18 ABSTRACTS OF CHEMICAL PAPERS.I n o rg a n i c C he m i s t r y.Preparation of Hydrogen Selenide and Hydrobromic Acid.By A. ETARD and H. MOISSAN (BUZZ. SOC. Chim. [2], 34, 69).-Theauthors prepare hydrogen selenide by a method analogous to thatemployed by Champion and Pellet for h-j-drobromic acid and hydrogensulphide, that is, by the action of bromine and sulphur respectivelyon paraffin. The hydrocarbon used in preparing hydrogen sulphidewas colophene, as its boiling point (300" C.) is considerably above thefusing point of selenium (250" C.). The reaction takes place in twostages : a t first a substituted product is formed, and this is subse-quently decomposed; at the end of the experiment nothing but amixture of unaltered colophene and carbon is left.Hydriodic acidmay be prepared by a similar proeess. V. H. V.Liquefaction of Ozone, and its Colour in the Gaseous State.By P. HAUTEFEUILLE and J. CHAPPUIS (Compt. Tend., 91, 522-525).-The authors obtained a mixture very rich in ozone by the action ofelectricity on oxygen at a very low temperature. This mixture wastransferred to the capillary tube of Cailletet's apparatus, and subINORGANIC CHEMISTRY. 19mitted to pressure, at a temperature of - 2.3". At the first fewstrokes of the piston an azure-blue colour was seen to fill the tubeand as the pressure increased the colour deepened, until when the gaswas under a pressure of several atmospheres, the colour had becomeindigo-blue. When the pressure was suddenly removed, a momentarywhite mist was observed within the tube, indicating a condensationinto the liquid, or perhaps solid state.The blue colour, being like itsodour, an essential property of ozone, may be seen whenever a suffi-cient thickness of a mixture containing it is viewed. Thus the oxygenissuing from Berthelot's silent-discharge apparatus exhibits a sky-bluecolour when viewed along a column 1 metre in length. I n a forth-coming communication, the author will discuss the agency of ozone asaffecting the colour of the atmosphere. R. R.Constancy of the Proportion of Carbonic Anhydride in theAtmosphere. By T. SCHLUESING (Cow@ rend., 90, 1410-1413) .-The author is of opinion that the sea plays an imporbnt part in regu-lating the quantity of carbonic anhydride present in.the atmosphere.He has shown (ibid., June and July, 1872) that water in contact withthe carbonate of an alkaline earth, and an atmosphere containing car-bonic anhydride, absorbs the latter, forming a quantity of bicarbonate,which increases with the tension of the carbonic anhydride in theatmosphere, according t o a given law. Moreover, if the water con-tains a neutral salt, the amount of bicarbonate formed is increased.Comparing this with the state of the sea and the atmosphere, it is seenthat the sea is in constant contact with air which contains carbonicanhydride, and with the earthy carbonates at its bottom. Fromanalyses of sea water, the author finds that I litre contains 98.3 mgrms.of carbonic anhydride, and a base combined with it equivalent to99.3 mgrms.sulphnric acid, so that the greater part exists in the formof bicarbonate. Now when the amount of carbonic anhydride in theatmosphere, which is proportionately very much less than that containedin sea water, increases beyond its norma1 amount, the surplus isabsorbed by the sea and a fresh portion of the earthy carbonates goesinto solution. On the other hand, when the quantity decreases, car-bonic anhydride escapes into the atmosphere. This action, togetherwith the continual motion of the atmosphere, tends greatly to equalisethe quantity of the gas present in the atmosphere. L. T. 0's.Proportion of Carbonic Anhydride in the Atmosphere. ByJ. REISET (Compt. rend., 90, 1457--1459).-This is a reply to Marie-Davy, in which the author maintains that the method of experimentused by the observer at Montsouris to determine the constancy ofthe proportion of carbonic anhydride in the air was not sufficientlyexact to eliminate all sources of erim : also that the experiments ofTruchot on the influence of altitude on the amount of carbonic anhy-dride require repetition, since no correction is made for the alterationin the standard sohtions due to evaporation a t such high altitudes,The author quotes his former remarks (this Journal, Abstr., 1880,605) * L.T. 07s.c 20 ABSTRACTS OF CHEMICAL PAPERS.Proofs of the Existence of Ozone in the Atmosphere. By E.SCHONE (Ber., 13, 1503-l508).