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J O U R N A LOFTHE CHEMICAL SOCIETY,ABSTRACTS OF CHEMICAL PAPERS PUBLISHED INBRITISH AND FOREIGN JOURNALS.General a n d P h y s i c a l Chemistry.Infra-red Radiation Spectra. By H. BECQUEREL (Compt. rend.,97, 71-74. Compare also Abstr., 1883, 761).-The author hasexamined the infra-red radiation spectra of several metals by themethod previously described (Compt. rend., 96, 121).Sodium gives two strong lines of wave-lengths 18190 and 10980,coincident with two lines in the solar spectrum. The line at 8190can be seen with an ordinary spectroscope, and coincides withBrewster’s solar line Y.Magnesium gives three strong lines at 8755, 10300, and 11300respectively, coincident with three lines in the solar spectrum.Calcium in the electric arc gives a strong band of mean wave-length about 8480, coincident with a group of lines in the solarspectrum.Potassium gives five strong lines at 7700, 10030, 10730, 11250 and11820 respectively.Silver gives two very strong lines at 7720 and 8290 respectively.Thalli.1m gives a very strong line at 11050, very near the secondsodium line, but much stronger than, and quite distinct from, thelatter.The infra-red region of the spectrum down to about wave-length8600 can be seen with an ordinary spectroscope by concentrating thelight on the slit and filtering out the more luminous rays by means ofa solution of iodine in carbon bisulphide.C. H. B.Copper Oxide Battery. B,y F. DE LALANDE and G. CHAPERON(Compt. rend., 9 7, 164-166) .-The elements of the battery are zinc,cupric oxide, and potassium hydroxide.The cupric oxide is in con-tact with a plate of iron or brass which forms the positive pole, orVOL. XLVI. 2 ABSTRACTS OF CHEMICAL PAPERS.the outer vessel of the battery is constructed of one of these metals.The cupric oxide is the depolarising element of the battery, and isreduced to metallic copper, its conductivity increasing therefore as thebattery is used. The electromotive force of this cell is about one volt,and its internal resistance is very low and does not sensibly alterwhile the batr;ery is in action. Small sizes give a current of twoamphres ; large sizes give as much as 30 amphres. Since the potashsolution has no action on the oxide of copper nor on the amalga-mated zinc, there is no waste when the battery is not in action.Thereduced copper can be reconverted into oxide by roasting. Thisbattery can be used for long periods through low resistances, sincedepolarisation is rapid and complete. C. H. B.Currents Produced by Immersion and Emersion, and by theMovement of a Metal in a Liquid. By KROUCHKOLL (Compt. rend.,97, 161--163).-1t has been known for some time that if two elec-trodes of the same metal are immersed in a liquid and one of them ismoved, the motion produces a current the direction of which dependson the nature of the metal and liquid. If, too, one of the electrodesis placed in the liquid and the other is immersed afterwards, a, currentis produeed a t the moment of immersion.The author finds that a current is also produced when one of theelectrodes is withdrawn from the liquid.The current a t immersionis in the opposite direction to that produced by movement of theelectrode in the liquid ; the current of emersion is in the same direc-tion as the current produced by movement. These immersion andemersion currents are produced when the metal is passed from aninsulating to a conducting liquid, as well as when the metal passesfrom the air into a liquid. The electromotive force produced bymotion is analogous to that produced by polarisation: i t is destroyedby solutions of salts of the metal of which the electrodes are com-posed, so that if the saline solutions are sufficiently strong, no currentis produced by moving the elecirode. These phenomena can beexplained by Helmholtz’s hypothesis of double layers of electricaltension.C. H. B.Determination of the Limits of Electrolysis. By C. TRUCHOT(Compt. rend., 97, 92--93).-Since the electromotive force requiredto decompose a given compound depends on the heat of formation ofthe compound, it follows that a determination of the minimum elec-tromotive force necessary to produce decomposition, furnishes ameasure of the heat of formation of the particular compound. Theauthor employs a small Grarnme dynamo, with a Jamin magnet, drivenby a Smidt’s water-motor fitted with a special regulating apparatus.The electromotive force is practically proportional to the velocity ofthe rotation of the dynamo, and this velocity can be regulated withinvery narrow limits.The actual electromotive force is determined bya volt-meter graduated by means of a Daniel1 element. Determina-tions of the minimum electromotive force required to electrolysewater, potassium sulphate, and other compounds, agree very closelywith thermochemical determinations. C. H. BGENERAL AND PHYSICAL CHEMISTRY. 3Pyro-electricity of Blende, Sodium Chlorate, and Boracite.By C. FRIEDEL and J. CURIE (Compt. rend., 97, 61--66).-Crystslsof the cubical system which show tetrahedral heinihedrism behavelike crystals of the hexagonal system. If heated or cooled regularly,i.e., so that the expansion or contraction is equal along all the axes ofhemimorphism, there is no development of pyroelectricity, b u t if theheating or cooling is irregular, so that tension is produced in differentparts of the crystal, then eIectricity is developed. These phenomenahave been observed with blende and with sodium chlorate.Mallardhas shown that boracite a t ordinary temperatures belongs to therhombic system, but at about 265" its form changes to one belongingto the cubical system. The authors find that if a plate of boracitecut parallel with one of the tetrahedral faces is heated at 300-320"for some time and then allowed to cool regularly, no electricity canbe detected until the temperature falls t o about 265", but at this pointthere is a considerable development of electricity, which graduallydiminishes in intensity and eventually changes in sign. I t appearstherefore that when boracite cools regularly it only becomes pyro-electric at the point a t which it ceases to belong to the mbicalsystem. C.H. B.Melting Points of Salts. By E. MAUMENO (Compt. rend., 97, 4548).-Pure potassium nitrate melts at 327" ; pure sodium nitrate at298". The following table gives the melting points of various mix-tures of these and other nitrates as calculated and as observed :-3KN03 + NaNO,'2KNO, +NaNO,RNO, + NaNO,KNO3 + 2NaN0,KNO, + SNaNO,KNOs + AgxO3NaN03 +AgN032NaN03 +AgxO,NaNO, + Ca(N03)zl.68KN03 + AgNO,AgNO,+KNO,+NaNO,Calculated. Observed. Difference.320.7 265-247" -55.7- 73.7"318.4 265-244 -55.7- 74.4313.8 265-219 --55*7- 94.8308.8 242-224 -66.8- 84.8306.2 267-2:37 -39.2- 69.2246.8 169-121 - 77'8-125.8262.5 191-131 - 71-5-131.5231.7 251.5" + l!i%"248.0 263.0 + 1s"258.5 190-130 - 68-128.5374 or 399"* 235-216' -158 or 18PThe first of the observed temperatures is the point at which crystalsbegin to form in the fused mixture, and the second is the point a twhich the whole mass becomes solid.The fall of temperature betweenthese two points is perfectly gradual, and there is no fixed inter-mediate point which can be regarded as Ihe true melting point of themixture. The mixtures of sodium and silver nitrates do not showthis irregularity, but have a definite melting point. Calcium nitrate,which cannot be fused alone without decomposition, melts readilywhen added in small quantities to fused sodium nitrate, and does notdecompose. Zinc nitrate behaves in a peculiar manner.When a pre-viously fused and resolidified mixture of sodium and calcium nitrates* According as the melting point of calcium nitrate is taken as 450" or 500".b 4 ABSTRACTS OF CHEMICAL PAPERS.in equivalent proportions is added gradually to gently heated zincnitrate, the fragments of the mixture decompose a t a temperature aslow as 210", and decomposition continues so long as any of the frag-ments remain undissolved, but ceases when the whole mass becomescompletely liquid. The same phenomenon is observed on each succes-sive addition of the mixture. A mixture of the three nitrates inequivalent proportions solidifies a t 170°, about 80.5" above the calcu-lated melting point.Barium Alcoholate. By DE FORCRAND (Compt.rend., 97,170-172). -Barium alcoholate is so readily decomposed by atmosphericmoisture, that it is almost impossible to obtain it free from hydroxide,and in thermochemical determinations it is necessary to make a cor-rection for this impurity. The heat of solution of the alcoholate at20" is + 19.76 cal., from which it follows that-2CaH60 liquid + RaO solid = (C,H,O),Ba solid + H,O solid2C,H60 liquid + BaH,O, solid = (C2H,0),Ba solid + 2H20 solidThis development of heat is somewhat smaller than that producedby the hydration of barium oxide. The reverse reaction (C2H,0)2Basolid + 2H20 liquid = 2CQH6O liquid + BaH,O, solid, develops + 4-56 cal. These results explain the known properties of the alcoho-late. In presence of excess of alcohoI i t is necessary to take intoaccount the heat of solution of the alcoholate in alcohol and the for-mation of secondary alcoholates similar to those of sodium.The heatof solution in a large excess of alcohol is + 20 cal.; if a saturatedsolution is formed it is + 12.50 cal. By reason of the dissociation ofthe secondary alcoholates, an alcoholic solution of barium alcoholatealways contains (C2H50)2Ba. If such a solution is mixed with a smallquantity of water, part of the alcoholate is converted into hydroxide,and the latter, being insoluble, is precipitated. The equilibrium of thesystem is thus disturbed, and the conversion of the alcoholate intohydroxide continues until all the water has been precipitated as bariumhydroxide.The folloiving table shows the relative stability of the metallicderivatives of certain alcohols and acids with respect to water andacids.It is, howe-rer, also necessary to take int'o account the forma-tion of secondary compounds (hydroxides, secondary alcoholates, basicsalts, &c.), since t,he heat of formation of these bodies may change thedirection of the reaction :-2C2H60 liquid + BaO solid = (C2H50),Ba solid + H,O solid2C2H,0 liquid + BaH,02 solid = (C2H50)2Ba solid + 2H,O solidBC,H,O liquid + Na,O solid = 2C,H5Na0 solid + H,O solidC2H,0 liquid + NaHO solid = C2H5Na0 solid + H,O solidC. H. B.develops + 14.48 cal.develops - 1-68 cal.develops + 14.48 cal.develops - 1.68 cal.develops + 34.70 cal.develops + 0.25 cal.GENERAL AND PHYSICAL CHEMISTRY. 52C2H,Na0, solid + NhO solid = 2CzHoNh03 solid + HzO solidC2H,Na03 solid + NaHO solid = CzH,N~OA solid + HzO solid2C6H60 solid + K,O solid = 2C6HaK0 solid + HzO solidC6H6O solid + KHO solid = C,H,KO solid + H20 solidH2S04 solid + NazO Bolid = NazS04 solid + HzO solidH,SO, solid +- 2NaHO solid = NhSO, solid + 2H20 soliddevelops + 34..54 cal.develops + 0.12 cal.develops + 76.4 cal.develops + 17.7 cal.develops + 103.6 cal.develops + 63.4 cal.{{ C.H. 33.Heat of Formation of Potassium Fluorides. By GUXTZ ( C ~ z p t ,rend., 97, 256--258).--Anhydrous Potassium Fluoride.-The neutral-isation of 1 mol. hydrofluoric acid (dilute) by potassium hyd~oxide(dilute) develops + 16.12 cal. The heat of solution of the aiihy-drous fluoride is 3.6 cal. These results agree with those of Thomsenand Favrt: respectively.KHO solid + HF liquid = KF rolid + H,O solid develops + 30-98 cal.KHO solid + HF gas = KF solid + H20 solid develops + 38.22 cal.Crystallised Potassium Fluoride, KF.2X20.-Heat of solution - 1-03cal.: heat of hydration, KF solid + 2H,O, liquid = KJ?,'LHzO solid,develops + 4 6 3 cal.; with 2H20 solid, + 1.8 cal.KHO solid + HF liquid + HzO solid = KF,2Hz0 solid develops + 34.17 cal.KHO solid + HF gaseous + H,O solid = KF,2H,O solid develops + 41.41 cal.The action of 1 mul. hydrofluoric acid on 1 mol. potassium fluoridein dilute solution is accompanied by an absorption of heat - 0.57cal. ; a phenomenon similar to that observed in the case of hydrogenpotassium sulphate.The heat of solution of potassium hydrogenfluoride, KF,HF is - 6.01 cal.KE' solid + HF gas = KF,HF solid develops + 21.04 cal.KHO solid + 2BF gas = KF,HB' solid + HzO solid developsKHO solid + 2HF liquid = KF,HF solid + HzO solid developsKF solid + HP liquid = HF,HF ,, ,, + 13-80 ),+ 53-13 cal.+ 38.65 cal.Compressibility and Liquefaction of Gases. By J. JAMIN(Compt. rend., 97,10-16; see also Abstr., 1883,898).-The author hasrepresented the results of Andrews' experiments by a series of curves,the ordinates of which represent the density of the gas, and theabscissae tlie pressure for the several temperatures 13-1", 2 1 . 5 O , 31.1",C. H. B6 ABSTRACTS OF CHEMICAL PAPERS.32.5", 35*5", a t which the experiments were made. Below the criticalpoint, the curve is a t first slightly convex with respect to the axis a,because the density increases more quickly than the pressure, but a t acertain point, B, the curve suddenly changes in direction.At thispoint, the gas has attained its maximum tension, and liquefactioncommences, the curve continuing in the new direction until liquefac-tion is complete, when it suddenly takes a direction correspondingwith a slow increase in density, this part of the curve being slightlyconcave because the compressibility gradually decreases. That thisinterpretation of the curve is correct is proved by the fact that themaximurn tensions of the gas a t the different temperatures correspondwith the points B, B', B", &c., at which the direction of the curvechanges.Comparison of the different curves shows that the minimumdensity of the liquid at the moment of its formation is a t first muchhigher than the maximum density of the gas when it begins toliquefy, but the difference between these two densities diminishes ast2he temperature rises, and at 35" the difference is nil, from which itfollows that below 35" the liquid ought t o form and separate from thegas by reason of its higher density, but above 35", although the liquidis ail1 formed, it cannot separate from the gas.. The author has calcu-lated the ratios between the density of the gas and the density of theliquid in Andrews' experiments, and also the coetficient of expansionbetween 31.1" and 35.5". These coefficients are very high, and undergoremarkable changes. Between 75.6 and 76 atmos.the coefficient ofexpansion rises suddenly from 0.0821 to 0.2716, which can only beexplained by supposing that at this pressure and at 31.1" tbe gas isreally liquefied, although apparently gaseous, and when the tempera-ture rises to 35.5" it again passes into the gaseous state. Again,between 82 and 83.4 atmos. the coefficient suddenly falls from 0.13114to 0.0703, a fact which can only be explained by supposing that a tthis pressure and even a t the higher temperature the gas is againliquefied, although apparently remaining gaseous. It would appearthat the homogeneous mass in the vessel under these conditions is notreally gaseous, because it has too high a density, nor yet really liquid,because it, has a high coefficient of expansion and compressibility, butthat it exists in an intermediate state. Detailed examination of thecurves corresponding with temperatures above the critical point sup-ports these views.The following table gives the successive incre-ments of density due to successive equal increments of pressure :-Atmos. 70 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100D'-D - 10 11 12 13 31 38 72 27 15 13 9 8 7 7 5It is evident that between 82 and 84 atmos. the gas is liquefied, andit is also evident that this change although very rapid is not abrupt.It becomes less rapid and takes place a t higher pressures as the tem-peritture rises. The results of Cailletet and Amagat's experimentswith oxygen, hydrogen, and similar gases at high pressures are repre-sented by curves similar t o those representing Andrews' experimentsabove the critical point.In every case the curve is convex at lowpressures and concave a t high pressures, with an intermediate pointof inflexion which, according to the author's view, is the point aGENERAL AND PHYSICAL CHEMISTRY. 7which the gas liquefies.experiments with oxygen at 0.3’ are given in the following table :-The increments of density in Amagat’sAtmos. 20 30 40 50 60 70 80 90 100 110 120 130D’-D - 76 77 77 78 78 79 79 82 83 77 78Atmos. 140 150 160 170 180 190D’-D 78 78 77 76 ‘75 75It would appear that the oxygen really liquefies between 100 and110 atmos., although the change is not so well marked as in the caseof carbonic anhydride.The following table gives the points of in-flexion and maximum compressibility (H) as determined by Amagat’sexperiments :-Point of inflexion. H.Oxygen ........ 102 atmos. 130 atmos.Methane ........ 95 ,, 127 ,?Ethylene.. ...... 67 ,, 83 7,Nitrogen ........ 55 ,, 109 97Hydrogen 0 ,, 0 Y , ......I t is evident that at a higher temperatme these points of inflexionand maximum compressibility will correspond with higher pressures,but at a sufficiently low temperature the point H will differ but littlefrom the point of origin of the curve, and experiments will give onlythat portion of the curve / beyond K, which always represents adiminishing compressibility ; but this is actually observed in thecase of hydrogen.It follows therefore that at the ordinary tempera-ture, and under a pressure of 3-4 atrnos., hydrogen has passed itspoint of inflexion, or, in other words, is really liquid. This conclusionis in accord with the law of continuity, and brings hydrogen, whichhas hitherto been regarded as an exception, under the general laws ofthe compressibility of gases.Change of Volume of Metals and Alloys at Melting. ByE. WIEDEMANN (Ann. Phys. Clzem. [2], 20,228-243).-The author hasmade a series of experiments on ihe expansion of volume at meltingpoint, and the relative rates of cooling of tin and certain alloys ofbismuth and lead.The dilntometer method was employed. The substance t o beexamined was enclosed in a closely fitting glass cylinder, at theupper end of which was fixed a capillary tube.The most con-venient liquid for filling the apparatus was found to be oil, whichhas the advantage of not evolving air when heated to 200”; more-over, it does not possess an appreciable vapour-tension at that tem-perature. When heated above that point the oil attacks the metal.The rate of cooling was determined by heating the metal to 260” in aniron vessel. A thermometer protected by a glass cap filled with oilwas enclosed within the molten mass. The whole apparatus was thenimmersed in a double walled metallic vessel, the intermediate spacebetween the walls being filled with water. The intervals of time re-quired for cooling 5” were carefully measured ; the reciprocal valueC. H. B8 ABSTRACTS OF CHEMICAL PAPERS.for these times may be taken as a measure for the velocity of coolingof the metal.In three experiments, it was found that tin on melting expanded involume 1.76, 1.69, 2.20 per cent.These results are in direct contra-diction to those of Nies and Winkelmann, who melted a largequantity of the metals and then dropped i n a solid fragment of thesame metal, and observed whet,her this fragment floated or sunk. Butthe author points out that in this method it would be exceedinglydifficult t o avoid convection currents, which would be liable t o carryup the solid fragments to +he surface in the centre of the vessel.Experiments also proved that soft solder expands almost 2 per cent.of its volume in melting.Alloys of Bismuth and Lead.-Pb2Bi of sp.gr. 11.4 begins to showan increase of expansion at about 120-136', which reaches its maxi-mum at 180". When heated to 240" and allowed t o cuol, the tempera-ture remained constant for long intervals of time at 180" and 125",the two melting points of the alloy. BiPb, sp. gr. 11.03, expandsabnormally between 127" and 132", melts at 146" and 125". PbBi,,sp. gr. 10.96, expands abnormally between 126" and 132", melts at140" and 124". PbBil, sp. gr. 9-73, expands most markedly between120" and 136", melts at 125" and 200". PbBi,, sp. gr. 8.6, melts par-tially between 125" and 130", contracts between 172" and 204"; itsmelting points are 170" and 120". The results of these experimentsshow that these allojs contain a definite compound of compositionbetween PbBi and PbBi2, whose melting point is about 125", and inwhich the excess of one metal, lead or bismuth, as the case may be,dissolves.For equal increments of temperature, the proportion of themetal dissolved rapidly increases. From the changes of volume attemperatures above the first melting point one can conclude whetherthe metal in excess expands or contracts on melting. The experi-ments would seem to indicate an expansion of lead and a contractionof bismuth, a result in accordance with previous observations. Forexample, the alloy PbBi, consists of an alloy of low melting point, inwhich the excess of bismuth dissolves ; if it be gradually warmed to120", the alloy and the excess of bismuth expand regularly. At thistemperature the alloy melts with marked expansion, and contains thesolid bismuth in suspension ; above that point, the bismuth graduallydissolves and melts, while the rate of expansion pari passzc decreases.V.H. V.Specific Volume of Saturated and Unsaturated Alkyl Salts.By b'. WEGER (Annulen, 221, 61--107).-The author has made aseries of determinations of saturated and unsaturated hydrocarbonsand alkyl salts, in order to ascertain the differences of specificvolume corresponding to known differences of molecular weight.The method adopted is that proposed by Kopp, with slight modifi-cations; the dilatometer was not heated in a bath of liquid, butwas wholly immersed in the vapour of some volatile liquid. By thismeans corrections for the cool part of the dilatometer projectingoutside the liquid, and its unequal heating from convection currenh,are avoided. The readings were made with the naked eye, and TABLE I.Name of Substance. Method of Preparation.Ethylbenzene, CaHIo............................Phenylethylene, C8H, ..........................Phenylacet,ylene, CaH6 .........................Phenyl bromide, C,H,Br ........................Acetylene dibroniide, C2H2Br2 ...................Methyl cimamate, C10Hlo02. ....................Ethyl cinnamate, CllHl20,.. ....................Propyl cinnamate, Cl2Hl402.. ...................Phenylpropionic acid, CgH,,O, ..................Methyl phenylpropionnte, CloHl~02 ..............Ethyl phenylpropionat,e, Cl1HI4O2 ...............Cinnamic acid, CgHaO,..........................Propyl phenplpropionate, CI2lj 1602 ...............Methyl acrylate, C,H,O, ........................Ethyl acrylate, C5H,02 .........................Prop71 acrylate, C6H1002. .......................Ethyl propionate, C5HIoO2 ......................up-Dibromopropyl alcohol, CH2Br.CHBr.CH2.0H. .Ethyl and phenyl bromidesnibromhydrocinnamic acidEthyl &'-dibromopropionateBromine on benzene .......Acetylene tetrabromide andFrom storax ..............Cinnttmic acid and methylCinnamic acid and ethylCiiinamic acid and propjlCinnamic acid and sodiumwith sodium.and potash.and potash.zinc.alcohol.alcohol.alcohol.amalgam.As methyl cinnamate.. .....As propyl cinnamate.. ..... As ethyl cinn'imate ........Methyl dibromopropionatewith zinc and sulphuricacid.As the methyl salt.........do. do. .........Silver propiunate and ethylAlly1 alcohol and bromine.. . iodide.8.61729.50699.72758.33689.91036'9205'7.50098.0078.41527.004s8.55159.25049.309813-5891 12.41411.5841 7'403TABLE I.--continued.Name of Substance.Ethyl aB-dibromopropionate, CH2Br.CHBr.COOEt.Dimethyl oxalate, COOMe.COOMe ...............Ethyl oxalate, COOEt.COOEt.. .................Methyl ethyl succinate, C7H,20q ................Diethyl succinate, C,H,,O, .....................Trimethjl phosphate, Me3P04 ...................Ethyl dimethyl phosphate, EtMe,PO, ............~ ~~Method of Preparation.~Oxidation of above com-pound with nitric acid,and then treated withmethyl alcohol.As the methyl salt ........--Silver ethyl succinate andmethyl iodide.Silver succinate and ethyliodide, succinic acid andalcohol.Silver phosphate and methyliodide.Silver dimeth;pl phosphateand ethyl iodide.~~089989.9111.99110.0309.194610.354110.5169.526GENERAL AND PHYSICAL CHEMISTRY. 11mirror to exclude errors of parallax. The boiling points were deter-mined by Kopp and Pawlewski's methods. The tables on pp. 9,10 and 11, contain a summary of the author's results. In Table I aregiven the reagents by which the several compounds were obtained,and the experimental values for b-*, cV9 in the general equationV = 1 + at + bt2 + ct3, representing the expansion of volume forincrease of temperature.I n Table I1 are the boiling points, sp. gr.a t 0" and a t boiling.point, and the specific volumes deduced from thedata.TABLE 11.Name of Substance,Ethylbenzene ...............PhenylethJlene .............P henyla ce t ylene .............Phenyl bromide.. ............Methyl cinnamate.. ..........Acetylene dibromide. .........Cinnainic acid ...............Ethyl ..............Propyl ..............Yhenylpropionic acid .........Methyl phenylpropionate .....Ethyl phenylpropionate ......Propjl phenylpropionate .....Methyl acrylate.. ............Propyl ................n/?-Dibromopropyl alcohol ....Ethyl propionate.. ...........Methyl ap-dibrom opropionate. .Ethyl ................Ethyl- ...Propyl- ...,,,,Methyl oxalate.. .............Ethyl ................Dimethyl succinate ...........Mcthyl ethyl .............TrimethTl phosphate .........Dimethyl ethyl phosphate. ....Diethyl .............Boilingpoint.136 *5146 '2141 -6153 -6109 -4300259 '627 1285 '1279 ' 8336 -6248 -1262 *180 -398 -5122.921998 -3205 '8214 *6233163 '3186195 -2208 '2215.4197 '2203 -33p. gr. at 0".--0.883160.92510 -946581 -52032 -29831 -03641 -041 51 -06621 -04352.071151 -04731 '03481 -01 520 93788C1 -939280 *919962 -16820.912241 -97771 -82791 -70141 *15791 -1031 *11621 -09251 * 05921 -23781 '1752Sp. gr. atb. p.0 -76120 -79140 -80321 *3082 -03520 -909740 -838880 *821430 -79170 * 87800 %38240 -801820 -778860 2371940 -819700 *78471.75350 -794721-6141 -45541 -33911 -00390 -876520 -9120-864820 -827261 -00190 -95188Specificvolume.--138 -93131 *11125 -8119 -791 '72162 -29188.17213 9 5239 -4.3170 -44195 -19221 -48245 *9698 -4121 -71x4*4 -95123 *96128 *06151 -99178 *14204 -09117 -26166 * i 8159 '72184 *58209 -85139 -45161 -45Homologous Compounds.-On comparing the specific volumes ofhomologous compounds uf analogoiis composition, it is found thatthe difference of specific volume for every CH, is very variable. I n.the case of the ethereal salts of phosphoric acid, the differenceis equal to Kopp's average value, 22; for the alkyl sa81ts of theacids of the acetic and acrylic series, the difference is rather greaterthan 23 ; for those of the succinic, phenylpropionic, and acrylic acidsit varies from 25-96. In the homologous alcohols, the specificvolume for the CH, group is about 20.Although the volume forCHz varies with different series of compounds, yet it is practicall12 ABSTRACTS OF CHEMICAL PAPERS.constant for various alkyl salta of one and the same acid, althoughnot for corresponding ethereal salts of homologous acids. Thus, forexample, the volume difference between ethyl oxalate and methylethyl succinate is not equal to that between methyl ethyl and ethylsuccinate. Facts such as these cause questions to be raised as to theprecise definition of homologous compounds.Isologous Compounds.- Similarly on comparing the results ob-tained for saturated and unsaturated compounds, the difference inspecific volume for H2 or nH, varies from 5 to 9 or some multiple ofthese numbers. The observations of the author in this respect are inaccordance with those of Buff, Zander, and Schiff.Thorpe assigned the number 5348 as the molecular volume ofbromine (this Journal, Trans., 1880, 384) ; in the author's results,differences of Br, in isologous compounds, as ally1 and dibromopropylalcohols, correspond with differences of specific volume varying from4996 to 59.14. Similar variations in the differences of specificvolume corresponding with uniform differences of C6H4 and C2H2Br2in the molecule are also observable.The specific volume values of the aromatic compounds examined bythe author were found t o be greater than the values calculated accord-ing to Kopp's general rules.V. H. V.Law O€ Smallest Volumes. By W. M~LLER-ERZBACH (Annalen,221, 125-132) .-In this communication, the author adduces furtherarguments in support of his law that in any chemical reaction theelements tend to arrange themselves in those forms of combinationwhich occupy the smdlest volume, or that greater condensation iscorrelated with greater affinity (comp. Abstr., 1882, 137, 451, 1G24).For example, the sum of the volumes of the trichlorides of phos-phorus and boron plus three atoms of bromine, or of silicon tetrachlo-ride plus four atoms of bromine, is greater than the sum of thevolumes of the tribromides of phosphorus and boron plus three atomsof chlorine, or of silicon tetrabromide plus four atoms of chlorine.Again, the experiments of Kammerer (Aniz.Phys. Chem., 138,290) have proved that hydrated chloric acid, HC1O,,7H2O, occupiesa molecular volume of 164.4, and hydrated iodic acid, H20,,9H20, of158.9 ; if to the molecular volume of chloric acid the number 36, orthe molecular volume of two molecules of water be added, the volumesof chloric and iodic acid will be in the ratio of 200 to 159. Accord-ing to the author's law, iodic should be more stable than chloric acid,and the experiments of Serullas have shown that an aqueous solutionof the former decomposes a t 40°, whilst those of Gay-Lussxc provethat only a partial decomposition of an aqueous solution of the lattercommences at 200".Kremers has demonstrated that there is an in-crease of volume when potash and soda are neutralised with nitric,hydrochloric, and sulphuric acids. The author has pointed out thatthis apparent discrepancy from his law may be explained by thegreater affinity of the molecules of water for the acid and the alkalion the one hand than for the resdtant salt on the other. Thus anexpansion instead of a contraction is the final result. I n this con-nection, the author cites the experiments of Ostwald, who proved thaGENERAL AND PHYSICAL CHEMISTRY. 13the volume occupied by a given weight of water containing in solutionan equivalent of potash is less than that occnpied by the same weightof water plus one equivalent of potash taken separately. The sameresult holds good in the case of sulphuric acid and water.Hence itmay be stated that the result of the neutralisation of potash and sodawith nitric, hydrochloric, and sulphuric acids is a contraction ofvolume, but that this contraction is so masked by the presence oflarge quantities of water that an expansion is the final result.V. H. V.Method of Correcting the Weight of a Body for the Buoyancyof the Atmosphere when the Volume is Unknown. By J. P.COORE (Chem. News, 48, 39--41).-1t is well known that correctionsfor the biioyancy of the atmosphere are seldom made because of thegreat trouble attached to obtaining the required data, and from them thenecessary correction.The author proposes to obviate these difficultiesin the following manner :-Assuming that the atmosphere within thebalance-case is dry, easily effected by open vessels of strong sulphuricacid, the only corrections required are for temperature and pressure.To effect this the author fixes on two standards, viz., 30 inches for thebarometric pressure, and 27" C. (= 300" on the so-called " absolutescale '7 for temperature : hence a variation of &th of an inch fromthis standard will cause a change of a+a in the resultant effect of thebuoyancy of the air on the load and its counterpoise, and according t othe law of Charles, the variation of 1" from 27" C. produces a similarchange.With these standards, corrections for temperature are made byreducing the barometric pressure to 27" C., and then by takingweighings of the object for which the correction is required undervarying conditions of temperature and pressure : the difference inweight corresponding to &th of an inch variation in the barometer iseasily found, and a constant for the object weighed is obtained bywhich the weights can be readily reduced to the standard 30-inchbarometric pressure, after having reduced them to the standard tem-perature, 27°C.It is simply necessary to multiply the differencebetween 300 and the reduced barometric pressure, and add or subtractthe product, as the case may be, from the observed weights. Anexample, chosen from an observation made by the author, will illus-trate the mode of working. In the first column of the subjoinedtable the weights of the same object are given under the varyingconditions registered in the subsequent columns, and in the lastcolumn the results of the application of the constant are given (thereare 15 observations in the original) :-HeightWeight Temperature of bar. in Heightof object. of balance ik ins. reduced. Result.a7.3447 23.5" C. 297.6 301.1 8 7.345187-3419 22.6 305.2 309.6 87.345187.3464 29.4 297.9 295.5 87.34514 ABSTRACTS OF CHEMICAL PAPERS.Greatest weight 87.3464 Barometer highest 309.6Smallest ,, 87.3419 7 ? lowest 295.5Differences 00.0045 14.1-:. Constant = 4.5 mgrms. i 14.1 = 0.319 mgrm.I n this way, the relative weight of even large vessels can be obtainedto a, &th milligram ; of course there is a limit to the accuracy ; how-ever it is noteworthy that the accuracy of the method is proportionalto the requirement, for the greater the bulk of the load, the moreaccurately can the " constant " be found. Great precision is requiredfor measuring temperatures and pressures in the case of loads of largevolume.From the data obtained by these observations and from the knomirnormal density of the air, the volume of the object can be calculated,and therefore the same constant may be made t o serve roughly forany given volume; thus in the case cited abore the volume of theobject exceeds that of the weights by 75 c.c., and the weight varies0.3 mgrm. for 1" C., or &th inch pressure. Hence with a difference ofvolume = 100 C.C. the weight would vary 0.4 mgrm. f o r 1' C., 6r &inchpressure, and so on. It is obvious that if the volume of the load wasvery large, the balance might be used for measuring the variations inatmospheric pressure and temperature, D. A. L

ISSN:0368-1769    

DOI:10.1039/CA8844600001

出版商:RSC    

年代:1884

数据来源: RSC

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14 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c C h e mi s t ry,Density of Liquid Oxygen. By S. WROBLEWSKI (Compt. rend.,97, 166-168).-A known volume of oxygen was liquefied at -130"in a calibrated tube, and the volume of t.he liquid was compared withthe volume of a known amount of carbonic anhydride liquefied in thesame tube at 0". The sp. gr. of the Iiquid oxygen was found to be0.89 and 0.90 ; mean, 0.895. C. H. B.Active Oxygen. By E. BAUMANN (Ber., 16, 2146--2152).-1t haslong been observed that substances which under ordinaiy conditionsare not affected by oxygen, are yet oxidised in presence of othersubstances, which combine directly with the oxygen of the air.Besides examples of these changes which have been brought for-ward by Hoppe-Seyler, the author, and also Leeds, have observed thatcarbonic oxide when passed over damp phosphorus is oxidised by theozone formed into carbonic anhydride. Remsen and Keiaer (Chem.SOC.J.. 1883, 454) have repeated these experiments, but with negativeresults, and they attribute the formation of carbonic anhydride totrhe oxidation by the ozone of the carbon of the corks used in theapparatus. The author has accordingly repeated his experimentswith an apparatus made entirely of glass, and has confirmed hiINORGANIC CHEMISTRY. 15former results. In one case 56.6 mgrm. of carbonic anhydride wereformed by the passage of 700 C.C. of carbonic oxide over phosphorus ;this represents an oxidation of 2.6 per cent,. of the carbonic oxide.In connection with the explanation of the phenomena of oxidationput forward on the one hand by Hoppe-Seyler and Leecls, and on theother by Traube, the author considers that the former is more satis-factory : for firstly it is simpler; secondly, it explains the greaternumber of phenomena ; and thirdly, Traube's hypothesis gives noaccount of the formation of ozone, hydrogen peroxide, and activeoxygen by the slow oxidation of dam.p phosphorus in the air.v. K. v,Conversion of Carbonic Oxide into Carbonic Anhydride byNascent Oxygen. By A. R. LEEDS (Clzeni. News, 48, 25-29).-The author refers to works which have been published in support ofand against the theory that ca,rbonic oxide is converted into carbonicanhydride during the oxidation of phosphorus in moist air ; he thenproceeds to describe the latest repetition of his original investigationin support of the theory.Sticks of phosphorus were put into a largeflat-bottomed bottle, fitted with a well ground stopper, filled withwater free from air and carbonic anhydride, and inverted in a,pneumatic trough. Well washed carbonic oxide and air, in equalvolumes, were now introduced, sufficient water being left in the bottleso as to partially cover the phosphorus. The stopper was put inwhile the neck of the bottle was still under water; the bottle wasthen reversed, and kept at a temperature of 24". After six days thegaseous mixture was withdrawn from the bottle ; and, the glass stopperbeing replaced by a cork saturated with paraffin, and fitted with thenecessary tubes, the .bottle was immediately inverted in a mercurytrough, and a little mercury allowed to enter in order to cover the cork.The tubes were respectively connected with an aspirator and an air-supply free from carbonic anhydride ; and the issuing gas was passedthrough baryta-water and potassium iodide solution.The baryta-watersoon became turbid, and was subsequently tested in a carbonic anhy-dride apparatus, when the potash bulbs in connection therewith hadincreased 0.0155 gram after the decomposition. The tube passing intothe barium hydrate became incrusted ; the incrustation when treatedwith acid evolved carbonic anhydride. There was no iodine set freein the potassium iodide solution, and therefore no ozone conld havebeen present.The author considers, therefore, that the above state-ment is now established by a rigid quantitative and qualitative analysis.D. A. L.Liquid Nitrous Anhydride. By R. H. GAINES (Chem. News, 48,97).-The author observes that this gas condenses at + 14.4" undera pressure of 755 mm., and when the liquid is heated, ebullition beginsat the same temperature. The pure liquid is dark green, but changesto blue on the addition of a very little water ; the blue and green liquidsare not readily miscible.Preparation of Caustic Potash and Soda. By LOWIG (Di?zyZ.polyt. J., 248, 260).-According to Lowig, an intimate mixture ofsodium or potassium carbonate and ferric oxide is exposed to a brightD. A. L16 ABSTRACTS OF CHEMICAL PAPERS.red heat until the whole of the carbonic anhydride has been expelled.The resulting melt of sodium or potassium ferride is treated with waterat 80-90", the ferride being decomposed into caustic soda or potashand ferric oxide.The latter on drying is used for a further opera-tion. D. B.History of the Preparation of Artificial Sodium Carbonatefrom Common Salt. By DUMAS (Compt. rend., 97, 209--214).-Ahistorical summary, eulogistic of Leblanc. C. H. B.Dimorphism of Silver Iodide. By MALLARD and LE CHATELIER(Co112pt. rend., 97, 102--105).-It has been shown (BUZZ. SOC. Min.,5, 214) that boracite belongs to the rhombic system at the ordinarytemperature, but changes to the cubic system at about 265" withabsorption of heat of 4-77 cal. for 1 gram, and retains this form up tothe melting point.Potassium sulphste behaves in a similar manner,passing from the rhomhic to the hexagonal system, and ammoniumnitrate, which belongs to the rhombic system at the ordinary tem-perature, suddenly changes to the cubic system at about 127". Silveriodide is dull red at a sufficiently high temperature, but is lightyellow at the ordinary temperature, and Wernicke has shown that at138-138.5" the colour suddenly changes from deep yellow to yellowish-white, or vice versc2, according as the temperature is rising or falling.By examination with polarised light, the authors find that when thesilver iodide is heated it suddenly passes from the hexagonal t o thecubic system, the change taking place at about 146", a temperaturenot very far removed from that determined by Wernicke. Measure-ments of the mean specific heat of the iodide between differentlimits of temperature, show that the passage from the hexagonal t othe cubic system is accompanied by an absorption of heat of 6.8 cal.for 1 gram.According t o Zepharovitch the ratio of the axes in thehexagonal form, h : a = 1.2294 : 1. In the cubic form, the ratio ofthe tertiary to the secondary axis will be h : a = 1.2247 : 1, fromwhich it appears that the hexagonal form closely approaches thecubic form, and that at the point of change from one form t o theother there must be contraction along the vertical axis, or expansionalong the horizontal axes, or both. This contraction and expansionhas been actually observed by Fizeau, and may be regarded as pre-paratory to the change of crystalline form.It follows from thesefacts that the cubicad expansion of silver iodide ought t o be normalabove 146", and Rodwell has observed that the iodide experiences asudden and considerable contraction between 142" and 145.5'. but . ..afterwards expands regularly up to the melting point,C. H. B.Chlorides of Lime and Lithia. By I(. KRAUT (Annalen, 221,108--124).-This communication contains no new experiments ; theauthor merely controverts Lunge's experiments and deductions there-from as t o the constitution of bleaching powder and the so-called'' chloride of lithia." V. H. VINORGANIC CHEMISTRY. 17Separation of Gallium. By L. DE BOISBAIJDRAN (Contpt. rend.,97, 66-67, 142-144) .-From TeZZurium.-The tellurium, whichmust be in the state of tellurous acid, is precipitated by hydrogen sul-phide in the cold, in presence of a considerable quantity of free hydro-chloric acid.The filtrate is concentrated if necessary, heated toboiling, and treated with a current of hydrogen sulphide, the pre-cipitate of tellurium sulphide being filtered off.From Sdicon.-The solution is made strongly acid with hydro-chloric acid (any free sulphuric acid having been previously neutm-lised), evaporated to dryness, and heated for some time a t 120-125".The residue is moistened with strong hydrochloric acid, and theevaporation and ignition repeated. The gallinm is then dissolwd outby boiling dilute hydrochloric acid, the solution filtered, and the silicawashed, first with dilute hydrochloric acid, and finally with water ;the last traces of gallium are removed from the silica by dissolving itin potassium hydroxide, acidifying with hydrochloric acid, and repeat-ing the above treatment.From JfoZybdenumf.-(l.) The molybdenum is precipitated in thecold by hydrogen sulphide in presence of a considerable quantitg ofhydrochloric acid, the precipitate being washed with dilute hydro-chloric acid saturated with hydrogen sulphide.The filtrate is heatedfor some time at sbost 70°, then boiled, and any precipitate whichforms is filtered off. The second filtrate is concentrated, and againtreated in the same way. (2.) The solution is supersaturated withammonia, mixed with ammonium sulphide in excess, gently heated,and then acidified with hydrochloric acid, heated t o expel hydrogensulphide, and filtered.The filtrate is concentrated, the ammoniumsalts destroyed by heating with aqua regia, and the solution againtreated with ammoninm sulphide. The molybdenum sulphide is dis-solved in aqua regia, and the precipitation repeated in order to removethe last traces of gallium. Before applying methods (1) and (2)chlorides and lower oxides of molybdenum must be oxidieed by meansof nitric acid, excess of the latter being expelled by boiling withhydrochloric acid. (3.) The solution is acidified with sulphuric acid,mixed with a slight excess of ammonium sulphate, and the galliumalum precipitated by concentrating the liquid and adding three orfour times its volume of alcohol of 85".The alum is purified byrecrystallisation. I n accurate analyses, the greater part of the molyb-denum should be precipitated as sulphide by (1) or (2), then thegreater part of the gallium removed as alum, the last traces Eeiiigseparated from the concentrated mother-liquor by (1) or (2).Salts of Aurous Oxide : Colorimetric Estimation of Gold. ByA. CARNOT (Coinpt. rend., 97,169-170).-When an aqueous solution ofhydrogen phosphide is added gradually to a very dilute solution of goldchloride, either alone or mixed with phosphoric or arsenic acid, a rosecoloration is produced. J t would appear that this rose coloration(this vol., p. 115) is not due simply to a complex compound of aurousoxide and ferric oxide, but is produced also by simple salts of aurousoxide, such as the phosphate or arsenate.The presence of ferricoxide apparently increases the stability of these salts, for if anyC. H. B.VOL. XLVI. 18 ABSTRACTS OF CHEMICAL PAPERS.foreign salt is added to a solution of the rose-coloured compound freefrom iron, the rose-coloured compound becomes blue and yields aslight bluish precipitate, whereas in presence of iron a purple pre-cipitate is formed, which can be dried a t 100" without alteration.This reaction furnishes a colorimetric method for the rapid approxi-mate estimation of gold. The intensity of the tint given by thesolution under examination is compared with that of solutions of goldcontaining different amounts of gold in a constant volume (100 c.c.)of liquid.To obtain comparable solutions, the neutral solution ofgold chloride is mixed with a drop of hydrochloric acid, one or twodrops of ferric chloride, and a, few drops of arsenic acid, andthen dilutedto 100 C.C. A small quantity of zinc powder is added, the liquidagitated, allowed to clarify by standing, and the clear liquid decantedoff. The mineral to be examined is finely powdered, dissolved inaqua regia, the solution diluted, filtered, evaporated twice to drynessafter addition of a little nitric acid, and heated to dull redness. Theresidue is treated with chlorine-water, which leaves the ferric oxideundissolved, the solution is filtered, the chlorine expelled by boiling,and the solution treated as above.C. H. B.Action of Hydrochloric Acid on Stannous Sulphide. ByA. DITTE (Compt. rend., 97, 42-45).-Dry hydrochloric acid gas hasno action on crystallised stannous sulphide at the ordinary tempera-ture, but on gently heating it, decomposition commences, and stannouschloride and hydrogen sulphide are formed.Aqueous hydrochloric acid, even in dilute solutions, attacks crystal-lised stannous sulphide a t the ordinary temperature, but the degree ofconcentration of the acid has great influence on the decomposition,the phenomena being similar to those observed by Berthelot in thecase of galena (Mkcan. Chim., 2, 562). Decomposition takes placewith a solution containing 8.3 per cent. of acid; stannous chlorideand hydrogen sulphide are formed, and after some time equilibrium isestablished under somewhat complex conditions.When hydrogen sulphide is passed into a solution of stannouschloride, deep brown stannous sulphide may be produced, but inmany cases the precipitate consists of brilliant reddish-brown mica-ceous plates of a stannous chlorosulphide, which is decomposed byhydrogen siilphide and by water.The heat of formation of this com-pound is probably intermediate between that of stannous chloride andthat, of stannous sulphide, and its more or less complete decomposi-tion by water plays a part in t'he establishment of equilibrium. Whenhydrochloric acid is brought in contact w i t h an excess of stannoussulphide, or when hydrogen sulphide is passed into a solution ofstannous chloride, equilibrium is eventually established between thehydrogen sulphide and the hydrochloric acid, the relative proportionsof the two bodies depending on the temperature.The conditions ofequilibrium are complicated by the fact that the solubility of hydrogensulphide in solutions of stannous chloride decreases as the concentra-tion of the latter increases. If, therefore, a dilute solution of hydro-chloric acid acts on stannous sulphide, a small quantity of hydrogensulphide is liberated, and dissolves in the liquid without saturating itINORGANIC CHEMISTRY. 19whilst at the same time a correspondingly small quantity of stannouschloride is formed. If, on the other hand, a current of hydrogensnlphide is passed into a strong solution of stannous chloride, in whichthe gas is almost insoluble, a small quantity of stannous sulphide isformed, and the hydrochloric acid which is liberated is sufficient t oestablish equilibrium with the small quantity of hydrogen sulphide bywhich the liquid is saturated.The greater part of the stannouschloride therefore remains unchanged. If, however, the experimentis arranged so that the proportion of free hydrogen sulphide is thesame in both solutions, the proportion of hydrochloric acid will alsobe the same in both, and equilibrium will be established, although thetwo solutions contain very different amounts of stannous chloride. Itwould appear, therefore, that the stannous chloride plays a consider-able, although mainly a mechanical, part in the establishment ofequilibrium, by virtue of the fact that its presence diminishes thesolubility of hydrogen sulphide.No hydrochloride of stannous chloride appears to exist.Whenhydrochloric acid gas is passed over hydrated stannous chloride,SnC1,,2H20, the latter melts and yields an acid solution of stannouschloride, and a new hydrate, SnC12,H,0. The same hydrate is formedby the action of concentrated aqueous hydrochloric acid ou thehydrate, SnCI2,2H,O. The decomposition of stannous sulphide byhydrochloric acid is also materially affected by the temperaturewhich not only accelerates the action of the acid, but at the sametime diminishes the solubility of the hydrogen sulphide.Hydrated stannous sulphide is attacked by hydrochloric acid at theordinary temperature, decomposition taking place in more dilutesolutions and with greater rapidity, than in the case of the anhydroussulphide, although the products of the reaction and the conditions ofequilibrium are the same in both cases.Stannoustelluride is decomposed when heated in a current of dry hydrochloricacid gas, but is not attacked by the aqueous acid in concentratedsolutions.C. H. B.Similar phenomena are observed with stannous selenide.Antimony Pentiodide. By J. H. PENDLETON (Chern. News, 48,97).-Evidence of the existence of pentiodides of phosphorus andarsenic have been obtained (Abstr., 1881, 507 ; and Chem. News, 44,194), and the author has now investigated a pentiodide of antimony.Pure antimony is fused with excess of iodine in an atmosphere ofan inert gas in a sealed tube, and the mixture is kept well fused for anhour or two ; the tube is then heated at 130" in a sulphuric acid-bath,one end which is cooled with wat,er serving to collect the surplusiodine which distils off.The residue is a dark-brown crystallinemass, decomposible by water or long exposure to moist air. It meltsat 78-79", but is very unstable, readily undergoing decompositionwhen exposed t o even a moderate increase of temperature. Analyticalresults correspond " pretty closely to the formula Sb15."Several experiments were tried in which the temperature of theacid-bath and time of exposure were varied. D. A. L.e 2 0 ABSTRACTS OF CHEMICAL PAPERS.Chromic Acid and Hydrogen Peroxide. By H. MOISSAN(Compt.rend., 97, 96-99). The dark-blue compound formed bythe action of hydrogen peroxide on chromic acid is rapidly decomposedby water, but is much more stable in ethereal solution, the stabilitybeing, however, much diminished by the presence of a small quantityof alcohol. By using carefully purified ether and a solution of50 grams of potassium dichromate per litre, it is possible to obtain a t0" an ethereal solution of the dark-blue compound containing 0.5 percent. of chromium. This solution may be digested over calciumchloride, and can be kept for six o r eight hours at 0" without under-going sensible decomposition, but in time it decomposes, chromic acidbeing deposited on the sides of the tube. Dilute solutions are morestable than concentrated solutions.The ethereal solution when eva-porated a t - Z O O in a vacuum leaves a deep indigo-blue oily liquid,which readily redissolves in ether. I n contact with sodium, it evolvesh-j-drogen, and when only very gently heated it rapidly decomposesinto oxygen and chromic acid. The volumes of oxygen and hydrogengiven off correspond with the formula CrO3,H2O2 ; it would thereforeappear that the blue substance is a compound of chromic acid andhydrogen peroxide. The ethereal solution, in contact with phosphoricanhydride or other dehydrating agents, is rapidly decomposed withevolution of oxygen. It is also decomposed by acids, bases, leaddioxide, carbon, manganese dioxide, red lead, mercuric oxide, andsodium : in the last case with evolution of a mixture of hydrogen andoxygen.The ethereal solution also bleaches the skin like hydrogenperoxide.The blue compound cannot be obtained by the action of ozone onchromic acid, and it is only formed by electrolysis when hydrogenperoxide is also produced. C. H. B.Reduction of Iron Oxide with Carbonic Oxide. By R. AKER-MANN and SARNSTROM (DiiLgZ. polyt. J., 248,291-239) .-Experimentson the reduction of ferric oxide prove that it is readily convertedinto ferrosoferric oxide, and that magnetite parts with its oxygen toform ferrous oxide more easily than does ferrous oxide to yield metalliciron. One volume of carbonic oxide diluted with 20 volumes of car-bonic anhydride reduces ferric oxide to ferrosoferric oxide a t 450'.One part of carbonic oxide with 2.1 parts carbonic anhydride effectsa similar reduction at 300-350". By raising the temperature to8.'JO-900° 1 volume of carbonic oxide to 2.6 volumes carbonic anhy-dride still reduces magnetite, but with the proportions of one tothree this is no longer the case even a t a temperature of 800".Ferricoxide is easily reduced to magnetite in layers 2 mm. thick withoutany further reduction taking place SO long as the gaseous mixturecoiitains a t least three volumes carbonic anhydride to one volume ofcarbonic oxide. Ferrous oxide is easily reduced to the metallic stateat 850" when the ratio of carbonic oxide to anhydride is 1 t o 0.4.Experiments were made to oxidise iron by heating it in mixtures ofcarbonic oxide and carbonic anhydride, the results were unsuccessful,however, as regards the production of ferrous oxide. The reducingpower of an equivalent of carbonic oxide on ferrous oxide does noMINERALOWCAL CHEMISTRY. 21equal the oxidising power of an equivalent of carbonic anhydride oniron. In both cases, however, an increase of temperature gives riseto increased action. To reduce magnetite at a temperature of 350" toferrous oxide, the quantity of carbonic anhydride must not exceedtwo volumes to one of carbonic oxide. The authors find that for theproduction of 100 kilos. iron at least 64.3 kilos. of carbon in the formof carbonic oxide are required. Much less than this, however, isrepe8tedly employed in blast furnaces ; it follows therefore that a re-duction has taken place by the carbon as such, a reaction requiringa, higher initial temperature than the reduction with carbonic oxide.In regard to the consumption of fuel, therefore, very little saving is tobe anticipated. D. B

