摘要:

J 0 U li N A L H. E. AKMSTRONG Ph.D. F.R.S. WTNDHAM R. DUNSTAN M.A. F.R.S. H. J. H. FENTON M.A. F.R.S. P. F. FI~ANICLAKD LL.D. F.R.S. H. MCLEOD F.R.S. E. DIVERS M.D. F.R.S. ( ,P THE CHEMICAL SOCIETY. Sir WI~,LIAM RAMSAY K.C.B. LL.I). J. EMEMON REYNOLDS Sc.D F.R.S. A. Scorn D.Sc. F.R.S. T. E. THORPE C.B. LL.D. F.R.S. XT. A. TILDEX D.Sc. F.R.S. F.R.S. ABSTRACTS O F PAPERS ox ORGANIC CHERIISTRY. U. F. BAKER Ph.D. B.Sc. C. H. BOTHAMLEY. W. A. DAVIS. T. EWAN B.Sc. Ph.D. A. FINDLAY M.A. Ph.D. E. GOULDING BSc. W. D. HALLIBURTON M.D. B.Sc. A. HARDEN D.Sc. Ph.D. 1’. A. HENRY D.Sc. L. M. JONES B.Sc. I,. DE KOXINGH. H. R. LE SUEUR D.Sc. D. A. LOUIS. T. M. LOWRY D.Sc. F.R.S. J. MOCLLAE P1i.D. N. H. J. MILLER Ph.D. G. 1’. MORGAN D.Sc. K. J. P. OKTON M.A. Ph.D. J. C. PHILIP M.A. Ph.D. R. H. YICICAILD DSe. P1i.D. T. H. POPE. E. C. ROSSITER. M. J. SALTER. W. P. SRERTCHLP. L. J. SPEWER M.A. J. J. SUDBOROUGH Ph.D. D.Sc. E. W. WHEELWRIGHT B.A. Ph.D. G. I-TOT~SG Ph.D. A. J. GEEKSAIVAY. 1902. Vol. LXXXII. Part I. LONDON GURNEY & JACKSON 1 PATERNOSTER ROW 1902.RICHARD CLAY & SONS LIMITED LONDON & BCSGAY.

ISSN:0368-1769    

DOI:10.1039/CA90282FP001

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

J O U R N A L OF THE CHEMICAL SOCIETY. ABSTRACTS O F PAPERS ON PHYSICAL INORGANIC MINERALOGICAL PHYSIOLOGICAL AGRICULTURAL AND ANALYTICAT C:HEMISTRY. H. E. ARMSTROXG Ph.D. F.1l.S. E. DIVERS M.D. F.R.S. TVPXDHAM R. DUNSTAN M.A. F. Et. S. H. J. H. FESTON M.A. F.R.S. P. F. FRANKLAND LTJ.D. F.R.S. H. MCLEOD F.R.S. Sir WILLIAM RAMSAY K.C. B. LL.1). J. EMERSON REYNOLDS Sc.D. F.R.S. A. Scow D.Sc. F.R.S. T. E. THOIEPE C.B. LL.n. F.R.P. JY. A. TILDES D.Sc. F.R.S. F. R. S. (C-bitas %:uXr-&bitos W. P. KSSSE D.Sc. F.R.S. A. J. GKEESAWAY c'. F. CAKER Ph.D. B.Sc. C. 11. BOTHAMLEP. W. A. DA~VIS. T. EWAN B.Sc. Pl1.D. A. FISDLAP K A . Ph. D. E. GOULDISG B.Sc. Jy. D. HALLIBUILTOS N.D. ILSc. A. HAI~DE?; D.Sc. P1i.D. T. A. HENRY DSc. H. R. LE SUEUR D.Sc. D. A. LOTXS. F.R.S. r,. 11. JONES B.s~. 1,. DE KONINGH. T. RI. LOWRY D.Sc. J. MCCRAE P1i.D. I\-. H. J. MILLER P1i.D. G. T. MOI~GAS D.Sc. I<. J. P. ORTON &I.A. 1'11.1). J. C. PHILIP ILA. P1i.D. R. H. PICI~ARD D.Sc. Y11.11. E. C. ROSSITEK. 11. J. SALTER. W. 1'. SILEILTCHLY. L. J. SPENCER M.A. J. J. SUDBOKOUGH Ph.D. D.Sc. G. Tousc P1i.D. T. 13. POPE. E. Jv. ~\r€IEELUTRIGHT B.A. 1'11.1) 1902. Vol. LXXXII. Part 11. LONDON GURNEY &- JACKSOIS 1 PATERNOSTER ROW 1902.RICHARD C L A Y & soh’$ LIMITED h N U O N & BUNG.IY.

ISSN:0368-1769    

DOI:10.1039/CA90282FP003

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

ERRATA. COLLECTIVE INDEX 1883-1892. .fnr ‘( Tolylacetylene ” read ( ( Tolylethylene.” VOL. LXVIII (ABSTR. 1895). PART IT. Page Line 504 15” . f o ~ “ Sylvanite” rend ‘( Sylvite.” VOL. LXXVIII (ABSTR. 1900). PART IT. 411 15” ) ‘( (MgOH),(K,Na,Li)Si,O,+ H@“’ rend (hIgOH),( K Na,Li),Si30 + H,O.” VOL. LXXX (ABSTR. 1901). PART I. 119 4” BBy-triinatJLyZpentane-ay-olidoic ctcid ” read “ yy8-trimethyl- 248 2.2” “ WILLY hZAItKWALD ” mad (‘ WILHELM &IARCK\VALD.” pcntnne-Be-olidoic acid.” 648 5 y O H = 4 6 2 ‘ 4’1,” rend (‘[(OH),=5 7 2 :4].” 7 “[OH=4:2‘:4’,” read “[(OH),=5:2’:4’].” PART 11. 3” col. .i for “ Willy Markwald ” ?-earl ‘( Wilhelm Marckwald.” 1 229 21” 766 {top 11 451 5” ,for (‘ 5.653”” read “ 5.653.’’ 451 4* ( ( 4’41”” ?*end ‘‘4.41.” VOL. LXXXII (ABSTR. 1902).PART I. G bottom “ y-i~~ethyZ-a-isotzctyZz.ccleric acid ” read ( ’ by- Dimethyl-a-isobutylvaleric acid.” 52 4” & 7” “Diclytra” read “Dielytra.” 51 86 20 “1901 i 795,” yead “ 1901 ii 705.” :$} “this vol. i 604 643” read “Abstr. 1901 i 604 643.” 283 10“ ( ( Tetrnbromohydroxytolzcltetone )’ read ( ( Tetrnclz~orobroniohydro~y- 299 20 “ Dibenzoyl-B-alizariiL )) read ‘( Dibenzoyl-B-nniinonli.ari?i. ” 491 10” (‘ l-Pyrrylurethane ” read 2-P~rr~luretJzane.” 492 i } “ Indole-l-carboxylic” read “ I~dole-2-cnrboxyliF.“ 492 8 ) <‘ l-Indole-urethane” read (( 2-Indoleurethane.” 616 22 (‘ as-dibromo-p-ethyl-3 5-+-phenoL ’’ read toluketone. ’’ ‘‘ a -3 Ei-tribromo-I,b-p -et Ji ylpJ~c 11 01 . 7 9 * From bottom,ERRATA (conti~tued). Page Line 616 24 .for ‘‘ OH*C,H,Er*CHRIeEr” rccrcl ( ‘ OH.CGH,Br;CHMeBr.” 679 23 ( ( B-p-glutamnil” read ( ( P-p-tolzJaglz~tarnnil.~’ 727 16” “ Davison ” read ‘( Davidson.” 741 13 14 ( ( Byy-Dimethyl-B-hydroxypentanedioic acid ” read ‘( p-Hydroxy- 798 10 (( Bcnzytidcne Camphor” read “ Eenxylidencca?~2pkor.” 834 1 2 ’I p r y - trimethylpentanedioic acid. ” PART 11. 408 ;; 1- (‘ Apophylite ” wrcd ( ( Apophyllite.” 16- . . ~’ACHIARDI ” wnrl ( ( D’ACHIAT~DI.’’ 650 17 .. “depressecl from 119’25” t o 42.5”” read ‘( depressed by an amount corresponding with the atomic depression 42*5”.” 14’ ‘‘sealed” read ‘(open,” 7‘ to 4“ (Mete ‘( The snbstances with the exception of carbon dioxide which have the latter action will also reduce the amonnt of any amorphous sulphur formed. ” From bottom.

