*C,H3Me*Nz~CHz.CPh NOH ; The corresponding acetophenone this crystallises in reddish-yellow needles and melts at 174". A. J. 0. Crystallographic Examination of some Organic Com- pounds. By J. ZINGEL (Zeit. Kyyst. Min. 10 41$-420).-The crystalline systems and axial ratios are as follows :-Metatrimeth- amidobenzoic acid chloride ~&fe3C10C6H4*COOH ; monosymmetric ; u b c = 1.9388 1 0,8757 ; /3 = 88" 49'. Metadimethamido- benzoic acid NMe2*C6H4*COOH; asymmetric; a c = 1 1.9403.ORGANIC CHEMISTRY.63 Dinitroparatoluidine (m. p. 69-71'). Rhombic; a b c = 0-9965 1 0.5184. 2 4-Dinit,rophenyl metanitrobenzoate asym- metric; a b c = 0.7137 1 1.7671. A. J. G. Phenylacetic Acid. By R. MEYER (Chem. Centr. 1885 516- 51 8) .-Orthoparadinitrophenylacctic acid is prepared by adding phenylacetic acid to conceritrated nitric acid and pouring the mixture into concentrated sulphuric acid. The acid crystallises in colourless needles melting a t 160" (Abstr. 1884 178). Ethyl dinitrophenylacetatP crystallises in colourless needles melting a t 35"; it is more stable than the acid. Paramido-orthonitrophenylncefic acid is formed by reducing the dinitro-compound with ammonium sulphide ; it crystallises in long reddish-yellow needles which are soluble in alkalis and also in acids ; it melts a t 184-186".Attempts made to convert this compound into ortlionitrophenylacetic acid by the diazo-reaction have been without sumess. Ethyl amidonitr~henylacefate crystallises in long yellow needles melting a t 100"; this compound when treated with an alcoholic solution of ethyl nitrite and hydrochloric acid yields it compound having the composition C,H,N205 which crystallises in needles melting at 163". When heated with hydrochloric acid in sealed tubes a t 150-160° this compound is resolved into ethy-l chloride carbonic anhydride ammonia and orthonitrobenzoic acid ; this owes its production to the formation of nitrosomethy lorthonitro- 7)enrene; it would therefore appear that the compound is ethyl orthonitrophenyl&trosoacefate NOz*C6H,*CH(NO)*COoEt [2 11.Nitrosonaethylorthonitropal.adiazobenzeiLe chloride NO,* C6H3' (NiCL) C HZNO is obtained by treating amidonitrophenylacetic acid with hydrochloric acid and amyl or ethyl nitrite. When heated with hydrobromic acid it yields the bromide NO2*C7H5BrNO which melts a t 151-152". The chloride boiled with alcohol yields nifrosornethylorthonltrobenzene NO,*C,H,*CH,*NO (1 21 which when heated in sealed tubes with hydrochloric acid a t 150-160" is resolved into ammonia and ortho- nitrobenzoic acid. Nitrosomethylnit'mbenzene when oxidiscd by potassium dichromate or permanganate or ferric sulphate yields orthonitrobenxaldehyde melting a t 43.5-44.5'. Reduced by ammonium sulphide it forms nitrosomethylorthailzidobenzerzs NH2*C6H1*CH2*N0 which crystallises in needles melting at 132-133".The methyl-derivative of nitrosomethylnitrobenzene N02*C6 B,*CHMe*NO melts a t 58"; the ethyl compound is an oil. Methylnitrosoamido- benzene TU'H;C6H4*CHMe*N0 is an oil volatile in steam ; its hydro- chloride crystallises in needles melting at 109". Orthonitrobenzo.nitrile N02*C6H4*CN [ 1 21 is formed by heating ni trosomethylnitrobenzene with acetic anhydride and sodium acetate. The nitrosomethylamidobenzene yields under like conditions a diacetyl compound NHAc*CsH,*CHAc-NO melting a t 127*5-128*5".64 ABSTRACTS OF CHEMICAL PAPERS. Dinitrophenylacetic acid reduced by tin and hydrochloric acid yields anlido-oxindole NH2*CsH3< ;%>GO from which by the diazo-reaction the paradiaxonitroso-oxindol e chloride has been prepared ; it crystallises in yellow needles and when boiled with alcohol yields nitroso-oxindole.Derivatives of Durene. By J. U. NEF ( B e r . 18 2801-2807). -Dur?ylic acid is best obtained by heating durene with dilute nitric acid (1 vol. acid of sp. gr. 1.4 to 3 vols. water) for three to four hours in a reflux apparatus ; the product is allowed to cool filtered and the residue extracted with sodium carbonate solution the un- altered durene being again treated with dilute acid. On adding hydrochloric acid to the alkaline solution durylic acid is precipitated together with some nitro-compounds which are removed by treatment with zinc and glacial acetic acid and distillation in a current of steam. The durylic acid obtained melts at 149" and agrees in all properties with the acid described by Janiiasch ( Z e i f s .f. Chenz. 6 449) whilst the yield amounts to 15-20 grams from 40 grams durene. Dinitrodwry lic acid (see also Gissmann Abstr. 1883 334) is best prepared by dissolving finely divided durylic acid in pure con- centrated sulphuric acid cooling with ice and gradually adding a solution of nitre in pure sulphuric acid with constant stirring. After four or five hours the product is poured upon ice the nitro-acid filtered off washed and purified by means of its calcium salt. Its properties have been described by Gissrriann (loc. cit.). When dinitrodurylic acid is dissolved in a dilute solution of potas- sium carbonate and potassium permanganate solution gradually added dinitropyrornellitic acid is produced.It has a strongly acid odour is readily soluble even in cold water extremely so in ether and crystallises from both solvents in very long silky colourless needles ; soluble also in alcohol and glacial acetic acid but insoluble in chloro- form benzene and light petroleum. When i t is heated in a capillary tube it loses water (100-160") and becomes yellow and it decom- poses a t 203" with evolution of gas. The silver salt C6(NO2),(COOAg) forms a golden-yellow amorphous precipitate. Attempts to reduce dinitropyromellitic acid to the diamido-acid proved unsuccessful. Ethy I d initroyyrom el Zit at e c6 (NO,) (CO OE t ) 1 obtained by heating the silver salt with ethyl iodide and ether for one to two hours at loo" forms magnificent colourless needles readily soluble in hot and sparingly in cold alcohol readily in benzene chloroform glacial acetic acid acetone and ethyl acetate more sparingly i n ether.It melts a t 130". When its hot solution in glacial acetic acid is treated with zinc-dust ethyl axopyi'ondlitate C&,( COOEt) is produced. This has a deep cinnabar-red colour is insoluble in water and dilute acids ; it yields a colourless salt with concentrated hydrochloric acid dissolves readily in glacial acetic acid alcohol and ether and melts a t 134". It sublimes without decomposition when heated. When P. P. B.ORGAXIC CHEMISTRY. G5 diamidodurene (from dinitrodurene) is treated with ferric chloiaide a green coloration is produced and at once chanqes to yellow owing to the formation of duroquinone C602Me4.This crystallises from light petroleum in long yellow needles melting a t 111". It sublimes rzadily emitting but a faint quinone odour dissolves very readily in ether chloroform benzene alcohol and acetone. Zinc-dust and sods solution sulphurous acid and sodium amalgam reduce it but it is reproduced on agitation with air. It is insoluble in alkalis and nearly so in hot water. Potassium permariganate and sodium carbonate solution and also chromic acid and glacial acetic acid decompose it. From the great stability of duroquinone the author hopes to succeed i n preparing the quinone of pyromellitic acid which would have the same composition as croconic acid. Dibromoparahydroxybenzoic Acid. By A. ALESSI (G'uszetta 15 242-247).-In order to determine the constitution of the di- bromoparnliydroxybenzoic acid obtained by Balbiano from the distil- lation of sodium dibronianisate with calcium oxide (Abstr.1834 1 172) dibromanisic acid was converted by excess of concentrated bydriodic acid into a dibromohydroxybenzoic acid. This was found to be identical with Bidbiano's acid. As in the acid from dibrom- nnisic acid the substituted groupings must be in the relative position OMe Br B r C0,H = 1 2 6 the composition of Ba1l)iano's Reid has the same constitution. V. H. V. A. K. M. Salts of Anisic Acid. By G. BORRELLA (Gazzettcx 15 304-305). -The copper manganese nickel cobalt zinc and cadmium salts of anisic acid crystallise with H,O ; there can also be obtained basic copper OMe*CGH4*COOCuOH and chromium salts.In analysing the metallic salts of the organic acids it is con- Yenient to precipitate the heavy metals in the form of oxalates t,he alcohol necessary for the complete precipitation serving to dissolve the liberated acid. V. H. V. Inner Condensations. By A. ROSSING (Cher12. Cerjtr. 188.5 598 -395).-~0rtho-~Zdehydo~henoxyncet~c acid COH*C6H1*OCH,*cOOH produced by the action of monochloracetic acid on salicylaldehyde crystallises in large yellow leaflets melting at 132". Its salts with the alkali metals and metals of the alkaline earths are soluble in water its copper and silver salts sparingly soluble in water. I t reduces ammo- niacal solutions of silver salts and forms a double compound with liydrogen sodium sulphite. It unites directly with aniline forming the compound This compound unites with acids forming well-defined salts froni which the base can be obtained by careful addition of ammonia 01- caustic alkalis or better still by decomposition with an alcoholic 6 olution of sod ium eth ox ide.Its ethyl salt melts a t 114". NH Ph* CH (OH)*CGH4* 0.C H C 0 0 H. VOL. L. I;66 ABSTRACTS OF CHENICAL PAPERS. Aldehydophenoxgacetic acid unites directly with phenylhydrazine forming the conipound N,HPh CH*C,H,*O.CH,*COOH which melts a t 105". By oxidising agents aldehydophenoxyacetic acid is con- verted into salicy Zoxy acetic acid CO OH*C6H~~O~@H,*CO@H which crystallises in white needles melting a t 186-187'. Ethyl salicyl- oxyacetate is a light yellow oil which decomposes when heated and is converted into the corresponding diamide NH,*CO*C,H,.O*CH,*CONH ; when heated in sealed tubes with ammonia; this crystallises in yellow needles melting a t 158".When aldehydo-pheiioxyacetic acid is heated with acetic oxide ant1 sodium acetate it yields orthocumaroayacetic acid CO OH* CH CH*C,H,* O-CH,. C 0 0 H wliich crystallises from water in needles melting a t 190". This corn- poiind like cinnamic acid combines with 'bromine to form a di- bromide melting a t 219-220" which when heated with alcoholic potash yields orthopropiolpheelzoxyacetic acid COOH*C i C*CsH4*O*CH,*COOH ; this forms small yellow crystals melting at 208". When aldehydo-phenoxyacetic acid is heated with five parts of acetic oxide and 4-5 parts of sodium acetate for three hours it yields an oil boiling a t 170° which is identical with cnmarone C6H,<- >CH (Abstr.1888 474). If orthocumaroxyacetic acid is heated with phosphoric acid it loses water and yields the anhydride CH CH CHGO C6H4<-0. C H,. C 0 ->O which melts & 176"; when boiled with water it is easily recon- verted into the acid. ' This anhydride unites directly with bromine forming the dibromide GH,< O.CH,.CO,O >CO crystallising in CHBrGHBr yellow needles melting a t 213". When the cornpound of aldehydo-phenoxyacetic acid and phenFl- hFdrazine is heated witrh sulphuric acid a bluish-green amorphous substance is produced which dissolves in alcohol forming a bluish- green solution and in alkalis forming cherry-red solutions. This cornpound is precipitated from its alcoholic solutions by ether as a lustroils black powder having the composition CgH7NO3 and melting a t 108".This same oompound can be prepared by heating a mixture of monochloracetic. acid with ortho-oxy benzylidene phenyl- hydrazine in sealed tubes a t 1'00". Orthoxybenzylidene phenylhydra- zine when heated with acetic oxide yields a diacetic derivative AcO*C,H.,CH N2AcPh which crystallises in needles or prisms melting a t 133". On dry distillation this compound yields acetanilide xud a reddish-yellow substance cont)aining nitrogen. The diacetyl- derivative forins a dibromide which is easily decomposed acd when boiled with alcohol yields ucetozydibromobeizxyZiden,ep~enylli~d~az~n(~,ORCANTC CHEJIIS'I'RY. 6 7 AcO*C,H,Br,*CH N,HPh melting a t 188" ; this is decomposed by boiling with caustic soda ; from the alkaline solution hydrochloric acid precipitates the compound H0.C,H2Br2.CH N?HPh melting a t 148".P. P. B. Constitution of the Phthalic Acids. By E. NGr,mG (Bey. 18 2687).-The constitution of the phthalic acids has long been known hut the proofs are of a complex nature. The author now advances a himple proof. The three xylenes when oxidised readily yield the three phthalic acids. Three isomeric nitroxylenes xylidines and xylenols are derived from metaxylene two from orthoxylene one only from paraxylene. Therefore tl ie carboxyl-groups must occupy the 1 3 positions in isophthalic acid the 1 2 positions in phthslic acid and the 1 4 positions in terephthalic acid. A. J . G. Nitration of Phenylparaconic Acid. Bp H. ERDIIASN (Be).18 2741-2743) .-Paranitrophenylparaconic acid is prepared by the niteration of phenylparaconic acid. It forms very bright yellow plates which melt a t 155". It is insoluble in carbon bisulphicle and dissolves sparingly in chloroform benzene and ether readily in alcohol glacial acetic acid hot xylene &c. When heated at 200" evolution of carbonic anhydride takes place. Potassium permanga- riate converts i t into paranitrobenzoio acid. I n the preparation of this acid the ortho-acid is also formed (compare Abstr. 1885 1224). N. H. A!€. Derivatives of Durene. By 0. JACOBSEN and E. SCHNAPAUFF (Bey. 18 2841-2844) .-When powdered durene is gradually added to about 2+ times its weight of cooled sulphuric monochloride tlurenesulphonic chloride is obtained as the chief product together with durylsulphone and alittle durenesulphonic chloride.On treating the product with ice and water the sulphuric hydrochloric and sulphonic acids are separated from the sulphonic chloridc a n d t,he sulphone and on adding an excess of soda to the acid filtrate thv sodium sulphonate separates out. The sulphonic chloride may bo separated from the sulphone by crystallisation from alcohol and finally from ether. Durenesui$honic acid C,H,*XO,H dissolves readily in water b u t only sparingly in moderately dilute sulphuric acid ; the sodium potassium barium and copper salts are described. DurenesuZphonic chloritle CloH13*S02C1 crystallises from warm ethcr in brittle prisnis of vitreous lustre melts a t 99" dissolves readily in warm sparingly in ice-cold alcohol and very readily in ether.D1iren~suZ~honnmide CIOH13.S02NH2 crystallises from alcohol in long prisms melting at 155" ; it is very readily solnble in hot sparingly in cold alcohol and in ether and is almost insoluble in cold water ; it is decomposed by concentrated hydrochloric acid a t 190". D;)Lr!jZsuZphone (CioH,3)2S0 is readily s9luble in alcohol ether benzene and light petroleum whilst boiling water dissolv2.s but ttwes. It can bc distilled under diminished pressure without decomposition but a t the It crptallises in long prisms melting a t 37". f 2G8 ABSTRAOTS OF CHEMICAL PAPERS. atmospheric pressure it yields sulphurous acid and durene. When heated with concentrated hydrochloric acid at 200" it splits up into durene and sulphuric acid.When sodium durcnesulphonate is fused with potash either durenol or hydroxydurjlic acid is produced accordingly to the temperature and time of heating. DzirenoZ CIOHl3-OH crystallises from warm alcohol in large flat prisms melts a t 117" and boils a t 249-250". Bwmodurenol C10H,2Br*OH crystallises from hot dilute alcohol in long vitreous prisms melting a t 118". It is readily soluble in alcohol and ether insoluble in water. Nitrodwend Cl0Hl2(NO2)*OH separates from hot dilute alcohol as a bright yellow inass. It melts a t 130" is almost insoluble in water very readily soluble in dcohol and also in alkalis and alkaline cai-bonates with dark yellow coloration. HydyoxpZurylic acid C,HMe,( OH)*COOH is almost insoluble in cold sparingly soluble in hot water but very readily in alcohol.Its constitution is [COOH OH Me = 1 2 3 4 G I . It crystal- lises i n small needles melts at 148" and may be sublimed without decomposition. Its salts give a didy brown precipitate with ferric chloride whilst a solution of the free acid in diIute alcohol gives a transient blue coloration. The calcium salt ( CI,H,0,),Ca + 2H,O is described. When the acid is heated at 190-200" with hydro- chloric acid carbonic anhydride and pseudocumenol (melting a t 85-88"> are produced. Phenylacridine. By A. CLAW and C. NICOLAYSEN (Ber. 18 2706-2712) .-Potassium permanganate acts on phenylncridine in presence of free sulphuric acid with formation of a mixture of paraphenylquinolinecarboxylic acids from which a di- and a mono- cwboxylic acid were separated. Yurap7ter~ylquinolilredicarbosylic acid I'h*CgNH,(COOH) forms lustrous needles melting at 200-215".The barium salt (with 4 mols. H,O) crystallises in slender colourless needles. Barium parnphenylpuinolinecarbo~y late ( CIbH10N02)2Ba,6H20 crjstallises in needles. Yhenylamidobenzoic <acid NHPh*C6H4*COOH is obtained by the oxidation of phenylacridine methyl chloride with potassium per- ruanganate. Itl forms small colourless needles rnelting at 2.22" (uncorr.) alniost insoluble in water readily soluble in ether chloro- form &c. The sodium saZt (with 4 mols. H,O) fornis coloarless 1 lates readily soluble in water; the barium (with 5 mols. H20) and silver salts are also described. An acid having all the properties of that just described is obtained by heating metamidobenzoic acid with aniline hydrochloride a t 220".Phenylacridine hydrochloride crystallises from pure water in red octahedra (with 5 mols. €LO) ; the long yellow anhydrous needles described by Bernthsen are obtained from a solution containing free 11s drocli loric acid. a-Naphthylaminephthale'in. By A. VANNI ( Gazzetta 15 346- 34i).-On heating phtlialic anh.ydride and a-niiplithjlamine in equal molecular pioportiuns at a temperature of lW" 5t fused mass is A. K. M. N. H. M.ORGANIC CHEJIISTRY. formed ; thin is heated with boiling alcohol and as it cools deposits a-naphthylaminephthalejin f i 9 the filtered so!ution in the form of colourless transparent prismatic tables. It is insoluble in water sparingly soluble in alcohol and ether and melts at 166".It is decomposed by concentrated sulphuric acid forming a pale yellow sii bstance which dissolves in ammonia with an orange-red coloration ; with concentrated potash it forms an oil which ultimately solidifies ; the compound formed gives a violet coloration with water. V. H. V. Relations of @- to p-Hydrojuglone. By F. MSLIUS ( J h . 18 2.567-2571).-The acetyl- or benzoyl-derivatives prepared froin a- and from P-hydrqjuglone are identical and seem to be the P-derivatives inasmuch as they yield @-hydrojuglone when treated with alkalis or sulphuric acid. The compoiind previously described as triacetyl-a-h.vdro jnglone (Abst'r. 1885 170) Ehould therefore be ternled t?.iac~tllZ-$-h?//Zrf!jtigtone. It cry stall ises in colourless prisms and melts at 129-130". Triberizoyl-3- h?ydr.oj!l'uy/one CIOH50JBzI crystallises in colourless needles melts a t 228-229" and like t h e acetyl-derivative can be sublimed unchanged.a-Hpdrojuglone when heated above its melting point in an atmo- sphere of hydrogen is conrerted into P-hydrojuglone which distils ; on the other hand when the p-compound is subjected to prolonged boiling with dilute hydrochloric acid it is converted into a-hydro- jnglone. A. J. G. (Monatsh. Cheiii. 6 754-~59).-dntlzragt~llolamida Action of Ammonia on Anthragallol. By S. V. GEORGIEVICS i s prepared by boiling anthragallol with excess of ammonia f i i ~ 20-30 minutes; the fine blue solution so obtained is evaporatrct down aiid the solid substance crystallised from alcohol or glaciitl acetic acid. It forms greenish-black needles or R reddish-brown crystalline powder sparingly soluble in hot water alcohol antt benzene &c. Alkalis a,nd srilphuric acid dissolve it uncbanged with formation of blue and intense red solutions respectively.Nitrous acid acts on it with formation of ayellom substance which melts at 190-200" ; it does not contain nitrogen and is probably dihydroxy- anthragallol [(OH) = 2 31. Two nitro-derivatives of anthragallol were obtained from gallic acid by the action of meta- and of para-nitrobenzoic acid. A~zthragallolsulpTonic acid is prepared by heating anthragallol with 3-4 times its weight of sulphuric acid at 130-140". The aqueous solution acquires a red colour when treated with the smallest trace of alkali. The sodium aiid potassium salts have cnloiiring properties.N. H. Id.70 ABSTRACTS OF CHEJIICAL PAPERS. Terpenes and Ethereal Oils. By 0. WALLACH (111) (Annulen 230 225-2'12).-Yure borneol prepared by the action of sodium on camphor melts a t 206-207" riot a t 198" as generally stated. This componnd behaves like a saturated secoridary alcohol but it has the property of uniting with bromine and hydrogen bromide &c. to form nnstable additive products. For example when bromine is added to a solution of horneol in light petroleum a crystalline preci- pitate is deposited which consists chiefly of Oorneol bromide CloHlsO*Br2 mixed with a small quantity of (C,oH,O),Hr,. Cineol like borneol unites with bromine in two different proportions forming compounds which have the same composition as the borneol bromides.When borneol bromide is covered with light petroleum and left for some time in a closed vessel decornposition ensues resulting in the formation of borneol and borneol hydrobromide (C,oH,80)2,HBr. The same compound is obtained as a white crystalline powder by the action of hydrogen bromide on a solution of borneol in light petroleum. It is dccornposed by water and alcxohol. The hydriodide (CloH,80)2,HI is tt white crystalline compound which decomposes spontaneously . Rornyl chZoride Cl0HI7C1 is easily prepared by adding boriieol to a mixture of phosphorus pentachloride and light petroleum. The action is finished in half an hour. The crude product is poured into water and repeatedly washed. Bornyl chloride is not identical with pinene hydrochloride. It is readily converted into camphene by heating with aniline. Camphene is decomposed by dehydrating agents such as zinc chloride and strong sulphuric acid or by the action of heat alone.In each case the decomposition products are liquid. Monobromocamphene is obtained as an oily liquid when bromine is added to a solution of camphene in alcohol and ether. Camphelie is formed by the action of dehydrating agents on borneol but the hydrocarbon cannot be isolated (except when potassium pyrosulphate is the dehydrating agent) as it is decomposed by zinc chloride or phosphoric anhydride or strong sulphuric acid. The so-called hydrocarbon " borneen," which Pelouze ( A n n a l e n 40 :327) Kachler (ibid. 164 78) and Oppenheim (this Journal 1874 891) obtained by the action of phosphoric anhydride on borneol is a mixture of the decomposition products of camphene.The author confirms Tilden's statement (Trans. 1878,SO and %I.) that Kussian and Swedish oil of turpentine contain the same cou- stituents namely austpalene splvestrene and dipeutene. The hydrocarbon obtained by decomposing sylvestrene chloride with auiline closely resembles sylvestrene but the identity of the bodies is not proved. The hydrocarbons yield a chloridc melting at 7 2 O and a liquid bromide. " !l'erpinol " described by Wiggers ( A n n a l e a 57 252) and by List (ibid. 67 367) does not exist. Terpine hydrate C10H2002 + H20 melts at 117". It is a saturated compound and is decomposed by boiling with acids or dehydrating agents yielding terpineol C,H,O and other products.When a Tiiixture of I part of sulphuric acid anti 2 of water is used terpiueol terpinene CJT and terpinulene are formecl. Wlicn veryORGANIC CHEXISTHY. 71 tlilute sulphuric acid is used the chief product is terpinene. Dilute phosphoric acid and glacial acetic acid on the other hand yield terpineol as the principal product. Terpine hydrate is almost completely converted into dipentene by prolonged treatment wit'li potassium pyrosulphate. Terpineol CIOH1,*OH is a nonsaturated monatomic alcohol. It is a thick liquid boiling a t 215" and is sparingly soluble in water. I t nnites with bromine to form an unstable bromide. Bipentene tetrabromide melting at 124" is formed by the action of r7,n excess of bromine on terpineol. The hydroxyl in terpineol is easily replaced by chlorine or iodine yielding for example the chloride CloHl,CI melting a t 50" and the iodide melting a8t 77".Terpineol unites with carbanil forming phenylterpinylurethane which crystallises in white needles melting a t 110". Boiling with dilute acids or treatment with dehydrating agents converts terpineol into terpene or dipentene but if ferpiiieol is left at the ordinary tempera- ture in contact with dilute sulphuric or hydrochloric acid it unites with water forming terpine hydrate CloHzo02 + H20. Terpine has the same boiling point as dipentene but the two cBompounds are not identical as the former yields a liquid bromine- clerivative. Terpine is formed by the inversion of pinene witb :ilcoholic sulphuric acid. It boils between 185; and 190" and yields an unstable tetrabromide crystal- lisiog in mouoclinic plates.The relation between camphene borneol and camphor is shown by tlie following formulE :- Terpinolen,e has not yet been obtained in a pure state. Cmiphenc. Borneo]. Camphor. Borneol bears the same relation to camphene that terpineol does to dipentene. w. c. w. Action of Picric Acid on Terebenthene. By - LEXTREIT (J. Pharna. [ 5 ] 11 211-213).-Terebentliene when heated with picric acid at 150" gives a limpid liquid which after further heating a t the same temperature deposits crystals on cooling. When freed from excess of picric acid and a brown colouring matter i t forms thiu friable transparent flakes which rapidly take a yellow tint whcn exposed to light. It is insoluble in water slightly soluble in cold alcohol readily in ether carbon bisulphide and boiling alcohol.When heated it first fuses aud then decomposes with a gentle defla- gration. It seems to be a compound of picric acid and camphene of the formula ClUHl6,C6H3( N02)30. It is more stable towards aqneous72 ABSTRACTS OW CHEXICXL PAPERS. alkalis than are the known picrates of hydrocarbons. Further with an alcoholic solution of potash a very explosive crystalline precipitate of a purplish-red colour is formed quite different from potassium picrate. The compound is rapidly decomposed by a boiling aqueous solution of soda; a white sublimate is carried over with the steam which is insoluble in water but soluble in almost all proportions in cold alcohol and ether. Its odour resembles both that of camphor and of camphcne. It fuses at 179" camphor at 175" and camphene a t 45".Its rotative power is aD = - 36". Its composition is very nearly the same as that of camphor. Natural Camphor Oils. By P. MACEWAN (Pharm. J. Trans. [ 3 ] 15 1045-1046) .-Borneo Formosa and Japanese oils are referred to. The Bornean oil sp. gr. about O W O consists chiefly of borneene with a small quantity of resinous matter but with no camphor (borneol) in solution. In contact witth copper it acquires a green colour in a day or two. The Formosa camphor oil sp. gr. 0.943 is a saturated oleaceous solution of camphor ; when rubbed on the hand there is at first a strong carnphoraceous odour which soon goes off and a sassafras-like odour remains but the oil dries quickly on the skin and leaves no mark.Japanese camphor oil in crude form according to Oishi (Abstr. 1885 270) has sp. gr. 0.959 and contains camphor. The sample examined by the author evidently purified of sp. gr. 0.951 had a strong sassafras-like odour and contained no camphor. Scarcely any of it distilled below 140" about 10-12 per cent. consisting of a liquid isomeride of camphor distilled between 180" and 185" nearly one-half distilled over up to about 205" ; t,he residue has a sp. gr. of 0519.5. Treated with nitric acid and then after a minute with water the Japanese oil yields a clear crimson solution the Formosa oil a very slightly green milky solution ; with hydrochloric acid they both yield salmon-coloured solutions. This oil is used in the United States to adulterate oil of wintergreen.Picric acid behaves similarly with thymol. J. T. D. A. L. Camphophenylhydrazine. By L. BALBIANO (Gazzattri 15 246- 245).-As the formation of camphoroxime seems to indicate the presence of the carbonyl-group in camphor (Abstr. 1883 728 ; 1884 SlO) although the evidence thus far is not sufficient to decide between the aldehjdic and ketonic groiips the author has studied the reaction between pheuylhydrazine hydrochloride and camphor in the presence of sodium acetate. Jn this way camphopheuylhjdrazine C,H,-N,HPh is produced. It is a yellowish oil distilling a t 235- 245" under a pressure of 170 mm. soluble in dry ether and decom- posed by hydrogen chloride to form phenylhydrazine hydrochloride. Borneo camphor does not react with hytlroxlamine under the same conditions in which camphor yields camphoroxime ; whilst by treat- ment with phenylhydrazine in the presence of diluents bromocamphor yields pl:enjlhydrazine hjdrobromide and resinous substances. V.H. V. Euonymin. By G. ROMM (Chem. Centr. 1885 442-445).-This glucoside is not to be confounded with the medical preparation of the same name as the latter contains no poison and is employed as anP 6) ORGANIC CHEMISTRY. 4 * ) aperient. The author prepares it by extracting the powdered rinds of Euyonrnus atropurpureus with $0 per cent. alcohol distilling and evaporating the extract diluting with water and filtering ; the filtrate is then precipitated by lead acetate again filtered and the clear liquor freed from lead by sulphuretted hydrogen. After neutralisa- tion with magnesium carbonate precipitation with tannic acid arid treatment with zinc oxide euonymin is obtained in ciystals on em- yoration of its ethereal solution.The bark of Euon?ynzu.s europpiis contains no euonymin. Constitution of Santonin. By S. CANNIZZARO (Ber. 18 2746- 2751).-After reviewing the evidence a t presmt available as to the const,itution of santonin the author suggest,s the formula- J. K. C. CH CH.CK*CHMe-CO as agreeing fairly with its reactions. Derivatives of Santonin. By V. Vrr,r,;\vrcccma (Ber. 18 28.79 -2864) .-Photosardonic acid C15H2205 is best obtain3d by exposing :I solution of 10 grams santonin in a litre of acetic acid (sp. gr. 1-06> to the action of light for about a month ; the product is evaporated to a syrupy consistence in a vacuum the residue washed with water aud then treated with a warm solution of sodium cstrbonate.The undis- solved residue may be dissolved i n alcohol from which it crystallises in prisms melting a t 182-183" and of the composition CI7H2?O5 namely 1 mol. santonin + 1 mol. acetic acid. On adding hydrochloric acid to the sodium carbonate extract photosantonic acid separates and is purified by repeated crystallisation from alcohol. Its properties agree with those assigned to i t by Sektini (Abstr. 1877 471). It loses 1 mol. H,O at loo" and melts a t 154-155". The composition of its salts indicates that the water lost at 100" is not water of crystallisa- tion as assumed by Sestini but that undried photosantonic acid bears the same relation to the dried acid as santonin does to santonic acid.Barium and silver photosantonates C,5H,0,Ba and ClsH,oO Agz are described. Photosantonin C I ~ H ? ~ O ~ is best prepayen by exposing a solution of santonin (20 grams) in alcohol (1 lit're) to the direct action of light for three months. The alcohol is distilled off in a vacuum and the thick residual oil treated with lukewarm sodium carbonate solut,ion to romove photosantonic acid. On treating the insoluble portion with ether two isomeric photosantonins C17Hz10~ are obtained ; one modi- fication forms platy crystals melting at 154-255" and is dex5ro- rotatory ; [aID = + 76.77" for a solution containing 0.3825 gram in 50 C.C. alcohol a t 13". The other modification which is the chief product melts a t 68-6b0 and is identical with Sestini's photo- santonin.It is readily soluble in alcohol and ether and almost insoluble in cold water; [ = - 121.6" for a solution containing 1*0010 gram in 50 C.C. alcohol a t 14" and - 118.4" for 1.0980 gram in 50 C.C. alcohol also at 14". The composition of photo- santonin shows that it is not the diethyl salt of photosantonic acid as74 ABSTRACTS OF CHEJCICAL PAPERS. Sestini assumed but the monethyl-derivative of dehydrated photo- santonic acid which is regarded as a lactonic acid thus:-Photo- santonic acid HO*C13H~g(COOH)z ; photosantonic acid dried a t 1 OO" CO0H*C,Hlg <:;> ; photosantonin COOEt*C,H,<$~>. The last compound may also be obtained from photosantonic acid alcohol and sulphuric acid and by the action of ethyl iodide on the silver salt.When gaseous hydrogen chloride is passed into a solution of photo- santonic acid in absolute alcohol the diethyl-derivative of an acid containing the elements of a inolecule of water less than photo- santonic acid is obt'ained ; it is termed ethyl cle72.ydropkotosantonate C,H,(COOEt) an! forms a colourless liquid which does not solidify a t - 10". A solution of 0.7306 gram in 25 C.C. alcohol has a dextro- rotatory power ah 20*4" [&ID = 3. 20.4". The free acid which is isomeric with dehydrated photosantonic acid melts at 132-133". It is very readily soluble in alcohol and ether ; its dextrorotatory power is [aID = + 31-9" for a solution containing 0.7114 gram in 50 C.C. alcohol. The barium salt C15HieOJ3a is very readily soluble. A. I(. M. Papain. By S. H. C.MARTIN (Pharm. J. Trans. [3] 15,129-130). -A glycerol extract of commercial papain retains the fermentative act,ivity of the powder and contains a heminlbumose in quantity together with a mere ,trace of globulin. When the latter is precipi- tated by magnesium sulphate and the hemialbumose by subsequent saturation with sodium sulphate the solution is no longer active. The aqueous solution of the precipitated hemialbumose is however very active and when tested on coagulated egg-albumin produced peptones ; it is therefore evident that the ferment OE papaw-juice is associated wihh the hemialbunwse but as yet bas not been separated from it. Papain acts on animal albumin in manner similar to pepsin but not so rapidly ; with milk i t behaves like pancreatic jnice tirst curdling it the curdling being intensified by raising ths temperature (but not above 62") and hindered by making the milk alkaline or by diluting it to some extent or by boiling previous to adding cold water; the curd is gradually dissolved with the production of peptones leucine and tyrosine.A hemialburnose is formed as an intermediate product between the case'in and peptones. With regard to the action of papain on the proteids of papaw- juice i t converts the globulins into an albumose corresponding with Vine's hemialbumose ; leucine and tyrosine being also formed but no tisue peptones have been dekected. D. A. L. Pyrrylene Dimethyl Ketone. By G. CTAMTCTAM and P. SILBER (Gazzetta 15 248-250).-1n this paper it is shown that pyrrylene dimethyl ketone (dipseudacetopyrroline) is producible not only from pseudacetopyrroline and acetic anhydride as indicated formerly (Abstr.1885 378) but also directly from pyrroline by nieans of the same reaction. By an excess of fuming nitric acid it is converted into a mono-nitro-derivative C4NH,( NO,) Ac melting a t 149" md possessing acid properties. V. H. V.ORGAXIC C HEJLISTRT. 75 Synthesis of Pyrroline-derivatives. By L. LEDERER and C. PAAL (Ber. 18 2591-8599).-1t has been already shown that pyrro- line derivatives are formed by the action of ammonia 011 acetophenone- acetone and on acetonylacetone (Abstr. 1885 516 1206) and of ammonia and primary amines on ethyl acetosuccinate (Knorr ibid. 554 994) the reaction is now extended to ethyl acetophenoneacetaacetnte. Ethy lie methylpheny lp yrrolinecarhoaylate C4NH,MePh*C 0 OE t [Me COOEt P h = 2 3 51 is obtained by allowing a mixtare of ethyl acetophenoneacetate and aqueous ammonia to remain for 24 hours; it crystallises in colourless tables or small needles and inel ts a t 120".C&NH:,MePh-COOH prepared from the ethyl salt by saponification &c. crystallises in long flat yellowish needles readily soluble in acetic acid benzene and hot alcohol. When heated it partially decomposes a t 175" and melts a t 190"; it sublimes in small part but does not yield methylphenyl- pyrroline. Ethylic dimethy~henylpyrrolineonrboxylate C,NHMe,Ph*COOEt [Me Me COOEt Ph = 1 2 3 51 preysred in manner similar with mbthylamine crystallises in colourless plates softens a t 90° melts a t 112" and is readily soluble in alcohol ether and benzene.Met hy Zp h e q idly lpy wolinecarboay lic acid CJIg CAN HMePh- C 0 OH LC3H5 Me Ph COOH = 1 2 8. 5j. The ethyt salt is prepared by heating ethyl acetophenoneacetoacetate wit,h allylamine and a little absolute alcohol in settled tubes a t 180" for an hour; it is a thick oil and does not crjstallise. The free acid crystnllises in .short lustrous prisms is readily soluble in alcohol ether benzene and acetic acid and melts at 158". B e t h y ip heiatllaZlyllpt/rroZine C,H,*C,NHMePh [I 2 51 is prepared by distilling the acid ; it crystallises in large plates melts at 58" to a colourless oil with blue fluorescence boils at ;277-278" and is soluble in all proportions in ether almhol benzene light petroleum and acetic acid.i~~ethy1~henyIpyrrolinecnrboxylic acid N e th y Idip hen y l p yrrolheca rbox y Z ic acid C,NHNePh,*COOH i P h I Me COOK Ph = 1 2 3 51 crystallises in small needles melts at 226" and is readily soluble in acetic acid and benzene. The ethyl salt C4NHMePh,*COOEt is pre- pared hy boiling ethyl acetophelloneacetoacetate (1 part) with aniline (1.5 part) dissolved in acetic acid; it crystallises i n small prisms melts a t loo" and is sparingly soluble in alwhol and acetic acid. L~~ethy7dipher~ylpyr~oline CBNH2MePh is prepared by heathg the free acid a t above 226" ; it crystaliises in large ca~ourless tables melts a t 81" i8 not very readily volatile with steam and is readily soluble in benzene and light petroleum. iUet R y lphenyEos.thotolylp yrrolinecarbox y I ic acid C6H1MaC4NHMePh*CO0 H ciystnllises in small prisms and melts a t 199" ; it is readily soluble in the udinarj- solvents except water.The ethyl salt is obtained by boil-76 ABSTRACTS OF CHEMICAL PAPERS. ing aniline acetic acid and orthotoluidine as a thick oil that cannot be crystallised. il/lethy123he?aylorthotolyl~~yr,.oline C6H4Me*C4NH2MePh [l 2 51 is obtained by the dry distillation of the free acid ; it crystnllises in plates melts a t 44" to a pale yellow fluorescent oil boils a t 325-328" and is readily soluble in alcohol ether benzene and light petroleum. Methylphenylpuratoly lcarboxylic acid C6H4Me*C4NHMePh.COOH resembles benzoic acid in appearance and melts at 227". The eth! E salt Cz1HZ1147O2 crystnllises in prisms or tables and melts a t 11.5".Methy~~l~enyl23aratolyl~2/rrrtline C6E14Me*C4NH2MePh crystnllises in concentric paups of slender needles or in tables melts at 91" boils above 550° and is readily soluble in light petroleum and benzene. 1C~efhyl;when2/l-a-n~phthylpyrrolinrcnrboxylic acid CloH7*C4NHMePh-COOH [ C J € Me COOH Ph = 1 2 3 51 is prepared by heating a-naphthylamine and ethyl acetophenoneacetate in sealed tubes at 13U0 and saponifying the uncrystallisable product. It crystallises in needles melts a t 244" and is readily soluble in alcohol benzene and acetic acid. Metky7phe97yI-a-naphthylpyrroliiap CI0H7*CsNH2MePh crystallises in plates melts at 74" boils above 360" and is very readily soluble in benzene light petroleum aBd alcohol. &Id h y Zp hen y I- @nap h thy lp y rrolin,e C,H7- CsN H,MeP h cry s t allises i n concetitrically grouped needles and melts a t 52".The carLozyZic (wid C ,H,.C,NH Ne Ph* C 00 H crystal lises in small white needles an( 1 melis at 249". Its ethyl salt C24HzlN02 crystallises in lustrous plates and melts at 115". A. J. G. Pyridine-derivatives. By H. WEIDEL and F. Bf,Au (itfOl70,f~h. Chern. 6,651-666) .-When 30 grams of dibroniopyridine are heated for 24 honrs at 160" with 80 C.C. of absolute alcohol and a slight excess of potash diethoxy- and ethoxy-hydroxypyridine are formed. Diethoxypyridine C5NHI,( OEt) forms an almost colourless oil which is heavier than water ; i t is readily soluble in alcohol and ether. It boils with decomposition at 243-246" under 749.9 mm. pressure. With mineral acids it yields crystalline salts which are very deli- quescent.The plntinoch Zoride forms lustrous yellow needles. DihydroxypyG%ze C5NHB(OH)P is obtained by hydrolysis of the diethy 1-derivative by hydriodic acid and amorphous phosphorus at 1.20". It forms small yellowish-white crystals which become brown a t 200" almost black a t 230° and melt with total decomposition a t 237-239". It dissolves readily in hot water alcohol alkaline caT- bonates and in dilute acids. When a neutral solution of dihydroxy- pyridine is treated witlh ferric chloride it acquires a reddish-brown colour. The compound is probably identical with the dihydroxy- pyridine prepared by Geigy (Inaug. Diss. Munich 1885) from pyri- dinedisulphonic acid. Ethoxyhydroxypyridine EtO*C,NX,*OH forms colourless plates which become yellowish when exposed to light; i t is sparingly soluble in water readily in alcohol and in a mixture of alcohol and ether. TheORGANIC CLIEMISTRY.77 crystals are triclinic; a 2 c = 0.97'408 1.01795 1; = $jo 1' ; y = 88" 29'; @ = 91" 04'. It melts a t 127-128" (uncorr.) atid does not dist8il without decomposition. The nityate and pZatino- chloride are described. When fused with potash it yields dihydroxy- pyridine. Sodium ethoxide acts on dibromopyridine at 150" with formation of diet,hylpyridine together with a trace of the monethyl salt. By t,he action of alcoholic potash on bromopyridine (the intermediate liroduct formed in the preparation of dibromopyridine) ethoxypridine was obtained ; it forms a colourless liquid which boils below 200° and when reduced yields a hydroxypyridine identical with that already obtained fmm /3-pyridinemonosulphonic aeid (compave A bstr.1884 1050 and 1370). It is therefore a meta-derivative and the dibromo- comDound obtained from it probablg has both bromine-atoms in the meti-position from the fact &at it yields only one monethyl salt. N. H. M. Constitntion of Synthetical Hydropyridine-derivatives. By A. HANTZSCH (Bw. 18 2x9-2586) .-The constitution of these compounds has never been definitely ascertained although it has been assumed that both the hydrogen-atoms are in union with carbon- - - CH-CH atoms in the pyridine-ring thus giving the formula N<c-c>C for the nucleus of this group. Kuckert has Iiowever recently shown that a substituted hydropyridine-derivative is obtained by the con- densation with paraldehyde and sulphuric acid of the product obtained by the action of methylamine on ethyl acetoacetate from this it f ,Ilows that the nitrogen must be exerting imidic functions and that the constitution of the hydropyridine nucleus must be HN<C C ' C .' c> CH.The ketone CsH,O obtained by the action of hydrochloric acid on ethyl hydrocolliclinecarboxy!ate (Abstr. 1883 84) when treated wit,h hydroxylamine jields a crystalline oximido-compound C,H NOH. By heating ethyl acetoacetate with benzaldehyde and methylamine two non-nitrogenous products C19H2406 and C19H,C)> are obtained. 'l'he part played by the methylamine in the reaction is obscure but unless it or some other primary amine is present thesa substances are not formed.J3thyZ benz y 2 idinediacetoacetate C19H,0s = C HP h (CH Ac-C 00 Et) crystallises in long white needles melts a t 15%-153° and is sparingly soluble in alcohol and ether ; when treated with bromine it yields a substitution-derivative Cl9HZ3Bro6 nieltitig at 159". Ethyl dehydrobenzylidinediacetoawtate C19H2,05 crystallises in lustrous prisms melts a t 87-38" and is readily soluble in nearly all solvents. The author assigns to i t the constitution CMe C(COOEt)>CHPh '<CMe C(CO0Et) regarcling it as a hgdropyridine-derivative in which the imido-group is replaced by oxygen. A. J. G.78 ABSTRACTS O F CHEMICAL PAPERS. p-Dipyridyl. By T. LEOKE and V. OLIvExr (Gazzetfa 15 274- 277).-A dipyridyl Cl,H6N7 is produced by the dry distillation of pyridinesulphonic acid and separation of the distillate by concentrated potash.It crystallises in c:olourless prisms melting at G8" and boiling a t 286-288" ; its platinochloride is an orange-yellow powder insoluble in water alcohol and ether This dipyridyl is probably identical with that obtained by Skraup and Vortmann by the dry distillation of dipyridyldicarboxylic acid (Abstr. 1883 88) as evidenced by its direct conversion into nicotinic acid and of the formation of the same acid from the sulphonic acid originally used. It is proposed to call it p-dipyridyl and to assign to it the following structure :- C,H,N*C,H,N [N CaH*;N = 1 31. V. H. V. Pyridin e- choline Pyridine-neurine and Pyridine -muscarine . By T. COPPOLA (Gazzetta 15 330-345) .-The alkaloids choline neurine and niuscarine are analogous not only in their chemical constitution inasmuch as they can be regarded as hydroxyethylene- ringl- and dihydroxyethylenetrimethgl ammonium hydroxides but also in the physiological symptoms producccl by them namely stimulation of the inhibitory ganglia of the heart arrestation of the diastole and excitation of the secretmy nerves.I n this paper the chemical pro- perties and functions of their pyridine-derivatives ape described. P!jridine-c?ioline hydrochloride OH*C2H4*C5H5NC1 obtained by heating a mixture of pyridine and ethylene chlorhydrin in equal molecular proportions forms colourless prismatic crystals very deliquescent and soluble in alcohol and water insoluble in ether. I t s plntino- and awo-ahlorides are yellow amorphous powders ; its hydroxide is very readily decomposed.Pyyidiiie-netwine l;yd&xIide C5H5( CzE3)NI obtained by heating the above compound with coilcentrated hydriodic acid crystallises in opaque white prisms very soluble in Bding alcohol aud water insoluble in ether. Its platino- and auro-ohlorides are yellow amor- phous powders. Pyridine-muscarhe hydi*ochZoriiie C2H3(OH),*C,H,NCI obtained from pyridine-choline by heating i b with nitric acid (sp. gr. 0.148),forms orange-yellow deliqnescen t laminae ; its platinochloi-idc! ci.ys tallises in orange-yellow needles its nurochloride is an amorphous powdei. The physiological function of the al3ove compounds is perfectly similar in that they all arrest voluntary movements and a t first excite but afterxards paralyse the cardiac pulsations. As regards their toxic efEects they differ considerably in degree.The variation of physiological function with chemical constitution more especially as regards the effect of the substitution of hydrogen-atoms by different groups especially h ydroxyl and the choline neurine and mnscarine radicles is discussed a t some length. By S. HOOGEWERFF and W. A. v. DORP (Rec. Frccv. Chim. 4 125-12s) .-By adding concentrated sulphuric acid to an alcoholic solutioii of the crude quinoline from coal-tar the sulphates of quinoline and isoquinoliae C9H,N are precipitated and by re- pented rectification of the free bases obtained from this precipitate two fractions are obtained one boiling from 230" to 236O which is chiefly V. H. V. Isoquinoline.ORUXNlC CHENLSTRP.7!) quinoline and the other boiling from 236" to 243" containing isoquino- line this is purified by the repeated recrly~t~allisation of its sulpliate from alcohol. The free base melts a t 18-23" and boils at 236-2.37.5" (uncorr.). The suZphate CsH7K,H,SOa forms hygroscopic prisms or tablets and melts a t 205-208". The chromate ( CSH7N),H,Cr,0 forms reddish-yellow needles and is decomposed a t about 150". The pZutinochZori.de ( CSH7N),I3[,PtCI6 + 2H20 forms slender yellowish- red needles ; i t becomes anhydrous a t 110". The picsrnte is but little soluble in alcohol or water and crystallises in yellow needles ; it melts a t 222-223.5'. A. P. Constitution of Quinoline-derivatives prepared from Meta- substituted Amines. By L. GATTERMANN and A.KAISER (Ber. 18 2602-2604) .-Whilst the constitution of quinoline-derivatives pre- pared from ortlio- and para-substituted amines is certain inasmuch as only one substance can be formed in each case ; in those from metn- compounds two quinoline-~erivatives are theoretically obt'ainable according as the linking of the pyridine-ring occurs a t the ortho- or para-position relatively to the substituting group. It seems as though this question can be solved by the use of compounds in which one or the other of these positions is occupied by halogens &c. ChZoronzeth?llquinoZine C9NH,MeC1 [Me Cl = 1 41 is prepared by Skraup's method from parachlorometatoluidine ; it crystallises in colourless needles of quinoline-like odour melts a t 49" and is soluble in water readily soluble in ether alcohol and benzene.The merciiro- chZoride C,H,NCI,HHgCl crystallises in broad needles or tables the platinochloride (C,oH8NCl)2,H2PtC16 forms yellowish-brown tables o r broad needles the picrate crystallises in large brownish-yellow tables nnd melts at 172". When heated with excess of hydrogen iodide dissolved in acetic acid the chlorine is replaced and a methylquinolino obtained. The author cannot as pet speak posit?ivel yas to the identity or non-identity of this with Skraup's " metatoluquinoline." A. J. G. Paraquinaniso'il. By 2. H. SKRAUP (Monatsh. Chem. 6 f60- $84).-Paraquinanisoil is best prepared by heating a mixture OE i 8 grams anisidine 50 grams nitraniso'il 320 grams glycerol and 125 grams sulphuric acid for two hours ; 50 grams more of sulphuric acid are added and the heating continued for two hours longer.The product is then diluted with water distilled with steam and the residue treated with potassium dichromate which causes a precipita- tion of quinanisoil chromate ; this is then purified. Pure quinanisoil forms a. yellowish oil which soon acquires a green then a reddish- violet colour ; it boils with slight decomposition at 304-305" (uncorr.). Sp. gr. a t 20" = 1.542 (water at 20" = 1). Para- puina&oiZ hydrochhride CsNHOMe,HC1 + 2H,O forms colourless prisms readily soluble in cold wnter and hot alcohol insoluble i n ether. The chromate forms long gold-coloured silky needles which when exposed to air lose their lustre and become brownish ; i t is very sparingly soluble in cold water.The nedral sulphate acid sdphate tartrate and other salts are described. The aqueous solutions of the salts all shorn a It loses its water of crystallisation orer sulpliuric acid.SO ABSTRACTS OF CHEMICAL PAPERS. blue fluorescence. Chlorine-water and ammonia act on the salts giving the green colour characteristic of quinine compounds. Paraquinanisoil rnethiodide crystallises from water in long gold- colourcd lustrous needles which melt with evolution of gas at 235". It is insoluble in ether readily soluble in hot water and alcohol. Thalline CSHloNeEO is prepared by reducing quinanisol with tin and hydrochloric acid ; it forms thick white prisms sparingly soluble i n water and light petroleum very readily in alcohol ether and benzene. It melts at 42-43" and boils a t 288" (uncorr.; bar. = 735 mm.). When treated with ferric chloride or other oxidising agents it acquires first a yellow afterwards a dark emerald-green colonr. Silver nitrate produces this coloration with separation of silver. ThaZZine hydrochloride C,H,NO,HCl crystallises in well-formed prisms sparingly soluble in alcohol. The sulphate (with 2 mols. H,O) and other salts are described. Acefylthtrlline CloHl,PU'O*Ac forms clear broad monoclinic prisms which melt at 46-47". Its bolubility resembles that of thalline. Bromine acts on thalline with formation of a compound CloH,Br3NO ; it is a pale yellow powder melting at 19t3-194". MethyZthal7ine CloH,2NOMe is prepared by the action of methyl iodide on thallme. I t forms a thick colourless oil which when kept lwcomes brown ; it boils at 277-278-5' (uncorr.).When a solution in dilute hydrochloric acid is treated with ferxic chloride i t acquires a cherry-red colour which changes to reddiah-yellow when kept long. The hydrochloride and sulphate crystallise in well-formed prisms readily soluble in water Thaliiie hydriodide ( CloH,NO),HI and p a t e r n a r y dirrzethylthall&w iodide CIOH12NOMe21 are formed in the preparation of methylthalline. 