ISSN:0368-1769    

DOI:10.1039/CA8844600014

出版商:RSC    

年代:1884

数据来源: RSC

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MINERALOWCAL CHEMISTRY.Mineralogi c a1 Chemistry.21Minerals of the Cryolite Group recently found in Colorado.By W. CROSS and W. F. HILLEBRAND (Amer. J. Xci. [3], 26, 271-294) .-Cryolite and several allied fluorides have been recently dis-covered in the Pike’s Peak region, Colorado. The country rock ofthe whole district is a coarse reddish biotite granite of the ArchEanformation.The minerals described occur in two veins of massive white quartz,about one-third of a mile apart. In the vein designated A, cryolite,pachnolite, thomsenolite, gearksutite, prosopite, and, probably ral-stonite appear. In vein I3, prosopite, fluorite, and mixed fluoridesappear intimately associated with zircon, kaolinite, and mica.The cryolite from vein A is of a faint pink colour, and contains as avisible impurity the Fe,O, represented in the analysis-Fez03. Al.Ca. Na. H,O. F. Total. Sp. gr.0.40 12.90 0.28 32.40 0.30 53.55 99.83 2.972Previous to the analysis by J. Brand1 (Abstr., 1882, 1176) of pach-n d i t e , carefully selected by Groth, pachnolite and thomsenolite wereconsidered t o possess the same chemical composition. The resultsof all earlier analyses agree very well with the formulaNaF,CaF2,A1F3,Hz0,so that Brandl’s analysis agreeing with the formula NnF,CaF,,AlF,caused great surprise. Groth explained the supposed anhydrousnature of yachnolite *by assuming that the mineral analyeed waslargely contaminated with thomsenolite, but as the percentage of waternever falls. below 7 per cent. in any of the analyses published, thisassumption necessitates a most improbable admixlure of thomsenolite.All the analyses made by the authors correspond with the formulaNaF,CaF2,A1P3,H,0. The results of an analysis made upon crystalscarefully identified as pachnolite by the rhombic section, were asfollows :22 ABSTRACTS OF CHEMICAL PAPERS.81.Ca. Na. H20. F. Total.12-36 18.04 10.25 8.05 (51.30) 100*00Hence it, appears that the pachnolite from Pike’s Peak and thomseno-lite are identical in chemical composition, unless the fact of all analysesof thomsenolite showing slightly more water than that required forthe formula NaF,CaF,,AlF,,H,O, may indicate a partial replacement offluorine by hydroxjl.I n small cavities in the massive pachnolite, a mineral was found,occurring sparingly in a few specimens, which seemed to be differentfrom any known species.Al.Ca. Rlg. E. Na. F. Total.11.40 0.72 0.22 28.94 9-90 46.98 98-16The analysis gave-from which may be deduced a formula analogous to that of cryolite,in which about two-thirds of the Na is replaced by K. The authorsare of opinion that this mineral and ralstonite are not identical, butfurther investigations will be made as soon as better material can beobtained for examination.Itis made up of exceedingly minute colourless needles, and resembleskaolin in a remarkable degree. The analytical results obtained wereas follows :-Gearksutite is abundant among the minerals from this locality.LossAl. Ca. Na. K. H,O. F. as oxygen. Tot,al.15.31 22.30 0.10 0.04 15-46 42.07 4-78 100.00I n this Journal (Trans., 1883, 140) Flight described a mineralobtained from the cryolite bed of Greenland, which he considerednew, and named evigtokite; but from the agreement of his analyseswith those previously published, the similarity in occurrence aridphysical characteristics, there can hardly exist a doubt that Flightamalysed gearksutite.The name evigtokite should therefore bedropped.The rare mineral prosopite is more frequent in rein B than invein A. The analytical results obtained were as follows :-81. Ca. Mg. Nrt. H20. I?. as oxygen. Total.Loss22.1‘7 17-28 0.17 0.48 13.46 33.18 13.26 100.00B. H. B.Stibnite from Japan. By E. S . DANA (Amer. J. Sci. [ 3 ] , 26,214--221).-1n the size and beauty of the crystals, and in the greatcomplexity of their form, the Japanese stibnite far exceeds specimensfrom other localities.The finest specimens known to the author arethose recently acquired by the Yale Museum. They were obtainedfrom Mount Hosang, near Seijo, in South Japan. They are of re-markable size. A simple group consists of two prismatic crystals,with vertical axes nearly parallel ; the longer of the two measures22 inches, and the other 15 inches in length, the thickness variesfrom 1i to 2 inches. The lustre is very brilliant, and can be compareMINERALOGICAL CHEMISTRY. 23only with that of highly polished steel. The complexity of formobserved among Japanese stibnites is their most remarkable character.Previous t o 1864 b u t 16 planes had been identified. Krenner (Ber.Wien.Akud., 1864, 436) added 28 new planes, and Seligmann (Juhrb.f. Mia., 1880, 1, 135) added one more. Of these 45 planes, 30 halebeen observed on the Japanese crystals, and, in addition t o these,40 new planes have been determined, thus increasing the list to 85.This list could be considerably enlarged if the planes admitting cfonly doubtful determination were to be added.*By W. C. EUSTIS (Chem. News, 48, 98).-The specimen examined had a dark-coloured incrustation containingiron, a little manganese, and traces of nickel and cobalt. The mineralwas greyish-white to nearly c~iourless, the surface was marnmillary,and the structure radiate o r fibrous. Lustre, sub-vitreous or slightlysilky in some parts; hardness, 3 ; sp.gr., 2.4. Before the blowpipeit whitens, and loses water, but does not fuse. Analysis yielded thefollowing results :-B. H. B.Gibbsite from Brazil.A1,03. H,O. Fe20,. CaO. MgO. SiOa. Total.63.81 25.85 0.49 0.30 0.03 0.20 = 100.68No aluminium phosphate could be detected. D. A. L.Corundum Gems in India. By C. U. SHEPARD (Amer. J. Xci.[3], 26, 339-340).-A remarkable deposit of sapphire and ruby hasbeen discovered at Sungchang in the Himalaya Mountains. Thematrix is a schistose or slaty rock, and the vein consists of quartz,amethyst, and several varieties of corundum, all beautifully crystal-lised. In addition t o these, massive corundum, chlorite, and a littlemagnetite also occur. There is a great analogy in the mode of occur-rence and other particulars between the crystals found in India andthose produced at several of the American localities, notably a t theLaurens district, S.Carolina; Pelham, Mass., and Burke Co.,N. Carolina. The resemblances are, in fact, sufficiently important tolead t o the belief that valuable corundum gems may yet be found inthe United States. B. H. B.Cassiterite, Spodumene, and Beryl from Dakota. ByW. P. BLAKE (Amer. J . Sci. [3], 26, 235).--Caseiterite has been dis-covered in the central region of the Black Hills, Dakota, in a mass ofcoarsely crystalline granite. The felspar, quartz, and mica are inunusually large crystals ; and, in addition to these minerals, there isan abundance of spodumene in gigantic crystals ranging from 2 to 6feet in length, and 8 to 20 inches in diameter.I n the midst of thespodumene and felspar crjstals, the first masses of tin-ore werefound. The chief associate of the tin-ore is a dense aggregation ofsmall mica, crystals. At another locality, where muscovite mica has* Since the above memoir was published, a much finer group of Japanese stibnitecrystals has been purchased from Mr. Henson for the British Musenm. The groupconsists of 120 crjstals from 0.5 to 2’5 inches wide and 13 inches long; weight,150 lbs.-B. H. B24 ABSTRACTS OF CHEMICAL PAPERS.been mined, the author found large crystals of beryl embedded ing u art z .Descloizite from Mexico. By S. L. PENFIELD (Amer. J. Sci. [3],26, 361--365).-The mineral analysed was said to be from Zacatecas,Mexico.In all physical properties it seems to be identical with trito-chlorite recently described by A. Frenzel (Abstr., 1882, 473). Theanalytical results obtained are given under I. Frenzel's analysis oftritochlorite is also given (11) for comparison :-B. H. B.V,O,. A S ~ ~ , . P,O,. PbO. CuO. ZnO.I.. ... 18.95 3.82 0.18 54-93 6.74 12.2411. .... 24.41 3.76 - 53.90 7-04 11.06FeO. H20. Si02. Total. Sp. gr.I. .... 0.06 2-70 0-12 99.74 6.2011. .... - - - 100.17 6.25The minerals have the same density, and are alike in many payti-culilrs, but i t seems hardly probable that Frenzel could have overlooked2.70 per cent. of water. The difference in the percentage of vanadicacid is also considerable. B. H. B.Manganese Ores.By M. LILL and L. SCHNEKDER (Dingl. poZyt.J., 248, 471).-The authors have analysed the following samples ofmanganese ores from Bukowina :-I. From Upper Arschitza ; 11.Lower Arschitza, and III and IV, from the mines Theresia andSchara. The following results were obtained :-MnO.. ....&ln,O, ....FeO ......Fe?03 ....AI,O, ....CaO.. ....Bn,O ......CUO.. ....co .. t...Alkalis.. ..SiO ?...... so, ......P20, ......( 3 0 2 ......H,O ......MnO, ....MgO ....I.0.828.2054.2 70.7716.710.461.080-47tracestracestraces0.4810-95traces0.8425.25-11.1-947-6039.580.6527.341-731.030.280.004traces0.3813.000.0941.1115.55I-111.0.67€Pi952.520.3016.272.021.800.30tracestracestraces0.3010.900.08G.53traces5.25IV.1-497.0147- 140-5 112.780.853-500.570.0060-4118.10traces0.630.1 86.50--100302 100-289 99.73 99.679D.B.Native Ferrous and Aluminium Sulphate from Mexico.By T. P. LIPPITT (Chem. News, 48, 98).-The specimen was a cornMINERALOGICAL CHENISTR Y. 25pact mass of flexible fibres resembling asbestos. It was of a palegreenish-white colour, and had a silky shining lustre. Hardness, 2 ;sp. gr. 1.89. When heated in a glass tube, it gave off acid water.A small quantity of gypsum was intermixed with the mineral, whichwas otherwise quite homogeneous. The mineral is soluble in water,and yielded on analysis the following numbers :-Fe (ferrous). Al. Ca.so,. H?O. Total.7.81 4.92 0.52 41.59 43.60 = 98.44The iron is all feryous. Subtracting the constituents of gypsumfrom the results the formula Fe,”Al,( S04),(H,0), is obtained, whichwould be equal to a mixture of 2 mols. of halotrichite + 1 mol.melantrite.2 { Fe”A12( S O&. (H,O) 22 ] + Fe”S 0, ( H20) ,.D. A. L.Occurrence, Association, and Probable Mode of Formationof Barytes, Celestine, and Anhydrite. By DIEULAFAIT (Compt.rend., 97, 51-43).Barytes is generally found associated with metallic ores containingsulphur, the metals present in these ores being antimony, arsenic,lead, silver, mercury, copper, cadmium, bismuth, zinc, and manganese.With the exception of the last two these metals have a strong attrac-tion for sulphur; they are precipitated by hydrogen sulphide fromacid solutions, and they are generally found in nature in the form ofsulphides, which appear to be their most stable compounds.Zincis frequently found as sulphide, b u t its most stable form is theoxide, although the tendency of the natural sulphide to pass into thestate of oxide does not appear. to be very great. The most stable form ofmanganese is the dioxide. Some of the sulphides with which barytesis associated are very volatile, others are decomposed when heated inpresence of air (which generally has access to metallic veins), and allare decomposed when fused with alkaline chlorides. These and otherfacts show that the barytes and the minerals with which it is associatedhave never been subjected to the action of even a moderately hightemperature, and have certainly not been formed in contact with thefused alkaline chlorides.CeZestine, unlike barytes, is generally found in saliferous deposits,in which it is associated with gypsum and rock-salt, and it exists iiismall quantities in the gypsum of such deposits. If the gypsums arerich in organic matter, as is the case in all those in which free sulphuris found, polysulphides of calcium and strontium are formed in theinterior of the rock.These polysulphides are dissolved and washedout by percolating water, and when brought ill contact with the airthey are decomposed, with formation of calcium sulphate, calciumcarbonate, strontium sulphate, and free sulphur, and the frequentoccurrence of crystals of celestine on the surface of crystals of sulphurshows that the former must have been deposited a t a temperaturebelow the melting point of the latter,Bqzhyldrife frequently alternates with gypsum, which agrees withGorgeu’s hypothesis, but, on the other hand, it is quite as commo26 ABSTRACTS OF CHEMICAL PAPERS.in gypsum, especially in the triassic deposits in the south-east ofFrance, where the anhydrite often passes insensibly into gypsum.Itcannot be supposed that the anhydrite alternating with gypsum hasheen deposited from fused sodium chloride, since the gypsum beginsto lose its water even below 100". I t would appear, therefore, thatGorgeu's hypothesis cannot be accepted as an explanation of themode of formation of barytes, celestine, and anhydrite existing inveins and in saliferous deposits, although it may be of value in con-sidering the chemical changes which accompany volcanic action.C.H. B.New Locality of Chalchuite. By W. P. BLAKE (Amer. J. Sci.[3], 25, 197-200).-The occurrence in New Mexico of a green tur-quoise, chalchuite, has already been described by the author (Amer.J. Sci., 1858, 25, 227). Chalchuite also occurs in Cochise County,Arizona, in an outlying ridge of the Dragoon Mountains, now knownas " Turquoise Mountain." The mineral is identical in appearance withthe New Mexican variety. It is of a light green colour, with a sp. gr.of 2.71-2-82. It is peculiarly interesting archEologically. It was ingeneral use among the Aztecs before the arrival of the Spaniards, andthe author proves its identity with the caZZais or callnina of Pliny.B.H. B.Scovillite, a new Phosphate of Didymium, Yttrium, andother rare Earths from Salisbury, Conn. By G. J. BRUSH andS. L. PENFIELD (Amer. J. Sci. [3], 25, 459--463).--This mineral wasdiscovered by J. S. Adam, occurring sparingly as an incrustation onsome of the iron and manganese ores from the Scoville ore bed. Theincrustation is one-sixteenth of an inch in thickness, and is frequentlybotyroiclal or stalactitic. It is of a pink to yellowish-white colour,and presents a radiated fibrous structure. H. = 3.5. Sp. gr. 3.94-4.01. The results obtained on analysis were as follows :-P,O,. Y203 + Er203. La203 + Di,O,. Fe203. Combined H,O.24.94 8.51 55.17 0.25 5-88HaO lost at 100".CO,. Total.1.49 3.59 99.83The presence of the carbonate is regarded as due to an admixtureof lanthanite, (La,L)i),(C02),,9H,0. The mineral as analysed is calcu-lated to be a mixture of 17-04 per cent. of lanthanite, and 82-79 percent. of the new phosphate, R2( POa),,H,O. Calculating the 82.79 percent. of Scovillite up to 100 per cent., we obtain-Y205. (YEr),O,. (LrtDi)203. Fe203. H,O. Total.30.12 10.28 55.73 0.30 3.57 100.00B. H. B.Analyses of Lithiophillite. By S. L. PENFIET~D (Amel-. J. Sci. [3],25, 176) .-The author has already published analyses of triphylliteand lithiophillito from the various known localities (Abstr., 1879,695). He now adds to these two analyses, one of lithiophillite froMINERALOGlCAL CHEMISTRY.27Norway, Me (I), the other (11) of a variety from Branchville, Conn.The results obtained were :-Sp. gr. P,O,. FeO. MnO. CaO. Li,O.I. ... 3.398 44.40 8.60 35.98 0.78 8.5011. ... 3.504 44-93 16.36 28.58 0.05 8.59Na-0. H20. Gangue. Total.I. .... 0.14 1-19 0-12 99.7111. .... 0.21 0.54 0.13 99.39These analyses fully substantiate the formula Li(MnFe)POj,already made out for the species. B. H. B.Determination of Alkalis in Lepidote from India. By M.PAGE (Chew,. News, 48, 109--IlO).-The mineral examined, of a leadgrey colour, was found in granite associated with a violet-red lepidote,quartz, and occasionally tinstone. The total alkalis and sodium andpotassium were determined in the usual way ; lithium was determinedas phosphate ; rubidium by fractional precipitation with platinic chlo-ride and numerous washings with boiling water.The results percent. are:-K20. Li20. Na,O. Rb,O.8.595 1.754 0.609 0.070D. A. L.Topaz from Maine, U.S. By C . M. BRADBURY (Chem. News, 48,IO9).-The sample examined consisted of large colourless translucenttopaz crystals; sp. gr. 3.54. An analysis yielded the followingfigures :-A1 27.14 ; Si 14.64; F 29.21 ; 0 28.56 ; total, 99.55. ThisIS very anomalous, as three-quarters and not half the oxygen, corre-sponding with silicon, is replaced by fluorine in ordinary topaz.Berzelius’s analytical method was employed. D. A. L.Analyses of Franklinite Ores from New Jersey. By P.RICKETTS (Dingl. polyt. J., 248, 523).Si02 ................ZnO ................FeO, Pe,03, and IE’e,04Al,03 ..............MnO ................CaO ................MgO ................c02 . .. . . . . . . . . . . .cu ..................I.11-8534.1 328-480.5814.1 35-510.134-960.0711.11.5940-8329.94traces8.354-160.794.12111.8.6434-7028.34traces15.505-701 *446.26tracesIV.1 O . i O33.0931.05traces15.514.590.274.38traces - -99.84 99.78 100.48 99.59The following composition corresponds with the latter analysis :28 ABSTRACTS OF CHEMICAL PAPERS.Franklinite. ............... 51.51Red zinc oxide ............ 6.40Rhodonite ................ 11.13Willemite ................ 20.23Manganese carbonate ...... 1.24Limestone ................ 8-7699.27-Analysis of the most important constituents gave :-Zinki te.Franklinite. Willemite.ZnO.. .. 95.20 Zn0.. .. 20.72 ZnO.. .. 69.97MnO. .. 3.19 MnO ... 12.72 MnO ... 1.14FeBOa.. . 63.90 Fe30a.. . tracesSiOz ... 16.81D. B.Chrysocolla from Arizona. By W. C. EUSTIS (Chem. News, 48,109).-The specimen for analysis was associated with a bluish-greenvariety of chryaocolla, and with much carbonate. The sample analysedwas emerald-green, transparent, and pseudomorphous, with vitreouslustre. Sp. gr. 2.3; hardness, 3.5. Analysis yielded CuO, 32.28;Si02, 34.08 ; H20, 31.65 ; total, 98.95. These figures approximate to theformula 3Cu0,4Si02,13H,0, which corresponds with some specimensof chrysocolla of the constitution CuSiOs,3H20, in which one quarterof the copper is replaced'by hydrogen ; the mineral analysed may belooked upon as a copper hydrogen silicate.D. A. L.Rocks of the Yellowstone Park. By W. BEAM (Amer. J. Xci.1. Porphyritic Obsidian.-Colour greenish-black, semi-transparent.[3], 25, 106).H. = 6. Sp. gr. = 2.4. The analysis gave-Al,O, andSiO,. Fe,03. CaO. MgO. Na20. K20. HzO. Total.77.00 13.40 1.25 1.19 3-43 3.62 0.70 100.592. Pebble of quartz trachyte covered with a deposit from E'chinusGeyser.-The pebble analysed was about 1.5 inches in diameter, of alight fawn colour, and contained small masses of colourless silica. Theanalytical results were as follows :-SiO,. A1,O,+Fe,Os. CaO. MgO. K20. Na,O. H,O. Total.77.90 14.55 0.40 trace 4.63 2.10 1.00 100.58B. H.B.Volcanoes of Northern California, Oregon, and Washington.By A. HAGUE and J. P. IDDINGS (Amer. J. Xci. [3], 26, 222-235).-During the year 1870 the geologists attached to the Geological Explo-ration of the Fortieth Parallel, made a preliminary survey of theextinct volcanic cones of North California, Oregon, and Washington,but a further study was never undertaken. As the rock specimensthen collected may be considered as representing the principal typeMINERALOGICAL CHEMISTRY. 29of the ejected lavas, a large number of thin sections have recentlybeen made, and their microscopic examination has been followed upby chemical investigaiion.The four great cones, Lassen’s Peak, Mt. Shasta, &It. Hood, andMt. Rimier, which may be taken as typical of the chain, are all ande-site volcanoes, with extrusions of basalt.Similar variations inmineral composition and minute details of structure are found a teach of the volcanoes. All the socks from these volcanoes niay beclassified under the heads of basalt, hypersthene-andesite, hornblende-andesite, and dacite.Hypersthene-andesike.-These rocks are generally very porous,varying in colour from blue-black t o steel-grey. They occur in allstages, from crystalline, dense forms to glassy pumice. They aregenerally crowded with very small porphyritic crystals, of which thefelspars are the most noticeable, the iron niagriesium silicates being moseapparent in the light-coloured varieties. A complete chemical analysisis given (I) of a pumice from which the hypersthene was extracted.The ground-mass is an almost pure glass, and the microscope sliows thatthe hypersthene was the first of the essential minerals to crystalliseout from the original magma.The analysis of this pumice does notvery materially differ from the analysis of the more compact lavas.After separating the heavier minerals from the felspar and glass, t’helatter were subjected to Thoulet’s solution, in order to isolate theglass from the felspar. Two separations of felspar were obtained,one with sp. gr. from 2.66-2.68, and the other from 2.64-2.66.Analyses of these are given (I11 and IV). These probably representthe same felspar rendered impure by foreign ingredients. An analysisof the glass which forms the base of the pumice is given under V.Sp.gr. = 2.29.SiO? ............FeO ............CaO ............MgO ............R,O ............NaQO ..........Mn 0. ...........TiO, ............P,Oj ............Ignition ........A1203 ..........I.62-0017.844.405.372-641.474-29trace0.1 70.291 -6611.50.330.9 722-001-8823.29 --0.64111.56.412 7.390.699-870.090.365.43IT.56.9527.47trace9.100.020.485-78Total .... 100.13 99.11 100.24 99.80Dacite.-This rock occurs near the highest point of Lassen’s Pea,k.It is probably the most recent extrusion from the peak, and is quiteunlike the rocks obtained from the other volcanoes. The specimensvary from a moderately compact rock to others of a pumice-like cha-racter.The rock is composed of quartz, mica, hornblende, andplagioclase, and is from 6-9 per cent. richer in silica than the pre30 ABSTRACTS OF CHEMICAL PAPERS.vailing rocks of the four main cones (Analysis VI).felspar (VII) and of the glass (VIII) are given.bably a mixture of andesine and oligoclase.Analyses of theThe felspar is pro-V.SiO,.. .......... 6994Al,O, .......... 15.63Fe,O, -FeO ............ 1.89CaO ............ 2.49MgO.. .......... 0.28K,O ............ 2-8.5Na,LO.. .......... 3.83Jgnition ........ 3-25Total .... 100.16..........VI .69-3616.230.881.533.1 71-343.024-060.45VII.65.7721.51trace5-720.835.920.34-VIII.76.7512.321-361.183983.550.54--200.04 100.09 99.68The four types of rocks, basalt, hypersthene-andesite, hornblende-andesite, and dacite, exhibit four well charscterised groups, but theyare not sharply defined and distinct forms, as between any two in theseries all possible intermediate varieties exist.Meteoric Iron from Georgia.By C. U. SHEPARD (Amer. J.[3], 26, 336--338).-The mass here described was found in 2879about 14 miles north-east of Dalton, Whitfield Co., Georgia. Itweighed 117 lbs. The surfaceis black and very little oxidised. The sp. gr. is 7.986, which is some-what higher than is usual in meteoric iron. The analysis gave thefollowing results :-B. H. R.Its shape is somewhat that of a pear.Fe. Ni . co. Total.9 4 66 480 0.34 99.80with traces of phosphorus, chromium and manganese.B.H. B.Geyser Waters and Deposits. By H. LEFFMANN (Amer. J. SC;.[3], 25, 104--105).-The specimens from which the following ana-lyses were made were collected from the Pellowstone Park in 1878.&st of the geysers and hot springs are siliceous, and in most of thewaters examined the silica is in the free condition. All the resultsare given in grains to the imperial gallon:-1. Pearl Geyser.CaSOd. Na2S 04. NaC1. SiO,. Total.1.40 1-89 61-39 7.84 72.52At the bottom of the bottle containing this water was a quantity ofgelatinous matter, which was found on analysis to be composed of79-1 per cent. SiOz and 4.9 HzO, together with traces of A1203,Fe303, and CaO.2. Jug Xpwhg.CaCO,. Na,CO,. N~I$~OJ. NaCl.SiOz. Total.0-79 49.14 2-12 31.57 14.56 98.1MINERALOGICAL CHEMISTRY. 313. Opal Spring.NaCl. CaSO,. CaCl,. SiO,. Total.72-18 3-22 4.06 53.76 143.22This is not a geyser but a spring having the temperature of 90' F.The water is opalescent.4. Deposit from Bronze Spring.-This occurs in convoluted layerswith bronze-coloured surfaces and fawn-coloured streak, H. = 5.5.The results obtained on analysis were as follows :-Fe203 Organic matterSiO,. and A1203. and water.83.1 1.2 13.6B. H. B.Solid and Gaseous Constituents of Sea Water and OceanicDeposits. By H. TONROE and L. SCHMELCK (Bied. Centr., 1883, 217-231) .--These investigations were made by the Norwegian NorthAtlantic Expedition in 18i6-78, when a tract of ocean lying between60" and 80" N.and 12"--37" E. was examined.Solid Constituents.-There is but very little variation of the sp. gr.found ; a few samples, however, were much lighter, but this was dueto the nejghbourhood of ice, or river mouth, as the solids still bore aconstant ratio to one another. As regards the percentages of chlo-rine, lime, magnesia, and sulphuric acid present in water taken fromvarious depths, they remain practically constant, neither are theyaffected by the latitude ; in those cases in which potassium has beenestimated (as chloride) no variation has been foiind. The authorsfound only 0.0025 gram per 100 C.C. of or ganicmatter, and no hydrogensulphide. When sea water is boiled, the evaporated water being con-stantly replaced, all the carbonic anhydride is expelled, and a precipi-tate of magnesium salt free from lime is formed; but if on the con-trary, the water be evaporated to say one-half, only part of the gas isdriven off, and the precipitate consists of calcium carbonate andgypsum ; in both cases the water becomes alkaline ; further concen-tlratiori causes the precipitation of gypsum and sodium chloride, themother-liquor containing all the magnesium and potassium salts.Air itt 8ea Wader.-Jakobsen in 1871-72 found less oxygen at lowerdepths than a t the surface.Buchanan found the percentage of oxygen in surface water to varywith the latitude: so do the authors, obtaining 33.93 per cent.(mean) in the German Ocean, 34.94 per cent.in latitude 50-70" N.,and 35.54 per cent. in latitude 70-80".As these results do not tally with those obtained by Bunsen, whostates that the composition of the absorbed air is constant for all tern-peratnres : experiments to elucidate the question were made, and theconclusion arrived a t was, that seeing that the percentage of nitrogenwas normal, there must be some unknown factor which causes thewater to be supersaturated with oxygen.When comparing the volumes of oxygen in the water collected fromdifferent depths, it was noticed that the reduction was at first veryrapid, but soon became less SO, and a t 1000 m.the minimum wa32 ABSTRACTS OF CHEMICAL PAPERS.reached, increasing slowly afterwards, being 0.4 per cent. a t 3000 m.The curves representing percentages of salt and nitrogen at differentdepths, show that the percentiige of nitrogen is inversely proportionalto that of salt.Deposits.-Schmelck collected 300 samples of the sea bottom, andall may be classed under the name of clay, but of this clay there arefive kinds-grey, transition, biloculine, rhabdamine, and volcanic.The grey clay covers the whole surface of the bed of the sea, but issuperposed a t depths of more than 1000 fathoms by biloculine ; inshallow seas, as along the coast of Norwa,y and Spitzbergen, muchsand, flint, and mussel shells are found, the percentage of calciumcarbonate being 9 per cent.At 500 fathoms, brown clay overlies thegrey; this brown clay is distinguished from tbe brown hiloculinewhich only appears a t 1000 fathoms by the coarse sand present, andthe paucity of Foraminifera ; it is this clay which has been termed“ transition.” Biloculine, which is distinguished from grey clay byits colour, and from trarisitional by its s’tructureless fineness and uni-formity of external appearance, is rich in Foraminifera, and conse-quently in lime : the principal Foraminifera present being Globigerinabiloculina, lituola, and nonionina ; the minerals are microscopic grainsof quartz and flakes of mica ; one difference is remarkable, that whereasthese particles are sharp-edged in this clay, these are all rounded inthe transition clay. The green or rhabdaminic clay is found in theshallow waters which lie between Norway, Beren’s Island, and NovaZembla, and cont’ains a large number of Foraminifera, but littlecalcium carbonate, much silica. Volcanic sands and dark green sandyclay is found about Jan Mayen’s Land, and contains lava, tufa, felspath,augite, hornblende, magnetit and olivin. All of these deposits varyconsiderably in their percentage of ferrous oxide, the lighter colourecikind containing least. E. w. P