-Hydrogen peroxide has been shownby the author (this Journal, 34, 552 and 703) to be a constituentof the atmosphere. This being the case, the evidence adduced bySchonbein and Honzeau to prove the existence of ozone in the atmo-sphere is of little value, for the results they obtained may have beenproduced by hydrogen peroxide.Little weight is to be attached tothe evidence brought forward hy Andrems (PhiZ. Mag. [4], 34, 312 ;and Nature, 8,347 and 364) ; or Fox (“ Ozone and Antozone,” London,1873, 48 and 216), in support of the existence of ozone in the atmo-sphere, these authors having ignored the presence of hydrogen per-oxide completely. The method of testing for ozone by exposing silverfoil is one to which many objections may be raised. The odourobserved after a flash of lightning and attributed by many to ozone,the author fails to recognise as resembling that of ozone.The author concludes that the evidence in favour of the existence ofozone in the atmosphere is by no means conclusive, yet in atmosphericelectricity we have power sufficient for its production.The existenceof hydrogen peroxide in the atmosphere does not exclude that ofozone, since these bodies decompose one another b u t slowly.P. P. B.Observations on the Atmosphere made with ThalliumPapers. By E. SCH~NE (Ber., 13, 1508--1514).-The observationsof the author and others show that the ozonometer of Schonbein(AnnuZen, 89, SZS), is too much influenced by the hygroscopic stateof the atmosphere to be of service in determining the combinedeffect of ozone and hydrogen peroxide present in the atmosphere.This ozonometer the author stigmatises as a crude hygrometer.Asthe oxidation of thallous hydrate by ozone or hydrogen peroxide isuninfluenced by the presence of moisture, the author has made aseries of daily and nightly observations by exposing to the atmo-sphere papers saturated with a 2 per cent. solution of thallous hydrate.A sca!e of numbers was made corresponding with the densities of thebrown colour produced by exposure. Observations were made simul-taneously with the ozonometer, the deductions from which were usuallythe opposite of those obtained from the thallous hydrate. The obser-vations with thallous hydrate show that the oxidation is greaterduring the day than during the night ; it is influenced by the directionof the wind.a southerly wind is attended with a stronger coloration ;clouds and rain have a marked influence, viz., the reduction of thecoloration of the thallium paper. Further allowance must be madefor the strength of the wind. The observations made with thalliumpapers agree with the results obtained by the author in the moreexact determination of the atmospheric hydrogen peroxide. Fromthis fact, the author thinks that atmospheric hydrogen peroxide issufficient to produce the observed oxidation, and that the presence ofatmospheric ozone is uncertain.ByA. ETARD (Comnyt. rend., 91, 627-629).-The author proposes toplace boron a t the head of the vanadium family of elements, formingP. P. B. .Position of Boron in the Series of Elementary BodiesINORGANIC CHEMISTRY.21a group intermediate between that of phosphorus and that of carbon.This juxtaposition of boron to the phosphorus group is supported bythe existence of the compounds BCl, and BOC13, recently discoveredby Councler, and by the existence of boric triethide or triethylborine,which is analogous to triethylphosphine in composition and properties.The relations of vanadium to the phosphorus group have been estab-lished by Roscoe, and the labours of Deville and Troost have doneas much for niobium and tantalum. Boron and vanadium areboth grey, pulverulent, carbon-like substances, combustible, and infusi-ble; both combine with chlorine, forming BCl, and VCl,, and theiroxychlorides, BOCI, and VOCl,, are yellow fuming liquids. Boronand vanadium, like the other members of the group, B, V, Nb, Ta,have also the somewhat rare property of directly absorbing nitrogen.The author will, in a subsequent communication, describe the proper-ties of an oxide of boron, U205, corresponding with V205 and Pz05.Action of Sulphur on Water. By A.COLSON (Bull. SOC. Ckim.[2], 34, 66-69).-The author was induced to study the action of sul-phur in the nascent state on boiling water, from difficulties whicharise in the determination of iron by the Marguerite process. Onadding a very dilute solution of sodium thiosulphnte to dilute hydro-chloric acid (1 : lo), the salt is completely decomposed, with forma-tion of hydrogen sulphide and sulphuric acid, the reaction beingS2OZ + H20 = SO, + HzS. In more concentrated solutions the de-composition is not so complete, part of the sulphur being deposited onthe sides of the flask.An experiment with sulphur dissolved in sodiumprotosulphide showed tha,t an amount of lead sulphide was obtainedgreater than that required by theory for the protosulphide employed.A comparison is drawn between the action of water on flowers of sul-phur and on sulphur liberated from the thiosulphate. The latter isenergetic, and takes place at once a t ordinary temperatures; theformer requires time, and the temperature of boiling water. The sul-phur deposited on the flask from the decomposition of the strongthiosulphate solution, was in the form of lemon-yellow grains, whlchhad no action on polarised light. The same form was obtained fromsulphur deposited from a benzene solution, and kept for some time incontact with boiling water.It would appear that sulphur loses itsPresence of Cerium in the Coal Measures of St. Etienne.By MAYENCON (Conzpt. reid., 91, 669).