'J'he former compound crystallises in flat prisms melting a t 155- 136" imoluble in ethylbenzene light petroleum readily soluble in hot alcohol. The latter compound forms long prisms insoluble in light petroleum readily soluble in alcohol and in water from which i t crystal- lises with 1 mol. H20. I t melts with evolution of gas a t 223-224".Boiling aqueous potash hydrochloric and nitric acids do not act on it. EtlujZtlialliize C,H,EtNO is a thick oil which boils a t 287- 287*5O with slight decomposition. It is insoluble in water very readily soluble in alcohol ether and in mineral acids. Some salts were prepared ; they are very hygroscopic and cryatallise with diffi- culty. EthyZtlLa2lirLe et7~iodide forms white needles readily soluble in alcohol and in water insoluble in ether ; it melts with evolution of ;'as a t 1:31-133° ; when distilled it decomposes into ethyl iodide and t' t hvlt ha1 lin e. Benzyl chloride acts on thalline with formation of a base probably Lenzylthalline ; when treated with ferric chloride it gives tho same characteristic red colour as methyl- and ethyl-thalline. The physiological properties of several of the compounds mentioned in the paper are described.The papei. concludes with remarks on the constitution of quinine. Para- and Ortho-phenylquinoline. By W. LA COSTE and C. SORGER (Aiinaleii 230 1-42).-l'arayhenylquinoline is prepared by N. H. M.ORGANIC CHEMISTRY. 81 the action of sulphuric acid glycerol and nitrobenzene on paramido- diphenyl. The base is precipitnted from the acid solution by the addition of an alkali collected dried and dissolved in warm benzene. The solution is left in contact with solid potassinm hydroxide for some hours and is then filtered. After removing the benzene by distillation. the residue is distilled under reduced pressure. Paraphenylquinoline CgNH,Ph [Ph = 31 melts at 110-111" nnd boils a t 260" under 77 mm.pressiire; its sp. gr. is 1.1945 at 20". It is sparingly soluble in water but dissolves freely in alcohol chloroform benzene and carbon bisul phide. Phenylqninoline is deposited from ether in rhombic pyramids from alcohol in combinations of the pyramid and basic plate and from benzene in twin pyramids ; all the salts are soluble in water fmming fluorescent solutions. The twtratp CgNH,Ph,H,C,HaO + 3H20 crystallises in needles melting a t 153". The dichromate (CgNH6Ph)2,H2Cr207 forms reddish-yellow needles which melt at 136". The methiodide C9NR6Ph,MeI + 2H20 crystal- lises in long needles melting at 194". The ethiodide crystallises with 2 mols. H20 in pale yellow needles and also with 1 mol. H,O in thick yellow prisms.When phenylquinoline is treaked with tin and hydrochloric acid i t unites with four atoms*of hvdroyen to form a tetrahydro-cornpound. The hydrochloride C9NH,Ph,HC1 + 1+H20 crystallises in needles. It is sparingly soluble in cold water and is partially decomposed by hot water. It also dissolves in alcohol and in chloroform. The picrote CgNH,Ph,C6H,(No2),*o~ is deposited from a hot aqueous solution in needles which dissolve freely in alcohol chloroform and benzene. It melts a t 165'. The nitroso-compound C9NHgPh.N0 forms yellow cryst#als freely soluble in benzene and chloroform. The acetyl-derivative C9NHgPhAc crystallises in white silky needles. It melts at looo and is freely soIuble in alcohol benzene chloroform and carbon bisulphide. The benzoyl-derivative forms white plates melting at 137".It is freely soliible in alcohol. Meth y ItetTa~~ydroparaphen~~ Zquinoline hydrochloride The free base is soluble in alcohol ether and hot water. C9NHgMePh HCl prepared by the action of tin and hydrochloric acid on phenylquino- line methochloride is a crystalline substance soluble in alcohol and chloroform. The hydriodide CgNH,MePh,HI resembles the hydrochloride but is more easily decomposed by water. It dipolves in alcohol chloroform and benzene. The methiodide melts a t 194". It crystallises in plates or prisms soluble in alcohol and in chloroform. The substitution products of paraphenylquinoline do not crystal- lise easily and can only be prepared with difficulty in the pure state. The mononitro-derivative CljNHlo*N02 is formed by the action of fuming nitric acid on an acetic acid solution of paraphenylquinoline.It melts at 173" and is soluble in alcohol ether benzene and in hot water. The compound also dissolves in dilute acids and forms two The platinoch loyide easily decomposes. The picrnte melts at 147". 9 VOL. L.82 ABSTRACTS O F CHEMICAL PAPERS. crgstallino platinochlorides of which one is insoluble in hot water. The dinitro-compound is obtained by adding phenylquinoline to fuming nitric acid. It melts at 208" and dissolves in alcohol and benzene. Phenylquinoline dissolves in cold fuming sulphuric acid yielding two isomeric monosulphonic acids. The a-snlphonic acid C,H,NSO + 2Hz0 can be separated from its isomeride by the greater solubility of the latter and also of its ammonium salt in water.The a-acid crystal- lises in lon5 needles soluble in hot water. It does not melt a t 300". When oxidised with potassium permanganate it yields parasulpho- benzoic acid. The ammonium salt of a-phenylquinolinesulphonic acid crystallises in plates which dissolve freely in hot water. Tbe sodiuni and calcium salts dissolve freely in water the potassium and barium salts are sparingly soluble. p$heizylq.uilzoZines.ulpkonic acid Cl5H,NSO3 + H20 dissolves freely in water but is insoluble in chloroform and ether. The ammonium salt crystallises in anhydrous scales. Ortho~henyZqi~inoli?te C9NH6Ph [Ph = 11 is prepared by a process analogous to that employed in the preparation of the para-compound. It is a thick fluorescent oil which darkens on exposure to the air.It dissolves freely in alcohol ether benzene carbon bisulphide and chloraoform and boils between 270" and 276' under a pressure of 80 mm. Tbe salts of the base are soluble in water forming fluorescent solutions. The platinochloride crystallises in needles ; the dichromnte in plates melting at 126" and dissolving in water and warm alcohol. The methiodide forms reddish-yellow plates melting' a t 163". It is freely soluble in water alcohol and chloroform. Ortlzop heny lyzcino- linemethyl platinochloride ( C,NH6PhMe),PtCl6 is a crystalline salt soluble in hot water. It melts at 198". w. c. w. Colouring Matters derived from the Quinoline Bases. By 0. DE CONINCK (Rec. Trau. Chim. 4 58-60).-The reaction of an alcoholic solution of potassium hydroxide on the iodides of the ethyl and methyl derivatives of the quinoline bases by which a red colour- ing matter is produced (Rec.Traw. Chim. 3 337) appears to be general for all the alkyl-derivatives of quinoline as the author has prepared a red crystalline colouring matter from the iodide of the propyl-derivative ; he also confirms the constitution assigned to ths cyanine-derivatives obtained by the action of potassium hydroxide on the iodide of ethyl-lepidine and ethylquinoline (Abstr. 1885 673). Quinoxalines. 111. By 0. HINSBERG (Ber. 18 2870-2875) .- A. P. Dihydro-ox y tolu puinoaaline is obtained by heating ethyl chloracetate (2 mols.) with toluylene- diamine (3 mols.) for several days on a water-bath and is purified by means of its sparingly soluble sodium-derivative. It crystallises in moderately large yellowish needles is readily soluble in hot waterOROANlC CHEMISTRY.8 3 and alcohol moderately in ether and also in alkalis and acid>. The potassium-derivative is readily soluble in water and in potash solution; the sodium-derivative C9H,N20Na + H20 forms lustrous scales and is almost completely precipitated from its aqnems solutions by the addition of soda. Dihydro-oxytoluquinoxaline in alkaline solution is oxidised by atmospheric oxygen to hydroxytol u- quinoxaline ; neutral solutions are not so readily acted on but are also oxidised by weak oxidising agents. When toluylenediamine and ethyl chloracetate are heated together in equal molecnlar proportions the compound C13H16N203 i s produced and may be purified by crysta1lisa.tion from alcohol.It forms colourless lustrous scales melts at l47" is sparingly soluble in water nearly insoluble in ether and moderately soluble in alcohol. Concentrated mineral acids and acetic acid dissolve it readily whilst alkalis dissolve it only on warming. Silver nitrate and nitrous acid oxidise it apparently t o a product melting a t 247-2418". On saponi- fying the substance C13H16N203 with alkali a sparingly soluble acid is obtained crystallising in white needles. The formation and constitu- tion of the above compound may probably be expressed thus :- + EtOH + CTH~(NH~C~),. A. K. M. Papaverine. By C. GOLDSCHMIEDT (Monatsh. Chern. 6 667-701 ; compare Abstr. 1885 1080).-Analyses of papaverine and of a large number of its salts confirm the correctness of the formula C20H,NOa assigned to papaverine by Merck and others.Papaverine cry stallises in rhomhic prisms a b c = 0.3193 1 0.4266. Crystallographic measurements of various derivatives and salts are also given. N. H. 31. Hydrobromapoquinine. By P. JULIUS (Monatslz . Chem. 6 750-753),-Hydrobrornapoquinine C,H23BrN2021 is prepared by heat- ing quinine hydrate a t 100" with three times its weight of water saturated with hydrobromic acid a t 0". It forms a white amorphous powder which melts a t N9-210" is insoluble in water readily soluble in alcohol. The hydrobmnide C19H23BrN202,2HBr + H20 crystallises in groups of white needles readily soluble in water and in alcohol. The pZatinochZoride is described. N. H. M. Cupreine and Homoquinine By 0. HESSE (AnfiaZen 230 55-73) .-The author confirms the accuracy of his former statement (Abskr.1885 276) that homoquinine is a compound of quinine and the new alkalo'id discovered by P a d and Cownley called cupreine. Many of the properties of cupreine have been already described. The base crystallises with 2 mols. H20 which are expelled a t 120". The anhydrous substance melts a t 198'. The alcoholic solution gives a dark reddish-brown coloration with ferric chloride and an intense green coloration m-ith chlorine and ammonia. The neutral salts of cupreine dissolve in water forming yellow solutions which are rendered colourless by the addition of acids. The solutions are not 08.2 ABSTRACTS OF CHEMICAL PAPERS. fliiorescent. The neutral sulphate ( C,H&"02),H,S04 + 6H,O crystallises in needles ; the hydrogen snlphate C1,HnN2O2,HzSO~ + H20 forms flat prisms sparingly soluble in cold water.There are two hydrochlorides C,H2,N,02,HC1 + H,O crystallising in colourless needles and C19H22N,02,SHCl forming pale yellow prisms. The normal platinochloride ( C,9H22N,0,)2,H2PtC16 + 4H20 is amorphous ; the acid salt forms orange-coloured plates. The normal tartrate and thiocyanate are sparingly soluble in water. Cnpreine does not combine with ammonia but it forms compounds with potassium sodium lead and silver. Anhydrous cupreiiie dissolves in acetic anhydride forming a diacetyl compound C19H,Ac2N202 crystallising in six-sided plates. It melts at 88" and is soluble in alcohol ether and chloroform. The hydro- chloride also crystallises in six-sided plates soluble i n alcohol and .water.Cupreine is converted into apoquinine by the action of hydrochloric acid at 140". Cupeine methiodide forms colourless crystals sparingly soluble in cold alcohol and water. The corresponding chloride ClsH,N202,MeC1 and platinochloride Cl9E2,NzO,MeHPtC1 + 2H20 are also crystalline. The sulphate crystallises in needles which are freely dissolved in water. By decomposing this salt with baryta-water the hydroxide is obtained. The aqueous solution of the hydroxide gives a red coloration with excess of bleaching powder in presence of ammonia and a green coloration when ammonia is added to a mixture of the acidified solution and a small quantity of bleaching powder. The alcoholic solution of the hydroxide is fluorescent.Homoquinine is easily prepared by adding ammonia to a solution of equal molecular weight of quinine and cupreine in dilute sulphuric acid and dissolving the precipitate in ether. Homoquinine is not a simple alkaloid but a compound of the composition Cocaine and its Salts. By B. H. PAUL (Pharrn. J. Trans. [3] 16 325-326).-The author's experiments indicate that the solubility of coca'ine i n water is much less than 1 in 700; moreover that on evaporating the aqueous solution the cocaine ia decomposed leaving a gummy mass whieh crystallises and has many properties similar to those attributed to ecgonine (compare Merck Abstr. 1885 997). It yields benzoic acid by the action of caustic soda lime or sodium arbonate bu.t not apparently by the action of hydrochloric acid.It combines with benzoic acid but can b4 separated from the acid by repeated crystallisation from water. Cocaline hydrochloride is only slightly soluble in water from which solution it can be crystallised with water of crystallisation but after prolonged heating on a water- bath it remains in a resinous state for a considerable time a t least. The acetate is very soluble and is diEcult to crystallise owing t o the volatilisation of the acetic acid during evaporation. The solution of the benzoate dries to a thick gummy residue. Ammonia precipi- tates the alkaloid without apparent decomposition and when added in excess does not redissolve it. D. A. L.ORGANIC CHEMISTRY. 85 Alkaloi'ds from Erythroxylon. By C. J. BENDER (Chem. Ce?zti*. 1885 490-493).-The author has subjected the leaves of the coca- plant (Eyythroxylon cocu) to a careful investigation.Besides cocaine he obtained an amorphous alkaloid to which he gives the name cocuzcine and a volatile base which he names erythroxyline. There also seem to be one or two other alkaloids present but the author was unable to obtain them in a pure state or to determine whether they were present in the %resh leaves or formed during the process of extraction. L. T. T. Bases in Jaborandi Leaves. By E. HARNACK (Chem. Centr. 1885 628-629) .-Besides pilocarpine and jaborine Merck (Harnack and Meyer Abstr. 1880 898) obtained from the leaves of the jaborandi a third syrupy alkaloid which yielded a nitrate crystallising in well-defined prisms. The author has investigated bhis alkalo'id to which he gives the name pilocurpidine.Jt very closely resembles pilocarpine both in physiological and chemical properties but it does not give a precipitate with auric chloride. Its formula is CloH14N202. It is easily converted into an amorphous base juboridine C10HlzN203 which resembles jnborine and atropine in properties. Jaboridine appears to be identical with jaborandine C10H12N203 ottained by Parodi (Rivista furm. 1875 3) from false jaborandi (Piper jaborundi) and by Chastaing by the oxidation of pilocarpine with fumiiig nitric acid. The anttior believes that the jaborine hitherto obtained has always contained jaboridine as an impuriby. From the formula and properties of pilocarpine C,IF16N202 this substance would appear to be a methyl-derivative of pilocarpidine ; and the author points out that the latter has the composition OP a di-hydroxy- derivative of nicotine or of an isomeride thereof. Jaboridine is an oxidation product of pilocarpidine formed by the replacement of two atoms of hydrogen in the latter by an atom of oxygen.Alkalo'ids of Fenugreek Seeds. By E. JAHNS (Ber. 18 2518 - 2523).-The seeds of Frigonellu fGenurn grGecum contain t rigonelline and a liquid base identified as choline. Trigonelline C7H7N02 + H20 crystallises in coburless flat prisms of feeble saline taste ; it is readily soluble in water sparingly soluble in cold alcohol insoluble in ether chloroform and benzene ; it is carbonised when heated. The reactions with the various reagents for alkalo'ids are described. The hydrochloride C7H7N02,HCl crystallises in an- hydrous tables ; the platinochloride ( C,H7N02),H2PtC16 crystallises in prisms.Two' atdrochlorides were obtained C7H7N02,HAuC14 crystallising in four-sided plates or flat prisms and melting at 198" and 4C7H7NO2,3HAuCl4 crptallising in slender needles and melting at 186". A. J. G. L. T. 2'. Products of the Action of Hydrochloric Acid on the Albumi- noids. By J. B ORBACZEWSKI (Monatsh. Chem. 6 639-650).- When 500 grams of elastin (previously freed from fat by extracting the finely powdered substance for two weeks with ether) are boiled for 72 hours with I litre of hydrochloric acid diluted with an equal86 ABSTRACTS OF CHEMICAL PAPERS. volume of water and 25 grams of zinc chloride a small quantity of ammonia is given off and the solution after precipitation of the zinc by hydrogen aulphide is found to contain leucine glycocine and tyrosine.Other compounds are also present but could not be isolated. The formation of these substances and the absence of glutaminic and aspartic acids and of hydrogen sulphide from the prodnet of %he reaction show that elastin does not belong to the'same class of compounds as do albumin and keratin. It also differs from the horn substances and all other albuminoids which have as yet been examined. PJ EL 11.3s ABSTRACTS OF CHEhlICAL PAPERS.Organic Chemistry.Melting and Boiling Points of Cyanogen Bromide. By E.3fULDER (Rec. Trav. Chim. 4 151-152).-Cyanogen bromide be-comes somewhat transparent a t 16" but melts a t about 52' it boils a t61.3" (corr.).A. P.Normal Cyanuric Acid. By E. MULDER (Rec. Tmv. C'him. 4,91-1Ol).-In continuation of his researches on the derivatives ofnormal cyanic acid (Abstr. 1883 304 and Rec. Tmv. Crlziliz. 2 133)the author finds that both normal ethyl cyanurate and the crudeprodact a(CN*OEt*C,H,O) (Abstr. Zoc. cit.) when saponified withaqueous soda at the ordinary temperature and then neutralised withltydrochloric acid yield a white crystalline deposit haring the compo-sition C3N303HEtZ and probably the constitution C.3N3(OEt)2*OH orC,N,(OEt);CONH. Normal ethyl cyanurate yields isoqanuric acidon acidification with hydrochloric acid normal cy;innric aqid seemingt o be incapable of existing in the free state. The author considersthat Wurtz's diethglcyanuric acid is most probably identical withthat obtained by Habich and Limpricht and has the constitutionc:,O,(NE!t), KK.A. P. *Additive Compounds of Normal Ethyl Cyanurate with'Cyanogen Bromide. By E. MULDER (Eec. Trac. Claim. 4 147-150) .-On treating normal ethyl cyanurate with excess of cyanogeiibromide an additive compound C,N30,Et,2CNBr is formed. I t I Sliquid a t the ordinary temperature crystallising a few degrees lower.The author considers that i t has the constitutionCBr(0Et)N C(0 Et)NC'N< CBr( OEt) --N (CN ) >When heated for several hours a t 125" until no further pressure isdeveloped a yellow liquid is formed which by continued heating a tthe same temperature in an open tube is converted into a hardand vitreous niass.On treating cyanogen bromide with excess of norms1 ethyl cyanurate,a second additive compound seems to be formed having the composi-tion C3N3O3Et,CNBr.A. P.Action of Ammonia and Amines on Methyl Thiocyanurateand Cyanuric Chloride. Normal Alkyl Melamines. By A. W.H.OFMANX (Ber. 18 2755-2781).-The final product of the action ofammonia on methyl thiocyanurate is melamine but by modifying theconditions of the experiment either of the intermediate products maybe produced. To obtain the primary aqnido-base C,N,( SMe)2.NH,the methyl tliiocjanurate is digested with a moderate excess of strongalcoholic ammonia for about five hours a t 100". The purified basecq-stallises from boiling alcohol in rhombic plates melting at 200; iOROAWC CIHIEJITSTKT. 39is readily soluble in hot more sparingly in cold alcohol and is notcluite insoluble in wat8er.I t s solutions give no reaction with vegetablecolours and no sulphur reaction with alkaline lead salts. The basedissolves sparingly in hydrochloric acid and is reprecipitated on theaddition of water. On boiling i t for a. long time with hydrochloricacid it is decomposed with production of mercaptan ammonia aridcyanuric acid. The platinochloride and aurochloride,are described. The secondary amido-base C3N,(NH2),.SMe is obtainedon digesting methyl thiocyanurate with alcoholic ammonia for aboutfive hours at 160". It differs from the primary basc by its readysolubility in water and more sparing solubility i n alcohol ; it melts a t268" dissolves readily in hydrochloric acid and yields a platino-chloride (C,H,N5S)2,H2PtC16.When boiled with hydrochloric acid itgives the same decomposition-products as the monamido-compound.The tertiary amido-buse meZumine can be obtained in nearly theoreticalamount by heating methyl thiocyanurate with an excess of strongaqueous ammonia for several hours a t 180". I t s properties agree wizhthose assigned to it by Liebig (Annnlen 10 el). The author has alsosucceeded in obtaining two plntinochlorides from it,( C3H,N6),H,PtC16 + 2H20 and C3H,N,H2PtCI (?).The amines are found to react with methyl thiocyanurate in the sameway as ammonia. The primary methy lamido-base C3N3( S3Je),*NHMe,i3 produced on heating methyl thiocyanurate with a 33 per cent.aqueous solution of methylamine for several hours at 100". It isreadily soluble in alcohol and ether and crystallises in well-formedprisms melting a t 174-175" ; it forms crystalline salts with hydro-chloric nitric and oxalic acids mid also yields a sparingly solublei'latinochloride and an aurochloride.Hydrochloric acid deconiposesthe base a t 100" into ethyl mercaptan methylamine and cyanuric acid.The secondary methylarnido-base C,N,(NHMe),*SMe is produced simul-taneously with the primary compound. It is very readily soluble inalcohol less so in ether and is best crystallised from a large bulk ofboiling water from which it separates in slender needles meltiug a t144". I t s salts are mostly very readily soluble the nitrate crystal-lising best ; the platinochloride is very sparingly and the aurochloridemoderately soluble.The base is decomposed by hydrochloric acida t 200" and yields the same products as the primary base.The tertiayy naethy lamido-base trimethylmelamine is prepared byheating methyl thiocyanurate with 33 per cent. aqueous methylaniinetor several hours a t 180" ; or a mixture of the primary and secondarybases may first be prepared at a temperature of 130-140" and thisthen heated at l70-18O0 with more methylamine. Trimethylmel-amine is very readily soluble both in water and in alcohol and theauthor has not succeeded i n obtaining it quite pure ; its hydrochlo-ride nitrate and sulphate are also extremely soluble the oxalate moresparingly so. Like melamine i t yields two platinochlorides,[ C,N,( N HMe)3]2,H2P t C Is and C3N3( NHMe),H,Pt C1,40 ABSTRACTS OF CHEMICAL PAPERS.By the action of ammonia on cyanuric chloride Liebig (Atznalen,10 45) obtained the compound C3H4N5C1 which he termed chloro-cyanamide but which the author shows to be C3N3(NHz),Cl that isan intermediate product between cyanuric chloride and melamine,and it may in fact be converted into the latter by a few hours'heatinq a t 100" with strong aqueous ammonia.A nearly theoreticalyield of melamine may likewise be obtained directly from cyanuricchloride. A solution of methylamine in absolute methyl alcohol like-wise reacts with cyanuric chloride with production of dimeth yZamido-cyariuric chloride C3N3( NHMe)?Cl; it is nearly insoluble in water,alcohol and ether soluble with slight decomposition in boiling glacialacetic acid from which hot water precipitates it in needles melting a t241" with decomposition.I n acid solutions the chlorine soon becomesreplaced by hydroxyl. When dimethylamidocyanuric chloride is heatedwith a solution of methylamine in methyl alcohol for a few hours at loo" it is converted into trimethylamine; this when heated a t 150"with hydrochloric acid splits up into methy lamine and cyanuric acid.On heating dimethylamidocyan uric chloride with aqueous ammonia a t150° the chlorine is displaced and a base produced which is withoutdoubt diniethyhnelumine C,N,(NHMe),*NH ; its salts are soluble thesulphate crystallising in six-sided plates and the oxalate in rhom-bic crystals ; i t yields two platinochlorides C,Hl,N6,H2PtCl6 andThe dimethylainidocyanuric acid C,N,(NHMe)2*OH obtained fromdimethylamidocyanuric chloride (see above) by the action of an acid(or of water at ZOO") is separated from its hydrochloride as a whiteindistinctly crystalline precipitate which is almost insoluble in boilingwater insoluble in alcohol and ether; its platinochloride has theformula ( C5 H BN50) ,HZPt C 1,.D irneth y lamidocy anuric acid formssalts both with acids aud with bases ; the hydrochloride and nitrateare crystalline and soluble without decomposition ; the sodium saltand the methyl salt (obtained from dimethylamidocyanuric chlorideand sodium methylate) crystallise in prisms.The mother-liquors from the preparation of dimethylamidocyanuricchloride contain (besides methylamine hydrochloride) a crystallinesubstance found to be methylamidonaetiioxycyanzLric chloride,MeO*C3N3C1*NHMe ;it forms acicular crystals melting at 155" is soluble in alcohol andether also in hydrochloric and nitric acids with formation of crystal-lisable salts.It may be boiled with acids without parting with itschlorine.Attempts to obtain hexamet?ylnaelam ine C3Ns(NMe2) by heatingmethyl thiocyanurate with dimethylamine were without success butits hydrochloride may be obtained by heating a mixture of equalweights of dimethylamine hydrochloride and cyannric chloride aslong as hydrogen chloride is evolved. The base ci.ystallises in needlesmelting at 171-172" ; its platinochloride and aurochloride are de-scribed.When it is heated with hydrochloric acid a t 200" it splitsup into cyannric acid and dimethylamine.Methyl thioayanurate is acted on by ethylamine in the same way as(C5H&),H,PtC16ORGANIC CHEMISTRY. 41by ammonia and by methylamine with formation of correspondingproducts. The primary et l ~ y Zir mid o- bn se C3N3( S Me) 2* NHE t cry stallisesfrom boiling dilute alcohol in lustrous needles melting a t 114" issparingly soluble in boiling water readily in cold alcohol ; i t yields aplatinochloride of the formiila ( C,H,2N4S,)z,H,PtC16. The secondaryetlr y/u)nido-base C3N3(NHEt),-SMe forms needles melting a t 83-8 &' ;its hydrochloride is crystitlline extremely soluble in water less so inalcohol aud insoluble in ether ; the nitrate is more sparingly soluble ;the oxalate forms slender very soluble needles whilst the snlp'iatedoes not crystallise.A plat inocliloride aurochloride and stanno-chloride have also 1 been obtaiued. The tertiirry eth!/Zitt,iido-Case,triethy Zmelainine CJN3(NHEt) can be obtained both from methylthiocy anurate and from cyanuric chloride and forms prisms meltingat 73-74'. It is soluble in alcohol ether and benzene ; the platino-chloride ( C9H,N6),H2PtC1 and aurochloride are described arid alsoa compound with silver nitrate ( C9Hl~N&,AgN03. Triethjlmel-amine is decomposed By hydrochloric ac4d at 150' into cyanuric acidand ethylamine.Hexethylmelamine C3N3(NEt2) is formed by the action of diethyl-amine on cyanuric chloride.The platinochloride ( C,H&6)2,H,Pt~16,and aurochloride CI5H,K6,HAuCl4 are described. Hydrochloric acida t 150" decomposes the base into diethjlamine and ojanurio acid.In order to shvw that the higher amines also react with methylthiocyanurate this latter -substance was digested with alcoholic amyl-amine at 10U". The primary anrylamido-base,. C3N,(SMe)z*NHC5H11,obtained crystallises in clusters of silky needles melting at 96".Hydrochloric acid decomposes- itL slowly a t the ordinary tempeiature.When the reac-tion bakes place at 200" the secondary base C3N3(NC5H,),*SMe is ob-tained and forms colourless crystals melting a t 106-107' ; itsplatrinoch1oride has the formula (~l~H,3~,S),HzPtC16. If the reactiontakes place a t 250° the tertiary base trip3iperidylnrelamip.Le,Piperidine also reacts with methyl thiocyanurate.C3&( N C5&3)3,is produced and crptallises in small needles melting at 213" ; it dis-solves rcadily in acids and yields a sparingly soluble platinochloride,( c,eH,N6)2,HzPtC16. Hydrochloric acid decomposes the base a t 150"into piperidine and cyanuric acid.Tripheitylmelamiwe CJN3(NHPh) may be obtained by the actionof aniline on methylthiocyanurate or cyanuric chloride and hexa-phenylmelamine C,N3(NPhZ) may likewise be obtained from dipheriyl-amine and cyanuric chloride.Alkyl Isomelamines derived from the Alkyl Cyanamides,and the Constitution of Melamine and of Cganuric Acid.A.K. M.been proposed for melamine the former is the one which most simplyexplains the formation of melamines and of mercaptan by the actionof ammonia or amiies on methyl thiocyanurate and of melamines an42 ABSTRACTS OF CHEMICAL PAPERS,lrydrocliloric acid from cyanuric chloride and ammonia or nmines(sse last Abstract).The second formula on the other hand wouldnecessitate the assumption of complicated molecular changes ; in theformation of the hexalkylmelamines by the action of a secondarpamine one alkyl group of the latter must be assumed to detach itselffrom one nitrogen-atom aud to attach itself to another and the ->NMe should resulting hexalkylmelamine NNe C<NMe.C(N31e) NMeG (NAIe)be split u p by the action of water into methyl cyanurate and methyl-amine ; cyanuric acid and dimethylamine are however produced.The formation of the piperidine-derivative of melamine is met bysimilar difficulties if the imido-formula be taken as correct whilst thenmido-formula readily explains all the reactions.Alkylmelamines corresponding with ail imido-melamine can how-ever be obtained but these yield no cyanuric acid; they split u pinto ammonia and alkyl cyanurates.l'rimethytisomelamine C3N3Me3 (NH) has been previously men-tioned by the author (Eer.3 264) and by Bauniann (Ber. 6 1372).I n order to obtain it monomethylthiocarbanride is treated with drymercuric oxide in absolute alcohol the methylcyanamide first formedr:x pidlg polymerising to trimetl-tylisomelamine. This i s very readilysoluble in water and alcohol insoluble in ether the solution exhibit-ing a distinctly alkaline reaction.It crystallises in well-formedneedles melts at 179" and readily sublimes ; the platinochloride,chN6H12,H2PtC16 and aurochloride C&GH,,H&.u?CI& are described.Hydrochloric acid at 100" decomposes the base into ammonia aridmethyl isocyanurate ; this decomposition takes place in stages and theauthor has succeeded in isolating one of the two intermediate pro-ducts namely NH C3N,Me,02; it forms a n aurochloride,CsHioNdOa HAu C 1,and a hydrochloride C6HloN402,HC1.Triethy~isometamine C3N3E t3( NH) has also been previouslymentioned (Hofmann Ber. 1 27). It forms stellate groups ofneedles melts at 92" and crystallises from water with 4 mols. H20.Platino- and auro-chlorides are described. It is decomposed by acidsin the same way as the trimethyl-derivative and here again the oneintermediate product HN C3N,Et30 can readily be isolated.In further support of the amido-nature of melamine the authormentions its decomposition by water into ammonia and cyanuric acid,the constitution of which he indicates to be HO*CeN.C(oH)>N.He points out that the formation of cyanuric acid from carbamidedoes not prove it t o have the constitution CO<NH,CO>NH as theconstitlution of carbamide has not been definitely established (comparethis Journal 1866 161). There also appears to be little ground forthe assumption of the iso-nature of cyanic acid. On the contrary theformation of cyanates from potassium cyanide the conversion ofxmmonium cyanate into carbamide and of cyanic acid with theelemmts of water into ammonia and carbonic anhydride run perfectlyN-C( OH)NH*CORGAXIC CHENIYTRY. 43parallel with the formation and behaviour of thiocjanic acid thenormal constitution of which is not doubted.The formation of alkylisocyanurntes from cyanuric acid may be accounted for by the factthat t,he normal ethers may be readily converted into the iso-ethers(Rer. 3 272 ; Rec. Tmv. Chinz. 1 191). The production of cyanuricchloride from phosphorus pentachloride and cjaiiuric acid and there-formation of the latter by the action of water on the chloride(Annalen 116 357) also support the view that cyanuric acid containsli-ydroxyl-groups. Phosphorus pentachloride acts in the same way onthe normal methyl salt of cyanuric acid with formation of methylchloride phosphorus oxytrichloride and cyanuric chloride.Methylisocyanurate however gives a very different reaction when heatedwith phosphorus pentachloride hydrochloric acid phosphorus tri-chloride and trichioromethyl isocyanui*ate,N(CH2C1)*CO>N(CH2C1),co<N(CH2Cl)*C0being formed. A. K. M.Allyl-sulphuric Acid. By F. SZYMAKSKI (AnnuZen 230 43-50).-The preparation of rtllyl-sulphuric acid by the action of sul-pbnric acid on allyl alcohol was first described by Cahours and Hof-Inann (Ani-,aZen 102 293). Beilstein and Wiegand (Abstr. 1885 740)have recently stated that allyl alcohol is completely carboriised bysulphuric acid. The author finds that this is not the case when thealcohol is slowly added to the acid.The best results are obtainedwhen the acid is diluted with an equal volunie of water. The bariumsalt has been previously described by Cahours and Hofmann (Zoc. cit.).The stroritiurn salt forms anhydrous rhombic prisms soluble in waterand in alcohol. The anhydrous calcium salt crystallises in quadratic1,lates. The copper salt crystallises in needles with 4 mols. H,O.It is soluble in water and alcohol On saturating allyl-sulphuric acidwith lead carbonate a basic salt (C,H,SO&Pb + PbO + 6H20 isobtained which is soluble in water.The magnesium saZt Mg(C3H5SOA)2 + 4H20 crystallises in trans-parent needles soluhle in water. The potassium arnmoniuni andsodium salts are hygroscopic and soluble in water. The f e w o u s saltforms quadratic plates soluble in alcohol.w. c. w. It is hygroscopic.Methylene-derivatives. By 1;. HENRY (Conzpt. rend. 101,599-GOO).-Diethoxy,izethane CH,(OEt) obt'airied by the action of diiodo-methane on sodium ethoxide is a colourless mobile limpid liquid with:L pungent taste and a peculiar agreeable odour quite different fromthat of acetsl. It is only slightly soluble in vc-ater and quite iiisolublein a concentrated solution of calcium chloride. It boils a t 82-83"under a pressure of 760 mm. ; sp. gr. a t 16.7" compared with the watera t the same temperature = 0.8275 ; vapour-density 3.44.C~I~Zorobromornetl~ane CH2C1Br obtained by the action of excess ofbromine on chloriodomethane is a mobile colourless liquid with auagreeable ethereal odour and a sweetish pungent taste.It is insolu-IAe in water does not decompose when exposed to light and boils a44 ABSTRACTS OF CHEMICAL PAPERS.68-69" under a pressure of 765 mm. ; sp. gr. at 19" compared withwater at the same temperature = 1.9907 ; vapour-density 4.43.R~orniodornethutze CH2RrT is obtained by the action of a limitedquantity of bromine or better of iodins chloride on diiodomethane. Itis a colourless liquid which becomes purple when exposed to light. Ithas an agreeable etherealsodour and a sweetish bitter taste is insolublein water and boils a t 138-140" under a pressure of 754 mm. ; sp. gr.a t 16.8" compared with1 water at tihe same temperature = 2.9262;vapour-density 7.65. C. H. B.Sulphatea of some Carbohydrates. By M HONIG and S.SCHUBERT (Mm~atsli.Chern. 6 708-749).-By the action of sulphuricacid on1 cellulose a t different temperatures varying from 7" to 40°,and subsequent treatment of tbe product with barium caiBbonate saltswere obtained which contained the same percentage of barium butwhich possessed a ,greatly varying rotatory p o m r ( [ a ] j = - 3.65" to + 72.99"). Further experiments made t o ascertain the influence ofthe quantity of acid used showed that salts varying in composition,but having the same rotatory power can be formed. Prolongedaction of sulpl~uric acid causes an increase of. barium in the salt aswell as an increase of rotdory power. When the action is allowed totake place at a& low temperature the product coiitains salts varyingmore from one another than if the reaction takes place a t a highertemperature.The following salts were separated :-They form white or yellowish-white voluminous powders with varyingsolubilities io water; the lead and calcium salts are similar. Thehydrogen su1phate.s form white amorphous very hygroscopic com-pounds which dissolve very readily in water and in alcohol ; they areinsoluble in ether. The aqueous solution decomposes slowly at theordinary temperature more quickly when boiled losing sulphnric acid.similar way ;but the action is much slower than in the case of cellulose.Theproducts have the same general formula C6,Hlo,0,-,( SO,) as thoseobtained from cellulose but turn po1arised:liglit to the right.When the hydrogen sulphates are boilea with alcohol they lose allthe sulphuric acid leaving modified forms of cellulose and starchrespectively. N.H. M.Organic Iodides of Nitrogen. Rg; F. RASCHKG (AnnuZen 230,221-224).-RfeOhylnmiiie~ hydrochloride is completely converted intom e t h y Zdiiodamine Nl,Me when the theoretical quantity of iodine(dissolved in potassium iodide) is- added to a solution of methylaminehydrochloride and sodium hydroxide MeNH2,HC1 + 41 + 3NaOH =NLMeI + NaCl + 2NaI -!- 3H,O.Dimeth.yZiodumine,NMezI is obtained from d imethylamine by a similarreaction as a yellow precipitate. It is sparingly soluble i n alcohol andether. I t soon decomposes and acquires a dark colour. A solution ofpotash changes tthe colour of the compou a d to greenish-yellow withoutAnhydrous starch is acted on by sulpliuric acid iORGASIC CBEMISTRI'.45affecting its composition. Iododimethylamine and di-iodomethylaminedecompose without exploding when they are touched by a hot body.Etkyldi-bdamine and diethyliodamiiie are obtained by sirnihrreactions in the form of brick-red and orange-coloured precipitates.They rapidly decompose into iodoform and a dark blue liquid. w. c. w.Synthesis of a Ketone from (Enanthylidhe. By A. &I. &$HAL(J. Pharm. [ 5 ] 811 155-158).-AmyZ meihyl ketone C5H,*COMe isobtained by dissolving mnanthylidine in sulphnric acid diluting withwater and distilling. It forms an oily liquid of pungent odour boilsa t 147-148" under 759.2 mm. pressure shows the property of aketone jieldiiig a hydrogen sodium sulpbite compound &c. and onoxidation is converted into aceticband valeric acids..A. J. G.Action of Bromine in Alkaline Solution on Amides. ByA. W. HOFMANN (Ber. 18 27~-2741).-Chloracetamide -is acted onby bromine in alkaline solution with formation of a compouud,CH,CI*NH*CO*NH.C,H,CLO. This substance me1 ts at; 180" and is spar-ingly soluble ; it is decomposed by acids or alkalis into chloracetic andhydrochloric .acids,*carbonic anhydride ammonia and met haldehyde.Ethoxyacetamide when treated with an a l h a h e solution of bromine,yields a compound EtO*CH~.*NH*CO*NH*C,H?O.OEt. It crystallisesin cdcmrless needles which melt at 80° and is decomposes by acidsand alkalis into et,hoxyacetic acid alcohal ammonia and mcth-aldehyde.When 1 mol.of phenylacetamide is acted on by 1 mol. bromine and4 mols. of a 5 per cent. solution of alkali and then distilled in steani,much benzylamine is obbained together with some bromobenzylamine,which may be 4 convert,ed by (the action of sodium amalgam intobenzylamine.IJy drocinnamamide is prepared. by heating ammonium hydrocinna-mate for five hours a t 220" ; it forms small thin needles which melta t 105". When treated with bromine in -alkaline solution and thendistilled with steam it yields a .mixture of phenylethylamine and abromine-derivative C8H8Br*NH2 which boils at 252-254". To obtainpure phenylethylamine the mixed product contained in the distillateis treated with sodium amalgam.The yield is about 60 per cent.of the theoretical..The yield is about 30 per cent.N. H. M.Action of Ethyl Acetoacetate on the. Amidines Pyrimidines,By A. PINNER (Bey. 18 2845-2852).-Jn order to test the generalcharacter of this -reaction (Abstr. 1885 158 751) the author hastried to prepare the corresponding pyrimidines from various amidines,and he finds that with the exception of formamidine all t h e nmidinesexperimented with are capable of yielding pyrimidines. Whenformamidine hjdrochloride (25 grams) is treatled with the calculatedamouirt of ethyl azetoacetate a 10 per cent. solution of sodiumcarbonate added and the whole allowed to remain several weeks asubstance is obtained which crystallises in long broad silky needles,melting at 70-71" is readily soluble in the ordinary solvents wit46 ABSTRACTS OF CHEMICAL PAPERS.the exception of water and has neither acid nor basic properties ; itscomposition indicates it to be ethyZ cyanoacetoacetate,CHS.C(CN) CH*COOEt.Acetamidine reacts readily with ethyl acet oacetate yielding di-nl.ethyZhycZroz~~?/1.imidine CMeqN C(oal>CH ; this forms lustrousneedles melts at 192" is readily soluble in water and alcohol sparinglyin ether and cold benzene.EtJi yZn7p,thyZhy~rox~pyrimI'dine CiHloN,O,obtained from propionamidine and ethyl acetoacetate forms ,slender,white needles melting at 160" and readily solnble in water andalcohol. The hydrochloride C,HloN20,HCi crystalliees in thickprisms melts at 240-2413' with decomposition is very readilysoIubIe in water and somewhat less so in alcohol.The platino-chloride forms thick yellow prisms melting a t 236" with decom-position.Succinimidine rezcts with ethyl acetoacetate wihh elimination ofonly one molecule of water and production of a compound,N -CMeC4HJT,HZ*C4H,O2.A description is given of some more derivatives of phenylmethyl-liydroxypyrimidine (Zoc. cit.). When a solution of silver nitrate isadded to a hot aqueous or alcoholis solution of the pyrimidine aclear solution is obtained from which ammonia throws down a white,granular precipitate of the silver salt ; i t is extremely soluble in excessof ammonia and in nitric acid. On adding bromine to a solution ofphenylmethylhydroxgp.yrimidine in chloroform four atoms of thehalogen are taken up with formation of the compound CllH10N20Br4,which crjstallises in yellow lustrous needles melting a t 245' withdecomposition.It dissolves slowly with decomposition when boiledwith alcohol and on cooling colourless transparent needles of thecomposition C1,H,N2Br separate melting a t 260". Phenylmethyl-hydroxypyrirnidine is not acted on by nascent hydrogen but maybe reduced by distillation with zinc-dust the pheny Znzethy Zpyri-midine CI,HI,Nz obtained melts a t 74-78' and yields a platino-chloride melting at 190" with decomposition. Chromic acid andalkaline potassium peymanganate have little action on the hydroxj-compound whilst acid permanganate oxidises i t readily with produc-tion of bcnzamide.Attempts to reduceg~henylmethy7c7~Zoropyi.imidiize CI1H9N2Cl (Abstr.,1855 159) by the action of sodium amalgam on its alcoholic solu-tion yielded phemylmethy k e t h o x ~ ~ y r i m i d i i z e CIIH9N2*OEt which how-ever is more readily obtained by boiling the chloropyrimidine withsodium nlcoholate.It forms thick colourless transparent prisms,melting a t 30-31° boils a t 300-301" is insoluble in water andihlkalis readily soluble in alcohol ether and acids. The hydro-chloride C,H,N20Et,HC1 + 2H,O crystnllises in slender white verysoluble needles and when dried melts a t 148-149" ; it breaks up atabout 150" into phenylmethylhydroxypyrimidine and ethyl chloride.The plutinochloride (C,H,N20Et)2,HzPtC16 melts a t 197" with decom-position. The hydriodide Cl,H9N20Et,HI( + &HzO 3) forms yelloORGANIC CHEJIISTRY. 47prisms or long needles very sparingly soluble in cold moderatelysolnble in hot water ; i t meIts a t 143.5".Phenylm ethy~~lyrin2idinean~~lide F,H,N,*NHPh is obtained on heat-ing the chloropyrimidine with a,niline.The hydrochloride formssmall slender needles which blacken a t 236" and melt with decompo-sition a t 240". The free base melts a t 150-153" and its nitrate at85-87". A. K. If.Condensation of Acetoacetates with Bibasic Acids. By.R. FITTIG (Bei-. 18 2526-2527).-Ethereal acetoacetates condensereadily with bibasic acids with elimination of 2 mols. HzO. Withsuccinic acid and ethyl acetoacetate %I crystalline compound CloH1205,melting a t 75-5-76' is obtained. This is the monethyl salt of abibasic acid C,H805 ; the free acid is crystalline melts a t 199-200°,and loses carbonic anhydride a t a slightly higher temperature.Fromethyl acetoacetate and sodium pyrotartrate the monethyl salt of thehomologous acid C9H1005 which melts a t 194O is obtained. Theinvestigation of these acids is proceeding.Condensation of Aldehydes with Bibasic Acids. By R.F~TTIG (Ber. 18 2523-2525) .-By the condensation of succinic acidwith acetaldehyde propaldehyde isobutaldehyde valeraldehyde orcpnanthaldehyde a single lactonic acid .is formed in each case inaccordance with the equation XmCHO + COOH*CH,-CH,*COOH =< ~ ~ ~ ~ 2 > C H * C O O H ; with pyrotartaric acid on the other hand,A. J. G.two isomeric lactonic acids,< ~ ~ ~ ~ z > CMe-COOH and < &,:%t>CH-COOH,are obtained. Benzaldehyde and pyrotartaric acid give i n addition tothe acid described by Penfield a second isomeric acid melting a t123.5".These lactonic acids when heated lose carbonic anhydride,arid are converted mainly into monobasic acids the isomeric lactonesbeing obtained as bye-products. The constitution of these unsaturatedacids is still uncertain except in the case of the acid C6H1,02,derived from the lactonic acid prepared from propaldehyde andsuccinic acid which has been shown to be identical with hydrosorbicacid.Salicylaldehyde and succinic aldehyde yield a dicozcniarin,very similar in chemical behaviour to coumarin.succinic aldehyde yield two acids of the formubAnisaldehyde andMeO*CsH4*CR CH*CH,*COOH andMeO*CGH,*CH CH.C(COOH) CHC6H,*OMerespectively. No description is given of these su bstnnces.A.J. G45 ARSTRACTS OF CHEMICAL PA1 ERS.Tartronic Acids. By A. PrNNEn (Rer. 18 2852-2854).--Theauthor finds that no better jield of this acid is obtained by Baponi-fying trichlorolactic acid directly,with haryta water and he preferst o use the method previously given (Abstr. 1885 759). Experimentsin which other precipitants (in the place of barium chloride) wereemployed gave unsatisfactory results.In the preparat>im of ethyl tartronate only a part of the acid isconverted into normal ethyl salt some hydrogen ethyl-derivatirnbeing also probably formed. The normal salt boils .at 222-225" isreadily decomposed by water and is readily converted into the amideby the aktion of ammonia.The only secondary products produced in the preparation oftartronic acid which the author has been able to confirm are di-chloracetic acid and a small quantity of oxalic acid.Tartivnnmide OH*OH ( CON Ha)z forms six-sided sales melting at195-1 96" with decomposition.I t is sparingly soluble in cold water,moderately in hotr and sparingly in alcdhol.Malic Acids. By H. VAN'T HOFF jun. (Bey. 18,2713-2714; corn-yare Abstr. IF8.5 1202).-Inactive mdlic acid from monobromo-succinic acid prepared from fumaric acid and hydrobrsmic acid(identical with that examined by Anschutz &id. p. 1049) and aninactiue nialic acid obtained by the action of soda and water ontnaleic acid are shown by crystallographic measurements to beidentical with .Pasteur's acid.A.K. M.N. H. M.Decomposition of Malic Acid obtained from Fumaric Acid.By G. J. W. BEEMER (Rec. Tmv. Chim. 4 180-182).-It is usuallyst,ated that the inactive malic aoid obtained from fumaric.acid is adistinct modification and cannot be decomposed into the lavo- anddextro-acids. :This is however not the rase as by the fractionalcrystallisation of its cinchonine salt it malic acid is obtained whosehydrogen ammonium salt shows a specific rotary power identical withthat of the corresponding salt of the natural acid (Ber.,.13 352).Constitution of Isosaccharic Acid. By H. KTLIANI (Bey. 18,2514-2518).-In the author's last paper on this subject (Abstr.,1885 'i44) the position of m e of the hydroxyl-groups was still leftunsettled ; he now shows that the dihydroxypropenyltricarboxplicacid obtained by oxidising isosaccharic acid (Zoc. cit.) yields a dihy-droxj-glutaric acid not identical with the /%V-dihydroxy-acid ; thismust therefore be the a-y-acid,A.P.COOH*CH( OH).CH,*CH(OH) 'COOH.From this isosaccharic acid must have the constitutionCOOH*C(OH) (CH2*OH)*CH,*CH( OH) *COOH.a-l- DiAydmzyg)Iutaric acid is best obtained by heating dih ydroxy-propenyltricarboxylic acid for four hours at 120" I t crystallises incolourless prisms begins to soften at 106" with loss of water andonly fuses completely at a considerably higher temperature; it iORGANIC CHEMISTRY. 4 9nearly insoluble in ether readily soluble in alcohol and water. Thecalcium salt C5H606Ca -k 3H20 forms white nodular crystals sparinglgsoluble in water.S- -Dihy droxyg Zutaric acid COO H*CH,*CH( OH) *CH( OH) *C 00 H,is obtained by converting glut'aconic acid,COOH-CH,*CH CH-COOH,into dibromoglutaric acid by treatment with bromine and boiling theproduct in dilute solution for two hours and a half with calcium car-bonate.It crystallises in needles or six-sided plates melts a t 155-156' and is sparingly soluble in alcohol very readily sduble in water.It is further distinguished from the a-yacid by the ready solubilityof its calcium and cadmium salts. A. J. G.Oxidation of Benzene. By J. G. HOLDER (Arner. Chew,. J. 7,114-116).-When treated in the cold with manganese dioxide and sul-phuric acid benzene yields carbonic anhydride and a small quantityof benzoic acid ; neither formic nor phthalic acid could be detectld.By gradually adding sulphuric acid to benzene and lead dioxide i Lvigorous reaction occurs and carbonic anhydride and benzoic acidsi r e formed ; no succinic acid was observed.Potassium permanqanateacts very slowly ; lead dioxide and boiling dilute nitric acid yield onlyoxalic acid ; chromic acid yields only carbmic anhydride. H. B.Parachlorometanitrotoluene and its Reduction-products.By L. GATTERMANN and A. KAISER (Ber. 18 2599-2602).-Thiscompound was prepared from metanitroparatoluidine hydrochlorideby treatment wit8h cuprous chloride and sodium nitrite. It crystallisesin yellow needles melts a t 7" to a strongly refractive golden-yellowoil of sp.gr. 1.297 at 22" (water at 62" = l) and boils at 260-261'under 745 aim. pressure. I t seems to be identical with the a-nitro.compound obtained by Wroblewsky by the direct nitration of pam-chlorotol uene.Parnc hlorometanityot oZuid ine C,H,MeC l-NH2 obtained by reductionof the nitro-compound crystallises in thin colourless tables melts at,29-30" and has an odour similar to that of naphthylamine. Thehydrochloride crystallises in colourless needles the salphate in broar 1needles or plates ; the acetyl compound crystallises in colourlessneedles and melts a t 96'. A. J. G.Action of Phenyl Cyanate on Polyhydric Alcohols. By H.TESMER (Ber. 18 2606-2610 compare Abstr. 1885 774) .-Theauthor coutirrns the formula C6H90 (O*CO*NHPh) previously givenfor t,he quinovide of phenylcarbaniic acid.Quercyl penta~heriylcnrba.nznte C6H7( O*CO.NHPh) is prepared byheating quercite and phenyl cyanate in sealed tubes at 165" for twohours; it is an amorphous white mass melts somewhere betwetn120-140" and is soluble in the ordinary solvents except light petro-leum. When heated with aqneous baryta a t 1-50" it is decomposedinto aniline quercite and carbonic anhydride.SucchttryL pher~yZc~~bimate C6H,O,(0.CO*NHPh> + CONPh pre-VOL.L 50 ABSTRACTS OF CHEMICAL PAPERS.pared in a similar manner from saccharin crystallises in silky inter-Iitced needles melts at 230-240J with decomposition. It is sparinglysoluble in benzene and alcohol soluble in ether readily soluble inaniline; aqueous baryta at 160-170" converts it in aniline andbarium carbonate and saccharate.Metasaccharyl pliemylcarbamate C6H,02( O.CO*NHPh) + CONPh isobtained as an amorphous white powder which softens a t 205" meltsabout 210" and is soluble in most solvents. With aqueous baryta ityields aniline and barium carbonate and metasaccharate.IsosacchnryZ plienylcarbamate C6H,02(0*CO-NHPh) + COKPh,also forms an amorph(lus white powder softens at 180" and melts at,181" ; with aqueous baryta it is decomposed in the same manner asthe preceding compounds.Quercetyl phenylcarbama,te C2&06(0*CO*NHPh) prepared by heat-ing quercetin and phenyl cyanate at 160° is a pale yellow amorphousmass.It melts a t 'LOO-205" and is insoluble in most solvents.Aqueous baryta at 270" decomposes it into quercetin aniline andbarium carbonate.Pl a v y u r p r y 1 p heny lcarbamate C J&03 ( 0 *C ONHP h ) 2 is preparedby heating flavopurpnrin and phenyl cyanate at 165" ; it crystallises inyellowish microscopic plates insoluble in most solvents ; boilinganiline dissolves it with formation of flavopurpurin and diphenyl-carbamide ; alkalis resolve it into flavopurpurin aniline and carbonicanhydride.A. J. G.Para- and Meta-phenylene Cyanate. By L. GATTEHMANN andE. WRAMPELMEYER (Ber. 18 2604-2606).