ISSN:0368-1769    

DOI:10.1039/CA8844600021

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

32 ABSTRACTS OF CHEMICAL PAPERS.O r g a n i c C h e m i s t r y .Bromine Substitution Products of Ethane and Ethylene.By R. ANSCH~~TZ (Anmden, 221, 133--157).--The author has carefullyexamined the physical properties of t h e bromine substitution-product8of ethylene and ethane, and many of the results have already appearedin this Journal (Abstr., 1880, 98). The boiling points and specificgravities of the compounds are given in the following table :ORGANIC CHEMlSTRP. 33b.p.CH,.CH2Br . . . . . . 38.4"CH,.CHBr, ...... 110.5CH,Br.CH,Hr , - . . 131 6CHBr,.CI-I,Br.. .. 187-188CBr2.CH,Br ...... 103*5*CHBr,.CHBr, .... 1 1 4 PCH,:CHBr ...... 16.0C Br, CH?. ....... 91.5CHBr: CHBr .... 110.0CBr, : CHBr.. .... 162.5t.15.0"21.521.521.521.521.511.021\*(i17.50.0td- 4.1.41892.083322-1 7672.61 072.93216296291.52862.1 7802.27142.6900From these results it appears that the addition of bromine raisesthe boiling point and increases the sp.gr. of the derivatives ofethane and ethylene. An unsymmetrical bromine-compound hasa lower boiling point and a lower sp. gr. than its symmetricalisorneride. The boiling points of the ethane derivatives are higherthan those of the corresponding ethylene compounds, but the specific w. c. w.Nitro-derivatives of Ethylene. By A. VILLTEHS (Compt. rend.,97, 2.%-260).-When the compound C2(N0,)4Br2,2KH0 (Abstr.,2882, 815) obtained by the combination of potassium hydroxide withtetranitroethylene bromide is treated with dilute acids, it yields nyellowish oily liquid with a penetrating odour.This liquid is pro-bably tetranitroethylene bromide. It may be heated to 100" withoutdetonation, but is very unstable even a t the ordinary temperature.The action of nitric acid on monobrometliylene bromide, and on mono-bromethane yields the same product as the action of nitric acid onethylene bromide. When this compound is treated with sodiumamalgam, or with zinc in presence of dilute alkali, if is reduced withformation of ammonia, hydrobromic acid, and hydrocyanic acid.With ammonium sulphide several products are formed. Tf the potas-sium componnd of tetranitroethylene bromide is mixed with ammoniaand a quantity of water insufficient to dissolve i t , and treated mithhydrogen sulphide for a very short time, the precipitated sulphur ismixed with a compound which dissolves easily on gently warming,and is deposited in crystals on cooling. This compound forms pale-brown crystals of the composition C4K2(N02)4.When heated gently,i t decrepitates a t a temperature below loo", and is converted into apowder without change of constitution. The same molecular changetakes place gradually a t the ordinary temperature. At 200" the com-pound detonates violently, and when treated with even very diluteacids, it is completely decomposed with a violent explosion.gravities are lower.C. H. B.Derivatives of Mannite Hexylene. By L. HEXRY ( C o ~ p t . rentl.,97, 260--263).-He~ylei~e monochlorhyclrin, CGH,,C1.OH, is obtained* Under a pressure of 14 mm.VOTA.XLVI. 34 ABSTRACTS OF CHEMICAL PAPERS.by the action of hypochlorous acid on hexylene or by the action ofhydrochloric acid on hexylene oxide. The product of the first reac-tion boils at about 170", and its sp. gr. = 1.018 a t 11'. As Dornac hasshown, it is the a-derivative, and has the constitution-C€IMe(OH). CHCl.CH,.CH,Me.The product of the second reaction is probably the @derivative, withthe constitution CHMeCl.C'H(OH).CH,.CH,&Ie. It is a slightlyviscous colourless liquid with a peculiar odour, and a very sharpsweetish taste. It is insoluble in water, and boils without decompo-sition under a pressure of 761 mm. ; its sp. gr. at 11" = 1.0143.Hez!/Zene monobromlzydrirz, C6H12Br.0H, obtained by the action ofhydrobromic acid on hexylene oxide, is a colourless slightly viscousliquid, which becomes yellowish after some time.It has a penetrat-ing odour, and a sharp taste, is insoluble in water, and boils at 188-i90" under a pressure of 769 mm. ; its sp. gr. a t 11" = 1.2959. It pro-bably has the constitution Me.CHBr.CH Pr(0H).HezyZene ~ o n i o d h y d r i ? a , C,H,,I.OH, obtained by the action ofhydriodic acid on hexylene oxide, is a colourless liquid which rapidlybecomes brown on exposure to light. It is insoluble in water, aildcannot be distilled.H e x y lene a~:etocl~lorhyd~-in, c6H&l.&o, formed by gently heatingthe monochlorhydrin witJh acetic cliloride, is a colourless liquid, in-soluble in water ; b. p. 188-190" ; its sp. gr.a t 6" = 1.04.R e z y Zene ch loronitrin, CGH12N03Cl, and hexylene d i n i t r i n , C6H,,(N0,),,are formed when hexylene oxide or the monochlorhydrin is added to acooled mixture of nitric and sulphuric acids. They are colourlesscombustible liquids, with a peculiar faint odour, insoluble in andheavier than water. They cannot be distilled.H e x y l e n e dichloride, obtained as a secondary product in the prepara-tion of the monochlorhydrin or by the action oE phosphorus penta-chloride on hexylene oxide, is a colourless mobile liquid, which isnot altered by exposure to light. It has a faint pungent odour and asweetish bitter taste ; its sp. gr. is 1.0527 at 11". It boils a t 162-165"under a pressure of 764 mm., and may be distilled over potash withoutundergoing alteration.~onochZoi.he:c.yler,e, C,HllCl? formed by the action of concentratedalcoholic potash on the dichloride, C6B&12, is a colourless mobileliquid insoluble in water, with a peculiar disagreeable odour, and itsharp taste.It is not altered by expobure to air, and boils a t 182"under a pressure of 768 mm. ; its sp. gr. at 11" = 0.9036; vapour-density 4.02.Heey Zeire ketone, CGHIZO, obtained by the action of sulphuric acidon nionochlorhexylene, is a colourless mobile liquid with an agreeablepungent odour and very sharp taste. It is insoluble in water, andboils a t 125" under a pressure of 753 mm. ; its sp. gr. a t 11" = 0.8343 ;vapour-density 3.45. The ketone is not decomposed by phosphoruspentachloride in the cold.Its constitution will depend on that ofthe monochlor-derivative, which has not yet been determined. c. H. BORQANIC CHEMISTRY. 35Reduction of Potassium Ferricyanide by PotassiumCyanide. By C . L. BLOXAM (Chem. News, 48, 73).-The potassiumcyanide employed contained but little carbonate, but on distilling itwith water hydrocyanic acid and ammonia were found in the distillate,whilst the liquid in the retort contained,-besides cyanide,-potassiumhydroxide, carbonate, and a little formate. When distilled with potas-sium ferricyanide, it yielded it distillate containing hydrocyanic acidand ammonium carbonate, the latter increasing in quantity towardsthe end of the reaction, whilst. the residual liquid, when cool, depositedabundant crystals of potassium ferrocyanide, leaving small quantitiesof potassium cjanate and formate i n the neutral mother-liquor.Theauthor gives the following equation representing this reaction :-K6Fe2C12N,z -+- 2KCN + 2H,O = 2&FeC6N6 + HCN + NHs + CO,.D. A. L.A Polymeride of Trichloracetonitril. By A. WEDDIGE (J. pr.C'hem. [a], 28, 188--189).-By heating ethyl paracyancarbonate(this Journal, 1874, 448) with phosphoric chloride, a thick yellowish-brown oil is obtained, which from its reactions appears to be para-cyancarbonic chloride. By further heating this oil with phosphoricchloride in sealed tubes at 155--160", a substance is obtained Lavingthe composition of trichloracetonitril, but different properties. Itcrystallises in large plates or prisms, melts at 91-92", is insoluble inwater, readily soluble in alcohol, ether, and benzene.By boilingwith alcoholic ammonia, it is converted into a compound of theformula C6H,CI,H4 or c6H3cl,[ NH2I2, crystallising well and melting at165". A chlorinated product of feeble basic properties is obtainedby heating in sealed tubes with aqueous or alcohol& ammonia.A. J. G.Action of Aldehyde on Propyl Glycol. By A. DE GRA;noNfr(Compt. rend., 97, 173).-Equal parts of aldehyde and isopropylglycol are heated together in sealed tubes a t about 160" for two days,and the product is distilled. That portion which boils between 75"and 110" is dried over calcium chloride and fractionated. In this waya colourless, highly refractive liquid of ethereal odour is obtained.Itboils a t about 93", and its sp. gr. is lower than that of water, i n which itis only slightly soluble. The analysis of the liquid and the determina-tion of its rapour-density did not give satisfactory results, but in allprobability it is propyleneacetal, formed by the union of aldehjdeand isopropyl glycol with elimination of water. I n contact withwater it yields aldehyde and isopropyl glycol.Isopropylene oxide has no action on aldehyde in sealed tubes below140", but above this temperature decomposition takes place withformation of volatile and carbonaceous products.Constitution of Natural Fats. By J. A. WANKLYN and W. Fox(Chem. News, 48,49).-The authors suggest that some fats, which donot yield glycerol on saponification, are in all probability ethers ofisoglycerol.Isoglycerol, CH2Me.C( OH),, exists in its ethers, cannot beisolated, and ought to be resolved into CHzMe.COOH + H,O.C. H. B.D. A. L.d 36 ABSTRACTS OF CHEMICAL PAPERS.New Derivatives of Mannitol. By A. GEUTHER (Annalen, 221,59-60) .-The author noticed that a white flocculent precipitate wasgradually separated from a perfectly clear sample of butyric acid;it was filtered off, purified from the adhering acid by heating to170°, and dissolved in water. On evaporating the aqueous solution,a gummy mass of the composition CI2H,,O7 was obtained. As theprocess of lactic and butyric fermentation is always accompanied by apartial conversion of the s u p w into mnnnitol, then this substance isprobably an anhydride of mannitol, C,,H,,O, = 2C,H1406 - 50H2,and is thus a homologue of mannitan, C,H,,O,, and mannide, C6131004.Relation between the Solubility and Rotation of Milk-sugar, and Rate of Transition of its Birotation into NormalRotation. By I?.URECH (Bey., 16, 2270-2271).-When finelydivided milk-sugar is agitated with a quantity of water insufficient todissolve it, a saturated solution is obtained, which exhibits birotation ;but, the solution gradually takes up more milk-sugar as the transitionfrom birotation to normal rotation takes place, showing that thesolubi1it)y is thereby increased. When two saturated solutions areprepared at temperatures differing by about 20") and the warmersolution is allowed to cool down to the temperature of the other, i twill still contain much more milk-sugar than the solution prepared a tthe lower temperature, the greater solubility a t the higher tempera-ture being due not only to the difference of temperature, hut, also tothe more rapid conversion at a raised temperature of the birotatorgsugar into the much more readily soluble sugar of normal rotation.The transition from birotation to normal rotation takes place slowly atatniospheric temperature, so that the rate of change can readily bemeasured by the polariscope and formulated in the same way as therate of inversion of saccharose.A. I(. M.V. H. V.Starch and its Transformations under the Influence ofAcids. By F. SALOMON (J. y ~ . Chenz. [2], 28, 82--158).-Theprincipal conclusions drawn by the author from this lengthy investiga-tion are as follows :-The transformation of starch by dilute sulphuricacid cannot be considered as a splitting up of the rriolecule intodextrin and dextrose, as assumed by Musculus.The products of theaction of sulphuric acid on starch are soluble starch, dextrin, anddextrose; the course of the reaction being that the complex starchmolecule is first converted into the more simple soluble starch, andnext into the still more simple dextrin, the hydrolysis of the latterinto dextrose commencing almost simultaneously. The rate of theconversion is proportional to the quantity of sulphnric acid present.The transformation of starch by organic acids (oxalic, tartaric, andcitric acids) proceeds in the same manner as with inorganic acids,but the action is less vigorous.Soluble starch, i f pure, gives a deep blue coloration with iodine,but if i t is contaminated with dextrin, a reddish-violet, coloration isobtained ; it does not reduce Fehling's solution, and has the specificrotary power [al,j = 211.5" (comp.O'Sullivan, Trans., 1879, 772).There is only evidence for the existence of a single dextrin ; it giveORGANIC CHEMISTRY. 37a brownish-red coloration with iodine, does not reduce Fehling'ssolution, and has the specific rotary power [a> = 216.5".ByW. FOSSEK (Afoi?atsh. Chem., 4, 660-662).-The author's method isbased on the property of the crystalline trimolecular modification ofisobutyraldehyde to change into the ordinary liquid aldehyde, underthe influence of strong snlphuric acid at the heat of the water-bath.The crude isobutyraldehyde was first partly purified by heating it, aspreviously described by the author (Abstr., 1888, 161), with a strongsolution of sodium acetate a t 150".It was then polymerised bymixing it with strong sulphuric acid (1 g. acid to 100 g. aldehyde), orwith hydrochloric acid, the formation of crystals being accelerated bycooling. These crystals were drained on a filter,.washed with water,dried between filter-paper, and preserved for use. To convert them,when required, into liquid isobutyraldehyde, they are fused on thewater-bath, mixed with a few drops of strong sulphuric acid, andheated on the water-bath in a reflux apparatus, whereb7, after aboutan hour's boiling, the whole of the polymeride is converted into liquidisobutyraldehyde, boiling constantly a t 63" (bar.741 mm. a t 0') andhaving a density of 0.8057 at 0" and 0.7898 at 20", referred to watera t the same temperatures. Its vapour, when inhaled, producesnaosea a,nd headache. H. W.A. J. G.Preparation of Isobutyraldehyde free from Acetone.A Derivative of Isobutyraldehyde analogous ts Hydro-benzoin. By W. FOSSEK (Monatsiz. Chem., 4, 663-678).-Theauthor has already shown (Abstr., 1883, 1278) that when the pro-ducts of the action of aqueous potash on isobutyraldehyde are distilledwith steam, a thick yellow oil remains, holding in solution twoisomeric crystalline bodies, C8HI8O2, resembling one another in theirchemical reyctions (which are those of the pinacones), but differing incrystalline form, solubility, and melting point, the more abundant ofthe two crystallising in plates, being moderately soluble in water, andmelting a t 151", whereas the other crystallises in groups of needles,dissolves but very sparingly in water, and melts at 91".The formerwas extracted from the oil by agitation with hot water ; the latterseparated out on adding light petroleum, This higher-meltingbody could not at first be satisfactorily examined, on account of thevery small quantity in which it was obtained; but the author hassince found that it may be prepared mnch more readily by acting onisobutyraldehyde with alcoholic instead of aqueous potash, formingindeed the chief product of the reaction, which likewise yields isobu-tyric acid and a hydroxy-acid to be described further on.The crystalline body melting a t 91" is found by analysis to have thecomposition C6H1802, and its reactions show that it consists of di-iso-propyl-glycol, CHPrp(OH).CHPrfi(OH). It dissolves readily inalcohol and ether, somewhat less readily in water, and separates onquick evaporation of its aqueous solution, as a supernatant oil, which,on contact with a solid body, suddenly solidifies to a cake.By veryslow evaporation, however, a t temperatures near 0", it may be ob-tJained in monoclinic crystals having the axial ratio a : b : c 35 ABSTRACTS OF CHEMICAL PAPERS.0.8223 : 1 : 1.9086, and the angle ac = 97" 30'. Obsrrred faces,m P s , OP, + P, -P.The crystals are flattened by predominance of~ P s . The vapour-density of thecompound is by experiment 67.71-70*03 ; calc. 7300.By oxidation with nitric acid, the glycol yields isobutyric andoxalic acids ; with potassium permanganate i n neutral solution, theisobutyric acid formed in the first instance is further oxidised to aceticand carbonic acids.Di-isopropyl glycol boiled for about two hsurs with a slight excessof acetic chloride, yields an oily diacetate,Treated with an equal weight of a mixture in equal parts of strongsulphuric acid and water, it dissolves in a few minutes, especially ifthe mixture be heated in a refiux apparatus, and there rises to thesurface an oil halving a camphorous odour; and on separating this oilafter boiling with ether for half an hour, washing the etheric solutionwith aqueous sodium carbonate, evaporating off the ether, and dryingthe remaining liquid with calcium chloride, a residue is obtainedwhich may be separated by fractional distillation into two liquids, thesmaller i n quantity smelling like camphor and boiling a t 120-122",whilst the other, which is viscid and nearly colourless, distils a t 260-262".Both these liquids have the composition C,H,,O. They are notaldehydes, and therefore the oxygen contained in them is probably re-lated to the other elements in the same manner as in oxides or inketones.The glycol heated for 6-8 hours in a sealed tube at 140" with tentimes its weight of fuming hydriodic acid, is converted into an iodidewhich, when decomposed by alcoholic potash, yields an octylene,CBHI6, in the form of a colourless mobile liquid, which has a strongodour of petroleum, distils for the most part a t 116-120", and unitesreadily with bromine, forming a very unstable addition-product.Themode of its formation from di-isopropyl glycol shows that it must berepresented by the formula CHPrB : CHPrp.The action of alcoholic potash on isobutyraldehyde gives rise alsoto isobutyric wid and a small quantity of a hydroxy-acid, C8H1,&which forms a white anhydrous crystalline powder, sparingly solublein water and in ether, easily in alcohol; does not volatilise withsteam ; melts a t 92", and distils a t a high temperature : its silver saltis amorphous, and melts at 120".The constitution of this acid hasnot yet been made out.The formation of di-isopropyl glycol and isobutyric acid from iso-butyraldehyde is represented by the equation-Twins occur united by this face.c ~ ~ H ~ ~ o ~ * = c~H~,(oG),o,.3PrWOH + KOH = CHPr~(OH).CHPrS(OH). + P@.COOK.H. W.Action of Carbonic Oxide on Mixtures of Sodium Alcoho-By M. SCRROEDER(Annden, 221, 3&-55).-The researches of Genther and Froelich,Looss and Poetsch (Abstr., 1883, 729) on the action of carbonic oxideQ In the original paper the foi-mula is printed C,,H,O,, which does not agret!either with the rational formula or with the analpis (C = 62.62, H = 9*52).-H. W.lates and Sodium Salts of Organic AcidsOHGASIC CHEMISTRY. 39on sodium alcoholates, have proved that a small quantity of the sodinmsalt of the corresponding carboxyl acid is formed.But in the pre-sence of a considerable quantity of this latter salt, sodium formate isobtained, together with the sodium salts of homologous and isologousacids. The first phase of this reaction may be expressed as follows :-CO + CnH2,+lNaOz + C,,bHz,-,Na02 = HCOONa + C,H,,_,(CnH2,+,)NaO~.The author has studied the same reaction in the case of sodiumphenates and the sodium salts of organic acids belonging to variousseries. When carbonic oxide is passed into a heated mixture ofsodium phenylate and acetate, a hydrogen-atom of the acetic acid isnot replaced by phenyl with formation of phenylacetic acid, butsodium salicylate is obtained in small quantity. This result is pro-bably due to the presence of sodium carbonate in the alcoholatewhich yields the carbonic anhydride.The supposition the authorconfirms experimentally. Similarly in the action of carbonic oxideon sodium ct,hylate and benzoate, the hydrogen of the benzoic acid isnot replaced by an ethyl-group. Conversely, when sodium phenyl-acetate is substituted for sodium benzoate, the sodium salts ofp h eny let b y lace tic, CHE tP h . C 0 OH, and ethenylbut enylph en ylacetic,CPhC,H3.C2HzEt.COOH, acids are formed ; in this respect phenyl-acctic behaves precisely as acetic acid.By the action of carbonic oxide on sodium ethylate and cinnamate,the sodium salts of diethylcinnamic acid, C,H,Et,O,, were formed inone set of experiments, when the mixture was more cornplt~telyexposed to the action of the gas.I n another set, the sodium salt ofdibutyl cinrinmic acid was obtaincd, derived doubtless from thediethylcinnamic acid by the replacement in each ethyl-group of ahydrogen-atom by another ethyl-group.Experiments on the action of carbonic oxide on mixtures of sodiumethylate and potassium oxalate or sodium succinate led to negativeresults, V. H. V.Behaviour of Chromium, Iron, and Aluminium Acetates.By B. REINITZER (Chem. News, 48, 114).--'YC'hen a solution of chro-mium sulphate or chloride is boiled with excess of sodium acetate, noprecipitate is formed, but if the boiling is conducted for a short timeonly, the solution becomes violet on cooling. The solution thus pre-pared behaves in the following manner in the cold :-Caustic alkalisand barium hydroxide change the colour a t first to olive-green andthen to emerald-green, and in 12 hours the liquid sets to a green jell?.Ammonia produces no immediate effect, but in 48 hours :I violet jellyis formed ; ammonium sulphide and carbonate act in a similar manner.after several days.When the violet chromium acetate solut,ion isboiled with any of these reagents, or with an alkaline or barium car-bonate, a precipitate is produced, immediately or otherwise, accordingto the strength and quantity of the reagent added. Sodium phos-phate does not precipitate the solution. This non-precipitating prc-perty of chromium acetate extends to iron and alumina in solution,for neither by boiling nor by treatment with the above-mentionedreagents can certain quantities of ferric oxide and alumina be de40 ABSTRACTS OF CHEMICAL PAPERS.tected in the presence of chromium acetate. The quantity of theseoxides thus retained is limited if the ferric oxide and alumina arepresent previous to boiling with sodium acetate ; if, however, thesesubstances are added subsequent to sodium acetate treatment, largequantities of iron and alumina can be dissolved.Ammonium sulphidemakes an exception in the case of iron, for it precipitates i t slowlybut completely. If the chromiiim solution and sodium acetate aresimply mixed in the cold, a t first the chromium can be precipitatedby the reagents referred to above ; after a day, however, the solutionacquires the solvent properties it would have done by boiling.D.A. L.Composition of Cocoa-butter. By M. C. TRAUB (Arch. Pharrn.[3], 21, 19-23).-Kingzett has stated (Trans., 1878, 38) that thisbutter contains two new fatty acids, the one apparently an isomerideof lauric acid, the other, called theobromic acid (m. p. 72*8"), andhaving the formula C64H12802. The momalous melting point of suchan acid led the author to make an investigation of cocoa-butter. Bya process of fractional precipitation with magnesium acetahe aftersaponification, an acid was obtained from the first portion of the pre-cipitate, which was not further resolved by precipitation, and afterrecrjstallising from absolute alcohol was proved to be arachic acid( C2,H4,0,). Fractional distillation under diminished pressure (100mm.) confirmed the results obtained by fractional precipitation.Inaddition to arachic acid, oleic, lauric, palmitic, and stearic acids werefound, but no acid isomeric with lauric acid. The author, therefore,cannot confirm the statement that cocoa-butter contains two new fattyacids, and maintains that its physical properties are due to the relativeproportions of arachic, oleic, lauric, palmitic, and stearic acids, whichare present. W. R. D.Carbonyl Iodide, COI,. By S. P. COWARDINS (Chern. NCZC'S, 48,97).-Several experiments were made with a view to prepare t h i ssubstance, but without success. Proportional parts of dry carbonicoxide and iodine in a flask were exposed to direct sunlight. Carbonicoxide and iodine yapour were passed through a tube surrounded byice and salt.Carbonic oxide was passed through heated arsenicpentiodide, and then through the cooled tube, also over red-hot leadiodide. Phosgene gas was passed over potassium iodide and into con-densing tubes. D. A. L.Action of Phosphorus Pentachloride on Succinic Chloride.Ry E. KAUDER (J.PY. Chenz. [Z], 28, 191--192).--By heating onepart of succinic chloride with three parts phosphorus pentachloride insealed tubes at 230", there was obtained, not as was expected thechloride C2H4(CCI3),, but a colourless liquid of sp. gr. 1.694, boiling at199-215", solidifying in large colourless plates at, low temperatures,and having the composition C4C160. If this is heated with sulphuricacid, it is decomposed into a substance of the formula C4Cl,0,,possibly dichloromaleic anhydride, C2C& : (CO), 0.It forms a whitemass, sparingly soluble in water, melts a t 119*5", and sublimes inwhite plates. A. J. GORGANIC CHEMISTRY. 41Tetric Acid and its Homologues. By W. PAU-LOW (Compt.rend., 97, 99-102) .-Ehhylic methylinonobromacetoacetate is slowlydecomposed a t ordinary temperatures and more rapidly when heated,yielding monobromethane and the tetTic acid described by Demarcay.This acid has the composition C5H603, and not C,,H,,O, as stated byDemargay. Ethylic isobutyl-monobromacetoacetate is decomposed ina similar manner when heated, and yields the heptic acid also describedby Demnrgay. This acid has the composition C 61.33, H 7.81, cor-responding with the formnla C8H1203, and not with Demargay'sformula 3(C7Hl,02),H20, which requires carbon 63.63 per cent.,hydrogen 8.08 per cent.The formation of these acids by simpleevolution of monobromethane indicates that they are unsaturatedcompounds, and tetric acid is found to combine readily with twoatoms of bromine. This fact, together with its mode of formation,shows that tetric acid has the formula MeCO.C(COOH) : CHZ, and isin fact acetoacrylic acid, the general formula of its homolcgues beingMeCO.C(COOH) : C,H,,. Its formation is expressed by the equationMeCO.CBrMe.COOEt - C2H,Br = MeCO.C(COOH): CH,. Ethylmonobromacetoacetate, MeCO.CHBr.COOEt, undergoes no similardecomposition. C. H. B.Carboxytartronic Acid. The Constitution of Benzene.By A.K E K C L ~ (Annalen? 221, 230-260).-After referrinq to theresearches of Gruber ( Wien. Acad. Ber., 1879 ; Ber., 12, 514), Barth( Wien. Acad. Ber., 1880 ; Wiener Monatshefte, 1, 869), and Werzig(Wien. Acad. Rer., 1882 ; Wiener Monatshefte, 3, 825), on carbosy-tartronic acid, and their bearing on the constitution of benzene, theauthor describes experiments proving that the so-called carboxjtnr-tronic acid is a dihydroxytartaric or tetrahydroxysuccinic acid. Amixture of racemic and inactive tartaric acid is formed by the actionof zinc and hydrochloric acid on sodium carboxytartronate ; andcarboxytartronic acid is produced as an intermediate product by thespontaiieous decomposition of nitrotartaric acid.The nitrotartaric acid is prepared by adding sulphuric acid to asolution of tartaric acid in 44 times its weight of fuming nitric acid.The crystalline mass is drained by means of a filter-pump, andbrought in small quantities a t a time into a mixture of ice and ether.After washing with ice-cold water, the ethereal solution is evaporatedin a vacunm.A solution of nitrous acid in alcohol is added to anetherial solution of nitrot,artaric acid, and after two or three days theliquid is shaken with ice-cold water. On the addition of sodiumcarbonate to the aqueous solution, sodium carboxytartronate is a t onceprecipitaLed. The sodium salt is decomposed by water a t 6d", withthe formation of carbonic anhydride and sodium tartronate.These experiments show that " sodium carboxytartronate " doesnot possess the coristitution generally ascribed to it, and that carhoxy-tartronic acid is closely related to tartaric acid. The exact composi-tion of the sodium salt has not yet been ascertained, as it loses firstwater, and then water and carbonic acid on drying ; but it is probablyC4Na2OG + 4H@.Since this compound does not contain three carbon-atoms directly united to each other, its formation from pyrocatecho42 ABSTRACTS OF CHEMICAL PBPERS.is no argument against the author's hypotheses on the constitution ofbenzene. w. c. w.Iaonitroso-acids. By A. F~~RTH (Ber., 16, 2180-2182).-0f theisonitroso-derivatives of the acids of the acetic series, only three areat present known, viz., isonitroso-propionic, -butyric, and yvalericacids. The author, following the process proposed by WJGugel, hasobtained, by the action of nitrous acid on ethylpropylacetoacetate,a-ison.itroso-waZeric acid, CH,Me.C Hz. C (N.OH) . C 0 OH. This acidcrystallises in needles which melt at 143" with complete decorr-position; it is soluble in alcohol and benzene, sparingly soluble inwater; its silver salt forms a white precipitate. By the action ofhydrDxylamine hydrochloride on ortho- and para-aldehydo-salicylicacid, the author has obtained the ortho- and para-aldoximesalicglicacids, COOH.C6H3(OH).CH(NOH). Both acids crystallise in smallgolden needles. The former melts at 193", the latter a t 179", and isinore sparingly soluble than its isomeride.Action of Nitrous Acid on Ethyl-glycocine Hydrochloride.By T.CURTIUS (Ber., 16, 2230--2231).-When a concentratedaqueous solution of the hydrochloride of the ethylic ether of glycocineis treated with sodium nitrite, a yellow oil is precipitated and can beextracted with ether. To purify it, it is treated with baryta-water,steam-distilled, dried over calcium chloride, and heated a t 95" on awater-bath. It is a neutral liquid of golden-yellow colour and ofpowerful characteristic odour, miscible in all proportions with etherand alcohol, but almost insoluble in water. It volatilises on ex-posure to air, and when heated t o about 110" is decomposed withviolence and with great evolution of heat. It shows great stability inthe presence of alkalis, but in contact with acids, water, or alcohol,it gives off nitrogen in nearly theoretical amount.With cold con-centrated hydrochloric acid, the decomposition takes place withexplosive violence, etlhyl chloracetate being formed. On boiling i twith water, the products are ethylic glycollate, glycollic acid, alcohol,and nitrogen, whilst with alcohol, ethylic ethylglycollate is produced.These reactions would indicate the body to be ethylic diazoacetate,CH,(N,OH).CQOEt, but analysis shows that its formula is-V. H. V.that is, ethylic diazoacetate minus the elements of a molecule of water.The author is continuing his experiments in the hopes of obtainingdiazo- and diazo-amido-derivatives of the fatty acids. A. K. M.Chemistry of Asparagine. By B. SCHULZE (LandvJ. Tersucl6s.-Stat., 29,2;%-240).--Having occasion to obtain rather large quanti-ties of aspartic acid from asparagine, the author made several experi-ments to ascertain which was the cheapest and best decomposingagent to use.Schlosing's apparatus was used for determining theamount of asparagine converted into ammonium aspartate, and it wasfound that milk o€ lime had no action in thc cold on asparagineuntil after 24 horirs' standingORGANIC CHEMlSTRY. 43Heated wit,h water alone, a t the ordinary pressure, asparagine isbut very slowly decomposed; after 12 hours' boiling only 2 per cent.of the nitrogen was converted into ammonium salt. Under higherpressure the amount decomposed is much greater, and increases slowlywith increase of pressure,The effect of boiling with lime-water or baryta was much morerapid ; when a large excess of baryta was used, one hour was sufficientfor the complete conversion into aspartic acid ; but if the boiling becontinued some hours longer, a further separation of ammonia takesplace, malic acid being formed.Boiling with dilute sulphuric acid in slight excess also effects thecomplete conversion of asparagine into ammonium aspartate.J. K.C.Metaisopropylmethylbenzene. By H. E. ARMSTRONG and A.R. MILLER (Ber. 16, 2748-2750) .-According to Kelbe (AlznaZen,210, 30) metaisocymene yields at least two monosulphonic acids, theRecond of which, the P-acid, he did not thoroughly investigate, but hedescribed the barium salt as being very readily soluble in water, andas cry stallising from a concentrated syrupy solution in small lustrousscales of the composition (C10H13S03)2Ba + HzO.The authors, whogive a full description of the method by which they prepare puremetaisocymene, also find that this hydrocarbon yields two sulphonicacids, which they separate by means of the barium salts, but Kelbe'sdescription is entirely inapplicable to the more soluble modification.Although very soluble, it crystallises very readily in long thin prismsof the composition (CloHl,S0,)2Ba + 9H20. The calcium salt,(C10H13S03)2Ca + 5&H,O, is very similar in appearance to the bariumsalt. The potassium salt, CloH,S03K + 2+H20, crystallises in longwell-formed prisms. A. K. M.Contributions to our Knowledge of Camphor. By H. .E.ARMSTRONG and A.K. MILLER (Bey., 16, 2255--226l).-By the actionof' zinc chloride on camphor, Fittig, Robrich, and Jilke (Arunalen, 145,129) obtained a hydrocarbon, C,,HI4, which they regarded as mostprobably identical with ordinary cymene, together with muchtoluene, xylene, pseudocumene, and Zaurene, the last-mentioned being,according to their analysis, a hydrocarbon of the formula CIIHl,. Bythe same reaction Montgolfier (Ann. Chim. Phys., 1878 [ 5 ] , 14, 87)obtained what he thought to be cymene and an isomeric hydrocarbonboiling a t about 195", from which he prepared a dibromo-derivativemelting at 199"; this isomeric hydrocarbon he assumed to beJannasch's tetramethylbenzene (1 : 2 : 3 : 5), and regarded it asidentical with Fittig's laurene.From the fraction 173-176", sup-posed to be cymene, Fittig, Robrich, and Jilke prepared a sulphonicacid, the barium salt of which contained 10.13 per cent. water,whereas ordinary barium cymenesulphonate contains 8.75 per cent.It would seem that Montgolfier prepared the same salt (with 10.74per cent. water) from the crude distillate boiling at about 195".Pittig's fraction boiling at 188" (Cl,H,o), was assumed to be a di-niethylpropylbenzene, as it yielded a tri bromo-derivative melting a44 ABSTRACTS OF CHEMICAL PAPERS.125", and on oxidation gave monobasic lauroxylic acid, C,H,,O?,melting at 155"The authors heat camphor with twice its weight of zinc chloride ata moderate temperature, until a homogeneous mixture is obtained,and then distil a t as low a temperature as possible.The crudedistillate is extracted with sodium hydroxide solution, then steam-dis-tilled, and the distillate is agitated with dilute sulphuric acid (4 vols.acid to 1 vol. water) to remove the unattacked camphor, and againsteam-distilled. On passing steam into the retort, a second distillateis obtained, consisting of camphorone, CDHIIO, and camphor mixedwith some hydrocarbon, which can be separated by means of sulphuricacid of the above strength, in which the camphorone is soluble; aresidue of zinc chloride mixed with a black carbonaceous mass remainsin the retort. The above-mentioned alkaline extract yields purecarvacrol on addition of an acid.When the mixture of hydrocarbons remaining after treatment ofthe crude distillahe with dilute sulphuric acid, is heated with sulphuricacid, a considerable amount of a saturated hydrocarbon, CIOHZO,remains undissolved, whilst the sulphuric acid solution containsprincipally beuzene hydrocarbons of the formula I=,,H,,, only a verysmall amount of lower and higher homologues being formed, togetherwith a hydrocarbon which has not yet, been isolated, and which iscarbonised by the action of heat on the dilute acid solution. Thechief constituents of the hydrocarbon mixture are a nzethylpropyl-benzene, a dimethylethylbenzene, and a tet?-amethylbenzene ; the pre-sence of ordinary cjmene has as yet not been detected.* Thesulphonic acid of the first-mentioned hydrocarbon yields a verysparingly soluble anhydrous barium salt, a sodium salt containing1 mol.H,O, and an anhydrous potassium salt, the last two crystal-lising in large lustrous plates. The hydrocarbon boils a t 176", isoxidised by dilute nitric acid to metatoluic acid, and is identicalwith the metaisopropylmethylbenzene discovered by Kelbe in rosinspirit. The dimethylethylbenzene (b. p. 189') is probably identicalwith Fittig's laurene; it yields paraxylic acid on oxidation, aricimust therefore have the constitution [Me : Me : Et = 1 : 2 : 41. Ityields two isomeric sulphonic acids. From the chief product there mayhe obtained a barium salt crystallising with 4H,O, and a magnesiumsalt containing about 25 per cent. water, magnesium cymenesul-phonate containing 16.6 per cent. The tetramethylbenzene isiden tical with Jannasch's isodurene, and yields a dibromo-derivativemelting at 2W0, as stated by Jacobsen.The chief products of the action of iodine on camphorare carvacrol,and the saturateu hydrocarbon, C,,H,,.Dimethylethylbenzene andtetramethylbenzene are also formed, but no cymene or meta-cymene.Ordinary cymene appears to be the only benzene hydrocarbonwhich is formed by the action of phosphoric anhydride on camphor,and is also the chief product of the action of phosphorous pentasul-phide, but in the latter case a considerable amount of metaisopropyl-* Subsequent investigation has shown that no cymene is present.-H. E. AORGANIC CHEMlSTRY. 45methylbenzene, and a small quantity of tetrnmethylbenzene are alsoobtained together with traces of higher and lower homologues, and asmall percentage of the hydrocarbon C,,H,,.The hydrocarbon whichcarbonises when its sulphuric acid solution is heated (see above) is alsoformed by the action of phosphorus compounds and of iodine oncamphor.The formation of these different hydrocarbons from camphorcannot well be represented by KekulB's formula, b u t can be to someextent accounted for by the assumption of the following formula,which is a slight moditication of that previously suggested byArmstrong (Rer., 11, 1698 ; 12, 1756).CH, CH CH/\HC CEI:AHC CPr/\H,C CH.CH,I IMeC C.CHMe2I IMeC CHI I IMeHC CMe.COv CH, \c/H Y€Camphor. Cymene. Metacy mene.CMe CHAHC CMeI IMeC CMe/\HC CEt1 1MeC CH\/CMeTetramethylbenzene. Dimethyle thylbenzene.A.K. M.Artificial Formation of Thiophene. By V. MEYER and T.SANDMEYER (Bey., 16, 2176).-I€ ethylene or acetylene is passedthrough boiling sulphur large quantities of carbon, hydrogen sulphide,and carbon bisulphide are foi-med. The last contains a small quantityof an oil which resembles thiophene in all its properties, giving theindophenine reaction with isatin and sulphuric acid, and dyestuffswith beirzoyl cyanide and sulphuric acid, and with phenylglyoxylicand metazophenylglyoxylic acids.The Thiophene Group. By V. MEYER and H. KREIS (Bey., 16,2172-2176 j .-One of the anthors bas recently isolated and describedthiophene, C4H,S (Abstr., 1833, p. 1091), a substance obtained fromcoal-tar benzene ; in the present communication some of its derivativesare described.Z'pJtrabromothiophene, C4Br4S, is formed by the action of bromine inexcess on the residue left in the course of the fractional distillation ofdibromotlhiophene.This substance crgstallises in white glisteningneedles melting at 112", and boiling at 26".Thiophenesulphonic acid, C,H3S.S03H, is obtained as a deliquescentcrystalline mass, of strongly acid reaction, and yielding thiophene ondry distillation. The corresponding acid chloride, C,H,S. SO,Cl, is aheavr golden oil, converted by trituration with ammonium caybonateV. H. V46 ABSTRACTS OF CHEMICAL PAPERS:.into thiophenesdpamide, C4H3S.S0,NH2, which forms delicate whitecrystals melting at 141".ThiopheiLenitriZ, C4H3S.CN, obtained by the distillation of potassiumcyanide and thiophenesulphonates, is an oil boiling a t 190", and smellinglike bitter almonds ; it is readily transformed into the carboxylic acid,C4H3S.COOH, on boiling with alkalis.Thiophenic acid resemblesbenzoic acid in appearance, smell, and manner of sublimation ; it is veryvolatile in vapour of steam, melts a t 118", and boils a t 258". I t s cal-cium salt forms spear-shatped crystais, its silver salt a precipitate,sparingly soluble when dried.The authors briefly note the presence of a sulphur compound boilinga t 110" in the purest toluene of commerce ; they are now engaged ininvestigating it, and the dye-stuffs derived from it, as also those fromthio p hene.Separation of Aniline, Paratoluidine, and Orthotoluidine.Ry LEWY (Dingl. potyt.J., 248, 260).-By decomposing the hydro-chlorides of the bases with sodium phosphate, Lewy obtains thosparingly soluble phosphates of aniline and paratoluidine besides freeorthotoluidine and readily soluble basic orthotoluidine phosphate.By warming the mixture after the decomposition is completed, it ispossible to dissolve the first-named salts ; the resulting supernatantoily layer of orthotoluidine is then decanted, and the aniline and para-toluidine salts are allowed to crystallise out. The mother-liquor con-tains the basic orthotoluidine phosphate. By liberating the bases withsodium hydroxide, the sodium phosphate originally used may berecovered. D. B.V. H. V.Meta-isocymidine. By W.KELBE and C. WARTH (Annalen,221, 157-178) .-Nitrometa-isocymene, CIoH,,NOa, prepared by theaction of strong riitric acid on meta-isocymene (Abstr., 1880, 8'78)is decomposed by boiling, but may be distilled in a current of steam.By the prolonged action of dilute nitric acid (1 of acid to 4 of water),it is converted into r&rotoZuic acid, CGHsMe(NO2).COOH(a), whichis not identical with either of the nitrotoluic acids described byJacobsen (Ber., 14, 2347), and must consequently have the formulaC6H2Me(N02)H. COOH (-0 o r C6HMe (NO,) H2. COOH (8). This acidis deposited from an alcoholic solution in glistening needles (m. p.214"). The b a r i u m salt crystallises in silky needles, freely soluble inalcohol and in water.illeta-isocyirkdine, CloHI3NH2, obtained by reducing nitro-isocymenewith tin and hydrochloric acid, is purified by conversion into thebenzoic-derivative, NHIE.Cl0HI3. This compound crystallises inneedles melting at 165", soluble in alcohol.It is decomposed by alco-holic potash a t 180", yielding meta-isocymidine, a strongly refractiveliquid boiling at 23'L0, freely soluble in alcohol, ether, benzene, andlight petroleum, The platinochloride of meta-isocymidine is unstable.The srdphate, ( C,oH13.NH2),H2S04 forms thin plates, sparingly solublein water and alcohol. The aqueous solution is decomposed by hoil-ing. The oxaZcrte, Cl,H,3.NH2,H.,C20J, is sparingly soluble in waterand alcoholORGANIC CHEMlSTRY. 47Acetic chloride acts readily on dry cymidine, forming acetoineta-isocymidide, NHAc.CloHl,, which crystallises in plates melting a t 118".By tlhe action ofst'rong nitric acid on benzoic isocymidide, the nitro-compound NHBz.CloH,2.N0, is produced.It is deposited from analcoholic solution in yellow needles melting at 177", which are spar-ingly soluble in ether. On oxidation with dilute nitric acid, benzoicisocymidide yields amidometatoluic acid, which melts below 100".Phthalic rnetaisocymidide, C6H4( CO)2N.C,oH13, is deposited from ahot alcoholic solution i n needles, which melt at 145". The nitro-product forms yellow needles melting at 167", soluble in alcohol ande t 11 e r.Il'ltaisocyii~iiay Zcarby Zair~ine, Cl0H,,NC, prepared by the action ofchloroform and alcoholic potash on cymidine, is a colourless liquidhaving a powerful odoiir.It is freely miscible with alcohol, ether,benzene, and light petroleum. It cannot be distilled without decom-position. Ili"TetaisocyminyZcarbamide, C loH13.NH. C ONH2, is obtained byboiling an excess of potassium isocyanate with a feebly acid solution ofcymidine sulphate. It forms lustrous needles melting at 176", solublei n alcohol. By the action of carbonyl chloride on cymidine dissolvedin absolute ether, dimetaisocimynylcarbamide, ( CloH,3NH)2C0, isproduced in colourless needles, freely soluble in alcohol, less solublein ether.~~etaisocynainyZuret7Lane, C,"H13 NH.COOEt, is a colourless crystal-line compound melting at Z9", soluble in alcohol and ether. Dbyminyl-thiocarbamide, ( CloH,,.NH),CS, prepared by the action of carbonbisulphide on cymidine, crystallises in needles melting at 160", solublein alcohol and ether.Neither naetaisoc?/rniizyZethy Zthiocarbnmide, C,,H,,.CSNH.NHEt, normetaisocyminylethylguanidine, CIOH13.C (NH)NH.NHEt, could be ob-tained in a crystalline condition.Nitrophthalylcymidide is decomposed by strong hydrochloric acidat 180", yielding nitroisocymicline, NO2.CloH,,.NH2, an oily liquidmiscible with alcohol and ether.~ ~ e t a i s o c y m i d i n e s u ~ h u n i c acid, CloHl,( NH,) .SO,H, forms thinyellow-coloured needles, very soluble in water.The Larium salt, (NH,.CloH12.S03)zBa, also crystallises in needles,Action of Dichloracetic Acid on Aromatic Amines (11).ByP. J. METER (Ber., 16, 2261-2269) .-The author previously showed(Ber., 16, 926) that the reaction of dichloracetic acid with orthotolui-dine is different from t h a t between dichloracetic acid and paratoluidine,the latter yielding a substituted imesatin.To prepare paratoZy?@ni a-methylimesatin (paramethylisafin-~aratul~limide), C8H4MeN0.NC7H,,dichloracetic acid (1 mol.) is heated with paratoluidine (4 mols.) at100" until a dark-red crystalline mass is formed, which is then treatedwith hot water t o remove the toluidine hydrochloride ; or an aqueousor alcoholic solution of dichloracetic acid may be digested with para-toluidine, or finally dichloracetamide (1 mol.) heated with paratolui-dine (3 mols.). It crybtallises in splendid lustrous gold-colouredneedles and scales. The react:on may be compared with the fcrmationwhich are very soluble in water.w. c. w48 ABSTRACTS OF CHEMICAL PAPERS.of qninoline from aniline and glycerol (Ber., 13, 2086) : 2C7H;.NH, +C2H7C1202 = CI6H,,N,O + 2IIC1 + H,O f H,. Paramethylisatin-paratolylimide melts a t 259", is insoluble in water, dissolves sparinglyin cold, more readily in hot alcohol, and in ether. With concentratedsoda solution, it yields a salt crystallising in red prisms, and which isdecomposed by water. Cold concentrated hydrochloric acid converts itinto paramethylisatin and toluidine ; hot dilute acid or long-continuedheating with soda solution decomposes it in the same way ; it can bereproduced by heating these products with absolute alcohol. Whenpararnethylisatin-paratolylimide is heated for 2 to 3 hours a t 100"with alcoholic ammonia, pwamethy lirn esntin (paramet hy lisa titiin? i d e ) ,C9H,N0.NH, is formed, and can be freed from toluidine and colour-ing-matter by repeated boiling with alcohol.I n its properties, itdiffers from Laurent's imesatin (J. pr. Chem. 25, 457); it has apale yellow colour, is insoluble in cold water and cold alcohol, andvery sparingly in boiling alcohol, from which it crystallises iiiextremely slender silky needles ; it is not converted into paramethyl-isatin by acids or bases, and bears a strong resemblance to Somma-ruga's diimidoisatin (Ar~nnlen, 190, 371; 194, 85 ; Ber., 12, 979).Pnran~efhyliscttin, CeH,MeNO,, obtained as above, is isomeric withthe substance obtained by Baeyer and CEconomides (Ber., 15, 2093)from isatin silver and methyl iodide ; it is odourless, separates fromalcohol or hydrochloric acid in deep red transparent crystals resem-bling chromic anhydride, and from water in lustrous red scales,melting at, 187" ; it is sparingly soluble in cold, more readily in hotwater, readily in hot hydrochloric acid and in alcohol ; with alkalis,it forms a deep violet-coloured solution, yielding methylisatates whenheated OF on long standing.It yields the indophenin-, and withliydroxylamine the ketone-reaction, and forms condensation and sub-stitution-derivatives similar to those of isatiii. Phenylparumethyl-irnesahrz (pnraniethylisatinphe.lzylimida), CeH4MeN0 : NPb, is ob-tained on adding the equivalent quantity of aniline to a concentratedsolution of paramethylisatin in absolute alcohol.It crystallises inthick, yellowish-red, transparent plates or prisms, melts a t 239-240°,is sparingly soluble in water or cold alcohol, more readily in hotalcohol, and in its properties resembles paratolylimide. Metabromo-pnratolylp arnrnefh?y lirnesat i r i (paramethy lisatinin et abro m oparatoly 1 irnide),CeH4MeK0 NC7HeBr, is prepared in the same way as the last corn-pound ; it crystallises from alcohol in transparent brick-red needlesand prisms, melting at, 2 10". Orthoto ly lp~(r,r~yrLethylimesntin (para-nzeth?llisatinorthotolylirnide), CBHQMeN0.NC7H5, isomeric with theabove paratolylimide, crystallises in red transparent prisms, me1 tingat 191". Par.nmethyl~zitroso-oxin~ole, C,H,(NO)NO, is prepared by theaction of liydroxylamine hydrochloride on paramethylisatin (Rer., 16,518).It forms long transparent yellow prisms, is sparingly solublein water, more readily in alcohol, dissolves in potash without decorn-position, and melts a t 225-226". On adding coal-tar benzene to asolution of paramethylisatin in concentrated sulphuric acid, a deepblue coloration is produced, and on agitating with water paramethy I-indqjhenin separates. The numbers obtained on analysis agree onlyapproximately with the formula C1,H,NOS. It forms am indigo-bluORGANIC CHEMlSTRY. 49powder, sparingly soluble in water, alcohol, and acetic acid, morereadily in concentrated sulphuric acid and hot phenol, from which itis reprecipitated by water or alcohol.When treated with zinc andglacial acetic acid, it yields a bright, green substance, which becomesblue again on exposure to the air,Difference in Chemical Behaviour of Aromatic Diamines.By E. LELLMANN (Annalen, 221 1--34).-The isomeric aromaticdiamines, in some cases, present characteristic differences in chemicalbehaviour. Thus for example, Ladenburg has observed that thehydrochlorides of the orthodiamines react with benzaldehyde accord-ing to the equation-C,Hy(NH,),,2HC1 + 2PhCHO = C,H,(NCHPh),,HCl+ 2H20 + HC1,A. K. M.whereas the meta- and para-derivatives are unaltered. Similarly,Hobrecker and Hiibner have shown that ortho-diamines are differen-tiated from the meta- and para-compounds in yielding the so-called.NH.anhydro-bases, C,H \C,H,.Again the reaction of nitrous Y\-,-kacid on the ortho- resembles that on the para-, but differs from thatwhich it exerts on the meta-compounds.The author has studied the reaction of potassium thiocyanate andcyanate, and of the thiocarbimides, on the aromatic diamines, with aview of tracing analogous differences in chemical behaviour.At the outset some remarks are made on the method of pre-paration of ortho- and para-phenylene diamines. It is found that toobtain the former it is best to nitrate benzanilide and not acetanilideas recommended in the text-books ; on the other hand, acetanilide ismore suitable for the preparation of the latter.Action of Thiocyarmtes o n the Diaw&aes.-The diamine thiocyanatesare easily obtained from the hydrochlorides of the diamines and thethiocyanates; but the compounds produced differ in their mode ofdecomposition, the meta- and para- thiocyanate yielding the correspond-ing phenylenedithiocarbamides, C6H4(NHCSNH2),, whilst the ortho-compounds give the corresponding thiocarbamide, C,H,<NH>CS,together with thiocarbamide, CS(NH&.Orthophenylenethiocarbarnide, C6H4 <,,>CIS, obtained by the eva-poration of an aqueous solution of 1 mol.orthophenylenediamine hydro-chloride and 2 mols. potassium thiocyanatc, crystallises in large leaflets,which melt at about 290" with considerable carbonisation.YHNHNH Metapcrrutolylenethiocarbnmide, c6H3Me<NH>cs, from metapara-tolylenediamine and potassium thiocyanate, crystallises in silveryleaflets melting a t 284", and soluble in soda and ammonia, but repre-cipitnted on acidifying the solution.H e t ap h en!/ 1 ened it 1~ iocar b am id e , C 6H (NH C S N H,) ?, cry s t a1 li s e s inmicroscopic leaflets melting a t 215" ; the corresponding para-compoundVOL. XLVI.50 ABSTRACTS OF CHEMICAL PAPERS.in colourless needles melting a t 218", soluble in alkalis, sparinglysoluble in alcohol.The action of potassium cyanate on the diamines is the same for allthree isomerides ; a phenylenedicarbami de is formed.Orthophenylenedithiocarbamide, C6H4(NH.CSNH,),, crystallises inhard needles melting a t 290°, easily soluble in alcohol, sparin8ly inwater, chloroform, or ether. The para-compound crystallises in silveryleaflets and decomposes completely at a high temperature withoutmelting ; khe ?,zeta-compound crystallises in small colourless needlesmelting at 280", soluble in eoncentrated hydrochloric acid, but repre-cipitated on the addition of alkalis,By the action of thzocarbarnides on the dianzines complex thiocarba-mid& of the generic formula C,H,(NH.CSNH.C,H,),, are produced,which in the case of the ortho- and para-compounds are decomposed,when melted, according t o the equation C,H,(NH.CSNH.C,H,), =C,Hy<:E>CS + CS(NH.C,H,),, while the meta-compound is un-changed,Dipheny ZnaetaparatoZy Zenedithiocarbaniide, C,H,Me (NH.CSN HPh), ,from tolylendiamine and phenylthiocarbamide, is a crystalline sub-stance which when heated to 140-150", is decomposed into diphenyl-thiocarbamide subliming in the upper part of the vessel, and rneta-parajtolylenethiocarbamide.Diethyln~ta~al-at~ly~enedith iocarbamide, C6H,Me (NH.CSNHE t)2,from ethylthioearbamide and tolylenediamine forms microscopiccrystals which melt between 149" and 153", and on more protractedheating are decomposed into metaparatolylene- and ethyl-thiocarba-mides. The former is a crystalline substance melting at 284", spar-ingly soluble in water, easily soluble in alcohol and hot soda.DiaZZyZ-meta~aratolylenedithiocarba~~de, CGH,Me(NH.CSNH.C,H,),, fromtolylenediamine and allylthiocarhamide, crystallises in delicate silkyneedles, melting a t 150", sparingly soluble in water, soluble in alcoholand chloroform.The corresponding di~ll.grZmeta~he~~yZene~~tl~i~carbamide,CJI~(NH.CSNH.C,H,),forms an amorphous white powder, which melts at 105", and is notdecomposed when heated.Di~~enylpnraphenyleneclitkiocarbamide,C,H,(NH.CSNHPh),, is a crystalline substance, soluble in hof sodasolution. When heated to 260" it is decomposed partly into para-phenylenethiocarbamide, C~&<NH> NH cs, which crystallises in smallleaflets, melting a t 270".C6H4( NH. C SNH.C3H5;,is a crystalline substance, insoluble in water, sparingly soluble inalcohol. It melts a t 200", with evolution of a gas and emission of asmell resembling diallylthiocarbamide : its decomposition may probablybe expressed by the equation, C6HI(NH.CSNH.C,H5), =DiaZly Ipara~henyllllertei~~io~a~barnide,C6H4<ZE>CS + CS(NH.C,H,),ORGANIC CHEMISTRY, 51The author also made some experiments on the reduction of theorthonitranilides and tolnides of phenylsulphonic acid.When phenyl-sulphonyl chloride is added to orthonitraniline dissolved in benzene,crystals of orthonitraniline hydrochloride separate out. On filteringthese and evaporating the filtrate, phenylsulphorthonitranilide,PhS O,.NH. CGH4.N02,is obtained, This substance is crystalline, moderately soluble inpetroleum, easily soluble in alcohol ; it is reduced by tin and hydro-chloric acid to the corresponding amidoanilide, PhS0,.NH.CfiH4.NH2.This compound crystallises in long colourless needles melting a t168", sparingly soluble in water, readily soluble in alcohol and chloro-form ; its hydrochloride forms large thick crystals.Phenylszilpho-1)2etunitroparntnluide, PhS02.NH.CfiH,Me.N02, obtained together withthe corresponding dinitro-derivative by the action of fuming nitricacid on phenylsulphoparatolnide, crystallises in cubes, which melt a t99". On reduction with tin and hydrochloric acid, it is convertedinto the corresponding arnido-derivative, which crystallises in long,coloui-less needles, melting a t 146*5", sparingly soiiible in water, solublein alcohol.I n a summary, the author remarks that the above observations donot form sufficient material for general conclusions with regard to thereactions of the diamines. To complete the study of these compounds,i t is necessary to compare the decomposition of the isomeric phenylene-diamines with the diamines of the paraffin series.As a step in thisdirection, Hof mann has observed that ethylenediaminethiocyanatewhen melted yields ethylenethiocarbarnide, a decomposition perfectlyanalogous to the decomposition of the corresponding orthodipheriylenecompound. V. H. V.Organic Hydroxylamine Derivatives. By C. SCHRAMM (Ber.,16, 2183--2188).-When a solution of bromacetophenone in aqueousalcohol is heated with an excess of hydroxylamine hydrochloride for12 hours on a water-bath, the alcohol evaporated, and the productextracted with ether, a yellowish oil is obtained which solidifies onstanding. It can be purified by precipitating its solution in soda withdilute sulphnric acid and extracting with ether ; i t then melts a t 162-163".I t s formula is CPh(N.OH).CH,.NH.OH. It dissolvesreadily in alcohol or ether, sparingly in hot water and benzene, and isinsoluble in light petroleum and in cold water. On heating it withconcentrated acids, hydroxylamine is given off. A silver derivatire,C8H,AgN,0,, is obtained by precipitating a solution in concentratedammonia with a concentrated solution of silver nitrate. Dibenzyl-hydroaylamine, (CH2Phj,N.0H, is obtained on heating a solution ofbenzyl chloride (3 grams), hydroxylamine hydrochloride ( 3 grams),and cq-stallised sodium carbonate (6 grams) in aqueous alcohol for halfan hour on a water-bath. On cooling, it separates in long white needleswhich melt a t 1-23', and are decomposed by dist,illation. It is solublein alcohol, ether, and benzene, less soluble in light petroleum, carbonbisulphide, and glacial acetic acid, sparingly in hot water, and insolublein ammonia, soda solution, and hydrochloric acid.A hydrochloride,s 52 ABSTRACTS OF CHEMICAL PAPERS.(C,H,),N.OH,HCl, can be obtained by the action of dry hydrochloricacid gas on its solution in absolute ether.2l/lethyZpropylglyoxh e, CMe (NOH) .C( NOH)Pr, obtained by theaction of hydroxylamine hydrochloride on a, solution of isonitrosopro-pylacetone in aqueous alcohol, forms spiral-like groups of needlesmelting a t 168". Phenylqlyozime, CPh(N.OH).CH : N.OH (m. p.152") is prepared by the action of alkaline hydroxylamine solution ondibromacetophenone, at a gentle heat, acidifying and extracting withether.It can be purified by precipitating the ethereal solutionwith light petroleurn and washing the precipitate with benzene,or by dissolving it in alkali, acidifying and extracting with ether. Thesilver derivative, C8H7AgN202, forms a yellowish-white curdy precipi-tate. On dissolving sodium in absolute alcohol and adding an etherealsoluhion of methylethylglyoxime, the sodium deyivative of the latter,C5HgNaN2O2, is thrown down as a white curdy precipitate. The di-acetyl-derivative of methylglyoxime, CMe(NO&).CH(NOG) is formedwhen a mixture of methylglyoxime with a slight excess of acetic anhy-dride is geiitly boiled until the mass begins to turn brown. The pro-duct is poured into shallow clock-glasses and exposed in a vacuumwhen needles are obtained melting at 51".It crystallises from lightpetroleum in white transparent prisms ; when heated, these explodewith evolution of hydrocyanic acid.The d iacety 1-derivatize of methy lethylg ly yoxims,CMe(NO&?).CEt(NOZ),crpstallises in flat prisms readily soluble in alcohol and in ether,sparingly in hot water. The diacet~jl-derivative of methylbenzyl-glyoxirne forms small white crystals melting a t 80".Hydrazines of Pyroracemic Acid. By E. PISCHER and F. JOUR-DAN ( B e y . , 16, 2241-2245).-Some of the compounds of the hydra-zines with ketones have been described by Reisenegger (Abstr., 1883,798). The reaction is a general one, and holds for the primary andsecondary hpdrazines of the fatty and aromatic series, and f o r allsimple and most of the more complicated ketones and diketones, theketonic acids combining with extreme readiness with the hydrazineseither in neutral or in acid solutions.Pyroracemic acid and phenyl-hydrazine combine with great violence, so that it is advisable to diluteeach substance with five volumes of ether, to cool well and to mixg radu a1 1 y .The phenylhydrazinepyroracernic acid, CSHI0N2O2, separaies as ayellowish crystalline powder which arter being washed with ether andcrystallised from boiling alcohol, forms hard lustrous needles, melt-ing at 169" with evolution of gas ; it is readily soluble in hot alcohol,very sparingly in ether, chloroform, carbon bisulphide, and lightpetroleum, readily in alkalis and alkaline carbonates. The sodiumsalt is sparingly soluble in an excess of concentrated soda solution,with which it can be boiled without decomposition.The formation ofphenylhydrazinepyroracemic acid takes place also in aqueous, aceticacid, and dilute hydrochloric acid solutions, aiid with such readinessthat the reaction can be employed for the detection of pyi*oracemicA. I(. MORGANIC CHEMlSTRY. 53acid (also of phenylglyoxylic acid and levulic acid) in very dilutesolutions. Heated above its melting point, it yields carbonic anhy-dride and ethylidenephenylhydrazine :-PhNzH : CMe.COOH = GO, +l'hNzH : CHMe. It can be boiled with dilute hydrochloric and sul-phuric acids without decomposition, and on boiling with alcoholicsulphuric acid, the ethyZ derivative, PhN,H : CMe.COOEt, is obtainedmelting a t 114-115", and soluble in alcohol, ether, and chloroform.By the action of sodium-amalgam on a cold dilute solution of phenyl-hydrazinepyroracemic acid, pheny1hydrazineprop.ionic acid,PhNzH,.CMeH. COOH,is produced, crystallking from boiling alcohol in white slender needlesmelting a t 152-1.53' with decomposition. It is very sparingly solublein cold alcohol, ether, and water, much more readily iu hot alcohol,also readily soluble in alkalis and in concentrated hydrochloric acid.Mercuric oxide and copper salts are readily reduced by it in alkalinesolution, ammoniacal copper solution reconverting it into phenyl-hydrazinepyroracemic acid.I n order to decide which of the formulae PhNH.N : CMe.COOH orPhN-CMe.COOH is correct, the action of pyroracemic acid onmethylphenylbydrazine was studied.This yields an acid of theformula PhNMe.N: CMe.COOH, the behaviour of which to mineralacids is, however, quite different from that of the acid obtained fromphenyl hydrazine.Metl~ylplaenylhyd~~axinepyro9-ac~mir, acid softens at 70": and melts a t78" ; i t crystallises in yellowish needles readily soluble in alcohol andin ether, sparingly in light petroleum and in water ; it is decomposedby long-continued boiling with water, but is stable in alkaline s o h -t,ions. On warming it with a 10 per cent. solution of hydrochloricacid it becomes red, and then dissolves, the coloiir disappearing as thetemperature is raised, whilst colourless slender needles separate, in-creasiug in quantity on cooling and as the liquid is diluted with water.This new substance, apparently of the formula C,JI,NOz, seems to beformed by the abstraction of ammonia from the methylphenylhydra-zinepyroracemic acid, a considerable quantity of ammonia being foundin the acid liquid.T t is readily soluble in hot alcohol, from which i tcrystallises in colourless needles melting at 206". It can be distilledunchanged, dissolves readily in soda, ammonia, and sodium carbonate,and can be reprecipitated by acids.By E. FISCHER (Ber., 16, 2236-2238) .-In pre-paring diacetonamine from acetone containing aldehyde, Heintz(Annalen, 189, 214) obtained a base CeH,,NO, (vinyldiacetonamine) ;this he afterwards obtained by the action of acetaldehyde on diace-tonnmine oxalate, and he thought it probable that it might be a lowerhomologue of triacetonamine ; this is now confirmed by the author.It is converted into an alkamine by the action of sodium-amalgam,and on heating this with concentrated sulphuric acid, a readily volatilebase is obtained, the properties of which show it to be a homologue oftriacetonine (Abstr., 1883,1155).\/NHA.I(. B!.Diacetonamine54 ABSTRACTS OF CHEMICAL PAPERS.Other aldehydes, both of the fatty and aromatic series, yield baseswith diacetonamine, and in this way numerous homologues of hydroxy-piperidine and piperidine can be obtained. Benzdiacefonarnine,C13H17N0, is prepared by boiling a solution of acid diacetonamineoxalate (1 part) in alcohol (3 parts) with bitter almond oil (1 part)for about ten hours; the product is filtered hot, and the oxalateformed is washed with hot alcohol.By the action of potash the freebase is obtained as an oil, which solidifies on standing ; it crystallisesfrom hot light petroleum in splendid colourless plates, melts a t 62-63", dissolves very readily in alcohol and in ether, sparingly in water ;the o x a l d e (Cl,H,7NO),C,H,04, forms white scales, very sparinglysoluble in alcohol and in water, readily in hydrochloric and oxslicacids. On adding gold chloride t o the hydrochloric acid solution, theaurochloride is precipitated as a yellow oil, which solidifies to mag-nificent gold-coloured needles. By the action of sodium-amalgam onan acidulated solution of benzdiacetonamine, the latter is partially con-ver ted into benzdiacetona Zkamine, C 13H19N0.The hydrochloride,C1,H,,NO,HC1, forms small hard crystals, readily soluble in water,sparingly in alcohol. On decomposing it with an alkali, the base isprecipitated as a thick colourless oil, Sulphuric acid acts on this baseor the hydrochloride in the same way as on triacetonalkamine, withformation of a new base, which is volatile in steam, has an odourresembling that of piperidine, and yields a sparingly soluble hydro-bromide.From these reactions, it is assumed that benzdiacetonamine has aconstitution similar to that of triacetonamine, its formation beingthus expressed :-H,C.CO.CH, H,C . CO . CH,PhCHO + I = l I + H,O.H2N.CMe2 PhCH.NH.CMe,The author intends to try the reaction with other aldehydes, withAction of Phosphorus Trisulphide on Phenols.By A.GEUTHER ( A n n a l e n , 221, 55- 59).-Kekul6 and Szuch ( J a h e s b e r . ,1868,628) have isolated from the products of the reaction of phosphoruspentasulphide on phenol, besides phenyl mermptm and sulphide,a small quantity of benzene. As the formation of this hydrocarboncan only arise from the reduction of the phenol, it is probable thatthe samples of pentasulphide contained some trisulphide as an impu-rity. In order to confirm this suggestion, the author has studied theaction of phosphorus trisulphide on phenol. On submitting the crudeproduct of the reaction to fractional distillation, it was separated intotwo portions, the one boiling below loo", the other above 280".The former was principally benzene, together with traces of phenylmercaptan and sulphide, the latter triphenylphosphate.The reactionsof phosphorus trisulphide and pentasulphide on phenol may probablybe expressed by the following equations :-(1) 8PhOH + P,S, =2Ph3PO, + SH,S + 2C6H6, and (2) 8PhOH + P,S5 = 2Ph,P04 +3H2S + 2PhSH.ethyl acetoacetate, and with pyroracemic and other ketonic acids.A. K. MORGANIC CHEMISTRY. 55As an analogous case, it is shown that, creeol is similarly reduced totoluene by phosphorus trisulphide ; the other products of the reaction,.which were not minutely examined by the author, are probably tolylmercaptan and tolylphosphate. V. H. V.A Fourth Monobromophenol. By A. FITTICA ( J .pr. Chenz. [a], 28, 176--188).-10 grams of phenol are dissolved in 10 gramsabsolute alcohol, 3 grams of amorphous phosphorus added, and17 grams of bromine allowed to flow in through a capillary tube ; thevessel is surrounded with cold water ; the temperature of the mixturemust not rise above 20". The product is shaken with water, withdilute sodium carbonate, again with water, dried and aistilled. Thefraction 235-240" repeatedly redistilled, finally yields the newmonobromophenol as a liquid boiling at 236-238", and not soli-difying a t 10-12". The pure substance cannot be distilled withoutdecomposition. No further description of its properties is given.The boiling and melting points of ortho-, meta-, and para-bromophenolare-Ortho. Meta.Para.Melting point . . . . (Liquid) 32-33' 64"Boiling point.. . . . . 194-195" 236-236.5 238By nitration in glacial acetic acid solution, a crystalline compoundmelting a t 60-65", and of the formulaC6H3Br ( N02).0H, CsH,Br (NO,) ,OH,is obtained. This on further nitration yields a bromdinitrophenol,C,H,Br(NO,),.OH, crystallisiiig in yellow prisms, and melting a t108-110". The same product is obtained on boiling with baryta-water, together with a substance melting at 68-70', and crystal-lising in stellate groups of yel1o.w needles, to which the authorassigns the formula 2C6H3Br(NOz) .0J3,C6H,Br(N02)z.0H.A. J. G.Action of Phenol on Ketonic Acids. By C. BOTTINGER (Ber.,16, 2071-2075).--Uy the action of phenol on pjroracemic acid in pre-sence of sulphuric acid, a condensation-product of the compositionC15H140a,H,0 is obtained.This substance, which the author proposesto name diphenylyropionic acid, forms a horny mass (m. p- 268"),soluble in acetone, insoluble in water, benzene, and chloroform. It, isa monobasic acid, and a soluLion of its ammonium salt gives precipibakswith salts of barium, calcium, lead, and silver.Dibroi,zopheno~ropionic acid is a pale golden amorphous and eIectricpowder, insoluble in water and alcohol ; on heating this with concen-trated hydrochloric acid at 230" in a sealed tube, it gives off bromineand carbonic anhydride, and is converted into a black substance.AcetyZdi23hennpro~ionir, acid is an amorphous yellowish substance,soluble in acetone, insoluble in chloroform ; its barium salt forms aninsoluble amorphous precipitate36 ABSTRACTS OF CHEMICAL PAPERS.Acetylclibromophenopropioizic acid is colonred a t first violet, and thendissolved by ammonia; it forms sparingly soluble barium salt.V.H. V.Derivatives of Thymol. By H. KOBEK (Ber., 16, 2096-2105).-Pnrathyrnotk aldehyde, C6H2MePP( OH).CHO (Me : OH : Pr : CHO= 1 : 3 : 4 : 6) obtained by heating thymol with chloroform andsoda, crystallises in long white glistening needles melting a t 133",sparingly soluble in water, soluble in alcohol and ether. It dissolvesin ammonia and sodium carbonate to form a golden-coloured solution.The author was unable to obtain a crystalline compound of the sub-stance with sodium hydrogen sulphite ; but its other general propertiescharacterise i t as an aldehyde.C6H,MePra( OH) .CHNPh,prepared by heating parathymotic aldehyde and aniline in molecularproportions, crystallises in golden needles melting at 142", insolublein water, soluble in alcohol and ether; i t is decomposed by boilingwitb water or dilute acids into the aldehyde and aniline.Pa7-athymotic alcohol, CGK2MePra( OH).CH,.OH, obtained by thereduction of the aldehyle with sodium-amalgam and water, forms agreyish amorphous powder, which melts gradually a t 120-130" ; itis insoluble in water, soluble in alcohol and ether.2IethyQ??arathymotic aldehyde, C6H,MePrcL( OMe) .CHO, preparedfrom parathymotic aldehyde, methyl iodide, and alcohol, is a goldenoil boiling a t 270", insoluble in water, soluble in alcohol and ether;it dissolves with difficulty in a solution of sodium hydrogen sulphite.Its anilide crjstallises in clear transparent tablets (m. p.SO"), inso-luble in water, r e a d i l ~ soluble in other menstrua. On oxidation withpotassium permanganate, it is converted into the correspondingcarbozyZic acid, c6H2MePr( OMe).COOH, which crystallises in longwhite silky needles melting at 137" ; a solution of this acid gives nocoloration with ferric chloride, and precipitates more or less sparinglysoluble, with salts of calcium, silver, copper, zinc, and lead.In order to determine the constitution of the compounds, and tocompare the parathymotic acid corresponding with the above-men-tioned aldehjde with the thymotic acid described by Kolbe andLautemann (AimaZem, 115, 205), the author prepared both acids, andstudied tlieir reactions.The former can be best obtained by heatingthymol with carbon tetrachloride and soda ; it crystallises in leafletsmelting a t 157" ; the latter by the joint action of sodium and carbonicanhydride on thymol melts at 123" and gives a deep blue colorationwith ferric chloride. This reaction, characteristic of those aromaticacids in which the hydroxyl is in the ortho-position to the carboxylgroup, taken in connection with the method of preparation, showsthat the tbjmotic acid of Kolbe and Lautemann is the ortho-acid,possessing the constituiionC6H,MePP(OH),COOH [Me : COOH : OH: Pro! = 1 : 2 : 3 : 41.On the other hand, the method of preparation of the author's acid,I t s anilids derivativeORGANIC CHEMlSTRY.57together with the absence of any reaction with ferric chloride, pointprobably t o its constitution as expressible by the formulaC,H,MePr(OH).COOH [Me: OH: Pr : COOK = 1 : 3: 4: 61.Thymodiuldehyde, C6H,MePr( OH) (CHO),, obtained in the course ofthe preparation of paratbymotic aldehyde, forms golden compactneedles melting at 80"; it gives a cherry-red coloration with ferricchloride; on boiling with sodium acetate and acetic anhvdride it isconverted into tl/,ymoparacryZic acid, C$H,MePr(OH) .CH : CH.COOH,which forms microscopic crystals melting a t 280'. The methyl deri-vative of the latter crystallises in golden needles melting at 141",sparingly soluble in water, soluble in alcohol and ether.Both acids givesparingly soluble calcium, barium, and copper salts ; their silver salts,however, differ, that of the former crystallises from water, that of thelatter dissolves in hot water, forming a resinous mass.V. H. V.A New Glycerol. By A. COLSON (Conyt. re%& 97, 177-179).-The aromaiic tribromhydrin, C,H,( CH,Br),, previously de-scribed (Abstr., 1883, 734), can be ohtained in crystals by pro-longed refrigeration, and the crystals, after recrystallisation fromalcohol, melt at 94.3". The tribromhydrin is decomposed by water,yielding mesitylene glycerol, C,H,( CH,OH),. To obtain t h i s com-pound, the crude product of the action of bromine on mesitylene isboiled for several hours with 25-30 parts of water and an excess oflead carbonate, the liquid filtered, and concentrated by evaporationin a vacuum.The crude product is mixed with a small quantity ofsilver oxide, then treated with hydrogen sulpbide in order to removelead, and the solution filtered and concentrated. The viscous liquidthus obtained is purified by successive treatment with ether, alcohol,and chloroform, and is finally concentrated in a vacuum. Mesityleneglycerol is a viscous liquid with a bitter taste ; if is insoluble in etherand in chloroform,, but is very soluble in alcohol and in water. Whentreated with hgdrobromic acid, it yields the original tribromhydvin.Hydrochloric acid forms a colourless oily liquid, which is in all pro-bability the triclilorliydrin : the same compound is obtained by theaction of chlorine on the vapoor of mesitylene ; it boils a t 170-180"i u a vacuum, and s t 277-284" with partial decomposition, underatmospheric pressure.It is decomposed by water with formation ofthe glycerol. acetic acid also combines with mesitylene gljcerol,forming a compound which is only slightly soluble in water.If the product of the saponification of the crude tribromhydrin istreated with ordinary ether after evaporation of the water, the etherdissolves a substance which separates o u t in crystals on evaporation.When purified by repeated crystallisation from water, this sub-stance forms nacreous plates which melt a t 126". They are tastelessand inodorous, soluble in 55 parts of boiling water, but only slightlysoluble in cold water, still less soluble in ether, but very soliible inalcohol.They have the composition, CgHg(OH),Br ; when boiled withwater and potassium carbonate, this compound is not decomposed ;and when treated with hydrobromic acid it yields a tribromide which,after recrystallisation from alcohol, melts a t 81-82". The compoun53 ABSTRACT8 OF CHEMICAL PAPERS.is therefore not a derivative of mesitylene glycerol, but is a mono-bromo-glycol, C6H2BrMe( CH,.OH), and its dibromohydrin,C,H,BrMe( CH2Br),,(m. p. 81-82'), is isomeric with mesitylene glycerol tribromhydrin.C. H. B.Quinone Derivatives. By R. WIETSKI (Bey., 16, 2092-2096) .-The author has &own that by passing nitrous acid into an etherealsolution of quinol, a dinitrohydroxyquinone, C,(OH),(NO,),O,, ornitranilic acid, is formed ; the same substance may also be obtainedeither by the action of fuming nitric acid on dinitroquinol, or by thenitration of diacetylquinol : all these methods of preparation, how-ever, are very unsatisfactory.In the present communication a detailedaccount is given of an improved process, which consists in acting ondiacetylquinol with nitrosnlphuric acid in the cold, and precipitatingthe characteristic sparingly soluble potassium nitranilate from an ice-cold solution of the crude product. The corresponding acid, which isvery unstable, may be obtained from this derivative. The potassium-derivative is converted by a, strongly acid solution of stannous chlorideinto nitramidotetrhydroxybenzene, C,(OH),( NH,) .NOa, which crystal-lises in needles, having a violet iridescence, insoluble in alcohol,ether, and benzene.Potassium nitranilate is further converted bystannous chloride, with an excess of kin, into a substance crystallisingin delicate iridescent green leaflets, resembling quinhydrol in appeal.-ance. This compound is probably a diimido-derivative of dihjdroxy-,NHquinone, C6(OH),0r/ 1 , and analogous to diimidonaphthol: a"I3view which receives some support from the similarity of phenomenaobservable in the preparation of these two substances,Action of Orthonitrobenzaldehyde on Acetaldehyde. BgA. BAEYER and V. DREWSEN (BRT., 16, 2205-2208).-1n a previouscommunication (Abstr., 1883, 341) the authors mentioned the forma-tion of a condensation-product by the action of alkalis on a solutionof orthonitrobenzaldehyde in acetaldehyde.It is prepared bygradually adding a 2 per ccnt. solmtion of sodium hydroxide to asolution of orthonitrobenzaldehyde in freshly prepared aldehyde keptcool with ice, until an alkaline reaction remains for a t least fiveminutes. The acetaldehyde is expelled by a current of air, thecrystalline product dried on a porous tile and crystallised from ether.It forms moderately large colourless monoclinic prisms, readily solublein alcohol and chloroform ; it softens a t 120" and melts at 125" withevolution of aldehyde vapour. Its formula, C9H9N01, C2H40, corre-sponds with that of a compound of orthonitrophenyllactic aldehydewith aldehyde.On passing a current of air through its solntion at4C-50", as long as the odour of aldehyde is perceptible, a non-crystallisable product ifi obtained (probably orthonitrophenyZZacticaldehyde), combining with acid sulphites and reddening rosanilinesulphite. Like the condensation-product, it yields indigo withaqueous alkalis. Orthonitro-~-~hen.yllactic acid,V. H. V.NO,.CGH,.CH( OH).CH,.COOHOltUANIC CHEMISTRY. 59(m. p. 126') is obtained on warnling a solution of the condensation-product in dilute alcohol with an excess of freshly precipitated silveroxide, until the addition of alkali no longer produces indigo ; the pro-duct is boiled with hydrochloric acid, filtered, and extracted withether, and the acid purified by means of the barium salt,.It crystal-lises in short well-formed prisms, readily soluble in water, alcohol,and ether, and is identica1 with the acid obtained by Einhorn from theaddition-product of orth onitrocinnamic acid with hy drobr omi c acid(see p. 66). Orthoizitrocinnamic aldehyde, N 0,.C,H4.CH : CH.CHO,is obtained on boiling the condensatiowproduct with acetic anhydrideuntil indigo ceases to be formed by the addition of soda solution. Itforms colourless needles melting at 127", readily soluble in boilingwater, very sparingly in cold water, readily in chloroform, less so inalcohol and ether. It forms a crystalline compound with hydrogen-sodium sulphite, reacts with rosaniliiie snlphite, reduces ammoniacalsilver solution with formation of orthonitwcinnamic acid, and on reduc-tion readily yields quinoline.From the above, it is seen that the con-densation of orthonitrobenzaldehyde with aldehyde takes place in thesame way as with acetone, the resulting ortl10nitro-/3-phenyllacticaldehyde, N02.Cs&.CH(OH).CH,.COH, forming, however, an un-stable compound with acetaldehyde.Benzoylacetone. By E. FTSCHER and H. KUZEL (Ber., 16, 2239-2241).--On boiling ethyl benzoylacetomcetate with 4 parts of 25 percent. sulphnric acid, carbonic anhydride, alcohol, acetic acid, andacetophenone are produced as stated by Bonn6 ( A n n u l e n , 187, 1).The authors find that a small quantity of benzoic acid and about4 per cent. of berhzoylucetone are also produced, the formation of thelatter corresponding with the production of nitrocinnamylacetonefrom ethyl nitrocinnamylacetoacetate (Abstr., 1883, 587).To isolatethe benzoylacetone, the oil is dissolved in ether, agitated with dilutesoda solution, which dissolves the benzoic acid and the benzoglacetone;the solution is then acidified, extracted with ether, and the residuefrom the evaporation of the latter dissolved in cold dilute sodasolution, from which the benzoylacetone is precipitated by carbonicanhydride as a colourless oil, which crystallises on cooling. It maybe obtained in larger quantity by boiling ethyl benzoylacetoacetatefor some hours with 7-8 parts water.A. E. M.Benzoylacetone,CH& . C 0.CH3,melts at 58", distils unchanged, is voIatiIe in steam, and has an agree-able penetrating odour.It dissolves sparingly in cold water, morereadily in hot water, very readily in alcohol and in ether. The alkalisdissolve it readily, sodic cnrbonate less so, whilst it is insoluble in theacid carbonates. The sodium salt of benzoylacetone is precipitated inthe form of Fellowish scales on adding concentrated alkali t o its solu-tion in dilute soda ; the silver salt, CIOHS02Ag, obtained on adding anexcess of silver nitrate to an ammoiiacal solution of benzoylacetone,forms a white crystalline precipitate, almost insoluble in water.Benzoylacetone gives an intense red coloration with ferric chloride.It is decomposed by boiling alkali with formation of acetophenoneGO ABSTRACTS OF CHEMICAL PAPERS.When warmed with phenylhydrazine, the two combine forming aslightly coloured oily product insoluble in alkali.Orthonitrobenxoylacetone is obtained in the same way from ethylorthonitrobenzoylacetoacetate, and likewise combines with phenyl-hydrazine, forming a compound of the formula-NO,.C,H,. C .CH2.CMeII IIPhNZH, N,H,PhThe hehaviour of benzoylacetone with alkalis shows that the hydrogenof the methylene-group can be substituted by metals, which is notthe case with the hydrazine-derivatives in which the oxygen of theCO-groups is replaced by nitrogen.Anthroxanaldehyde and Anthroxanic Acid. By A. SCHIL-LINGER and S. WLEGGEL (Ber., 16, 2322--2236).-When a solution oforthonitrophenyl hydroxyacrylic acid in an equal weight of glacialacetic acid is heated on a water-bath as long as carbonic anhydride isevolved, and then diluted with water, neutralised with chalk, andsteam-distilled, A distillate is obtained from which ether extractsunthroxnnaldehyde mixed with anthranil ; the latter is removed byboiling with light petroleum, from which solvent anthroxanaldehydeorystaliises in long yellowish needles of a slightly aromatic andpenetrating odour ; it dissolves readily in boiling water, and volatiliseseasily in steam.It melts at 72.5", and can be sublimed withoutdecomposition. Its formula, C8H5N02, shows it to be isomeric withisatin. An intense reddish-violet coloration is produced on addingzinc-dust to its solution in very dilute ammonia and warming. Whenan aqueous solution, containing also anthranil, is boiled with ferroussulphate, slender red silky ueedles separate, which, after crystallisationfrom chloroform, contain no iron; this substance melts above 21.5"with decomposition ; it has basic properties.Anthroxanaldehyde dis-solves readily in concentrated hydrogen-sodium sulphite, and pro-duce a red coloration with rosaniline sulphite. When it is warmedwith aniline, an oil is obtained which solidifies t o large fan-shaped crystals, melting a t about 40". Anthrozaaic acid, CeH5NOs, isprepared by adding tbe calculated quanbhy of a 4 per cent. perman-ganate solution to a cold solution of the aldehyde in very dilute soda,filtering and slightly acidifying. The solution is warmed with animalcharcoal, filtered, and dilute sulphuric acid added, when anthroxanicm i d separates in delicate white needles.It is moderately soluble inhot water, almost insoluble in cold water, readily in acetone, moresparingly in glacial acetic acid, and still less readily in benzene andother solvents. It melts a t 190-191" with decomposition. Onwarming its solution in dilute ammonia with ferrous sulphate, filter-ing and acidulating, isatin is obtained.A. I(. M.C .COOHThe authors assign to this acid the constitution C H ' I ' 04\N/ 3,CO.C.COOHanalogous to isstogenic acid, CsH1' / I , which it resembles"-ORGANIC CHEMlSTRY. 61in its behaviour to feeble reducing agents. Unsuccessful attemptswere made to decompose it into carbonic anhydride and anthroxane,C8H/ I ' 0 , which, if capable of existing, would be isomeric witha.nbhrani1.Possibly anthrosane becomes converted into the latter inthe same way as isatogen into isatin.CH\&/A. K. 51.Constitution of Anthranil. By P. FRIEDLANDER and S. WLE~~GEL(Ber., 16, 2227-2229) .