ISSN:0368-1769    

DOI:10.1039/CA902820X005

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

10 ABSTRACTS OF CHEMICAL PAPERS. lnorganic Chemistry. Reactions of Hydrogen Peroxide. By ARNOLD NABL (Moncctsh., 1901, 22, 737-744. Compare Abstr., 1901, ii, 16, 94)-Hydrogen peroxide and sodium thiosulphate react according to the equation : 2Naj2S20, + H202 = 2NaOH + 2Na,S40,. If the alkali is not neutralised, 75 per cent. of the thiosulphate remains unoxidised and the reaction leads to the formation of sulphate and dithionate as well as tetrathion- ate : 2Na2S20, + 7H202 = 2Na2S04 + H2S206 + 6H20 j H2S206 + H202 = 2H,SO,. Barium sulphite and hydrogen peroxide give a small quantity of dithionate as well as of sulphate when the sulphite is in excess, The reactions represented by the equations 2H2S0, + H202 = 2H,O + H2S206 and H2S206 + H202 = 2H2S04, therefore take place simultaneously.K. J. P. 0. Alkali Salts of Hydrogen Peroxide in Aqueous Solution. By HARRY T. CALVERT (Zeit. physikal. Chem., 1901, 38, 513-542)- An historical account of the peroxides of the alkali metals is given. For the experiments, the hydrogen peroxide was prepared by repeated distillation until the conductivity was constant, and then concentrated on the water-bath. The distribution ratio of hydrogen peroxide between water and ether a t 20' is 15.6 and is independent of the con- centration. A constant ratio (7.03 a t 25*, and 6.65 a t 0') was also found when the ether was replaced by amyl alcohol, and this is not altered by the addition of acids, I n presence of alkalis, the distribu-INORGANIC CHEMISTRY. 11 tion ratio is increased and the curve representing the change of ratio with increasing concentration of hydrogen peroxide approaches asymptotically to a line denoting the ratio on the assumption that 1 mol. of alkali fixes 14 mols.of hydrogen peroxide. Addition of hydrogen peroxide diminishes the saponifying power of sodium hydroxide, indicating that hydroxyl ions disappear. The conductivity of hydrogen peroxide solutions was determined in a modified Kohlrausch cell, in which the electrodes consisted of tinned iron, which does not catalyse the solution. The conductivity of alkali salt solutions is very slightly diminished by addition of hydrogen peroxide ; that of solutions of hydroxides of the alkali metals is very greatly reduced, This is explained on the assumption t'hat with the -hydroxyl ions tke hydrogen peroxide forms superoxide ions, the migration-velocity of which is small compared with that of the hydroxyl ions.Using the Ostwald-Walden rule, the author calculates the migration-velocity of this new anion to be 48.5 (Kohlrausch and Holborn units), the same value being found from solutions containing the cations Li., Na*, K*, Rb*, and Cs*. The migration of the superoxide anion has been proved experi- mentally by the method described by Noyes and Blanchard (Abstr., 1901, ii, 91), lead oxide being used as indicator. From the depression of the freezing point of water containing sodium hydroxide and hydrogen peroxide, using excess of the latter to diminish the hydrolysis, it is shown that the anion is univalent and is derived from the liydroxyl ion and neutral hydrogen peroxide (Abegg and Bodlander, Abstr., 1899, ii, 542).The results are in agreement with the assumption that the ion is O', and the compound formed from sodium hydroxide and hydrogen peroxide is NaO,. The solubility of potassium chlorate in hydrogen peroxide is much greater than that in pure water, and consequently such a determination could not be used to ascertain if the hydrogen peroxide forms a com- plexion with the cation. Molecular Compounds of Hydrogen Peroxide with Salts, By SIMEON L. TANATAR (Zeit. anorg. Chem., 1901, 28, 255-257).- The compound KF,H,O, is obtained by dissolving potassium fluoride in 15 per cent. hydrogen peroxide and evaporating a t 5OOso long as no serious decomposition occurs. It crystallises in monoclinic needles, is not hygroscopic, but exceedingly soluble in water, is not decomposed at 70" and only partially so at l l O o , and is fairly stable when dry.A similar compound is obtained by dissolving sodium sulphate in 3 per cent. hydrogen peroxide and has the composition Na2S0,, 9H,0,H20,. With sodium nitrate, the double salt, NaNO,,Na,O,,SH,O, is obtained. It is very unstable. Generalisations on Halogeln Double Saits. By HORACE L. WELLS (Amer. Chem. J., 1901, 26, 389--408).-A long list is given of halogen double salts of the alkali metals, ammonium, and univalent thallium, with negative metals ; the salts are arranged according to types, which are designated by ratios indicating the number of atoms of each metal present. J. McC. E. C. R.12 ABSTRACTS OF CHEMICAL PAPERS. The remarkable similarity in the prominent types of the series of different valencies leads t o the conclusion that the valency of the metal of a negative haloid has no influence on the types of double salts which i t forms.The molecules of alkali haloids have nearly the same combining power as molecules of negative haloids. Salts of simple types (particularly the 2 : 1 and 1 : 1 ratios) predomi- nate. Remsen’s law which states that the number of alkali haloid molecules which can combine with a negative haloid molecule is not greater than the valency of the metal of the latter, must be aban- doned. The double haloids appear to increase in variety and ease of formation from the iodides t o the fluorides. They may be classified in three groups, based upon their behaviour in solution.(1) Salts, such as potassium platinichloride, which undergo ionisstion into alkali metal ions and complex negative ions. (2) Salts which readily separate into their component haloids in solution, but can be recryst,al- lised unchanged from water or from dilute acid solutions. (3) Salts which require the presence of an excess of one of their component haloids i n solution for their formation. E. G. By YUKICHI OSAKA (Zeit. yhysikal. Chem., 1901, 38, 743--749).--The addition of iodine to a solution of potassium iodide or hydrogen iodide produces a rise of the freezing point proportional t o the quantity of iodine added, and greater for the hydrogen than for the potassium salt. Hence it follows that the total concentration of ions and undissociated molecules is decreased by the addition of iodine. This necessitates a greater affinity constant for the iodides than for the tri-iodides, so that Damson’s assumption t h a t these affinity constants are equal is incorrect (Trans., 1901, 70, 238).Tri-iodides. L. M. J. Influence of the Concentration of the Hydrogen Ions on the Action of I o d a t e s on Haloid S a l t s . By HUGO DITZ and B. M. MARGOSGHES (Zeit. angew. Chem., 1901, 14, 1082-1091).- Potassium iodate and iodide readily react in the presence of a sniall amount of an acid (hydrogen ions) liberating iodine, and the amount thus deposited is directly proportional t o the amount of acid present (Fessel, Zeit. anorg. Chem., 1900, 23, 66). Potassium bromide and iodate do not react so readily in the presence of an acid (Bugarszky, Abstr., 1896, ii, 216) and the iodine ions are only transformed into free iodine when the concentration of the hydrogen ions exceeds a certain minimum.Potassium chloride reacts less readily than the bromide and the necessary concentration of hydrogen ions is much greater. When definite amounts of hydrochloric or sulphuric acid are zdded t o a potassium iodide solution mixed with an excess of iodate, the amounts of iodine liberated and of iodate left are found t o corre- spond with t8he amounts required for the given quantities of acid employed. The free iodine was extracted with toluene and titrated with N/lO thiosulphate and the residual iodate was titrated by means of the same reagent. When acetic acid is added to a potassium iodide-iodate mixture, the reaction is not normal and the residual iodat,e is always less than that required by theory j similar resultsINORGANIC CHEMISTRY.13 have been obtained when acetic acid was used i n presence of sodium acetate. The anomaly is probably due to the formation of an organic kiYl%Tl3 u i j va i?i g-6, Boric acid is not capable of liberating iodine from an iodide-iodate mixture except in the presence of glycerol or dextrose. The same acid does not liberate free halogen from a bromide-iodate mixture, wen in the presence of glycerol. Phenol also is incapable of liberat- ing iodine, but picric acid liberates a small amount from an iodide- iodate mixture. With mixtures of bromide, iodide, and iodate in the presence of acetic or hydrochloric acid, the amount of iodine liberated corresponds with the reaction between the iodide and iodate.A bromate-iodide mixture also yields iodine on treatment with acids, but requires the addition of several C.C. of N/lO acid before the liberation of iodide is started. A bromide-bromate mixture in the presence of acetic acid and. sodium acetate yields no free halogen. A chlorate-iodide solution, even in the presence of considerable! excess of dilute hydrochloric acid liberates but little iodine ; coneen-- trated acid, on the contrary, liberates a much larger amount. J. J. S. Supposed Anomalous Behaviour of Oxygen at Low Pres- sure. By MAX THIESEN (Ann. Phys., 1901, [iv], 6, 280-301).-Tht? author's observations are quite unfavourable t o the supposed existenc6: of an anomaly for oxygen under 0.7 mm.pressure (compare Bohr, Ann. Yhys. Chern., 1886, [ii], 27, 459; Eayleigh, Abstr., 1901, ii, 542). J. C. P. Dissociating Power of Hydrogen Sulphide. By WM. T. SKILLING (Afizer. Chem. J., 1901, 26, 383--384).-When a solution o;F potassium chloride in liquid hydrogen sulphide is placed in a tube pro-- vided with platinum electrodes and connected with a battery ojE 40 volts, no conduction takes place. E. G. &+a1~3+j,c: T?wu+jAwis. 11. Drnxt~~fisi+i~~~~ ~f ChlAwnwiL-- phonic Acid into Sulphuryl Chloride and Sulphuric Acid. By OTTO RUFF (Be?.., 1901, 34, 3509--3515).-At 170°, the re- action, 2S03HC1=S3,C1,+ H,SO,, isareversible one, and after 72 hours, the equilibrium reached is 1SO,Cl2 : 1H2S0, : 2.5S03HC1 ; sulphur di- oxide and chlorine are not formed between 170'and 190°, although a t a higher temperature they begin to be noticeable.Obviously, therefore, the sulphuryl chloride is not formed by the union of sulphur dioxide and chlorine, initially produced by complete dissociation of the chloro- sulphonic acid (compare Heumann and Kochlin, Abstr., 1883, 781), but is a direct decomposition product ; this is emphasised by the fact that, when the formation of the sulphuryl chloride occurs at the boil- ing point of the chloiosulphonic acid owing to the presence of a catalytic agent its amount is not increased by the passage of a current of chlorine and sulphur dioxide through the liquid. When sulphur dioxide and chlorine are produced at a high temperature, they14 ABSTRACTS OF CHEMICAL PAPERS. are due to the latter causing decomposition in the sense of the equation Mercuric salts rapidly decompose chlorosulphonic acid a t its boiling point into sulphuryl chloride and sulphuric acid, and several other salts effect a similar result, only more slowly.The figures after the names of the following salts indicate the number of grams of sulphuryl chloride formed by boiling 50 grams of the acid for 60 minutes with 1 gram of the salt. Nercuric chloride and sulphate, each 13.0 ; mer- cury, 12 ; antimony penta- and tri-chloride, 7.5 ; stannic chloride, 5.8; bismuth chloride, 3.3 ; platinic chloride, 2.5 ; uranyl chloride, 1.7 ; gold chloride, 1.2 ; copper sulphate, 0.8 ; tungsten chloride, 0.8 ; lead chloride, 0.7 ; cobalt sulphate, 0.5, and magnesium chloride, 0.5 ; the chlorides of zinc, aluminium, iron, calcium, and sodium are without action.As the whole of the chlorosulphonic acid is easily decomposed by boiling with mercuric chloride, the method is probably capable of commercial application for the manufacture of sulphuryl chloride, The mercuric chloride is not changed a t all in the action, but mer- curic sulphate is converted into mercuric chloride ; sodium chloride dissolves in chlorosulphonic acid with evolution of hydrogen chloride and production of the sodium salt, ONa*SO,*Cl, which is precipitated by the addition of sulphuryl chloride and is readily decomposed by water. W. A. D. SO, + 2HC1= SO, + H20 + Cl,. Formation of Dithionic Acid. By JULIUS MEYER (Ber., 1901, :34, 3606--3610)-The formation of barium dithionate, by passing r;ulphur dioxide into water in which manganese dioxide is suspended, i's probably to be represented by the following equations : 2Mn0, + :3H,SO, = Rln,(SO,), + 3H,O + 0 = MnS,O, + MnSO, + 3H,O + 0,asman- i;anous sulphite and sulphate are always formed in appreciable quan- t;ity.Ferric hydroxide and sulphurous acid, in the absence of air and c t t low temperatures, yield ferrous sulphite and ferrous dithionate, lFe,(S0,)3 = FeSO, + FeS,O,.. Cobaltic and nickelic hydroxides react iivith sulphurous acid in a similar manner. Lead, barium, magnesium, :md sodium peroxides do not yield dithionates on treatment with sul- ]?hurous acid (compare Carpenter, Trans., 1902, 81, 1) The electrical conductivities and freezing points of barium dithionate r;olutions are given, and the formula H,S,O, for the acid is considered lto be proved (compare Ostwald, Zed.physikal. Chem., 1887, 1, 106). J. J. S. So-called Sulphimide. By ARTHUR HANTZSCR and A. HOLL ((Be?., 1901, 34, 3430-3445. Compare W. Traube, Abstr., 1892, 1389; 1893, ii, 268)-Sulphamide is unimolecular, and, in the pure rstate, not an electrolyte, and corresponds with carbamide ; sulphimide, Ion the other hand, is termolecular and corresponds with cyanuric acid. lsulphamide is best purified by repeated crystallisntion from ethyl :alcohol ; it forms rhombic plates melting at 91.5' (Traube, 75-81°), .is perfectly tasteless, and quite neutral. I n the preparation of sulph- :amide by the action of sulphuryl chloride on a light petroleum solu- .tion of ammonia, several bye-products are formed, but the composition (of these has not been determined.INORGANIC CHEMISTRY.15 Trisulphimide, O H * S O < ~ ~ ~ $ ~ ~ { > N , is crystalline, but the yield \ , is extremely small, and the analytical results do not agree with those required for the pure compound; it may be, however, that it contains combined water. It crystallises from methyl alcohol in colourless, glistening needles, melts at about 161°, is odourless, but has a sharp, acid taste, dissolves in alcohol, and also sparingly in ether, but is insoluble in benzene or chloroform. Aqueous solutions are fairly stable, except when warmed. Ebullioscopic determinations of the molecular weight in ethyl acetate solution point to the formula (SO,*NH), The values obtained for the molecular conductivities of trisulphimide and its salts in aqueous solution show (1) that trisulph- imide behaves as a strong acid; (2) that it is tribasic.Further, the conductivity of the potassium salt is nearly the same as that of potassium ferricyanide. The molecular conductivity of silver trisulph- imide is much lower than that of potassium trisulphimide a t the same dilution. Pyridine silver trisulphimide, (S02N),Ag3,6C5NH5, crystallises in prisms and is gradually decomposed at 140". The N-methyl derivative, NMe*So2>NMe, obtained from the silver salt, forms colonrless SO,<NMe* so, crystals melting at 121' and readily soluble in most organic solvents. It is not hydrolysed by alkalis and only very slowly byacids, yielding met hylamine and sulphuric acid.Tribenxo y ZsuZphimide, (SO,N* COPh) 3, crystallises in prisms melting a t 112'. Isomorphism of Selenates and Tellurates. By JAME~ F. NORRIS and WILLIAM A. KINGMAN (Amer. Chem. J., 1901, 26, 318--324).--The authors have attempted to prepare isomorphous selenates and tellurates, but without success. All the tellurates except those of the alkali metals are insoluble and the soluble tellurates do not resemble the corresponding selenates in crystalline form, solubility, or amount of water of crystallisation. Rubidium hydrogen tellurute, RbHTeO,,&H,O, is a crystalline salt, soluble in about 20 parts of cold water, and slightly more so in hot water. The cesium salt, CsHTeO,,&H,O, forms small, cubic crystals and is soluble in about 30 parts of cold water.Rubidium hgdrogen selenate, RbHSeO,, is a hygroscopic, well crystal- lised salt, which dissolves in about its own weight of water. The cesium salt, CsHSeO,, crystallises in large, flat plates with pointed ends and is extremely hygroscopic. Rubidium tellurate, Rb,TeO,,SH,O, crystnllises in prisms with pyramidal ends and is soluble in about 10 parts of water. Aqueous Ammonia Solutions. By FRANZ GOLDSCHMIDT (Zeit. ccnorg. Chem., 1901, 28, 97--139).-The partial pressure and the conductivity of ammonia solutions (0*5N, 0*75N, and IN) were deter- mined and the same constants for solutions to which carbamide (1N and 1.5N) had been added. The vapour tension was measured by the method previously used by Gaus (Abstr., 1901, ii, 7). The increase of the partial pressure of the ammonia is almost, exactly proportional to the amount of carbamide added.The values of k found from the expression J. J. S. E. G.16 ABSTRACTS OF CHEMICAL PAPEItS (k + H20)/(k + H20’) = A2p’/AI2p is negative and almost exactly constant; k is the hydration constant, H,O the active mass of the water (taken as loo), H20’ the active mass after the addition of the carbamide, X and A’ are the conductivities, and p and p’ the ammonia partial pressures of the solutions with and without the carbamide. The variation of the active mass of the water is taken as proportional to the variation of the vapour pressure, on the assumption that only a monohydroxide is formed. KO significance can be attributed t o the fact that the value of k is negative. From the conductivity of ammonia solutions (which show a maximum molecular conductivity), it is found that the dissociation constant ( K ) varies from 22.1 x to 0.23 x 10-6 for solutions which are 0.0109N to 12.89 A‘.As the solution becomes dilute, the value of Kapproaches a constant, and assuming that this begins a t the concentration 0*02N, the value of K is 19.1 x 10-6. The inconstancy of the values of K cannot be attributed to the formation of complex ions such as NH,*NH,*, for the lowering of the freezing point of water containing ammonia and ammonium salts corresponds with the value calculated for the quantity of material added. The addition of ammonia diminishes the conductivity of aqueous salt solutions. The diminution is directly proportional to the quantity of ammonia added and amounts t o 2 to 3 per cent.of the value of the conductivity per gram-mol. of ammonia per litre. Lithium salts are most affected in this way by ammonia, sodium salts less so, and potassium salts least. The action of ammonia is independent of the nature of the anion present. It is concluded that the speed of migra- tion of the ions is reduced by the presence of ammonia, and this is also proved thermodynamically. The influence of ammonia on the conductivity of ammonium chloride, mono-, di-, and tri-methylamine hydrochloride and piperidine hydro- chloride is of the same nature as, but much smaller than, that on the alkali salts ; with tetramethylammonium chloride, the eRect is of the same magnitude as with potassium nitrate. J. McC. Chemical Equilibrium in the Reduction of Nitric Acid by means of Nitric Oxide.By A. V. SAPOSCIINIKOFF (J. Buss. Phys. Chen8. Xoc., 1901, 33, 506-516. Compare Abstr., 1900, ii, 722).- The author’s previous experiments ( h e . cit.) on the decomposition of nitrous acid according to the equation, 3HN0, = HNO, + 2N0 + H,O, having failed to yield the equilibrium constant of the reaction, he has now studied the inverse change, the method of experiment being to pass nitric oxide through nitric acid of a cert’ain strength and to determine from time to time the electrical conductivity of the solution. A t the end of each experiment, the amount of nitrous and nitric acids and of nitric oxide in the liquid was determined. On calculating the constants of equilibrium for acids of varying concentration from the formula, K=cY/x2c12, where c and c1 are the concentrations of the nitrous and nitric acids respectively in the final solution, and x the degree of dissociation of the nitric acid, it is found that for nit,ric acids of AT t o i V / l O initial concentration, the constant ( x 10,000) varies within the limits 142 and 178 and has a mean value of 159; forINORGANIC CHEMISTRY.17 acid of 0*05Nconcentration, the constant is 232, the high value being probably due to the fact that at such great dilution the reaction proceeds very slowly and possibly does not reach its final point; with acids of higher concentration than normal, the constant falls regularly, a behdviour probably explained by the final product of the reaction consistii-g partly of oxides of nitrogen mixed with the nitrous acid.The coefficient of absorption o€ nitric oxide in litres of gas per litre of acid is given for each dilferent nitric acid employed ; Kahlbaum’s acid, having H, sp. gr. 1.517 at 15’/4”, contains 0.88 per cent. of nitric oxide, the coefficient of absorption in this case being 12.5. The speed of the abmrption of nitric oxide by nitric acid varies to a very large extent with the concentration of the acid, as is shown by curves connecting litres of the gas absorbed with time in hours. By RUDOLF WEGSCHEIDER and FELIX KAUFLER (Monatsh., 190 1,22, 700-706).-Red and yellow phosphorus may be either polymorphous or chemically different (isomeric or poly- meric). If the two forms are polymorphous, the liquid forms must be identical, and molten yellow phosphorus or a concentrated solution should, on addition of red phosphorus (which is the stable form), change into the latter.Experiments show that such is not the case. A saturated solution of yellow phosphorus in carbon disulphide sown with red phosphorus shows no perceptible change, and, on lowering the temper- ature, yellow phosphorus separates. Similar molten yellow phosphorus at 20Oo, to which red phosphorus has been added, does not change, The two forms are not polymorphous, but chemically different. T. H. P. Allotropy of Phosphorus. K. 5 . P. 0. Metaphosphates. By ARTHUR WEISLER (Zeit. anos-g. Chsm., 1901, 28, 177--909).-Sodium trimetaphosphate, when prepared according to Flei t mann’s and Henneberg’s methods, and when prepared from sodium hydrogen phosphate and ammonium nitrate according t o Knorre’s method (Abstr., 1900, ii, 651), has an electrical conductivity which indicates that it is a salt of a tribasic acid.The trimetaphosphate, in aqueous solution (1/32N), is not altered by boiling ; neither orthophos- phste nor pyrophosAphate is formed. Bdrium, manganese, and silver trimetaphosphates are described ; of these the manganese salt has a n electrical conductivity corresponding with that required for a salt of a tribasic acid. The other two salts are too insoluble for the determination of their electrical conductivities. Cropper trimetaphosphate could not be obtained from sodium trimeta- phosphate, tbe product being a pyrophosphate of the formula Cu2P,07,5H,0. I n the case of zinc, a sodium zinc pyrophosphate is produced.The sodium cadmium trimetaphosphate, CdNa,(P0,)6,4 H20, is obtained by adding cadmium iodide to the sodium salt. Sodium hexametaphosphate, prepared from sodium pyrophosphate according t o Knorre’s method (Zeit. angew. Chenz., 1892, 641)’ has a n electric conductivity A,, = 31.2, which is evidence that the salt has a more complicated composition than the trimetaphosphate (A,? = SY.4). The hexametaphosphate is easily decomposed in aqueous solution and LXXXII. ii. A d when heated at 40” yields the pyrophosphate. E. c. K. >18 ABSTRACTS OF CHEMICAL PAPERS. Chemical Reactions produced by Radium. By MARCELLIN P. E. BERTHELOT (Compt. rend., 1901,133,659-664).-The radiations from radium decompose iodic acid, with liberation of iodine, and also decompose nitric acid, the changes in both cases being endothermic.They do not, however, promote the oxidation of oxalic acid, or the conversion of sulphur into the variety insoluble in carbon disulphide, nor do they, like the silent electric discharge, cause the polymerisation of acetylene. The author confirms the statement that the rays gradually turn glass black, a change which he attributes to the reduc- tion of lead compounds to the metallic state, and has also observed the production of a violet colour similar to that produced by the action of light on certain glasses containing manganese. It would seem, therefore, that the radiations cause a reduction and an oxidation simultaneously, and possibly the one change is consequent on the other. C.H. B. Action of Bromine on Metallic Silver in the Light and in Darkness. By V. VON CORDIER (Monatsh., 1901, 22, 70’7-716. Compare Abstr., 1900, ii, 343,723).-By use of a specially constructed apparatus, the action of bromine on metallic silver illuminated by an arc lamp, an incandescent gas lamp, or diffused daylight, and in dark- ness was investigated. Whilst light assists the combination of silver and chlorine (Zoc. cit.), it hinders that of silver and bromine, Bromine is not given off in the light from silver bromide in the presence of carbon dioxide. K. J. P. 0. Action of Hydrogen Peroxide on Silver Oxide. By MARCELLIN P. E. BERTHELOT (Compt. vend., 1901, 133, 555-569).-The author has investigated in the calorimeter the action of several acids on (1) silver oxide, and (2) silver oxide which had been treated with hydro- gen peroxide.The development of heat differs considerably in the two cases, both in rate and amount, and the results, which are described in detail, confirm the author’s previous conclusions as to the formation of a higher oxide of silver (Abstr., 1899, ii, 149). C. H. B. Reduction of Copper by Solutions of Ferrous Salts. By H. C. BIDDLE (Amer. Chern. J., 1901, 26, 377--382).-The precipita- tion of copper by solutions of ferrous salts is a reversible action, the direction of which in any case is determined by the relative concentra- tion of the ferrous, ferric, and copper (cuprous and cupric) ions. This statement is justified by the following experimental evidence, I n a solution containing an appreciable quantity of ferric ions, or in which these would be formed in the course of the reaction, copper is not deposited ; this is shown by the fact that ferrous chloride and sulphate are incapable of reducing the corresponding copper salts.In a solu- tion containing a few ferric ions, and in which the reaction does not cause an appreciable increase of them, a sufficient concentration of ferrous and copper ions will produce the deposition of copper. The tendency of ferrous salts to reduce those of copper is shown by the precipitation of cuprous thiocyanate when ammonium thiocyanate isINORGANIC CHEMISTRY. 19 added to a solution of ferrous and cupric chlorides. From a mixture of ferrous and cupric hydroxides, crystals of cuprous oxide slowly separate. When an excess of ammonium carbonate is added to a solution of ferrous and cupric chlorides, a yellow liquid is obtained which gradually deposits a mirror of metallic copper.If a solution of cupric and ferrous chlorides is treated with sodium carbonate in slight excess or with potassium hydrogen carbonate, reduction slowly takes place with loss of carbon dioxide and formation of basic ferric carbonate and copper. E. G. Mixed Crystals of Copper Sulphate and Zinc Sulphate. By H. W. FOOTE (Amey. Chern. J., 1901, 26, 418--428).-1t is well known that from solutions of copper sulphate containing zinc sulphate an isomorphous mixture of triclinic crystals separates consisting of CuS0,,5H20 together with a smaller quantity of ZnS0,,5H20. AS the quantity of zinc sulphate is increased in the solution, an iso- morphous mixture of monoclinic crystals is obtained containing CuS04,7H20 and ZnS04,7H20, and in presence of a still larger pro- portion of zinc sulphate, rhombic crystals of ZnS04,7H20 with a small amount of CuS0,,7H20 are produced.It has been shown by van't Hoff, from theoretical considerations, that the composition of mixed crystals a t their mixing limit' (which represents the com- position of mixed crystals of one salt with a maximum of another) ought to be a function of the temperature ; the same conclusion is arrived a t by application of the phase rule. The authors have carried out experiments on the mixing limit ' of copper sulphate and zinc sulphate a t 12', 25', 35'; 40°, and 4 5 O , which confirm the accuracy of the above assumption, and also show that whilst the composition of mixed crystals varies with the temperature, the salts mentioned do not form completely isomorphous crystals between 12' and 56'.It is also found that i n solutions yielding two forms of crystals, the amount of copper sulphate in solution remains nearly constant, whilst the quantity of zinc sulphate increases con- siderably with rising temperature. By MAX GRGCIER (Zeit. anorg. Chern., 2901, 28, 154--161).-When cuprous chloride is treated with water in an atmosphere of hydrogen or carbon dioxide, the chlorine passes almost completely into solution and a dark red residue, consisting of cuprous oxide and copper, is left. The separation of the copper is due to the action of light, for when the extraction is carried out in the dark the residue is almost pure cuprous oxide, Water acting on cuprous chloride in presence of a little air gives an orange-red residue of cuprous oxide mixed with about 6 per cent.of basic cupric chloride. The amount of cupric compound left in the residue is always small, showing that most, of the oxidation product of the cuprous chloride passes into solution, By the action of water and air sufficient for the complete oxidation, a residue was obtained which had the composition 3CuO,CuCl2,4H2O. The primary action is the hydrolysis of the cuprous chloride, and the liberated hydrochloric acid, in presence of oxygen, acts upon more cuprouB chloride forming the cupric corn- E. G, Cuprous Chloride. 2-220 ABSTRACTS OF CHEMICAL PAPERS, pound. Secondarily, the cupric chloride reacts with the cuprous oxide (hydrolytic product) forming cuprous chloride again and basic cupric chloride.Very dilute hydrochloric acid in an atmosphere of carbon dioxide changes the colour of cuprous chloride through green, almost black, to a dark copper brown. The residue in this case consists of metallic copper formed by the decomposition Cu2CI2 = Cu + CuCl? ; but as copper is deposited on the cuprous chloride it protects thls from total decomposition. Cuprous chloride in a solution of cupric chloride, when protected from the action of the air, remains perfectly white even in sunlight, showing that cupric chloride prevents the direct decomposition of the cuprous compound. Perfectly dry cuprous chloride remains unchanged in the air and light has no effect upon it.The method recommended for the preparation of cuprous chloride is to dissolve 42 grams of cupric chloride in 200 C.C. of hydro- chloric acid of sp. gr. 1.175 and 100 C.C. of water, and heat the solution with copper foil on the water-bath until it is decolorised. The solution is then poured into 2 litres of water, the precipitate filtered (in diffused light) and washed, first with dilute sulphuric acid (1 : 20), then with absolute alcohol, drained as dry as possible on the pump and dried quickly in the water-oven. J. McC. Mercury Oxychlorides. By N. TARUGI (Gazxetta, 1901, 31, ii, 3 13-32O).-The author has examined the various oxychlorides of mercury described by different authors, and finds that, without excep- tion, they consist of mixtures, in indefinite proportions, of mercuric oxide and chloride.The three compounds described below are there- fore the first oxychlorides of mercury obtained. The oxychtoride, HgCI,,SHgO, is obtained by adding small cubes of perfectly white statuary marble of a sugar-like structure into satur- ated aqueous mercuric chloride at 15'. After remaining for 15-20 days in diffused light, the liquid deposits the oxychloride in small, yellow crystals which continue to increase in number and size, and are separated, washed with water, and dried in a vacuum. When heated or when boiled with water or alkali solution, the oxychloride decom- poses into i t s constituents, whilst dilute nitric acid converts i t into a white, amorphous powder. If the saturated mercuric chloride solution is diluted with twice its volume of water and treated as before, an oxycidoride of the formula HgC1,,2HgO, is obtained in very thin, black crystals; whilst if three volumes of water are added to the saturated mercuric chloride solu- tion, a compound of the composition HgCl,,HgO, is produced in very thin, red crystals.These two oxychlorides have the same chemical properties as the first described. T, H. P. Alkali Double Nitrite8 of Mercury and Zinc. By ARTHUR ROSENHEIM and KURT OPPENHEIM (Zeit. anoyg. Chem., 1901, 28, 171-1 '74).-Mercuric nitrate, when treated with a concentrated solution of potassium nitrite, dissolves and the solution becomes warm, Mercuric oxide separates out and from the filtrate yellow crystalsINORUANIC CHEMISTRY.21 of potclssiztm ~ c u q nitrib of the composition K3Hg(N02)S,H,0 are deposited. The salt crystallises in rhombic forms [ a : b : c = 0.8594 : 1 : 0*7681] and is soluble in cold water without decomposi- tion. If the solution of this salt contains a slight excess of potassium nitrite, ill-defined crystals of the compound KHg(NO,), are formed. Sodium mercury nitrite, Na,Rg(NO,),, has been prepared by re- crystallising the product obtained by the action of a concentrated solution of sodium nitrite on mercuric nitrate. Potmsium zinc nitrite, K3Zn(N02)5,3H20 is produced when nitrous acid is passed into a solution of potassium nitrite containing zinc hydroxide in suspension. - It forms very hygroscopic, yellow crystals. J. McC. Copper-Aluminium Alloys. By L ~ O N GUILLET (Cmpt.vend. , 1901, 133, 684--686).-The author has prepared various copper aluminium alloys by heating pure cupric oxide with granular aluminium in proportions varying from those which should yield pure copper to those which should yield the alloy CuAl,. By treating the products with acids, he has isolated three distinctly crystalline, definite alloys, Cu,Al, CuAl,, and CuA1, the last being mixed with a small quantity of copper aluminium silicide. Compounds of Aluminium Bromide with Bromine and Carbon Disulphide. 11. By WLADIMIR A. PLOTNIKOFF (J. Buss. Php. Chem. SOC., 1901, 33, 429-432. Compare Abstr., 1901, ii, 31 6).-The compound of the composition AlBr,,Br,,CS,, previously described (Zoc. cit.) by the author as obtained by the action of bromine on a carbon disulphide solution of aluminium bromide, is only formed when the bromine is employed in excess.If, however, to a well- cooled solution of aluminium bromide (1 mol.) in carbon disulphide a quantity of bromine not greater than 1 atomic proportion is added slowly in drops, an almost theoretical yield of an oily compound is obtained, having the composition 2A1Br3,Br4,CS2. When left in a warm place or when shaken repeatedly with carbon disulphide, the oil deposits a brownish, crystalline mass, which, when dry, melts at about 80° and begins to dissociate into aluminium bromide and CS2Br, at about looo; dissociation also occurs under the influence of even traces of moisture. C. H. B. The compound is soluble in ether or benzene. T. H. P. By SAMUEL A. TUCKER and HEBBEBT R.MOODY (J. Xoc. Chm. Ind., 1901,20, 970-971).-1n the electric furnace, aluminium oxide is not reduced by carbon, but if lime is added calcium carbide is formed and this reduces the alumina. Calcium carbide reduces alumina and the yield of aluminium is increased by the presence of free carbon. The heat should not be applied longer than 15 minutes, for after that time aluminium carbide is formed. Periodic System and the Propertiels of Inorganic Compounds. 111. The Solubility of Alums aa a Function of Two Variables. By JAMES LOCKE (Amr. Chem, 2, 1901, 26, 332--345).-The author The Reduction of Alumina by Calcium Carbide. J. McC.22 ADSTRACTS OF CNEMICAL PAPERS, has previously determined the solubility at 25’ of the alums of aluminium, vanadium, chromium and iron severally with ammonium, thallium, rubidium and csesium (Abstr., 1901, ii, 656).When the solubilities of these 16 compounds expressed in gram-mols. per litre of water are plotted as a function of the atomic weights of the tervalent metals, a figure of remarkable regularity is obtained, from a aonsider- ation of which it is evident that the lines joining the solubility points of the successive univalent metals with two given tervalent metals have approximately a common point of intersection. It must be assumed, therefore, that the points representing the solubilities stand in fixed mathematical relation t o one another, Hence it is shown that if the difference in the solubility of the alums of a given tervalent metal with two alkali metals is termed the increment of solubility for the latter,’’ the general law is obtained that the ratio between the in- crements of solubility of the corresponding alums of two tervalent metals for any two alkali metals is constant.’’ The accuracy of this law is fully confirmed by observation.A general equation for the solubility of any of the sixteen alums is deduced from this law, all the terms of which can be referred to two variables, one-applying to the tervalent element in the compound and the other to the univalent metal. Determinations made at other temperatures than 25” indicate that it will be possible to derive a general solubility formula for all temperatures. E. G. The Reaction of Sodium Thiosulphate with Potassium Per- manganate. By A. ALANDER (Zeit. unaE. Chern., 1901,40,574-577).-Both qualitative and quantitative proofs are given that in alkaline solutions the reaction 8KMn0, + 3Na2S20, = 3Na2S0, + 3K,SO, + 8Mn0,+K20 is the principal one, but that a small quantity of the thiosulphate (about 1.3 per cent.) is oxidised only to tetrathionabe. M. J. S. Separation of Iron. By PAUL NICOLARDOT (Compt. rend., 190lj, 133, 686-688).-When ferric chloride is heated a t 125’ it is converted. into a complex compound in which the ratio of iron to chlorine is 1 : l,, whilst the corresponding sulphate is insoluble, Thejron alloy (1 gram), or compound is dissoved in aqua regia, the nitric acid expelled, andl the liquid evaporated to dryness and heated at 125’ for 4 hours. It is! then diluted with water to 500 c.c., heated to boiling, and about 1 graml of ammonium sulphate added.After boiling for about 15 minutes, the very finely divided precipitate is filtered off, If mercury 01’ cadmium is present, the substance cannot be heated a t 125O without; loss, and therefore the liquid is exactly neutralised with ammonia!, mixed with ammonium sulphate, boiled, and filtered. It is again mixed1 with ammonia until a slight precipitate is formed and again boiled, when the whole of the iron is precipitated. Selenates, phosphates, arsenates,vanadates, and molybdates precipitate iron in a similar manner, and the iron is readily separated from the precipitate by fusion withi an oxidising mixture or an alkali. Ferric Oxide and Hydroxides. By OTTO RUFF (Bey., 1901, 34, 3417-3430. Compare Tommssi, Bey., 1579, 12, 1929, 2334).--- The red, colloidal ferric hydroxide may be converted into true hydrates3 C.H. B.INORGANIC CHEMISTRY. 23 by the aid of considerable pressure under water. At a temperature of 42.5", it yields brown ironstone, at 42.5-62*5', gothite, and at higher temperatures, hydrohaematite. Yellow ferric hydroxide is not a true colloid, as its percentage of water under high pressure does not vary between temperatures of 40' and 70". The red hydroxide appears to lose water a t the ordinary atmospheric temperature and pressure and, at the same time, but somewhat more slowly, takes up water and becomes converted into brown ironstone, the only stable hydrate under ordinary conditions. J. J. 5. Influence of the Separation of Sulphur on the Preoipita- tion of Iron Salts.By A. COPPADORO (Gaxxetta, 1901, 31, ii, 21 7-221).-When hydrogen sulphide is passed through an acidified solution of a ferric salt, a precipitate of sulphur is formed containing small quantities of iron compounds, which the most exhaustive washing is incapable of removing. By dissolving the sulphur from the dried precipitate by means of carbon disulphide, however, the author has succeeded in determining the amount of iron enclosed in the precipi- tate. He finds that the quantity of iron is proportional to that of the ferric salt taken and to that of the precipitated sulphur, but is independent of the amount of acid added to the solution and of the time during which the hydrogen sulphide is kept passing through the liquid. If a precipitate of sulphur is produced in a solution of a ferrous salt, for example, by the addition of thiosulphate and acid, the precipitate is found to contain iron.The author suggests that possibly the presence of iron in these precipitates is connected with Graham's observation that when solutions of two colloids are mixed they are precipitated together. Crystallographic Examination of some Luteocobaltic Salts. By TIMOTHBE KLOBB (Chem. Centr., 1901, ii, 970; from BUZZ. Xoc. fianp, Min., 24, 307-322. Compare Abstr., 1901, ii, 103).-Luteo- cobaltic selenate, Co(NH,)6(8e04),,5H?10, prepared by neutralising luteocobaltic hydroxide with selenic acid and slowly evaporating the solution, separates in thick, brownish-yellow, monoclinic crystals [a : b : c = 1.1350 : 1 : 1*4023. ac= 90'35'1. Luteocobaltic sulphate, Co(NH,),(S04),,5H,0, forms lustrous, monoclinic crystals [a : 6 : c = 1.1230 : 1 : 1.4143.Luteocobaltic hydrogen sulphate, 2Co(NH,),(S0,),,5H,SO4, 10H,O, obtained by adding sulphuric acid to an aqueoub solution of the normal salt, crystallises in small, rhombic octahedra [a; : b : c = 0.99913 : 1 : 1.00061 and is decomposed by water. Lu t eoco bal t ic hydrogen selenate, Co (NH,),( SeO,),, H,SeO,, 5 H,O, pre- pared by adding excess of selenic acid to luteocobaltic hydroxide or to the normal selenate, crystallises in triclinic crystals, of ten twinned [a : b : c = 0.84550 : 1 : 0.47285, bc = 88"50', ac = 80°50', ab = 86'47'1, and is not decomposed by water. Luteocobaltic chlorosulphate, obtained from cobalt chloride or sulphate or by treating luteocobaltic chloride withsulphuric acid or a sulphate,is rhombic [a: 6 : c = 0.99855 : 1 : 1.05381.Luteocobaltic chloroselenate is rhombic [a : b : c = 0.99869 : 1 : 1*0563]. Luteocobaltic ammonium sulphate, [Go( N Ha)Jz( SO4),,( NH,),S04, 8H2.0, prepared by crystallising luteocobaltic sulphate in presence of ammonia, T. H. P. ac = 90'18'1.24 ABSTRACTS OF CHEMICAL PAPERS. separates in rhombic octahedra or thick plates. When moistened with water, the crystals become opaque, but in concentrated ammonium sul- phate solution they remain transparent and ultimately dissolve. Luteo- cobaltic ammonium selenate, [ Co( NH3)6]2( Se04),, ( NH4),Se04,8 H,O, obtained by neutralising a solution of luteoco baltic hydrogen selenate with ammonia, is isomorphous with the preceding salt [ a : b : c = 0,95953 : 1 : 1.20241.After the separation of this hydrate, a hydrate crystallising with 4H,O crystallises out in large, monoclinic prisms [a : b : c == 1.4285 : I : 0.64688. Luteocobaltic chloro- ammonium sulphate, [CO(NH~)~]~(SO~),C~,,~( N.H,),SO,,GH,O, prepared by evaporating a solution of luteocobaltic chlorosulphate with a n excess of ammonium sulphate, crystallises in octahedra and is de- composed by water. ac = 94'42'1. E. IT, w. Crystallographic Study of Alvisi's Luteocobaltiammine Per- chlorates. By FEDERICO MILLOSEVICH (Gaxxetta, 1901, 31, ii, 285). -Luteoco bal tiamm onium diperchlorat e chloride, CO( NH3)(jC1(C1O4)2 , forms rhombohedra), orange-yellow crystals, a = 70'41'. Luteocobaltiammonium perchlorate, CO(NH,)~(C~O,),, gives orange- yellow crystals of the cubic system.T. H. P. Researches on Perchlorates. Luteocobaltiammine Per- chlorates and Observations on Metallo-Ammoniums. I. By UGO ALVISI (Gaxxetta, 1901, 31, ii, 289-301).-The author has pre- pared various luteocobaltiammine perchlorates and gives the methods used by him for their analysis. Luteocobaltiammonium diperchlomte chloyide, Co(NH3),CI(C10,),, pre- pared by the interaction of cold saturated solutions of ammonium perchlorate (3 mols.) and luteocobnltiammine chloride (1 rnol.), crystal- lises from water in hexagonal, yellow plates having a pearly lustre; when rapidly heated, i t gradually loses ammonia, and at about 188' explodes, water vapour, chlorine, and nitrogen being evolved and cobalt oxide and chlorides left. Luteocobaltiammoniurn perchlorate, Co( NH,)6(C104)B is prepared (1) by heating aqueous cobalt perchlorate with excess oi ammonium per- chlorate and ammonia and adding potassium (or better sodium) per- manganate until the liquid assumes a n intense, golden-yellow colora- t i o n ; or (2) by heating a solution of cobalt perchlorate with lead dioxide, ammonia, and excess of ammonium perchlorate until the filtered liquid becomes intensely orange-yellow in colour.It crystallises from water in orange-yellow octahedra belonging to the cubic system and with hydrochloric acid yields the diperchlorate chloride just described. Theoretical considerations are put forward by the author as to the mode of combination of nitrogen in the cobaltiammonium compounds with the other elements present.T. H. P. Cause of the Brown Coloration of Ammonium Sulphide in Presence of a Nickel Salt, By UBALDO ANTONY and G. MAGRI (Gaxxetta, 1901, 31, ii, 265--274).-When hydrogen sulphide or ammonium polysulphide solution is added to an ammoniacal solutionIKORGANIC CHEMISTRY. 25 of nickel acetate in quantity insufficient to precipitate all the nickel as sulphide, the precipitate obtained has the composition NiS, and in the latter case is mixed with sulphur. When, however, an excess of ammonium polysulphide is added to an ammoniacal nickel solution, the precipitate formed is of very variable composition but the dark liquid almays contains a sulphide of the composition NiS,. This sulphide, which is obtained as a black powder, is only slightly athacked by hydrochloric acid but reacts vigorously with nitric acid, sulphur being liberated.In an atmosphere of carbon dioxide, it loses sulphur at 300°, being converted into nickel sulphide, whilst when heated in water in presence of air it slowly oxidises, .giving nickel sulphate and sulphuric acid. Hydrogen sulphide solution has no action on it, but it is dissolved by a solution of sulphur or ammonium polysulphides giving a brown liquid. With ammonia solution, it yields an azure-blue liquid containing nickel, but all the sulphur is deposited in a very fine state of division. Measurements of the electrical conductivity of solutions of nickel tetrasnlphide in ammonium sulphide show that the nickel salt is not present in a state of true solution or in a really colloidal condition, the author regarding it as existing in an inter- mediate state.T. H. P. Action of Sodium Thiosulphate on certain Metallic Salts. By FRANZ FAKTOR (Cfiem. Centr., 1901, ii, 878; from Pharrn. Post, 34, 485-487. Compare Abstr., 1900, ii, 598, 627, 688, 691, and 692)- Ammonium molybdate is reduced by a solution of sodium thiosulphate, forming molybdenum trioxideand the hydrate of thedioxide, Mo02,3H,0, whilst sodium tiingst'ate, when warmed with sodium thiosulphate and a small quantity of nitric acid, yields tungsten dioxide, trioxide, and heptoxide. By the action of sodium thiosulphate on uranyl nitrate, a yellow precipitate of uranyl thiosulphate, U0,S20,, is formed ; the thiosulphate, on ignition, yields the green oxide, U,O,. Beryllium thiosulphate, BeS203, 1 1 H20, is prepared from sodium thiosulphate and beryllium sulphate.Quinone is reduced by sodium thiosulphate, forming first quinhydrone and then quinol. By the action of sodium thio- sulphate and hydrogen dioxide on manganese salts, a brown precipitate of manganese hydroxide is obtained ; when treated in the same way, chromates are reduced to chromic hydroxide, cobalt salts give a black and nickel salts a pale green precipitate. E. W. W. By F. MAWROW (Zeit. unorg. Chent., 1901, 28, 162--166).-0n addition of hypophos- phorous acid to a solution of ammonium molybdate in concentrated hydrochloric acid, a bluish-green solution is produced and a violet deposit with a coppery lustre obtained. Thisdeposit is soluble in cold water, giving a green solution, which, on exposure to air, becomes blue. It is decomposed by alkali, forming a green precipitate.It is soluble in con- centrated sulphuric acid with a blue colour, and on dilution a yellowish brown precipitate is formed. Heated on platinum foil, it explodes and leaves a grey residue. Its composition can be represented by On heating an aqueous solution of this, it becomes blue and on evaporating a t 90-95' a blue residue is obtained which is soluble in Two Phosphorus-Molybdenum Compounds. Mo,O,(H,P02)7,3H,O.26 ABSTRACTS OF CHEMICAL PAPERS. water or alcohol with a blue colour and explodes when heated. I t s composition is represented by Mo,O,,(H,PO~)~,H,O. Both these compounds are strong reducing agents, indicating that the phosphorus is present in the condition of hypophosphorous acid, It is doubtful if the formulz given are correct, but it is certain that the substances are not compounds of molybdic acid, but of a lower oxide of molybdenum.The blue solution gives characteristic precipitates with salts of ammonium, barium, lead, and bismuth. J. McC. Behaviour of Hydrochloric Acid Solutions of Metaatannic Acid towards Hydrogen Sulphide, By GUNNER JORGENSEN (Zeit. anorg. Chem., 1901, 28, 140--153).-Hydrogen sulphide gives with hydrochloric acid solutions of metastannic acid, precipitates which vary in composition according to the concentration of the hydrogen sulphide, the concentration of the hydrochloric acid, the temperature, and the time. At first, the precipitate consists for the greater part of metastannic acid mixed with a small quantity of stannic sulphide. When kept, the precipitate absorbs hydrogen sulphide slowly and only after a very long time (two months) does the composition corre- spond with that of stannic sulphide.Increase of the concentration of metastannic acid, or of hydrogen sulphide, or rise of temperature lead to an increase in the proportion of stannic sulphide formed, Increase of the concentration of hydrochloric acid diminishes the absorption of hydrogen sulphide. The rate of formation of the stannic sulphide is extremely slow and it decreases to a far greater extent than the law of mass action would indicate; this is possibly due to the formation 05 s$i&h ' i i ' i A ~ + u ~ . i ~ i ~ + u ~ h~fi. 3.9k9J. Thiocyanates of Quadri valent Titanium. By ARTEUR ROSEN- HEIM and ROBERT COHN (Zeit.anorg. Chern., 1901, 28, 167-170). Compare this vol., ii, 244).-Thiocynnic acid solution dissolves large quantities of titanic acid, and on evaporation of the saturated solution in a vacuum over sulphuric acid a brownish-red, crystallirze powder is obtained which is soluble in cold water, exhibits the reactions of thiocyanates, and possesses all the properties of a titanium salt, It has jh ymqnmition TiO{SCN!,. 2H,O. A solution of titanic acid in thiocyanic acid, when mixed with potass- ium thiocyanate and evaporated over sulphuric acid, gives hygroscopic, deep red, rhombic crystals of K,TiO(SCN),,H20. This is soluble in cold water, but on standing it is decomposed with decolorisation. The corresponding ammonium, sodium, and barium salts have been obtained, but not quite pure.The pyridine compound, (C5NH,),H,TiO(SCN),, as a purple pre- cipitate, is obtained when a concentrated hydrochloric acid solution of pyridine in alcohol is added to a solution of thiocyanic and titanic acids. The precipitate can be recrystallised from the mother liquor and is then obtained in well-defined, bluish-black crystals. The quinoline salt, (C,NHt),H2TiO(SCN),,4H,0, can be prepared in the same way. By recrystallisation from the mother liquor, it separates in deep red crystals, which could not be obtained pure but are probably anhydrous. J. McC.INORGANIC CHEMISTRY. 27 Fluorovanadium Compounds. By PETR G. MELIKOFF and P. KASANEZKY (Zeit. nnoy-g. Chem., 1901, 28, 242-254),-Potassium vanadium dioxyfluoride, VO,F,BKF, when treated with successive portions of hydrogen peroxide, behaves like a compound of the con- stitution VF,(KO),. The fluorine is gradually replaced by oxygen, and orange to red crystalline compounds are obtained containing succes- sively less fluorine, the final product of the reaction being pervan- adate. The corresponding ammonium salt reacts in a similar manner. E, C. R. Preparation of Pure Stibine. By KARL OLSZEWSKI (Rer., 1901, 34, 3592--3593).-With reference to the statements of Stock and Doht (Abstr., 1901, ii, 556), the author points out that the pheno- menon previously observed by him (Abstr., 1886, 977) was a decom- position, not a dissociation, of liquid stibine, and that in his experi- ments air had access to the liquid. Stibine boils at about - 1 8 O , probably somewhat lower than this. A. H. Gold Haloids. By FELIX LENGFELD (Anzer. Chem. J., 1901, 26, 324-332).-Aurous chloride is insoluble in water and dilute nitric acid, and is decomposed by strong nitric acid with production of auric chloride and gold. When nitric acid is added to an ammoniacal solution of the salt, a white, curdy, unstable precipitate is formed. If aurous chloride is added to solution of potassium bromide, gold separ- ates, and a brownish-red liquid is obtained, containing potassium aurichloride and auribromide. It dissolves in a solution of sodium chloride with formation of an unstable double salt, probably NaAuC1,. Aurous bromide is insoluble in water and nitric or sulphuric acid, but dissolves in ammonia with partial decomposition ; on addition of nitric acid to the ammoniacal solution, an unstable precipitate is produced. Potassium cyanide dissolves the salt without decomposition. Potass- ium bromide yields potassium auribromide and gold. With hydro- bromic or hydrochloric acid, it is converted into bromoauric or chloro- auric acid and gold. Both aurous chloride and bromide are slowly decomposed by ether, alcohol, or acetone. Auroso-auric bromide (aurous auribromide), obtained by the action of bromine on gold, is a steel-blue substance, stable in the absence of water, but easily decomposed by water and many organic solvents. Chloroauric and bromoauric acids form the compounds HAuCI,, 3H,O, HAuBr4,3H,0, and HAuBr4,6H,0, but the compounds HAuCI4,4H,O and HAuBr,,5H20 probably do not exist. When solutions of chloroauric acid and silver nitrate are mixed a t Oo, a yellow precipitate is formed which rapidly darkens and decom- poses. If an alcoholic solution of potassium aurichloride is shaken with silver carbonate, silver chloride and auric chloride are produced. E. G.

