INORGANIC CHEMISTRY. In o rg ani c C he mi s t r y. The Non-luminous Flame of the Bunsen Burner. By R. BLOCHMANN (Ann. Chem. Pharm. clxvii 295-358). THEprocesses which go on in the interior of the Bunsen flame were studied by aspirating and analysing the gases from various parts of a flame 120 mm. high. In the first series of experiments the gases were taken from the atmosphere surrounding the flame at a distance of 10 mm. Up to a height of 20 mm. no products of combustion had diffused into the air but from 30 mm. to 120 mm. carbon dioxide and water vapour were found in slowly and irregularly increasing quantities. In the second series the gases were drawn from the periphery of the flame at every 10 mm. vertically. The quant'ity of free oxygen pre- sent indicated that from 29.4-48 volumes of air had become mixed with the products of combustion from 100 volumes of gas.After correcting for the carbon dioxide and moisture in the air and coal gas? the following table of the volumetric composition of the gas from the periphery of the flame was calculated :-Height from burner. 10 mm. cop3.30 H20. 14-36 0. 8.29 N. 74.05 =20 cop 4.35 - 3.49 14.95 7-95 73.61 4-29 4.07 14.68 8.31 72.94 3.63 3.95 12.90 8.94 74-21 3.27 3-64! 11-22 10.03 75-11 3-08 3.92 11-02 9.72 75-34! 2.81 4.35 10.82 9.20 75.63 2.49 4.91 10.73 8.92 75-44 2.18 5.38 10.72 8.60 75.30 1.99 5.73 10.81 7.76 75.70 1.89 6-58 10.97 6.61 75.84 1.67 7.18 11.14 6.17 75.51 1-55 The complete combustion of the coal gas would have given 2.27 as the ratio of water to carbon dioxide.It is thus seen that the gas does not burn equably the hydrogen burning chiefly in the lower and the carbon in the upper parts of the flame. This appears to be due to the VOL. XXVII C ABSTRACTS OF CHEMICAL PAPERS. low specific gravity of hydrogen which enables it to diffuse from the dark cone into the zone of combustion more rapidly than the other gases. The relatively large proportion of burnt gases at the very base of the flame when connected with the facts that a space exists between the burner arid the base of thc? flame and that the inner and outer zones of combustion meet at that point seems to indicate t,hat a portion of the gas has time to form with tlie exterior air an explosive mixture which ignites as a whole when its temperature becomes sufficiently high.In the third series the gases were aspirated from the interior of the flame at four points viz. 10 mm. below the orifice of the burner and 25 50 75 mm. above it The point of the inner cone was about 55-60 mm. from the burner. The composition of the mixture from the interior of the burner showed that the gas was at that point only mixed with about 40 per ceiit. of the air required for complete cornbus- tion. Below the point of the inner cone little or no combustion takes place for combustible gases aiid free oxygen are found in presence of one another. Above this point the combustion is almost complete only 6 per cent. of combustible gases being found at 75 mm. These consist of hydrogen carbon monoxide and traces of marsh-gas ;oxygen is entirely absent.The carbon monoxide of which both here and at 50 mm. there is far more than is contained in the original gas is evi-dently formed in the inner zone of combustion. A portion at least of the hydrogen found at 75 mm. must be due to the decomposition of the hydrocarbons since between 25 and 50 mm. it rapidfy disappears while at 75 mm. there is scarcely less than at 50 mm. The additional fact of a decided expansion (independent of temperature) of the gases while passing the point of the inner cone points to some such reaction as'C2H4+ O2=2CO + H4. The author has also repeated and extended Knapp's experiments on the extinction of the luminosity of a gas-flame by the admixture of other gases in place of air.Oxygen nitrogen carbon dioxide and monoxide and hydrogen all produce this effect. When an inert gas is used the space between tlie burner and the basc of the flame is greatly increased; as much as 1.5 mni. was observed. On augmenting the supply of inert gas the flame either opens at one side the opening be- ginning at the bottom and extending upwards to the summit or else the top of the flame vanishes altogether leaving a mere ring with the upper side very irregular. It was noticed that when the luminosity of the gas was destroyed by