-From the close relationship of anthranil toanthroxanic acid (see last Abstract) an attempt was made to preparethe latter by heating anthranil with ethyl chlorocarbonate at 120-140". Of the three possible formulae for anthranil-co ,C.OHC6H4 11 9 'NcIjH4( IN NH'the first alone could yield anthroxnnic acid, the second an isomericanthra,nilcarboxylic acid, whilst the third could not yield a carboxylicacid.The product of the reaction was an acid (anthranilcarboxylic acid)isomeric with anthroxanic acid, but possessing different properties.It dissolves sparingly in the usual solvents, most readily in acetoneand in ether, and crystallises from hot water in slender needles melt-ing a t about 230" with evolution of carbonic anhydride, but anthranilis not re-formed.The presence of a carboxyl-group is proved by itssolubility in dilute ammonia and in a,lkaline carbonates, mineral acidsreprecipitating it unchanged. It dissolves in a one per cent. soda solu-tion, showing a blue fluorescence which soon disappears, and on thenacidifying with acetic acid and extracting with ether, the equivalentquantity of anthranilic acid is obtained. This change probably takesplace thus :--.coC6H4' -1 + HZO = COOH.CsH4.NH.COOH\N.COOHAnthranilcarboxylic acid is decomposed by hot concentrated sodasolutlion, with formation of anthranilic acid and of a high-melting acid,probably a derivative o€ diphenylcarbamide.On gently heating a mixture of dry anthranil with benzoic chloride,an abundant evolution of hydrochloric acid takes place, whilst benzoyl-alzthaanil, C6H4' I , is formed.The product crystallises oncooling, a,nd can be purified by recrjstallisation from dry benzenewith the addition of light petroleum. It forms long white needlesreadily soluble in the ordinary solvents, insoluble in water and lightpetroleum ; it melts at 122-123", and distils above 360" nea,rly un-changed. Like anthranil, it readily takes up the elements of waterCO'N.COP62 ABSTRACTS OF CHEMICAL PAPERS.with formation of bemoylanthranilic acid, COOH.C6H1.NH.COPh ;the change being effected by solution in hot dilute alkalis or by crys-tallisation from dilute alcohol, when the melting point is raised from123" to 180-181".The benzoylanthranilic acid obtained is identicalwith the acid obtained from nrithranilic acid and benzoic chloride(AnnuZen, 205, 130). It yields sparingly soluble barium aud calciumsalts, and a nearly insoluble stable silver salt, C,,H,,NO,Ag.These results prove that anthranil is represented by the second ofthe above formulae, and that it is the lactam of anthranilic acid.A. K. M.Action of Hydroxylamine on Diketones. By H. GOLDSCHMIDT(Bey., 16,2176-2180).-The author and V. Meyer have isolated anddescribed a diphenylglyoxime (m. p. 237"), C14H12N202, obtained bythe action of hydroxylamine on benzil.Under other conditions, theauthor has obtained an isomeride which in contradistinction to thefirst named substance may be called P-diphenylglyoxime ; it differsfrom its isomeride in its melting point (2OC;"), its appearance, and itsgiaeater solubi1it.y in water arid alcohol. The a-glyoxime may be con-verted into the @-isomeride by heating to 180".On heating phenanthraqui none with alcohol and hydroxylaminehydrochloride, a monisonitroso - derivative of phensnthraquinone,Cla &NO2, is formed.This substance crystallises in small golden needles melting a t 158O,soluble in alcohol; it dissolves i n soda to form a green, and in sul-phuric acid to form a red solution. It is converted by hydroxylaminehydrochloride into a dioximide derivative of phenanthraquinone, ofC6H4.C : N,possible constitution, I 1 )0, which crystallises in goldenC6Hd.C Nneedles melting a t 181", insoluble in soda.When anthraquinone isheated with alcohol and hydroxylamine hydrochloride, in a flask fittedwith an inverted condenser, no reaction takes place.I n order to obtain the monisonitroso-derivatire of anthraquinone,it is necessary to heat the reacting substances in a sealed tubeat 180",when the compound separates out as a pale red powder, soluble inalcohol, to form a red solution. I t sublinies a t 2OO", volatilising com-pletely, without melting. Its constitution may be expressed by theformula, c6H,<~~~H>C6H~. V. El. V.Derivatives of Benzil. By B. S. BURTON (Ber., 16, 2232-2233).-With the view to obtain diphmyltartaric acid, the author has madeexperiments on the saponification of Zinin's nitril of diphenyltart aricacid, CI,H,,O2(CHN),, obtained by the action of anhydrous hydro-cjanic acid on an alcoholic solution of benzil (Annnleiz, 34, 189).Thefinely powdered nitrile is introduced into a large excess of glacialacetic acid saturated a t 0" with hydrobromic acid, and frequentlyagitated. After some weeks, the unaltered substance is separated, andthe clear liquid yields monoclinic crystals of a vitreous lustre. Onadding ammonium carbonate to the filtrate, a white precipitate,CONH,.CPh(OH) .CPh(OH.).CONHZ, is produced, insoluble in colORGANIC CHEMlSTRY. 63water, but which can be crystallised from dilute alcohol ; it crystallisesfrom hot water in small needles.It softens gradually on heating,begins to darken at 150", becoming completely liquid a t 230". I t sbasic properties are very feeble, as it crystallises unchanged from hotconcentrated hydrochloric acid, although it yields a crystalline hydro-bromide. It has no acid properties, is not dissolved by sodium carbo-nate solution, but is soluble in soda solution with decomposition. Onboiling it with hydrochloric acid, acid substances are obtained stillcontaining nitrogen. The above mentioned monoclinic crystals con-sist of the hydrobromide of the amide ; this melts a t 185" with evolu-tion of hydrobromic acid. Sodium carbonate conrerts it into theamide. A. K. M.Benzoylacetic Acid.By A. BAEBER and W. H. PERKIN, Jun.(Rer., 16, 2128--2133).-One of the authors has recently shown thatethyl phenylpropiolate is converted by sulphuric acid into ethylbenzoylacet.ate, thus : PhC C.COOEt + H20 = COPh.CH,.COOEt(see Abstr., 1882, 336). The latter is a colourless oil resemblingethyl acetoacetate in odour ; when quickly heated, it distils with slightdecomposition between 268-270" ; it is coloured by ferric chloride.On boiling with water or acids, it is decomposed according to theequation, CH&.COOE% + H20 = PlaCOlle + CO, + EtOH. Inorder to prepare benzoylacetic acid, a solution of the alkyl salt insoda is left a t rest ; after filtration, the solution is cooled with iceand carefully acidified, and then exhausted with ether. The acidis obtained from the ethereal extract as a hardcrystalline mass, whichmelts a t 85-90" with evolution of earhonic anhydride ; it is solublein alcohol and ether, and its solution is coloured violet by ferricchloride.EfhyZbenzoyZacetic acid, CHEtE.COOH, is obtained as an ethylsalt by the joint action of sodium and ethyl iodide on ethyl benzoyl-acetate; on subsequent saponification of this salt, the pure acid isobtained. This latter melts a t 112-115", and is generally contami-Iliited by benzoic acid.On boiling the ethyl salt with alcoholic potash,like ethyl acetoacetate, it yields either a mixture of acids, or a ketone,according to the concentration of the alkali, thus :-(1.) CHEt(COPh).COOEt -+ 2KOH = PhCOOR + CHJWCOOK + EtOH, or(2.) CHEt(COPh).COOEt -+ 2KOH = COPh.CH,Et + EtOH + I(zc03.Diethy Zbenzoic acid, CEt&.COOH, obtained by a repetition of theprocess used for the acid above, forms a colourless, crystalline massmelting a t 128-130° ; when heated with alc-oholic potash, it yieldsdiethylacetophenone, boiling a t 230", thus :-CEtz(COPh).COOH + 2KOH = COPh.CHEt,, + &co3.AZZy Zbenxoylacetic acid, CHE(C,H,) .COOH, prepared by the actionof ally1 iodide on the ethyl salt of sodium benzoylacetic acid, isisomeric with benzoyltetramethylenecarboxylic acid from trimethy-lene bromide and ethyl henzoylacetate. The former exists 3s a colour64 ABSTRACTS OF CHEMICAL PAPERS.less crystalline mass melting at 122-125", soluble in all menstruaexcept water ; when its ethyl salt is heated with alcoholic potash, ityields allylacetophenone (b.p. 235O), thus :-CI-E(COPh) (C,H,).COOEt + 2KOH = COPh.CH,(C,H,) + K2CO3 + EtOH.Ethy7nitrosobenzoyZacetate, CO Ph.CNOH.COOEt;, formed by theaction of nitrous acid on ethyl benzoglacetate, crystallises in longneedles melting a t 121", which dissolve in alkalis to form a goldensolution. On long standing in contact with soda, it is converted intoan acid, COPh.CH (OH) .COOH, crystall ising in small prisms.Dibenzoylacetic acid, CHE,.COOB, obtained by the action of benzoicchloride on ethyl sodium beneoylacetate, and subsequent saponification,crystallises in needles melting at log", sparingly soluble in alcohol.This substance on protracted heating with water is converted intodibenzoylmethane with evoliitiou of carbonic anhydride, thus :-CHE2.COOH = CH&2 + ( 3 0 2 .This latter compound crystallises in large tables belonging to therhombic system, which melt a t 81" and boil a t 200".By the combinedaction of sodium and benzoic chloride it is converted into trihenzoylmethniie, CHI%,, which crystallises in small needles (m. p. 224O), andsublimes wiChout decomposition. V. H. V.Action of Ethylene Bromide on Ethyl Aceto- and Benzoyl-Acetates. By W. H. PERKIN, Jun. (Bey., 16, 2136--214O).-By thecombined action of ethylene bromide and sodium on ethyl acetoace-fate, the ethyl salt of acetyl trimethyleme carboxylic acid is formedaccording to the equations : I. CHGNa.COOEt + CH&r.CH,Rr =CHiG(C2H4Br).COOEt + NaBr ; and 11. C%Na(C2€€,Br).C0OEt =CH?1 )CZ.COOEt + NaBr.CH2This substance is a colourless oil boiling a t 193--1c35", aud yields thecorresponding acid as a thick oil on saponification and subsequentlyacidifying the alkali salt.The silver salt crystallises in characteristicwarty masses.CH2,Similarly, bemoyl trimethylene carboxylic acid, 1 CE.COOH,may be obtained ; it crystallises in the monoclinic system, and meltsa t 148" with evolution of carbonic anhydride. Its silver salt forms awhite flocculent precipitate, the ethyl saltl a colourless oil boiling at 280-28:Y'. Benzoyl trimethylene carboxylic acid when heated to 200"yields benzoyl trimethylene with evolution of carbonic anhydride,thug 1 \C%.COOH = I 'CHB; + GO,.CH2'CH, CH2/ CH,' CH,The author is engaged ill investigating homologues of the sub-stances above described. v.H. vORGANIC CHEMISTRY. 65Phenylhydroxyacetimidoether and Amidine. By C. BEYEE(J. pr. Chem. [2], 28, 190--191).-Benzaldehyde cyanhydrin is dis-solved in ether, 1 mol. proportion of alcohol added, and a stream ofdry hydrochloric acid passed into the liquid. The resulting hydro-chloride, CHPh(OH).C(OEt) : NH,HCl, crystallises in needles, melts at121", and on treatment with otash and ether, yields phenyZhydroxy-imidoether, CHPh( OH.) .C( 08t) : NH, crystallising in fine needlesand melting at 71-72". On strongly heating the hydrochloride, it isresolved into ethyl chloride and mandelamide ; on treatment withwater, it yields ethyZ mandelate, CHPh(OH).COOEt, as a heavycolourless liquid of faint jasmine-like odour, boiling at 253-255", andsolidifying to a crystalline mass in a freezing mixture.By the action of alcoholic ammonia on the imidoether hydrochloride,the corresponding p henylhydroxyamidine hydrochloride,CHPh(OH).C(NH,) NH,HCI,was obtained crystallised in fine prisms, melting a t 213-214".Thefree amidine could only be obtained in an impure state, and thenformed stellate groups of needles having a strongly alkaline reactionand melting a t 110". A. J. G.Derivatives of Orthonitrocinnamic Acid. By A. EINHORN( Ber., 16, 2208-2216). - Orthonitrophenyl-P-bromopropionic acid,N02.C6H4.CHBr.CH,,COOH, is prepared by heating orthonitrocinna-mic acid (10 grams) with a solution'of hydrobromic acid in glacialacetic acid (100 grams) saturated at 0".The mixture is heated in asealed tube for about half an hour on zt water-bath, and frequentlyshaken until the nitro-acid is dissolved. The product is purified byboiling i t with benzene and recrystallising from chloroform ; it formspale yellow monoclinic crystals melting at 139-140", with decompo-sition, I t dissolves readily in the ordinary solvents, but is onlysparingly soluble in benzene. It dissolves to a small extent in warmwater, decomposition however taking place with formation of indoxyl.Boiling concentrated sulphuric acid is almost without action on it,whilst alkalis very readily decompose it. On treating the powderedacid with an excess of cold sodium carbonate solution, a clear solutionis obtained, which soon assumes a bright red colour, whilst aprecipi-tate forms which the author assumes to be the lactone of orthonitro-phenyl-&lactic acid, N02.C6H4. CH<-ol> GO.The filtrate containssmall quantities of orthonitrocinnamic acid, orthonitrophenyl-p-lacticacid, and orthonitrostyrene. The lactone is readily soluble in chloro-form, acetone, benzene, and glacial acetic acid, sparingly in ether andin absolute alcohol, whilst alkalis convert it into the correspondinghydroxy-acid. It is converted into orthonitrostyrene and carbonicanhydride by boiling with water, some indoxyl, indigo, and probablyalso orthonitrophengl-P-lactic acid being simultaneously produced.Indigo is also formed when it is boiled with glacial acetic acid oracetic anhydride.By the action of zinc-dust and hydrochloric acidon a solution of the nitro-lactone in glacial acetic acid, hydrocarbo-CHVOL. XLVI. 66 ABSTRACTS OF CHEIIICAL PAPERS.styril is formed, and not the expected amido-lactone. When finelypowdered orthonitrophenyl-6-bromopropionic acid is added to a hotsolution of sodium carbonate and the product steam distilled, an oil isobtained solidifying in a freezing mixture to a white crystalline mass,which melts a t about 12-13.5." When orthonitrostyrene, CsH,N02,is heated with concentrated sulphuric acid, it assumes a blue colour.On adding a solution of bromine in chloroform to nitrostyrene alsodissolved in chloroform, the liquid being kept cool with ice, orthonitro-styrene dibrornide, N02.C6H4.CHBr.CH,Br, is obtained, melting a t 52"and volatile in steam.Besides nitrostyrene (10 per cent.), ortho-nitrocinnamic acid (16 per cent.), and orthonitrophenyl-p-lactic acid(42 per cent.), are formed in the above reaction, and the latter com-pound can also be obtained by warming the lactone with baryta-water. The purified acid, No2.C6H~.CH(OH).CHE-r,.COOH, is readilysoluble in alcohol and in water, crystallising from the latter in six-sided monoclinic prisms, melting at 126". When heated with dilutesulphuric acid a t 190", it yields orthonitrocinnamic acid ; with con-centrated sulphuric acid it yields indo'in. The methyl derivative meltsat 51"; the barium salt, (C,HsNO6),Ba + 2H20, crystallises inneedles. A direct comparison of this acid, with that obtained byBaeyer and Drewson (p.59), shows that the two are identical.A. I(. M.Substituted Coumarins. By H. v. PECHMANN and C. DUISBERG(Ber., 16, 2119- 2128).-The ethyl salts of aceto- and benzoyl-aceticacids react witlh the phenols in presence of a dehydrating agent toform substituted coumarina or hydroxycoumarins. T hns, for example,phenol and ethyl acetoacetate, in presence of strong sulphuric acid,yield methylcoumarin, thus :C,H,.OH + MeCO.CH,.COOEt = C6H4< CMe:CH>CO 0 + H,O+ EtOH.In this communicat'ion a description is given of the preparation andproperties of various substituted coumarins obtained by means of thisgeneral method.p-2Methyz.umbelZiferone, O H . C , H , < ~ ~ ~ -- ' 'H,>co, from resorcinoland ethyl acetowletsate, crystallises in prisms or needles melting at185", insoluble in water, soluble in alcohol and in ammonia and causticalkalis.Its solutions are of a pale yellow colour, and display a cha-racteristic blue fluorescence. When heated with potash, it yieldsresacetophenone and also resorcinol, and in this connection the authormentions that traces of resorcinol can be detected by the fluorescenceformed on adding ethyl acetoacetate and sulphuric acid to the sus-pected solution. The resacetophenone, C,H,(OH),.CO&fe, is identicalwith the substance obtained by Nencki and Sieber from resorcinoland acetic acid. The acetyZ and benzoyZ derivatives of @-methyl-umbelliferone crgstallise in needles, soluble in alcohol, sparinglysoluble in water and ether; the former melts a t 150°, the latterat 160."The methyl-ether of p-methylumbell~ferone is a crystalline substancORGANIC CHEMISTRY.67(m. p. 159"), resembling in all its properties the correspondinghydroxyl-compound mentioned above ; when heated with potash, it isconverted into a carboxyl-acid, C6H,(0Me) (OH) .C%fe : CH.COOH,crystallising in four-sided tables, which melt at 140" with evolution ofcarbonic anhydride, and are insoluble in water, easily soluble in alco-hol. Dimethyl-B-resorcyZirJ acid, C6H,(OMe)2.COOH, obtained byfurther methylntion and subsequent oxidation of the above-mentionedmethyl-ether, crystallises in white needles (m. p. 108").and ethyl benzoylacetate, crystallises in colourless leaflets melting at244" ; up-dimethylumbeltiferone, C6H3(OH)< ''Ie ' c M 6 > ~ ~ , fromresorcinol and etbyl dimethylacetoacetate in colourless needles melt-ing at 256" ; /3-wwthyZcowmarin from phenol and ethyl acetoacetatein colourless needles ; meta-toluene-B-metla y lcoumarin,from paracresol and ethyl acetoacetate in large refracting needles ;dihydroxymethy lcoumarin, C6&( OH)z< ':>CO, in colourlessneedles (m.p. 235").exception of the last named, display a well-marked blue fluorescence.The sohtions of a11 these substances, with theV. H. V.Bsculetin. By W. WILL (Bey., 16, 2106-2119).-The author,associated with Tiemann, has shown that dimethylaesculetin resemblesin many points methplumbelliferone and coumarin (Abstr., 1882, 199).As the.former has been recognised to be a monhydroxyl-derivativeof coumarin, it becomes exceedingly probable that aesculetin is adihydroxyl-derivative. In order to obtain further evidence in supportof this conjecture, the author has repeated with aesculetin Perkin'sresearches on coumarin (this Journal, Trans., 1881, 409), and provesthat the former undergoes transformation precisely similar t o thelatter, yielding isomeric a,- and /l-aesculetic acids, related to oneanother as the a- and @-ortlhomethoxyphenylacrylic acids.Monethy Zcesculetin, gg>c6H2<cH-' ' z > C o , is obtained, togetherwith the di-derivative, by heating aesculetin with solid potash andethyl iodide in alcoholic solution ; the two prodncts may be separatedby ether which dissolves the di-derivative.Monethylaesculetin formsmore or less colourless crystals (m. p. 143"), soluble in dilute alkalis ;its solutions give a blue fluorescence. Diethylcesculetin,crystallises in glistening leaflets (m. p. log"), sparingly soluble inwater, readily soluble in ether and benzene. It dissolves in hot soda,forming a red solution, from which the sodium compound separatesf 68 ABSTRACTS OF CHEMTCAL PAPERS.out on evaporation.there is formed the ethyl salt of P-triethylcesculetic acid,If the residue be digested with ethyl iodide,C6H2(OEt),.CH : CH.COOEt.This substance crystallises in glistening tablets melting a t 75", boilingat 360", insoluble in water, readily soluble in dilute acids andalkalis ; on saponification it is converted into @-triethyltesculetic acid,C,H,(OEt),.CH : CH.COOH.This acid forms colourless glistening prisms melting at 144" ; a solu-tion of its ammonium salt gives precipitates with salts of lead, mercury,copper, and silver. If in the preparation of the ethyl salt of P-tri-ethylaesculetic acid an excess of ethyl iodide be avoided, and the timeof heating be not more than 4-5 hours, the ethyZ salt of the isomerica-acid is produced.It forms thick golden prisms melting at 51", boil-ing a t 230", insoluble in water, soluble in alcohol and ether ; whenheated to its boiling point it is transformed into the isomeric @-corn-pound. a-Triethylcescwletic acid can be obtained by the saponificationof the corresponding ethyl salt ; it is a crystalline substance meltingat 102", and a solution of its ammonium salt gives precipitates withsalts of lead, zinc, cop,per, and mercury.When heated to its boilingpoint or with hydrochloric acid, it is converted into the isomeric &acid.On reduction with sodium-amalgam, both the a- and P-triethyltesculeticacids yield the same triethoxyp henylpropionic acid,which crystallises in leaflets melting a t 77" ; it solution of its ammo-nium salt gives precipitates with salts of lead, silver, mercury, andcopper. a- and P-trietiiyla3sculetic acids are converted by oxidationwith alkaline permanganate in the cold into the game triethoxybenzal-dehyde, C6&,(OEt),.CHO, forming colourless crystals melting a t 95",insoluble in water, soluble in alcohol and ether.It has all the cha-racteristic properties of an aldehyde. If the oxidation of the triethyl-aesculetic acid be effected a t 60" instead of the aldehyde, friethoxybenzoicacid, C6HZ(OEt),.C00H, is obtained : this substance crystallises indelicate needles melting at 134O, and solution of its ammonium saltgives precipitates with salts of lead, mercury, and silver. On dis-tilling the potassium salt of this acid with potash, it is convertedinto a substance crystallising in needles melting a t 57", which givesthe characteristic phloroglucol reaction with ferric chloride. Fromwant of material the anthor was unable t o examine the compoundmore fully.a-DimetiiyZumbelZic acid, c6H3(oMe)*cH : CH.COOH, obtained byheating 1 mol. methylumbelliferone with 1 mol.of sodium dissolvedin methyl alcohol, and 1 mol. methyl iodide, crystallises in colourlessneedles melting at 138", soluble in alcohol, ether, and benzene. Onboiling with hydrochloric acid, it is converted into the more stableisomeric compound.Both a- and /3-dimethylumbellic acids when reduced by sodium-amalgam yield the same dimethoxyprqionk acid,C,H:,(OEt),.CH,.CH,.COOH,C5H3(OMe),.CH3[,.CH,.COOHORGANIC CHEMlSTRY. 69which forms a white crystalline powder melting at 105" ; its ammoniumsalts give precipitates with salts of silver, lead, and mercury. a-Di-methylumbellic acid is converted by oxidation into a dimethoxy-benzoic acid, C6H3(OMe),.COOH-, identical with the @-dimethyl-resorcylic acid, C6H3(OMe)2.COOH [COOH : OMe : OMe = 1 : 2 : 4.1,obtained by the oxidation of t'he corresponding aldehyde.Bromine acts readily on dietliylsesculetin dissolved in carbon bisul-phide to form monobrorndiethylssculetin, CI3Hl3O4Br, a crystallinesubstance melting at 1 6 9 O , and converted on boiling with concentratedalcoholic potash into diethoxycournarilic acid, CI3HI4O5, which crystal-lises in delicate transparent needles melting at 195".On reduction withsodium-amalgam, it is converted into a substance probably homologouswith hydrocoumarilic acid. V. H. V.Benzylsulphonic Acid. By G. MOHE (Annalert, 22 1, 215-229).--Nitrobenzylsulp~ohorzic acid, C6H4(N02). CH,. SO&, prepared by themethod described by Biihler (Anniclen, 154, 50 ; Ber., 5, SSS), yieldsa chloride which is decomposed by heat into sulphurous oxide, andparanitrobenxyl chloride (m.p. 71.5" j mixed with a small quantity ofthe ortho-compound. On reducing an ammoniacal solution of thenitrobenzylsulphonic acid with sulphuretted hydrogen, paramido-benzykulphonic acid, C6H4( NH2). CH,. SO3€€, is deposited in colonrlessneedles. The mother-liquor: contains a mixture of the para- andortho-compounds. The para-acid is sparingly soluble in cold water ;100 grams of the solution at 11" contain 0.097 gram acid. The saltsare crystalline, and freely soluble in water. The diaao-compound,CH/-- \N, is prepared by passing nibrous acid into the amido-acid suspended in water. As soon as an evolution of nitrogen isobserved, the mixture is filtered. On adding alcohol to the filtrate,the diazo-compound is obtained in colourless microscopic crystals.When boiled with water it is decomposed, yielding parabydroxybenzyl-sulphonic acid, C6H4( OH).CH2.S03H, which crystallises in deliquescentneedles, freely soluble in alcohol..The solution of the acid or of itssalts gives with ferric chloride a blue coloration, which is destroyedby alcohol. The potassium and the barium salts crystallise in prismssoluble in water. The former contains, 0-5, and the latter 7.5 mols.H,O.By the action of hydrobromic acid on the diazo-compound, para-bromobenzylsulpphonic acid, C6HIBr. CH2. S03H, is obtained as a syrupyliquid. The barium salt, (C6H4Br.CH2.S0&Ba + 1+H20, formscolourless plates, soluble in water. The chZoride (m.p. 107") is solublein benzene and ether.The d iazo-compound is decomposed by absolute alcohol underpressure, yielding paraethoxy lbenzylsulphonic acid,N4'CH2S03'C,K,(OEf) .CH2. SOJXThe barium salt of this acid crystallises with 2 mols. E,O.PuruzobenzyZdisu$ honic acid, CGH, (CH,. S 0,H) .N2 .C6H&H2. S O,H70 ABSTRACTS OF CHEMICAL PAPERS.prepared by the oxidation of amidobenxylsulphonic acid with potassiumpermanganate, forms the following salts : C&&2N2S2061(2 + liHzO,orange-coloured plates, soluble in water ; C14H12N2S206Ba + l&HzO,yellow needles, sparingly soluble ; C1JL2NZSz06Ag~,H20, yellow needles,soluble in hot water. The chloride forms crystalline leaves meltinga t 149", soluble in beneene.Nitrobenzylsulphonic acid is converted into the dinitro-acid by theaction of a mixture of strong sulphuric and nitric acids.The anhy-drous potassium salt, and the lead and barium salts containing 4 mols.HzO, are soluble in water. Amidonitrobenzylsu~ho~ic acid is sparinglysoluble in cold water. The potassium salt forms purpl6 anhydrouscrystals, and the barium salt, [ C6H3(NH2) (NO2) CH2SO3I2Ba,2H2O,yellow needles or plates.Diamidobenzylsulphonic acid, C6H3(NHJ2.CH2.S0,H, crystallises incolourless needles, soluble in acids or alkalis. The ammoniacal solu-tion gives, with silver nitrate, a white precipit'ate which rapidly turnsblack. w. c. w.Parabromotoluenedisulphonic Acid. By 0. KORNATZKI (AnnaZen,221,191-~02).-Para~romotoluenedisulphonic acid, prepared by pass-ing snlphuric anhydride into it solution of bromotoluene in sulphuricacid, forms a deliquescent crystalline mass.The potassturn salt, C,H,Br( SOJK), + H,O, crystallises in colour-less needles or rhombic prisms, which dissolve freely in cold water.The barium salt, C7H5BrSzOsBa + 5H20, forms colourless prisms,needles, or plates, soluble in hot water, and the lead salt, C7H5BrS206Pb + 2H20, crystallises in colourless needles, which dissolve easily inwater.The chloride, C7H,Br( SOpCI)2, is deposited from an etherealsolution in colmrless rhombic plates melting at 99". The amideis sparingly soluble in water and alcohol.Parabromotolzienedisulphonic acid is slowly attacked by strong nitricacid with the formation of sulphuric,:dibromonitrotoluenesulphonic,nitrotoluenedisulphonic, and bromodisulphobenzoic acids.Potassium parabromodisulphobenzoate, C6HzBr(COOK) (S03K)2 +HzO, forms colourless plates, soluble in water.The barium saltcrystallises in plates containing 12 mols. HeO. The chloride is depo-sited from an ethereal solution in rhombic plates melting a t 151". Theamicle crystallises in prisms soluble in ammonia and in warm water.It melts above 250".Potassium dibrornonitrotoluenesubhonate, C7H4Brz.(.NO)2S03K +H20, is soluble in alcohol and water, The barium salt forms thinplates, containing 3+ mols. H,O.P0tnssiu.m nitro to luenedisulp honate, C7H,N02 ( S 0,K) 2, crystallises inthin needles, soluble in warm water. The amidotoluenedisu~honic acid,obtained by the action of ammonium sulphide on this salt, is notidentical with either of the amido-acids described by Pechmann(Alznalen, 173, 217), or Lorenz (ibid., 172, 188).It forms yellowneedles or prisms, which dissolve freely in water. The toluenedisul-phonic acid, which is formed by the reduction of sodium parabromo-t oluenedisulphonate, is not identical with any of the toluenedisul-phonic acids described by Blomstrand and Haknnsson (Ber,, 5, l084),It melts above 260"ORGANIC (IHEMlSTRY. 71Claesson and Berg (ibid., 13, 1170), or Senhofer (AnnaZen, 164, 126).It yields an anhydrous potassium salt, and a barium salt,C ~ H ~ ( S O ~ ) Z B ~ + 4HzO,both of which are very soluble in water. The chloride crystallises inprisms melting at 86*5", soluble in ether and light petroleum, and theamide forms colourless needles which melt above 260".w. c . w.Azotoluenedisulphonic Acids. By 0. KORNATZKI (Annalen, 2 21,179-191) .-The author finds that the only satisfactory generalmethod of preparing azotoluenesulphonic acids is by the oxidation ofthe potassium salt of the amido-acids.Ort hazoto ZuenediparasuZphonic acid, and parazotoluenediorthosulpiioninacid, which Neale (Annulen, 203, 73) prepared by reduciug the corre-sponding nitrotoluenesulphonic acids with zinc-dust and potash solu-tion, are also formed by the action of potassium permanganate onort hamidotolueneparasulphonic acid (described by Hayduck, Arznalen,172, 2C4), and on paramidotolueneorthosulphonic acid.Parazotoluenedimetasul~lio~zic acid, obtained by a similar reactionfrom the corresponding amido-acid (ibid., 173, 195) yields a bariumsalt, C1&,zBaN2S206 + 3H20, which forms small red crystals,sparingly soluble in water.Orthuzotoluensdimetasul~honic acid crystallises in plates of a redcolour, which dissolve freely in alcohol or water.The potassium salt,C14H12K2N2S206, also forms beautiful red-coloured plates, soluble inwarm water. The barium salt, C14H,2BaN2S206 + H,O, formssparingly soluble microscopic plates, which effloresce on exposure tothe air. The calcium salt crystallises in microscopic needles contain-ing 3 mols. H,O. The lead salt, Cl4H1,PbN2S2o6 + H20, is depositedfrom a solution in hot nitric acid, in needles which effloresce inthe air. The chloride, CIiH,,N,( S02Cl),, crystallises in dark redneedles melting at 218", soluble in benzene.The amide,C,Hl2N2( SO,NH,),,forms rhombic plates which melt a t 250°, and are soluble in ammonia.Dibromoparamidotolueneorthosulphonic acid, described by Jenssen(ibid., 172, 234) is slowly converted into dibromazotoluerLeaisulrphonicacid by oxidation with potassium permanganate. The azo-acidcrystallises in glistening red plates which dissolve freely in water.The potassium salt, C14H,oKI(,Br,N,S206 + 4H20, forms six-sidedplates, soluble in hot, water. The orange-coioured barium salt,C,4H,oBaBr,N2S206 + 5H20, and the red calcium salt,ClaHloCaBr,N,Sz06 + 44Hz0,forms microscopic plates, sparingly soluble in hot water. The leadsalt is deposited from hot dilute nitric acid in beautiful rhombicprisms containing 5 mols.H20. The chloride, C14HloBr2Nz( SO,Cl),,crystallises from benzene in pale red prisms melting a t 226'. Theanzicle melts at 260"72 ABSTRACTS OF CHEMICAL PAPERS.Tetrabrornorthoazotoluenedi23arasulponic ucid, prepared from Hay-duck's dibromamidotoluenesi~lphonic acid (ibid., 172, 211), formsglistening red plates, which dissolve easily in water and alcohol.The potassium salt forms microscopic plates, containing 2 mols. HzO.It, is sparingly soluble. The barium salt, C14H,BaBr4N2S,06 + 9H20,crystnllises in six-sided plates, which are sparingly soluble in hotwater. The calcium salt, CIIH8CaBr4NzSz06 + 8110, and the leadsalt, C,,H,PbBr,N,S,O, + 9H,O, form red-coloured plates. ThechZoride, C1*H8Br4N2( SO,Cl),, is deposited from benzene in dark redplates, which melt at 243" with decomposition.A hydrazo-acid is not produeed by the action of stannous chlorideon the potassinm salt, w. c.w.Amidobenzenernetasnlphonarnide. By F. HYRBENETH (Annalei,,221, 204-208) .-The preparation of nmidobenzenemetasu lph,onan? ide,C6H4(NH2).S02NH2 (m. p. 142O), has been previously described(Annden, 172, 72). The oxalate, nitrate, and hydrochloride arecrystalline. When nitrous acid is passed int#o a mixture of absolutealcohol and the sulphonamide, am orange-coloured diazo-compound isproduced. I f nitric acid is substituted for alcohol, either an orange-coloured powder soluble in water, or a yellow crystalline compound,will be obtained. The orange-coloured substance has the compositionC6H4(S02NHz).N,,N03. It is decomposed by boiling with water oralcohol, yielding nitrogen and benzenesulphonamide (m.p. 156").The yellow crystalline compoundNHZSOz.C,jH4.N2.NH.C6H4. SOZNH?,previously mentioned, is insoluble in water. It melts a t 183" withdecomposition. It is decomposed by hydrochloric acid, yieldingchlorobenzenesulphonamide fm. p. 148"), which was first prepared byKieselinsky (Annalen, 180, 110).2[C6H4(NH,).SO2NK,] + RNO, =NH,SOz.CJ€,.NH.N,. CJ&. SOzNHz.The conditions which determine khe formation of either of the twocompounds have not yet been ascertained. w. c. w.Orthamidotolueneparasulphonamide. By W. PAYSAN (Annalen.,221, 210-215) .-The amide of orthamidotolueneparasulphonic acid,NHz.C611,Me.SOzNHz, prepared by the action of sulphuretted hydrogenon an ammoniacal solution of orthonitrotolueneparasulphonamide(m. p. 12so), crystallises in four-sided prisms melting at 175", whichare sparingly soluble in cold water o r alcohol. It forms a series ofcrystalline salts.The diazo-compound, NHzSO2.CsH,Me.N,.NHC6H,~~e.SO2NH2, isobtained as a pale-yellow powder, when niti-ons acid is passed into amixture of the sulphonamide and alcohol. It detonates feebly whenheated, and is also easily decomposed by dilute acids, e.g., by hydro-chloricacid, i t is split up into nitrogen, amidotoluenesnlphonamidehydro-chloride and or thochloro t olueneparasulphonamide, C6H3Me C1. SOZNHORGANIC CHEMlSTRY. 73(m. p. 135"). The latter compound crystallises in white needles orplates, whichare sparingly soluble in water.By the action of hydm-chloric acid at 150", it is converted into orthochlorotolueneparasnl-phonic acid. The acid exists as an oily liquid. I t s potassium and bariumsalts do not contain water of crystallisation. The chloride is also anoily liquid. When nitrous acid is passed into orthamidotolueneparasul-phonamide, made into a paste with nitric acid, an exceedingly unstablecolourless diazo-compound is produced, which is decomposed by boilingalcohol, yielding the ethyloxidetoluenesulphonic acid described byHayduck (Annalen, 172, 215). w. c. w.Paramidotolueneorthosulphonamide. By A. HEFFTER ( A n n a Zen,2 21,208-210) .-Paramidotolueneorth osulp honam ide,is obtained by the action of sulphuretted hydrogen on a warmam moniacal solution of paranitro toluenesulphonamide ( A n n a Zen, 17 2,233).It crystallises in silky needles or plates which melt at 164", anddissolve in alcohol or warm water. It forms a crystalline nitrate,oxalate, and hydrochloride. When nitrous acid is passed into analcoholic solution of the snlphonamide, a yellow amorphous compoundis produced, which is decomposed by hot absolute alcohol, yielding theamide of tolueneorthosulphonic acid (m. p. 154"), which has beendescribed by Claesson aod Wallin (Bey., 12,1850). A diazo-derivativeof amidotoluenesulphonamide could not be isolated. ParachZorotoZuene-orthosdphonamide (m. p. 138") is produced when nitrous acid acts onthe sulphonamide in presence of hydrochloric acid.The S02-group inparamidotoluenesulphonamide is not eliminated by oxidation with potas-sium permanganate ; but the amide of azotoluenedisulphonic acid(m. p. 270"), described by Neale (Annalelz, 203, 52), is formed. w. c. w.Compounds of the Indigo-group. By A. BAEYER (Ber., 16,2188-2.204) .-Part IV.-The author has finally est>ablished theposition of the hydrogen-atom (external to the benzene-ring) in indigo,showing that tlhe latter is an imido-body, produced by the union oftwo indogen-groups. In the conversion of isatin and indoxyl intomembers of the true indigo-group, an isomeric change takes place,pseudoisatin and pseudoindoxyl existing however only in corn bination :co coNHCBH4< $OH, ca,( >GO,Isatin. Pseudoisatin.co\ COHNH NHC6H4( >CH, C6H4( /CHZ.Indoxyl.Pseudoindoxyl.For the stability of pseudoisatin it is sufEcient to replace thehydrogen of the NH-group by a monad radicle, whilst in the case o74 ABSTRACTS OF CHEMICAL PAPERS.pseudoindoxyl, a dyad-group must replace both hydrogen-atoms of thegroup CH,.Action qf Nitrous Acid on Indoxyl and Indoayl-compounds.-On treat-ing a solution of indoxyl with sodium nitrite and then acidifying,slender yellowish needles separate which, from their similarity to thenitrosamine of ethylindoxyl (obt'ained in the same way), and fromtheir behaviour to hydrochloric acid, must be the nitrosamine of indo%$,.C(OH>. \ I \CH. By the action of indoxyl on dinzobenzene hydro-C"'(N(ON)/chloride .in 'dilute aqueous solution, ,phenylazoindoxy Z, Cl4HI1NO3,separates in very sparingly soluble red needles; it is moderatelysoluble in alcohol, from which it crystallises in thick orange-colouredprisms of yellowish-green metallic lustre; it melts a t 236Owith decom-position, and dissolves in warm soda solution, from which it is repre-cipitat,ed by carbonic anhydride. Zinc-dust decolorises the alkalinesolution, and on exposure to air indigo is formed. Isonitrosopseudo-**indoayl ( pseudoisatin-a-oxime), C6H4< :E >CNOH, was previouslydescribed as nitrosoindoxyl (Alostr., 1882, l l O Z ) , but an examinationof its ethers shows that it is an isonitroso-derivative. The first ether,pseudoisatin-d-ethyZoxim.e, is obtained on heating an alcoholic solutionof pseudoisatoxime with ethyl iodide and sodium ethylate (1 mol.).It yields isatin on reduction and oxidation, showing that the ethyl-group does not replace the imido-hydrogen ; neither can it be derived.COH,from a nitrosoindoxyl of the formula C6H/ \C.NO, for it can\-NH-/be boiled with concentrated hydrochloric acid without undergoingchange ; nor from CsH,< >CHNO, as such a compound, containingethyl attached to the a-carbon atom, would not be so readily convertedinto isatin.I t s formula must therefore be C6H,<NH>CNOEt,and that of the parent-substance the one given above. This ethyl-derivative is a weak acid, dissolves in alcoholic potash with a violetcolour, and in alcoholic sodium ethylate with a blue colour.To pre-pare the second ether (ethylpseudoisatin-a-ethyloxirne) an alcoholic soh-t ion of pseudoisatosime, mixed with ethyl iodide and sodium ethylate(1 mol.), is boiled until the sodium salt first formed is completely dis-solved, when a quantity (1 mol.) of sodium ethylate aud ethyl iodide isadded, and the boiling continued for about half an hour ; the alcohol isremoved by distillation, the product dissolved in ether, and washed withdilute soda solution. It is readily soluble in alcohol and in ether, spar-ingly in hot water, from which it crystallises in yellow needles meltingat 99" ; it is neither attacked by alkalis nor by boiling hydrochloric acid.Its formula is C6Ha<NEt>CNOEt. Isatoxime and its two ethers,pseudoisatoxime and its first, ether, all yield isatin on reduction andsubsequent oxidation, whilst the second ether of pseudoisatoxime(containing ethyl attached to nitrogen) yields ethylpseudoisatin,NHcocORGANIC CHEMlSTRY.75C6H4<$it >CO. This crystallises in large blood-red plates meltinga t 95", is readily soluble in hot wat,er and i n alcohol, less so in ether.It dissolves in alkalis with a yellow colour and formation of ethyl-isatates. Acetylpseudoisatin behaves in a similar manner, being a tonce converted into an acetylisatate. On acidulating a solution ofan ethylisatate, ethylpseudoisatin is a t once precipitated, whilstacetylisatic acid is perfectly stable. Barium ethylisatate-obtained by dissolving ethylpseudoisatin in warm baryta-water, crys-tallises in silky yellow needles; the silver salt forms flat yellowneedles, moderately soluble in water.Ethylpseudoisatin yields anindopheiiin with coal-tar benzene and sulphuric acid, which forms ablue solution with ether (distinction from isatin). Ethylpseudoisatin,even when heated with concentrated hydrochloric acid for seven hoursat 150-160c, is in great part unattacked, whilst ethylisatin is saponifiedby cold dilute alkalis. By the action of a solution of hydroxylaminehydrochloride and sodium carbonate in dilute alcohol, ethy Zpsezdo-isatin-p-ozirne, C6H4<-NEt->C0, is obtained crgstallising inyellow four-sided prisms (m. p. 160-162"). On reduction and sub-sequent oxidation, it yields ethylpseudoisatin ; it does not yield indigowith ammonium sulphide.Action of Aldehydes and Ketonic Acids on IndoxyL-On treating anaqueous solution of indoxyl with aldehyde, or with benzaldehyde, andthen acidulating with hydrochloric acid, an extremely unstable yellowprecipitate is obtained, whilst paranitrobenzaldehyde, terephthalicaldehyde, anthroxanaldehyde, and pyroracemic acid, when treated inthe same way, yield very stable red precipitates.On cautiously heatinga mixture of dry indoxylic acid (7 parts) and benzaldehyde (10 parts)carbonic anhydride is evolved ; this ceases as soon as the temperatureis raised to 120". When the action is completed, the excem of benz-aldehyde is removed by steam-dist illation, and the residue crystallisedfirst from alcohol and then from ether. The indogenide of benanldehydethus obtained crystallises in long, flat, orange-yellow needles, meltingat 175-176".It dissolves readily in alcohol and chloroform, moresparingly in ether, with which i t forms a fluorescent solution ; it isdissolved by concentrated sulphuric and hydrochloric acids, but isreprecipitated on adding water; it is iiisoluble in aqueous, butsoluble in alcoholic alkalis. Its formation from indoxyl and benz-aldehyde takes place thus: CsH,NO + C7H60 = C15Hl,N0 + H,O,similar t o the action of nitrous acid on indoxyl, and from the similarityof both products and their behaviour with sodium ethylate, it isevident that they are similarly constituted, and that the formula ofC(N0H)rinthe indogenide of benzaldehyde is C,H,<;g>C : CHPh.It yieldsR blue solution with sodium ethylate, showing the indigo-spectrum,the blue colour disappearing on the addition of alcohol. The indo-genide of paranitrobenzaldeh?lde, Cl5Hl0N2O3, is prepared by adding asolution of paranitrobenzaldehyde in glacial acetic acid to an aqueou76 ABSTRACTS OF CHEMICAL PAPERS.solution of indoxyl acidulated with hydrochloric acid, and thentreating the precipitate several times with boiling water, and recrystal-lising it from acetone. It forms small red needles melting a t 273".The indogenide of pyroracemic acid, C6H4<NH>C co CMe.COOH, isobtained by adding concentrated hydrochloric acid to an aqueoussolution of indoxyl and pyroracemic acid, and can be purified bypassing a current of air through its solution in ammonia, filtering andprecipitating with hydrochloric acid ; it crystallises in red needles, andmelts a t 197".It, is readily soluble in acetone and in alcohol, is astrong acid, forms brownish-red solutions with the alkalis andalkaline carbonates, and a blue solution with sulphuric acid. It isreduced by ammonia and zinc-dust, forming a colourless solution,which becomes yellow on exposure to air, and yields a yellow flocculentprecipitate on the addition of an acid.Action of lsatin and Ethylpseudoisatin on Idoxyl.-The formationof indirubin from indoxyl and isatin may be compared to the abovereactions, in which case indirubin must be regarded as the indogenideof isatin, thus :-Pseudoindoxyl. Isatin.co C(OW\= CeH4( >C C' ,N + H,O.NH '-(&H4Indirnbin.When a hot aqueous solution of indoxyl is poured into a hotsolution of ethylisatin mixed with one-fourth its volume of con-centrated hydrochloric acid, a violet-coloured liquid is obtained, whichyields crystals of the 8-indogenide of ethylpseudoisatin.It crystallisesfrom boiling alcohol in needles of a coppery lustre, sparingly solublein acetone, more readily in chloroform. It melts at 197-l%", and at,higher temperatures volatilises in yellowish-red vapours. Thepowdered substance is violet, its concentrated solution in chloroformred, and its dilute solution pink, showing a broad band in the middleof the spectrum. It is reduced by zinc-dust and alkalis, yields abrown solution with concentrated sulphuric acid, which changes toviolet when heatcd, and behaves like indigo.From the fact that inthe reduction of ethylpseudoisatin, the CO-group next to the benzenenucleus is the one attacked, and also in the reaction with hydroxyl-amine, it may be assumed that this is also the case in the condensation-product with indoxyl. Its formula is therefore-C6H4<gg>C : C<zgi>NEt,and it is possible that indimbin has a corresponding constitution.Diethy Zindigo.-Assuming the probability of indigo being an indigo-body, the author attempted to convert ethyl- and benzyl-amidoacetoORGANIC CHEMlSTRY. 77phenone into ethyl- and benzyl-indigo, but without success. By thereduction of the second ether of pseudoisatin-a-oxime by alcoholicammonium sulphide, diethylindigo can be obtained, in which ethyl isattached to the nitrogen, and which still possesses the properties ofindigo.It crystallises in blue needles with coppery lustre, it is dis-tinguished from indigo by its moderate solubility in alcohol; but isinore sparingly s o h ble in acetone, chloroform, aniline, ether, andcarbon bisulphide. Its solutions are of a pure blue colour, and givean absorption-spectrum very like that of indigo. It forms a greenish-hlue solution with concentrated sulphuric acid, which changes to blueon warming (from formation of a sulphonic acid). When heated, ityields purple vapours, condensing in the form of thick blue prisms.With alkalis and zinc-dust, it yields a reduction-compound, and onoxidation, ethylpseudoisatin, proving that the ethyl in diethylindigo isunited with nitrogen.In the same way that diethylindigo is obtainedfrom ethylpseudoisatin-a-ethyloxime, indigo can be obtained frompseiidoisatin-a-oxime, and also by the action of ammonium sulphideon isatin chloride and on +ethylisatin, but from the formula of thesethree indigo-producing substances it will be seen that by their reduc-tion and the splitting of€ of hydroxylamine, hydrochloric acid, andalcohol respectively, each is capable of yielding an indogen-group orindoxyl.The constitution of indigo can be adduced from the following con-siderations :-1. Indigo contains the imido-group ; 2. From its forma-$ion from diphengldiacetylene, the carbon-atoms must be arrangedthus: Ph.C.C.C.C.Ph; 3.It can only be obtainedfrom such compoundsin which the carbon-atom next to the benzene nucleus is also unitedto oxygen; 4. Its formation arid properties show that it is closelyrelated to indirubin and to the indogenide of ethylpseudoisatin ;5 . This last substanee is formed by the union of the a-carbon-atom ofpseudoindoxyl with the 6-carbon-atom of pseudoisatin. Indigo musttherefore be the a-indogenide of pseudoisatin, although from thewant of activity of the a-oxygen-atom in isatin it cannot be directlyobtained from indoxyl and isatin.co C6H4<NH>CHZ + co<:g 6 1 >NEtPseudoindoxyl. E thylpseudoisatin.CO co = CJL<NH>C : C<C6H,>NEt + K O -Indogenide of ethylpseudoisatin.co co C~H~<NH>C& CO<NH>C~J%Pseudoindoxyl.Pseudoisatin.co co = c6H1<,H>c : C<NH>c6H4 + HZO.Indigo.The half molecule (CsH5NO) of indigo is called by the aniho78 ABSTRACTS OF CHEMICAL PAPERS.indogen, and compounds in which this dyad-group replaces anoxygen-atom, indogenides. The indogenides are of a yellow to bluish-red colour, and some of them yield blue salts showing the indigo-spectrum. A. K. M.Chemical Constitution of Acetylisatin and AcetylisaticAcid. By H. KOLBE (J. pr. Chem. [2], 28, 79-82).-The authorobjects to the formulae assigned by Baeper to isatin and its deriva-tives ; he regards isatin as having the constitution C,H,N.CO.COH(the nitrogen-atom acting as a monovalent element, and replacingone of the hydrogen-atoms in phenyl), and represents the conversionof acetylisatin into sodium acetylisatinate by the equation-CGH4N.C0.COAc + NaOH = C6H4(NH&).C0.COONa.A. J.G.Quinisatin. By A. BAEYER and B. HOMOLKA (Rer., 16, 2216-2221).-Baeyer obtained isatin from oxindole by converting the latterinto a nitroso-derivative, then into the amido-derivative which yieldsisatin on oxidation. The authors have obtained the isatin of quino-line in the same way from yhydroxycarbostyril (Abstr., 1883, 197).To prepare nitroso-nphydroxycarbostyril, CSH6N203, y-hydroxycar-bostyril is dissolved in dilute soda solution, a slight excess of sodiumnitrite added, and the mixture gradually poured into cold dilute sul-phuric acid. The precipitate is washed with water, dried and c r ptallised from alcohol, when it is obtained in small orange-colouredprisms, sparingly soluble in water, cold alcohol, ether, benzene andchloroform, readily in glacial acetic acid and in hot alcohol.It meltsat 208" with decomposition. Alkaline carbonate and ammonia dis-solve it, forming a green solution, whilst the fixed alkalis yieldreddish-brown solutions. On boiling it with concentrated hydro-chloric acid, it decomposes into isatin and hydroxylamine. Promits resemblance to isatoxime, the authors consider the following con-stitution probable,CO.C(N.OH)By the action of zinc-dust on its solution in glacial acetic acid,acetyldihydroxytetrahydro~u~nol~ne, CIlHJ'J 0 3 , is obtained, crystallisingin long colourless silky needles. When exposed to the air in a moiststate, it is rapidly oxidised to a violet-red product, from which theoriginal substance can be obtained by reduction. Acetyldihydroxy-tetrahydroquinole is very sparingly soluble in cold water, alcohol andether, moderately in glacial acetic acid, especially on warming ; it dis-solves in alkali to a violet solution or in excess of the lattler to a bluesolution, acids reprecipihating it in reddish coloured flocks whichgradually become white.On reducing nitroso-7-hydroxycarbostyril by means of a saturatedsolution of stannous chloride in concentrated hydrochloric acid, andsubsequently decomposing the tin salt with hydrogen snlphide, a com-pound of the formula, C9H7N03, is obtained, which is probablyC(OH)->ORGANIC CHEMlSTRY.79long colourless nsedles, very sparingly soluble in water, ether andbenzene, readily ia alcohol.Heated to 260", it becomes converted intoa brown substance infusible at 310". With dilute alkalis it yield8 ablue solution, which becomes decolorised on exposure to the air withformation of a violet precipitate. On adding soda to its solution inalcohol and ether, a deep blue flocculent gelatinous precipitate is pro-duced. When finely powdered 6-y-dihydroxycarbostyril is treatedwith a solution of ferric chloride in hydrochloric acid a t 70-80", areddish-yellow liquid is obtained from which quinisatic acid,NH,. C,jHd. CO. C 0. C 0 OH,crystallises out on cooling. It is moderately soluble in cold water,very readily in hot, water, from which it crystallises in pale straw-coloured prisms.The alkali salts are nearly colourless and readilysoluble ; the silver salt forms a yellowish-green unstable precipitate.On reducing a solution in glacial acetic acid with zinc-dust, and ex-posing the filtrate to the air, an indigo-blue coloured precipitate isformed, insoluble in water, ether, and chloroform, but soluble inalcohol, the supernatant liquid assuming a green coloration. Bothcolours are destroyed by acids, but reproduced on adding an alkali.On heating crystallised quinisatic acid for a short time a t 120-125"water is given off, and the red anhydride, quinisutin, CsH,NO,,formed : this readily combines with water forming quinisatic acid.I t darkens in colour above 185", melting between 255" and 260".Sodasolution dissolves it to a reddish-yellow solution, which is rapidlydecolorised. It forms compounds with aniline and benzene, whichare soluble in alkalis, but reprecipitated by carbonic anhydride,showing that quinisatin is not a carboxylic acid. Its formula is pro- c0.co co.cobably either C,H/ 1 or CGHd'NH.CO <N k(OH)* A. K. AT.So-called Pyrocressol. By H. SCHWARTZ (Ber., 16, 2141-2145).-In this paper the author mentions that the results of vapour-densitydetermination of the so-called pyrocressol were not in accordance withthose obtained in the combustion analyses : the latter correspondedwith a formula CZ8H2,O2, the former to C,,Hl4O (comp. Rer., 16,1056). Both have been repeated, and the latter formula confirmed ;pyrocressol, therefore, may have the constitution of a ditolyl or dibenzylketone, CGH4Me.C0.C6H4Me or CH,Ph.CO.CH,Ph, although its pro-perties are not in accordance with either of these substances.Similarly,it is shown that the a-pyrocressol oxide obtained by the oxidation ofpyrocressol with chromic acid has the empirical formula C,,H,,O, ; itforms a tetranitro-derivative, C15H8(NOz)40,, crystallising in goldenneedles, and a tetrabrom-derivative C16H8Br402, crystallising in longwhite leaflets melting at 215".Derivatives of a- and p-Naphthol. By E FRIEDL~NDER (Bey.,16, 2075--2092).-The monohydroxy-phenols readily react with theV. H. V80 ABSTRACTS OF CHEMICAL PAPERS.monamines yielding the dismines with elimination of water ; the bestdehydrating agent for effecting this change is calcium chloride, andfrom the author's experiments it foliows that the gqeatest yield is ob-tained when 1 mol.of the phenol and 2 mols. of the amine are heatedwith 1 mol. of calcium chloride. I n this communication, the variouscompounds obtained by the action of aniline and the three toluidineson a- and &naphthols are described.Phenyl-6-naphthyzamine, CloH7.NHPh, crystallises in white needlesmelting a t 108" ; phenyl-a-nap hthy lamine in white leaflets melting at60".Paratolyl-13-naphthy lamine, CloHT.NH.C7H7, forms white glisteningleaflets melting at 108" ; its acetyl and benzoyl-derivatives crystallisein needles ; with excess of bromine a tetrabrom-compound is obtained,which forms glistening needles melting at 168".Paratolyl-oc-naphthyl-amine forms white prisms melting a t 79" ; orthotolyl-a-naphthylamineglisteniug needles melting a t 95'. Orthotolyl-p-naph thy lamine crystal-lises from petroleum in white leaflets melting a t 96" ; its picrate inreddish- brown needles, and its benaoy Z-derivative in leaflets.All the above-mentioned amines give colour-reactions with nitricand chromic acids ; when heated with hydrochloric acid they are re-converted into the corresponding phenol and the hydrochloride of theamine. V. H. V.Naphthalene-derivatives. 111. By F. GRAEFF (Ber., 16, 2246-2255).-The action of nitric acid on naphthonitril takes place intwo stages, nitronaphthonitril being first formed, and the CN-groupsubsequently converted into COOH, so that it is possible to stop theaction after the first phase, and obtain nitronaphthonitril.For theiiitrntion of the a-compound (20 grams) a mixture of 50 C.C. fumingnitric acid, sp. gr. 1.48, with 200 C.C. nitric acid, sp. gr. 1.3, is recom-mended, whilst for the @compound 150 C.C. of the stronger acid to100 C.C. of the weaker acid are employed. a-Naphthonitril yieldsthree mononitro-derivatives, the chief product melting at 205" as pre-viously stated (Abstr., 1881, 882). Another more scluble nitronaph-thonitril melts at 152-153", whilst the third compound, which hasnot yet been obtained pure, melts between 100" and 130". A mono-nitro-derivative melting a t 172-173" is readily obtained fromP-naphthonitril, but the chief product melts between 95" and 120'.Nitro-a-naphthonitriz, CloH6N0,.CN (m.p. 152-153"), is morereadily soluble in boiling water than its isomeride melting a t '205",very sparingly in light petroleum, more readily in carbon bisulphide,moderately in alcohol and glacial acetic acid, and very readily inbenzene and in chlorofwm. It crystallises in yellowish colouredneedles from alcohol, ether, and glacial acetic acid, and in lustrousscales from light petroleum. Nitro-6-naphthonitril (m. p. 172-173") is very sparingly soluble in hot light petroleum, and sparinglyin alcohol and glacial acetic acid, from which it separates either insingle long crystals of golden lustre or in fern-like clusters; it ismoderately soluble in ether and carbon bisulphide, more readily inbenzene, and extremely soluble in chloroform. It may be obtained inlarge nearly white needles of great purity by sublimation.These nitroORGANIC CHEMlSTRY. 81naphthonitrils are saponified by heating them with Concentratedhydrochloric acid for five hours at 150-160".Nitro-a-naphthoic aedd (m. p. 241-242") obtained from the nitro-naphthonitril melting a t 205", is moderately soluble in hot alcoholand glacial acetic acid, less so in ether and chloroform, still momsparingly in benzene and carbon bisulphide, and very sparingiy inlight petroleum and in water. It crystallises from spirit in flat, con-centrically-grouped needles, and sublimes in the form of splendidlustrous scales.The potassium salt, C~oHfiNOz.GOOK + HzO, forms hard yellowishcoloured crystals of a vitreous lustre, On boiling the acid with anexcess of barium, carbonate,is obtained.The silver salt forms a yellowish amorphous precipi take sparinglysoluble in water ; the lead snZt resembles the silver salt, and separatesfrom its solution in boiling water in small wart-like forms ; the coppersalt is sparingly soluble in water, from which it separates in smallbluish-green crystals ; the methy Z-derivative forms small yellowneedles melting at 109-llO", and readily soluble in alcohol; theethyl-derivative is much more sparingly soluble in alcohol, and crys-tallises in long, slender, well-formed needles melting at 93" ; theisopropy Z-derivative forms lustrous crystals melting at 101*5", andsparingly soluble in alcohol.Nityo-a-naphthoic acid melting a t 255" dissolves readily in mostsolvents, and sublimes in long colourless needles.For want ofmaterial it has not been further examined.Nityo-8-napJrthoic acid melts at 295", and in most of its propertiesresembles the acid melting atl 241-242". It is insoluble in water,sparingly soluble in ether, light petroleum, benzene, chloroform andcarbon bisulphide, moderately in hot alcohol and glacial acetic acid ;it sublimes in small nearly colourless needles. The potassium saZt,CloH6NOz.COOK + H20, forms small clusters of lustrous needles veryreadily soluble in water. OR boiling the acid with barium carbonate,two salts are obtained, a more sparingly soluble acid salt,6 [ (C ,,H,NO,. C 0 O)2Ba], C: &LN 0 2 . C 0 OH + 24H20,crystallising in sniall lustrous scales; and a more sohble norntal saltalso crystallising in scales.The methyl-derivative is sparingly solublein alcohol, from which it crystallises inclusters of large bright yellowneedles, melting at 112" ; the ethyZ-derivative is readily soluble inalcohol, and crystallises in large well-formed dark yellow needlesmelting at 109" ; the isopropyZ-derivative forms long silky needlesmelting at 75-76', and readily soluble in alcohol. This acid appearsto be the same as that obtained by Ekstrand (Ber., 12, 1395) from/3-naphthoic acid, but which melted a t 280" owing to the presence ofimpurities. A. K. &I.Reduction of Dichlorophenanthrone. By B. LACHOWICZ (J. pr.C'hern. [2], 28, 168-1 75)-The preparation and properties of di-chlorphenanthrone (phenanthrenedichloroketone) have already beensparingly soluble basic salt,5 [ (CloHfiNOz.C00)2Ba],Ba0 + 10H20,VOL.XIrVI. 82 ABSTRACTS OF CHEMICAL PAPERS.described by the author (Abstr., 1883, 666). The formation ofresinous bye-products is minimised by adding excess of benzene tothe phenanthraquinone before running in the phosphoric chloride.Nitric acid readily converts it into the nitro-derivatives of anthra-quinone.Monochlorphennnthrone, C14H90Cl, is obtained by the reduction ofdichlorophenanthrone with iron and acetic acid ; it crystallises inlarge yellow prisms, melts at 122-123", is readily soluble in alcohol,ether, benzene, light petroleum, &c. It dissolves without decomposi-tion in alkalis, and is not decomposed by long boiling with alcoholicammonia. By heating with nitric acid of sp.gr. 1.3 i t yields nitro-pliennnthroqirinone, C14H,N04, crystallising in orange-yellow plates,melting a t 281-282", and soluble in glacial acetic acid and nitricacid.Phenanthrone, C,aHloO, is obtained by the long-continued action ofnascent hydrogen on dichloranthrone, best by gradually a,dding ironfilings to a solution of dichloranthrone in glacial acetic acid heated to1CO-110". Too strong heating leads to the formation of resinousproducts. It crystallises in brilliant brownish-red tables, melts a t148-149", resembles the monochloro-derivative in solubilities, andlike it, is not decomposed by aqueous alkalis.The authors consider that phenanthrone has the structural formulaCeH.i.CH21 - - I - , whilst the isomeric compound obtained by Japp andC,H,.COStreat'feild from et8hy1 phenanthroxyleneisocrotonate (Trans., 1883,33) may probably be represented by I I ',O.CsH,.CHc 6 ~ 4 . c H/ A. J. G.Coloured Essential Oils. By K. HOCK (Arch. Pharnz. [ 3 ] , 21,17-18) .-The essential oils of chamomile, wormwood, and mille-folium, although differing in colour, were found by the author tohave the same absorption-spectrum, namely, three bands in the redand orange. When these oils were submitted to fractional distillation,in each case the portion which distilled a t 260" was deep blue, andyielded the same absorption-bands with great distinctness. The blueoils obtained from Matricaria chaworni2la, Perula sunzbul, Nectnndyapuchury, Inula lielenium, Pogostervlon patschuly, also by the dry dis-tillation of galbanum, guaiacum, and asafcetida resins, as well asa blue product from oil of valerian, gave the same characteristicabsorption-spectrum. From these results, the author concludes thatall these blue oils contain the same colouring-matter, azulene, whichin some cases is present in the plant from which the oil is obtained,in others, is produced by the action of water on some constituent ofthe plant during distillation, and sometimes is formed by destructivedistillation.I n the case of those essential oils from which the blueportion was obtained by distillation, an oil oxidised by keeping appearedto yield a larger quantity of the blue product than the same quantityof the fresh oil.W. R. DORGANIC CHEMlSTRY. 83Destructive Distillation of Colophony. By A. RENARD (Compt.rend., 97, 111-1 12).-When colophony is introduced into an eartheu-warc retort heated to dull redness it is decomposed, and yields a largequantity of combustible gas rich in hydrogen, and a black, somewhatfluid tar, mixed with a small quantity of water. The t a r when dis-tilled a t a temperature rising to 300' yields a resin which solidifieson cooling, and a liquid which cont.ains benzene and its homologues,a small quantity of naphthalene, and other oils which hare not beenstudied. The residue from the distillation of this liquid is mixedwith the resin, and the mixture distilled as far as possible.A residueof coke is left, arid an oil was obtained which becomes semi-solid oncooling. This oil contains two isomeric hydrocarbons, cozophanthrenes,which bave the following composition :-White.T---A--- 7 Yellow.Carbon .......... 93.02 93.20 93.20Hydrogen.. ...... 7.18 7.01 6.71The yellow colophanthrene is very sIightly soluble in alcohol, fromwhich it separates in yellow crystals with a greenish fluorescence. Itboils at about 360°, and by repeated crystallisation from alcohol itappears to be converted into the white isomeride. The white colo-phanthrene is much more soluble in alcohol, from which it is depositedin brilliant white cryst,als, with a violet fluorescence. It melts a t about87", boils a t about 340", and by repeated distillation is partially con-verted into the yellow isomeride.It also acquires an orange-yellowtint when exposed to light. Both hydrocarbons begin to decomposeat the boiling point of sulphur (440'). Wheu oxidised by chromicacid in acetic acid solution, they both yield carbonic anhydride and adiketone, which yields a sulphonic acid. The potassium salt of thisacid when heated in a seaIed tube at about 170" with a concentratedsolution of potassium hydroxide is converted into a deep violet snb-stance ; this dissolves in water, and is decomposed by hydrochloricacid, yielding a colouring-matter, which imparts to cotton mordantedwith alumina a shade similar to that given by alizarin.Extraction of Colouring-matters by a Solution of Borax,By R. PALM (Chenz.News, 48, 114).-For the extraction of alizarinand purpurin from ga,rancin, the author digests the garancin with acold saturated borax solution until a deep blood-red solution is ob-tained ; this is filtered, and precipitated with sulphuric, hydrochloric,or acetic acid. The precipitate is boiled with a saturated solution ofalum, filtered, and cooled ; the alizarin and purpurin then depositedare filtered off, and a further quantity of the colouring-matter is pre-cipitated from the filtrate on adding sulphuric acid. The author alsoemploys borax solution for the extraction of santalin from sanderswood, and violet colouring-matter not identical with carmine fromcoc b ineal.C. H. B.D. A. L84 ABSTRACTS OF CHEMICAL PAPERS.Cochineal Dye-stuffs.By H. F~RTH (Ber., 16, 2169-2171).--By acting on carmine with sulphuric acid, Liebermann and v. Dorphave obtained a brown amorphous dye-stuff , ruficoccine, C,6H&67which on distillation with zinc-dust is converted into an anthracene-like hydrocarbon of composition C16H12 (Annalen, 163, 97). Theauthor has succeeded in obtaining this hydrocarbon not only fromcoccinine, a quinone derivative of carmine, but also directly fromcarmine. This hydrocarbon, which condenses in small green-goldleaflets when coccinine or carmine are distilled with zinc-dust, meltsat 1%", and is soluble in ether, alcohol, and benzene. By heatingacetic chloride and coccinine in sealed tubes a t loo", an acetyl-deriva-tive is obtained, which forms small golden crystals insoluble in water,soluble in alcohol ; i t cannot be sublimed without decomposition.Ascoccinine yields a c16 hydrocarbon on distillation, the compositionCI4H1?O5, assigned to it by Hlasiwetz and Grabowsky, must be alteredto C16H1406, and its acetyl-compound will then be a tetra-derivative,C ~ ~ H ~ O O ~ A C ~ . Coccinine is thus a tetrahydroxy-qninone, C1,H,oO,(OH),,which formula is in accordance with its quinone-like characteristics.V. H. V.Preparation of Diquinoline. By .R. C. TRESSIDER (Chern. News,48, 31).-Quinoline hydrochloride is heated with an equal weight ofzinc chloride a t 350" for five or six hours, the flask being fitted witha reflux arrangement. Soda is added to t'he product until the zinchydroxide first precipitated is redissolved, the mixture is steam dis-tilled to remove any unchanged quinoline, and the residue which isblack and solid is well washed with water, boiled with a large quantityof alcohol, and filtered hot.The filtrate is decolorised with animalcharcoal, and again filtered hot, : on cooling, diquinoline separatesout, and is recrystallised from alcohol. The yield is not large.D. A. L.Hydroxycinchonic Acid. By W. KOXIGS and G. KORNER (Ber.,16, 2152-2160) .-By fusing cinchoriic acid with potash, one of theauthors has obtained a hydroxycinchonic acid, CgH,N(OH).COOH(Abstr., 1879, 472) ; this acid is converted into a chloro-derivative,C,H,ClN.COOH, by phosphorus pentachloride, and by heating withhydriodic acid and phosphorus into the amorphous hydroquinoline,(C9H,N),.This last reaction shows that the hydroxyl-group is notin the benzene, but in the pyridirie nucleus ; and in the present com-munication this supposition is confirmed, and it is further shown thathydroxycinchonic acid is a carboxyl-derivative of carbostyril.The authors were unable to obtain a hydroxyquinoline by distillinghydroxycinchoiiic acid with bases; but on heating its silver salt,C,H,(OH) .COOAg, in a current of carbonic anhydride, a sublimatewas formed crystallising in needles, and having the characteristicproperties of carbos tyril.Chlorocinchonic acid, when heated with sodium alcoholate, yieldsethoxycinchonic acid, C,H,N(OEt).COOH, which crystallises in hairyneedles melting a t 145", soluble in hot water, alcohol, and dilute mineraORGANIC CHEMISTRY.85acids; its siZver and lead salts are sparingly soluble precipitates, ofwhich the former is an acid salt of compositionCgH,N (OEt) , CO OAg,CgH,N (OE t) . COOH ;its platinochloride, [ C9H5N (OEt) ,C00E],.H2Pt C16, is crystalline.When ethoxycinchonic acid is heated to a temperature slightlyabove its melting point, it is transformed into the isomeric ethyl saltof hydroxycinchonic acid, C,H,N(OH) .COOEt, also obtained by theaction of ethyl iodide on silver hydroxycinchonate. This salt crystal-lises in needles melting a t 206", and, unlike its isomeride, is insolublein dilute acids or alkalis. The intermolecular change of the ethoxy-acidinto the ethyl salt of the hydroxy-acid probably prevents the elimina-tion of carbonic anhydride from the acid, when it is heated with lime.When the silver hydrogen salt is heated in a current of carbonic anhy-dride, ethylcarbostyril and the ethyl salt of ethoxycinchonic acid areproduced.The latter substance, which can also be prepared from ethyliodide and the silver salt, crystallises in fine needles melting at 86".From these researches it follows tbat hydroxy- and ethoxy-cinchonicacids are derived from carbostyril, and as cinchonic acid is convertedinto pgridine tricarboxylic acid by oxidation with potassium yerman-ganate, the carboxyl-group is in the pyridene nucleus.In cinchonic and hydroxycinchonic acids, the N-atom and the carbonto which the COOH-group is united, are probably in the para-positionto one another, The authors have also succeeded in converting quino-linic, or pyrididinecarboxylic acid, into hydroxyquinolinic acid bymelting the former with potash.The relations of these acids isevident from the following formulae : -CH CHCO0H.C CH CO0H.C (i CHCO0H.C \NH C.OHCooH.C 'iC*The latter forms colourless crystals melting at 254' of strongly markedacid properties; its aqueous solution gives a deep red colorationwith ferric chloride, and voluminous precipitates with copper, lead,and silver salts. Its hydrogen barium salt crystallises in tufts ofneedles ; its hydrogen silver salt, when heated in a current of carbonicanhydride yields a compound haying all the characteristic propertiesof oxypyride, C5H5N0.Oxidation of Morphine. By L.BARTH and H. WE~DEL (Monatsh.Chem., 4, 70&-703).-The action of most oxidising agents on mor-phine does not yield very definite results ; potassium permanganntehowever in slightly alkaline solution acts on it somewhat moreenergetically, yielding as chief product a light-brownish uncrystallis-able acid syrup, which forms amorphous salts, and when mixed withcupric acetate, remains clear at first, but becomes turbid on boiling,depositing a blue-green flocculent precipitate, which redissolves oncooling. This result is like that which is obtained by similar treat-V. H. V86 ABSTRACTS OF CHEMICAL PAPERS.ment of cinchomeronic and pyridine-tricarboxylic acids. Morphinesubjected to dry distillation with lime yields a basic oil having a,decided odour of pyridine.Arsenic acid acts but slowly on mor-phine even in sealed tubes, yielding a base which appears t o containone methyl-group less and one hydroxyl-group less than morphine ;the action is however variable and so are the products. Whenmorphine is heated with potassium hydroxide till the surface of themelt begins to glow, and the product, after cooling, is acidulated,brown-black non-ni trogenous flocks are deposited, and a solution isobtained from which ether extracts a considerable quantity of sub-stance ; and on expelling the ether, digesting the residue with. water,precipitating the filtrate with lead acetate, decomposing the precipi-tate with hydrogen sulphide, evaporating, and repeatedly crystallisingthe residue, a product is obtained, consisting of protocatechuic acid.The filtrate freed from lead and evaporated yields more protocate-chuic acid, together with another acid which crystallises in prisms,and gives no colour-reaction with iron salts.When the melting with potash was conducted in 8 silver retort, andthe vapours were received in dilute hydrochloric acid, methylaminewas obtained, together with n small quantity of another base.The absence of aromatic compounds amongst the products formedby oxidising morphine with permanganate, and the non-occurrence ofderivatives of pyridine (or quinoline) in the oxidation of this alkalo'idwith caustic alkali, seem t o show that the mode of combination ofthe aromatic and of the pyridine- (or quinoline-) groups in it, is dif-ferent from that which exists in narcotine, which, it is well known, iseasily resolved into its two principal constituents.H. W.Constitution of Quinine and Quinidine. By Z. H. SKRAUP(Monatsh. Chem., 4, 695-699) .-The author has already shown(Abstr., 1882, 279) that these two alkaloids, when oxidised bychromic acid, yield carbonic anhydride and quininic acid, CllH9N03,which latter, when heated with hydrochloric acid, gives methylchloride and xanthoqninic acid, CloH7N03, resolvable by heat intoCO, and a hydroxyquinoline, C9H,N0 = CgH6(OH)NO2; further thatquininic acid is converted by oxidation with permanganate into apyridine-tricarboxylic acid, C,H,N(COOH),, identical with that whichis obtained from cinchoninic acid : hence it, is probable that quininicacid is a, derivative of quinoline, and that its methyl-group is situatedin the benzene-residue of the quinoline-molecule ; hence also it maybe inferred that the hydroxyquinoline obtained from xanthoquinicacid has its hydroxyl-group situated in the benzene residue.Accord-ing to existing views there should be only four hydroxyquinolinesthus constituted. Three are already known, and the main object ofthe present investigation is to ascertain whether the hydroxy-quinoline obtained in the manner just mentioned is identical witheither of these three, or consists of the hitherto unknown fourthmodification.Xanthoquiiiic acid is for the most part resolved at 310" into car-bonic anhydride and a hydroxyquinoline, which when purified byconversion into platinochloride, &c., crpstallises from absolute alcohoORGANIC CHEMlSTRY. 87in slender white prisms, soluble in alcohol without coloration, thesolution however acquiring, on addition of water, a faint yellowcolour, which disappears on further addition of alcohol.Thisbehaviour dis tingnishes the hydroxyquinoline in question from themeta-moditication, the alcoholic solution of which exhibits a splendidgreen fluorescence. From the ortho-modification it is distinguishedby giving, on addition of ferric chloride to its alcoholic solution, nota green, but a reddish coloration. With para-hydroxyquinoline onthe other hand it agrees very nearly in its melting point (194"), andfurther in the yellow coloration of its alcoholic solution by ferricchloride ; in giving with picric acid slender yellow prisms meltinga t 235-235.5" ; with cupric acetate, first a fine blue-green colour,then gradually violet prisms which dissolve iu boiling alcohol with afine lea€-green colour, and remain unaltered on evaporation.This hydroxyquinoline dissolves readily when gently heated withfour times its weight of strong nitric acid, and the solution,when quicklycooled and cautiously diluted with cold water, deposits orange-redcrystals, easily soluble in hot water, the solution slowly mixed withpotash-lye, depositing yellowish prisms, which, after recrystallisationfrom dilute alcohol, melt, like nitro-p-hydroxyquinoline, at 140-141".The alcoholic solution, mixed with cupric acetate, first turns brightgreen, and then deposits a copper-brown precipitate, or if a trace ofalkali be added, a green precipitate. The barium salt of the nitro-compound forms orange-red needles, slightly soluble in cold, muchmore freely in boiling water,Cinchoninic, quininic, and xenthoyainic acids may be representedby the following constitutional formulae :-COOH COOH COOHCinchonic acid.Qnininic acid. Xanthoquinic acid.H. W.Cinchonamine. By ARNAUD (Compt. r e d . , 97, 174-1 76, Seealso Abstr., 1882, p. 229) .-Cinchonamine, C19H24N,0, exists inRem,ijia piwdiana, but is not contained in B. pedunculata, which con-tains quinine. To extract cinchonamine, the finely powdered bark isexhausted with very dilute snlphuric acid, the solution filtered, boiled,and precipitated with milk of lime. The precipitate is dried onporous tiles, and digested with boiling ether.The ethereal solutionis decanted from iindissolved resinous substances, &c., washed withdilute hydrochloric acid, which removes the cinchonamine, and theacid solution of cinchonamine hydrochloride is evaporated to crystal-lisation. The hydrochloride is dissolved in boiling dilute acid,filtered through animal charcoal, and recrystallised. The free base isobtained by adding ammonia to a solution of the hydrochloride, andcrystallking the alkaloid from boiling ether. An alcoholic solutionof the alkaloid is dextrogyrate, its rotatory power at 97" bein88 ABSTRACTS OF CHEMICAL PAPERS.[.ID = 123.2". According to Dr.Laborde, cinchonamine is highlypoisonous, even in very small doses.The salts of cinchonamine generally crgstaliise readily, aud are butslightly soluble in water, especially in presence of free acid. Theydissolve in hot alcohol, from which they crystallise on cooling. Thehydrochioride crystallises from an acid solution in thin, brilliant,anhydrous, pismatic lamellae, very slightly soluble in acidulatedwater. From. a neutral aqueous solution, the salt crystallises inopaque flattened prisms containing 1 mol. HzO. These crystalseffloresce, and are much more solttble in water than the anhydroussalt. This property of the hydrochloride to crystallise in an anhy-drous condition from acid solutions furnishes a method of separatingcinchonamine from all the alkalo'ids with which it is associated inR.purdiana. The hyilrobrowaide forms brilliant, slender, anhydrousneedles, slightly soluble in cold water, much more soluble in hotwater. The kydriadide crystallises in micaceous plates, almost insol u-ble in cold water. The nitrnte is only slightly soluble in cold alcohol,but is much more solubae in hot alcohol, from which it crystallises inIiard, thick, short prisms. This salt is slightly soluble in pure water,but is insoluble in acidulated water, and is precipitated on addingnitric acid to even a dilute aqueous solution of any cinchonaminesalt. The precipitate is at first flocculent, lout, on standing, it rapidlybecomes crystalline, the crystals being small prisms, which polariselight.At 15", 100 parts of alcohol of 94" dissolve 0'825 part of thesalt; 100 parts of water at the same temperature dissolve 0.2 part ofsalt. Asolution of the salt in water containing 1 mol. H,S04 has a rofiatorypower a t 15" [all, = + 43.5; at 25" [a]= = + 42.2, The formatecrystallises with difficulty. The acetate is very soluble in water, fromwhich it is deposited as a resinous mass on evaporation. By spon-taneous evaporation of the aqueous solution the salt is obtained indeliquescent crystalline concretions. The oeaZcnte does not crystallisefrom an aqueous solution, but is deposited in a resinous form. Thetartrate forms a crystalline powder consisting of small hexagonalprisms which polarise light. 100 psrts of water a t 15" dissolve 1.150parts of the salt.The maZate forms brilliant nacreous plates, veryslightly soluble in cold water, but somewhat soluble in boiling water.The crystals retain 1 mol. H,O at 120°, but melt and become anhy-drous at 160". 100 parts of water at 15" dissolve 1 part of malate.The citrate is deposited from a boiling solution on cooling as a resin-ous mass, which gradually becomes crystalline, forming concretionscomposed of brilliant prisms which polarise light. 100 parts of waterat 16" dissolve 1.950 parts of the citrate.Conversion of Brucine into Strychnine. By HANRIOT (Compt.i*eizd., 97, 267-268) .--The author has repeated Sonnenschein'sexperiments (Ber., 8, 212), and finds that strychnine is not producedby the action of nitric acid on pure brucine. Sonnenschein's experi-ments were probably made with impure brucine. Brncine has thepower of completely masking the ordinary reaction for strychnine(with sulphuric acid and dichromate), even when the latter is presentThe suZp23hute can be purified by crystallisation from alcohol.C. H. BORGANIC CHEMISTRY. 89to the extent of 50 per cent. It is evident therefore that the presenceof strychnine in many samples of brucine may easily have been over-looked, and this will probably account for the confusion which existsas to the physiological action of brucine. Morphine, quinine, methylalcohol, and many other substances also have the property of maskingthe strychnine reaction.Products of the Bacterial Fermentation of AlburninoYds.By A. GADTIER and A. ETARD (C'ompt. rend., 97, 263-267. Seealso Abstr., 1882, 1115 ; and 1883, 100 and 224.)-The authors havepreviously shown that the putrefaction of albumino'ids results in theformation of leucines, glucoprotejins, nitrogenous and nsn-nitrogen-ous acids, phenol, skatole, indole, tyrosine, trimethylamine, ammonia,and ptomai'nes. Whatever the variety of the ferment and the sourceof the putrefying flesh, the principal ptomaines formed are constantin properties and composition.The liquid and solid putrid matter is distilled in a vacuum a t a lowtemperature. The distillate (A) contains ammonium carbonate,phenol, skatole, trimethylamine, and volatile fatty acids ; the residueis treated successively with ether and alcohol. The ethereal solution(B) contains ptomajines and a fatty acid, and holds in suspension verylight, brilliant, white nacreous plates. The alcoholic solution (C)contains fatty acids and crystallisable nitrogenous compounds. Theresidue insoluble in ether and alcohol is boiled with very dilute hydro-chloric acid out of contact with air, the solution evaporated andtreated with alcohol (D).The ethereal solution (R) when distilled leaves a brown oil, fromwhich a large quantity of fatty acid crystallises out. The mother-liquor is acidified with sulphuric acid, saturated with potash, andagitated with ether, which dissolves the ptomaines. A solution ofthe ptomajines from beef treated in the cold with platinum tetra-chloride, care being taken to avoid an excess, yields a precipitate ofthe coniposition (C,H3N)2,H2PtC16. It is the platinochloride of ahydrocollidine, identical with the base previously obtained from fish(Zoc. cit.). The mother-liquor from this platinochloride containsanother platinochloride, which forms yellowish crystals of the com-position C, 28'73; H, 5.8; N, 7.19; Pt, 27-99. It is partiallydecomposed at 100" with development of the hawthorn-like odour ofits alkalo'id.The brilliant plates held in suspension by the ethereal solutionconsist of the calcium salt of amido-stearic acid, C,,H3,(NH,)0,. Thisis almost insoluble in all solvents, but is dissolved slightly by alcohol,When treated with hydrochloric acid, it yields amido-stearic acid,which is insoluble in water, only slightly soluble in cold alcohol,but readily in hot alcohol, from which it crystallises in aggregatedneedles on cooling. It melts at 63", and when heated a t about 140"it loses 1 mol. of water, and yields the anhydride, C,,H,,NO. Theamido-stearic acid is obtained from beef: the nacreous plates obtainedfrom putrid fish are soluble in alcohol and in potash, but are insolublein water and acids. By treatment with inorganic acids they yield anacid of the composition, CsH,,N,03. When they are fused withC. H. B90 ABSTRACTS O F CHEMICAL PAPERS.potassium hydroxide, ammonia is given off, and a mixture of alkalinecaprylate, caproate, and acetate is formed.The alcoholic solution (C) contains the greater part of the leucinesand leucoproteins. After evaporation, the residue is treated withinorganic acids, the aqueous liquid separated from the liberated fattyacids, concentrated by evaporation, and treated with alcohol, whichdissolves out leucines and leucelnes, particularly those containing C,and Cc. The principal compound thus obtained from putrid fish formswhite rhombcidal lamellae, somewhat soluble in water, and somewhateasily sublimed ; it has the composition CllH26N2065 and appears tobe the hydroxide of the glucoprotein, CllHz2NzO4, obtained bySchutzenberger from the products of the decomposition of albumi-nolds by baryta. It has the general properties of amido-acids, anddissolves in dilute alkalis ; when fused with potassium hydroxide, ityields hydrogen, ammonia, and potassium carbonate, butyrat,e, andvalerate, a portion splitting up a t the same time into the correspond-ing leucines and leuceines. When distilled at about 280', it yields anamylamine boiling a t 92-93', which is probably formed together withamido-valeric acid in accordance with the equation CllHz6N2D6 =CsHlsN + C,H,NOz + GO, + 2H20. C. H. B.Albumin, Nuclein, and Plastin. By E. ZACHARIAS (Bid Cmtr.,1883,405-407).-The principal portions of the nitrogenous substancesof plant cells, insoluble in alcohol, consist of albumin, nuclein, andplastin, the two latter are attacked but slightly, or not a t all, by thegastric juices ; on the contrary, they readily dissolve albumin, Plas-tin is insoluble in very dilute solutions of alkalis, nuclein is easilysoluble in these menstrua; plastin and nuclein are the soluble andinsoluble nucleins of other authors. The supposition of Schimpersthat the substance from which starch is produced is similar to albumin,at least to a great degree, the author believes he has confirmed byresearches on the leaves of Tradascantia virginea and orchis.Albumin diminishes and plastin increases in the protoplasm of thecells examined ; according to Hartig's reaction: sections soaked ina dilute solut'ion of potassium ferrocyanide, and then transferred tg avery dilute solution of ferric chloride, show the nucleus deep blue,whilst in the ducts no trace of a blue colour is visible. When por-tions of the epidermis of the leaves of those plants are so treated, thestarch material becomes intensely blue, the cell protoplasm remainscolourless, or is coloured only in points. The nuclei show a bluecoloration, as also the nucleoli ; the plastin is colourless or very slightlycoloured.The author does not think that the chemical constitution of thenuclei and nucleoli can be ascertained from these reactions, but theyare aids to that kuowledge. J. F