-The paper notes the author'sdiscovery of cerium in some mineralogical products of the miningdistrict of St. Etienne. The cerium is found particularly in certainhard nodules of carbonate of iron, where it appears to exist in thestate of carbonate. R. R.R. R.crystalline form before entering into combination. V. H. v.Sesquioxide of Chromium. By H. MOISSAN (BUZZ. SOC. Chin%.[2), 34, 70-73).-The author compares the action of various re-agents on ignited chromium sesquioxide and the oxide rendered anhy-drous by heating it a t 440" C.in a current of nitrogen or carbonicanhydride. Hydrogen sulphide and selenide, chlorine, bromine, an22 ABSTRACTS OF CHEMICAL PAPERS.oxygen have no action on the former modification. The actions ofsome of these substances on the &her modification are studied.Action, of Hydrogen Sz1bpl&ie.--By exposing the anhydrous oxide toa current .of hydrogen sulphide, whether dry or moist, at 140" C., it isconverted into the corresponding black sulphide, clr,S,. The substanceis not attacked by any acid except nitric acid and aqua regia. Byreducing it in hydrogen, a black protosulphide, CrS, is formed.Actiou of Oxygen.--The sesquioxide when heated in this gas is con-verted into the dark grey dioxide, CrOz, which resembles the corre-sponding manganese dioxide, MnOz, in its reactions.ktCtiO.12 of ChZoriwe.-By exposing the hydrated sesquioxide to acurrent of dry chlorine and gradually raising the temperature, redvapours of chlorochromic acid begin to be evolved at 440" C., butwith the anhydrous sesquioxide, dry chlorine forms the sesquichloride,the reaction being very incomplete : moist chlorine gives chlorochromicacid with the anhydrous sesquioxide or sesqnichloride.It mouldappear from these experiments that the presence of small quantities ofwater determine the formation of chlorochromic acid, the necessaryoxygen being furnished by the water. By stopping the reaction at acertain stage, the sesquioxide is converted into the brown oxychlorideof Moberg, an intermediat<e body less oxidisecl than chlorochromicacid, and decomposable by water.The sesquioxide of chromium isa type of those oxides in which a change of properties is accompaniedby an evolution of heat. V. H. V.Preparation of Chlorine. By BERTHELOT (Compt. rend., 91,252-256) .--The author's experiments were undertaken to elucidatethe first stage of the reaction which occurs in the preparation ofchlorine by the action of hydrochloric acid on manganese dioxide.When these subst'ances are mixed in the cold, a brown liquid isformed, which was supposed by Forchammer to contain a, sesquichlo-ride of manganese, by NicklAs and by Fisher (this Journal, 3, 409)t o contain manganese tetrachloride.Actim of Chlorine on Ma.lzgn~ious C1doride.- A concentrated solutionof manganous chloride, saturated with chlorine, and placed in contactwith an atmosphere of this gas, dissolves only about half the quantitydissolved under the same circumstances by pure water, and about thesame amount of heat is evolved in proportion to the chlorine dissolvedin the two cases.The liquid slowly deposits a precipitate of manganesedioxide, absorbing a t the same time an additional quantity of chlo-rine, but even after two months the ratio of chlorine absorbed tomanganous chloride taken did not exceed 1 : 55. By diluting theoriginal solution of manganous chloride saturated with chlorine withnine times its volume of water, an abundant precipitate OC manganesedioxide is formed a t once, which increases during a certain time.Atthe end of two months, the liquid still contained manganous chlorideand free chlorine, coexisting with the hydrochloric acid and manganesedioxide formed : there is in fact an equilibrium established.Action of Hydrochloric Acid OY& Manganese Dioxide.-Manganesedioxide mixed with a nearly equivalent quantity of a dilute (10 C.C. =0.16 gram) solution of hydrochloric acid, evolves chlorine, and IN ORGANIC CHEiIIISTRY. 