admixture of nitrogen it could be partially restored by addition of a little air. Attention is also drawn to the opposite effects produced by oxygen according as it is mixed with the gas before combustion or immediately at the point of ignition in which case as is well known it greatly enhances the luminosity.The cause of the luminosity of flames is discussed but without any definite conclusion being arrived at. M. J. S. INORGANIC UHEMISTRY Proportion of Carbonic Acid in Atmospheric Air; Variation at Different Heights. By P. TRUCHOT (Compt. rend. lxxvii 675-678). THEamount of carbon dioxide was determined by passing a known amount of air through a solution of barium hydrate of known strength contained in four Wolfe'a bottles and by subsequent titration. Ten litres of air were found sufficient for a determination. The observa- tions were made at Clermont Ferrand during the months of July and August both on an elevated terrace and on the country.Carbon dioxide Vo1. in per litre. 10,000 air. m.gr. During the day ...... 0 "701 3-53 On the terrace.. ........ { During the night .... 0 -801 4*03 Removed froin Shy.. .............. 0.624 3 -14 .. { Night.. ........... 0.753 3 *78 In the sun.. .. 0 *703 3 *54 country In the shade . . 0 *825 4 *15 Night.. ............ 1-290 ti -49 These figures show that the amount of carbon dioxide is larger during the night than in the daytime and that the amount does not materially vary in tJhe neighbourhood of a town. The sun influences the quantity of carbon dioxide near vegetation. From observations made at different elevations it was found that the quantity of carbon dioxide diminishes considerably as the altitude increases.COz Vol. in Tempe-Pressure.per litre loo>ooo 'pot of Date. observation. Height. rature. at. 0" air at Oo and 760. and 760. m. mm. 26th 28th 1 30th Bug. Clermont Ferrand.. 395 25' 725 0.623 3.13 3873 .... 27th Bug. { Top Of Puy-do) 1446 21' 638 0.405 2-03 D8me ........ 29th Bug. .. Peak of Sancy .... 1884 6' 5'78 0.342 1-72 These results may be explained when we consider that the carbon ioxide is evolved from the surface of the earth and that its specific avity is greater than that of air. W. R. Apparatus for Dissolving Hydrogen Sulphide under Pressure. By J. P. COOKE,Junr. (Chem. News xxviii 64). THEapparatus consists of three bottles A B C; a bottle D four times the size of one of these and a small wash-bottle.A is the generator and is furnished with one exit-tube by which it is con-c2 ABSTRACTS OF CHEMICAL PAPERS. nected with the mash-bottle which acts better if it contains moistened sponge than if the gas simply passes through water. The gas is thence conducted through B and C in the usual manner to D which is fur- nished with three tubes. Two of these extend a short distance below the stopper (which like all the others is of india-rubber) ; one is the inlet and the other is a vent. The third tube reaches to the bottom of the bottle and is placed in connection with a water-head. When the generator is charged and the connections are made the vent of D is opened till the air is driven from the apparatus. The.vent-tube is then connected with a manometer and when the pressure equals that which it is known the water-head will exert.the vent is closed. The water- supply is then turned on cautiously at first] lest water should be forced back into the generator but afterwards at full pressure. The solution of the gas is drawn from B or C by adapting a tube to the inlet in such a way t.hst a syphon is formed. 100 C.C. of such a solution made under a pressure of two atmospheres will precipitate a gram of antimony. To ensure the solution of the sulphate formed in the generator it is advis- able to place the latter near a source of gentle radiant heat. In dis-mounting the apparatus care must be taken to relieve the pressure on the generator cautiously otherwise the hot solution of sulphate will boil over.The expanditure of hydrogen sulphide in a large labora- tory was reduced by this apparatus to five per cent. of its usual amount. B. J. G. Existence and Decomposition by Heat (Dissociation) of Sulphur Tetrachloride. By A. MECHAELIS and 0. SCHIF-FERDECKER (Deut. Chem. Ges. Ber. ri 993-996). BY saturating sulphur sulphochloride (S,Cl,) cooled to -20" with chlorine the author has obtained a light-brown clear liquid which on