ISSN:0368-1769    

DOI:10.1039/CA8844600032

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

PHYSIOLOOICAL CHEMISTRY.P h y s i o l o g i c a l C h e m i s t r y .91Influence of Respiration on Elimination. By F. PENZOLDT andR. FLEISCHER (Ried. Centr., 1883, 285).-Want of oxygen sufficient toinduce the dyspnoeic condition, causes an increased excretion of urineand urea, as also of phosphoric acid ; the after-action is lowering ofphosphoric acid, but raising of urea, the absolute result being nochange in the total excretion of acid and urea, and no separation ofsugar or albumin. l f , however, the animal is fasting, then whilstthere is a want of oxygen, there is a slight increase in urine, a con-siderable rise in urea and phosphoric acid ; during the after-actionurea still increases, but phosphoric acid decreases, so that there is anabsolute increase in the excretion of urea, but no phosphoric acid,albumin, sugar, nor allanto’in.When no dyspnoea accompanied thewant of oxygen, then a well-nourished dog excreted more urine andphosphoric acid, but less urea, whilst during the after-action therewas an increase in water, urea, phosphoric and sulphuric acids. Onthe whole, an absolute increase of these four compounds with tracesof albumin; the case was similar when a fasting dog was experi-mented on, save that sodium chloride behaved as urea.The diminished supply of oxygen when accompanied by d-ppnaicaction affects birds, and causes them t o excrete an excess of uric acid.Apnma causes a rise of urea, a fall of phosphoric acid, and afterwardsa considerable increase of both. Increased elimination of water isaccompanied by a lowered excretion of urea.Increased -muscularaction induces great increase of urea, at first a large decrease, later onan increase, and on the whole a slight absolute increase of phosphoricacid. Reduction of the temperature of the body is followed by in-crease of urea. E. W. P.Exhalation of Carbonic Acid by Frogs. By H. AUBERT (Bied.Cewtr., 1883, 427).-The author finds that the process of exhalation isas active in an atmosphere which is deprived of oxygen as in onewhich contains it. The same observation has been made by Pfluger,and cnn only be explained on the supposition that the process dependson the decomposition of organic compounds independent of the pre-sence of atmospheric oxygen. J. F.Alteration of Cane-sugar in the Human Stomach.By W.LEUBE ( B i e d . Centr., 1883, 427).-100 C.C. of a 10-15 per cent. cane-sugar solution were introduced into an empty stomach seven hoursafter a previous meal, or in the morning before the subject had eaten,the stomach having been previously rinsed and the rinsings testedwith Trommer’s test to negative reaction. Half an hour after intro-ducing the sugar, there was no reaction, or very trifling, whereas in aknown unhealthy stomach the reaction was considerable. The expla-nation appears to be that in the healthy stomach the inverted sugar isabsorbed, which is not the case in the unhealthy one. The gastri92 ABSTRACTS OF CHEMICAL PSPERS.juices of both healthy and sick persons cause the inversion of cane-sugar equally outside the body, but if a solution is introduced inequal parts into the stomachs of living subjects and withdrawn halfan hour afterwards, the difference in the reducing power is mostmarked, the healthy stomach showing no reaction, whilst the un-healthy does very strongly.Comparative Value of Artificial and Natural Butter asArticles of Food.By A. MAYER (Landw. Versuchs.-Stat., 29, 215--232).-In estimating the value of any article of food, the points tobe dwelt on are chiefly its nutritive qualities, taste, and action on thesystem, whether injurious or otherwise. In the case of butters ofvarious origin, the last two points are easily settled, as a positivelyinjurious influence has never been seriously ascribed to artificialbutter.The nutritive qualities of butter were therefore the subjectof this investigation.Experiments were made with a man and a boy, who received a cer-tain quantity of food per diem, as t o whether artificial or naturalbutter was the more easily absorbed by the system. The first threedays they were fed with various mixtures of bread, milk, eggs, andvegetables, together with natural butter ; then followed two days’ restwith ordinary diet, and afterwards three days with precisely the samediet as before, with the exception that, artificial was substitutled fornatural butter. On each successive day of the experiment the solidevacuations were collected and analysed, commencing 24 hours afterthe beginning of the experiment. The amount of fat in these wasestimated, and hence the quantity of fat absorbed into the system wasfound.This quantity is given in percentage of the whole amount inthe food in the table below :-J. F.Man.Day of experiment.r--h-- 71. 2. 3.Natural butter .......... 97*0 99.4 98.7Artificial ,, .......... 94.6 97.9 96.7Boy.Natural butter .......... 97.8 94.8 98-7Artificial , , .......... 9 5 . 3 94-6 97.6On the average, therefore, about 1.6 per cent. less of the artificialbutter was absorbed than of the natural. As this quantity is, how-ever, very small in comparison to the total amount absorbed, thedifference in value of the two substances as articles of food can beset down as only trifling, and except in cases of illness may be over-looked with safety.Digestive Fluid and Digestive Power of the Horse.ByELLENBERGER and HOFMJCISTER ( B i d Centr., 1883,386-589) .-It beingdifficult to obtain the natural digestive fluid of the horse, an artificialJ. K. CPHYSIOLOGICAL CHEMISTRY. 93one was prepared by cutting up the coating of the stomach containingthe ducts into very small bits ; it was then washed and neutralised,either at once or after treatment with alcohol, dried, and left from24 hours to eight days in contact with an extracting fluid, whichtreatment dissolves out all the ferments and acids. The flnids usedwere :-1. Water ; 2, glycerol ; 3, 0.2 to 0.5 per cent. HCl ; 4, 0.2 to0.5 per cent. lactic acid ; 5, 0.2 t o 0.5 HCI in glycerol ; 6, same pro-portion lactic acid in glycerol.The extract obtained from the part near the intestine containedmore mucin, acids.and ferments, and dissolved albumin more easilythan the extract from the region of the pylorus.The extract from the whole stomach contains both hydrochloricand lactic acids, but not more than 0.04 per cent. apparently. It alsocontains a very active ferment, which alters albuminous substances t opeptones, and so changes gelatin that it becomes easily diffusible andloses its properties. The ferment is sparingly soluble in water,glycerol, hydrochloric acid, or in alkaline solutions, and it is precipi-tated by alcohol, lead acetate, carbonate of magnesia, &c. It is onlyactive in presence of acids, and is destroyed by putrefaction andalcoholic yeasts. Lactic ferments do not influence its activity whenthe lactic acid is not too highly concentrated.Its activity is greatestic presence of 0.15 to 0.5 pel- cent. hydrochloric acid ; too much or toolittle acid impedes the action of the pepsin, much lactic acid in thestomach disturbs the digestion through irritation of the coating of thestomach.Pepsin must be present in certain quantity in the digestive fluid ;its activity increases according t o its quantity up t o a certain point,when further quantity is injurious. It works only in presence ofwater, and best at a temperature of 37" to 55" ; raising and loweringthe temperature disturbs the operation ; at 60" it becomes quite inert.Pure gastric juice contains rennet, lactic acid, fat and starch ferment,the two 1at)ter in unimportant quantity.The gastric juice of the horse does not dissolve cellulose, and withdifficulty the substance of bone or horn, but acks readily on muscle,sinew, fat, and flesh.Pepsin extract may be preserved for a longtime in weak carbolic or salicylic acid solution, and even in pureglycerol without losing its properties. J. F.Milk Secretion. By SCHMIDT (Bied. Centr., 1883, 382-386) .-The author, after reviewing much of the previous literature of thesubject, reports the result of his own investigations on the activity oft,he milk glands of the cow : the experimental animal was of Dutchbreed, middle aged, yielding 12 litres of milk daily. The experi-ments were conducted thus: 500 C.C. were taken from the two hinderspins of the udder at the commencement of the morning milking, andthe same quantity from the same spins at the conclusion of the milk-ing ; both were carefully anslysed according to the usual methods.Only the results of the first day's analysis are given, the others differ-ing slightly, if at all, and not affecting the author's conclusions.100 grams of the milk contained94 ABSTRACTS OF CHEMICAL PAPERS.First milk.Last milk.Total solids ........ 9.20 grams. 13.64 grams.Case’in ............ 2.24 ,, 2.11 ,,Albumin .......... 0.31 ,, 0.29 ,,Peptone .......... 0.10 ,, 0.12 ,,Pat .............. 0.76 .. 5.60 ,,Sugar ............ 5-08 ,, 4.92 ,,Ash ............. 0.69 ,, 0.66 ,,It wiil be seen that the difference between the total solids consistsalmost entirely in the fat, which is almost absent from the first milk ;this is explained by the theory that the fat corpuscles of the milkadhere to the walls of the ducts, and besides that in the udder itselfa certain separation takes place.The author had an opportunity ofexamining the udder of a cow killed immediately after milking, andfound that the ducts did actually contain a notable residue of richmilk.The fat excepted, the great body of milk secreted by a cow appearsto have a tolerably uniform composition, and the separation of the fatin the udder to be a mechanical operation, and that the whole of thefat is rarely obtained in the milking. J. P.Percentage of Fat in Milk of Cows of Different Breeds.(Bied. Cent,*., 1883, 285.)-Pnre Simmenthal gave 13 per cent.cream,after 12 hours’ standing ; Dutch, 7 per cent. cream, afier 24 hours,8 per cent.; cross between Simmenthal and Graabiinden, 12 percent., after 24 hours, 12.5 per cent. ; cross of Dutch and Simmenthal,9 to 9.5 per cent. ; pure Granbiinden, 13 per cent.; cross betweenDutch and Graubiinden, 10 per cent.By A. B. GRIFFITHS (Chem. News, 48, 37).-The author observed somepeculiar roundish masses of a dark-coloured substance in the anteriorportion of the liver of the cuttle fish ; some of these were collectedand examined. When ignited, they charred, and left an ash, whichcontained copper. The following are the results of observations madeunder the microscope : the masses were stained brown by a solutionof iodine in pota,ssium iodide ; potash dissolved them ; a red colourwas produced with Millon’s reagent; and nitric acid produced ayellow coloration, which was turned red by potash.On boiling themwith hydrochloric acid, a blue colour is formed, which changes to violet,and finally beconies brown. On heating them with solid potash,ammonia is evolved. By boiling a solution of the substance in potashwith lead hydroxide, lead sulphide is produced. From these resultsthe author infers that these masses are albumindid in character, andassuming them to be deposited from the secretion, it is evident thatthe secretion must contain albumin; and as the pancreatic fluid inhigher animals is one of the few secretions which contain solublealbumin, the author is of opinion that this investigation suppliesfurther support to the supposition that the liver of the cephalopod isnot a true liver, but is pancreatic in function.The copper is derivedE. W. P.Excretory Product from the Liver of the Cuttle FishPHYSIOLOGICAL CHEMISTRY. 95from the blood.superficial covering. D. A. L.The dark colour of the masses was a very thinBehaviour of Blood with Ozone, By BINY (Ried. Centr.,1883, 283).-The red corpuscles i n blood are unaffected by remainingfor an hour in contact with ozone, unless the quantity of blood issmall, or the duration of contact long; then a gradual change ofcolour and shape occurs. Oeonised air passed through blood is notcompletely altered. E. W. P.Cattle Disease occasioned by Town Sewage.(Bied. Cetitr.,18133, 285.)-The death of many cows was occasioned by fungoidgrowths in the grass of meadows irrigated with sewage.E. W. P.Observations on Different Diseases of Animals. By RQLOFFand others (Bied. Centr., 1883, 389-393).-Experiments were madeat the Veterinary School, Berlin, by RolofF, on the protective inocula-tion of cattle against lung disease. Two cows, two heifers, and twocalvcs were inoculated with the preparation and placed in infectedstables ; none of them took the disease, but neither did a non-inoculated animal placed in the same stable: the experiment wastherefore abortive. Opinions of other observers are cited OIL thequestion of protective inoculation against this particular disease.Pasteur finds that the specific poison cannot be cultivated in chickenor veal broth; that it preserves its vitality when kept at a hightemperature in a dry room, and does not produce micrococci, but that,when kept without such precaution, it does produce them and losesits vit,ality.If the poison is fouled by the addition of a few cow hairs beforeuse, it is harmless ; the portion kept at ordinary temperatures repro-duces itself in the inoculated animal, and lymph taken from thatanimal communicates it to others, After six to eight weeks fromtaking the poison from an infected animal, it loses its vitality : a calfinto whose jugular vein such old poison was injected, withstood it.The discovery of the bacillus of glanders by Lofler and Schutz is nextnoticed ; the rods were isolated from sections of a diseased organ, andcultivated in the blood of horses and sheep.It was tried on rabbits,mice, and guinea-pigs with success, but white mice did not take theinfection. The material used for inocula,tion was cultivated for eightto ten weeks, and then used on two horses, one two years old, theother 20 years. Both died with all the symptoms of virulentglanders in about 12 days.Pasteur and Thullier report the discovery of the microbe whichcauses swine fever, a disease by which, in the year 1882, farmers ofthe Rhone Valley lost 20,000 animals. The microbe is very minuteand liable to be overlooked even when the greatest care is used in itsobservation ; it resembles that of chicken cholera, and is of the form ofthe figure 8.Inoculation by a very small quantity communicates thedisease ; poultry are not affected, but rabbits die. The infection hasbeen cnltivat,ed and weakened, so as by its inoculation to protect swin96 ABSTRACTS OF CHEMICAL PAPERS.from fatal effects.sustained from this cause.cning in animals, horses and swine particula,rly.it to continued feeding on bran and other fodder poor in lime.Pasteur hopes scon to prevent the heavy lossesThe remainder of the paper relates to osteoporosis, or bone weak-Piitz attributesJ. F.Cattle Plague and Protective Inoculation. By KOCH andothers (Bied. Ceiitr., 1883, 394-398) .-Koch considers that Pasteur’smode of procedure is not quite correct, but liable to yield uncertainresults. He thinks that the bacilli of the disease are propagated inde-pendently of animals ; that they exist on dead vegetable substances,and probably on low marshy soils, on the surface of t’he earth ; andhe says that animals have been known to take the disease in suchplaces where no diseased carcases had been buried.He denies theageocy of earthworms in bringing the disease germs to the surface,for the plague appears in countries where the low temperature of thesoil does not permit the existence of earthworms. He also deniesPasteur’s assertion that the eating of the prickly fodder mounds themouth and facilitates the taking of the disease.The weakening of the poison, and the protection given by inocula-tion, has been successful only with horned cattle and sheep, and Kochdoubts if the lymph is as successful, even with those animals, asPasteur believes. The most carefully conducted experiments madewith it in Germany show a loss of 10 to 15 per cent. of the inoculatedanimals, and there is danger to men by its employment. Koch doesnot undervalue the researches of Pasteur, but wishes to point outdeficiencies in this particular case, which any day may be supplied.Instances are given of the deaths of sheep from plague, which hadbeen duly inoculated. Dr. Azary gives results of niimerous inocula-tions by Pasteur’s fluid in the neighbourhood of Buda Pest, chieflywith sheep, also with horned cattle and horses; some losses tookplace, but on the whole the operations were successful. Arloing andothers have experimented on the duration of the protective influence,and faund it lasted a t least 16 months; and that calves born ofinoculated cows were not liable to disease for some time after theirbirth. J. I?

ISSN:0368-1769    

DOI:10.1039/CA8844600091

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

96 ABSTRACTS OF CHEMICAL PAPERS.Chemistry of Vegetable Physiology and Agriculture.Occurrence of the Higher Fatty Acids in the Free State inBy E. SCHMIDT and H. ROEMER (Arch. Pharm. [3],The Fat of COCCUZUS indicus.-The fat which is contained in theseeds of this plant was dissolved in alcohol and precipitated with analcoholic solution of barium acetate, by which means the free fattyacids were separated from the glycerides with which they are asso-Vegetable Fats.21, 34-38)VEGETABLE PHYSIOLOGY AND AGRICULTURE. 97ciated in the original fat. After boiling for some time, the bariumprecipitate was filtered off, and when dry boiled with light petroleum.The nearly pure barium salt thus obtained was decomposed with hydro-chloric acid. I n this way 39 per cent.of free fattay acid was yieldedby the original fat. By this means and by repeated crystallisation ofthe original fat from alcohol, as well as by distillation under diminishedpressure, and also by partial precipitation with barium acetate, anacid was obtained which was recognised by analysis and physical pro-perties as stearic acid. The substance obtained from Cocculus indiczts,known as menispermin, was found by the authors to c0nsis.t of stearicacid.The Fnt of Myristica moschata.-This fat, commonly known as nut-meg butter, or oil of mace, contains from 3-4 per cent. of free fattyacid, which was separated by fractional distillation under diminishedpressure. At 248" the distillate, after recrystallisation from alcohol,yielded an acid, the formula of which was G14H2800,, agreeing in itsproperties with myristic acid.The distillate, which came over at ahigher temperature, was partially precipitated with barium acetate,and the acid which was recrystallised from alcohol, and analysed, gavenumbers agreeing with the formula GJ€&O2, and was identical inphysical properties with stearic acid.The Fat of Lawus n0biti.s.-This fat, when distilled under diminishedpressure, yielded a distillate, by the fractional precipitatlion of whichan acid was obtained, which appeared to be palmitic acid.Chemistry of the Nucleus. By A. KOSSEL (Bied. Centr., 1883,401-404).-T he regular relations between phosphoric acid and nitro-genous matters, which have been noticed both in vegetable andanimal cells, have given rise to the idea of a compound of albuminand phosphates or phosphoric acid.I n all the discussions on thesubject, it seems to have been overlooked that lecithin and nuclei'nare organic phosphorus-compounds, which are sufficient t o explainthese appearances. Among the products of their decomposition, theauthor found a body which had almost the identical percentage com-position of albumin. The usual mode of estimating nucle'in is by itsresistance to the action of pepsin, but the author considers this liable togreat error, and prefers a plan of his own. He found this phos-phorganic compound in the organs examined-in the spleen, liver,pancreas, kidneys, testicles, brain, embryonic and grown muscles ofanimals, pus, and in human dropsical and healthy blood.Accordingto experiments made with hens, doves, and yeast, the author regardsnuclein as a reserve material on which the organs subsist, or from whichthey draw supplies, to be incorrect ; he finds hypoxanthine and xanthineto be characteristic decomposition products of nucle'in, and guanineaccompanies them in many organs ; this by oxidation yields guanidineand urea. The fact that a substance exists in most animal organs,which furnishes urea by simple oxidation, he thinks important froma physiological point of view.W. R. D.J. F.Flowers of Rosa Centifolia. By NIEDERSTADT (Landw. VWSUC~X-VOL. XLVI. hStat., 29, 251--252).-Red roses were found t o contain 86 per cent'98 ABSTRACTS OF CHEMICAL PAPERS.of water, 3.64 per cent.nitrogen, and 3.5 per cent. ash ; in white roseswere found 91-7 per cent. water, 3-16 per cent. nitrogen, and 3.9 percent. ash. The composition of the ash-of each is given below :-Red roses.Potash.. . . . . . . . . . . . . . . . . . . 43-81Soda ....................... 1-12Lime.. .. . _ . ............... 6.02Magnesia .................. 6.2 7Ferric oxide and Alumina.. .. 1.05Phosphoric acid ............ 16.47Sulphuric acid . . . . . . . . . . . . 7-81Silica .................... 1.49Chlorine .................. 0.69Carbonic acid .............. 15-38White roses.42.051-538.056.411.9711-325.072 404.2817.83J. I(. C.Ash of Leaves of Plants Grown in the Earth under Water-culture: By C. COUNCLER (Landw. Vei-sz~chs.-Xtnt., 29, 241-245) .-Several samples of Bcer negundo were grown in a glass house, Nobbe’smethod of water-culture being used.The leaves were collected afterfalling, dried and analysed. At the same time leaves were carefullygathered from young trees of the same kind in a neighbouring wood,to compare with those obtained by water-culture. The percentage ofpure ash in the leaves varied considerably, nearly twice as much beingobtained from those grown by water-culture. In 100 parts ash w e ~ e - - iound-Wa.ter-culture.Potash .................... 45.52Soda.. .................... 0.58Lime.. .................... 14-92Ferric oxide . . . . . . . . . . . . . . 0.91Alumina ..................Phosphoric aci.d ............ 12-21Sulphuric acid.............. 18.30Silica .................... 4.00Magnesia.. . . . . . . . . . . . . . . . 3.55-Soil.33.910.6627.234.710.924-003.457.2917-85The leaves of the soil plants contained, therefore, nearly twice asmuch lime, and more than four times as much silica as those of theplants grown by water-culture, whilst the latter contain much largerquantities of potash, phosphoric and sulphuric acids. These dif-ferences are no doubt i n great part due to the soil in which the plantswere grown; i t is very rich in potash, but comparatively poor inphosyhat es. J. K. C.Examination of an Apple-must and of the Cider obtainedtherefrom. By R. KAYSER (Dingl. po7yt. J., 248, 347).-Borsdorfapples were cut into small pieces and pressed.The resulting mustwas then tested before and after fermentation. 100 C.C. gaveVEGETABLE PHYSIOLOGY AND AGRICULTURE. 99Must (filtered).- Alcohol ..............Extract .............. 16.2.5 g.Mineral matter (ash) . . 0.35Malic acid. ........... 0.33Acetic acid ..........Sugar .............. 12-50Pectins .............. 0.62Potash .............. 0.106Lime.. .............. 0.025Magnesia ............ Op018Phosphoric acid ...... 0-024-Sulphuric acid.. ...... 0.009Glycerol ............ -Cider.5-80 C.C.0.310 310.0800.750traces0.1050.0240.01800220.0080-6802.36 g.Tartaric and citric acids were not present : hence cider can be dis-tinguished from wine by the entire absence of tartaric acid, arid bythe larger amount of lime which it contains.By a judicious additionof tartaric acid or of wine containing much acid, a product can beobtained, which it would be difficult t o distinguish from real wine.D. B.Analysis of CLTobacco Stems" from Virginia. By C. G.MEMMINGER (Chem. News, 48, llO).-" Tobacco stems " consist of themidribs of tobacco leaves from which the membranous portions havebeen stripped. The analytical results are as follow :-In origi?zal substance. In organic matter.Moisture at 100". ....... 17.52 Nicotine .............. 1-30Total ash, excluding CO, 16.47 N as nicotine .......... 0.22COz determined ........ 6.87 N as nitrate.. .......... 0.45(CO, calculated = 6.73) N as. albuminojid (by diff.) 1.51r diff.) 59.41 -1 -- TotalN............ 2.18100~00organic matter (bjK20. Na,O.42.95 6-53In ash.CaO. MgO. A1203. Fe,O,.24.56 6.20 0.04 0.84 per cent.Mn,04. SiOp. P,O,. SO,. C1.0.09 6.18 4.80 3.10 6.04 per cent.D. A. L.Phylloxera. By HENNEGUY and others (Bied. Cenfr., 1883, 272-274) .-Henneguy found the galls on many American pines, especiallyY i n u s ripnria, and but seldom on native vines ; in large galls, severalyoung insects have been found besides the egg producers, and Hen-iieguy found thiocarbonate a good specific against the attacks.E. Cheysson approves of carbou bisulphide. A. Guillamont statesthat a mixture of 10 parts wood-ashes, 10 ferrous sulphate, and 2 cod-tar, is a good specific for destroying the phylloxera. E. W. P100 ABSTRACTS OF CHEMICAL PAPERS.Valuation of Fodder.By A. EBMERLING (Bied. Centr., 1853,252-255).-The relative value of albnminoi'ds to fat and to carbohydrates istaken as 5 : 5 : 1. Multiplying emh of these factors by the correspond-ing figures representing the digestible material in the food, we obtaina figure representing the sum of nutrient units. As a standard, ryeis employed thus : Albuminoids, 9.9 per cent. ; fat, 1%; carbohydrates,65.4, which figures, when treated as above, 9.9 x 5 + 1.6 x 5 + 65.4 x 1,produce 122.9 n. u. ; and, taking 8 marks per centner as the marketvalue of rye, 1 mu. costs 6.5 pfennigs. Employing this method thefeeding value of any material may be calculated; for example, inearth-nut cake we have albuminoids 45, fat 7, carbohydrates 25, ofwhich the digestible coe5cients are 90.9, 85.7, and 98.1 respectively,giving digestible matter present to the extent of 40.9, 6.0, and24.5. Then 4 0 9 x 5 + 6 x 5 + 24.5 = 259 n.u.; and having laiddown a table of the value of nutrient units for grain and other foods,which units vary according as the price of rye rises or falls, theauthor shows that when pye is at 8 marks the value of these 259 n.u.of earth-nut cake is 10.10 marks ; but this cake only costs 9 marks,consequently there is a gain in using it.A similar method is employedt o calculate thsvalue of foods for manures, employing in this casethe factors 0.5 for N, 0.2 for P205, and 0.1 for K20 : by this he showsthe manurial value of a centner of earth-nut cake t o be 404 marks,and this, with the exception of cotton-cake, is the most valuable of allfoods. E.W. P.Examination of Clover at different Stages of Growth. By5. P. KALLEN and A. STVTZER (Bied. Centr., 1883, 410-411).-Partof a series of experiments made in order to ascertain the period atwhich grasses contain most nutritive matter, with a view t o harvest-ing them at such times. A. field sown with red clover and differentgrasses, chiefly English rye-grass, was the subject of experiment: asquare meter was cut on 17th, 24th, 31st May, and 20th June, andexamined. The results are given in a table, and the recommendationis made to cut at the end of May or early in June. J. I?.New Fodder Plant. By F. T. (Bz'ed. Centr., 1883, 287).-Lavatera arboren Sields an oily seed, which after expression of theoil forms a good cake for cattle, and good fibre for paper making, rope,and cord.The plant is biennial, and crops well. E. w, P.Feeding Horses with Earth-nut Meal. By C. FREYTAG and€3 ECKE (Bied. Centr., 1883, 284) .-Earth-nut meal may well replacetwo-thirds of the oats generally given to horses.Storage of Acorns. By LODEMAN (Bied. Centr., 1883, 286).-Collect as late as possible, pile in heaps 30 c.m. high, cover withleaves and pine twigs ; in the spring remove the covering to retardgermination. E. W. P.By DIETRICH (Bied. Centr.,1883, 428) .-A considerable quantity of this article has lately beenE. W. P.Undecorticated Cotton-seed MealWCGETBBLE PHYSIOLOGY AND AGRICULTURE. 101sent from England to Germany; it is less valuable than the mealmade from the decorticated seed, and is of a dark colour. Twosamples had the following composition :-1.2.Protejid matter ............ 23.56 23.06Fat.. .................... 6.26 7-01Non-nitrogenous extract. ... 24.94 27.12Cellulose ................ 25.i3 25.53Mineral matters .......... 8.15 6.59Water.. .................. 11.36 10.69J. I?.Cultivwtion and Preservation of Potatoes. By MXRCKER andothers (Bied. Centr., 1883, 268-270).-Stappaerts removes all eyessave three, and by Betting only large sets obtains a higher yield,which ripens early. Marcker has preserved potatoes in a silo, whenthe nutrient ratio is increased by fermentation from 1 : 30 to 1 : 17.6 ;much of the albuminoid and amido-constituents are lost.L. Nagj-enumerates and classifies the sorts of potatoes ; he divides them into12 principal classes, with 30 sub-classes. E. W. P.Experiments OM Potatoes with different Manures. By E. ITT.PEwosrr and R. 8waNwIcs (Tyans. Highl. and Agr. Xoc., Scotland,1882, 283-299). - In these experiments the actions of “ bone,”‘‘ mineral,” superphosphates, and insoluble phosphates (85.5 per cent.Ca32P04) were employed, likewise an addition of ammonium sulphate,kainite, and potsshes to the phosphates was made, with the results ashereinafter stated. The potato employed was the Champion, and thesoil divided into plots of -&% acre, contained 62 per cent. sand, Al,O,8.114, K,O 0.764, N 0.39, NH, and P205 0.284; all the plots werein triplicate.The “ unaided ” phosphates produced nearly equalcrops, but the addition of 2 cwt. Am2S04 caused the bone supert o produce the highest yield obtained, viz., 12 tons 12 cwt., whilstthe blank plots only yielded 7 tons 4 cwt., and insoluble phosphatewith ammonia 9 tons 15 cwt. The addition of potash to the mixtureof “ super ” and ammonia, rather lowered the yield, and but littledifference was noticed when kainite or potashes were employed. Thishowever was not the case with the insoluble phosphate, for thenpotashes increased the yield by a tenth. Farmyard manure gaveonly a moderate yield. In the second portion of this paper arethe analyses of the potatoes as produced under the above conditions :the highest percentage of starch was found in potatoes grown withbone superphosphate, and taking the average of all the plots, itappears that the further addition of ammonia or kainite lowers thepercentage, which is however raised again by potashes ; but there isa great difference between the percentage of starch from the bonesuper plot and from the “ insoluble ” plot, the former being 25.6, thelatter only 21-96.The expenses of the whole experiments aredetailed, as also the value of the various crops, and we find thatwhether we judge the value of the manure by the total crop it yieldsor by the production of starch, the mixture of bone superphosphat102 ABSTRACTS OF CHENICAL PAPERS.with ammonia was the most satisfactory. The effect on the amountof nitrogen present is also detailed, not merely as total nitrogen, but asnitrogen in amides and in albumin ; ammonia increases the albumi-noYd nitrogen, but the increase is somewhat counteracted by potash,the unmanured plot containing least.The amides were likewiseincreased by ammonia (av. = 0.1399 N), but again kainite exer-cised a lowering action : an extraneous experiment is here referred to,which points to the conclusion that the amide nitrogen is muchdecreased as the ratio of potmh to " super '' increases. Phosphatesand ammonia produce the highest ash (1*31), whilst in the superphos-phate plots the percentqe is reduced almost to that found in theblank plot (0.995); this is in accordance with the results found byFleischer (Bied. Centr., 1880), what has been said €or ash holds goodfor fibre.Attempts were made to estimate the percentage of starchby the method recommended by Heidepriem (Landw. Versuchs.- Stat.,20), but they were fruitless, as the results were very far from thetruth, and Lherefore untrustworthy.Influence of Manuring on the Composition of Potatoes. ByX. MARCKER (Bied. Centr., 1883, 365-366).--Four plots of ground,each half a morgen loamy marl, on which barley and clover had beeniweviously grown, were planted with "alcohol" potatoes ; one plot wasleft unmanured, the other three each received 20 lbs. of soluble phos-phoric acid, and different quantities of Chili saltpetre, the first100 lbs., the second 200 lbs., the third 300 lbs. The yield per morgenwas-E. W. P.Unmanured plot. 100 lbs. 200 lbs.300 lbs.Centner . . . . . . 112.0 28.0 124.5 139.0the use 0% the saltpetre had therefore increased the gross weight ofthe crop, but the percentage of dry matter and starch did not cor-~espond, being-Dry matter . . .. . . 24-80 23.50 22.50 20.90Starch per cent. . . 7i.51 77.07 73.95 63.64the use of large quantities of saltpetre having reduced the net quan-tity of starch, the actual amounts obtained being-Plot 1. Plot 2. Plot 3. Plot 4.21.58 23.18 20.74 18.43 centner.J. F.Artificial Manures in Potato-growing. By S. GURADZE ( R i dCentr., 1883, 377--379).-The author reports five experiments as tothe effect of different chemical manures on the growth of potatoes,combined in different proportions ; they consisted of a newly intro-duced potash magnesia (containing 50 per cent.potassium sulphate,and 34 per cent. magnesium sulphate) superphosphate, and Chilisaltpetre. All the experimental plots but two received a considerablequantity of stable manure, in addition to the artificial. The cropswere in all cases exceptionally good, and the plants healthy ; the proVEGETABLE PHYSIOLOGY AND AGRICULTURE. 103portion of starch in the tubers good, and the value of the increasedproduction repzying the extra cost of the manures employed. Theauthor strongly recommeuds the use of artificial fertilisers in thegrowing of potatoes. J. F.Manuring Experiments with Rye and Wheat. By M.M~RCKER (Bied. Centr., 1883, 373--377).-The first experimenhnoted were made with rye, on a good sandy soil, in order to observethe effects of phosphoric acid in bone-meal and in purely mineralphosphates, blood-meal being added t o the latter equal t o the nitrogenin the bone-meal.The quantity of phosphoric acid used was10 kilos. per morgen, applied in autumn. The experiments werecarried out by five farmers, independently of each other ; the resultswere slightly in favour of the mineral phosphate with blood-meal.Steamed bone-meal produced good crops, the net result of the experi-ment being that a nitrogenous manure mixed with phosphate is mostuseful. Similar experiments were made on light and poor sandy soilswith a different result, the steamed and fermented bone-meal givingthe best crops, the other manures not repaying the extra cost. Certainplots of wheat were manured with Chili saltpetre, and others withammonium sulphate, with a view of testing their manurial value.The manures were applied at different periods, the Chili saltpetre wasfound greatly superior, aud the superiority was most marked when itwas applied in May.The yield of both1 grain and straw was con-siderably larger than from all the ohher plotsl J. F.Manuring Vines. By A!.. STUTZER (Bied. Creibtr., 1883, 381-382).--Vineyards in the Ahrthal have generally been manured with stablemanure. The author found that a compost containing 7 per cent.soluble phosphoric acid, 6 per cent. potash, and 2 i to 3 per cent.nitrogen, applied in 100 gram doses to each vine, produced an averageincrease of 20 per cent. grapes more than the stable manured plants,and that the must was also richer in sugar.The cost of the manuremd labour was not greater than that of the stable manure employed ;the wood of the vines was stronger and healthier. J. F.Manuring Beet. By EOLDEFLEISS ( B e d . Centr., 1883, 380-381).-The author recommends a moderate use of stable manuresupplemented by Chili saltpetre as being most suitable for the fullproduction of sugar in the beet. Manures which are too rich innitrogen, such as sheep dung, or even too much Chili saltpetre, aredecidedly injurious. In the absence of stable manure, a mixture ofsuperphosphate with the saltpetre should be employed.Influence of Soil, Size of Seed, Period of Sowing, &c., on theQuality and Yield of Sugar-Beet. By G.MAREK (Bied. Cenir.,1883, 263-268).-The weakest growth was in sandy soil, better onsandyloam, strong on clay and humous sand, and luxuriant on moor-land; as regards the leaf growth, this was most abundant on thehumous soil, and this class of land also is most suitable for n heavycrop ; but the opposite is the case as regardssp. gr. of juice, for thereJ. F104 ABSTRACTS OF CHEMICAL PAPERS.the clay lands are most advisable, and this is true for the percentage ofsugar : the size of seed is not of much importance. The highest yieldis obtained when the c ~ o p is put in between the middle of April andend of May. It is advisable on all accounts to sow on the flat with40 : 20-25 cm., and on the ridge distance 45 : 20-25, and thehighest results, both yield ,and sugar, are obtained by sowing on theridge by Bertel's method, which consists in throwing up ridges 44 cm.apart, rolling them, and employing a combined manure and turnipdrill.E. W. P.Ammonia in Rain-water. By HOUZEATJ (Bied. Centr., 1883,425) .-The principal agents which increase or diminish the amount ofammonia are light and heat. In July the observer was not ableto detect even a trace of it in rain-water. He found that waterexposed to the action of sunlight for a long time lost a large part ofits ammonia. The amount of rainfall also has an influence; thesmaller the amount the more ammonia it contains. J. F.Origin of Combined Terrestrial Nitrogen. By A. M ~ ~ N T Zand E. AUBIN (Conzpt. rend., 97,240-243).-The principal source ofcombined nitrogen appears to be nitric .acid and oxides of nitrogen,formed by the action of atmospheric electricity on the nitrogen in theair.The main causes producing a diminution in the amount of com-bined nitrogen are, rapid combustion, which operates only to a limitedextent ; slow combustion, which is the most important cause of all ;and the yeduction of nitrates in water and soils, which plays a veryinsignificant part. I n order to ascertain whether these increasing anddiminishing forces are in equilibrium, it is necessary to determine theamount of nitric acid in the rain-water on different parts of the earth'ssnrface, and especially in tropical regions. The accurate estimationof nitrates can be performed only in a properly appointed laboratory,and it is advisable therefore, to collect the samples of rain-water insuch a way that they can be transported to a distance.The authorsrecommend to evaporate the rain-water to small bulk with potassiumhydroxide, out of contact with air and products of combustioil. Theconcentrated liquid is mixed with alcohol, and the authors find thatin this condition it may be preserved for any length of fime withoutundergoing any alteration. To apply this method to river water, &c.,3-45 litres of the water are evaporated to about 30 c.c., and mixedwith 60 C.C. of alcohol.Many cases of rapid combustion are accompanied by the formationof considerable quantities of nitric acid. The authors fiud that when1 gram of hydrogen burns in air, 0.001 gram of nitric acid is pro-duced, whilst the combustion of 1 gram of magnesium is accompaniedby the formation of 0.1 gram of nitric acid.It is probable, therefore,that a large quantity of nitrates were formed in the earlier stages ofthe earth's history during the process of cooling, and the luxuriantdevelopment of animal and vegetable life in prehistoric times waspossibly due to the presence on the earth's surface of a large quantityof combined nitrogen in an assimilable form. It would appear, there-fore, that the total amount of combined terrestrial nitrogen is graduallVEGETABLE PHYSIOLOGY AND AGRICULTURE. 105diminishing, unless the sources of loss are balanced by the action ofatmospheric electricity. C. H. B.By SCHULTZ and others(Bied.Centr., 1883, 232-243) .-Schultz considrers that the cultiva-tion of lupines is the cheapest method of supplying the soil withnitrogen, as they abstract this constituent from the air. According tohis experiments a soil in which lupines had grown showed an amountof nitrogen double that in grass land, and more than that found inpotato and rye land. According to Schultz all that is necessary for a,good crop of lupines is the addition of kainite ; phosphates do not givea satisfactory result. Drechsler criticising Schultz’s statements, showsthat lupines do not add nitrogen to the soil, but rather, like all large-leafed crops, even when they draw their supplies of nitrogen from thesubsoil, are consumers of nitrogen instead of collectors, and he alsoconsiders that the Lupitz system, unless nitrogen is added to theland, cannot last.Blomeyer’s opinion is that the leguminose are‘‘ nitrogen collectors,” and for this reason, that they keep the surfaceof the soil moist, and so prevent the volatilisation of ammoniacalcompounds. Marcker is unable to answer the qnestion whence theexcess of nitrogen which is present in the Lupitz soil is derived, for6751bs. N have in 15 years been withdrawn, and only that nitrogenadded from the usual natural, viz., t’he atmospheric, not artificialsources. It is possible that the deep rooting lupines may separatenitrogen from solutions which are too dilute for okher plants, and theretention of nitrates on the surface soil may be due to the shelterafforded by the foliage, preventing loss by rainfall.He believes thatby the continued use of kainite the nitrogen in time will be lost, andthat though phosphates are now useless, they will hereafter berequired; in the 1 5 years 3.000--2000 kilos. lime per hectare havebeen removed, by reasdn of the potash manure, so that this consti-tuent will before long be required, Marcker believes that potassiumchloride as carnallite is a better manure than the sulphate as kainite.The Lupitz Method of Cultivation.E. W. P.Moss and Turf Fibre as Cattle Litter. By M. FLETSCHER andothers (Bied. Centr., 1883, 368--373).-The use of so-called “ mosslitter ” obtained from certain bogs in Northern Germany has becomevery general. The authors of this paper have examined samples ofordinary fibrous peat, separated artificially, and intended as substitutesfor the former, one sample procured from Wiirtemburg, the otherfrom a Silesian bog.They found that air-dried samples containing20 per cent. of moisture, absorbed 6g-95 times their weight of water,and their power of absorbing carbonate of ammonia for 1000 parts ofmoss, 13-16 parts of ammonium carbonate.1000 partsof each contain -The manurial value of the different samples is given.Wiirtemburg Silesian North Germanfibre. fibre. moss.Nitrogen . . . . . . . . 22.0 parts 29.0 parts 9.0 partsPhosphoric acid.. 0% ,, 0.6 >, 0.4 ,9Lime , . . . , . . . . . 17.2 ,, 31.0 ,, 2-0 ,106 ABSTRACTS O F CHEMICAL PAPERS.The two samples of fibrous turf are consequently much morevaluable as manure than the moss ; and containing much lime, theirnitrogen is probably more readily decomposed, and available for plantnutrition.Analysis of turf fibre employed as absorbents in public and privatemiddens in Bremen, and in horse stables, yielded the following results,calculated to 1000 parts of the dry substance :-Public Privatelatrines.la trines. Stables.Nitrogen.. ...... 46.6 27.8 17.3Mineral matters.. 118.8 ? 167.0Potash.. ........ 23.3 9.3 7.9Phosphoric acid.. 18.7 10.6 7.0The samples were free from smell, and although containing a con-siderable amount of moisture, formed a compact and portable mass.The remainder of the paper is occupied with experiments on variouscrops with the moss after being used as litter, and in all cases theresults were satisfactory.J. I!.Sea Mud. By M. FLEISCHER', A. KONIG, and B. KISSLING (Bied.Centr., 1883, 243--250).-3hd is deposited at the mouths of mostrivers, which it is advantageous t o the harbour authorities andto the farmer to remove. Analyses show that with but slightvariation the deposits are of the same composition, the principalvariant being sand. This mud when exposed to the air dries to afirm compact and plastic mass, and at the same time that it loses water,it also diminishes in volume ; in one case the ratio of loss of wat,er toloss of volume was 1 : 0.55. The changes effected by long storageare of considerable importance to the agriculturist, for the physicalcharacter changes, the mud becoming more pulverulent, and conse-quently more easily applied to the land, and this is especially the caseafter frost; also water being lost and volume reduced, transportexpenses are lowered, chloimdes are lost, ferrous oxide and sulphidebecome oxidised, plant and animal remains become more decomposed,and but little, if any, nitrogen is lost.Further changes are inducedby frost and thawing, for the dry matter is raised from 45-6-6546 percent., and the whole becomes still more friable, and a higher per-centage of soluble sulphate and lime is obtained. E. W. P.Destruction and Utilisation of the Bodies of Animals whichhave Died from Contagious Diseases, especially from Anthrax.By A. GIRARD (Cowpt.. r.e?zd., 97, 74--77).-The body, withoutremoval of the skin, 6s dissolved in tlhe cold in concentrated sulphuricacid of about 60".Complete solution1 takes place with comparativerapidity, and the acid can be used repeatedly until its degree of con-centration is diminished to 43". Direct experiments have proved thatall germs are destroyed in the process of solution. The acid liquidobtained contains a considerable proportion of nitrogen, and has thepower of readily attacking natural phosphates yielding highly nitroVEGETABLE PEYSJOLOGY AND AGRICULTURE. 107genous superphosphates. A layer of fattymatter floats on the surfaceof the acid solution, and may be removed and purified.C. H. B.Guano recently discovered in Australia. By A. B. GRIFFITHS(Bied. Centr., 1883, 427).-The following is the analysis of twosamples :-No.1. No. 2.Nitrogenous organic matterand ammoniacal salts .... 46.72 4G73Phosphoric acid .......... 15.02 15. LOLime .................... 18.00 17.99Alkaline salts ............ 1.42 1.41Sand .................. 2.71 2-71Water .................. 15.92 16.0799.79 100*01--J. F.Manurial Value of Sewer Slime. By M. FLEISCHER (Bied.Centr., 1883, 426--427).-1n Brernen several sewers connected withhouses, and containing much urine, are led into a small stream with agentle fall ; the solids precipitate, and are removed for agriculturalpurposes. An analysis of a sample yields the following :-With 45 perDry. cent. of water.Potash.. .............. 6.3 3.5Lime ................ 17.2 9.5Phosphoric acid ........8.0 4.4Total nitrogen. ......... 11.6 6.4The reaction is acid, and it contains soluble iron salts ; ignited in aplatinum capsule sulphurous acid is evolved. The wet material whenheaped up yields a drier mass of 50-60 per cent. ; it must be exposeda, long while t o the air in consequence of the sulphur compounds.Another sample drawn from a pond into which the night soil froma part of the city was for a long time allowed to flow. This samplealso gave an acid reaction. The addition of hydrochloric acid causesevolution of sulphuretted hydrogen.This sample yielded in 1000 parts-Water ..............Combustible matter . .Nitrogen ............Insoluble in HC1.. ....Potash ..............Soda ................Lime ................Magnesia ............Iron and alumina ....Phosphoric acid......Sulphuric acid ......Fresh.F89-7027.201.4654.250.980.34191-1-3518-250.523.65Dried at 100".I251.013.2498.88.93-117.312.2165.54.733.1J. F108 ABSTRACTS OF CHEMICAL PAPERS.Constituents and Properties of some Water Plants. ByNIEDERSTADY (Landw. 7ersuchs.-Stat., 29, 247-250).Strntiotes a1oides.-The use of this as manure has been followed byexceedingly good results, bekter in fact than with any other ordinarymanure. Analysis of the ash shows that it is very rich in alkalis andphosphates. I t contailis 19.5 per cent. of ash, and 15.7 per cent.protejin. I n the ash was found 14.2 per cent. soda, 15.9 per cent.potash, and 11.4 per cent. phosphoric acid..Nymnphcea aZba.-The leaves of this plant yielded 11.1 per cent.of ash, consisting chiefly of alkaline chlorides and calcium carbonate,and the same may be said of the ash of the leaves of Nuplzay lutez6na.The flowers of these plants contained large quantities of chloride andphosphate of potassium.Kainite as Potato Manure. By M. FLEISCHER (Bied. Centr.,1883, 366-367).-These experiments were made at the inst'ance of theCentral Moor Commission, in order to learn the effects of early andlate applications of kainite to potatoes. Four plats were manuredwith precipitated phosphate and Chili saltpetre ; t o one no potashsalt was applied; No. 2 received kainite in September; No. 3 kainitein December, and No. 4 immediateIy previous t o planting, the effectof the kainite was remarkable, the average of the crop taken off thethree plots on which it was used, being three times as great asthat from the other plot. The yield of the three plots treatedwith kainite was nearly alike, but the flavour of the Septembermanured plot was best ; the yield of starch, however, determined byKonig's sp. gr. method, was :-J. K. C.September plot. December plot. At sowing.100 67 64Similar experiments were made by Wild% in 1882. The time ofapplying the kainite did not appear to affect the gross weight of thecrop, but the starch percentage was greatly diminished by late appli-cations. When the kainite was applied at the under-mentionedperiods the net yield of starch and its proportion, taking the highestfigure as 100, were :-Pour weeksAutumn. Early spring. before planting. At planting.Centner .. 20.9 18.8 18.1 17-5100 90 87 84The author ascribes the loss of starch to the presence of chlorides.J. P