-ParaphenyZene cyanate,C6H4(N CO) is prepared by the actlion of carbonyl chloride onparaphenylenediamine ; it crystallises in white needles melts a t 91",boils a t 231" under 745 mm. pressure. It shows a close resemblancein reactions and properties to pbenyl cyanate giving paraphenylene-dicarbamide wit'h ammonia diphenylphenylenedicnrbamide wi tli ani-line &c.When heated with absolute alcohol it yields prrraphenylene-urethane C6H,(NH*COOEt)2 which crystallises in colourleso prisms,and melts at 193". Paraphenylenecarbamide is also formed in thepreparation of paraphenylene cyanate.Metaphenylene cyanate is prepared in similar manner to and closelyresembles the para-compound.Resorcinol-derivatives. By G. ERRERA (Gurzetta 15 261-274).-Trinitrodi~benzo~~lresorcino7 ?J02.CsH,(0.C0.C6H,*N0,)2 obtained bythe action of nitric acid (sp. gr 1.4) on dibenzoylresorcinol is a,yellow amoiaphous substance melting at 123- 124" insoluble in water,sparingly soluble in alcohol readily in benzene and chloroform.It isnot decomposed by hydrochloric acid but is saponified completelyby alcoholic potash into nitroresorcinol together with iso-dinitro-resorcinol and metlanitrobenzoic acid or the latter and benzoic acid,according to the conditions of the experiment. The nitroresorcinoland metanitrobenzoic acid can be separated by treatment with aceticchloride o r by the different solubility of the copper salts or by theetherification of the acid.A. J. GORGANIC CHEMISTRY. 51Trinitrodibenzoylresorcinol is reduced by tin and hydrochloric acidto amidoresorcinol and amidobeneoic acid.Mononitrodibenzoylresorcinot N02*C6H3(OEh)2 prepared either b ythe action of zinc-dust on a mixture of nitrosoresorcinol (1 mol.)with benzoic chloride (2 mols.) or by the nitration of dibenzoylresor-cinol by a mixture of nitric and slslphuric acias crystallises in acicularneedles melting a t 110" ; on hydrolysis it yields mononitroresorcinoland benzoic acid and on reduction benzoic acid and amidoresor-cinol .Mononitromonobenzoy I r e s o r c ~ ~ o Z N02*C6E3( OH) GBz obtained byheating a mixture of nitiwresorcinol and benzoic chloride in equi-molecular proportions crystallises in pale-yellow needles.Mononitrodiacetylrcorcino~ NOz*C6H3(OAe)2 from acetic chlorideand nitroresorcinol forms long lamellar colourless crystals melting a t90-91" ; it is converted by bromine into Weselsky's dibromonitro-resorcino1.V. H. V.Fluoresceins from Maleic Acid. By R. BUECKHARDT (Ber. 18,2864-2870) .-This is a continuation of the work published L-yLunge and Burckbardt (Abstr.1884 1340).CH ' 'IX is formen Dinzethy I m a l e ~ ~ u o r e s c e i i z 0 <C6H3(0Me) > C <o-co > C,H3( OMe)when a solution of rnalei'nfluoresce'in'in mkthyl alcohol is boiled witlialcoholic potash and methyl iodide and crystallises in red needles.Unsuccessfiil att.empts were made to obtain a bromine-derivativecorresponding with eosin but no definite product could be obt,ained.Male'influormceh reacts with acetic chloride yielding a diacetyl-derivu-t h e C16HL006A~2 crystallising in yellowish-white needles me1 ting at157" ; it is sparingly soluble in alcohol readily in glacial acetic acid,and insoluble in water chloroform cai*bon bisulphide and benzene.CH'CH a-NuphthoZma1e~f2uoresceinn < co'o> CfC,oH,*OH) obtained onheating maleic anhydride (1 mol.) with a-naphthol (2 mols.) and zincchloride a t 160° forms a violet powder which yields a red solutionwith alcohol the addition of ammonia producing an intense green-redfluorescence ; t,he solution changes on exposure to the air becomingfirst violet and then dirty brown.The compound is also soluble inether glacial acetic acid chloroform ethyl acetate and methyl alcohol,but is insoluble in benzene and carbon bisnlphide. It melts a t 118-120". A second compound Cl4H,O4 is formed simultaneously withthe last substance by the union of maleic anhydride (1 mol.) witha-naphthol (1 mol.). I t crystallises in small hygroscopic needlesmelting a t go" dissolves in the ordinary solvents with the exceptionof benzene toluene and carbon bisulphide ; also in hydrochloric acid,water and ammonia.It forms a lead salt of the compositioti@-Naphthol yielded no fluorescent product with maleic anhydride,the statement previously made (Zoc. cit.) referring to the employmentof fuiuaric acid. The product of the latter reaction forms a yellowsolution witli alcoh:)I which exhibits an intense moss-green fluor-escence on the addition of ammoilia.C?,Hl,Pb04.e 52 ABSTRACTS OF CHENICAL PAPERS.The reactions of several other phenols with maleic anhydride harealso been tested qualitatively.C hloro- and Ltromo-derivatives of Phloroglucinol. By K.HAZURA and R. Bmxm" (Monatsh. Chem. 6,702-707).-Heleabrorno-1) hloroglucinol dibrornide C.16Br3(O13r)3,Br2 is obtained together withphlorobromine when a solution of 10 grams of phloroglucinol in1 litre of water (at 40") is treated with 96 grams of bromine added24 grams a t a time.It dissolves very readily in chloroform fromwhich it arptallises in small yellowish-white needles melting a t 118".Sulphurous acid converts it into tribromophloroglucinol melting a t151". When heated a t 156" it gives off a part of its bromine.Hexahyd.F.otrichloroy~loroy lucinol C6H9cl& 4- 3H20 is prepared fromthe above compound by the action of tin and hydrochloric acid ; itforms long white crystals which melt a t 125O. At 100" it loses itswater of cry stallisa tion.TrichlorophlorogZuc~no7~ C6CI,H30s + 3H20 is prepared by the actionof chlorine on a solution of phloroglucinol in glacial acetic acid.Itsoftens when heated a t 120" amd melts at 129". At 100" it loses3 mols. of water. N. H. M.A. K. M.Thymolphosphoric Acids. By G. DISCALZO (Gazxetta 15 278-282).-Monothy~nolpl~osphonyZ chloride POC12*O*C6H,MePr preparedby heating a mixture of phosphorus oxychloride and thymol in equi-molecular proportions is a colourless mobile liquid boilin5 with slightdecomposition a t 280-285". When heated with water it is convertedinto the corresponding acid PO(OH),*O*C6H3MePr a thick oily liquid,sparingly soluble in wa%er soluble in alkalis decomposed completelyon distillntion into thymol and metaphosphoric acid. I t s barium saltcrystallises in prismatic laminae.DithymoZphosphonyZ chloride POCl (OC8H3MePr) prepared from amixture of thymol ( 2 mols.) with phosphorus oxychloride (1 mol.) is acolourless fluorescent liquid boiling at 330-340" under a pressure of320 mm.It is decomposed by water forming ditkymoZphosphoric acid,PO( OH)(O*C6H3MePr)2. This substance is insoluble in water ; itsbarium salt crystallises with 5Hz0 in delicate colourless needles.V. H. V.Nitration of Parabromaniline. By H. HAGER (Bey. 18 2578).-When parabromaniline is nitrated the bromine-atom is displacedand picramide (trinitraniline) formed.Action of Isbutyric Acid on Aniline. By F. L. BARDWELL (Amer.Chem. J. 7,116-118).-Aniline and isobutyric acid do not react witheach other until zinc chloride is added when isobutyranilide isformed ; the yield is increased by heating the mixture.It crystal-lises in colourless prisms and melts at 102.5". By the action ofbromine-vapour on the aqueous solution a yellow precipitate is formed,which when treated in alcoholic solution with charcoal yields colour-less needles of parabromisob?ctyrnnilide C6H4Br*NHCaH,0 ; itJ melts a t128" and when heated wit11 aqueous hydrochloric acid yields para-A. J. GORQANIC CHEMlSTHY. 53bromaniline ; treated with nitric and sulphuric acids it yields para-bromorthonit'raniline. H. B.Metadinitroazoxybenzene and Orthazoxytoluene. By H.KLINGER and H. PITSCHKE (Bsr. 18 2551-2556) .-Metadinitroazozy-benzene N0,.C6H4.N2(~.C6HI*N0 is obtained by treating metadinitro-benzene with a small quantity of sodium methoxide dissolved inmethyl alcohol.It crystallises in long straw-yellow needles melts a t141-142" is sparingly soluble in alcohol somewhat more soluble inether and carbon bisulphide moderately soluble in benzene and toluene.Metndinitrohydroxyazobenxene N02*C6H,*N2*C6H3(OH) *No2 is ob-tained by heating a solution of the azoxy-compound in sulphuric acidat 140" ; it forms a yellowish-brown indistinctly crystalline mass andmelts a t 172-173". It dissolves in dilute alkalis with yellowish-redcolour. The silver salt C,2H,NaOa*OAg is obtained as a red crystallineprecipitate.Orthazoxytoluene C6H,Me.N20*C6H4Me is prepared by the action ofsodium mcthoxide on orthonitrotoluene ; it cry stallises in yellow,monosymmetric tables or needles a b = 044158 1 ; @ = 68" 37' ;observed faces OP mPm o3P; melts at 59-60" and explodeswhen more strongly heated.When distilled with iron it yields orth-azotoluene together with a little orthotoluidine. When heated withsulphuric acid it undergoes a peculiar decomposition much orthazo-toluene being formed (44-48 per cent.) together with amorphoussubstances. A. J. G.Methylene-Blue Group. By A. BERNTHSEN (Annalen 230 i3-21 1) .-A considerable portion of this research has already appearedin this Journal (Abstr. 1883 916; 1884 595 1156; 1885 259).L euco t hionine or &amid ot hiod ip hen y 1 amine,NH<c6H3(NH2)>S [NI-I NH NH S = 4 1 4 61,LHs(NH2)is formed by the action of tin and hydrochloric acid on a-dinitro-diphenylamine sulphoxide Under similar treatment /%dinitro-diphenylamine sulphoxide NH<C6H'(No2) >SO yields Zeuco-isotl~io-nirze c6H4<~~>c6H,(NH2)~.On oxidation with ferric chloride,isothionine NH/~6H2(NK2)>S is produced. I& is a dark crystal-line powder sparingly soluble in water and freely soluble in alcohol,yielding violet-red solutions. It dissolves sparingly in warm benzene,forming an orange-coloured liquid. The hydrochloride C,H,N3S,2HCl,is freely soluble in water and alcohol. The aqueous soluhion is violet-red and dyes silk amethyst. The addit,ion of strong hydrochloricacid does not turn the solution blue as is the case with thionine. Thesalt dissolves in strong sulphuric acid with violet coloration.The composition of methylene-blue was ascertained from theanalysis of the hydriodide C,H,N,SI and the hydrochloride,C6H3(N02)'N0c6H4 54 ABST LlACTS OF CHEMICAL PAPERS.C,H,N,SCl+ 3H,O.The aqueous solution of the free base (tetra-methylthionine hydroxide) is obtained by treating a dilute solution oftJhe hydriodide lwith freshly precipitated silver oxide. On evaporat-ing the solrmbiion in a vacuum over sulphuric acid a t the ordinary tem-perature the Tree base remains as a dark amorphous mass. It dis-solves freely in alcohol and in water. The preparation and propertiesof leucomethylene-blue (formerly called methylene-white) have beenalready described (Absts. 1883 916). Pentamethylleucothionine-dimethiodide C,H,N,S,ZMeI is formed by the action of methyliodide arid methyl alcoliol on leucomethylene blue a t 110".The com-pound is soluble in hot water but insoluble in ether. It is decom-posed by moist oxide of silver yielding the ammonium base,CsH3(NMe3*OH)JZ-<C,H3(NMe,*OH)>S'On evaporating the alkaline liquid the base remains its a brittle,amorphous mass soluble in alcohol and in water. It is decomposedby heat yielding methjl alcohol and pentamethylleucothionine. Theconsthtion of leucomethylene-blue or tetramethylparadiamidothio-dipheylamine is proved to beby the fact thad it yields on methylation the same pentamethylleuco-thioninedimethylammonium iodide which is obtained from leuco-thionine. The free base of methylene-blue is represented by theformula HO*NMe/ ICsHi---- S'N*CsH3 (NMe)Nethylene-red is obtained as a bye-product in the preparation ofmethylene-blue.It is contained in the mother-liquor from which theniethylene-blue has been precipitated. The pure compound isdeposited from alcohol in glistening green prisms soluble in water.The aqueous and alcoholic solutions exhibit a purple colour whichdisappears on the addition of an alkali. The coloiir does not re-appear on acidification. A blue colour is produced by oxidation.Reducing agents also destroy the purple colour and in this case sul-phuretted hydrogen is liberated. The hydrochloride of methylene-red has the composition CIsHI,N4S4,2HC1. On the addition of am-monia to methylene-red a yellow-coloured base is precipitated. Itis soluble in alcohol and in ether. I t is precipitated from the alcoholicsolution by water.When methylene-blue is treated with a dilute solution of an alkali,it mixture of methylene-violet methylene-azure leucomethylene-blue,and other leuco-products is formed.Methylene-violet is best ob-tained in the pure state by decomposing methylene hydriodide withsilver oxide and boiling the aqueous solution of the base for severalhours. The solution deposits crystals of pure methylene-violet andthe mother-liquor contains methylene-azure. The precipitate ofsilver iodide is mixed with a considerable qnantity of leuco-bases.>Metky lene-violet orr3osited from alcoholORGANIC CHEMISTRY.\CGHS- sdimet h y It hionol ine O<r?.C,tr,(NMe,) /> isin long needles soluble i n chloroform55de-andSparingly soluble in hot water.The solutions have a red or violet-red colour and are fluorescent. The hydrochloride C14HI,N2S0,HC1,crystallises in long needles of a dark green colour. It is insoluble incold dilute hydrochloric acid. The aqueous solution dyes wool orsilk violet. The iodide and chromate are very slightly soluble in hotwater; in other respects they resemble the corresponding salts ofmethylene- blue. Leucorn ethylene-violet is deposited from alcohol inwhite plates or scales. The solution in acids is stable but the solu-tion in alkalis absorbs oxygen with great avidity and depositsmethylene-violet. The hydrochloride i H crystalline. I n order toobtain methylene-azure in a state of purity the mother-liquor fromwhich the methylene-violet has been deposited is treated with an alka-line solution of stannous chloride.The liquid is mixed with half itsvolume of alcohol and left for some time in a closed vessel. Theleuco-azure which is deposited as a crystalline mass is washed dissolvedin dilute hydrochloric acid and oxidised by ferric chloride. On theaddition of common salt rnethylene-azure is precipitated. It is dis-solved in water reprecipitated and converted into the hydriodide.This salt is more soluble in water than methylene-blue hydriodide,which it closely resembles. The hydrochloride is also very solublein water. The solution dyes silk blue. The hydrochloride dissolvesin strong hydrochloric acid with a blue coloration and in strongsulphuric acid with a green colour.It is decomposed by boiling witha strong solution of potassium hydroxide with formation of dimethyl-amine.The preparation of oxythiodiphenylimide and hydroxythiodip henyl-amine has been already described (Abstr. 1885 260). The constitutionof these compounds may be represented by the formulm-0/76H3*S > and C,H4<kg> C,H,*OH.'N*C6H4Silk immersed in an alkaline solution of the latter compound is dyedcrushed strawberry.S,treating thiodiphenylamine with sulphuric acid diuted with one-fifth itsweight of water at 160" for 24 hours. The product of the reactionis poured into water mixed with excess of sodium hydroxide andfiltered. On the addition of hydrochloric acid t o the hot filtrate,thionol hydrochloride is deposited in glistening green crystals.The free base is insoluble in cold water but dissolves freelyin acids.It is deposited from glacial acetic acid in plates.The alcoholic solu-tion is of a purple colour and the solution in strong sulphuric acid isblue. The sulphate 2ClaH,NS02,H2S04 forms green needles. Thebarium salt C1zH7NSO3Ba crystallises in plates exhibiting a gree56 ABSTRACTS OF CHEBlICAL PAPJIRS.lustre. Silk immersed in a solution of thionol in potassium car-bonate acquires a violet colour which turns red on exposure to tlieair. Thionol is formed in small quantities by the continued action ofalkalis on methyletie-blue ; it is also a product of the action of alkalis,or of strong sulphuric acid on thionine.C6H3(0H)>S is formed by treating an am- Leucothionol NH<It is deposited from itsOn treatment with') is formed by adding ferric chlorideto amidophenol which has been saturated with snlphuretted hy-drogen.It is also produced by the prolonged boiling of thionine inwater NCI2H6S(NH2)NH + H,O = NC12H6S(NH,)0 + NH3.Thionoline dissolves in hot alcohol forming a purple solution ; theC6H3(NH2)>S is soluble in acids and in alkalis. leuco-compound NH<The nitrate sulphate and hydrochloride of thionoline crystallise inneedles. Strong sulphuric acid dissolves thionoline forming a blueC6H4 OH)nioniacal solution of thionol with zinc-dust.ethereal solution as a crystalline colourless mass.acetic anhydride it yields a triacetyl derivative.'N-C6H3(NH2)CsH -Thionoline Q/ IC6H3( OH)-solution. Methylene-violet is dimethylthioDoline.w. c. w.Benzyl Compounds. By 0. BORGMANN (Chern. Centr. 1885,456-458). -This communication contains an account of severalmetabenzyl compounds prepared from metanitrobenzyl alcohol Homeof which have already been described (Abstr. 1883 1121).Pyiniary metanitrobenzy lanaine N02*C,H1*CH2*NH is formed bytreating metaiiitrobenzyl chloride with alcoholic ammonia ; it is ayellowisli oil absorbs carbonic anhydride from the air forming a solidsalt and yields a sparingly soluble oxalate and platinochloride. Thesecondary amine NH(N02*C6H4*CH2) formed with the primary crystal-lises in yellowish rhombic leaflets melting at 87" ; its hydrochlorideand platinochloride are both sparingly soluble salts.When reducedbp tin and hydrochloric acid it forms an anlido-compound the hydro-chloride of which crystallises from concentrated hydrochloric acid inlong reddish needles having the composition N(NH2*C6H4*CH2)2,SHC1.The base crystallises in prisms melting at 86-87'.Z'ertiary metanitrobenzylanzine N (NO,*C,H,*CH,) is formed bydigesting met anitrobenzyl chloride with aqueous ammonia ; it crystal-lises in monoclinic prisms melts at 162O is soluble in glacial acetic acidand benzene but only sparingly in alcohol is insoluble in ether anddoes not unite with hydrochloric acid. When reduced with tin andhydrochloric acid it yields the tertiary amido-compound whichcrystallises in colourless needles melts at 142O and forms a sparinglysoluble platinochloride.Amidobenzyl chloride is very unstable and is formed by thereduction of the niti-o-compound with tin and hydrochloric acid.Metar~itrodibenzylnzethylamine NMe( NO2*C6H4-CH2) is formed byacting on nitrobenzyl chloride with an aqueous solution of methyl-amine ; i t melts at 81".By the action of dimethylamine metnnifroORGASIC CHEJlIST RT. 577/enz~ZdinzethyZamine N0,*C6H,*CH,*NMe is formed ; it is a yellowishoil and forms a well-defined platinochloride.MetanitrobenzyZphenyZamine Ilu'0,*CsH4.CH,*NHPh is formed by theaction of aniline on nitrobenzyl chloride; it crystallises in long,orange-red needles melting a t 86" ; its hydrochloride forms whiteleaflets is an unstable compound and does not form a platiuochloride.When reduced by tin and hydrochloric acid this base forins nzetamido-benzyZ~l~enllZai,ziize NH,.C,H',*CH,*NHPh melting a t 67".Metanitrobenzaldehyde when treated wit'h concentrated sodiumhydroxide yields meta-azoxybenzoic acid ON,( C6H,*C0 OH),.P.P. B.Ethylortholuidines. By R. L. CHASE (Amer. Chem. J. 7 118-120).-These compounds have been prepared by Reinhardt and Staedel(Abstr. 1883 578). Ethylortholuidine formed from ethyl iodide andorthotoluidine boils a t 204-206" ; its salts are exceedingly solublein water ; the chloride platinochloride iodide acetyl- and nitroso-compounds are mentioned.Diethylorthotohidine was prepared from the monethjl-derivativeand ethyl iodide it boils between 203-208" ; the hydriodide crystal-lises well from water it contains 1 mol.H,O. H. B.Consecutive Orthoxylidine and Orthoxylenol. By A. TOHL( Ber. 18,2561-2562).-Mo~tonitrodibromortho-xylene C6H~fe,Br,.N02[Me Br NO = 1 2 3 4 51 is obtained together with thedinitro-compound by adding 4 5 dibromortho-xylene to cold fumingnitric acid. It crystallises in colourless needles and melts a t 141".Dinitrodibromortho-xy Zene C6Me2Br2(N0,) crys tallises in small needles,and melts at about 250".Uibronaort/io-xyZidine C6HMe2Br,.NH2 is prepared from the mono-nitro-derivative by heating it with iron and acetic acid. It crystallisesin colourless needles melts at lOS" distils with steam is readilysoluble in alcohol ether and glacial acetic acid and does not yieldsalts with acids. The bromine is to a great extent removed by iongtreatment with tin and hydrochloric acid but complete replacementcan only be effected by the action of sodium amalgam on a warmalcoholic solution.Ortho-xy Zidine C6H,Me2*NH2 [Me Me NH = 1 2 31 so obtained,is a colourless oil which turns brown on long exposure to air doesnot solidify at - 15" and boils a t 2.21-222".The hydrochloride,C6H3Me2*NH2,HC1 + H20 crystallises in large lustrous tables andsublimes readily; the nitrate and sulpbate are also described.AcetzyZide C6H3Me,-NHAc cry stallises in long slender needles andriielts at 131".Ortho-xyZemZ C6H3Me2.0H [Me OH = 1 2 31 prepared in theusual way from the xylidine crystallises in very long slender needles,melts a t 75" boils at 218O and yields a blue coloration with ferricchloride in aqueous solution.The tribroino-deiivative C,Me,Br,-OH,crystallises in slender needles and melts at 184". A. J. G.Paraxylidine. By E. NOLTING 0. WITT and S. FOREL (Ber. 18,2664-2668).-Crude xylidine was found to contain about 25 per cent58 ABSTRACTS OF CEEitlICAL PAPERS.of pnraxylidine boiling a t 215" under 739 mm. pressure. Sp. gr. = 0.980(water at 15" = 1). Nitraceto-xylide melting a t 166" is obtained bynitrating the acetyl-derivative ; it yields a nitro-zylidine which meltsa t 142" and crystallises from benzene in brownish-yellow lustrouscrystals readily soluble in alcohol and ether. When nitro-xylidine isreduced xylenediainine is formed ; this cryshllises from benzene insmall white needles melting at 146.5-147" which when oxidised,yield paraxyloquinone.Ethyl nitrite acts on nitro-xylidine with formation of the ethyl saltof nitioparaxylenol ; it is a yellow substance melting at 85"."N. H. M.The Six Isomeric Xylidines. By E. NOLYING and S. FOREL(Ber. 18 2668-2681).-A description of these compounds and somederivatives is given. When consecutive ortho-xylidine is oxidised ityields ortho-xyloquinone C6H2Mez02 [Me2 0 2 = 1 2 3 61. Thiscompound sublimes in yellow needles which melt a t 55" ; it is ratherreadily soluble in alcohol ether &c. It is reduced by sulphurousacid to the quinol a white substance melting a t 221". Ortlzo-xylenol[Me2 OH - 1 2 31 is obtained from the diazo-derivative of thebase; it crystnlliscs from water in white needles melts at 73" andsublimes uiichanged.The aqueous solution acquires a pale-violetcolour when treated with ferric chloride.171etaxylylquinone C6H,Me,0 [Me2 0 = 1 3 2 51 is preparedby oxidising metaxylidine ; it forms splendid yellow needles whichmelt a t 73". The corresponding qwin,oZ forms white needles meltinga t 149". When symmetrical metaxylidine is nitrated a nitro-derivative[Me2 NH2 NO = 1 3 5 41 melting at 54" is formed; this,when reduced yields metaxyleneorthodiamine melting a t 77".When the hydrochlorides of the xylidines are heated with methylalcohol a t 300-320" amidotrimethylbenzenes are formed. Consecutiveortho-xylidine yields a liquid amidotrimeth2/lbenzene boiling a t 240' ;the acety2-derivaticve meits at 1130". Symmetrical metaxylidine yieldeda crystalline isocumidine which melts a t 67-68" and boils a t 245"(uncorr.) ; the acetyl-derivative melts a t 163-164" ; the cumenol meltsat 98-99".N. H. M.Arnidoazo-derivatives of the Three Xylenes. By E. NOLTINGand S. FOREL (Bey. 18 2681-2686). - Amidoazometaaylene,C6H3.Me2-"L*C6H2Me2.NH:! [Me Me N Me NH Me = 4 2 1 2 3 41,is prepared by the action of 69 grams of a 20-25 per cent. solutionof sodium nitrite on a well-cooled mixture of 121 grams ineta-xy lidine and 157 grams metaxylidine hydrochloride. The product isextracted with ether and the resiciue left on evaporating the ether iswarmed with 120 grams of metaxylidine and 10-15 grams of meta-xylidine hydrochloride at about 50". It is then boiled with dilutehydrochloric acid and the sparingly soluble hydrochloride thusobtained is washed with water alcohol aod ether.The base isliberated by means of ammonia and crystnllised from alcohol orbenzene. It forms orange-yellow plates which melt at 78" is almostinsoluble in water readily soluble in hot alcohol and in benzene. The7aydrocl~Zoride forms a bright Fellow crystalline powder ; its alcoholifiolution is peen. When reduced it yields a diamine melting atAmido-azometnxylene [Me Me N2 :Me Me NH = 6 2 1 3 5 41,crystallises in yellow plates melting at 77.5" ; it dissolves readily inalcohol and in benzene. The alcoholic solution of the hydrochlorideis red.Amido-azometazyZene [N Me Ne NH = 1 2 6 41 cryst'al-lises from alcohol in yellow plates melting at 95".The solution ofthe hydrochloride in phenol is violet.Amido-axortho-zy Zene [Me Me N2 Me Me NH = 3 2 1 2 3 41,forms yellow plates and melts at 110.5".Amido-axortho-xylene [Me Me N Me Me NH = 6 3 1 4 5 21,forms yellow plates melting at 179" ; it is sparingly soluble in alcohol.The solution of the hydrochloride in phenol is green.Amido-azopuraxylene [Me Me N Me Me NH = 5 2 1 3 6 41,crystallises from alcohol in red plates melting at 150". The hydro-chloride is red ; its solution in phenol is violet-red. When the base isreduced a diamine melting a t 146.5-147" is formed.Experiments made by the authors show that the nmidoazoxylenedescribed by Nietzki (Abstr. 1880 552) is a mixed amidoaso-metapara-xy7ene [Me Me K Me Me NH2 = 4 2 1 3 6 41 ; it meltsat 110-111".N. H. M.77-78'.Azo-derivatives of Carvacrol. By G. MAZZARA ( Gazzetta 15,305 -315) .-In continuation of experiments on the azo-derivatives ofthymol and carvacrol (Abstr. 1885 904 and 1132) the authordescribes the preparation of an azo-compound by heating 1 mol. ofbidiazotriphenylmethane with 2 mols. carvacrol dissolved in potash.There is thus formed a purplish-red amorphous substance carvacrol-bidiazotriphenylmet hane to which is ascribed the composition[OH*CsB2MePh~N,~C,H,*CHPh*CsH4*N,C,H2MePh]20. It melts at130" and is soluble in ether and chloroform ; its potassium-derivativeis a red precipitate ; when heated with bidiazobenzene it is convertedinto a red crystalline substance the composition of which has not yetbeen definitely established.By 33.HAGER ( B e r . 18,2573-2577).-Diphenylurethane is best obtained by heating diphenyl-amine with ethyl ch lorocarbonate.Di-orthonitrophenylurethaize (N02G,H,)2N.COOEt is obtainedtogether with the para-compound by adding diphenylurethane to nitricacid of sp. gr. 1.44 and pouring the solution into much water ; the mix-ture is separated by treatment with a little hot benzene from which thepara-compound crystallises on cooling. The ortho-compound forms abrown syrupy. mass readily soluble in alcohol and seems to be misciblein all proportions with benzene. Potash convert,s it into orthonitrodi-phenylamine. When heated alone it yields a mixture of products fromwhich a colonrless liquid boiling at 141-143" and of the formulaC,HIoO was isolated.This is insoluble in water readily soluble inether and unites with bromine to form a yellow liquid yielding ondistillation an oil which gives a nitro-derivative melting a t 181-182".V. H. V.Derivatives of Diphenylurethane60 ABSTRACTS OF CHENICAL PAPERS.Di-paralLitrophe~ylui.ethane crystallises in yellow needles melts a t133-134" is readily soluble in benzene sparingly in alcohol andyields paranitrodiphenylamine when boiled with potash.Di-pnmmidophenylurethane ( NH,*C6H4),N*COOEt + H,O is pre-pared by reducing the nitro-compound with tin and hydrochloricacid ; it crystallises in violet needles and melts at 101" with decom-position. When treated with benzoic chloride it yields a benzoyZ-derivative (NHBZ.C~H~)~N*COOE~ crystallising in flesh-colouredneedles and melting at 210" ; this is not identical with the substanceto which the author had previously and erroneously assigned thisformula (Abstr.1885 150).Hexabronzod~phenyluretl~ane (C,H,Br,),N*COOEt is obtained by theaction of bromine on solutions of dipheriylurethane ; it crystallism inlong greenish-brown needles and melts a t 184". When treated withnitric acid it yields a nitro-compound crystalliving in yellowish- bro wnneedles and melting a t about 245" with decomposition,New Synthesis of Vanillin. By M. ULRICH (Ber. 18 2571-2573).-1n 1881 Meister Lucius and Briining patented a methodfor obtaining three isomeric mononitrometamethoxybenzaldehydes.Tiemann (Abstr.1883 189) and Schnell (Ber. 17 1381) have statedthat this method yields not mononitro- but two diiiitro-derivatives ;t'he author however finds that when metamethoxybenzaldehyde isnitrated according to the directions of the patent the three rnono-nitro-derivatives are formed.The main product of the reaction is a-nitro-metametl~oaybenznlde-hyde ; it crystallises in thick yellow prisms and melts a t 107". /?-nitro-rnetanzethoeybenzaldehyde is formed in small quantity ; it crystallises inneedles and melts at 82-83" As both these acids give the indigoreaction they must be the two ortho-nitro-compounds [ COH Me NO,= 1 3 2 and I 3 61 ; there is no evidence as to which is which.The third ni tro-compound crystallises in cauliflower-like masses inter-spersed with prisms melts at 97" and does not give the indigoreaction; it has the constitution [COH Me NO = 1 3 51.Ptrranitrometl~oxybenzalde7~yde [COH Me NO2 = 1 3 41 is ob-tained as follows methyl metamethoxycinnamate is nitrated a t 0"with nitric acid of sp.gr. 1.46 and the paranitro-methyl saltseparated by crystadlisation from the product when it is obtainedin flat white needles melting a t 163". The free pnranitro-acidirepared f r o m the methyl salt is then oxidised with aqueous potassiumpermanganate by which means it is converted into paranitromethoxy-benzaldehyde. This crystallises in hair-like needles me1 ts a t 62",and is soluble iu water alcohol and benzene. When treated withacetone and soda it yields a colourless solution from which after atime colourless needles melting at 84" separate.By replacing thenitro-group by hpdroxyl vaniZlin is obtained.Paramidacetophenone Ortharnidometacetyltoluene andsome of their Derivatives. By J. KLINGEL (Ber. 18 2687-2706).-Paramidacetopheiione is best prepared by boiling a mixtureof 2 parts aniline 3 parts zinc chloride and 5 parts acetic anhydrideA. J. G.A. J. GORGASIC CHEMISTRY. 61for five hours; the product is boiled with hydrochloric acid andtreated with sufficient soda solution to precipitate and redissolvethe zinc hydroxide. A brown oil then appears which is sepa-rated and distilled with steam to expel aniline. The residueis extracted several times with boiling water and the unitedextracts evaporated down; on cooling the amide separates. Theyield is 50-60 per cent.of the weight of aniline used. Several saltsare described. Acetylamidacetophenone COMe*C6H4 NHAc formssmall white needles which melt a t 166-167" ; it is readily soluhle inhot water and in alcohol. Hydroxyacetophenone COMe.C6H4*OH= 2 4 is prepared by acting with sodium nitrite on a well-cooledsolution of the base in dilute hydrochloric acid and then slowlyheating the product with water until it boils. The phenol isextracted with ether. It forms white needles melting a t 107" readilysoluble in hot water alcohol and ether. When the aqueous solutionis treated with ferric chloride it acquires a dark-brown colour.IocloacetoJihenone C,&I*COMe is prepared from the amide by meansof the diazo-chloride; it crystallises in white plates which have anagreeable odour and melt a t 79".It dissolves readily in alcohol andether. When oxidised it yields pariodobenzoic acid. Dimethylamid-acetophenone COMe*CsHc*NMez is obtained by the action of methyliodide on amidacetophenone and forms yellowish plates melting at58-59". It is readily soluble in alcohol ether and hot water.Acetopkenonea,zonaplLthoZ COMe*CGH,N NGloH6*OH is preparedby the action of the sodium compound of /%naphthol on the diazo-chloride obtained from amidacetophenone. It forms groups of slender,red needles with a slightly green metallic lustre insoluble in water,sparingly soluble i n ether readily in alcohol. Dilnte alkali dissolvesit readily with formation of a dark-red solution.Orthar?zidonzefacetotoluene [COMe Me NH = 5 1 21 is pre-pared from toluidine in a manner similar to amidacetophenone asdescribed above.I n appearance it is very similar to amidacetoplienone ;it melts a t 102" and boils at 280-284". It dissolves readily in hotwater alcohol ether and dilute alkali and is almost insoluble in lightpetroleum and benzene. Several salts are described ; they resemblethe salts of amidacetophenone. The acety 1-derivative melts at 143-144" ; it is readily soluble in warm water and in alcohol.Acetocresol COMe*C7H,- OH is prepared similarly to hydroxy-acetophenone ; it crystallises in reddish prisms melting a t 104",readily soluble in alcohol ether and hot water.When treated withferric chloride it gives a yellowish-brown coloration.Diwiethy Zamido-acetotohene COMe*C7H6*N&2 crystallises in groupsof flat prisms melting a t 95'; it is readily soluble in alcohol ether,and hot water almost insoluble in light petroleum.Acety Ziodotoluene COMe*C7H61 is prepared by the action ofhydriodic acid on the corresponding diazo-chloride ; it forms ayellowish crystalliue mass melting at 3Y" very readily soluble inalcohol and ether sparingly soluble in light petroleum benzene andhot water. When oxidised it yields iodophthnlic acid. This crystal-lises in slender white needles which melt a t 203-204" is verysparingly soliible in boiling water and dissolves readily in glacia62 ABSTRACTS OF CHEIIICAL PAPERS.acetic acid alcohol ether and warm chloroform.The barium saltforms slender white needles very sparingly soluble in boiling water ;the calcium copper and silver salts were also prepared. Wheniodophtbalic acid is treated with concentrated potash solution it ispartially converted into parahydroxybenzoic acid ; nascent hydrogenconverts it into benzoic acid. N. H. M.Mixed Axo-compounds. By E. BAMBERGER and A. CALMAN(Rer. 18 2563-2567 ; compare Abstr. 1885 157).-A mixture ofphenylazoacetophenone and ethyl phenylazobenzoylacetate is o btaineclby mixing aqueous solutions of diazobenzene chloride ethyl benzoyl-acefate and soda.Phenylazoacetophenone COPh*CH2*Nz*Ph is obtained by heatingthe mixtu1.e with alcoholic potash and precipitating with water ; i tcrystallises in slender golden-yellow needles melts a t 128.5" and isreadily soluble in hot alcohol or acetic acid.Pheny Zazobenzo y 1 acetic acid COP h* CH (N,Ph) *C 0 OH obtainedfrom the potash salt prepared as above crystal!ises in long citron-jellow needles melts a t 141" is soluble in ether alcohol and aceticacid and yields phenylazoacetophenone when boiled for some timewith dilute soda.Orthonitrophenylazoacetophenone ?J02*C6H4*N2*CH2*COPh crystal-lising in lustrous golden-yellow needles melting at 140-141" andortlhonitropheny Zazobenz oy Zacetic acid NOz* C,H4*N2*CH( C 0 Ph) *C 0 OH,crystallising in sulphur-yellow needles and melting a t 177" areformed in similar manner from orthonitrodiazobenzene chloride.When heated for some time a t the melting point the acid losescarbonic anhydride and is converted into the ketone.By the actionof hydroxylamine hydrochloride on the ammonium salt the compoundNO*C6H4-Na*CH( CPh NOH)*COOH is formed ; this crystallises inorange-yellow needles and melts at 142".M~tartitrotoly2i3arccxobelzxo2Jlacetic acid,NO2*C6H3Me*N2* CH ( C OPh) C 0 OH,prepared from metanitroparatoluidine crystallises in silky golden-yellow needles melts at 194" and is very sparingly soluble in coldalcohol or acetic acid.NOz-C6H3Me*Nz*CH2*COPh,crystallises in lustrous citron-yellow needles melts at 168" andwith hydroxylamine yields the ketozime,NOz*C,H3Me*Nz~CHz.CPh NOH ;The corresponding acetophenone,this crystallises in reddish-yellow needles and melts at 174".A.J. 0.Crystallographic Examination of some Organic Com-pounds. By J. ZINGEL (Zeit. Kyyst. Min. 10 41$-420).-Thecrystalline systems and axial ratios are as follows :-Metatrimeth-amidobenzoic acid chloride ~&fe3C10C6H4*COOH ; monosymmetric ;u b c = 1.9388 1 0,8757 ; /3 = 88" 49'. Metadimethamido-benzoic acid NMe2*C6H4*COOH; asymmetric; a c = 1 1.9403ORGANIC CHEMISTRY. 63Dinitroparatoluidine (m. p. 69-71'). Rhombic; a b c =0-9965 1 0.5184. 2 4-Dinit,rophenyl metanitrobenzoate asym-metric; a b c = 0.7137 1 1.7671. A. J. G.Phenylacetic Acid. By R. MEYER (Chem. Centr. 1885 516-51 8) .-Orthoparadinitrophenylacctic acid is prepared by addingphenylacetic acid to conceritrated nitric acid and pouring the mixtureinto concentrated sulphuric acid.The acid crystallises in colourlessneedles melting a t 160" (Abstr. 1884 178). Ethyl dinitrophenylacetatPcrystallises in colourless needles melting a t 35"; it is more stablethan the acid.Paramido-orthonitrophenylncefic acid is formed by reducing thedinitro-compound with ammonium sulphide ; it crystallises in long,reddish-yellow needles which are soluble in alkalis and also in acids ;it melts a t 184-186". Attempts made to convert this compoundinto ortlionitrophenylacetic acid by the diazo-reaction have beenwithout sumess. Ethyl amidonitr~henylacefate crystallises in long,yellow needles melting a t 100"; this compound when treated withan alcoholic solution of ethyl nitrite and hydrochloric acid yields itcompound having the composition C,H,N205 which crystallises inneedles melting at 163".When heated with hydrochloric acid insealed tubes a t 150-160° this compound is resolved into ethy-lchloride carbonic anhydride ammonia and orthonitrobenzoic acid ;this owes its production to the formation of nitrosomethy lorthonitro-7)enrene; it would therefore appear that the compound is ethylorthonitrophenyl&trosoacefate NOz*C6H,*CH(NO)*COoEt [2 11.Nitrosonaethylorthonitropal.adiazobenzeiLe chloride,NO,* C6H3' (NiCL) C HZNO,is obtained by treating amidonitrophenylacetic acid with hydrochloricacid and amyl or ethyl nitrite. When heated with hydrobromic acidit yields the bromide NO2*C7H5BrNO which melts a t 151-152".The chloride boiled with alcohol yields nifrosornethylorthonltrobenzene,NO,*C,H,*CH,*NO (1 21 which when heated in sealed tubes withhydrochloric acid a t 150-160" is resolved into ammonia and ortho-nitrobenzoic acid.Nitrosomethylnit'mbenzene when oxidiscd by potassium dichromateor permanganate or ferric sulphate yields orthonitrobenxaldehyde,melting a t 43.5-44.5'.Reduced by ammonium sulphide it formsnitrosomethylorthailzidobenzerzs NH2*C6H1*CH2*N0 which crystallisesin needles melting at 132-133".The methyl-derivative of nitrosomethylnitrobenzene,N02*C6 B,*CHMe*NO,melts a t 58"; the ethyl compound is an oil. Methylnitrosoamido-benzene TU'H;C6H4*CHMe*N0 is an oil volatile in steam ; its hydro-chloride crystallises in needles melting at 109".Orthonitrobenzo.nitrile N02*C6H4*CN [ 1 21 is formed by heatingni trosomethylnitrobenzene with acetic anhydride and sodium acetate.The nitrosomethylamidobenzene yields under like conditions a,diacetyl compound NHAc*CsH,*CHAc-NO melting a t 127*5-128*5"64 ABSTRACTS OF CHEMICAL PAPERS.Dinitrophenylacetic acid reduced by tin and hydrochloric acid,yields anlido-oxindole NH2*CsH3< ;%>GO from which by thediazo-reaction the paradiaxonitroso-oxindol e chloride,has been prepared ; it crystallises in yellow needles and when boiledwith alcohol yields nitroso-oxindole.Derivatives of Durene.By J. U. NEF ( B e r . 18 2801-2807).-Dur?ylic acid is best obtained by heating durene with dilute nitricacid (1 vol. acid of sp. gr. 1.4 to 3 vols. water) for three to fourhours in a reflux apparatus ; the product is allowed to cool filtered,and the residue extracted with sodium carbonate solution the un-altered durene being again treated with dilute acid.On addinghydrochloric acid to the alkaline solution durylic acid is precipitatedtogether with some nitro-compounds which are removed by treatmentwith zinc and glacial acetic acid and distillation in a current ofsteam. The durylic acid obtained melts at 149" and agrees in allproperties with the acid described by Janiiasch ( Z e i f s . f. Chenz. 6,449) whilst the yield amounts to 15-20 grams from 40 gramsdurene. Dinitrodwry lic acid (see also Gissmann Abstr. 1883 334) isbest prepared by dissolving finely divided durylic acid in pure con-centrated sulphuric acid cooling with ice and gradually adding asolution of nitre in pure sulphuric acid with constant stirring.Afterfour or five hours the product is poured upon ice the nitro-acidfiltered off washed and purified by means of its calcium salt. Itsproperties have been described by Gissrriann (loc. cit.). Whendinitrodurylic acid is dissolved in a dilute solution of potas-sium carbonate and potassium permanganate solution graduallyadded dinitropyrornellitic acid is produced. It has a strongly acidodour is readily soluble even in cold water extremely so in ether andcrystallises from both solvents in very long silky colourless needles ;soluble also in alcohol and glacial acetic acid but insoluble in chloro-form benzene and light petroleum. When i t is heated in a capillarytube it loses water (100-160") and becomes yellow and it decom-poses a t 203" with evolution of gas.The silver salt C6(NO2),(COOAg),forms a golden-yellow amorphous precipitate. Attempts to reducedinitropyromellitic acid to the diamido-acid proved unsuccessful.Ethy I d initroyyrom el Zit at e c6 (NO,) (CO OE t ) 1 obtained by heatingthe silver salt with ethyl iodide and ether for one to two hours at loo" forms magnificent colourless needles readily soluble in hot andsparingly in cold alcohol readily in benzene chloroform glacialacetic acid acetone and ethyl acetate more sparingly i n ether. Itmelts a t 130". When its hot solution in glacial acetic acid is treatedwith zinc-dust ethyl axopyi'ondlitate C&,( COOEt) is produced.This has a deep cinnabar-red colour is insoluble in water and diluteacids ; it yields a colourless salt with concentrated hydrochloric aciddissolves readily in glacial acetic acid alcohol and ether and meltsa t 134".It sublimes without decomposition when heated. WhenP. P. BORGAXIC CHEMISTRY. G5diamidodurene (from dinitrodurene) is treated with ferric chloiaide agreen coloration is produced and at once chanqes to yellow owing tothe formation of duroquinone C602Me4. This crystallises from lightpetroleum in long yellow needles melting a t 111". It sublimesrzadily emitting but a faint quinone odour dissolves very readily inether chloroform benzene alcohol and acetone. Zinc-dust andsods solution sulphurous acid and sodium amalgam reduce it but itis reproduced on agitation with air.It is insoluble in alkalis andnearly so in hot water. Potassium permariganate and sodiumcarbonate solution and also chromic acid and glacial acetic acid,decompose it.From the great stability of duroquinone the author hopes to succeedi n preparing the quinone of pyromellitic acid which would have thesame composition as croconic acid.Dibromoparahydroxybenzoic Acid. By A. ALESSI (G'uszetta,15 242-247).-In order to determine the constitution of the di-bromoparnliydroxybenzoic acid obtained by Balbiano from the distil-lation of sodium dibronianisate with calcium oxide (Abstr. 1834,1 172) dibromanisic acid was converted by excess of concentratedbydriodic acid into a dibromohydroxybenzoic acid. This was foundto be identical with Bidbiano's acid.As in the acid from dibrom-nnisic acid the substituted groupings must be in the relative positionOMe Br B r C0,H = 1 2 6 the composition of Ba1l)iano's Reidhas the same constitution. V. H. V.A. K. M.Salts of Anisic Acid. By G. BORRELLA (Gazzettcx 15 304-305).-The copper manganese nickel cobalt zinc and cadmium salts ofanisic acid crystallise with H,O ; there can also be obtained basiccopper OMe*CGH4*COOCuOH and chromium,salts. In analysing the metallic salts of the organic acids it is con-Yenient to precipitate the heavy metals in the form of oxalates t,healcohol necessary for the complete precipitation serving to dissolvethe liberated acid. V. H. V.Inner Condensations. By A. ROSSING (Cher12.Cerjtr. 188.5 598-395).-~0rtho-~Zdehydo~henoxyncet~c acid COH*C6H1*OCH,*cOOH,produced by the action of monochloracetic acid on salicylaldehyde,crystallises in large yellow leaflets melting at 132". Its salts with thealkali metals and metals of the alkaline earths are soluble in water itscopper and silver salts sparingly soluble in water. I t reduces ammo-niacal solutions of silver salts and forms a double compound withliydrogen sodium sulphite. It unitesdirectly with aniline forming the compoundThis compound unites with acids forming well-defined salts froniwhich the base can be obtained by careful addition of ammonia 01-caustic alkalis or better still by decomposition with an alcoholic6 olution of sod ium eth ox ide.Its ethyl salt melts a t 114".NH Ph* CH (OH)*CGH4* 0.C H C 0 0 H.VOL.L. I66 ABSTRACTS OF CHENICAL PAPERS.Aldehydophenoxgacetic acid unites directly with phenylhydrazine,forming the conipound N,HPh CH*C,H,*O.CH,*COOH which meltsa t 105". By oxidising agents aldehydophenoxyacetic acid is con-verted into salicy Zoxy acetic acid CO OH*C6H~~O~@H,*CO@H whichcrystallises in white needles melting a t 186-187'. Ethyl salicyl-oxyacetate is a light yellow oil which decomposes when heated andis converted into the corresponding diamide,NH,*CO*C,H,.O*CH,*CONH ;when heated in sealed tubes with ammonia; this crystallises inyellow needles melting a t 158".When aldehydo-pheiioxyacetic acid is heated with acetic oxide ant1sodium acetate it yields orthocumaroayacetic acid,CO OH* CH CH*C,H,* O-CH,.C 0 0 H,wliich crystallises from water in needles melting a t 190". This corn-poiind like cinnamic acid combines with 'bromine to form a di-bromide melting a t 219-220" which when heated with alcoholicpotash yields orthopropiolpheelzoxyacetic acid,COOH*C i C*CsH4*O*CH,*COOH ;this forms small yellow crystals melting at 208".When aldehydo-phenoxyacetic acid is heated with five parts of aceticoxide and 4-5 parts of sodium acetate for three hours it yields anoil boiling a t 170° which is identical with cnmarone C6H,<- >CH(Abstr. 1888 474). If orthocumaroxyacetic acid is heated withphosphoric acid it loses water and yields the anhydrideCHCH CHGOC6H4<-0. C H,. C 0 ->O,which melts & 176"; when boiled with water it is easily recon-verted into the acid.' This anhydride unites directly with bromine,forming the dibromide GH,< O.CH,.CO,O >CO crystallising in CHBrGHBryellow needles melting a t 213".When the cornpound of aldehydo-phenoxyacetic acid and phenFl-hFdrazine is heated witrh sulphuric acid a bluish-green amorphoussubstance is produced which dissolves in alcohol forming a bluish-green solution and in alkalis forming cherry-red solutions. Thiscornpound is precipitated from its alcoholic solutions by ether as alustroils black powder having the composition CgH7NO3 and meltinga t 108". This same oompound can be prepared by heating amixture of monochloracetic. acid with ortho-oxy benzylidene phenyl-hydrazine in sealed tubes a t 1'00".Orthoxybenzylidene phenylhydra-zine when heated with acetic oxide yields a diacetic derivativeAcO*C,H.,CH N2AcPh which crystallises in needles or prismsmelting a t 133". On dry distillation this compound yields acetanilidexud a reddish-yellow substance cont)aining nitrogen. The diacetyl-derivative forins a dibromide which is easily decomposed acd whenboiled with alcohol yields ucetozydibromobeizxyZiden,ep~enylli~d~az~n(~ORCANTC CHEJIIS'I'RY. 6 7AcO*C,H,Br,*CH N,HPh melting a t 188" ; this is decomposed byboiling with caustic soda ; from the alkaline solution hydrochloricacid precipitates the compound H0.C,H2Br2.CH N?HPh meltinga t 148". P. P. B.Constitution of the Phthalic Acids. By E. NGr,mG (Bey. 18,2687).-The constitution of the phthalic acids has long been known,hut the proofs are of a complex nature.The author now advances ahimple proof. The three xylenes when oxidised readily yield thethree phthalic acids. Three isomeric nitroxylenes xylidines andxylenols are derived from metaxylene two from orthoxylene oneonly from paraxylene. Therefore tl ie carboxyl-groups must occupythe 1 3 positions in isophthalic acid the 1 2 positions in phthslicacid and the 1 4 positions in terephthalic acid. A. J . G.Nitration of Phenylparaconic Acid. Bp H. ERDIIASN (Be). 18,2741-2743) .-Paranitrophenylparaconic acid is prepared by theniteration of phenylparaconic acid. It forms very bright yellow plateswhich melt a t 155". It is insoluble in carbon bisulphicle anddissolves sparingly in chloroform benzene and ether readily inalcohol glacial acetic acid hot xylene &c.When heated at 200",evolution of carbonic anhydride takes place. Potassium permanga-riate converts i t into paranitrobenzoio acid.I n the preparation of this acid the ortho-acid is also formed(compare Abstr. 1885 1224). N. H. A!€.Derivatives of Durene. By 0. JACOBSEN and E. SCHNAPAUFF(Bey. 18 2841-2844) .-When powdered durene is gradually addedto about 2+ times its weight of cooled sulphuric monochloride,tlurenesulphonic chloride is obtained as the chief product togetherwith durylsulphone and alittle durenesulphonic chloride. On treatingthe product with ice and water the sulphuric hydrochloric andsulphonic acids are separated from the sulphonic chloridc a n d t,hesulphone and on adding an excess of soda to the acid filtrate thvsodium sulphonate separates out.The sulphonic chloride may boseparated from the sulphone by crystallisation from alcohol andfinally from ether. Durenesui$honic acid C,H,*XO,H dissolvesreadily in water b u t only sparingly in moderately dilute sulphuricacid ; the sodium potassium barium and copper salts are described.DurenesuZphonic chloritle CloH13*S02C1 crystallises from warm ethcrin brittle prisnis of vitreous lustre melts a t 99" dissolves readilyin warm sparingly in ice-cold alcohol and very readily in ether.D1iren~suZ~honnmide CIOH13.S02NH2 crystallises from alcohol in longprisms melting at 155" ; it is very readily solnble in hot sparingly incold alcohol and in ether and is almost insoluble in cold water ; it isdecomposed by concentrated hydrochloric acid a t 190".D;)Lr!jZsuZphone (CioH,3)2S0 is readily s9luble in alcohol ether,benzene and light petroleum whilst boiling water dissolv2.s butttwes.It can bcdistilled under diminished pressure without decomposition but a t theIt crptallises in long prisms melting a t 37".f G8 ABSTRAOTS OF CHEMICAL PAPERS.atmospheric pressure it yields sulphurous acid and durene. Whenheated with concentrated hydrochloric acid at 200" it splits up intodurene and sulphuric acid.When sodium durcnesulphonate is fused with potash eitherdurenol or hydroxydurjlic acid is produced accordingly to thetemperature and time of heating. DzirenoZ CIOHl3-OH crystallisesfrom warm alcohol in large flat prisms melts a t 117" and boils a t249-250".Bwmodurenol C10H,2Br*OH crystallises from hot dilutealcohol in long vitreous prisms melting a t 118". It is readilysoluble in alcohol and ether insoluble in water. Nitrodwend,Cl0Hl2(NO2)*OH separates from hot dilute alcohol as a bright yellowinass. It melts a t 130" is almost insoluble in water very readilysoluble in dcohol and also in alkalis and alkaline cai-bonates withdark yellow coloration.HydyoxpZurylic acid C,HMe,( OH)*COOH is almost insoluble incold sparingly soluble in hot water but very readily in alcohol.Its constitution is [COOH OH Me = 1 2 3 4 G I . It crystal-lises i n small needles melts at 148" and may be sublimed withoutdecomposition.Its salts give a didy brown precipitate with ferricchloride whilst a solution of the free acid in diIute alcohol gives atransient blue coloration. The calcium salt ( CI,H,0,),Ca + 2H,O,is described. When the acid is heated at 190-200" with hydro-chloric acid carbonic anhydride and pseudocumenol (melting a t85-88"> are produced.Phenylacridine. By A. CLAW and C. NICOLAYSEN (Ber. 18,2706-2712) .