ISSN:0368-1769    

DOI:10.1039/CA9028205010

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

28 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Fusibility of Minerals and their Solubility in Magmas. By CORNELIUS DOELTER (Chem. Centr., 1901, ii, 826-827 ; from Tsck. Min. Mitth., 1901, 20, 307-330). --The results are given of detailed obser- vations of the manner in which various minerals are attacked by molten magmas. As a rule, minerals with a very high melting point (quartz, corundum, olivine, leucite) are more sparingly soluble than those with a lower melting point (felspar, augite, mica), I n general, however, the soliibility of a mineralin a magma depends on the pressure, the temperature, and the chemical composition of the magma, as well as on the fusibility of the particular mineral. Retinite from Thessaly. By CONSTANTIN ZENGELIS (Chem. Centr., 1901, ii, 833; from l'sch.Min. Mitth., 1901, 20, 356).-This retinite is yellowish-red, almost opaque, hard and readily combustible, sp. gr. 1,0023. At 290°, it softens and fuses with decomposition. Benzene dissolves 17.4 per cent. The following analysis corresponds with that required for the formula C,,H,,O : L. J. 5. C. H. S. 0. Ash. Moisture. 78-47 9.23 0.39 10.616 1.4'7 0.214 L. 3. s. Calaverite. By SAMUEL L. PENFIELD and W. E. FORD (Amer. J. h'ci,, 1901, [iv], 12, 225-246. Compare Abstr., 1896, ii, 3l).-A detailed crystallographic account is given of crystals of calaverite from Cripple Creek, Colorado. They are interpreted as being monoclinic and elongated in the direction of the axis of symmetry, but the faces have very high indices and do not fall into zones.The axial ratios, a : b : c = 1.6313 : 1 : 1.1449, axial angle, p= S9'47$', and, twinning, resemble those of sylvanite, but calaverite differs from this mineral in having no distinct cleavage, The general formula (Au, Ag)'re, expresses the chemical composition of both calaverite and sylvanite, but the latter contains more silver, and its formula approximates to AuAgTe,. The following analyses are given of the material now described : All. Ag- Te. Gangue. Total. Sp. gr. 40.99 1.74 [57*25 0.02 100.00 9.328 42.77 0.40 l56.753 0.0s 100*00 9.388 The colour of the brightest calaverite crystals is silver-white, some- times with a yellowish cast ; i t is not bronze-yellow as often described. L. J. S. Monazite from New Granada. By NICHOLAS J. BLUMAN (Chem. News, 1901, 84, 175).-A sample of reddish-brown colour, sp.gr. 6.001 and hardness 5, gave the following numbers on analysis : Ce,O,. La,O,. Tho,. MnO. CaO, SnO,. P,O,. Fe,Zn,S. Total. 25.02 22.41 18.00 1.21 2.13 3-00 28.23 traces 100.00 D. A. L,MINEKALOGICAL CHEMISTRY. 29 Triplite from Moravia and its Decomposition Products. By FRANTIGEK KovAG and FR. SLAVIK (Julwb. &!fin., 1901, i, Ref., 354-356 ; from Vedh. geol. Reichsanst., 1900, 397-404. Compare Abstr., 1901, ii, 248).--Cleavage masses of triplite, more or less altered, occur in large nests in pegmatite at Wien and Cyrillhof in Moravia. The optical characters and the following analyses are given : I and I1 are of weathered material from Wien, sp. gr. 3.901 ; calculating the iron as ferrous, these agree with the usual formula, (R'ln,Pe,Mg),PO,(F,OH). I11 is of fairly fresh material and IV of much weathered material from Cyrillhof ; the latter decomposes hydrochloric acid with the liberation of much chlorine.Further alteration of the material results in the formation of a cellular mass of dufrenite and hydroxides of iron and manganese with a colourless hydrated phosphate of iron and manganese : analysis of this mixture gave VI. The dufrenite, separated as far as possible from the other substances, gave V, agreeing with the usual formula Fe,(OH),PO,. The insoluble residue is shown by analysis and micro- scopical examination to consist of quartz, felspar and muscovite. Fe,O, .............. FeO .................. I'ln,O, ............... MnO .................. A1,0, ...............CaO .................. Alkalis ............... MgO .................. P,O, .................. co, .................. H,O .................. P ....................... Insol. ............... I. 2.80 26.10 29.17 0.49 4.58 31.67 trace 4.1 6 1.1 1 0.84 - - - 11. 4-26 24.31 28.85 0.56 4.74 50.89 0.59 4.80 trace 0.35 - - - 111. 7.78 33.37 17-92 1.27 0.40 0.1 9 32.44 4.4s 0.S8 2.37 - - - I v. 37.0s 16.24 0.35 1.68 0-56 0.63 17.56 13 68 13.35 - -_ - - VI. 5-56 41.80 2-87 0.13 0.47 0.12 31.31 11.36 7.26 - - - -- ___ ------ Total (less 0 for F). 100.45 99.75 100.73 101.13 100.42 100*88 The first stage in the alteration of the triplite is the replacement of fluorine by hydroxyl with the formation of triploidite. This is then oxidised and decomposed with the separation of hydroxides of iron and manganese along cracks, and finally yields the mixture of dufrenite, &c, Near the nests of triplite, the quartz of the pegmatite is represented only by empty cavities, and it is suggested that this mineral has been removed by the fluorine set free on the alteration of the triplite.L. J. S. Emerald and Beryl from the Uralian Emerald Mines. By PETR A. ZEMJATSCHENSKY (Jahrb. Min., 1901, ii, Ref., 190-191; from Trav. Xoc. Nut. 8t. Petersburg, 1900, 29, l-l9).-The emerald mines on the Takowaja river, 85 versts north-east of Ekaterinburg, have, since 1832, yielded fair amounts of emerald, beryl, phenakite and alexandrite. The emeralds are embedded in a dark mica-schist, or30 ABSTBACTS OF CHEMICAL PAPERS. occur, intergrown with tourmaline and felspar, in masses of quartz and felspar in the mica-schist ; they are usually cloudy and enclose scales of mica, whilst along the frequent fractures felspar is deposited.The crystals have a zonal structure and are optically anomalous. Analyses 1-111 are of pale colour emerald, and IV-V of the dark brown mica in which they are embedded, Loss on SiO,. A1,03. Fe,03. BeO. MgO. K,O. Na,O. Mn,O,. ignition. Total. I. 66'65 18.43 trace 12.9 - - - - 2-19 100.17 11. 66.96 18.58 - 13.1 - - - - 2-1 100.74 111. 65-95 18.95 trace 12'89 - - - - 2'20 99'99 IV. 40.20 26.22 13.31 - 6'69 10'44 0.87 trace 1-81 99'55 V. 40.12 26'19 13'50 - 6.10 10.23 o a a o - 1-87 98'81 L. J. S. Minerals from the Ilmen Mountains. By P. SUSCHTSCHINSKY (Jahrb. Min., 1901, i, Ref., 361-363 ; ii, Ref., 205-206 ; from Trav.Xoc. Nat. Xt. Petersbui*g, 1900, 29, 21--46).-Minerals from the mchynite, aquamarine and zircon mines, near Miask, are described. .Aquamarine gave, on analysis, the results under I. Black, rhombic dodecahedra of garnet in mica-slate gave 11. Dark green crystals of Egirine-augite from druses in gneiss gave I11 (anal. by Antipoff). SiO,. A1,0,. Fe,O,. FeO. BeO. CaO. MgO. Na,O. H,O. Total. I. 66.02 18.81 - - 13.27 -- - - 1.45 99-55 99'96 111. 50'58 5'47 3-92 23-18 - 3.85 2-19 8.17 - 97.36 - - 11. 35.34 19-51 - 40.20 - 4.91 - L. J. S. Composition of Plagioclase. By W. TARASSENKO (Jahrb. Bin., 1901, ii, Ref., 180-189; from Mem. Nat. Soc. K&fl [Russ.], 1900, 16, 365-496. Compare Abstr., 1900, ii, 354).-The plagioclase of labra- dorite-rocks from (I) Selistsche (Gov.Volhynia) and (11) Gorodistsche (Gov. Kieff) was separated into several portions according to sp. gr. and each portion examined in detail. The eleven analyses, of which the means are given below, differ among themselves for each felspar only within the limits of errors of observation. The variation in the sp. gr. is attributed to the porosity of the material, due to the presence of fluid enclosures, cleavage cracks, &c. SiO,. A1,0,. CaO. Na,O. K,O. Sp. gr. Formula. I. 55.28 28.27 10.18 5.17 1.10 2-647-2.710 AblAnl 11. 53.05 29.77 12.08 4.30 0.80 2-697-2.756 Ab,An, It is concluded that the plagioclases are not isomorphous mixtures, but compounds of the albite and anorthite molecules in definite pro- portions. L. J. s. By FERRUCCIO ZAMBONINI (Jahyb.Min., 1901, ii, Ref., 19; from Riu. Min. Crist. Ital., 1900, 24, 13).-Small crystals of sodalite from an '' erratic block " at 5. Sisto, near Viterbo, gave, on analysis : Total (less SiO,. Al,O,. Fe,Os. Na,O. CaO, C1. H,O. OforC1). 36-60 34.26 1.85 17-75 0*90 4-31 5-14 99%4 Soddite from Viterbo. L. J. S.MINERALOGICAL CHEMISTRY. 31 [Amphibole in] Soda-syenite from Miask. By ARRIEN JOHNSEN (Jahrb. Min., 1901, ii, 117--127).-Descriptions are given of five rocks of the soda-syenite group from Miask in the Urals. One of these, called an segirine-augite-soda-syenite, consists of albite, a little micro- cline, aegirine-augite, and a peculiar amphibole. This amphibole is pleochroic and has a wide angle of optical extinction (c : c = 36') ; sp.gr. 3*15 ; an approximate analysis gave the following results : SiO,(+TiO,?). A1,0,. Fe203. FeO. MnO. MgO. CsO. 58.50 12.38 14.32 4.79 3.16 4.30 0.92 Na,O. K,O. Total. 4.09 0.48 102.94 It appears to be intermediate between riebeckite and glaucophane. L. J. S. Andalusite from the Rhaetian AJps. By AUGUST GRAMANN (Jahrb. Mirn., 1901, ii, Ref., 193-197; from separate publ. Zurich, 1899, 57 pp.).-At several localities in the Fluela and Scaletta districts in Switzerland, crystals of andalusite occur with cordierite, kyanite, sillimanite, muscovite, biotite, orthoclase, pmicline, &c., in quartz lenticles in biotite-gneiss, but not in the gneiss itself. The sp. gr. of the andalusite is lower than usual, being 3*0532-3*0829. The colour is peach-blossom-red or violet, and the crystals have sometimes a darker coloured kernel.The colouring matter appears to be TiO, (rutile) rather than Ti,O,. The extremes of five analyses are : SiO,. Al,03( + FeO). Fe203. H,O . 33.76-34'7 1 63.93-64.69 Nil-0.44 0*49-1*78 The alteration product of the andalusite is a white, scaly, sericitic material containing much quartz and carbonates. By the aggregation of numerous scales of this secondary sericite, large plates of muscovite are formed, analysis of which gave the following results, agreeing with those required for the formula 4H20,K,0,(Ca,Mg)0,6A1203, iOSi0, : SiO,. A1,0,. MgO. CaO. K,O. Na,O. H20. Total. 43.09 42.16 0.29 2-54 6.79 trace. 5.11 99.98 L. J. S. Fire-clay from Moravia. By FRANTISVEK Kov& and ANT. HA~KOVEC (Juhrb. Hin., 1901, ii, Ref., 226 ; from Zeit.chem. Ind. Prag, 1899,s pp.).-Beds of fire-clay occur in the Quader sandstone at Vranovd near Kunstadt. Analysis I .is of whitish, and 11, of dark greyish, more sandy, material. Loss on SiOz. TiO,. AI,O,. Fe,O,. CaO. MgO. Alkalis. SO,. ignition. Total, I. 52-42 tiace 33.56 1.17 0.77 0.38 1'28 - 10.84 100.42 [I. 52-11 0.17 27'73 5.92 0'91 0.57 1.07 0'21 12'78 100'47 L. J. 8.32 ABSTRACTS OF CHEMICAL PAPERS. Separation of Titaniferous Iron Ores in Basic Igneous Rocks By JOHAN H. L. VOGT (Chem. Centr., 1901, ii, 829 ; from Zeit. prakt. Geol., 1901, 289-296. Compare Abstr., 1900, ii, 63 ; 1901, ii, 319). -A graphic representation of analyses shows that as concentration takes place, a decrease in silica is accompanied by a decrease in alumina and alkalis and an increase in titanium and iron oxides, while the variations in the lime show no regularity.Very advanced stages in the differentiation cannot be explained by a simple addition or sub- traction of material, since, with varying conditions, the processes of differentiation are more or less changed as they proceed. In all prob- ability, the differentiation is effected by the transference of a dissolved constituent in a solvent ; the former being the bulk of the titanium and iron oxides and magnesia, and the latter a part of the silica with alumina, lime, and alkalis. The materials are concentrated in the same order in which they crystallise out from the magma, namely: (1) apatite ; (2) sulphides ; (3) titanium and iron oxides with spiuel ; (4) ferromsgnesian silicates. Cases are, however, lrnown in which all of these may be concentrated together. By GEORGE A. GOYDER (Trans. Roy. Xoc. South Aust~alia, 1901,25, 14).-This iron, of which the weight is 7+1bs., shows Widmanstatten figures and twin-lamellae (Neumann lines) on the etched surface and consists of blades of kamacite with L. J. S. A South Australian Meteorite. I thin plates of taenite and grains of troilite. Analysis by Chapman gave : Fe. Ni. co. S. P. Insol. Total. 88.85 9.07 0.34 0.75 0.27 0.03 99.31 L. w. s. Sp. gr. 7-693 J. 8. Analysis of the Sulphurous Waters of Vernet-les-Bains. By LBON PERRER (J. Phamz. Chim., 1901, [vi], 14, 385-389).-l'he waters of Vernet-les-Bains belong to the class of thermal sulphuretted alkaline waters. Complete analyses of samples from seven different springs are given in t h e paper. H. R. LE 8.

ISSN:0368-1769    

DOI:10.1039/CA9028205028

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

32 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. Artificial Parthenogenesis. By S. J. HUNTER (Amer. J. Yhysiol., 1901, 0, 17?-180).-The experiments were made on the eggs of Ada&, and show that sea water concentrated by evaporation will produce the formation of imperfect larvz. This is regarded as con- firming Loeb’s osmotic theory of artificial parthenogenesis. W. D. H. Influence of Spermotoxin on Reproduction. By MDLLE. C . DE LESLIE (Compt. y*end., 1901, 133, 544--546).--On inject,ing into the white male rat spermotoxic serum from the guinea pig, it loges allPHYSIOLOGICAL CHEMISTRY. 33 power of reproduction, The sterility lasts for 16-20 days. Sterility may be similarly produced in the female. The injection does not otherwise influence the well being of the animals; the males even continue to produce mobile spermatozoa ; these, however, have lost their power of fertilisation.Quantitative Observations on Gastric Digestion. By FRIEDRICH KRUGER (Zeit. Biol., 1901,41, 467-483. Compare Abstr., 1901, ii, 561).-The general belief that the action of pepsin, like that of other enzymes, is inhibited by the presence of digestive products is well founded. The addition of peptone to the mixture lessens the digestive action. Tables are given which show that the inhibitory action of the digestive products is proportional to their quantity! pro- vided the amount of hydrochloric acid is kept constant ; in ordinary digestion, this is not the case ; the loss of power is greater and is to be in part explained by diminution in the amount of free acid.The amount of free hydrochloric acid which is most favourable is from 0.18 to 0.4 per cent. Blood Analysis in Relation t o Metabolism. By G. ASCOLI (PJuger’s Avchiu, 1901, 87, 103--!15).-1t is pointed out that in studying metabolism, the examination of the excreta alone daes not teach the details of the metabolic cycle. Intermediate stages, especially in relation to nitrogenous metabolism in the organs, should be searched for, by the examination of the blood for such substances as purine compounds, carbamic acid, creatine, &c. W. D. H. W. D. H. W. D. H. Influence of Sodium Nitrate on Metabolism in Dogs. By E. ROST (Chenz. Ce?zti*., 1901, ii, 864 ; from Arbb. Kais. Ges.-A,, 18, 78-99).-Small doses of sodium nitrate have practically no effect on metabolism. Large doses given in water produce diuresis and a ‘ nitrogen-sparing ’ action.If insufficient water is given, there is an increase of proteid kataboliem. Among different sodium salts, the carbonato produces the greatest increase in the breakdown of proteid material in the body. By ERWIN VOIT (Zeit. Biot., 1901, 41, 502-549 ; 550 -571).-These two papers are largely critical. The main conclusion arrived a t is that proteid kata- bolism in starvation is largely influenced by the amount of reserve and circulating fat in the body. When the quantity of fat is large, no increase of proteid disintegration occurs, but when it sinks below a certain limit, disintegration begins. Length of life during starvation t.herefore depends largely on the amount of f a t to start with.Death is due, not to destruction of the total cell-masses of the body, but on katabolic changes in a few organs of essential importance. The second paper deals at greater length with the influence of fat on proteid katabolism. R& of Purine Derivatives in Human Metabolism. Ey KICIIARD EURIAN and HEINRICH SCHUR (Pfliiger’s Archiv, 190 1, 87, 239-354. Compare Abstr., 1900, ii, 489).-In birds, uric acid is W. D. H. [Proteid Metabolism in Inanition.] W. D. H. VOL. LXXXII. ii. 8:3 4 ABSTRACTS OF CHEMICAL PAPERS. the main end-product of nitrogenous metabolism. I n mammals, the question is a debatable one whether the uric acid and other purine derivatives which these animals excrete are to be regarded as terminal or intermediate products.A full and critical review of the extensive literature on the subject shows how diverse are the views which are held. The purine derivatives of the urine have R double origin, exogenous from the nuclein and purine compounds of the food, and endogenous from tissue metabolism. The problem is complicated by the fact that the organism not only forms purine compounds, but it also has the power of destroying them. This property is especially possessed by the liver, so that the excretion of purine compounds is no measure of the amount found unless a t the same time the amount destroyed is also known. The relationship between the two processes can be ascertained by the injection of known quantities of purine compounds either into the blood stream or subcutaneously. Such experiments show mainly the fate of exogenous purine, but endogenous purine is apparently acted on in the same way.The result of the experiments shows that uric acid and purine derivatives are in the main intermediate producte of metabolism, but that a certain fraction of these intermediate products is excreted as such by the kidneys. This fraction varies in different animals, but in animals of the same class the integration factor (that is, the number by which the urinary purine must be multiplied in order to obtain the total) is very constant ; in carnivora i t is 20-30, i n the rabbit 6, in man 2 ; that is, in man, half the uric acid formed is excreted in the urine. W. D. H. Amount of Fluorine in Teeth and Bones. By JODLBAUEH, [with JOSEF BRANDL] (Zed. Biol., 1901, 41, 487--492).-Hempel’s method of estimating fluorine in bone and teeth gives more trust- worthy figures than that of Wohler-Fresenius.By B. SLOWTZOFF (Beity. chern. Physiol. Path., 1901, 1, 281-288).-When arsenic is given to animals and accumulates in the liver, it unites with the nuclein, and after gastric digestion is found in the precipitate of nuclein. Mercury, on the other hand, unites with the globulin con- stituents of the cell-protoplasm, W. D. H. By F. SIEGERT (Beitr. chern. P?qsiol. Path., 1901, 1, 183--lS8).-Langer (Abstr., 1882, 240) originally stated that the amount of solid fatty acids in the subcutaneous f a t of new-born children is relatively great, and that with growth oleic acid increases. This statement has not been con- firmed by all subsequent observers (Thiemich, Abstr., 1899, ii, 234).In the present research, a large number of observations is recorded ; the mean iodine number for new-born children is 43.36 ; in successive months, the number is 42.5, 46.9, 47.5, 53.2, 45.5, 49.9, 48.9, 54.75, 58.55, until a t 12 months it rises to 62.35, the number for the adult being 65. W. D. H. By F. SIEGERT (Bietr. chern. Physiol, Pctth,, 1901, 1, 114--120).--Four W. D. H. Compounds of Mercury and Arsenic in the Liver. Composition of the Fat in Young Children. Behaviour of Fat during Autolysis of the Liver.PHYSIOLOGICAL CHEMISTRY. 35 experiments were made with dogs’ livers. The amount of ethereal extract and of higher fatty acids was estimated before and after autolysis (from 7 to 9 days, putrefaction being prevented).The amounts of both are practically the same before and after autolysis. W. D. H. Autolysis and Blood-clotting. By H. CONRADI (Beitr. chem. Physiol. Path. 1901, 1, 136--182).-The juices expressed from various animal organs without exception hasten blood-clotting. After autolysis, the same organs yield solutions which hinder blood-clotting. Both substances are soluble in water and precipitable by alcohol, the one which favours coagulation is rendered inert by boiling, is not diffusible, does not filter through a Chamberland filter, and is rendered still more active by calcium chloride. The substance which hinders coagulation is not influenced by heat or by calcium chloride, diffuses readily, and passes partially through a Chamberland filter.The blood itself when kept also gives rise to this substance. It appears to be analogous to peptozyme. Formation of Bactericidal Substances in Autolysis. By H. CONRADI (Beitr. chem. Physiol. Path., 1901, 1, 193-225).- Bactericidal power is absent from the juices expressed from fresh organs as a rule. It is present in the juice from lymph glands and slightly in that from the spleen. After autolysis, the expressed juice of muscle, liver, spleen, lymph glands, testis, thymus, suprarenal t)ody and duodenum is strongly bactericidal. The juice from bone marrow, ovary, lung, tonsil, kidney, jejunum and ileum has the same power to a less degree, It is absent in the juice after autolysis from fcetal intestine, pancreas, thyroid, submaxillary gland, and brain. The bactericidal substances are hydrolytic decomposition products of pro- teids, and from their reactions and solubilities are probably derived from the aromatic complex of the proteid molecule.They give Dlillon’s, the xanthoproteic, and bromine reactions. Thsy are soluble in alcohol. and are precipitated from their alcoholic solutions by ether. W. D. H. W. D. H. Function of Brunner’s Glands. By KARL GLAESSNER (Beit?.. chem. Physiol. Puth., 1901, 1, 105--113).--The fluid obtained by autolysis of the mucous membrane of the small intestine has certain digestive powers. If a portion is taken which contains both Brunner’s and Lieberkiihn’s glands, the action is both proteolytic and diastatic. Tf there are only Lieberkuhn’s follicles, proteolytic power is absent. If the upper part of the duodenum is taken and the surface layer containing Lieberkuhn’s follicles removed and only Brunner’s glands left, the diastatic power is absent, Inverting action on cane sugar, and emulsifying action on fats were absent throughout.The proteolytic enzyme of the Brunner’s glands acts in weakly alkaline, neutral, and feebly acid solutions; i t is regarded as identical with the enzyme, separated from the pyloric end of the stomach, which the author has named pseudopepsin. By OTTO VON FUWH (Beit?.. them, Physiol. Path., 1901, 1, 252-25S.)-The gluco-proteid of the egg W. D. H. Gluco-proteids of Lower Animals. 3-236 ABSTRACTS OF CHEMICAL PAPE:HS. covers of sepia, or of the ground substance of chondrosia were in- vestigated. The reducing substance obtained in each case was an amino-sugar of the type of glucosamine.W. D. H. Nucleo-histon. By IVAR BANG (Beit?.. chern. Phpiol. Path., 1901, 1, 189--192).--Further reasons are advanced which bear out the author’s previous contention that nucleo-histon in the sense of Lilienfeld and Kossel does not exist. W. D. H. Formation and Secretion of Chymosin (Rennin). By ~Ll3xANDElt~~INoGRADoFF(~$iige~~’s Avchiv, ~901,87,170-228).--There is an inverse proportion between the quantity of rennet ferment and time of coagulation. A method is described for estimating t,he amount of theferment,. The ferment is believed to participate in the regeneration of proteid from peptone, and the results obtained by estimating its power of forming plastein are identical with those obtained in experi- ments on milk.After a meal, the formation of rennin by the gastric mucous membrane increases from the first to the ninth hour; there are two maxima, namely, from the second to the fifth, and from the ninth to the eleventh hour. Even after this time, the ferment is still secreted in small quantities. The amount in the gastric juice is proportionaJ to that in the mucous membrane and very closely follows the curve of pepsin for mation, W. D. H. Tyrosinase in Animals. By OTTO VON EURTH and HUGO SCHNEIDER (Be&. chern. f’hysiol. Pccth., 1901, 1, 229-242).-Tyro- sinase is an enzyme, described by Bertrand as occurring in the juices of certain p1ant.s (Abstr., 1896, ii, 571), which oxidises tyrosine and leads to the darkening of the juice. It is apparently analogous to the lac- case of certain other plants.It has been found by Biedermann (Abstr., 1898, ii, 614) in the intestine of the meal worm. The present research shows that it is a constant constituent of the blood .of insects and other arthropods, and is the cause of the darkening of the blood on exposure to the air. The chemical nature of the chromogen in the blood is left uncertain; it is, how- ever, not tyrosine. The melanin formed contains C, 55.44 ; H, 4.45 ; N, 13.74; it is believed to be related to the indole group, but its chemical nature is also left uncertain. W. D. H. Excretion of Uric Acid. By HELLMUTII ULRICI (Chenz. Centr., 1901, ii, 1024-1025 ; from Arch. exp. Path. I’lwrnz., 46, 321-337),- Sodium benzoate increases the excretion of uric acid, Gallic acid acts in the same way.Quinic acid and tannin have no influence on metabolism or the excretion of uric acid. Salicylic acid produces a great stimulation of metabolic processes, increases the total output of nitrogen, and especially raises that of uric acid; this is followed by a diminution in the excretion of the acid. W. D. H. Physiological Action of Chloral Hydrate and Acetone. By C. AHCIIANGELSKY (Chem. Centis., 1901, ii, 1028-1039 ; from Arch. exp. Path. Y l ~ w n ~ , 46, 347--371).-A method of estimating chloralPHYSIOLOGICAL CHEMISTRY. 37 hydrate in the blood and tissues is described. I n dogs, 0.03 to 0.05 per cent. in the blood causes narcosis; 0.05 to 0.07 abolishes the corneal reflex ; and 0.1 1 to 0.1 2 causes cessation of breathing ; in the rabbit, rather larger doses are necessary.I n the blood, most of the chloral is present in the corpuscles ; a t first, the brain contains less than the blood ; that in the liver remains small, but the brain tissue which is believed to have a special affinity for chloral hydrate soon contains much more than the blood. Acetone in the blood to the extent of 0.5 per cent. causes narcosis; it is chiefly present in the corpuscles. The brain contains more, the liver less, than the blood. The central nervous system has also a special affinity for this drug. Both narcotics a.re believed to be united to tche fatty constituents of protoplasm. W. D. H. Acid Poisoning in Dog and Rabbit. By KARL SPIRO re it^. chem. Physiol. Path., 1901, 1, 269-280).-Mauy previous observers have pointed out that carnivora are less susceptible to the toxic influence of acids than herbivora, and some have attributed this t o a fundamental difference between the animals, the carnivora, by production of am- monia, being able to neutralise the acid.It is now pointed out that the difference, although i t exists, is orly a quantitative one, and that acids and acid phosphates stimulate the kidney to increased activity in the dog more than in the rabbit; the dog thus rapidly eliminates the harmful material. Other diuretics (caffeine and its homologues) also act more powerfully on the dog’s kidney than on that of the rabbit ; the dog’s kidney, moreover, has a higher resistance towards poisonous sub- stances. W. D. H. Condition of the Blood and Marrow in Chronic Arsenical Poisoning.By I. C. MUIR (J. Pathol. Bacteriol., 1901,7, 420-446). -In chronic arsenical poisoning in man, the blood is richer in red corpuscles and hemoglobin when there is deep cutaneous pigmentation than when the skin is but slightly pigmented. Pigmentation is not due to destruction of hzmoglobin, but melanin may be a precursor of haemoglobin. Arsenic stimulates t’he erythroblastic action of red marrow, especially when t,he skin has a store of melanin in it. W. D. H. Behaviour of Calcium Hypophosphite [when administered internally]. By MASSOL and GAMEL ( J . PRccrm. Cl~irn., 1901, [vi], 14, 337-342).-Contrary to the usually accepted statements, it is definitely shown from the results of experiments carried out on dogs, that when calcium hypophosphite is administered internally, the hypophosphite is not oxidised t o phosphate, but is entirely eliminated by the urine as sodium hypophosphite, and that the calcium is elimin- ated by the faeces.The volume of urine, the total nitrogen, and the amount of urea are not changed, but the acidity of the urine, the amount of uric acid, and tb.e ratio of uric acid to urea are diminished. Complete analyses of the urine, before and after treatment, are given in the original paper. H. R. LE 5,38 ABSTRACTS OF CHEMICAIA PAPERS. Antagonism of Curare and Physostigmine. By JULTUS C. KOTHBERGER (PJiigeT’s Archiv, 1901, 87, 117--169).-Bilnteral an- tagonism exists between curare and physostigmine so far as their action on muscles is concerned. Those muscles which, like the diaphragm, are last paralysed by curare, are first set free again by the injection of physostigmine. Physostigmine also stimulates the respira- tory centre, There is no antagonism between the two drugs in vitro. W. D. H. Action of Fluorescent Materials on Ciliated Epithelium. By RICHARD JACOBSON (Zeit. Biol., 1901, 41, 444--466).:Light increases the poisonous action of fluorescent substances on ciliated epithelium. Non-fluorescent poisonous substances act equally vigor- ously in light and darkness, Non-poisonous fluorescent substances act in the same way in light and darkness. Chemical Action of the Microsporon Audouini. By W. D’ESTE EMERY (J. Pathol.’ Bacteriol., 1901, 7, 400--408).-1t has been surmised that the ringworm fungus (Microsporon audozcini) has the power of digesting keratin. The fungus, however, secretes a proteolytic enzyme which finds its proteid pabulum near the hair bulbs, and the action of which is to set up slight folliculitis ; the loss of hair is in part due to this, and in part to splitting caused by mechanical pressure. W. D. H. This view is not confirmed. W. D. H. Phloridzin Diabetes in Gats. By JULIUS F. ARTEAGA (Amer. J. Physiol., 1901, 6, 173--176).-1n the fasting cat, just as in the rabbit and goat, the urinary ratio between dextrose and nitrogen in phloridzin diabetes is 2.8 : 1, a striking example of biological uniformity. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9028205032