ISSN:0368-1769    

DOI:10.1039/CA8844600096

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY.A n a1 y t i c a1 C h e m i s t r y .109Estimation of ChIorine, Sulphurie Acid, and Chromium inPresence of Organic Matter. By C. T. POMEROT ( C h m . News,48, 41-42).-To determine these substances in the presence oforganic matter, it is first of all necessary t o remove the latter byignition with an alkaline carbonate and nitrate ; some of the nitrateis thereby reduced to nitrite, which, during subsequent operations,reduces the chromates, and interferes with the estimation of chlorine ;moreover, if the sulphuric acid is precipitated in this solution, thebarium sulphate always retains chromic oxide. To obviat'e thesedifficulties the mass from the fusion with alkaline carbonate andnitrate is dissolved and filtered ; potassium nitrite and nitric acid inexcess are added to the filtrate, which is allowed to stand 12 hours inthe cold.'On adding ammonia and boiling, the chromium hydroxide isthrown down ; i t should be filtered off hot, washed with hot water,and estimated as usual. The sulphuric acid is precipitated from thefiltrate from the chromium hydroxide by means of barium nitrate,and the chlorine estimated in the filtrate from the barium sulphatein the usual way. In theanalysis of ordinary chrome yellow, even the lead passes entirely intosolution when snfficient sodium nitrite and nitric acid are added,and the mass boiled..The published results agree very well.D. A. L.Formation of Methylene-blue as a Reaction for HydrogenSulphide. By E. P~SCHER (Ber., 16, 2234--2236).-To test forhydrogen sulphide in aqueous solution, the latter is treated with one-fiftieth volume of concentrated hydrochloric acid, a few grains ofparamidodimethylaniline sulphate are added, and when this is dis-solved, 1-2 drops of a dilute solution of ferric chloride.In the caseof a solution containing 0.00009 gr. hydrogen sulphide in a litre ofwater, coloration took place in a few minutes, and in half an hour theliquid had assumed a strong blue colour, which lasted for days. Asolution of the same strength, but without hydrochloric acid? yieldedonly a light brown coloration with lead acetate. In a solution con-taining 0.0000182 gr. hydrogen sulphide in a litre of water, themethylene-blue reaction still gave a distinct blue coloration, whilst noeffect was produced either by lead acetate or sodium nitroprusside.This reaction is recommended as the most delicate and certain testf o r neutral or acid solutions of hydrogen sulphide.Paramido-dimethylaniline is most conveniently prepared from commercialhelianthin, Me2N.C6H4.N : N.C,H,.SO,H ; this is finely powdered,mixed with 5 parts of water and an excess of ammonium sulphide ;the mixture is frequently agitated, and when (after about 24 hours)the reduction is complete the amidodimethylaniline can be extractedwith ether; the ethereal solution is then agitated with a little whitelead suspended in water, and the filtrate treated with an etherealsolution of concentrated sulphuric acid. The ether is separated fro110 ABSTRACTS OF CHEMICAL PAPERS.the crystalline sulphate, and this is heated with absolute alcohol untilit is converted into slender white needles, which after being washedwith alcohol can be pressed and dried on a water-bath.A.I(. M.Volumetric Estimation of Phosphoric Acid. By G. C.CALDW ELL (Chern. Netus, 48, 61-62).-The author finds Pemberton’smethod (Abstr., 1882, 1318) efficient ; he has introduced an improve-ment to facilitate the final test filtrations. A test-tube is fitted witha double-bored cork, through which pass two tubes, a short onebent at right angles and a longer one bent at a convenient anglefor introduction into a beaker; the bore of the tube is 1 mm., theend of the longer one has a conical enlargement or mouth with adiameter of 5 mm.To prepare the apparatus for use a perforatedplatinum cone is fixed in this mouth, and while suction is applied tothe short bent tube, the mouth of the tube with the cone is justdipped into very thin asbestos pulp and then into water, the suctionbeing continued until the water comes through quite clear. Theapparatus is now ready for use; suction is again applied, the filterdipped into the liquid to be tested, and when the desired quantityof filtered solution is obtained, the filter is withdrawn ; the suctionmust be sustained all the time to prevent the cone and asbestos fromfalling out, The liquid is treated in the test-tube, and then returnedt o the beaker. Before the next test is made the filter and tube arewashed by a small quantity of the liquid, which is drawn through thefilter and returned to the beaker.D. A. L.Quantitative Separation of Potash and Soda from FerricOxide, Alumina, Lime, and Magnesia in Silicates. By W.KNOP (Chem. News, 48, 110-111). The new method is based onthe formation of alkaline silicofluorides insoluble in acidulatedmixtures of alcohol and ether, by the combined action of hydrochloricand hydrofluoric acids on silicates. When the alkalis are in excessit is necessary to add silica before treatment with the acids.The weighed substance, mixed with a small quantity of water, and,if necessary, silica also, is treated, in a platinum capsule, with fuminghydrofluoric acid, evaporated to dryness, treated with strong hydro-chloric acid and absolute alcohol, and after some time with excess ofether.In 12 hours’ time the silicofluorides are filtered off, washedwith alcohol, dried, and removed from the filter, which is incinerated.The ash and the precipitate are mixed together in a crucible withconcentrated sulphuric acid, and as soon as the evolution of siliconfluoride ceases the crucible is ignited at a low temperature, so as t oleave the alkalis as acid sulphates. The mass is treated wit.hammonia, evaporated to a paste, rendered alkaline with ammonia, andafter an hour, to ensure complete separation of iron and alumina, istreated with ammonium carbonate solution and left for 12 hours.The iron, alumina, lime, and magnesia, are filtered off and washed withammonium carbonate, &c. The filtrate is evaporated to dryness-a,quantity of ammonium hydrogen tartrate equal to the ammonium sul-phate present being added t o prevent spurting-and ignited.ThANALYTICAL CHEMISTRY. 111residue is taken UD with wat,er, tested with ammonium carbonate foriron, &c., and the Lsolution is then evaporated to dryness aud weighed.D. A. L.Methods of Analysing Columbates by means of HydrofluoricAcid. Separation of Thoria from the other Oxides. Estima-tion of Didymium. By J. L. SMITH (Chem. News, 48, 13-15 ; 29--31).-After a review of the work done on this class of minerals byRose, Herniann, Marignac, &c., the author observes that they havespecial interest, because there are always some of the rarer earthsassociated with them, and the reasons amongst others which haveprevented their being more perfectly studied are, firstly, the scarcityof the minerals, and secondly, the difficulty attached to the process ofdecomposing them.The first obstacle was removed by the discoveryof large quantities of columbite and samarskite in the United States,and the second is set aside by the methods described in this paper.I n a previous communication (Amer. J. Xci., 1877, 360), the authorhas described these minerals, columbites and tantalites from theUnited States, both as regards their mineralogy and their chemicalcomposition, but owing to the defects in the manner of working, hecould neither give the relative proportions of columbic and tantalicacids, nor could he detect conclusively cerium or thorium.All doubton this head has been dispelled hy the use of his new method.Analysis of Xamarskite (and other Columbcites containing EarthyOxides).-5 grams of the finely powdered mineral dried a t 150” (lossby ignition is determined in a separate quantity) are placed in aplatinum capsule (50 C.C. capacity is sufficiently large) moistened withwater and treated with 4 to 5 C.C. of concentrated hydrofluoric acid ;after two or three minutes, a second and similar quantity of this acidis added, and the whole well stirred; vigorous action soon sets in,and in 5 or 10 minutes all black specks have disappeared, showingthe decomposition to be so far complete. The capsule is now heatedon a water-bath ; the contents consist of a clear solution (A) contain-i n g the metallic acids, iron and manganese, and an iusoluble portion (B)containing the earths and uranium oxide.These two parts are butvery slightly intermixed. The contents of the capsule are mixed with30 C.C. of water, warmed, filtered on a gutta-percha or silver funnel,the filtrate being received in a platinum capsule, and washed with hotwater containing a few drops of hydrofluoric acid. The solutiou isevaporated over a water-bath, and before it is dry, is treated withexcess of concentrated sulphuric acid to decompose the fluorides ; itis heated until nearly all the sulphuric acid is driven off, and whencool is washed into a glass flask and boiled with very dilute hydro-chloric acid. The whole mass is then filtered and washed with hotwater.The precipitate, consisting of columbic, tantalic, and small quan-tities of tungstic and stannic acids is dried, ignited and weighed ; sub-sequently the tungstic and stannic acids are separated in the mannerrecommended by Rose, and the columbic and tantalic acids by Marig-nac’s method. The filtrate contains iron and manganese, which areestimated in the iisual manner. The insoluble portion is washed intoa platinum capsule, treated with a sufficient quantity of concentratedsulphuric acid to decompose the fluorides, heated carefully until nearl112 ABSTRACTS OF CHEMICAL PAPKRS.all the snlphuric acid is driven off, and when cool is warmed with50 C.C. of water, in which all dissolves to a green solution, exceptperhaps a very minute quantity belonging to portion A.The greensolution is heated, and after the addition of a little nitric acid, ispoured into a beaker and made up t o about 250 C.C. with water. Itis now nearly neutralised with ammonia, and the earths precipitatedwith ammonium oxalate or oxalic acid. After six or eight hours, theearthy oxaZates (C) are filtered off and washed. The soIution contaJnsall the uranium with a trace of iron ; both are estimated ; the iron ispraecipitated as sulphide, and the urmium estimated by the ordinarymethod. The earthy oxnlates are dried, ignited, and weighed. Thepowder, which is of a pale yellow colour, is dissolved in nitric acid,evaporated to a syrup, and before it solidifies is mixed with a con-centrated solution of sodium sulphate, and subsequently small crystalsof the sulphate are added (50 C.C.o€ the solution and 4 grams of thecrystals for 1 or 2 grams of mineral), a precipitate (D) soon begins toform. After 24 hours it is very abundant and is filtered off and washedwith concentrated sodium sulphate solut,ion. The filtrate containingyttrium and erbium is treated with oxalic acid or ammonium oxalate,the precipitated oxalates ignited, redissolved, reprecipitated, ignited,and weighed. The oxides are dissolved in dilute sulphuric acid,evaporated carefully, and heated until the weight is constant: thenfrom the weight of oxide and of sulphate, the relative prnportion ofyttria and erbia is found by Bahn and Runsen’s formula. The sodiumsulphate precipitates are separated by fractional precipitation ; theyare washed with solution of t,he salt, dissolved in very diluted hydro-chloric acid, nearIy neutralised with ammonia, precipitated byammonium oxalate, ignited, redissolved, reprecipitated, and weighed.No cerium was found in the first precipitate, but instead a darkoxide soluble in very dilute nitric acid, which the author calledmosandrnm oxide.In the precipitate D are found the other ceriumoxides and tthoria. After being treated in the usual manner with hydro-chloric acid, ammonia, oxalic acid, &c., and ignited, the msultingoxides dissolved in dilute nitric acid, thus again showing absence ofcerium oxide. This fact was now confirmed by treating tjhe nitricacid solution with caustic soda and chlorine, no indications of ceriumwere obtained, all the oxides passing into solution with the exceptionof a small quantity of thoria, which forms 0% per cent.of the mineral.Some experiments were now conducted on a large scale, lead vessels,capable of working more than a kilo. of mineral a t a time, were em-ployed instead of platinum ones, The conduct of the process is thesame as described above, the earthy fluorides are decomposed withsulphuric acid, &c., and after the separation of uranium oxide, &c.,the solution is boiled up with steam, nearly neutralised, and the oxa-lates precipitated. The yttria is separated as above described ; thethoria can be separat,ed quantitative1.g by treating the solution withlarge quantities of soda and passing chlorine f o r two or three hours asabove described, or less completely by dissolving the mi-ths, separatedby the sodium sulphate, in nit& acid, concentrating the solution on awater-bath, diluting abundantly, boiling with a current of steam, andadding sufficient ammonia t o the boiling solution to precipitate about ANALYTICAL CHEMISTRY.113of the oxides present. The gelatinous precipitate containing all thethoria and a little of the other oxides, is filtered off, washed, and dis-solved in dilute sulphuric acid ; this sulphate of thoria can be easilypurified by the usual methods. The filtrate from the thoria containeda mere trace of thoria,, and no lanthanum, therefore the only oxide ofthe cerium series to be looked for was didymium, which the authorrecognised by the spectroscope.Quantitative E s t i m a t i o n of Didytn ium.-Solutions of didymum oxideof known strength are placed in tubes of uniform diameter, these arecompared before the spectroscope with similar tubes containing anitric acid solution of the oxides to be tested, until the bands pro-duced by the tubes correspond in intensity ; the author in this mannerarrived at the quantity of didymium in solution.From these resultsit is evident that the samarskite examined by the author containedthoria, and other mixed oxides in place of the cerium oxide.Columbite and tantalite are more difficult to decompose thansamarskite. They must be very finely pnlverised ; to effect this withtantalite, the powder in the mortar is covered with (95 per cent.com-mercial) absolute alcohol, and the t rituration coutinued under thesecircumstances. The trituration of 1 gram of columbite requires a quarterof an hour; 1 gram of tantalito 20 minutes. They are then decom-posed by heating with hydrofluoric acid of the usual strength used bythe author, and treated as described above. D. A. L.Dialysis of Arable Land.' By A. PETERMAN (Bied. Centr., 1883,36 1--364).-The employment of strong mineral acids in the analysisof soils has led the author to think that substances pass into solutionand are estimated, which under the ordinary conditions of cultivationare not attacked, and are useless to the plant. He has, therefore,tried a system of dialysis with distilled water, which he believesfollows better the processes of nature. The dialyser employed wassomewhat, but not materially different from the ordinary apparatus.It was found that after a dialysate of 10 days, not only the soluble' salts but a notable proportion of organic matter had passed into thedistilled water, colouring it yellow, yielding a dark brown residue aftercautious evaporation, and a carbonaceous residue on ignition.This sub-stance is different from the matiire noire of Grandeau, which does notpass through parchment,-paper. The author refers to old experinientsof Risler made in 1858, showing that plants derive a portion of theircarbon from the soil, and not entirely from the atmosphere.J. F.Titration of Copper by Means of Potassium Cyanide. ByJ.J. and C. BERINGER (Chem. News, 48, lll-l13).-The authorshave studied some of the conditions which affect the accuracy of thismethod for the determination of copper, and publish the results, &c.,in this paper.E f e c t of Manizer of Workin.q.-The result is not so much affectedby the time occupied in the entire titration as it is by the rate withwhich the last 2 or 3 C.C. are run in. The manner of finishing is,therefore, of paramount importance; and in order to obtain con-cordant results, a fictitious finishing point must be adopted.VOL. XLVI. 114C.C. Cyanide required . .Do. in presence of soda. .ABSTRACTS OF CHEMICAL PAPERS.With With With WithWithout' chloride. sulphate. nitrate. carbonate.24 *2 25 *7 25-7 25 .6 25 -625 '6 26.75 26.7 26-76 26.4------- --- -----Efect of Variations of Temperatwe.IC.C.Ammonia added.. 0c.c.Cyaniderequired.. 21.8----~ ~ ~~Temperature in C. 10". 20°. 30". 47O.-----_I--------C . C . Cyanide required . . . . . . . . . . 1 23.5 ! 23.3 I 23.05 I 22.85----------lo 1 2o 30 I 50 loo2 522.5 22.8 33.0 23.3 23.4 23.7 24.2- ~~Efect of Ammonium Xalt.Grams AmN03.C.C. Cyanide required..0-___________---24 '2 24 -6C.G. Cyanide 24.9 { required.Efect of Alkali Xalts.With Withsodium sulphatc. chloride.--.------,-24 -90 24 *9525 *05 25 *OO25 '10 25 '10C.C. Soda. 0C.C. Cyanide required . . 25.8Withnitrate.1 5 10 20 5026'0 26.4 26.9 27-25 28-__-------------24.9024 '9024 *9ANALYTICAL CHEMlSTRY. 115these may be summed up thus ; when the copper, ammonia, and volumeof liquid vary, but retain their relative proportions, the quantity ofcyanide used is proportional to the copper present.If, however, thecopper and volume are constant, whilst the ammonia increases, morecyanide is required. On the other hand, if the ammonia and copperare constant, whilst the bulk increases, less cyanide is necessary.Hence the authors inferred that by adding water and ammonia inproper proportions these errors might be got rid of. They have em-ployed successfully 15 C.C. of 0.880 ammonia to each 300 C.C. of liquid,in slightly alkaline solution, titrating with the necessary precau-tions. D. A. L.Colorimetric Estimation of Gold. By A. CARNOT (Co~zpt.rend., 97, 169-170.(See below.)New Reactions of Gold. By A. CARNor (Compt. rend, 97, 105-108).-A dilute solution of auric chloride is mixed with a smallquantity of arsenic acid, two or three drops of ferric chloride solution,and the same quantity of hydrochloric acid diluted with 100 C.C. ofwater, and a fragment of zinc are added. A purple colour is soon deve-loped in the neighbourhood of the zinc, and on agitation the liquidacquires a rose or purple tint. The same colour is also immediatelyproduced if, instead of zinc, the solution be mixed with a few dropsof an acid solution of ferrous chloride, or of the solution obtained byacting on metallic iron with arsenic and hydrochloric acids. This re-action succeeds with less than 0*0001 gram of gold in 100 C.C. ofwater.With phosphoric acid in place of arsenic acid, a violet orbluish coloration is obtained. Hydrochloric acid alone gives a lessintense rose coloration. Hydrogen gas, mixed with small quantitieso€ hydrogen sulphide, may be used instead of zinc or ferrous chloride.The rose o r purple liquid is perfectly transparent, can be filteredwithout being decolorised, and is unaltered at the end of threemonths. It is, therefore, a true solution, and is not a liquid holdingfinely-divided gold in suspension. If the solution is not distinctlyacid, or if it be mixed with certain salts, especially ammonium salts,a flocculent purple precipitate is slowly deposited. If the liquid istoo acid, the reaction does not take place, but finely-divided gold isprecipitated. The same decomposition occurs if the reducing agentis added too rapidly, or if the precipitate, when once formed, is re-dissolved in hydrochloric acid.I f the reducing agent is addedgradually, a considerable excess appears to have no action on therose or purple compound. The precipitate has a composition cor-responding with the formula Au20,19Fe20,,15As0,. It would appear,therefore, that the action of the reducing agent is only partial, aurousoxide and ferric oxide being formed. The ferric chloride, the presenceof which is essential, in all probability acts as a restrainer of thereducing action. C. H. B.Estimation of Arsenic: Pearce’s Process. By 0. J. FROST(Chem. News, 48, 85-86, Compare Abstr., 1883, 1034--1035).-1nthis process, the finely-powdered substance is fused with six to ten timesi 116 ABSTRACTS OF CHEMICAL PAPERS.its weight of the sodium carbonate and potassium nitrate mixture andthen proceed as described (Zoc.cit.), the solution, however, instead ofbeing evaporated to dryness, is exactly neutralised with ammonia andnitric acid, and filtered, if necessary. Excess of neutral silver nitratesolution is uow added ; the silver arsenate filtered off and washed withcold water, and the filtrate tested to see that precipitation is complete.The amount of silver is determined and the arsenic calculated from it.This is best effected by dissolving the arsenate on the filter in dilutenitric acid (any chloride is thus left behind), and titrating the filtratefor silver, with thiocyanate. Good results have been obtained bythis method, which the author states can be worked in half an hour.Molybdic and phosphoric acids interfere with the process ; antimonydoes not, on account of the insolubility of sodium antimonate.D. A.L.Volumetric Method for the Estimation of Arsenic. ByA. H. Low (Chem. News, 48,85).--d dcfenct.: of Pearce’s process (seelast abstract) a-gainst some criticisms made by McCay. The author con-siders that dissolving the precipitated silver arsenate in dilute nitricacid and titrating the silver is better than determining the excess ofsilver as McCay does (Abstr., 1883, 1035), for any chlorine present asimpurity in the reagents would have no effect in the first case,because any silver chloride present would not be dissolved, but wouldlower the results in the latter mehhod.He also recommends the useof a platinum instead of porcelain crucible for the fusion, as it can bemore easily cooled, and, from experience, he states that it remainsa(pparent1y uninjured, even after many times using.Test for Bismuth Subnitrate. (Dingl. p07yt. J., 248, 260.)-According to Hager, bismuth subnitrate and bismuth subamenatedissolve in eight parts of nitric acid of sp. gr. 1.185, forming clearsolutions ; the latter is, however, not completely soluble in a solutionsaturated with bismuth nitrate. Hence, by treating 0.5 gram of thesubnitrate with 4 grams nitric acid, a clear solution should be obtainedwithin half an hour, otherwise arsenate is present.D.A. L.D. B.Estimation of Manganese in Iron Ores. (DirzgZ. polyt. J.,248, 259.)-Zulkowsky recommends incineration of the manganoussulphide precipitate in a plttinum capsule, and moistening the residuewith aqueous sulphurous acid. The solution is evaporated on a water-bath, the residue taken up with water and two t o three drops of dilutenitric acid, and titrated with pot.assium permanganate. For thispurpose, the solution is transferred to a flask, diluted with water to150 to 200 c.c., and boiled. To the hot solution, potassium perman-ganafe is added from a burette, and the mixture boiled after each addi-tion until the supernatant liquid shows a pale red colour. Accordingto the formula 3Mn0 + Mn,O, = 5Mn02, 1 C.C. of a decinormal solutionof potassium permanganate corresponds with 1-65 mgrm.manganese.Volumetric Method of Estimating Manganese, especially inIron and Steel. By R. SCHOFFEL and E. DONATH (Din&poZyt. J.,248, 421--484).-To conduct this method, a solution of sodium car-D. BANALYTICAL CHEMISTRY. 117bonate is required, which does not reduce potassium permanganateeren on boiling ; also a solution of potassium permanganate of knownstrength. For this purpose sodium hydrogen carbonate is convertedinto the normal carbonate by strongly heating it. A saturated soln-tion of the carbonate is then prepared, which is heated to boilingand treated with a solution of potassium permanganate until themixture assumes a faint reddish colour, which remains on continuedboiling.The fluid is kept in well-stoppered bottles, and although itscolour soon disappears, it no longer nff ects potassium permanganate.The solution of potassium permanganate is titrated with pure ironwire or with ammonium ferrous sulphate. As this reaction is illus-trated by the equation lOFeO + Mn20, = 5Fe,O3 + 2Mn0, and theequation which explains the act'ion of potassium permanganate on themanganese salt is 3Mn0 + Mn20, = 5Mn02, 10 atoms of iron cor-respond with 3 atoms of manganese ; so that by multiplying the ironvalue by 02946, the permanganate value is obtained.For the analysis of samples rich in manganese, such as pig iron,spiegeleisen, and ferromanganese, 2 to 1 grams,-for poorer samples,4 to 3 grams,-are dissolved in boiling hydrochloric acid.The mixtureis allowed t o cool, treated with a small amount of potassium chlorate,and again boiled until all chlorine has been expelled. The solution, iftoo acid, is evaporated to a small bulk, partly neutralised with sodiumcarbonate, and made up to 100 C.C. 50 to 60 C.C. of the solution ofsodium carbonate are then transferred to a flask holding 700 to800 c.c., diluted with 400 to 500 C.C. distilled water heated to boiling,and treated with standard potassium permanganate. The test solutionis then run in from a burette, the mixture being stirred all the while.From the instant the colour becomes fainter, the solution should beadded with caution, and the mixture allowed to settle from time totime. The operation is concluded as soon as the red colour of thefluid has disappeared.The amount of permanganate solution usedshould be so regulated that one-half, or at least one-third of the testsolution is required, otherwise the results will be vitiated too much bythe limits of error. D. B.Suspended Matter in Water. By E. MARCHAND (Compt. rmd.,97, 49-50).-The water under examination is placed in a flask sur-rounded by black paper, in which are cut two opposite rectangularapertures, and a beam of light is passed through the water. Thismethod of examination reveals the existence of a large number ofsuspended particles which are invisible under ordinary conditions,but which the author has found to exist in large numbers in all formsof natural water, and even in distilled water which has been exposedfor some time to the air.Some of these particles are vacuoles con-taining water or gas, others have A shape resembling thatl of discoidaldiatoms. They have a sp. gr. higher than that of sea-water (in whichthey are very abundant), and they are not athacked by dilute acids oralkalis. Amongst these suspended corpusc!es are germs of Euglenea,a fact which explains the development of green growths in all placesexposed to light and moisture, and they also include organisms whichprobably play an important part in the oxidation of the organi118 ABSTRACTS OF CHEMICAL PAPERS.matter contained in water. Although some of them have a diameteras great as 2 mni., they are so flexible that they pass through theclosest filters, and when taken into the body they can pass throughthe kidneys, and are found in the urine.Test for Glycerol and Woody Fibre (Dingl.poZyt. J., 248,259.)-According t o Reichl, minute quantities of glycerol can bedetected by boiling the solution to be examined with a small amountof pyrogallol and a few drops of sulphuric acid diluted with an equalvolume of water ; this causes the formation of a red colour, which ischanged to purple on adding stannic chloride. Carbohydrates andcertain alcohols must be absent, as they produce similar colours. Byboiling woody fibre in a solution of stannic chloride mixed wih a fewdrops of pyrogallol, a fine purple colour is formed. This reaction canbe used as a meaiis of dyeing wood.C. H. B.3.). B.Valuation of Sugar-beets by their Density.By A. v. WACHTEL(Bied. Centr., 1883, 421422).--The custom of valning beet-rootsby their weight is a rough and ready rule ; the beet-juice on analysisfrequently shows considerable differences. The author recommendsKrocker’s process, that is, to prepare several mixtures of calciumchloride or cane-sugar solutions of different sp. gr., then with asampling tool to take pieces out of the root, placing them in solutionsof different densities until they float. Considerable differences arecaused by the manner in which the roots are cleansed f o r sampling,roots which are brushed and wiped showing a greater percentage ofsugar than those cleaned with warm water. J. F.Detection of Silver Cyanide. By C. L. BLOXAM (Chenz.News,48, 49).-The following test is of use in qualitative work. Precipi-tated silver cyanide appears amorphous under the microscope ; if,however, it is treated with ammonia and warmed, it forms needles.Silver chloride, treated in similar manner, forms octohedrons. In a,mixture of the two, both constituents can be recognised in this way.Silver thiocyanate also forms needles under like conditions, theabsence of thiocyanic acid must therefore be ascertained by the irontest, Silver cyanide also crystallises when boiled with a strong s o h =tion of sodium carbonate, or when moistened with strong nitric acidand warmed. Silver cyanide can be separated from silver chloride bytreating the mixture with hot dilute nitric acid in which the cyanideis soluble.If the solution is cooled, and the tube containing it iskept still, the cyanide separates in a semi-transparent gelatinous form ;if, however, the tube is agitated, the precipitate collects suddenly intoopaque masses (generally) of microscopic needles. D. A. L.Reactions with Silver Cyanide, Ferrocyanide, and Ferri-cyanide. By c. L. BLOXAM (Chenz. News, 48, 73--74).-Whenwhite silver ferrocyanide is shaken with ammonia it forms an opa-lescent liquid. When heated it becomes brownish-grey in colour, andmetallic silver is deposited. When treated with nitric acid, the greyprecipitate jields a solution of silver nitrate and ferric nitrate, leavinANALYTICAL CHEMISTRY. 119a residue of ferric oxide, mixed with a little silver ferricyanide.Nocyanide could be detected in this precipitate by means of ammoniumsulphide. With hydrochloric acid, a solution containing both ferrousand ferric chlorides is obtained.The ammoniacal solution neutralised with nitric acid yielded silverand ammonium cyanide. When silver ferrocyanide is treated with acold strong potash solution, a heavy brown precipitate forms. Thesupernatant liquid is colourless, stains paper brown, and on being heateddeposits silver ; it contains a trace of potassium cyanide, but no ferro-or ferri-cyanide. The brown precipitate contains metallic silver, andsilver ferro- and ferri-cyanide. Apparently, then, a part of the silverferrocyanide is converted into ferricyanide with separation of silver ; andthe ferricyanide t>hus formed forms a compound with the unchangedferrocyanide, which compound is not decomposed by cold potash or warmammonia. Boiling with potash entirely decomposes the ferrocyanide,yielding a solution of potassium and silver cyanide, and leaving a residueof ferrous and ferric oxides and silver.By boiling together precipitatedsilver oxide, silver ferrocyanide, and water, the colour changes frombrown to black, and silver and silver cyanide and ferricyanide areproduced. When silver ferricyanide is treated with potash in thecold it becomes black, yielding silver oxide and potassium ferricyanide ;on boiling, the black precipitate changes to pink, and ammonia isevolved, but on continuing to boil the precipitate again becomesblack. The pink precipitate contains a compound of silver cyanidewith silver ferricyanide insoluble in ammonia, along with silvercyanide, silver ferrocyanide, and ferric oxide.The pink precipitatecan be exactly reproduced by boiling silver oxide with potassinmferricynnide, on continuing the ebullition ammonia is evolved and theprecipitate becomes black. The filtrate from the pink precipitatecontains potassium cyanide and silver ferrocyanide in large quantities,and small quantities of silver cyanide and potassium formate. Thefinal black precipitate consists of metallic silver and ferric oxide ; thefiltrate from it contains the same constituents as the pink precipitatefiltrate, with the exception that there is no potassium formate, butinstead silver ferricyanide.When ammoniacal solutions of silvercyanide and silver ferricyanide are boiled together, a buff precipitateis produced, which behaves like the above-mentioned pink precipitate(thus synthesising the compound of silver cyanide with silver ferri-cyanide). The potassium cyanide then reduces the remaining silverferricyanide to ferrocyanide thus: 2Ag6Fe2Cy,, + 4KCN + 4H20 =SAglFeCy6 + K,FeCy, + 2HCN + 2C02 + 2NH3. When silver oxideand silver ferrocyanide are boiled together, the pink precipitate, silvercyanide, and f erricoxide are produced : Ag,Fe2Cyl, + 3Ag20 = l2AgCy +Fe,03. Several equations are given t o illustrate the reactions whichprobably take place during these changes. D. A. L.Test for Gallic Acid. By S. YOUNG (ohem. News, 48,31-32).-When aqueous gallic acid is treated with potassium cyanide solution,a red coloration is produced, which disappears in a short time if theliquid remains undisturbed.If, however, the liquid is shaken ener-getically the colour reappears, but again disappears on standing. Th120 ABSTRACTS OF CHEMICAL PAPERS.colonr can be reproduced in this manner from 15 to 20 times, thesolution finally becoming brownish-yellow. Pure tannic acid, freefrom gallic, is not coloured by potassium cyanide. D. A. L.Examination of Fatty Almond Oil. By H. HAGER (Diwql.Yolyt. J., 248, 524).-The author draws attention to the fact that theoil obtained from bitter almonds differs from that of sweet almondsby the ela'idin test, as it gives only a small amount of solid ela'idin.For the examination of the oil, 1 gram is treated in a small porcelaindish with 4 drops of concentrated sulphuric acid, and the mixturestirred together with a glass rod.A yellow colour rapidly changingt o yellow-red appears, which is Boon converted into a permanentbrown with green tinge, or green with brown tinge. By mixingequal volumes of fuming nitric acid and water with 7 volu. of almondoil, and agitating the mixture, the oil from sweet almonds gives a,white colour, whilst that from bitter almonds yields light to dark-yellow shades. D. €3.By A. v. BASTELAER ( B i d Centr., 1883, 419).-In order to determine the relations of water, fat, casein, and salt,the author takes 10 grams from the centre of a butter sample, placesit in a porcelain dish of 5 o r 6 cm.diameter ; dried at 100-120" toconstant weight, the loss is water; the residue is extracted withrectified benzene, the first portion poured on without stirring t o allowthe case'in to separate, the last two portions stirred up with a glassrod, and again dried ; the loss shows fat ; residue ignited is cssejin byloss ; the ash is salt. The limiis of a large number of determinationsare given :-Butter Analysis.Pure butter fat.. .... 75 to 85 per cent.Water ............ 9 to 15 ,,Case'in ............ 1 to 3 ,,Sodium chloride .... 5 to 10 ,,J. F.Tests for Vegetable Alhaloi'ds. By R. PALM (Chem. News,48, 65-66).-The author has shown previously that the alkaloidsare precipitated by solutions of alkaline sulphides or persulphides,and moreover that in contact with a solution of sodium thioantimo-nate, solutions of the alkaloid salts form characteristically colouredprecipitates consisting of the alkaloid hydrosulphides mixed with anti-mony sulphide. When the solutions of the alkaloid and reagent aredilute, these precipitates appear as colourless turbidities, which becomeyeliow on exposure to the air ; whilst with concentrated solutionsthey are yellow t o reddish-brown, and in saturated solutions theyform resinous masses.The precipitation is more complete in dilutesolutions, and is accelerated by gently heating, or by the addition ofstrong alcohol. In most cases the yellow precipitates are dissolvedby excess of the thioantimonate; they are, with few exceptions,amorphous, and dilute acids only partially separate the alkaloid fromthem.The chemical composition of the precipitates has not beendetermined. Sodium thioantimonate produces the following changeANALYTICAL CHEMISTRY. 121with the alkaloids referred to. With quinine sulphate in diluteneutral solutions, a white turbidity ; in stronger solutions, yellowflocks, which on shaking form resinous lumps, and become darker.When hot solutions of the quinine salt and reagent are mixed, resin-ous masses form at once, which when dry fall to a fine yellow powderlike lead iodide. With cinchonine sulphate, in dilute solutions, darkyellow (leather colour) flocks form at once; they do not coagulateeither on standing or heating. With quinidine sulphate, the eifect isalmost exactly the same as with the quinine salt, with the exception thatthe whole of the precipitate does not become resinous, and when dry isof a darker yellow colour (an intense dark chrome-yellow) : t'he pre-cipitation is also more complete.With morphine hydrochloride indilute solutions,. yellow flocks are at once deposited, which are darkerin strong solutions, and when dry resemble powdered gamboge incolour. With codeine hydrochloride, a flocculent precipitate is pro-duced, which when dry resembles the qninidine precipitate in tone,being a paler yellow than the morphine precipitate. With narcotine,in concentrated hot solutions, the precipitate coagulates in resinousmasses, which when dry have the colour of dry precipitated ferrichydroxide.With strychnine nitrate, the reaction is more sensitivethan with all the other veget'able alkalo'ids, the strychnine beingentirely precipitated, and moreover the precipitate is not soluble inexcess of the reagent. I n dilute solutions of strychnine nitrate,colourless flocks separate which become yellowish in air ; in concen-trated solutions, yellow flocks form which do not coagulate on stand-ing, and when dry are of a fine intense deep golden-yellow colour.With brucine nitrate, when the reagent is added in successive portionsto a, moderately concentrated solution of this alkaloid salt, three dis-tinct precipitates are obtained : 1. Reddish-yellow, which collects inresinous masses. 2. Light golden-yellow flocks. 3. Colourless flocks,which form a crust on the surface of the liquid.When the mixedprecipitates are boiled with water, the greater part dissolves, leavingan amorphous deep orange residue. The solution deposits yellowcrystals of the double sulphide.With atropine sulphate in strong solutions, a yellow deposit isformed, which coagulates on shaking or heating, but when dry is notso dark as the dry morphine precipitate.With bebeerine hydrochloride, a dark-coloured precipitate is formedwhich coagulates in strong, and especially in hot, solutions, and whendry is greyish-brown. The alkaloids also form double sulphides withother metallic sulphides.Lead chloride can be used as a reagent for vegetable alkalcids ; itshould be dissolved in a solution of sodium chloride, which dissolvesmore of the lead salt than cold water does. The precipitates aregenerally crystalline, and consist of a mixture of lead chloride andan alkalo'id salt. Quinine and brucine form crystalline powders ;cinchonine, morphine, and code'ine small fine needles : the strychnineprecipitate when dry forms a crystalline asbestos-like felted mass.The lead chloride is not so delicate a test as the thioantimonate.A strong solution of sodium chloride completely precipitates bebeerinefrom its solutions. D. A. L122 ABSTRACTS OF CHEMICAL PAPERS.Estimation of Urea. By L. HUGOUNENQ (Compt. rend., 97, 48-49).-Urine is filtered through animal charcoal, diluted with water,and heated in sealed tubes at a temperature above 140°, the ammo-nium carbonate which is formed being estimated by means of standardacid with “ methyl orange ” as indicator. This method is applicableto albuminous urine, if the albumin is previously removed by coagula-tion, but i t is not applicable to urine containing glucose or a notablequant,ity of magnesium. C. H. B.Estimation of Gluten in Flour. By L. REED (Chern. News, 48,63)-The proposed method of estimation is based on the fact that ayellow nitro-body is produced by the action of nitric acid on albumi-noids.Half a gram of flour is put in a test tube, which is graduated fromthe bottom to about half way up into 4 parts of equal capacity, wateris added up to the 4th mark, and the tube violently shaken. Thecontents are now temporarily transferred to a dry tube, the graduatedtube is masbed, and a quarter of the liquid poured back up to 1stmark, and colourless nitric acid is added up to 3rd mark. After fiveminutes’ standing, with occasional shaking, the liquid is filteredthrough a dry filter into a dry receptacle ; a standard flour is treatedin the eame way, aad the clear yellow solutions are examined colori-metrically, the qualities of the flours being inversely as the heights ofequal colour. D. A. L

ISSN:0368-1769    

DOI:10.1039/CA8844600109

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

122 ABSTRACTS OF CHEMICAL PAPERS.T e c h n i c a1 C h emi s t ry.Heat of Combustion of Coal.rend., 9 7, 268--271).-A criticism of Bunte and Stohmann’s experi-ments (Munich, 1879, 1880, 1882).Influence of Artificial Lighting on the Atmosphere ofDwellings. By F. FISCHER (Dirigl. polyt. J., 248, 375-379).-Theanthor shows that the preference given to solar oil or rock oil asilluminating agents is not only based on grounds of economy, .butdepends on the fact that these oils contaminate the air of rooms lesslargely than coal-gas. Gas is, however, a more convenient andeffective illuminant. The use of regenerative gas-burners, or of theelectric light especially in the form of incandescent lamps workedfrom accumulators, is strongly recommended, as little or no heat isgiven off, whilst the atmosphere is not contaminated with injurioussubstances, D.B.By SCHEURER-KESTNER (Compt.C. H. B.Chemical Composition of the Water of the Danube aboveVienna in the year 1878. By J. F. WOLFBAUEK (Monatsh. Chem.,4, 417--435).--This paper gives the results of a series of analyses ofDanube water made in the year 1878, chiefly with the view of ascerTECHNICAL CHEMISTRY. 123taining the value of the water for irrigating a tract of land known asthe Marohfeld, situated between the rivers Danube and March. Forthis purpose 23 samples of water were taken at Grafenstein, about20 kilomet,ers above Vienna, at intervals of 16 days from January20, 1878, to January 16, 1879, the height of the river being observedat each taking. The quantities of solid constituents of the water inthe forms of dissolved and of suspended matter (mud) were then deter-mined in each sample, and the several samples were submitted tochemical analysis.The results are given in the following table,TABLE I.-Average Chemical Composition and Hardfiess of DanubeWater i n Four Periods of the Year 1878.10,000 parts by weight of turbidwater contain :Suspended matter (mud)Total amount ..................Including : organic matter andchemically combined water (lossby ignition). .................Carbonates, &c. ................Sand and clay.. ................Dissolved non-rolatile substances :total directly determined ......Organic matter ................Silica.. ......................Ferrous oxide ..................Lime..........................Magnesia. .....................Soda ........................Potash ........................Chlorine ......................Sulphuric anhydride ............Nitric anhydride.. ..............Carbonic anhydride (combined) . .Total. .......Deducting oxygen equivalent tochlorine ....................there remains for calculated sumof dissolved fixed substances. , , .I n the periods :~~ ~I. 1 Ir. I 111. 1 IV.including the samples fromJan. 1 1 May 7 1 Sept. 10 1 Nov. 9toMay 2 I Bug. 26 1 Oct. 23 I Jan. 16Parts by weight.1 *2190 -0790 *5100 -6301 *7270 *0700 -0540 *0040 -6080 -1760 -0490 0170.0340 -1180 -0200 -6211 *7710*0081 '7631 *6540 -0720.7660 *8161 '4610.0420 *0390 -0050 -5430.1280 -0280.0160 *0160 -1060 -0130 -5241 '4600 *0041 *A560 -7650,0210 -3550 -3891 -7810 '0520 -048tJ '0020 *6430 *1750 -0360.0240.0180 *1230 *0130 '652--1 *7S60 9041 -7820 -1480 -0030 -0720 *0731 -9520 -0590 -0520 -0020 * 7 l O0 -1990 -0400'0200,0240 -1540 ti240 -7061 *9900 *0051.985Annualaverage0 -0560 -0480 TO30 *6160.1660 *0380 *0190.0240 '1230 -0180.6151 *7260 -0051 -72124 ABSTRACTS OF C€€EMIOAL PAPERS.TABLE I (continued).or combining the Acids and Rases :-10,000 parts by weight of turbidwater contain :Calcium carbonate ..............Magnesium carbonate ..........Ferrous carbonate ..............Calcium sulphate ..............Potassium sulphate ............Sodium sulphate................Sodium nitrate ................Sodium chloride ................Silica ........................Organic matter ................Total. .......permanent ..........total ..........................I n the periods :I. I 11. 1 111. I IV.including the samples fromJan. 1 I May 7 1 Sept. 10 1 Nov. 9toMay 2 I Bug. 26 I Oct. 23 I Jan. 160 *9690 *3700 *0060.1580 *0310.0180 -0310 -0560 *0540 -0701 %3Parts by weight.0 -8640 -2690 -0080.0300 *0150 -0200.0260 -0390.0420 '14.31 '4561 -0410 -3680.0030 -1460 -0440 -0290.0210 -0300.0480.0521 -782I n Fehling's degrees.1.1050 -4180 -0030 *2290 -0370.0120 -0370.0400 -0520.0591 -9855 -54 -64.64.54.66 *O5 -46 -210-1 1 9.1 1 10.6 I 11.6Annualtverage.0 *9790 '3490 *0050 -1650 *0340 -0180 *0280 *0390 .0480 *0561.721which shows the average composition of the Danube water in fourseasons of the year 1878, together with the average for the wholeyear; also the degrees of hardness according to Fehling's scale, inwhich 1" of hardness indicates the presence of 1 part by weight ofcalcium oxide in 100,000 parts of water.The numbers in Table I show that the minima of dissolved sub-stances and of hardness occur in the spring and early summer months,when the river is swollen by rainfalls and by the melting of theAlpine snows.The variations in the proportion of mud at differentseasons are much greater than those of dissolved matters, the mini-mum 0.96 per cent. being observed on the 11th of December, and themaximum 3.383 on the 6th of July. The water is clearest from thebeginning of October to the middle of January, from which time tillthe beginning of autumn incessant fluctuations take place in the heighTECHNICAL CHEMISTRY. 125Argil- Organic Carbonates, laceous sub-matter soliibleand chem. silicates,:omb. water &c., soluble(loss by in nitric by strongignition). acid. sulphuric acid.of the river, and in the quantity of mud which it carries along. Thegeneral result of all these observations is that as the river rises, itbecomes more muddy and softer, and us it sinks, it becomes clearerand harder.Sand'TABLE 1I.--Average Quantity and Composition of the Mud.0'02530.03480 -15050 -05610 *00290 -003'70 *l7200 '00170 *018810,000 parts ofturbid water containsuspended aa mud :0 '019'70.04330 '00310 -00530 -00200 '0093 --0 -1020Ferric oxide..........Alumina ............Lime.. ..............Soda ................Potash ..............Carbonic anhydride . .Silica ..............Magnesia.. ..........Phosphoric ,, ..0.050 I 0 -33620 *03310 -03280 -00060 *00190 '00800 *0045--0 *2853I 1.03770 '04810 -11190 -1 5420 '06330'01290 '01750 '17200 00170 -4061The preceding data afford the means of estimating the quantities ofmud and of plant-constituents which the water of the Danube iscapable of yielding for irrigation.According to t,he proposed schemefor irrigating the Marchfeld, 1.2 litre of water per second would bemade to flow over each hectare of surface, during the normal irrigationperiod, from April to September inclusive.This amounts to 18,000 kilos. per hectare, or, in other words, thedepth of the layer of water added daily to the soil mould amount to10 mm. With this quantity of water there would be added to thesoil-Floating particles (mud) .............. 2500 kilos.Dissolved matter (total) ................ 2800Potash, dissoivcd 31 kilos.in the form of zeolitic silicatesand clay ......... . 3 1 kilos.Sodium nitrate........................ 46.0............ } 62,,Phosphoric acid ...................... 4-1For the better appreciation of these numbers, it may be added tha126 ABSTRACTS OF CHEMICAL PAPERS.the quantity of potash thus added to the soil might be estimated toincrease the production of ha.y by 4000 kilos. per hectare. The phos-phoric acid in the water may be roughly estimated as equivalent tothe production of 970 kilos. per hectare. H. W.Organisms in the Air around Carlsberg. By E. C. HANSEN( B i d Cewtr., 1883, 279-283).- By employing sterilised hopped beer-wort the author has examined the air in various localities a t Carls-berg, including the fermenting cellars of a brewery. He gives along list of the various organisms found, and states that all theorganisms found in different parts of the brewery were also found in agarden, excepting Xacch.glutinis and sarcina, Ba. spirilla andspirochetis were never found. Grains should not remain in a brewery,as bacteria proceed from them, which may set up acid fermentation.Alcohol ferments proceed from ripe fruits and the soil, and of theseferments mildew is the most abundant and saccharomyces the leastf requent. E. W. P.Coking of Coal with Conversion of its Nitrogen intoAmmonis. By SCHEURER-RESTNER (Conp rend., 97,179-1 82).-The loss of heat-producing power resulting from the preliminarycoking of coal is only compensated by the value of the condensedammonia compounds when the price of the original coal is extremelylow. C.H. B.Manufacture of Sulphuric Acid free from Arsenic andSelenium. By H. BORNTR~GER (DkgZ. polyt. J., 248, 380).-Withthe view to facilitate the drying and roasting operations, the authorrecommends to filter-press the iron sulphide formed in the manufac-ture of sulphuric acid from the soda residues of the Leblanc processby the aid of spent pyrites (ibid., 243, 151) instead of draining it onfilters. It is also suggested to utilise the resulting liquors for thepreparation of sodium thiosulphate, as they are free from metallicsulphides. D. B.Manufacture of Sulphuric Acid. By H. PEMBERTON (DiTtg Z.pclyt. J., 248, 424),-The author has experimented on the manufac-ture of sulphuric acid fromsulphur, with the view of determining therelation between the consumption of nitre and the chamber-space.His results are of interest, as they include a system which works withGay-Lussac towers.From the amount of denitrated Gay-Lussacacid, the quantity of nitre which passed through the chambers for100 parts of sulphur is calculated. The percentage of nitre consump-tion found is 15.6, which includes 3.5 per cent. of nitre lost.Hurter, in his dynamic theory of the manufacture of sulphuricacid, found that the product of chamber-space into nitre consumptionis approximately a constant number when the chamber-space corre-sponds to 1 per cent. of loss of nitre for works not using Gay-Lussacto tvers. The chamber-space is inversely proportional to the nitrogencompounds present, provided, however, that the loss of sulphur is thTECHNICAL CHEMISTRY.127same, and the same strength of acid is made. For works makingweak acid the necessary chamber-space is much smaller.The following results by Hurter are yearly averages of five Englishworks using pyrites. The aut,hor’s numbers refer to works wheresulphur is exclusively used. The two are not, however, comparative,as in the author’s case the loss of sulphur and the concentration ofthe acid is not shown :-Hurter’s Results (only Pyrites).Chamber space for1 pound of sulphur.cubic feet.A . . . . 32.3B... . 29.8 c . . .. 24.5D.. .. 22.3E.. .. 22.81.. .. 26.82.. .. 29.83.. . . 35.74.. .. 19.2Nitre usedfor 100sulphur.10.011.212.013.79.5Product of nitre,consumption intochamber space.32333429430521 7Acid producedfrom100 sulphur.431392345386405Pemberton’s Results (Xdphur).10.0 268 -9.0 268 -8.0 285 -15.6 300 -Sp.gr.Ofacid.1-551.651-651.651.50In the case of A and E the acid is much weaker ; the produce fromA is larger, and the chamber-space in the case of E much smaller.No. 4 was worked with Gay-Lussac towers, the loss of nitre being3.5 per cent. D. B.Formation of Sodium Sulphate in Bricks. By G. CHRISTEL(Arch. Pharm. [3], 21, 39--41).-The author found that a mass ofeffloresced salt, which appeared upon some bricks in cold weather,consisted of sodium sulphate with a trace of sodium carbonate. Theprincipal chemical constituents of the materials used in the manufac-ture of the bricks were aluminium silicate, iron pyrites, and sodiumsilicate.The author supposes that the formation of sodium sulphatemay be due to one or all of the following reactions :-(l.) The ironpyrites, under the influence of heat in presence of water, absorbedoxygen, forming iron sulphate and sulphuric acid ; the latter actingon sodium silicate would form sodium sulphate ; the sulphuric acidformed in the above manner would also act on aluminium silicate,giving rise to sodium alum, which, when heated, would yield aluminaand sodium sulphate. (3.) The existence of calcium sulphate or ot,hersulphate in the original materials, which, during manufacture, wouldact on a sodium salt yielding sodium sulphate by double decomposi-tion.W. R. D.New Process for Producing a Bronze-coloured Surface onIron. By L. MAFER (Dingl. polyt. J., 248, 249).-The cleanedobjects are exposed to the vapours of a heated mixture of concentrate128 ABSTRACTS OF OHEMICAL PAPERS.hydrochloric and nitric acid (1 : 1) for a few minutes, and heated to atemperature of 300-350°, the heating being continued until thebronze coloixr appears. The objects are then cooled, rubbed withVaseline, and heated, until the latter begins to decompose. Thisoperation is then repeated. A bronzy oxide coating is obtained byusing acetic acid in conjunction with the above-mentioned acids. Byvarying the proportions of the different acids, it is possible t o obtainlight or dark brown shades. The author has coated iron T-bars inthis manner and exposed them for about a year to the atmosphereof his laboratory witgout the slightest change ';r sign of corrosiin.D.B.Production of a Gold-coloured or Green Surface on Brass.By C. PUSCHER (Din,gZ. polyt. J., 248, 3@4).-40 grams of causticsoda, 40 of milk-sugar, and 1 litre of water, are boiled together for15 minutes. 40 grams of a cold saturated solution of sulphate ofcopper are then added padually, the mixture being stirred con-tinually. A short immersion ofthe articles to be coated results in the formation of a gold colour, Alonger digestion yields a bluish-green tint, whilst after a very longimmersion iridescent colours are obtained.The solution is then cooled to 75".D. B.Adulteration of Cement. (Din$. poZyt.J., 248, 245-249).-A t the sixth general meeting of the Society of German Cement Manu-facturers, held in Berlin, a long discussion on the adulteration ofPortland cement took place, and the following propositions wereunanimously agreed to :-(1.) Portland cement is a product formed by intimately mixinglime and alumina, burning the mixture t o the point at which themass begins to slag, and disintegrating i t to the fineness of flour.(2.) Every product which is formed in a different manner orreceives foreign additions during or after burning, is not t o beregarded as Portland cement. Additions of 2 per cent. of gypsumare, however, admissible.(3.) The sale of cement containing foreign substances as Portlandcement is an imposition on the consumers.(4.) Good Portland cement is not improved by mixing foreign sub-stances like calcium silicate (ground blast-furnace slag) trass, groundclay, slate, limestone, &c., with it.But supposing it could be shownthat such additions were of advantage, they should not be allowed, asthe consumer cannot cont'rol the quantity or quality sufficiently toenable him to guard himself against fraud.(5.) Every addition is therefore to be regarded as the commence-ment of the preparation of mortar, and concerns, not the manufacturer,but the consumer.(6.) As the test which is used at the present time is unavailablewhen Portland cement is adulterated with foreign substances, and thecharacter of cement is altered when such additions are made, it isuseless to apply the same in comparing mixed with unmixed cement.D. BTECHNICAL CHEMISTRY.129Metallurgy of Nickel. By W. P. B L ~ ~ K E (Chem. News, 48, 87-89).-In an interesting address, the author remarks that for many yearsafter its discovery nickel was produced only as a bye-product in theworking of cobalt ores, and even when it came into use, it appearedonly as an alloy, and until 1876, when Wharton in America investi-qated the subject and produced considerable quantities of the metal,pure nickel was as rare as thallium is at the present time. Subse-quently Fleitman improved and cheapened the refining. operations,and reduced the liability to the presence of blow-holes in nickel cast-ings, by adding a very small quantity of magnesium to the moltenmetal in the pot.By this means the carbonic anhydride is destroyed,magnesia and graphite being formed. Since then large quantities ofthe pure metal have been produced, and many uses found for it.Nickel welds well with iron, and the two metals when rolled togetherat the proper temperature, become so firmly united that they maybe rolled down together to any thinness. There are all thicknessesof nickel upon iron.In scrap or waste, the nickel is recovered by dissolving away theiron with sulphuric acid. Formerly nickel plates, &c., were beatendirectly under the hammer : hence there was a great, loss by scaling,as with iron, but now this is avoided by covering the nickel with athin sheet of iron, which is afterwards dissolved off.This nickellediron is extremely useful ; the coating is much more firmly attached,and hence more durable than the electrically deposited nickel, whilstf o r domestic purposes, for covers, saucepans, &c., it surpasses tinned irono r copper, for the nickel is not only lighter, harder, and stronger, butis also less liable t.0 tarnish and corrode, so that it can always be keptpolished. It moreover will wear longer, and cannot be melted off byoverheating . D. A. L.Novelties in the Iron Industry. (DilZ@ poZyt. J., 248, 498-509.)-In a paper read at the August meeting of Mechanical Engi-neers, Cochrane referred to the working of blast furnaces, and espe-ciaily to the effect which the position of the tuyeres has on theworking of t'he furnace. The position of the tuyeres if badly chosenmay often annul the saving effected by working with large furnacesand a specially hot blast.By drawing back the tuyeres a great ad-vantage is gained ; thus by increasing the distance of the tuyeres from1.83 meters to 2.13 the make of iron was raised from an average of483 tons t o 599 tons, the consumption of coke being practically thesame in both cases (603 tons).According to Delafond, the dephosphorisation of pig-iron in basiclined open hearths has the following advantages ov,er the converter.The preparation and maintenance of the basic lining is not attendedwith the same difficulties. The addition of lime and the removal ofslag can be effected at any period of the operation.Gautier states that the pressing of fluid steel during the process ofcooling is conducted at the Whitworth Steel Works by pouring thefluid metal into moulds composed of a series of superposed steel ringslined with a refractory material.The moulds are placed on wheels,and when full are run under the hydraulic presses. A refractoryVOL. XLVI. 130 ABSTRACTS OF CHEMICAL PAPERS.stone prevents the ram of the press from being welded together withthe steel. Steelprepared by compression is said to gain considerably in hardness.The longer the surface of a casting is allowed to remain in the fluidstate, the more uniformly will it contract on cooling, and the smallerwill be the number of hollow spaces which are formed. Krupp hasutilised this circumstance in practice by surrounding the upper sidesof the castings with fluid slag or sand.Gmelin recommends the use of a jacketted cylinder cooled by waterfor the walls of cupolas.Dufren6 has patented a new arrangement in cupolas heated by gas,the generator being in direct communication with the furnace.Inthe lower part of the collecting space immediately above the openingthrough which the fire gases enter, an intermediate hearth is arranged,consisting of a series of barrelled ribs, so as to allow the flame to passinto fhe charge which is placed on the hearth.Besson has modified the construction of cupolas by coiinecting thechamber of the furnace with a separate iron hearth and a specialcombustion space, which is said to accelerate the fusion.Reusch works up scrap iron by heating it to redness in a furnacewith a reducing flame, whereupon it is pressed into moulds and rolledout to bars, plates, &c.Red Wine Manufacture in Germany. By NESSLER (Bied.Centr., 1883, 422--423.)-The growth of a taste for red wines inGermany, and the planting of new vineyards to supply it in the vinedistricts, has induced tlbe author to publish the recommendations con-tained in the present paper.They relate to situation of the vineyard,and the descriptions of grapes which should be grown ; he discussesthe kind of vats which should be used, and recommends a large cham-ber or other place which can bc kept a t a uniform temperature of 16-20°, in which the process of fermentation should be carried on in-dependent of outside temperature : he cautions the wine makeragainst the use of unripe or spoiled grapes.Extractive Matter in Tyrolese Wine, 1883 Vintage.By A.HENECKE ( B i d Gentr., 1883, 426)-It is the custom to examine theyearly averages of wines grown in the district; as those of 1882 wereof inferior quality to those of many previous years, it was expected thatthe extractive matter would have been very low. The reverse wasthe case, however, and the author endeavours to explain this by sup-posing that in plentiful years the poor and spoiled bunches are left,the superior chosen for wine making. During the year in question,there were few choice bunches, and the decayed or unripe grapesyielded a large extract. The wine of the year was thick and muci-laginous, cleared badly, and developed bacteria in quantity.Heattributes it to the low proporbion of alcohol in the wine.Preservation of Wines. . By E. HOUDART (Compt. rend., 97, 55).The second fermentation of light wines rich in sugar, such as the" vins de coupage," when kept in casks for daily consumption, maybe prevented by carefully heating the wine to 55-60° in a speciallyconstructed apparatus, and storing it in casks pile viously well washedThe pressure used is equal to 600 atmospheres.D. B.J. F.J. FTECHNICAL CHERIISTHT- 131Corny.with boiling water. The air which enters the cask when the wine isdrawn off, is filtered through cotton-wool. This treatment does notappreciably affect the composition, colour, flavour, nor any other pro-perty of the wine.Wine and its Examination. (DingZ.polyt. J., 248, 293-296.)According to 1SIIaumen6, mnocyanin, the colouring matter of wine, iscolourless at the commencement of the ripening of grapes, and isrendered blue by oxidation ; iron takes no part in this change.For the preparation of wine from roots, Brin recommends the fol-lowing method. Beetroots are boiled, triturated and pressed ; thejuice is brought into fermenting vats provided with steam pipes andfermented with yeast, malt, or apple-juice. The requisite quantity oftannic acid is then added, the mixture allowed t o settle, filtered, andthe product treated like ordinary grape-wine. This product is saidto form a suitable adulterant for red wines. Turnips yield a whitecoloured wine when treated in a similar manner; it is, however,advisable to add a small quantity of nitric acid to the mass at thebeginning of the fermentation.Lorraine Wir~es.-Weigelt has prepared a number of wines fromgrapes of the year 1881, and examined the same with the followingresults :-C.H. B.S t . Julien ,nearMetz."Alcohol per cent. by w-eight..Extract ..................Non-volatile acid ..........Volatile acid ..............Free tartaric acid.. ........Glycerol ..................Mineral substances ........Sulphuric anhydride ......Phosphoric anhydride ......Polarisation ..............Alcohol per cent. by weight..Extract ..................Yon-volatile acid . . . . . . . . . .I'olatile acid ..............Free tartaric acid ..........Glycerol ..................Mineral substances ........Phosphoric anhydride .. . .Polarisation ..............Sulphuric anhgdridi.. . . . . . . .~~ ~~~ ~-dorching6 -2102 -1180 -4200 -1950 '0260 *6380 -1680 *0060 '024t oirs on thtMoselle.7 -4702 '2640.4800-1550 '0290 '4390 -2060 '0090 *047-0 '2Iayingen. Novthnt.6 *2802 *0670 *4200.1170.0150-5030 '1 690 '0080.0350 *16 -5702 '0000 *4950 -1170 '0230 '4030 '156O s O 0 40 '026*O7.0002 -0780 '5280.1570 *0280 -2440 *1900 '0040 *028f OMarsal. Barzel-lona.7.9302 -7870 -4800 *2020 '0330 '3800 *2550 -0070 *033- 0 . 110 '4.602 -2610 *9070 -1350 -0410 -1550 -0040 -036-+0*212 -0002 '5280'4120 -1870 '0590 '7730 -2050.1260 '031-0.27 -2701 -9810.4950 -1700.0340 *5290 *1760 -0060 *030to91* Red and white grapes132 ABSTRACTS OF CHEMICAL PAPERS.Fresenius and Borgmann (Zeitschr.And. Chew., 1883, 46) give adescription of their investigation on pure grape wines.Borgmann confirms the assumption that wine which contains lessthan 7 pts. glycerol for 100 pts. alcohol, has been treated with alcohol.Preparation of Spirit and Pressed Yeast. (DingZ. p d y t . J.,248, 464--46Y.)-At the annual meeting of the Society of GermanSpirit Manufacturers, t.he more recent experience gained in the mazu-facture of spirit and pressed yeast was discussed.Delbriick treated of the improvements which have been effected inthe manufacture of spirit by the introduction of new mashing appa-ratus.Referring to the preliminary mashing vats used for mixingthe malt and the stuff coming from the steamers, both of which areintroduced a t different temperatures, it is stated that the main objectis to obtain perfect agitation, so that no differences of temperaturecan be noticed a t any period of the mashing. With regard to themode of cooling, ft very advantageous arrangement is the use of anexhauster, although cooling by means of water is more trustworthy.According to Marker, Goutart's ma,shing apparatus is the mostperfect in mechanical construction and working power ; a very con-centrated mash is obtained by its use.Francke discussed in detail the conditions necessary to produce thehighest yield of yeast.Bread Making.By V. MARCANO (Compt. rend., 96, 1733-1734).-In experiments on bread-making made in Venezuela, the authorfound that the fermenting paste is free from saccharomyces, but con-tains a large number of moving sphero-bacteria. During fermenta-tion, the gluten and a small portion of the albumino'ids are partiallydissolved and converted into peptones not precipitable by tannin.These results agree with those of Chicandard (Abstr., 1883,1179), butthe author found that contrary to the statement of this chemist, thepaste at the commencement of fermentation contained a considerableproportion of erythro-dextrins and a relatively small quaiitity ofsoluble starch, whilst a t a later stage i t also contained a notable pro-portion of achroo-dextrins. I n Venezuela, the bread is made from amixture of flour and starch which is comparatively poor in gluten.The bacterium does not a,ttack the starch unt,il after it has destroyedthe albumino'ids, hence the necessity for using a very active fermentdeveloped by means of maize, potatoes, &c.Similar fermentationtakes place whenever any grain, fruit, root, &c., is exposed to the airin the tropics. If European yeast is placed in moistened starch, theyeast gradually disappears, and is replaced by bacteria. Attempts torepeat these experiments in Paris have yielded negative results, thestarch always remaining unat,tacked. It would appear, therefore, thatin all experiments on fermentation, it is necessary to take into accountthe local conditions, which may exert great influence on the natureand progress of the change.Fermentation of Bread.By L. BOUTROUX (Compt. ~eitd., 97,116--119).--Leaven from rye-bread made at a farm at a considerableD. B.D. B.C. H. BTECHNICAL CHEMISTRY. 133distance from a brewery was found to contain bacteria and four otherdistinct organisms, viz., JIycoderma vini, two distinct species of yeastdifferent from that of beer and wine, and an organism which appearsto be Sacchnrornyces minor, but which has no power as a ferment.The bacteria were very abundant, but the other organisms could onlybe recognised by careful cultivation, and it would appear thereforethat the bacteria are the DrinciDal apents of fermentation, the other I " organisms playing a secoidary and comparatively insignificant part.C.H. B.Percentage of Sugar in Beet. By I(. STAMMER and P. DEGENER(Bied. Centr., 1883, 274-278) .-Stammer has ir?troduced a pulperwhich enables a higher percentage of sugar to be obtained in themanufacture of beet-sugar, and he shows the gain obtained by sue-cessive pressings of the pulp. Beets which have gone to seed andothers which hare withered, are by no means wanting in sugar. Afterthe mash has been extracted with 50 per cent. alcohol, it still yieldssugar to 75 per cent. alcohol. Degener describes his method for esti-mating the value of roots, which method yields higher results thanthat of Scheibler, as modified by Seckel.E. W. P.Strontia Process. B y C. SCHEIRLER (Dingl. polyt. J . , 248,426428).-The author mixes a 20 to 25 per cent. solution of purecane-sugar heated to 70" to 75" with strontium hydroxide in theproportion of 1 mol. sugar to 1 mol. SrHz0,,8Hz0, stirring the liquorcontinually. On cooling, a supersaturated solution of strontiummonosaccharate is obtained, from which, after some time, eitherunaltered strontium hydroxide crystallises o u t or monosaccharateseparates according as the saturated solution has been treated witha few crystals of strontium hydroxide, or a small amount of mono-saccharate. The saccharate, C12H22011Sr0,5Hz0, is formed in thecold by introducing the requisite quantity of finely-divided stron-tium hydroxide into a cold sugar solution, with constant agitation.The author utilises this reaction for the recovery of sugar frommolasses.He dissolves 0.5 k. of strontium hydroxide in 1.5 k. ofboiling Walter, and mixes it with 1 k. molasses. The clear solutionis allowed to cool and stirred frequently, small quantities of mono-saccharate being added at the same time. After 12 to 24 hours, thestrontium ssccharate has crystallised out ; it is freed from the mother-liquor by filter presses, and washed with water or a cold saturatedsolution of strontium hydroxide. I n order to recover the sugar whichremains in the liquors, an excess of strontium hydroxide is added, andthe mixtnre boiled f o r some time : thus nearly all the sugar is preci-pitated as strontium disaccharate ; the strontium hydroxide remainingin solution is precipitated with carbonic anhydride.The disaccharatewhich is saturated with mother-liquor is converted into monosaccharateby dissolving it in molasses and adding a hot saturated solution ofstrontium hydroxide (1 mol. total sugar requires 1.25 mols. strontiumhydroxide). The strontium monosaccharate is separated in themanner just described. From the latter, the sugar is recovered bythe ordinary methods, or the strontium hydroxide may be first partlyseparated as such and again used for a further operation. E'or thi134 ABSTRACTS OF CHEMICAL PAPERS.,purpose the saccharate is dissolved in hot, but not boiling water, audthe solution allowed to cool without agitating it, when strontiumhydroxide crystallises out.The author has determined the solubility of strontium.mono-saccharate in water a t different temperatures. The following t,ablegives the solubilities to 60", the temperature at which the decom-position of the saccharate commences :-6 2&EikE-r -0246810121416182r I2224262830323 4363840424446485052545658Monosaccha-rate,C,2H,cO,,SrO.grins.28 '430 *232 *O33 -935 *737.539 -541 -643 -846.248 -651 *253.956 -759.762.765 .tl69 *373.277.582 -387 *893 *8100 *7109 a 7121.9124.3147 '0162 -9185 -1One litre contains-Sugar.--grms.21 *8023 '1824.5626 -0327'4128 -7930 '3231 *9333 *6235 -4637.3139 '3 141.3843.5345 *8348 -1350 *5153 *2056 *1859 *4963 -1867 -4072 *0177 *3184 -2193.58103 -10112.85125.05142 -103 t ron t ium)xide, S r 0 .--grms.6 *607 '027 *447.878.298.719-189-6710 -1810 -7411 -2911 -8912 -5213'1713 *8714.5715 -2916 .l o17 -0218 *0119 -1220 *4021 -7923 *3925.4928.3231 -2034-1537 -854.3 '00Crptallinestrontium hy-droxide,H2Sr0,.8H,0.grms .16 *9318 *OO19 -0720 *2121 -2822 *3523 -5424 -7926 -1027.5328 *9fi30 -5132 -1233.7935 -5837 '3739 -2141 -3043 *6246.1949 '0552 -3355.9060 *0165 *3872 -6580 *0457 -6197 -08110 *31Sp. gr. ofthe mono-saccharatesolutionit + 17.5".1.017751 'OM921 '020001 -011.1191 *022311 '023441 -024691 -026001 '027381 *028a81 *030381 -032001 -033691 *035441 * 037311 *039191.041131 *043311 '045751 '04.8441 '051441.054881.058631 '062941 -068561.076191 '083941 '091881 *lo1811 *11569Corre-:ponds withdegrees,Brix.--4 *514 *815 -085 '375 -655 -936 -246.566 -907 -277 -648.038.448 *879 *329 -7710 -2410 *7611-3411 '981 2 *6913 -5014 '3715 '3716 -6718 *4020.1 421 *9124 -0827.06D.B.Preparation of Potato Starch. (Diiigl. po7yt. J., 248, 381.)-Nitykowski has made a seyies of comparative tests on the cultivationof potatoes. He found that the recent heavy rains have reduced thetotal yield of potatoes by about 25 per cent. of the average of thelast ten years.Thirty-seven varieties were examined, the yieldrt-tnging from 9697 kilos. per 5000 square meters (containing 19.1TECHNXCAL CHEMISTRY. 135per cent. starch, equal to 1838 kilos.) to 41.67 kilos. (containing 16.38per cent. starch, equal to 683 kilos. starch per 5000 square meters).The so-called " alcohol potatoes" proved to be the most mealy andrichly flavoured. The yield was 7500 kilos. per 5000 square meters(containing 19.26 per cent. starch, equal to 1445 kilos.).Miirker states that potatoes rich i n starch should be used for seed.Samples of a Saxon variety of potatoes were analysed, and a greatdifference was found in the amount of starch present.In expe-rimenting on the effects of different manures on the potato, it wasshown that the produce was increased with potassium salts, especiallythe chlorides, whilst the amount of starch was diminished. Markerstrongly condemns the manufacture of starch without the utilisationof the refuse water for the irrigation of meadows and arable land, asthis water contains valuable fertilisers.According to Saare, the great loss in the manufacture of starch isdue to the want of efficient disintegrating machines.Experiments with Nielsen and Petersen's Centrifugal Sepa-rator. By W. FLEISCHMANN (Bied. Centr., 1883,411-415).-A descrip-tion of the machine and some results of working with it ; the yield ofcream is good ; and rate of revolution being but 1600 revolutions perminute against 423'2 revolutions in the Lava1 separator, there is con-siderably less danger of accident.In eight experiments, where thetemperature of the milk was gradually increased from 5" to 40°, thefat left in the skim milk decreased from 0.8508 in the first to 0.2229in the eighth, which the author takes toprove the beneficial influenceof a temperature of 40". Suggestions are made for improvements oradditional appliances, but would not be understood without a longdescription. J. F.Comparison of Various Systems of Butter-making. By N.FJORD and others (Bied. Cenfr., 1883, 415-416) .-The authors havefor a year compared five different systems of butter-making : the iceprocess; cooling by water at 10"; churning; and the centrifugalmachine of Nielsen and Petersen.The yield from all processesvaried considerably, but the centrifugal showed the best ; andwhereas the average of the ice process required 27.5 lbs. of milk tomake 1 lb. of butter, the centrifugal required 3 lbs. of milk less.Faults in Butter Manufacture. By OTTO (Bied. Ceiztr., 1883,417).-The author draws attention to certain precautions whichshould be taken not only in butter-making, but with the milk fromwhich butter is made, as many mistakes do not show themselvesuntil after the butter has been stored some time.Cows should not be irrationally fed ; they should not be constantlyfed on one material, but on various descriptions of fodder in reasonablevariety. The milk of old cows which is slightly bitter should only beused in moderate proportion with other milks.Ventilation of stablesmust be carefully attended to, the cows kept clean, and the milkquickly removed from the stable lest it should acquire a bad flavour.The locality of the dairy should be carefully attended to. A freeD. €3.J. F136 ABSTRACTS OF CHEMICAL PAPERS.current of fresh air should play around it, and the floor should not bemade of a porous material, such as bricks. The cleansing of thevessels is of the greatest importance. The rancidity of butter is fre-quently due t o want of attention to this ; they should be cleaned withsoda, steam, &c. The souring of the cream should not be continuedlonger than 24 hours, or the butter will have a slightly bitter taste.J.F.Fixing Indigo on Cotton. By PCHLIEPER and Bmx (Chem. News,48,64--65).-For this purpose, the indigo is ground up for two dayswith caustic soda and water ; it is then mixed with a mixture of Britishgum, maize starch, water, and caustic soda, and the whole heated a t55" in a water-bath, well stirred, and cooled immediately. Thecolour ought now to be gelatinous, and is printed on the cloth, whichis prepared with glucose and well dried. The dyed cloth is thensteamed for 10-15 minutes. Light or dark shades are obtained byusing more or less indigo with more or less soda. The o d y goodr e s i s t is Precipitated sulphur, and thickening. A yeZZow resist isformed with cadmium chloride, precipitated sulphur, and thickening.A red resist is made of red liquor, tin-crystals, calcined starch, andprecipitated sulphur. Light blue, the cloth prepared with glucose, isprinted with caustic soda, thickened with dextrin and maize starch,steamed for 15 seconds, arid padded with indigo colour. In using thered resist, the soda must be remo-red, or the cloth must be passed intoammonium chloride. An indigo colour is easily discharged on Turkey-reds. Fm a Turkey-red mordant, heat gelatinous alumina with causticsoda, add water, neutralise with hydrochloric acid, and add more water.For padding, this mixture is also used in a more dilute form ; it isdried and aged on the cloth, then passed t'hrough lukewarm chalkwater, which converts the sodium into calcium aluminate. This mor-dant can withstand the action of sulphiiric acid without losing muchof its depth, and on this property the production of indigo dixhargestyles is founded. For the production of indigo Turkey-red, the clothpreviously mordanted for, or dyed with dizarin, is saturated withglucose. The indigo is now printed on, the fabric steamed, washed,exposed to the air for a few minutes, passed into sulphuric acid (So B.)for about 20 seconds, washed, passed into weak sodium carbonate, andagain washed, The red pieces are soaped at a boil, the alizarin isdissolved, and the blue colour appears. To obtain white on Turkey-red or indigo-blue, a dark blue and strong soda-lye are printed onbefore proceeding as indicated, or a strong lye is priiited on the Turkey-red mordant, then steam, dry, and print on the indigo,D. A. L.Process for preparing a Mineral White. (Dingl. pol,yt. J.,248, 260.)-According to C'obley, a solution of magnesium sulphaheis converted into magnesium chloride by the addition of calciumchloride. Gal-cium hydroxide throws down a white precipitate from the mixed sola-tion. A cheaper white is obtained by precipitating a solution of thecorresponding snlphates with calcium hydroxide.10 per cent. of aluminium chloride are then added.D. B