-Potassium permanganate acts on phenylncridine inpresence of free sulphuric acid with formation of a mixture ofparaphenylquinolinecarboxylic acids from which a di- and a mono-cwboxylic acid were separated. Yurap7ter~ylquinolilredicarbosylic acid,I'h*CgNH,(COOH) forms lustrous needles melting at 200-215".The barium salt (with 4 mols. H,O) crystallises in slender colourlessneedles. Barium parnphenylpuinolinecarbo~y late ( CIbH10N02)2Ba,6H20,crjstallises in needles.Yhenylamidobenzoic <acid NHPh*C6H4*COOH is obtained by theoxidation of phenylacridine methyl chloride with potassium per-ruanganate.Itl forms small colourless needles rnelting at 2.22"(uncorr.) alniost insoluble in water readily soluble in ether chloro-form &c. The sodium saZt (with 4 mols. H,O) fornis coloarless1 lates readily soluble in water; the barium (with 5 mols. H20) andsilver salts are also described.An acid having all the properties of that just described is obtainedby heating metamidobenzoic acid with aniline hydrochloride a t 220".Phenylacridine hydrochloride crystallises from pure water in redoctahedra (with 5 mols.€LO) ; the long yellow anhydrous needlesdescribed by Bernthsen are obtained from a solution containing free11s drocli loric acid.a-Naphthylaminephthale'in. By A. VANNI ( Gazzetta 15 346-34i).-On heating phtlialic anh.ydride and a-niiplithjlamine in equalmolecular pioportiuns at a temperature of lW" 5t fused mass isA. K. M.N. H. MORGANIC CHEJIISTRY.formed ; thin is heated with boiling alcohol andas it cools deposits a-naphthylaminephthalejin,f i 9the filtered so!utionin the form of colourless transparent prismatic tables. It is insolublein water sparingly soluble in alcohol and ether and melts at 166". Itis decomposed by concentrated sulphuric acid forming a pale yellowsii bstance which dissolves in ammonia with an orange-red coloration ;with concentrated potash it forms an oil which ultimately solidifies ;the compound formed gives a violet coloration with water.V.H. V.Relations of @- to p-Hydrojuglone. By F. MSLIUS ( J h . 18,2.567-2571).-The acetyl- or benzoyl-derivatives prepared froina- and from P-hydrqjuglone are identical and seem to be theP-derivatives inasmuch as they yield @-hydrojuglone when treatedwith alkalis or sulphuric acid. The compoiind previously describedas triacetyl-a-h.vdro jnglone (Abst'r. 1885 170) Ehould therefore beternled t?.iac~tllZ-$-h?//Zrf!jtigtone. It cry stall ises in colourless prisms,and melts at 129-130". Triberizoyl-3- h?ydr.oj!l'uy/one CIOH50JBzI,crystallises in colourless needles melts a t 228-229" and like t h eacetyl-derivative can be sublimed unchanged.a-Hpdrojuglone when heated above its melting point in an atmo-sphere of hydrogen is conrerted into P-hydrojuglone which distils ;on the other hand when the p-compound is subjected to prolongedboiling with dilute hydrochloric acid it is converted into a-hydro-jnglone.A. J. G.(Monatsh. Cheiii. 6 754-~59).-dntlzragt~llolamida,Action of Ammonia on Anthragallol. By S. V. GEORGIEVICSi s prepared by boiling anthragallol with excess of ammonia f i i ~20-30 minutes; the fine blue solution so obtained is evaporatrctdown aiid the solid substance crystallised from alcohol or glaciitlacetic acid. It forms greenish-black needles or R reddish-brown,crystalline powder sparingly soluble in hot water alcohol anttbenzene &c.Alkalis a,nd srilphuric acid dissolve it uncbanged,with formation of blue and intense red solutions respectively.Nitrous acid acts on it with formation of ayellom substance which meltsat 190-200" ; it does not contain nitrogen and is probably dihydroxy-anthragallol [(OH) = 2 31.Two nitro-derivatives of anthragallol were obtained from gallic acidby the action of meta- and of para-nitrobenzoic acid.A~zthragallolsulpTonic acid is prepared by heating anthragallol with3-4 times its weight of sulphuric acid at 130-140". The aqueoussolution acquires a red colour when treated with the smallesttrace of alkali. The sodium aiid potassium salts have cnloiiringproperties. N. H. Id70 ABSTRACTS OF CHEJIICAL PAPERS.Terpenes and Ethereal Oils.By 0. WALLACH (111) (Annulen,230 225-2'12).-Yure borneol prepared by the action of sodium oncamphor melts a t 206-207" riot a t 198" as generally stated. Thiscomponnd behaves like a saturated secoridary alcohol but it hasthe property of uniting with bromine and hydrogen bromide &c. toform nnstable additive products. For example when bromine isadded to a solution of horneol in light petroleum a crystalline preci-pitate is deposited which consists chiefly of Oorneol bromide,CloHlsO*Br2 mixed with a small quantity of (C,oH,O),Hr,. Cineol,like borneol unites with bromine in two different proportions formingcompounds which have the same composition as the borneol bromides.When borneol bromide is covered with light petroleum and left forsome time in a closed vessel decornposition ensues resulting in theformation of borneol and borneol hydrobromide (C,oH,80)2,HBr.The same compound is obtained as a white crystalline powder by theaction of hydrogen bromide on a solution of borneol in light petroleum.It is dccornposed by water and alcxohol.The hydriodide (CloH,80)2,HI is tt white crystalline compound,which decomposes spontaneously .Rornyl chZoride Cl0HI7C1 is easily prepared by adding boriieol to amixture of phosphorus pentachloride and light petroleum. Theaction is finished in half an hour.The crude product is poured intowater and repeatedly washed. Bornyl chloride is not identical withpinene hydrochloride. It is readily converted into camphene byheating with aniline. Camphene is decomposed by dehydratingagents such as zinc chloride and strong sulphuric acid or by theaction of heat alone.In each case the decomposition products areliquid. Monobromocamphene is obtained as an oily liquid whenbromine is added to a solution of camphene in alcohol and ether.Camphelie is formed by the action of dehydrating agents on borneol,but the hydrocarbon cannot be isolated (except when potassiumpyrosulphate is the dehydrating agent) as it is decomposed by zincchloride or phosphoric anhydride or strong sulphuric acid.The so-called hydrocarbon " borneen," which Pelouze ( A n n a l e n 40,:327) Kachler (ibid. 164 78) and Oppenheim (this Journal 1874,891) obtained by the action of phosphoric anhydride on borneol is amixture of the decomposition products of camphene.The author confirms Tilden's statement (Trans. 1878,SO and %I.),that Kussian and Swedish oil of turpentine contain the same cou-stituents namely austpalene splvestrene and dipeutene.Thehydrocarbon obtained by decomposing sylvestrene chloride withauiline closely resembles sylvestrene but the identity of the bodies isnot proved. The hydrocarbons yield a chloridc melting at 7 2 O and aliquid bromide." !l'erpinol " described by Wiggers ( A n n a l e a 57 252) and byList (ibid. 67 367) does not exist.Terpine hydrate C10H2002 + H20 melts at 117". It is a saturatedcompound and is decomposed by boiling with acids or dehydratingagents yielding terpineol C,H,O and other products. When aTiiixture of I part of sulphuric acid anti 2 of water is used,terpiueol terpinene CJT and terpinulene are formecl. Wlicn verORGANIC CHEXISTHY.71tlilute sulphuric acid is used the chief product is terpinene. Dilutephosphoric acid and glacial acetic acid on the other hand yieldterpineol as the principal product. Terpine hydrate is almostcompletely converted into dipentene by prolonged treatment wit'lipotassium pyrosulphate.Terpineol CIOH1,*OH is a nonsaturated monatomic alcohol. It is athick liquid boiling a t 215" and is sparingly soluble in water. I tnnites with bromine to form an unstable bromide.Bipentene tetrabromide melting at 124" is formed by the action ofr7,n excess of bromine on terpineol. The hydroxyl in terpineol iseasily replaced by chlorine or iodine yielding for example thechloride CloHl,CI melting a t 50" and the iodide melting a8t 77".Terpineol unites with carbanil forming phenylterpinylurethane whichcrystallises in white needles melting a t 110".Boiling with diluteacids or treatment with dehydrating agents converts terpineol intoterpene or dipentene but if ferpiiieol is left at the ordinary tempera-ture in contact with dilute sulphuric or hydrochloric acid it uniteswith water forming terpine hydrate CloHzo02 + H20.Terpine has the same boiling point as dipentene but the twocBompounds are not identical as the former yields a liquid bromine-clerivative. Terpine is formed by the inversion of pinene witb:ilcoholic sulphuric acid.It boilsbetween 185; and 190" and yields an unstable tetrabromide crystal-lisiog in mouoclinic plates.The relation between camphene borneol and camphor is shown bytlie following formulE :-Terpinolen,e has not yet been obtained in a pure state.Cmiphenc.Borneo].Camphor.Borneol bears the same relation to camphene that terpineol does todipentene. w. c. w.Action of Picric Acid on Terebenthene. By - LEXTREIT (J.Pharna. [ 5 ] 11 211-213).-Terebentliene when heated with picricacid at 150" gives a limpid liquid which after further heating a t thesame temperature deposits crystals on cooling. When freed fromexcess of picric acid and a brown colouring matter i t forms thiu,friable transparent flakes which rapidly take a yellow tint whcnexposed to light. It is insoluble in water slightly soluble in coldalcohol readily in ether carbon bisulphide and boiling alcohol.When heated it first fuses aud then decomposes with a gentle defla-gration.It seems to be a compound of picric acid and camphene ofthe formula ClUHl6,C6H3( N02)30. It is more stable towards aqneou72 ABSTRACTS OW CHEXICXL PAPERS.alkalis than are the known picrates of hydrocarbons. Further withan alcoholic solution of potash a very explosive crystalline precipitateof a purplish-red colour is formed quite different from potassiumpicrate. The compound is rapidly decomposed by a boiling aqueoussolution of soda; a white sublimate is carried over with the steam,which is insoluble in water but soluble in almost all proportions incold alcohol and ether. Its odour resembles both that of camphor andof camphcne.It fuses at 179" camphor at 175" and camphene a t 45".Its rotative power is aD = - 36". Its composition is very nearly thesame as that of camphor.Natural Camphor Oils. By P. MACEWAN (Pharm. J. Trans. [ 3 ] 15,1045-1046) .-Borneo Formosa and Japanese oils are referred to.The Bornean oil sp. gr. about O W O consists chiefly of borneene witha small quantity of resinous matter but with no camphor (borneol) insolution. In contact witth copper it acquires a green colour in a dayor two. The Formosa camphor oil sp. gr. 0.943 is a saturatedoleaceous solution of camphor ; when rubbed on the hand there isat first a strong carnphoraceous odour which soon goes off and asassafras-like odour remains but the oil dries quickly on the skinand leaves no mark.Japanese camphor oil in crude form accordingto Oishi (Abstr. 1885 270) has sp. gr. 0.959 and contains camphor.The sample examined by the author evidently purified of sp. gr. 0.951,had a strong sassafras-like odour and contained no camphor. Scarcelyany of it distilled below 140" about 10-12 per cent. consisting of aliquid isomeride of camphor distilled between 180" and 185" nearlyone-half distilled over up to about 205" ; t,he residue has a sp. gr. of0519.5. Treated with nitric acid and then after a minute with water,the Japanese oil yields a clear crimson solution the Formosa oil a veryslightly green milky solution ; with hydrochloric acid they both yieldsalmon-coloured solutions. This oil is used in the United States toadulterate oil of wintergreen.Picric acid behaves similarly with thymol.J.T.D. A. L.Camphophenylhydrazine. By L. BALBIANO (Gazzattri 15 246-245).-As the formation of camphoroxime seems to indicate thepresence of the carbonyl-group in camphor (Abstr. 1883 728 ; 1884,SlO) although the evidence thus far is not sufficient to decidebetween the aldehjdic and ketonic groiips the author has studied thereaction between pheuylhydrazine hydrochloride and camphor in thepresence of sodium acetate. Jn this way camphopheuylhjdrazine,C,H,-N,HPh is produced. It is a yellowish oil distilling a t 235-245" under a pressure of 170 mm. soluble in dry ether and decom-posed by hydrogen chloride to form phenylhydrazine hydrochloride.Borneo camphor does not react with hytlroxlamine under the sameconditions in which camphor yields camphoroxime ; whilst by treat-ment with phenylhydrazine in the presence of diluents bromocamphoryields pl:enjlhydrazine hjdrobromide and resinous substances.V.H. V.Euonymin. By G. ROMM (Chem. Centr. 1885 442-445).-Thisglucoside is not to be confounded with the medical preparation of thesame name as the latter contains no poison and is employed as aP 6) ORGANIC CHEMISTRY. 4 * )aperient. The author prepares it by extracting the powdered rindsof Euyonrnus atropurpureus with $0 per cent. alcohol distilling andevaporating the extract diluting with water and filtering ; the filtrateis then precipitated by lead acetate again filtered and the clearliquor freed from lead by sulphuretted hydrogen.After neutralisa-tion with magnesium carbonate precipitation with tannic acid aridtreatment with zinc oxide euonymin is obtained in ciystals on em-yoration of its ethereal solution. The bark of Euon?ynzu.s europpiiscontains no euonymin.Constitution of Santonin. By S. CANNIZZARO (Ber. 18 2746-2751).-After reviewing the evidence a t presmt available as to theconst,itution of santonin the author suggest,s the formula-J. K. C.CH CH.CK*CHMe-COas agreeing fairly with its reactions.Derivatives of Santonin. By V. Vrr,r,;\vrcccma (Ber. 18 28.79-2864) .-Photosardonic acid C15H2205 is best obtain3d by exposing :Isolution of 10 grams santonin in a litre of acetic acid (sp. gr. 1-06>to the action of light for about a month ; the product is evaporated toa syrupy consistence in a vacuum the residue washed with water audthen treated with a warm solution of sodium cstrbonate.The undis-solved residue may be dissolved i n alcohol from which it crystallises inprisms melting a t 182-183" and of the composition CI7H2?O5 namely,1 mol. santonin + 1 mol. acetic acid. On adding hydrochloric acidto the sodium carbonate extract photosantonic acid separates and ispurified by repeated crystallisation from alcohol. Its properties agreewith those assigned to i t by Sektini (Abstr. 1877 471). It loses1 mol. H,O at loo" and melts a t 154-155". The composition of itssalts indicates that the water lost at 100" is not water of crystallisa-tion as assumed by Sestini but that undried photosantonic acid bearsthe same relation to the dried acid as santonin does to santonic acid.Barium and silver photosantonates C,5H,0,Ba and ClsH,oO Agz aredescribed.Photosantonin C I ~ H ? ~ O ~ is best prepayen by exposing a solution ofsantonin (20 grams) in alcohol (1 lit're) to the direct action of lightfor three months.The alcohol is distilled off in a vacuum and thethick residual oil treated with lukewarm sodium carbonate solut,ion toromove photosantonic acid. On treating the insoluble portion withether two isomeric photosantonins C17Hz10~ are obtained ; one modi-fication forms platy crystals melting at 154-255" and is dex5ro-rotatory ; [aID = + 76.77" for a solution containing 0.3825 gram in50 C.C. alcohol a t 13".The other modification which is the chiefproduct melts a t 68-6b0 and is identical with Sestini's photo-santonin. It is readily soluble in alcohol and ether and almostinsoluble in cold water; [ = - 121.6" for a solution containing1*0010 gram in 50 C.C. alcohol a t 14" and - 118.4" for 1.0980gram in 50 C.C. alcohol also at 14". The composition of photo-santonin shows that it is not the diethyl salt of photosantonic acid a74 ABSTRACTS OF CHEJCICAL PAPERS.Sestini assumed but the monethyl-derivative of dehydrated photo-santonic acid which is regarded as a lactonic acid thus:-Photo-santonic acid HO*C13H~g(COOH)z ; photosantonic acid dried a t 1 OO",CO0H*C,Hlg <:;> ; photosantonin COOEt*C,H,<$~>. Thelast compound may also be obtained from photosantonic acid alcohol,and sulphuric acid and by the action of ethyl iodide on the silver salt.When gaseous hydrogen chloride is passed into a solution of photo-santonic acid in absolute alcohol the diethyl-derivative of an acidcontaining the elements of a inolecule of water less than photo-santonic acid is obt'ained ; it is termed ethyl cle72.ydropkotosantonate,C,H,(COOEt) an! forms a colourless liquid which does not solidifya t - 10".A solution of 0.7306 gram in 25 C.C. alcohol has a dextro-rotatory power ah 20*4" [&ID = 3. 20.4". The free acid which isisomeric with dehydrated photosantonic acid melts at 132-133". Itis very readily soluble in alcohol and ether ; its dextrorotatory poweris [aID = + 31-9" for a solution containing 0.7114 gram in 50 C.C.alcohol.The barium salt C15HieOJ3a is very readily soluble.A. I(. M.Papain. By S. H. C. MARTIN (Pharm. J. Trans. [3] 15,129-130).-A glycerol extract of commercial papain retains the fermentativeact,ivity of the powder and contains a heminlbumose in quantity,together with a mere ,trace of globulin. When the latter is precipi-tated by magnesium sulphate and the hemialbumose by subsequentsaturation with sodium sulphate the solution is no longer active.The aqueous solution of the precipitated hemialbumose is however veryactive and when tested on coagulated egg-albumin produced peptones ;it is therefore evident that the ferment OE papaw-juice is associatedwihh the hemialbunwse but as yet bas not been separated from it.Papain acts on animal albumin in manner similar to pepsin but notso rapidly ; with milk i t behaves like pancreatic jnice tirst curdling it,the curdling being intensified by raising ths temperature (but notabove 62") and hindered by making the milk alkaline or by dilutingit to some extent or by boiling previous to adding cold water; thecurd is gradually dissolved with the production of peptones leucine,and tyrosine.A hemialburnose is formed as an intermediate productbetween the case'in and peptones.With regard to the action of papain on the proteids of papaw-juice i t converts the globulins into an albumose corresponding withVine's hemialbumose ; leucine and tyrosine being also formed but notisue peptones have been dekected. D.A. L.Pyrrylene Dimethyl Ketone. By G. CTAMTCTAM and P. SILBER(Gazzetta 15 248-250).-1n this paper it is shown that pyrrylenedimethyl ketone (dipseudacetopyrroline) is producible not only frompseudacetopyrroline and acetic anhydride as indicated formerly(Abstr. 1885 378) but also directly from pyrroline by nieans of thesame reaction. By an excess of fuming nitric acid it is convertedinto a mono-nitro-derivative C4NH,( NO,) Ac melting a t 149" mdpossessing acid properties. V. H. VORGAXIC C HEJLISTRT. 75Synthesis of Pyrroline-derivatives. By L. LEDERER and C.PAAL (Ber. 18 2591-8599).-1t has been already shown that pyrro-line derivatives are formed by the action of ammonia 011 acetophenone-acetone and on acetonylacetone (Abstr. 1885 516 1206) and ofammonia and primary amines on ethyl acetosuccinate (Knorr ibid.554,994) the reaction is now extended to ethyl acetophenoneacetaacetnte.Ethy lie methylpheny lp yrrolinecarhoaylate C4NH,MePh*C 0 OE t[Me COOEt P h = 2 3 51 is obtained by allowing a mixtare ofethyl acetophenoneacetate and aqueous ammonia to remain for24 hours; it crystallises in colourless tables or small needles andinel ts a t 120".C&NH:,MePh-COOH,prepared from the ethyl salt by saponification &c. crystallises in long,flat yellowish needles readily soluble in acetic acid benzene and hotalcohol. When heated it partially decomposes a t 175" and melts a t190"; it sublimes in small part but does not yield methylphenyl-pyrroline.Ethylic dimethy~henylpyrrolineonrboxylate C,NHMe,Ph*COOEt[Me Me COOEt Ph = 1 2 3 51 preysred in manner similarwith mbthylamine crystallises in colourless plates softens a t 90°,melts a t 112" and is readily soluble in alcohol ether and benzene.Met hy Zp h e q idly lpy wolinecarboay lic acid CJIg CAN HMePh- C 0 OHLC3H5 Me Ph COOH = 1 2 8.5j. The ethyt salt is preparedby heating ethyl acetophenoneacetoacetate wit,h allylamine and a littleabsolute alcohol in settled tubes a t 180" for an hour; it is a thick oil,and does not crjstallise. The free acid crystnllises in .short lustrousprisms is readily soluble in alcohol ether benzene and acetic acid,and melts at 158". B e t h y ip heiatllaZlyllpt/rroZine C,H,*C,NHMePh[I 2 51 is prepared by distilling the acid ; it crystallises in largeplates melts at 58" to a colourless oil with blue fluorescence boils at;277-278" and is soluble in all proportions in ether almhol benzene,light petroleum and acetic acid.i~~ethy1~henyIpyrrolinecnrboxylic acid,N e th y Idip hen y l p yrrolheca rbox y Z ic acid,C,NHNePh,*COOH i P h I Me COOK Ph = 1 2 3 51,crystallises in small needles melts at 226" and is readily soluble inacetic acid and benzene.The ethyl salt C4NHMePh,*COOEt is pre-pared hy boiling ethyl acetophelloneacetoacetate (1 part) with aniline(1.5 part) dissolved in acetic acid; it crystallises i n small prisms,melts a t loo" and is sparingly soluble in alwhol and acetic acid.L~~ethy7dipher~ylpyr~oline CBNH2MePh is prepared by heathg the freeacid a t above 226" ; it crystaliises in large ca~ourless tables melts a t81" i8 not very readily volatile with steam and is readily soluble inbenzene and light petroleum.iUet R y lphenyEos.thotolylp yrrolinecarbox y I ic acid,C6H1MaC4NHMePh*CO0 H,ciystnllises in small prisms and melts a t 199" ; it is readily soluble inthe udinarj- solvents except water.The ethyl salt is obtained by boil76 ABSTRACTS OF CHEMICAL PAPERS.ing aniline acetic acid and orthotoluidine as a thick oil that cannotbe crystallised. il/lethy123he?aylorthotolyl~~yr,.oline,C6H4Me*C4NH2MePh [l 2 51,is obtained by the dry distillation of the free acid ; it crystnllises inplates melts a t 44" to a pale yellow fluorescent oil boils a t 325-328",and is readily soluble in alcohol ether benzene and light petroleum.Methylphenylpuratoly lcarboxylic acid C6H4Me*C4NHMePh.COOH,resembles benzoic acid in appearance and melts at 227". The eth! Esalt Cz1HZ1147O2 crystnllises in prisms or tables and melts a t 11.5".Methy~~l~enyl23aratolyl~2/rrrtline C6E14Me*C4NH2MePh crystnllises inconcentric paups of slender needles or in tables melts at 91" boilsabove 550° and is readily soluble in light petroleum and benzene.1C~efhyl;when2/l-a-n~phthylpyrrolinrcnrboxylic acid,CloH7*C4NHMePh-COOH [ C J € Me COOH Ph = 1 2 3 51,is prepared by heating a-naphthylamine and ethyl acetophenoneacetatein sealed tubes at 13U0 and saponifying the uncrystallisable product.It crystallises in needles melts a t 244" and is readily soluble inalcohol benzene and acetic acid.Metky7phe97yI-a-naphthylpyrroliiap,CI0H7*CsNH2MePh crystallises in plates melts at 74" boils above360" and is very readily soluble in benzene light petroleum aBdalcohol.&Id h y Zp hen y I- @nap h thy lp y rrolin,e C,H7- CsN H,MeP h cry s t allises i nconcetitrically grouped needles and melts a t 52". The carLozyZic (wid,C ,H,.C,NH Ne Ph* C 00 H crystal lises in small white needles an( 1melis at 249". Its ethyl salt C24HzlN02 crystallises in lustrous plates,and melts at 115". A. J. G.Pyridine-derivatives. By H. WEIDEL and F. Bf,Au (itfOl70,f~h.Chern. 6,651-666) .-When 30 grams of dibroniopyridine are heatedfor 24 honrs at 160" with 80 C.C. of absolute alcohol and a slightexcess of potash diethoxy- and ethoxy-hydroxypyridine are formed.Diethoxypyridine C5NHI,( OEt) forms an almost colourless oil,which is heavier than water ; i t is readily soluble in alcohol and ether.It boils with decomposition at 243-246" under 749.9 mm.pressure.With mineral acids it yields crystalline salts which are very deli-quescent. The plntinoch Zoride forms lustrous yellow needles.DihydroxypyG%ze C5NHB(OH)P is obtained by hydrolysis of thediethy 1-derivative by hydriodic acid and amorphous phosphorus at1.20". It forms small yellowish-white crystals which become browna t 200" almost black a t 230° and melt with total decomposition a t237-239". It dissolves readily in hot water alcohol alkaline caT-bonates and in dilute acids. When a neutral solution of dihydroxy-pyridine is treated witlh ferric chloride it acquires a reddish-browncolour.The compound is probably identical with the dihydroxy-pyridine prepared by Geigy (Inaug. Diss. Munich 1885) from pyri-dinedisulphonic acid.Ethoxyhydroxypyridine EtO*C,NX,*OH forms colourless plates whichbecome yellowish when exposed to light; i t is sparingly soluble inwater readily in alcohol and in a mixture of alcohol and ether. ThORGANIC CLIEMISTRY. 77crystals are triclinic; a 2 c = 0.97'408 1.01795 1; =$jo 1' ; y = 88" 29'; @ = 91" 04'. It melts a t 127-128" (uncorr.),atid does not dist8il without decomposition. The nityate and pZatino-chloride are described. When fused with potash it yields dihydroxy-pyridine.Sodium ethoxide acts on dibromopyridine at 150" with formationof diet,hylpyridine together with a trace of the monethyl salt.Byt,he action of alcoholic potash on bromopyridine (the intermediateliroduct formed in the preparation of dibromopyridine) ethoxypridinewas obtained ; it forms a colourless liquid which boils below 200° andwhen reduced yields a hydroxypyridine identical with that alreadyobtained fmm /3-pyridinemonosulphonic aeid (compave A bstr. 1884,1050 and 1370). It is therefore a meta-derivative and the dibromo-comDound obtained from it probablg has both bromine-atoms in themeti-position from the fact &at it yields only one monethyl salt.N. H. M.Constitntion of Synthetical Hydropyridine-derivatives. ByA. HANTZSCH (Bw. 18 2x9-2586) .-The constitution of thesecompounds has never been definitely ascertained although it has beenassumed that both the hydrogen-atoms are in union with carbon- - -CH-CH atoms in the pyridine-ring thus giving the formula N<c-c>Cfor the nucleus of this group.Kuckert has Iiowever recently shownthat a substituted hydropyridine-derivative is obtained by the con-densation with paraldehyde and sulphuric acid of the product obtainedby the action of methylamine on ethyl acetoacetate from this itf ,Ilows that the nitrogen must be exerting imidic functions and thatthe constitution of the hydropyridine nucleus must beHN<C C ' C .' c> CH.The ketone CsH,O obtained by the action of hydrochloric acid onethyl hydrocolliclinecarboxy!ate (Abstr. 1883 84) when treated wit,hhydroxylamine jields a crystalline oximido-compound C,H NOH.By heating ethyl acetoacetate with benzaldehyde and methylamine,two non-nitrogenous products C19H2406 and C19H,C)> are obtained.'l'he part played by the methylamine in the reaction is obscure butunless it or some other primary amine is present thesa substances arenot formed.J3thyZ benz y 2 idinediacetoacetate C19H,0s = C HP h (CH Ac-C 00 Et),crystallises in long white needles melts a t 15%-153° and is sparinglysoluble in alcohol and ether ; when treated with bromine it yields asubstitution-derivative Cl9HZ3Bro6 nieltitig at 159".Ethyl dehydrobenzylidinediacetoawtate C19H2,05 crystallises inlustrous prisms melts a t 87-38" and is readily soluble in nearlyall solvents.The author assigns to i t the constitutionCMe C(COOEt)>CHPh,'<CMe C(CO0Et)regarcling it as a hgdropyridine-derivative in which the imido-groupis replaced by oxygen.A. J. G78 ABSTRACTS O F CHEMICAL PAPERS.p-Dipyridyl. By T. LEOKE and V. OLIvExr (Gazzetfa 15 274-277).-A dipyridyl Cl,H6N7 is produced by the dry distillation ofpyridinesulphonic acid and separation of the distillate by concentratedpotash. It crystallises in c:olourless prisms melting at G8" and boilinga t 286-288" ; its platinochloride is an orange-yellow powder insolublein water alcohol and ether This dipyridyl is probably identicalwith that obtained by Skraup and Vortmann by the dry distillation ofdipyridyldicarboxylic acid (Abstr. 1883 88) as evidenced by itsdirect conversion into nicotinic acid and of the formation of the sameacid from the sulphonic acid originally used.It is proposed to call itp-dipyridyl and to assign to it the following structure :-C,H,N*C,H,N [N CaH*;N = 1 31. V. H. V.Pyridin e- choline Pyridine-neurine and Pyridine -muscarine .By T. COPPOLA (Gazzetta 15 330-345) .-The alkaloids choline,neurine and niuscarine are analogous not only in their chemicalconstitution inasmuch as they can be regarded as hydroxyethylene-,ringl- and dihydroxyethylenetrimethgl ammonium hydroxides but alsoin the physiological symptoms producccl by them namely stimulationof the inhibitory ganglia of the heart arrestation of the diastole andexcitation of the secretmy nerves. I n this paper the chemical pro-perties and functions of their pyridine-derivatives ape described.P!jridine-c?ioline hydrochloride OH*C2H4*C5H5NC1 obtained byheating a mixture of pyridine and ethylene chlorhydrin in equalmolecular proportions forms colourless prismatic crystals verydeliquescent and soluble in alcohol and water insoluble in ether.I t s plntino- and awo-ahlorides are yellow amorphous powders ; itshydroxide is very readily decomposed.Pyyidiiie-netwine l;yd&xIide C5H5( CzE3)NI obtained by heatingthe above compound with coilcentrated hydriodic acid crystallises inopaque white prisms very soluble in Bding alcohol aud water,insoluble in ether.Its platino- and auro-ohlorides are yellow amor-phous powders.Pyridine-muscarhe hydi*ochZoriiie C2H3(OH),*C,H,NCI obtainedfrom pyridine-choline by heating i b with nitric acid (sp.gr. 0.148),formsorange-yellow deliqnescen t laminae ; its platinochloi-idc! ci.ys tallises inorange-yellow needles its nurochloride is an amorphous powdei.The physiological function of the al3ove compounds is perfectlysimilar in that they all arrest voluntary movements and a t first excitebut afterxards paralyse the cardiac pulsations. As regards theirtoxic efEects they differ considerably in degree. The variation ofphysiological function with chemical constitution more especially asregards the effect of the substitution of hydrogen-atoms by differentgroups especially h ydroxyl and the choline neurine and mnscarineradicles is discussed a t some length.By S. HOOGEWERFF and W. A. v. DORP (Rec. Frccv.Chim.4 125-12s) .-By adding concentrated sulphuric acid to analcoholic solutioii of the crude quinoline from coal-tar the sulphatesof quinoline and isoquinoliae C9H,N are precipitated and by re-pented rectification of the free bases obtained from this precipitate twofractions are obtained one boiling from 230" to 236O which is chieflyV. H. V.IsoquinolineORUXNlC CHENLSTRP. 7!)quinoline and the other boiling from 236" to 243" containing isoquino-line this is purified by the repeated recrly~t~allisation of its sulpliatefrom alcohol. The free base melts a t 18-23" and boils at 236-2.37.5"(uncorr.). The suZphate CsH7K,H,SOa forms hygroscopic prisms ortablets and melts a t 205-208". The chromate ( CSH7N),H,Cr,0,forms reddish-yellow needles and is decomposed a t about 150".ThepZutinochZori.de ( CSH7N),I3[,PtCI6 + 2H20 forms slender yellowish-red needles ; i t becomes anhydrous a t 110". The picsrnte is but littlesoluble in alcohol or water and crystallises in yellow needles ; it meltsa t 222-223.5'. A. P.Constitution of Quinoline-derivatives prepared from Meta-substituted Amines. By L. GATTERMANN and A. KAISER (Ber. 18,2602-2604) .-Whilst the constitution of quinoline-derivatives pre-pared from ortlio- and para-substituted amines is certain inasmuch asonly one substance can be formed in each case ; in those from metn-compounds two quinoline-~erivatives are theoretically obt'ainable,according as the linking of the pyridine-ring occurs a t the ortho- orpara-position relatively to the substituting group.It seems as thoughthis question can be solved by the use of compounds in which one orthe other of these positions is occupied by halogens &c.ChZoronzeth?llquinoZine C9NH,MeC1 [Me Cl = 1 41 is prepared bySkraup's method from parachlorometatoluidine ; it crystallises incolourless needles of quinoline-like odour melts a t 49" and is solublein water readily soluble in ether alcohol and benzene. The merciiro-chZoride C,H,NCI,HHgCl crystallises in broad needles or tables theplatinochloride (C,oH8NCl)2,H2PtC16 forms yellowish-brown tables o rbroad needles the picrate crystallises in large brownish-yellow tables,nnd melts at 172". When heated with excess of hydrogen iodidedissolved in acetic acid the chlorine is replaced and a methylquinolinoobtained.The author cannot as pet speak posit?ivel yas to the identityor non-identity of this with Skraup's " metatoluquinoline."A. J. G.Paraquinaniso'il. By 2. H. SKRAUP (Monatsh. Chem. 6 f60-$84).-Paraquinanisoil is best prepared by heating a mixture OEi 8 grams anisidine 50 grams nitraniso'il 320 grams glycerol and125 grams sulphuric acid for two hours ; 50 grams more of sulphuricacid are added and the heating continued for two hours longer. Theproduct is then diluted with water distilled with steam and theresidue treated with potassium dichromate which causes a precipita-tion of quinanisoil chromate ; this is then purified. Pure quinanisoilforms a. yellowish oil which soon acquires a green then a reddish-violet colour ; it boils with slight decomposition at 304-305"(uncorr.).Sp. gr. a t 20" = 1.542 (water at 20" = 1). Para-puina&oiZ hydrochhride CsNHOMe,HC1 + 2H,O forms colourlessprisms readily soluble in cold wnter and hot alcohol insoluble i nether. Thechromate forms long gold-coloured silky needles which when exposed toair lose their lustre and become brownish ; i t is very sparingly solublein cold water. The nedral sulphate acid sdphate tartrate and othersalts are described. The aqueous solutions of the salts all shorn aIt loses its water of crystallisation orer sulpliuric acidSO ABSTRACTS OF CHEMICAL PAPERS.blue fluorescence. Chlorine-water and ammonia act on the salts,giving the green colour characteristic of quinine compounds.Paraquinanisoil rnethiodide crystallises from water in long gold-colourcd lustrous needles which melt with evolution of gas at 235".It is insoluble in ether readily soluble in hot water and alcohol.Thalline CSHloNeEO is prepared by reducing quinanisol with tinand hydrochloric acid ; it forms thick white prisms sparingly solublei n water and light petroleum very readily in alcohol ether andbenzene. It melts at 42-43" and boils a t 288" (uncorr.; bar. =735 mm.). When treated with ferric chloride or other oxidising agents,it acquires first a yellow afterwards a dark emerald-green colonr.Silver nitrate produces this coloration with separation of silver.ThaZZine hydrochloride C,H,NO,HCl crystallises in well-formedprisms sparingly soluble in alcohol.The sulphate (with 2 mols.H,O) and other salts are described. Acefylthtrlline CloHl,PU'O*Ac,forms clear broad monoclinic prisms which melt at 46-47". Itsbolubility resembles that of thalline. Bromine acts on thalline withformation of a compound CloH,Br3NO ; it is a pale yellow powder,melting at 19t3-194".MethyZthal7ine CloH,2NOMe is prepared by the action of methyliodide on thallme. I t forms a thick colourless oil which when keptlwcomes brown ; it boils at 277-278-5' (uncorr.). When a solutionin dilute hydrochloric acid is treated with ferxic chloride i t acquiresa cherry-red colour which changes to reddiah-yellow when kept long.The hydrochloride and sulphate crystallise in well-formed prisms,readily soluble in water,Thaliiie hydriodide ( CloH,NO),HI and p a t e r n a r y dirrzethylthall&wiodide CIOH12NOMe21 are formed in the preparation of methylthalline.'J'he former compound crystallises in flat prisms melting a t 155-136" imoluble in ethylbenzene light petroleum readily soluble in hotalcohol. The latter compound forms long prisms insoluble in lightpetroleum readily soluble in alcohol and in water from which i t crystal-lises with 1 mol.H20. I t melts with evolution of gas a t 223-224".Boiling aqueous potash hydrochloric and nitric acids do not act on it.EtlujZtlialliize C,H,EtNO is a thick oil which boils a t 287-287*5O with slight decomposition. It is insoluble in water veryreadily soluble in alcohol ether and in mineral acids. Some saltswere prepared ; they are very hygroscopic and cryatallise with diffi-culty. EthyZtlLa2lirLe et7~iodide forms white needles readily soluble inalcohol and in water insoluble in ether ; it melts with evolution of;'as a t 1:31-133° ; when distilled it decomposes into ethyl iodide andt' t hvlt ha1 lin e.Benzyl chloride acts on thalline with formation of a base probablyLenzylthalline ; when treated with ferric chloride it gives tho samecharacteristic red colour as methyl- and ethyl-thalline.The physiological properties of several of the compounds mentionedin the paper are described.The papei. concludes with remarks on theconstitution of quinine.Para- and Ortho-phenylquinoline. By W. LA COSTE and C.SORGER (Aiinaleii 230 1-42).-l'arayhenylquinoline is prepared byN.H. MORGANIC CHEMISTRY. 81the action of sulphuric acid glycerol and nitrobenzene on paramido-diphenyl. The base is precipitnted from the acid solution by theaddition of an alkali collected dried and dissolved in warmbenzene. The solution is left in contact with solid potassinmhydroxide for some hours and is then filtered. After removing thebenzene by distillation. the residue is distilled under reduced pressure.Paraphenylquinoline CgNH,Ph [Ph = 31 melts at 110-111" nnd boilsa t 260" under 77 mm. pressiire; its sp. gr. is 1.1945 at 20". It issparingly soluble in water but dissolves freely in alcohol chloroform,benzene and carbon bisul phide. Phenylqninoline is deposited fromether in rhombic pyramids from alcohol in combinations of thepyramid and basic plate and from benzene in twin pyramids ; all thesalts are soluble in water fmming fluorescent solutions.The twtratp,CgNH,Ph,H,C,HaO + 3H20 crystallises in needles melting a t 153".The dichromate (CgNH6Ph)2,H2Cr207 forms reddish-yellow needles,which melt at 136". The methiodide C9NR6Ph,MeI + 2H20 crystal-lises in long needles melting at 194". The ethiodide crystallises with2 mols. H20 in pale yellow needles and also with 1 mol. H,O in thick,yellow prisms.When phenylquinoline is treaked with tin and hydrochloric acid i tunites with four atoms*of hvdroyen to form a tetrahydro-cornpound.The hydrochloride C9NH,Ph,HC1 + 1+H20 crystallises in needles.It is sparingly soluble in cold water and is partially decomposed byhot water.It also dissolves in alcohol and in chloroform.Thepicrote CgNH,Ph,C6H,(No2),*o~ is deposited from a hot aqueoussolution in needles which dissolve freely in alcohol chloroform andbenzene. It melts a t 165'.The nitroso-compound C9NHgPh.N0 forms yellow cryst#als freelysoluble in benzene and chloroform. The acetyl-derivative C9NHgPhAc,crystallises in white silky needles. It melts at looo and is freelysoIuble in alcohol benzene chloroform and carbon bisulphide.The benzoyl-derivative forms white plates melting at 137". It isfreely soliible in alcohol.Meth y ItetTa~~ydroparaphen~~ Zquinoline hydrochloride,The free base is soluble in alcohol ether and hot water.C9NHgMePh HCl,prepared by the action of tin and hydrochloric acid on phenylquino-line methochloride is a crystalline substance soluble in alcohol andchloroform.The hydriodide CgNH,MePh,HI resembles the hydrochloride butis more easily decomposed by water.Itdipolves in alcohol chloroform and benzene. The methiodide meltsa t 194". It crystallises in plates or prisms soluble in alcohol and inchloroform.The substitution products of paraphenylquinoline do not crystal-lise easily and can only be prepared with difficulty in the pure state.The mononitro-derivative CljNHlo*N02 is formed by the action offuming nitric acid on an acetic acid solution of paraphenylquinoline.It melts at 173" and is soluble in alcohol ether benzene and in hotwater. The compound also dissolves in dilute acids and forms twoThe platinoch loyide easily decomposes.The picrnte melts at 147".9 VOL.L82 ABSTRACTS O F CHEMICAL PAPERS.crgstallino platinochlorides of which one is insoluble in hot water.The dinitro-compound is obtained by adding phenylquinoline tofuming nitric acid. It melts at 208" and dissolves in alcohol andbenzene.Phenylquinoline dissolves in cold fuming sulphuric acid yielding twoisomeric monosulphonic acids. The a-snlphonic acid C,H,NSO +2Hz0 can be separated from its isomeride by the greater solubility ofthe latter and also of its ammonium salt in water. The a-acid crystal-lises in lon5 needles soluble in hot water. It does not melt a t 300".When oxidised with potassium permanganate it yields parasulpho-benzoic acid. The ammonium salt of a-phenylquinolinesulphonicacid crystallises in plates which dissolve freely in hot water.Tbesodiuni and calcium salts dissolve freely in water the potassium andbarium salts are sparingly soluble. p$heizylq.uilzoZines.ulpkonic acid,Cl5H,NSO3 + H20 dissolves freely in water but is insoluble inchloroform and ether. The ammonium salt crystallises in anhydrousscales.Ortho~henyZqi~inoli?te C9NH6Ph [Ph = 11 is prepared by a processanalogous to that employed in the preparation of the para-compound.It is a thick fluorescent oil which darkens on exposure to the air. Itdissolves freely in alcohol ether benzene carbon bisulphide andchloraoform and boils between 270" and 276' under a pressure of80 mm.Tbe salts of the base are soluble in water forming fluorescentsolutions. The platinochloride crystallises in needles ; the dichromntein plates melting at 126" and dissolving in water and warm alcohol.The methiodide forms reddish-yellow plates melting' a t 163".It isfreely soluble in water alcohol and chloroform. Ortlzop heny lyzcino-linemethyl platinochloride ( C,NH6PhMe),PtCl6 is a crystalline salt,soluble in hot water. It melts at 198". w. c. w.Colouring Matters derived from the Quinoline Bases. By0. DE CONINCK (Rec. Trau. Chim. 4 58-60).-The reaction of analcoholic solution of potassium hydroxide on the iodides of the ethyland methyl derivatives of the quinoline bases by which a red colour-ing matter is produced (Rec. Traw. Chim. 3 337) appears to begeneral for all the alkyl-derivatives of quinoline as the author hasprepared a red crystalline colouring matter from the iodide of thepropyl-derivative ; he also confirms the constitution assigned to thscyanine-derivatives obtained by the action of potassium hydroxide onthe iodide of ethyl-lepidine and ethylquinoline (Abstr.1885 673).Quinoxalines. 111. By 0. HINSBERG (Ber. 18 2870-2875) .-A. P.Dihydro-ox y tolu puinoaaline,is obtained by heating ethyl chloracetate (2 mols.) with toluylene-diamine (3 mols.) for several days on a water-bath and is purified bymeans of its sparingly soluble sodium-derivative. It crystallises inmoderately large yellowish needles is readily soluble in hot wateOROANlC CHEMISTRY. 8 3and alcohol moderately in ether and also in alkalis and acid>.The potassium-derivative is readily soluble in water and in potashsolution; the sodium-derivative C9H,N20Na + H20 forms lustrousscales and is almost completely precipitated from its aqnemssolutions by the addition of soda.Dihydro-oxytoluquinoxaline inalkaline solution is oxidised by atmospheric oxygen to hydroxytol u-quinoxaline ; neutral solutions are not so readily acted on but are alsooxidised by weak oxidising agents.When toluylenediamine and ethyl chloracetate are heated togetherin equal molecnlar proportions the compound C13H16N203 i sproduced and may be purified by crysta1lisa.tion from alcohol. Itforms colourless lustrous scales melts at l47" is sparingly soluble inwater nearly insoluble in ether and moderately soluble in alcohol.Concentrated mineral acids and acetic acid dissolve it readily whilstalkalis dissolve it only on warming.Silver nitrate and nitrous acidoxidise it apparently t o a product melting a t 247-2418". On saponi-fying the substance C13H16N203 with alkali a sparingly soluble acid isobtained crystallising in white needles. The formation and constitu-tion of the above compound may probably be expressed thus :-+ EtOH + CTH~(NH~C~),.A. K. M.Papaverine. By C. GOLDSCHMIEDT (Monatsh. Chern. 6 667-701 ;compare Abstr. 1885 1080).-Analyses of papaverine and of a largenumber of its salts confirm the correctness of the formula C20H,NOaassigned to papaverine by Merck and others. Papaverine cry stallisesin rhomhic prisms a b c = 0.3193 1 0.4266. Crystallographicmeasurements of various derivatives and salts are also given.N. H.31.Hydrobromapoquinine. By P. JULIUS (Monatslz . Chem. 6,750-753),-Hydrobrornapoquinine C,H23BrN2021 is prepared by heat-ing quinine hydrate a t 100" with three times its weight of watersaturated with hydrobromic acid a t 0". It forms a white amorphouspowder which melts a t N9-210" is insoluble in water readilysoluble in alcohol. The hydrobmnide C19H23BrN202,2HBr + H20,crystallises in groups of white needles readily soluble in water and inalcohol. The pZatinochZoride is described. N. H. M.Cupreine and Homoquinine By 0. HESSE (AnfiaZen 230,55-73) .-The author confirms the accuracy of his former statement(Abskr. 1885 276) that homoquinine is a compound of quinine andthe new alkalo'id discovered by P a d and Cownley called cupreine.Many of the properties of cupreine have been already described.The base crystallises with 2 mols.H20 which are expelled a t 120".The anhydrous substance melts a t 198'. The alcoholic solution givesa dark reddish-brown coloration with ferric chloride and an intensegreen coloration m-ith chlorine and ammonia. The neutral salts ofcupreine dissolve in water forming yellow solutions which arerendered colourless by the addition of acids. The solutions are not.fluorescent. The neutral sulphate ( C,H&"02),H,S04 + 6H,O,crystallises in needles ; the hydrogen snlphate C1,HnN2O2,HzSO~ +H20 forms flat prisms sparingly soluble in cold water. There are twohydrochlorides C,H2,N,02,HC1 + H,O crystallising in colourlessneedles and C19H22N,02,SHCl forming pale yellow prisms.Thenormal platinochloride ( C,9H22N,0,)2,H2PtC16 + 4H20 is amorphous ;the acid salt forms orange-coloured plates. The normal tartrate andthiocyanate are sparingly soluble in water. Cnpreine does notcombine with ammonia but it forms compounds with potassium,sodium lead and silver.Anhydrous cupreiiie dissolves in acetic anhydride forming a diacetylcompound C19H,Ac2N202 crystallising in six-sided plates. It meltsat 88" and is soluble in alcohol ether and chloroform. The hydro-chloride also crystallises in six-sided plates soluble i n alcohol and.water.Cupreine is converted into apoquinine by the action of hydrochloricacid at 140". Cupeine methiodide forms colourless crystals sparinglysoluble in cold alcohol and water. The corresponding chloride,ClsH,N202,MeC1 and platinochloride Cl9E2,NzO,MeHPtC1 + 2H20,are also crystalline. The sulphate crystallises in needles which arefreely dissolved in water. By decomposing this salt with baryta-water,the hydroxide is obtained. The aqueous solution of the hydroxidegives a red coloration with excess of bleaching powder in presence ofammonia and a green coloration when ammonia is added to a mixtureof the acidified solution and a small quantity of bleaching powder.The alcoholic solution of the hydroxide is fluorescent.Homoquinine is easily prepared by adding ammonia to a solution ofequal molecular weight of quinine and cupreine in dilute sulphuricacid and dissolving the precipitate in ether. Homoquinine is not asimple alkaloid but a compound of the compositionCocaine and its Salts. By B. H. PAUL (Pharrn. J. Trans. [3],16 325-326).-The author's experiments indicate that the solubilityof coca'ine i n water is much less than 1 in 700; moreover that onevaporating the aqueous solution the cocaine ia decomposed leaving agummy mass whieh crystallises and has many properties similar tothose attributed to ecgonine (compare Merck Abstr. 1885 997). Ityields benzoic acid by the action of caustic soda lime or sodiumarbonate bu.t not apparently by the action of hydrochloric acid. Itcombines with benzoic acid but can b4 separated from the acid byrepeated crystallisation from water. Cocaline hydrochloride is onlyslightly soluble in water from which solution it can be crystallisedwith water of crystallisation but after prolonged heating on a water-bath it remains in a resinous state for a considerable time a tleast. The acetate is very soluble and is diEcult to crystallise owingt o the volatilisation of the acetic acid during evaporation. The solutionof the benzoate dries to a thick gummy residue. Ammonia precipi-tates the alkaloid without apparent decomposition and when added inexcess does not redissolve it. D. A. LORGANIC CHEMISTRY. 85Alkaloi'ds from Erythroxylon. By C. J. BENDER (Chem. Ce?zti*.,1885 490-493).-The author has subjected the leaves of the coca-plant (Eyythroxylon cocu) to a careful investigation. Besides cocaine,he obtained an amorphous alkaloid to which he gives the namecocuzcine and a volatile base which he names erythroxyline. Therealso seem to be one or two other alkaloids present but the author wasunable to obtain them in a pure state or to determine whether theywere present in the %resh leaves or formed during the process ofextraction. L. T. T.Bases in Jaborandi Leaves. By E. HARNACK (Chem. Centr.,1885 628-629) .-Besides pilocarpine and jaborine Merck (Harnackand Meyer Abstr. 1880 898) obtained from the leaves of thejaborandi a third syrupy alkaloid which yielded a nitrate crystallisingin well-defined prisms. The author has investigated bhis alkalo'id,to which he gives the name pilocurpidine. Jt very closely resemblespilocarpine both in physiological and chemical properties but it doesnot give a precipitate with auric chloride. Its formula is CloH14N202.It is easily converted into an amorphous base juboridine C10HlzN203,which resembles jnborine and atropine in properties. Jaboridineappears to be identical with jaborandine C10H12N203 ottained byParodi (Rivista furm. 1875 3) from false jaborandi (Piperjaborundi) and by Chastaing by the oxidation of pilocarpine with,fumiiig nitric acid. The anttior believes that the jaborine hithertoobtained has always contained jaboridine as an impuriby. From theformula and properties of pilocarpine C,IF16N202 this substancewould appear to be a methyl-derivative of pilocarpidine ; and theauthor points out that the latter has the composition OP a di-hydroxy-derivative of nicotine or of an isomeride thereof. Jaboridine is anoxidation product of pilocarpidine formed by the replacement of twoatoms of hydrogen in the latter by an atom of oxygen.Alkalo'ids of Fenugreek Seeds. By E. JAHNS (Ber. 18,2518 - 2523).-The seeds of Frigonellu fGenurn grGecum containt rigonelline and a liquid base identified as choline. Trigonelline,C7H7N02 + H20 crystallises in coburless flat prisms of feeble salinetaste ; it is readily soluble in water sparingly soluble in cold alcohol,insoluble in ether chloroform and benzene ; it is carbonised whenheated. The reactions with the various reagents for alkalo'ids aredescribed. The hydrochloride C7H7N02,HCl crystallises in an-hydrous tables ; the platinochloride ( C,H7N02),H2PtC16 crystallisesin prisms. Two' atdrochlorides were obtained C7H7N02,HAuC14,crystallising in four-sided plates or flat prisms and melting at 198",and 4C7H7NO2,3HAuCl4 crptallising in slender needles and meltingat 186". A. J. G.L. T. 2'.Products of the Action of Hydrochloric Acid on the Albumi-noids. By J. B ORBACZEWSKI (Monatsh. Chem. 6 639-650).-When 500 grams of elastin (previously freed from fat by extractingthe finely powdered substance for two weeks with ether) are boiledfor 72 hours with I litre of hydrochloric acid diluted with an equalvolume of water and 25 grams of zinc chloride a small quantity ofammonia is given off and the solution after precipitation of the zincby hydrogen aulphide is found to contain leucine glycocine andtyrosine. Other compounds are also present but could not beisolated. The formation of these substances and the absence ofglutaminic and aspartic acids and of hydrogen sulphide from theprodnet of %he reaction show that elastin does not belong to the'sameclass of compounds as do albumin and keratin. It also differs fromthe horn substances and all other albuminoids which have as yetbeen examined. PJ EL 11