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

38 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Assimilation of Free Nitrogen by Soil Bacteria without Symbiosis with Leguminosa By JULIUS * KUIIN (Bied. Centv., 1901, 30, 660-663 ; from Fiihling’s Lnnduj. Zeit., 1901, 2).-The results of field experiments on rye during 21 years show that the yields of grain and straw on the iznmanured plot and on the plot which has had only non-nitrogenous manures tend to increase rather than diminish. The soil evidently contains fair amounts of available mineral matter, whilst experiments with nitrogenous manure indicate a limited supply of available nitrogen. The conclusion is therefore drawn that fixation of elementary nitrogen is going on under the influence of soil organisms. Kriiger has isolated x micro-organism from the soil, which, in culti- vations in artificial solutions, assimilated not inconsiderable amounts of free nitrogen.VEGETABLE PHYSIOLOGY AND AGRICULTURE.39 The yield of rye on the different plots was as follows (kilos. per 1 iectare) : 1879. 1894-1898. 1899. Grain. Straw. Grain. Straw. Grain. Straw. 1. Dung ..................... 2400 3870 2774 5696 2405 5565 2. Minerals .................. 1770 2520 1976 4363 1640 4020 3. ,, + ammonium sulphate+nitrate ...... 2570 4080 2926 5968 2675 5950 4. Ammonium sulphate + nitrate ................. 2560 3570 2664 5224 2370 5030 5. Unmanured ............... 1820 2490 1974 3914 1750 3730 +7 - The season of 1899 was unfavourable to grain production. N. H. J. M. Decomposition of Nitrates and Nitrites by Bacteria. By ALBERT MAASSEN (Chem.Centr., 1901, ii, 820-821; from Arb. k. Ges.-A,, 18, 1-77).--Potassium nitrate in 0.5 per cent. solutions con- tainin! peptone ( 5 per cent.) was reduced to nitrite by 85 of the 109 varieties of microbes examined. Fifty varieties destroyed nitrites, four of them liberating free nitrogen, Many bacteria which reduced nitrites, without liberation of nitrogen, had very little or no effect on nitrates. The presence of carbohydrates is favourable to denitrifica- tion, whilst in absence of organic nitrogen, nitrates and nitrites are attacked by microbes which have no effect when proteids are present. TheIso-called denitrifying organisms destroy nitrates independently of the nature of the nutritive solutions, whilst the others act only in presence of certain carbon compounds.The action of both classes of microbes is retarded by the presence of highly oxygenated compounds, such as chlorates, without injury to their growth. Some bacteria, such as Bacterium paepollens, act on nitrates only in symbiosis with other varieties, liberating nitrogen and producing potassium carbonate. The co-operating bacteria, in the case of B. praepollens, are exclusively those which reduce nitrates to nitrites. N. H. J. M. Decompositions of Nitrogen Compounds in Soil by Lower Organisms. By IT. KRUUER and W. SCHNEIDEWIND (Chem. Centr., 1901, ii, 824-825; from Landw. Jaiirb., 30, 633-4548. Compare hbstr., 1901, ii, 470)-Application of straw, in field experiments, resulted in a lessened assimilation of nitrogen and a diminished crop.The injurious effect of fresh organic matter on the assimilation of nitrogen by the crop is to a great extent due to production of insoluble nitrogenous compounds, under the influence of denitrifying and other microbes and fungi. The nitrogen not only of nitrates but especially of ammonium salts and amides becomes unavailable. The insoluble nitrogen becomes available only slowly ; most of it, perhaps, not a t all. Ammonium sulphate (but not nitric nitrogen) is ptrtly converted into proteids even in absence of fresh organic manure. This explains why ammonium salts supply less nitrogen to crops than nitrates when the latter are not subjected to loss by drainage. N. H. J. M.40 ABSTRACTS OF CHEMICAL PAPERS. Effect of Methylal on some Fresh-water AlgE.By RAOUL COUILHAC ( C o ~ y ~ t . rend., 1901, 133, 75 1 -753).--Nostoc and Annbaena are able to grow in presence of methyla1 when the amount of light is insufficient for the decomposition of carbon dioxide; in absence of methylal or other organic matter, there is no growth under these conditions. A certain amount of light is necessary when methylal is present. Experiments are proposed to ascertain whether methyl alcohol and formaldehyde respectively can replace methylal. N. H. J. MI. Constituents of Coffee Berries. By L. GRAF (Zeit. ccngew. Ckeiii., 1901,14, 1077--1082).-Coffee berries do not contain dextrose or any reducing sugars in the free state, The presence of sucrose in the methyl alcoholic extract has been established. It appears that sucrose after crystallisation from methyl alcohol melts a t 169-170", but after crystallisation from ethyl alcohol at 179-180O. Caffetannic acid is also a constituent of coffee beans; although gen- erally regarded as a glucoside, it does not yield a sugar on treatment with dilute acids, concentrated alkali, bromine or dilute nitric acid (compare Kunz-Krause, Abstr., 1893, ii, 3 2 7 ; lS97, i, 530 ; F.Koch, ibid., 1895, ii, 410; Hlasiwetz, AnnaZen, 1867, 142, 219 ; Cazeneuve and Haddon, Abstr., 1897, i, 529). J. J. 8. Presence of Salicylic Acid in Strawberries. Errors of Analysis which may result therefrom, By L. PORTES and A. DESMOULI~REX (J. P?mrm.Chim., 1901, [vi], l4,342--351).--Salicylic acid has been actually isolated from ten different varieties of strawberries, and is shown to be a normal constituent of this fruit.The acid is most probably present as methyl salicylrtte. The amount present, although small, 1 mg. having been obtained from 1 kilogram of the fruit, is sufficient to answer to the reactions employed for the detection of salicylic acid in cases of suspected adulteration. H. R. LE 8. Formation of the Perfume of Vanilla. By HENRI LECOMTE (Compt. rend. 1901, 133, 745--748).-The fruit of plunifolia does not possess the characteristic odour of vanilla a t the period of cropping ; the odoiir is developed during the process to which the fruit is subsequently subjected. Evidence is adduced in support of the view that v:\nillin is formed by the action of a ferment on coniferin, the coniferyl alcohol thus produced being transformed by an oxydase into vani 1 lin.Oxydase was found in the best preparations of vanilla (from Mexico, Reunion, Mayotte, and Seychelles), but was absent, or nearly so, in inferior preparations from Tahiti and in '' vanillon " from Guadeloupe. All the materials examined contained manganese. N. H. J. M. Production of Milk and Butter. Variations in the Richness of Milk in Fat. By L. NALPEAUX and E, DOREZ (Ann. Agron., 1901, 27, 449--461).-The minimum and maximum amounts of different constituents found in milk were as follows :--water, S4.5-89.6 ; fat, 10.4-15.5 ; casein, 2.9-3.8 ; lactose, 4.6-5.4 ; ash,VEQETABLE PHYSIOLOQY AND AGRICULTURE. 41 0.6-0.9 per cent. A low percentage of f a t is not necessarily coincident with a large yield of milk. The last portion of the milk obtained in milking was found to be much richer in fat than the first portion, but contained somewhat less of the other constituents.Soon sfter calving, the amount of fat is above the average, but subsequently there is a regular decrease, which, in some cases, may be considerable. N. H. J. M. Poisoning by Potassium Perchlorate. By F. R. JUNGNER (Bied. Cents.., 1901, 30, 711 ; from Deut. Zundw. Prssse, 1900, No. 62).- Germination experiments were made with rye both with and without sodium nitrate (1 gram, corresponding with the amount usually applied per acre). I n presence of perchlorate eight different symptoms of injury mere observed, and there were also differences in composition. N. H. J. M. Effect of Various Mechanical Conditions of the same Soil on Barley.By JOHANN J. VAGHA (Bied. Centr. 1901, 30, 654-657; from Zeit. Lccndw. Yemuchs- Wes. Oesterr., 1901, 4, 99).-Barley was grown in pots containing loamy clay soil, and the same soil t o which varying;amounts of sand and of silt respectively had been added. The same manures and the same amount of water were added t o each pot. As the fineness of the soil increased there was an increase in the yield of grain and straw ; the number, length, and weight of the ears and the weight of the grain were also increased. Light sandy soil favoured the production of mealy grain, and the grain is smaller and accumulates more ash constituents than in heavy soil. The amounts of nitrogen and ash in the grain produced in the normal soil (l), and in the soil with 2 sand (2), and with 8 silt (3), were as follow :--N (1) 1.667, (2) 1.530, andi(3) 1.575.Ash, (1) 2.600, (2)f2*740, and (3) 2.432 per cent. I n the original paper, fifty different properties of the single plants are discussed. Analyses of the ears and the grain are given. N. H. J. M. Assimilation by Oats with different Amounts of Moisture in the Soil and with different Manures. By 1,. LANGER and BERNHARD TOLLENS ( J . Landw., 1901, 49, 209--229).-An increase in the amount of water in the soil gave rise to increased production of grain and straw; a t the same time, the percentage amount of phosphoric acid and also that of potassium (when the soil contained plenty of potassium, but not otherwise) in the produce were raised. The percentage amount of nitrogen in grain and straw diminished as the amount of soil moisture increased.Root production diminished when the amount of water in the soil mas increased, and vice versa. Exclusive phosphoric acid manuring increased the total produce in soils de6cient in nitrogen when the soil moisture mas increased. The produce contained the greatest amount of phosphoric acid when grown on soil poor in phosphoric acid.42 ABSTRACTS OF CHEMICAL PAPERS Excess of potassium manure in conjunction with much water promoted the growth of straw, but diminished the yield of grain. Heinrich’s results, indicating that the roots show deficiency of manures in the‘soi1,’qare generally confirmed ; but minimum numbers have to be modified according to the amount of water. Langer, in opposition to Tollens, considers that the results of the analysis of oats give indications as good as, or better than, soil analysis as to the manurial constituents of the soil (compare Atterberg, Abstr., 1901, ii, 573).N. H. J. M. Manurial Experiments with Beans and Barley on Heavy Marsh Soil. By LILIENTHAL (Bied. Centy., 1901, 30, 666-668; from RihZing’s Landw. Zeit., 1901, SO).-Field experiments with beans followed by barley on limed and unlimed plots, without manure, and with basic slag! guano, and a mixture of basic slag, sodium nitrate, and kainite respectively. It was found that lime neutralises to a great extent the injurious effect of salts on heavy marsh land and that the amount of lime present in basic slag is not sufficient to obtain the greatest yields. When liming is adopted for rich marsh land, manures must at first be applied with caution, especially for cereals, to avoid the crop being laid.Horse beans do not require nitrogenous manure on marsh land; fixation of nitrogen increases with the supply of phosphoric acid in the soil. The phosphoric acid of basic slag is more effective on marsh land than that of crude guano. N. H. J. M. Sweet Potato. By LOUIS BONNIN (Ann. Agron., 1901, 27, 491-492 ; from Bull. Assoc. Chirn. suer. dist., 1901, Il028).-The following analyses are given of (1) the meal obtained by grinding the sun-dried tubers of Ipomum batatos, (2) the creepers, and (3) the residues obtained after extracting the starch (13-14 per cent.) from the meal : Nitrogenous. Non-nitrog. 71Ta t er. Fat. matter. matter. Cellulose.Ash. (1) 11-40 1*96 3.06 78.77 2-69 3.12 (2) 84.51 0.56 2.03 8.16 2 4 7 1.37 (3) 24.86 0.48 0.55 69.49 3.82 0.80 The meal and the extracted meal form suitable cattle foods when mixed with molasses, whilst the creepers are used for COWS. N. H. J. M. Conditions of Temperature and Moisture of a Loamy Soil with different Crops and different Manures. By CONRAD VON SEELHORST (J. Landw., 1901, 49, 231--250).-The result of pot experiments showed that the unmanured soil gave up the most water and the soils which received potassium manure and sodium nitrate, or a mixture of both, the least water. Superphosphate had not much effect. The pot with potassium manure and superphosphate lostVEGETABLE PHYSIOLOGY AND AGRICULTIrRE. 43 water more quickly than the superphosphate pot, whilst potassium carbonate alone strongly retained water.In subsequent experiments with sand, it was again found that the evaporation was greatest without manure or with superphosphate. Calcium carbonate had practically no effect. A large number of moisture determinations were made in soils growing different crops and with different manures. The soil of plots which received no nitrogen always contained the greatest amounts of water owing to the increased evaporation from the crop. The differ- ence in the amount of moisture exists long after the removal of the crop. Manuring has only an indirect influence on the temperature of the soil, due to the greater amount of shade by denser crops. The differ- ences, however, do not seem to be of practical importance.N. H. J. M. Relative Manurial Value of Ammonium Salts [and Sodium Nitrate]. By PAUL WAGNER (Bied. Centr., 1901, 30, 668-670; from Mitt. deut. Zanclw. Ges., 1901, Nos. 10 and ll).-The results of field experiments in 1899 and 1900 in which rye, oats, barley, sugar beet, mangels, and potattoes were manured with sodium nitrate and ammonium salts respectively, showed the relative value of the two forms of nitrogen to be as 101 : 67 for grain and as 100 : 65 for straw, in the case of the three cereals taken together. The season was, how- ever, in both years, unfavourable for the utilisation of ammonium salts. I n the case of roots, the value of the ammoniacal nitrogen was only 48 as compared with nitric nitrogen = 100. This is, perhaps, t o be partly attributed to the action of the sodium of the nitrate. None of the soils on which the experiments were made were, physi- cally, exceptionally unfavourable for ammonium salts ; but it is possible that some, even those richer in calcium, contained too little calcium carbonate for the rapid conversion of ammonia into nitrate.N. H. J. N. Manurial Experiments with Sodium Nitrate in the Red- wine District of Ahrthal. By PAUL KULISCH (Bied. Centr., 1901, 30, 670-671 ; from Ber. k. Lehranstcdt Ohst-, Wein-, u. Gartenbau, Geiseniieinz a. Blhein, 1900, 103).-The application of sodium nitrate (300 kilos. per hectare) had 5 very striking effect on the stony, hilly land ; more stem and leaf were produced, whilst tho development of the grapes was improved. I n the case of humous loam, nitrate had very little effect.Any differ- encesiwhich were observed were in favour of the manured plots. Sodium nitrate had no injurious effect on the must. N. H. J. M. Employment of Ammoniacal Manures on Calcareous Soils. By ERCOLE GIUSTINIANI (Ann. Agron., 1901, 27, 462-486. Compare Abstr., 1899, ii, 692).-Ammonium manures may be used with advantage on damp, and generally on stony, soils containing calcium44 ABSTRACTS OF CHEMICAT, PAPERS. carbonate. I n rich soiIs, nitrificntionis slow, and the effect of ammo- nium salts is less rapid, but more durable, than that of sodium nitrate. Ammonium salts should not be applied to sandy soils which contain no calcium carbonate, or to sandy: calcareous soils. A light soil, with 5-20 per cent. of calcium carbonate, may, if not too dry, benefit by application of ammoniacal manures ; the manure might, with advan- tage, be added by degrees.When basic slag and ammonium sulphate are employed for the same soil, the former should be applied some days in advance in order to convert the free lime into carbonate. N. H. J. M. Solubility of Phosphatic Manures in some Organic Acids. By WALTER F. SUTHERST (Chenz. News, 1901, 84, 199-200).-A gram of the phosphate and a gram of citric acid, or a quantity of acetic or tartaric acid to give the same total acidity, were made up to 100 C.C. with water, left in contact for 24 hours with frequent agitation, then filtered, and the phosphoric acid estimated in the solution with the following results per cent., calculated as tricalcium phosphate. Acetic acid.Tartaric acid. Citric acid. Coprolite.. ................... 10.1 3 32-60 17.17 Basic slag .................. 12.30 15.85 19.67 Basic superphosphate.. .... 18-53 28.37 24-79 Precipitated phosphate ... 43.72 78-12 71-27 The phosphates contained respectively 84.29, 29.13, 28*38, and 80.73 per cent. of phosphoric acid calculated as tricalcium phosphate. D. A. L. Manurial Experiments. By JOHN SEBELIEN (Bied. Cenfr., 1901, 30, 671-681 ; from Norsk. Landm-bl., 1901, Nos. 12, 13, and 14).- Excessiveamounts of artificialmanures (more than 10,000 kilos, of kainite per hectare) proved to be very injurious to peas, whilst more than 5000 kilos. of potassium sulphate were beneficial. I n the case of carrots, the large amount of kainite was not injurious, but slightly increased the yield (5.9 per cent.), whilst potassium phosphate increased the yield by 32 per cent.The injnrious effect of the kainite on peas lasted over the second year when the kainite was applied alone ; in the case of the plot which received an excessive amount of superphosphate in addition t o the kainite, there was no injury the second year. The results of pot experiments in which ammonium sulphate and sodium nitrate were compared showed no marked difference, except in absence of potassium, in which case the nitrate gave the greatest yield of barley straw and grain. Similar experiments with potassium chloride and sulphate showed that the chloride raised the yield of grain, whilst the sulphate increased the yield of st'raw. N. H. J. M. [Manurial] Action of various Calcium and Magnesium Compounds.By DIEDRICR &!!EYER (Chem. Centr., 1901, ii, 825; from Landw. Jcdnb., 30, 619-631).-1n pot experiments, i t was foundANALYTLCAL C'HEMiS'f HY. 45 that with a mixture of Eolium perenrze and lucerne and oats, addition of more than 1 gramof calcium oxide in the form of gypsum consider- ably diminished the yield. Potatoes were not affected by gypsum. Addition of calcium or magnesium carbonate prevented any injurious action by gypsum; addition of soil to the sand also reduced the injurious effect to a minimum, so that there can be no objection, in practice, t o the relatively small amounts of gypsum which are employed. Small amounts of magnesium carbonate increased the yield of LoZium and lucerne, whilst large amounts were injurious ; horse beans and vetches mere not injured by large quantities. Calcium carbonate may be almost completely replaced by magnesium carbonate, but a mixture of the two gives the best results, even-when anexcess of lime is present.Dolomite marl is therefore at least as suitable as pure lime marl. Drainage Water. By CREYDT, CONRAD VON SEELRORST, andl WILMS (J. Landw., 1901, 49, 251--275).-The field from which thf? drainage was collected had an area of 4.81 hectares. The cropping; had been as follows: 1897, roots; 1898, wheat; 1899, beans, andl 1900, roots, The manures applied were ammonium sulphate, sodiurri nitrate, and superphosphate. The daily amounts of rainfall and th(3 estimated amounts of drainage from July, 1899, to August, 1900, an3 given in tables. Analyses were made in a large number of mixeci samples of the drainage. It was found that in winter there was more drainage than rain, and the constituents of the winter drainage were therefore not derivetl from the surface of the field alone. The maximum and minimum amounts of the different substanceis forind in the drainage were as follows: K,O, 1.75-3-69 ; CaO, 157*0-184.0 ; RilgO, 31.3-46-4 ; SO,, 43.5-59.2 ; and N,O,, 1 .O-S*2 per million. Increased temperature seemed to increase thfe amount of lime, owing to greater production of carbon dioxide. Tracej3 of phosphoric acid were always present in the drainage. The estimated losses per hectare are as follows : K,O, 8-4; CaO, 630 ; 2fig-0, 'ik'b ; BO,, I%% ; ax& I 3 , 4% ' ~ 3 0 s . Tne 'loss of pobassium is very slight, whilst that of phosphoric acid is still less. N. H. J. M. N. H. J. Rf.

