摘要:

J O U R N A L E. F. ARMSTRONG Ph.D. C. F. BAKER Ph.D. B.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. B.Sc. T. EWAN B.Sc. Ph.D. E. GOULDING B.Sc. P. HAAS B.Sc. Ph.D. W. D. HALLIBURTON M.D. B.Sc. T. A. HENRY D.Sc. L. M. JONES B.Sc. L. DE KONINOH. D. A. LOUIS. T. M. LOWRY D.Sc. F.R.S. G. D. LANDER D.Sc. OF A. MCKENZIE M.A. D.Sc. N. H. J. MILLEB Ph.D. K. J. P. ORTON M.A. Ph.D. J. C. PHILIP M.A. Ph.D. R. H. PICKARD D.Sc. Ph.D. T. H. POPE B.Sc. E. C. ROSSITER. M. J. SALTER. G . SENTER Ph.D. B.Sc. W. P. SKERTCHLEY. L. J. SPENCER M.A. J. J. SUDBOROUGH Ph.D. D.Sc. If. A. WHITELEP D.Sc. G. YOUNG Ph.D. E. w. M'HEELWRIGHT B.A. Ph.D. THE CHEMICAL SOCIETY. ABSTRACTS O F PAPERS ON ORGANIC CHEMISTRY. H. T. BROWN LL.D. F.R.S. A. W. CROSPLEY D.Sc. Ph.D. WYNDHAM R. DUNSTAN M.A. LL.D. BERNARD DYER D.Sc. M. 0. FORSTER D.Sc. Ph.D. F.R.S. F. R. S. H. MCLEOD F.R.S. R. MELDOLA F.R.S. E. J. MILLS D.Sc. LL D. F.R.S. SirW. RAMSAY K.C.B. LL.D. F.R. S. A. SCOTT D.Sc. F.R.S. W. A. TILDEN D.Sc. F.R.S. m i f o r %P,JY- &biflYr G. T. MORGAN D.Sc. A. J. GREEXAWAY. 1905. Vol. LXXXVIII. Part I. LONDON GURNEY & JACKSON 10 PATERNOSTER ROW. 1905.RICHARD CLAY & SONS I-IXITED BREAD STREET RILL E.C. AND BUNGAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA90588FP001

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

J O U R N A L O F THE CHEMICAL SOCIETY ABSTRACTS O F PAPERS PHYSICAL INORGANIC MINERALOGICAL PHYSIOLOGICAL AGRICULTURAL ANALYTICAL CHEMISTRY. ON AXD dammitfee af H. T. BROWN LL. D. F. R.S. A. W. CROSSLEY D.Sc. Ph.D. WYNDHAM R. DUNSTAN M.A. LL. D. BERNARD DYER D.Sc. M. 0. FOKSTER D.Sc. Ph.D. F.R.S. P. R. S. g nblicatiolr H. MCLEOD F.R.S. R. MELDOLA F.R.S. E. J. MILLS D.Sc. J.L.D. F.R.S. Sir W. RAMSAY K.C. B. LL.T). ,F. R.S. A. SCOTT D.Sc. F.R.S. W. A. TILDEN D.Sc. F.R.S. (&bitar MY-fibitar g~aisfrnrt Sub.- gbifar C. H. DESCH D.Sc. Ph.D. 3b.atrattrrrl; G. T. MORGAN D.Sc. A. J. GREENAWAY. E. F. ARMSTRONG Ph.D. C. F. BAKER Ph.D. B.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. B.Sc. T. EWAN B.Sc. Ph.D. E. GOULDING 13.S~. P. HAAS B.Sc. Ph.D. W. D. HALLIBURTON M.D. B.Sc. T. A. HENRY DSc. L. M. JOKES B.Sc. L. DE KONINGH. G. D. LANDER D.Sc. D. A. LOUIS. T. M. LOWRY D.Sc. F.R.S. A. MCKENZIE M.A. D.Sc. N. H. J. MILLER Ph.D. K. J. P. ORTON M.A.. Ph.D. J. C. PHILIP M.A. Ph.D. R. H. PICKAIZD D.Sc. Ph.D. T. H. POPE B.Sc. E. C. ROSSITER. M. J. SALTER. G. SENTER Yh.D. B.Sc. W. P. SKEETCHLEY. L. J. SPENCER M.A. J. J. SUDBOROUGH Ph.D. D.Sc. E. W. WHEELWRIGHT B.A. Ph.D. M. A. WHITELEY D.Sc. G. YOUNG Ph.D. 1905. Vol. LXXXVIII. Part 11. LONDON GURNEY & JACKSON 10 PATERNOSTER ROW. 1905.RICHARD CLAY & SONS LIMITED BREAD STREET HILL E.C. AND BUNOAK SUFFOLH.

ISSN:0368-1769    

DOI:10.1039/CA90588FP003

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

JOURNALS FROM WHICH ABSTRACTS ARE MADE. All references to Journals should give the abbreviated title the year of publication the series the volume and the page ; thus Ber. 1901 34 2455 ; BzJZ. SOC. chim. 1901 [iii] 25 794 ; Gazxettn 1901 31 i 554. ABBREVIATED TITLE. Amer. Chem. J. . . Amer. J. Pharm. . Amer. J. PJzysioZ. . Amer. J. Sci. . . Analyst . . . Annalen . . . Ann. Physik . . Ann. agron. . . Ann. Chirn. anal. A m . Chim. Phys. . Ann. Inst. Pasteur . Ann. sci. Univ. Jassy Arch. Hygiene . . Arch. NderZand. . . Arch. Pharm. . . Arch. Xci. Dhws. nat. . Arkiv Ke&. kin. Geol. . Atti R. Accad. Sci. Torino. Atti 3. Accad. Lincei . Beitr. chem. Physiol. Path. . Ber. . . . * Biei cenentr. . . . Bihang K. Svenska Vet.- BdZ. Acad. r q . Belg. . Bull. Acad. Xci. Cracow .Bdl. Coll. Agr. Toky6 . Bull. Geol. Soc. Amer. . Bzill. SOC. chim . . BulZ. Soc. franc. Min. . BUZZ. SOC. ind. Mulhozcse . Centr. Bakt. Par. . . Centr. Min. . . . ”Chcm. Centr. . . . Akad. Handl. JOURNAL. American Chemical Journal. American Journal of Pharmacy. American Journal of Physiology American Journal of Science. The Analyst. Justus Liebig’s Annalen der Chemie. Annalen der Physik. Annales agronomiques. Annales de Chimie analytique appliquke B 1’Indus trie Annales de Chimie et de Physique. Annales de 1’Institut Pasteur. Annales scientifiques de 1’Universitk de Jassy. Archiv fur Hygiene. Archives NQerlandaises des sciences exactes e t natur- Archiv der Pharmazie. Archives des Sciences physiques et naturellcs. Arkiv for Kemi Mineralogi och Geologi. Atti della Reale Accademia delle Scienze di Torino.Atti della Renle Accademia dei Lincei. Beitriige fur chemische Phyaiologie und Pathologie. Berichte der Deutschen chemischen Gesellschaft. Biedermann’s Centralblatt fur Agrikul turchemie und Bihang till Kongl. Svenvka Vetenskaps-Akademiens Acadkmie royale de Belgique-Bulletin de la Classe Bulletin international de l’Acadkmie des Sciences de Bulletin of the College of Agriculture Imperial Uni- Bulletin of the Geological Society of America. Bulletin de la Soci6tB chimique de Paris. Bulletin de la Soci6t6 franpaise de MiiiBralogie. Bulletin de la SociAt6 industrielle de Rlulhouse. Centralblatt fur Bakteriologie Parasitenkunde und Centralblatt fur dl ineralogie Geologie und Palaeonto- Chemisches Centralblatt. B I’Agriculture B la Pharmacie et h la Biologie.elles. rationellen Laiidwirtschafts-Betrieb. Handlingar. des Sciences. Cracovie. versity Tokyo. Infektionskrankheiten. logie. * Abstracts from the Centmlblntt are niade only in the case of papers publitilied in journals other than those included in this list.JOURNALS FROM WHICH ABSTRACTS ARE MADE. ABBREVIATED TITLE. Chem. News . . . mem. RCV. Fett-Hnrz-lid. Chem. Zeit. . . . Conapt. rend. . . . Compt. rend.80~. Biol. . Electro-Chern. Metall.. . Exper. Stat. Record . . Gazzctta . . . Geol. Mag.. . . . Jahrb. Min. . . . Jahrb. Min. BeiZ.-Bd. . Jahrb. Radioaktiv. Elektro- J. Amer. Chem. Xoc. . . J. Biol. Chem. . . . J. Chim. phys. . . . J. Geol. . . . J. Hygiene. . . . J. Inst. Brewing . . J. Landw.. . . . J. Med. Research . .J. Path. Bact. . . . J. Pharm. Chim. . . J. Physical Chem. . . J. Physiol. . . J. Physique . . . J. pr. Chenz. . . . J. Roy. Agric. Xoc. . J. Roy. SOC. New South J. Russ. Phys. Chenz. SOC. . J. SOC. Chem. Ind. K. Sveiiska Vct-Akad.kandZ h n d w . Versuchs-Stat. . L’Orosi . . . . Mem. Accad. Xci. Torino . nik. Wales. Mem. Coll. Sci. Eng. Kycita. illem. Manchester Phil. Soc. Milch Zcit. . . . Nilch. Zentr. . . . Min. Mag. . . . Nonatsh. . . . . Nuovo Cim. Ofver K. Vet. -ikad. Forh.‘ PJliiger’s Archiv. . . Pharm. Arch. . . Pharm.J.. . . . Pharm. Rev. . . . Phil. Mag. . . . . JOURNAL. Chemical News. Chemische Revue uber die Fett- und Harz-Industrie. Chemiker Zeitung. Comptes rendus hebdomadaires des Skances de Comptes rendus des SCances de la Socikt6 de Biologie. The Electro-Chemist and Metallurgist. Experiment Station Record.Gazzetta chimica italiana. Geological Magazine. Neues Jahrbuch fur Mineralogie Geologie und Pal- aeontologie. Neues Jahrbuch fur Mineralogie Geologie nnd Pal- aeontnlogie. Beilage-Band. Jahrbuch der Radioaktivitat und Elektronik. Journal of the American Chemical Society. Journal of Biological Chemistry New York. Journal de Chimie physique. Journal of Geology. Journal of Hygiene. Journal of the Institute of Brewing. Journal fur Landmirtschaft. Journal of Medical Research. Journal of Pathology and Bacteriology. Journal de Pharmacie et de Chimie. Journal of Physical Chemistry. Journal of Physiology. Journal de Physique. Journal fiir praktische Chemie. Journal of the Royal Sgricultural Society. Journal of the Royal Society of New South Wales. Journal of the Physical and Chemical Society of Russia.Journal of the Society of Chemical Industry. Kongl. Svenska Vetenskaps-Akademiens Handlingar. Die landwirtschaftlichen Versuchs-Stationen. l’Acad8mie des Sciences. b L’Orosi. Memorie della Reale Accademia delle Scienze di Torino. Memoirs of the College of Science and Engineering Ky6t6 Imperial University. Nemoirs and Proceedings of the Manchester Literary arid l’hilosophical Society. Milch Zeitung. Milchwirtschaftliches Zentralblatt. Mineralogical Magazine and Journal of the Mineral- ogical Society. Monntshefte fiir Chemie und verwandte Theile anderer Wissensehaften. Jl Nuovo Cimento. Ofversigt af Kongl. Vetenskaps- Akademiens Forhand- lingar. Archiv fur die gesammte Physiologie des Menschen und der Thiere.Pharmaceutical Archives. Pharmaceutical Journal. Pharmaceutical Review. Philosophical Magazine (The London Edinburgh and Dublin).JOURNALS FROM WHICH ABSTRACTS ARE MADE. ABBREVIATED TITLE. Phil. Trans. . . . Proc. Amer. PJL?ysiol. SOC. . Proc. Cn,mb. Phil. SOC. . Proe. K. Akad. Wcten,sck. Proc. Phil. Soc. Glasgozv . Proc. Plqsiol. Soc. . . Proc. Roy. Soc. . . . Proc. Roy. Xoc. Edin. . Quart. J. Geol. Soc. . . Rend. Accad. Sci. Fis. Mat. Rev. intern. Falsif. . . Rcc. trav. chim. . . Amsterdam. Nc~poli. Sci. Proc. Roy. Dzcbl. Soc. . Sci. Trans. /toy. Dubl. SOC. Sitzungsber. K. Akad. Wiss. Sitzungsber. K. Akad. iViin- Trans. Amcr. Inst. Mining Trans. Faraday SOC. . . Trans. Nova Scotia Inst. Trans. Path. Soc. . . Tram. Ro!y.Soc. Camdrc. . Trans. Roy. Irislh Acnd. . Tsch. itfin. Mitth. . . U.S. A. Dept. Agric. Bull. . U.S.A. Dept. Agric. Izep. . Wiss. Abhandl. Phys. -Tech. Zcit. anal. Chcm. . . Zeit. angcw. Chem. . . Zeit. anorg. Chem. . . Zeit. Biol. . . . . Zeit. Elektrockcm. . . Zeit. Fwb Tmt. Ind. . Zeit. Kryst. &fin. . . Zcit. Nahr. Gc~~ussna. . Berlin. chcn. Erin. Sci. .&ichsc6nsk% It. Zeit. offcntl. Chem. . . Zeit. pkysikal. CJwnz. . . Zeit. physiol. Chem. . . Zeit. prcckt. Geol. . . Zeit. Vcr. deut. Zzcckcrind. . Zeit. Zuckcrind. Bohm. . JOURKAL. Philosophical Transactions of the Royal Society of Proceedings of the American Physiological Society. Pr Iceedirigs of he Cambridge I’hi1o;ophical Society. Proceedings of the Glasgow Philosophical Society. Procec,diilgs of the Physiological Society.Koninklijke Akademie van Wetenschappen te Amster- dam. Proceetlings (English version). Proceeding- of thr Royal Society. Proceeilings of the Royal Society of Edinburgh. Qnar erly Journal of the Geoloqical Society. Rendiconto dell’ Accadeiiiia delle Scienze Fisiche e Revue internittionale drs Falsifications. Recenil cle3 trav:tux chimiques des Pays-Bas e t de la S,.ientific I’voceedings of the Royal Dublin Society. Scientific Transactions of the Roval Dublin Society. Sitzungsherichte rler Kii~iiglicli Preussischen Akademie Sitxungsherichte der kijiiiglich bayerischen Akademie Transactions of the American Iiistitute of Mining Transactions of the Faraday Society. Transactions of the Nova Scotia Institute of Science. London. blii temntiche-Napoli. Relgitlne. der Wissens..hafteii zii Berlin. der Wissenschafteii zii Munc hen. Engineers. Transactions of the Pathological Society. Transactions of the Royal Society of Canada. Trans>:ctioiis of the Royal Irish Academy. Tscherniak’s M ineralngische Ill ttheilungen. Bulletins of the Department of Agriculture U. S. A. Reports of the Department of Agriculture U.S.A. Wissenschaftliche Abliandlnngen der Physikalisch- Tech~iische~i Reichsanstalt. Zeitschrift fiir analytische Chemie. Zeitschrift fiir angewandte Chemie. Zritschrift f u r ariorgaiiische Chemie. Zeitschrift fiir Riologie. Zeitschrift fiir Elektrochernie. Zeitschrift fiir Farben und Textil-Industrie. Zeitschrift fiir Krystallographie und Mineralogie. Zeitschrift fur Untersuchung der Nahrungs- und Zeitschrift fiir offentliche Chemie. Zeitschrift fiir physikalische Chemie Stochiometrie und Verivaridtschaftslehre. Hoppe-Sryler’s Zeitschrift fur physiologische Cheniie. Zeitschrift fiir praktische Geologie. Zeitschrift des Vereins der deutschen Zucker-Industrie. Zeitschrift fiir Zucicerindustrie in Bijhmen. Genuismi! tel.