ISSN:0368-1769    

DOI:10.1039/CA8865000038

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

86 ABSTRACTS OF CHEMICAL PAPERS. P h y s i o l o g i c a l C h e m i s t r y . Digestion of Cellulose. By W. HE~EBEW and F.. STORMARK (Zsit. Biol., 21, 613-6'24) .--The author's discussion of this subject has special reference to the recent investigations of Tappeiaer (ibid., 20, 52), which have shown that the main products of fer- mentation of cellnlose, excluding the gases, are acetic and butyric acids. Having po'intcd out certain errors in the statement of the results of his experiments, they substitute the following :- Carbonic anhydride .......... 33.63 Marsh-gas, .................... 4.70 Hydrogen ... .................. 0.33 Butgric acid.. ................ 33.63 Acetic acid .................. 33-51 Tetal products.. .... 105.82 which may be summed up in the equation- 21C6H,,05 + 11H20 = 26C02 + IOCH, + 6H2 + P9C,H40a + In regard to the utilisation of malacdarr energy, the above resolution may be expressed as under :- 13CdHsO~.100 grams cellulose (100 x a146 >... ......... 414,600 cal. 33.5 Carbonic anhydride ................ 0 4.7 Marsh-gas (4.7 x 13344) .......... 62717 336 Acetic acid (336 x 3505) .......... 117768 33.6 Butyric acid (33-6 x 5647) ......... 189739 Heat of resolution ...................... 44376 414600 Supposing with Tappeiner that the marsh-gas is excreted directly,PHYSIOLOGICAL CHEMISTRY. 87 which, however, is by no means certain, and consequently that the corresponding amount of energy, 15 per cent. of the whole, is lost to the organism, cellulose would still seem to be a food-stuff of high value, apart from any subsidiary mechanical functions which it may perform in digestion. The authors have assumed the correctness of Tappeiner’s experi- mental results as the basis of this discussion ; at the same time they do not admit that he has established his position.There is still a probability that in the bydrolysis of cellulose intermediate products belonging to the carbohydrate group are formed, which, at least in The Presence of Glycogen in the Protozoa. By 0. B~~TSCHLI (Zeit. B i d , 21, 603-612) .-The author’s experiments were under- taken as a confirmation of previous investigations which have been recently criticised by Frenzel (Arch. f. Mikr. Anat., 24, 545). The subject in question is the composition of the granules. of the entoplasm of the gragorinae.From a number of qualitative results (of a some- what indefinite character), the author concludes that the substance composing these granules is glycogen, or a compound of similar nature (“ paraglycogen ”). The author has identified such a substance also in the infusoria Nyctotherns, Ovalis, and Strombidium, confirming, therefore, the observations of Certes (Compt. rend., 90, 70). Albuminoi’d Substance in Urine. By F. M~~LLER (Chem. Centr., 188Fi, 597--598).-l’his substance is precipitated from urine by acetic acid, and is regarded as a modification of albumin by the author, as it is precipitated both by magnesium sulphate, and on boiling; moreover it resembles other albumino’id bodies in its behnviour with nitric acid. P. P. B. Amount of Volatile Acids in the Excrements of Ruminants. By H.WILSING (Zeit. B i d , 21, 625--630).-The author’s experiments were undertaken as a development of Tappeiner’s observations on the formation of acetic and butyric acids as the main products of the digestive hydrolysis of cellulose. The subject of the experiments was a goat receiving 1.5 kilo. meadow hay per diem ; the results obtained are Fsummarised in the following table :- part, are directly assimilated. c. 3‘. c. C. F. C. Experiment. I . . . . . . . . I1 .. .. *. .. 111 .. *. .. .. IV v . . . . . . . . . . . . . . . . Total in 24 hours. 992 830 81 5 1241 812 Urine. Fseces. Volatile acids. Total. 2-937 2 854 1-444 3 -711 1 *a59 Excl. HCl + PhSCOOH. 2 -201 2 -1’75 0 *935 2 -934 1 -270 Total in 24 hours. ? ? 565 668 ? Vol. acids.-- 1 ’802 1 -802 1 ‘800 1 -803 1 -802 Aggregate. Vol. fatty acids. -- 4 -003 3 *997 2 ‘735 4 9-37 3 -07288 ABSTRACTS OF CHEMICAL PAPERS. The hay contained 25.9 “crude fibre,” of which 60 per cent. was found to disappear in the process of digestion, whence, the author states, 233 grams ceZZuZose are digested in the 24 hours; and as this quantity would yield, according to Tappeiner’s observations, 15 7 grams volatile fatty acids, it is seen that of the latter 97.4 per cent. Abstractor’s Note.-It is to be observed that agricultural chemists continue to apply the term cellulose collectively to plant fibres, disregarding the variations in composition of the fibre substance. Pathological Urine. By A. VILLIERS (J. Phurm. [ 5 ] , 11, 246- 249).-Contrary to Bouchard and Pouchet, the author finds that normal urine never contains alkaloids.Operating always on two litres, he first evaporated by heat, then in a vacuum, took up the residue with absolute alcohol, evaporated the filtered alcoholic solution in a vacuum, and took up this second residue with a drop of water. In this solution, the alkaloids were detected by alternate precipitation with an alkaline carbonate in presence of ether, and re-solution in water acidified with hydrochloric acid. When care was takea to obtain normal urine, the results were always negative, but alkalo’ids were found in the urine when the subject was sujfering from a slight att,ack of bronchitis, indisposition with fever, measles, pneumonia, abscess in the head ; in one case of tetanus, alkaloids were not found.Physiological Action of Rubidium Salts. By C. RICHET (Conzpt. rend., 101, 667--669).-The toxic effect of rubidium chloride depends on the mode of introduction into the system. If the solution is injected under the skin, the minimum fatal dose is about 1 gram per kilo. of body weight, but if injected directly into the veins, about 0.5-0-6 gram per kilo. of body weight is sufficient to cause death. In both cases the poison acts directly on the heart aiid stops its movements. Physiological Action of Salts of Lithium, Potassium, and Rubidium. By C. RICHET (Compt. rend., 101, 707-710).-Aqueous solutions of the chlorides of the three metals were injected under the skin of various animals, and the minimum dose sufficient to cause death was determined.The effects of lithium chloride appear very slowly, hut the action of rubidium and potassium chlorides is evident in a few hours. Leaving out crayfish, which are very easily poisoned by the chlorides, and snails, which offer considerable resistance to their action, i t was found that the minimum fatal dose per kilo. of body weight was practically the same for teuch, tortoises, frogs, pigeons, guinea-pigs, and rabbits, being 0.1 gram for lithium,* 0.5 for potassium, and 1.0 for rubidium. These numbers are almost in exactly the same ratio as the atomic weights of the three metals, namely, 7, 39, and 85. In* other words, lithium, potassium. and rubidium, if taken in molecular proportion instead of in equal weights, * These numbers represent, not the amount of chloride, but the amount of metal in the form of chloride. are assimilated, and 2.6 per cent.only excreted. c. I?. c. J. T. Rubihum is less poisonous than potassium. C. H. B.PHYSIOLOGICAL CHEMISTRY. 89 are equally poisonous. It would seem, therefore, that the toxic action is really a chemical action, and it is probable that these three chlorides act by displacing, molecule for molecule, the sodium chloride present in the tissues. C. H. B. Physiological Action of Liebig's Extract of Meat. By K. B. LEHMANN (Chem. Centr., 1885, 665).--Neither this extract nor potassium salts, even when taken in large doses, have a specific action on the rate, strength, or regularity of the pulse. The action which has been observed is only the general reflex action of all salts on the stomach and intestines.The cont,inued consumption of large quantities of the extmct, even up t o 1 per cent. of the whole weight, of the body, had not an ill, but apparently a very favourable effect. L. T. T. Adipocere. By E. ZILLNER (Chena. Centr., .1885,441-442).-From the results of several minute microscopical and chemical investiga- tions the author concludes that adipocere is formed from the various fats present in the body at the moment of death, and that the albuminoi'ds do not play any part in this transformation. After a few months' putrefaction, the animal tissues are no longer impervious to the transmission of the fat, which then wanders and collects in masses, there to undergo further decomposition, and eventually lose its glycerol and oleic acid, leaving a crystallised fatty acid behind.To this end thorough moistening of the corpse is necessary to carry away mechanically the liquid products. As the crystallised acid occupies a much greater space than the amorphous form, the apparent transformation of parts of the body into fat is explained. J. K. C. Post-mortem Imbibition of Arsenic. By F. S. Srrmoiv (Amer. Chem. J., 7, 75--87).-But little is known of the distributiou of arsenic and other poisons when introduced into the body after death, it being generally assumed that the transfusion of arsenic is prevented by the sulphuretted hydrogen evolved by the decomposition. That it can travel t o the liver and some other viscera when injected into the stomach or rectum has been pointed out, but whether it can reach the brain is a contended point ; if this is impossible, and Scolosuboff's stahement that arsenic is deposited during life in the brain and spinal cord is true, then a means is afforded of distinguishing between poisoning by arsenic and post-mortem injections containing it.The author made injections of 3 grains arsenious oxide into the stomach and rectuni of dogs killed by chloroform 24 hours previously, and found that after burial for periods of from 3 to 102 days, arsenic could be detected in the liver, the kidneys, and the brain, and that the longer the time of burial, the greater was the quantity of arsenic, especially in the case of the brain. H. B.86 ABSTRACTS OF CHEMICAL PAPERS.P h y s i o l o g i c a l C h e m i s t r y .Digestion of Cellulose. By W.HE~EBEW and F.. STORMARK(Zsit. Biol., 21, 613-6'24) .--The author's discussion of this subjecthas special reference to the recent investigations of Tappeiaer(ibid., 20, 52), which have shown that the main products of fer-mentation of cellnlose, excluding the gases, are acetic and butyricacids. Having po'intcd out certain errors in the statement of theresults of his experiments, they substitute the following :-Carbonic anhydride .......... 33.63Marsh-gas, .................... 4.70Hydrogen ... .................. 0.33Butgric acid.. ................ 33.63Acetic acid .................. 33-51Tetal products.. .... 105.82which may be summed up in the equation-21C6H,,05 + 11H20 = 26C02 + IOCH, + 6H2 + P9C,H40a +In regard to the utilisation of malacdarr energy, the above resolutionmay be expressed as under :-13CdHsO~.100 grams cellulose (100 x a146 >............ 414,600 cal.33.5 Carbonic anhydride ................ 04.7 Marsh-gas (4.7 x 13344) .......... 62717336 Acetic acid (336 x 3505) .......... 11776833.6 Butyric acid (33-6 x 5647) ......... 189739Heat of resolution ...................... 44376414600Supposing with Tappeiner that the marsh-gas is excreted directlyPHYSIOLOGICAL CHEMISTRY. 87which, however, is by no means certain, and consequently that thecorresponding amount of energy, 15 per cent. of the whole, is lost tothe organism, cellulose would still seem to be a food-stuff of highvalue, apart from any subsidiary mechanical functions which it mayperform in digestion.The authors have assumed the correctness of Tappeiner’s experi-mental results as the basis of this discussion ; at the same time theydo not admit that he has established his position.There is still aprobability that in the bydrolysis of cellulose intermediate productsbelonging to the carbohydrate group are formed, which, at least inThe Presence of Glycogen in the Protozoa. By 0. B~~TSCHLI(Zeit. B i d , 21, 603-612) .-The author’s experiments were under-taken as a confirmation of previous investigations which have beenrecently criticised by Frenzel (Arch. f. Mikr. Anat., 24, 545). Thesubject in question is the composition of the granules. of the entoplasmof the gragorinae. From a number of qualitative results (of a some-what indefinite character), the author concludes that the substancecomposing these granules is glycogen, or a compound of similar nature(“ paraglycogen ”).The author has identified such a substance alsoin the infusoria Nyctotherns, Ovalis, and Strombidium, confirming,therefore, the observations of Certes (Compt. rend., 90, 70).Albuminoi’d Substance in Urine. By F. M~~LLER (Chem.Centr., 188Fi, 597--598).-l’his substance is precipitated from urineby acetic acid, and is regarded as a modification of albumin by theauthor, as it is precipitated both by magnesium sulphate, and onboiling; moreover it resembles other albumino’id bodies in itsbehnviour with nitric acid. P. P. B.Amount of Volatile Acids in the Excrements of Ruminants.By H. WILSING (Zeit.B i d , 21, 625--630).-The author’s experimentswere undertaken as a development of Tappeiner’s observations onthe formation of acetic and butyric acids as the main products of thedigestive hydrolysis of cellulose. The subject of the experiments wasa goat receiving 1.5 kilo. meadow hay per diem ; the results obtainedare Fsummarised in the following table :-part, are directly assimilated. c. 3‘. c.C. F. C.Experiment.I . . . . . . . .I1 .. .. *. ..111 .. *. .. ..IV v . . . . . . . . . . . . . . . .Totalin 24hours.99283081 51241812Urine.Fseces.Volatile acids.Total.2-9372 8541-4443 -7111 *a59Excl. HCl +PhSCOOH.2 -2012 -1’750 *9352 -9341 -270Totalin 24hours.??565668?Vol.acids.--1 ’8021 -8021 ‘8001 -8031 -802Aggregate.Vol.fattyacids.--4 -0033 *9972 ‘7354 9-373 -0788 ABSTRACTS OF CHEMICAL PAPERS.The hay contained 25.9 “crude fibre,” of which 60 per cent. wasfound to disappear in the process of digestion, whence, the authorstates, 233 grams ceZZuZose are digested in the 24 hours; and as thisquantity would yield, according to Tappeiner’s observations, 15 7grams volatile fatty acids, it is seen that of the latter 97.4 per cent.Abstractor’s Note.-It is to be observed that agricultural chemistscontinue to apply the term cellulose collectively to plant fibres,disregarding the variations in composition of the fibre substance.Pathological Urine. By A. VILLIERS (J. Phurm. [ 5 ] , 11, 246-249).-Contrary to Bouchard and Pouchet, the author finds thatnormal urine never contains alkaloids.Operating always on twolitres, he first evaporated by heat, then in a vacuum, took up theresidue with absolute alcohol, evaporated the filtered alcoholic solutionin a vacuum, and took up this second residue with a drop of water.In this solution, the alkaloids were detected by alternate precipitationwith an alkaline carbonate in presence of ether, and re-solution inwater acidified with hydrochloric acid. When care was takea toobtain normal urine, the results were always negative, but alkalo’idswere found in the urine when the subject was sujfering from a slightatt,ack of bronchitis, indisposition with fever, measles, pneumonia,abscess in the head ; in one case of tetanus, alkaloids were not found.Physiological Action of Rubidium Salts.By C. RICHET(Conzpt. rend., 101, 667--669).-The toxic effect of rubidiumchloride depends on the mode of introduction into the system.If the solution is injected under the skin, the minimum fatal dose isabout 1 gram per kilo. of body weight, but if injected directly intothe veins, about 0.5-0-6 gram per kilo. of body weight is sufficient tocause death. In both cases the poison acts directly on the heart aiidstops its movements.Physiological Action of Salts of Lithium, Potassium, andRubidium. By C. RICHET (Compt. rend., 101, 707-710).-Aqueoussolutions of the chlorides of the three metals were injected under theskin of various animals, and the minimum dose sufficient to causedeath was determined.The effects of lithium chloride appear veryslowly, hut the action of rubidium and potassium chlorides is evidentin a few hours. Leaving out crayfish, which are very easily poisonedby the chlorides, and snails, which offer considerable resistance totheir action, i t was found that the minimum fatal dose per kilo. ofbody weight was practically the same for teuch, tortoises, frogs,pigeons, guinea-pigs, and rabbits, being 0.1 gram for lithium,* 0.5for potassium, and 1.0 for rubidium. These numbers are almost inexactly the same ratio as the atomic weights of the three metals,namely, 7, 39, and 85. In* other words, lithium, potassium. andrubidium, if taken in molecular proportion instead of in equal weights,* These numbers represent, not the amount of chloride, but the amount of metalin the form of chloride.are assimilated, and 2.6 per cent.only excreted. c. I?. c.J. T.Rubihum is less poisonous than potassium.C. H. BPHYSIOLOGICAL CHEMISTRY. 89are equally poisonous. It would seem, therefore, that the toxic actionis really a chemical action, and it is probable that these three chloridesact by displacing, molecule for molecule, the sodium chloride presentin the tissues. C. H. B.Physiological Action of Liebig's Extract of Meat. ByK. B. LEHMANN (Chem. Centr., 1885, 665).--Neither this extract norpotassium salts, even when taken in large doses, have a specific actionon the rate, strength, or regularity of the pulse. The action whichhas been observed is only the general reflex action of all salts onthe stomach and intestines.The cont,inued consumption of largequantities of the extmct, even up t o 1 per cent. of the whole weight,of the body, had not an ill, but apparently a very favourableeffect. L. T. T.Adipocere. By E. ZILLNER (Chena. Centr., .1885,441-442).-Fromthe results of several minute microscopical and chemical investiga-tions the author concludes that adipocere is formed from the variousfats present in the body at the moment of death, and that thealbuminoi'ds do not play any part in this transformation. After a fewmonths' putrefaction, the animal tissues are no longer impervious tothe transmission of the fat, which then wanders and collects in masses,there to undergo further decomposition, and eventually lose itsglycerol and oleic acid, leaving a crystallised fatty acid behind.Tothis end thorough moistening of the corpse is necessary to carry awaymechanically the liquid products. As the crystallised acid occupiesa much greater space than the amorphous form, the apparenttransformation of parts of the body into fat is explained.J. K. C.Post-mortem Imbibition of Arsenic. By F. S. Srrmoiv (Amer.Chem. J., 7, 75--87).-But little is known of the distributiou of arsenicand other poisons when introduced into the body after death, it beinggenerally assumed that the transfusion of arsenic is prevented by thesulphuretted hydrogen evolved by the decomposition. That it can travelt o the liver and some other viscera when injected into the stomach orrectum has been pointed out, but whether it can reach the brain is acontended point ; if this is impossible, and Scolosuboff's stahementthat arsenic is deposited during life in the brain and spinal cord istrue, then a means is afforded of distinguishing between poisoningby arsenic and post-mortem injections containing it.The author made injections of 3 grains arsenious oxide into thestomach and rectuni of dogs killed by chloroform 24 hours previously,and found that after burial for periods of from 3 to 102 days, arseniccould be detected in the liver, the kidneys, and the brain, and thatthe longer the time of burial, the greater was the quantity of arsenic,especially in the case of the brain. H. B

ISSN:0368-1769    

DOI:10.1039/CA8865000086

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

90 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Invert Sugar and Selective Fermentation. By E. MAUMENB (Compt. rend., 101, 695).-A contribution to the controversy between Berthelot, Leplay, and Maurnen4 on this subject (Abstr., 1885, 1003, 1085, 1152). Comparative Researches on the Formation of Amides during the Germination of Various Seeds in the Dark. By B. SCHULZE and E. FLECHSIQ (Landw. Verswhs-Stat., 1885, 137- 149).-Altahough we are in possession of much iiiformation con- cerning the change of albumin into nsparagine, yet we are still ignorant whether the %hole of the albumino'ids are converted into asparagine and its congeners or not. One special object of this investigation was to discover if, when legumes and cereals germinate in the dark under the same conditions, relatively corresponding amounts of amides were produced from the albumin in each.All the details of the methods employed and of the analytical results are given. The analyses show that in all cases the conversion is very gradual and different, the legumes as a rule producing, not only absolutely but also relatively, larger quantities of amides ; this is most remarkable in the case of lupines. It may also be taken for granted that seeds when germinating do not of necessity produce an amount of amides ah all proportional t o their nitrogen reserve matter, but that the individual character of the plant itself has very considerable influence. E. W. P. Action of Saline Solutions on Germination. Ry M. JARIUS (Landw. Versuchs-Stat., 1885, 149--178).-These experiments were instituted with the object of completely answering the question as to whether the solutions of manures in the soil have, or have not, a detrimental action on the germination of the seed sown.The first portion of the article is occupied in discussing and reviewing other work on the subject, after which the author's own experiments and results are given in very full detail. The strengths of the saline solutions employed were 0.41, 1.0, and 2.0 per cent., and the seeds were in some cases allowed to soak for 2 M 8 hours, and in other cases 1-5 days. The solutions employed were of sodium and potassium chlorides, potassium and ammonium sulphates, cdcium hydrogen phosphate, potassium and sodium nitrates, and a solution containing all the nourishing constituents of plants.Peas steeped in a 2 per cent. solution for 24-48 hours increase in weight and volume regularly, but this increase is less than that which takes place when distilled water is employed. After 48 hours, the volume experiences a lesser increase than the weight, and this increase is reduced as the solutions become more concentrated, and the longer the period of steeping is continued, so that the ratio between volume and weight in 2 per cent. solutions and after 48 hours is the widest, that is, theVEGETABLE PHYSIOLOGY AND AGRICULTURE. 91 sp. gr. is then the highest. The sp. gr., as also the increase in weight and volume, is after 24 hours now raised, now lowered, when solutions of 0.2, 0.4, and 1 per cent. are used.Only in the cases of sodium chloride and nitrate in all concentrations, and from the beginning to the end of the steeping, is a constant increase in sp. gr. found ; whilst in the other solutions under all conditions, the increase in weight and volume is less than that when the liquid is water. The greatest amount of variation is found in the 0.4 and 1.0 per cent. solutions of salts of potassium after 24 hours. Finally the increase in weight and volume of peas attains its maximum in the shortest possible time the more concentrated the solutions are ; the time being dependent on the salt dissolved. The influence of the solutions on germination was tested under various conditions, such as 1-5 days with full and partial supply of air. The resalts are as follows: germination is decidedly aided by 0.2-0.4 per cent.solutions, but 1-2 per cent. solutions do harm, the shoots being feeble and abnormal, &c.; this harmful action is the more marked when there is not a plentiful supply of air, and also the good done by the weaker solutions is less when air is not freely accessible to the seed. Leguminosae and Crucifem are much assisted by the " nutritive solution," 0.4 per cent. solutions of potassium nitrate, and sodium chloride, whilst even 0.2 and 0.4 per cent. Rolutions of ammonium sulphate and calcium hydrogen phosphate are distinctly harmful to the above classes of plants. Grass seeds are not liable to much harm. Even 2 per cent. solutions are productive of good, the most damage being done by sodium chloride and nitrate in '2 per cent.solutions; summer rye is less subject to influence, whilst maize is more easily affected for good by 0.4 and 1.0 per cent. solutions than all the other grasses. The results of the investigation show that no harm can possibly come of the use of manures, as their solution in the soil can never be stronger than 0.4 per cent. Still the seed should not be sown immediately on the manure, as in such a, case it is possible that a solution stmnger than 0.4 per cent. may be formed. There is an interesting table given fihowing the ratio between the growths of lthe radicle and plumule of several seeds when subject during growth t o various strengths of a solution. E. W P. Composition of the Pollen of the Common Pine. By A. VON PLANTA (Landau. Versuchs-Stat., 1885, 215-'230).-The author fully describes every process which he has employed for the estimation of the constituents of pollen : the results are as follows :- Water.................... N. ....................... (N x 6.25 ................ Non-nitrogenous matter .... Ash. ..................... Hyponanthine and guanine. . Saccharose. ............... Shmh .................. Cuticula.. ................ 7.66 per cent. 2.65 ,, 16.56) ,, 72.48 ,) 3-30 ,, 0-04 3Y 11.24 ,, 7.06 ,, 21.97 ,,92 ABSTRACTS OF CHEMICAL PAPERS. Wax-like compounds . . . . . . Fatty acids . , . . . . . . . . . . . .. ,, Resinous bitter compounds.. 7.93 ,, 3.56 per cent. 10.63 Under the name cuticula is to be understood that chemically changed cellular matter, which overlays stru~turm, and is in direct contact with the air.It was estimated by digesting the pollen for three days with a 5 per cent. alcoholic potash solution, whereby fat, &c., was removed from the pollen grains ; the residue was boiled with semi-normal hydrochloric acid for two hours ; this removed the last traces of starch, and then ether removed any further soluble matters there might be, so that pure cuticula remained. The Sugar of Symphoricarpus Racemosa. By P. HERRMANN and B. TOLLENS ( A n n u l e n , 230, 50-55). - The authors have examined the sugar contained in the fruit of Syn?phoricarpus racenzosa, and find that it consists of a mixture of dextrose and laevulose. E. W. P. w. c. w. Conditions of the Development, and of the Activity, of Chlorophyll. By J. H. GILBERT (Brit.A ssoc.,* 1885) .-The foliage of different plants presents a great variety of shades of green, and i t may be stated that, a t any rate so far as our common agricultural plants are concerned, somewhat characteristic shades of colour are shown according to the natural order to which they belong, the Leguminosae differing from the Graminze, the Cruciferae, the Cheno- podiaceae, and so on. But the same description of plant will exhibit very characteristic differences, not only a t different stages of growth, but a t the same stage in different conditions of luxuriance, as affected by the external conditions of soil, season, manuring, &c., but especi- ally under the influence of different conditions as to manuring. The Rothamsted field experiments show that in a series of com- parable experiments with the same crop, depth of green colour by no means necessarily implies a finally greater amount of carbon assimi- lation ; whilst it has long ago been experimentally proved that the deeper colour was associated with a relatively high percentage of nitrogen in the dry o r solid substance of the herbage; and this obviously means a lower relation of carbon to nitrogen.Comparative determinations of the amounts of chlorophyll were made by Russell in parallel specimens to those in which the author determined the percentages of dry matter and of nitrogen. The following table gives the results of some of these experiments; namely, the percentages of nitrogen, and the relative amounts of chlorophyll, in the separated gramineous, and the separated legu- minous plants, in the mixed herbage of grass land, in specimens of wheat grown by a purely nitrogenous manure, and by the same nitrogenous manure with a full mineral manure in addition ; and in specimens of barley grown by a purely nitrogenous manure, and by a mixture of the same nitrogenous manure and mineral manure in addition.It is to be borne in mind that the specimens were collected * Read in Section B, at the meeting of the British Association at Aberdeen, September, 1885.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 93 whilst should are. as the plants were still quite green, and actively growing. It be further explained t h a t the amounts of chlorophyll recorded stated in the table, relative and not actual ; that is to sa,y, the figures show the relative amounts for the individual members of each pair of experiments, and not the comparative amounts as between one set of experiments and another.-- Hay. Gramineze ................... Leg uminosm ................. Wheat. Ammonium salts only.. ........ Ammonium salts and mineral manure .................... Barley. Ammonium salts only ......... Ammonium salts and mineral manure.. .................. Nitrogen per cent. in dry substance. 1 -190 2 -478 *la 227 +O -566 "1 ' 474 +O -792 Relative amounts of chlorop h y 11. A- 0 -77 2 -40 2 -00 1 -00 3'20 1 *46 Carbon assimilated per acre per annum. Actual. lbs. - - 13% 2222 1403 2088 Difference. -- lbs. - - - 824 - 685 JI: Not fully dried. Thus the separated leguminous herbage of hay contained a, much higher percentage of nitrogen in its dry substance than the separated gramineous herbage ; and also a much higher proportion of chloro- phyll.Indeed, under comparable conditions, the Leguminosae eventually maintain a much higher relation of nitrogen to carbon than the Gramineze; in other words, in their case, carbon is not assimilated in so large a proportion to the nitrogen taken up. The wheat plants manured with ammonium salts alone show a much higher percentage of nitrogen tham those manured with the same amount of ammonium salts, but with mineral manure in addi- tion. The high proportion of chlorophyll again goes with the high nitrogen percentage ; but the last column of the table shows that, with the ammonium salts without mineral manure, with the high percentage of nitrogen, and the high proportion of chlorophyll, in the dry substance of the green produce, there is eventually very much less assimilation of carbon.The result is exactly similar in the case of barley. It is evident that the chlorophyll formation has a close connection with the amount of nitrogen assimilated, but that the carbon assimi- lation is not in proportion to the chlorophyll formed, if there be not n sufficiency .of the necessary mineral constituents available. No doubt there had been as much, or more, of both nitrogen assimilated,94 ABSTRACTS OF CHEMICAL PAPERS. and chlorophyll formed, over a given area,, where the mineral as we11 as the nitrogenous manure had been applied, the lower proportion of both in the dry matt,er being due to the greater assimilation of carbon and consequent greater formation of non-nitrogenous substances. It is of interest t o observe that these results of experiments in the field are perfectJy consistent with those obtained by vegetable physio- logists in the laboratory; they having found that the presence of certain mineral, or ash constituents, and especially that of potassium, is essential for the assimilation of carbon, no st,arch being formed in the grains of chlorophyll withouf; the aid of that substance.Sachs says, " Potassium is as essential for the assimilating activity of chloro- phyll as iron for its production." Adonis Vernalis and Adonidin. By J. MORDAGNE ( P h ~ m . J. Trans. [ 3 ] , 16, 145-146) .-Adonis vernaiis amongst other substances contains aconitic acid and a glucoside, adonidin.To obtain the latter, the leaves and stalks are dried, extracted with 58" alcohol, treated with basic lead acetate, fhe excess of lead removed with sodium carbonate, the liquid made alkaline with ammonia, and the glucoside precipitated by means of tannin. The tannate is digested with zinc hydroxide and alcohol at a gentle heat for several hours, the alcohol is then distilled 08, and tEie glucoside extracted with absolute alcohol, carefully evaporated and dried over sulphuric acid. The yield is 2 grams per 10 kilos. The substance forms a rather hygroscopic canary-yellow powder, but, after proloiiged desiccation forms radiating crystals, Ammonia prevents crystallisation. It is soluble in water, alcohol, and amyl alcohol'; insoluble in anhydrous ether, chloroform, turpentime oil, and benzene ; and has a persistent bitter taste.Heated a t 80-85" i t loses 3.14 per cent. water, but does not alter physically ; between 85-90" it becomes brown; and at 100" nearly black. It contains no nitrogen, ia neutral to litmus, and only reduces Fehling's solution when heated with it in presence of hydrochloric acid. Ammonia turns it brown, tannin precipitates it, and basic lead acetate produces a cloudiness in its solutions, whilst baryta and alkaloid reagents do not react wiCh it. When decomposed, it yields a resinous substance soluble in ether, and develops a persistent odour of cut hay. Owing to its imperfect and troublesome crystallisation a good sample can scarcely be obtained for analysis, but the mean of several experi- ments gives per cent.C, 42,623 ; H, 7 5 4 7 ; 8. = 49.830. D. A. 11. Arum Italicurn. By G. SPICA and Gl BISCARO (Gazzetta, 15, 238- 242).-As the symptoms occurring in three cases of poisoning by eating the spadices of the Arum italicurn were peculiar, the authors have made a chemical and a physiological study of this species, From the spadices, a glucoside has been extracted, identical with saponin ; the symptoms produced by the hypodermic injection of h0t.h sub- stances into frogs were compared, and found to be practically the same. In both cases, general paralysis of the nervous and muscular systems supervened, ending, in most cases, in death : the symptoms are not those of tetanus as at first supposed. V. H. V.VEGETABLE PHYSIOLOGY AND AGRICULTURE.95 Researches on Gourds. By R. ULBRICHT (Landw. Versuchs- Stat., 1885, 230-240) .--The author details the physical composit#ion of many gourds, showing the proportion of rind to flesh and seed, and the chemical constituents of all parts of various gourds, as well as the composition of the ash. Illiciurn Religiosum. By J. P. EIJKRIAN (Eec. Trav. Chim., 4, 32--54).-The liquid obtained by distilling the leaves and fruits of I l l i c i u m reZigiosum with water consists of euqenol, a terpene to which the author gives the name of schikirnene, and safrole, besides a small quantity of some indefinite compounds of high boiling point, which are probably formed by the polymerisation of the previous com- pounds. Schikimene boils at about 170", and i8 a fragrant, limpid, mobile, colourless liquid; its sp.gr. = 0.865 ; with conceiitrated sulphuric acid it yields a magnificent orange colour, and on warming with nitric acid it deflagates with violence, it also explodes on con- tact with iodine ; its specific rotatory power is [ a ] , = - 22*5", but if heated for some time over metallic sodium, it is reduced to - 0.85". The author finds that by heating safrole gently with an equal quantity of an aqueous solution of potassium permsnganate (1 part in 40 of water) piperonic acid is formed (comp. Abstr., 1884, 1338), and from this and the measurement of the refractive index he considers that the constitution of safrole is probably best E. W. P. n expressed by the formula C,H,Pr<~>CHZ [Pr : QCHz = 1 : 3 : 41 (compare Abstr., 1884, 1339).The residue left after the removal of the above compounds by distillation, when subjected to strong pres- sure, yields a clear syrup which contains protocatechuic acid, schi- kirnic acid, and schikimipicrin ; schikirnic acid, C7Hl0O6, which is present in large quantities, is a white, crystalline compound, insoluble in alcohol, ether, and chloroform, but readily soluble in wat'er, dilute alcohol, and also in concentrated sulphuric acid; it is not precipi- tated from its solution by metallie salts, and is not affected by ferric chloride, Fehling's solution, or smmoniacal silver solution ; an alka- line solution of auric chloride, however, acts on it readily, oxalic acid being formed ; bromine also acts violently on its aqueous solu-. tion ; by fusion with potassium hydroxide, i t appears to yield proto- catechuic acid.It is a strong acid, readily decomposing carbonates ; it melts a t about 178-180" (uncorr.), and bas a speci6c rotatory power = - 200.4", its salts are difficult to crystallise, being very soluble in water. Schihimipicrin forms large, transparent crystals, readily soluble in warm water or alcohol, b u t insoluble in ether, chloroform, and light petroleum, it melts a t 200" (uncorr.), its reaction is neutral, and it has an extremely bitter taste. Analyses of Varieties of Lupines, Beans, and Maize grown under like Conditions. By E. FLECHSIG (Lnndw. Versuchs-Stat., 32, 179-195 j.--Full tables are given, showing the analytical results obtained with 10 varieties of lupines, 12 varieties of beans, and 9 varieties of maize, grown under identical conditions as regards soil, manuring, &c.A. P.96 ABSTRACTS OF CHEMICAL PAPERS. Nitrogenous Organic Compounds in the Soil. By G. LOGES (Landw. Versuchs-Stat., 1885, 201-202).-HydrochIoric acid extracts from the soil, besides humic acid, a nitrogenous compound. This compound could not be separated by dialysis, but it forms a volu- minous, yellow precipitate with phosphotungstic acid. The composition of this humic substance is still uncertain ; samples prepared from two kinds of soils contained N = 6.8 and 6.5 per cent., C = 45.4 and 37.3 per cent. E. W. P.90 ABSTRACTS OF CHEMICAL PAPERS.Chemistry of Vegetable Physiology and Agriculture.Invert Sugar and Selective Fermentation. By E. MAUMENB(Compt. rend., 101, 695).-A contribution to the controversy betweenBerthelot, Leplay, and Maurnen4 on this subject (Abstr., 1885, 1003,1085, 1152).Comparative Researches on the Formation of Amidesduring the Germination of Various Seeds in the Dark.ByB. SCHULZE and E. FLECHSIQ (Landw. Verswhs-Stat., 1885, 137-149).-Altahough we are in possession of much iiiformation con-cerning the change of albumin into nsparagine, yet we are stillignorant whether the %hole of the albumino'ids are converted intoasparagine and its congeners or not. One special object of thisinvestigation was to discover if, when legumes and cereals germinatein the dark under the same conditions, relatively correspondingamounts of amides were produced from the albumin in each.All thedetails of the methods employed and of the analytical results aregiven. The analyses show that in all cases the conversion is verygradual and different, the legumes as a rule producing, not onlyabsolutely but also relatively, larger quantities of amides ; this is mostremarkable in the case of lupines. It may also be taken for grantedthat seeds when germinating do not of necessity produce an amountof amides ah all proportional t o their nitrogen reserve matter, butthat the individual character of the plant itself has very considerableinfluence. E. W. P.Action of Saline Solutions on Germination. Ry M. JARIUS(Landw. Versuchs-Stat., 1885, 149--178).-These experiments wereinstituted with the object of completely answering the question as towhether the solutions of manures in the soil have, or have not, adetrimental action on the germination of the seed sown.The firstportion of the article is occupied in discussing and reviewing otherwork on the subject, after which the author's own experimentsand results are given in very full detail. The strengths of thesaline solutions employed were 0.41, 1.0, and 2.0 per cent., andthe seeds were in some cases allowed to soak for 2 M 8 hours, and inother cases 1-5 days. The solutions employed were of sodium andpotassium chlorides, potassium and ammonium sulphates, cdciumhydrogen phosphate, potassium and sodium nitrates, and a solutioncontaining all the nourishing constituents of plants. Peas steeped ina 2 per cent. solution for 24-48 hours increase in weight and volumeregularly, but this increase is less than that which takes place whendistilled water is employed.After 48 hours, the volume experiences alesser increase than the weight, and this increase is reduced as thesolutions become more concentrated, and the longer the period ofsteeping is continued, so that the ratio between volume and weight in2 per cent. solutions and after 48 hours is the widest, that is, thVEGETABLE PHYSIOLOGY AND AGRICULTURE. 91sp. gr. is then the highest. The sp. gr., as also the increase in weightand volume, is after 24 hours now raised, now lowered, when solutionsof 0.2, 0.4, and 1 per cent. are used. Only in the cases of sodiumchloride and nitrate in all concentrations, and from the beginning tothe end of the steeping, is a constant increase in sp.gr. found ; whilstin the other solutions under all conditions, the increase in weight andvolume is less than that when the liquid is water. The greatestamount of variation is found in the 0.4 and 1.0 per cent. solutionsof salts of potassium after 24 hours. Finally the increase in weightand volume of peas attains its maximum in the shortest possible timethe more concentrated the solutions are ; the time being dependent onthe salt dissolved.The influence of the solutions on germination was tested undervarious conditions, such as 1-5 days with full and partial supply ofair. The resalts are as follows: germination is decidedly aided by0.2-0.4 per cent. solutions, but 1-2 per cent. solutions do harm, theshoots being feeble and abnormal, &c.; this harmful action is themore marked when there is not a plentiful supply of air, and also thegood done by the weaker solutions is less when air is not freelyaccessible to the seed.Leguminosae and Crucifem are much assistedby the " nutritive solution," 0.4 per cent. solutions of potassiumnitrate, and sodium chloride, whilst even 0.2 and 0.4 per cent.Rolutions of ammonium sulphate and calcium hydrogen phosphate aredistinctly harmful to the above classes of plants. Grass seeds arenot liable to much harm. Even 2 per cent. solutions are productiveof good, the most damage being done by sodium chloride and nitratein '2 per cent. solutions; summer rye is less subject to influence,whilst maize is more easily affected for good by 0.4 and 1.0 per cent.solutions than all the other grasses.The results of the investigationshow that no harm can possibly come of the use of manures, as theirsolution in the soil can never be stronger than 0.4 per cent. Still theseed should not be sown immediately on the manure, as in such a,case it is possible that a solution stmnger than 0.4 per cent. may beformed. There is an interesting table given fihowing the ratio betweenthe growths of lthe radicle and plumule of several seeds when subjectduring growth t o various strengths of a solution. E. W P.Composition of the Pollen of the Common Pine. By A. VONPLANTA (Landau. Versuchs-Stat., 1885, 215-'230).-The author fullydescribes every process which he has employed for the estimation ofthe constituents of pollen : the results are as follows :-Water....................N. .......................(N x 6.25 ................Non-nitrogenous matter ....Ash. .....................Hyponanthine and guanine. .Saccharose. ...............Shmh ..................Cuticula.. ................7.66 per cent.2.65 ,,16.56) ,,72.48 ,)3-30 ,,0-04 3Y11.24 ,,7.06 ,,21.97 ,92 ABSTRACTS OF CHEMICAL PAPERS.Wax-like compounds . . . . . .Fatty acids . , . . . . . . . . . . . .. ,,Resinous bitter compounds.. 7.93 ,,3.56 per cent.10.63Under the name cuticula is to be understood that chemicallychanged cellular matter, which overlays stru~turm, and is in directcontact with the air.It was estimated by digesting the pollen forthree days with a 5 per cent. alcoholic potash solution, wherebyfat, &c., was removed from the pollen grains ; the residue was boiledwith semi-normal hydrochloric acid for two hours ; this removed thelast traces of starch, and then ether removed any further solublematters there might be, so that pure cuticula remained.The Sugar of Symphoricarpus Racemosa. By P. HERRMANNand B. TOLLENS ( A n n u l e n , 230, 50-55). - The authors haveexamined the sugar contained in the fruit of Syn?phoricarpus racenzosa,and find that it consists of a mixture of dextrose and laevulose.E. W. P.w. c. w.Conditions of the Development, and of the Activity, ofChlorophyll. By J. H. GILBERT (Brit. A ssoc.,* 1885) .-The foliageof different plants presents a great variety of shades of green, and i tmay be stated that, a t any rate so far as our common agriculturalplants are concerned, somewhat characteristic shades of colour areshown according to the natural order to which they belong, theLeguminosae differing from the Graminze, the Cruciferae, the Cheno-podiaceae, and so on. But the same description of plant will exhibitvery characteristic differences, not only a t different stages of growth,but a t the same stage in different conditions of luxuriance, as affectedby the external conditions of soil, season, manuring, &c., but especi-ally under the influence of different conditions as to manuring.The Rothamsted field experiments show that in a series of com-parable experiments with the same crop, depth of green colour by nomeans necessarily implies a finally greater amount of carbon assimi-lation ; whilst it has long ago been experimentally proved that thedeeper colour was associated with a relatively high percentage ofnitrogen in the dry o r solid substance of the herbage; and thisobviously means a lower relation of carbon to nitrogen.Comparative determinations of the amounts of chlorophyll weremade by Russell in parallel specimens to those in which the authordetermined the percentages of dry matter and of nitrogen.The following table gives the results of some of these experiments;namely, the percentages of nitrogen, and the relative amounts ofchlorophyll, in the separated gramineous, and the separated legu-minous plants, in the mixed herbage of grass land, in specimens ofwheat grown by a purely nitrogenous manure, and by the samenitrogenous manure with a full mineral manure in addition ; and inspecimens of barley grown by a purely nitrogenous manure, and bya mixture of the same nitrogenous manure and mineral manure inaddition.It is to be borne in mind that the specimens were collected* Read in Section B, at the meeting of the British Association at Aberdeen,September, 1885VEGETABLE PHYSIOLOGY AND AGRICULTURE. 93whilstshouldare. asthe plants were still quite green, and actively growing. Itbe further explained t h a t the amounts of chlorophyll recordedstated in the table, relative and not actual ; that is to sa,y, thefigures show the relative amounts for the individual members of eachpair of experiments, and not the comparative amounts as betweenone set of experiments and another.--Hay.Gramineze ...................Leg uminosm .................Wheat.Ammonium salts only..........Ammonium salts and mineralmanure ....................Barley.Ammonium salts only .........Ammonium salts and mineralmanure.. ..................Nitrogenper cent.in drysubstance.1 -1902 -478*la 227+O -566"1 ' 474+O -792Relativeamounts ofchlorop h y 11.A-0 -772 -402 -001 -003'201 *46Carbon assimilatedper acre per annum.Actual.lbs. - -13%222214032088Difference. --lbs.--- 824- 685JI: Not fully dried.Thus the separated leguminous herbage of hay contained a, muchhigher percentage of nitrogen in its dry substance than the separatedgramineous herbage ; and also a much higher proportion of chloro-phyll.Indeed, under comparable conditions, the Leguminosaeeventually maintain a much higher relation of nitrogen to carbonthan the Gramineze; in other words, in their case, carbon is notassimilated in so large a proportion to the nitrogen taken up.The wheat plants manured with ammonium salts alone show amuch higher percentage of nitrogen tham those manured with thesame amount of ammonium salts, but with mineral manure in addi-tion. The high proportion of chlorophyll again goes with the highnitrogen percentage ; but the last column of the table shows that,with the ammonium salts without mineral manure, with the highpercentage of nitrogen, and the high proportion of chlorophyll, inthe dry substance of the green produce, there is eventually verymuch less assimilation of carbon.The result is exactly similar inthe case of barley.It is evident that the chlorophyll formation has a close connectionwith the amount of nitrogen assimilated, but that the carbon assimi-lation is not in proportion to the chlorophyll formed, if there be notn sufficiency .of the necessary mineral constituents available. Nodoubt there had been as much, or more, of both nitrogen assimilated94 ABSTRACTS OF CHEMICAL PAPERS.and chlorophyll formed, over a given area,, where the mineral as we11as the nitrogenous manure had been applied, the lower proportion ofboth in the dry matt,er being due to the greater assimilation of carbonand consequent greater formation of non-nitrogenous substances.It is of interest t o observe that these results of experiments in thefield are perfectJy consistent with those obtained by vegetable physio-logists in the laboratory; they having found that the presence ofcertain mineral, or ash constituents, and especially that of potassium,is essential for the assimilation of carbon, no st,arch being formed inthe grains of chlorophyll withouf; the aid of that substance.Sachssays, " Potassium is as essential for the assimilating activity of chloro-phyll as iron for its production."Adonis Vernalis and Adonidin. By J. MORDAGNE ( P h ~ m . J.Trans.[ 3 ] , 16, 145-146) .-Adonis vernaiis amongst other substancescontains aconitic acid and a glucoside, adonidin. To obtain the latter,the leaves and stalks are dried, extracted with 58" alcohol, treatedwith basic lead acetate, fhe excess of lead removed with sodiumcarbonate, the liquid made alkaline with ammonia, and the glucosideprecipitated by means of tannin. The tannate is digested with zinchydroxide and alcohol at a gentle heat for several hours, the alcoholis then distilled 08, and tEie glucoside extracted with absolute alcohol,carefully evaporated and dried over sulphuric acid. The yield is2 grams per 10 kilos. The substance forms a rather hygroscopiccanary-yellow powder, but, after proloiiged desiccation forms radiatingcrystals, Ammonia prevents crystallisation. It is soluble in water,alcohol, and amyl alcohol'; insoluble in anhydrous ether, chloroform,turpentime oil, and benzene ; and has a persistent bitter taste. Heateda t 80-85" i t loses 3.14 per cent.water, but does not alter physically ;between 85-90" it becomes brown; and at 100" nearly black. Itcontains no nitrogen, ia neutral to litmus, and only reduces Fehling'ssolution when heated with it in presence of hydrochloric acid.Ammonia turns it brown, tannin precipitates it, and basic lead acetateproduces a cloudiness in its solutions, whilst baryta and alkaloidreagents do not react wiCh it. When decomposed, it yields a resinoussubstance soluble in ether, and develops a persistent odour of cut hay.Owing to its imperfect and troublesome crystallisation a good samplecan scarcely be obtained for analysis, but the mean of several experi-ments gives per cent.C, 42,623 ; H, 7 5 4 7 ; 8. = 49.830.D. A. 11.Arum Italicurn. By G. SPICA and Gl BISCARO (Gazzetta, 15, 238-242).-As the symptoms occurring in three cases of poisoning byeating the spadices of the Arum italicurn were peculiar, the authorshave made a chemical and a physiological study of this species, Fromthe spadices, a glucoside has been extracted, identical with saponin ;the symptoms produced by the hypodermic injection of h0t.h sub-stances into frogs were compared, and found to be practically thesame. In both cases, general paralysis of the nervous and muscularsystems supervened, ending, in most cases, in death : the symptomsare not those of tetanus as at first supposed.V. H. VVEGETABLE PHYSIOLOGY AND AGRICULTURE. 95Researches on Gourds. By R. ULBRICHT (Landw. Versuchs-Stat., 1885, 230-240) .--The author details the physical composit#ionof many gourds, showing the proportion of rind to flesh and seed,and the chemical constituents of all parts of various gourds, as wellas the composition of the ash.Illiciurn Religiosum. By J. P. EIJKRIAN (Eec. Trav. Chim., 4,32--54).-The liquid obtained by distilling the leaves and fruits ofI l l i c i u m reZigiosum with water consists of euqenol, a terpene to whichthe author gives the name of schikirnene, and safrole, besides a smallquantity of some indefinite compounds of high boiling point, whichare probably formed by the polymerisation of the previous com-pounds.Schikimene boils at about 170", and i8 a fragrant, limpid,mobile, colourless liquid; its sp. gr. = 0.865 ; with conceiitratedsulphuric acid it yields a magnificent orange colour, and on warmingwith nitric acid it deflagates with violence, it also explodes on con-tact with iodine ; its specific rotatory power is [ a ] , = - 22*5", but ifheated for some time over metallic sodium, it is reduced to - 0.85".The author finds that by heating safrole gently with an equalquantity of an aqueous solution of potassium permsnganate (1 partin 40 of water) piperonic acid is formed (comp. Abstr., 1884,1338), and from this and the measurement of the refractiveindex he considers that the constitution of safrole is probably bestE.W. P.nexpressed by the formula C,H,Pr<~>CHZ [Pr : QCHz = 1 : 3 : 41(compare Abstr., 1884, 1339). The residue left after the removal ofthe above compounds by distillation, when subjected to strong pres-sure, yields a clear syrup which contains protocatechuic acid, schi-kirnic acid, and schikimipicrin ; schikirnic acid, C7Hl0O6, which ispresent in large quantities, is a white, crystalline compound, insolublein alcohol, ether, and chloroform, but readily soluble in wat'er, dilutealcohol, and also in concentrated sulphuric acid; it is not precipi-tated from its solution by metallie salts, and is not affected by ferricchloride, Fehling's solution, or smmoniacal silver solution ; an alka-line solution of auric chloride, however, acts on it readily, oxalicacid being formed ; bromine also acts violently on its aqueous solu-.tion ; by fusion with potassium hydroxide, i t appears to yield proto-catechuic acid. It is a strong acid, readily decomposing carbonates ;it melts a t about 178-180" (uncorr.), and bas a speci6c rotatorypower = - 200.4", its salts are difficult to crystallise, beingvery soluble in water. Schihimipicrin forms large, transparentcrystals, readily soluble in warm water or alcohol, b u t insoluble inether, chloroform, and light petroleum, it melts a t 200" (uncorr.), itsreaction is neutral, and it has an extremely bitter taste.Analyses of Varieties of Lupines, Beans, and Maize grownunder like Conditions. By E. FLECHSIG (Lnndw. Versuchs-Stat.,32, 179-195 j.--Full tables are given, showing the analytical resultsobtained with 10 varieties of lupines, 12 varieties of beans, and9 varieties of maize, grown under identical conditions as regards soil,manuring, &c.A. P96 ABSTRACTS OF CHEMICAL PAPERS.Nitrogenous Organic Compounds in the Soil. By G. LOGES(Landw. Versuchs-Stat., 1885, 201-202).-HydrochIoric acid extractsfrom the soil, besides humic acid, a nitrogenous compound. Thiscompound could not be separated by dialysis, but it forms a volu-minous, yellow precipitate with phosphotungstic acid. The compositionof this humic substance is still uncertain ; samples prepared from twokinds of soils contained N = 6.8 and 6.5 per cent., C = 45.4 and37.3 per cent. E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8865000090