analysis yields numbecs closely agreeing with those required by the formula SCI,. On being removed from the freezing mixture the liquid boils and evolves chlorine. The following tables show the decomposition of sulphur tetrachloride at various degrees of temperature :-I. Swlphw tetrachloride.Increase Temp. Diff. sc14. SCl> Diff. for 1". -22 100~00 0.00 7 58.05 8-3 15 41.95 58.05 5 13-22 2% 10 27-62 72.38 3 5.66 1.9 7 21.137 78-03 5 10.04 2.0 2 11.93 88.07 + 0.7 2.7 8.87 91.13 3.06 1.1 5.5 6.4 1.1 6.2 943 97.57 INORGANIC CHEMISTRY. II Sulphur dichlomkle. sc12. S&12. Diff. for 10". + 20 93.45 6.55 6.23 30 87-22 12-78 6.41 50 75-41 24.59 5.79 65 66.78 39-22 6-36 85 54-06 45.94 90 26.48 73-52 7.03 100 19.45 80.55 7.10 110 12.35 87-65 6.91 120 3.a 94.56 130 0.00 100.00 5 *44 M. M. P. M. Sulphur Oxytetrachloride. By A. MICHAELIS and 0. SCHIF-FERDECKER (Deut. Chem. Ges. Ber. vi 996-999). WHEN sulphuryl hydroxychloride (CI-S02-0H) is mixed with sulphur tetrachloride and the mixture cooled to -18' and saturated with dry chlorine a white crystalline mass is obtained which after purification has the formula S20sCJ4.This substance is therefore identical with that which Millon obtained by passing moist chlorine into sulphur chloride saturated with chlorine. The authors assign to it the rational formula SC13-0-S02C1. It melts at 57" giving off chlorine and sulphur dioxide. The residue after cooling contains thionyl chloride and pyrosulphuric chloride. 4s203c& s,05c124-5S0C12+ c11 -+ SOZ. =* After long keeping this substance is changed into a yellow liquid which possibly contains the theoretic isomeride SOC13-0-SOC1. M. M. P. M. Solidification of Nitrous Oxide. By T H o M A s W 1 LL S. NITROUS OXIDE was one of those gases which Faradq succeeded in liquefying almost at the beginning of his scientific work in 1823.Dry nitrate of ammonia was enclosed in one end of a bent sealed glass tube and exposed to the action of heat ; the salt was decomposed with some difficulty but eventually the decomposition was complete and the pressure exerted by the first portion of the generated gas proyed sufficient to liquefy the remainder for at the conclusion of the experiment two layers of liquid remained in the tube the lower one proving to be water and the upper one liquid nitrous oxide. The interior pressure as indicated by one of Faraday's mercurial gauges was 50 atmospheres and the temperature 45" F. Thilorier and after- wards Natterer obtained the same result by the direct compression of the gas with a force-pump.Faraday again worked at the subject of the liquefaction and solidifi- cation of gases in 1845 and then succeeded in freezing the liquid nitrous oxide into a mass of transparent crystals by exposing it in a sealed tube to the cold of a bath of solid carbonic acid and ether i?z ABSTRACTS OF CHEMICAL PAPERS. vacuo the pressure in the interior of the tube at the time as indicated by the gauge sinking to less than one atmosphere. Therefrom Faraday concluded that nitrous oxide could not be solidi- fied by the cold produced by its own evaporation unless aided by the external withdrawal of the pressure. This belief was corroborated by his experience; for on opening several tubes containing the liquid a large portion of it was immediately converted into gas but the remainder was only cooled without showing any sign of solidifica- tion.Some experiments made by Natterer with much larger quantities of the liquid (using indeed as much as a quarter of a litre at a time) in which he also failed to obtain the solid by spontaneous evaporation seemed further to confirm this conclusion. It is possible that in the above observation the gauge after cxposure to such high pressures may not have been sufficiently trustworthy to register low ones. The above result is directly opposed to that obtained with carbonic acid. The melting or freezing point of carbonic acid is -7O" or -72" F. and the pressure of its vapour at this point is equal to 5.3 atmospheres ; hence it is seen how readily it can become solid by its own evaporation at a pressure of only one atmosphere.In fact this spontaneous evaporation will cool the solid carbonic acid down to a temperature of about -148" F. or 78" F. below its freezing point and possibly the solid nitrous oxide in the sealed tube at the time when the gauge registered less