ISSN:0368-1769    

DOI:10.1039/CA905880X008

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 21 Inorganic Chemistry. Reduction of Perchlorate by the Wet Method. B. SJOLLEMA (Zeit. anorg. Chern. 1904 42 127-128).-Potassium perchlorate when boiled in aqueous solution with ferrous hydroxide in the absence of free alkali is reduced quantitatively to chloride. A. McK. Rate of Crystallisation o1 Plastic Sulphur. JOSEPH H. KASTLE and WALTER PEARSON KELLEY (Amer. Chem J. 1904 32 483-303).-The rate of change of plastic sulphur into the crystalline variety has been studied by sp. gr. and dilatometric methods. A specimen of sulphur was heated to 200' and poured into cold water ; one portion was left in water a t the ordinary temperature whilst another was kept in water a t 70"; the sp. gr. of each mas determined at intervals of an hour. In another experiment the sulphur was heated to 444" before being poured into water; portions of this specimen were kept at 80° 60° and 40" respectively whilst another portion was left in cold water ; the sp.gr. was determined a t intervals in each case. The results indicate that the rate of change of plaatic into crystalline sulphur varies according to the temperature to which the sulphur is heated before being poured into water and also with22 ABSTRACTS OF CHEMICAL PAPERS. the temperature a t which the product is preserved. The higher the initial temperature to which the sulphur is heated the slower is the crystallisation ; and the higher the temperature at which the sulphur is kept the more rapid is the change. I n another series of experiments a specimen of plastic sulphur was divided into five portions which were kept under water dilute ammonia 95 per cent.alcohol dilute bromine water and N/10 iodine solution respectively the sp. gr. being determined at intervals in each case. It was found that ammonia alcohol and bromine accelerate whilst iodine retards the crystallisation. A study of the effect of heat has shown that plastic sulphur has no definite melting point the effect of any increase of temperature being merely to diminish its viscosity and to increase its tendency t o pass into the crystalline form. The stability of any particular specimen of plastic sulphur can be judged from its colour ; light amber-coloured specimens crystallise easily whilst reddish-brown varieties remain plastic for longer periods. Experiments have shown that when the plastic and orthorhombic forms of sulphur are heated a t 120-125' for a sufficient length of time they become alike in colour a state of chemical equilibrium being ultimately reached in each case.Experiments made with the object of determining the effect of tension on the crystallisation showed that specimens of sulphur under tension crystallise more rapidly than those not under tension. Determinations of the rate of change by the dilatometric method showed that plastic sulphur prepared by pouring into water sulphur that has been heated only to a moderately high temperature crystallises rapidly whereas that which has been heated to near the boiling point before being poured into water crystallises very slowly. The velocity of the change of plastic into crystalline sulphur begins comparatively rapidly about 10 per cent.of the total change taking place in the first 30 minutes and then gradually diminishes. This gradual decrease in the rate of crystallisation indicates that several molecular forms are present in the supercooled liquid some of which change to the crystalline variety of the element more rapidly than others. E. G. The Chlorides of Sulphur. Sulphur Tetrachloride and its Compounds. OTTO RUFF (Ber. 1904 37 4513-4521. Compare Ruff and Fischer Abstr. 1903 ii 204).-The author has re-examined the double compounds of sulphur tetrachloride described in the literature and has corrected some erroneous analyses. The so-called sulphur dichloride was employed in the preparations and the author's view is confirmed that this substance is a solution of largely dissociated sulphur tetrachloride in sulphur chloride.Sulphur tetrachloride prepared by the slow combination of sulphur chloride with liquid chlorine in a sealed tube is st yellowish-white substance melting a t - 30.5'to - 31' t o a red liquid. Its dissociation pressure reaches 1 atmosphere a t a few degrees above its melting point. Water decomposes it in a sealed tube almost quantitatively forming sulphurous acid.INORGANIC CHEMISTRY. 23 The double compounds of sulphur tetrachloride are designated by their forruulze. [With GEORG FL~CIIE~L ]-The coinpound SCl,,SbCI prepared by adding sulphur chloride to .a cold solution of aritiinouy peritachloride in sulphuryl chloride and draining by means of the apparatus described by Ruff and Plato (Be?- 1901 34 1749) forms slender white needles melting a t 125-126" in an atmosphere of chlorine in a sealed tube to a yellow liquid and subliming a t 150'.Water decomposes it vigorously. No solid compound could bt. obtained from sulphur tetra- chloride and phosphorus pentachloride. The salt SC14,TiC14 crystallises in slender yellow needles of ten radially grouped melts at 62-64" in an atmosphere of chlorine sublimes at about 1 00" and dissolves in sulphuryl chloride chloroform carbon disulphide or light petroleum. 2SC1,,SnC14 forms large yellow crystals melts a t 37" and de- coiriposes at about 40". It fumes in air but is more stable than the titanium compound and dissolves readily in chloroform light petroleum sulphuryl chloride carbon disulphide phosphorus oxy- chloride ether or benzene.The corresponding compound with zirconium tetrachloride is very unstable and could not be isolated in a pure form. A silicon compound could not be obtained. [With ETNBECK.]-~C~,,F~C~ prepared in phosphorus oxychloride solution forms a yellow crystalline precipitate decomposing rapidly on warming. The compound 2FeCl3,POC1 was obtained on warming the constituents together on the water-bath in the form of a bright yellow crystalline mass. [With GEORG FISCHER.] -SCl4,2IC1 forms yellow crystals de- composing without fusion on even slight warming. No compounds could be obtained from arsenic trichloride antimony trichloride or chromic chloride. [With KURT TRIEL.]-SC~,,~ASF~ forms yellow crystals and only attacks glass slowly but decomposes or chars thionyl chloride carbon tetrachloride carbon disulphide alcohol ether benzene or light petroleum.No compounds were obtained from antimony tin or titanium fluorides or from the chlorides of uni- or bi-valent metals. G'. H. D. Theory of the Lead Chamber Process. 11. FRITZ RASCITICI A reply to (Zeit. angew. Chern. 1904 17 1777-1785).-Polemical. Lunge (ibid. 1659). A. McK. Catalytic Phenomena in the Preparation of Persulphuric Acid. G. I. PETRENKO (J. Buss. Phys. Chena Xoc. 1904 36 1081-1OSS).-The yield of persulphuric acid obtained by the electro- lysis of sulpliuric acid is dependent on the use of a platinum anode which apparently oxidises and then exerts a catalytic action diminish- ing the yield of the peracid.The yield of the latter is almost doubled by the addition of hydrochloric acid. With an iridium anode the yield is considerably less than with platinum and the iridium goes into solution more readily than platinurn. T. 13. P.24 ABSTRACTS OF CHEM1CA4L PAPERS. Ultramicroscopical Observations. I. Separation of Sulphur from Thiosulphuric Acid and of Selenium from Selenious Acid. WILHELM BILTZ and WILLY GAHL (Chem. Centr. 1904 ii 1367 ; from Ncichr. K. Ges. JViss. Gottingen 1904 300-310).-By means of Raehlmann’s ultr.imicroscope homogeneous or ‘‘ optically empty ” solutions may be more readily distinguished from turbid solutions and the phenomena of precipitation more closely followed. By means of the arrangement used a field of 0*00004 cm. was illumin- ated.Filtration or contact with cover glasses or india-rubber destroys the optical homogeneity of solutions. Distilled water must be rendered clear before distilling and must be protected from access of air during distillation and afterwards. A Pukall cell may be used for filtration the air which enters the filter being made to pass through cott on-wool. Thiosulphuric acid decomposes as soon as it is formed the non-dis- sociated acid being the less stable. By means of the ultramicroscope it has been shown that the process of decomposition is not ‘‘ continu- ous,” the discontinuity becoming apparent a t about the same time as the opalescence is visible to the naked eye. Colourless supersaturated solutions of the acid in water can therefore exist. Colloidal aqueous solutions of the acid appear to be blue and are extremely unstable.The action of sulphurous acid on selenious acid has also been found to be optically discontinuous. E. w. w. Colloidal Tellurium. IV. ALEXANDER GUTBIER (Zeit. anorg. Compare Abstr. 1902 ii 653; 1904 Chenz. 1904 42 177-183. ii 61 3).-A detailed account of results already published. A. McK. Action of Hydrogen Peroxide on Tellurium. ALEXANDER GUTBIER and F. RESENSCHECIC (Zeit. ccnorg. Chefiz. 1904 42 174-176. Compare Gutbier and Wagenknecht Abstr. 1904 ii 613).-When hydrogen peroxide is added to a solution of tellurium in concentrated aqueous potassium hydroxide telluric acid is produced in small yield. A. McK. Apparatus for Separating Nitrogen Quickly and Com- pletely from a Mixture of Gases containing it.FERDINAND HENRICH (Zeit. angew. Chern. 1904 17 1755-1757).-An apparatus is described by means of which nitrogen is separated automatically from a mixture of gases containing it the mixed gases being repeatedly passed over heated copper and copper oxide soda lime phosphoric oxide and a heated mixture of magnesium and quicklime. A full descrip- tion is appended to the sketch of the apparatus in question. A. McK. Formation of Nitric Oxide at High Temperatures. WALTHER NERNST (Chem. Centr. 1904 ii 1368 ; from Nachr. k. Ges. Vhs. Gottinyen 1904 261-276. Compare Muthmann and Hofer Abstr. 1903 ii 206).-If a system which is in equilibrium at a high tempera- ture is rapidly cooled the composition of the mixture at the lowerINORGANIC CHEMISTRY. 25 temperature will not accurately represedt the condition a t the higher since the cooling cannot be effected instantaneously.I n all cases no matter in which direction the composition of the gaseous mixture deviates from thatl of the equilibrium state the proportion of the product formed at the higher temperature will be too small except for a small temperature interval in which the curve calculated from thermodynamical data touches that obtained from observed values. I n cases in which it is impossible t o allow sufficient time for the state of equilibrium to be attained because the temperature is too low and the velocity of the action too small the velocities of the opposing reactions may be measured by experiments on streams of gas at different velocities. The concentration at which both reactions have the same velocity and hence the equilibrium constant may be calcu- lated.When gases are brought to very high temperatures for a very short time as for instance when a mixture of hydrogen and oxygen in the proportions contained in water is exploded with air and the mixturd rapidly cooled an examination of the products of the explosion may serve under certain conditions to ascertain the conditions of equilibrium at such temperatures. A litre of air was passed through platinum or iridium tubes and the nitric oxide absorbed in sulphuric acid. The temperature was estimated by means of a thermo-element or a photometer. At temperatures above I 700° equilibrium was attained when one litre passed through the tube in 20 minutes. At 1760° the equilibrium concentration of the nitric oxide was found to be 0.64 per cent,.by volume and at 1922' 0.97 per cent. The "heat-toning" of the reaction calculated from these data is 45,600 cals. whilst the value found by experiment was 43,200. A state of equilibrium could not be obtained in the platinum furnaces a t 153s'. The velocities of the opposing reactions show that the reaction is bimolecular and that the equilibrium concentration of the nitric oxide is 0.37 per cent. by volume. From Bunsen's deter- minations of the decrease of volume caused by exploding mixtures of hydrogen and oxygen with air i t has been calculated that at 3500' the mixture contains about 5 per cent. by volume of nitric oxide when equilibrium is established. Under the ordinary atmospheric pressure t,he time required to convert half the nitrogen of air into nitric oxide is about 100 seconds a t 1540O and 3.5 a t 1737'.The following table shows the observed and calculated equilibrium constants x a t tempera- tures from 1500-3200° Temp. (abs.). x observed. x calculated. 181 1" 0.37 0.35 2033O 0.64 0.67 2 195O 0.97 0.98 3200' about 5 4.4 E. W. W. Preparation of Yellow Arsenic. ALFRED STOCK and WERNER SIEBERT (Ber. 1904 37 4572-4575).-A special form of apparatus is described and figured by means of which arsenic is sublimed in a vacuum and the vapour immediately cooled by liquid air. Under26 ABSTRACTS OF CHEMICAL PAPERS. these conditions a yellow modification of arsenic is deposited which when exposed to light is instantly converted into the black modifica- tion.A similar change takes place in the dark when the yellow form is allowed to assume the ordinary temperature but the change is not accompanied by any luminescence phenomena. E. F. A. The Preparation of Pure Boron Trifluoride and Silicon Tetra- fluoride and some Physical Constants of these Compounds. HENRI MOISSAN (Conzpt. rend. 1904 139 71 1-714).-Boron tri- fluoride prepared by heating a mixture of boron trioxide calcium fluoride and sulphuric acid and purified by passing through cylinders containing sodium fluoride and finally by solidifying in a vacuum (compare Abstr. 1903 ii 642) melts a t - 127" and boils a t -101' (compare Abstr. 1904 ii 331); the corresponding constants of the synthetical compound are - 126' and - 99' respectively. Silicon tetrafluoride similarly prepared and purified and also the synthetic compouT\-d solidifies at - 9 7" under atmospheric pressure and volatilises without passing through the liquid stage (compare Olszewski Abstr.1884 816) under tt pressure of 2 atmospheres. Silicon tetrafluoride melts a t - 77' t o a transparent mobile liquid which boils a t - 65' under 181 cm. pressure ; the critical temperature is - 1.5" and the critical pressure 50 atmospheres. M. A. W. Action of Boric Acid on the Alkali Peroxides. Formation of Perborates. GEORGE F. JAUBERT (Compt. rend. 1904 139 796-798).-When an intimate mixture of 248 grams of boric acid and 78 grams of sodium peroxide is gradually added to 2 lltres of cold water .a clear solution is first obtained from which the perborate Na2B,08,10H20 crystallises after a time in 90 per cent.yield. The aqueous solution of the perborate contains free hydrogen peroxide. Its solubility at ll' 22") and 32" was found to be 42 71 and 138 grams per litre. The perborate cannot be recrystallised from its aqueous solution When a quantity of hydrochloric acid equivalent to half the sodium in the perborate is added to this solution a perborate NaB03,4H20 separates in the form of white crystals which are very stable a t the ordinary temperature and are not affected by atmospheric carbon dioxide. This salt is less soluble than the first perborate ; its aqueous solution slowly decomposes at 50-60" and evolves oxygen rapidly a t 100". The solution has all the properties of hydrogen peroxide and on account of its stability in the air the crystalline salt may con- veniently be used as a means of obtaining an aqueous solution of hydrogen peroxide. H.M. D. Tension of Carbon Dioxide in Sea Water and the Reciprocal Influence of the Carbon Dioxide of the Sea and of the Atmos- phere. AUGUST KROGH (Conapt. rend. 1904 139 896-898).-The ocean contains about 6-55 x 10IG kilograms of carbon dioxide in the form of readily dissociated salts or twenty-seven times the quantity containedINORGANIC CHEMISTET. 27 in the atmosphere and the variation of this quantity with the pressure is expressed in the following table Pressure per cent. Quantity in kilos. 0.01 4.57 x 1016 0.02 5.89 x 1016 0.03 6.55 x 1016 0.04 7.04 x 10'6 0.05 7.36 x 1016 A series of determinations of the tension of carbon dioxide in the sea and in the atmosphere has given the following results (1) in the north af the Atlantic Ocean the tension of carbon dioxide is much lower in the water than in the atmosphere; (2) the atmosphere over the Atlantic Ocean and its shores contains less carbon dioxide (0.029 per cent,) than in Central Europe (0.033 per cent.) ; (3) in the south- ern hemisphere where the ocean covers the major part the atmosphere contains less carbon dioxide than in the northern hemisphere (0.026 per cent,).It follows therefore that the percentage of carbon dioxide in the atmosphere is increasing and that the sea compensates for the increase by absorbing the gas. M. A. W. Action of Potassium Cyanide Solution on Various Metals. ANDRI$ BROCHET and JOSEPH PETIT (Bull.Xoc. chim. 1904 [iii] 31 1255-1257. Compare Abstr. 1904 ii 229 230 and 414).-Alumin- ium and magnesium are readily attacked in the cold by potassium cyanide solution copper and zinc less readily yielding respectively the salts Cu2(CN),,6KCN and Zn(CN),,2KCN and other metals very slowly except on heating. Cadmium and silver are attacked by potassium cyanide solution in presence of oxygen but mercury is unaffected and the amalgamation of a metal retards the action of the salt on it. Deville and Debray (Compt. rend. 1876 82 241) and Glaser (Abstr. 1903 ii 242) have shown that platinum dissolves in solutions of potassium cyanide. The author finds that this does not occur unless the solution of the cyanide is heated and that the effect is diminished by polishing the platinum.T. A. H. Action of Potassium Cyanide on Metallic Electrodes ANDRB BROCHET and JOSEPH PETIT (BUZZ. Xoc. chim 1904 [iii] 31 1257-1261. Compare Abstr. 1904 ii 229 230 and 414).-Most metals behave as soluble anodes when placed in potassium cyanide solution under the influence of an alternating current. A number Q€ metals including copper zinc silver and cadmium dissolve quantita- tively when the current is weak. Nickel dissolves quantitatively so long as the current does not exceed 2 amperes per sq. decimetre; beyond this the dissolution diminishes reaching a minimum of 80 per cent of the theoretical when the current density is 8 amperes per sq decimetre (compare Le Blanc and Schick Abstr. 1904 ii 230). Cobalt dissolves irregularly and the anode becomes pitted.Mercury is almost immediately covered by a black precipitate which preventa28 ABSTRACTS OF CHEMICAL PAPERS. further action but amalgamation has no effect on the dissolution of copper and zinc. Silver begins to deposit on the cathode almost as soon as it appears in the electrolyte and cadmium behaves similarly but copper zinc and nickel deposit only with difficulty whilst with cobalt and iron no deposition occurs. The observation of Glaser (Abstr. 1903 ii 242) that platinum is dissolved when employed as a cathode in potassium cyanide solution is confirmed and it is shown that the action is much more marked when barium cyanide is employed as the electrolyte. This dissolution of platinum under these conditions is due to the disintegration of the cathode probably with the transitory formation of an alloy with the alkali metal and the dissolution in the electrolyte of the finely-divided platinum particles so liberated (compare Bredig and Haber Abstr.1899 ii 78; Hnber and Sack Abstr. 1902 ii 441 ; Bran ibid. ii 442). I n favour of this view is the slow evolution of hydrogen which takes place from the cathode immediately after the current has been stopped. Lead is almost without action. T. A. H. Theory of the Dissolution of Metals in Potassium Cyanide Solution u n d e r t h e Influence of an Alternating Current. ANDRE BROCHET and JOSEPH PEwi7 (&d$. 8oc. dim. 19(:4 31 126 1- 1265. Compare preceding abstracts).-Such metals as silver which are quantitatively dissolved from the anode and deposited on the cathode are insoluble in potassium cyanide solution under the action of an alternating current.On the contrary copper zinc nickel and cobalt which are either not deposited or deposited only with difficulty are soluble in potassium cyanide solution. The cases of iron and platinum which behave as insoluble anodes and slightly soluble cathodes and yet are readily dissolved by potassium cyanide solution under the action of an alternating current are not so easily explicable. Platinum also dissolves in the cyanide solution under the action of a continuous current frequently interrupted and it is probable that its dissolution is due to disintegration while it momentarily acts as a cathode the dissolution of the detached particles being facilitated by the oxidising action of the platinum electrode immediately afterwards functioning as an anode.The original paper contains a series of curves showing (a) the influ- ence of current frequency (from 5 to 100 per second) on the rate of dissolution of various metals and (6) the simultaneous influ- ence of current density and frequency on the rate of dissolution of nickel. The first set of curves shows that as the frequency is increased copper dissolves less quickly whilst iron nickel and cobalt exhibit a maximum and then diminish; with platinum the maximum is unattainable under these conditions. The second series of curves appears to shorn that nickel behaves like copper when the current density is less than 7 amperes per sq. decimetre but above this behaves like iron and that when frequency and density are simultaneously and sufficiently increased no solution should occur.The latter deduc- tion is not in harmony with the experimental observation recorded in the preceding abstract. T. A. H,INORGANIC CHEMISTRY. 29 Reactions between Salts in Non-aqueous Solutions. 11. In Acetone. ALEXANDER NAUMANN [and in part with WILHELM EIDMANN MAX M~LLER PAUL SC'HULZ and ERNST VOIC-T] (Bey. 1904 37 4328-4341. Compare Abstr. 1904 ii 819).-Pure anhydr- ous acetone of sp. gr. 0.795 a t 1 8 O f 4 O was used. The following salts are readily soluble aluminium bromide nminonium bromide tri- chromate iodide nitrate perchlorate and thiocyanate ; antimony tri- bromide chloride (0*186) and iodide ; barium bromide and iodide ; bromine ; cadmium bromide (64.5) chlorate iodide (4) and nitrate ; cmiuru nitrate ; calcium bromide chlorate dichromate iodide and nitrate ; cerium bromide chloride iodide and nitrate ; chromic nitrate ; chromic anhydride ; ferric chloride (1.59) and nitrate ; ferrous chloride ; erbium nitrate ; iodine ; potassium bromide chloro- chromate ferricyanide ferrocyanide iodide permanganate mercuri- iodide and thiocyanate ; cobalt chloride (36*4) bromide iodide and nitrate ; cupric bromide chloride (34*7) and chlorate ; lanthanum nitrate ; lithium bromide chloride iodide and nitrate ; magnesium bromide chlorate chloride and iodide ; palladous chloride ; platinic chloride ; mercuric chloride ( O T ) bromide and nitrate ; rubidium nitrate ; sulphur ; silver nitrate (22'7) and nitrite ; thallous nitrate ; uranium bromide ; uranyl chloride iodide and nitrate ; bismuth tri- chloride (5.59) and tri-iodide ; zinc chloride (2.3) and iodide ; stannous chloride (1 ' 8 ) ; stannic chloride bromide and iodide.The numbers in brackets indicate the number of grams of acetone required to form a saturated solution with 1 gram of the salt a t 18". The following salts are very sparingly soluble aluminium chloride and nitrate ; ammonium chromate diborate and thiosulphate ; barium chlorate and nitrate ; lead bromide and nitrate ; cadmium chloride ; calcium chloride ; potassium nitrate ; lithium diborate ; sodium di- chromate ; mercuric iodide ; rubidium bromide ; strontium chloride and nitrate ; thallic chloride ; thorium nitrate. A list of some 197 insoluble compounds is given. Ammonia yields precipitates with acetone solutions of the following salts cupric bismuth antimony cobaltous mercuric stannous and ziuc chlorides silver nitrate cadmium bromide and cadmium iodide.The pre- cipitates in all cases are additive compounds of the salt and ammonia. The following yield precipitates of silver haloids with silver nitrate in acetone solution bismuth antimony ferric cobaltous mercuric strontium and zinc chlorides cadmium bromide arid iodide. Hydrogen sulphide precipitates the metals of stannous chloride bismuth chloride silver nitrate and cadmium bromide as sulphides. It precipitates mercuric chloride as HgC1,,2HgS and cadmium iodide as CdI,,BCdS. Double decomposition has been observed between cadmium bromide and mercuric chloride cupric chloride and calcium bromide bismuth chloride and potassium iodide mercuric chloride and cadmium iodide mercuric chloride and bismuth iodide and also between potassium thiocyanate and solutions of the following salts zinc chloride silver nitrate and cobalt chloride.Cupric ferric and mercuric chlorides are reduced by stannous chlor- ide. Ferric and cupric chlorides are reduced by potassium iodide and ferric chloride partially by hydrogen sulphide.30 ABSTRACTS OF CHEMICAL PAPERS. Acetone solutions of silver nitrate yield precipitates with hydrogen qhloride bromide or iodide and in the case of the bromide and iodide the precipitate dissolves in an excess of the acid. Silver nitrate and sulphur yield Ag,S,. Mercuric chloride and cuprous bromide yield mercurous bromide cuprous chloride and chlorine ; cadmium bromide is decomposed by an acetone solution of chlorine and cuprous chloride which is insoluble in acetone yields with an acetone solution of chlorine cnprbc chloride with bromine a mixture of cupric chloride and bromide and with an iodine solution cuprous iodide and capric chloride.Mercurous chloride suspended in acetone is only slightly affected by chlorine but with bromine and iodine yields mixtures of mercuric chloride with the bromide and iodide. J. J. S. Reactions between Salts in Non-aqueous Solutions. 111. 4609-4614. Compare Abstr. 1904 ii 819).-The solubility of a large number of inorganic salts in pyridine was determined qualitatively. The compound HgC12,C5H,N prepared by the addition of mercuric chloride to pyridine crystrtllises in needles.I t s behaviour when dissolved i n pyridine towards ammonia hydrogen sulphide and stan- nous chloride is similar to that of mercuric chloride. With ammon- ium thiocyanate and silver sulphate it gives precipitates of ammonium chloride and mercuric sulphate respectively. The compound CuC1,,2C5H,N prepared by the addition of cupric chloride to pyridine separates from alcohol in needles. I t s behaviour and that of the compound AgN0,,2C5H,N (in pyridine solution) and of a solution of silver sulphate in pyridine towards various reagents is described in considerable detail. ALEXANDER NAUMANN [and JOHANNES SCHROEDER] (Bey. 1904 37 A. McK. Sodamide and certain of its Reaction Products. W. PHILLIPS WINTER (S. Amer. Chem. SOC. 1904 26 l.484-1512).- A convenient method is described for the preparation of sodamide. When sodamide is exposed to dry air it slowly assumes a yellowish- brown colour and is found to contain nitrous and hyponitrous acids.When sodamide is decomposed by water hydrogen and nitrogen are produced. The relative proportions of these gases vary with the con- dition of the sodamide. It has been found that the proportiou of hydrogen is high in the case of sodamide which has been insufficiently heated owing to the presence of unchanged sodium but is low when the sodamide has been properly prepared. Nitrogen is always evolved to a small extent and is formed in larger proportion from sodamide which has been kept for some time than from freshly prepared speci- mens. The production of the nitrogen is probably due to the presence in the sodamide of sodium azoimide or some analogous compound formed by oxidation of ammonia either in the process of manufacture of the sodnmitle or during its exposure to dry air.If finely powdered sodamide is sprinkled into a vessel containing water heated ncarly to boiling through which a current of carbonINORGANIC CHEMISTRY. 31 dioxide is being passed a shower of brilliant sparks is piocluced and a solution of disodium cyanamide is formed. When sodamide is treated with phosphorus pentachloride a violent reaction takes place and a white sitblirnnte is produced which consists of ammonium chloride sodium chloride traces of phosphorus com- pounds a i d a small quantity of a substance iiisoluble in water. This insoluble compound cannot be isolated but when the soluble substances are removed from the sublimate by means of nitric or acetic acid a white nearly tasteless odourless con~poz~nd PO,N or PH,O,N is obtained which is not affected by hot strong mineral acids.When sodamide is warmed with yellow phosphorus an energetic reaction occurs and the product consists of sodium phosphide and other substances including oxy-acids of phosphorus and probably a n amide of phosphorus. E. G. Supercooled Fusions and Solutions of Sodium Thiosulphate. STEWART W. YOUNG and J. P. MITCHELL (J. Amer. Chenz. Soc. 1904 26 1389-1 413).-Sodium thiosulphate pentahydrate exists in three forms the ordinary commercial or a-form the @form described by Parmentier and Amat (Abstr. 1884 S19) and the y-form discovered in the course of the present investigation The p-form is obtained most readily by heating the a-form at 80-100" for a few minutes in a sealed glass tube and cooling to - 10" or - 20° when the product solidifies in long needles.The y-form is produced occasionally instead of the p-form; the conditions necessary for its formation have not been fully investigated but it appears tbat the presence of a small excess of water in the tube favours its production. This y-modification is obtained as a compact opaque mass which melts a t a little above Oo whilst the p ar,d a-forms melt a t about 32' and 49" respectively. Each ol these forms on melting is converted into a saturated solution and a lower hydrate. The a-form is obtained when the a-pentahydrate is melted and left a t the ordinary tempera- ture for a day or two.The 6-form is produced by the partial fusion of the a-form the d-form by the partial fusion of the P-pentahydrate and the c-form by the partial fusion of the y-pentahydrate. A large number of experiments have been made with the object of ascertaining the conditions under which these various forms are produced from supercooled solutions and fusions attention being paid particularly to the form of the thiosulphate from which the solution or fusion was prepared the rate a t which the tubes were cooled the temperature to which they were heated and the length of time for which the heating was continued For the details of these experiments and the results obtained the original must be consdted. I n order to afford an explanation of the results of this investigation a hypothesis is put forwnrd based on that proposed by Jaff6 (Abstr.1903 ii 469) which ascribes the initiation of the crystallisation to the preseiico of nuclci. It is suggested that these nuclei consist of frag- ment s of crystalliiic aggregates left in the licliiid after the breaking down of the crystnlliiie structure and that under certain conditions. Four different lower hydrates are described.3 2 ABSTltACTS OF CHEMICAL PAPERS they unite to form crystalline aggregates which are capable of starting the crystallisation. E. G. Composition and Solubility of the Hydrates of Sodium Thiosulphate. STEWART W. YOUNG and W. E. BURKE (J. Amer. Chern. Soc. 1904 26 1413-1422. Compare preceding abstract).- Considerable clifficul ty was experienced in determining the composition of the various hydrates of sodium thiosulphate owing to the fact that all the other forms are metastable with respect to the a-form and are rapidly converted into this form if a trace of it is present. Parnientier and Amat (Abstr.1884 819) have shown that the p-form consists of a pentahydrate. There is little doubt that the y-form is also a penta- hydrate although hitherto it has not been analysed. Analyses have been made of the a- 6- and d-forms which show that the first two consist respectively of a monohydrate and a dihydrate and that the d-form is probably a tetrahydrate. The composition of the c-variety has not been ascertained Determinations of the solubility of these different hydrates have given the following results which are expressed as the number of parts of the anhydrous salt Na,S,O in 100 parts of water.The solubility of the a-form of sodium thiosulphate is 59.69 at lo' 70.07 a t 20' 75.90 a t 25' 82.45 at 30° 91.24 at 35O 103.37 at 40' and 123.87 a t 45'. I n the case of the p-form the values obtained were 97.55 a t ZOO 108.98 a t 25O 119.69 at 2S0 12650 a t 29*5O and 130.26 at 30'. The solubility of the a-form is 163.92 at 20° 168.32 a t 25' and 174.20 a t 30'. For the b-form the values found were 122.68 at ZOO 127.43 a t 25' 13397 at 30° 138.84 at 35O 144.92 a t 40° and 165.11 at 50'. In the case of the d-form the solubility was found to be 141.45 at 33.5' 153.23 a t 36.2' and 168.82 a t 38.6O. The solubilities of the y- and e-forms have not been determined.These solubility data have been plotted as curves which are of particular value as defining exactly the ranges of supercooling and supersaturation of the forms studied. E. G. Formation and Constitution of Bleaching Powder. NAZARENO TARUGI (Gaxxetta 1904 34 ii 254-260).