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

96 ABSTRACTS OF CHEMICAL PAPERS. A n a 1 y t i c a 1 Chemistry. Apparatus for the Quick Reduction of Measured Gas Volumes to Normal Condition. By C. WINKLER (Be?.., 18,2533- 2535).-A modification o€ Kreusler's apparatus (Abstr., 1884, 775). New Arrangement of the Volumetric System. By C. WINKLER (Ber., 18, 2527-2533) .-The author thinks that the volumetric system should be derived from the molecular weights, and not from the equivalent weights, as is the case a t present. A Method of Filtration by Means of easily soluble and easily volatile Filters. By F. A. GOOCH (Amer. Chem. J., 7,87- 90).-Anthracene is proposed as a substitute for asbestos for filtering in cases where the use of paper is objectionable. The anthracene is moistened with alcohol, then mixed with water, and applied to a per- forated cone or crucible in the same way as asbestos.If necessary, a finer coating, made by dissolving anthracene in hot alcohol and pre- cipitating by water, is afterwards added. .After filtration, the anthra- cene may be removed by treating in a small beaker with warm benzene ; on adding water the benzene solution rises, and may be removed by filtration through a wet filter-paper if thought necessary. The anthracene may also be removed by gentle heating. H. B. Estimation of Water of Crystallisation in Organic Corn- pounds By E. OSTERHAYER (Chem. Celztr., 1885, 603-604) .-The method described by the author is one employed to estimate the amount of water in the salts of iodonaphtholsulphonic acid, which, like many other organic compounds, loses iodine on heating.A weighed quantity of the salt is heated in a current of dry air in a tube placed in an oil-bath a t 110-120" ; the tube is connected with one containing a silver spiral, and this with a chloride of calcium tube. The silver is gently heated, and combines with the iodine given off, whilst the water is collected by the calcium chloride, the increase in weight of the latter giving the amount of water. Diphenylamine as a Reagent for Free Chlorine. By H. HAGER (Chem. Centr., 1835, 588).-As a very delicate test for traces P. P. B.ANALYTICAL CHEMISTRY. 97 of free chlorine, the author nses a solution of diphenylamine in strong sulphuric acid, poured gently down the side of the vessel containilig the liquid to be t,ested. Should no blue coloration be formed, even after standing for a few minutes with subsequent agitation, a small quantity of pure concentrated sulphuric acid should be added, when even very small traces of free chlorine will show themselves bv a blue ring forming a t the junction of the two liquids.Naphthol as a Reagent for Free Chlorine and Bromine. Bp H. HAGER (Chem. Centr., 1885, 692--693).-A 1 per cent. alcoholic solution is used ; about; 0.5 C.C. of this is poured gently into a narrow cylinder containing 4-5 C.C. of the liquid to be tested. After standing for a few minutes, traces of free chlorine or bromine are shown by the formation of a; milky ring where the two liquids meet. Nitric acid and ferric chloride should be well diluted before apdying the test. J. K. C. J. K. C. Estimation of Iodine.By G. WEISS (Chem. Centr., 1885, 634, and ?12--713).-The author has lately received samples of iodine, which, when estimated by the ordinary method of titration with hyposulphite, gave over 100 per cent. of iodine. This was found to be due to the presence of about 3 per cent. of bromine, an impurity due to the fact that the iodine was obtained from the last mother- liquors in the preparation of nitre, by precipitation as cuprous iodide. The greasy nature of this precipitate renders the complete washing out of the chlorides and bromides present exceedingly uncertain. The author describes a simple method for the quantitative separa- tion of iodine, bromine, and chlorine. The halogens must be present in the form of simple and easily decomposable metallic compounds.Concentrated ferric sulphate solution is added and the whole boiled, when the following reaction takes place : Fe,(S04)9 + 2KI = 2FeS04 + KZSO, + Iz. During the heat'ing, a current of air is passed through the solution, and then into a solution of potassium iodide. When all the iodine has been carried over int,o this latter, it is removed for titra- tion and replaced by dilute ammonia. After the residue in the decomposing flask has cooled, a slight excess of potassium perman- ganate is added to it, and the flask warmed to 50-60". Evolution of bromine soon commences, and the latter is carried over into the ammonia by the current of air, and thvn estimat,ed gravimetricdly or by titration. The chlorine can be estimated in the residue, or better, by difference, from a determination of the total quantity of iodine, bromine, and chlorine present in the original substance.If the halogens are present as oxy-acids, they must be reduced by sulphuretted hydrogen o r other suitable means ; if in the free state they are best converted into zinc iodide by treatment with zinc-dust. L. T. T. Detection and Determination of Fluorine. By G. TAMMANX (Zeit. anal. Chem., 24, 328-343) .-Fresenius' method (Zeit. anal. Chew., 5, 190) of absorbing t,he silicon fluoride by water and weighing gives good results. For destroying admixed carbonates, evaporation with potash-alum is as effective as boiling with acetic acid. Sulphurous VOL. L. h98 ABSTRACTS OF CHEMlOAL PAPERS. anhydride may be arrested by a tube containing chromic acid dissolved in strong sulphuric acid. This does not retain silicon fluoride; whereas solutions of potassium dichromate and permanganate in sulphuric acid, and peroxide of lead as proposed by Kupfer, all absorb the fluoride.I n substances free from boron, fluorine may be detected by heating with quartz powder and sulphuric acid a t 170" in a stream of air, which is then passed through water. As little as 0.0002 gram of fluorine yields a ring of silica in the wetted part of the tube. The water will then contain hydrofluosilicic acid, besides silica, sulphuric acid and a trace of sulphurous acid. Hydrofluosilicic acid is best precipitated by an alcoholic solution of barium bromide or acetate. Barium silicofluoride can be completely washed with 50 per cent. alcohol, 1 litre of which dissolves 0.0257 gram of it.If evaporation be required, the acetate must be used, since acetic acid does not expel hydrofluosilicic acid, whilst hydrobromic acid does. The acetate ~hould be strongly acidified, and the residue must be treated with hydrobrornic acid, to reconvert into silicofluoride any barium fluoride which may ha,ve been formed. It is then washed with 75 per cent. alcohol, converted into snlphate and weighed. Test analyses showed that even in highly dilute solutions, the fluorine can be thus deter- mined without serious loss. Soluble fluorides can be annlysed in similar manner after conversion into silicofluorides by addition of hydrobromic acid and silica. The excess of silica is removed by hydrofluoric a d d after the washing with alcohol.Barium silicofluoride may be separated from the sulphate by igniting the mixture, and extracting the fluoride of barium by hydrochloric acid. Attempts to determine fluorine in fluorspar and cryolite by the above processes gave very low results, owing to the fact observed by Landolt, that the action of moist air on silicon fluoride produces an insoluble compound containing fluorine (5-12 per cent.). This body is not decomposed by evaporation with baryta, but is easiIy solubIe in potash. This led to the following method, which gave good results. To the water in which the silicon fluoride has been absorbed, an excess of potash is added, and the whole evaporated to dryness. The residue is treated with hydrochloric acid, and excess of potassium acetate added.It is then mixed with 3 vols. of 80 per cent. alcohol, and the precipitated potassium silicofluoride titrated with potash (Stolba). The same process may be applied without distillation to soluble fluorides, adding silica before the acid, but with fluorspar, &c., distilla- tion is necessary. Lastly, the author condemns Wilson's method for estimating fluorine in organic compounds, and shows that a loss of from 7 t,o as much as 68 per cent. of the fluorine may take place during the incinera- tion alone, even when much sodium carbonate or baryta is added. M. J. S. Estimation of Carbon in Iron and Steel. By W. GINTL (BingZ. poZyt. J., 257, 527).-The estimation of carbon in iron, according to Wohler's method-heating in a current cif chlorine and igniting the residue to convert the carbon into carbonic anhydride-isANALYTICAL CELEMlSTRY.99 said to give low results, owing to the difficulty of obtaining chlorine free from oxygen. The author proposes to wash and dry the gas carefully, and pass it over a layer of red-hot charcoal, pre- viously ignited in a current of chlorine before applying it to Wiihler's method. D. B. Detection of Thiosulphates i n Water- By G. NEUHUFFER (Chem. Cmty., 16, 459)-Such impurities are to be found in the water obtained from the neighbourhood of gasworks, and at times from those in the neighbGurhood of vineyards. The presence of thio- sulphates may be ascertained by adding lead acetate to a litre of the water, collecting the precipitate, washing, and boiling it with sodium carbonate solution.The filtmte is evaporated to dryness, and the residue is tested for thiosulphates by treating it with hydrochloric acid and pure zinc. P. P. B" Ferrous Ammonium Sulphate as a Reagent for Nitric Acid, By A, ROSA (Gazxetta, 15,295-296) .-Ferrous ammonium snlphate is a delicate reagent for the presence of nitric acid ; it is much more sensitive than ferrous sulphate (compare Abstr., 1884, 493). U. H. V. Diphenylarnine and Crystallised Phenol as Reagents for Nitrates and Nitrites. By H. HAGEB (Chem. Centr., 183.5, 536- 588).-As stock solution, 1 gram of diphenylamine is dissolved in 30 C.C. of absolute alcohol and mixed with four or five times its bulk of pure concentrated sulphuric acid. The liquid to be tested is poured into a test-tube, and the diphenylamine solution allowed to run gently down the side: nitric or nitrous acid in the strength of one drop of a 30 per cent.solution to 60 C.C. of water is easily detected by this test, a blue coloration being formed at the point of contact of the two liquids. The absence of all ohher axidiz- ing or reducing substances must of course be first asoentained. That the blue coloration is not due to chlorine may be ascertained by a control experiment with crystallised phenol in hydrucldoric acid : the liquid to be tested is mixed with this in a test-tube, and sulphuric acid poured gently down the side : a, red coloration is. formed by the presence of nitrogen acids. J. I(. C. Naphthol and Sulphuric Acid as a Reagent for Nitric and Nitrous Acids and Free Chlorine. By H. HAGEE (Chem, Centr., 1885, 693-694).-Mix the liquid to be tested with half its bulk of a, 1 per cent.alcoholic naphthol solution, and pour sulphuric acid gently down the side of the vessel: a brownish-red coloration denotes the presence of nitrogen acids or free chlorine : if no ring is formed, shake up, allow t o stand for a few minutes, and pour in gently pure con- centrated sulphuric acid. J. K. C. Arsenic in Bleaching Powder and in Potassium Chlorate. By L. GARNIER (J. Phann. [ 5 ] , 11, 9).-In 1881, Schlagdenhauffen and the author detected the prssence of arsenic in certain samples of hi4I00 ABSTRACTS OF CHEMICAL PAPERS. bleaching powder. The author reports that recently potassium chlorate, intended to be used in Fresenius and Babo’s method of arsenic estimation in organic matter, was found to contain decided traces of arsenic.The presence of the metal is ascribed to impurity in the chlorine employed in manufacturing the salt. J. T. Estimation of Arsenic in Ores, Mattes and Metallic Copper. By G. W. LEHMANN and W. MAGER (Amer. Chem. J., 7, 112--113). -R. Pearce’s met(hod (Enyin. Mi%. J., 1883, 256) is found to be the most trustworthy and convenient. The material is fused with nitre and sodium carbonate, and the filtered solution acidified with nitric acid and boiled. Silver nitrate and ammoni:t are added, the pre- cipitate of silver arsenate is washed, and the silver in it estimated by Volhsrd’s method. Metallic copper must be dissolved in nitric acid, and the arsenic precipitated as ferric arsenate by addition of a ferric salt and ammonia in excess; the precipitate obtained is treated as above.Satisfactory test analyses are given. H. B. Swedish Method of Testing for Arsenic. By A. ATTERBERG (Chem. Centr., 16, 600-602).-A small portion of the substance is treated in a test-tube with dilute hydrochloric acid, zinc and ferrous sulpbate. A plug of cotton-wool moistened with lead acetate is placed above the mixture, and in the mouth of the test-tube are sus- pended two strips of paper moistened with lead acetate and silver nitrate respectively. If the silver nitrate remains unaltered after 12 hours, the substance is declared free from arsenic. If arsenic is found by the above method, then the substance is distilled with hydrochloric acid and ferrous sulphate. A portion of the distillate is tested for arsenic as above, and in another portion, the arsenic is pre- cipitated RS sulphide, and metallic arsenic obtained from the sulphide by reduction with potassium cyanide and sodium carbonate in a current of carbonic anhydride ; the density of the arsenic mirror de- termining the condemnation, or otherwise, of the goods.The author proposes to evaporate the distillate with nitric acid: the arsenic is then obtained in the form of arsenic acid, the presence of which can be easily recognised by the characteristic reaction with silver nitrate. Eyster’s Scheme for Qualitative Analysis. By R. B. WARDER P. P. B. (Arner. Chem. J., 7, 110-112). Eyster’s scheme is described in Amer. Chem. J., 7, 21-26 ; a modification is here proposed for the detection of cadmium, copper, nickel, and cobalt : the cadmium is precipitated by ammonium sulphide in presence of potassium cyanide ; addition of acetic acid to the filtrate throws down the copper as sulphide, and On adding hydrochloric acid to the filtrate from this, nickel is pre- cipitated as sulphide, whilst the cobalt remains in solution.H. B. Separation of Iron and Aluminium. By M. ILINSPI and G. V. KEORRE (Ber., 18, 2728-2734).-The metals must be present as sul- phates or chlorides, as in the case of nickel and cobalt (this vol., p. 840). The very slightly acid solution is treated with an equal volume of 50 per cent. acetic acid, and an excess of nitroso-P-naphthol (dis-ANALYTICAL CHEMISTRY. 101 solved in 50 per cent. acetic acid), and the whole stirred.After 6-8 hours it is filtered, and the precipitated ferrinitrosonaph tho1 mashed, first with cold 50 per cent. acetic acid, t'hen with water, dried, ignited with pure oxalic acid, and weighed as Fe203. Ferrircitroso-p-nnphthoz, (CIoHsO-N0)3Fe, forms a voluminous brownish-black precipitate, soluble in warm moderately dilute hydro- chloric or sulphuric acid ; it is also soluble in glacial acetic acid and in alcohol. Benzene, aniline, and phenol dissolve it with formation of dark-brown solutions. Warm concentrated potash solution decom- poses it with formation of ferric hydroxide and a green potassium salt of nitrosonaphthol. Ferroiiitroso-P-na~hthol is formed when a very dilute solution of a ferrous salt is treated with an aqueous solution of nitroso-naphthol : the solution becomes green, and after a long time a separation of green flakes of ferronitrosonaphthol takes place.This compound is very susceptible towards free mineral acids, and is therefore not formed in a strong solution of ferrous sulphate. N. H. M. Estimation of Manganese. By DEEHL (Chem. Centr., 1885, 713-714) .-The author previously recommended the estimation of manganese in the presence of iron by precipitation of the mixed oxides, FerOs and MnO,, by hydrogen peroxide, conversion of these by ignition intoMn,O, and Fe203, and estimation of the iron by titra- tion and of the manganese by difference. He now finds that unless carbonates or organic salts of the fixed alkalis are present,, the old method of precipitation of the mixed oxides, Mn,O, and Fe?04, by bromine and ammonia, is as quick, and more exact.Volumetric Estimation of Manganese by Means of Potas- sium Chlorate. By W. HAMPE (Chem. Centr., 1885, 714--715).-1t is well known that potassium chlorate precipibates manganese as peroxide from a boiling solution in concentrated (1.4) nitric acid. The author employs this process in the estimation of manganese in alloys of manganese and iron, &c. The alloy is dissolved in boiling nitric acid, the peroxide precipitated, collected, and titrated. The results are very good. The process may also be used for the estima- tion of manganese in ores, &c. The presence of cobalt, lead, and bismuth is injurious, and necessitates a re-solution and second pre- cipitation of the peroxide. Sulphuric and hydrochloric acids, if present, must be removed by barium nitrate or by boiling with nitric acid respectively.L. T. T. L. T. T. Assay of Nickel Coins. By W. C . ROBERTS (Pharm. J. Trans. [3], 15, 1072).-Half a gram of the alloy is dissolved in a small quantity of nitric acid, 1.5 gram of strong sulphuric acid is added, and the whole evaporated to dryness. The residue is dissolved, diluted to about 60 c.c., put int,o a platinum dish which forms the negative elec- trode of an electric circuit, the positive electrode being a flat platinum spiral suspended in the liquid ; the solution should be distinctly acid ; two pint " gravity " cells are sufficient for the deposition of the cop- per, which is complete in 12 hours, when the copper is washed, &c.102 ABSTRACTS OF CHEMICAL PAPERS.The solution and washings are heated, made ammoniacal, any pre- cipitated iron removed, and evaporated to about 60 c.c., the solution is then put into a platinum dish, and electrolysed, using three cells ; the nickel is deposited forming a white, coherent layer. Nitrates must not be present except in the smallest possible quantity. D. A. L. Electrolysis of Molybdenum Solutions. By E I?. S b m H and W. S. HOSKINSON (Amer. Chem. J., 7, 90--92).-In a previous paper (Amer. Chem. J., 1, No. 5 ) if was shown that molybdenum could be completely separated by electrolysis from alkaline molybdic acid solu- tions, but only after a lapse of 100 hours. It, has since been found that precipitatisn is complete in two to three hours if the solutions employed are faintly acid or neutral.The dense black deposit is in all cases Mo2o3,3H20, and not metallic molybdenum, as stated in the Handaoorterbuch der Chenzie. A number of very satisfactory teat analyses are given. H. B. By J. HERZ (Chem. Certtr., 1885, 5'23),-200 C.C. of the beer are acidified with phosphoric acid, and 100 C.C. distilled over ; the amonnt of sulphurous acid in the distillate is finally determined as barium snlphate. Beer brewed a t the Court Brewery gave by this method from 0.00179 to 0.00261 gram SO2 per litre, whilst 0.00373 gram per litre represents the mean of the results obtained with 84 samples of different beers. In the light of these results, the author would regard as suspicious any beer which, when treated as above, .yields a distillate giving from 5-10 mgrms.of barium sulphate, and if above 10 mgrms. of barium sulphate there can be no doubt as to the presence of sulphites. Oxidation of Carbohydrates by Means of Chromic Acid. By C. F. CROSS and E. J. BEVAN (Chem. News, 52, 207-208).- Having observed considerable qcantities of carbonic oxide in the gas evolved during the oxidation of cellulose, sugar, &c., by means of a mixture of chromic and salphuric acids, the authors have resorted for quantitative work to a volumetric method, and have successfully employed a modification of Schei bler's carbonic anhydride apparatus for the purpose. The chromic acid is introduced in a small tube into a small flask connected with the apparatus, and containing the sub- stance mixed with stroug sulphuric acid, the levels are adjusted, and then the contents of the flask are mixed by inclining and shaking.The authors intend extending the application of this method. Estimation of Uric Acid. By E. LUDWIG (Ghem. Centr., 1885, 523).--100 C.C. of the urine are treated with magnesia mixture and an ammoniacal solution of silver nitrate ; in this way a precipitate of magnesium silver urate and magnesium ammonium phosphate is obtained. The precipitate is digested with a solution of potassium sulphide and filtered, the filtrate cont'ains potassium urate, from which, after concentration, the uric acid is precipitated by hydrochloric acid. The uric acid is collected on a filter of glass-wool, freed from sulphur by washing with carbou bisulphide, dried and weighed. If the urine Determination of Sulphurous Acid in Beer.P. P. B. D. A. L.ANALYTICAL CHEWISTRY. 103 contains albumin this must be first removed by boiling with solution of salt and acetic acid, and treating the filtrate as above. The author finds the precipitation of uric acid by hydrochloric acid is never complete, even after several days. P. P. B. The Detection of Adulteration. in Oils. By 0. C. S. CARTER (Amer. Chem. J., 7, 92-96).-Cotton-seed oil may be detected when added to olive oil or to lard oil, by adding 5 vols. of absolute alcohol and an equal volume of a 1 per cent. solution of silver nitrate in absolute alcohol ; if cot,ton-seed oil is present, the mixture will rapidly darken on warming to 84". The presence of much of the drying oils, such as linseed, hemp-seed, or poppy-seed oil, is shown by treatment with nitrogen peroxide ; they do not solidify from formation of elaidin. The ease and completeness with which an oil may be saponified is a valuable test ; lard oil saponifies easily ; shark-liver oil and African fish oil resist saponification.Detection of Fat Oils in Mineral Oils. By F. Lux (Zeit. anal. Chent., 24, 357--362).--Wben colza oil is heated with potassium, or sodium, or their solid hydroxides, soaps are formed. The higher the temperature, the more rapid is the saponification. Between 200" and 250" the soaps dissolve in the oil, which, on slight cooling, gelatinises or even solidifies (varying with the alkali used). Mineral oils simi- larly treated do not alter in fluidity. The author tested numerous mixtures of petroleum and lubricating oils with colza, linseed, and olive oils, and found that 2 per cent.of the fat oil in all cases, and per cent. in some, could be detected with certainty by the gelatini- sation which occurred on cooling, after 15 minutes' heating a t 300" with sodium or solid caustic soda. With less than 2 per cent., it is necessary to heat the test-tube in a paraffin-bath and to avoid agita- tion during both heating and cooling, but with larger proportions a short boiling over the free flame suffices. Examination of Oils containing Unsaponifiable Fats. By T. MORAWSKI aiid H. DEMSKI (Dinyl. polyt. J., 258, 39-42).-For the estimation of unsaponifiable fats in oils, the authors recommend the following method, having special reference to the difficulty experienced in completely separating the saponified oil from the unsaponifiable fat.10 grams of the oil are treated in a flask with -50 C.C. of alcohol and 5 grams of caustic potash dissolved in a small amount of water. The mixture is boiled for half an hour in a reflux apparatus. The liquid is then diluted with 50 C.C. of water, cooled as ra.pidly as possible, transferred to a separating funnel, and agitated with light petroleurn. The mixture is allowed to settle, the lower layer drawn off, and the petroleum washed repeatedly with water. To remove t'he last particles of water, the petroleum extract is first poured into a dry flask and then transferred to a, tared flask from which the petro- leum is expelled by distillation. Test for Adulteration in Butter. By A. WAGNER (Chem.Centr., 2885, 412--413).-This method depends on the fact that natural H. B. M. J. S. D. B.104 ABSTRACTS OF CHERlICAL PAPERS. butter forms an emulsion much more easily t,han other fats. About 0.6 gram of butter is put in a flask with 12 C.C. of water and 2 drops of a 2 per cent. soda solution, and the whole well shaken ; it is then heated on a water-bath at 37", and transferred to a separating funnel, being washed out with water at the same temperature. From time to time, the emulsion is allowed to run out, being replaced with water at 37" until the water becomes quite clear; it is then carefully run out, and after cooling, the walls of the funnel are covered with a finely divided cheese-like mass if pure butter has been operated'upon, but the presence of any other fat is made apparent by oily drops which are visible also during the previous process.J. K. C. Critical and Experimental Study of the Knop - Hiifner Method of determining Urea. By C. JACOBJ (Zeit. anaZ. Chern., 24, 307-328).-The author defends the hypobromite process against the objections of Arnold (Bbstr., 1883, 1141), and maintains that if the operation be carried out in a uniform way, the use of an empirical constant for calculabing the nitrogen into urea will always give satisfactory results. Hufner by using 5 C.C. of a 1 per cent. urea solu- tion and 100 C.C. of Knop's original bypobromite reagent, obtained 354.3 C.C. of nitrogen (at 0" and 760 mm.) from 1 gram of urea. Using this constant, the author made a series of determiuations with pure urea solutions, varying in strength from 0.666 to 3.0 per cent. by both the Liebig-Pfluger and the Knop-Hiifner methods, and found that the latter gave on the whole the smaller errors.These were in almost all cases errors of deficit, and the deficiency increased some- what-though not proportionally-with the strength of the urea solution, whilst Liebig's method gave more irregular results, some- times much above the truth. With normal urine, and also with that of fever patients, Liebig's method invariably gave higher numbers than Hufner's, the difference being greatest with the pathological urine. With diabetic urine, containing 3 or 4 per cent. of sugar, Hufner's method still gave the lower numbers, but with a specimen containing 6 per cent., the use of the constant 354.3 led to a result higher than that yielded by Liebig's process. Determinations by both methods in solutions of pure urea, to which varying quantities of grape-sugar had been added, showed that the amount of nitrogen liberated increases with increasing quantities of sugar, although with as much as 6 per cent.it did not reach its theoretical limit. Sub- stituting f o r the sugar 1 to 5 per cent. of ethylic acetoacetate (the presence of which in diabetic urine has been suspected), practically the theoretical quantity of nitrogen was obtained, instead of the usual deficiency of 8 per cent., and with healthy urine, to which 1 per cent. of the ether had been added, the use of the theoretical constant 371.4 gave approximately the same results as the use of 354.3 in the ab- sence of the ether.Liebig's method gave higher results, supporting the view that mercuric nitrate precipitates other substances from urine besides urea. The author recommends that 4 per cent. of the ether should be added to diabetic urine, and the constant 371.4 used in the calculation. Finally it is argued that the results of this method are affectedANALYTICAL CHEMISTRY. 105 only to an insignificant extent by the other nitrogenous constituents of urine, except albumin and ammonia salts, of which the former is easily removed, and the latter, even if it be not right to calculate it as urea (which is almost certainly formed in the system by the de- hydration of ammonium carbonate), can be determined by Schlosing's or Schmiedeberg's method, and allowed for.M. J. S. Presence of Glutamine in Sugar-beet. By E. SCHULZE and E. BOSSHARD (Landw. Versuchs-Xtat., 1885, 129--136).-1n a previous communicat,ion (Abstr., 1885, 658), the authors have shown that glutaminc can be precipitated by means of mercuric nitrate from the juice of sugar-beet ; Scheibler has also obtained glutamic acid from beet molasses. In this paper the method employed to precipitate and estimate the glutamine in the crude juice is described; the quantity (1 gram per litre) obtained by this process is far below that which is really present (5.96 grams per litre) ; the difference is due to the imperfect precipitation, &c. It is this glutaminc which, after boiling, is converted into the glutamic acid detected by Scheibler. Estimation of Alkaloids in the Leaves of Atropa Bella- donna.By W. R. DUNSTAN and P. RANSOM (Pharm. J. Tyans. [3], 16, 237-238).--20 grams of dried and finely-powdered leaves are exhausted with about 100 C.C. of absolute alcohol. The alcoholic liquid is diluted with about an equal volume of water slightly acidified with hydrochloric acid, warmed and extracted with chloroform to remove chlorophyll, fat, &c. The aqueous residue is rendered alkaline with ammonia and again extracted with chloroform. The chloroform solution on evaporation leaves a residue of the pure alkaloid which is dried at 100" and weighed. Foreign leaves have been found to con- tain 0.22 per cent. total alkaloid, and English leaves overheated in drying 0.15 per cent. E. W. P. D. A. L. Sulpho-conjugate Colouring Matter in Wines. By CARLES (J.Phscrm. [5], 11, 109--110).-The author finds that the method recommended for the detection of these colouring matters in wine is not generally applicable. It consists in removing sulphates by means of barium chloride, removing the barium salt by means of an alkaline carbonate, then evaporatirig and calcining the residue ; sulphates thus produced are supposed to indicate the artificial colouring matters jn question. Erroneous results were obtained not only with wines known to be pure non-plastered, but also with wines made by the author from choice grapes in glass vessels (1) without any addition, ( 2 ) plastered with sulphurous gelatin. J. T. By W. CHLUDINSKY (Landw. Versuchs-Stat., 1885, 117--128).-The author describes his method of estimating the composition of fleeces, and enters into considerable detail concerning the apparatus (Eurianalyser) which he has designed for the removal of the grease by means of carbon bisulphide.As regards the composition of various wools, it is stated that the hygroscopic properties of different wools are almost Composition of Long-wool and Merino Fleeces.106 ABSTRACTS OF CHEMICAL PAPERS. identical ; merino fleeces have less impurity in them than other fleeces, but are richer in insoluble suint ; of other than merinos, Southdown fleeces are most largely contaminated with impurities, whilst the highest percentage of pure wools is found in fleeces from short-tailed sheep. E. W. P. Diagnosis of Keratin in Animal Tissues. By H. STEINBREGGE (Zeit. Biol., 21, 631--635).-The author has applied Ewald and Kuhne’s method (Verh.Med. Vereins z. Beidelberg, 1, 4.51) to the investigation of the tissues of the ear of mammalia for the presence of keratine as a normal constituent, which was a probability to be inferred from the morphological relationship of the tissues to the ectoderm of the ovum. The sections examined were 20 in number, obtained from various sources. They were digested in a trypsin solution prepared in the usual way from pancreas. Very divergent results were obtained in regard to the degree of resistance to the act,ion of this solution, which was the criterion adopted by the authors above mentioned for the presence of keratin. Investigation showed that these divergencies corresponded with the degree of action of the hardening solutions employed in preparing the tissues for cutting, and that the criterion in questioc is worthless.C. F. C.96 ABSTRACTS OF CHEMICAL PAPERS.A n a 1 y t i c a 1 Chemistry.Apparatus for the Quick Reduction of Measured GasVolumes to Normal Condition. By C. WINKLER (Be?.., 18,2533-2535).-A modification o€ Kreusler's apparatus (Abstr., 1884, 775).New Arrangement of the Volumetric System. By C. WINKLER(Ber., 18, 2527-2533) .-The author thinks that the volumetricsystem should be derived from the molecular weights, and not fromthe equivalent weights, as is the case a t present.A Method of Filtration by Means of easily soluble andeasily volatile Filters. By F. A. GOOCH (Amer. Chem. J., 7,87-90).-Anthracene is proposed as a substitute for asbestos for filteringin cases where the use of paper is objectionable.The anthracene ismoistened with alcohol, then mixed with water, and applied to a per-forated cone or crucible in the same way as asbestos. If necessary, afiner coating, made by dissolving anthracene in hot alcohol and pre-cipitating by water, is afterwards added. .After filtration, the anthra-cene may be removed by treating in a small beaker with warm benzene ;on adding water the benzene solution rises, and may be removedby filtration through a wet filter-paper if thought necessary. Theanthracene may also be removed by gentle heating. H. B.Estimation of Water of Crystallisation in Organic Corn-pounds By E. OSTERHAYER (Chem. Celztr., 1885, 603-604) .-Themethod described by the author is one employed to estimate theamount of water in the salts of iodonaphtholsulphonic acid, which,like many other organic compounds, loses iodine on heating.Aweighed quantity of the salt is heated in a current of dry air in a tubeplaced in an oil-bath a t 110-120" ; the tube is connected with onecontaining a silver spiral, and this with a chloride of calcium tube.The silver is gently heated, and combines with the iodine given off,whilst the water is collected by the calcium chloride, the increase inweight of the latter giving the amount of water.Diphenylamine as a Reagent for Free Chlorine. By H.HAGER (Chem. Centr., 1835, 588).-As a very delicate test for tracesP. P. BANALYTICAL CHEMISTRY. 97of free chlorine, the author nses a solution of diphenylamine in strongsulphuric acid, poured gently down the side of the vessel containiligthe liquid to be t,ested.Should no blue coloration be formed, evenafter standing for a few minutes with subsequent agitation, a smallquantity of pure concentrated sulphuric acid should be added, wheneven very small traces of free chlorine will show themselves bv a bluering forming a t the junction of the two liquids.Naphthol as a Reagent for Free Chlorine and Bromine. BpH. HAGER (Chem. Centr., 1885, 692--693).-A 1 per cent. alcoholicsolution is used ; about; 0.5 C.C. of this is poured gently into a narrowcylinder containing 4-5 C.C. of the liquid to be tested. After standingfor a few minutes, traces of free chlorine or bromine are shown bythe formation of a; milky ring where the two liquids meet.Nitricacid and ferric chloride should be well diluted before apdying thetest. J. K. C.J. K. C.Estimation of Iodine. By G. WEISS (Chem. Centr., 1885, 634,and ?12--713).-The author has lately received samples of iodine,which, when estimated by the ordinary method of titration withhyposulphite, gave over 100 per cent. of iodine. This was found tobe due to the presence of about 3 per cent. of bromine, an impuritydue to the fact that the iodine was obtained from the last mother-liquors in the preparation of nitre, by precipitation as cuprous iodide.The greasy nature of this precipitate renders the complete washingout of the chlorides and bromides present exceedingly uncertain.The author describes a simple method for the quantitative separa-tion of iodine, bromine, and chlorine.The halogens must be presentin the form of simple and easily decomposable metallic compounds.Concentrated ferric sulphate solution is added and the whole boiled,when the following reaction takes place : Fe,(S04)9 + 2KI = 2FeS04 + KZSO, + Iz. During the heat'ing, a current of air is passed throughthe solution, and then into a solution of potassium iodide. When allthe iodine has been carried over int,o this latter, it is removed for titra-tion and replaced by dilute ammonia. After the residue in thedecomposing flask has cooled, a slight excess of potassium perman-ganate is added to it, and the flask warmed to 50-60". Evolutionof bromine soon commences, and the latter is carried over into theammonia by the current of air, and thvn estimat,ed gravimetricdly orby titration. The chlorine can be estimated in the residue, or better,by difference, from a determination of the total quantity of iodine,bromine, and chlorine present in the original substance.If the halogens are present as oxy-acids, they must be reduced bysulphuretted hydrogen o r other suitable means ; if in the free statethey are best converted into zinc iodide by treatment with zinc-dust.L. T.T.Detection and Determination of Fluorine. By G. TAMMANX(Zeit. anal. Chem., 24, 328-343) .-Fresenius' method (Zeit. anal.Chew., 5, 190) of absorbing t,he silicon fluoride by water and weighinggives good results. For destroying admixed carbonates, evaporationwith potash-alum is as effective as boiling with acetic acid.SulphurousVOL. L. 98 ABSTRACTS OF CHEMlOAL PAPERS.anhydride may be arrested by a tube containing chromic acid dissolvedin strong sulphuric acid. This does not retain silicon fluoride;whereas solutions of potassium dichromate and permanganate insulphuric acid, and peroxide of lead as proposed by Kupfer, allabsorb the fluoride.I n substances free from boron, fluorine may be detected by heatingwith quartz powder and sulphuric acid a t 170" in a stream of air,which is then passed through water. As little as 0.0002 gram offluorine yields a ring of silica in the wetted part of the tube. Thewater will then contain hydrofluosilicic acid, besides silica, sulphuricacid and a trace of sulphurous acid.Hydrofluosilicic acid is bestprecipitated by an alcoholic solution of barium bromide or acetate.Barium silicofluoride can be completely washed with 50 per cent.alcohol, 1 litre of which dissolves 0.0257 gram of it. If evaporationbe required, the acetate must be used, since acetic acid does not expelhydrofluosilicic acid, whilst hydrobromic acid does. The acetate~hould be strongly acidified, and the residue must be treated withhydrobrornic acid, to reconvert into silicofluoride any barium fluoridewhich may ha,ve been formed. It is then washed with 75 per cent.alcohol, converted into snlphate and weighed. Test analyses showedthat even in highly dilute solutions, the fluorine can be thus deter-mined without serious loss.Soluble fluorides can be annlysed insimilar manner after conversion into silicofluorides by addition ofhydrobromic acid and silica. The excess of silica is removed byhydrofluoric a d d after the washing with alcohol.Barium silicofluoride may be separated from the sulphate by ignitingthe mixture, and extracting the fluoride of barium by hydrochloricacid.Attempts to determine fluorine in fluorspar and cryolite by the aboveprocesses gave very low results, owing to the fact observed by Landolt,that the action of moist air on silicon fluoride produces an insolublecompound containing fluorine (5-12 per cent.). This body is notdecomposed by evaporation with baryta, but is easiIy solubIe in potash.This led to the following method, which gave good results.To thewater in which the silicon fluoride has been absorbed, an excess ofpotash is added, and the whole evaporated to dryness. The residueis treated with hydrochloric acid, and excess of potassium acetateadded. It is then mixed with 3 vols. of 80 per cent. alcohol, and theprecipitated potassium silicofluoride titrated with potash (Stolba).The same process may be applied without distillation to solublefluorides, adding silica before the acid, but with fluorspar, &c., distilla-tion is necessary.Lastly, the author condemns Wilson's method for estimatingfluorine in organic compounds, and shows that a loss of from 7 t,o asmuch as 68 per cent. of the fluorine may take place during the incinera-tion alone, even when much sodium carbonate or baryta is added.M.J. S.Estimation of Carbon in Iron and Steel. By W. GINTL(BingZ. poZyt. J., 257, 527).-The estimation of carbon in iron,according to Wohler's method-heating in a current cif chlorine andigniting the residue to convert the carbon into carbonic anhydride-iANALYTICAL CELEMlSTRY. 99said to give low results, owing to the difficulty of obtainingchlorine free from oxygen. The author proposes to wash and drythe gas carefully, and pass it over a layer of red-hot charcoal, pre-viously ignited in a current of chlorine before applying it to Wiihler'smethod. D. B.Detection of Thiosulphates i n Water- By G. NEUHUFFER(Chem. Cmty., 16, 459)-Such impurities are to be found in thewater obtained from the neighbourhood of gasworks, and at timesfrom those in the neighbGurhood of vineyards.The presence of thio-sulphates may be ascertained by adding lead acetate to a litre of thewater, collecting the precipitate, washing, and boiling it with sodiumcarbonate solution. The filtmte is evaporated to dryness, and theresidue is tested for thiosulphates by treating it with hydrochloricacid and pure zinc. P. P. B"Ferrous Ammonium Sulphate as a Reagent for Nitric Acid,By A, ROSA (Gazxetta, 15,295-296) .-Ferrous ammonium snlphate isa delicate reagent for the presence of nitric acid ; it is much moresensitive than ferrous sulphate (compare Abstr., 1884, 493).U. H. V.Diphenylarnine and Crystallised Phenol as Reagents forNitrates and Nitrites.By H. HAGEB (Chem. Centr., 183.5, 536-588).-As stock solution, 1 gram of diphenylamine is dissolved in30 C.C. of absolute alcohol and mixed with four or five times its bulkof pure concentrated sulphuric acid. The liquid to be tested ispoured into a test-tube, and the diphenylamine solution allowed torun gently down the side: nitric or nitrous acid in the strengthof one drop of a 30 per cent. solution to 60 C.C. of water is easilydetected by this test, a blue coloration being formed at the pointof contact of the two liquids. The absence of all ohher axidiz-ing or reducing substances must of course be first asoentained. Thatthe blue coloration is not due to chlorine may be ascertained by acontrol experiment with crystallised phenol in hydrucldoric acid : theliquid to be tested is mixed with this in a test-tube, and sulphuricacid poured gently down the side : a, red coloration is.formed by thepresence of nitrogen acids. J. I(. C.Naphthol and Sulphuric Acid as a Reagent for Nitric andNitrous Acids and Free Chlorine. By H. HAGEE (Chem, Centr.,1885, 693-694).-Mix the liquid to be tested with half its bulk of a,1 per cent. alcoholic naphthol solution, and pour sulphuric acid gentlydown the side of the vessel: a brownish-red coloration denotes thepresence of nitrogen acids or free chlorine : if no ring is formed, shakeup, allow t o stand for a few minutes, and pour in gently pure con-centrated sulphuric acid. J. K. C.Arsenic in Bleaching Powder and in Potassium Chlorate.By L.GARNIER (J. Phann. [ 5 ] , 11, 9).-In 1881, Schlagdenhauffen andthe author detected the prssence of arsenic in certain samples ofhiI00 ABSTRACTS OF CHEMICAL PAPERS.bleaching powder. The author reports that recently potassiumchlorate, intended to be used in Fresenius and Babo’s method ofarsenic estimation in organic matter, was found to contain decidedtraces of arsenic. The presence of the metal is ascribed to impurityin the chlorine employed in manufacturing the salt. J. T.Estimation of Arsenic in Ores, Mattes and Metallic Copper.By G. W. LEHMANN and W. MAGER (Amer. Chem. J., 7, 112--113).-R. Pearce’s met(hod (Enyin. Mi%. J., 1883, 256) is found to be themost trustworthy and convenient. The material is fused with nitreand sodium carbonate, and the filtered solution acidified with nitricacid and boiled.Silver nitrate and ammoni:t are added, the pre-cipitate of silver arsenate is washed, and the silver in it estimated byVolhsrd’s method. Metallic copper must be dissolved in nitric acid,and the arsenic precipitated as ferric arsenate by addition of a ferricsalt and ammonia in excess; the precipitate obtained is treated asabove. Satisfactory test analyses are given. H. B.Swedish Method of Testing for Arsenic. By A. ATTERBERG(Chem. Centr., 16, 600-602).-A small portion of the substance istreated in a test-tube with dilute hydrochloric acid, zinc and ferroussulpbate. A plug of cotton-wool moistened with lead acetate isplaced above the mixture, and in the mouth of the test-tube are sus-pended two strips of paper moistened with lead acetate and silvernitrate respectively.If the silver nitrate remains unaltered after12 hours, the substance is declared free from arsenic. If arsenicis found by the above method, then the substance is distilled withhydrochloric acid and ferrous sulphate. A portion of the distillate istested for arsenic as above, and in another portion, the arsenic is pre-cipitated RS sulphide, and metallic arsenic obtained from the sulphideby reduction with potassium cyanide and sodium carbonate in acurrent of carbonic anhydride ; the density of the arsenic mirror de-termining the condemnation, or otherwise, of the goods. The authorproposes to evaporate the distillate with nitric acid: the arsenic isthen obtained in the form of arsenic acid, the presence of which canbe easily recognised by the characteristic reaction with silver nitrate.Eyster’s Scheme for Qualitative Analysis.By R. B. WARDERP. P. B.(Arner. Chem. J., 7, 110-112). Eyster’s scheme is described in Amer.Chem. J., 7, 21-26 ; a modification is here proposed for the detectionof cadmium, copper, nickel, and cobalt : the cadmium is precipitatedby ammonium sulphide in presence of potassium cyanide ; additionof acetic acid to the filtrate throws down the copper as sulphide, andOn adding hydrochloric acid to the filtrate from this, nickel is pre-cipitated as sulphide, whilst the cobalt remains in solution. H. B.Separation of Iron and Aluminium. By M. ILINSPI and G. V.KEORRE (Ber., 18, 2728-2734).-The metals must be present as sul-phates or chlorides, as in the case of nickel and cobalt (this vol.,p.840). The very slightly acid solution is treated with an equal volumeof 50 per cent. acetic acid, and an excess of nitroso-P-naphthol (disANALYTICAL CHEMISTRY. 101solved in 50 per cent. acetic acid), and the whole stirred. After6-8 hours it is filtered, and the precipitated ferrinitrosonaph tho1mashed, first with cold 50 per cent. acetic acid, t'hen with water,dried, ignited with pure oxalic acid, and weighed as Fe203.Ferrircitroso-p-nnphthoz, (CIoHsO-N0)3Fe, forms a voluminousbrownish-black precipitate, soluble in warm moderately dilute hydro-chloric or sulphuric acid ; it is also soluble in glacial acetic acid andin alcohol.Benzene, aniline, and phenol dissolve it with formation ofdark-brown solutions. Warm concentrated potash solution decom-poses it with formation of ferric hydroxide and a green potassiumsalt of nitrosonaphthol.Ferroiiitroso-P-na~hthol is formed when a very dilute solution of aferrous salt is treated with an aqueous solution of nitroso-naphthol :the solution becomes green, and after a long time a separation ofgreen flakes of ferronitrosonaphthol takes place. This compound isvery susceptible towards free mineral acids, and is therefore notformed in a strong solution of ferrous sulphate. N. H. M.Estimation of Manganese. By DEEHL (Chem. Centr., 1885,713-714) .-The author previously recommended the estimation ofmanganese in the presence of iron by precipitation of the mixedoxides, FerOs and MnO,, by hydrogen peroxide, conversion of theseby ignition intoMn,O, and Fe203, and estimation of the iron by titra-tion and of the manganese by difference.He now finds that unlesscarbonates or organic salts of the fixed alkalis are present,, the oldmethod of precipitation of the mixed oxides, Mn,O, and Fe?04, bybromine and ammonia, is as quick, and more exact.Volumetric Estimation of Manganese by Means of Potas-sium Chlorate. By W. HAMPE (Chem. Centr., 1885, 714--715).-1tis well known that potassium chlorate precipibates manganese asperoxide from a boiling solution in concentrated (1.4) nitric acid.The author employs this process in the estimation of manganese inalloys of manganese and iron, &c.The alloy is dissolved in boilingnitric acid, the peroxide precipitated, collected, and titrated. Theresults are very good. The process may also be used for the estima-tion of manganese in ores, &c. The presence of cobalt, lead, andbismuth is injurious, and necessitates a re-solution and second pre-cipitation of the peroxide. Sulphuric and hydrochloric acids, ifpresent, must be removed by barium nitrate or by boiling with nitricacid respectively. L. T. T.L. T. T.Assay of Nickel Coins. By W. C . ROBERTS (Pharm. J. Trans.[3], 15, 1072).-Half a gram of the alloy is dissolved in a smallquantity of nitric acid, 1.5 gram of strong sulphuric acid is added, andthe whole evaporated to dryness. The residue is dissolved, diluted toabout 60 c.c., put int,o a platinum dish which forms the negative elec-trode of an electric circuit, the positive electrode being a flat platinumspiral suspended in the liquid ; the solution should be distinctly acid ;two pint " gravity " cells are sufficient for the deposition of the cop-per, which is complete in 12 hours, when the copper is washed, &c102 ABSTRACTS OF CHEMICAL PAPERS.The solution and washings are heated, made ammoniacal, any pre-cipitated iron removed, and evaporated to about 60 c.c., the solutionis then put into a platinum dish, and electrolysed, using three cells ;the nickel is deposited forming a white, coherent layer.Nitrates mustnot be present except in the smallest possible quantity. D. A. L.Electrolysis of Molybdenum Solutions.By E I?. S b m H andW. S. HOSKINSON (Amer. Chem. J., 7, 90--92).-In a previous paper(Amer. Chem. J., 1, No. 5 ) if was shown that molybdenum could becompletely separated by electrolysis from alkaline molybdic acid solu-tions, but only after a lapse of 100 hours. It, has since been foundthat precipitatisn is complete in two to three hours if the solutionsemployed are faintly acid or neutral. The dense black deposit is inall cases Mo2o3,3H20, and not metallic molybdenum, as stated inthe Handaoorterbuch der Chenzie. A number of very satisfactory teatanalyses are given. H. B.By J. HERZ(Chem. Certtr., 1885, 5'23),-200 C.C. of the beer are acidified withphosphoric acid, and 100 C.C. distilled over ; the amonnt of sulphurousacid in the distillate is finally determined as barium snlphate.Beerbrewed a t the Court Brewery gave by this method from 0.00179 to0.00261 gram SO2 per litre, whilst 0.00373 gram per litre representsthe mean of the results obtained with 84 samples of different beers.In the light of these results, the author would regard as suspiciousany beer which, when treated as above, .yields a distillate giving from5-10 mgrms. of barium sulphate, and if above 10 mgrms. of bariumsulphate there can be no doubt as to the presence of sulphites.Oxidation of Carbohydrates by Means of Chromic Acid.By C. F. CROSS and E. J. BEVAN (Chem. News, 52, 207-208).-Having observed considerable qcantities of carbonic oxide in the gasevolved during the oxidation of cellulose, sugar, &c., by means of amixture of chromic and salphuric acids, the authors have resortedfor quantitative work to a volumetric method, and have successfullyemployed a modification of Schei bler's carbonic anhydride apparatusfor the purpose.The chromic acid is introduced in a small tube intoa small flask connected with the apparatus, and containing the sub-stance mixed with stroug sulphuric acid, the levels are adjusted, andthen the contents of the flask are mixed by inclining and shaking.The authors intend extending the application of this method.Estimation of Uric Acid. By E. LUDWIG (Ghem. Centr., 1885,523).--100 C.C. of the urine are treated with magnesia mixture andan ammoniacal solution of silver nitrate ; in this way a precipitate ofmagnesium silver urate and magnesium ammonium phosphate isobtained.The precipitate is digested with a solution of potassiumsulphide and filtered, the filtrate cont'ains potassium urate, from which,after concentration, the uric acid is precipitated by hydrochloric acid.The uric acid is collected on a filter of glass-wool, freed from sulphurby washing with carbou bisulphide, dried and weighed. If the urineDetermination of Sulphurous Acid in Beer.P. P. B.D. A. LANALYTICAL CHEWISTRY. 103contains albumin this must be first removed by boiling with solution ofsalt and acetic acid, and treating the filtrate as above. The authorfinds the precipitation of uric acid by hydrochloric acid is nevercomplete, even after several days. P.P. B.The Detection of Adulteration. in Oils. By 0. C. S. CARTER(Amer. Chem. J., 7, 92-96).-Cotton-seed oil may be detected whenadded to olive oil or to lard oil, by adding 5 vols. of absolute alcoholand an equal volume of a 1 per cent. solution of silver nitrate inabsolute alcohol ; if cot,ton-seed oil is present, the mixture will rapidlydarken on warming to 84". The presence of much of the drying oils,such as linseed, hemp-seed, or poppy-seed oil, is shown by treatmentwith nitrogen peroxide ; they do not solidify from formation of elaidin.The ease and completeness with which an oil may be saponified is avaluable test ; lard oil saponifies easily ; shark-liver oil and Africanfish oil resist saponification.Detection of Fat Oils in Mineral Oils.By F. Lux (Zeit. anal.Chent., 24, 357--362).--Wben colza oil is heated with potassium,or sodium, or their solid hydroxides, soaps are formed. The higher thetemperature, the more rapid is the saponification. Between 200" and250" the soaps dissolve in the oil, which, on slight cooling, gelatinisesor even solidifies (varying with the alkali used). Mineral oils simi-larly treated do not alter in fluidity. The author tested numerousmixtures of petroleum and lubricating oils with colza, linseed, andolive oils, and found that 2 per cent. of the fat oil in all cases, andper cent. in some, could be detected with certainty by the gelatini-sation which occurred on cooling, after 15 minutes' heating a t 300"with sodium or solid caustic soda. With less than 2 per cent., it isnecessary to heat the test-tube in a paraffin-bath and to avoid agita-tion during both heating and cooling, but with larger proportions ashort boiling over the free flame suffices.Examination of Oils containing Unsaponifiable Fats.By T.MORAWSKI aiid H. DEMSKI (Dinyl. polyt. J., 258, 39-42).-For theestimation of unsaponifiable fats in oils, the authors recommend thefollowing method, having special reference to the difficulty experiencedin completely separating the saponified oil from the unsaponifiablefat. 10 grams of the oil are treated in a flask with -50 C.C. of alcoholand 5 grams of caustic potash dissolved in a small amount of water.The mixture is boiled for half an hour in a reflux apparatus. Theliquid is then diluted with 50 C.C.of water, cooled as ra.pidly aspossible, transferred to a separating funnel, and agitated with lightpetroleurn. The mixture is allowed to settle, the lower layer drawnoff, and the petroleum washed repeatedly with water. To removet'he last particles of water, the petroleum extract is first poured into adry flask and then transferred to a, tared flask from which the petro-leum is expelled by distillation.Test for Adulteration in Butter. By A. WAGNER (Chem. Centr.,2885, 412--413).-This method depends on the fact that naturalH. B.M. J. S.D. B104 ABSTRACTS OF CHERlICAL PAPERS.butter forms an emulsion much more easily t,han other fats. About0.6 gram of butter is put in a flask with 12 C.C. of water and 2 dropsof a 2 per cent.soda solution, and the whole well shaken ; it is thenheated on a water-bath at 37", and transferred to a separating funnel,being washed out with water at the same temperature. From timeto time, the emulsion is allowed to run out, being replaced with waterat 37" until the water becomes quite clear; it is then carefully run out,and after cooling, the walls of the funnel are covered with a finelydivided cheese-like mass if pure butter has been operated'upon, butthe presence of any other fat is made apparent by oily drops whichare visible also during the previous process. J. K. C.Critical and Experimental Study of the Knop - HiifnerMethod of determining Urea. By C. JACOBJ (Zeit. anaZ. Chern.,24, 307-328).-The author defends the hypobromite process againstthe objections of Arnold (Bbstr., 1883, 1141), and maintains that ifthe operation be carried out in a uniform way, the use of an empiricalconstant for calculabing the nitrogen into urea will always givesatisfactory results.Hufner by using 5 C.C. of a 1 per cent. urea solu-tion and 100 C.C. of Knop's original bypobromite reagent, obtained354.3 C.C. of nitrogen (at 0" and 760 mm.) from 1 gram of urea.Using this constant, the author made a series of determiuations withpure urea solutions, varying in strength from 0.666 to 3.0 per cent.by both the Liebig-Pfluger and the Knop-Hiifner methods, and foundthat the latter gave on the whole the smaller errors. These were inalmost all cases errors of deficit, and the deficiency increased some-what-though not proportionally-with the strength of the ureasolution, whilst Liebig's method gave more irregular results, some-times much above the truth.With normal urine, and also with thatof fever patients, Liebig's method invariably gave higher numbersthan Hufner's, the difference being greatest with the pathologicalurine. With diabetic urine, containing 3 or 4 per cent. of sugar,Hufner's method still gave the lower numbers, but with a specimencontaining 6 per cent., the use of the constant 354.3 led to a resulthigher than that yielded by Liebig's process. Determinations byboth methods in solutions of pure urea, to which varying quantitiesof grape-sugar had been added, showed that the amount of nitrogenliberated increases with increasing quantities of sugar, although withas much as 6 per cent.it did not reach its theoretical limit. Sub-stituting f o r the sugar 1 to 5 per cent. of ethylic acetoacetate (thepresence of which in diabetic urine has been suspected), practicallythe theoretical quantity of nitrogen was obtained, instead of the usualdeficiency of 8 per cent., and with healthy urine, to which 1 per cent.of the ether had been added, the use of the theoretical constant 371.4gave approximately the same results as the use of 354.3 in the ab-sence of the ether. Liebig's method gave higher results, supportingthe view that mercuric nitrate precipitates other substances fromurine besides urea. The author recommends that 4 per cent. of theether should be added to diabetic urine, and the constant 371.4 usedin the calculation.Finally it is argued that the results of this method are affecteANALYTICAL CHEMISTRY.105only to an insignificant extent by the other nitrogenous constituentsof urine, except albumin and ammonia salts, of which the former iseasily removed, and the latter, even if it be not right to calculate itas urea (which is almost certainly formed in the system by the de-hydration of ammonium carbonate), can be determined by Schlosing'sor Schmiedeberg's method, and allowed for. M. J. S.Presence of Glutamine in Sugar-beet. By E. SCHULZE andE. BOSSHARD (Landw. Versuchs-Xtat., 1885, 129--136).-1n a previouscommunicat,ion (Abstr., 1885, 658), the authors have shown thatglutaminc can be precipitated by means of mercuric nitrate from thejuice of sugar-beet ; Scheibler has also obtained glutamic acid frombeet molasses. In this paper the method employed to precipitate andestimate the glutamine in the crude juice is described; the quantity(1 gram per litre) obtained by this process is far below that which isreally present (5.96 grams per litre) ; the difference is due to theimperfect precipitation, &c.It is this glutaminc which, after boiling,is converted into the glutamic acid detected by Scheibler.Estimation of Alkaloids in the Leaves of Atropa Bella-donna. By W. R. DUNSTAN and P. RANSOM (Pharm. J. Tyans. [3],16, 237-238).--20 grams of dried and finely-powdered leaves areexhausted with about 100 C.C. of absolute alcohol. The alcoholicliquid is diluted with about an equal volume of water slightly acidifiedwith hydrochloric acid, warmed and extracted with chloroform toremove chlorophyll, fat, &c. The aqueous residue is rendered alkalinewith ammonia and again extracted with chloroform. The chloroformsolution on evaporation leaves a residue of the pure alkaloid which isdried at 100" and weighed. Foreign leaves have been found to con-tain 0.22 per cent. total alkaloid, and English leaves overheated indrying 0.15 per cent.E. W. P.D. A. L.Sulpho-conjugate Colouring Matter in Wines. By CARLES(J. Phscrm. [5], 11, 109--110).-The author finds that the methodrecommended for the detection of these colouring matters in wine isnot generally applicable. It consists in removing sulphates by meansof barium chloride, removing the barium salt by means of an alkalinecarbonate, then evaporatirig and calcining the residue ; sulphates thusproduced are supposed to indicate the artificial colouring matters jnquestion. Erroneous results were obtained not only with winesknown to be pure non-plastered, but also with wines made by theauthor from choice grapes in glass vessels (1) without any addition,( 2 ) plastered with sulphurous gelatin. J. T.By W.CHLUDINSKY (Landw. Versuchs-Stat., 1885, 117--128).-The authordescribes his method of estimating the composition of fleeces, andenters into considerable detail concerning the apparatus (Eurianalyser)which he has designed for the removal of the grease by means ofcarbon bisulphide. As regards the composition of various wools, it isstated that the hygroscopic properties of different wools are almostComposition of Long-wool and Merino Fleeces106 ABSTRACTS OF CHEMICAL PAPERS.identical ; merino fleeces have less impurity in them than other fleeces,but are richer in insoluble suint ; of other than merinos, Southdownfleeces are most largely contaminated with impurities, whilst thehighest percentage of pure wools is found in fleeces from short-tailedsheep. E. W. P.Diagnosis of Keratin in Animal Tissues. By H. STEINBREGGE(Zeit. Biol., 21, 631--635).-The author has applied Ewald andKuhne’s method (Verh. Med. Vereins z. Beidelberg, 1, 4.51) to theinvestigation of the tissues of the ear of mammalia for the presenceof keratine as a normal constituent, which was a probability to beinferred from the morphological relationship of the tissues to theectoderm of the ovum. The sections examined were 20 in number,obtained from various sources. They were digested in a trypsinsolution prepared in the usual way from pancreas. Very divergentresults were obtained in regard to the degree of resistance to theact,ion of this solution, which was the criterion adopted by the authorsabove mentioned for the presence of keratin. Investigation showedthat these divergencies corresponded with the degree of action of thehardening solutions employed in preparing the tissues for cutting,and that the criterion in questioc is worthless. C. F. C