ISSN:0368-1769    

DOI:10.1039/CA9028205038

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

ANALYTLCAL C'HEMiS'f HY. Analytical Chemistry, 45 Microcheinical Test for Alkalis and Acids ; Detection of small Qantities of Ozone and Water. By FRIEDRICH ERIICH (Xonatsh., 1901, 22, 670-678).-As a microchemical test for alkalis and acids, the author uses silk dyed either with red or blue litmus. A drop (0.95 mg.) of the liquid the reaction of which is to be tested is placed on a glass slide and observed under a microscope magnifying46 ABSTRACTS OF CHEMICAL PAPERS. 200 times, a condenser being used. Into this drop, a silk thread coloured with litmus is introduced. It is found that a perceptible colour change is given by the following quantities of alkalis, stated as millionths of a milligram ; 0.3 of sodium or potassium hydroxide, lithium, or czesiixm carbonate ; 0.5 of sodium, potassium, or rubidium carbonate; 30 of barium hydroxide and 10 of calcium hydroxide; and of acids 0.5 of sulphuric, hydrochloric, or nitric acid ; 1 of oxalic and 3 of acetic acid.Solutions of lithium, potassium, or rubidium carbonate, which have no effect on the colour of the flame, will yet give a marked reaction with the above reagent. Silk coloured with litmus can also be used for the detection of ozone, in the presence of potassium iodide or potassium ferrocyanide when red litmus is used, or of sulphur or potassium thiocyanate with blue litmus. Methods of Standardising Acid Solutions. By CYRIL G. HOPKINS (J. Amer. Chem. Xoc., 1901, 23, 727--740).-The author has studied the respective merits of the following irtethods for standard- king volumetric acids : the silver chloride method, conversion into ammonium sulphate, use of metallic sodium, use of pure crystallised borax, electrolysis of copper sulphate, and standardising oxalic acid by means of metallic iron and potassium permanganate. Of these, the first two methods gave the best results.I n the silver chloridemethod, a carefully measured quantity of approxi- mately correct hydrochloric acid is precipitated with silver nitrate and the resulting silver chloride is collected in a Gooch crucible, washed, dried at 130-150°, and weighed. The ammonium sul- phate method consists in neutralising a definite volume of approxi- mately correct sulphuric acid with ammonia and drying the residue at Normal Alkalis and Indicators in Acidimetry. By C. A. JUNGCLAUSSEN (Chew.Centr., 1901, ii, 896--S97 ; from Apotl~. Zed., 16, 664--666).--Normal potassium hydroxide may be conveniently made from fresh ordinary ‘( caustic potash purified by alcohol.” The solution should then be standnrdised with normal hydrochloric or oxalic acid, phenolphthalein being used as indicator. Although the solution may not be free from carbon dioxide, this does not matter in the least whether titrating from acidity to alkalinity or the reverse way, pro- vided the liquid is cold and t h a t phenolphthalein is employed. A deci- or centi-normal solution may be prepared from the above normal solution and used for the titration from acid to alkaline reac- tion only, using iodeosin as indicator ; the solutions should, however, be checked with N/10 o r N/100 hydrochloric acid and the necessary correction applied.In cases where haematoxylin is used as indicator, the alkali should be completely freed from carbon dioxide by cautious addition of barium By LUDWIG W. WINKLER (Zeit. anal. Clhern., 1901, 40, 596 -600).-In titrating chlorides by Mohr’s method, the rerjnlts are seriously too high when K. J. P. 0. 120’ (compare Weinig, Abstr., 1893, ii, 245). L. DE K. hydroxide. L. DE K. Estimation of Chlorine in Natural Waters.ANALYTICAL CHEMISTRY. 47 the chlorine present is less than 25 mg. per litre, because a certain amount of silver nitrate is needed to produce a visible precipitate of silver chromate. Using a silver nitrate solution, of which 1 C.C. equals 0.001 gram of chlorine, the amount to be subtracted, when working in the manner here prescribed, is shown in the following table : Solution used, c.c.....0'2 0.3 0'4 0.5 0-6 0.7 0.8 0.9 1.0 2.0 Correction, C.C. ....... 0'2 0.25 0'3 0.33 0-36 0'38 0.39 0'40 0'41 0'4-2 From 2 C.C. up to 10 c.c., the correction increases regularly by 0.02 C.C. for each additional C.C. of solution used. I n each of two bottles of 150 C.C. capacity, there is placed 1 C.C. of a 1 per cent. solution of potassium chromate. To the first bottle is added about 90 C.C. of the water to be titrated and just enough silver solution to produce a red colour, which is then removed by another 10 C.C. of the water. This mixture then serves as a standard for com- parison. To the second bottle, 100 C.C. of the water are added and then silver nitrate until a just visible red coloiir persists for 5-10 minutes.The bottles must be protected from light as'much as possible. The re- sults of some titrations of very weak chloride solutions show that even when the correction is three times the amount to be estimated, very close agreement with gravimetric determinations can be obtained. M. J. 8. Estimation of Sulphur and Phosphorus in Iron and Steel. By UEALDO ANTONY (Gaxxetta, 1901, 31, ii, 274-277).-To rapidly determine sulphur and phosphorus in iron, the author recommends the use of an oxidising mixture consisting of 4 parts of manganese dioxide, 1 of potassium permanganate, and 2 of dry sodium carbonate, the procedure being as follows : 5 grams of the finely powdered sample are well mixed in a platinum crucible with 40 grams of this oxidising mixture, a layer of the latter being also laid on the surface and the whole heated gradually at first, afterwards more strongly, and finally to a bright red heat by means of a blowpipe flame, the mass being meanwhile kept well stirred with a platinum wire.When cool, i t is extracted with boiling water, the filtrate acidified with nitric acid and evaporated to a volume of about 30 c.c., t o which is added a little ferric chloride, then ammonium chloride and ammonia, the liquid being then heated and filtered ; by this means, silica, phosphates, and arsenates are removed. The filtrate is used for the estimation of the sulphur as barium sulphate, whilst the precipitate is dissolved in hydro- chloric acid, the solution evaporated to dryness, and the residue main- tained for some time a t 120-130°, t,o insure the insolubility of the silica.The mass is then dissolved in dilute hydrochloric acid and any arsenic removed by means of hydrogen sulphide, the excess of whichis then boiled off. Ammonium molybdate is then added to precipitate the phosphoric acid, which is afterwards reprecipitated as ammonium magnesium phosphate and weighed as magnesium pyrophosphste. Other elements, such as tungsten, chromium, sto., often present in steel, can also be detected and determined by this method. T. H. P.48 ABSTRACTS OF CHEMICAL PAPERS, New Nitrometer for use with the Sprengel Pump. By GIUSEPPE ODDO (Gazxettcc, 1901, 31, ii, 215-217),-This nitrometer, which is especially adapted for collecting and measuring nitrogen in its estimation in organic compounds, is a modification of Schiff’s and is fitted near the bottom with three apertures, one for running off the mercury, the second for connecting with the Sprengel pump, and the last, which is slightly above the other two, for the entry of the potash solution.A sketch of the apparatus is given. T. H. P. Action of Ammonium Carbonate on the Arsenic Sulphides By LUDWIG VANINO and C. GRIEBEL (Zeit. anal. Chem., 1901, 40, 589--591).-Solutions of arsenious or arsenic sulphide in ammonium carbonate should, when acidified, yield in the form of sulphide the whole of the arsenic they contain, without the necessity for adding hydrogen sulphide. Practically, however, some hydrogen sulphide is always given oft’ on adding acid, and the precipitation is consequently incomplete.If, however, the solution is largely diluted and acidified in a bottle, which is then closed for 24 hours, the hydrogen sulphide is re- absorbed and every trace of arsenic is precipitated. If a n open vessel is used, or a concentrated solution is acidified, addition of hydrogen sulphide is indispensable. I n separating the arsenic sulphides from those of tin and antimony by concentrated hydrochloric acid, boiling must be avoided, or a loss of arsenic by volatilisation will occur. AT. J. S. Gravimetric Estimation of Boric Acid. By ALFRED PARTHEIL and J. A. KOSE (Bey., 1901, 34, 3611--3612).--The distribution ratio obtained by shaking N/10 boric acid solution witb ether at 26’ is 34.2 : 1. The boric acid solution, acidified with hydrochloric acid, is extracted with ether for some 18 hours in a specially constructed extractor or ‘ perforator,’ in which the ether is made to work i t s way continually t.hrough the aqueous solution contained in a spiral tube, The flask containing the ethereal solution is afterwards placed in a vacuum desiccator over sulphuric acid and the residue weighed.The ether must not be distilled off at the atmospheric pressure, as boric acid volatilises with ether vapour. The method gives good results and may be employed for estimating the acid in various minerals. Sulphuric, phosphoric, and nitric acids, or appreciable amounts of iron, must not be present. J. J. 8. Separation and Estimation of small amounts of Potassium in Saline Mixtures. By FREDEEIK H. VAN LEENT (Zeit.anal. ChenL., 1901,40, 569--5’73).-From solutions containing small amounts of potassium with large quantities of sodium chloride, magnesium and calcium salts, the potassium is best separated a s potassium cobalti- nitrite, after which it may be weighed as perchlorate or platinichloride. The calcium and most of the magnesium should be removed by sodium carbonate. The filtrate is then slightly acidified with acetic acid and treated with ths .cobalt reagent, which is prepared by mixing, just heFore use, equal volumes of sodium nitrite solution (180 grams per litre) and cobalt solution containing 19.16 grams of crystallised cobaltANALYTICAT, CHEMISTRY. 49 chloride, and 50 C.C. of glacial acetic acid in a litre. The precipitate is allowed to subside for 6-7 hours a t 40-50°, and then all night in the cold, and after collecting on a filter is washed once with the re- agent and then thoroughly with 80 per cent.alcohol. The dried pre- cipitate is decomposed by evaporating with hydrochloric acid ; per- chloric acid is then added, and the mixture evaporated until white fumes are given off. The potassium perchlorate is triturated and washed with 96 per cent. alcohol, to which 0.2 per cent. of perchloric acid has been added, and then on the filter with ether-alcohol. I t is dried on the filter at 120-130' and weighed. For weighing as platinichloride, the yellow prezipitate should be decomposed by gentle ignition, the potassium nitrite dissolved out by a weak sodium chloride solution (to prevent the cobalt oxide from passing through the filter), and evaporated with hydrochloric acid to convert it into potassium chloride.34. J. S. Ekdima&ion of Byd,r,nlrlde in the P*r&%Rce of AJkaJi Carbonate. By W. E. RIDENOUR (Chem. News, l901,84,202).-The author has tested the process of titration of alkali hydroxide in the presence of carbonate, using first phenolphthalein and then methyl- orange; he finds that phenolphthalein does not indicate half the carbonate, either alone or in presence of the hydroxide. To ascertain the number of C.C. of normal acid corresponding with the carbonate in a mixture of alkali hydroxide and carbonate he multiplies by 3 the number of c,c. of normal acid indicated by methyl-orange, using phenol- phthalein, then methyl-0ran.e. and divides Qv 104.5726.D. A. L. Estimation of Cadmium. By EDRIUND H. MILLER and ROBERT W. PAGX (Zeit. an0s.g. Chepnz., 1901, 28, 233-241).-The electrolytic method of estimating cadmium is convenient and gives trustworthy results if care is taken t o avoid a large excess of potassium cyanide and the presence of other salts. A current of 0.1 to 0.15 ampere is employed and the estimation takes about 16 hours, The estimation by precipitation with sodium carbonate gives very unsatisfactory results. A convenient and accurate method is to precipitate the cold neutral cadmium solution with an excess of diammonium phosphate. The precipitate must be allowed to remain f o r some time and is then transferred to a weighed filter aiid dried a t 1 0 5 O , or is converted into pyrophosphate and then weighed.The solution must not be heated, since the precipitate of ammonium cadmium phosphate gives off ammonia on boiling and is partially converted into cadmium ortho- phosphate. E. C. R. Estimation of Mercury in Antiseptic Solutions containing Mercuric Chloride, Iodide, or Cyanide. By G. MEILLERE (J. Pharm. Chim., 1901,[vi],14,356--359).-Attention is drawn to the fact that mercurial antiseptic solutions contain, as a rule, other substances besides the mercury salt, so that mere evaporation of the solution and weighing the residue gives erroneous results. With solutions con- taining mercuric chloride or iodide, accurate results may be obtained by extracting them with ethyl acetatme and veighing the residue VOL. LXSXIJ. ii. 450 ABSTRACTS OF CHEMICAL PAPERS.left on evaporation of the ethereal solution. Mercuric cyanide may be estimated by means of a standard solution of iodine in the presence of an excess of an alkali hydrogen carbonate. It is necessary t o add a n excess of the iodine solution, which excess may be estimated by means of a standard solution of sodium thiosnlphate. H. R. LE S. Gravimetric and Volumetric Estimation of Mercury, Copper, and Zinc. By ROBERT COHN (Bey., 1901, 34, 3502--3508).- Volumetric estimation of mercury.--An excess of ~11/10 ammonium thiocyanate is added to the solution of mercury and the excess determined after the addition of nitric acid and ferric alum by means of N/lO silver nitrate; it is best in the titration to add more silver nitrate than is necessary for decolorisation, and to titrate back with the thiocyanate as in Volhard’s method.The method depends on the formation of sparingly soluble, non-dissociating mercury thiocyanate, Volumetric estimation of copper and zinc.-A solution of mercuric chloride (0.1 mol.) and ammonium thiocyanate (0.4 mol.) in water (1 litre) is standardised by means of N/10 silver nitrate according t o Volhard’s method ; on adding t o an excess of this a known volume of the copper or zinc solution, a precipitate of the type M”Hg(SCN), is formed, and, after filtering, an aliquot portion of the liquid is titrated againpt the silver nitrate solution. From the difference in the values for the titration of the same quantity of mercuric thiocyanate solution before and after precipitation, the amount of copper or zinc follows from the relationship Cu(or Zn) : SCN = 1 : 2.The equations involved are, for example, (1) HgCI, + 4NH,SCN + 4AgN0, = Hg(SCN), + 2AgSCN Hg(SCN),,Cu(SCN), + 2AgC1+ K,SO, + SNH,NO,. Gravirnetric estimation of the three metals.-In the case of copper and of zinc, the precipitate of the type MHg(SCN), is left for two hours i n the cold, filtered, and ignited ; with copper, the filter paper and precipitate are burned together, and when a large quantity has t o be weighed, the product is converted into cuprous sulphide by reduction in a stream of hydrogen and the addition of sulphur. With smaller amounts, the product is ignited with pure mercuric oxide, and weighed as copper oxide. I n the case of zinc, the procedure is similar, but the filter paper has to be initially removed.To estimate mercury, it is precipitated b y a solution of zinc sulphate (1 rriol.) and alkali thiocyanate ( 4 mols.), and the zinc oxide, ultimately obtained, weighed. H!dCNS),. + 2AgCl+ 4NH,NO, ; (2) HgCI, + 4NH4SCN + CUSO, + 2AgN0, = W. A. D. Volumetric Estimation of Manganese. By HUGH RAMABE (C”1~e.m.. News. 1901, 84, 209-210).-To correct for various incidental reactions, the method for titrating manganese described by the author and Reddrop (Trans., 1895, 47, 268) has been modified so far as wrought iron, steel, and pig-iron are concerned:-1.1 gram of the sample is dissolved by boiling with 30 C.C. of dilute nitric acid, the solu- tion is cooled, then boiled for 3 minutes with 0.5 gram, or more, of sodium bismuthate, cooled again, treated with a slight excess of sulphurous acid, reoxidised with 1.5 gram of sodium bismuthate, and filtered.Hydrogen peroxide is run in at first until the reddish colour givesANALYTICAL CHEMISTRY. 51 place to a clear yellow solution, then 0.6 to 1.0 in excess is added. The solution is titrated with N/10 permanganate. D. A. L. Detection of Chromic Acid by Hydrogen Peroxide in presence of Vanadic Acid. By C. REICHARD (Zeit. ccntcl. Chem., 1901, 40, 577--586).--The blue colour attributed to perchromic acid, produced by the action of hydrogen peroxide on chromic acid, is destroyed or prevented by the addition of vanadic acid with production of a brown colour. The blue ethereal solution of perchromic acid is decolorised by ammonium metavanadate. Addition of sodium phosphate or arsenate annuls the action of vanadic acid ; a nitrate has no such effect.Molybdates and tungstates also destroy perchromic acid, but not so energetically as vanadates. Estimation of Uranium. By EDWARD F. KERN (J. Amer. Chem. Xoc., 1901, 23, 685-’726).-Uranium solutions may be freed from the- metals of the fifth or sixth group by a current of hydrogen sulphide providing 50 parts of the liquid contain no more than 1 part of free hydrochloric or nitric acid. From metals-of the third or fourth group, it may be isolated by boiling for 15 minutes with a large excess of sodium carbonate. Ferric iron may be completely separated from uranium by shaking the hydrochloric acid solution three times in succession with pure ether; it is, however, essential that the acid should have a sp.gr. of 1-1 and that the ether be previously saturated with the acid. From an acetic acid solution containing alkalis or alkaline earths, uranium may be precipitated as hydrated oxide, U30$,3H,0, by electrolysis, or i t may be separated by a thrice repeated precipitation in a hot solution with ammonia in the presence of ammon- ium chloride ; the ammonium uranate, at first slimy and yellow, becomes darker and crystalline after 20 minutes’ boiling and is readily con- verted into U,O, by ignition over the blast with free access of air. Uranium may be also separated from alkalis by precipitating the boiling liquid with ammonium phosphate in the presence of ammonium acetate. After boiling for 15 minutes, the precipitate becomes crys- talline, and, like the ammonium uranate, it is washed with a 2.5 per cent.solution of ammonium chloride and then ignited i n a porcelain crucible. It is then moistened with nitric acid, reignited, and weighed as uranyl pyrophosphate. Several methods are given for the separa- tion of uranium from phosphoric acid, the most convenient process being the treatment of the nitric acid solution with metallic tin a t the boiling temperature. The most rapid estimation of uracium is accomplished by reducing the sulphuric acid solution with metallic zinc and titrating the resulting uranous sulphate with standard per- manganate in an atmosphere of carbon dioxide. Full particulars will be found in the original paper. Reduction of a hydrochloric acid solution either by zinc or stannous chloride gives unsatisfactory results.The assay of uraninite (pitchblende) is best made by the ether method, which is briefly as follows : The mineral is dissolved in nitric acid and repeatedly evaporated with addition of hydrochloric acid. After removing lead, copper, &c., by hydrogen sulphide, the filtrate is M. J. S.52 ABSTRACTS OF CHEMICAL PAPERS. boiled and oxidised with nitric acid and precipitated whilst boiling with ammonia. The precipitate which also contains ammonium uranabe, is, after washing, dissolved in hydrochloric acid and agitated with ether to remove the ferric chloride. The aqueous acid solution is nearly neutralised with ammonia and then boiled with a large excess of ammonium carbonate. The filtrate which contains the uranium is then boiled down to a small bulk, the precipitate redissolved by addition of hydrochloric acid, and the solution again boiled t o expel carbon dioxide.The uranium is then precipitated as directed by ammonia, or by ammonium phosphate, or estimated volumetrically after expelling the chlorine by means of sulphuric acid, or precipitated by electrolysis. Some ores of uranium such as carnotite contain vanadium. This may be got rid of by simply evaporating the nitric acid solution to dryness, and dissolving the residue in a hot solution of ammonium nitrate which dissolves the uranium and leaves the vanadium un- dissolved; no phosphates should be present. I t may also be re- moved by excess of sodium hydroxide or by neutralising the nitric acid solution with mercuric oxide and then adding mercurous nitrate.L. DE K. Detection and Estimation of Traces of Antimony in presence of large quantities of Arsenic. By GEORGIES DENIGBS (Compt. rend., 1901, 133, 688-689).-1f tin is used instead of zinc in contact with platinum for the detection of antimony by deposition on the platinum in the form of a dark stain, the reaction becomes much more delicate and will detect 0.002 mg. of antimony in 0.05 C.C. of hydro- chloric acid (1 : 4) provided that the quantity of arsenic present does not exceed 5 mg. per C.C. The rapidity with which the stain appears is a function of the quantity of antimony present and for a given time the depth of the stain is also a function of that quantity. The reaction can be used quantitatively by making precisely similar tests with solutions containing known quantities of antimony.A still more sensitive reaction is obtained with antimony cssium iodide. The antimony compound is dissolved in dilute hydrochloric acid (1 : 4) or dilute sulphuric acid (1 : lo), and the reagent is made by dissolving 1 gram of potassium iodide and 3 grams of czesium chloride in 10 C.C. of water. A drop of the antimony solution and one of the reagent are mixed and examined uader the microscope, when the antimony cmium iodide is seen to form in yellow or garnet-red hexagonal lamells, often grouped in stellate macles. The reaction will detect 0*0001 mg. of antimony in presence of 500 times the quantity of arsenic. I t is important that the quantity of arsenic does not exceed 50 mg. per c.c., as with a larger quantity iodine will probably be liberated.Qnantitative results can be obtained by the method of comparison. c. 13. B. Analysis of White Metal Alloys, By FRED IBBOTSON and HARRY BREARLEY (Clhem. News, 1901, 84, 167--169).-Antimony as precipitated reduces solutions of stannic chloride in the cold very slowly, whereas pulverised smelted antimony is inactive. The authors thereforeANALYTICAL CHEMISTRY. 53 employ the latter a t the boiling point in place of iron for the estima- tion of tin, With finely powdered metal, the reduction takes place rapidly, and when complete the solution is allowed to cool in an atmosphere of carbon dioxide and titrated with iodine. One-fifth the volume oE strong hydrochloric acid is usually employed, but in the presence of copper one-third the volume is used, and in the presence of lead there must be plenty of acid to prevent the formation of cuprous iodide in the one case, or lead iodide in the other.Iron, chromium, nickel, zinc, manganese, aluminium, bismuth, tungsten, phosphorus, sulphur, mercury, molybdenum, and cobalt are inactive or exert a negligible influence in the cold. Arsenic, however, is precipitated and carries some tin with it; and in the case of antimony, when iron is used for the reduction, the tin is all reduced before the appearance of the antimony, a result which serves as an indication that all the stannic chloride is reduced. D. A. L. Estimation of Chloroform. By WILLIAM A. PUCKNER (Pl~cwnz. Arch,, 1901, 4, 124-128).-The following process is recommended as being particularly suitable for the estimation of chloroform in a mixture of chloroform and ether.A quantity of the mixture equal to 0.05-0.2 gram of chloroform is put intoa strong flask containing 10 C.C. of N alcoholic potassium hydroxide free from chlorine, the flask is closed with a sound cork, covered with cloth and tied down firmly. After gently mixing the liquids, the flask is put in boiling water for 3 hours. When cold, the contents arecarefully neutralised with N sulphuric acid, using pheriolphthalein as indicator, and the chlor- ine is then estimated by means of silver nitrate and potassium chromate. Or the cold liquid may be acidified with nitric acid and titrated by Volhard’s thiocpanate process. From the amount of chlorine thus found, the percentage of chloroform in the mixture is readily calculated. If the percentage of chloroform in the sample is quite unknown, it may be determined approximately by digesting 1 C.C.for an hour with 25 C.C. of N alcoholic potassium hydroxide and titrating the excess of alkali, One C.C. of Nalkali consumed x 0,02977 equals the amount of chloroform per C.C. L. D E K . Estimation of Cyanide in the presence of a Chloride. By FRANK B. GATEHOUSE (Chem News, 1901, 84, 197).-When silver nitrate is added to a solution of potassium cyanide, the soluble double cyanide, KCN,AgCN, is first formed, pcnd no precipitate is obtained so long as there is cyanide in solution. Therefore, titration with N/lO silver nitrate until a permanent turbidity appears may be used to estimate the cyanide; each C.C.used =0*013036 gram of potassium cyanide. An equal volume of the N/lO solution is then added, the burette read, potassium chromate introduced as indicator, and the chloride estimated in the usual way. D. A. L. Estimation of Alcohol in Ether. By FRANZ FREYER (Chenz. Centr., 1901, ii, 900 ; from Zeit. Zandw. Verszcclk-Wes. Oesterr., 4, 955--959).-The amount of alcohol and water is estimated by agitat-54 ABSTBACTS OF CHEMICAL PAPERS. ing 20 C.C. of the sample with a saturated solution of calcium chlor- ide and noticing the diminution in volume. Twenty-five C.C. of the sample (which should not contain more than 1 gram of alcohol and water, otherwise it should be diluted with anhydrous ether) are put into an Erlenmeyer flask, iiiixed with 50 C.O.of a 10 per cent. solu- tion of acetyl chloride in chloroform and the flask closed with an india- rubber cork, through which passes a separating funnel containing 100 C.C. of water. After the lapse of an hour, a little of the water is in- troduced, and the whole well shaken and then titrated with 2 N alkali, phenolphthalein being used as indicator. A blank experiment is then made with 50 C.C. of the acetyl chloride solution, mixed with anhydrous ether, which is titrated in the same manner, The difference in the two titrations represents the alcohol, inasmuch as by the action of alcohol on acetyl chloride only 1 mol. of free acid is formed, whilst water liber- ates 2 mols. One C.C. of 2 N alkali = 0.092 gramor 0.1157 C.C. of alcohol. L. DE K. Quantitative Esterification and Estimation of Alcohols and Phenols.By ALBERT VERLEY and FR. BOLSING (Ber., 1901, 34, 3354--3358).-Esterifcation takes place rapidly and completely whena mixture of acetic anhydride and pyridine is used in p1ace:of acetic anhy- dride. For quantitative esterification, a mixture of 120 grams of acetic anhydride and 880 grams of pyridine is used ; this is titrated with stand- ard alkali, and again after heating with a known weight of the alcohol or phenol. The method has been successfully used with ethyl alcohol, amyl alcohol, cinnamic alcohol, menthol, phenylglycol, glycerol, phenol, P-naphthol, guaiacol, saligenin, thymol, eugenol, carvacrol, and santalol, but geraniol, terpineol, vanillin, benzyl alcohol, and linalool could not be satisfactorily determined by this method.Estimation of Eugenol in Oil of Cloves. By ALBERT VERLEY and FR. BGLSING (Ber., 1901, 34, 3359-3362).--Eugenol can be satisfactorily estimated in oil of cloves by quantitative esterification with a mixture of acetic acid and pyridine, provided that other phenols and alcohols are absent. Umney’s method (Pharm,J., 1895,25, [iii],950), in which the oil is extracted with 10 per cent, alkali and the residue weighed, is liable to large errors; Thorns’ method (Abstr., 1892, 250) gives small values with oils rich in terpenes. T. M. L. T. M. L. Nickel Salts as Reagents for Reducing Sugars. By MAURICE DUYK (Avzrz. Chim. ancd. appZ., 1901, 6, 364).-The reagent is best prepared by adding to 25 C.C. of a 20 per cent. solution of nickel sulphate 20 C.C. of aqueous sodium hydroxide of sp.gr. 1.33 and 3 grams of tartaric acid dissolved in 50 C.C. of water. A clear, slightly green liquid is thus obtained which does not change on boiling, but is a t once reduced on adding a reducing sugar, with separation of a lower oxide having a brown, or even intense black, colour. The re- agent is likely to be of great service in urine analysis, as it is not in the least affected by normal urine. Sollmann (Abstr., 1901, ii, 535) has also applied nickel salts, but his conclusions differ somewhat from those of the author. L. DE K.ANAT,YTICAL CHEMISTRY. 5 5 Detection of Sucrose in Plants by means of Invertin, and of Glucosides by means of Emulsin. By EMILE BOURQIJELOT (Compt. rend., 1901, 133, 690-692).-The presence of sucrose in vege- table extracts is most conveniently detected, and its quantity esti- mated, by the action of invsrtase, the rotatory power of the liquid being determined before and after the action of the ferment.Tnver- tase also hydrolyses gentianose and raffinose, but these substances are comparatively rare, and the products of hydrolysis are readily dis- tinguished from those of sucrose. Emulsin may be employed with advantage in the same manner for the detection and estimation of glucosides. For example, the pericarp of COCOS Yatai and the seed of asparagus were found to contain a considerable proportion of sucrose but no glucosides, whilst the rhizome of Xcrophularia nodosa contained a considerable quantity of a lzvorotatory glucoside. C. H. B. Estimation of Starch in the Grain of Cereals. By L ~ O N LINDET (J.Phama. C/’&L, 1901, [ vi], 14, 397-400. Compare Abstr., 1897, ii, 525).-The process only differs from the one previously de- scribed in that, instead of collecting the starch on a tared filter, the amylaceous liquid is siphoned off, and the starch which is left behind is washed by decantation, and then hydrolysed with dilute sulphuric acid. The resulting glucose and dextrin are then estimated by means of Fehling’s solution and the polarimeter. H. R. LE: 8. Estimation of Formaldehyde. By LUDWIG VANINO and E. SEITTER (Zeit. rind, Chew,., 1901, 40, 587-589).-An excess of potass- ium permanganate strongly acidified with sulphuric acid oxidises formaldehyde quantitatively to carbon dioxide and water. The pro- portions recommended are 30 grams of concentrated sulphuric acid, 50 C.C.of water (mixed and cooled), 35 C.C. of N/5 permanganate, and 5 C.C. of a 1 per cent. solution of formalin. After 10 minutes, the excessof permanganate is titrated by an empirical solution of hydrogen per- oxide. The results agiee well with those obtained by Romijn’s method, which is adopted by the Verein fur Chemische Industrie in Mainz [Abstr., 1900, ii, 326). M. J. 8. Some sources of Error in the Estimation of the Volatile Acidity of Wines. By CURTEL (Ann. Chim. ~ 6 d . appl., 1901, 6, 361--364).-The author states that the total acidity of a wine as found by direct experiment is always less than the sum of acids exist- ing in it, and has investigated the cause of this phenomenon. The volatile acids mill be found too high if the wine should contain neutral acetates or similar salts, as, on boiling, part of thoacid is liber- ated by the action of potassium hydrogen tartrate, or even tannic acid.Several experiments are given showing that the volatile acids thus formed may be equivalent to as much as 0.06 per cent. of acetic acid. Another serious source of error is the introduction of carbon dioxide by means of the steam which is passed through the wine when esti- mating the volatile acids. The steam should be generated from recently boiled distilled water. The error may amount to 0.029 per cent, expressed as acetic acid. A third, although less important, source5 G ABSTRACTS OF CHEMICAT, PAPERS. of error is the presence of ethyl acetate, which, when boiled with water, yields a faintly acid distillate, which may account for 0.009 per cent.of volatile acid. I n orcler to avoid these errors, the author first estimates the total acidity, less carbon dioxide. Twenty-five C.C. of the mine and 25 C.C. of water are introduced into a small flask furnished with a doubly per- forated cork and placed on a heated sand-bath, and steam is passed through at such n rate that the ?liquid does not undergo any sensible alteration in volume. After the lapse of an hour, the acidity is again determined, the difference between the two experiments being the volatile acidity. Supposed Use of Oxalic Acid for the Preparation of Hydro- ~ I I f i - ~ ~ ~ i d t ~ By AO-GVSTE ATiLvLGE (C~C[~G. Ccfltc, .i!&n~, ii, 834-835 ; from Xon. scient., [iv], 15, ii, 576. Compare Abstr., 1901, ii, 622).-The following process is proposed for the detection of oxalic acid in commercial hydrogen peroxide. Five hundred C.C. of the sample are evaporated to dryness on the water-bath with addition of pure sodium hydroxide, the well-dried residue is dissolved in dilute nitric acid, about 50 c.c.of water are added, together with calcium nitrate or chloride, and then excess of ammonia. The liquid is heated, the precipitate washed free from soluble salts by decantation, and then heated a t 50" with 30 C.C. of sulphuric acid of sp. gr. 1.2-1.4. The filtrate and washings are evaporated on the water-bath i n a vacuum until about 30 C.C. are left ; on cooling, any oxalic acid will crgstallise, and may then be further identified. The author has not as yet succeeded in detect- Probable Errors of Analysis resulting from the Presence of Salicylic Acid in Strawberries. By L. PORTES and A. DES- MOULI~RES (J. Pliaym., 1901, [ vi], 14, 342--351).-Compare this vol., ii, 40. L. DE K. ing oxalic acid in commercial hydrogen peroxide. L. DE K. New Process for the Detection and Estimation of Salicylic Acid. By HENR~ PELLET (Ann. Chirn. ancd fippZ., 1901,6, 364-365). -Twenty C.C. of the liquid to be tested are acidified and boiled down in a beaker and from time to time a cold stirrer is held over the liquid so as to condense the vapour, which is then tested for salicylic acid by dropping it on a slightly greased porcelain slab on which are placed minute' drops of ferric chloride. The author has noticed that no reaction will be obtained until the salicylic acid reaches the con- centration of 0*06-0*07 gram per litre. Supposing, therefore, that the liquid has to be boiled down to 6 C.C. before the test is obtained, then the 20 C.C. contain 10 : 6 =0*0006-7 or about 0*0004 gram of salicylic acid. Liquids containing much salicylic acid must first be suitably diluted. When dealing with wines, the process should be applied to the product resulting from the extraction of the wine with benzene. L. DE K