-The author finds that the formation of bleaching powder containing a maximum amount of active chlorine is influenced by the presence of oxygen. When lime is completely hydrated and left in contact with air after some time it exhibits the reactions of peroxides-blue coloration with guaiacum resin red coloration with ferrous sulphate and potassium thiocyanate and blue coloration with chromic acid and ether. I n the formation of bleaching powder the chlorine acts on the water yielding hydrogen chloride and oxygen the latter then converting a part of the lime into calcium peroxide 4C1+ 2H,O = 4HCl+ 0 ; CaO,H,O + 0 = CaO,,H,O ; CaO,,H,O + 2HC1= Ca02C1 + 2H,O.The author's experiments indicate that hypochlorites must in general be regarded as chlorides of peroxides and that bleaching powder containing 44.09 per cent. of chlorine (which is the maximum proportion obtainable in the commercial product) is the chloride ofINORGANIC CHEMISTRY. 33 calcium peroxide plus 1 mol. of water Ca(OC1)2,H,0. This constitu- tion for bleaching powder is in accord with its action on mercury which is converted quantitatively into mercuric chloride Ca0,C12 + Hg = CaO + HgC1,. This method is the subject of a patent for the manufacture of corrosive sublimate.T. H. P. Action of Water on the Phosphates of Calcium. FRANK K. CAMERON and ATHERTON SEIDELL (J. Amer. Chem. Soc. lY04 26 1454-1463. Compare Rindell Abstr. 1902 ii 208).-A study has been made of the extent to which the three calcium phosphates are decomposed by water and experiments have been made to ascertain the effect of calcium sulphate calcium carbonate and carbon dioxide on the hydrolysis. Since tricalcinm phosphate and monocalcium phosphate always contain an excess of either base or acid the results of the solubility determinations cannot be regarded as of absolute value but are useful as indicating the nature of the reaction between the phosphates and water. I n each experiment a weighed quantity of the phosphate was placed in x bottle with distilled water and maintained for several weeks at 25".with occasional shaking. Portions of the clear solutions were withdrawn and the amounts of calcium and phosphoric acid in them were estimated. The results shorn that tricalcium and monocalcium phosphates both undergo considerable decomposition but that di- calcium phosphate is more stable and only slightly decomposed by water. I n the case of the mono- and tri-calcium phosphates the amouiit of decomposition and the concentration of the resulting solu- tion are found to depend on the relative proportions of phosphate and water employed. I n presence of calcium sulphate the amount of phosphoric acid dissolved from tricalcium phosphate is increased. A slight increase also takes place with monocalcium phosphate but a considerable decrease occurs in the amount of phosphoric acid dissolved from the dicalcium salt.I n presence of calcium carbonate the amount of phosphoric acid dissolved is decreased in all three cases. Carbon dioxide causes an increased quantity of phosphoric acid t o be dissolved from tri- or di-calcium phosphate but is without effect on the action of water on the monocalcium salt. E. G. Action of Amalgams on Solutions. GUSTAVE FERNEKES (J. Physical Chem. 1904 8 566-570).-A reply to some criticisms by G. McP. Smith (Abstr. 1904 ii 400) of the author's explanation of the action of amalgams on water (Abstr. 1904 ii 263). The author adds the results of some further experiments. It was first shown that barium is not replaced in its rmalgam by either sodium or potassium when acted on by n concentrated solution of a salt.It was found however that barium amalgam reacts with water about three times as quickly as with a solution of potassium chloride. This is readily explic- able on Kahlenherg's theory as each molecule of the salt would influence the surrounding water molecules. Molecular quantitios uf VOL. LXXXVIII. ii. 3ABSTRACTS OF CHEMICAL PAPERS. 34 sodium and potassium chlorides were also allowed to act on sodium amalgam for 15 minutes a t the end of which time the amalgam was found to contain only potassium; this fact and also the anomalous behaviour of sodium hydroxide solutions are not explicable by the ionic theory. L. M. J. Equilibrium in the System G10 SO H20. CHARLES L. PARSONS (J. Amer. Chem. Soc. l904,26,1433-1446).-It is found that the only definite hydrated sulphat es of glucinum are GlS0,,4H20 and GlS04 2H20 no evidence being obtainable of the existence of the heptahydrate de- scribed by Klatzo (Zeit.Chem. 1869 12 129). The tetrahydrate has an aqueous vapour pressure equal to or greater than the pressure of its own water of crystallisation; it has been found by tensimeter experi- ments that this pressure over phosphoric oxide at 20" is equivalent to 20 mm. of olive oil and increases rapidly with the temperature The dihydrate is stable in the air a t the ordinary temperature but loses water slowly at 100-110". The anhydrous sulphate cannot be ob- tained quite pure on account of the difficulty of removing the last traces of water without incurring the loss of sulphur trioxide.An examination of the various so-called basic sulphates of glucinum has shown that these substances are not definite compounds but consist of solid solutions of the sulphate in the hydroxide. E. G. Zincum Boricum or Oxyboricum. E. HOLDERMANN (Arch. P&arm. 1904 242 567-56S).-When a solution of zinc sulphate and another of borax are mixed in varying proportions the second solution containing also just enough sodium hydroxide to complete the conver- sion of the sulphate into sodium sulphate the filtrate gives no further precipitate with either solution when the zinc sulphate and borax have been mixed in the proportion of 3 2 mols. The composition of the precipitate therefore is Zn,(B,O,),(OH),. The Complexity of Dissolved Sulphates. ALBERT COLSON (Cornpt.rend. 1904 139 857-859. Compare Abstr. 1904 ii 377 532).-A solution of copper sulphate containing 0.75 gram-moi. in 2 litres gave a depression of the freezing point of 0.70° whilst the sulphuric acid solution obtained by exactly precipitating the copper in khe same solution by hydrogen sulphide gave a depression of 1-51" at least twice 0*70°; it follows therefore that the second solution contains twice as many molecules as the first and the molecular com- plexity of copper sulphate in solution is represented by the formula (CUSO,)~ and similar results were obtained in the case of magnesium sulphate. The author suggests that the sulphates of the bivalent metals in aqueous solution have the formula (HSO,M),O and may be regarded as being formed by the condensation of 2 mols.of sulphuric acid with the hydroxide (OH*M),O ; this explains the acidic nature of the metallic sulphates. On the other hand the metallic hydroxides are sufficiently strong bases to displace sodium or ammonium hydr- oxide from solutions of their sulphates for when a solution of sodium sulphate is added to zinc oxide neutral to phenolphthalein suspended in water the mixture becomes increasingly alkaline towards the indi- C E. B.INORGANIC CHEMISTRY. 35 cator owing to the liberation of sodium hydroxide and the formation of the basic salt SO,(ZnaO*ZnOH),; similarly a blue coloration is developed when copper oxide is added to a solution of ammonium sulphate. M. A. W. A New Cause of Dissociation of Mercuric Chloride and its Influence on the Antiseptic Properties of Solutions of Corro- sive Sublimate.HENRI VITTENET (Bull. SOC. chin$. 1904 [iii] 31 1133-1138).-When equal parts of ammonium and mercuric chlorides are dissolved in tap-water there slowly forms a precipitate which is a t first white and has the composition N(HgCl) but on further standing gradually becomes yellow. The production of this substance was traced to the presence of acid carbonates in the water and its forma- tion was found to be inhibited by previous ebullition of this. When the two salts are dissolved in distilled water to which sodium hydrogen carbonate or carbonate has been added the precipitate formed is white and has the composition N(HgC1),,3NH4C1 but gradually becomes yellow when washed with water and the final product is bright yellow and has approximately the composition required by the formula N(Hg*OH),*Hg*OCl.The formation of these precipitates in such solu- tions used as antiseptic baths leads t o a diminution of efficiency and it is suggested that in preparing these the water should first be boiled or t'he ammonium chloride should be replaced by sodium chloride; with either of these precautions no precipitation occurs. T. A. H. Yttrium Earth related to Gadolinium. GEORGES URBAJN (Compt. rend. 1904 139 736-738).-By means of three separate methods of fractional crystallieation the author has obtained from the yttrium earths 100 grams of a rare earth which consists chiefly of the oxide of Lecoq de Boisbaudran's new element Z6 (compare Abstr. 1896 ii 249 ; also Demarqay Abstr.1900 ii 656). The methods employed were (i) Fractional crystallisation of the double nitrates of the rare earths and of nickel. The fractions containing the element Z6 were intermediate between those of gadolinium and dysprosium. (ii) Fractional crystallisation of the nitrates of the earths in the presence of bismuth nitrate (compare Abstr. 1904 ii 37,43,173 ; also Demarpy Abstr. 1900 ii 347). The nitrate of Z6 has the same solubility as bismuth nitrate. (iii) Fractional crystallisation of the ethyl sulphates of the rare earths (compare Abstr. 1900 ii 346). The emth thus separated exhibits only the absorption band X = 488 characteristic of Z6 but this does not preclude the possibility of ZS being a mixture of elements some of which possess no absorption spectra.ANTON WAEGNER (Zeit. anorg. Chew. 1904 42 118-126. Compare Abstr. 1903 ii 729).-That very varying statements have been made as to the colour of neodymium oxide Nd203 is probably due to the oxide under investigation having been in many cases contaminated with other rare earths and particularly with praseodymium. The crude neodymium chloride used by the author which con- tained traces of praseodyiniuni and lanthanum was converted into the M. A. W. Neodymium Oxide. 3-236 ABSTRACTS OF CHEMICAL PAPERS. oxalate; this when carefully heated in a platinum boat in a current of oxygen formed a pink residue from which carbon dioxide could be obtained a t a higher temperature. When the oxalate is heated a t ft bright red heat an oxide of the probable composition Nd,O is formed ; prepared in this manner it is brownish-pink and resembles Brauner’s oxide Nd,O in being converted by prolonged heating with the blowpipe or in a current of hydrogen into the oxide Nd,O,.Further its brown tint is clue to a trace of praseodymium peroxide since when heated moderately in a current of hydrogen the traces of praseodymium peroxide are reduced to sesquioxide and the true colour of the neodymium oxide namely a sky-blue colour with a violet tint is rendered evident;. The existence of a higher neodymium oxide was also rendered prob- able by the spectrometric observations with the two oxides. The spectrum from the oxide Nd,O is quite different from that of the oxide Nd,07. A. McK. Deposition of Aluminium from Ethyl Bromide Solution. HARRISON E.PATTEN (J. Physical Chern. 1904 8 548-565).-1t has been shown by Plotnikoff (Abstr. 1902 ii 639) that aluminium bromide dissolved in ethyl bromide yields a conducting solution from which aluminium may be deposited and the author has further studied this deposition. I n a 4.38 per cent. solution no aluminium was deposited even with currents of fairly high density; evidence was however obtained of the formation of protective films on the aluminium and this in a solution which was almost perfectly free from oxygen. I n a solution of 40.95 per cent. of aluminium bromide aluminium was deposited when the current density reached 0*0083 ampere per sq. em. ; the electrolytic metal reacts on the solution vigorously a gas probably butane being evolved ; below the current density given the rate of dissolution exceeds that of deposition.The potential of the aluminium against the solution was 1.10 volts and that of the bromine was - 1-20 volts. Using the aluminium as anode further evidences of film formation were obtained but no high counter-pressures were obtained. During the work aluminium bromide was obtained in the form of large rhombohedra1 crystals of a pale yellow colour. Stimulating and Paralysing Influences of certain Sub- stances in the Production of Rust. LEON LINDET (Contpt. reizd. 1904 139 S59 -862).-The catalytic action exercised by certain metals on the oxidation of organic compounds has been studied by Livache (Abstr. 1883,756 ; 1884,532) by Trillat (Abstr. 1903 i 222 ; ii 201 589 ; 1904 ii 38) and by Duchemin and Dourlen (Abstr. 1904 i 961).The author finds that the rusting of iron is accelerated by the presence of copper and retarded by such metals as tin lead zinc manganese aluminium or magnesium; the phenomena are to be attributed to the hydroxide of the metal which dissolves in the water for similar stimulating or paralysing effects are produced on the iron by water which has been in contact with the metal.. Arsenic and its compounds exercise a paralysing effect on the rusting of iron and when present in large quantities stop it altogether; in this case the dissolved L. M. J.INORGANIC CHEMTSTRY. 37 iron hydroxide forms colloidal ferrous or ferric arsenite. Soluble salts such as the chlorides and sulphates of the alkali metals have a stimulating effect on the rusting of iron probably due t o their electro- lytic dissociation whilst among organic substances such compounds as sugar phenol or resorcinol stimulate the formation of rust ; alcohol or methyl salicylate has a retarding effect and acetic or salicylic acid dissolves the iron as rapidly as it is oxidised.A. V. DUMANSKY (J. Russ. Phys. Chem Xoc. 1904 36 1067-1069).-The colloidal ferric hydroxide examined mas prepared by saturating a solution of ferric chloride with ammonium carbonate and purifying the solution obtained by dialysis. The liquids thus prepared contain as much as 5.3 grams of ferric oxide per litre but no iron ions are present; the solution also contains chlorine probably in combination with ammonia. On electrolysis or with electrolytes such as barium hydroxide potassium thiocyanate hydrochloric acid zinc sulphate &c.the solution is coagulated but with mercuric or mercurous nitrate or ferric chloride it forms first a complex colloid; besides this salts of mercury or copper convert a part of the iron into salts of their acids. By ammoniacal solution of copper oxide the colloid is precipitated together with cupric oxide whilst in the presence of organic hydroxy-acids and on heating the cupric oxide is reduced to cuprous oxide; the same occurs with ammoniacal silver oxide solution. When the solution is boiled with Fehling’s solution the colloid is precipitated together with cuprous oxide. T. H. P. Perchromic Acid and the Perchromates. HORACE G. BYERS and E. EMMET RETD (Amer. Chenz. J. 1904 32 5O3-513).-The blue compound produced when chromic acid is treated with hydrogen peroxide has been the subject of numerous investigations and various formuh have been assigned to it.Recently Patteii (Ahstr. 1903 ii 431) has stated that this substance is not perchromic acid but that the chromium is present in the chromous state. When the ethereal solution of the blue compound is treated with potassium a t - 20° hydrogen is evolved arid a purplish-black precipi- tate is produced. This compound which has the composition KCrO or K,Cr,O is unstable and rapidly decomposes with evolution of oxygen and formation of potassium dichromate. By the addition of an alcoholic solution of potassium cyanide to the blue solution Wiede (Abstr. 1S9S ii 295) obtained a similar compound to which he ascribed the formula KCr05,H202.When the blue solution is pre- pared without employing an excess of hydrogen peroxide the compound obtained on the addition of potassium cyanide has the same com- position as that produced by the action of potassium. Thc corre- sponding sodium aminoniuum Zitluiunz magnesium cuZciurn barium and zinc salts were prepared. A study of the blue ethereal solution has shown that it contains perchromic acid H,Cr,O,. When the solution is prepared in presence of an excess of hydrogen peroxide it is probable that a more highly M. A. W. Colloidal Ferric Hydroxide oxidised compound is also produced. E. G.38 ABSTRACTS OF CHEMICAL PAPERS. Perceri tage of dissolved Tempera- salt. sp. gr. ture. Derivatives of Complex Inorganic Acids. ALLEN ROGERS and Com- EDGAR F.SMITH (J. rliizer. Gltem. Soc. 1'304 26 1474-1484. pare Abstr. 1903 ii 375).-Amiuonium manganitungstate 4(NH4)20,Mn203 1 2W0,,23H20 (Brubaker Thesis 1904) prepared by boiling ammonium paratungstate and manganic hydroxide with ~1 ater forms large red octahedral crystals and is very soluble in water. Amino&m nickelitungstate 3(NH4),0,Ni,O3,l 6W03 22H2O ob- tained by boiling the hydrated sesquioxide of nickel with an am- moniacal solution of ammonium paratungstate forms a greenish-white crystalline powder and is sparingly soluble in water. On adding barium chloride to a solution of this salt ba?*iunz nickelitungstate 19BaO,Ni,O 16 WO,? is produced as a white precipitate. When ammonia is passed into the solution of ammonium nickelitungstate another ccn~nzoniun~ salt (NH4),0,Ni,0,,4 W0,,7H20 is obtained which is dark blue when moist but of a light blue colour when dry.The following compounds were prepared by boiling the respective hydroxides with an aqueous solution of ammonium paratungstate for 8 hours filtering and evaporating the filtrate to dryness on the water- bath. Ammonium prccseodymitujagstate 2 (NHJ20,Pr2O3,l 6W03,1 6H20 is obtained as a green transparent gum. and 6Ba0,Pr,0,,16W03,9H,0 form white powders. 4 Ag,0,Pr20i3 16 W0,,8H2O is of a greenish-white colour. the barium salt 6Ba0,Nd,03,16W03,17H,0 are of a pink colour. the ba&m and silver salts 5 BaO La203 16 WO 16H,O and form white powders. as a red transparent glass. When dry all the salts were quite insoluble. The bnrium salts 4Ba0,Pr20,,1 6W0,,7H20 The silver salt Ammonium neodgmitungstcde 3(NH,),0,Nd203,16W03,20H,0 and Anzmoniurn Iantl~aizitungstale 2(NH,),0,Ln,03 16 W 0 16H,O and 5Ag20,La2O3 16 WO 1 6H,O Ainnzoniunz ceritungstate 2(NH,),O,Ce,O,,l 6W03,2H,0 is obtained E.G Percentage of dissolved Tempera- salt. Sp. g c ture. 1 1.0056 14.6" 2 1.0112 16.3 3 14161 13.7 4 1.0215 13.1 5 1-0260 14.2 6 1.0313 15.2" 7 1.0366 14.3 8 1.0418 14.5 9 1.0469 15 10 1,0517 14.8 When uranyl chloride is heated in dry air it is decomposed into chlorine and the dioxide UO which is oxidised to the higher oxides UO and U,O and is similarly decomposed when heated withINOltGANIC CHEMISTRY. 39 calcium hydroxide or calcium oxide the final products being calcium uranate or a mixture of calcium uranate and diuranate [pyrouranate a] and similar results were obtained with barium or strontium oxides or hydroxides.By the action of fused potassium or sodium hydroxide uranyl chloride is converted into a mixture of the alkali chloride and diuranate [pyrouranate 't] together with a little alkali uranate ; the alkali diuranates [pyrouranates '13 are insoluble in water but soluble in dilute nitric acid. By the action of sulphuric nitric or selenic acid uranyl chloride yields uranyl sulphate nitrate or selenite respectively and it is reduced to uranous oxide UO by the action of hydrogen hydrogen sulphide zinc dust or iron filings a t a high temperature. A neutral aqueous solution of uranyl chloride gives the following qualitative reactions with potassium hydroxide an orange precipitate ; with ammonia or methylamine a yellow precipitate insoluble in excess of the reagent; with sodium hydrogen carbonate an evolution of carbon dioxide and no precipitate ; with potassium or sodium carbonate or sodium phosphate or potassium cyanide a yellow gelatinous precipitate insoluble in excess of the reagent; with ammonium sulphide a brown precipitate becoming red ; with hydrogen sulphide a slight brown precipitate after 24 hours ; with potassium ferrocyanide or ferricyanide a deep reddish-brown precipitate insoluble in excess of the reagent.M. A . W. Tin Amalgams. WILLEM J. VAN HETEREN (Zeit. nnorg. Chem. 1904 42 129-173).-1n the liquid state tin and mercury are miscible in every proportion. The points a t which such mixtures solidify rise from tin to mercury and form two curves the first from 231.6" to - 34.5" for concentrations of 100-0.3 atomic percentage of tin the second from -34-5" to - 38.6' for concentrations of 0-3-0 atomic percentage of tin.The first curve is almost a straight line until 120° when it gradually bends till 40" is reached a t which point it falls almost perpendicularly along the temperature axis. Consequently at low temperatures the amount of tin in the saturated liquid amalgams is exceedingly small. From the liquid amalgams represented by this curve either pure tin separates or tin with very little mercury. The solid phase a t 25' contained 94 per cent. of tin as determined analytically and 99 per cent. as determined by electrical means. The potential differences of amalgams of from 0.001 to 100 per cent.of tin were measured at 25" against an amalgam with 15.95 per cent. With hhe liquid amalgams the potential difference increases rapidly the higher the amount of tin until the saturation point with 1.2 per cent. of tin is reached. Contrasted with pure tin the difference is about 0.5 millivolt more. By comparison of the potential differences a t 25' and 50" respectively the deduction is made that a t 25" the conversion of 1 gram atom of tin into liquid amalgam with 0.01 to 1-00 atomic percentage of tin that is almost pure mercury involves an amount of heat equal to about 3000 calories. Amalgams containing 0.3 to 85 atomic percentage of tin exhibit at - 34.5" a transformation which with the addition of heat is accom- panied by contraction.A new solid phase results mixed crystals being40 ABSTRACTS OF CHEMICAL PAPERS. probably,produced where the tin may be supposed to exist in a form unknown in the free state Between - 34.5" and - 38.6" those mixed crystals separate and an expansion occurs which decreases when the percentage of tin is considerable and disappears with an atomic percentage of 60 to 70 of t'in. All amalgams up to 60 per cent. of tin solidify a t - 38.6". A. McK. Stannichlorides of the Types M,'SnCl and M"SnC1,. 11. EUGEN VON BIRON (J. Buss. Phys. Chem. Xoc. 1904 36 933-947. Compare Abstr. 1904 ii 567)-On repeating the experiments of Engel (Abstr. 1897 ii 376; 1898 ii 29 119) the author obtains tin meta- and para-chlorides having properties identical with the products obtained by Engel.The meta-chloride differs slightly in composition from that prepared by this author From the results obtained together with t'hose of other investigators the following conclusions are drawn. When a-stannic acid undergoes change it yields an uninterrupted series of varieties of P-stannic acid differing as regards their degree of condensation which becomes greater as the temperature rises. The action of hydrochloric acid on these various p-stannic acids gives rise to oxychlorides which have an indefinite composition and contain a larger or smaller proportion of chlorine according as the condensation of the P-acid is small or great. The oxychlorides differing considerably in composition exhibit differences in properties similar to those shown by the tin meta- and para-chlorides of Engel. The reverse reactions by which the oxychlorides are converted into a derivative of the a-acid namely stannic chloride proceed the more readily the less the condensation.T. H. P. Stannates. ITALO BELLUCCI and N. PARRAVANO (Atti R. Accad. Lincei 1904 [v] 13 ii 339-346. Compare Abstr. 1904 ii 823). -Lead stannate PbSn(OHj is obtained as a white amorphous precipitate and loses 3H,O on heating to redness. The barium ( + 4H,O) calcium and strontium salts were also prepared and analysed. All these salts are of the type X'Sn(OH) and contain a far more stable complex than the stannichlorides (see Abstr. 1904 ii 822). This greater stability of the stannates is borne out by conductivity measurements of solutions of potassium stannate. T. H P.Titanium. I. Hydrates of Titanium Trihaloids. ARTHUR STAHLER (Ber. 1904 37 4405-4410).-The author was unable to obtain the green compound TiC1,,4H20 described by Glatzel (this Journal 1877 i 688). Tit3 nium trichloride hexahydrate TiC1,,6H20 prepared by the elect,rolytic reduction of the tetrachloride is violet Titanium rubidium chloride TiCI 2RbUl,H,O prepared by passing hydrogen chloride into an aqueous solution of a mixture of rubidium and titanium chlorides which was heated on the water-bath is green andINORGANIC CHEMISTRY 41 forms a violet solution with water. Titanium cesium chloride TiC1,2CsC1,H20 is green. TiBr,,GH,O prepared by the electrolytic reduction of titanium tetrabromide is violet and more unstable than the corresponding chloride. Titanium tri-iodide hezahydrate TiI,,6H20 prepared by the electrolytic reduction of titanium tetraiodide is violet and very unstable. Titanium tribromide hexahydrate A.McK. Zirconium Salts. Constitution of Normal Zirconium Sul- phate. RTJDOLF RUER (Zeit. cinorg. Chem. 1904 42 87-99).- Normal zirconium sulphate does not give the chai.itcteristic reactions with oxalic acid and ammonium oxalate respectively such as the chloride gives These reactions do not take place with solutions of zirconium oxychloride to which normal ammonium sulphate or sodium sulphate is added. The conclusion is drawn accordingly that zir- conium sulphate in aqueous solution is constitutionally different from zirconium chloride or nitrate; its behaviour in aqueous solution is best expressed by formulating it as ZrOS0,,H,S04.Since this compouLd is represented as a dibasic acid i t forms sodium and ammonium salts of the type ZrOSO,,SO,M the complete electrolytic dissociation of which is represented by ZrOS04,M2S0 = ZrOSO,,SO," + 2M" zirconium being present in the complex anion. The constitution of crystalline zirconium sulphate is very probably ZrOS0,,H2S0,,3H,0 and not Zr( S0,)2,4H20. Complex formation with concentrated solutions of sodium salts such as sodium chloride and sodium nitrate was also noted. I n such complex salts the zirconium is present in the cathion. Zirconium oxgchloride in aqueous solution is gradually decomposed when left at the ordinary temperature or when heated. A. McK. Red Derivatives of Hydrated Vanadium Trichloride. ARTHUR STAHLER (Ber.1904 37 441 1-441 2).- Vccnadiuna rubidium chloride VdC1,Rb2,H20 prepared by evaporating a solution of hydrated vanadium chloride saturated with hydrogen chloride forms a red crystalline powder which is sparingly soluble in water. Similar anamonium potussiuna and c ~ s i u n ~ compounds were obtained ; the magnesium compound has the composition VdCl,hlg,H,O. These substances are probably analogous to the chromium derivative CrC1,(OH,)Rb2 (Werner and Gubser Abstr. 1901 ii 453). W. A. D. Purification of Sodium Vanadate Liquors ; the Processes of Double Decomposition for the Industrial Separation of Metals. H. HERRENSCHMIDT (Compt. rend. 1904 139 862 -864).- I n the separation of vauadic acid from the mixture of sodium vanadate and silicate (compare Abstr. 1904 ii 824) the use of sulphuric acid is to be avoided as it necessitates a concentration of the liquors introduces a third substance namely sodium sulphate which has to be removed and precipitates the vanadic acid with the silica whereas the addition of a slight excess of vanatlic acid t o the dilute42 ABSTRACTS OF CHEMICAL PAPERS.solution of sodium vanadate and silicate causes the complete pre- cipitation of the silica the vanadic acid remaining in solution. I n all cases of separation of metals the author recommends the use as a reagent of a compound cf one of the metals already present; thus the separation of iron from manganese is effected by the carbonate or sesquioxide of manganese according to the state of oxidation of the metals in solution. 31. A. W.Preparation of Aurous Iodide by the Action of Iodine on Gold. FERNAND MEYER (Cowzpt. rend. 1904 139 733-736).- Pure dry iodine has no action on gold a t the ordinary temperature but combines with it to form green amorphous aurous iodide AuI at temperatures between 50' and the melting point of iodine ; a t higher temperatures the iodide is obtained in the form of lemon-yellow crys- talline plates but the reaction is reversible and at 190" the iodide is completely decomposed into iodine and gold. I n order to free aurous iodide from uncombined iodine it is heated a t 30" whereby the latter is volatilised it being impossible t o employ any solvent for this purpose as alcohol ether chloroform or benzene decomposes the iodide. I n the presence of water in a closed vessel iodine reacts with gold to form aurous iodide provided the iodine is in excess. M.A. W. Volatilisation of Platinum. GEORGE A. HULETT and H. W. BERGER (J. Amer. Chem. Xoc. 1904 B 1512-1515).-An account is given of a series of experiments carried out with the object of deter- mining the conditions under which platinum is volatilised. A large sheet of platinum foil was heated by means of an electric furnace and the loss in weight determined a t intervals. I n order to ascertain whether the volatilisation was influenced by the impurities present some experiments were made with a specimen of platinum of a high degree of purity; the results showed that the pure platinum behaved in the same way as the foil. Platinum begins t o volatilise in air a t a temperature of about 800" and the rate of loss increases rapidly as the temperature rises. No volatil- isation occurs when the metal is heated in the absence of oxygen and it is suggested therefore that a t high temperatures the platinum is converted into a volatile oxide which undergoes decomposition a t temperatures below SOOO. E. G. Absorption of Hydrogen by Rhodium. L. QUENNESSEN (Compt. rend. 1904 130 795-796).-Wilm's statement (A bstr. 1881 514) that hydrogen is more readily absorbed by rhodium than by palladium is contradicted. Rhodium was purified by heating it with sodium chloride in a current of chlorine dissolving the product in water con- verting into sodium rhodium nitrite and crystallising the latter. The metal regenerated from this does not absorb a measurable amount of hydrogen when heated and cooled in a current of the gas. It acts as a catalyser in promoting the union of hydrogen and oxygen. H. M. D.1\IINERALOGICA4L CHEMISTRY. 43 IricEium Smquisulphate and its Aluma LUIGI MARINO (Zed. ccnoiy. CizRnt,. 1904 32 213-224. Compare Abstr. 1903 ii 376).- Iridium sesquisdphate Ir,(SO,),,xH,O j s prepared by crystallisation from a solution of the hydrated sesquioxide in dilute sulphuric acid in the absence of air. Iridium ccesizcnz aZum Ir,(SO4),,Cs,SO4,2-fH20 separates in regular octahsdra crystallographic measurements of which are quoted. Its aqueous solution is yellow and becomes pink when warmed above 40'. It melts a t 109-110" to a yellowish-red liquid. Iridium rubidium alum (Zoc. cit.) is less solubIe than t,he caesium alum; it melts at 108-109" t o a yellowish-red liquid. Iridium potassium ult~m Ir,(S04),,K2S0 24I'i,O forms yellow octa- hedra and melts at 102-103'. Iridium a~nmonium ccZunz Ir2(S0,)3,(NH4)2S04,24H,0 forms yellow- ish-red octahedra and melts at 105-106" t o a reddish-violet liquid. When it is heated a t a red heat iridium is formed. Iridiurq thalliurn alum Irg( SO,),,T1,SO4,24H,O forms golden-yellow octaheara. A. McR.