than one atmosphere was thus cooled below its freezing point. In comparing the behaviour of carbonic acid and nitrous oxide it must however be borne in mind that solid car- bonic acid is exceptional. Faraday himself pointed out the remarkably high tension of its vapour when in the solid state and showed the somewhat paradoxical result that if the boiling point of a liquid be defined (as it usually is) as that point at which the tension of its vapour balances the pressure of the atmosphere then the boiling point of carbonic acid is colder than its freezing point by about 40' F.boiling point = -110" IF.; melting or freezing point = -70" F. Dumas in 1848 actually obtained a rery small quantity of solid nitrous oxide by the evaporation of the liquid but apparently in too small quantities to allow- of any accurate observations being made. Having lately had some facilities afforded me for working with large quantities of liquid nitrous oxide I have endeavoured by a few experiments to obtain it in the solid state by means of the cold arising from its own evaporation and to some extent these experiments have been successful. Solid carbonic acid is produced with great ease when the liquid issues fiom almost any jet into almost any kind of receiving vessel and the use of special apparatus is only to obtain it with the greatest economy in the consumption of gas ; perhaps for this purpose the ordi- nary circular brass box of Thilorier's is the best.To obtain lipid carbonic acid in a vessel freely open to the air is extremely difficult if not absolutely impossible. Nitrous oxide on the other hand can be kept readily in the liquid state in open vessels for a consider-able time without alteration provided the vessel is kept still. For the production of solid nitrous oxide the above-mentioned brass box is of no use the evaporation of the liquid not being sufficiently INORGANIC CHEBlISTRY.promoted. It seemed possible however by the introduction together with the liquid of a strong stream of air to aid this evaporatioii ; and this proved to be the case fbr a very small quantity of the solid was by this means produced. By altering the arrangement and substituting for the brass box a straight glass tube somewhat contracted at its orifice the result obtained was better. Finally an arrangement some- thing like an injector was adopted A very fine steel tube (such tubes as are used in some surgical operations) was directed into the axis of a thin brass cone having a small opening about the eighth of an inch at its apex. On causing a stream of the liquid to issue from the jet' it is retained in the cone f'or a moment and is then forcibly blown out at the apex together with a strong stream of air.The solid is in this way formed in some quantity and may be collected in a dish lined with filter-paper or other suitable vessel. XOdoubt for this result there is a large consumption of gas. The appearance of the solid is more compact than that of the well- known carbonic snow which is probably accounted for by the fact that larger particles of the liquid are frozen this freezing taking place with carbonic acid immediately ihe jet of liquid leaves the tube and while it is yet in the state of fine spray ; but in the case of nitrous oxide only after it has to some extent been collected into larger drops. Unlike solid carbonic acid nitrous oxide will melt and boil if gently warmed before assuming the gaseous condition.Hence if touched with the fingers or placed in contact with the skin it melts and produces a painful blister. The temperature of its freezing or melting point is -120" F. or -99"C. as observed with an alcohol thermometer. The boiling point usually said to be -88" C. is according to my experi- ments -109" F. or -92" C. but I should give more credence to the lower figure. The readings of alcohol thermometers at such low tem- peratures are no doubt, somewhat untrustworthy Those used iu this case have been graduated from actual observations above zero ; but below zero the degrees have simply been placed at equidistant inter- vals. As probably the alcohol gets rather thick and more viscid at this lower point and the contraction consequently less the above figures will still be too high.The proximity of the boiling and freez- ing points caused me to try to freeze the liquid by simply blowing