ISSN:0368-1769    

DOI:10.1039/CA8865000096

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

106 ABSTRACTS OF CHEMICAL PAPERS. T e c h n i c a l C h e m i s t r y . Oxalate Developer for Gelatin Plates. By H. W. LORD (Chew, Cmtr., 1885, 668).-10 grams of sodium sulphite are dis- solved in 175 C.C. of a concentrated solution of potassium oxalate and 50 C.C. of a concentrated solution of ferrous sulphate added. About 1 C.C. sulphuric acid is then dropped in, until the mixture smells of sulphurous acid. This forms a very energetic developer, and the same quantity may be used several times. L. T. T. New Photographic Copying Paper. By H. J. SHAWCROSS (Chenz. Ceiztr., 1885, 668) .-The author covers the prepared paper with the powdered solid developer (tnnnic acid or other compound giving coloured precipitates with ferric but none with ferrous salts), which is well rubbed in.After exposure under the drawing to be copied the paper is laid in water, and the excess of developer removed with the aid of a sponge. A separate developing bath is thus avoided. L. T. T. Electric Aecumulators. By S. SCHENEK and S. FARBAKY (Dingl. polyt. J., 257, 357-369 and 458465).-1n 1883 the Academy of Mining and Forestry in Schemnitz, Hungary was furnished with incandescent lamps, the electric current being supplied by about 90 accumulators. The present paper describes the construction of the accnmulators employed, and gives an account of some observa- tions made by the authors. To study the behaviour of the sulphuricTECHNICAL CHEMISTRY. 107 acid during the condensation and the discharge of the current, a series of experiments was made. It was found that when the accumulators are charged the sulphates are decomposed, sulphuric acid being liberated, whilst on discharging, the sulphates are again formed, the free acid being recombined.To determine the, ratio of accrnmulated energy to acid set free, and the ratio of dis- charged energy to acid fixed, a further series of trials had to be made. The results appear to show that when the acciimulators are charged, 2.23 grams of sulphuric acid are liberated per ampitre per hour, and that during their discharge 2.25 gmms of acid are fixed, giving a mean value of 2.24. The authors term this number the electro- chemical equivalent of sulphuric acid for an electric force of one amfire per hour. From this value, some useful data in regard to the preparation, treatment, and application of electric accumulators are said to be derived.Selenium Battery. By C. E. FRITTS (Diiigl. polyt. J., 258, 44). -The author in conjunction with Hopkinson has patented selenium cells of a certain construction, capable ot generating a current of electricity under the action of rays of light. A description of this battery is given in the original paper and more fully in Engineering, 39, 398 (see also this vol., p. 2). Gas Analyses. By F. FISCRER (Dirtgl. polyt. J. 258, 28).- Analyses of the gases from regenerative furnaces of the Hasse-Didier type and from pyrites kilns are given. Liquid Carbonic Anhydride. By H. HERBERTS (Chew,. Centr., 188.5, 543-5444 558-560, and 57d).-The author describes in detail the various methods at present employed f o r the manufacture of this product on the large male, as well as the objects and uses to which it may be applied.He has patented an apparatus and method for making the gas by the action of sodium bisnlphite ou a suitable carbonate, and also describes a process for obtaining it from alkaline bicarbonates. He proposes to employ liquid carbonic anhydride as a motive power where fuel is expensive. Further Experiments on the Decomposition of Ammonium Sulphate by Means of Sodium Sulphate. By G. BLATTNER (Dingl. polyt. J., 25 7, 4?4--479).-1n a previous communication (Abstr., 1885, 613), the author gave an account of some experi- ments made with the view of testing the correctness of Carey and Hurter’s reaction of obtaining ammonia from ammonium sulphate by decomposition with sodium sulphate, the sulphuric acid being utilised simultaneously.These experiments were made without the use of superheated steam, and it was found that from 1 5 t o 18 per cent, of the ammonia originally present in the ammonium sulphate employed was lost by decomposition. The object of the present investigation was to ascertain whether by the use of superheated steam it was possible to avoid the loss of ammonia or to reduce it to a minimum. The results showed that although the loss of ammonia was diminished (to from 1 to 3 per cent.), a large pro- D. B. D. B. I). B. J. K. C.I08 ABSTRACTS OF CHEMICAL PAPERS. portion remained in the residue, and sublimed in the form of hydrogen ammonium sulphate, only from SO t o 90 per cent. of the ammonia being liberated as such, The author considers that the success of this process on a large scale depends on the complete removal of these difEcul ties.D. B. Treating Celestin and Heavy Spar. By I?. KONTHER (Dingl. polyt. J., 258, 46).-Heavy spar, celestin, or gypsum is introduced into fused sodium or potassium chloride, when the impurities sink to the bottom. The fused mass is then drawn off, cooled, and lixiviated with water, the object being to obtain the sulphates in a finely divided state suitable for further chemical treatment (with sodium carbonate, ammonium carbonate, &c.). The resulting mass may be used also as a pigment for stucco-work, &c. Treating Raw Phosphates. By P. DIETRICH (DingZ. poZyt. J., 25 7 , 484) .-Crude phosphates containing calcium oxide or carbonate are treated with sdphurous anhydride to form gypsum, so that by the subsequent treatment with dilute acids only tlhe phosphate is attacked.To effect the complete conversion of the calcium oxide into gypsum, a mixture of air and sulphurous anhydride is allowed to act on the phosphate in the presence of superheated steam. D. B. D. B. Preparation of Alumina. By G. ROSENTHAL (Dingl. polyt. J., 257, 539) .-On evaporating a solution of aluminium sulphate and magnesium chloride, alumina, magnesium sulphnte, and hydrochloric acid are obtained. The residue is mixed with a small amount of caustic lime, and subjected to the action of superheated stea,m a t 300". After lixiviation, alumina mixed with ferric oxide remains. Owing to the higher specific gravity of the latter, its separation from the alumina may be effected by elutriation.D. B. Preparation of Chromic Acid. By W. A. ROWELL (Dingl. polyt. J., 258,47).-It is proposed to treat the solution of a chromate with a soluble stront'ium salt, a precipitate of strontium chromate being obtained. The filtrate, contaiiiing some strontium chromate in solution, is treated with barium chloride. The barium chromate thus formed is decomposed with hot dilute sulphuria acid in large excess. The mixture of dilute chromic and sulphuric acids having been separated from barium sulphate is treated hot with an amount of strontium chromate equivalent to the sulphuric acid present. This results in the formation of chromic acid. which is seDarated from the precipitate of strontium sulphnte and evaporated to dryness.D. B. Irregularities in the Composition of Steel Ingots. By P. ZETSCHE (Dingl. yoZyt. J., 258, 2l).--From an examination of the composition of different sections of steel ingots, the author infers that the metttlloids sulphur and phosphorus predominate in the inner parts of the castings, whilst silicon and manganese are found mainly in the outer portions, D, B.TECHNICAL CHEMISTRY. 109 Improvements in Metallurgy. (Dingl. polyk. J., 258, 31- 39.)-To work up tin scrap, Lambotte proposes subjecting the metal to the action of dilute gaseous chlorine a t a temperature exceeding the boiling point of chloride of tin. The rapours of stannic chloride evolved are condensed in chambers or passed into a solution of stannic chloride. For the production of an alloy of high conductivity Shaw mixes 100 parts of copper with 1 to 5 parts of aluminium, and adds 0.05 to 1 part of phosphorus.The aluminium previously mixed with palm oil is gradually stirred into the fused copper. The phosphorus is then introduced, and the mass poured into flat moulds. Guillemin prepares alloys of copper and cobalt of great' firmness and tenacity by fusing copper and cobalt with boric acid and charcoal. The tensile strengt,h of the resulting alloy amounted to 40 kilos. per square mm. It contained 48.3 per cent. of cobalt, 50.3 per cent. of copper, 1 per cent. of nickel, and 0.4 per cent. of iron. According to Crooke molten lead does not take up the silver, arsenic, and antimony from copper ores unless it is mixed intimately with the ore at a temperature below the fusing point of copper. In precipitating copper from sulphate solutions by electrolysis, using insoluble anodes, Hartmann prevents polarisation by saturating the solution with sulphurous anhydride aud heating it.The electro- lytic purification of copper is discussed in detail by Kiliani in the original paper (see also Bergund, Hi&. Zeit., 1885, 249). Demercurising Gold. By B. FISCEER (Chern. Centr., 1885, 447).-The gold is rubbed well with a paste of powdered iodine and alcohol, and then placed in strong potassium iodide solution. This process is repeated until all the mercury is dissolved, and the gold is then polished with whiting. Electrolytic Extraction of Gold. By H. R. CASSELL (Chem. Centr., 1885, 6'23-624 and 637-638) .-The author employs nascent chlorine, liberated from a chloride of sodium solution by electrolysis, as a solvent for the gold to be extracted. The chlorine appears to have a selective affinity for the gold, gold chloride being formed before any of the other metals present are acted on.The solution must be kept alkaline by the addition of slaked lime, as otherwise the hydrochloric acid which is always formed by the electrolptic process, acts on the iron present in the ore to form ferrous chloride, which a t once precipitates the gold that has gone into solution. As long as excess of lime is present, no ferrous chloride is formed. The apparatus employed consists of a vertical cylinder about 3 feet long and 4 feet in diameter, revolving in a wooden vat.The cylinder is isolated from the vat, and has its surface of porous material. The positive wire from the dynamo passes into the cylinder and terminates in a number of thick carbon rods, the negative wire ends in the vat, in zt roll of copper foil. Both vat and cylinder are charged with a strong solution of sa.lt, and the dynamo started. The pulverised ore is then gradually introduced into the upper end of the cylinder (which is given about ten revolutions per minute) so that in falling D. B. J. K. C.110 ABSTRACTS OF CHEMICAL PAPERS. it comes in contact with the positive poles of the battery. The process takes about four hours for completion. The solution con- taining all the gold can then be decanted or filtered off, and the gold precipitated by iron or other suitable substance.If the surface of the cylinder is covered with asbestos cloth, or other suitable filtering material, the gold chloride passes through, and the gold is then pre- cipitated as a black powder a t the copper negative pule, and may be collected and melted. This latter plan is the best in general practice. Solubility of Mercuric Iodide in Fatty Compounds and other Solvents. By C. MBHU (J. Pharm. [ 5 ] , 11, 249--255).-0iZ of sweet almonds heated on a steam-bath dissolves about 13 parts of iodide per 1000 of oil, but on cooling about two-thirds of this is deposited. Heated a t 180°, about 80 parts iodide per 1000 parts oil are dissolved, but 8 considerable proportion is deposited at 150" in yellow crystals, which rapidly pass into the red modification on the filter. About 4 parts per 1000 may be considered as the amount retained in the cold. This amount can be increased by the addition of potassium iodide.Olive &Z behaves in much the same manner as oil of sweet almonds. White oil at. 100" dissolves 15.35 parts of iodide per 1000. A solu- tion of 10 parts per 1000 remained quite clear when kept for six days in a cellar. Nut oil a t 100" dissolves about 15 parts per 1000, and retains 13 parts in the cold. Castor oil is one of the most powerful solvents for mercuric iodide. About 40 parts per 1000 are dissolved a t 100". About 20 parts are retained on cooling. A mixture of 80 parts iodide with 48 parts mercuric chloride is dissolved in 1000 parts of oil on the steam-bath, and on cooling only a small quantity of the mixture separates out.About 100 parts of a mixture of equal equivalents of the iodide and chloride are almost completely retained in solution by 1000 parts of oil. L. T. T. Potassium iodide largely increases the solubility of the iodide. Lard retains about 4.5 parts iodide per 1000 in the cold. Vaseline dissolves only about 0.25 part per 1000. Phenol retains less than 10 parts per 1000. Bei~zewe dissolves 20 grams a t loo", but retains only 4 parts per 1000 in the cold. The author has experimented with mercury benzoate and other compounds, with a view to obtaining oils containing metallic com- pounds, but the results obtained with mercuric iodide appear most valuable. J. T. Preparation of Ferrocyanides. By A. STERNRERG (Din g l . polyt. J., 257, 539).-The author has found that the sulphur contained in the thiocyanogen-group CNS is readily given up to a metal if the latter can form ferrocyanides simultaneously.The thiocyanate to be treated is mixed with twice the weight of iron filings required to form iron sulphide, and twice the a,mount of freshly precipitated ferrous hydroxide required to form ferrocyanide. The mixture is agitated in a closed vessel a t 110--120". After twelve hours' digestion aboutTECHNICAL CHEMISTRY. 111 80 per cent. of the thiocyanate will have been converted into Prussian blue and ferrocyanide. D. B. Improvements in the Manufacture of Sugar. (DingZ. pdyt. J., 257, 372-378 and 420--$31).-1t is stated by Koch that on storing beet highly manured with nitrogen, it loses much saccharine matter.Van Hennekeler has recently tried Despeissis’ process of refining sugar by electrolytic means. He found that the mineral constituents pass from the positive to t$e negative pole, and that the amount of cane-sugar a t the positive pole is augmented. Landolt has attempted the destruction of the colouring matters in beet juice by electricity, but has been unsuccessful. I n discussing the processes used for refining beet-juice, Degener observed that for the treatment of bad roots the sulphurous acid process was indispensable, on account of the antiseptic properties of this acid. Although, according to Bergmann, it is more economical and less troublesome to refine without animal charcoal, the quantity of sugar yielded is largely affected. Experiments conducted a t the Dahmen Sugar Works proved that with the use of animal charcoal it was possible to obtain about 8 per cent.more sugar, a8 against a saving in working expenses of 6 pfennigs per 100 kilos. of beet realised when animal charcoal was not employed. According to Frost, an important element in the success of the defecation process is the use of lime in a finely divided state, and its freedom from grit. Steffen recommends heating the waste liquors and removing the last portions of calcium saccharate by hot filtration. The latter may then be added to fresh molasses, or washed with hot water and mixed with calcium saccharate from preceding operations. Bodenbender, in referring to the determination of invert sugar, an operation of some importance as it is required by the English market, observed that other substances present in beet affect copper solutions in a manner similar to invert sugar.To obtain results approaching nearer to accuracy, it is suggested that the sugar under treatment should be titrated with Fehling’s solution before and after boiling with caustic soda. The use of Schmidt and Hansch’s polarisation apparatus is recommended by Sickel. Landolt doubts the accuracy of plates of quartz, and expresses the opinion that more trustworthy results are obtained when polarising apparatus are tested with saccharine solu- tions of definite composition. Kleemann proposes the use of pulverised lignite for the purification of saccharine juices. Degener has made a series of experiments with the object of studying the influence of lead acetate on the optical behaviour of certain nonsaccharine substances present in beet-juice.He finds that lead acetate converts the levo-rotation of asparagine into a d e x t r o p a t e action. The laevo-rotation of the potassium salt under- goes a similar change when an excess of lend acetate is used. Alcohol increases the rotary power of this salt. Glutamic acid is dextro-112 ABSTRACTS OF CHEMICAL PAPERS. rotary, and insoluble in alcohol. Its potassium salt is soluble i n alcohol. Lead acetate imparts to glutamic acid a laevorotary action. Malic acid is lzevorotary, its optical power however depends on the concentration and alkalinity of its soliitions. Alcoholic solutions are optically inactive. The malates are insoluble in alcohol, but, in the presence of a large excess of lead acetate a laevorotary action is obtained.Arabic acid, if present in small quantities, does not affect the polarisation of saccharine juices. Tartaric acid is optically inactive. Caustic alkalis or carbonates impart to saccharose a Zaevorotary action. Lead acetate first decreases the dextrorotary power of saccharose, and finally changes it t o lsevo-rotation. Aqueous solutions of albumin are not precipitated by lead acetate. I n spite of these reactions Degener concludes that the degree of accuracy obtainable with the methods involving the use of alcohol and lead acetate is illfinitely greater than that obtained by the use of other processes hitherto recommended. It is necessary, however, to adhere strictly to the conditions as to the proportion of alcohol and sugar (3 vols.t o 1 vol.), and to moderate the quantity of lead acetate employed as much as possible. (DhqZ. poZyt. J., 25 7, 812.) -According to the Budische -4nilin urtd Xodufubrik, tetrachlorindigo is obtained by treating orthonitrodichlorobenzaldehyde witb acetone and caustic soda. A dye is produced which closely resembles indigo. (Compare Absfr., 1884, 1028.) Percentage of Water in Different Wood-papers. By B. LEPSIUS (Ber., 18, 2491--2492).-1n commerce, paper is bought by its '' air-dry " weight, and this is taken as the weight, a t 100" + 12 per eerit. added for moisture. The author has examined several papers, and finds that whereas for mechanically-pulped aspen and pine papers (holzschleifstoffen) this is true, for chemically-prepared (soda, or sul- phite processes) cellulose papers the addition should only be 10 per cent.L. T. T. Chemical Products of Putrefaction in their Relation to Dis- infection, By B. SANDERSON (Pharm. J. Trans. [3], 15, 897-898, 911-912, and 991-992), from the Thirteent.h Annual Report of the Local Government Board. Modification of Siemens' Pyrometer. By J. SPOHR (Dingl. pobyt. J., 257, 315).-The author proposes the use of the telephone in the place of the Toltameter. High Pressure Digesters (Autoclaves) for Chemical Labo- ratories. By R. MUENCKE (Dingl. polyt. J., 25 7, 283) .-The appa- ratus consists of a cylindrical copper vessel, provided with a cover, which is firmly fastened down by a screw. In order to close the vessel hermetically a leaden ring is placed between the edge8 of the cover and the vessel.For low tensions (under 25 atmos.) the cover is made of gun-metal or cast iron, whilst for higher tensions phosphor- bronze is employed. The interior of the cylinder may be lined with lead or enamelled as required. D. B. Preparation of Tetrachlorindigo. D. B. D. B. D. B.106 ABSTRACTS OF CHEMICAL PAPERS.T e c h n i c a l C h e m i s t r y .Oxalate Developer for Gelatin Plates. By H. W. LORD(Chew, Cmtr., 1885, 668).-10 grams of sodium sulphite are dis-solved in 175 C.C. of a concentrated solution of potassium oxalate and50 C.C. of a concentrated solution of ferrous sulphate added. About1 C.C. sulphuric acid is then dropped in, until the mixture smells ofsulphurous acid. This forms a very energetic developer, and thesame quantity may be used several times.L. T. T.New Photographic Copying Paper. By H. J. SHAWCROSS(Chenz. Ceiztr., 1885, 668) .-The author covers the prepared paperwith the powdered solid developer (tnnnic acid or other compoundgiving coloured precipitates with ferric but none with ferrous salts),which is well rubbed in. After exposure under the drawing to becopied the paper is laid in water, and the excess of developer removedwith the aid of a sponge. A separate developing bath is thusavoided. L. T. T.Electric Aecumulators. By S. SCHENEK and S. FARBAKY (Dingl.polyt. J., 257, 357-369 and 458465).-1n 1883 the Academy ofMining and Forestry in Schemnitz, Hungary was furnished withincandescent lamps, the electric current being supplied by about90 accumulators.The present paper describes the constructionof the accnmulators employed, and gives an account of some observa-tions made by the authors. To study the behaviour of the sulphuriTECHNICAL CHEMISTRY. 107acid during the condensation and the discharge of the current,a series of experiments was made. It was found that when theaccumulators are charged the sulphates are decomposed, sulphuricacid being liberated, whilst on discharging, the sulphates areagain formed, the free acid being recombined. To determine the,ratio of accrnmulated energy to acid set free, and the ratio of dis-charged energy to acid fixed, a further series of trials had to be made.The results appear to show that when the acciimulators are charged,2.23 grams of sulphuric acid are liberated per ampitre per hour, andthat during their discharge 2.25 gmms of acid are fixed, giving amean value of 2.24.The authors term this number the electro-chemical equivalent of sulphuric acid for an electric force of oneamfire per hour. From this value, some useful data in regard to thepreparation, treatment, and application of electric accumulators aresaid to be derived.Selenium Battery. By C. E. FRITTS (Diiigl. polyt. J., 258, 44).-The author in conjunction with Hopkinson has patented seleniumcells of a certain construction, capable ot generating a current ofelectricity under the action of rays of light. A description of thisbattery is given in the original paper and more fully in Engineering,39, 398 (see also this vol., p.2).Gas Analyses. By F. FISCRER (Dirtgl. polyt. J. 258, 28).-Analyses of the gases from regenerative furnaces of the Hasse-Didiertype and from pyrites kilns are given.Liquid Carbonic Anhydride. By H. HERBERTS (Chew,. Centr.,188.5, 543-5444 558-560, and 57d).-The author describes in detailthe various methods at present employed f o r the manufacture of thisproduct on the large male, as well as the objects and uses to which itmay be applied. He has patented an apparatus and method formaking the gas by the action of sodium bisnlphite ou a suitablecarbonate, and also describes a process for obtaining it from alkalinebicarbonates. He proposes to employ liquid carbonic anhydride as amotive power where fuel is expensive.Further Experiments on the Decomposition of AmmoniumSulphate by Means of Sodium Sulphate. By G.BLATTNER(Dingl. polyt. J., 25 7, 4?4--479).-1n a previous communication(Abstr., 1885, 613), the author gave an account of some experi-ments made with the view of testing the correctness of Careyand Hurter’s reaction of obtaining ammonia from ammoniumsulphate by decomposition with sodium sulphate, the sulphuricacid being utilised simultaneously. These experiments were madewithout the use of superheated steam, and it was found thatfrom 1 5 t o 18 per cent, of the ammonia originally present in theammonium sulphate employed was lost by decomposition. The objectof the present investigation was to ascertain whether by the use ofsuperheated steam it was possible to avoid the loss of ammonia orto reduce it to a minimum.The results showed that although the lossof ammonia was diminished (to from 1 to 3 per cent.), a large pro-D. B.D. B.I). B.J. K. CI08 ABSTRACTS OF CHEMICAL PAPERS.portion remained in the residue, and sublimed in the form of hydrogenammonium sulphate, only from SO t o 90 per cent. of the ammoniabeing liberated as such, The author considers that the success of thisprocess on a large scale depends on the complete removal of thesedifEcul ties. D. B.Treating Celestin and Heavy Spar. By I?. KONTHER (Dingl.polyt. J., 258, 46).-Heavy spar, celestin, or gypsum is introducedinto fused sodium or potassium chloride, when the impurities sink tothe bottom.The fused mass is then drawn off, cooled, and lixiviatedwith water, the object being to obtain the sulphates in a finely dividedstate suitable for further chemical treatment (with sodium carbonate,ammonium carbonate, &c.). The resulting mass may be used also asa pigment for stucco-work, &c.Treating Raw Phosphates. By P. DIETRICH (DingZ. poZyt. J.,25 7 , 484) .-Crude phosphates containing calcium oxide or carbonateare treated with sdphurous anhydride to form gypsum, so that bythe subsequent treatment with dilute acids only tlhe phosphate isattacked. To effect the complete conversion of the calcium oxide intogypsum, a mixture of air and sulphurous anhydride is allowed toact on the phosphate in the presence of superheated steam.D.B.D. B.Preparation of Alumina. By G. ROSENTHAL (Dingl. polyt. J.,257, 539) .-On evaporating a solution of aluminium sulphate andmagnesium chloride, alumina, magnesium sulphnte, and hydrochloricacid are obtained. The residue is mixed with a small amount ofcaustic lime, and subjected to the action of superheated stea,m a t300". After lixiviation, alumina mixed with ferric oxide remains.Owing to the higher specific gravity of the latter, its separationfrom the alumina may be effected by elutriation. D. B.Preparation of Chromic Acid. By W. A. ROWELL (Dingl.polyt. J., 258,47).-It is proposed to treat the solution of a chromatewith a soluble stront'ium salt, a precipitate of strontium chromatebeing obtained. The filtrate, contaiiiing some strontium chromate insolution, is treated with barium chloride.The barium chromate thusformed is decomposed with hot dilute sulphuria acid in large excess.The mixture of dilute chromic and sulphuric acids having beenseparated from barium sulphate is treated hot with an amount ofstrontium chromate equivalent to the sulphuric acid present. Thisresults in the formation of chromic acid. which is seDarated from theprecipitate of strontium sulphnte and evaporated to dryness.D. B.Irregularities in the Composition of Steel Ingots. ByP. ZETSCHE (Dingl. yoZyt. J., 258, 2l).--From an examination of thecomposition of different sections of steel ingots, the author infers thatthe metttlloids sulphur and phosphorus predominate in the innerparts of the castings, whilst silicon and manganese are found mainlyin the outer portions, D, BTECHNICAL CHEMISTRY.109Improvements in Metallurgy. (Dingl. polyk. J., 258, 31-39.)-To work up tin scrap, Lambotte proposes subjecting the metalto the action of dilute gaseous chlorine a t a temperature exceeding theboiling point of chloride of tin. The rapours of stannic chlorideevolved are condensed in chambers or passed into a solution of stannicchloride.For the production of an alloy of high conductivity Shaw mixes100 parts of copper with 1 to 5 parts of aluminium, and adds 0.05 to1 part of phosphorus. The aluminium previously mixed with palmoil is gradually stirred into the fused copper. The phosphorus is thenintroduced, and the mass poured into flat moulds.Guillemin prepares alloys of copper and cobalt of great' firmnessand tenacity by fusing copper and cobalt with boric acid and charcoal.The tensile strengt,h of the resulting alloy amounted to 40 kilos.persquare mm. It contained 48.3 per cent. of cobalt, 50.3 per cent. ofcopper, 1 per cent. of nickel, and 0.4 per cent. of iron.According to Crooke molten lead does not take up the silver,arsenic, and antimony from copper ores unless it is mixed intimatelywith the ore at a temperature below the fusing point of copper.In precipitating copper from sulphate solutions by electrolysis,using insoluble anodes, Hartmann prevents polarisation by saturatingthe solution with sulphurous anhydride aud heating it. The electro-lytic purification of copper is discussed in detail by Kiliani in theoriginal paper (see also Bergund, Hi&. Zeit., 1885, 249).Demercurising Gold.By B. FISCEER (Chern. Centr., 1885,447).-The gold is rubbed well with a paste of powdered iodine andalcohol, and then placed in strong potassium iodide solution. Thisprocess is repeated until all the mercury is dissolved, and the gold isthen polished with whiting.Electrolytic Extraction of Gold. By H. R. CASSELL (Chem.Centr., 1885, 6'23-624 and 637-638) .-The author employs nascentchlorine, liberated from a chloride of sodium solution by electrolysis,as a solvent for the gold to be extracted. The chlorine appears tohave a selective affinity for the gold, gold chloride being formedbefore any of the other metals present are acted on.The solutionmust be kept alkaline by the addition of slaked lime, as otherwise thehydrochloric acid which is always formed by the electrolptic process,acts on the iron present in the ore to form ferrous chloride, which a tonce precipitates the gold that has gone into solution. As long asexcess of lime is present, no ferrous chloride is formed.The apparatus employed consists of a vertical cylinder about 3 feetlong and 4 feet in diameter, revolving in a wooden vat. The cylinderis isolated from the vat, and has its surface of porous material. Thepositive wire from the dynamo passes into the cylinder and terminatesin a number of thick carbon rods, the negative wire ends in the vat,in zt roll of copper foil. Both vat and cylinder are charged with astrong solution of sa.lt, and the dynamo started.The pulverised oreis then gradually introduced into the upper end of the cylinder(which is given about ten revolutions per minute) so that in fallingD. B.J. K. C110 ABSTRACTS OF CHEMICAL PAPERS.it comes in contact with the positive poles of the battery. Theprocess takes about four hours for completion. The solution con-taining all the gold can then be decanted or filtered off, and the goldprecipitated by iron or other suitable substance. If the surface ofthe cylinder is covered with asbestos cloth, or other suitable filteringmaterial, the gold chloride passes through, and the gold is then pre-cipitated as a black powder a t the copper negative pule, and may becollected and melted.This latter plan is the best in general practice.Solubility of Mercuric Iodide in Fatty Compounds andother Solvents. By C. MBHU (J. Pharm. [ 5 ] , 11, 249--255).-0iZof sweet almonds heated on a steam-bath dissolves about 13 partsof iodide per 1000 of oil, but on cooling about two-thirds of this isdeposited. Heated a t 180°, about 80 parts iodide per 1000 partsoil are dissolved, but 8 considerable proportion is deposited at 150"in yellow crystals, which rapidly pass into the red modification on thefilter. About 4 parts per 1000 may be considered as the amountretained in the cold. This amount can be increased by the additionof potassium iodide.Olive &Z behaves in much the same manner as oil of sweet almonds.White oil at. 100" dissolves 15.35 parts of iodide per 1000. A solu-tion of 10 parts per 1000 remained quite clear when kept for six daysin a cellar.Nut oil a t 100" dissolves about 15 parts per 1000, and retains13 parts in the cold.Castor oil is one of the most powerful solvents for mercuric iodide.About 40 parts per 1000 are dissolved a t 100".About 20 parts areretained on cooling. A mixture of 80 parts iodide with 48 partsmercuric chloride is dissolved in 1000 parts of oil on the steam-bath,and on cooling only a small quantity of the mixture separates out.About 100 parts of a mixture of equal equivalents of the iodide andchloride are almost completely retained in solution by 1000 parts ofoil.L. T. T.Potassium iodide largely increases the solubility of the iodide.Lard retains about 4.5 parts iodide per 1000 in the cold.Vaseline dissolves only about 0.25 part per 1000.Phenol retains less than 10 parts per 1000.Bei~zewe dissolves 20 grams a t loo", but retains only 4 parts per1000 in the cold.The author has experimented with mercury benzoate and othercompounds, with a view to obtaining oils containing metallic com-pounds, but the results obtained with mercuric iodide appear mostvaluable.J. T.Preparation of Ferrocyanides. By A. STERNRERG (Din g l . polyt.J., 257, 539).-The author has found that the sulphur contained inthe thiocyanogen-group CNS is readily given up to a metal if thelatter can form ferrocyanides simultaneously. The thiocyanate to betreated is mixed with twice the weight of iron filings required to formiron sulphide, and twice the a,mount of freshly precipitated ferroushydroxide required to form ferrocyanide.The mixture is agitated ina closed vessel a t 110--120". After twelve hours' digestion abouTECHNICAL CHEMISTRY. 11180 per cent. of the thiocyanate will have been converted into Prussianblue and ferrocyanide. D. B.Improvements in the Manufacture of Sugar. (DingZ. pdyt. J.,257, 372-378 and 420--$31).-1t is stated by Koch that onstoring beet highly manured with nitrogen, it loses much saccharinematter.Van Hennekeler has recently tried Despeissis’ process of refiningsugar by electrolytic means. He found that the mineral constituentspass from the positive to t$e negative pole, and that the amount ofcane-sugar a t the positive pole is augmented.Landolt has attemptedthe destruction of the colouring matters in beet juice by electricity,but has been unsuccessful.I n discussing the processes used for refining beet-juice, Degenerobserved that for the treatment of bad roots the sulphurous acidprocess was indispensable, on account of the antiseptic properties ofthis acid. Although, according to Bergmann, it is more economicaland less troublesome to refine without animal charcoal, the quantityof sugar yielded is largely affected. Experiments conducted a t theDahmen Sugar Works proved that with the use of animal charcoal itwas possible to obtain about 8 per cent. more sugar, a8 against a savingin working expenses of 6 pfennigs per 100 kilos. of beet realised whenanimal charcoal was not employed.According to Frost, an important element in the success of thedefecation process is the use of lime in a finely divided state, and itsfreedom from grit.Steffen recommends heating the waste liquors and removing the lastportions of calcium saccharate by hot filtration.The latter may thenbe added to fresh molasses, or washed with hot water and mixed withcalcium saccharate from preceding operations.Bodenbender, in referring to the determination of invert sugar, anoperation of some importance as it is required by the English market,observed that other substances present in beet affect copper solutionsin a manner similar to invert sugar. To obtain results approachingnearer to accuracy, it is suggested that the sugar under treatmentshould be titrated with Fehling’s solution before and after boilingwith caustic soda.The use of Schmidt and Hansch’s polarisation apparatus isrecommended by Sickel.Landolt doubts the accuracy of plates ofquartz, and expresses the opinion that more trustworthy results areobtained when polarising apparatus are tested with saccharine solu-tions of definite composition.Kleemann proposes the use of pulverised lignite for the purificationof saccharine juices.Degener has made a series of experiments with the object ofstudying the influence of lead acetate on the optical behaviour ofcertain nonsaccharine substances present in beet-juice. He findsthat lead acetate converts the levo-rotation of asparagine into ad e x t r o p a t e action.The laevo-rotation of the potassium salt under-goes a similar change when an excess of lend acetate is used. Alcoholincreases the rotary power of this salt. Glutamic acid is dextro112 ABSTRACTS OF CHEMICAL PAPERS.rotary, and insoluble in alcohol. Its potassium salt is soluble i nalcohol. Lead acetate imparts to glutamic acid a laevorotary action.Malic acid is lzevorotary, its optical power however depends on theconcentration and alkalinity of its soliitions. Alcoholic solutions areoptically inactive. The malates are insoluble in alcohol, but, in thepresence of a large excess of lead acetate a laevorotary action isobtained. Arabic acid, if present in small quantities, does not affectthe polarisation of saccharine juices. Tartaric acid is opticallyinactive.Caustic alkalis or carbonates impart to saccharose aZaevorotary action. Lead acetate first decreases the dextrorotarypower of saccharose, and finally changes it t o lsevo-rotation. Aqueoussolutions of albumin are not precipitated by lead acetate. I n spiteof these reactions Degener concludes that the degree of accuracyobtainable with the methods involving the use of alcohol and leadacetate is illfinitely greater than that obtained by the use of otherprocesses hitherto recommended. It is necessary, however, to adherestrictly to the conditions as to the proportion of alcohol and sugar(3 vols. t o 1 vol.), and to moderate the quantity of lead acetateemployed as much as possible.(DhqZ. poZyt. J., 25 7, 812.)-According to the Budische -4nilin urtd Xodufubrik, tetrachlorindigois obtained by treating orthonitrodichlorobenzaldehyde witb acetoneand caustic soda. A dye is produced which closely resembles indigo.(Compare Absfr., 1884, 1028.)Percentage of Water in Different Wood-papers. By B.LEPSIUS (Ber., 18, 2491--2492).-1n commerce, paper is bought by its'' air-dry " weight, and this is taken as the weight, a t 100" + 12 pereerit. added for moisture. The author has examined several papers,and finds that whereas for mechanically-pulped aspen and pine papers(holzschleifstoffen) this is true, for chemically-prepared (soda, or sul-phite processes) cellulose papers the addition should only be 10 percent. L. T. T.Chemical Products of Putrefaction in their Relation to Dis-infection, By B. SANDERSON (Pharm. J. Trans. [3], 15, 897-898,911-912, and 991-992), from the Thirteent.h Annual Report of theLocal Government Board.Modification of Siemens' Pyrometer. By J. SPOHR (Dingl.pobyt. J., 257, 315).-The author proposes the use of the telephone inthe place of the Toltameter.High Pressure Digesters (Autoclaves) for Chemical Labo-ratories. By R. MUENCKE (Dingl. polyt. J., 25 7, 283) .-The appa-ratus consists of a cylindrical copper vessel, provided with a cover,which is firmly fastened down by a screw. In order to close thevessel hermetically a leaden ring is placed between the edge8 of thecover and the vessel. For low tensions (under 25 atmos.) the cover ismade of gun-metal or cast iron, whilst for higher tensions phosphor-bronze is employed. The interior of the cylinder may be lined withlead or enamelled as required.D. B.Preparation of Tetrachlorindigo.D. B.D. B.D. B