ISSN:0368-1769    

DOI:10.1039/CA9058805021

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

1\IINERALOGICA4L CHEMISTRY. 43 Mineralegical Chemistry. Origin of Naphtha. K. W. CHARITSCHKOFF (J. Russ. Phys. Chem. Soc. 1904 36 1091-1096).-The author discusses the bearing of the results of Rakusin (Abstr. 1904 i 641) on the “organic” and ‘‘ inorganic” theories of the origin of naphtha (see also Charitschkoff Abstr. 1904 ii 180). He gives also analyses of gases evolved from the marshy volcanoes of the Caucasus. T. H. P. Investigation of the Canon Diablo Meteorite. HENRI MOISSAN (Cornpt. reclad. 1904 139 773-730. Compare Abstr. 1893 ii 288).-A block of the meteoric iron weighing 183 kilograms was cut through. Whilst one half of the section (area = 625 cm.2) appeared to be homogeneous and had the colour and brilliancy of iron the other half revealed the presence of five large elliptical nodules and three smaller ones.The nodules are of a grey or black colour and ext’remoly hard ; under the microscope they have a markedly crystalline appear- ance. Insol. in Pe. Ni. Co. Mg. S. F’. Si. C. h o t HC1. I. 95.37 3.945 - - trace 0’144 trace not det. 0.260 66.95 1.93 trace trace 22.15 2.37 trace 1.96 - Analyses of (I) the matrix (11) the nodules gave 11. { 67‘51 1.77 - trace 19.91 2.30 trace - - From the residue insoluble in hydrochloric acid crystals of iron phosphide Fe3P2 have been separated. Amorphous. carbon graphite diamond (black and transparent) and carbon silicide were also found in this residue.44 ARS'I'RACTS OF CHEMICAL PAPERS. The authors suggest that the nodule; mere originally nodules of cementite which have been acted on a t a later period by the sulphur with separation of carbon. According to Le Chatelier and Ziegler's experiments suIphide of iron can diffuse readily through masses of iron. H. M. D.