a stream of air through it ; in which I succeeded perfectly. Liquid nitrous oxide is immiscible with water as seen in Faraday's original experiment the tube containing two layers of liquid. An experiment on a larger scale has fully confirmed this fact and it is somewhat curious that a gas comparatively so soluble in water shonld when it becomes a liquid be immiscible with that fluid. Water and nitrous oxide were pumped together into an iron vessel and the vessel afterwards inverted. On opening the cock the whole of the water was expelled before any of the nitrous oxide appeared.An additional quantity of water was placed in the vessel while still in its inverted position and nitrous oxide again pumped in beneath it. On standing for twenty-four hours the cock was again opened with the same result 8s before ;the liquid nitrous oxide having ascended through the heavier water. The specific gravity of the liquid I believe to be 0.9004 ; and from ABSTRACTS OF CHEMICAL PAPERS. some experiments I am inclined to think the liquid is exceedingly compressible but of this I a,m not able to speak with certainty. If the solid be placed upon water it does not appear to come into contact with it no doubt being protected by a film of its own vapour. I hope shortly to be able to continue these experiments in other directions. T.W. Zinco-magnesium Chloride. By G. WARN E R (Chemical News xxviii 186). WHEN magnesium chloride is dissolved to saturation in a hot solution of zinc chloride having a specific gravity of 1.6 a salt having tlhe composition ZnClz.MgCIz.6H20 is deposited on cooling. It forms deliquescent rhombic prisms with truncated summits. The following table shows the amount of water absorbed from the air in a given time by equal weights of various chlorides the amount absorbed by calcium chloride being t’aken as unity :-Calcium chloride ....................... 1.00 79 , crystallised .............. 0.52 Zinc chloride crystallised ................ 1.00 Zinco-barium chloride crystallised. ......... 0.40 Zinco-magnesium chloride crystallised.. ....0.59 Magnesium chloride. ..................... 0.43 T.B. Chemical and Crystallographic Notices on some Salts of Glucinum and the Metals of Cerite. By C. MARIGNAC (Ann. Chim. Phys. [4] xxx 45-69). I. XaZts of GZueiwum.-The author has reinvestigated the double Buo- rides of glucinum with the alkali-metals whose existence had been denied by Klatzo. They are easily obtained by concentrating mixed solutions of the respective fluorides and admit of recrystallisation from water. The potassium salt GF2.2KF generally forms hard mammil- lated crust,s but by cooling a somewhat dilute solution it may be obtained in crystals derived from a right rhomboidal prism. They generally present the form of thin hexagonal plates the basal planes being largely developed.When the solution contains excess of potas-sium fluoride the crystals have the appearance of rectangular prisms owing to the elongation of one of the secondary axes. The salt is soluble in 19 parts of boiling water or in 50 parts at 20’. When heated it decrepitates and melts at a low red heat it contains no water. By concentrating a solution containing a large excess of glucinum fluoride a second salt was obtained of the formula GF2,KF. It forms a hard vitreous mammillated crust from which no deternii- nable crystals could be extracted and it cannot be recrystallised from water. Corresponding salts of gZuci?cum and sodium were prepared. The compound GF2.2NaE’ exists in two forms one derived from a right and the other from an oblique rhomboldal prism.It is soluble in 34 INORGANIC CHEXISTRY. part-s of boiling water or in 68 parts at 18'. After fusion at a red heat it solidifies to a transparent' glass which falls to powder spon-taneously. The compound G;F,.NaF is veyy similar to the potassium salt. The awmonium salt GF,.2NHIF forms prismatic crystals isomorphous with the potassium salt. Numerous measurements of the angles of the preceding salts are given in the paper. The fluosilicate bromate and iodate of glucinum could not be pre- pared in the solid form ; neither could the double chloride of glncinum and mercury announced by Bonsdorff. The salt GK,( S04)2.2H20 pre- sents hard white opaque mammillated crystals the form of which could not be determined. The hex-hydrated sulphate was obtained