ISSN:0368-1769    

DOI:10.1039/CA8844600122

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

137 General and Physical Chemistry. Photographic Investigations of the Ultra-Violet Spark Spectra emitted by Metallic Elements and their Combina- tions under Varying Conditions. By W. N. HARTLEY (Chem. News, 48, 195-196).-It has been shown (Brit. Assoc. Jour.? 1882) that t,he spectra of metallic solutions are the same as those from metallic electrodes, the principal difference being that short lines in the spectra from the metals become long in the spectra from solutions, whilst very short lines sometimes disappear, as for example in the case of zinc. This is probably due to the solution not being able to contain a sufficient quantity of metal to yield an image of them : thus the very short lines of the aluminium spectrum are not repro- duced in solutions of the chloride unless the solutions ai-e extremely concentrated.With regard to the short lines being lengthened by moistening iridium electrodes with calcium chloride, it has now been shown that moistening with water has the same effect : hence the sup- position that a chloride of the metal was formed is untenable. The very short lines in the zinc spectrum are also lengthened by moisten- ing the electrodes with water. This variation in the spectra appears to be due t o the cooling action of the water on the negative electrode, since heating the electrodes produces a reverse result. Carbon gives two spectra in air when dry, and a third when moistened with water ; the three have been photographed, but cannot be exactly described without maps. Numerous experiments have been tried to determine which non-metallic.elements are capable of yielding spark spectra when they are combined with metals. Chlorides, bromides, iodides, snlphides, nitrates, sulphates, selenates, phosphates, carbonates, and cyanides yield none. Hydrochloric acid solutions of arsenites, areenates, and antirnonates yield spectra of arsenic and antimony respectively, afid solutions of borates and silicates yield characteristic spectra (see below) of the non-metallic constituents ; even if sodium salts are employed no metallic lines appear in the case of borates, and with silicates only the strongest sodium line ( h = 3301) is visible, even in concentrated solutions. Spark. r--" (wave-lengths) . (wave-lengths) . Boron ----Kz 3450.1 2881-0 2497.0 2631.4 2496.2 2.541.0 2528.1 2523-5 2518.5 2513.7 25013.3 2435.5 251 5.5 VOL.XLVI. Carbon spectra lines (Liveing and Dewar). r----- 7 Spark. Arc. - 2881.0 2541.0 - 2528.2 2528.1 2523-6 2523.9 2518.7 2518.8 2515.8 2515.8 2514.0 2514.1 2506.3 2506.6 2478-3 2434.8 1138 ABSTRACTS OF CHEMICAL PAPERS. It will be observed that these silicon lines are identical with those (annexed table) attributed by Liveing and Dewar (Proc. Roy. Soc., 33, 403) to carbon, and from many hundred spectra taken between graphite poles it is apparent that in the arc spectrum carbon yields but one line (2478.3 wave-length) in the ultra-violet. The ultra-violet spectrum of beryllium has been obtained from the solution of its chloride, and the following lines were observed :- Wave-lengths. 3320.1 3129.9 2649.4 2493.2 24’77.7 Description. Strong, sharp.Very strong, extended. Strong, sharp. Strong, sharp. Strong, sharp. From these observations and the general grouping of the lines, the author feels inclined to regard beryllium as the first member of the dyad series to which barium, calcium, and strontium belong. Reasons are given for not classing beryllium with other metals. D. A. L. Production of Electricity by Condensation of Aqueous Vapour. By S. K~LISCHER (Ann. Phys. Chew%. [2], 20, 614-620). -The production of electricity by condensation of aqueous vapour presents a problem of considerable meteorological importance as regards the origin of atmospheric electricity. It is, however, pro- bable that the production of electricity observed is in most cases due to the friction between the water particles and the condensing surface.Tn this paper the problem is examined experimentally by means of an apparatus which permitted the condensation of aqueous vapour by cooling. It consisted essentially of a series of beakers filled with ice, and covered externally with tinfoil; the beakers were placed on a plate of galvanised iron connected with a quadrant electrometer, and the whole combination was enclosed in a metallic box. Although deviations of the needles of the electrometer were observed, yet they were of the same magnitude and direction whether the beakers were filled with ice or not; aud secondly, they were sometimes in one, and sometimes in the other direction. Other experiments are described in which air was compressed in, and then allowed to expand from a vessel resembling the electric egg, the metallic stopcock of which was in connection with a quadrant electrometer.But in this case, although a pressure of 25 atmospheres was used, and the aqueous vapour fell in the form of fine dew on releasing the pressure, yet there was no development of electricity. V. H. V. Measurement of the Quantity of Electricity produced by a Zamboni’s Pile. By E. RIECKE (Ann. Phys. Chem. [2], 20, 512- 524) .-This paper contains a series of determinations in absolute measure of the quantities of electricity produced by three Zamboni’s piles containing a large number of platinum plates iiiterposed between strips of silk. A long series of tables of those quantities obtained on days of different relative hcmidity are given, and formulaeGENERAL AND PHYSICAL CHEMISTRY.139 for their calculation as well as for diffeibences of potential are also quoted. V. H. V. Influence of Galvanic Polarisation on Friction. B-y K . WAITZ (Ann. Phys. Chem. [2], 20, 285--303).-In 1874 Edison noticed that the friction between a metallic and a porous plate moistened with some conducting liquid, was diminished when an electric current was sent through this combination from the porous to the metallic plate. Further changes in the friction are produced by variations in the intensity of the current. This fact has been prac- tically applied in the construction of telephones and electromoto- graphs. In this memoir the phenomenon is more completely investigated. The apparatus consists in the main of a clay cylinder filled with acidulated water, and enclosed within a glass vessel filled with water of t>he same concentration. A platinum foil is introduced into the inner, and a strip of glass in the outer vessel, on which a small platinum foil is stretched ; this latter is connected with a mechaiiical arrangement whereby the platinum foil on the glass strip can be pressed against the clay cylinder with various degrees of pressure. The whole aryangement is enclosed in circuit with two Daniell's cells, a metallic arrangement to measure the degree of pressure, and a, rheostat to vary the intensity of the current.In many experiments it was found that the friction between the platinum and the porous cell is materially diminished when the intensity of the current is sufficient to decompose the acidulated water. As the contact of the platinum and the clay was not found to be sufficiently perfect, a polished glass cylinder was substituted.The alteration of friction between glass and various metals, platinum, palladium, gold, and nickel, introduced into such solutions as sulphuric acid, potash, and soda, and potassium ferrocyanide was carefully examined : in the original memoir extensive tables are given of the results obtained in the course of the investigation. As a general result it may be stated that there is a diminution of resistance when the metallic plate is the anode, but an increase when the plate is the kathode, and the intensity insufficient to decompose the electrolytic liquid. This latter fact is contrary to the experience of Koch, who found no alteration in the case of the kathode.As the diminut'ion of resistance appears only when bubbles of gas appear at the surface of the plate, it appears probable that the occlusion of the gas by the electrode is the cause of the phenomenon. Another hypothesis is that the formation of an electric double stratum, called forth by the polari- sation on the surface of the electrodes, alters the external friction between the metallic surface and the glass on the one hand, and the glass and the liquid on the other. Further experiments will decide bet ween these two hypotheses, but the writer inclines t o the latter. V. H. V. Relations between Coefficients of Friction and Galvanic Conduction. By E. WIEDEXANN (Ann. Plqs. Chenz. [ d ] , 20, 537- 538).-In connection with a remark of G.Wiedemann ou certain rela- 1 2140 ABSTRACTS OF CHEMICAL PAPERS. tions existing between coefficients of friction and galvanic conduction, and the theoretical deductions drawn therefrom, a series of investiga- tions has been made on this point. However, in order to prove how far these relations hold good, the author examined solutions of crys- talline zinc sulphate in water and aqueous glycerol of varioue concen- trations. The coefficients of friction were measured by Spring’s apparatus, those of conduction by a Wheatstone’s bridge. Ratio of coefficient Ratio of coefficient of friction of conduction Strength of solution r--h-- 7 r----- 7 1 per cent ......... 1 68.7 1 12.1 2 Y, ........ 1 29.8 1 9.52 5 9 ) ........1 6.5 1 3.68 These numbers show that the ratios existing between the co- efficients of friction and conduction are not simple, and further that the nature of the solvent and also its concentration exert a most marked influence on them. V. H. V. ZnS047H20. I n water. I n glycerol. In water. I n glycerol. Galvanic Temperature CoefRcient. By V. STOUHAL and C. BAROS (Ann. Phys. Chew. [2], 20,525-536).-Previous reseawhes have not established any differences of specific resistance as factors of the temperature corresponding to known differences of composition of various forms of iron and steel. It appeared, however, probable to the writer that iron, whose coefficient of resistance varies according to its degree of hardness and temper, should also possess various temperature coefficients.In this connection it has been shown by Matthiessen and Vogt that, the temperature coefficients of platinum- silver alloys decrease with the proportion of platinum ; like dif- ferences have been observed by the authors in the case of German silver. Similarly it is to be expected that iron, containing various proportions of carbon, which may funct.ion as the second metal, should display similar varia,tions. Experiments were accordingly made on steel tempered a t various “heats,” and specimens of bar and pig-iron. I n the case of steel the temperature coefficient of the steel varies as its coefficient of resistance continuously with the hardness of the steel, and decreases with increase of the temperature a t which it is tempered. Tlie experiments of Matthiessen and Vogt on bar-iron, and those quoted in this memoir on pig-iron, show that the temperature coeffi- cient varies with the proportions of carbon, and further, that the specific resistance of the latter is far greater than that of the hardest 5: teel.The above observations point to a marked anarlogy existing between alloys and steel in their galvanic relations, and to a general law that in all cases of homogeneous substances differences of specific resist- ance cause similar differences of temperature coefficients, increments of the former corresponding to diminutions of the latter. In alloys it is the small proportion of added metal which raises the specific re-GEXERAL AND PHYSICAL CHEMIfjTRY. 141 Boiling point. sistance, in steel the carbon produces the same effect.It is also most probable that the magnetic, as the galvanic, temperature-coefficients vary with the degree of hardness in the same way. Other experiments are also promised on the analogy existing between alloys and steel as regards their physical properties. v. H. v. Dependence of the Boiling Point on Pressure. By G. W. A. KAHLBAUM (Ber., 16, 2476--2484).--It has usually been assumed that a dinhution of pressure of 1 cm. lowers the boiling point 1". Experiments made in an apparatus in which the pressure could be kept constant whilst a considerable amount of liquid distilled, showed thak this assumption is quite erroneous. The experiments were mainly for pressures of 5-100 mm. The nature of the variations is best shown by the results obtained with some of the fatty acids.P* R~. Formic acid. Boiling point. mm. Pressure. --- 24 '84 27 *66 32 -58 41 *40 49 *66 74.54 760 -00 P. R* Boiling point. I-- -- P* R* 56.5' 57.6 63-5 68'8 69.2 7 0 4 139.4 Propionic acid. 0'112 0'111 0*1U4 0'098 0.098 0.097 - mm. Pressure. ---- 21'31 22 '46 31 -34 41 -70 44 '20 47 *30 '760 .OO 63.5" 75.2 81.4 87.5 89-8 161.5 - 0.131 0-171 0.110 0.103 0.101 - - 21.8' 22.6 24.6 2'7.9 30.5 37-6 100.6 Butyric acid. 0.1071 0.1065 0*104 0.101 0.099 0.092 - mm. Pressure. --- 10 -06 21 -48 31 *94 43 -12 48 *go 760 *OO - From these results it will be Been that the variations are peculiar to each suhstance and pressure. The figures in the third column of the tables give the ratio of the diminution of boiling point to diminu- tion of pressure (from the boiling point at 760 mm.), termed by the author the specijic remission.On obtaining by means of curves the specific remission for 0 mm. pressure, it appears that for the snb- stances experimented with (lower fatty acids, alcohols, and anhydrides) n diference in the composition of CH, corresponds with a diference 91' 0.01 in the spec@ remission f o r 0 mm. pressure. A. J. G. Heat of Combination of Carbon and Oxygen. By A. BOILLOT (Conzpt. rend., 97,41)0--491).-Thermochemical investigations should determine the quantity of heat due to each individual constituent entering into combination or being liberated by decomposition, but, up to the present the determinations made measure only the sum or the difference of the effects due to the different constituents.In the combination of carbon and oxygen, how much heat is developed or absorbed by the carbon and oxygen respectively? Let A be the heat developed by the combination of 2 vols. of oxygen (weighing 2.666) with 2 vols." of carbon vapour (weighing 1) to form 2 vols. of car- * The volume ratios and weights are given as in the original paper.142 ABSTRACTS OF CHEMICAL PAPERS bonic anhydride (weighing 3.666), B the heat developed by 1 vol. of oxygen combining with 2 vols. of carbonic oxide to form 2 vols. of carbonic anhydride, then A - B will be the heat developed by the union of 1 vol. of oxygen wit.h 2 vols. of carbon vapour with forma- tion of 2 vols. of carbonic oxide. Let x be the heat absorbed by the unit weight of carbon passing into the state of vapour occupving 2 vols., then A - 13 + a: will he the heat furnished by 1 vol.of oxygen combining with 2 vols. of carbon vapour to form 2 vols. of carbonic oxide, and A - B + 2 = B, whence 2 = 2B - A. Using 6 grams of diamond, the results will be A = 47 cal., A - €3 = 12.9 cal., B = 34.1 cal., and x = 21.2 cal. A + x = 68.2 cal. will be the total heat furnished by the combination of 2 vols. of oxygen (weighing 16 grams) with 2 vols. of carbon vapour (weighing ti grams] to form 2 vols. of carbonic anhzdride (weighing 22 grams). Of these 68.2 cal., 21.2 cal. are absorbed by the carbon. C. H. B. Sodium Alcoholates. By DE FORCRAND (Compt. rend., 97, 108- Ill).-The heats of solution of the three known alcoholates in water a t 20" are as follows :- C2H5Na0, solid + 13.47 cal.C,H5Na0,2C2H60, solid + 10.46 ,, CzH5Na0,3C2H,0, solid + 12.34 ,, and the heats of formation are therefore- 'LC2H60, liquid, + Na,O, solid, = C2H,Na0, solid, + H,O liquid .................... develops + 34-70 cal. C2H60, liquid + NaHO, solid, = C2H5Na0, solid, + H20 liquid.. ........................ 7, + 0.25 99 It would appear, therefore, that the heat of formation of sodium alcoholate from sodium hydroxide, like that of sodium glycollate, is practically nil. C,H,NaO, solid + 2C2H,0, liquid, = C,H,NaO, solid + 3c2H60, liquid, = C:H5Na0,2C2H,0, solid + C2H60, liquid, = C2H,Na0,2C2H,0, solid.. ................ develops + 8.06 cal. C2H,Na0,3CzH60, solid. ................. 9 , + 8-64! 9 1 C2H,Na0,3C2H,G, solid. ................. 9 , + 0.58 7 , A considerable proportion of this development of heat is due to the solidification of the alcohol.C,H,NaO, solid + H20 liquid = C2H60 liquid, + NaHO C2HsNa0,2C,H,0, solid, + H,O liquid = 3C,H,O liquid C2H,Na0,3C2H,0, solid + H,O liquid = 4CzH60 liquid The inverse reactions give- solid.. ........................................ + 1.19 cal. + NaHO, solid ................................ - 6.82 ,, + NaHO, solid ................................ - 7.44 ,, The decomposition of the alcoholates by water in excess takes placeGENERAL AND PHYSICAL CHEMISTRY. 143 by reason of the development of heat which accompanies the hydration of the two products of the reaction, a development which amounts to + 17.78 or + 19.78 cal., according as the amount of alcohol is 3C2H60 or 4c2H60.From these data it follows that C2H,0 iiquid + Na solid = C,H5Na0 solid + H gas develops + 32.13 cal., zt number very similar to that developed by the action of sodium on wat'er. Direct determination of the heat developed by the action of sodium in a large excess of alcohol gives the heat of solution of the anhydrous alcoholate in excess of alcohol as 12.65 cal., a value closely approaching the heat of solution of sodium hydroxide by water. These results show that water and alcohol have almost equivalent functions with respect t o sodium and sodium oxide. This fact and the dissociation of the sec0ndar.y hydrates and alcoholates explain the equilibrium which is established in liquids containing alcohol, water, and sodium oxide. C. H. B. Aqueous Solution. By J.A. GROSHANS (Ann. Phys. Cl~enz. [2], 20, 492--512).--The sp. gr. of an aqueous solution of 1 mol. of a substance in 4 mols. of water can be expressed by the interpolation formula a = 1 + in which a is the molecular weight of the substance, 18 that of water, a is a constant, and X = __ where /3 is another constant. I n this communication, certain relations exist- ing between aa for the hnlo'id salts and the nitrates of certain metals me brought out. Thus, for example, the differences of the values for zn for the iodide and bromide of strontium is equal to the difference between the same values for the iodide and bromide of mdtgnesium. The same difference exists between the values for the bromides and chlorides of magnesium and cadmium. A few exampIes are quoted below :- i 8 ( ~ + xj' a Value for an.Value for aa. SrI, .......... 283.85 MgT,.. ...... 226.93 SrBr, ........ 211.37 MgBr2.. .... 152.38 72.48 74.55 MgBr, ........ 152.38 CdBr, ...... 226.93 MgC1, ........ 78.47 CdCl, ...... 152.38 73.91 74-53 Hence it follows, for these salts, that R(12 - Br,) = R(Brll, - Cl,, = I, - Br2 = Br, - C1, = 73.80. Similarly these differences for au are the same, not only for the non-metallic but also for the metallic radicles. Thus Pb - Ba (aa) = Cd - Mg (au) = 72.48 to 74-35: so also Ba - Sr = Sr - Ca = 43.15. A series of analogous differences is quoted in this memoir, derived not only from the above formula, b u t also from modifications of it in which other constants144 ABSTRACTS OF CHEMICAL PAPERS. are introduced. The compounds more especially investigated are the halogen acids and their salts together with the nitrates of the alkaline earth and the magnesium-zinc-cadmium-group. V.H. V. Specific Gravity of Normal Salt Solutions. By C . BENDER (Ann. Plys. Chena. [ 21, 20, 560-578).-Valson has noticed (Compt. rend., 73 and 77) certain differences existing between the sp. grs. of metallic salts containing 1 gram of salt in 1 litre. For example, there is a constant difference between the sp. grs. of the potassium and ammonium salts, whatever be the non-metallic radicle associated with them, and, conversely, there is a constant difference between the sp. grs. of the chlorides and nitrates, whatever be the metallic radicle. So that to each metallic and non-metallic radicle there can be assigned a certain value or modulus with which it may be said to enter into solution. The following table explains the above statement :- c1.Br. I. I(.. .......... 1.0444 1.0800 1.1135 NH4.. ........ 1.0157 1.0520 1.0847 0.0287 0*0280 0.0288 K. Na. NH,. NOj.. ........ 1.0591 1.0540 1.0307 C1 ............ 1-0444 1.0396 1.0157 0.0147 0.0144 0.0150 If, then, the sp. gr. of one salt, preferably that of ammonium chlo- ride as the lowest, be taken as a standard, then the sp. gr. of other salts can be deduced from it, by means of the equation d = d, + mb + ms, in which d, is the sp. gr. of ammonium chloride, and nq,.rns the moduli of the metallic and non-metallic radicle respectively. Valson has also observed that similar relations exist between the refraction equivalent of the metallic salts.From these facts, the following general law may be deduced:- Elements or radicles, entering into conabination, are endowed with certain plzysizal constants which are independent of the chentical nature o f the resaiIta<nt compounds. It is, however, pointed out that these observations were restricted to salt solutions of the same strength, and presupposes the same coefficient of expansion for each of the salt solutions. I n this paper these observations are extended to solutions contain- ing one or more molecules of salt; it is shown that the modulus (vide g/,pra) divided by the number of molecules in solution is a constant. This statement is explained by the table below, in which /A. represents the number of molecules and A the modulus :- A P - A NaCl.A. - p. NH4C1. KC1. A. 1.. 1-0157 1.0444 287 2 i 7 1.0401 244 244 2 . . 1.0308 1.0887 579 289 1.0788 450 240 3.. 1.0451 1.1317 866 289 1.1164 713 238GENERAL AND PHYSICAL CHEMISTRY. 145 A series of analogous examples of a large number of metallic salts is given in the original memoir ; some of the values for the modulus in =Am units at O", deduced from various experiments, are given below :- Metal. A. Element or Radicle. A. 0 Cl.. .......... 0 NH, .......... K ............ 289 Br .......... 373 NO 163 Na .......... 238 L i . . (SO,), ........ 206 .......... 78 +Ba C2H302.. ...... -15 .......... 735 +Sr .......... 500 +Mg .......... 210 +M.n .......... 356 t Z n .......... 410 +Pb .......... 1087 From these data the following will be the general equation for calculating the sp.gr. of a salt solution containing p molecules in solution : dp = d(p.)o +p(mb + m), in which cia, mb, and mS represent the same values as in the equation above. Attention is drawn to the general interest attached to these relations, and to their wider appli- cation to the more complicated organic combinations. A New Liquid of High Specific Gravity, Refraction Equiva- lent, &c. By C. ROHRBACH (Ann. Phys. Chem. [2], 20, 169-174).- Schaffgotsch, Church, and Klein have proposed various liquids of high sp. gr. for the practical separation of minerals. In the present memoir, a solution of the double salt of barium and mercuric iodide is recommended for this purpose, which forms a highly refractive golden-coloured liquid of sp.gr. 3.575 to 3.588. It boils at about 145", evolving with the steam red vapours of mercuric iodide. It has the advantage that it neither decompose carbonates, nor absorbs carbonic anhydride from the air, but readily takes up water. Tables are given of various minerals which may be separated by means of this liquid. The following refraction values for Praunhofer's lilies were obtained :- V. H. V. F. nF-nC - C. D. E. nC. iodide sp. gr. = 1.7754: 1.7930 1.8065 1.8488 0.409 Barium mercuric 3.564 ........ 1 G and the following Fraunhofer's lines could not be measured, owing to strong absorption in the violet. The high dispersive power of the liquid is also shown by the well-defined separation of the two D lines nD1 and nD2. This liquid may possibly be available for other mineralogical and physical investigations. V.H. V. Compressibility of Gases. By E. H. AMAGAT (Ann. Chim. P h p [ 5 ] , 28, 456-464).-The author contradicts Cailletet's statements (Ann. Chim. Phys. [5], 19), (1) t,hat mercury absorbs oxygen at the146 ABSTRACTS OF CHEMICAL PAPERS. Pressure em. 50". cm. ------- 74 1-0037 72 291 1.0143 282 3 47 1.0075 143 100". cm. 200". cm. 1 300". 1-002'7 '71 1*0009 72 1-0003 1.0085 250 1*0041 287 1.0017 -__----- 1.0051 141 1.0025 143 1.0015GENERAL AND PHYSICAL CHEMISTRY. 147 carbonic anhydride was observable ; (3) within temperature o€ + 23" to - 8" a rise of temperature produces an acceleration, a fall a corre- sponding retardation of the absorption. In the three years 5.135 C.C. of carbonic anhydride under standard conditions were absorbed by 1 square metre of the glass wool.The results of these experiments are in direct contradiction to others on the same phenomenon ; this discrepancy is, however, due to the fact that in former experiments the phenomenon was supposed to be finite and not continuous. As the chemical affinity of the silicic anhydride for the basic sub- stances in t'he glass is greater than that of the carbonic anhydride, the supposition of a combination of the latter with the glass is pre- cluded ; thus it appears thak the carbonic anhydride is condensed as such. The long continuation of the phenomenon can be explained by an imperfect interpenetration of the glass by the molecules of the liquid carbonic anhydride. Further experiments will be required to prove whether after a sufficiently long interval of time this interpene- tration becomes a sufficiently diminishing quantit,y ; when this point is reached, the conditions remaining the same, neither condensation nor evaporation of the liquid carbonic anhydride would take place, although either one or the other might be caused by a change of the conditions.It would thus be not altogether impossible that for every series of temperatures there would he a corresponding series of levels of the layer of the carbonic anhydride. It was further found by experiment that atmospheric air behaves towards a glass surface exactly as carbonic anhydride. V. H. V. Similarity of the Behaviour of Ultramarine in a very fine State of Division to that OF Metallic Sulphides in the Colloidal State.By P. EBELL (Ber., 16, 2429--2432).-Ultramarine in a very finely divided state, as it is obtained by grinding and elutriation in the course of its manufacture, shows great similarity in behaviour to the colloidal metallic sulphides described by Spring (Abstr., 1883, 904). The finer parts will remain siispended in pure water for months ; the liquid passes unaltered through several thicknesses of Swedish filter paper, does not show any sign of turbidity when examined in a layer 2 cm. thick, and on evaporation leaves the ultramarine in a lustrous layer on the walls of the vessel. Microscopic examination ( x 1200) shows only points appearing partly colourless, partly pale blue by transmitted light, deep blue by reflected light. The addition of small quantities of salts, &c., to the liquid caiises the separation of the ultramarine : on washing with pure water or very great dilution, the ultramarine passes again into suspension.The author regards it as doubtful if the copper sulphide in the so-called colloidal state is really in solution in water, or whether it is not rather in suspension in a state of division far finer than that in which ultramarine ca,n be obtained by mechanical means. A. J. G . Specific Volumes of Liquid Substances. By H. KOPP (Bw., 16, 2458--2460).-The author thinks it advisable to call attention to148 ABSTRACTS OF CHEMICAL PAPERS. the fact that in his original paper (AnmaZen, 96, 155) the relations between composition and specific volume as derived from the observa- tions then accessible were not advanced as being the correct ones, but only as useful approximations. In comparing the calculated and observed volumes, it is necessary to bear well in mind the real nature of any difference : for instance, taking methyl alcohol (cal.vol. 40.8, obs. 42.1, diff. 1.3) and amyl benzoate (cal. 240 0, obs. 247.7, diff. 7*7), there is not, as a t first sight appears, a much greater divergence in the latter case, but in each case the difference is the same, = 3.2 per cent. of the calculated specific volume. The results obtained by the later experiments with bodies whose relations to one another are now more clearly known, certainly show less agreement with a law of atomic volume than was expected from the earlier experiments ; but the agreement of individual substances with many so-called laws is often more general than absolute.A. J. G.137General and Physical Chemistry.Photographic Investigations of the Ultra-Violet SparkSpectra emitted by Metallic Elements and their Combina-tions under Varying Conditions. By W. N. HARTLEY (Chem.News, 48, 195-196).-It has been shown (Brit. Assoc. Jour.? 1882)that t,he spectra of metallic solutions are the same as those frommetallic electrodes, the principal difference being that short lines inthe spectra from the metals become long in the spectra from solutions,whilst very short lines sometimes disappear, as for example in thecase of zinc. This is probably due to the solution not being able tocontain a sufficient quantity of metal to yield an image of them :thus the very short lines of the aluminium spectrum are not repro-duced in solutions of the chloride unless the solutions ai-e extremelyconcentrated. With regard to the short lines being lengthened bymoistening iridium electrodes with calcium chloride, it has now beenshown that moistening with water has the same effect : hence the sup-position that a chloride of the metal was formed is untenable.Thevery short lines in the zinc spectrum are also lengthened by moisten-ing the electrodes with water. This variation in the spectra appearsto be due t o the cooling action of the water on the negative electrode,since heating the electrodes produces a reverse result. Carbon givestwo spectra in air when dry, and a third when moistened with water ;the three have been photographed, but cannot be exactly describedwithout maps.Numerous experiments have been tried to determinewhich non-metallic. elements are capable of yielding spark spectrawhen they are combined with metals. Chlorides, bromides, iodides,snlphides, nitrates, sulphates, selenates, phosphates, carbonates, andcyanides yield none. Hydrochloric acid solutions of arsenites,areenates, and antirnonates yield spectra of arsenic and antimonyrespectively, afid solutions of borates and silicates yield characteristicspectra (see below) of the non-metallic constituents ; even if sodiumsalts are employed no metallic lines appear in the case of borates, andwith silicates only the strongest sodium line ( h = 3301) is visible,even in concentrated solutions.Spark.r--"(wave-lengths) .(wave-lengths) . Boron ----Kz3450.1 2881-02497.0 2631.42496.2 2.541.02528.12523-52518.52513.725013.32435.5251 5.5VOL. XLVI.Carbon spectra lines (Liveing andDewar).r----- 7Spark. Arc.- 2881.02541.0 -2528.2 2528.12523-6 2523.92518.7 2518.82515.8 2515.82514.0 2514.12506.3 2506.62478-32434.8138 ABSTRACTS OF CHEMICAL PAPERS.It will be observed that these silicon lines are identical with those(annexed table) attributed by Liveing and Dewar (Proc. Roy. Soc.,33, 403) to carbon, and from many hundred spectra taken betweengraphite poles it is apparent that in the arc spectrum carbon yieldsbut one line (2478.3 wave-length) in the ultra-violet.The ultra-violet spectrum of beryllium has been obtained from thesolution of its chloride, and the following lines were observed :-Wave-lengths.3320.13129.92649.42493.224’77.7Description.Strong, sharp.Very strong, extended.Strong, sharp.Strong, sharp.Strong, sharp.From these observations and the general grouping of the lines, theauthor feels inclined to regard beryllium as the first member of thedyad series to which barium, calcium, and strontium belong.Reasonsare given for not classing beryllium with other metals.D. A. L.Production of Electricity by Condensation of AqueousVapour. By S. K~LISCHER (Ann. Phys. Chew%. [2], 20, 614-620).-The production of electricity by condensation of aqueous vapourpresents a problem of considerable meteorological importance asregards the origin of atmospheric electricity.It is, however, pro-bable that the production of electricity observed is in most cases dueto the friction between the water particles and the condensing surface.Tn this paper the problem is examined experimentally by means of anapparatus which permitted the condensation of aqueous vapour bycooling. It consisted essentially of a series of beakers filled with ice,and covered externally with tinfoil; the beakers were placed on aplate of galvanised iron connected with a quadrant electrometer, andthe whole combination was enclosed in a metallic box. Althoughdeviations of the needles of the electrometer were observed, yetthey were of the same magnitude and direction whether the beakerswere filled with ice or not; aud secondly, they were sometimes in one,and sometimes in the other direction.Other experiments are described in which air was compressed in,and then allowed to expand from a vessel resembling the electric egg,the metallic stopcock of which was in connection with a quadrantelectrometer.But in this case, although a pressure of 25 atmosphereswas used, and the aqueous vapour fell in the form of fine dew onreleasing the pressure, yet there was no development of electricity.V. H. V.Measurement of the Quantity of Electricity produced by aZamboni’s Pile. By E. RIECKE (Ann. Phys. Chem. [2], 20, 512-524) .-This paper contains a series of determinations in absolutemeasure of the quantities of electricity produced by three Zamboni’spiles containing a large number of platinum plates iiiterposedbetween strips of silk.A long series of tables of those quantitiesobtained on days of different relative hcmidity are given, and formulaGENERAL AND PHYSICAL CHEMISTRY. 139for their calculation as well as for diffeibences of potential are alsoquoted. V. H. V.Influence of Galvanic Polarisation on Friction. B-y K .WAITZ (Ann. Phys. Chem. [2], 20, 285--303).-In 1874 Edisonnoticed that the friction between a metallic and a porous platemoistened with some conducting liquid, was diminished when anelectric current was sent through this combination from the porous tothe metallic plate. Further changes in the friction are produced byvariations in the intensity of the current.This fact has been prac-tically applied in the construction of telephones and electromoto-graphs.In this memoir the phenomenon is more completely investigated.The apparatus consists in the main of a clay cylinder filled withacidulated water, and enclosed within a glass vessel filled with waterof t>he same concentration. A platinum foil is introduced into theinner, and a strip of glass in the outer vessel, on which a smallplatinum foil is stretched ; this latter is connected with a mechaiiicalarrangement whereby the platinum foil on the glass strip can bepressed against the clay cylinder with various degrees of pressure.The whole aryangement is enclosed in circuit with two Daniell's cells,a metallic arrangement to measure the degree of pressure, and a,rheostat to vary the intensity of the current.In many experimentsit was found that the friction between the platinum and the porouscell is materially diminished when the intensity of the current issufficient to decompose the acidulated water.As the contact of the platinum and the clay was not found to besufficiently perfect, a polished glass cylinder was substituted. Thealteration of friction between glass and various metals, platinum,palladium, gold, and nickel, introduced into such solutions as sulphuricacid, potash, and soda, and potassium ferrocyanide was carefullyexamined : in the original memoir extensive tables are given of theresults obtained in the course of the investigation. As a general resultit may be stated that there is a diminution of resistance when themetallic plate is the anode, but an increase when the plate is thekathode, and the intensity insufficient to decompose the electrolyticliquid.This latter fact is contrary to the experience of Koch, whofound no alteration in the case of the kathode. As the diminut'ion ofresistance appears only when bubbles of gas appear at the surface ofthe plate, it appears probable that the occlusion of the gas by theelectrode is the cause of the phenomenon. Another hypothesis is thatthe formation of an electric double stratum, called forth by the polari-sation on the surface of the electrodes, alters the external frictionbetween the metallic surface and the glass on the one hand, and theglass and the liquid on the other.Further experiments will decide bet ween these two hypotheses,but the writer inclines t o the latter.V. H. V.Relations between Coefficients of Friction and GalvanicConduction. By E. WIEDEXANN (Ann. Plqs. Chenz. [ d ] , 20, 537-538).-In connection with a remark of G. Wiedemann ou certain rela-1 140 ABSTRACTS OF CHEMICAL PAPERS.tions existing between coefficients of friction and galvanic conduction,and the theoretical deductions drawn therefrom, a series of investiga-tions has been made on this point. However, in order to prove howfar these relations hold good, the author examined solutions of crys-talline zinc sulphate in water and aqueous glycerol of varioue concen-trations. The coefficients of friction were measured by Spring’sapparatus, those of conduction by a Wheatstone’s bridge.Ratio of coefficient Ratio of coefficientof friction of conductionStrength of solution r--h-- 7 r----- 71 per cent .........1 68.7 1 12.12 Y, ........ 1 29.8 1 9.525 9 ) ........ 1 6.5 1 3.68These numbers show that the ratios existing between the co-efficients of friction and conduction are not simple, and further thatthe nature of the solvent and also its concentration exert a mostmarked influence on them. V. H. V.ZnS047H20. I n water. I n glycerol. In water. I n glycerol.Galvanic Temperature CoefRcient. By V. STOUHAL andC. BAROS (Ann. Phys. Chew. [2], 20,525-536).-Previous reseawheshave not established any differences of specific resistance as factors ofthe temperature corresponding to known differences of compositionof various forms of iron and steel.It appeared, however, probable tothe writer that iron, whose coefficient of resistance varies accordingto its degree of hardness and temper, should also possess varioustemperature coefficients. In this connection it has been shown byMatthiessen and Vogt that, the temperature coefficients of platinum-silver alloys decrease with the proportion of platinum ; like dif-ferences have been observed by the authors in the case of Germansilver. Similarly it is to be expected that iron, containing variousproportions of carbon, which may funct.ion as the second metal,should display similar varia,tions. Experiments were accordinglymade on steel tempered a t various “heats,” and specimens of bar andpig-iron.I n the case of steel the temperature coefficient of the steel varies asits coefficient of resistance continuously with the hardness of thesteel, and decreases with increase of the temperature a t which it istempered.Tlie experiments of Matthiessen and Vogt on bar-iron, and thosequoted in this memoir on pig-iron, show that the temperature coeffi-cient varies with the proportions of carbon, and further, that thespecific resistance of the latter is far greater than that of the hardest5: teel.The above observations point to a marked anarlogy existing betweenalloys and steel in their galvanic relations, and to a general law thatin all cases of homogeneous substances differences of specific resist-ance cause similar differences of temperature coefficients, incrementsof the former corresponding to diminutions of the latter.In alloysit is the small proportion of added metal which raises the specific reGEXERAL AND PHYSICAL CHEMIfjTRY. 141Boilingpoint.sistance, in steel the carbon produces the same effect. It is also mostprobable that the magnetic, as the galvanic, temperature-coefficientsvary with the degree of hardness in the same way.Other experiments are also promised on the analogy existingbetween alloys and steel as regards their physical properties. v. H. v.Dependence of the Boiling Point on Pressure. By G. W.A. KAHLBAUM (Ber., 16, 2476--2484).--It has usually been assumedthat a dinhution of pressure of 1 cm.lowers the boiling point 1".Experiments made in an apparatus in which the pressure could bekept constant whilst a considerable amount of liquid distilled, showedthak this assumption is quite erroneous. The experiments weremainly for pressures of 5-100 mm. The nature of the variations isbest shown by the results obtained with some of the fatty acids.P* R~.Formic acid.Boilingpoint.mm.Pressure.---24 '8427 *6632 -5841 *4049 *6674.54760 -00P. R*Boilingpoint.I-- --P* R*56.5'57.663-568'869.27 0 4139.4Propionic acid.0'1120'1110*1U40'0980.0980.097 -mm.Pressure.----21'3122 '4631 -3441 -7044 '2047 *30'760 .OO63.5"75.281.487.589-8161.5-0.1310-1710.1100.1030.101 - -21.8'22.624.62'7.930.537-6100.6Butyric acid.0.10710.10650*1040.1010.0990.092 -mm.Pressure.---10 -0621 -4831 *9443 -1248 *go760 *OO -From these results it will be Been that the variations are peculiarto each suhstance and pressure.The figures in the third column ofthe tables give the ratio of the diminution of boiling point to diminu-tion of pressure (from the boiling point at 760 mm.), termed by theauthor the specijic remission. On obtaining by means of curves thespecific remission for 0 mm. pressure, it appears that for the snb-stances experimented with (lower fatty acids, alcohols, and anhydrides)n diference in the composition of CH, corresponds with a diference 91'0.01 in the spec@ remission f o r 0 mm.pressure. A. J. G.Heat of Combination of Carbon and Oxygen. By A. BOILLOT(Conzpt. rend., 97,41)0--491).-Thermochemical investigations shoulddetermine the quantity of heat due to each individual constituententering into combination or being liberated by decomposition, but,up to the present the determinations made measure only the sum orthe difference of the effects due to the different constituents. In thecombination of carbon and oxygen, how much heat is developed orabsorbed by the carbon and oxygen respectively? Let A be the heatdeveloped by the combination of 2 vols. of oxygen (weighing 2.666)with 2 vols." of carbon vapour (weighing 1) to form 2 vols. of car-* The volume ratios and weights are given as in the original paper142 ABSTRACTS OF CHEMICAL PAPERSbonic anhydride (weighing 3.666), B the heat developed by 1 vol.ofoxygen combining with 2 vols. of carbonic oxide to form 2 vols. ofcarbonic anhydride, then A - B will be the heat developed by theunion of 1 vol. of oxygen wit.h 2 vols. of carbon vapour with forma-tion of 2 vols. of carbonic oxide. Let x be the heat absorbed by theunit weight of carbon passing into the state of vapour occupving2 vols., then A - 13 + a: will he the heat furnished by 1 vol. ofoxygen combining with 2 vols. of carbon vapour to form 2 vols. ofcarbonic oxide, and A - B + 2 = B, whence 2 = 2B - A.Using 6 grams of diamond, the results will be A = 47 cal., A - €3= 12.9 cal., B = 34.1 cal., and x = 21.2 cal. A + x = 68.2 cal.will be the total heat furnished by the combination of 2 vols.ofoxygen (weighing 16 grams) with 2 vols. of carbon vapour (weighingti grams] to form 2 vols. of carbonic anhzdride (weighing 22 grams).Of these 68.2 cal., 21.2 cal. are absorbed by the carbon.C. H. B.Sodium Alcoholates. By DE FORCRAND (Compt. rend., 97, 108-Ill).-The heats of solution of the three known alcoholates in watera t 20" are as follows :-C2H5Na0, solid + 13.47 cal.C,H5Na0,2C2H60, solid + 10.46 ,,CzH5Na0,3C2H,0, solid + 12.34 ,,and the heats of formation are therefore-'LC2H60, liquid, + Na,O, solid, = C2H,Na0,solid, + H,O liquid .................... develops + 34-70 cal.C2H60, liquid + NaHO, solid, = C2H5Na0, solid, + H20 liquid.. ........................ 7, + 0.25 99It would appear, therefore, that the heat of formation of sodiumalcoholate from sodium hydroxide, like that of sodium glycollate, ispractically nil.C,H,NaO, solid + 2C2H,0, liquid, =C,H,NaO, solid + 3c2H60, liquid, =C:H5Na0,2C2H,0, solid + C2H60, liquid, =C2H,Na0,2C2H,0, solid.................. develops + 8.06 cal.C2H,Na0,3CzH60, solid. ................. 9 , + 8-64! 9 1C2H,Na0,3C2H,G, solid. ................. 9 , + 0.58 7 ,A considerable proportion of this development of heat is due to thesolidification of the alcohol.C,H,NaO, solid + H20 liquid = C2H60 liquid, + NaHOC2HsNa0,2C,H,0, solid, + H,O liquid = 3C,H,O liquidC2H,Na0,3C2H,0, solid + H,O liquid = 4CzH60 liquidThe inverse reactions give-solid.. ........................................ + 1.19 cal.+ NaHO, solid ................................- 6.82 ,,+ NaHO, solid ................................ - 7.44 ,,The decomposition of the alcoholates by water in excess takes placGENERAL AND PHYSICAL CHEMISTRY. 143by reason of the development of heat which accompanies the hydrationof the two products of the reaction, a development which amounts to + 17.78 or + 19.78 cal., according as the amount of alcohol is3C2H60 or 4c2H60. From these data it follows that C2H,0 iiquid + Na solid = C,H5Na0 solid + H gas develops + 32.13 cal., ztnumber very similar to that developed by the action of sodium onwat'er. Direct determination of the heat developed by the action ofsodium in a large excess of alcohol gives the heat of solution ofthe anhydrous alcoholate in excess of alcohol as 12.65 cal., a valueclosely approaching the heat of solution of sodium hydroxide bywater.These results show that water and alcohol have almost equivalentfunctions with respect t o sodium and sodium oxide.This fact and thedissociation of the sec0ndar.y hydrates and alcoholates explain theequilibrium which is established in liquids containing alcohol, water,and sodium oxide. C. H. B.Aqueous Solution. By J. A. GROSHANS (Ann. Phys. Cl~enz. [2],20, 492--512).--The sp. gr. of an aqueous solution of 1 mol. of asubstance in 4 mols. of water can be expressed by the interpolationformula a = 1 + in which a is the molecular weight ofthe substance, 18 that of water, a is a constant, and X = __ where/3 is another constant. I n this communication, certain relations exist-ing between aa for the hnlo'id salts and the nitrates of certain metalsme brought out.Thus, for example, the differences of the values forzn for the iodide and bromide of strontium is equal to the differencebetween the same values for the iodide and bromide of mdtgnesium.The same difference exists between the values for the bromides andchlorides of magnesium and cadmium. A few exampIes are quotedbelow :-i 8 ( ~ + xj'aValue for an. Value for aa.SrI, .......... 283.85 MgT,.. ...... 226.93SrBr, ........ 211.37 MgBr2.. .... 152.3872.48 74.55MgBr, ........ 152.38 CdBr, ...... 226.93MgC1, ........ 78.47 CdCl, ...... 152.3873.91 74-53Hence it follows, for these salts, that R(12 - Br,) = R(Brll, - Cl,,= I, - Br2 = Br, - C1, = 73.80.Similarly these differencesfor au are the same, not only for the non-metallic but also for themetallic radicles. Thus Pb - Ba (aa) = Cd - Mg (au) = 72.48 to74-35: so also Ba - Sr = Sr - Ca = 43.15. A series of analogousdifferences is quoted in this memoir, derived not only from the aboveformula, b u t also from modifications of it in which other constant144 ABSTRACTS OF CHEMICAL PAPERS.are introduced. The compounds more especially investigated are thehalogen acids and their salts together with the nitrates of the alkalineearth and the magnesium-zinc-cadmium-group. V. H. V.Specific Gravity of Normal Salt Solutions. By C . BENDER(Ann. Plys. Chena. [ 21, 20, 560-578).-Valson has noticed (Compt.rend., 73 and 77) certain differences existing between the sp.grs. ofmetallic salts containing 1 gram of salt in 1 litre. For example, thereis a constant difference between the sp. grs. of the potassium andammonium salts, whatever be the non-metallic radicle associated withthem, and, conversely, there is a constant difference between thesp. grs. of the chlorides and nitrates, whatever be the metallic radicle.So that to each metallic and non-metallic radicle there can be assigneda certain value or modulus with which it may be said to enter intosolution. The following table explains the above statement :-c1. Br. I.I(.. .......... 1.0444 1.0800 1.1135NH4.. ........ 1.0157 1.0520 1.08470.0287 0*0280 0.0288K. Na. NH,.NOj.......... 1.0591 1.0540 1.0307C1 ............ 1-0444 1.0396 1.01570.0147 0.0144 0.0150If, then, the sp. gr. of one salt, preferably that of ammonium chlo-ride as the lowest, be taken as a standard, then the sp. gr. of othersalts can be deduced from it, by means of the equation d = d, + mb + ms, in which d, is the sp. gr. of ammonium chloride, and nq,.rns themoduli of the metallic and non-metallic radicle respectively. Valsonhas also observed that similar relations exist between the refractionequivalent of the metallic salts.From these facts, the following general law may be deduced:-Elements or radicles, entering into conabination, are endowed withcertain plzysizal constants which are independent of the chentical natureo f the resaiIta<nt compounds.It is, however, pointed out that these observations were restrictedto salt solutions of the same strength, and presupposes the samecoefficient of expansion for each of the salt solutions.I n this paper these observations are extended to solutions contain-ing one or more molecules of salt; it is shown that the modulus (videg/,pra) divided by the number of molecules in solution is a constant.This statement is explained by the table below, in which /A.representsthe number of molecules and A the modulus :-AP- ANaCl. A. - p. NH4C1. KC1. A.1.. 1-0157 1.0444 287 2 i 7 1.0401 244 2442 . . 1.0308 1.0887 579 289 1.0788 450 2403.. 1.0451 1.1317 866 289 1.1164 713 23GENERAL AND PHYSICAL CHEMISTRY. 145A series of analogous examples of a large number of metallic saltsis given in the original memoir ; some of the values for the modulusin =Am units at O", deduced from various experiments, are givenbelow :-Metal.A. Element or Radicle. A.0 Cl.. .......... 0 NH, ..........K ............ 289 Br .......... 373NO 163 Na .......... 238L i . . (SO,), ........ 206 .......... 78+Ba C2H302.. ...... -15 .......... 735+Sr .......... 500+Mg .......... 210+M.n .......... 356t Z n .......... 410+Pb .......... 1087From these data the following will be the general equation forcalculating the sp. gr. of a salt solution containing p molecules insolution : dp = d(p.)o +p(mb + m), in which cia, mb, and mS representthe same values as in the equation above. Attention is drawn to thegeneral interest attached to these relations, and to their wider appli-cation to the more complicated organic combinations.A New Liquid of High Specific Gravity, Refraction Equiva-lent, &c.By C. ROHRBACH (Ann. Phys. Chem. [2], 20, 169-174).-Schaffgotsch, Church, and Klein have proposed various liquids ofhigh sp. gr. for the practical separation of minerals. In the presentmemoir, a solution of the double salt of barium and mercuric iodideis recommended for this purpose, which forms a highly refractivegolden-coloured liquid of sp. gr. 3.575 to 3.588. It boils at about 145",evolving with the steam red vapours of mercuric iodide. It has theadvantage that it neither decompose carbonates, nor absorbs carbonicanhydride from the air, but readily takes up water.Tables aregiven of various minerals which may be separated by means of thisliquid. The following refraction values for Praunhofer's lilies wereobtained :-V. H. V.F. nF-nC - C. D. E. nC.iodide sp. gr. = 1.7754: 1.7930 1.8065 1.8488 0.409Barium mercuric3.564 ........ 1 G and the following Fraunhofer's lines could not be measured, owingto strong absorption in the violet. The high dispersive power of theliquid is also shown by the well-defined separation of the two D linesnD1 and nD2. This liquid may possibly be available for othermineralogical and physical investigations. V. H. V.Compressibility of Gases. By E. H. AMAGAT (Ann. Chim. P h p[ 5 ] , 28, 456-464).-The author contradicts Cailletet's statements(Ann. Chim.Phys. [5], 19), (1) t,hat mercury absorbs oxygen at th146 ABSTRACTS OF CHEMICAL PAPERS.Pressure em. 50". cm. -------74 1-0037 72291 1.0143 2823 47 1.0075 143100". cm. 200". cm. 1 300".1-002'7 '71 1*0009 72 1-00031.0085 250 1*0041 287 1.0017-__-----1.0051 141 1.0025 143 1.001GENERAL AND PHYSICAL CHEMISTRY. 147carbonic anhydride was observable ; (3) within temperature o€ + 23"to - 8" a rise of temperature produces an acceleration, a fall a corre-sponding retardation of the absorption. In the three years 5.135 C.C.of carbonic anhydride under standard conditions were absorbed by1 square metre of the glass wool.The results of these experiments are in direct contradiction toothers on the same phenomenon ; this discrepancy is, however, due tothe fact that in former experiments the phenomenon was supposedto be finite and not continuous.As the chemical affinity of the silicic anhydride for the basic sub-stances in t'he glass is greater than that of the carbonic anhydride,the supposition of a combination of the latter with the glass is pre-cluded ; thus it appears thak the carbonic anhydride is condensed assuch.The long continuation of the phenomenon can be explainedby an imperfect interpenetration of the glass by the molecules of theliquid carbonic anhydride. Further experiments will be required toprove whether after a sufficiently long interval of time this interpene-tration becomes a sufficiently diminishing quantit,y ; when this pointis reached, the conditions remaining the same, neither condensationnor evaporation of the liquid carbonic anhydride would take place,although either one or the other might be caused by a change of theconditions.It would thus be not altogether impossible that for everyseries of temperatures there would he a corresponding series of levelsof the layer of the carbonic anhydride.It was further found by experiment that atmospheric air behavestowards a glass surface exactly as carbonic anhydride.V. H. V.Similarity of the Behaviour of Ultramarine in a very fineState of Division to that OF Metallic Sulphides in the ColloidalState. By P. EBELL (Ber., 16, 2429--2432).-Ultramarine in a veryfinely divided state, as it is obtained by grinding and elutriation in thecourse of its manufacture, shows great similarity in behaviour to thecolloidal metallic sulphides described by Spring (Abstr., 1883, 904).The finer parts will remain siispended in pure water for months ; theliquid passes unaltered through several thicknesses of Swedish filterpaper, does not show any sign of turbidity when examined in a layer2 cm. thick, and on evaporation leaves the ultramarine in a lustrouslayer on the walls of the vessel. Microscopic examination ( x 1200)shows only points appearing partly colourless, partly pale blue bytransmitted light, deep blue by reflected light. The addition of smallquantities of salts, &c., to the liquid caiises the separation of theultramarine : on washing with pure water or very great dilution,the ultramarine passes again into suspension. The author regards itas doubtful if the copper sulphide in the so-called colloidal state isreally in solution in water, or whether it is not rather in suspensionin a state of division far finer than that in which ultramarine ca,n beobtained by mechanical means. A. J. G .Specific Volumes of Liquid Substances. By H. KOPP (Bw.,16, 2458--2460).-The author thinks it advisable to call attention t148 ABSTRACTS OF CHEMICAL PAPERS.the fact that in his original paper (AnmaZen, 96, 155) the relationsbetween composition and specific volume as derived from the observa-tions then accessible were not advanced as being the correct ones, butonly as useful approximations.In comparing the calculated and observed volumes, it is necessaryto bear well in mind the real nature of any difference : for instance,taking methyl alcohol (cal. vol. 40.8, obs. 42.1, diff. 1.3) and amylbenzoate (cal. 240 0, obs. 247.7, diff. 7*7), there is not, as a t first sightappears, a much greater divergence in the latter case, but in eachcase the difference is the same, = 3.2 per cent. of the calculatedspecific volume.The results obtained by the later experiments with bodies whoserelations to one another are now more clearly known, certainly showless agreement with a law of atomic volume than was expected fromthe earlier experiments ; but the agreement of individual substanceswith many so-called laws is often more general than absolute.A. J. G