ISSN:0368-1769    

DOI:10.1039/CA9058805043

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

44 ARS‘I’RACTS OF CHEMICAL PAPERS. Physiological Chemistry. Micro-respirometric Investigations. ToRsTm THUNBERG (Centr. P?~gsioZ. 1904 18 553-556).-The question whether nerves partici- pate in respiratory activity has been a.nswered in the affirmative by Baeyer Frohlich and others in confirmation of Waller’s long-expressed opinion (which however is not quoted) that carbon dioxide is produced during the activity of nerve fibres. By means of an appwatus termed the “ micro-respirometer,” previously described in a Swedish publication (Upsala Lak. s. Forh. 1902-1904) the respiratory exchanges in small objects like nerves can be actually measured. A number of results are given as also are some in which the exchanges in small animals like snails were estimated. W. D. H. Excretion of Carbon Dioxide during Exercise.GEORGE 0. HIGLEY and W. P. BOWEN (Amer. J. Physiol. 1904 12 311-335).-- An instrument called the chemograph is described for obtaining a graphic record of carbon dioxide excretion in man. At the beginning of work (bicycling) the amount excreted rises after a latent period of about 20 seconds ; the maximum is reached in about 2 minutes; if the work remains uniform the output of carbon dioxide then remains uniform also and on the cessation of work there is a latent period again of about 20 seconds followed by a fall to the normal in about 2 minutes. There is apparently no connection between carbon dioxide production and the secondary rise of pulse rate which occurs. W. D. H. Passage of Food-stuffs from the Stomach and through the Small Intestine.W. 16. CANNON (Amer. J. PhysioZ 1904 12 387-41 S).-A continuation and amplification of the author’s previous work by means of the Rontgen rays ; the method is capable of yielding data on the rate of peristalsis and of segmentation into masses. This is most rapid with carbohydrate food. Carbohydrates reach the large intestine in 4 fats in 5 and proteids in 6 hours. Data are also given when these different kinds of food are mixed or administered in succession. The animals used were cats. W. D. H. Influence of Surgical Operations on Carbohydrate Metabolism. EDUARD PFLUGER BERNHARD SCHONDORFF and FRIEDRICH WENZEL (P’iiger’s Archiv 1904 105 121-1 76).-Gly-PHYSIOLOGICAL CHEMISTRY. 45 cosuria is often described as a common sequel t o surgical operations.The grounds for this opinion are not regarded as satisfactory ; the urine may contain a reducing substance but this is not necessarily sugar. A discussion follows (largely polemical) concerning the best tests for sugar in urine. Even the fermentation test is untrustworthy. Most reliance should be placed on the polarimetric test and Worm- Muller’s modification of the copper test. From the examination of some hundreds of urines the conclusion is drawn that many forms of so-called transitory glycosuria (including those produced surgically and by anwkhesia) do not exist.. W. D. H. The Behaviour of Carbohydrates in Autolysis. CARL NEUBERG and RICHARD MILCHNER (Chenz. Cent?. 1904 ii 1422; from Bedin klin. Woch. 41 10Sl-l0S4).-In autolysis of the liver the proteid matter of which contains 3.6 per cent.of glucosamine no hydrolysis of the latter takes place with the liberation of a unimolecular sugar. On the other hand in autolysis of the pancreas I-xylose is liberated from the nucleo-proteid ; in this autolysis differs from tryptic diges- tion. It is believed that the pentose group is united not to the proteid molecule as is the glucosamine of liver proteid but to the nucleic acid of the pancreatic proteid (guanylic acid) after the manner of a gluco- side and this will explain the difference seen in autolysis. The nitrogen-free ‘L transport sugar ” of blood globulin (Langstein) is also probably combined as in a glucoside. W. D. H Utilisation of Proteids without the Intervention of Digestion. LAFAYETTE B. MENDEL and ELBERT W.ROCKWOOD (Amey. J. Physiol. 1904 12 336-352).-Recent research tends to shorn that during digestion proteolysis is more profound than was formerly con- sidered to be the case and that the tissue proteids are reconstructed from the simple decomposition products; Experiments were therefore undertaken to study the fate of proteids introduced directly into the blood stream or into the peritoneal cavity. Edestin (from hemp seed) and excelsin (from Brazil nuts) were introduced slowly and were apparently retained for the most part. A t any rate they were not discovered in the urine or bile. Rapid injection causes toxic symptoms especially inhibition of heart and respiration. The urine contained a proteose-like substance after injection of excelsin but not of edestin.If edestin or casein is introduced into a loop of intestine from which digestiop processes are excluded they are not absorbed but their proteoses and peptones rapidly disappear. W. D. H. Inanition Studies. 111. In Libella. IV. In Bees. B. SLOWTZOFF (Beitr. Cherri. yhysiol. Path. 1904 6 163-169 170-174).-A con- tinuation of the author’s work on inanition on the lines of his previous reE earches. W. D. H. Further Proof of Ionic Action in Physiological Processes. C. HUGH NEILSON and ORVILLE H. BROWN (Amer. J. Plqsiol. 1904 12 374-356).-Non-electrolytes have no effect,except in solutions of 1 mol. concentration or more on the decomposition of hydrogen per-46 ABSTRACTS OF CHEMICAL PAPERS. oxide by platinum black or by an aqueous extract of kidney; in con- centrations greater than 1 mol.there is an inhibitory effect which increases with the concentration. A salt in dilute concentration exerts either a depressing or stimulating effect the former depending on the positive the latter on the negative ion. W. D. H. Action of Salts on Muscle and Nerve. ERNST OVERTON (P’uger’s Arc&v 1904 105 176 -290).-The experiments were mainly made with thin muscles like the frog’s sartorius. Solutions of potassium chloride isotonic with blood kill the muscles in a few minutes and cause them to increase in weight. I n a mixed solution of the chlorides of sodium and potassium the muscle remains almost impermeable to potassium chloride until it is injured by that salt Other potassium haloids and potassium nitrate behave in the same way.Loss of indirect excitability occurs rapidly when quite a small percentage (0.06 to 0.07) of potassium chloride is added t o a sodium chloride solution; this effect is removed by the addition of calcium chloride or by placing the preparation in Ringer’s solution (confirma- toryof Locke). The harmful action attributed to potassium ions is like that caused by curare. Rubidium caesium and ammonium salts act like potassium with some differences of detail which are fully described. Strontium acts like calcium as an antagonist to these but barium and magnesium salts do not. I t cannot therefore as Loeb supposes be a simple question of valency of ions. W. D. H. Biological Importance of Iron. ALESSANDEO BALDONI (Chem. Centr. 1904 ii 1476 ; from Arch. exp. Pccth. Pharm.52 61-68).- Iron in nutriment is not only of importance in haemoglobin formation for all the tissues contain iron. The blood-free epidermis the crystal- line lens the tissues of the crayfish and among plants Iceland moss were investigated and all were found to contain small amounts of iron. W. D. H. Influence of Local Temperature on Glycolysis in the Capillaries. RAPHAEL LI~PINE and BOULUD (Conzpt. rend. 1904 139 622-625).-After section of the sciatic nerves in dogs one leg was immersed in cold water the other in warm water. Ten minutes later blood was withdrawn from the carotid artery and both crural veins. The venous blood contained less sugar than the arterial but the loss was greatest in the venous blood of the cooled limb. Exceptions to the rule were noticed but the total number of experiments performed is not recorded. If the blood is collected and kept .glycolysis occurs most rapidly in the blood where it occurred most rapidly in uivo.W. D. H. Formation of Aromatic Fatty Acids in the Animal Body. FRANZ ENOOP (Heit?.. chem. Physiol. Path. 1904 6 150-162).-A study of the metabolism of fatty compounds in especial relationship to the origin in the body of those containing an aromatic nucleus. A large number were administered to animals ; some were excreted un-PHYSIOLOGICAL CHEMISTRY. 47 changed others were oxidised in various ways whilst in others the amino-group was removed. Production of Choline from Lecithin and Brain Tissue. ISIDOR H. CORIAT (Amer. J. Physiol. 1904 12 353-364).-1n view of the work of Mott and Halliburton on the importance of recognising choline as a sign of breakdown of nervous tissues the theory is advanced that the splitting off of choline from lecithin is due to ferment action but attempts to isolate the enzyme were unsuccessful.The enzyme i s destroyed by heating and acts best in slightly alkaline media. It comes into play during autolysis but the yield of choline is small. During putrefaction the yield is larger. Pepsin and trypsin fail to act on the lecithin of brain tissue and inhibit autolysis. Lipase however is capable of splitting lecithin. Of the methods tried heating lecithin with barium hydroxide was the only one which led to a theoretical yield of choline. W. D. H. W. D. H. Receptivity of Cells in Normal and Immunised Animals. MARTIN JACOBY (Beitr.chem. Physiol. Putlt,. 1904 6 113-1 31).-A contribution to the study of immunity in its various stages with theo- retical deduction on its mechanism. Some of the more important results are as follows the receptor groups in the blood corpuscles for ricin are fixed there firmly and cannot be removed by washing by great pressure or by digestive ferments. After blood corpuscles are treated with eel serum the toxicity of the latter poison is diminished ; in some cases it is increased this is explained by the presence of a mixture of toxoids and toxins the former being taken up by the corpuscles first. At Oo rabbits’ corpuscles are only agglutinated by eel serum; a t 3 5 O they are completely haemolysed. Varieties of cor- puscles which are not very susceptible to a toxin have their suscepti- bility increased during the progress of immunisation.W. D. H. The Individuality of Trypsin. LEO POLLAK (Beitr. chem. Phpiol. Puth. 1904 6 95-1 l2).-That trypsin is not a single substance has been stated by Vernon and others. It is regarded as possible that the pancreatic enzyme really consists of a number of specific ferments each acting on different proteids. I n support of this i t is shown that treatment of a pancreatic extract with acid destroys its power of digesting serum egg-white and fibrin but not of digesting gelatin. The latter property is therefore ascribed to a specific ferment glutinase. Attempts by fractional methods to obtain a ferment acting only on serum proteids were unsuccessful but led to the discovery of an anti- glutincbse.This is not dialysable but is not a ferment not being destroyed by boiling. I t is not identical with the anti-trypsin of blood serum. W. D. H. Haemolysinogenic and Agglutininogenic Action of Laked Corpuscles. GEORGE N. STEWART (Anzer. Phyaiol. 1904 12 363-373).-Further experiments in support of the author’s earlier conclusion that the stromata and liquid of water-laked corpuscles cause the production of sera with specific hsmolytic and agglutinating power.48 ABSTRACTS OF CHEMICAL PAPERS. The latter is the more marked effect as is also the case with t,he serum obtained after the injection of stromata laked by freezing and thawing. Filtration through porous earthenware removes the agglutininogens and hzemolysinogens from the liquid of corpuscles laked by freezing and thawing and by foreign serum.W. D. H. Action of Radium Emanations on Chymosin. SIGVAL SCHMIDT- NIELSEN (Beitr. chenz. I’hysiol. Path. 1904 6 175-1 76).-Even long exposure to radium emanations causes no marked deterioration in the activity of chymosin (rennin). W. D. H. Anti-substances against Crotin in the Normal Organism. FRANZ ALEXANDER LUST (Beitr. chem. Physiol. Path. 1904,6,132-149). -The anti-substance found in the pig’s gastric mucous membrane is resistant to heat and is active in neutral weakly acid or weakly alka- line media. It is precipitable by alcohol or ether or by saturation with ammonium sulphate. It is not dialysable and is not destroyed by artificial gastric digestion. It does not give the biuret reaction or any reaction with iodine-potassium iodide solution.It is not present in other organs except in small quantities in those like the lungs and liver which are rich in blood. Various animals differ a good deal in their susceptibility to crotin. W. D. H. Urinary Indoxyl. LEON GRIMBERT (J Z’harm. CJhn. 1904 [ vi] 20 398-407).-Hnman urine always contains indoxyl ; its presence is not pathological; the amount varies with food work fatigue and intestinal disorders Even large quantities have no necessary impor- tance; there is no ground for supposing it to be due to liver disease. Scatoxyl pigments do not occur in the urine for by oxidation in the body scatole loses its methyl group and is converted into indoxyl. Red colours attribntcd to scatoxyl are produced by indirubin.W. D. H. Studies in Diuresis. X. The Situation in the Kidney where Foreign Substances are Excreted. JOH. BIBERFELD (Pjiiyer’s Archiv 1904 105 308-320). -The experiments were made with pigments especially Berlin-blue and they lead to the conclusion that this substance is excreted by the convoluted tubules. This work confirms in the main von Soberieranski’s recent researches with indigo- carmin; a few points of diil‘erence are discussed. Some of the observations throw doubt on Ludwig’s doctrine of reabsorption of water in the tubules. W. D. H. A Case of Leuczemia. F. PARKES WEBER (Trans. Pufhol. SOC. London 1904 55 288-296).-A case is described in which some resemblances to pernicious anzemia are noted; but there was no abnormal amount of urinary pigment and no reaction for ‘‘ free iron ” in spleen liver and kidneys.There was great hyperplasia of the spleen and prevertebral hEmolymph glands but not of the lymphatic glands proper. The bone marrow was abnormally firm and contained excess of connective tissue. W. D. H.PHYSIOLOGICAL CHEMISTRY. 49 Pseudo-lipzemia JOHN FAWCETT and A. E. BOYCOTT ( T r a ~ Patho2. SOC. Lofidon 19(14 55 332-336).-In a fatal caGe of sarconia of the pancreas the blood-plasma was creamy but prolonged centrifugalisation produced hardly any change. The creamy appear- ance is due to extremely minute particles of irregular shape which are insoluble in ether or in I per cent. acetic acid. They arc stained blue by Jenner's stain but give no reaction for fat with osmic acid or Soudan 111. The amount of fat in the blood was only 0.38 per cent. a number which comes within normal limits.The blood corpuscles showed nothing noteworthy. The creamy appearance is attributed as in some cases recorded by others to proteid material. W. D. H. The Action of Alcohols on Echinoderm Eggs. HERMANN FUHNER (Chem. Centr. 1904 ii 1517-1518 ; from Arch. e q . Path. Pharnz. 52 69-82).-A large series of alcohols was investigated a d the general conclusion drawn that each successive member of a series is more toxic towards the eggs than the preceding. The secondary alcohols w e less active. Urethane is about twice as poisonous as n-propyl alcohol and about the same as n-butyl alcohol. Chloral hydrate approaches octyl alcohol in toxicity and is 90 times more poisonous than urethane.Urea has no action. Glycerol mannitol and sucrose cause greater harm than can be explained by osmotic phenomena. Mixtures of alcohol with colloids multivalent alcohols with urea and with sugar are more toxic than the alcohols alone. Injurious effects in the more advanced larv2e are also described. W. D. H. The Action of Cobalt Rhodium and Chromium-ammonium Compounds on the Animal Organism. JOHAENES BOCK (Chem. Centr. 1904 ii 1515-1517 ; from A~clt,. exp. Path. Phnrm. 52,l-29 30-38).-Hexa~mminecobalt chloride is strongly toxic its most marked action being like that of curare. Aquopentamminecobalt sulphate acts similarly but is not so toxic. Diaquotet'ramminecobalt sulphate is 100 times less poisonous. A number of other similar compounds were also investigated.A comparison of the lethal doses in frogs and mammals shows that the amount of cobalt present makes no difference but the toxic action depends on the number of ammonium and H20 groups and on the nature of the acid residues in the complex radicles. The corresponding compounds of rhodium and chromium gave analogous results. Non-toxic doses of hexamminecobalt chloride cause in frogs fascicular clonic contractions which are due to excitation of motor nerve bundles. W. D. H. Toxicity of Amylene @-Chlorobydrin L. LAUNOY (Compt. rend. 1904 139 650-652. Compare Abstr. 1904 ii 501).-The toxic action of this substance was tested on the dog rabbit mouse guinea- pig fowl and pigeon. The above order is that of decreasing receptivity ; that is the animal most easily killed is placed first. In uitro amylene chlorohydrin has a glohulicidal action which is not exercised in civo. VOL. LXXXVIIT. ii. 4 W. D. H.50 ABSTRACTS OF CHEMICAL PAPERS. Toxins and Antitoxins. Diphtheria Poison. SVANTE AR- RHENIUS and THORYALD MADSEN (Chem. Cent?.. 1904 ii 1420 ; from Bull. ucccd. ~ o y . Banemnrk 1904 No. 4).-This contribution to immunity is largely polemical against Ehrlich. No foundation is discovered for the existence of prototoxoids or toxones. The dissocia- tion constant varies bat little. The diphtheria toxin is regarded as a homogeneous substance and behaves like r2 unimolecular material. The loss of activity it undergoes is attributed to its gradual conversion into an atoxic substance or toxoid. The toxin and its toxoid react in equivalent qiiantities with the same amount of antitoxin both products called toxinan and toxoidcm respectively being non-poisonous. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9058805044

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

50 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture Epidemic or Bacillary Dysentery. R'. H. FIRTH (Tmns. Pathol. Soc. London 1904,55 340-375).-Two types of bacilli are obtainable from dysenteric excreta one non-pathogenic is able to decompose maltose galactose and mannitol with the formation of acid but not of gas and also able to produce indole ; the other which is pathogenic and to which the term Bacillus dysenterice should be restricted does not possess these characters. The former may be a degraded or transitional form of the latter but this is uncertain as also is their relationship if any t o the bacilli of enteric fever. The prospects of establishing an acquired imniunity against bacillary dysentery are not encouraging ; experiments on rabbits and guinea-pigs show that passive immunity is brief although active immunity is of longer durat,ion.Development of Organic Matter in Seeds during Matura- tion. GUSTAV ANDRB (Compt. Tend. 1904 139 805-807).-ln the maturation of lupin and haricot seeds the percentage amount of ash was always greater a t tho commencement than at the end. The same was observed as regards total nitrogen except in the case of lupins. The non-nitrogenous organic matter is a t first in the form of soluble carbohydrates. W. D. H. N . H. J. M. Desiccation of Plants and Vegetable Tissues. Period of Maturation not Reversible. Final Equilibrium in Average Atmospheric Conditions. MARCELLIN BERTHELOT (Compt. Tend. 1904 139 693-702).-!L'he water retained by plants a t the ordiuary temperature under given conditions of temperature and atmospheric moisture corresponds with an equilibrium or limit.This limit varies much less for a given interval than tho temperatiire of the air or the vapour tension of t h e air. provided t,hnt extremes are avoided. N. H. J. 31.VEGETABLE PHYSIOLOGY AND AGRTCUL'I'URE. 51 Absolute Desiccation of Plants and Vegetable Substances Period of Artiflcial Desiccation. Reversibility by Atmos- pheric Moisture MARCELLIN BERTHELOT (Compt. rend. 1904 139 702-716).-The results of experiments with different plants estab- lished the reversibility between evaporation in perfectly dry air of t,he water retained in ordinary air and the absorption of aqueous vapour i n ordinary air by plants dried by heating at 110'. The amount of water fixed by a dried plant is generally less than the amount necessary to a live plant.The reciprocity is therefore inde- pendent of vital action. N. H. J. M. Desiccation of Plants. Period of Vitality. Humectation by Liquid Water. Reversibility Imperfect. MAWELLIN BERTHELOT (Gompt. rend. 1904 139 '76 1-773).-Experiments on the absorption and exhalation of water by plants are described. Importance of Calcium and Magnesium Salts for Plants. FR. GOSSEL (Chem. Centr. 1904 ii 115'7 ; from Verb. Ges. Deut. iVtJ Aerxte 1903 ii 101-104).-The results of water- and soil-culture experiments failed to confirm Loew's theory that there must be a cer- tain relation of CaO MgO. I n water cultures the highest yields of barley and beans were obtained when CaO MgO = 0.4 1 instead of 1 1 for barley and 3 1 for beans as Loew states.The conclusion is drawn that a definite relation between the two bases is unnecessary and that the effect of lime depends espeoially on the character of the soil. N. H. J. &I N. H. J. M. Organic Compounds of Metals in Plants. CHARLES F. SCHLAGDENHAUFFEN and E. REEB (Compt. rend. 1904 139,980-983). -The residue obtained after incinerating the light petroleum extract of ripe barley consists of phosphoric acid and the phosphates of sodium calcium manganese and iron which existed in the plant as the distearylglycerophosphate of neurine and the metallic derivatives of other lecithins respectively (compare Abstr. 1902 ii 625). The residue similarly obtained from oats rye and wheat contained potass- ium instead of sodium.M. A. W. Evolution of the Weight and the Organic Matters of Leaves during Necrobiosis in White Light. L. REULAYUUE (Compt. rend. 1904 139 81 4-81 6).-AnaIyses are given of leaves of Bougainvillea spectab& which had been dried at 110" immediately after being detached and of similar leaves allowed to die gradually in boxes of colourless red yellow green and blue glass. These analyses were first made on the second day and again a t intervals of two days. The leaves mere well mixed every day. In' the present paper the results obtained with colourless glass are discussed. The total carbohydrates (in 100 leaves) diminished gradually from 3.566 grams on the second day to 2.400 grams on the twelfth. The sugar diminished slightly to the sixth day then slightly increased.The non-digestible proteid nitrogen and the nitrogen as nuclein increased regularly from 0.195 to 0.387 gram and from 0.182 to 0.273 4-252 ABSTRACTS OF CHEMICAL PAPERS. gram respectively. The nitrogen as amides was almost exactly the same on the twelfth day as on the second day but somewhat irregular results were obtained on the intermediate days. The results relating to total and to digestible proteids also show irregularities. N. H. J. M. Non-proteid Nitrogenous Constituents of Agricultural Plants. XRNST SCHULZE (J. Landw. 1904 52 305-336).-The amount of non-proteid in seeds varies considerably ; i t is highest in leguminous and lowest in cereal and oily seeds. Choline was found in all the seeds examined; betaine was found in vetches sunflower and wheat ; trigonelline in peas hemp and oats.Etiolated seedlings contain either asparagine or glutamine ; if both occur in the same plant the amount of the one greatly predominates over that of the other. Leguminous seedlings cereals and grasses and poppy contain asparagine whilst glutamine is found in pumpkins ricinus sunflower white mustard rape cress and radish Puc. Gluts- mine is however much less abundant than asparagine the maximum amount in these plants being 2.5 per cent. in the dry matter. More than 25 per cent. of asparagine is sometimes found. Etiolated plants also contain the hexone bases aminovaleric acid leucine phenyl- alanine and tyrosine. Nnclein bases occur only in small amounts. Roots and tubers resemble etiolated seedlings as regards their nitro- genous constituents.Asparagine or glutamine is nearly always the most abundant amide. Asparagine occurs in potatoes glutamine in sugar beet and mangolds. Tyrosine was obtained from potatoes ancl mangolds leucine arginine lysine and histidine from potatoes. Sugar beet contains besides glutamine aspnragine leucine tyrosine betaine arginine guanidine nuclein-bases carnine allantoin choline vernin and ricine. The green parts of plants contain a con- siderable number of amides but the amount actually separated was small. As regards food value it is probable that amides are more like proteids than carbohydrates as stated by Lehmann. N. H. J. M. Milk of Castilloa Elastica. ANNE W. K. DE JVNG (Be?.. 1904 3'7 4398-4399. Compare Abstr. 1904 ii 762,763).-The following were detected in the juice of Castilloa elastica proteids tannic acid an acid (C17H300& potassium chloride a sugar and a sub- stance the neutral solution of which assumed a green colour on exposure to the atmosphere.A. McK. Chemistry of Celery (Apium Graveolens). llilas BAMBERGEB and ANTON LANDSIEDL (iMonatsh. 1904,25 1030 -1034).-The aqueous extract of freshly-cut celery roots is found to contain asparagine tyrosine and mannitol. c. Y. Composition of Orange Juice. K. FARNSTEINER ancl W. STUBER (Zeit. Ncchr. Genussm. 1904 8 603-605).-The juices to which the following results refer were obtained from the various oranges afterVEGETABLE PHYSIOLOGY AND AGRICULTURE. 53 the peel spongy. tissue and seed had been removed. juice only came into contact with wooden vessels.The expressed From oranges From of unknown origin. Valencia Grains per 100 c. c. Fresh. 1.0439 Specific gravity at 15' ...... Total solids dried 23 hours at 100" ..................... 10.73 Citric acid (anhydrous) ...... 1 a19 Total sugars(as invert sugar) S.26 mineral matters (ash) ...... 0.41 Alkalinity of ash (c.c. N/l acid) ........................ 5.40 Nitrogen ..................... 0.064 Glycerol ........................ 0.38 Alcohol ........................ 1.44" Polarisation in 200 mm. tube direct ............... - Polarisation in 200 mm. tube after inversion ...... 9 after boiling 1,0454 Phosphoric acid ............... - - Fermeked. oranges. 1.0084 1 *0464 1.0159 1.0466 3.55 10.92 1 *25 1.79 0-38 7-65 0-42 0.52 5.62 7.20 0.953 0.099 0.026 0.027 0-61 0.34 4.29 - - - 0.11" - - 3.16" From Messina oranges.1.045 1 1.0455 10.85 1-47 7.86 0.50 6.40 0.075 0.042 0.28 - + 2.45' - 3.66' w. P. s. The Formation of Formaldehyde in the Combustion of Tobacco. AUGUSTE TRILLAT (Compt. rend. 1904 139 742-744. Compare Abstr. 1904 i 713).-Tobaccos from various sources were burnt in the form of cigars cigarettes or in clay or wooden pipes and the formaldehyde in the products of combustion estimated as tetramethyl- diaminodiphenylmethane with the result that the quantity of form- aldehyde formed varies little with the origin of the tobacco and amounts to 0.05 t o 0.1 per cent. of the weight of the substance burnt ; the yield was slightly higher in the case of the clay than of the wooden pipe probably owing to surface catalytic action.The formaldehyde does not however exist in the free state in the products of combustion but combines with the nitrogenous bases (such as nicotine) (compare Schindelnieister Abstr. 1903 ii 115) also present in the tobacco smoke to form compounds which possess none of the deleterious properties of the two constituents. &I. A. W. Treatment of Soil with Ether Carbon Disulphide Chloro- form Benzene and Hydrogen Peroxide. Effect on the Growth of Plants. FRIEDRICH NOBBE and L. RICHTER (Landw. Versuchs- #tat. 1904 60 433-448).-Application of ether and hydrogen peroxide to soil in which peas were grown failed to sterilise i t and were rather favourable to growth than unfavourable. Ether applied as a n emulsion increased the produce 41.5 per cent.* A small quantity of aii alcoholic solution of salicylic acid had been added to this juice.54 ABSTRACTS OF CHEMICAL PAPERS. Further experiments in which oats were grown in soil treated with ether benzene carbon disulphide and chloroform showed that higher yields were obtained in every case than with untreated soil and that larger amounts of nitrogen and total ash were assimilated. The action extended to second crops after the odour of the substances applied had disappeared It is shown that the soils underwent no change. The increased results would seem to be due to a directly stimulating action of the substances employed or of their products of decomposition. N. H. J. M. Effect of Soil Sterilisation on Plant Development. CARL SCHULZE (Bied. Centr.1904 33 748-751 ; from Jahresb. Ver. Vertret. ccng. Bot. 1904).-Experiments are described in which various plants mere grown in normal and in sterilised arable and meadow soils. Sterilisation was effected by heating at 100' or a t 125". The different plants showed very different degrees of sensitiveness towards the decomposition products of the soil and the results also varied ac- cording to the nature of the original soil sterilised meadow soil being more injurious than sterilised arable soil. Mustard proved to be particularly sensitive whilst oats grown in sterilised arable soil showed very slight signs of injury. Plants which were able to recover from the injury due to the heating of the soil were sometimes much more luxuriant than those grown in normal soil.Sterilisation had least injurious effect on garden soil; oats grown in the sterilised soil showed no signs of injury and the yield was raised by 30-7'0 per ceut. The injurious effect of sterilisation on meadow soil is almost entirely overcome by the application of calcium carbonate. The yield OF mixed grasses was raised by more than 100 per cent. by sterilising and adding calcium carbonate. N. H. J. M. Similar results were obtained with mustard. Solubility of Soil Constituents. FELIX MACH (Chem. Centr. 1904 ii 1164-1165; from JTerh. Ges. Deut. iQf. Aerxte 1903 ii 9 1-94).-Ferric aluminium and tricalcium phosphates were dissolved t o some extent by water. Water containing hydrated silica only dissolved aluminium phosphate somewhat more than water alone. Water and humic acid dissolved two or three times as much a saturated solution of carbon dioxide much less ferric and aluminium phosphates but twice as much calcium phosphate as pure water. Calcium and magnesium carbonates are about twice as soluble in water and silica as in water alone.The solubility of gypsum was about the same in all the solvents. Carbon dioxide somewhat in- creased the solubility of felspar and oligoclase and still more the solubility of the calcium of desmine and natrolite. I n the case of muschelkalk and basalt carbon dioxide increased the solubility of every constituent except sulphuric acid and silica. N. H. J. M. Black Soils of Legienen Rossel in East Prussia. EDWIN BLANCK (Landw. Yersuchs-Stat 1904 60 407-418).-Complete chemical analyses and mechanical separations of several samples ofANALYTfCAL CHEMISTRY. 55 surface and subsoil ape giveii. The black soils both of East and West Yrussia contain riiuch less hunins than those of Russia. N. H. J. M. Humic Acids of Grey Sand and Brown Sandstone. ADOLF MAYER (Landw. Ver.suclis-Stcct. 1904 60 4’i5-480).-The humic acids of brown sandstone contain less carbon than those of grey sand. It is probable that the humic acids of grey sand are oxidised when ferric oxide is present and dissolve as ferrous salts of oxyhuiiiic acids. These are oxidised in the subsoil to insoluble ferric salts N. H. J. 31. Beet Molasses of Various Origin. TH. I_)iETRICH and FELIX MACH (Land,io. Vewuclis-Sttcct. 1904 60 347-357).-Analyses of twenty samples of molasses. The results include dry matter ash total sugar invert sugar total nitrogen proteid nitrogen nitric nitrogen carbon dioxide lime and alkalinity or acidity. N. H. J. 31.