accidentally.It forms foliated prismatic crystals which are very eBorescent and lose their brilliancy on removal from the mother- liquor. A solution. of glncinum ditliionate gives off sulphur dioxide on concentration and yields crystals of the sulphate. The perchlorate is very deliquescent. Attempts to prepare the double salts of glucinum sulphate with cupric and ferrous sulphates described by Klatzo were unsuccessful the two salts always crystallising separately. The same want of success attended efforts to combine glucinum nitrate with magnesium lanthanum and didymium nitrates and the sulphate with aluminium sulphate or with soda-alum so that the only existing evidence from isomorphism respecting the atomicity of glucinum is derived from the similarity in the forms of phenakite Si02.2G0 and willemite SiO2.22n0.11. On some Salts of Cerium Lautimwn alzd Didymiurn.-The author confirms the observations of Ceudnowicz and Hermann who had con-tradicted his own earlier researches on the crystalline form and amount of hydration of cerous sulphate. By evaporation in a vacuum at ordinary temperatures the salt 3CeS04.8H20 separates in right rhom- bo'idal octahedrons ; but when the. solution is evaporated in the air at 40"-,50" hexagonal prisms are obtained having the composition CeS04,3H20. The latter is absolutely isomorphous with the corre-sponding lanthanum salt. Two similar salts of didymium exist ; the trihydrated is hexagonal but that with 8 equlvalents of water is not isomorphous with the cerium salt.The nitrates of lanthanum and didymium contain 4 molecules of water. They belong to the same crystallographic system but though very similar in appearance cannot apparently be referred to the same primitive form. The a.tnnzonio-Zanth,anum nitrate La,(NK,)z(NOs)io,8H20 and the corresponding didymium salt are perfectly isomorphous. They form oblique rhombo'idal prisms with the basal edges replaced by octohedral planes. The awmojiio-cerous .nitrate (notl analysed) examined by Des Cloizeaux is also isomorphous with the above. The chZoropZatimtes of the three metals 4RCl2.3PtCl4.36H20,are isomorphous aiid very similar. They form square pyramids with basal planes. They are very soluble crystallising only from syrupy solu- tions.They lose half their water at 100". ABSTRACTS OF CHEMICAL PAPERS. Note on the Atomic Weight of Zunthanum.-Four. determinations of the weight of oxide in lanthanum sulphate which had been crystallised a great number of times and was almost perfectly free fi.om didymium, gave numbers leading to the atomic weights 92.52 92.56 92.24 and 92.48. The first two were made by simple ignition the others by pre-cipitation with ammonium oxalate. The author therefore adopts the number 92.5. M. J. S. Action of Sodium Sulphite and of Sulphurous Acid upon Lead Iodide. By A. MICHAELIS and G. KOETHE(Deut. Chem. Ges. Ber. vi 999-1000),. SODIUM SULPHITE and lead iodide form sodium iodide and lead sulphite. Sulphurous acid decomposes lead iodide forming lead sulphite and hydriodic acid.M. M. P. M. Chlorides of Molybdenum. By L. PAUL and B. KEMPE LIECHTI (Deut. Chem. Ges. Ber. vi 991-993). BYthe action of dry chlorine upon metallic molybdenum there is pro-duced the black pentuchloride MoC15. This compound is crystalline ; it can be fused and sublimed without decomposition. At a tempera-ture of about 250" it is reduced by hydrogen to the trichloride MoCI3 which is a reddish-coloured amorphous mass unchanged in the air and insoluble in water. When heated in a stream of carbon dioxide this compound is split up in accordance with the equation i., 2M0C13 = WOCIZ + MoClp. The dichloride which remains behind is a yelIow amorphous sub- stance insoluble in nitric acid but easily soluble in strong hot hydro- chloric acid from which solution a salt crystallises out having the formula Mo2Cl,.3H20.The tetrachloride which is carried over with the carbon dioxide forms a semi-crystalline brown sublimate easily decomposed by moisture. M. M. P. M. Action of Iodine on Chromium Dichloride. By R. W. EME ttSON MCIVOR (Chem. News xxviii 138). THE chromium chlorochroniate the preparation and properties of which are described by Thorpe (Chemn. ATews xx 245) can be formed by heating chromium dichloride with dry iodine. The following reac-tion takes place :-:3Cr02C12+ 41 = CrzOsC12+ 41C1. B. J. G.