ISSN:0368-1769    

DOI:10.1039/CA8844600137

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

148 ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c Chemistry. Critical Temperature and Pressure of Liquid Oxygen. By S. WRORLEWSKI (Compt. rend., 97, 309-310).-When oxygen is liquefied by pressure in a bent tnbe surroutided by liquid ethylene which is caused to evaporate rapidly, it is found that, as the amount of liquefied oxygen increases so that it rises above the surface of the ethylene, the pressure necessary to continue liquefaction gradually increases, and when the liquid oxygen rises t o a certain height in the tube, the meniscus becomes indistinct and finally disappears. These results are due to the fact that the temperature of that part of the tube above the liquid ethylene gradually increases as the distance from the ethylene increases. The disappearance of the meniscus takes place at a, pressure of about 50 atmos., and on slightly reducing the pressure the meniscus reappears.Carbonic anhydride was liquefied by pressure in a tube, the lower part of which was placed in melting ice, whilst the upper part was heated to 50°, the intermediate portions being of course at inter- mediate temperatures. As the liquefied gas approached the heated portion of the tube, the pressure required to continue liquefaction gradually increased until at about 76 atmoa. the meniscus disap- peared, but it reappeared on slightly reducing the pressure and con- sequently reducing the volume of the liquid. The disappearance and reappearance of the meniscus in both cases evidently takes place at that part of the tube which is at the critical temperature for the particular gas, and the pressure observed at the time of disappearance is the critical pressure.The critical pressure for oxygen is about 50 atmos., and the critical temperature is approximately - 113". C. H. B.INORGANIC CHEMISTRY. 149 Critical Point of Oxygen. By E. SARRAU (Compt. rend., 97, G9-490) .-The critical pressure and temperature calculated by means of Clausius’ formula from the results of Amagat’s experiments on the compressibility of oxygen, are 48.7 atmos., and - 105.4” respectively. These values agree fairly well with Wroblewski’s determinations (see preceding Abstract). Conduct of Moist Phosphorus and Air towards Carbonic Oxide. By I. REMSEN and E. H. KEISER (Chenz. News, 48, 199- 201).-In reference to the work of Hoppe-Seyler (dbstr., 1880, 3), Baumann (ibid., 1882,691), Traube (ibid., 1882, 795), and Leeds (ihid., 1880, 237), on the existence of an active form of oxygen distinct from ozone, the authors have repeated some of the experiments.A repeti- tion of Traube’s experiment led the authors t o confirm his statement, viz., that the oxidation of palladium-hydrogen is due to bhe formation of hydrogen dioxide. And again, several repetitions of Leeds’s and Baumann’s experiments, in which great care was taken to prevent the mixed gases from inside the apparatus coming in contact with organic matter, led the authors to negative Leeds’s and Baumann’s conclu- sions; under these conditions no oxidation of carbon monoxide to dioxide took place. In these experiments ad1 the stoppers were covered with water or mercury, connections were made with pieces of glass tubing bent twice a t right angles, so as 00 avoid india-rubber joints, and all necessary plugs were of asbestos.I n some experiments, the asbestos plugs were replaced by cotton-wooll with the result that the gas which previously contained no carbonic anhydride, now precipitated baryta-water ; this explains Leeds’s error. No satisfactory explanation is given of the negative results obtained by Leeds and Baumann when no carbonic oxide was used. The ant,hors are of opinion that the action of air and moist phosphorus on carbonic oxide furnishes no evidence of the existence of the so-called active oxygen. C. H. B. D. A. L. Atomic Refraction of Sulphur. By R. NASINI (Gazzetta, 13, 2 9 6 4 1 1 ) .-Bruhl’s labours on atomic refraction have shown that the same element may have different.atomic refractions according to its mode of union with the other elements, but up to the present time the atomic refraction of sulphur in its various compounds has not been made the object of special study. After noticing what bas been already done i n determining the refractive indices of various sulphur compounds, the author points out that the questions he proposes to solve are: 1. To ascertain the value of the atomic refraction of sulphur cor- responding with oxygen, where bivalent sulphur is united with two univalent groups, as i n the mercaptans. 2. Its atomic refraction where the two valencies of sulphur are satisfied by the same carbon-atom. 3. To ascertain whether a variation in valency has any influence on its atomic refraction, by a study of inorganic sulphides and deri- vatives of carbon acids in which the sulphur is quadrivalent or sexavalen t.150 ABSTRACTS OF CHEMICAL PAPERS.?a. ---- 5 ' 0 1.3 2.8 3.4 9.8 2 - 4 The experiments were all made with liquids: these for the most part were supplied by Kahlbaum, but were purified before the deker- minations were made. The author employed the empirical formula n-1 used by Landolt and Bruhl, as being but little affected by varia- tions of temperature. H. A. Lorentz and L. Lorenz have recently shown (Wied. Ann., 9, 64, and 11, 70) that the formula 7 is the correct expression for the refractive power of a substance ; it gives excellent results, and has also been used bg the author.The values for this formula, calculated by Landolt from Bruhl's nume- rous experiments, are given in the subjoined table, where ra and rA represent the atomic refmctions of the elements with respect to the line a of the hydrogen spectrum, and with respect to the con- n--1. stant A of Cauchy's formula as functions of the old formula - d ' and T ' ~ and r'* the same values for the new formula. 9?? - 1 n + 2 d r A . 4.86 1-29 2-71 3.29 9-53 2'00 Carbon c .................. Hydrogen H .................. Chlorine c1. ................. Increment for each double bond.. ........ Oxygen (alcoholic) 0' ................ .. (aldehydic) 0" ................ 2-48 1.04 1.58 2.34 6-02 1*78 ?i-1 d ' ~ 2'43 1.02 1-56 2-29 5.89 1.59 n2-1 (a: + 2)d' The determinations of the refractive index were nearly all made at 20" with a spectrometer of Bartels and Diedcrichs, by the method of minimum deviation, using the lines a, p, and y of the hydrogen spectrum and the D sodium line. The sp.gr. of the substance was determined at 20°, referred to water at 4", reducing it t o a vacuum by means of the formula dt4 = - (2-1) +A, where rn is the weight of the substance at a temperature t, w that of the water at the same ternpe- rature, and X the mean density of the atmosphere. The substances examined were ethyl mercaptan, EtHS ; ethyl sul- phide, Et,S ; ethyl bisulphide, EtS, ; isobutyl mercaptan, C4H,.SH ; ethyl monothiocarbonate, OC(OEt)(SEt) ; isopentyl mercaptan, C,H,,.SH ; isopentyl sulphide, ( C5HI,),S ; diethyl dithiocarbonate, OC( SEt), ; carbon bisulphide, CS, ; the compound, CS( OEt), ; sul- phurous anhydride, SO, ; and sulphuric acid, H2SOa.The results are given in three tables, and from an inspection of them it appears that the atomic refraction of sulphur, like that of oxygen, has two values, according as the two vdencies are satisfied by two differeut univalent rn WINORGANIC CHEMISTRY. 151 Sulphur with two single bonds . . . . . . . . . . ,, ,, a double bond . . . . .. .. .. . . groups, as in mercaptian, &c., or by the same carbon-atom as in carbon bisulphide. These two values are as follows :- ra . VA. r', . r'A. -- -- --- 14 -10 13 -53 7 *87 7-65 15-61 15-09 9.02 8-04 n2- 1 (.Z + 2)d' I n the case o€ the oxygenated compounds of sulphur, it would seem that the atomic refraction has only one value, although it differs considerably from those given above.It is now established that the atomic refraction of an element may var-y, not only as it is more or less closely united with other elements -that is, by single or double bonds-but also that the nature of the atoms or variation in the capacity of saturation of the element may greatly influence the value of the refraction-constant. Comparative researches on other mnltivalent elements, such as phosphorus and arsenic, will no doubt throw light on this most important question. C. E. G. Basic Sulphates. By 5. HABERMANN (Monatsh. Chem., 4, 78i).- Preliminary Notice.-The basic copper sulphate, 6Cu0,2S03,5H,0, which Reindel obtained as a blue-green precipitate on adding ammo- nia in sufficient quantity to a boiling solutioii of normal cupric sul- phate (Gmelin-Kraut, 6 Aufl., vol.iii, p. 628), is also formed by boiling a solution of the normal sulphate (Pickering, C. J., 1883, Abstr., 853), and the author of the present notice has obtained it by treating the solution of the normal sulphate with ammonia or with sodium carbonake in certain proportions. Basic sulphates of nickel, cobalt, zinc, and cadmium are formed in like manner with either of these precipitants, but the salts thus ob- tained are not analogous in composition to the copper salt. Further details are promised. H. W. Action of Potassium Permanganate on certain Sulphur- compounds. By 11. HONIG and E. ZATZEK (nlonatsh. Chem., 4, 738 -'752).-In this paper the authors describe a large number of expe- riments on the action of potassium permanganate on the thiosulphates, sulphites, and sulphides of the alkali-metals, the results of which may be summarised as follows :- 1.The thiosulphates of the alkali-metals are completely oxidised by the permanganate at ordinary temperatures, only in alkaline solu- tion. Whatever may be the concentration of the permanganate solution, the complete oxidation of 1 part sodium thiosulphate (Na$3,0,,5H20) requires 1.6366 part potassium permangsnate. The152 ABSTRACTS OF CHEMICAL PAPERS. composition of the resulting precipitate is best represented by the for mu1 a KH,Mn,O,. 2. The s u l p h i t e s of the alkali-metsls are completely oxidised at ordinary temperatures both in neutral and in alkaline solution. The quantity of permanganate required for oxidation of I part by weight of sodium sulphite (Na,S03) depends on the concentration of the permangsnate solution, being less in proportion as that solution is more dilute, The composition of the resulting manganese precipitate is variable, m d likewise depends on the concentration of the per- manganate solution.3. The action of permanganate at ordinary temperatures on the mono- a,nd poly-sulphides of the alkali-metals gives rise to sul- phuric acid, trithionic acid, and free sulphur ; at the boiling heat all or nearly all the sulphur is oxidised to sulphuric acid. Direct Union of Nitrogen and Hydrogen. By H. B. BAKER (Chem. News, 48, 187--188).-This communication is a reply to Johnson (Trans., 1881, 128,130). The author describes various expe- riments with Johnson's and other apparatus, and ultimately comes to the conclusion that nitrogen prepared from air, either by the removal of the oxygen by cold phosphorus, or by patassium pyrogallate, or by hydrogen in the presence of warmed platinum sponge, does not com- bine directly with hydrogen to form ammonia.When, however, the hydrogen was passed through a solution of silver nitrate, and subse- quently through three bottles containing a saturated solution of ferrous sulphate, the author always obtained a brown coloration in the second Nessler tube. Note.-Johnson has discontinued the use of silver nitrate for the pur$catiort of his hydrogen (Chem. News, 48,202). H. W. D. A. L. Nitrogen Iodides. By A. GUYARD (Compt. rend., 97, 526-531). -Nitrogen iodide in contact with water or aqueous ammonia is as sensitive to luminous vibrations as to calorific, sonorous, or material vibrations.When exposed to light, the iodide is rapidly decomposed with effervescence and gives off pure nitrogen, ammonium iodide and a small quantity of ammonium iodate being also formed. I n presence of water, the decomposition usually terminates in a violent explosion, but in presence of ammonia it proceeds quietly to the end. Nitroqen iodide is as sensitive to diffused light as to direct rays, the rapidity of decomposition being proportional to the intensity of the light. The decomposition takes place equally well a t lo, 5", lo", or the ordinary temperature. The infra-red spectrum has no influence on the decom- position, but the visible spectrum acts powerfully, the maximum effect being produced by the yellow rays and the minimum by the violet.Nitrogen iodide of the composition NH, is decomposed by light in presence of water, without explosion, in accordance with the equation 2NBJ = NHJ, + N. Nitrogen iodide, however, rarely has this composition, and usually contains a greater or lesser proportion of other iodides. The compound therefore generally decomposes a t first in accordance with the above equation, but explodes when the iodide,INORGANIC CHEMISTRY. 153 NH31, begins to decompose. The decomposition of the typical iodide, NH12, in presence of ammonia, takes place in accordance with the equation 5NH1, + = lONHII + 7N. One and the same nitrogen iudide will give off more nitrogen in presence of ammonia than in presence of water; in the first case ammonium iodide is formed, in the second the diiodide.The decomposition of nitrogen iodide in ammonia may be used photometrically to determine the chemical and mechanical equivalent of light. The apparatus employed consists of a small flask with a long neck graduated in cubic centimeters, and provided with a stopper. The neck also carries a side tube similar to that of a Gay- Lussac burette. 1.27 gram of iodine is placed in the flask, which is then completely filled with ammonia of 22", carefully stoppered, with exclusion of air babbles, and exposed to light. 1.27 gram of iodine gives off 33.5 C.C. of nitrogen. The final reaction is the same whether nitrogen iodide or a mixture of iodine and ammonia is employed, and whether the mixture of iodine and ammonia is exposed t o light at once, or time is given for the formation of nitrogen iodide.The decomposition takes place in accordance with the equation 13NH3 + 101 = 10NHIL + 3N. Preparation of Ammonium Iodide and Iodwte.-When a mixture of iodine with excess of ammonia is exposed to light, nitrogen is given off, the free iodine entirely disappears, and ammonium iodide and iodate are formed. The ammonia is driven off and the liquid con- centrated, when the ammonium iodide cryddlises out, and the iodate remains in solution.. When iodine is mixed with aqueous ammonia, part of the iodine forms ammonium iodide, and the remainder is converted into nitrogen iodide. Afterwards, in presence 0% light and an excess of ammonia, more ammonium iodide is formed and nitrogen is given off.The first part of the change is chemical, the second photochemical. The principal reaction is represented by Odling'sequation 3NH3 -t 21, = 2NHJ + NH12. When the iodine is in excess, ammonium diiodide is formed, and the nitrogen iodide produced has approximately the composition NHJ ; with proper proportions of iodine and ammonia, the nitrogen iodide has approximately the composition NHI, ; with an excess of ammonia, a greater proportion of ammonium iodate is formed. Nitrogen iodide of the composition NHI, is but slightly affected by washing with pure water. Ammonia added to ammonium diiodide forms nitrogen iodide with the second atom of iodine. Under ordinary conditions, z(NH,O) + 233(NH40) + I,, = NH,O,I& + 154NHdI + 10(N8Hg115) + 227H0 + x(NH40),* where aNHIO represents the excess of ammonia which must always be used, is the simplest equation which expresses the observed facts.The formula N,HgIl5 is approxima'tely 8NHIz. With twice the excess of ammonia, about twice the amount of ammonium iodate is formed, and the nitrogen iodide consists mainly of N,H,15, or approximately 3NH I,. The formulae given by previous investigators are probably correct, b u t refer to bodies prepared under different conditions. * This equation is given exactly as it is in the original, it is, however, incorrect, aa the two sides are N233,H932,1303,(328 = N:36,H93pT305,0Q39. YOL. XLVI. m154 ABSTRACTS OF CIIEMICAL PAPERS. Nitrogen iodides are decomposed even by very dilute sulphuric, hydrochloric, or sulphurous acid, a t first with effervescence, but afterwards with violent explosion.They dissolve in sodium thiosul- phate, with formation of sodium iodide, ammonium snlphate, and free ammonia. The free ammonia is that existing in the nitrogen iodide ; the ammonium in the ammonium sulphate is derived from the nitrogen existing in the nitrogen iodide in the form of triiodamine. Nitrogen iodide is partially decomposed by potassium iodide in the dark, with formation of potassium diiodide free from ammonia, and a nitrogen iodide insoluble in the alkaline iodide, that is, the iodide NHI, loses an equivalent, or part of an equivalent, of iodine, and yields a new iodide. When exposed t o light, however, the nitrogen iodide is completely decomposed by the potassinm iodide, and the liquid con- tains ammonium iodide.Potassium cyanide dissolves nitrogen iodide even in the dark, with evolution of nitrogen. Nitrogen Copper Iodide.-When an ammoniacal solution of a copper salt is mixed with potassium diiodide, a brilliant, crystalline, garnetL coloured precipitate of the composition Cu12,2NH21 is gradually deposited. When dried, this compound is very stable, but it is entirely decomposed by water, with formation of ammonium diiodide, and a bronze-coloured cupric oxyiodide, CuOJ, which is decomposed by heat into black cupric oxide, iodine, and oxygen. The double copper nitrogen iodide is decomposed by aqueous ammonia, with for- mation of an ammoniacal solution of cupric iodide and a residue of an explosive nitrogen iodide free from copper.When the double iodide is heated, iodine and the products of the decomposition of nitrogen iodide are given off, and a residue of perfectly pure cuprous iodide is left. When distilled, the double iodide yields cuprous iodide, and brown, violet, and ammoniacal vapours. The brown vapours condense to a black product, decomposed by water witoh formation of a black crystalline nitrogen iodide, which resembles iodine in appearance, but which differs from all the other nitrogen iodides by dissolving with effervescence in a solution of potash or soda, nitrogen or hydrogen being given off, and a, considerable quan- tity of ammonia formed. When Schweitzer’s reagent, prepared by Peligot’s method, is mixed with potassium diiodide, a crystalline black double iodide of nitrogen and copper is formed, which resembles the preceding compound in its general properties, but yields an explosive cupreous residue when decomposed by washing with water.By I. REMSEN and E. H. REISER (Chem. News, 48, 201--202).-1n course of the experiments alluded to in this vol, p. 149, the authors had a suspicion that the phosphorus with which they were working might have contained some carbon- aceous matter. To remove this the phosphorus was distilled in an atmosphere of purified hpdrogen, and the vapour condensed in cold water. The distilled phosphorus presented a peculiar appearance ; it floated on the surface of the water, forming a snow-white layer, and when placed in warm water changed into ordinary phosphorus.After many experiments the authors found that this variety of phosphorus C. H. B. White Phosphorus.INORGANIC CHEMISTRY. 155 could be prepared in the following manner : Sticks of phosphorus are placed in a tuhulated retort, the neck of which is inclined upwards, and projects into a double-necked globular receiver, containing a layer of water and ice 18 in. deep in the deepest part. The receiver is supported in a vessel of cold water, and the bent tube, which passes from the other neck of the receiver, dips into cold water. A glass tube is fitted into the tubulure of the retort to supply purified hydro- gen, which is passed until the apparatus is filled with i t ; the current is then stopped, and the distillation proceeded with ; this is conducted steadily so that the vapour as it issues from the retort does not con- dense to a liquid.In successful operations a thin white cake is found floating on the water. The apparatus is allowed to cool, the retort disconnected, and the receiver with its contents put under water to displace the hydrogen and remove the phosphorus ; if this precaution is not taken, the phosphorus is liable to take fire, and give rise to an explosion of the mixture of hydrogen and air. White phosphorus is light and plastic ; if it is placed on bibulous paper as it dries, it fumes, melts without taking fire, and changes to ordinary phosphorus, with which its melting point is identical. It iR soluble in carbon bisulphide, and is not affected by sunlight so readily us ordinary phosphorus ; a sample after a year became slightly yellow, but was otherwise unchanged.I). A. L. By A. GAVAZZI (Gazzetta, 13, 324-325) .-0 n passing gaseous hydrogen phosphide through a neutral aqueous solution of platinic chloride, an ochreous yellow precipitate of the composition PtPHz is obtained: this is insoluble in water and hydrochloric acid. It ignites when heated to 100-llO", or when moistened with fuming nitric acid. Arsenic phosphide, ASP, is formed by the action of hydrogen phos- phide on a solution of arsenious anhydride in hydrochloric acid. An aqueous solution of potassium permanganate absorbs hydrogen phosphide at a low temperature, the reaction being represented by equations- Reactions of Gaseous Hydrogen Phosphide. PH, + 2RMnQa = KzHPOs + 2MnOz + HzO PH, + 2KMnOd = KzHPOd + Mnz03 + H20.C. E. G. Preparation of Phosphorus Oxychloride. By E. DERVIN (Compt. rend., 97, 576--578).-When phosphorus trichloride is mixed with potassium chlorate a violent reaction takes place, phosphorus oxychloride and potassium chloride being formed in accordance with the equation KC10, + 3PC1, = 3Pocl3 + KC1. This reaction may be utilised for the preparation of phosphorus oxychloride. 500 gram8 of pure phosphorus trichloride free from uncombiried phoPphorus are placed in a retort of 750-1000 C.C. capacity, connected with an inverted condenser, and 160 p m s of finely powdered potassium ohlorate is added through the tubulure i n quantities of about 4 grams st a time, care being taken to wa.t each time uirtil ebullition ceases before adding more chlorate.When the whole of the chlorate has been added, the liquid is distilled. The yield is very satisfactory, and the oxychloride contains but mere traces of chlorine. C. H. B. m 2156 ABSTRACTS OF CHEMICAL PAPERS. Action of Sunlight on Phosphorous Anhydride. By A. IRVING (Chem. News, 48, 173).-The author prepared his phosphorous anhydride by passing a slow current of dry air over molten phos- phorus, and found that the product turned brown, and changed into free phosphorus and phosphoric anhydride when exposed in sealed tubes to direct sunlight (compare Lewes, Trans., 1884, 10). D. A. L. Boron. By A. JOLY (Cornpt. rend., 97, 456-458).-The products of the reduction of boric anhydride by aliirninium are : (1.) The boride, BAl, which forms golden-yellow hexagonal lamellze, described by Deville and Wohler.(2.) The boride, B6A1, which forms large black la,mells, analysed by Hampe (Annnlen, 183, p. 75). (3.) Yellow quadratic crystals of adamantine lustre containing carbon and alu- minium. (4.) A boron carbide, or more probably several carbides formed by the alteration of the preceding compounds, at a high tem- perature, in presence of carbon and excess of boric anhydride. This carbide forms small black very hard crystals, with a bright metallic lustre, insoluble in boiling nitric acid. They have a sp. gr. of 2.542 a t 17", and contain 15.7 per cent. of carbon, corresponding with the formula B,C. C. H. B. New Silver Compounds. By T. POLECK and K. TH~~MMEL (Ber., 16, 2435-2448) .-Gutzeit has shown (Plznrm. Zeit., 1879, 263) that when gases containing arseniuretted hydrogen impinge on a piece of filter-paper moistened in its centre with one drop of a concentrated solution of silver nitrate, the wet spot assumes a lemo~-yellow colonr, whilst a t the periphery a brownish-black ring forms, which slowly broadens towards the centre until the whole spot becomes black.If the spot, whilst still yellow, is moistened with water, it blackens over the whole surface, and a t the same time shows a strongly acid reaction. Hydrogen sulphide, phosphide, and antimonide give similar results. The present paper details experiments on the chemical nature of these reactions. Hydrogen sulphide is passed into a concentrated solution of silver nitrate (1 part AgNO, in 0.7-1.0 part, water) kept constantly agitated, when a yellowish-green precipitate of the formula Ag2S,AgNOa is ob- tained.The supernatant liquid has a strongly acid reaction, does not contain sulphuric acid, and yields a considerable quantity of ammonia when distilled with potash. The precipitate can be heated to 180" without decomposition, and then forms a dark-green powder. It is decomposed into silver nitrate and silver sulphide by treatment with water or alcohol. On oxidation with nitric acid of sp. gr. 1.18 an orange-red coloured powder is frequently obtained. This compound is also obtained by the action of sulphur on a boiling concentrated solution of silver nitrate, and after purification gave results corre- sponding with the foraiula Ag,S, Ag,S04. It dissolves in boiling nitric acid, is decomposed by boiling water into silver sulphide and sulphate, and by cold hydrochloric acid into silver sulphide and chloride.Arsenic trihydride acting on dilute solution of silver nitrate has long been known t o yield metallic silver, arsenious anhydride, andINORGANIC CHEMISTRY. 157 nitric acid; with a concentrated solution, however, the reaction is very different. The first few bubbles of gas produce a deep lemon- yellow coloiation, no precipitate is formed, and the liquid acquires an acid reaction; this colomtion remains for one or two devs, then the liquid becomes colourless, silver is precipitated, and the solution contains arsenious m d arsenic acids. If a r,ipid stream of arsenic trihydride be passed into a concentrated solution of silver nitrate a t O", the whole liquid solidifies to a yellow crjstalline mass, but rapidly blackens from separation of silver.Many experiments were tried to isolate tbe compound, but its instability was too great. Analysis by an indirect method pointed to the formula With Concentrated solutions of silver nitrate, hydrogen phospbide gave results exactly similar in appearance to those obtained with arsenic trih ydride. The composition of the yellow precipitate from indirect determinations was Ag3P,3 A gN 0,. d ello ow precipitate is also obtained by the action of antimony hri- hydride on concentrated solution .of silver nitrite. It could not be isolated, but indirect determinations gave the formula Ag,Sb,3AgN03. Unlike arsenic, phosphorus, and sulphur, metallic antimony does not yield the double compound ; when it is placed in a solution of silver nitrate, A@b is first formed, but is soon converted into antimonious oxide and silver. A.J. G. Ag3 AS. 3 AgN03. Silver Nitrite and Ammonia. By A. REYCBLER (Bey., 16, 2425-2428) .-On dissolving silver nitrite in concentrated aqueous ammonia heat is evolved, aud the liquid soon deposits well-formed brilliant yellow prisms of the formula AgNO,,NH,, soluble in water, sparingly soluble in alcohol, nearly insoluble in ether, and melt.ing at 70". Long-continued heating above the melting point decomposes the compound, all the ammonia being expelled, and the residue con- sisting mainly of silver nitrite. On gently heating the compound with ethyl iodide, it yields silver iodide, ethyl nitrite, and ammonia. On heating the nionammonia compound with alcoholic ammonia and precipitating with ether, the diammonia compound SgNO,[NH,), is obtained as a white crystalline mass, rapidly losing ammonia on exposure to air.The finely powdered monammonia compound rapidly absorbs ammonia gas, with considerable evolution of gas, and apparently yields a triammonia compound, AgN02(NH3), ; it, is readily soluble in water, and rapidly loses ammonia on exposure to the ah. Crystallised Calcium Silicophosphate produced in the Dephosphorisation of Iron. By A. CARNOT and RICHARD (Compt qserid., 97, 316--320).-The slag formed in working the Thomas- Gilchrist process at Joeuf (Meurthe-et-Moselle) has a brownish 01. blackish colonr, and is more or less crystalline, some parts consisting of transparent crystalline matter, which acts strongly on polarised light, whilst other parts have a reddish colour, and resemble brown Immatite.The surface of the slag is covered with black crystals, some of which are slender needles, whilst others are right' rhombic A. J. a.158 ABSTRACTS OF CHEMICAL PAPERS. prisms with brilliant faces. These crystals are frequently aggregated in columnar masses, which terminate i n small vitreous perfectly translucid blue crystals. Similar blue crystals are found in the cavities in the slag, and appear to form one of its principal con- stituents. These are very constant in composition, but frequently enclose small black needles or particles, which can, however, be removed by means of a magnet. The blue crystals have h e com- position- Pz05 SiO,.Al2O3. CaO. MgO. FeO. MnO. 29.65 16-42 2.76 53.20 traces 1.80 traces = 99.83. Vanadium could not be detectred. The numbers correspond with the formula 8P,0,,8SiOa,A1,0,,Fe0,36Ca0. Regarding the crystals as consisting essentially of calcium silicophosphate, the formula becomes P,05,Si02,5Ca0 or Ca,P20B + C%,SiO,. The composition of the crystalline slag is variable ; it contains a lower proportion of phos- phoric acid than the blue crystals, and a considerable excess of ferrous and manganese oxides. The calcium silico-phosphate crystals belong to the rhombic system, the angles being riam = 113” 10’ and e’e’ (on p ) = 64’. They are strongly doubly refractive, and exhibit well-marked dichroism. When the plane of their optical axis is parallel with the principal section of the Nicol’s prism, they have a cobalt-blue colour; when i t is perpen- dicular, they are almost colourless.C . H. B. Presence of Yttrium in the Sphene of Biellese Syenite. 13;. COSSA (Gazzetla, 13, 326)’.-The author has found yttrium arid cerium in the sphene of Biellese syenite to the amount of about 2.3 per cent. This is an important fact, as it affords additional evidence of the analogy between the syeiiite of Biellese and those of Planceuschen- giund and Sweden. Besides showing that substances exist in the Alps which were formerly believed to be exclusively confined to Northern Europe, it proves that these rare metals are widely diffused, and their association with calcium compounds may be important in relation to their valency.C. E. G. Separation of Gallium. By L. DE BOWBAUDRAN (Compt. rend., 97, 295-297, and 521--522).-From Vanadium-(I.) The feebly acid hydrochloric acid solution is mixed with arsenious acid and an excess of acid ammonium acetate, and treated with hydrogen sulphide. Vanadium is not precipitated, but the arsenious sulphide carries down the whole of the gallium. The precipitate is washed with water con- taining ammonium acetate and hydrogen sulphide, and treated with aqua regia. The arsenic acid is reduced with sulphurous acid, and a current of hydrogen sulphide is passed through the strongly acid liquid, when the arsenic is precipitated alone, all the gallium remain- ing in solulion. This is the only process which gives accurate results when used alone, and it is especially useful fur separating small q-ntities of gallium from large quantities of vanadium.(2.) TheINORGANIC CHEMISTRY. 159 solution is almost neutralised with ammonia, mixed gradually with an excess of ammonium sulphide, and agitated. Dilute hydrochloric acid is then added in considerable excess with constant agitation, and the precipitated vanadyl sulphide is filtered off and washed with dilute hydrochloric acid containing hydrogen sulphide. The filtrate is boiled with aqua regia to destroy ammonium salts, the nitric acid is then expelled, and precipitation repeated six or seven times. The vafiadyl sulphide is also dissolved in aqua regia, and reprecipitated several times. (3.) The hydrochloric acid solution is made alkaline with ammonia, and boiled until the liquid is neutral.The precipitate is redissolved and reprecipitated two or three times ; the filtrake is treated by method (1) in order to separate the last traces of gallium. (4.) The solution is mixed with sulphuric acid and ammonium sul- phate in proper proportions, and the gallium alum is purified by recrystallisation. If the amount of gallium is very small, process (1) is used ; if the proportion of gallium is large, and that of vanadium small, the greater part of the gallium is removed in the form of alum, and the mother- liquid is treated by the following method. When the gallium and vanadium are present in approximately equal proportions, khe liquid is twice boiled with ammonia (2), and the filtrate treated by (1). The precipitated gallium hydroxide is converted into alum, and the mother-liquor is again boiled with ammonia.The filtrate is treated by (1) : the precipitate is mainly converted into gallium alum, and the mother-liquor is finally treated by (1). From Tungsten.-The tungsten is converted into alkaline tnngstate, and the solution evaporated almost to dryness at a gentle heat in pre- sence of a considerable excess of hydrochloric acid, a small quantity of water is then added, and the liquid again evaporated almost to dryness. The residue is treated with a moderately large quantity of very dilute hydrochloric acid, gently heated, and the liquid filtered. The filtrate is free from tungsten; the traces of gallium in the precipitate are removed by dissolving it in ammonia, and repeating the process. From Phosphoric Acid.-(1.) The gallium is precipitated by potas- sium ferrocyanide in presence of a large quantity of hydrochloric acid, and the precipitate is washed with water strongly acidified with hydrochloric acid. (2.) The solution is mixed with about one-third its volume of strong nitric acid, and the phosphoric acid precipitated by meam of ammonium molybdate, the gallium and molybdenum being afterwards separated by the method previously described. (3.) The feebly acid solution is mixed with arsenious acid and ammonium acetate, and treated with hydrogen sulphide, as described above.C. H. B. The solution contains small quantities of gallium. Diffusion of Vanadium in the Mineral and Vegetable King- doms. By L. RICCIARDI (Gazzetta, 13,259-262).-After a recapitu- lation of the results obtained by various authors on the occurrence of vanadium in rocks and minerals, the author gives the results of his own experiments on the existence of that metal in volcanic emana- tions ancient and modern.These are as follows, the numbers denot-160 ABSTRACTS O F CHEMICAL PAPERS. i n g the percentage of vanadium sesquioxide found in the several substances examined :- Lava of Vesuvius (1 868) ........ Y , ,, (1871) ......... 7 , ,, (1872) . . . . . . . Ashes from Vesuvius (18i.2) .... Lava of Vesuvius (1851) ........ Lava of Etna (1669) ............ 7 9 ,, (18’79) ............ Basalt of Pachino .............. Basalt of the Isola dei Ciclopi.. ..... 0.0063 per cent. 0.0075 ,, 0.013 ,, 0.105 ,, 0.0081 ), ~0.0102 , 7 0.0034 ), 0.006 ,, 0.0084 ,, Scacchi has found vanadium in incrustations of the Vesuvian lava of 1631.E. Rechi (Atti della It. Accademia dei Lincei [3], 3,403 [1878-79]), after having found this element in argillaceous limestones, in schists and in sands, has established its presence in plante, especially i n those growing on clay soils. The author of the present paper bas also found it in the ashes of grasses growing on the Etna lava of 1660, b u t the proportion was too small for qnantitative estimation. Its occnrrence in plants may be regarded as having some relation to the isomorphism of vanadic and phosphoric acids. H. W. Sulphur Compounds of Molybdenum. By G. KRGS (Ber., 16, 2044--2051).-According to Berzelius, molybdenum forms not only R di- and tri- but also a tetra-Pulphide, MoS,, a compound which would point to molybdenum as possessing a quanticalence of eight, and would be analogous to the uranium tetroxide.The author has sue- ceeded in isolating this tetrasulphide by melting molybdic acid with potassium carbonate, exhausting the melt with water, and passing hydrogen sulphide into the solution when heated to the boiling point. A black powder together with a crystalline substance separates out. This mixed material is washed first with cold water, then with hot water to dissolve out the molybdennm di- and tri-sulphide, and the resultant chocolate-brown powder is heated in a current of hydrogen sulphide until its weight is constant. The result of the analysis show that this substaiice is molybdenum tetraadphide. The author also describes a series of compounds intermediate between the salts of molybdic and sulphomolybdic acids, which may be designated by the generic term oxythirmolybdates. Ammonium o r t l ~ o x ~ t h i o i ~ ~ ~ l y b d ~ r t e , prepared by passing hydrogen sulphide into an ammoniacal solution of ammonium moly bdate, crys- tallises in golden-Fellow needles of the composition (NH&Mo02S,, which was assigned to the substance by Debray.The corresponding potassium salt, forms reddish- golden needles. Besides the crystalline orthoxythiomolybdnte, a number of amor- phous oxysnlphomolybdates are obtained by the decomposition of the molybdates by the alkaline hydrosulphide. Ammonium pyroxy- thiomolybdate, prepared by decomposing ammonium moly bdate with ammonium hydrosulphide, is a reddish-golden precipitate having tht!INORGANIC CHEMISTRY.161 composition H,Mo,O,S, (= 2H2Mo0,S2 - H2S), which evidently stands to orthoxymolybdate in the same relation as ortho- t o pyro-phos- phoric acid. The corresponding sodium salt is a golden amorphous powder. Thiomollybdates. - These compounds were obtained by Berzelius by passing hydrogen sulphide into the tnolybdates and evaporating the liquid; the substances formed by t,he process are, however, far froin pure, owing to a loss of hydrogen sulphide and formation of the oxythiomolybdates. The potassium salt c m best be prepared by fusing together potassinm carbonate, sulphur, aiid a large excess of the natural molybdenum sulphide. Bit hio )n o 2y bclat es.-On passi rig hydrogen sul phid e into a solution of potassium molybdate containing a large excess of free alkali, an orange-yellow precipitahe separates out ; this has the composition KGMo2S9, or potassium dithionwly bdute.V. H. V. Complex Inorganic Acids. By W. GIBBS (Chew. News, 48, 155) .--Two communications from ,the author on this subject have already appeared in this Jonrnal (Abstr., 1882, 469, i O 2 ) . In these communications only binary compounds have been referred to, and these can be represented by the general formula:- mR~03.nR’205.~RJ‘z0, in which m = any even number from 10 to 48 ; R = either molybde- num or tungsten ; R’ either phosphorus or arsenic ; and R” the basic radical. He has now extended the genesalisation, and states that the phosphorus and arsenic may be replaced by vanadium or antimony, or possibly by niobium acd tantalum ; for example, well-defined and beautifully crystalline vanadio-moly bdates have been obtained haring the formulae :- ~ M o O , , V , ~ ~ , ~ A ~ ~ O , H ~ C ) + 4Aq.16Mo03,V20,,5Ba0,H~0 + 28Aq. Moreover, ihe group R’?05 may be replaced by the group R,O, as As,O,,Sh 0 Thus the formula of an ammo- nium phosphoroso-molybdate is - O,, and probably V,O,. 243100, 2PzO3,5Am20 + 20Aq. These R,03 compounds are converted by oxidation into the salts con- taining the group R205. Klein has described salts containing R,03 ; salts of this class containing hypophosphorous acid have also been obtained, such as the ammonium hypophosphomolybdate of the formula 24Mo03,6P02,6Am20 + 7Aq. There are a great many ternary compounds of a similar character containing moljbdic or tungstic oxide united with two other oxities.A great many have the general formula, mR03ri,R’205,~~R’205rrRJ’?0, in which RO, = molybdic or tungstic oxide, whilht R’2@5 and R”O5 = two different oxides of the same type ; for example, P2O5 and V,O,. It has not as Jet been proved that any two known oxides of the type R205 can enter together into such compounds. The following are some examples of these salts :-162 ABSTRACTS OF CHEMICAL PAPERS. 14M003,8Vz05,Pz0,,8Amz0 + 50Aq. 48MoO3,V205,2PzO6,7Arn20 + 30Aq. 60W03,Vz05,SPz05,10Am20 + 60Aq. But the compounds containing Moo3 or WO, in combination with oxides of two types are still more numerous. They have the follow- ing general formulae :- 16~03,3V205,P20,,5A~lzO + 37Aq.rnR03,nR’~051pR”z03,rR”‘z0 ; mR03,nR’2U5pR20;~,rR’‘’z0 ; in which Rz05 may be Pz06, V205, As,05, Sbz05, and probably NbZ05 and T%05, whilst RzOs may be B303, P203, V&, Asz03 Sbz03. The author has also prepared salts belonging to the ternary compounds with the general formula mR03,nRz05,pR”Oz,rR”’02. None of this series containing R‘*03 in place of R20a have as yet been prepared. Quarternary compounds also exist, for the author has obtained the following in well-defined crystals :-GO WO3,3P2O~,V2Q~,V0~,18€3a,Q + 150H,O, which is reducible to the general formula :- mR03,nR”~05,~R’zOa,rR’‘’zO ; ~R~Z,U~~’~~~,~R”~O~,~R”’O~,~R’‘’It is evident that the possible number of various combinations in this group is very great. Besides the above types, the author has obtained other compounds containing neither molybdenum nor tungsten ; for example : p hosp h o-vanada tes, arseno-vanadates, and aniimon y-vana- dates, which are frequently crystalline, and hare the general formula m ft’z05,nR’’z05,pR20.I), A. L.148 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c Chemistry.Critical Temperature and Pressure of Liquid Oxygen. ByS. WRORLEWSKI (Compt. rend., 97, 309-310).-When oxygen isliquefied by pressure in a bent tnbe surroutided by liquid ethylenewhich is caused to evaporate rapidly, it is found that, as the amountof liquefied oxygen increases so that it rises above the surface of theethylene, the pressure necessary to continue liquefaction graduallyincreases, and when the liquid oxygen rises t o a certain height in thetube, the meniscus becomes indistinct and finally disappears.Theseresults are due to the fact that the temperature of that part of thetube above the liquid ethylene gradually increases as the distancefrom the ethylene increases. The disappearance of the meniscus takesplace at a, pressure of about 50 atmos., and on slightly reducing thepressure the meniscus reappears.Carbonic anhydride was liquefied by pressure in a tube, the lowerpart of which was placed in melting ice, whilst the upper part washeated to 50°, the intermediate portions being of course at inter-mediate temperatures. As the liquefied gas approached the heatedportion of the tube, the pressure required to continue liquefactiongradually increased until at about 76 atmoa.the meniscus disap-peared, but it reappeared on slightly reducing the pressure and con-sequently reducing the volume of the liquid.The disappearance and reappearance of the meniscus in both casesevidently takes place at that part of the tube which is at the criticaltemperature for the particular gas, and the pressure observed at thetime of disappearance is the critical pressure. The critical pressurefor oxygen is about 50 atmos., and the critical temperature isapproximately - 113". C. H. BINORGANIC CHEMISTRY. 149Critical Point of Oxygen. By E. SARRAU (Compt. rend., 97,G9-490) .-The critical pressure and temperature calculated bymeans of Clausius’ formula from the results of Amagat’s experimentson the compressibility of oxygen, are 48.7 atmos., and - 105.4”respectively.These values agree fairly well with Wroblewski’sdeterminations (see preceding Abstract).Conduct of Moist Phosphorus and Air towards CarbonicOxide. By I. REMSEN and E. H. KEISER (Chenz. News, 48, 199-201).-In reference to the work of Hoppe-Seyler (dbstr., 1880, 3),Baumann (ibid., 1882,691), Traube (ibid., 1882, 795), and Leeds (ihid.,1880, 237), on the existence of an active form of oxygen distinct fromozone, the authors have repeated some of the experiments. A repeti-tion of Traube’s experiment led the authors t o confirm his statement,viz., that the oxidation of palladium-hydrogen is due to bhe formationof hydrogen dioxide. And again, several repetitions of Leeds’s andBaumann’s experiments, in which great care was taken to prevent themixed gases from inside the apparatus coming in contact with organicmatter, led the authors to negative Leeds’s and Baumann’s conclu-sions; under these conditions no oxidation of carbon monoxide todioxide took place.In these experiments ad1 the stoppers were covered with water ormercury, connections were made with pieces of glass tubing bent twicea t right angles, so as 00 avoid india-rubber joints, and all necessaryplugs were of asbestos.I n some experiments, the asbestos plugs werereplaced by cotton-wooll with the result that the gas which previouslycontained no carbonic anhydride, now precipitated baryta-water ; thisexplains Leeds’s error. No satisfactory explanation is given of thenegative results obtained by Leeds and Baumann when no carbonicoxide was used.The ant,hors are of opinion that the action of airand moist phosphorus on carbonic oxide furnishes no evidence of theexistence of the so-called active oxygen.C. H. B.D. A. L.Atomic Refraction of Sulphur. By R. NASINI (Gazzetta, 13,2 9 6 4 1 1 ) .-Bruhl’s labours on atomic refraction have shown thatthe same element may have different. atomic refractions according toits mode of union with the other elements, but up to the present timethe atomic refraction of sulphur in its various compounds has notbeen made the object of special study.After noticing what bas been already done i n determining therefractive indices of various sulphur compounds, the author pointsout that the questions he proposes to solve are:1.To ascertain the value of the atomic refraction of sulphur cor-responding with oxygen, where bivalent sulphur is united with twounivalent groups, as i n the mercaptans.2. Its atomic refraction where the two valencies of sulphur aresatisfied by the same carbon-atom.3. To ascertain whether a variation in valency has any influenceon its atomic refraction, by a study of inorganic sulphides and deri-vatives of carbon acids in which the sulphur is quadrivalent orsexavalen t150 ABSTRACTS OF CHEMICAL PAPERS.?a. ----5 ' 01.32.83.49.82 - 4The experiments were all made with liquids: these for the mostpart were supplied by Kahlbaum, but were purified before the deker-minations were made. The author employed the empirical formulan-1 used by Landolt and Bruhl, as being but little affected by varia-tions of temperature.H. A. Lorentz and L. Lorenz have recentlyshown (Wied. Ann., 9, 64, and 11, 70) that the formula 7is the correct expression for the refractive power of a substance ; itgives excellent results, and has also been used bg the author. Thevalues for this formula, calculated by Landolt from Bruhl's nume-rous experiments, are given in the subjoined table, where ra andrA represent the atomic refmctions of the elements with respect tothe line a of the hydrogen spectrum, and with respect to the con-n--1. stant A of Cauchy's formula as functions of the old formula - d 'and T ' ~ and r'* the same values for the new formula.9?? - 1n + 2 dr A .4.861-292-713.299-532'00Carbon c ..................Hydrogen H ..................Chlorine c1..................Increment for each double bond.. ........Oxygen (alcoholic) 0' ................ .. (aldehydic) 0" ................2-481.041.582.346-021*78?i-1d ' ~2'431.021-562-295.891.59n2-1(a: + 2)d'The determinations of the refractive index were nearly all made at20" with a spectrometer of Bartels and Diedcrichs, by the method ofminimum deviation, using the lines a, p, and y of the hydrogenspectrum and the D sodium line. The sp. gr. of the substance wasdetermined at 20°, referred to water at 4", reducing it t o a vacuum bymeans of the formula dt4 = - (2-1) +A, where rn is the weight of thesubstance at a temperature t, w that of the water at the same ternpe-rature, and X the mean density of the atmosphere.The substances examined were ethyl mercaptan, EtHS ; ethyl sul-phide, Et,S ; ethyl bisulphide, EtS, ; isobutyl mercaptan, C4H,.SH ;ethyl monothiocarbonate, OC(OEt)(SEt) ; isopentyl mercaptan,C,H,,.SH ; isopentyl sulphide, ( C5HI,),S ; diethyl dithiocarbonate,OC( SEt), ; carbon bisulphide, CS, ; the compound, CS( OEt), ; sul-phurous anhydride, SO, ; and sulphuric acid, H2SOa. The results aregiven in three tables, and from an inspection of them it appears thatthe atomic refraction of sulphur, like that of oxygen, has two values,according as the two vdencies are satisfied by two differeut univalentrnINORGANIC CHEMISTRY.151Sulphur with two single bonds .. . . . . . . . . ,, ,, a double bond . . . . .. .. .. . .groups, as in mercaptian, &c., or by the same carbon-atom as in carbonbisulphide. These two values are as follows :-ra . VA. r', . r'A. -- -- ---14 -10 13 -53 7 *87 7-6515-61 15-09 9.02 8-04n2- 1(.Z + 2)d'I n the case o€ the oxygenated compounds of sulphur, it wouldseem that the atomic refraction has only one value, although it differsconsiderably from those given above.It is now established that the atomic refraction of an element mayvar-y, not only as it is more or less closely united with other elements-that is, by single or double bonds-but also that the nature of theatoms or variation in the capacity of saturation of the element maygreatly influence the value of the refraction-constant. Comparativeresearches on other mnltivalent elements, such as phosphorus andarsenic, will no doubt throw light on this most important question.C.E. G.Basic Sulphates. By 5. HABERMANN (Monatsh. Chem., 4, 78i).-Preliminary Notice.-The basic copper sulphate, 6Cu0,2S03,5H,0,which Reindel obtained as a blue-green precipitate on adding ammo-nia in sufficient quantity to a boiling solutioii of normal cupric sul-phate (Gmelin-Kraut, 6 Aufl., vol. iii, p. 628), is also formed byboiling a solution of the normal sulphate (Pickering, C. J., 1883,Abstr., 853), and the author of the present notice has obtained it bytreating the solution of the normal sulphate with ammonia or withsodium carbonake in certain proportions.Basic sulphates of nickel, cobalt, zinc, and cadmium are formed inlike manner with either of these precipitants, but the salts thus ob-tained are not analogous in composition to the copper salt.Furtherdetails are promised. H. W.Action of Potassium Permanganate on certain Sulphur-compounds. By 11. HONIG and E. ZATZEK (nlonatsh. Chem., 4, 738-'752).-In this paper the authors describe a large number of expe-riments on the action of potassium permanganate on the thiosulphates,sulphites, and sulphides of the alkali-metals, the results of which maybe summarised as follows :-1. The thiosulphates of the alkali-metals are completely oxidisedby the permanganate at ordinary temperatures, only in alkaline solu-tion. Whatever may be the concentration of the permanganatesolution, the complete oxidation of 1 part sodium thiosulphate(Na$3,0,,5H20) requires 1.6366 part potassium permangsnate.Th152 ABSTRACTS OF CHEMICAL PAPERS.composition of the resulting precipitate is best represented by thefor mu1 a KH,Mn,O,.2. The s u l p h i t e s of the alkali-metsls are completely oxidised atordinary temperatures both in neutral and in alkaline solution. Thequantity of permanganate required for oxidation of I part by weightof sodium sulphite (Na,S03) depends on the concentration of thepermangsnate solution, being less in proportion as that solution ismore dilute, The composition of the resulting manganese precipitateis variable, m d likewise depends on the concentration of the per-manganate solution.3.The action of permanganate at ordinary temperatures on themono- a,nd poly-sulphides of the alkali-metals gives rise to sul-phuric acid, trithionic acid, and free sulphur ; at the boiling heat allor nearly all the sulphur is oxidised to sulphuric acid.Direct Union of Nitrogen and Hydrogen. By H. B. BAKER(Chem. News, 48, 187--188).-This communication is a reply toJohnson (Trans., 1881, 128,130). The author describes various expe-riments with Johnson's and other apparatus, and ultimately comesto the conclusion that nitrogen prepared from air, either by the removalof the oxygen by cold phosphorus, or by patassium pyrogallate, or byhydrogen in the presence of warmed platinum sponge, does not com-bine directly with hydrogen to form ammonia.When, however, thehydrogen was passed through a solution of silver nitrate, and subse-quently through three bottles containing a saturated solution offerrous sulphate, the author always obtained a brown coloration inthe second Nessler tube.Note.-Johnson has discontinued the use of silver nitrate for thepur$catiort of his hydrogen (Chem. News, 48,202).H. W.D. A. L.Nitrogen Iodides. By A. GUYARD (Compt. rend., 97, 526-531).-Nitrogen iodide in contact with water or aqueous ammonia is assensitive to luminous vibrations as to calorific, sonorous, or materialvibrations. When exposed to light, the iodide is rapidly decomposedwith effervescence and gives off pure nitrogen, ammonium iodide anda small quantity of ammonium iodate being also formed.I n presenceof water, the decomposition usually terminates in a violent explosion,but in presence of ammonia it proceeds quietly to the end. Nitroqeniodide is as sensitive to diffused light as to direct rays, the rapidity ofdecomposition being proportional to the intensity of the light. Thedecomposition takes place equally well a t lo, 5", lo", or the ordinarytemperature. The infra-red spectrum has no influence on the decom-position, but the visible spectrum acts powerfully, the maximumeffect being produced by the yellow rays and the minimum by theviolet.Nitrogen iodide of the composition NH, is decomposed by light inpresence of water, without explosion, in accordance with the equation2NBJ = NHJ, + N. Nitrogen iodide, however, rarely has thiscomposition, and usually contains a greater or lesser proportion ofother iodides.The compound therefore generally decomposes a t firstin accordance with the above equation, but explodes when the iodideINORGANIC CHEMISTRY. 153NH31, begins to decompose. The decomposition of the typical iodide,NH12, in presence of ammonia, takes place in accordance with theequation 5NH1, + = lONHII + 7N. One and the samenitrogen iudide will give off more nitrogen in presence of ammoniathan in presence of water; in the first case ammonium iodide isformed, in the second the diiodide.The decomposition of nitrogen iodide in ammonia may be usedphotometrically to determine the chemical and mechanical equivalentof light. The apparatus employed consists of a small flask with along neck graduated in cubic centimeters, and provided with astopper.The neck also carries a side tube similar to that of a Gay-Lussac burette. 1.27 gram of iodine is placed in the flask, which isthen completely filled with ammonia of 22", carefully stoppered, withexclusion of air babbles, and exposed to light. 1.27 gram of iodinegives off 33.5 C.C. of nitrogen. The final reaction is the same whethernitrogen iodide or a mixture of iodine and ammonia is employed, andwhether the mixture of iodine and ammonia is exposed t o light atonce, or time is given for the formation of nitrogen iodide. Thedecomposition takes place in accordance with the equation 13NH3 + 101 = 10NHIL + 3N.Preparation of Ammonium Iodide and Iodwte.-When a mixture ofiodine with excess of ammonia is exposed to light, nitrogen is givenoff, the free iodine entirely disappears, and ammonium iodide andiodate are formed.The ammonia is driven off and the liquid con-centrated, when the ammonium iodide cryddlises out, and the iodateremains in solution..When iodine is mixed with aqueous ammonia, part of the iodineforms ammonium iodide, and the remainder is converted into nitrogeniodide. Afterwards, in presence 0% light and an excess of ammonia,more ammonium iodide is formed and nitrogen is given off. The firstpart of the change is chemical, the second photochemical. The principalreaction is represented by Odling'sequation 3NH3 -t 21, = 2NHJ +NH12. When the iodine is in excess, ammonium diiodide is formed,and the nitrogen iodide produced has approximately the compositionNHJ ; with proper proportions of iodine and ammonia, the nitrogeniodide has approximately the composition NHI, ; with an excess ofammonia, a greater proportion of ammonium iodate is formed.Nitrogen iodide of the composition NHI, is but slightly affected bywashing with pure water.Ammonia added to ammonium diiodideforms nitrogen iodide with the second atom of iodine.Under ordinary conditions, z(NH,O) + 233(NH40) + I,, =NH,O,I& + 154NHdI + 10(N8Hg115) + 227H0 + x(NH40),* whereaNHIO represents the excess of ammonia which must always beused, is the simplest equation which expresses the observed facts.The formula N,HgIl5 is approxima'tely 8NHIz. With twice the excessof ammonia, about twice the amount of ammonium iodate is formed,and the nitrogen iodide consists mainly of N,H,15, or approximately3NH I,.The formulae given by previous investigators are probablycorrect, b u t refer to bodies prepared under different conditions.* This equation is given exactly as it is in the original, it is, however, incorrect,aa the two sides are N233,H932,1303,(328 = N:36,H93pT305,0Q39.YOL. XLVI. 154 ABSTRACTS OF CIIEMICAL PAPERS.Nitrogen iodides are decomposed even by very dilute sulphuric,hydrochloric, or sulphurous acid, a t first with effervescence, butafterwards with violent explosion. They dissolve in sodium thiosul-phate, with formation of sodium iodide, ammonium snlphate, and freeammonia. The free ammonia is that existing in the nitrogen iodide ;the ammonium in the ammonium sulphate is derived from thenitrogen existing in the nitrogen iodide in the form of triiodamine.Nitrogen iodide is partially decomposed by potassium iodide in thedark, with formation of potassium diiodide free from ammonia, and anitrogen iodide insoluble in the alkaline iodide, that is, the iodide NHI,loses an equivalent, or part of an equivalent, of iodine, and yields anew iodide.When exposed t o light, however, the nitrogen iodide iscompletely decomposed by the potassinm iodide, and the liquid con-tains ammonium iodide. Potassium cyanide dissolves nitrogen iodideeven in the dark, with evolution of nitrogen.Nitrogen Copper Iodide.-When an ammoniacal solution of a coppersalt is mixed with potassium diiodide, a brilliant, crystalline, garnetLcoloured precipitate of the composition Cu12,2NH21 is graduallydeposited.When dried, this compound is very stable, but it isentirely decomposed by water, with formation of ammonium diiodide,and a bronze-coloured cupric oxyiodide, CuOJ, which is decomposedby heat into black cupric oxide, iodine, and oxygen. The doublecopper nitrogen iodide is decomposed by aqueous ammonia, with for-mation of an ammoniacal solution of cupric iodide and a residue ofan explosive nitrogen iodide free from copper. When the doubleiodide is heated, iodine and the products of the decomposition ofnitrogen iodide are given off, and a residue of perfectly pure cuprousiodide is left. When distilled, the double iodide yields cuprousiodide, and brown, violet, and ammoniacal vapours.The brownvapours condense to a black product, decomposed by water witohformation of a black crystalline nitrogen iodide, which resemblesiodine in appearance, but which differs from all the other nitrogeniodides by dissolving with effervescence in a solution of potash orsoda, nitrogen or hydrogen being given off, and a, considerable quan-tity of ammonia formed.When Schweitzer’s reagent, prepared by Peligot’s method, is mixedwith potassium diiodide, a crystalline black double iodide of nitrogenand copper is formed, which resembles the preceding compound in itsgeneral properties, but yields an explosive cupreous residue whendecomposed by washing with water.By I.REMSEN and E. H. REISER (Chem.News, 48, 201--202).-1n course of the experiments alluded to inthis vol, p. 149, the authors had a suspicion that the phosphoruswith which they were working might have contained some carbon-aceous matter. To remove this the phosphorus was distilled in anatmosphere of purified hpdrogen, and the vapour condensed in coldwater. The distilled phosphorus presented a peculiar appearance ; itfloated on the surface of the water, forming a snow-white layer, andwhen placed in warm water changed into ordinary phosphorus. Aftermany experiments the authors found that this variety of phosphorusC. H. B.White PhosphorusINORGANIC CHEMISTRY. 155could be prepared in the following manner : Sticks of phosphorus areplaced in a tuhulated retort, the neck of which is inclined upwards,and projects into a double-necked globular receiver, containing alayer of water and ice 18 in.deep in the deepest part. The receiveris supported in a vessel of cold water, and the bent tube, which passesfrom the other neck of the receiver, dips into cold water. A glasstube is fitted into the tubulure of the retort to supply purified hydro-gen, which is passed until the apparatus is filled with i t ; the currentis then stopped, and the distillation proceeded with ; this is conductedsteadily so that the vapour as it issues from the retort does not con-dense to a liquid. In successful operations a thin white cake is foundfloating on the water. The apparatus is allowed to cool, the retortdisconnected, and the receiver with its contents put under water todisplace the hydrogen and remove the phosphorus ; if this precautionis not taken, the phosphorus is liable to take fire, and give rise to anexplosion of the mixture of hydrogen and air.White phosphorus islight and plastic ; if it is placed on bibulous paper as it dries, itfumes, melts without taking fire, and changes to ordinary phosphorus,with which its melting point is identical. It iR soluble in carbonbisulphide, and is not affected by sunlight so readily us ordinaryphosphorus ; a sample after a year became slightly yellow, but wasotherwise unchanged. I). A. L.By A. GAVAZZI(Gazzetta, 13, 324-325) .-0 n passing gaseous hydrogen phosphidethrough a neutral aqueous solution of platinic chloride, an ochreousyellow precipitate of the composition PtPHz is obtained: this isinsoluble in water and hydrochloric acid.It ignites when heated to100-llO", or when moistened with fuming nitric acid.Arsenic phosphide, ASP, is formed by the action of hydrogen phos-phide on a solution of arsenious anhydride in hydrochloric acid.An aqueous solution of potassium permanganate absorbs hydrogenphosphide at a low temperature, the reaction being represented byequations-Reactions of Gaseous Hydrogen Phosphide.PH, + 2RMnQa = KzHPOs + 2MnOz + HzOPH, + 2KMnOd = KzHPOd + Mnz03 + H20.C. E. G.Preparation of Phosphorus Oxychloride. By E. DERVIN(Compt. rend., 97, 576--578).-When phosphorus trichloride is mixedwith potassium chlorate a violent reaction takes place, phosphorusoxychloride and potassium chloride being formed in accordance withthe equation KC10, + 3PC1, = 3Pocl3 + KC1. This reaction maybe utilised for the preparation of phosphorus oxychloride. 500 gram8of pure phosphorus trichloride free from uncombiried phoPphorus areplaced in a retort of 750-1000 C.C.capacity, connected with aninverted condenser, and 160 p m s of finely powdered potassiumohlorate is added through the tubulure i n quantities of about 4 gramsst a time, care being taken to wa.t each time uirtil ebullition ceasesbefore adding more chlorate. When the whole of the chlorate has beenadded, the liquid is distilled. The yield is very satisfactory, and theoxychloride contains but mere traces of chlorine. C.H. B.m 156 ABSTRACTS OF CHEMICAL PAPERS.Action of Sunlight on Phosphorous Anhydride. By A.IRVING (Chem. News, 48, 173).-The author prepared his phosphorousanhydride by passing a slow current of dry air over molten phos-phorus, and found that the product turned brown, and changed intofree phosphorus and phosphoric anhydride when exposed in sealed tubesto direct sunlight (compare Lewes, Trans., 1884, 10). D. A. L.Boron. By A. JOLY (Cornpt. rend., 97, 456-458).-The productsof the reduction of boric anhydride by aliirninium are : (1.) Theboride, BAl, which forms golden-yellow hexagonal lamellze, describedby Deville and Wohler. (2.) The boride, B6A1, which forms largeblack la,mells, analysed by Hampe (Annnlen, 183, p. 75).(3.) Yellowquadratic crystals of adamantine lustre containing carbon and alu-minium. (4.) A boron carbide, or more probably several carbidesformed by the alteration of the preceding compounds, at a high tem-perature, in presence of carbon and excess of boric anhydride. Thiscarbide forms small black very hard crystals, with a bright metalliclustre, insoluble in boiling nitric acid. They have a sp. gr. of2.542 a t 17", and contain 15.7 per cent. of carbon, correspondingwith the formula B,C. C. H. B.New Silver Compounds. By T. POLECK and K. TH~~MMEL (Ber.,16, 2435-2448) .-Gutzeit has shown (Plznrm. Zeit., 1879, 263) thatwhen gases containing arseniuretted hydrogen impinge on a piece offilter-paper moistened in its centre with one drop of a concentratedsolution of silver nitrate, the wet spot assumes a lemo~-yellow colonr,whilst a t the periphery a brownish-black ring forms, which slowlybroadens towards the centre until the whole spot becomes black.Ifthe spot, whilst still yellow, is moistened with water, it blackens overthe whole surface, and a t the same time shows a strongly acid reaction.Hydrogen sulphide, phosphide, and antimonide give similar results.The present paper details experiments on the chemical nature of thesereactions.Hydrogen sulphide is passed into a concentrated solution of silvernitrate (1 part AgNO, in 0.7-1.0 part, water) kept constantly agitated,when a yellowish-green precipitate of the formula Ag2S,AgNOa is ob-tained. The supernatant liquid has a strongly acid reaction, does notcontain sulphuric acid, and yields a considerable quantity of ammoniawhen distilled with potash.The precipitate can be heated to 180"without decomposition, and then forms a dark-green powder. It isdecomposed into silver nitrate and silver sulphide by treatment withwater or alcohol. On oxidation with nitric acid of sp. gr. 1.18 anorange-red coloured powder is frequently obtained. This compoundis also obtained by the action of sulphur on a boiling concentratedsolution of silver nitrate, and after purification gave results corre-sponding with the foraiula Ag,S, Ag,S04. It dissolves in boilingnitric acid, is decomposed by boiling water into silver sulphide andsulphate, and by cold hydrochloric acid into silver sulphide andchloride.Arsenic trihydride acting on dilute solution of silver nitrate haslong been known t o yield metallic silver, arsenious anhydride, anINORGANIC CHEMISTRY.157nitric acid; with a concentrated solution, however, the reaction isvery different. The first few bubbles of gas produce a deep lemon-yellow coloiation, no precipitate is formed, and the liquid acquiresan acid reaction; this colomtion remains for one or two devs,then the liquid becomes colourless, silver is precipitated, and thesolution contains arsenious m d arsenic acids. If a r,ipid stream ofarsenic trihydride be passed into a concentrated solution of silvernitrate a t O", the whole liquid solidifies to a yellow crjstalline mass,but rapidly blackens from separation of silver.Many experimentswere tried to isolate tbe compound, but its instability was toogreat. Analysis by an indirect method pointed to the formulaWith Concentrated solutions of silver nitrate, hydrogen phospbidegave results exactly similar in appearance to those obtained witharsenic trih ydride. The composition of the yellow precipitate fromindirect determinations was Ag3P,3 A gN 0,.d ello ow precipitate is also obtained by the action of antimony hri-hydride on concentrated solution .of silver nitrite. It could not beisolated, but indirect determinations gave the formula Ag,Sb,3AgN03.Unlike arsenic, phosphorus, and sulphur, metallic antimony does notyield the double compound ; when it is placed in a solution of silvernitrate, A@b is first formed, but is soon converted into antimoniousoxide and silver.A. J. G.Ag3 AS. 3 AgN03.Silver Nitrite and Ammonia. By A. REYCBLER (Bey., 16,2425-2428) .-On dissolving silver nitrite in concentrated aqueousammonia heat is evolved, aud the liquid soon deposits well-formedbrilliant yellow prisms of the formula AgNO,,NH,, soluble in water,sparingly soluble in alcohol, nearly insoluble in ether, and melt.ing at70". Long-continued heating above the melting point decomposesthe compound, all the ammonia being expelled, and the residue con-sisting mainly of silver nitrite. On gently heating the compoundwith ethyl iodide, it yields silver iodide, ethyl nitrite, and ammonia.On heating the nionammonia compound with alcoholic ammoniaand precipitating with ether, the diammonia compound SgNO,[NH,),is obtained as a white crystalline mass, rapidly losing ammonia onexposure to air.The finely powdered monammonia compound rapidly absorbsammonia gas, with considerable evolution of gas, and apparentlyyields a triammonia compound, AgN02(NH3), ; it, is readily solublein water, and rapidly loses ammonia on exposure to the ah.Crystallised Calcium Silicophosphate produced in theDephosphorisation of Iron.By A. CARNOT and RICHARD (Comptqserid., 97, 316--320).-The slag formed in working the Thomas-Gilchrist process at Joeuf (Meurthe-et-Moselle) has a brownish 01.blackish colonr, and is more or less crystalline, some parts consistingof transparent crystalline matter, which acts strongly on polarisedlight, whilst other parts have a reddish colour, and resemble brownImmatite. The surface of the slag is covered with black crystals,some of which are slender needles, whilst others are right' rhombicA.J. a158 ABSTRACTS OF CHEMICAL PAPERS.prisms with brilliant faces. These crystals are frequently aggregatedin columnar masses, which terminate i n small vitreous perfectlytranslucid blue crystals. Similar blue crystals are found in thecavities in the slag, and appear to form one of its principal con-stituents. These are very constant in composition, but frequentlyenclose small black needles or particles, which can, however, beremoved by means of a magnet. The blue crystals have h e com-position-Pz05 SiO,. Al2O3. CaO. MgO. FeO. MnO.29.65 16-42 2.76 53.20 traces 1.80 traces = 99.83.Vanadium could not be detectred. The numbers correspond with theformula 8P,0,,8SiOa,A1,0,,Fe0,36Ca0.Regarding the crystals asconsisting essentially of calcium silicophosphate, the formula becomesP,05,Si02,5Ca0 or Ca,P20B + C%,SiO,. The composition of thecrystalline slag is variable ; it contains a lower proportion of phos-phoric acid than the blue crystals, and a considerable excess of ferrousand manganese oxides.The calcium silico-phosphate crystals belong to the rhombic system,the angles being riam = 113” 10’ and e’e’ (on p ) = 64’. They arestrongly doubly refractive, and exhibit well-marked dichroism. Whenthe plane of their optical axis is parallel with the principal section ofthe Nicol’s prism, they have a cobalt-blue colour; when i t is perpen-dicular, they are almost colourless. C .H. B.Presence of Yttrium in the Sphene of Biellese Syenite. 13;.COSSA (Gazzetla, 13, 326)’.-The author has found yttrium arid ceriumin the sphene of Biellese syenite to the amount of about 2.3 per cent.This is an important fact, as it affords additional evidence of theanalogy between the syeiiite of Biellese and those of Planceuschen-giund and Sweden. Besides showing that substances exist in theAlps which were formerly believed to be exclusively confined toNorthern Europe, it proves that these rare metals are widely diffused,and their association with calcium compounds may be important inrelation to their valency. C. E. G.Separation of Gallium.By L. DE BOWBAUDRAN (Compt. rend.,97, 295-297, and 521--522).-From Vanadium-(I.) The feeblyacid hydrochloric acid solution is mixed with arsenious acid and anexcess of acid ammonium acetate, and treated with hydrogen sulphide.Vanadium is not precipitated, but the arsenious sulphide carries downthe whole of the gallium. The precipitate is washed with water con-taining ammonium acetate and hydrogen sulphide, and treated withaqua regia. The arsenic acid is reduced with sulphurous acid, and acurrent of hydrogen sulphide is passed through the strongly acidliquid, when the arsenic is precipitated alone, all the gallium remain-ing in solulion. This is the only process which gives accurate resultswhen used alone, and it is especially useful fur separating smallq-ntities of gallium from large quantities of vanadium.(2.) ThINORGANIC CHEMISTRY. 159solution is almost neutralised with ammonia, mixed gradually with anexcess of ammonium sulphide, and agitated. Dilute hydrochloricacid is then added in considerable excess with constant agitation, andthe precipitated vanadyl sulphide is filtered off and washed withdilute hydrochloric acid containing hydrogen sulphide. The filtrateis boiled with aqua regia to destroy ammonium salts, the nitric acid isthen expelled, and precipitation repeated six or seven times. Thevafiadyl sulphide is also dissolved in aqua regia, and reprecipitatedseveral times. (3.) The hydrochloric acid solution is made alkalinewith ammonia, and boiled until the liquid is neutral.The precipitateis redissolved and reprecipitated two or three times ; the filtrake istreated by method (1) in order to separate the last traces of gallium.(4.) The solution is mixed with sulphuric acid and ammonium sul-phate in proper proportions, and the gallium alum is purified byrecrystallisation.If the amount of gallium is very small, process (1) is used ; if theproportion of gallium is large, and that of vanadium small, the greaterpart of the gallium is removed in the form of alum, and the mother-liquid is treated by the following method. When the gallium andvanadium are present in approximately equal proportions, khe liquidis twice boiled with ammonia (2), and the filtrate treated by (1).The precipitated gallium hydroxide is converted into alum, and themother-liquor is again boiled with ammonia.The filtrate is treatedby (1) : the precipitate is mainly converted into gallium alum, andthe mother-liquor is finally treated by (1).From Tungsten.-The tungsten is converted into alkaline tnngstate,and the solution evaporated almost to dryness at a gentle heat in pre-sence of a considerable excess of hydrochloric acid, a small quantityof water is then added, and the liquid again evaporated almost todryness. The residue is treated with a moderately large quantity ofvery dilute hydrochloric acid, gently heated, and the liquid filtered.The filtrate is free from tungsten; the traces of gallium in theprecipitate are removed by dissolving it in ammonia, and repeatingthe process.From Phosphoric Acid.-(1.) The gallium is precipitated by potas-sium ferrocyanide in presence of a large quantity of hydrochloric acid,and the precipitate is washed with water strongly acidified withhydrochloric acid.(2.) The solution is mixed with about one-thirdits volume of strong nitric acid, and the phosphoric acid precipitatedby meam of ammonium molybdate, the gallium and molybdenumbeing afterwards separated by the method previously described.(3.) The feebly acid solution is mixed with arsenious acid andammonium acetate, and treated with hydrogen sulphide, as describedabove. C. H. B.The solution contains small quantities of gallium.Diffusion of Vanadium in the Mineral and Vegetable King-doms. By L. RICCIARDI (Gazzetta, 13,259-262).-After a recapitu-lation of the results obtained by various authors on the occurrence ofvanadium in rocks and minerals, the author gives the results of hisown experiments on the existence of that metal in volcanic emana-tions ancient and modern.These are as follows, the numbers denot160 ABSTRACTS O F CHEMICAL PAPERS.i n g the percentage of vanadium sesquioxide found in the severalsubstances examined :-Lava of Vesuvius (1 868) ........Y , ,, (1871) .........7 , ,, (1872) . . . . . . .Ashes from Vesuvius (18i.2) ....Lava of Vesuvius (1851) ........Lava of Etna (1669) ............7 9 ,, (18’79) ............Basalt of Pachino ..............Basalt of the Isola dei Ciclopi.. .....0.0063 per cent.0.0075 ,,0.013 ,,0.105 ,,0.0081 ),~0.0102 , 70.0034 ),0.006 ,,0.0084 ,,Scacchi has found vanadium in incrustations of the Vesuvian lavaof 1631.E.Rechi (Atti della It. Accademia dei Lincei [3], 3,403 [1878-79]),after having found this element in argillaceous limestones, in schistsand in sands, has established its presence in plante, especially i n thosegrowing on clay soils.The author of the present paper bas also found it in the ashes ofgrasses growing on the Etna lava of 1660, b u t the proportion was toosmall for qnantitative estimation. Its occnrrence in plants may beregarded as having some relation to the isomorphism of vanadic andphosphoric acids. H. W.Sulphur Compounds of Molybdenum. By G. KRGS (Ber., 16,2044--2051).-According to Berzelius, molybdenum forms not onlyR di- and tri- but also a tetra-Pulphide, MoS,, a compound which wouldpoint to molybdenum as possessing a quanticalence of eight, andwould be analogous to the uranium tetroxide.The author has sue-ceeded in isolating this tetrasulphide by melting molybdic acid withpotassium carbonate, exhausting the melt with water, and passinghydrogen sulphide into the solution when heated to the boiling point.A black powder together with a crystalline substance separates out.This mixed material is washed first with cold water, then with hotwater to dissolve out the molybdennm di- and tri-sulphide, and theresultant chocolate-brown powder is heated in a current of hydrogensulphide until its weight is constant. The result of the analysisshow that this substaiice is molybdenum tetraadphide.The author also describes a series of compounds intermediatebetween the salts of molybdic and sulphomolybdic acids, which maybe designated by the generic term oxythirmolybdates.Ammonium o r t l ~ o x ~ t h i o i ~ ~ ~ l y b d ~ r t e , prepared by passing hydrogensulphide into an ammoniacal solution of ammonium moly bdate, crys-tallises in golden-Fellow needles of the composition (NH&Mo02S,,which was assigned to the substance by Debray.The correspondingpotassium salt, forms reddish- golden needles.Besides the crystalline orthoxythiomolybdnte, a number of amor-phous oxysnlphomolybdates are obtained by the decomposition of themolybdates by the alkaline hydrosulphide. Ammonium pyroxy-thiomolybdate, prepared by decomposing ammonium moly bdate withammonium hydrosulphide, is a reddish-golden precipitate having thtINORGANIC CHEMISTRY.161composition H,Mo,O,S, (= 2H2Mo0,S2 - H2S), which evidentlystands to orthoxymolybdate in the same relation as ortho- t o pyro-phos-phoric acid. The corresponding sodium salt is a golden amorphouspowder.Thiomollybdates. - These compounds were obtained by Berzeliusby passing hydrogen sulphide into the tnolybdates and evaporatingthe liquid; the substances formed by t,he process are, however, farfroin pure, owing to a loss of hydrogen sulphide and formation of theoxythiomolybdates. The potassium salt c m best be prepared byfusing together potassinm carbonate, sulphur, aiid a large excess ofthe natural molybdenum sulphide.Bit hio )n o 2y bclat es.-On passi rig hydrogen sul phid e into a solutionof potassium molybdate containing a large excess of free alkali, anorange-yellow precipitahe separates out ; this has the compositionKGMo2S9, or potassium dithionwly bdute. V. H. V.Complex Inorganic Acids. By W. GIBBS (Chew. News, 48,155) .--Two communications from ,the author on this subject havealready appeared in this Jonrnal (Abstr., 1882, 469, i O 2 ) . In thesecommunications only binary compounds have been referred to, andthese can be represented by the general formula:-mR~03.nR’205.~RJ‘z0,in which m = any even number from 10 to 48 ; R = either molybde-num or tungsten ; R’ either phosphorus or arsenic ; and R” the basicradical. He has now extended the genesalisation, and states that thephosphorus and arsenic may be replaced by vanadium or antimony,or possibly by niobium acd tantalum ; for example, well-defined andbeautifully crystalline vanadio-moly bdates have been obtained haringthe formulae :-~ M o O , , V , ~ ~ , ~ A ~ ~ O , H ~ C ) + 4Aq.16Mo03,V20,,5Ba0,H~0 + 28Aq.Moreover, ihe group R’?05 may be replaced by the group R,O, asAs,O,,Sh 0 Thus the formula of an ammo-nium phosphoroso-molybdate is -O,, and probably V,O,.243100, 2PzO3,5Am20 + 20Aq.These R,03 compounds are converted by oxidation into the salts con-taining the group R205. Klein has described salts containing R,03 ;salts of this class containing hypophosphorous acid have also beenobtained, such as the ammonium hypophosphomolybdate of theformula 24Mo03,6P02,6Am20 + 7Aq. There are a great manyternary compounds of a similar character containing moljbdic ortungstic oxide united with two other oxities. A great many have thegeneral formula, mR03ri,R’205,~~R’205rrRJ’?0, in which RO, = molybdicor tungstic oxide, whilht R’2@5 and R”O5 = two different oxides of thesame type ; for example, P2O5 and V,O,. It has not as Jet been provedthat any two known oxides of the type R205 can enter together intosuch compounds. The following are some examples of these salts :162 ABSTRACTS OF CHEMICAL PAPERS.14M003,8Vz05,Pz0,,8Amz0 + 50Aq.48MoO3,V205,2PzO6,7Arn20 + 30Aq.60W03,Vz05,SPz05,10Am20 + 60Aq.But the compounds containing Moo3 or WO, in combination withoxides of two types are still more numerous. They have the follow-ing general formulae :-16~03,3V205,P20,,5A~lzO + 37Aq.rnR03,nR’~051pR”z03,rR”‘z0 ;mR03,nR’2U5pR20;~,rR’‘’z0 ;in which Rz05 may be Pz06, V205, As,05, Sbz05, and probably NbZ05and T%05, whilst RzOs may be B303, P203, V&, Asz03 Sbz03. Theauthor has also prepared salts belonging to the ternary compoundswith the general formula mR03,nRz05,pR”Oz,rR”’02. None of thisseries containing R‘*03 in place of R20a have as yet been prepared.Quarternary compounds also exist, for the author has obtained thefollowing in well-defined crystals :-GO WO3,3P2O~,V2Q~,V0~,18€3a,Q + 150H,O, which is reducible to the general formula :-mR03,nR”~05,~R’zOa,rR’‘’zO ;~R~Z,U~~’~~~,~R”~O~,~R”’O~,~R’‘’It is evident that the possible number of various combinations in thisgroup is very great. Besides the above types, the author has obtainedother compounds containing neither molybdenum nor tungsten ; forexample : p hosp h o-vanada tes, arseno-vanadates, and aniimon y-vana-dates, which are frequently crystalline, and hare the general formulam ft’z05,nR’’z05,pR20. I), A. L

ISSN:0368-1769    

DOI:10.1039/CA8844600148

出版商:RSC    

年代:1884

数据来源: RSC