ISSN:0368-1769    

DOI:10.1039/CA9058805050

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

ANALYTfCAL CHEMISTRY. 55 An alytical Chemistry. Modified Gas-burettes. JULIUS ZHZAWY (Chevz. Zeit. 1904 28 1172).-Hempel burettes so constructed that it is possible to read the volunie of gas to 0.01 C.C. L. DE K. A New Burette for Testing Normal Solutions. A. HESSE (Clmn. Zeit. 1904 28 1172).-The burette is fitted with a beaker- shaped cup. The first 0.5 C.C. and the last 43-51 C.C. are divided to l j l 0 0 c.c. the tube being drawn out a t these places; the remainder is dividled as usual to 1/10 C.C. The parts drawn out are not calibrated It is mereIy intended for checking normal solutions. L. DE K. Determination of the Neutralisation Point by Conductivity Measurement. 11. FRIEDRICH W. KUSTER MAS GRUTERS and W. GEIBEL (Zeit. u n o ~ y Cheiiz. 1904 42 225-231. Compare Abstr.1903 ii 611).-Ten C.C. of X / l O sulphuric acid were diluted with 500 C.C. of water and then N/10 sodium hydroxide gradually added the conductivity of the solution being measured after the addition of each C.C. of alkali. The conductivity of the sulphuric acid falls regu- larly as the neutralisation proceeds until a minimum value is attained exactly at the neutralisation point ; an increase in the value occurs when more sodium hydroxide is added. By this method the end-point may be determined much more sharply than by the use of any indicator. Phosphoric acid behaves as a inonobasic acid; the break of the con- ductivity curve coincides with the results obtained by titrating phos- phoric acid with methyl-orange as indicator.56 ABSTRACTS OF CHEMICA4L PAPERS. I n order t o show how the method may be applied when indicators fail 20 C.C. of N/lO potassium dichromate were mixed with 10 C.C.N/lO sulphuric acid and then titrated with N/10 sodium hydroxide by conductivity measurement as before ; the sulphuric acid present can be titrated as sharply as if the dichromate were absent. Similar measurements were made with potassium permanganate in the s o h tion instead of potassium dichromate. The presence of precipitates also does not impair the accuracy of the method thus citric acid may be titrated by barium hydroxide. When weak organic acids were titrated by the gradual addition of sodium hydroxide the minimum of conductivity was attained too soon ; the method yields correct results however when the acid is added t o the alkali. Acetic lactic tartaric and citric acids were titrated in this manner.Determinations of the amount of acetic acid in a strongly coloured vinegar examined are quoted. The total acid in a specimen of red wine was also determined. Magnesia and various alkaloids were similarly titrated. A. McK. The Theory of Indicators and its Bearing on the Analysis of Physiological Solutions by means of Volumetric Methods. GEORGE H. A. CLOWES (Amer. J. Pharm. 1904 ’76 453-467 611-525).-This paper has for its object the outlining of the nature of the various classes of indicators used in acidimetry and alkalimetry studying their behaviour towards various weak bases and acids which may occur in the course of physiological work; further to make a series of tests on artificial and normal stomach contents pancreatic fluids blood serum &c.With regard to the behaviour of amino-acids asparagine glycine leucine tyrosine and aspartic acid towards indica- tors experiments were made in which their action was compared with that of the ammonium salts of formic acetic and lactic acids acet- amide formamide and urea Poirrier’s blue was found to be sensitive to all the free acid groups and entirely indifferent to ammonia and amino-groups. Phenolphthalein is less sensitive to acid groups and far more sensitive to ammonia than Poirrier’s blue. Alizarin is sensi- tive to both ammonia and strong acid groups b u t is indifferent to the weak acid groups in asparagine tyrosine &c. and also to the amino- group of these compounds. Phloroglucinvanillin is entirely indifferent to all weak organic acids This indicator is of great value in differentiating the weak bases being sensitive not only to ammonia but also to the amino-group in aspara- gine glycine leucine and tyrosine and indifferent to the amino-groups present in acetamide formamide and urea.From the experiments with proteids &c it seems possible that some sort of relationship obtains between the various nitrogen-containing groups in the pro- teid and the end-points of different indicators. The comparison of volumetric with gravimetric analyses of normal and pathological stomach contents showed that provided a purely proteid test meal was employed the phenolphthalein end-point indicates fairly accu- rately the total available hydrochloric acid present both free andANALYTICAL CHEMISTRY.57 combined more or less feebly with proteids. The actual free acid is given by phloroglucinvanillin. After allowing for the influence of phosphates and traces of organic acids the range of titration between the end-point of phloroglucinvanillin and that of phenolphthalein may be sa.id to be a function of the basic affinities of the proteids and their decomposition products present. Under conditions where peptic diges- tion fails to take its normal course the above rules are no longer applicable. Jn tryptic digestion the range of titration after allowing for the influence of carbon dioxide is a t first more or less proportionate to the amount of proteid brought into solution but subsequently increases in undue proportion t o the total nitrogen as the digestion proceeds.The wide variation between the end-points of phenol- phthalein alizarin and phloroglucinvanillin in estimating the alkali- nity of blood serum emphasises the necessity of certain uniform stand- ards for this purpose. With regard to urine the titration results are fairly dependent on the amount of phosphates present. I n the presence of any considerable quantity of ammonia which exerts a more powerful effect on alizarin and phenolphthalein than urea the urine will be less acid or even alkaline to phenolphthalein and more strongly alkaline to alizarin than is normally the case. w. P. s. Standardisation of Normal Solutions. MAX SCHOLTZ (Arch. Plmrm. 1904 242 575-578).-0f an approximately 0.01N sodium hydroxide solution 10 C.C.required the following volumes? I of an approximately 0.01 N hydrochloric acid ; and of the same acid 10 C.C. required the following amounts 11 of the same alkali ; according to the indicator employed Phenol- Rosolic p-Nitro- Methyl- ph thalein. Litmus. asid. phenol. Iodoeosin. orange. I. 9.68 9.83 9.87 10.00 9.80 10.70 C.C. 11. 10.08 9 92 9.92 9-99 9.68 9.28 When standard solutions as weak as these are being used it is evidently important that the indicator and the direction of the change of colour in the standardisation should be the same as are employed in the act,ual estimation. The results are discussed from the point of view of the theory of electrolytic dissociation (compare Abstr. 1904 ii 771). C. F. B. Potamium Bromide as Indicator when using Fehling's Solution.PIO BERTI (CYhern. Centr. 1904 ii 1433 ; from Bull. Assoc. Cl~ivz. Xucr. et Dist. 21 1234-1236).-A drop of the liquid is put on to a double piece of filter paper resting on a porcelain plate and after removing the paper the moist spot is touched with a particle of potass- ium bromide and a drop of sulphuric acid. I f there should still be a trace of dissolved copper a violet colour is noticed owing to the forma- tion of cuprous bromide L. DE K. Apparatus for Extraating Liquids with Chloroform. ERICR BAUM (Chem Zed. 1904 28 1172).--A modification of the van Rijn58 ABSTRACTS OF CHEMICAL PAPERS. apparatus (Abstr. 1896 ii 17) which consists in fixing the overflow tube (siphon) in the lower part of the extractor thus allowing the use of solvents heavier than water.L. DE K. New Extractor. ANDREA SANNA (Gazxelta 1904,34 ii 224-228). -This extractor consists of a flask fixed obliquely and filled about half-full with the substance to be extracted and the solvent. Through the double-bored stopper of the flask pass the bent inner-tube of an in- verted condenser and a short glass tube furnished with a cock and an india-rubber tube The upper end of the condenser tube is also bent and passes into an Xrlenmeyer flask through the stopper of which passes also a short glass tube with a cock. The latter is left open during the heating of the substance with the solvent. When the extraction is complete the condenser and Erlenmeyer flask are turned round so that the end of the bent condenser tube is now a t the lowest part of the round flask whilst the Erlenmeyer flask is a t a still lower level The cock attached to the round flask is then opened and the solution forced through the condenser tube into the Erlenmeyer flask. The apparatus is then inclined so that the round flask is lower than the Erlenmeyer and the solvent distilled off from the latter into the round flask tho cock attached to the Erlenmeyer flask being meanwhile kept closed.The extracted material then remains in the Erlenmeyer flask. These operations may be repeated until the extraction is complete The apparatus gives good results for the extraction of liquids or solids as for example in the determimtion of fat in cheese butter &c. and it acts more quickly than a Soxhlet or Garralowschy extractor.I n determining f a t in a material like cheese it is advisable to pack the substance in filter paper tied up with cotton as this prevents solid particles from being carried away. T. H P. Palladium-Hydrogen as a Reducing Agent in Quantitative Analysis. ALFRED c. CHAPMAN (Ancilyst 1'304,29 346-357).-1n an investigation undertaken for the purpose of ascertaining t o what extent palladium-hydrogen could be employed as a quantitative reducing agent it was found that ferric salts as well as potassium ferricyanicle were completely and readily reduced. Chromates in acid solutions were reduced to chromic salts. The palladium was employed in the form of foil of such thickness that a piece 2 inches square weighed about 8 grams. A piece of thick palladiuin wire was welded to this and the foil was charged by being made the negative electrode in an ordinary cell containing dilute snlphuric acid the current being obtained from the main or from accumu- lators.The charged metal was after washing suspended in the boiling solution under examination. In the case of cupric stannic arsenic manganic vanadic and moly bdic compounds the reduction was either incomplete or imperfect Potassium chlorate was only partly reduced whilst bromates and iodates mere not attacked. C'eric salts were reduced to cerous salts which latter could be titrated with ferrous ammonium sulphate solution as the lower oxide was itself capable of oxidising the ferrous solution. w. P. s,ANALYTICAL CHEMISTRY 59 Action of Hydrochloric Acid on Potassium Chlorate.A. KOLB and E. DAVIDSON (Zeit. nypu. Chena. 1904 17 1883-1887).- During the action of hydrochloric acid on potassium chlorate in the presence of potassium iodide atmospheric oxygen and especially the oxygen in solution causes oxidation of the hydriodic acid formed and the iodine thus liberated accelerates the action. The error thus caused in the estimation of chlorate may be obviated by conducting the operation in the absence of oxygen The reaction between hydro- chloric acid and potassium chlorate proceeds at the ordinary tempera- ture only in the presence of a considerable excess of hydrochloric acid and is quickly completed; chlorates may be estimated in this way. The substitution of cadmium iodide for potassium iodide has no special advantage whilst aluminium iodide and mercuric iodide are unsuitable.An acceleration of the reaction was not observed when antimony chloride or cerium sulphate was present,. The action is retarded by the addition of water. A. McK. Estimation of Iodine in Soluble Iodides also in the presence of Bromides and Chlorides. HUGO DITZ and BENJAMIN 1%. l)~ARaoSCHES (Clem. Zed. 1902 28 1191-1 194).-The solut3ion con- taining the iodide is mixed with a sufficiency of potassium iodate and then with a slight excess of dilute sulphuric acid. The liberated iodine is extracted with toluene and finally titrated with sodium thio- sulphate. Jf a known amount of iodate has been added the excess of this may be estimated in the aqueous liquid by adding potassium iodide and dilute sulphuric acid and titrating with sodium thiosulphate. The shaking with toluene may even be omitted and the iodine expelled by distillation when the distillate which is collected in a solution of potassium iodide may be a t once titrated; as however this renders the process somewhat tedious it is more convenient t'o boil off the iodine and titrate the residual iodate.If bromides or chlorides are present the same process applies if the iodine is estimated in its toluene solution and not indirectly in the aqueous liquid. If the excess of iodate is t o be estimated in the aqueous liqnid after shaking with toluene acetic acid should be substituted for sulphuric acid. 1,. DE K. Estimation of Sulphur by Aid of Sodium Peroxide. ALBERT NEUMANN and JOSEPH MEINERTZ (Zeit. ylrysiol. Chenz. 1904 43 37-40 Compare During Abstz.1 S97 ii 63).-The substance is fused in a nickel crucible with a mixture of sodium and potassium carbonates and sodium peroxide. The peroxide should be added gradually in 3 or 4 distinct portions. It is found that a gas flame may be employed without causing error. J. J. S. Estimation of Sulphates in Vegetable Products. GEORGE S. FRAPS (Chem. Centr. 1904 ii 1433 ; from IZep. Chenaist North Carolina Agric. Experim. Stat. 1902 1903).-Five grams of the substance are treated for half an hour with 50 C.C. of 1 per cent. hydrochloric acid and the residue is washed with the same acid until the filtrate measures60 ABSTRACTS OF CHEMICAL PAPERS. about 250 C.C. barium chloride as usual. This is then heated to boiling and precipitated with A number of result,s are communicated. L.DE K. Apparatus for the Estimation of Nitrogen. EMILE NICOLAS and DELAUD (Bull. SOC. chim. 1904 [iii] 31 1193--1194).-This apparatus is a slightly modified form of that described by Porcher and Brisac (Abstr. 1903 ii 179). T. A. H. Sodium Peroxide i.n Organic Analysis. FRITZ VON KONEK and ARTHUR ZOHLS (Zeit. cmgew. Chem. 1904 17 lSS7. Compare Abstr. 1904 ii 775).-As much as 90 per cent. of the nitrogen in organic substances which are difficult t o burn and which are rich in nitrogen may be converted into nitrate by means of sodium peroxide. A. McK. Rapid Estimation of Nitrogen in Steel or Iron. HJALMAR BRAUNE (C'hem. Centr. 1904 ii 1167 ; from Oestew. Zed. Befag. Hutt. 52 491).-One gram of the sample is dissolved in 10 C.C.of ammonia- free hydrochloric acid of sp. gr. 1,124 and the filtered solution intro- duced into a distilling flask containing 250 C.C. of boiling water and 20 C.C. of an alkali hydroxide solution sufficiently strong t o neutralise tho acid. The distillate is then '' Nesslerised " in the usual manner. L. DE K. Estimation of Ammonia and Amides. JEAN EFFRONT (Bey.. 1904 37 4290-4295).-The reaction between alkali hypochlorites and nitrogen compounds may be more accurately followed by determin- ing the loss of active chlorine than by measuring the nitrogen evolved. Amines imines nitriles amides and amino-acids react with sodium hypochlorite the active chlorine disappearing being proportional to the weight of organic compound added ; tetra-alkylamnionium com- pounds and betaine do not react.A detailed method of carrying out the determination is desct ibed. Ammonia is completely oxidised by sodium hppochlorite at the ordinary temperature (compare Thiele Abstr. 1893 ii 317) the nitro- gen evolved containing a trace of nitrogen chloride. The ammonia in samples of water may be determined by this method to 0.2 milligram per litre. Proteids may also be determined in water after expelling free ammonia by boiling with sodium carbonate. Proteids show a con- stant reducing power towards hypochlorites peptones also show a con- stant but lower reducing power. C. H. D. Estimation of Ammonia in Vegetable Products Beets &c. EUGENE SELLIER (Clzena. Centr. 1904 ii 1433-1 434 ; from Bull Assoc. Chim. SUCT. Dist. 21 1223-1 232).-Ammonia may be completely expelled from beetroot juice by the author's magnesia process (Abstr.1903 ii 329). I n the presence of oxamide the distillation with magnesia should take place below 40'. Liquids containing urea should be distilled below 80'. Acid ammonium uratsANALYTICAL CHEMISTRY. 61 should be treated for a short time with dilute hydrochloric acid and then distilled with magnesia a t 36-42'. As hydrochloric acid how- ever may hydrolyse urea the author recommends distilling urine or sediments containing acid urates with calcium oxide a t a moderate temperature. Methylamine if present partially passes over with the ammonia. If the products should happen to contain magnesium ammonium phosphate they should be digested for some time with dilute acids ; the ammonia will then be completely expelled by boiling with magnesia but not at a lower temperature.L. DE K. Electrolytic Estimation of Nitric Acid with a Rotating Anode. LESLIE HOWARD J N G m w (J. Ame.r. Chem. sot. 1904 26 1251-1255).-The author has tried a process suggested in 1890 by Vortmann (Abstr. 1890 1467) for the electroljtic estimation of nitric acid and obtained satisfactory results. The solution of the nitrate is mixed with a known volume of standard sulphuric acid a definite amount of copper sulphate is added and the mixture sub- mitted to electrolysis. The ammonia formed by the reduction of the nitrate neutralises a portion of the acid and from the amount of free acid left (which includes that of the copper snlyhate) the amount of nitric acid is readily calculated.The best conditions for a successful experiment were found to be 25 C.C. of copper sulphate solution ( = 0.2533 gram of copper) 0.5 gram of potassium nitrate 25 C.C. of normal sulphuric acid; 9 volts 4 amperes time 30 minutes speed of rotating anode I I? = about 230 revoluticns per minute]. L. DE K. The Evolution of Hydrogen for Marsh's Arsenic Test. CARL RIA1 and H. HURT (Zeit. anal. Chenz. 1904 43 557-559).-To accelerate the evolution of hydrogen from zinc and sulphuric acid it is usual to add a small quantity of a salt of some electro-negative metal. Many of these howevei. diminish the sensitiveness of the test copper and platinum seeming to be the only unexceptionable agents. With the former the evolution of gas is more regular than with the latter.. Iron in any form must be moat carefully avoided since in its presence comiderable quantities of arsenic may be over- looked M.J. 8. Detection of Arsenic in the Ashes of Cremated Bodies. CARL MAI (Zeit. ctiaccl. Chew. 1904 43 617-619).-0n the occasion of the examination of the ashes of a cremated body the larger bone fragments after careful cleaning were found to be absolutely free from arsenic whilst the mixed pulverulent portion of the ash in which iron was also present was highly arsenical. Some iron nails and screws found in the urn also contained much arsenic and i t is assumed that the presence of that element in the illiscellaneous powder was entirely due to the metals employed in the construction of the coffin. From a forensic point of view it is advisable that neither metal nor pigments should be used in cofTins intended for cremations. M.J. S.62 ABSTRACTS OF CHEMICAL PAPERS. Improvement of Drown and Shimer’s Method of Estim- ating Silicon in Irons. J. THrLL (Zeit. anal. Chem. 1904 43 552-553).-Tf it is attempted to accelerate the tedious evaporation of the iron solution by substituting the direct heat of a lamp for that of the water-bath there is danger of loss from bumping and spirtiog. The addition of ammonium chloride obviates this difficulty. The author’s practice is as follows a litre of concentrated sulphuric acid is mixed with an equal volume of water and (after cooliog) a litre of nitric acid of sp. gr. 1.4 and a solution of 240 grams of ammonium chloride in a litre of water are added. Of this reagent 50-70 C.C.are used for dissolving 1-2 grams of iron. Solution and evaporation can then be carried on in a beaker over a Bnnsen burner with interposed wire gauze and an estimation completed within an hour. M. J. a. Qualitative Detection of Silica. JULIUS PETERSEX (Zeit. GL~CGZ. &em. 1904 43 619-623).-A modification of the method suggested by Daniel (Abstr. 1904 ii 289) permits the detection of 2-5 mg. of silica with certainty. I n a small platinum crucible is placed a mixture of the substance (0.5 gram) with cryolite (0.25 gram) R few milligrams of magnesite and some concentrated sulphuric acid. The crucible is lowered t o the bottom of a test-tube t o which is then fitted a cork carrying a glass rod nearly reaching the crucible. The rod is flattened a t its lower end which is covered with asphalt varnish and from it a drop of water hangs.The whole of the glass rod and the interior of the test-tube have first been coated with collodion contain- ing 2 vols. per cent of castor oil. This film protects the glass com- pletely from the action of hydrofluoric acid. The bottom of t.he tube is then plunged into water of 60’. A t this temperature the formation of silicon fluoride is sufficiently rapid to give a white film on the sur- face of the drop of water in five minutes. M. J. S. Estimation and Separation of Calcium in presence of Phos- phoric Acid. K. K. JXRVINEN (Zeit. cciaccl. Chern. 1904 43 559-562). -The estimation of calcium in presence of phosphoric acid is liable to two sources of error incomplete precipitation of the lime and con- tamination of the precipitate with phosphoric acid.The following inode of operating gives fairly satisfactory results the solution which must be as free as possible from ammonium salts is mixed with ammonia until calcium phosphate j u s t begins to precipitate and the precipitate is redissolved by a drop of hydrochloric acid. The liquid is heated to boiling and poured slowly into a mixture of equivalent quantities of ammonium oxalate and oxalic acid. Ammonia not stronger than 1 per cent. is then added drop by drop until the mixture is alkaline and the estimation is finished in the usual manner. M. J. S. Estimation of Calcium Oxide in Burnt Lime. Solubility of Calcium Carbonate in Solutions of Ammonium Nitrate. GEORG BERJU and WLADTSTAUR KOSINEXKC) (Lcmclzo.Trers?tchs-Strtt 1904 60 41 9-425).-Bodenbender and Ihleo’s method for determin- ing calcium oxide in burnt lime (Zeit. Biibenxuckerind 1879) by boilingANALYTICAL CHEMISTRY. 6.3 with ammonium nitrate can give correct results only under certain conditions owing t o the varying amounts of calcium carbonate dis- solved. It is found that calcium carbonate is practically insoluble in N/5 ammonium nitrate when the mixture of varbonate and oxide contains 8 per cent. or more of the latter. According to the amount of carbon- ate present (determined with a Pcheibler apparatus) 3-5 grams of substance are treated with 1 litre of N / 5 ammonium nitrate in a rotatory apparatus turning about 40 times a minute. The calcium oxide is afterwards determined in the usual manner in a n aliquot portion of the filtered or subsided solution.N. H. J. 11. Use of a Rotating Anode in tbe Electrolytic E s t i m a t i o n of Zinc. LESLIE 13. IKGHAX (J. Amer. C'hem. h'oc. 1904 26 1269-1283). -A lengthy investigation as t o the best and quickest method of electrolytic zinc assay. The ore is oxidisecl with nitric acid and repeatedly evaporated with hydrochloric acid and the iron is removed by a doiible precipitation with ammonia. The ammoniacal filtrate after adding some more ammonium chloride is then submitted to electrolysis using a rotating anode ; for working details the original paper should be consulted. Good results are also obtained by t,he electro- lysis of solutions containing sodium acetate or formate. L. DE I<.Volumetric E s t i m a t i o n of Lead. GUIDO C'ERVI (C'r'tem. Caut~. 1904 ii 1343-1344 ; from L71ndustric~ C'hemicn 6 889-290).-A slight modification of the process recoinmended by Guess ( l'~ni2s. AULW. I y ~ t . Zin. Ethg. i 904). The nentralised solution of the lead is acidified with acetic acid sodium acetate is added the solution is heated to boiling and the lead precipitated with standard solution of potassium dichromate. When cold the liquid is diluted to a definite volume and in a n aliquot part of the filtrate the excess of dichromste is estimated as usual by adding dilute sulphuric acid and potassium iodide and titrat- ing the liberated iodine with standard sodium thiosulphate. I n the presence of antimony or iron the lend should be first separated as sulphate which is then dissolved and titmted.L. DE E(. [Analysis of] Commercial Lead. AUGUSTE HOLLARD and L. BERTIAUX (BUZZ. Soc. c l ~ i ) ~ ~ 1904 [ iii] 31 11 24-1 128. Compare Abstr. 1899 ii 523).-Five grams of commercial lead are dissolved in 86 C.C. of nitric acid of 36" B. previously diluted with water. The liquid is made up t o 300 C.C. and the lead removed as the peroxide using a current of 0.8 ampere (compare Abstr. 1903 ii 294). Five C.C. of sulphuric acid are then added to the lead-free liquid and this is evaporated down until sulphuric acid funies are copiously evolved ; it is then diluted to 300 C.C. and the copper determinetl electrolytically the precautions already indicated (Abstr. 1904 ii 6S2) being taken to obtain a copper deposit free from arsenic antimony or bismuth.Nickel and zinc are separately estimated in the ix-sidual liquid by the process previously described (Abstr. 1903 ii 335 ; 1904 ii 92 and 682) and iron by titration with iodine (Abstr 1904 ii 368 and 592).e4 ABSTRACTS OF CHEMICAL PAPERS. For the estimation of arsenic and antimony a fresh portion of lead is treated with sulphuric acid and the arsenic separated by distillation after the addition of ferrous sulphate and hydrochloric acid (Abstr. 1900 ii 438). The residual liquid is placed in a flask having the bottom coated outside with fireclay and to it is added zinc chloride solution of sp. gr. 2 ; the antimony chloride is distilled off in a current of hydrogen chloride and finally estimated electrolytically. From a hot nitric acid solution of ths lead silver is precipitated as the chloride the latter is dissolved in potassium cyanide solution and the metal determined electrolytically.Sulphur is precipitated as barium sulphate from a nitro-hydrochloric acid solution of the original material Bismuth is separated as the basic nitrate which is then converted into sulphide and freed from arsenic antimony and tin by means of ammonium hydrosulphide and is finally estimated by elect yo- lysis of a solution of the sulphate (Abstr. 1904 ii 684). The tin obtained as the sulphide in the separation of the bismuth is freed from antimony by electrolysis in presence of potassium cyanide and finally detmmined electrolytically in hydrochloric acid solution in presence of ammonium oxslate. A tabular statement showing.the comDosition of v thirteen samples of commercial lead is given in the original. T. A. H. Electrolytic Separations possible with a Rotating Anode. DONALD S. ASHBROOK (J; Amer. Chem. Soc. 1904 26 1283-1290).- A paper unsuitable for adequate abstraction. Working details are given as to the electrolytic separation of copper from aluminium anti- mony arsenic cadmium chromium cobalt iron lead magnesium manganese nickel uranium and zinc ; cadmium from aluminium chromium cobalt iron magnesium manganese nickel and zinc ; silver from aluminium. L. DE K. Electrolytic Estimation of Copper. AUGUST KUFFERATH (Zeit. angew. Chern. 1904 17 1785-1786).-About 1.5 grams of the sub- stance containing copper are dissolved in dilute sulphuric acid with the aid of nitric acid ; if an excess of the latter is carefully avoided there is no need for evaporating to dryness.After diluting to about 130 c.c. 2 grams of formaldehyde are added and the copper is deposited as usual by heating at 60-65" and using a current of 2.5-3 amperes and 2 volts. Without interrupting the current the deposit is washed first with water then with alcohol and finally with ether and is then dried in a vacuum over sulphuric acid and weighed. Iron nickel and cobalt are not deposited in the presence of formaldehyde. L. DE K. Titratiorr of Copper by Potassium Iodide and Applicability of the Method in presence of Iron and Arsenic. L. MOSER (Zed. arzal. Chem. 1904 43 597-616).-Both the original method of De Haen and Rumpler and Low's modifications (Abstr.1896 ii 450) are affected by sources of error and the variation suggested by Litterscheid (Abstr. 1902 ii 531) is useless in presence of iron orANALYTICAL CHEMISTRY. 65 arsenic. The author has reinvestigated De Haen's method employing thiosulphate for the titration of the iodine. When free acids are absent the results are only satisfactory if the solutions are sufficiently con- centrated but in presence of free sulphuric acid correct results are obtained even when the dilution and amount of free acid are largely varied. Hydrochloric and nitric acids as acidifying agents are inadmissible but acet,ic acid may be used. Although the action of potassium iodide on a cupric salt indubitably consists at first in the formation of cupric iodide in the presence of free acid the decomposi- tion into cuprous iodide and free iodine is so rapid and complete that titration may be commenced two minutes after making the mixture ; n delay of ten minutes does not materially affect the results but after an hour higher numbers are obtained.The following is the form in which the process is recommended the copper solution (50 C.C. con- taining about 0.15 gram of copper as sulphate) is placed in a 300 C.C. stoppered bottle ; 5 C.C. of 10,V sulphuric acid and 2 grams of solid potassium iodide are added and the bottle is shaken for two minutes. The free iodine is then titrated with N/10 thiosulphate adding starch when near the end. To render the method applicable in presence of iron ancl arsenic the solution of the metals (as sulphates) is treated with an excess of sodium pyrophosphate sufficient to redissolve the precipitate at first formed. If the original solution contained free sulphuric acid some sodium acetate is added then 4-5 grams of potassium iodide and 5-10 C.C.of 80 per cent. acetic acid. I n these circumstances the copper alone liberates iodine but to obtain good results it is advisable to avoid dilution as far as possible wherefore solid sodium pyro- phosphate should be used for the precipitation and if the amount of iron exceeds that of copper by more than one-third the quantity of ptassium iodide should be increased; a somewhat longer time (15 mmutes) is allowed before titrating and the thiosulphate run in very slowly. M. J. S. Detection and Elstirnation of Minute Quantities of Mercury.CONSTANTIN ZENGELIS (Zed. unal. Chena. 1904 43 544-547).-For the detection of mercury in urine the urine is feebly acidified with hydrochloric acid and left in contact for 12 hours with a spiral of copper and platinum wires. The spiral is then washed with dilute sodium hydroxide water alcohol and ether and dried completely over sulphuric acid. It is then thrust to the bottom of a narrow test-tube the upper part of which is moistened with a solution of iodine in anhydrous ether Holding the tube horizontally the coil is heated and the evolved mercury vapour is arrested by the ring of iodine solution and converted into mercuric iodide. Complete absence of water is indispensable 0.2 milligram of mercury can be detected in 200-300 C.C. of. urine. For quantitative estimation the urine is boiled with an excess of sodium hydroxide and a little of a reducing sugar.The phosphate precipitate is dissolved in nitric acid and the solution electrolyaed at 40-50" with a weighed piece of platinum foil as cathode. M. J. S. VOL LXXXVIII. ii. 5Gbi ABSTRACTS OF CHEMICAL PAPERS. Detection and Estimation of Traces of Mercury in Urine with the aid of the Nernst Balance. ERNST JANECKE (Zeit. anal. Chev~. 1904 43 547-552).-1t is often desirable to be able to estimate with accuracy quantities of mercury not exceeding 0.5 mg. yr litre of urine. The use of the Nernst balance (Abstr. 1903 ii 571) enables this t o be done with 250 C.C. of the urine. The organic matter is destroyed by heating the urine with potassium chlorate and hydrochloric acid and the met’cury is then precipitated on a spiral of clean copper mire.The spiral is dried and strongly heated in a test-tube which has been drawn out to a capillary at the open end. The mercury is thus collected in the capillary tube. This is then crushed under a mixture of nitric and sulphuric acids and after heating to dissolve the mercury a little potassium sulphate is added and the solution measuring 10 c.c. is electrolysed with a coil of gold wire as cathode and a spiral of platinum wire as anode. These coils are conveniently kept from contact during the electrolysis by placing one inside and the other outside a short plass tube open at both ends. The gold wire is weighed before and after the electrolysis by substi- tuting it for the scale-pan of the Nernst balance.Since the gold absorbs hydrogen during the electrolysis a correction is made by inserting into the circuit a second similar coil in a cell free from mercury. The actual presence of mercury on the gold should be confirmed by expelling it into a capillary tube containing a trace of iodine. The author has succeeded by this method in detecting 0.01 mg. of mercury which had been added to two litres of urine. M. J. S. A Modifled Form of the Persulphate Method of Estimating Manganese in Iron and Steel. H. PROCTER SMITH (Chem. Newe 1904 90 237).-The following modification of this process is described 0.2 gram of the sample and the same weight of a steel containing a known quantity of manganese are bot,h placed in test-tubes and each gently heated with 10 C.C.of nitric acid of sp. gr. 1.2 until dissolved. The solutions are boiled to expel red fumes and 10 C.C. of silver nitrate solution (1.7 grams per litre) and about 1 grain of ammonium per- sulphate are added. After heating until the latter is nearly dissolved the sides of the tubes are washed down with water and the contents cooled. The perfectly cold pink solutions are then transferred to china basins and titrated with sodium amenite solution. The latter is pre- pared by dissolving 5 grams of arsenious oxide and 15 grams of sodium hydrogen carbonate in 250 C.C. of boiling water and diluting to 1 litre. Forty C.C. of this solution diluted to 500 C.C. form the titration solution which for each set of analyses must be standardised on a steel con- faining a known quantity of manganese.w. P. s. Volumetric Estimation of Iron. NAZARENO TARUGI aid S. SILVATICI (Chern. Centr. 1904 ii 1341-1342 ; from Boll. Chint. Fwrn. 43 637 -641).-The solution which must contain the iron in the ferric state is carefully neutralised with sodium hydroxide and after adding some potassium thiocyanate the liquid is titrated with i V / l O potassium oxalate until the colonr changes to yellowish-green. One C.C. of theANALY‘I‘ICAL CHEMISTRY. 67 oxalate solution = 0.00186673 gram of metallic iron. to make a blank experiment using 5 C.C. N/10 fevric chloride. It is advisable L. DE K. Colorimetric Estimation of Iron in Blood. ADOLF JOLLES (Zeit. c c m l . Clbenz. 1904 43 537-539).-The author’s most recent modification of his original method (Abstr.1897 ii 126) consists in cciiiparing the colour of the iron solution obtained from 0.05 C.C. of blood with that of the glass wedge of Fleischl’s hsmometer and he regards the apparatus foy this form of estimation to which he gives the name ‘‘ clinical ferrometer,” as the simplest and most convenient for cliiiical pwposees (compare Oerum Abstr. 1904 ii 449). Whereas in general the percentage of iron in the blood is proportional to that of the hEmoglobin in many pathological conditions such as ansmia icterus &c. the relation undergoes a marked alteration. M. J. S. Analysis of Commercial Tin and its Alloys. AUGUSTE HOLLARD and 1,. BEHTIAUS (Bull. SOC. chim. 1904 [iii] 31 1128-1131).-A complete scheme for the analysis of commercial tin is given. Arsenic is cletermiried by distillation with hydrochloric acid and ferrous sulphste the distillate being titrated with iodine (Abstr.1900 ii 438). The copper bismuth and lead are separated from the tin by precipita- tion as sulpliides in presence of ammonium sulphide and the bismuth and lead from copper by precipitation as sulphicles in presence of ammonia and potassium cyanide. Finally the lead and bismuth are separated and estimated electrolytically as already described (Abstr. 1904 ii 684). Antimonyis estimated by dissolving 1 gram of the tin in nitro-hydrochloric acid evaporating down repeatedly with hydro- chloric acid adding a little sodium hydroxide to the residue and electro- lysing under the conditions previously described (Abstr. 1903 ii 455). For the estimation of copper and sulphur 5 grams of tin are treated with nitric acid and the whole evaporated to dryness; the residue is washed thoroughly with water containing a little nitric acid and in these washings the copper is estimated electrolytically and the sulphur by precipitation as barium sulphate.For lead-tin alloys 1 gram of the alloy is treated with 50 C.C. of nitric acid (water should be added if the alloy is rich in lead) in presence of 10 grams of copper. The liquid is diluted to 300 C.C. and warmed to cause the tin oxide to ngglomerate. When cold the lead is estimated electrolytically as the peroxide (Abstr. 1899 ii 523; 1904 ii 294); to obtain the last t’races of lead the anode should be withdrawn when the greater part of the lead has been deposited and the mixture shaken and left in a warm place for a time.The anode should then be replaced and the electro- lysis continued. T. A. H. Estimation and Separation of Gold in the Electrolytic Way. SARAH P. MILLER (J. Amer. Chena. h’oc. 1904 26 1255-1369).-A lengthy article unsuitable for adequate abstraction showing the conditions under which gold can be satisfactorily separated from iron cadmium silver zinc cobalt nickel and copper. The gold is deposited68 ABSTRACTS OF CHEMICAL PAPERS. from solutions containing either potassium cyanide phosphoric acid or sodium sulphide. L.. DE K. Inadmissibility of Soap for Estimating Hardness of Ferru- ginous Water. A. GAWALQWSKI (Zeit. anal. Chem. 1904 43 533-536).-A sample of well-water containing 0.036 gram of ferrous oxide per litre in the form of sulphate gave on titration with soap solution results widely a t variance with the amounts of calcium and magnesium estimated gravimetrically neither could concordance be es- tablished by including in the calculation the amount of soap consumed by the iron present.An attempt to titrate with soap after the removal of the iron by potassium ferrocyanide also failed to give a satisfactory result. M. J. S . Estimation of Ammonia and Proteid-Nitrogen in Waters. JEAN EFFRONT (Cham. Centr. 1904 ii 1253-1254; from Mon. Sci. [ iv] 18 669-674).-An accurately titrated solution of bleaching powder is mixed with a definite volume of the sample of water to be tested and the loss in active chlorine represents the nitrogen of the ammonia and proteids. The experiment is then repeated with water from which the ammonia has been expelled by evaporation with sodium hydroxide ; the result is the proteid-nitrogen only.The active chlorine is estimated by adding excess of sodium arsenite and titrating the excess with standard iodine. L. DE K. Addenda to Simple Method f o r Decarbonising Substances. Estimations in the Decarbonised Product. ALBERT NEUMANN (Zeit. physiol. Chem. 1904 43 32-36. Compare Abstr. 1903 ii 243).-Further manipulative details are given for the processes and estimations already described. J. J. S Alkaloid Reactions. IV. Morphine. C. REICHARD (Chem. Zeit. 1904 28 1102-1105. Compare Abstr. 1904 ii 791 992).-The author communicates a new reaction for morphine which is quite characteristic. If morphine is gently warmed with strong sulphuric acid containing some arsenious or arsenic acid an intense and per- manent purple coloration is developed. In practice it is best to make a solution of arsenious acid in strong aqueous sodium hydroxide; to this may be added first the morphine and then an excess of very strong sulphuric acid. Morphine is also coloured red by antimonious chloride without using sulphuric acid. Stannous chloride in conjunction with sulphuric acid also causes the reaction. L. DE K. Mechanical Andysis of Soils and Sub-soils by Centrifugal Action ; with Notes on Treatment of Samples. J. R. KILROE (&con,. Proc. Roy. Dublin Soc. 1904 1 223-230).-A centrifugal apparatus is described by means of which mechanical separations can be made rapidly and with comiderable accuracy. The amount of soil employed for a determination is 20-30 grams and very little distilled water is required N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9058805055