ISSN:0368-1769    

DOI:10.1039/CA9028205045

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

57 General and Physical Chemistry. A Method for the production of Coloured Flames. By STSCHEGLAYEW (Zeit. physikal. Chem., 1901,39, 11 1-1 13).-'I'o obtain a flame colonred by a metallic salt, lasting for n considerable time in a steady state, the author suggests a blast of air blown horizontally into the surface layer of a saturated solution of the salt and then forming the air current of a bunsen burner. It is stated that if a motor be eniployed to yield a regular air stream at about 60 mm. pressure, most satisfactory results are obtained. L. M. J. Photographs of Spark Spectra. I. Ultra-violet Spark Spectra of Iron, Cobalt, Nickel, Ruthenium, Rhodium, Pallad- ium, Osmium, Iridium, Platinum, Potassium Chromate, Potassium Permanganate, and Gold. By WALTER E. ADENEY (Trans. Roy.Dublin Soc., 1901, ii, 7, 331--338).-Reference must be made to the photographic reproductions accompanying the paper. I n these, many lines observed by Eder and Valenta, as well as by Exner and Haschek, are absent, probably owing, in the majority of cases, to the different methods of sparking employed. J. C. P. Theory of Fluorescence. By WOLDEMAR VOIGT (Arch. NZer. sci. exact. nat., 1901, [ ii], 6, 352-366).-Fluorescent and phosphor- escent phenomena are due to free, incoherent vibrations within the excited substance. The author discusses the electron theory and from results so far obtained concludes that the molecules of fluorescing substances are capable of existing in two conditions, in which the electrons have different periods of vibration. The change from one state to the other is conditioned by molecular relationships, but an exciting light wave has also the power of aiding or starting the transi- tion.The electrons pass into the new condition with speeds and elongations which are influenced by the motion given t o them by the exciting wave in the old condition and they perform free, incoherent vibrations with a period corresponding with the new condition. The periods of vibration in the two conditions are very different and one is damped to a much greater extent than the other. J. McC. Chemical Effects produced by Radium Radiations. By HENRI BECQUEREL (Compt. rend., 1901, 133, 709--712).-Various chemical ef-fects produced by radiations from radium have been already observed, as, for example, the action on silver gelatino-bromide, or barium platinocyanide, destructive action on the skin, the coloration produced in rock salt, sylvite, and in varieties of glass or porcelain. The author has observed the following additional actions.(1) The transformation of yellow phosphorus into red, which may be brought about by immersing a sealed glass tube containing radium, enveloped in alnminium foil, into a glass vessel containing the phosphorus, the whole being kept in the dark. The transformation does not continue LXXXII. ii. 558 ABSTRACTS OF CREMTCAL PAPERS. after the removal of the radium. (2) The reduction of mercuric chloride by oxalic acid which takes place in the dark if the radium tube be placed in the mixed solutions. (3) Destruction of the germin- ative power of seeds by exposure to the radiation before planting.Mustard and cress seeds were divided into two portions, of which one was exposed for a week or more to the radiations ; none of the seeds so exposed germinated, whilst of the others used for comparison, 80 per cent. germinated. L. M. J. Induced Radioactivity excited by Radium Salts. By P. CURIE and A. DEBIERNE (Compt. rend., 1901,133,931-934. Compare Abstr., 1901, ii, 216,298).-Tho phenomena of induced radioactivity excited by radium salts are more regular, and the activity is more intense, when an aqueous solution is used instead of the solid salt, The intensity of the induced activity is the same for all substances, whatever their chemical. nature, under the same conditions, and is independent of the pressure of the gas surrounding the exciting and excited bodies.The induced radiation, like the exciting radiation, consists of some rays which are de- flected in a magnetic field and some which are not. Other conditions being the same, the intensity of the induced radiation depends on the free space in front of the excited body; if, for example, several copper plates are placed parallel with one another and about 1 rum. apart, they acquire little activity, but if about 30 mm. apart they all become strongly active. The intensity of the radioactivity which can be excited in a given enclosure depends only on the quantity of radium introduced into it in the form of a solution. The glass of the enclosing vessel generally becomes luminous, and the luminosity finally acquired by any part of the vessel is independent of the position of the radium solution.If a radium solution and zinc sulphide are placed in separate flasks connected by a glass tube bent twice at right angles, the sulphide becomes and remains phosphorescent, and a t the same time exhibits radioactivity, the intensity of the activity being independent of the phosphorescence and equal to that which would be acquired by any other substance under the same conditions. C. H. B. Influence of Radioactive Substances on the Luminescence of Gases. By ALEXANDER DE HEMPTINNE (Compt. vend., 1901, 133, 934-935).-Gases subjected to the influence of radioactive substances become luminous under the electric discharge at higher pressures than under normal conditions. I n this respect,, the Becquerel rays, therefore, resemble Rontgen rays; in both cases also the phenomenon is more marked the higher the molecular weight of the gas.Electromotive Efficiency of the Elementary Gases. 11. Note by EMIL BOSE (Zeit. physikal. Chem., 1901, 39, 114).-A note in which the author acknowledges priority of Richarz regarding some points of his work on this subject (Ahstr., 1901, ii, 589). Observations on the Determination of Transport Numbers of the Ions during Electrolysis of their Solutions. The Be- haviour of Diaphragms during the Electrolysis. By WILHELM HITTORF (Arch. Nger. sci. exact. nat., 1901, [ii], 6, 671-688).--The C. H. B. L. M. J.GENERAL AND PHYSICAL CHEMISTRY. 59 transport numbers recently determined do not in all cases agree with the early determinations of the author, and the divergence is greater than can be accounted for by experimental error.This led the author to a n examination of the influence of diaphragms of porous porcelain, fine silk, and animal membrane in the conductivity cell. These diaphragms are used to keep the concentration of the electrolyte in the middle unchanged by preventing diffusion. I n the case of copper salphate, silver nitrate, and the chlorides of potassium, ammonium, sodium, barium, calcium, magnesium, and cadmium, the transport number is the same whether no diaphragm or one of silk or porous por- celain be used. With cadmium chloride, when animal membrane is used, the transport number of the cation is smaller than when no diaphragm is used. The animal membrane has the power of separating the solution into a more and a less concentrated part, and the less concentrated solution goes in the direction of the negative current, in this way leaving the solution round the cathode more dilute than it would be if no diaphragm were used.The use of animal membrane as diaphragm is without influence on the transport numbers of the ions of the chlorides of potassium, ammonium, and sodium. J. McC. Dissociation of certain Acids, Bases, and Salts at Different Temperatures. By HARRY C. JONES and JAMES M. DOUGLAS (Amel.. Chem. J., 1901, 26, 42S--453j.-The substances investigated mere hydrochloric, nitric, and sulphuric acids, potassium hydroxide, chloride, bromide, iodide, nitrate, sulphate and permanganate, sodium nitrate and ammonium nitrate.The temperature coefficient of conductivity increases (1) with dilution for acids, bases, and snlts ; (2) with rise of temperature for salts ; in the case of acids and bases, chnuge of temper- ature has no appreciable effect on the temperature coefficient of con- ductivity. The amount of dissociation in solutions of the above sub- stances, as measured by the conductivity, is independent of the temper- ature. This fact, in conjunction with the observation that the conductivity of the solutions increases with the temperature, shows that rise of temperature affects the velocities of the ions. J. C. P. Effect of Temperature and Moisture on the Emanation of Phosphorus, and a Distinction in the Behaviour of Nuclei and of Ions. By CARL BARUS (Amer. J. Sci., 1901, [iv], 12, 327-346).-A physical paper dealing with the ionisation of air by its passage over phosphorus at various temperatures.J. c1. P. Pressure as Supplement to Temperature in the Phenomenon of Inflammation. By WALTHERE SPRING ( A ~ c h . N6er. sci. exact. nat., 1901, [ii], 6, 257-261).--No combination took place on subject- i n g an intimate mixture of 2 mols. of cupric oxide and 3 mols. of sulphur to a pressure of 10,000 atmospheres. Combination took place violently when the pressure on a mixture of 2 mols. of cuprous oxide and 3 mols. of sulphur rose to 8000 atmospheres; the pressure was increased gradually so that no heating by compression took place. Sulphur dioxide was formed and the residue consisted only of cuprous sulphide ( 2Cu20 + 3s = 2Cu2S -f- SO,).The ignition temperature of this 5-260 ABSTRACTS OF CHEMICAL PAPERS, mixture at the ordinary pressure is about 126', and pressure to the extent of SO00 atmospheres has the effect of lowering this by moro than 1 0 0 O . The ignition temperature of the mixture of cupric oxide and sulphur could not be determined for the sulphur inflamed at 350°, but it must be higher than this. It would appear that the point of inflam- mation is a function of the pressure, and the experirnents are being continued to ascertain if this is quite general. J. McC. Isotherms for Mixtures of Hydrogen Chloride and Ethane. By N. QUINT GZN (Zeit. physika2. Chem., 1901, 38, 14-26).-1so- therms for hydrogen chloride, ethane, and mixtures containing S6*S3, 59.68, 38.33, and 28-59 per cent. of hydrogen chloride respect- ively, were determined at temperatures from 15' to 55' and the critical phenomena investigated.The mixtures behave very similarly to the mixture of nitrous oxide and ethane investigated by Kuenen (Abstr., 1896, ii, lo), and the author uses his results to test the validity of vander Waals' expression in the case of mixtures. Satisfactory agreement between calculated and observed numbers is obtained. L. M. J. Minimum Value of the Total Heat of Combination. By ROBERT DE FORCRAND (Compt. rend., 1901, 1.33, 681-684).-Thc, author has previoiisly enunciated the relation(L + s)/Y'= 30, or, in the! case of a dissociative change in which a gas isproduced, ( A -t S+ q)/T= 30,where q is the heat of combination. I n the case of a gas and a dis-.sociable compound of this gas, therefore, ( L + S)/T = (,L+X+q)/T'' = 30, hence q/(T' - T) = 30, that is, the heat of combination is propor- tional to the elevation of the boiling point, and when T- T is small, L + X+ q (or the total heat of combination, Q) approximates to L + 8., This deduction is tested chiefly by examples of compounds of ammonia, with metallic salts, in which the value T" is but slightly greater than 234*5',the boiling point of ammonia, for each of which also the totall heat of combination is about 7 to 8 C d , the value L + X for ammonia, being calculated as 7.03 Cal. (Abstr., 1901, ii, 372, 594). L. M. J. Determination of the Heat of Dissociation and of Combus - tion of Acetylene, Ethylene, and Methane. By WILLIAM G,, MIXTER (Amer. J. Sci., 1901, [iv], 12, 347-357).--The heat of disso-.ciation of acetylene is found by explosion in a bomb to be 53300 cnl,, (Thomsen, 47770 cal, ; Berthelot,, 51400 cal.) ; the heat of combustionl of acetylene is 313800 cal. (Thomeen, 310050 cal. ; Berthelot, 3157001 cal.). The heat of dissociation of ethylene was found by exploding a, mixture of ethylene and acetylene, and subtracting the thermal effect; due t o the acetylene ; the author's results vary rz good deal, but indi-, cate that ethylene may be more endothermic than has been supposed The heat of combustion of ethylene is 345800 cal. (Thomsen, 3333501 cal. ; Berthelot, 341100 cal.). The heat of dissociation of methane:, determined in the manner described for ethylene, is found to be, - 19000 cal. (Thomsen, - 211iO cal.; Berthelot, - 21500 cal.). J. C. P.GENERAL AND PHYSICAL CHEMISTRY. 61 New Method of representing Heats of Solution. By HENDRIK W. BAKHUIS ROOZEBOOM (Arch. N&r. sci. exact. nat., 1901, [ii], 6, 430-441).-The heat of solution can best be represented diagramatically by referring the concentration of the solution, not as is usually done, to the number of mols. OF solvent per mol. of dissolved substance, but so that the sum of the number of molecules of solvent and dissolved sub- stance is equal to unity (or 100). The advantage gained is that the curve obtained is a complete one and does not run to infinity. Three forms of curve for heat of mixture of liquid components are known : (1) positive heats only; (2) negative heats only; (3) positive and negative heats according to the relative quantities of the components.The heat of solution of solid substances can be easily obtained from these heat of mixture curves if the heat of fusion is known, and from them also can be deduced the theoretical heat of solution, that is, the heat change which occurs when 1 mol. of salt is dissolved in an infinite quantity of its saturated solution, J. McC. Fusion and Crystallisation. The Theory of Tammann. By PIERRE DUHEM (Arch. NSer. sci. exact. ncct., 1901, [ii], 6, 93-102).- According to the Clausius formula dY’/dP = l/E.Y’/L.(v’ - u) for the variation of the point of fusion with the pressure, in which P is the pressure, 1’ the fusion point a t pressure P, L the heat of fusion at pressure P and temperature T, v the specific volume of the crystalline phase a t P and T, v’ the specific volume of the isotropic phase a t P a n d T, and E the mechanical equivaient of heat, since the valiies of 1/E and Y’/L are positive, the sign of d T / d P must be the same as that of (v’ - v).It is probable that for some substances the value of (v’ - v) is positive up to a maximum value of P, then assumes the value 0, and finally becomes negative ; in these cases, the curve of fusion is concave towards the pressure axis on a system of coordinates. Tammann has found that when an isotropic phase is gradually cooled, the tendency to crystallise is small just below the fusion point; it increases to a maximum as the temperature falls and a t low tem- peratures again becomes small. Tammann interprets this by assuming that if the temperature be lowered sufficiently and the pressure kept constant, a second fusiou point is reached, that is, a second tempera- ture a t which the isotropic and the crystalline phases are in equilibrium.The author shows that the phenomena can be better explained by assuming, instead of a curve of second fusion, a line of false equilibrium. Tammann’s view assumes that there will always be a line along which (v’-v)=O, and a line along which L=O. The new view does not necessitate these lines, which, indeed, are in some cases difficult to admit. J. McC. Folding Point Curves in Ternary Systems. By FRANZ A. H. SCHREINEMAKEBS (Arch. Nier. sci. exact. nut., 1901, [ii], 6, 1’70-192. Compare Abstr., 1901, ii, 224, 305, 372, 436, 641).-The author con- tinues the discussion of the vapour pressure of ternary mixtures.A foldiug point indicates a critical solution, as in this point two liquid layers must be identical. The conditions for critical liquids of the first and second order are developed, and it is shown that if on the curve of62 ABSTRACTS OF CHEMICAL PAPERS. a critical liquid of the first order under constant pressure there rests a critical liquid of the second order, then a t the point of contact the tem- perature must be either a maximum or a minimum. The author develops a formula by means of which it can be foretold whether the temperature at which two liquid layers are identical is raised or lowered by addition of a third component. A critical liquid at a given temperature can only be in equilibrium with vapour a t a certain defi- nite pressure, and change of temperature alters, not only the pressure, bnt also the composition of both liquid and vapour.The effect of chmge of pressure is also fully discussed. J. McC. An Equation for Osmotic Pressure in Concentrated Solution. By C. H. WIXD ( r l r d . N6er. sci. exuct. nut., 1901, [ ii], 6, 714-726) -From considerations similar to those employed by van der Waals in the development of the gas equation of condition, the author deduces the equation of condition in concentrated solution, lil’= [LV+ (cc - a’>/V2] [ V - Obg/V], as a more complete statement of van’t Hoff’s law. N is the osmotic pressure, V the total volume of the system, and ci, CL’, b and 8 are constants. This equation differs from that of van der W a d s inasmuch as the pressure correction may be negative (if u’ is greater .than a) and in that the volume correction contains V in the denominator.The equation correctly expresses the results obtained by Ewan (Abstr., 1900, ii, 195) and by By1 (Pvoefschrift, AmtevJccm, 1901). J. McC. Neutral Salts. By KURT ARNDT (Zeit. anorg. Chenz., 1901, 28, 364--370).-!L’he degree of dissociation of 0-1N solutions of the following are : HC1, 0.9 1 ; HNO,, 0.92 ; &H,SO,, 0.58 ; KOH, 0.89 ; NaOH, 0.84. I n solutions of chloride and nitrate of potassium and sodium, there will be about the same quantity of hydrogen and hydroxyl ions produced by hydrolysis. Since sulphuric acid is less dissociated than potassium or sodium hydroxides, in the solution of thc sulpbates theremill be a slight excess of hydroxyl ions.This excess is too small to be detected by indicators, but the influence of potassium sulphate on the catalysis of ethyl acetate is very ditferent from that of chlorides or nitrates and resembles that of alkalis (Arrhenius, Abstr., 1888, i, 340). The inversion of sucrose by hydrochloric acid is increased by addition of chlorides ; the inversion by snlphuric acid is diminished by potassium or sodium sulphate (Spohr, Abstr., 1885, 1181). The small quantity of the hydroxyl ion can be even more sharply detected by its influence on the birotation of dextrose. The influence of sulphates on the rotation of dextrose is similar t o that of weak basesllevy, Abstr., 1895, i, 586 ; Trey, Abstr., 1897, ii, 299). J. McC. Velocity of Solution of Solid Substances.11. By LUDWIK BRUNER and STANISLAW TOLLOCZKO (Zeit. anorg. Chem., 1901, 28, 314-330. Compare Abstr., 1901, ii, lo).-Experiments on the velocity of solution of benzoic acid cast into a cake and rotated in water show that some of the solid is mechanically rubbed off and becomes suspended in the solution. Drucker’s results (Abstr., 1901, ii, 376) are vitiated by this circumstance. From experiments withGENERAL AND PHYSICAL CHEMISTRY. 63 alabaster, it is proved that the rate of rotation of the plate has a great influence on the velocity of solution, but the volume of the liquid used is without influence. Hydrogen ions are without influence on the speed of solution of calcium sulphate. The velocity of solution is dependent on the structure of the solid substance, smooth gypsum crystals being dissolved more slowly than the granular alabaster.J. McC. The Investigation of Complex Compounds. By GUIDO BODLANDER (Chenz. Centy., 1901, ii, 1109-1 11 1. ; from Sonderabdruck ccus der Festschy. xur Feier desksiebxigsten Geburtstccges Richard Bedekind, 153--182).-Complex compounds are often formed in solution by the combination of a sparingly soluble compound with a molecule or an ion of a soluble one. I n some cases, as, for instance, when silver cyanide dissolves in solutions containing cyanogen ions, the quantity of the more insoluble compound which goes into solution is equivalent to that of the soluble compound, whilst in others, the proportions vary with the quantities present. The solution of silver chloride by ammonia or of cuprous chloride by hydrochloric acid is an example of the latter type.I n such cases, the law of mass action may be applied, and an indication of the composition of the dissolved ions may be derived from the solubility of the less soluble in an excess of the soluble component. Assuming, for instance, the formula Cu,Cl,+, t o represent the complex ions in a solution of cuprous chloride in presence of a soluble chloride, then (CuC1)Wl" = Cu,Cl,+,k, and since the quantity of active cuprous chloride is constant, C1n = Cu,Cl,+,k,. This gives no indication, however, of the value of In, for if n= 2 then the formula of the complex ions may be CuCI,, Cu,C14, or Cu,Cl,, &c. The formula of the complex ions may be calculated from measure- ments of the E.Jf.F.between electrodes of the same metal as that in the complex in a concentration cell containing two solutions which must have either the same concentration in respect of the complex and different concentrations of the soluble component or vice uerstl. The E.M.Y. between silver electrodes immersed in solutions containing equal quantities of silver but unequal quantities of ammonia may be calcu- lated from thelaw of mass action. Assuming the formula of the corn- plex ions to be Ag,(NH,),, then k[Ag,(NH,),] = AgTn.(NH,)n for one solution and k[Agm( NH3),Il = Agl"(NH3)ln for the other. Since the concentration of the complex ions is the same in both solutions, Neglecting the difference of potential at the boundary of the two (Ag = [(NH3)1: (NH3)In.solutions, then the E.M.F. is If the concentration of the free ammonia is the same in both solutions but that of the complex ions different, then : E = 0.058 log(Ag :Agl) = 0*058,, log[(NH,), : (NH,)]. [AeTn(NHQ)n]l:[a~.m(NHQ)n] = (Agl :Ag)Tn, and E; = 0,058 log(Ag,: Ag) = 0.058,m log([Ag,,(NH,),,] : [Agm(NH3)n]). Hence, from E and El, rn and n can be calculated. It has been found by this method that silver chloride or silver nitrate in ammoniacal solution contains the ion Ag(WH,),, cuprous oxide in ammoniacal solution the ion Cu(NH,),, and cuprous chloride64 ABSTHACTS OF CHEMICAL PAPE&8. i n solutions of chlorides the ion CuCl, or CuCI,, according to the concentration. E. W. W. Dissolution of Metals. By T. ERICSON-AUREN and WILHELM PALMAER (Zeit.physikul. Chem., 1901, 39, l-lS).--The law of mass action cannot be applied to calculate the velocity of dissolution of zinc in acids, as the values so calculated do not agree with the experimental results. The authors consider that dissolution is purely electrolytic and occurs solely as a result of local currents; to this is due the slow velocity of dissolution of pure metals. On this assumption, an expres- sion is deduced for the rate of dissolution of a metal in acids of any concentration, the expression, however, involving an unknown quantity, the resistance capacity. This may, however, be deduced from one set of determinations and the velocity of dissoluticn under other conditions then calculated. The values so obtained were found to agree well with those determined experimentally.The tempera- ture coefficient between loo and 50° was found t o be in general about 1.5 t o 2 per cent. per degree. This is far smaller than the usual temperature coefficient of a chemical reaction, but is approximately that of the increase of E.M.R., a result in accord with the theoretical views. L. M. J. By KURT ARNDT (Zeit. yhysikal. Chem., 1901, 39, 64--90).-The velocity of decomposition of aqueous solutions of a,mmonium nitrite was deter- mined at temperatures varying from 60' t o SO0, and at concentra- tions varying from 0.6 ' molar ' t o 0.3 ' molar.' It was found that in the solutions of the higher concentration the increase of tem- perature from 60' to 80' caused a n increase in the rate of evolu- tion of nitrogeu from 0.37 c.q.per min. t o 3.2 C.C. per min, It was observed that the addition of small quantities of acid increases to a very great extent the velocity of decomposition, whilst ammonia causes an equally marked decrease. This suggested that the decom- position is really due to interaction between the ammonium nitrite and nitrous acid produced by hydrolytic dissociation. Erom the effect of the addition of sulphuric acid, it was calculated, on this assumption, that the hydrolytic dissociation is about 0.25 per cent. at TO", a value which agreed with that calculated from the effect of the addition of ammonia. Ammonium srilphate increases the velocity, probably owing to the increase of undissociated ammonium nitrite, whilst sodium nitrite, by increasing also the free nitrous acid, causes a more marked increase of the velocity, The addition of other neutral salts causes, as expected, a decrease of the decomposition.That the decomposition is not a simple change is also indicated by the approximate proportion- ality of the velocity t o the third power of the concentration. Velocity of Decomposition of Ammonium Nitrite. L. M. J. Equilibrium between Carbonates and Bicarbonates in Aque- OUB Solution. By FRANK K. CAMEHON and LYMAN J . BRIGCIS (J. Physicul Cherri., 1901, 5,537-555).-Solutions of sodium carbonate or * The term ' molar ' is used by the author to indicate the niolecnlar w i g h t of a substauce in grams per litre.GENERAL AND PHYSICAL CHEMISTRY. 65 of hydrogen sodium carbonate attain a state of equilibrium in which both salts are present, the composition being dependent on the total concentration, the temperature, ai id the pressure of carbon dioxide in the vapour phase.The concentration of the two salts in solution was determined by titration with hydrogen potassium sulphate with (1) phenolphthalein, (2) methyl-orange as indicator. Curves are given which show the percentage present as normal carbonate at different concentrations and temperatures. At all temperatures, the quantity of normal salt rapidly increases with the concentration until a concentre- tion of about 0*4N, when it remains almost constant ; the proportion of normal carbonate also increases with rise of temperature. I n certain solutions, the author considers a maximum in thecurve is indicated, but fuller examination is deferred.Solutions of potassium carbonate gave perfectly analogous results. Calcium carbonate exists in solution :ilmost entirely as the hydrogen salt, but solutions of magnesium carbonate may contain 50 per cent. of the normal salt. In both cases, the equilibrium and total solubility are greatly affected by the pressure of the carbon dioxide. L. M. J. Precipitation of Colloids by Electrolytes. By WILLIS R. WHITNEY and J. E. OBER (J. Arne?.. Chern. Xoc., 1901, 23, 842-863). -When 30 C.C. of a 1 per cent. solution of barium chloride were added to 200 C.C. of a 1 per cent. colloidal arsenious sulphide solution, complete precipitation of the arsenious sulphide immediately occurred ; it was found that the precipitate contained 0.0152 gram of barium and that an equivalent amount of hydrogen chloride had been pro- duced.By employing an arsenious sulphide solution of half the above strength, it was shown that the composition of the precipitated colloid is independent both of the concentration of its solution and of t h a t of the barium salt. Experiments in which the chlorides of calcium, strontium, and potassium were used showed that the precipitated colloid contained the metals, barium, strontium, calcium, or potassium in the pxoportions of their equivalent weights ; this result supports Whetham’s hypothesis (Abstr., 1900, ii, 62). An index to the literature of colloids is appended. The Standard for Atomic Weights. By THEODOR W. RICHARDS (Zeit. cmoyy. Chenh., 1901, 28, 355-360. Compare Abstr., 1901, ii, 231, 379).-The author supports the proposal of the International Commission to take as standard 0 = 16.On pedagogic grounds, objection cannot be taken to this if, in the development of Avogadro’s rule, use is made of the densities (experimental) of the gases, that is, the actual weights of 1 litre of the various gases at O”, instead of “ specific gravities.” J. McC. By S. H. HARRIS (J. Physical Chem., 1901, 5, 577--586).-The author shows sundry connections between the atomic weights of elements in cliff erent series and calculates the atomic weights of a number of unknown elements to fill the blank spaces in the periodic table. By L. E. 0. DE V~SSER (Rec. Frccv. Chim., 1901, [ ii], 20, 388--393).-Stas has frequently etuphasised the E. G. Mathematical Expression of the Periodic Law. L.M. J. Purification of Gases.66 ABSTRACTS OF CHEMICAL PAPERS. incomplete purification of gases effected by passing them through tubes containing absorbent solids or liquids ; a complete purification can, however, easily be obtained by passing the gas first through a layer of cotton wool which has previously been impregnated with a solution of the absorbent solid and dried in the air and subsequently through closely packed, pure cotton. If the gas attacks the latter, asbestos or fine-threaded glass wool may be used. I n this way, carbon dioxide, generated from marble and hydrochloric acid, can be entirely freed from hydrogen chloride, although Stas has shown the latter to be present in the gas purified by passage through aqueous and solid sodium hydrogen carbonate. W. A. D. A New Method of Manipulating Liquefied Gases in Sealed Tubes. By HENRI MOISSAN (Compt. rend., 1901, 133, 768-771).- When a current of nir at 18' is passed through a mixture of solid carbon dioxide and ethyl or methyl alcohol, the temperature obtained is constantly - 8 5 O ; with methyl chloride or aldehyde, - 90' ; with ethyl acetate, - 9 5 O , and with acetone, - 98'. If the current of air is previously cooled to - 80', the temperature obtained with the solid dioxide and acetone is - 110'. For lower temperatures, recourse must be had to liquid air or liquid oxygen. When liquefied gases have to be sealed up in glass tubes, the opera- tion is greatly simplified by first cooling the tube, so that the gas becomes solid. For EL pressure of 200 atmos., the tube should be of 10 mm. external and 6 mm. internal diameter ; for higher pressures, 7 mm. external and 3 mm. internal diameter ; and for pressures as high as 300 atmos., 6 mm. external and 1.5 mm. internal diameter. The method is applicable when the liquefied gas is to act on some other substance, and if, after the reaction is finished, the tube is again strongly cooled before being opened, the products of the reaction can be distilled off fractionally. The method is not, however, applicable to reactions in which hydrogen is liberated. The author calls atten- tion to the importance of allowing glass tubes which have been strongly cooled to return very slowly to the ordinary temperature. C. H. B.