23brown liquid is formed, but the reaction is very incomplete. If thesame mixture be heated in a sealed tube at 100" for 20 hours, the re-action proceeds further, but remains incomplete. After cooling, man-ganese dioxide slowly separates out on the wall of the tube, provingthat the equilibrium is dependent on the temperature.Action of Chlorine on Manganous Chloride and Hydrochlo& Acid-On passing a current of chlorine into a concentrated solution ofnianganous chloride mixed with its own volume of strong hydro-chloric acid, the liquid turns brown almost immediately, but depositsno precipitate even after three months.If the preceding solutionbe diluted ten times before saturating with chlorine, it absorbs aboutthe same quantity of that gas without any coloration or precipitatebeing at first, produced, but after some weeks a small quantity ofmanganese dioxide separates out on the walls of the flask. The heatevolved during the absorption of chlorine by manganous chloride inpresence of hydrochloric acid is several times as great as that evolvedin the absence of hydrochloric acid.The author concludes from these experiments that the brown colouris due to the formation of a compound perchloride, which may beconsidered as HCl.Cl, + nMnCl,, or as nHCl + MnC14.On the firstview, this perchloride is derived from the perchloride of hydrogen,HC1.Cl2, described by the author in a previous paper. This compounddissociates under the influence of heat, and the dissociation is renderedcomplete when the chlorine is removed as fast as it is liberated. Whenthe experiment is conducted in sealed tubes, reabsorption of the chlorinetakes place on cooling, attended with separation of manganese dioxide.The influence of dilut,ion is twofold ; in the first place the manganouschloride is partly decomposed by the water int,o oxide and free acid,and the oxide is peroxidised by the combined action of the five chlorineand water ; in the second place, absorption of energy takes place byt,he formation of definite hydrates of hydrochloric acid, and in con-sequence of this loss of energy, the mauganous chloride may bepartly transformed into dioxide even iu presence of hydrochloric acid,the equation MnC1, (dilute) + 2H,O + C1, (gas) = MnO, + 4HC1(dilute) corresponding with a disengagement of 3.7 thermal units.This reaction is never complete, on account of the secondary forma-tion of HC1, + nMnC1,.The equation MnO, + 4HCl = MnCl, (anhydrous) + 2C1 (gas) + 2H20 (gas), corresponds with a disengagement of 12.9 thermalucits, and this takes place to a greater or less extent in concentratedsolutions, in which a portion of the hydrochloric acid is not combinedwith the water as a stable hydrate, the heat of formation of which isfi*om 10 to 12 thermal units.J. M. H. M.Borodecitungstic Acid and its Sodium Salts. By D. KLEIN(Compt. rend., 91, 474-475 j.-When a solution containing boraxand boric acid in the proportion of 1 mol. of the former to 2 mols.of the latter is heated with an excess of tungstic acid (hydrated), aportion of the latter is dissolved. On cooling the filtered solutiondeposits crystals of boric acid and polyborates of sodium, and by con-tinuing the evaporation of the mother-liquor in vaczco crystals of bora24 ABSTRACTS OF CHEMICAL PAPERS.are first obtained, and then a salt excessively soluble in water, and verydifficult to purify by recrystallisation. This salt has the composition2Na20.2Hz0.10WO3.B2O3 + 11Aq.The crystals belong to the clino-rhombic system, but are ill-defined, with dull faces. The reaction isfaintly acid to litmus. On adding a trace of alkali, the acid reactionis changed to alkaline, but reappears after a time. By adding asmuch sods as is already present, and evaporating, a second crystallinesalt is obtained, which has not yet been analysed.Sodium borodecitungstate is precipitated by salts of mercury, andfr.om this precipitate the acid may be obtained. This acid and boro-duodecitungstic acid correspond with the silicodecitungstic and silico-duodecitungstic acids described by Marignac, and their salts have verysimilar properties.Boroduodecitungstie Acid. By D. KLEEIN (Cowpi. rend., 91,495--498).-When tungstic hydrate in large excess is added to a boil-ing solution of potassium pentametaborate, potassium boroduodecitnng-state is formed. The author ascribes to this compound the formula2K20.B20,.12W03.2H~0 + 15Aq. It is a very soluble salt, crystal-lising in needles resembling those of potassic tungstoborate. Themother-liquor yields white tabular crystals of another salt!, of theformula 4K2O.B,O3.12 WO, + 21Aq. By treating the insoluble mer-curous salt with the requisite quantity of hydrochloric acid, andevaporating the solution after removal of the mercurous chloride,boroduodecitungstic acid is obtained as a syrupy liquid.J. M. H. M.R. R