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

69 General and Physical Chemistry. Enhanced Lines of Titanium Iron and Chromium in the Fraunhoferic Spectrum. Sir J. NORMAN LOCKYER and F. E. BAXANDALL (Proc. Roy. Xoc. 1904 74 255-267).-The contents of this paper are summarised as follows. The enhanced lines of titanium and iron are practically all represented in the Fraunhofer spectrum but in some cases the corresponding solar lines are compound and only partly due to one or other of these metals. The corresponding solar lines are generally speaking comparatively weak ones The majority of the chromium enhanced lines occur in the solar spectrum although some appear to be missing. Some of the Fraunhofer lines correspond with metallic lines special to the spark spectrum and lacking in the arc and probably for this reason they were left unorigined by Rowland.J. C. P. Spectrum Regularities and the Atomic Weight of Radium. GEORGE RUDORF (Zeit. pIt,ysiknZ. Chew,. 1904 50 100-1 10. Compare Runge and Precht Abstr. 1903 ii 346 ; Watts Abstr. 1904 ii 720). -The author finds that frequency differences (d) and atomic weights ( A ) are not exactly related according to the equation d/A” = const. ; hence the formula logA = CL + b log d is not exactly valid and any con- siderable extrapolation based on the straight line formula may lead to error. It is shown that certain graphical relationships exist between the values of A and 100d/A2 vhich permit of the calculation of d for other elements. The value 225 should for the present be taken as the atomic weight of radium. J . C. P. Racemism. GIUSEPPE BRUNI ( A t t i I?.Accad. Limei 1904 [v] 13 ii 373-381. Compare Bruni and Finzi this vol. ii 2 ; Bruni and Padoa Abstr. 1908 i 343).-The freezing-point surface and the course of the isotherms of solutions of mixed optical isomerides give ZL clue to the molecular condition of the dissolved substances and indicate the existence or non-existence of racemic molecules in the liquid. On adding to a p-xylem or ethylene bromide solution of methyl diacetyl- tartrate increasing quantities of methyl diacetylracemate it is found that the freezing-point depressions are always less than the normal values; the molecular weights are hence abnormally great so that there must be a certain number of undissociated racemic molecules in solution. The abnormality diminishes as the concentration of the racemic compound increases which must be attributed to the fact that the excess of the diacetyltartrate undergoes a continuous relative decrease its influence in retarding the dissociation thus becoming less.If temperatures are bken as ordinates and total concentrations as nbscisw the freezing points of the solutioiis of methyl diacetyltartrate and diacetylracemate and the cryohydrate point of the mixed solutions lie on a straight line if the racernic compound undergoes complete VOL. LXXXVIII. ii. 670 ABSTRACTS OF CHEMICAL PAPERS. dissociation in the solution ; where there is partial racemisation this is no longer the case. The three dimeiisional curves obtained with the concentrations of the d- and I-compounds and the temperature as co-ordinates also have different forms for the cases where t>here is partial raceinisation and complete dissociation.RIethyl diacetylracemate also exists partially non-dissociated in solution in diphenylmethane or naphthalene in the latter solvent a t temperatures as high as 80”. The freezing-point constant for diphenyl- methane is 71 and not 67 as was stated by Eijkman (Abstr. 1890 324). Ethyl r-dibrornophenylpropionate is partially non-dissociated in naphthalene solution in presence of the rl-cornpound. T. H. P. Possibility of Resolving Racemic Compounds by Circularly Polarised Light. The Primary Production of Optically Active Substances. ALFRED RYK (Zeit. physiknl. Chenz. 1904,49,641-687 ; Ber. 1904 37 4696-4700).-As a starting point Cotton’s experi- ment is taken according to which the d- and I-components of Fehling’s solution possess different coefticients of optical absorption for circularly polarised light of definite sign.It can also be shown that the positions of the maxima of optical absorption and of photochemical sensitiveness coincide and the conclusion is drawn that the extent of decomposition of these sensitive compounds in circularly polarised light is not the same for each. On the strength of Ostwald’s work on the independelit optical absorption of the ions in dilute solution the author drams the further conclusion that this difference of sensitiveness persists in the inactive Fehling solution and must therefore result in this solution gradually becoming active under the decompobing influence of circularly polarisecl light.For the details of each step in this indirect proof reference must be made to the original. The extensive occurrence of optically active compounds in nature may thus be referred to the production in excess of one kind of circu- larly polarised light at the earth’s surface. This result is reached by the reflection of the plane polarised rays of sunlight from the enrface of the sea assisted by the influence of the earth’s magnetism. Incidentally it was found that the same effect was produced by cl- and by I-circularly polarised light on sensitive optically active photo,ar,iphic preparations (silver tartrate paper and silver bromide plates sensitised with chlorophyll). The progressive dissociation with dilution of a racemic salt was followed in the case of Fehling’s solution and it WRS shown that the production of the racemic salt obtained by mixing tl- and I-Fehling’s solutions is accompanied by a change of colour.J. C. P. Formation of Salts in Solution especially in the Case of Substances Exhibiting Tau tomerism (Pseudo-acids Pseudo- bases). I. JULIUS W. BRUHL and HEINRICH SCHRODER (Zeit. physikal. C‘hem. 1904 50 1-42).-Pull details are given of the spectrochemical investigation of the esters of camphorcarboxylic acid and the sodium derivatives formed from these. The chief conclusions arrived at have already been reported (Abstr. 1904 i 646 and 969). As a further aid secondary result of the investigation following from observationsGENERAL AND PHYSICAL CHEMISTRY. 7 1 made on the variation of the specific refraction of sodium in methyl and ethyl alcohols and its constancy in amyl alcohol (see Abstr.1904 i 969) it seems that the value of the specific refraction for the sodium ion is 12-15 per cent. less than the value for sodium in an unionised compound. J. C. P. Luminescope for Comparing Substances under the Influ- ence of Radium Rays. C. S. STANFORD WEBSTER (J. Soc. Chem Ind. 1904 23 1185-1 186).-The instrument has been designed to facilitate the comparison of different substances in regard to their ‘‘ glow ” and scintillating power under the influence of radium rays. It resembles the spinthariscope but the draw tube with the system of lenses is mounted on one side of a circular metal box which contains a metal disc carrying four screens. By turning a handle the disc can be rotated and the screens brought into position under the observation tube as required.One of the screens is temporarily fixed by wire-spring clips and can be replaced a t will. H. M. D. Induced Radioactivity. KARL A. HOFNANN L. GONDER and VALENTIN W~LFL (Ann. Phpsik 1904 [iv] 15 615-632. Compare Abst4r. 1902 ii 261 397; 1903 ii 402).-Although a uranium salt can be separated into a more and a less active portion the two por- tions finally exhibit the same activity (compare Becquerel Abstr. 1902 ii lli’) so that uranium is itself a radioactive element. When small quantities of salts of other metals are dissolved in concentrated solutions of uranium nitrate and after a few weeks are separated from the uranium by chemical methods the precipitated sulphate sul- phide or oxalate as the case may be is found to have an induced radioactivity which gradually disappears.The degree of activity of the precipitate depends on the nature of the inactive metal it contains ; thus the activity transmitted to lead and bismuth sulph’des is much greater than that transmitted under similar conditions to the sulphides of palladium platinum and mercury. When two inactive metals acquire an induced activity from the same uranium solution their relative activity is independent of the order in which they have been separated from the solution. When the metals are arranged according to the relative activity induced under the above conditions the order is roughly the same whether uranium or radium is used as the inducing agent but is quite different when radiolead or radiobismuth is the inducing agent.For iridium palladium rhodium and platinum are distinguished by the marked activity which is induced in them by radiolead. The chloride iii each case was kept f o r three weeks in common solution with raclioleacl chloride and then the metal was pre- cipitated by formaldehyde o r hyclroxylamine. The a-activity thus induccd 011 these metals is removed on ignition at a bright red heat but the P-activity is oiily slightly diminished by that treatment. This observation leads to the suggestiou that the a-activity is occluded but in conflict with this view i t has been shown for platinum that the activity of the metal is not greater than that of the sulphide obtained by precipitation from the same radiolead solution.At the ordinary temperature the induced P-activity disappears more rapidly than the 6-272 ABSTRACTS OF CHEMICAL PAPERS. a-activity. When the metals palladium iridium and silver (platinum and gold in a less degree) in the solid form have been immersed for several days in an active lead chloride solution obtained from pitch- blende and kept a t 60° they exhibit marked radioactivity. When active bismuth salts prepared from pitchblende are used as inducing agents in the manner previously described they lose their own activity and do not regain it i n contrast to the radiolead preparations. The process of induction is supposed to consist in the emission of particles from the primarily active substance those particles adhering then to the atoms and ions which are susceptible to the induction.J. C. P. Action of Redium Rays on Caoutchouc. RUDOLF DITMAR (Chem. Centr. 1904 ii 1652-1653 ; from Gummi-Zeit. 19 3-4. Compare Abstr. 1904 i 757).-The power of radium rays of pene- trating caoutchouc has been examined by Madame Curie’s radiographic method. A ‘‘ coucentrated ” preparation of de Haen’s radium barium bromide was used but the action of this substance was not sufficiently powerful to induce radioactivity in the caoutchouc itself. The follow- ing conclusions have been derived from the results of the experiments of the author and the investigations of Madame Curie. The radium rays (y-rays) penetrate both crude and vulcanised rubber but the former more readily than the latter probably owing to its porosity. Caoutchouc itself may be rendered radioactive (Madame Curie).The loss of act,ivity of caoutchouc in air does not take place in accordance with the law which usually obtains for solids. E. W. W. Variation of the Resistance of Bismuth in a Feeble Magnetic Field. C. CARPINI (A’uovo Cim. 1904 [v] 8 171-1 86).-The variation of the resistance of bismuth in both feeble and strong magnetic fields is a hyperbolic function of the strength of field and is also a sine function of the angle made by the coil of bis- muth with the lines of force No hysteresis phenomena were observed on changing the strengthof field. When an alternating current is em- ployed the change of resistance is far smaller than with the corre- sponding direct current. The curves appear to depend in a very com- plicated manner on the amplitude and period of the alternating cumen t T.H. P. Electric Conductivity of Phosphorus Emanation and of Freshly Prepared Gases. EUGDNE BLOCH (Ann. Chim. Phys. 1905 [viii] 4 25-144. Compare Abstr. 1903 ii 206 ; 1904 ii 11’7).- The electric conductivity of dry air which has passed over phosphorus or oE freshlyprepared gases (such as hydrogen or carbon dioxide ob- tained by the action of acid on metals or marble respectively) is in each ca.se due to the same cause namely the presence of ions which diffsr in their mobility and their coefficient of recombination from the ordinary ions. M. A. W. Electrolytic Conductivity of Colloidal Solutions. G. E. MALE’ITANO (Conipt. rend. 1904 139 1221-1323).-Cnrefully purifiedGENERAL AND PHYSTCAJ CHERITSTRY. 73 colloidal solutions have an electrolytic conductivity greater than t'hat of water ; this is however due to the small quantity of soluble electro- lytes unavoidably present in such solutions and not to the colloidal granules themselves which appear to be without electric charge for the clear liquid obtained after filtering a colloidal solution through a collodion membrane lias the same electrolytic conductivity as the original solution or the residual liquid rich in colloidal granules ; thus a solution of ferric chloride which had been heated to 100' and con- tained 0.371 per cent.of clilorine and 0.132 per cent. of iron had k = 0.02301 the clear colourless filtrate contained 0.367 per cent. of chlorine and 0.077 per cent. of iron and had k=0*02299 and the residual colloidal liquid contained 0.350 per cent.of chlorine 0.182 per cent. of iron and had k = 0.02273 and similar results were obtained with colloidal solutions of arsenic pentasulphide or white of egg. 11. A. W. Conductivities of Certain Electrolytes in Water Methyl and Ethyl Alcohols and Mixtures of these Solventp. Relation between Conductivity and Viscosity. HARRY C JONFS and CHARLES G. CARROLL (Amer. Chem. J. 1904 32 521-583. Compare Jones and Lindsay Abstr. 1903 ii 55)-The conductivity of cadmium iodide bas been determined a t 0' and 25' in water methyl and ethyl alcohols and mixtures of water with each of these alcohols. The determinations were made a t dilutions varying from 16 to 256. The results show that cadmium iodide does not exhibit a minimum in mixtures of methyl alcohol and water at 25' but that a minimum appears a t 0' in a mixture containing 76 per cent.of the alcohol a t concentrations of not less than 64 but disappears a t greater dilutions. In mixtures of ethyl alcohol and water a t 2 5 O no minimum is observed. Determinations of the conductivity of sodiuni iodide a t 0' and 25' in water and in methyl alcohol of 25 50 and 75 per cent. strength have shown that a minimum is exhibited but is more pronounced a t 0' than a t 25". A t 25' a minimum occurs in 75 per cent. methyl alcohol a t a concentration of 32 but beyond this dilution the minim:L are only observed in the 50 per cent. mixture. A t O' the minimum appears in the 50 per cent. mixture only. The conductivity of solutions of calcium nitrate in water methyl alcohol ethyl alcohol and mixtures of each of these alcohols with water was determined a t 0' and 26" but in no case was a minimum observed.Determinations of the conductivity of hydrogen chloride in methyl alcohol of 50 69.75 90 and 100 per cent. strength gas70 results which show that in each case the molecular conductivity decreases as the concentration increases. In the 69.75 per cent. mixture a maximum is obtained both at 0' and 25'. I n the 90 per cent mixture the results are regular and a limiting value is reached at a dilution of 157.67. It is found that hydrochloric acid shows a minimum both in the 69.75 and the 90 per cent. mixtures A t 25' the minimum appears a t a dilution 178.75 and a t 0' it appears at all dilutions.The conductivity of sodium acetate in acetic acid of 25 50 75 and74 ABSTRACTS OF CHEMICAL PAPERS. 100 per cent. strengths was determined at 2 5 O but the results were irregular and led to no definite conclusions. The dissociation of potassium iodide sodium iodide ammonium bromide ammonium iodide and lithium nitrate in 50 per cent. methyl alcohol WAS calculated from conductivity determinations. I n the case of potassium and sodium iodides it was found that the dissociation is greater in the mixture of methyl alcohol and water than in either of the pure solvent; and that the dissociation of potassium bromide is greater in the mixture than in pure water. The dissociation of hydrochloric acid in methyl alcohol of 69.15 per cent. strength is also greater than in water at the corresponding dilution but this is not the case for the 90 per cent.alcohol. The dissociation of potassium and sodium iodides in water methyl alcohol and ethyl alcohol is found to agree quantitatively with the hypothesis of Dutoit and Astoii (Abstr. 1897 ii 456). It is suggested that the greater dissociation found in the 60 per cent. mixture of methyl alcohol and water is due to the presence of a hydrate CH3*OH,3H,O formed by the association of four simple mole- cules whereas in water the number of molecules associated with one another a t the ordinary temperature is less than four. An explanation has been suggested by Jones and Lindsay (Zoc. cit.) t o account for the occurrence of the minimum point in the conductivity values. It is now shown however that t'his explanation is not alto- gether satisfactory and that the decrease in the coiiductivity of electrolytes in binary mixtures of various alcohols and water some- times accompanied by a minimum conductivity is due mainly to a diminution in the fluidity produced on mixing the solvents arid the consequent decrease in ionic mobility.The hypothesis of Kohlrausch (Abstr. 1903 ii 403) that each ion is invested with an atmosphere of the solvent of considerable thickness is shown to be true in the case of binary electrolytes not only in aqueous solutions but also in methyl and ethyl alcohols. The relation between conductivity association and viscosity is discussed and the hypothesis is put forward that the cmductivities of comparable equivalent solutions of binary electrolytes in certain solvents such as methyl and ethyl alcohols arid acetona are inversely proportional to the coefficient of viscosity of the solvent and directly praportional to its association factor.This relation has been tested in a number of cases and found to be true in each. The results of the experiments are tabulated an(l are also plotted as curves. E. G. Relation betwaen the Size of the Molecular Complex and the Temperature-coefflcient of Expansion in Different States of Aggregation. WILHELM VAUBEL (J. pv. Chevz. 1904 [ii] 70 503-508).-As the molecular vibrations and the consequent tempera- ture-coefficients of expansion of a substance in the gaseous and in the liquid states of aggregation must be in direct piLoportion to the size of the molecules it is proposed to calculate the number of gas-molecules associated in the liquid-molecule from the relation to each other of t hc coe ffici en t s .GENERAL AND PHPSICAL CHEMISTRY.75 The results so obtained agree with those from other methods for chlorine bromine phosphorus bismuth water ether acetone and methyl ethyl and propyl alcohols ; in most other cases the results are too high. Contrary to previous determinations of the molecular weights of homologous series of organic conipounds iii the liquid state the value obtained by the present method increases with the vapour density. G. Y. Effect of Mechanical Vibration on Carbon Dioxide near the critical Temperature. ~VALTER P. BRADLEY A. w. BROWNE aucl C. F. HALE (Physical Review 1904 19 25S-272).-When a system containing bot-h liquid and gaseous carbon dioxide between temperatures of 29' and 31.2" is subjected in a Cailletet apparatus t o proper mechanical vibration a peculiar fog effect is produced.This is due not to impurities in the gas but to a change of state in the liquid and vapour phases resulting respect'ively in the formation of minute bnbbles and drops. The change of state is produced by a1tern:ite compression and dilatation effected by the vibrations of a steel rod clamped t o the pressure jacket of the apparatus. Under given conditions of temperature pressure length of mercury column and relative volume of the phases vibrations of a certain definite pitch are required in order to produce the fog effect. The present paper deals with the measurement of variables determining the pitch of the effective vibrations.J. C. P. Regularities in Homologous Series. OTTO BIACH (&it. physikal. C'hem 1904 50 43-64).-1t is well known that in certain homologous series the melting point alternately rises and falls (com- pare also Lnmouroux Abstr. 1899 i 479 ; Henry ibicl. 735) and in the present paper the author attempts to show that this oscillatory variation is characteristic of all physical constants. T.V hen the constants themGelves vary more or less regularly their differences may be found to oscillate or the differences between these first differences may exhibit the required peculiarity. By way of explanation the author makes the supposition that the vttlency of hydrogen is not exactly one-fourth that of carbon.J. C. P. Rate of Chemical Auto-heating (Adiabatic Reaction Kinetics). GE~RGE BREDIG and P. EPSTEIN (Xeit. cmorg. Chem. 1904 42 341-352).-A theoretical paper i n which the following question is discussed. Given a chemically reactive system of the initial concen- tration a and having a t constant temperature the rate constant kYL which is variable wit11 the temperature T,,whilst in the reaction in ques- tion the amount of heit 9 is evolved for each formula-weight g ; it being assumed that the reaction proceeds in a vessel impermeable to heat so that the system is thus heated or cooled by its own heat of reaction. After what period oE time 2 will n definite temperature 2'; and a t the same time a definite chemical transformation x be reached ? To illustrate the equations deduced the action 2H,O = 2H20 + 0 w n s studied under the catalytic influence of potassium iodide and so far as possible under adiabatic conditions.A t a definite time a76 ABSTRACTS OF CHEMICAL PAPERS. mixture of hyclrogen peroxide and potassiuin iodide was introduced into a Dewar-Weinhold flask and the auto-heating of the syst'em estimated after definite intervals of time. A. McK. Some Thermochemical Rules relating to the Possibility and Prognostication of Reactions. MARCELLIN BERTHELOT (Compt. rend. 1904 139 1005-1009).-A theoretical paper not suitable for abstraction. If. A. W. Thermochemical Studies. DAMEL LAGERL~FF (J. pr. Chew. 1904 [ii] 70 621-559. Compare Abstr. 1904 ii 382 605).-The conclusion of the author's mathematical discussion of the theory of the heat of formation of carbon compounds.G. Y. Combustion of Sulphur in the Calorimetric Bomb. H. GIRAN (Compt. vend. 1904 139 1219-1221).-Tho author has measured the heat of combustion of sulphur in oxygen in a calorimetric bomb under varying pressures estimated the sulphur dioxide and sulphur trioxide in the gaseous products and calculated the heat of formation of sulphur dioxide under different pressures; the results show that the heat of formation of sulphur dioxide and the proportion of sulphur converted into the trioxide increase with the pressure and the following table comprises the results Ratio of weight of snlphur converted into trioxide to Heat of Pressure. formation of SO,. total weight of sulphur. 2.5 ) ) 70-43 0.142 5 ) 71.60 0.165 10 ) ? 72'19 ) 0-184 75 ,) 74-45 ) ) 0.188 25 ) ) 77.88 0.228 80 ) 78'41 0.272 35 9 80.26 0'294 40 2 80.88 0.307 1 ntlllo.;.69.80 Cal. (by extrapolation) - 'LO > 75-52 0.219 45 ) ) 81.13 0.312 I t is probable that the increase with the pressure in the heat of formation of sulphur dioxide is due to the formation of tt higher oxide of sulphur as the residue contained in the bomb shows the characteristic properties of the anhydride of persulphuric acid. The heat of formation of sulphur dioxide under atmospheric pressure is 69.80 Cal. M. A. W. Villari's Critical Point in the Case of Nickel. I(. HONDA and s. SHrMrzu (Ann. Physik 1904 [ iv] 15 855-859).-The authors adhere to their former conclusion (Ann. Yhysik 1904 [iv] 14 791) that nickel does not exhibit this critical point.J. C. P. Fusion of Dissociating Compounds and the Degree of Dissociation of the Fused Substance. ROBERT KREMANN (ilrfofiatsh. 1904 25 1215-1269).-From theoretical considerations itGENERAL AND PHYSTCAL CHEMISTRY. 77 is shown that if curves are constructed with melting points as ordinates and molecular percentages of one substance which forms an additive compound with the other as abscissa the more strongly the additive compound dissociates on melting the flatter is the curve near the maximum Tut its melting point. The melting point of the additive compound is affected less by addition of one of the components than of an indifferent substance as the former takes part in the equilibrium between the additive com- pound and its components.The molecular depression of the melting point of the additive cornpound is calculated from the heat of fusion or is determined directly by addition of iudifferent substances unless these act as solvents when the molecular depression produced increases with the dielectric constant. The extent to which the additive compound dissociates on melting can be determined within 1 per cent. by comparison of the theoretical with the experimental curve. The additive compound of aniline with phenol has the molecular depression of the melting point A = 0*278" and when fused dissociates to the extent of 20 per cent. The curve for mixtures of phenol and picric acid has eutectic points a t 36" and SOo for mixtures containing 7 and 59 molecular per cent. respectively of picric acid ; the additive compound has A = O04Ol0 and a dissocia- tion degree of 27 per cent.For mixtures of trinitrotoluene and naphthalene the curve has eutectic points a t 72" and 71" representing 12 and 85 molecular per cent. respectively of trinitrotoluene ; the additive compound melts a t 96.5". The curve for the mixtures of naphthalene and picric acid (compare Saposchnikcff and Rdultowsky Abstr. 1904 i 399) has eutectic points at 78' and 111" for mixtures containing 4 and 92 inolecular per cent. respectively of picric acid; the additive compound melts a t 147'. The mixtures of nitroso- dimethylaniline and aniline show eutectic points a t - 10' and 75" representing 2.5 and 90 molecular per cent. respectively of nitroso- dimethylaniline ; the additive compound contains 33 molecular per cent.of aniline melts a t 93" has A=O*202' and when melted dissociates to the extent of 15 per cent. Influence of Substitution in the Components on the Equilibrium of Binary Solutions. ROBERT KREMANN (Moncctslh. 1904 25 1271-1310. Compare foregoing abstract).-The melting point curve of mixtures of 2 4-dinitrotoluene and naphthalene has eutectic points at 53' and 56" for mixtures containing 28 and 69 molecular per cent. respectively of naphthalene ; the maximum for the additive compound is 59'. The curve for mixtures of nitrotoluene and naphthalene falls to one eutectic point a t 37" for a mixture con- taining 38 molecular per cent. of nitrotoluene. The curve for mix- tures of trinitrobenzene and naphthalene falls to eutectic points at 77" and 114' for mixtures containing 8 and 88 per cent.respectively of naphthalene ; the maximum for the additive compound (Hepp Abstr. 1883 317) lies a t 151". The curve for mixtures of rre-dinitrobenzene and naphthalene falls to eutectic points a t 50.3' and 50.5" for mixtures containing 60 and 42 molecular per cent. of naphthalene; the curve between the eutectic points is extremely flat the maximum G. Y.78 ABSTRACTS OF CHEMICAL PAPERS. the melting of the easily dissociated additive compounds lies at 60%' ; such mixtures are termed by the author $-isomorphic. The curve for mixtures of nitrobenzene and naphthalene falls to one eiitectic point a t - 6.8' for a mixture containing 14 molecular per cent. of naphthalene. The curve for mixtures of o-nitrophenol and naphthalene has one eutectic point a t 303 for a mixture containing 30 molecular per cent.of naphthalene. The curve for mixtures of p-nitrophenol and naphthalene falls to a eutectic point a t 73" for a mixture coiitaiiiing 77 molecular per cent. of naphthalene. The curve for mixtures of s-trinitrobenzene and aniline has a eutectic point at 101' for a mixture containing 18 iiiolecular per cent. of aniline and another a t - 6 " for a mixture containing 0.3-0.7 molecular per cent. of trinitrobenzene ; the maximum a t 125' repre- sents an equimolecular mixture. The curve for mixtures of nz-dinitrobenzene and aniline falls from the melting point of dinitrobenzene to 40" where there is a break and then to a eutectic point a t - 8' for a mixture containing 4 molecular per cent.of nz-dinitrobenzene ; the break a t 40' represents an additive compound containing 20 molecular per cent.. of nz-dinitrobenzene which melts a t 40". Mixtures of nitrobenzene and aniline give a curve which falls to a eutectic point a t - 39.8" for a mixture containing 41 molecular per cent. of nitrobenzene. The curve for mixtures of trinitrotoluene and aniline falls t o eutectic points a t 60' and - 8" for mixtures containing 85 and 1.5 molecular per cent. respectively of trinitrotoluene ; the maximum between the eutectic points is 85'. The curve for mixtures of dinitrotoluene and aniline falls in an almost straight line from the melting point of the former to a eutectic point at - 13' for a mixture containing 11 molecular per cent. of dinitrotoluene.The curve for mixtures of nitrotoluene and aniline has one eutectic point at - 17" for a mixture containing 15 molecular per cent. of nitrotoluene. G. Y. Additive Compounds of Nitrosodimethylaniline. ROBERT KREMAPU" (MonaGtsI~ 1904 25 1311-1329. Compare foregoing abstracts).-Examination of the melting point curves for mixtures of nitrosodimethylaniline with p-toluidine o-toluidine m-xylidine P-naphthylamine and phenol shows that the following additive com- pounds are formed. The additive compound with ptoluidine contains 66.6 per cent. of nit rosoclimethylaniline ; the eutectic points a t 28' and 48.5" represent mixtures containing 27 and 33.4 per cent. of p-toluidine. The additive compound with o-toluidine contains 66 per cent. of nitrosodimethylaniline and melts a t about 70" ; the eutectic points a t 67" and below - 18' represent mixtures containing 26 and over 95 per cent.of o-toluidine. The additive compound with P-naphtliylamine contains 60 per cent. of nitrosodimethylimiline aiid melts at 86" ; the eutect.ic points a t 81' The percentages are in molecular equivalents.GENERAL AND PHYSICAL CHEMISTRY. 79 :md 75" represent mixtures containing 35 and 82 per cent. of nitroso- dimethylaniline. The additive compound with phenol contains 6 6.6 per cent. of nitrosodimethylaniline and melts at 91"; the eutectic points at 24' and 74" represent mixtures containing 21 and 88 per cent. of nitrosodimethylaniline. Two additive compounds are formed with m-xylidine; the one contains 60 per cent. of nitrosodimethylaniline and melts a t 48"; the other contains 25 per cent.of nitrosodimethylaniline and melts a t 26" ; the eutectic points at 46*5" 2 5 O and below - 11" represent mixtiires containing 63 30 and about 2 per cent. of nitrosodimethylaniline. The melting point curre for mixtures of nitrosobenzene and aniline falls to a eutectic point a t - 13" for a mixture containing 19 per cent. of aniline ; no additive compound is formed. G. Y. Polymerisation in the Liquid and Solid States. GEORGE G. LONGINESCU ( A ~ t n . 5%. Univ. Jc~ssy 1904 3 26-34. Compare Ahstr. 1904 ii 1 1 2 ; 1903 ii 531).-Making use of the relationship (T/G.D)2 = ?a conclusions are drawn in regard to the state of aggregation of a number of organic substances containing bromine or iodine of several orgmo-metallic compounds and of various inorganic substances in the solid or liqriid condition.The bromo- and iodo-derivatives and the organo-metallic compounds consist of simple molecules ; thi3 is also the case for the chlorides and bromides of arsenic and antimony for chrom y 1 chloride germanium chloride nickel carbonyl lead t etra- chloride and selenium oxychloride. Other inorganic compounds for example lead chloride lead bromide and cadmium chloride consist of very complex molecules the association factor being greater than 50. The value of C appears to b j a function of the atomic weights of the constituent elements and a method of ascertaining it is described. The ralationship is also applied to the elements and the molecular complexity of 45 elements in the solid state and 13 in the liquid state is deduced. It would appear that carbon silicon lithium and calcium contain more than 200 atoms in the molecule glucinum magnesiuni and strontium more than 100.Sodium and potassium appear to be more highly polymerised in the liquid than in the solid state. Gener- ally speaking in any periodic group the degree of polymerisation decreases as the atomic weight increases. H. 31 D. Distribution of Soluble Substances between Water and Amy1 Alcohol. WALTER HERZ and HERBERT FISCHER (Ber. 1904 3'7 4746-4753).-Measurernent:; are given of the constants of distribution between water and amyl alcohol of several acids and bases. I n the case of the weaker acids (phenol and acetic acid) a constant value is obtained for all concentrations b J t in the case of the stronger acids (succinic oxdic and picric acids) allowance has t o be made for their degree of dissociation a constaiit value for different concentrations being then obtained for the distribution of the undisso- ciated substance With the bases ammonia methylamine and triethyl- amine the constant is independent of the concentration.The distribution ratio of iodine between the two solvents is constant80 ABSTRACTS OF CHEMICAL PAPERS. for all concenti*ations. But with nmyl alcohol and aqueous potass- ium iodide very different values are obtained for different concen- trations the ratio being also dependent on the nature of the potassium iodide solution. W. A. D. Determination of Molecular Weights in Solid Solutions. FRIEDRICH X7. KUSTER [with WALTER WURFEL] (Zed.pluysikal. Chenz. 1904 SO 65-80. Compare Abstr. 1894 ii 274 ; 1895 ii 439),-The freezing point curve for mixtures of p-dichloro- and p-di bromo-benzenes ascends regularly from the freezing point of the former to that of the latter and is slightly convex to the concentration axis. The separating solid in each case is therefore an isomorphous mixture of the two consti- tuents. The composition of the liquid phase in equilibrium with each isomorphous mixture may be deduced from its boiling point for the boiling point curve of mixtures of the two substances is regular and somewhat similar in form to the freezing point curve. The solubility of the isomorphous mixtures in slightly diluted ethyl alcohol has also been determined and these solubility experiments indicate that the molecules of the crystallised compounds are on the average greater than C,H4C1 and C,H,Br2 but smaller than (C,H,CI,) and (C6H4BrJ2.The increase of solubility from the value for pure p-dibromobenzene is nearly proportional t o the percentage of pdichlorobenzene in the isomorphous mixture. Mixtures of 2 4 6-trichlorophenol and 2 4 6-tribromophenol have been similarly investigated. The former compound is djmorphous and the form which primarily separates on solidification is labile a t the ordinary temperature. Tribromophenol does not exhibit dimor- phism and the form in which i t separates on solidification is iso- morphous with that form of trichlorophenol which is stable a t the ordinary temperature. The freezing point of each compound is lowered by the addition of the other and mixed crystals separate from the liquid mixtures; the mixed crystal series however exhibits a gap.The solubility of mixtures of the two substances in dilute methyl alcohol was studied. It is found that whilst the composition of the solutions changes regularly the mixed crystals in equilibrium with the solutions undergo a t one point an abrupt change both in appearance and in composition. When the concentrations of the cldoro- and bromo- compounds in solution are plotted against the molecular concentration of the bromo-compound in the solid phase two straight lincs are obtained for each compound corresponding with the labile and stable forms. The solubility of each form of trichlorophenol is proportional to its concentration in the solid phase the solubility of the labile form being greater than that of the stable form. I n the case of the mixed crystals containing labile tribromophenol the solubility of the latter is proportional to its concentration in the solid phase but on the other hand the solubility of the stable form of tribromophenol increases as its concentration in the solid phase diminishes. This peculiarity is pro- bably due to an associating tendency on the part of tribromophenol and this view is supported by determinations of the molecular weight in alcoholic solution. J. C. P.INORGANIC CHEMISTRY. 81 Stoichiometrical Lawa end the Atomic Theory. LOUIS HENRY (BUZZ. Acad. Roy. Relg. 1904 975-983).-The author dis- agrees with Ostwald’s view that since the stoichiometrical laws are deducible. from the principles of chemical dynamics the atomic theory has become unnecessary for this purpose (Trans. 1904 85 508). T. A. H. Lecture Experiments. [Liquid Ozone. Solid Nitrogen. J HUGO ERDMANN ( B e y . 1904 3’7 4739-4744).-An apparatus is described for storing and manipulating a solution of liquid ozone in liquid air also another apparatus used f o r the preparation of solid nitrogen by kapidly boiling off the liquid gas and suitable for demonstra- tion on the lecture table. E. F. A. Bunsen Burner with Sieve Attachment. FELIX A LLIHN (Chent. Zed. 1905 29 34).-A piece of gauze is attached to the top of the ordinary Marshall burner whereby a flame is obtained which is uniformly hot a i d especially suitable f o r heat,ing ylr?.tinum vessels. A. McK.