ISSN:0368-1769    

DOI:10.1039/CA9028205057

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

66 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Place of Hydrogen in the Periodic System. By BOHUSLAV BRAUNER ( C l ~ m . News, 1901, 84, 233--234).-A theoretical paper dealing mainly with the question as t o whether hydrogen should be regarded as the first member of the halogen group, or whether the old view that it should stand at the head of the first group is still most in accordance with facts. D. A . L. Positive and Negative Halogen Ions. By JULIUS STIEGLITZ (J. Arner. Chem. Xoc., 1901, 23, 797-'799).-Attention is drawn t oINORGANIC CHEMISTRY. 67 the existence of positive chlorine ions in aqueous solutions of chlorine and hypochlorous acid, experimental proof of which is furnished by the work of Jakowkin (Abstr., 1899, ii, 736). E. G. Formation of Ozone. By ALBERT LADENBUHG (Ber., 1901, 34, 3849-3851).-1n preparing ozone by means of the ‘ silent discharge,’ the proportion of ozone reaches a maximum for intermediate values of the current strength, but increases progressively with falling tempera- ture.The maximum percentage recorded is 10.71). T. M. L. Production of Ozone. By A. CHASSY (Compt. rend., 1901, 133, 789--791).--The quantity of ozone formed in a Berthelot’s apparatus a t 20°increases with the time, according to a law which is independent of the intensity of the discharge. The curve representing the rate of in- crease is asymptotic t o a line parallel with the axis of time, and the quantity of ozone formed tends towards a limit which depends on the temperature and is. independent of the intensity of the discharge. The formation of a given quantity of ozone requires less expenditure of energy in the form of electric discharge when the percentage of ozone is low than when it is high.C. H. B. Decomposition of Potassium Iodide Solutions by Ozone. By KANL GARZAROLLI-THURNLACKH (Monatsh., 1901, 22, 955-975. Compare Brunck, Abstr., 1900, ii, 572 ; Pkchard, A.bstr., 1900, ii, 536). -In the product obtained by the action of ozone on solutions of potass- ium iodide, the amount of iodine which could be extracted by carbon disulphide was determined by titration with potassium arsenite ; the iodine present as hypoiodite or other compound and the total iodine were also estimated. When a concentrated solution of potassium iodide has been exposed to the action of ozone for five minutes, the solution contains iodine, hypoiodite, iodate, periodate, and potass- ium hydroxide.Further changes then take place, the quantity of h ypoiodi te and periodate gradually decreases, the former ultimately dis- appearing, whilst the amounts of iodine, potassium hydroxide, and iodate increase. Conditions more favourable for the formation of per- iodate, but less favourable for that of hypoiodite, are obtained by passing the ozone into the solution of the iodide. Attempts to obtain direct evidence of the presence of potassium peroxide or hydrogen peroxide failed, however. The fume which is formed when ozone acts on potass- ium iodide contains a n iodine oxide which is attacked by potassium arsenite. By the action of ozone on a solution of potassium bromide, hypobro- mite and bromate are formed together with some bromine.E. w. w. Pure Tellurium and its Atomic Weight. By PAUL KOTHNER (AnnoZen, 1901, 319, 1--58).-The communication contains a biblio- graphy of the subject and a discussion of the relationship of tellurium to i t s neighbouring elements in the periodic classification. Tellurium may be separated from its common impurities (copper, silver, gold,68 ABSTEACTS OF CHEMICAL PAPERS. bismut b, antimony, arsenic, and selenium) by dissolving the crude substance in hydrochloric acid containing a little nitric acid, evaporating off the excess of the latter.reagent, diluting the cooled solution with. water until the deep yellow colour of tellurium tetra- chloride disappears, filtering from the precipitate of silver chloride and the oxgchlorides of antimony and bismuth, and treating the warm filtrate with sulphur dioxide.The precipitated metalloid is again subjected to the foregoing treatment and fractionally precipitated by the reducing agent. Three fractions are employed, and after repeating the operation two or three times the middle fraction consists of pure tellurium ; the first portions contain arsenic, whilst the third fraction shows traces of copper and gold. The element may be obtained in a crystalline form by passing sulphur dioxide into a hot solution of the tetrachloride in concentrated hydrochloric acid (20.3 per cent.) ; the crystals being opaque with a silvery Iustre. Telluric acid, prepared by Staudenmaier’s method (Abstr., 1896,ii, 96), even after repeated crystallisation, exhibits, in its spectrum, lines characteristic of silver, copper, and antimony.The basic nitrate, OH*TeO*O-TeO*ONO,, employed by Norris, Fay, and Edgerly (Abstr., 1900, ii, 272), is conveniently prepared by dissolving small quantities of tellurium in a slight excess of nitric acid and evaporating the solution obtained from several experiments. In this way, the separation of tellurium is reduced to a minimum. This salt, however, even after repeated crystallisation, still contains traces of silver and copper. Tellurium can be separated from all other elements except antimony by distillation in a vacuum, and since this element is removed in purifying the basic nitrate, it follows that a combination of the two processes should lead t o the production of pure tellurium.The product obtained by reducing the recrystallised uitrate with sulphur dioxide is distilled under 9-12 mm. pressure in a tube divided into segments by asbestos partitions. After repeated distillation through three or four of these compartments, a specimen is obtained which is quite free from impurities. The spectrum of this product agrees in every respect with that of the element prepared from diphenyl telluride (Steiner, Abstr., 1901, ii, 235, 236). The foregoing method is more readily carried out and is far less wasteful than that based on fractional precipitation with sulphur dioxide. Telluric acid, Te(OH),, the basic sdphate, 2TeO,,SO,, and the double chlorides with ammonium and rubidium are not suitable for the atomic weight determination, the compound finally selected being the recrystallised basic nitrate.The atomic proportions of tellurium and nitrogen were determined by decomposing the basic nitrate in a modi6ed Dumas apparatus and estimating the nitrogen, water, and residual tellurium dioxide. I n this way, three experiments gave a mean atomic weight of 126.8; the method, however, is open to objection, owing to the errors incidental to the absolute method of estimating nitrogen. The atomic weight was finally obtained with greater accuracy by heating the pure salt and weighing the dioxide. The results of sevenINORGANIC CHEMISTRY. 69 determinations which were very concordant showed that tellurium, obtained by the author's process, has an atomic weight of 126.7 (H = 1) or 127.88 (0 = 16).The ultra-vio!et spectrum seems to be the best criterion of the purity of the tellurium, and photographs of the spectra of different preparations are included in the communication. Experiments on the Atomic Weight of Tellurium. By GIOVANNI PELLINI (Bey., 1901, 34, 3807--3810).-To purify the tellurium, diphenyl telluride was repeatedly fractionated under diminished pressure and then converted into the dibromide, which was purified by recrystallisation from benzene and then oxidised to telluric acid. The tellurium obtained from the acid was distilled in a vacuum. For the atomic weight determinations, tellurium was in one series oxidised by nitric acid t o dioxide; in another series, the dioxide was reduced to tellurium in a current of hydrogen. The mean value of six determinations in the first series was 127.65 (maximum 128.05, minimum 127.41) ; in the second series, the mean value of three de- terminations was 127.62 (maximum 128.02, minimum 127.30) when G.T. M. ' 0 = 1 6 . K. J. P. 0. Preparation of Nitrogen from Ammonium Nitrate. By JUL. MAI (Ber., 1901, 34, 3805--3806).-0n heating a mixture of glycerol (2 parts) and ammonium nitrate (1 part) a t 190", 8 reaction begins, which continues withoiit further application of heat until the temperature has fallen to 150'. The gas evolved is mainly nitrogen mixed with a small quantity of carbon dioxide. The reaction begins a t a lower temperature, and the gas is evolved more regularly if 2 or 3 drops of concentrated snlphuric acid are added t o the mixture. The glycerol is oxidised to glyceric acid and at the same time a very small amount of pyridine bases is formed.From 10 grams of ammo- nium nitrate, 2690 C.C. of nitrogen were obtained instead of 2775 C.C. theoretically possible (at N.T.P.). K. J. P. 0. The Condition Diagram for Phosphonium Chloride. Ey GUSTAV TAMMANN (Arch. NZer. sci. exact. nnt., 1901, [iil, 6, 244--256).-The melting curve of phosphonium chloride is given by the equation: t = 28.5 + 0.0329 ( p - 50) - 0*00000366 ( p - 50)* up to a pressure of 1550 kilos,, and above this by t = 28.5 + 0,0295 ( p - 50) - 0*00000159 ( p - 50)2. The change of volume on fusion was determined by the method already described (Abstr., 1900, ii, 714) ; at the triple point, the change in volume amounts to 0.87 C.C. per gram, that is five times greater than the greatest (naphthalene) known up to the present.The calculated heat of fusion, 180 C R I . per gram, is more than double that of water, and the high value is probably due to the fact that phos- phonium chloride does not melt without dissociation. Phosphonium chloride exists at low temperatures as a white (amorphous 9) mass ; at higher temperatures, in clear crystals. The transition point is near - 4 1 O and the crystals (supercooled) have the higher vapour pressure. Phosphonium chloride can be obt,ained in the hypercritical condition, which was found to be impossible in the case of carbon dioxide (Abstr., 1899, ii, 635). J. McC.70 ABSTRACTS OF CHEMICAL PAPERS. Oxidation of Boron to Silica and Reduction of Boric Acid to Silicic Acid.By FRIEDRICH FITTICA (Chem. Zeit., 1901, 25, 929--930).-It is claimed that when amorphous boron is oxidised with barium rleroxide, with potassium chlorate and sulpliiiric acid, or with other oxidising agents, considerable amounts of silica are formed, and also that when boric acid is reduced by the addition of sodium t o a solution of boric acid in strong alkali or by the aid of zinc dust, silicic acid is formed. It is suggested that B, = SiO. J. J. S. The Supposed Conversion of Boron into Silica and of Boric Acid into Silicic Acid. By CONSTANTIN COUNCLER (CIkm. Zeit., 1901, 25, 977--978).-A criticism on Fittica's communication (preceding abstract). J. J. S, Oxidation of Boron and Reduction of Boric Acid to Silicon Compounds. By FRIEDRICH FITTICA (Chem.Zed., 1901, 25, 978).- A reply to Councler (preceding abstract), Influence of High Temperature on the Texture of t h e Hydrogel of Silicic Acid. By JACOBUS M. VAN BEMMELEN (Arch. N6er. sci. exact. nat , 1901, [ii], 6, 607-624. Compare Abstr., 1897, ii, 137; 1899, ii, 12, 84).-'rhe hydrogel of silicic acid when ignited loses its power of absorbing water. Ignition for A short time causes only partial loss of this power, and the water which is then ab- sorbed merely fills up the spaces in the network of the silica. Pro- longed ignition causes the complete disappearance of these spaces, with consequent contraction of the whole mass. The sp. gr. after ignition is 2.2 ; the sp. gr. of the material forming the network of the hydrogel is higher than this (2*5-3.0), which indicates that the substance expands when dehydrated.J. J . S. J. McC. Direct Conversion of Gas Carbon into Diamond. By ALBERT LUDWIG (Chem. Zeit., 1901, 25, 979--980).-Diamond crystals are formed when an electric current is passed through an iron spiral embedded in powdered gas carbon and surrounded by an atmosphere of hydrogen under great pressure. The same transformation occurs in the absence of iron, but a much higher temperature is required. J. J. S. Decomposition of the Chlorides of Alkali Metals. By C. W. VOLNEY (J. Arner. Chem. Xoc., 1901, 23, 82Q-834).-When sodium chloride (1 mol.) is treated at 18' with sulphuric acid (1 mol.) of sp. gr. 1.84, the following reaction takes place without any develop- ment of heat : 2NaCl-i- 2H,S04 = NaHSO,,H,SO, + HC1+ NaCl.On heating the residue to 120°, a further quantity of hydrogen chloride is evolved, in accordance with the equation : NaHSO,,H,SO, + NaCl = 2NaHS0, + HC1. When potassium chloride is treated with concen- trated sulphuric acid at 17-18", the temperature rises to 30' and then gradually falls to 17', whilst in the case of ammonium chloride under the same conditions the temperature rapidly falls from 18' to lo. E. 0.INORGANIC CHEMISTRY. 71 Electrolysis of Ammonium Chloride [and Ammonium Iodide] in Solution in Liquefied Ammonia. By HENRI MOISSAN (Compt. rend., 1901, 133, 713-714. Compare Abstr., 1899, i, 410 ; ii, 152).-The electrolysis of ammonium chloride, bromide, and iodide in solution in carefully dried liquefied ammonia was carried out in a U-tube of glass, platinum electrodes being used (compare Ruff, Abstr., 1901, ii, 653).At -50", the iodide was very soluble, the bromide moderately, the chloride little, soluble, and ammonium fluoride nearly insoluble in liquefied ammonia. Liquefied ammonia, prepared with care, is practically a non- conductor (Frenzel, Abstr., 1900, ii, 474). When ammonium chloride is dissolved in it, chlorine is evolved at the anode, and a t - 60' to - SOo is free from nitrogen ; a t the same time, the liquid becomes yellow from the presence of dissolved chlorine ; no chloride of nitrogen is produced. Pure hydrogen is evolved continuously a t the cathode. I n the case of a solution of ammonium iodide, iodine is deposited at the anode, and does not react with, or dissolve in, the liquid ammonia a t - TO", even after 24 hours. If the temperature is allowed to rise, the iodine crystals disappear and a very heavy, dark-coloured liquid is formed, which falls to the bottom of the tube (compare Hugot, Abstr., 1900, ii, 274).K. J. P. 0. Study of Ammonium Amalgam, By HENRI MOISSAN (Compt. rend., 1901, 133, 803-808).-The previous work on the existence of ammonium amalgam is discussed, and it is pointed out that the first problem is the accurate measurement of the ammonia and hydrogen evolved in the decomposition of the amalgam. To solve this problem, the author prepares the amalgam by acting on sodium amalgam with a solution of ammonium chloride (or ammonium iodide) in liquefied am- monia at - 35' ; sodium chloride (or iodide) and a metallic mass are rapidly formed ; no gas is evolved.The liquid ammonia is poured OE from the metal and the latter washed with liquid ammonia and finally with dry ether, saturated with hydrogen,and cooled to - SOo. At - SOo, the metal becomes very hard ; at - 40°, it begins to liquefy, and at - 30' to increase in volume ; at + 15O, the volume bas increased twenty- five or thirty fold, and a characteristic pasty mass is formed, In the decomposition accompanying this increase in volume, heat is developed, aria the temperature is ra'lsea 5-ba above the surroundings. I n order to measure the gases evolved in the decomposition, a portion of the metal, which was cooled t o - 80°, was placed in a glass tube, which was then exhausted whilst the temperature was maintained be- tween - 80Oand - 90".At t h i s temperature, no decomposition took place during the exhaustion. The temperature was allowed to rise, and after twelve or fifteen hours,decomposition was complete. I n all the experi- ments, the gas evolved consisted accurately of two volumes of ammonia and one of hydrogen. I n some of the experiments, the cooled metal was washed with sulphuric acid or ether saturated with hydrogen chlor- ide ; although part of the amalgam was destroyed, the remainder gave up the same proportion of ammonia and hydrogen. The author, how- ever, believes that the radicle ammonium is not present in the metal, but that an ammoniacal hydride is formed, for when an aqueous solution7 2 ABSTRACTS OF CHEMICAL PAPERS. of ammonia is caused to act on pasty sodium amalgam, hydrogen is slowly evolved, whilst if the amalgam contains sodium hydride, the metal immediately swells up and forms a pasty mass. When hydrogen is passed over sodium heated a t 320°, the gas is rapidly absorbed and a transparent, crystalline, hygroscopic hydride, Nrt2H, is formed, which, as a powder, takes fire in air or oxygen, and in chlorine (Troost and Hau tefeuille, Abstr., 1874, 767).When heated in a vac~~um, the hydricle decomposes into sodium and hydrogen. The hydride can be readily separated from excess of metallic sodium by treating the mixture with dry liquid ammonia, when the sodium dis- solves as sodium-ammonium, leaving the pure hydride. K. J. P. 0. Decomposition of Calcium-Ammonium agd of Lithium- Ammonium by Ammonium Chloride. By HENRI MOISSAN (Compt.rend., 1901, 133,715-717. Compare Abstr., 1901, ii,600,653). -In order to ascertain if ammonium is capable of existing at about - loo', the author has caused calcium-ammonium (Ca[ NH3I4) to inter- act with ammonium chloride in the presence of liquefied ammonia. Pure, dry ammonia was led over a known weight of calcium con- tained in a U-tube, one of the arms of which was constricted. A crystal of dry ammonium chloride was placed in the constriction, On cooling the tube until the ammonia liquefied, calcium-ammonium wa? formed and dissolved in the excess of liquid ammonia. As more ammonia liquefied, the ammonium chloride became immersed in and dissolved by the liquid. The reddish-brown colour of the calcium- ammonium then rapidly disappeared, hydrogen gas was evolved, and collected in a special apparatus connected with the U-tube.After the evaporation of the ammonia, a compound of calcium chloride and ammonia remained in the U-tube. The volume of the hydrogen obtained showed that at the temperature wed ( - SO') ammonium does not, exist. Exactly similar results were obtained when lithium was employed instead of calcium. K. J. P. 0. Ammonium : Action of Hydrogen Sulphide on Metallo- ammonium. By HENRI MOISSAN (Arch. N6er. sci. exact. nat., 1901, [ii], 6, 490-496; and Compt. rend., 1901, 33, 771-774).-After tracing the history of the searches after ammonium, the author shows that when liquid hydrogen sulphide acts on a known weight of lithium-ammonium or calcium-ammonium a t between - 75" and - roo, the sulphide of the metal is produced along with free ammonia and hydro- gen, according to the equations (LiNH,), + H,Y = Li,Y + 2NH, + H,, and Ca(NH3),,2NH3 + H,S = CaS + 6NH3 + H,.There is therefore no evidence of the existence of ammonium a t this low temperature. Ruff's results (Abstr., 190 1, ii, 653) have been confirmed. J. BlcC. Solubility of Silver Bromide and Iodide in Water. By FRIEDRICH KOHLRAUSCH and F. DOLEZALEK (Sitxungsbey. K. Akad. Wiss. Bedin, 1901, 1018--1023).--The determination of solubility is based on the increase in the conductivity of water shaken up with these compounds (compare Kohlrausch and Rose, Abstr., 1894, ii, 7). It is found that saturated solutions of silver bromide and iodideIKORGANIC CHEMISTRY. 73 (at 21°)contain, respectively, 0.107 mg.and 0.0035 mg. of the salt per litre. These values are smaller than those previously obtained (Zoc. cit.), owing probably to the precautions taken, but agree fairly well with the values based on the potential differences between a silver electrode and the saturated solutions referred to (compare Dmneel, Abstr., 1900, ii, 467). By KOLOMAN EMSZT (Zeit. anorg. Chem., 1901, 28, 346-354).--Vogel claims to have prepared silver subhaloids by the action of cuprous chloride, bromide, and iodide on silver nitrate, and concludes that these are not mixtures of silver and silver haloid. Analysis leads to the formula Ag,Cl, for the subchloride ; when the substance is treated with nitric acid, however, 2 mols. of silver are dissolved and 2 mols. of silver chloride are left, whilst ammonia or sodium thiosulphate extracts 2 mols.of silver chloride and leaves 2 mols. of silver. On continued shaking with mercury, silver is ex- tracted, Light is supposed to produce on the photographic plate a subhaloid of silver which is acted on by the developer. The substances prepared from cuprous salts are themselves acted on by light and are Dot affected by developers. The author concludes that these supposed subhaloids are merely mixtures of silver and silver haloid produced by the reaction : Cu,Cl, + 4AgN0, = 2Ag + 2AgC1+ 2Cu(N0J2. The so-called Silver Peroxynitrate. By SIMEON L. TANATAR (Zeit. anorg. Chem., 1901, 28, 331-336).-The u silver peroxynitrate ” was obtained by electrolysing a 25 per cent. solution of silver nitrate be- tween platinum electrodes at Oo, the anode and cathode being separated by a porous cylinder.The substance is deposited a t the anode in dark green crystals with a metallic lustre (with 10 dichromate cells, 5 grams can be obtained in an hour). Different preparations had the same composition ; the crystals are free from water (Mulder, Abstr., 1896, ii, 561 ; 1897, ii, 260 ; gulc, Abstr., 1897, ii, 99) and contain 8.09 per cent. of peroxide oxygen, ‘79.44 of total silver, and 18.13 of silver nitrate -amounts corresponding with those required for the formula Ag7NOl1. With potassium iodide, the crystals give iodine and potassium iodate. Electrolysis of other nitrates in neutral and alkaline solutions gives nothing indicating the formation of pernitrates and there is no evi- dence of the production of pernitrates by the action of hydrogen per- oxide on the nitrates of the alkali or alkaline earth metals.By the electrolysis of silver fluoride, LL product is obtained which very closely resembles “ silver peroxynitrate.” The product, on being heated, evolves oxygen violently ; it contains more peroxide oxygen than silver oxide (Ag,O,). A.nalysis (8.3 per cent. of peroxide oxygen) leads to the formula Ag,,F,O,,. It is highly improbable that in this compound oxygen is-directly united to fluorine, and since the ratio of silver to oxygen is not 1 : 1, it is to be assumed that silver forms another peroxide besides Ag,O, and the salt may be a molecular compouiid, 4Ag,04,3AgF. Analogously, (‘ silver peroxynitrate ” is 2Ag304,;lgN0,. Ag,,F,Ol,, when digested on the water-bath, and washed with hot water gives the compound 2Ag304,AgF (of the same type as the nitrate) with 8.94 per cent.of peroxide oxygen. J. C. P. Silver Subhaloids. By elutriation, the composition is changed. J. McC. J. McC. VOL. LXXXII. ii. 674 ABSTRACTS OF CHEMICAL PAPERS. Solubility of Silver Sulphate and Mercurous Sulphate. By KARL DRUCKER (Zed. anorg. Chem., 1901, 28, 361-363).--The solu- bility of these sulphates in water, sulphuric acid, and potassium sulphate solutions at 25" are as follows, the solubility being expressed in gram- mols. per litre, and c being the concentration of the acid or salt solution used : Mercurous sulphate. C. Solubility. H20 .................. - 11.71 x lo-, +H,SO, ............... 0.0400 8.31 x lo-* +H,SO, ...............0.1000 8.78 x 10-4 +K,SO, ............... 0.2000 9.05 x 10-4 $H2S0, ............... 0*2000 8.04 x Silver sulphate. H,O .................. +H2S0, ............... +H,SO, ............... +H,SO, ............... +H2S0, ............... $K2S04 ............... +K2S0, ............... $K,SO, ............... +K2S04 ............... - 0*0200 0-0400 0*1000 0.2000 0*0200 0.0400 0~1000 0~2000 2.57 x 2.60 x 2.64 x 10-2 2.71 x 10-2 2.75 x 10-2 2.46 x 2-36 x 10-2 2.31 x 10-2 2-32 x 10-2 I n the case of silver sulphate, the increase of solubility with increas- ing concentration for sulphuric acid indicates the existence of a new salt the solubility of which more than compensates for the normal isohydric depression. J. McC. The Formation of Natural Anhydrite and the R81e of Time in Chemical Transformations.By JACOBUS H. VAN'T HOFF [with FREDERICK G. DONNAN, EDWARD F. A RMSTRONG, WILLY HINRICHSEN, and FRITZ WEIGERT] (Arch. NZer. sci. exact. mat., 1901, [ii], 6, 471-489. Compare Abstr., 1900, ii, 531 ; 1901, ii, 506).-Gypsum is only very slowly transformed into the hemihydrate or into anhydrite a t the transition temperature. The tension of water vapour from gypsum attains the value of one atmosphere with formation of the hemihydrate, (CaS04)2,H20, at 101.45' ; this point has been found by noting the rise of temperature produced by the addition of common salt to a mixture of gypsum and water, and then by adding water to a mixture of higher boiling point, the temperature remaining constant until, in the first case, the gypsum was completely converted into the hemihydrate, and in the second case until the hemihydrate was com- pletely transformed into gypsum. The transition is greatly accelerated by the presence of solvent liquids; in a tensimeter containing a mixture of precipitated gypsum and the hemihydrate moistened with a solution of magnesium chloride, the tension at 50' became constant a t 49.5 mm.after 7 days. At 25", the tension is 9.1 mm. and 4.99 mm. a t 17'. The connection between tension and temperature is given by the equation log p = log p' + 1.493 - 567*'7/(t + 273), where p is the ten-INORGANIC CHEMISTRY. 75 sion of gypsum, p' that of water, both at the temperature t. When p =p' (970 mm.), t = 107.2' ; this would indicate that 2CaS04(H20), rt (CaS0,),,H20 + 3H20 takes place at this temperature, and in a dilato- meter, containing moist gypsum and using mercury as indicating liquid, a change of volume has Seen observed at about 107'.I n presence of a solution containing 20 per cent. of sodium chloride, gypsurn commences to dehydrate at 93'. For the transformation of gypsum into soluble anhydrite, neither natural nor precipitated gypsum is suitable, but gypsum obtained by treating plaster of paris with much water gave good results. The vapour tension of gypsum in forming anhydrite is higher than that when the hemihydrate isproduced : logp = log p' + 1.41 - 51S*S/(t + 273). The transition temperature (at which p =p') corresponding with the re- action CaSO,(H,O), = CaSO, + 2H,O is 95'. The hemihydrate is un- stable and a t 90' it contracts with production of gypsum, 2(CaSO&H_,O = CaSOa(H_,O),, + 3CaSO,,, then expands slowly owing to formation of anhydrite, CaS04(H20), = CaSO, + 2H20.The formation of natural anhydrite takes place extmmely slowly, but has been observed a t 37'. The temperature of formation is de- pressed by the presence of sodium chloride or other salts, and in this way the natural deposits may be accounted for without assuming a high temperature at the time of formation. Transitions, such as those referred to above, take place a t very dif- ferent speeds. In the case of salts, double salts, and their hydrates, if the acid is monobasic and the metal monatomic, the transformation is rapid. If the acid is dibasic or the metal diatomic, it is slower (compare supersaturation of sodium sulphate and carbonate, calcium chloride, &c.), and if the acid is dibasic and the metal di- or tri-atomic, hours, or even days, may be required for the change t o take place completely (compare the very slow deposition of ferric chloride from its supersaturated solu- tion).I n the case of the non-metals, the resistance to transformation increases with the molecular magnitude (ozone and oxygen, plastic and ordinary sulphur, white and red phosphorus, the various modlfications of carbon). The idea of '' false equilibrium " may be in some measure accounted for by this influence of time on reaction. J. McC. Solubility of Gypsum in Aqueous Solutions of Sodium Chloride. By FRANK K. CAMERON (.I Physical Chenz., 1901, 5, 556-576).-The solubility of gypsum is greatly increased by the addition of sodium chloride, thus, a t 260 the solubility per 100 grams of water is 0.2126 gram, but by the addition of 15.2 grams of sodium chloride it is increased to 0.76 gram.Below 37*5', a maximumof solu- bility is obtained when the quantity of sodium chloride present is about 135-140 grams per litre; a t higher temperatures, the existence of this maximum is doubtful. The transition temperature of the gypsum to the hemihydrate is shown to be dependent on the medium with which it is in contact; in paraffin, change does not occur until about 145O, although in presence of a strong sodium chloride solution it occurs a t 101.45'. The rate of dissolution of gypsum in pure water is exceed- ingly slow, a fact which probably accounts for the diverse numbers which 6-Z76 ABSTRACTS OF CHEMICAL PAPERS.have been given for its solubility; the author's results are, a t 26', about 1 part of gypsum in 372 parts pure water. The theoretical explana- tion is not fully discussed, but the author considers that the maximum point of the solubility cannot be accounted for by our present hypo- theses regarding solutions. Density and Expansion by Heat of Solutions of Magnesium Chloride. By GUSTAV J. W. BREMER ( A ~ c h . NZer. sci. exact. nat., 1901, [ ii], 6, 455--470).-The densities of solutions of magnesium chloride of differea t concentrations have been determined a t various tempera- tures; for the solutions examined, the density a t any particular tem- perature can be ascertained by means of the formula clt = do (1 -at - bt2), the values of do, GI, and 6 being : Grams of magnesium chloride per L.M. J. 100 C.C. of solution. do. a. b. 20.0004 1.160503 2.2738 x loW4 1.3443 x 13.3111 1.11055 2.0072 x 1.7534 x 9,9506 1.08451 1.858'7 x 10-4 2.0482 x 6.7158 1.059117 1.7208 x 1 0 - 4 2,2884 x The density at O', do, expressed as a function of the weight of mag- nesium chloride, p , in 100 C.C. of solution, is do = I + (9.1729 x x p ) - (5.507 x x p ) . The coefficient of expansion, a, increases with the concentration, whilst b diminishes, which indicates that the expansion is the more regular the higher the concentration. The curves repre- senting the expansion of the four solutions intersect near 60'. J. McC. Formation of Tachyhydrite. By JACOBUS H. VAN'T HOFF, F.B. KENRICK, and HARRY M. DAWSON (Zeit. physikal. Chern., 1901, 39, 27-63).-The solubility relations of magnesium chloride and calcium chloride were investigated and the saturation fields obtained for the compounds CaC12,6H20 ; MgC12,6H20 ; CnCI2,4H20, and tachyhydrite. Equilibrium between tachyhydrite and the two hexachlorides occurs at 22.39', at which temperature the double salt is first deposited ; a t 29*4', the hexahydrate of calcium chloride passes into the tetrahydrate, but the temperature is lowered by the addition of magnesium chloride, so that the equilibrium temperature of CaCI,,6H20 ; CaC12,4Hz0, and tachyhydrite is only 25'. A diagram is given representing the solubilities between 16.7' and 32'. Jncrease of pressure causes a rise of temperature of formation of tachyhydrite and by direct determina- tion with a manocryometer the temperature coeflicient was found to be +0*0162' per atmosphere.The value may be calculated by the expression dT/dP = 1033*35!'(w, - w,)/42500r, where w2 and w1 are respectively the specific volumes of the tachyhydrite with its saturated solution and the equivalent simple hydrates, and T is the thermal value of the change. Direct determination led to v2 - wl = 0,06342 C.C. ; the densities were found to be, MgC12,6H20 = 1,5907 ; CaC12,6H20 = 1.7183 ; tachyhydrite = 1.6655, saturated solution 1,4477, and hence v2- wl=O*06323 C.C. The value of T, obtained indirectly from theINORGANIC CHEMISTRY. 77 heats of solution of the various compounds, is 33.82 cal., and from these numbers, the result dT/dP = 0.01 35" per atmosphere is obtained, a value which agrees well with the direct determinations (see Abstr., 1900, ii, 12).By W. HERZ (Zed. anorg. Chena., 1901, 28, 474-476).