ISSN:0368-1769    

DOI:10.1039/CA8865000106

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

113 G e n e r a l a n d P h y s i c a l Chemistry. New Absorption Spectroscope. By &I. DO THIERRY (Compt. q*end., 101, 811--813).-An absorption spectroscope provided with a reflected scale and an eye-piece micrometer, and arranged so that columns of liquid varying in length from 0.1 m. to 10 m. can be examined, the source of illumination being an oxyhydrogen light. C. H. B. Electric Conductivity of Serpentine. By E. WIECHERT (A12n. Phys. Chem. [Z], 26, 336).-The conductivity of serpentine is very yariable ; the value of its specific resistance in terms of the mercury unit was found to lie between t,he limits of 20 and 30000 millions; its use as a perfect insulator is thus undesirable. Marble does not appear to conduct electricity under any observed conditions. V. H. V.Coefficient of Conductivity of Electrolytes in very dilute Solutions. By F. KOHLRACSCB (Ann; P h y . Chew. [2], 26, 161- 226).-A few years ago the author in conjunction with Nippolclt determined the coefficient of conductivity for several electrolytes, and showed that these could be arranged in groups, such as the halogen salts of the same metals, the potassium and auimonium salts, the chlorides of the alkaline earths, and the sulphates of magnesium, zinc, and copper. Further, in the case of neutral salts, the values of the temperature coefficients varied within very narrow limits with increase of dilution. As a general result, curves were drawn in which the proportions of salt in solution were taken as abscisse, and the coefficients of con- ductivity as ordinates ; the values of the former multiplied by the chemical equivalents are designated the spec?& molecular con- ductivities.The researches of Hittorf on the migration of the ions naturally cause an extension of the above researches in the case of very dilute solutions, as offering a possible means for the determination of the mean distance of the molecules. The method adopted was that of rapidly alternating currents, the results of former observers having shown thiit in working this rnethod, even when pushed to the most extreme limits, Ohm’s law is valid. The molecular proportions or values, m, of electrolytes in unit volume of solutions are understood to be the quantity in grams divided by the molecular weight ; such solutions were prepared in which the values for 7 t ~ were varied proportionally from 0.1 to 0.0001.The means adopted for preparing such solutions and their estimation, the detjr- mination of their conductivity, the correction for temperature, and other details are described at length in the paper. A series of tables are given of the coeficients of conductivity, KtlOlO, in terms of the mercury unit of such molecular solutions o€ VOL. L, i114 ABSTRACTS OF CHEMICAL PAFERS. various degrees of concentration of ammonium, sodium, li thium, barium, and zinc chlorides, barium, potassium, sodium, and silver nitrates, potassium, sodium, lithium, magnesium, zinc, and copper sulphates, sodium and potassium carbonates, of potassium iodide, chlorate, and acetate, and of nitric, hydrochloric, and sulphuric acids.Conductivity of Salts.-These determinations show that the con- ductivity atl first varies directly as the molecular proportion, but in the more dilute solutions the value for this ratio gradually diminishes ; the former divided by the -latter, kfm, is the specific molecular con- ductlziit?y (comp. supra). The values for k / m can best be interpreted by considering them as proportional to the relative velocity of the ions under the influence of a constant electromotive force. If then the values for 1O87c/rn be multiplied by 0*00011, one obtains the velocity in mm./seconds with which the ions pass one another, under the influence of the force of one volt acting through 1 mm. Unequal values are thus obtained, as shown by the following table :- Kations. I(. PTH,.Na. Li. Ag. H. +Bn. +ME. +Zn. ?u = l@*k/m x 0*00011 52 30 32 24 42 272 30 26 '20 w = lO*X./nz x 0.00011 84 55 48 42 26 143 It is thus seen that potassium and ammonium, magnesium and zinc, and in dilute solutions Sod, I, C1, and NO3, can be classified together in separate groups, a, result in accordance with the experi- ments of Lenz. Further, it is shown that the water of crystallisation has no influence on the conductivity of the salts. Ceretain experiments of Faraday and Gmelin are also repeated, ~ihich tend to show that in the case of very dilute solutions not only the dissolved electrolyte, but also, under certain conditions, the water itself is decomposed. Thus if a trace of ammonium carbonate be added to solutions of magnesium and copper sulphates, a precipitation of the hydroxide of the metal appears generally in a dendritic form.Bouty's law of equivalents (Thbis, Paris, 1885) is examined and not found to be generally valid. The temperature coefficients of solutions containing m = 0.01 of the various salts examined were found to be approximately equal. Conductivity qf Alkalis and Acids.--The coefficient of these Fiibstamces relatively to dilution at first increases, reaches a maximum, :.nd then decreases ; the maximum occurs with solutions in which '1t1 5= 0-OM. The following results are also mentioned : (1) the specific conduc- tivities of potassium and sodium hgroxides are approximately equal, a s also those of the halogen and nitric acid ; (2) solutions of ammonia and of phosphoric and acetic acids, are exceedingly bad conductors ; (3) the curve representing the conductivity of sulphuric acid shows minimum points of inflexion corresponding with the formation of the nionohydrate H2S04,H,0, the pure acid H2S04, and the anhF-dride respectively.The temperature coefficients of alkalis and acids, with the exception of sulphuric acid, are also approximately equal. Anions. C1. I. NO,. C103. C,H,O,. OH.GENERAL AND PHYSICAL CHEMISTRY. 115 Researches are also promised on the application of the determina- tions of conductivity for ascertaining the interaction of acids and bases when in the same solution. V. H. V. Electrical Conductivity of Mixtures of Ethyl Alcohol and Ether. By E. W. R. PFEIFFER (Ann. Phys. Chem. [2], 26,226-239). I n Continuation of the author’s researches on the conductivity of organic liquids (Abstr., 1885,1029), an account is given of determina- tions of the specific Conductivity of mixtures of alcohol and ether as functions (1) of the percentage proportion of the latter, the tempe- rature being constant ; and (2) of the temperature, the mixtures being of identical composition.Firstly. The conductivity of such a mixture decreases a t first regularly with increase of proportion of ether, until the liquid con- tains 75 per cent. ; a t this point the curve representing conductivity in terms of percentage of ether shows a point of inflexion, and thence approaches more gradually to the axis of the abscissze, until with pure ether the conductivity cannot be measured. It was observed inci- dentally that the conductivity of such mixtures, kept a t constant temperature, slowly decreases from the moment of mixing until a minimum point is reached after a variable interval of time ; from this point, the conductivity again increases. As it is improbable that the mere passage of the current should effect the conductivity, this phe- nomenon may be due to t(he chemical action between inevitable impurities in the liquids or between the liquids themselves.Secondly. The temperature coefficient is negative for mixtures con- taining less than 24 to 29 per cent. ether, a t which point it becomes zero ; thence it increases, reaches a maximum with 35 per cent., and then again decreases. Thus both pure alcohol and ether, as also mixtures of them in certain proportions, resemble metallic conductors as regards the negative value of their temperature coefficient.By A. XENARD (Cowpi. rend., 101, 747 -7‘49) .-From the results of experiments with aqueous solutions of various salts containing from 0.0001 to 0.1024 gram-equivalent of the metals in 100 grams of solution, the author concludes (1) that iE the solution be sufficiently dilute the quantity of metal precipitated is proportional to the concentration of the solution ; (2) that if the same current is passed through several solutions, the quantities of the different metals precipitated are in the ratios of their equivalents ; (3) that, according to Faraday’s law, the quantity of metal precipi- tated being proportional to the intensity of the current, the conduc- tivity of all solutions containing equivalent proportions of the different metals is the same, as Bouty has shown by direct experi- ment.C. H. B. V. H. V. Electrolysis of Salts. New Method of Determining the Heat of Combustion of Organic Substances. By D. DIACONOFF ( J . RUSS. Chem. XOC., 1885, 283 -284) .-The anthor burns the compound under investigation in admixture with finely powdered asbestos and glycerol ; the former i 2116 ABSTRACTS OF CHEMICAL PAPKRS. divides the particles of the difficultly combustible substance, and secures its entire combustion, the latter maintains the temperature necessary for combustion. A. T. Relations between the Heat of Formation of Salts and the Initial Rate of their Formation. By A. POTILITZIN (Rer., 18, 1522--1527).-When silver chloride is shaken in the dark with equally concentrated solutions of metallic bromides for three minutes and then allowed to rest for 25 minutes, varying percentages of silver bromide are obtained according to the metallic bromide used.T h e n these percentages are divided by the heat of formation of silver bromide from the metallic bromide, a constant number is obtained; in this case the number is 11.17. Similar results are obtained if instead of silver chloride and a bromide, equivalent quantities of AgN03 + RCl + RBr are employed. Comparisons were also made of the percentages of carbonates formed by the action of alkaline carbonates on the chlorides of the alkaline earths and of the heat of formation. I n this case also a con- stant, namely 1 4 . 1 , was obtained by dividing the percentage by the heat of formation.I n these experiments, dilute solutions must be used ; further, the initial rates of formation of different salts can only be compared in the case of reactions which take place under quite similar circum- stances. N. H. M. Air or Hydrogen Thermometer for Low Temperatures. By J. J. COLEMAN (J. Soc. Chem. Ind., 4, 43).-This instrument is a constant pressure thermometer, and has been specia,lly constructed for taking low temperatures, say to 300" below zero Fahrenheit. New Form of Gas Thermometer. By G. BEILBY ( J . XOC. Chem. Ind., 4, 40).-The author has attempted the construction of a com- pact thermometer on the principle of measuring a t known and con- stant temperature and pressure the gas expelled from a bulb or vessel of unknown temperature. D.B. D. B. Source of Error in Vapour-density Determinations. By W. ALEXEEFF ( B e y . 18, 2898-2906) .-In order to explain the discordant results obtained by Meyer and Pond (Abstr., 1885, 1033) on the one hand, and by Menschutkin and Konowalow (Abstr., 1884,1119) on the other hand, in experiment's on the dissociation of tertiary amyJ acetate and chloride induced by glass (Abstr., 1884, 1119), the author men- tions the fact that the glass used in Russia is much more readily attacked by acids and other reagents than German glass. Experiments are quoted with propyl bromide which show that in a Meyer's appa- ratus no dissociation takes place a t the boiling point of nitrobenzene, whereas 40 per cent. is dissociated a t 200". This latter result can be interpreted by the removal of the traces of hydrobromic acid by the vapour of water produced by a chemical action on the glass.If this interpretation be correct, the amount of dissociation will be greater, the greater the ratio of the glass surface to vapour present, a resultGEXERAL AND PHYSICAL CHEMISTRY. 117 Of temperature. in accordance wit,h the most recent experiments of Menschntkin and Konowalow. V. H. V. tion. Of pressure. Dissociation of the Hydrate of Hydrogen Bromide. By H. W. B. ROOZEBOOM (Rec. Trav. Chim., 4, 108--124).-The curve of tensions of the hydrate of hydrogen bromide between the temperatures of - 11.3" and - 15.6' recurves in a negative direction, there being three different tensions of dissociation for a given temperature between these points.At the lower tension a t 11*3", the aqueous solution of the hydrate surrounding the solid reaches such a concentration that it has a composition identical with that of the solid hydrate itself. Van der Waals has already pointed out that when this takes place a t a lower temperature than that at which the acid or chlorous product of dissociation is given off in the liquid form, the curve of dissociation tensions will take a negative direction limited by a point whose position depends on the heat of formation of the compound in question ; the curve then once more assumes a positive direction, and the tension rises with the temperature in the normal manner. The hydrate of hydrogen chloride (Eec. Trtsv. Chim., 3, 94) shows a similar phenomenon, but the length of the recurved portion is much shorter.A. P. - 9.5" to - 2.6" - 2.6 ), + 12.1 + 16.2 ), + 17'1 Dissociation of the Hydrates of Sulphurous Anhydride, Chlorine, and Bromine. By H. W. B. ROOZEBOOM ( B e c . Trav. Chim., 4, 65--73).-1n Continuation of his researches on this subject ( R e c . T ~ a v . Chim., 3, 28-104) the author finds that the curves representing the tensions of dissociation of these compounds a t diiTerent temperatures, are each broken into three segmental curves having different directions, the points of intersection being coincident with the temperatures at which a change ,of state takes place in one of the products of dissociation. The main detai-1s are given in the following tables :- 150 mm. to 211 mm. 211 mm. ,, 177 cm. H& liquid and SO2 ,, 177 cm.,, 250 atm. H20 ), and SO2 liquid H,O solid and SO, gaseous I. SO, + 7H,O. Points of intersecfion at - 2 *ti" and +- 12 *lo.118 Of temperature. ABSTRACTS OF CHEMICAL PAPERS. Of pressure. IT. C1, + 8H,O. Intervals - loo to - 0.24' - 0.24' ,, + 28.T + 28-7" ,, - 156 mm. to 248 mm. 248 mm. to about 6 atm. 6 atm. to - Products of dissocia- tion. H,O solid and C1, gaseous H,O liquid and C1, ,, H,O ,, and C1, liquid Points of intersection a t - 0.24' and + 28.7". 111. Br, + 1OH,O. Of temperature. ~ Intervals Produats of dissocia- tion. Of pressure. - 10' to - 0.30 - 0.3' ,, + 6 . 2 f 6'2" ,, - -I------ -- 25 mm. to 43 mm. 43mm. ,, 93mm. 93mm. ,, - H,O solid and Br, gaseous H,O liquid and Br2 ,, H,O ,, and Br2 liquid Points of inteasection at - 0.3" and + 6.2".A. P. Air-pump Regulator. By N. v. KLOBUKOW (Zeit. anal. Chem., 24, 399-402).-A. simple apparatus by means of which the reduced pressure obtained by means of a water jet air-pump may be rendered constant within 1.0 cm. at whatever pressure required, and however the rate of fiow Q€ the water may vary. A. P.113G e n e r a l a n d P h y s i c a l Chemistry.New Absorption Spectroscope. By &I. DO THIERRY (Compt.q*end., 101, 811--813).-An absorption spectroscope provided with areflected scale and an eye-piece micrometer, and arranged so thatcolumns of liquid varying in length from 0.1 m. to 10 m. can beexamined, the source of illumination being an oxyhydrogen light.C. H. B.Electric Conductivity of Serpentine. By E. WIECHERT (A12n.Phys.Chem. [Z], 26, 336).-The conductivity of serpentine is veryyariable ; the value of its specific resistance in terms of the mercuryunit was found to lie between t,he limits of 20 and 30000 millions;its use as a perfect insulator is thus undesirable.Marble does not appear to conduct electricity under any observedconditions. V. H. V.Coefficient of Conductivity of Electrolytes in very diluteSolutions. By F. KOHLRACSCB (Ann; P h y . Chew. [2], 26, 161-226).-A few years ago the author in conjunction with Nippolcltdetermined the coefficient of conductivity for several electrolytes, andshowed that these could be arranged in groups, such as the halogensalts of the same metals, the potassium and auimonium salts, thechlorides of the alkaline earths, and the sulphates of magnesium,zinc, and copper. Further, in the case of neutral salts, the values ofthe temperature coefficients varied within very narrow limits withincrease of dilution.As a general result, curves were drawn in which the proportions ofsalt in solution were taken as abscisse, and the coefficients of con-ductivity as ordinates ; the values of the former multiplied by thechemical equivalents are designated the spec?& molecular con-ductivities.The researches of Hittorf on the migration of the ions naturallycause an extension of the above researches in the case of very dilutesolutions, as offering a possible means for the determination of themean distance of the molecules.The method adopted was that of rapidly alternating currents, theresults of former observers having shown thiit in working this rnethod,even when pushed to the most extreme limits, Ohm’s law is valid.The molecular proportions or values, m, of electrolytes in unit volumeof solutions are understood to be the quantity in grams divided by themolecular weight ; such solutions were prepared in which the valuesfor 7 t ~ were varied proportionally from 0.1 to 0.0001.The meansadopted for preparing such solutions and their estimation, the detjr-mination of their conductivity, the correction for temperature, andother details are described at length in the paper.A series of tables are given of the coeficients of conductivity,KtlOlO, in terms of the mercury unit of such molecular solutions o€VOL.L, 114 ABSTRACTS OF CHEMICAL PAFERS.various degrees of concentration of ammonium, sodium, li thium, barium,and zinc chlorides, barium, potassium, sodium, and silver nitrates,potassium, sodium, lithium, magnesium, zinc, and copper sulphates,sodium and potassium carbonates, of potassium iodide, chlorate, andacetate, and of nitric, hydrochloric, and sulphuric acids.Conductivity of Salts.-These determinations show that the con-ductivity atl first varies directly as the molecular proportion, but inthe more dilute solutions the value for this ratio gradually diminishes ;the former divided by the -latter, kfm, is the specific molecular con-ductlziit?y (comp. supra). The values for k / m can best be interpretedby considering them as proportional to the relative velocity of theions under the influence of a constant electromotive force.If thenthe values for 1O87c/rn be multiplied by 0*00011, one obtains the velocityin mm./seconds with which the ions pass one another, under theinfluence of the force of one volt acting through 1 mm. Unequalvalues are thus obtained, as shown by the following table :-Kations. I(. PTH,. Na. Li. Ag. H. +Bn. +ME. +Zn.?u = l@*k/m x 0*00011 52 30 32 24 42 272 30 26 '20w = lO*X./nz x 0.00011 84 55 48 42 26 143It is thus seen that potassium and ammonium, magnesium andzinc, and in dilute solutions Sod, I, C1, and NO3, can be classifiedtogether in separate groups, a, result in accordance with the experi-ments of Lenz.Further, it is shown that the water of crystallisation has no influenceon the conductivity of the salts.Ceretain experiments of Faraday and Gmelin are also repeated,~ihich tend to show that in the case of very dilute solutions not onlythe dissolved electrolyte, but also, under certain conditions, the wateritself is decomposed.Thus if a trace of ammonium carbonate beadded to solutions of magnesium and copper sulphates, a precipitationof the hydroxide of the metal appears generally in a dendritic form.Bouty's law of equivalents (Thbis, Paris, 1885) is examined andnot found to be generally valid.The temperature coefficients of solutions containing m = 0.01 of thevarious salts examined were found to be approximately equal.Conductivity qf Alkalis and Acids.--The coefficient of theseFiibstamces relatively to dilution at first increases, reaches a maximum,:.nd then decreases ; the maximum occurs with solutions in which'1t1 5= 0-OM.The following results are also mentioned : (1) the specific conduc-tivities of potassium and sodium hgroxides are approximately equal,a s also those of the halogen and nitric acid ; (2) solutions of ammoniaand of phosphoric and acetic acids, are exceedingly bad conductors ;(3) the curve representing the conductivity of sulphuric acid showsminimum points of inflexion corresponding with the formation of thenionohydrate H2S04,H,0, the pure acid H2S04, and the anhF-driderespectively. The temperature coefficients of alkalis and acids, withthe exception of sulphuric acid, are also approximately equal.Anions.C1. I. NO,. C103. C,H,O,. OHGENERAL AND PHYSICAL CHEMISTRY. 115Researches are also promised on the application of the determina-tions of conductivity for ascertaining the interaction of acids andbases when in the same solution. V. H. V.Electrical Conductivity of Mixtures of Ethyl Alcohol andEther. By E. W. R. PFEIFFER (Ann. Phys. Chem. [2], 26,226-239).I n Continuation of the author’s researches on the conductivity oforganic liquids (Abstr., 1885,1029), an account is given of determina-tions of the specific Conductivity of mixtures of alcohol and ether asfunctions (1) of the percentage proportion of the latter, the tempe-rature being constant ; and (2) of the temperature, the mixtures beingof identical composition.Firstly.The conductivity of such a mixture decreases a t firstregularly with increase of proportion of ether, until the liquid con-tains 75 per cent. ; a t this point the curve representing conductivityin terms of percentage of ether shows a point of inflexion, and thenceapproaches more gradually to the axis of the abscissze, until with pureether the conductivity cannot be measured. It was observed inci-dentally that the conductivity of such mixtures, kept a t constanttemperature, slowly decreases from the moment of mixing until aminimum point is reached after a variable interval of time ; from thispoint, the conductivity again increases. As it is improbable that themere passage of the current should effect the conductivity, this phe-nomenon may be due to t(he chemical action between inevitableimpurities in the liquids or between the liquids themselves.Secondly. The temperature coefficient is negative for mixtures con-taining less than 24 to 29 per cent.ether, a t which point it becomeszero ; thence it increases, reaches a maximum with 35 per cent., andthen again decreases.Thus both pure alcohol and ether, as also mixtures of them incertain proportions, resemble metallic conductors as regards thenegative value of their temperature coefficient.By A. XENARD (Cowpi. rend., 101, 747-7‘49) .-From the results of experiments with aqueous solutions ofvarious salts containing from 0.0001 to 0.1024 gram-equivalent of themetals in 100 grams of solution, the author concludes (1) that iE thesolution be sufficiently dilute the quantity of metal precipitated isproportional to the concentration of the solution ; (2) that if the samecurrent is passed through several solutions, the quantities of thedifferent metals precipitated are in the ratios of their equivalents ;(3) that, according to Faraday’s law, the quantity of metal precipi-tated being proportional to the intensity of the current, the conduc-tivity of all solutions containing equivalent proportions of thedifferent metals is the same, as Bouty has shown by direct experi-ment.C. H. B.V. H. V.Electrolysis of Salts.New Method of Determining the Heat of Combustion ofOrganic Substances. By D. DIACONOFF ( J . RUSS. Chem. XOC., 1885,283 -284) .-The anthor burns the compound under investigationin admixture with finely powdered asbestos and glycerol ; the formeri 116 ABSTRACTS OF CHEMICAL PAPKRS.divides the particles of the difficultly combustible substance, andsecures its entire combustion, the latter maintains the temperaturenecessary for combustion. A.T.Relations between the Heat of Formation of Salts and theInitial Rate of their Formation. By A. POTILITZIN (Rer., 18,1522--1527).-When silver chloride is shaken in the dark withequally concentrated solutions of metallic bromides for three minutesand then allowed to rest for 25 minutes, varying percentagesof silver bromide are obtained according to the metallic bromideused. T h e n these percentages are divided by the heat of formationof silver bromide from the metallic bromide, a constant number isobtained; in this case the number is 11.17.Similar results areobtained if instead of silver chloride and a bromide, equivalentquantities of AgN03 + RCl + RBr are employed.Comparisons were also made of the percentages of carbonatesformed by the action of alkaline carbonates on the chlorides of thealkaline earths and of the heat of formation. I n this case also a con-stant, namely 1 4 . 1 , was obtained by dividing the percentage by theheat of formation.I n these experiments, dilute solutions must be used ; further, theinitial rates of formation of different salts can only be compared inthe case of reactions which take place under quite similar circum-stances. N. H. M.Air or Hydrogen Thermometer for Low Temperatures.ByJ. J. COLEMAN (J. Soc. Chem. Ind., 4, 43).-This instrument is aconstant pressure thermometer, and has been specia,lly constructedfor taking low temperatures, say to 300" below zero Fahrenheit.New Form of Gas Thermometer. By G. BEILBY ( J . XOC. Chem.Ind., 4, 40).-The author has attempted the construction of a com-pact thermometer on the principle of measuring a t known and con-stant temperature and pressure the gas expelled from a bulb or vesselof unknown temperature. D. B.D. B.Source of Error in Vapour-density Determinations. By W.ALEXEEFF ( B e y . 18, 2898-2906) .-In order to explain the discordantresults obtained by Meyer and Pond (Abstr., 1885, 1033) on the onehand, and by Menschutkin and Konowalow (Abstr., 1884,1119) on theother hand, in experiment's on the dissociation of tertiary amyJ acetateand chloride induced by glass (Abstr., 1884, 1119), the author men-tions the fact that the glass used in Russia is much more readilyattacked by acids and other reagents than German glass.Experimentsare quoted with propyl bromide which show that in a Meyer's appa-ratus no dissociation takes place a t the boiling point of nitrobenzene,whereas 40 per cent. is dissociated a t 200". This latter result can beinterpreted by the removal of the traces of hydrobromic acid by thevapour of water produced by a chemical action on the glass. If thisinterpretation be correct, the amount of dissociation will be greater,the greater the ratio of the glass surface to vapour present, a resulGEXERAL AND PHYSICAL CHEMISTRY.117Of temperature.in accordance wit,h the most recent experiments of Menschntkin andKonowalow. V. H. V.tion.Of pressure.Dissociation of the Hydrate of Hydrogen Bromide. By H.W. B. ROOZEBOOM (Rec. Trav. Chim., 4, 108--124).-The curve oftensions of the hydrate of hydrogen bromide between the temperaturesof - 11.3" and - 15.6' recurves in a negative direction, there beingthree different tensions of dissociation for a given temperature betweenthese points. At the lower tension a t 11*3", the aqueous solution ofthe hydrate surrounding the solid reaches such a concentration thatit has a composition identical with that of the solid hydrate itself.Van der Waals has already pointed out that when this takes place a ta lower temperature than that at which the acid or chlorous productof dissociation is given off in the liquid form, the curve of dissociationtensions will take a negative direction limited by a point whoseposition depends on the heat of formation of the compound inquestion ; the curve then once more assumes a positive direction, andthe tension rises with the temperature in the normal manner.Thehydrate of hydrogen chloride (Eec. Trtsv. Chim., 3, 94) shows asimilar phenomenon, but the length of the recurved portion is muchshorter. A. P.- 9.5" to - 2.6"- 2.6 ), + 12.1 + 16.2 ), + 17'1Dissociation of the Hydrates of Sulphurous Anhydride,Chlorine, and Bromine. By H. W. B. ROOZEBOOM ( B e c . Trav.Chim., 4, 65--73).-1n Continuation of his researches on this subject( R e c . T ~ a v . Chim., 3, 28-104) the author finds that the curvesrepresenting the tensions of dissociation of these compounds a tdiiTerent temperatures, are each broken into three segmental curveshaving different directions, the points of intersection being coincidentwith the temperatures at which a change ,of state takes place in oneof the products of dissociation. The main detai-1s are given in thefollowing tables :-150 mm. to 211 mm.211 mm. ,, 177 cm. H& liquid and SO2 ,,177 cm. ,, 250 atm. H20 ), and SO2 liquidH,O solid and SO, gaseousI. SO, + 7H,O.Points of intersecfion at - 2 *ti" and +- 12 *lo118Of temperature.ABSTRACTS OF CHEMICAL PAPERS.Of pressure.IT. C1, + 8H,O.Intervals- loo to - 0.24'- 0.24' ,, + 28.T + 28-7" ,, -156 mm. to 248 mm.248 mm. to about 6 atm.6 atm. to -Products of dissocia-tion.H,O solid and C1, gaseousH,O liquid and C1, ,,H,O ,, and C1, liquidPoints of intersection a t - 0.24' and + 28.7".111. Br, + 1OH,O.Of temperature.~IntervalsProduats of dissocia-tion.Of pressure.- 10' to - 0.30 - 0.3' ,, + 6 . 2f 6'2" ,, --I------ --25 mm. to 43 mm.43mm. ,, 93mm.93mm. ,, -H,O solid and Br, gaseousH,O liquid and Br2 ,,H,O ,, and Br2 liquidPoints of inteasection at - 0.3" and + 6.2".A. P.Air-pump Regulator. By N. v. KLOBUKOW (Zeit. anal. Chem.,24, 399-402).-A. simple apparatus by means of which the reducedpressure obtained by means of a water jet air-pump may be renderedconstant within 1.0 cm. at whatever pressure required, and howeverthe rate of fiow Q€ the water may vary. A. P

ISSN:0368-1769    

DOI:10.1039/CA8865000113

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

118 ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c Chemistry. Chlorine Monoxide. By K. GARZAROLLI-THVRNLACKH and G. SCHACHERL (AnnaZen, 230, 2 73-286) .-Chlorine monoxide, prepared by the action of dry chlorine gas on well-dried precipitated mercuric oxide, is a dark bi-own liquid boiling at 5" under a pressure of 738 mm. The vapour has a yellowish-brown colour ; its density at 10" is 43-35, It is not decomposed by exposure to light. It dissolves in water,INORGANlC CHEMISTRY. 119 forming a yellow solution. When chlorine monoxide is passed over lime, chlorine is evolved and calcium hypochlorite formed. The oxide decomposes with explosive violence when it is brought in contact with organic matter. w. c. w. Bromine Absorption. By E. J. MILLS and J. MUTER ( J . 800. Chern.Ind., 4, 96-$%).--In the present paper, the authors hare tabulated a series of constants of bromine absorption f o r most of the important resins, a few elementary substances, and some interesting substances of a different nature. The absorplion was effected either in carbon bisulphide o r in carbon tetrachloride, and was determined by titration with P-naphthol or sodium thiosulphate and decinormal iodine, or by simple colorimetric comparison. Benzoic, cinnamic, and salicylic acids, camphor, naphthalene, and benzaldehyde gave no absorption in carbon tetrachloride. At ll", anthracene absorbs in tetrachloride 88.67 per cent. of bromine, corresponding with the ratio Cl4Hl0 : Br, ; at about 17" the absorption corresponds with CI4Hl0 : Br4. Of resinous substances, the absorption of shellac is below all other substahces of its class.As a rule, but not invariably, the greater the solubility of a gum resin the greater is its bromine absorption. The results with elementary substances are remarkable. Thus, tin-dust gives no absorption of bromine, arsenic absorbs in 12 hours 2.85 per cent., and aluminium in 1 hour 8-97 per cent. of bromine, carbon tetrachloride being used as the solvent. Zinc-dust takes u p bromine in the proportion Zn : Br2, and antimony in the pro- portion Sb : Brg. It has already been shown that aniline dissolved in carbon bisulphide absorbs bromine in the proportion 1 : 2. The authors consider it probable in this case, as in that of the toluidines, that additive and not substitution compounds are formed.The chemical activity of paratoluidine in carbon bisulphide, is less than in the case of tetrachloride, but, owing to the formation of yellow bye-products, carbon bisulphide is a better solvent for analyticnl purposes. carbon bisulphide being the solvent. In conclusion, it is shown that if the bromine absorption of mixtures of aniline with parat-oluidine is known, the composition of the mixture admits. of ready calculation. Solubility of Hydrogen Bromide at Different Temperatures and Pressures. By H. W. €3. ROOZEBOOM (Ren. Trav. Chinz., 4, 102-107) .-Determinations of the solubility of hydrogen bromide under pressures varying from 0 to 760 mm. were made at six temperatares between - 25" and 0". The results obtained formed similar curves for each temperature, the curves seem to be parabolic.The weight of gas dissolved by one part of water varies between 2.52 parts at - 25", and 2.2 parts a t 0", both under 760 mm: pressure, to 1.1 parts a t any temperature between - 25" and 0" when under 0.2 mm. pressure, A. P. 2C,H,N : Brz, Orthotoluidine takes up bromine in the proportion C7HgN : Br,, D. B.120 ABSTRACTS OF CHEMICAL PAPERS. Action of Nascent Hydrogen in Increasing the Activity of Oxygen. By F. HOPPE-SEYLER (Zeit. physioZ. Chein., 10, 36-39).- Tlie author criticises the views put forward on this subject by W. Pfeffer (Unters. not. Inst. Tubingen, 1, 636), arid by M. Traube (Rer., 16, 117, 1197), and affirms the accuracy of his own theory (Abstr., 1880, 3 ) . Reaction between Carbonic Oxide and Steam. By A. N A u M m N and c.PISTOR (Bey., 18, 2894-%397).-1n this paper, experiments are described made with a view of ascertaining the tern- perature at which carbonic oxide and steam react to form carbonic anhydride and hydrogen. The niet,hod consisted in passing carbonic oxide, freed from carbonic anhydride and oxygen, over water heated a t SO", so as to obtain an approximately equiiiiolecular proportion of carbonic oxide and vapour of water. The mixed gases were passed through a porcelain tube the temperature of which was roughly determined by introducing into it certain salts or spirals of various metals ; the resultant gas was then analysed by the usual methods. The following results were obtained :-At 560" no reaction took place, a t 600" 2 per cent., a t 900' 8 per cent., and a t 904" 10.5 per cent.of the carbonic oxide was converted into carbonic anhydride. All the conditions which militate against a reaction between carbonic anhydride and hydrogen are favourable to that between steam and carbonic oxide, inasmuch as such a change would be exothermic (+ 10730 cal.), and the resultant carbonic anhydride is very stable a t high temperatures, whilst the steam is readily decomposed into hydrogen and oxygen, the latter of which can burn the carbonic oxide. ATote by Abstractor.-The author seems to be unaware of, o r a t least docs not mention, the elaborate experiments of Dixon on the chemical interaction alluded to above (Abstr., 1885,479, and Trans., 1886,941). V. H. V. Crystalline Form of Calcium Hydroxide. By S. GLINKA (J. Auss.Chern. Soc., 1885, 451-452).-Crystals of the hydroxide, which had separated on the surface of samples of bydraulic cement, were found to belong to the rhombic system, notwithstanding their hexagonal appearance. Gay-Lussac obtained calcium hydroxide in the form of hexagonal plates by evaporating lime-water in a vacuum. A. T. Schloesing's Law Concerning the Solubility of Calcium Carbonate in Water containing Carbonic Anhydride. BJ- R. ENGEL (Compt. rend., 101, 949-951 ).-The author has already shown (Abstr., 1885, 484) that, the solubility of magnesium carbonate in water saturated with carbonic anhpdride, follows Schloesing's law up to a pressure of 6 atmos. Cnro's experiments (Arch. Pharnz. [3], 4, 145) indicate, however, that the law does not hold for calcium carbonate at pressures higher than that of the atmosphere. The author has therefore investigated the solubility of calcium carbonate at high pressures, the method of experiment being the same as ifi the case of the magnesium compound.The results obtained show thatINORGANIC CHEMISTRY. 12 1 Caro's experiments were inexact, and that the solubility of calcium carbonate follows Schloesing's law up to a pressure of 6 atmos., beyond which the experiments were not carried. The value actually found is, however, always slightly less than that calculated by means of Schloesing's formula, and the difference becomes greater the higher the pressure. The author's formula for the solubility of magnesium TKalso holds good for the calcium compound. 1 carbonate, y = - 16 Barium carbonate likewise obeys Schloesing's law a t high pressures, the results obtained being of the same order as in the case of calcium carbcnate.C. H. B. Normal Magnesium Carbonate. By R. ENGEL (Compf. rend., 101, 814-816).-When magnesium potassium hydrogen carbonate, MgCO,,KHCOJ + 4H20, is strongly heated, it melts arid yields a normal magnesium potassium carbonate, but if the triple carbonate is gradually and carefully heated up to 15U" or even W O O , i t does not melt but loses its water of crystallisation and half the carbonic anhydride previously combined with the potassiuni, and leaves a residue of transparent crystals which retain their original forin. These crystals are not a double magnesium &potassium carbonate, for if they are treated with water potassium carbonate is dissolved and magnesium carbonate is left in crystals which retain the form of t h o original crystals.If the normal magnesium carbonate thus obtained is left in contact w t l i water, it rapidly combines with it with development of heat, forming the pentahydrate if the temperature is below 16", and the trihydrate if it is above 16". The anhydrous carbonate even absorbs moisture from the air. It is much more soluble in water than the 113 drated carbonates, and its solution gradually deposits c q stals of the hydrated salt. properties from the natural carbonatc, and also from the aitificial crystals obtained hy Senarmont. If the mixture of potassium carbonate and magnesium carbonate is heated in an atmosphere saturated with aqueous vapour, water is absorbed and the carbonates combine without fusing to form a hydrated double carbonate which has the same crystalline form as the original compound, but is not transparent and seems to be black.This compourid is decomposed by water, but does not yield anhjdrous magiicsiurri ciirbonate, the 11 jdrated carbonate being foriiiecl in I ropor- tion as the decompositioii takes place. The same result is observed w lien the magnesium potassium hydrogen carbonate is decomposed by water. C. H. B. r 1 l h i s form of magnesium carbonate is obviously very different in its Combination of Normal Magnesium Carbonate with Potassium Hydrogen Carbonate. By R. ENGEL (Corn& rend., 101, 749--751).-The author has investigated the conditions under which normal magnesium carbonate combines with potassium hydrogen carbonate, and finds that for the same solution of potassium hydrogen carbonate the velocity of the reaction decreases as the122 ABSTlZXCTS OF CHEMICAL PAPERS.temperature rises. I f the temperature remains constant, the velocity increases with the initial concentration of the potassium solution. Combination ceases when it att,ains a certain limit, which is measured by the concentration of the solution of the potassium salt remaining in contact with excess of magnesium carbonate without combining with it. This limit increases with the temperature, and its variation is given by the formula y = m + nt + pt2, where y is the number of cubic centimetres of standard sulphuric acid required to neutralise the carbonates remaining in solution, and m, n, and f are constants having the values 2.5236, 0.0051 7, and 0.0031086 respectively.The product of the combination, MgC03,KHC0, + 4H20, is decomposed by water, and the decomposition tends towards a limit which is not identical with the limit of combination, but is always inferior to i t by a quantity which is practically the same for a'll temperatures. C. H. B. Double Nitrates of Silver and the Alkalis. By A. DITTE (Compt. rend., lO1,878--882).-When a solution containing silver and potassium nitrates is slowly concentrated, potassium nitrate at first crystallises alone, but as soon as the liquid contains a t least 3 mols. of silver nitrate for each mol.. of potassium nitrate bulky, transparent, right rhombic prisms are formed. These prisms are highly modified and have the composition AgNOa,KN03.This double salt is always foiamed when a solution of the two nitrates contains so much of the silver salt that both nitrrates can crystallise simultaneously. If the double salt is treated with water, the silver nitrate is gradually removed. Rubidium nitrate yields a strictly analogous double salt, and in all probability cmium nitrate will behave in the same way. If a solution of silver and ammonium nitrates is gradually concen- trated, the silver salt, being less soluble, cr.ystallises alone, but after a time the double nitrate AgNO3,NH,NO3, separates in crystals similar to t,hose of the potassium compound. This double s a l t is eaqily obtained whenever the mixed solutions contain an excess of the ammonium salt.Rose stated that a solution of silver and sodium nitrates contailling an excess of the former, first yields crystals of silver nitrate only, and afterwards crystals of the double nitrates AgN03,2NaN0, ; and AgNO3.4NaNO3. The author finds that when the silver nitrate is in excess, this salt crystallises alone in its ordinary form, but as soon as sodium nitrate begiris to separate also, the two salts crystdlise together, and the crystals take the ordinary form of sodium nitrate. Whatever the original composition of the solution, the composition of the crystals and the mother-liquor varies continuously, however, and no definite compounds are formed. From this result it follows that silver nitrate is dimorphous, and that one of its forms is iso- morphous with sodium nitrate, but the author has not been able to obtain pure silver nitrate in rhombohedrons. Lithium nitrate crystallises below 10" in prismatic needles con- taining 5H20, and if a mixture of silver and lithium nitrates is allowed to crystallise a t this temperature, the two salts crystalliseISORGANIC CHEMISTRY.123 separately. Above 15", however, lithium nitrate forms anhydrous crystals similar to those of sodium nitrate, and if a solution of silver and lithium nitrates is concentrated a t this temperature, the two salts crystallise together in rhombohedrons, but the composition of the crystals and the mother-liquor varies continuously as in the case of sodium nitrate, C. H. R. Anhydrous Cerium Chloride, and Cerium Silicate. By P. DIDIER ( C o n y f .rend., 101,882-884) .--Anhydrous cerium chloride is readily obtained by passing a carefully dried mixture of chlorine and carbonic oxide over cerosoceric oxide contained in a carbon dish. It is somewhat easily fusible, but only slightly volatile, highly deli- quescent, and dissolves completely in waber with considerable develop- ment of heat. Oxygen decomposes it at, a dull red heat with liberation of chlorine and formation of cerosoceric oxide. If bhe cerous chloride is previously mixed with sodium cliloride, the cerosoceric oxide forms crpfals which seem to belong to the cubic system, and have a metallic lustre and a brilliant red colour if they have been produced a t a high temperature. This variety of cerosoceric oxide seems to be identical with the crystals obtained by Grandeau by a different method (Abstr., 1885, 8i2).Cerous chloride is also decomposed by steam at a high temperature with formation of cerosoceric oxide and hydrochloric acid ; b u t if a mixture of steam and nitrogen is passed over a fused mixture of cerous and sodium chlorides, the oxychloride Ce302C12 is obtained in iridescent, micaceous scales with a silvery lustre. This compound is formed whenever hydrochloric acid and cerium oxide, or cerous chloride and water, are brought in contact at a high temperature, bnt if oxygen is also present, cerosoceric oxide is also formed. Cerous oxychloride is easily soluble in dilnte acids, and when heated in the air gives off hydrochloric acid, a residue of cerosoceric oxide being left. When silica and cerous chloride are heated together in a platinum dish in a non-oxidising atmosphere, the greater part of the silicon is volatilised in the form of tetrachloride, and long, colourless needles insoluble in water are left mixed with the excess of cerous chloride.These crystals have the composition Si02,2Ce0,2CeC12 ; they act on polarised light, undergo very little change in contact with water, but oxidise and become brown when exposed to the air. If cerium oxychloride is fused with silica and either sodium or calcium chloride, cerium silicate is obtained in highly modified prisms of sp. gr. 4.9, which act strongly on polarised light, and are more or less rapidly attacked by hydrochloric, nitric, and sulphuric acids, according to the concentration of the acid. This silicate has the composition SiO,,BCeO, and is therefore analogous to peridote.Lead Tetrachloride. By T. NIKOLUKINE ( J . Russ. Chem. XOC., 1885, 207-210).-The author finds that by the action of hydro- chloric acid on lead peroxide, the reaction being conducted a t a low temperature, lead tetrachloride is formed together with the dichloride. Potassium chloride forms with the tetrachloride a double salt, similar C. H. B.124 ABSTRACTS OF CHEMICAL PAPERS. to that with stannic chloride, soluble in a saturated solution of potassium chloride, lead dichloride being very sparingly soluble therein. With ammonium chloride, the reverse is the case, its double salt with lead tetrachloride being insoluble, and lead dichloride soluble in the saturated solution. Lead tetrachloride is a strong oxidking agent, acting even on platinum ; its solutions evolve chlorine after a time, and deposit crystals of the dichloride; when heated, chlorine is rapidly evolved.With caustic alkalis and their carbonates, a dark brown precipitate of lead peroxide is formed. I n the action of hydrochloric acid on lead peroxide, a double com- pound of the acid with the tetrachloride is most probably formed. Lead tetrachloride is decomposed by small quantities of water with evolution of chlorine ; with large quantities of water a red-brown coloration of the liquid occurs, apparently due to tlie formation of lead peroxide. A. T. Double Salts of Ferric Chloride with other Metallic Chlorides. By G. NEUMANN (Ber., 18, 2890--2894).-When a large quantity of ferric chloride is dissolved in hot fuming hydrochloric acid, and to it is added the metallic chloride whose double salt is required, and the liquid filtered, double salts of the general formula Pe2C1,,4RC1 + 2H,O separate out, on cooling.These crjstallise in the regular system, generally as microscopic octohedra or rhombic dodecahedra. In this paper, such double salts of ferric chloride with potassium, ammonium, rubidium, magnesium, and beryllium chlorides are described. Mdybdenum Residues. By W. VENATOR (Arch. Plmrm. [3], 23, 713-i14).-1f the residues contain no iron, sufficient ferric chloride is added to give a brownish-yellow colour to the solution. To separate the phosphoric acid, ammonia is added, the precipitate filtered off, and the filtrate is treated with barium chloride, whereby barium rnolybdate and sulphate are precipitated. The precipitate is well washed with hot water, and boiled for a long time with an equiva- lent amount of ammonium sulphate and water, with active agitation. The barium sulphate is filtered off, and the ammonium molybdate crystallised out..Crystallised Tin. By H. v. FOULLON (Juhrb. f. Min., 1885, 2, Ref., 266-268) .-From a series of measurements, the author concludes that only the following allotropic modifications may be regarded as diiferent :-Grey tin (sp. gr. 5.781 to 5.809) ; rhombic tin (sp. gr. 6.S.L to 6-56> ; and tetragonal tin (sp. gr. 7.196). The author is doubtful whether tlie moditication described as previously melted tin (sp. gr. 7.2795) differs from the tetragonal modification, as the differences in the sp.gr. of the two are not greater than the differences in the values obtained by different observers with tetragonal tin. These differences are obviously due to the numerous gas inclusions. V. H. V. The product thus obtained is very pure. J. T. B. H. B. Platinum Silicide. By C. G. NEMMINGER (Amer. Chern. J., 17%- 175).-Topax was inteusely ignited in a platinum crucible placed in a graphite crucible; at the end of the operation the platinum wasMISERALOGICAL CHEMISTRY. 125 found to be fused, having been converted into a brittle, fusible sub- stance containing 1.61 per cent. of silicon. H. B. Colour Reaction of Rhodium. By E. DEMARCAY (Corn@. rend., 101, 951-952).-A neutral or feebly acid solution of ammonium rhodiochloride, if sufficiently concentrated, gives a yellowish precipi- tate with a slight excess of sodium hypochlorite.If a 20 per cent. solution of acetic acid is added drop by drop to the liquid, with con- tinual agitat,ion, the precipitate dissolves and forms a somewhat intense orange-coloured solution, which rapidly decolorises, deposits a greyish precipitate, and finally acquires an intense sky-blue colour. This colour persists for severat hours, and then gradually disappears, but can be reproduced by repeating the same operations with the colourless liquid. The disappearance of the blue coloration is accele- rated by the presence of any free nitric or sulphuric acid, or of a large excess of acetic acid, and by a rise of temperature. The sodium hypochlorite solution should be freshly prepared and somewhat con- centrated ; an excess- exerts no injurious effect.It is immaterial whether the rhodium solution be originally yellow or red. Chlorides of other metals of the platinum group give no reaction with sodium hypochlorite under the same conditions. Small quanti- ties of rhodium can be detected in a mixture if two equal portions of the solution are taken for comparison, and one is diluted with water up to the same bulk as that with which the test is performed. I n this way, 0*0001 gram of rhodium can be detected in 3 C.C. of liquid, but the blue colour is very faint, and appears slowly. Wihh potash, the blue solutions of rhodium give a greenish precipi- tate which dissolves in acetic acid, with production of a dark-blue solution.C. H. B.118 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c Chemistry.Chlorine Monoxide. By K. GARZAROLLI-THVRNLACKH and G.SCHACHERL (AnnaZen, 230, 2 73-286) .-Chlorine monoxide, preparedby the action of dry chlorine gas on well-dried precipitated mercuricoxide, is a dark bi-own liquid boiling at 5" under a pressure of 738 mm.The vapour has a yellowish-brown colour ; its density at 10" is 43-35,It is not decomposed by exposure to light. It dissolves in waterINORGANlC CHEMISTRY. 119forming a yellow solution. When chlorine monoxide is passed overlime, chlorine is evolved and calcium hypochlorite formed. The oxidedecomposes with explosive violence when it is brought in contactwith organic matter. w. c. w.Bromine Absorption. By E. J. MILLS and J.MUTER ( J . 800.Chern. Ind., 4, 96-$%).--In the present paper, the authors haretabulated a series of constants of bromine absorption f o r most of theimportant resins, a few elementary substances, and some interestingsubstances of a different nature. The absorplion was effected eitherin carbon bisulphide o r in carbon tetrachloride, and was determinedby titration with P-naphthol or sodium thiosulphate and decinormaliodine, or by simple colorimetric comparison. Benzoic, cinnamic,and salicylic acids, camphor, naphthalene, and benzaldehyde gave noabsorption in carbon tetrachloride. At ll", anthracene absorbs intetrachloride 88.67 per cent. of bromine, corresponding with the ratioCl4Hl0 : Br, ; at about 17" the absorption corresponds with CI4Hl0 : Br4.Of resinous substances, the absorption of shellac is below all othersubstahces of its class. As a rule, but not invariably, the greater thesolubility of a gum resin the greater is its bromine absorption.Theresults with elementary substances are remarkable. Thus, tin-dustgives no absorption of bromine, arsenic absorbs in 12 hours2.85 per cent., and aluminium in 1 hour 8-97 per cent. of bromine,carbon tetrachloride being used as the solvent. Zinc-dust takesu p bromine in the proportion Zn : Br2, and antimony in the pro-portion Sb : Brg. It has already been shown that aniline dissolvedin carbon bisulphide absorbs bromine in the proportion 1 : 2.The authors consider it probable in this case, as in that of thetoluidines, that additive and not substitution compounds are formed.The chemical activity of paratoluidine in carbon bisulphide,is less than in the case of tetrachloride, but, owing to the formation ofyellow bye-products, carbon bisulphide is a better solvent for analyticnlpurposes.carbon bisulphide being the solvent.In conclusion, it is shown thatif the bromine absorption of mixtures of aniline with parat-oluidineis known, the composition of the mixture admits. of ready calculation.Solubility of Hydrogen Bromide at Different Temperaturesand Pressures. By H. W. €3. ROOZEBOOM (Ren. Trav. Chinz., 4,102-107) .-Determinations of the solubility of hydrogen bromideunder pressures varying from 0 to 760 mm. were made at sixtemperatares between - 25" and 0". The results obtained formedsimilar curves for each temperature, the curves seem to be parabolic.The weight of gas dissolved by one part of water varies between 2.52parts at - 25", and 2.2 parts a t 0", both under 760 mm: pressure, to1.1 parts a t any temperature between - 25" and 0" when under0.2 mm.pressure, A. P.2C,H,N : Brz,Orthotoluidine takes up bromine in the proportionC7HgN : Br,,D. B120 ABSTRACTS OF CHEMICAL PAPERS.Action of Nascent Hydrogen in Increasing the Activity ofOxygen. By F. HOPPE-SEYLER (Zeit. physioZ. Chein., 10, 36-39).-Tlie author criticises the views put forward on this subject by W.Pfeffer (Unters. not. Inst. Tubingen, 1, 636), arid by M. Traube (Rer., 16,117, 1197), and affirms the accuracy of his own theory (Abstr.,1880, 3 ) .Reaction between Carbonic Oxide and Steam. By A.N A u M m N and c.PISTOR (Bey., 18, 2894-%397).-1n this paper,experiments are described made with a view of ascertaining the tern-perature at which carbonic oxide and steam react to form carbonicanhydride and hydrogen. The niet,hod consisted in passing carbonicoxide, freed from carbonic anhydride and oxygen, over water heated a tSO", so as to obtain an approximately equiiiiolecular proportion ofcarbonic oxide and vapour of water. The mixed gases were passedthrough a porcelain tube the temperature of which was roughlydetermined by introducing into it certain salts or spirals of variousmetals ; the resultant gas was then analysed by the usual methods.The following results were obtained :-At 560" no reaction took place,a t 600" 2 per cent., a t 900' 8 per cent., and a t 904" 10.5 per cent.ofthe carbonic oxide was converted into carbonic anhydride.All the conditions which militate against a reaction between carbonicanhydride and hydrogen are favourable to that between steam andcarbonic oxide, inasmuch as such a change would be exothermic(+ 10730 cal.), and the resultant carbonic anhydride is very stablea t high temperatures, whilst the steam is readily decomposed intohydrogen and oxygen, the latter of which can burn the carbonic oxide.ATote by Abstractor.-The author seems to be unaware of, o r a t leastdocs not mention, the elaborate experiments of Dixon on the chemicalinteraction alluded to above (Abstr., 1885,479, and Trans., 1886,941).V.H. V.Crystalline Form of Calcium Hydroxide. By S. GLINKA(J. Auss. Chern. Soc., 1885, 451-452).-Crystals of the hydroxide,which had separated on the surface of samples of bydraulic cement,were found to belong to the rhombic system, notwithstanding theirhexagonal appearance. Gay-Lussac obtained calcium hydroxide in theform of hexagonal plates by evaporating lime-water in a vacuum.A. T.Schloesing's Law Concerning the Solubility of CalciumCarbonate in Water containing Carbonic Anhydride. BJ-R. ENGEL (Compt. rend., 101, 949-951 ).-The author has alreadyshown (Abstr., 1885, 484) that, the solubility of magnesium carbonatein water saturated with carbonic anhpdride, follows Schloesing's lawup to a pressure of 6 atmos. Cnro's experiments (Arch.Pharnz. [3],4, 145) indicate, however, that the law does not hold for calciumcarbonate at pressures higher than that of the atmosphere. Theauthor has therefore investigated the solubility of calcium carbonateat high pressures, the method of experiment being the same as ifithe case of the magnesium compound. The results obtained show thaINORGANIC CHEMISTRY. 12 1Caro's experiments were inexact, and that the solubility of calciumcarbonate follows Schloesing's law up to a pressure of 6 atmos.,beyond which the experiments were not carried. The value actuallyfound is, however, always slightly less than that calculated by meansof Schloesing's formula, and the difference becomes greater the higherthe pressure. The author's formula for the solubility of magnesiumTKalso holds good for the calcium compound.1 carbonate, y = -16Barium carbonate likewise obeys Schloesing's law a t high pressures,the results obtained being of the same order as in the case of calciumcarbcnate.C. H. B.Normal Magnesium Carbonate. By R. ENGEL (Compf. rend.,101, 814-816).-When magnesium potassium hydrogen carbonate,MgCO,,KHCOJ + 4H20, is strongly heated, it melts arid yields anormal magnesium potassium carbonate, but if the triple carbonate isgradually and carefully heated up to 15U" or even W O O , i t does notmelt but loses its water of crystallisation and half the carbonicanhydride previously combined with the potassiuni, and leaves aresidue of transparent crystals which retain their original forin.These crystals are not a double magnesium &potassium carbonate, forif they are treated with water potassium carbonate is dissolved andmagnesium carbonate is left in crystals which retain the form of t h ooriginal crystals.If the normal magnesium carbonate thus obtained is left in contactw t l i water, it rapidly combines with it with development of heat,forming the pentahydrate if the temperature is below 16", and thetrihydrate if it is above 16".The anhydrous carbonate even absorbsmoisture from the air. It is much more soluble in water than the113 drated carbonates, and its solution gradually deposits c q stals of thehydrated salt.properties from the natural carbonatc, and also from the aitificialcrystals obtained hy Senarmont.If the mixture of potassium carbonate and magnesium carbonate isheated in an atmosphere saturated with aqueous vapour, water isabsorbed and the carbonates combine without fusing to form ahydrated double carbonate which has the same crystalline form as theoriginal compound, but is not transparent and seems to be black.This compourid is decomposed by water, but does not yield anhjdrousmagiicsiurri ciirbonate, the 11 jdrated carbonate being foriiiecl in I ropor-tion as the decompositioii takes place.The same result is observedw lien the magnesium potassium hydrogen carbonate is decomposed bywater. C. H. B.r 1 l h i s form of magnesium carbonate is obviously very different in itsCombination of Normal Magnesium Carbonate withPotassium Hydrogen Carbonate. By R.ENGEL (Corn& rend.,101, 749--751).-The author has investigated the conditions underwhich normal magnesium carbonate combines with potassiumhydrogen carbonate, and finds that for the same solution of potassiumhydrogen carbonate the velocity of the reaction decreases as th122 ABSTlZXCTS OF CHEMICAL PAPERS.temperature rises. I f the temperature remains constant, the velocityincreases with the initial concentration of the potassium solution.Combination ceases when it att,ains a certain limit, which is measuredby the concentration of the solution of the potassium salt remainingin contact with excess of magnesium carbonate without combiningwith it. This limit increases with the temperature, and its variationis given by the formula y = m + nt + pt2, where y is the number ofcubic centimetres of standard sulphuric acid required to neutralisethe carbonates remaining in solution, and m, n, and f are constantshaving the values 2.5236, 0.0051 7, and 0.0031086 respectively.The product of the combination, MgC03,KHC0, + 4H20, isdecomposed by water, and the decomposition tends towards a limitwhich is not identical with the limit of combination, but is alwaysinferior to i t by a quantity which is practically the same for a'lltemperatures.C. H. B.Double Nitrates of Silver and the Alkalis. By A. DITTE(Compt. rend., lO1,878--882).-When a solution containing silver andpotassium nitrates is slowly concentrated, potassium nitrate at firstcrystallises alone, but as soon as the liquid contains a t least 3 mols.ofsilver nitrate for each mol.. of potassium nitrate bulky, transparent,right rhombic prisms are formed. These prisms are highly modifiedand have the composition AgNOa,KN03. This double salt is alwaysfoiamed when a solution of the two nitrates contains so much of thesilver salt that both nitrrates can crystallise simultaneously. If thedouble salt is treated with water, the silver nitrate is graduallyremoved.Rubidium nitrate yields a strictly analogous double salt, and in allprobability cmium nitrate will behave in the same way.If a solution of silver and ammonium nitrates is gradually concen-trated, the silver salt, being less soluble, cr.ystallises alone, but after atime the double nitrate AgNO3,NH,NO3, separates in crystals similarto t,hose of the potassium compound.This double s a l t is eaqilyobtained whenever the mixed solutions contain an excess of theammonium salt.Rose stated that a solution of silver and sodium nitrates contaillingan excess of the former, first yields crystals of silver nitrate only,and afterwards crystals of the double nitrates AgN03,2NaN0, ; andAgNO3.4NaNO3. The author finds that when the silver nitrate is inexcess, this salt crystallises alone in its ordinary form, but as soon assodium nitrate begiris to separate also, the two salts crystdlisetogether, and the crystals take the ordinary form of sodium nitrate.Whatever the original composition of the solution, the compositionof the crystals and the mother-liquor varies continuously, however,and no definite compounds are formed.From this result it followsthat silver nitrate is dimorphous, and that one of its forms is iso-morphous with sodium nitrate, but the author has not been able toobtain pure silver nitrate in rhombohedrons.Lithium nitrate crystallises below 10" in prismatic needles con-taining 5H20, and if a mixture of silver and lithium nitrates isallowed to crystallise a t this temperature, the two salts crystallisISORGANIC CHEMISTRY. 123separately. Above 15", however, lithium nitrate forms anhydrouscrystals similar to those of sodium nitrate, and if a solution of silverand lithium nitrates is concentrated a t this temperature, the two saltscrystallise together in rhombohedrons, but the composition of thecrystals and the mother-liquor varies continuously as in the case ofsodium nitrate, C.H. R.Anhydrous Cerium Chloride, and Cerium Silicate. ByP. DIDIER ( C o n y f . rend., 101,882-884) .--Anhydrous cerium chlorideis readily obtained by passing a carefully dried mixture of chlorineand carbonic oxide over cerosoceric oxide contained in a carbon dish.It is somewhat easily fusible, but only slightly volatile, highly deli-quescent, and dissolves completely in waber with considerable develop-ment of heat. Oxygen decomposes it at, a dull red heat with liberationof chlorine and formation of cerosoceric oxide. If bhe cerous chlorideis previously mixed with sodium cliloride, the cerosoceric oxide formscrpfals which seem to belong to the cubic system, and have a metalliclustre and a brilliant red colour if they have been produced a t a hightemperature. This variety of cerosoceric oxide seems to be identicalwith the crystals obtained by Grandeau by a different method (Abstr.,1885, 8i2).Cerous chloride is also decomposed by steam at a high temperaturewith formation of cerosoceric oxide and hydrochloric acid ; b u t if amixture of steam and nitrogen is passed over a fused mixture ofcerous and sodium chlorides, the oxychloride Ce302C12 is obtained iniridescent, micaceous scales with a silvery lustre. This compound isformed whenever hydrochloric acid and cerium oxide, or cerouschloride and water, are brought in contact at a high temperature,bnt if oxygen is also present, cerosoceric oxide is also formed.Cerousoxychloride is easily soluble in dilnte acids, and when heated inthe air gives off hydrochloric acid, a residue of cerosoceric oxidebeing left.When silica and cerous chloride are heated together in a platinumdish in a non-oxidising atmosphere, the greater part of the silicon isvolatilised in the form of tetrachloride, and long, colourless needlesinsoluble in water are left mixed with the excess of cerous chloride.These crystals have the composition Si02,2Ce0,2CeC12 ; they act onpolarised light, undergo very little change in contact with water,but oxidise and become brown when exposed to the air. If ceriumoxychloride is fused with silica and either sodium or calcium chloride,cerium silicate is obtained in highly modified prisms of sp.gr. 4.9,which act strongly on polarised light, and are more or less rapidlyattacked by hydrochloric, nitric, and sulphuric acids, according to theconcentration of the acid. This silicate has the composition SiO,,BCeO,and is therefore analogous to peridote.Lead Tetrachloride. By T. NIKOLUKINE ( J . Russ. Chem. XOC.,1885, 207-210).-The author finds that by the action of hydro-chloric acid on lead peroxide, the reaction being conducted a t a lowtemperature, lead tetrachloride is formed together with the dichloride.Potassium chloride forms with the tetrachloride a double salt, similarC. H. B124 ABSTRACTS OF CHEMICAL PAPERS.to that with stannic chloride, soluble in a saturated solution ofpotassium chloride, lead dichloride being very sparingly solubletherein.With ammonium chloride, the reverse is the case, its doublesalt with lead tetrachloride being insoluble, and lead dichloridesoluble in the saturated solution. Lead tetrachloride is a strongoxidking agent, acting even on platinum ; its solutions evolvechlorine after a time, and deposit crystals of the dichloride; whenheated, chlorine is rapidly evolved. With caustic alkalis and theircarbonates, a dark brown precipitate of lead peroxide is formed.I n the action of hydrochloric acid on lead peroxide, a double com-pound of the acid with the tetrachloride is most probably formed.Lead tetrachloride is decomposed by small quantities of water withevolution of chlorine ; with large quantities of water a red-browncoloration of the liquid occurs, apparently due to tlie formation oflead peroxide.A. T.Double Salts of Ferric Chloride with other Metallic Chlorides.By G. NEUMANN (Ber., 18, 2890--2894).-When a large quantity offerric chloride is dissolved in hot fuming hydrochloric acid, and to it isadded the metallic chloride whose double salt is required, and theliquid filtered, double salts of the general formula Pe2C1,,4RC1 + 2H,Oseparate out, on cooling. These crjstallise in the regular system,generally as microscopic octohedra or rhombic dodecahedra. In thispaper, such double salts of ferric chloride with potassium, ammonium,rubidium, magnesium, and beryllium chlorides are described.Mdybdenum Residues. By W. VENATOR (Arch.Plmrm. [3],23, 713-i14).-1f the residues contain no iron, sufficient ferricchloride is added to give a brownish-yellow colour to the solution.To separate the phosphoric acid, ammonia is added, the precipitatefiltered off, and the filtrate is treated with barium chloride, wherebybarium rnolybdate and sulphate are precipitated. The precipitate iswell washed with hot water, and boiled for a long time with an equiva-lent amount of ammonium sulphate and water, with active agitation.The barium sulphate is filtered off, and the ammonium molybdatecrystallised out..Crystallised Tin. By H. v. FOULLON (Juhrb. f. Min., 1885, 2, Ref.,266-268) .-From a series of measurements, the author concludesthat only the following allotropic modifications may be regarded asdiiferent :-Grey tin (sp.gr. 5.781 to 5.809) ; rhombic tin (sp. gr. 6.S.Lto 6-56> ; and tetragonal tin (sp. gr. 7.196). The author is doubtfulwhether tlie moditication described as previously melted tin (sp. gr.7.2795) differs from the tetragonal modification, as the differences inthe sp. gr. of the two are not greater than the differences in thevalues obtained by different observers with tetragonal tin. Thesedifferences are obviously due to the numerous gas inclusions.V. H. V.The product thus obtained is very pure. J. T.B. H. B.Platinum Silicide. By C. G. NEMMINGER (Amer. Chern. J., 17%-175).-Topax was inteusely ignited in a platinum crucible placed ina graphite crucible; at the end of the operation the platinum waMISERALOGICAL CHEMISTRY. 125found to be fused, having been converted into a brittle, fusible sub-stance containing 1.61 per cent. of silicon. H. B.Colour Reaction of Rhodium. By E. DEMARCAY (Corn@. rend.,101, 951-952).-A neutral or feebly acid solution of ammoniumrhodiochloride, if sufficiently concentrated, gives a yellowish precipi-tate with a slight excess of sodium hypochlorite. If a 20 per cent.solution of acetic acid is added drop by drop to the liquid, with con-tinual agitat,ion, the precipitate dissolves and forms a somewhatintense orange-coloured solution, which rapidly decolorises, depositsa greyish precipitate, and finally acquires an intense sky-blue colour.This colour persists for severat hours, and then gradually disappears,but can be reproduced by repeating the same operations with thecolourless liquid. The disappearance of the blue coloration is accele-rated by the presence of any free nitric or sulphuric acid, or of a largeexcess of acetic acid, and by a rise of temperature. The sodiumhypochlorite solution should be freshly prepared and somewhat con-centrated ; an excess- exerts no injurious effect. It is immaterialwhether the rhodium solution be originally yellow or red.Chlorides of other metals of the platinum group give no reactionwith sodium hypochlorite under the same conditions. Small quanti-ties of rhodium can be detected in a mixture if two equal portions ofthe solution are taken for comparison, and one is diluted with waterup to the same bulk as that with which the test is performed. I n thisway, 0*0001 gram of rhodium can be detected in 3 C.C. of liquid, but theblue colour is very faint, and appears slowly.Wihh potash, the blue solutions of rhodium give a greenish precipi-tate which dissolves in acetic acid, with production of a dark-bluesolution. C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8865000118

出版商:RSC    

年代:1886

数据来源: RSC