-Zinc hydroxide, precipitated from a solution of zinc sulphate by dilute potassium hydroxide, readily dissolves in excess of potassium hydroxide and is completely dissolved when for 1 Zn there are 6 OH groups. If, however, the zinc hydroxide is proviously dried at 60-70" in a vacuum desiccator, it becomes comparatively difficult to dissolve, and is completely dissolved when for 1 Zn there are 35.8 OH groups in the solution. Lead hydroxide, on the other hand, is not altered in solubility by drying a t 60-70". It is completely dissolved when for 1 P b there are 8.5 to 8.8 OH groups in the solution.By STANISLAV R ~ ~ I ~ K A (Arch. Hygiene, 1901, 41, 23-45).-The action of yater and solutions of salt,s on bright metallic lead was examined by placing the lead in cylinders containing the various liquids, inserting the stopper SO that the cylinder contained no air, leaving the whole for 24 hours, and then estimating the amount of lead contained in the liquid. The nitrates, chlorides, sulphates, and carbonates of' potass- ium, sodium, calcium, magnesium, and ammonium were employed, and i t was found that the influence of these salts is independent of the base and that whilst nitrates increase the action of the water, or in certain concentrations leave i t unaltered, chlorides, sulphates, and carbonates diminish the action, the effect increasing in the order named.When the different salts are present together, they preserve this mode of action. Thus the addition of a nitrate increases the action of solutions of chlorides, sulphates, or carbonates ; the addition of a carbonate diminishes the action of solutions of nitrates, chlorides, or sulphates ; the addition of a sulphate diminishes the action of solutions of nitrates or chlorides, but has no effect on those of carbonates ; finally, the addition of a chloride diminishes the action of solutions of suL- phates and nitrates, and either increases or leaves unaltered those of carbonates. When the same piece of lead is exposed to the action of fresh solutions containing carbonate, the amount of lead taken up diminishes very greatly and the surface of the lead becomes covered with a thin film which cannot easily be removed by rubbing.The same diminution occurs even in the presence of nitrates and free oxygen, provided that the carbonate be present in sufficient pro- portion (more than half the equivalent of the nitrate). Free carbon dioxide also greatly diminishes the action of water and salt solutions on lead, both when present as a saturated solution at the commence- ment of the experiment, and when a current of the gas is passed through the liquid throughout the experiment. The presence of air in all cases greatly increases the solvent action. The action of various organic substances was also examined, and i t was found that infusions of grass leaves and of radish leaves dimin- ished the action of water, whilst infusion of peat greatly increased i t L.M. J. Hydroxides of Zinc and Lead. E. C. R. Action of Water on Lead.78 ABSTRACTS OF CHEMICAL PAPERS. The action of the salts is ascribed to the varying solubility of the lead salts of the corresponding acids, the nitrate being the most soluble and the sulphate and carbonate the least. By FRITZ GIESEL (Bey., 1901, 34, 3772-3776. Compare Abstr., 1901, ii, 99).-The assumption that radio- active lead contains a new active element is scarcely justifiable unless it can be shown that this material possesses properties differing from those of the known radioactive elements (compare Abstr., 1901, ii, 19, 159, 216, and 655). The activity of radioactive lead sulphate, indicated either by its effect on the electroscope or by its photographic action, is not dimin- ished on keeping, neither is it increased by the action of the cathode rays.The photographic action of the sulphate is also exhibited by the carbonate, chloride, and sulphide. The author has noticed the phos- phorescence of radioactive lead sulphate, but the action is so slight that an experienced eye is required to detect it. A sample of radioact,ive lead sulphate, wrapped in black paper and laid on the glass of a photographic plate, did not produce any effect even after fifteen hours ; an impression was obtained, however, when the specimen was enclosed in transparent paper. This result is ob- tained with the sulphate and not with the corresponding chloride or A feebly active radium preparation enclosed in black paper affects a photographic plate when placed directly on the film; the radio- active lead sulphate enveloped in tracing paper produces an appreciable effect, even through the glass of the plate.I n the former case, the Becquerel rays are operative, whilst in the latter the action is due to light rays. An artificial mixture of inactive lead and radium, con- taining so little of the latter substance that its presence cannot be detected by chemical means, is nevertheless distinctly radioactive, this property being noticeable j n the lead sulphide and also in the iodide prepared from it. The new product obtained by the author from the radium mother liquors (Abstr., 1901, ii, 99) resembles actinium and radium in retain- ing its radioactivity for a year. Polonium preparations, when pre- served for a similar period, exhibit a marked diminution of activity. The rare earths of the cerium group, containing cerium, lanthanum, and didymium as the chief constituents, give photographic impressions after 5 hours' exposure.The precipitate obtained from a thorium nitrate solution by the action of hydrogen peroxide is also strongly radioactive. I n all these cases, the activity, however, rapidly dimin- ishes, this result indicating the absence of actinium. The wa,ter distilled off from crystallised radium-barium chloride is strongly radioactive, a t first even more so than the residual chloride. That this activity is not due to any radium which might have been mechanically carried over into the distillate is shown from the fact that the action diminishes in the course of a few days.By KARL A. HOFMANN and EDUARD STRAUSS (Ber., 1901, 34, 3970-3973. Compare Abstr., 1901, ii, 655).-A reply to Giesel (preceding abstract). Further experiments are A. H. Radioactive Substances. sulphide, G. T. M. Radioactive Substances.INORGANIC CHEMISTRY. 79 described which tend to prove that the radioactive lead sulphate is $fi%$rm-rdlm, ‘LtLeinilunL, “&dl pJm-nrn1. 5.5.a. Action of Carbon Dioxide and Alkali Salts on Metallic Oxides and the Relative Strength of Hydrochloric and Nitric Acids. By OTTO KUHLTNQ (Ber., 1901,34,3941-3945. See Abstr., 1901, ii, 656).-From a consideration of the previous experi- ments (Zoc. cit.), it would appear that nitric acid is a stronger acid than hydrochloric acid. Experiments are now described in which the copper oxide is replaced by mercuric oxide and lead oxide.Mercuric oxide, in the presence of sodium chloride and carbon dioxide, is slowly converted into the oxychloride, 2HgCl,,HgO, but, iE the sodium chloride is replaced by sodium nitrate, the oxide is not attacked. Similar results, although not so definite, were obtained with lead oxide. R. H. P. Identity of the Red and Yellow Oxides of Mercury. By J. KOSTER and S. J. STORK (Rec. Trrccv. Chim., 1901, [ ii], 20, 394-397). -When the red oxide is finely powdered for 2 hours in an agate mortar, i t is almost as easily acted on by aqueous oxalic acid as the ye1l.o~ oxide, although the different action of this acid on the two oxides has hitherto been used as a pharmaceutical distinction.Obviously, as maintained by Ostwald (Zeit. p?upikrccZ. Chem., 1895, 18, 159 ; Abstr., 1900, ii, 712), the oxides are identical and not isomeric (compare Cohen. A hstr.. 1900. ii. 184. 381). W. A . T). Thallium Chlorobromides of the Type Tl,X,. By VICTOR THOMAS (Cornpt. rend., 1901,133, 735-737. Compare Abstr., 1901, ii, 159).-Cushman (Abstr., 1900, ii, 725) obtained two isomeric compounds of the formula Tl,Cl,Br,, crystallising in characteristically diEerent forms (orange plates and blood-red crystals). The author finds that the chlorobromide, Tl,Cl,Br, (Zoc. cit.), crystallises usually in a mixture of needles and plates, which appear to belong to the same crystalline system. Both forms, when heated alone or in presence of the solution from which they have been deposited, become blood-red ; on cooling, they regain their original orange colour.The one form readily passes into the other, K. J. P. 0. Place of the Rare Earth Metals among the Elements. By I~ERTRAM D. STEELE (Chem. News, l901,84,245--247).-Arguments are ztdvanced in favour of regarding the rare earth metals as an inter- 1)eriodic group between groups IV and V of a modified periodic system with seven elements each in groups I and 11, and seventeen edements in each of the groups I11 and IV. D. A. L. Metals of the Cerium Group. By THEODOR H. BEHRENS (Arcll. ilTiei-. sci. exuct. nut., 1901, [ ii], 6, 67-91).-The metals of this group, l,anthanum, cerium, praseodymium, neodymium, and samarium, can be s,eparated from the metals accompanying them in minerals by pre- cipitation as formates in slightly acid solution, If the quantity of cerium metals is small, the other metals should first be removed,80 ABSTRACTS OF CHEMICAT, PAPERS.thorium as oxnlate, metals of the yttrium group by precipitation with sodium sulphate, ammonium carbonate or ammonium lactate, and zirconium as lactate. The formates of the metals of the cerium group are sparingly soluble and crystallise in the pentagonal dodecahedron form. Lanthanum and praseodymium formates are the least soluble and consequently can be separated by addition of formic acid in insufficient quantity. The acetates are easily soluble and difficult to obtain crystallised. On boiling the solutions, basic acetates are formed. Basic lanthanum acetate with iodine turns red, then violet, and finally blue.The oxalates are precipitated as monoclinic crystals sparingly soluble in water, but easily so in concentrated hydrochloric acid or nitric acid. Ammonium succinate precipitates the metals of the cerium group either in spheroidal aggregates or prismatic crystals depending on the substances present in the solution. Solutions in which cerium and praseodymium nitrates predominate give flocculent masses which appear bluish in reflected light, neodymium and thorium nitrates give smooth, brown plates and spheroids. Prismatic crystals are precipitated from solutions containing much lanthanum nitrate ; the crystals show brilliant polarisation colours of the second and even of the third order, and the lanthanum succinate can always be recognised amongst the other succinates.After being warmed with ammonia, cerium SUC- cinate, when moistened with hydrogen peroxide, turns brown, and can thus be distinguished from the other succinates, which remain ~ d O U Y l M 5 l . The metals of the cerium group can also be distinguished by con- version into benzoates or salicylates. It is possible to obtain cerium pure by repeated crystallisation of the ammonium double nitrates ; pure neodymium can only be prepared in this way with the aid of some precipitant, and on account of the isomorphous nature of the double nitrates i t is not possible to separate pure praseodymium. No separation of lanthanum and praseodymium can be attained by crystallisation of the acetates. A pure solution of lanthanum can be obtained by extracting the mixed “cerite” oxide with nitric acid of sp.gr. 1.2 for 10 minutes; even better results are obtained with dilute sulphuric acid. When cerium is precipitated with an oxidising agent (sodium hypo- chlorite, hydrogen peroxide, potassium permanganate) in presence of sodium acetate, lanthanum is constantly carried down with it, and if persulphuric acid is ueed, the cerium precipitate is further contaminated with double sulphates of calcium and the metals of the cerium group. By the addition of ammonia, samarium is first precipitated, then neodymium, praseodymium, and lanthanum, but no satisfactory separa- tion can be made on this basis. Cerium nitrate, when boiled with much water, is Precipitated as basic nitrate, but the precipitate constantly contains very appreciable quantities of lanthanum, samarium, and neodymium.In the same way, basic cerium sulphate can be obtained, and if care be taken that some free sulphuric acid is present, so that the cerium is not completely removed in the precipitate, an almost pure cerium Enlt is obtained,INORGANIC CHEMISTRY. 81 Mosander’s method of separating lanthanum, neodymium, and praseodymium as &ma1 sulphates does not lead to pure products, neither does Delafontaine’s modification in which the solution is shaken with alcohol. The author does not regard i t as yet possible to give a satisfactory method of separating the metals of this group in a pure form. J. McC. Mechanism of Action of Hydrogen Peroxide on Perman- ganic Acid. By A. BACEI (Bey., 1901, 34, 3851--3855).-Traube has suggested that the reduction of permanganic acid by hydrogen peroxide is due to the readiness with which the hydrogen of the per- oxide is oxidised; Berthelot, on the other hand, has suggested that the peroxide first becomes oxidised to the higher oxide, H,O,, which then decomposes into water and oxygen.I n order to test these views, the behaviour of ethyl hydrogen peroxide towards permanganic acid and of ‘ Caro’s acid ’ towards permanganic oxide were studied ; it is suggested that on Traube’s hypothesis these compounds should only reduce half as much oxygen as the equivalent of hydrogen peroxide, whilst on Berthelot’s hypothesis the reducing power should be the same. Actually, the ethyl hydrogen peroxide behaves exactly like hydrogen peroxide, whilst Cyaro’s acid shows a somewhat lower reduc- ing power, and this is regarded as affording support to Berthelot’s hypothesis, T.M. L. Passive Iron. By ALEXIS FINKELSTEIN (Zeit. physikd Chem., 1901, 39, 91-1 lo).-Determinations of the polarisation capacity and resistance of passive iron indicate that it cannot be covered by a coat- ing of badly conducting oxide, and the numbers are very nearly equal t o those obtained for platinum. Passive iron does not behave as an iron electrode, but as an oxygen electrode of variable oxygen concen- tration. The E.M.F. of iron electrodes against various solutions were determined ; addition of potassium cyanide to the solutions greatly lowers the E.M.P., and in solutions of mixed ferrous and ferric salts the E.M.P. decreases as the ferrous salt becomes replaced by ferric.The polarisation curves were investigated, and the non-existence of an oxide layer again indicated. The author discusses the cause of the passivity, and shows that i t may be accounted for by the assumption that the surface of passive iron consists solely of tervslent iron, the formation of passive iron by oxidising agents and electrolysis being due t o the replacement of the bivalent by tervalent iron. Isomerism in the Cobalt-tetrammine Series. By KARL A. HOFMANN and A. JENNY (Bey., 1901,34, 3855--3873).-Two isomeric disulphitotetramminecobalt salts, CO(NH,),(SO,)~NH,,~H,O and result from the action of sulphurous acid on the carbonatotetrammine chloride, or on a solution, oxidised by exposure to air, of ammoniacal cobalt acetate.The first of these has already been described (Hof- mann and Reinsch, Abstr., 1898, ii, 377), but it has since been found that all the water can be driven off without destroying the compound, and its formula must therefore be written ia the form given above. L. M. J. Co(NH,),(SO,),NH,,4H,O,82 ABSTRACTS OF CHEMICAL PAPERS. It forms brown, birefringent prisms belonging to the monoclinic system [a : b : c = 0.859 : 1 : 0.534 ; /3 = 11 1'23'1 ; it affords no coloration with ammoniacal sodium nitroprusside, and no precipitate with mer- ciirous nitrate, but slowly gives a flocculent precipitate with thallium nitrate; in aqueous solution, i t has half the normal mol. weight and is regarded as dissociating into the ions NH, and Co(NH,),(SO,),. When dissolved in sulphuric acid, hydrochloric acid precipitates the praseo-chloride, [Co(NH,),CI,]CI,H,O.The second salt crystallises from water in reddish-yellow prisms which are fairly stable in air but rapidly effloresce in a vacuum ; like the preceding salt, it is readily converted into the praseo-chloride, and behaves in a similar manner with thallium nitrate, mercurous nitrate, and ammoniacal nitroprusside. These two isomeric salts cannot be regarded as merely polymorphous forms of one salt, as they give different colour reactions with sulphuric acid and are not converted into one another by recrystallisation. The two corresponding sodium salts usually crystallise with 2H,O and 4H20 respectively. The first salt is brown in colour and has already been described (Hofmann and Reinsch, Zoc.cit. ; Werner and Griiger, Abstr., 1898, ii, 379); it forms square tablets, probably belonging to the monoclinic system, and is precipitated unchanged from a concentrated aqueous solution on adding alcohol, but separates from a dilute solution in reddish-brown, orthorhombic needle3 with 3H20; in aqueous solution, it shows half the normal mol. weight. The isomeric sodium salt forms golden-yellow needles of the formula CO(NH,)~(SO,),N~,~H,O, readily effloresces, and loses all its water in a vacuum. The salt Co2(NH,),(S03),,6H,0 is prepared from a bye-product obtained in making the ammonium salts described above; it forms birefringent prisms, and is completely dehydrated a t 85' ; when dis- solved in sulphuric acid and mixed with hydrochloric acid, i t gives chloropentamminocobalt chloride (purpureo-chloride), CoCl(NH,),Cl,, and is therefore regarded as a double salt of a pentammine sulphite with a triammine sulphite.Compl'ex salts of the formnuke CO,(A~H~)~(&'O,)~~~~~, 6H20 and CO,(NH,)~(SO,)~N~~,~K,O are described. The acid sulphite, CO(NH,)~(CO,)*SO,H, forms violet-red crystals, and is shown to be R true tetrammine by its conversion into the praseo- chloride. Three sulphito-compounds containing 3 mols. of NH, are described : a dark-brown salt, CO,(NH~)~(SO,),,~H,O, crystallking in prisms ; a dark-brown salt, CO(NH,),(SO,)~H,~H,O, crystallking in hexagonal tablets, and a dark-brown sodium salt, CO(NH,)~(H,O)(SO ) Na,2H,O, which will only part with 2H20 without decomposition. "?. M. L. Some Allotropic Modifications of Inorganic Compounds. By W.HERZ (Zeit. anory. Chem., 1901, 28, 342-345. Compare Abstr., 1900, ii, 728 ; 1901, ii, 513).-Nickel sulphide, precipitated with ammonium sdphide, shows the same phenomena as cobalt sulphide. The nickel sulphide, exposed to the air, oxidises very readily t o sulphate.INORGANIC CHEMISTRY. 83 Chromium hydroxide, precipitated by alkali, is easily soluble in excess of the reagent ; after being dried in a vacuum, however, the hydroxide is insoluble in alkalis. In these cases, the less stable form is first produced and gradually changes to the more stable form. Zinc oxide heated to 250' shows a faint yellow colour and if the yellow (hot) and the white (cold) oxide were allotropic forms i t would be expected that on prolonged heating at this temperature the change t o the yellow modification would be complete.The intensity of the colour does not, however, increase, irdicating that there is no transition and that the two forms cannot be considered as allotropic modifications. J. McC. Chromium Halogen Compounds with Alcohol. By IWAN KOPPEL (Zeit. cmorg. Chem., 1901, 28, 461--473).-The salt CrCI3,3EtOH is obtained by treating metallic chromium with a concentrated solution of dry hydrogen chloride in absolute alcohol. It crystall.ises in deep red needles, is fairly stable in dry air, in damp air is quickly converted into green chromium trichloride hexahydrate, and when heated yields alcohol and ethyl chloride. It dissolves in water t o a red solution which quickly turns green, the same colour phenomenon taking place more slowly in alcohol, chloroform, or acetone solution.A n examination of the electrical conductivity of the solution in absolute alcohol shows that this colour change is due t o causes similar to t h a t observed by Werner and Gubser (Abstr., 1901, ii, 453) in the case of the green chromium chloride, the change of colour from red into green being accompanied by a n increase in the electrical conductivity. This salt is also obtained by heating the violet chromium chloride with absolute alcohol and a stick of metallic zinc. The corresponding chromium bromide salt, obtained in a similar manner, crystallises i n dark reddish-brown crystals which give brown solutions t h a t quickly turn green. It was not, however, obtained in a pure state.E. C. R. Silicomolybdates. By WLADISLAW ASCH (Zed. cLnorg. Clhem., 1901,28, 273- 313).-Molybdic acid, when added to a boiling solution of sodium silicate (Na2Si0,,9H20) dissolves readily at first and some gelatinous silicic acid is separated. By further addition of molybdic acid to the saturation point, the silicic acid redissolves and the solution (which becomes intensely yellow) when evaporated at 45" deposits yellow crystals of sodium silicomolybdate, 2Na20,Si02, 12Mo0,, 2 1 H,O. This salt is dimorphous. Attempts to obtain any other sodium silico- molybdate proved futile. Solutions of sodium silicomolybdate with solutions of salts of potassium, ammonium, rubidium, czesium, thallium, barium, strontium, calcium, nickel, cobalt, cadmium, aniline, pyridine, and quinoline give corresponding silicomolybdates.Of these, only the following have been analysed : BK,O,SiO,, 12Mo0,,1 6H20 ; 2Mg0,Si02,1 2M00,,30H20 ; 2Ba0,Si02, 1 2M00,,24H20, and 2CaO,SiO2!1 2Mo0,,24H20, With a dilute solution of silver nitrate, sodium silicomolybdate gives a small quantity of ruby crystals and a yellow salt having the composition 2Ag20,Si02,12Mo0,,12H20.84 ABSTRACTS OF CHEMICAL PAPERS. With concentrated silver nitrate, a yellow precipitate of 4Ag,0,Si02, 12M00,,15H20 is obtained. By treating the sodium or potassium salt (1 mol.) with hydrochloric acid (4 to 8 mols.)compoands of the formuh 1~Na20,Si02,12M00,,17H,0 and 1~K20,Si02,12M00,,14H20 are formed, and these salts can also be prepared by adding the calculated quantity of alkali to the free acid.This potassium salt gives, with silver nitrate, yellow crystals of l~Ag,0,Si02,12M00,,1 1H20, as well as ruby crystals which have not been analysed. With a1 knli OF sodium carbonate, sodium silico- molybdate (with 1+Na20) gives only sodium trimolybdate. Silico- molybdic acid, Si0,,12Mo03,32H20 (or 2H20,Si0,,12M00,,30H,0), was obtained by decomposing the sodium salt with dilute sulphuric acid and extracting with ether. By dialysing a 5 percent. solution of the salt 2K20,Si0,,12M003,16H20 i t was found that the ratio of K,O : SiO, :MOO, was the same in the diffused solution as in the original, indicating that the silicic and molybdic acids form a complex ion. The conductivities and densities of solutions of the acid and of the potassium salt have been determined at loo, 20°, 30°, and 40".The results indicate that the silicomolybdates are fairly stable and only suffer decomposition a t high dilution, and tbnt this decomposion is increased by rise of temperature. By measuring the depression of the freezing point of Glauber's salt (Locvenherz, Abstr., 1896, ii, 149), caused by the addition of the sodium salt, it was found that the mol. weight corresponds with that required for trhe formula Na,SiMo,,O,o. The salts 2R20,Si0,,12Mo0,,aq are to be regarded as normal salts of tetrabasic silicomolybdic acid, whilst the salts 1+R20,Si02,12Mo0,,aq are acid salts of the same acid (BR,O being replaced by +H,O). At loo", 2Na,0,Si02,12M00,,21H20 loses 17;- mols. of water, and 1 ~Na20,SiOZ,12Mo03,17H20 loses 13 mols.; that is, the normal salt has 3+ mols. of' water of constitution and the acid salt has 4. In the analysis of the compounds the silica was determined after removing the molybdic acid by heating to a high temperature in a current of hydrogen chloride. J. McC. Uranous Sulphate. By WILLIAM OECHSNER DE CONINCK (BUZZ. Acad. Roy. Belg., 1901, 483-485).-The sp. gr. of' aqueous solutions of uranous sulphate as well as of solutions in sulphuric acid and hydro- chloric acid have been determined. A 1 per cent. solution in water has asp, gr. 1.0058, a 10 per cent. solution 1.0539. A 1 per cent. solution in suphuric acid of sp. gr. 1-14 has a, sp. gr. 1.1442, a 5 per cent. solution 1.1626. I n solution in hydrochloric acid of sp. gr. 1.046, a 1 per cent. solution has a sp.gr. 1.0525, a 5 per cent. solution 1.0744. Water acts on uranous sulphate, producing a basic salt and a sub- stance of the formula 2US04,3U0,4H,0 has been isolated. J. McC. Tin-Aluminium Alloys. By L ~ O N GUILLBT (Cowapt. rend., 1901, 133, 935--937).-The action of stannic oxide on aluminium is very energetic, but the limit of inflammation is reached with a mixture corresponding with A1,Sn. The product from tbis mixture, whenINORGANIC CHEMISTRY. 85 tyeated with dilute hydrochloric acid, yields lamellar and filiform crystals of the compound A1,Sn. Similarly, mixtures corresponding with Sn,Al, SnAl, and SnA1, yield lamellar and filiform crystals of the compound AlSn. C. H. B. New Element associated with Thorium. By CHARLES BASKER- VILLE (J. Amer. Chem.Soc., 1901, 23, 761-774. Compare Brauner, Proc., 1901, 17, 67).-Freshly precipitated thorium hydroxide mas dissolved in hydrochloric acid ; the solution was neutrahsed with ammonia and saturated with sulphur dioxide. A basic sulphite separated, and on addition of ammonia to the filtrate a further pre- cipitate was obtained. Each of these precipitates was carefully ignited ; the resulting oxides had the sp. gr. 9.38 and 10.367 respectively. On heating a solution of thorium hydroxide in saturated citric acid solution, a white, amorphous precipitate of the hydrated citrate of real thorium was obtained, which yielded specimens of the oxide of sp. gr. varying from 9.188 to 9.253, whilst the citrate obtained by concen- trating the filtrate furnished an oxide of sp.gr. 10.50. After the removal of the insoluble citrate from a large quantity of the saturated citrate solution, the filtrate slowly deposited a small quantity of heavy crystals which, on ignition, yielded 31.61 per cent. of oxide of sp. gr. 8.47-8-77; the author suggests this may be the oxide of the new metal discovered by Hofmann and Prandtl (Abstr., 1901, ii, 387) in euxenite ; on evaporation of the filtrate, several fractions of the crystalline citrate were obtained, the oxide from which had a sp. gr. The radioactivity of the oxide (sp. gr. 9-25) obtained from the insoluble citrate is very slight, whilst the oxides of high specific gravity are quite active, the activity increasing with the sp. gr. These experiments indicate the presence of a new element, the oxide of which has a high sp.gr. ; its atomic weight (calculated for a quad- rivalent element) appears t o lie between 260 and 280. The author proposes for this metal the name carolinium. The atomic weight of thorium, obtained by analysis of the tetra- chloride, was found as the mean of two experiments to be 222-223.3. By IWAN KOPPRL and-E. C. BEHRENDT (Ber., 1901, 34, 3929-3936).- Vanadyl sulphite forms two series of double salts with the sulphites of the alkalis, the salts of one series being blue, and having the empirical formula, R,0,2S0,,3V02,aq, those of the other being green, with the formula R’,0,2S0,,B02,aq. The salt, (NH,)20,2S03,3V0,,H,0, obtained when a solution of ammonium metavanadate (1 mol.) and ammonia (1 mol.) is saturated with sulphur dioxide and evaporated in the presence of the same gas, crystallises in long, blue, rectangular tablets, which are quite stable in air.When a saturated solution of ammonium metavanadate is mixed with a large excess of a neutral solution of ammonium sulphite and evaporated, green, microscopic crystals of the salt, (NH,),O, 2SO,,VO,, 2IX,O, are obtained. 10.1 4-1 1.26. E. G. Sulphites and Sulphates of Quadrivalent Vanadium.86 ABSTRACTS OF CHEMICAL PAYERS. The corresponding potassium and sodium salts are obtained by analogous methods. The blue potussiuna salt crystallises in microscopic tablets, which dissolve in water without decomposition ; the green potassium salt crystallises, with 5&H20, from water in rectangular tablets, and is stable in air. The blue sodium salt was obtained in long, prism- atic crystals with 4H,O, and the green sodium salt with 5H20 as a microcrystalline powder, both, however, decomposing when kept in air.When barium metavanadate suspended in water is reduced with sulphur dioxide, a solution is obtained which, when evaporated in the presence of sulphur dioxide, deposits a dark brown, microcrystalline powder having the composition 3V0,,2S0,,4&H20 ; this may be either vanadyl sulphite or vanadyl sulphurous acid. Double sulphates of the alkalis and vanadyl can be obtained by crystallisation of the mixed sulphates a t 100' or above from solutions containing sulphuric acid. Ammonium vanadyl sulphate, 2VOS0,,(NH,)2S04,H,0, potassium vun- adyl sukhate, 2VOS04,K2S04, and sodzui?z vanadyl sulphccte, 2VOS04,Na,S0,,2~H20, were obtained as extremely hygroscopic, microcrystalline tablets, An ammoniurnvanadyl sulphute of the composition (NH4),S04,V0S0,,3~H20, was also prepared. R. H. P. Compounds of Gold and Chlorine. By FERNAND MEYER (Compt. Tend., 1901, 133, 815--818).-1f gold is treated with liquid chlorine in a sealed tube a t the ordinary temperature, the metal is superficially attacked and converted into a crystalline, red mass. When the tubes containing the gold and chlorine are heated intermittently a t loo', the gold entirely dissolves, forming a deep yellow solution, and, on cooling, auric chloride separates in wine-red, very hygroscopic crystals. The dissociation of auric chloride has been studied in a specially constructed apparatus. A t 1 SO', the dissociation becomes marked, and a greyish-green solid (a mixture of aurous chloride and gold) and chlorine are formed. The dissociation pressure was measured up to 205", when the system ceases t o ha.ve only one variable, as the auric chloride begins to volatilise. If at a given temperature, t, the chlorine (which was a t a given pressure, p ) was slowly removed from the appar- atus, until all the auric chloride had disappeared, the pressure assumed a new value, p', which remained constant until only gold was left in the tube. Auric chloride, therefore, dissociates into aurous chloride and chlorine. Aurous chloride is sensibly dissociated a t 170" ; the dissociation pressure was measured up to 240'. These experiments show that there is only one compound of gold and chlorine, namely, aurous chloride, containing less chlorine than auric chloride, K. J. P. 0. Ruthenium. IV. The Chlorides. By JAS. LEWIS HOWE (J. Amey. Chena. Soc., 1901, 23, 7 75- 788).--Cmsium andrubidium yutheni- cltlovides, Cs2RuC1, and Rb,RuUl,, crystallise in black, almost opaque, regular octahedra and are slightly soluble in water. The oxyrutheni- chlorides, Cs2Eu0,Cl4 and Rb,RuO,Cl,, form dark purple, cubic crystals, and are instantly decomposed by water with production of a black precipitate. Caesium and rubidium chlorides unite withMINERALOGICAL CHEMISTRY. 87 ruthenium trichloride t o form the double salts, Cs2RuC1,,H20 and Rb,RuCl,,H,P, which are dark brown powders fairly soluble in water. When a slightly acid solution of caesium ruthenichloride is heated with water and alcohol, a rose-coloured salt, 2CsCl,Ru(OH,)CI,, is produced, which crystallises in prisms and is very slightly soluble in water. By electrolytic reduction of ruthenium trichloride and addi- tion of cssium chloride t o the product, a bluish-green substance, 3CsC1,2RuCl,,H20, is precipitated which rapidly oxidises in the air. E. G.

ISSN:0368-1769    

DOI:10.1039/CA9028205066

出版商:RSC    

年代:1902

数据来源: RSC