ISSN:0368-1769    

DOI:10.1039/CA9058805069

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 81 Inorganic Chemistry. Atomic Weight of Iodine PAUL KOTHNER ancl E. AEUER (Annulon 1904 337 123-169).-A preliminary account of this determination of the atomic weight of iodine has already been published (Abstr. 1904 ii 556). I n the present paper the earlier work on this subject is discussed more especially the recent work of Ladenburg. A detailed account of the methods employed in purifying the material and of the apparatus used in the various experiments is given. Tn discussing the results it is pointed out that the new value for the atomic weight of iodine 126.03 (H = l ) agrees more closely with the values given by Ladenburg (126.008) ancl by Scott (126.01 and 126.03) than with Stas's mean value (1 2590). K. J. P. 0. Revision of the Atomic Weight of Iodine.GREGORY P. BABTEB (J. Amw Chern. h'oc. 1904 26 1577-1595).-Determinations of the atomic weight of iodine have been made by converting a known weight of pure silver into silver iodide. The silver was dissolved in nitric acid and the solution was diluted with water and afterwards boiled to remove nitrous acid and nitrogen oxides. The solution was now treated with an excess of ammonia and afterwards with dilute solution of pure ammonium iodide prepared from highly purified iodine. Great pre- cautions were taken in the purification of the materials and the collec- tion of the silver iodide. Two samples of iodine were employed one of mliich was collected in four fractions the element being liberated from hydriodic acid by the action OF potassium permanganate which was82 ABSTRACTS OF CHEMICAL PAPERS.added in four successive quantities distillation being carried out after each addition. The average result of 15 experiments gave the atomic weight of iodine 126,973 (hg = 107*930) a result which is probably slightly too low. The very small differences in the results show that the samples of iodine were identical and lead to the conclusion that no new halogen of higher atomic weight than iodine existed in the material employed in the investigation. I n another series of experiments the ratio of silver to iodine was investigated by ascertaining the exact weight of silver required to combine with a weighed quantity of iodine. The average of three determinations gave the atomic weight of iodine 136.977. In a third series of experiments four determinations of the ratio of silver iodide to silver chloride were made by converting a weighed quantity of pure silver iodide into the chloride by heating it in a quartz crucible in a current of chlorine.Two determinations were made by heating silver iodide in a current of car5on dioxide and bromine and afterwards in chlorine. From the ratios obtained in these six experiments the average atomic weight of iodine was found to be 126.975 (Ag = 107,930 ; C1= 35.467 ; 0 = 16). The close agreement of this 1 esult with the average of the results of the first two series indicates that the atomic weight of iodine is 126.975 and is additional evidence in favour of the value 35.567 for the atomic weight of chlorine which was found by Richards and Wells in an investigation hitherto unpublished.In connection with the experiments described in this paper the sp. gr. of pure fused silver iodide was determined and found to be 5.674 at 25'14'. E. G. Flowers of Sulphur and Sublimed Sulphur. A. DOMERGUE (Anw. China. anal. 1904 9 445-449).-According to the author the name of YZowem of suZphu~ should be restricted to samples which when newly made contain a minimum of 33 per cent of sulphur insoluble in carbon disulphide. If containing less than this the name sublimed sulphur should be applied. L. DE K. Contact Method for the Manufacture of Sulphuric Acid. FRIEDRICH w. KUSTER [with FRANKE and GEIBEL] (Zed. ccnorg. Chem. 1904 42 453-469).-1n order to maintain a uniform current of the mixture of sulphur dioxide and oxygen the gases were passed from a copper gasholcler which is described in detail.Platinum vanadium pentoxide and ferric oxide induce f o r equal temperatures the same state of equilibrium bet ween sulphur dioxide oxygen and sulphur trioxide. Platinum is the most effective of the three catalysts mentioned and is the only one of technical importance. Water has considerable influence on the catalytic activity of ferric oxide and vanadium pent oxide. The catalytic effect of ferric oxide is iiiipaired by its sensitiveness towards mechanical and chemical influences. The effect of increasing amounts of arsenious oxide on it is gradually to destroy its activity. Vanadium pentoxide is not however so sensitive in this respect. A. McK.I NO K G AN 1C C H E M ISTR Y.83 Raschig’s Theory of the Lead-chamber Procem. EDWARD DIVERS (J. SOC. Chem. Ind. 1904 23 (24) 1178-1 182).-The author gives a &sum5 of the facts adduced in support of the theories of Lunge and of Raschig and suggests a modification of Raschig’s theory. According to this view there is no significant quantity of any oxide of nitrogen in the actually gaseous part of the contents of the chamber in those regions where the change is in active operation but nitrogen peroxide is present where the activity is much leas. On entering t’he chamber from the Glover tower the whole of the oxides of nitrogen together with sulpliur dioxide and water condense to form a mist ; sulphur dioxide oxygen and water then condense together upon the liquid particles of the mist and unite wider the catalytic influence of the nitrous acid present in the particles;.In Raschig’s theory of the chaniber process there is no place for nitrososulphuric acid although according t o Lunge its presence is certain and of prime importance. I n the author’s opinion the nitrous acid in the liquid iuist particles is present in the form of nitroso- sulphuric acid which is to be looked on as a mixed anhydride of pyrosulphuric and nitrous acids and the mechanism of the process call be expressed by writing nitroso-sulphuric acid for nitrous acid in Raschig’s equations 2H,O + 20N.0*S03H + 2S0 = 2H2S04 + 20N*SO,H Nit rosusul pliuric Ni troiosulphoiiic acid. acid. 20N.S03H + 20N*0*803H = 4N0 + 20(S03H) Pyrosul phuric acid. According to this two molecules of sulphur dioxide and on0 molecule of oxygen are absorbed simultaneously by the liquid mist particles and under the influence of the catalyser which is supposed t o be alter- nately nitrososulphuric acid and nitrososulphonic acid sulp tiuric acid is continuously produced.H. M. D. Electrolytic Preparation of Persulphates. CONSORTI UN F u i t Compare Muller and Priedberger Abstr. 1902 ii 450; and Levi Abstr. 1903 ii 474).-ln the preparation of potassium persulphate by electrolysis without a diaphragm the yield is greatly increased by the addition of hydrofluoric acid becoming equal to that obtained in the preparation of ammonium persulphate. Potassium persulphate may thus be prepared directly instead of by double decomposition from the ammonium salt. There is no loss of fluorine and the anode remains bright throughout the process.In the electrolysis of ammo- nium sulphate the yield of persulphate is not increased but no evolution of nitrogen is observed. ‘the influence of fluorine ions on electrolytic oxidation has been observed by Skirrow (Abstr. 1903 ii 69). C . H. D. ELEKTROCHEMISCHE INDUSTRIE t!k ERICH ?dULLE€L (D.R.-P. 155805.84 ABSTRACTS OF CHEMICAL PAPERS. Aution of Hydrogen Sulphide on Selenious Acid. I. Sensitiveness of Selenium Sulphide towards Light. ALEXANDER GUTBIER and J. LOHMANN (Zed. anorg. Chem. 1904 42 325-328).- When the yellow hydrosol obtained by passing hydrogen sulphide into an aqueous solution of selenious acid is boiled in presence of hydrochloric acid a bright red precipitate is formed. This formation of the red hydrogel may also be induced by the influence of light.From the experiments described it appears that the formation of red aelenium sulphide is conditioned by the four factors heat time light and pressure. A. McK. Reactions between Nitric Oxide and Oxygen or Atmo- spheric Air. GEORGLUNGE and E. BERL (Chem. Zed. 1904 28 1243-1245).-The formation of nitric acid by the action of an excess of oxygen on nitric oxide is chiefly dependent on the amount of water present. With an optimum of the latter nitric acid is formed in quantitative yield; with larger amounts of water nitraus acid is formed in addition and the more water is present the greater the amount of nitrous acid formed. The presence of free nitrogen when atmospheric air is substituted for oxygen has no appreciable effect on the reaction since nitric acid is also produced in this case in quantitative amount if the optimum quantity of water is present.The formation of nitric acid is a time- reaction. A. McK. A Method for the Preparation of a Mixture of Nitric Oxide and Nitric Peroxide. J. MATUSCHEK (Chem. Zeit. 1905 29 31)- A mixture of nitric oxide and nitric peroxide is Formed by the action of an aqueous solution of ferric chloride on sodium nitrite as represented by the equations Fe3C1 + GNaNO = Fe,(N0,)6 + 6NaCl and Fe,(NO,) + 3H,O = Fe,(OH) + 3N0 + 3N0. Ferrous sulphate or ferric sulphate may be substituted for ferric chloride in the reaction. If sodium nitrite is placed under carbon disulphide and hydrated ferric chloride suspended in carbon disulphide is added nitric oxide is alone evolved the nitric peroxide remaining dissolved in the carbon disulphide.A. McK. Theory of the Action of Metals on Nitric Acid. EDWARD DIVERS (J. Soc. Chew&. Ind. 1904 23 (24) 1182-1185. Compare Trans. 1883,43,443;Veley Abstr. 1891 i 525; 1892 i 41O).-Silver and mercury only act on nitric acid in the presence of nitrous acid which acts as catalyst and molecular quantities of nitrite and nitrate are primarily produced according to the equation 2 Ag + 2HN0 = AgNO + AgNO + H20. I n this interaction nitrous acid nitrogen per- oxide and nitric oxide only appear as secondary products. The nitrous acid is formed by the action of nitric acid on the primary nitrite and the nitrogen peroxide by the interaction of the nitrous and nitric acids when the proportion of water is small.Nitric oxide results from the decomposition of nitrous acid when the proportion of water is large and that of nitric acid small. The primary products of the action of zinc or tin on nitric acid areINORGANIC CHEMISTRY. 85 zinc or stannous nitrate and either ammonia nitrous oxide or nitrogen these three reduction products being produced independently of each other and without the formation of intermediate products. The primary formation of hydroxylarnine only takes place if a stable acid such as sulphuric or hydrochloric acid is present. Nitrous acid or nitrite only appears as a secondary product and nitric oxide and nitrogen peroxide are to be placed in the same category. The author thinks it possible to place all the metals in regard t o their action on nitric acid in one of the above two classes.Bismuth and copper belong to the former whilst all the strongly basic metals belong to the latter. H. M. I). Action of Carbon Dioxide on the Hydroxides and Carbon- ates of the Metals of the Alkalis and Alkaline Earths. PAUL N. RAIKOW (Chem. Zeit. 1904 28 1247-1252).-Normal potassium carbonate in aqueous solution is completely converted into potassium hydrogen carbonate by an excess of carbon dioxide no tetracarbonate being formed. The experiments made did not indicate the existence of the sesqnicarbonate K,H,( CO,),. When normal lithium carbonate is dissolved in water containing carbon dioxide lithium hydrogen carbonate is probably formed ; a little lithium tetracarbonate is probably also produced.By the action of water containing carbon dioxide on normal sodium carbonate the latter passes comple’ely into the sodium hydrogen salt the intermediate formation of sodium sesquicarbonate not having been observed. Similarly in the formation of riibidium hydrogen carbonate from the normal salt no tetracarbonate was formed ; calcium strontium and barium carbonates respectively under similar conditions did not form tetracarbonates. Evidence is submitted to indicate the formation of hydrogen carbonates of lithium calcium strontium and barium when an excess of carbon dioxide is passed into water containing the hydroxides or normal carbonates of those metals A. McK. Affinity of Alkali Oxides towards Various. Anhydrides. D. G. GERASSIMOFF (Zeit.nnorg. Chem. 1904 42 329-340).-The author has studied the action of sulphur trioxide on alkali tungstates and vanadstes respectively and the action of carbon dioxide on the latter salts and also on alkali niobates tantalates titanates and aluminates respectively. The avidity of alkali oxides towards carbon dioxide and sulphur trioxide respectively increases with the molecular weight of the alkali oxide. This is the case for all systems in which the following anhydrides take part CO and SiO (Wittorf) CO and TiO (Smith) CO and WO CO and V,O SO and WO SO and V20 (the author). By coqarison of the relative affinity of the non-volatile anhydrides it is found that in the systems where (a) sulphur trioxide and tungsten trioxide and ( b ) sulphur trioxide and vanadium pentoxide are respectively concerned vanadium pentoxide has a greater affinity than tungsten trioxide. When carbon dioxide competes with one of the anhydrides V205 Nb,O SO WO A1,0 TiO and Ta205 the VOL.LXXXVIII. ii. 786 ABSTRACTS OF CHEMICAL PAPERS. sequence quoted represents the relative affinity of the latter anhydrides The following indicates the number of molecules of carbon dioxide expelled by one’molecule of the various anhydrides from two molecules of sodium carbonate a t 880° where the partial pressure of the carbon dioxide is 0.07 atmospheres V,O 2.000 ; Nb,O 1.891 ; SiO 1.310 ; WO 1.047 j A1,0 1,019 ; TiO 0.779 ; Ta,O 0.72‘7. A. McK Dissociation of Ammonium Chloride in its Analytical Relations. LUIGI SANTI (Chem. cent^. 1904 ii 1625-1626; from Boll.Chint. Fawn. 43 673-681).-Iron drillings are readily attacked by a hot concentrated solution of ammonium chloride with evolution of hydrogen and ammonia and yield the compound FeC12,2NH,01. Magnesium powder is attacked even in the cold forming the double salt llgCI2,2NH,C1. Calcium zinc cerium manganese and tin are also more or less attacked. On heating cobalt and nickel oxides with dry ammonium chloride they are reduced to the metallic state but other oxides are converted into chlorides On boiling calcium nickel manganous and ferrous oxides with a solution of ammonium chloride they are converted into chlorides with evolution of ammonia ; sesqui- oxides such as ferric oxide are not attacked. Carbonates of calcium magnesium copper cobalt and nickel are also converted into chlorides with evolution of ammonium carbonate.The sulphides of tin and antimony are attacked by heating with dry ammonium chloride whilst the sulphide of manganese and in a less degree that of zinc is attacked even by solutions of ammonium chloride Sodium thio- sulphate solution on boiling with ammonium chloride is decomposed according to the equation Na,S,O -!- 2NH4C1 = 2NaCl + H,O + ZNH + SO + S ; if heated on a distilling apparatus the distillate contains ammonium sulphide and polysulphide. BIanganates are converted into permanganates chromates into dichromates ; the Iatter then even yield free chromic acid. Barium dioxide when treated with ammonium chloride in the cold yields hydrogen peroxide but on heating there is an abundant formation of oxygen.Potassium persulphate yields chlorine and nitrogen and even hypochlorous acid. Glucosides (salicin amygdalin) are practically unaffected by ammonium chloride. L. DE K. [Silver Dichromate.] OTTO MAPER (Bey. 1904 3’7 4646).-A reply t o Autenrieth’s claim for priority (Bw. 1904 37 3886). W. A. D. Certain Properties of the Alloys of Silver and Cadmium. T. KIRKE ROSE (Proc. Roy. Xoc. 1904 ’74 218-230).-The investi- gation consists in a determination of the temperatures of solidification of alloys of different composition and i n a study of their micro- structure. Evidence has been obtained of the existence of the COM- pounds AgCd? Ag,Cd AgCd Ag,Cc12 Ag,Cd and Ag,Cd. The solid alloys containing from 0-25 per cent. of silver consist of crystals of AgCd set in a matrix of cadmium Those witli 25-40 per cent.consist of the compound Ag,Cd set in a matrix which consists mainly of AgCcl,. The 50 per cent. alloy contains crystals of a substance richINORGANIC CHEMISTRY. 87 in silver set in a matrix consisting mainly of AgCd,. The matrix or eutectic solidifies a t 420° nearly 300' below the freezing point of tho crystals. The alloys containing 50-60 per cent. of silver consist above 420° of mixtures of two different solid solutions one composed chiefly of the compound AgCd and the other of Ag,Cd,. Traces of the eutectic freezing a t 420' are still visible. When more than 80 per cent. of silver is present the alloys consist of a mixture of two substances at temperatures between the liquidus and solidus curves but these unite to form a single solid solution a t points on the solidus curve.The alloys containing over 80 per cent. of silver do not ordinafily undergo segregation and are practically homogeneous and uniform in composition. They are well suited as a material for the manufacture of trial-plates. J. G'. P. Metallic Calcium. KURT ARNDT (Bey. 1904 37 4733-4738. Compare Abstr. 1903 ii 76).-Metallic calcium prepared on a large scale by the electrolysis of fused calcium chloride has been examined in detail by the author. The metal contains traces of silicon and aluminium as impurity and when acted on by water yields almost pure hydrogen. The sp. gr. is 1.54 but rises to 1.56 on remelting owing t o an increase in the percentage of silicon ; when purified by distillation the metal has a sp.gr. 1.52. Calcium melts a t 800' and sublimes even below this temperature; the vapour reacts very vigorously with atmospheric air and combines with oxygen and nitrogen even more readily than magnesium does. Calcium Carbide as an Explosive in Mining Operations. MARCEL P. S. GU~DRAS (Compt. rend. 1904 139 1225-1226).-An explosive mixture of acetylene and air obtained by the action of water on calcium carbide in a limited space and fired by means of an electric spark can be used for blasting operations in mining and the author describes a cartridge containing an air chamber and charged with calcium carbide (50 grams) and water separated by a membrane which can be mechanically pierced after the cartridge is placed in the bore-hole ; after five minutes the acetylene (15 litres) mixed with the air is fired electrically.Preparation of Barium. ANTOINE GUNTZ (Ann Chim Plqs. 1905 [ viii] 4 5-25).-A risunzS of work already published (com- pare Abstr. 1901 ii 385 ; 1902 ii 138 ; 1903 ii 369 410)-The purest specimen of the metal obtained contained 98.35 p e ~ cent. of barium melted at about 850' and boiled a t about 1150'. E. F. A. 31. A. W. M. A. W. Decomposition of Barium Nitrate by Heat. E. BASCH (Chem. Zeit. 1905 29 31).-The author corroborates Gottlieb's results (Abstr. 1904 ii 403). Decomposition of Alkaline Earth Carbonates by Alkali Chlorides in Presence of Water. H. CANTONI and G. GUGU~LIA (BzlZZ. Xoc. chim. 1905 [iii] 33,13-27. Compare Abstr. 1904 ii 334). -The iQfluence of temperature time and concentration on the rate of A.MoK. 7-288 ABSTRACTS OF CHEMICAL PAPERS. decomposition of barium carbonate by solutions of potassium and sodium chlorides has been investigated and some further observations have been made on the action of sodium potassium and ammonium chlorides on alkaline earth carbonates at the ordinary temperature over comparatively long periods. The results which are tabulated and graphically represented in the original show that under all conditions the action of potassitim chloride on barium carbonate is initially greater than that of sodium chloride and increases more rapidly with increase of concent ration rise of temperature and lapse of time although the last factor exerts less influence than the two former in differentiating the action of the two chlorides. A t the ordinary tempera- ture the activity of the three chlorides diminishes in the following order ammoniuni potassium sodium ; whilst the resistance of the three alkaline earth carbonates towards all three chlorides increases in the order barium calcium.strontium. SAutions of sodium or potassium chloride have practically. no action on strontium carbonate. T. A. H. Silicates. IV. EDUARD JORDIS and E. H. KANTER (Zeit. ano9.g. Chem. 1904 42 418-432. Compare Abstr. 1903 ii 475 542 595).-Details are given of the preparation and analysis of the silicates of the alkaline earths previously described. I n concentrated barium hydroxide solutions the metasilicate BaSiO,,H,O is formed. By the action of strontium hydroxide on metasilicic acid a compound was obtained colztaining 2/3Sr0 to 1Si0 ; another preparation contained the proportion 1 /3Sr0 1Si0,. By the action of calcium hydroxide on silicic acid the metasilicate was not formed but a compound containing 2/3Ca0 1Si0,.The reaction between silicic acid and calcium hydroxide in presence of 111 mol. calcium chloride solution was studied. Mixtures were obtained. The authors were unable to confirm the results of Wahl (Abstr. 1902 ii sol) who claims to hnve obtained the silicate BaSiO,,GH,O by the action of barium hydroxide on quartz. A. McK. Separation of Glucinum from Aluminium and Iron. G. VAN OORDT (D.R.-I?. 155466).-.The salts of glucinum with fatty acids dissolve in chloroform (Lacombe Abstr. 1902 ii 122). Glucinum may be separated from aluminium and iron by converting the mixed salts into acetates digehting with glacial acetic acid and extracting with chloroform in which the pure glucinum acetate only dissolves.The treatment with glacial acetic acid is necessary in order to convert the insoluble acetate into the crystalline form soluble in chloroform. A solution of glucinum hydroxide in hydrochloric acid is quite colourless when free from iron. C. H. D. Salts and Substances for Incandescent Lighting. HANS BUNTE (Chem. C'entr. 1904 ii 1627-1628 ; from J. Gasbel. 47 1011-1013).-Since Eitner has found that the temperature of the Bunsen flame is itself considerably higher (1390-1545") than that ofINORGANIC CHEMISTRY 89 tht? mantle at corresponding points (1 265- 1395*) the temperature of the latter cannot be appreciably affected by a catalytic action of the incandescent mass.According to Schmidt the light emitted by pure thorium oxide become; of a bluer t i n t as the temperature rises whilst the nature of the light from cerium oxide is the same a t all tem- peratures of the flame. When the proportion of cerium oxide to thorium oxide is gradually increased to 0.5 per cent. the lumino4ty of the mantle becomes p e a t e r and the light of a bluer tint. Further addition of cerium oxide up t o 1.5 per cent. still increases the luminosity but the light now appears to be tinged with red. The illuminating power is decreased by larger proportions of cerium oxide and the character of the light approaches more and more to that emitted by the pure oxide. The first effect of rise of temperahre is to increase the blue rays but when the light has attained a great intensity a11 the rays w e affected in prnctically the same WRY.It has been found that when mantles of different weights but of the Sam9 composition a r e employed the light obtained from the heavier mantles is not so blue as that emitted by the lighter. The high temperiiture of the cerium oxide in the fhme is partly due to ils state of division and partly t o the smnll amount present whilst the lighting effect is primarily the result of selective radiation. E. w-. w. The Element z6. 1'. fi. 1,~cog 1 ) ~ BoISBAUDRAN (Compt. rend. 1904 139 1015-1016).-Contrai~y to the statement of Urbain (compare thiq vol. ii 35) the author maintailis that the elemeiitai~y nature of 26 was fully establishetl by him in 1895 (compare Abstr.1896 ii 24'3) although he did not succeed in obtaining the element free from dysprosium. M. A. W. Basic Alumino-silicates containing Haloids. Z. WEYBERG (Centr. Min. 1904 729-794).-By fusing kaolin with calcium chloride Gorgeu (Abstr. 1888 228) obtained tetrahedra of t h e compound 3Si0.2,..7A120,,6C:i0,2Ca~l*. This result is confirmed and by fusing kaolin with calcium bromide tetrahedra with the composition 5Si0,,8A120,,1 2Ca0,4CaRr2 were obtained. In both cases prismatic crystals of another alumino-silicate were also formed. Kaolin when fused with a small amount of calcium bromide gave tetragons1 prisms with the cornposittion SiO A1,03,2Ca0. L. J. S. Products of Weathering of Silicates in Clay Volcanic and Laterite Soils respectively.JAKOB M. VAN REMMELEN (Zeit. anorg. Chem. 1904 42 265-314. Compare Abstr. 1902 ii i0).-In soils where the products of weathering contain much alumina relatively to silica all determinations of silica made by extracting it with hydro- chloric acid are without value since the extraction is incomplete. If however the soil after treatment with hydrochloric acid is agitated for several minutes with dilute sodium or potassium hydroxide a t about 50° the residual silicic acid is dissolved. The ratio of alumina to silica as determined in a large number of the products of weathering of alluvial plastic clays soils of volcanic origin and laterite soils respectively was not constant I n ordinary90 ABSTRACTS OF CHEMICAL PAPERS. alluvial clays the portion extracted from the disintegrated silicate by hydrochloric or by snlphuric acid indicated that the weathering had taken place in a single stage whilst with the volcanic and laterite soils examined various stages of weathering were recognisable the products consisting of a mixture of silicates. The progress of the weathering was best exhibited with the laterites the final product being in those cases hydrargillite.The metals of the alkalis and of the alkaline earths are also present in varying amounts in the products of weathering examined but not in sufficient amount to conclude that chemical compounds were present of the composition m(Si02),ra(A120,),o(lWO),p(H20) where m n 0 and p are whole numbers. The amount of those bases present diminishes the further the weathering has proceeded.Estimations of the amount of water in air-dried clays showed that ordinary clays contain very little water which is lost at 15' when the clay is exposed to an atmosphere dried with concentrated sulphuric acid. They contain about 2H29 which is lost at a higher temperature. The laterites examined contained more than 2H20. The more basic the products of weathering are the more readily do they dissolve in hydrochloric acid. The amount of iron oxide in various soils was also determined. This iron oxide generally contains a t the ordinary temperature a little more than 1H20 and a t 100' rather under lH,O. The constitution of the silicates obtained by the weathering of clays and the process of weathering itself are discussed. Tables of the various analyses made are appended.A. McK. Absorption of water by Clay. JAKOB M. VAN BEMMELEN (Zed. cworg. Chem. 1904 42 314-324).-Various soils were dried a t looo and the percentage of water absorbed at 15' under varying vapour pressures was estimated. The process of absorption is reversible ; the hydration and dehydration can be repeated as often as desired and the amount of hysteresis varies with the amount of absorption. Determinations of the rate at which the water absorbed was expelled show that it was not essentially different from the rate a t which water itself evaporates under similar conditions. Reduction of Manganese Oxides by Amorphous Boron. Preparation of a New Manganese Boride. RINET DU JASSONNEIX (Compt. rend. 1904 139 1209-121 l).-Manganese oxides are readily reduced when heated with boron in an electric furnace for a few seconds with a current of 400 amperes and 100 volts ; if excess of boron is used the product consists of a mixture of manganese and a new manganese boride MnB (compare Troost and Hauteville Abstr.1876 i 883) which can be isolat,ed in the form of a crystalline powder having a sp. gr. 6.2 at 15' by the limited action of chlorine on the mixture a t a dull red heat Manganese boride burns in fluorine at the ordinary temperature is attacked by chlorine or bromine a t a red heat whilst the action of iodine at a high temperature is only superficial; it forms a fusible borate when heated in oxygen is not attacked by nitrogen; it slowly decomposes cold water forming manganic hydroxide and boric Mid j A.McK.INORGANIC CEIEMI8TIiY. 91 dissolves in dilute hydrochloric acid and is attacked by hydrogen chIoride or hydrogen fluoride nitric or sulphuric acids; by the action of ammonia at lOOO' a compound is obtained which contains nitrogen is not attacked by acids and yields manganates with evolution of ammonia on fusion with alkali carbonates. 3%. A. W. Composition of the Four Sulphides of Manganese. JOHN C. O L S E N ~ ~ ~ W. S. RAPALJE(J. An2er. Chem. Soc. 1904,26,1615-1622). -An investigation of the sulphides of manganese has shown that three sulphides exist two of which the red and the green are anhy- drous whilst the grey sulphide contains a large proportion of water. The pink sulphide of manganese obtained by the action of ammonium sulphide on a qeutral solution of manganous chloride appears to be a mixture of the grey and red sulphides in varying proportions.The pink sulphide is not uniform in composition and contains from 4 to 14 per cent. of free sulphur and a varying amount of water. When heated a t 360° in an atmosphere of hydrogen it is gradually converted into the green modification. When precipitation is effected with colourless sodium sulphide a brick red sulphide of fairly constant composition is obtained contain- ing about 0.75 per cent. of water. On heating the pink sulphide with hydrogen sulphide the product obtained consists of lumps which are grey on one side and red on the other. The reason that the sulphide precipitated by sodium sulphide cannot be converted into the green modification whilst that produced by ammonium sulphide readily undergoes this change is probably that the latter product contains varying amounts of the grey sulphide.The green modification is the most stable form of the sulphide is more distinctly crystalline than the other forms and is probably more complex in structure. E. G. Influence of Water Vapour on the Reduction of the Oxides of Iron by Mixtures of Carbon Monoxide and Carbon Dioxide. OCTAVE BOUDOUARD (Compt. rend. 1906 140 40-42).- Comparative measurements of the reduction of ferric oxide by gaseous mixtures containing equal volumes of carbon monoxide and carbon dioxide have been made the gas being dried in one series of experi- ments and saturated with water vapour at room temperature in another. The gas was passed over the ferric oxide contained in a porcelain boat which was heated in a n electric resistance furnace maintained at; constant temperature each experiment lasting one hour.The following numbers give the percentage loss af weight of the ferric oxide Temperature ......... 400° 550° 800' 925O 1050' Dry gas ............... 0.87 4.3 4.0 5.6 6.5 Moist gas ............ 0.45 3.8 2.65 4.4 6.9 The reduction effected by the dry gas is considerably greater a t t,he lower temperatures but there appears t o ,be little difference in the action a t about 100OO. Similar data were obtained in experiments on92 ABSTRACTS OF CHEMICAL PAPERS. the reducing action of dry and moist carbon monoxide on ferrous oxide at 850". The author considers that the results are in harmony with the increased economy which accompanies the use of dry air in the blast furnace.H. M. D. Formation and Solubility of Double Chlorides of Iron and the Alkali Metals. F. WILLY HINRICHSEN and EUGEN SAcIisEL (Zeit. pAysikaZ. Chem. 1904 50 8 1-99).-Determinations of solu- bility and dilatometric investigation show that in the case of sodium and ferric chlorides there is no formation of double salt between 0" and 60'. At 21° potassium and ferric chlorides form a double salt of the composition FeC1,,2KC1,H20 ; if however the potassium chloride is in excess mixed crystals are formed (compare Itoozeboom Abstr. 1892 13S4). The temperature a t which the double salt is formed from the separate salts is 22.0-225O. No evidence could be found for the existence of the double salt FeC13,3KC1 referred t o by Werner.I n the case of cmiium and ferric chlorides a t 21° two double salts are stable (1) a yellow salt PeCl3,3CsC1,H,O produced when the solution contains excess of cresium chloride (2) a red salt FeCl,,2CsCl,H20 formed in presence of excess of ferric chloride a t 39.5-39-8'. The authors were unable to isolate the compound FeCI,,CsCl,&H,O described by Wslden (Abstr. 1895 ii 165). The compounds FeC1?,2KCI,H20 and FeC1,,2CsC1,H2O are in harmony with Werner's views regarding the 6' co-ordination number " (see Abstr. 1902 ii 554). The other msium double salt FeC1,,3CsCI,H20 is not in harmony with these views. Incidentally the solubility of cmium chloride has been determined at several temperatures between Oo and 40°. J. C. P.Preparation of Iron Pbosphide from Calcium Phosphate. GUSTAVE GIN (D.R.-P. 156087).-1ron phosphide may be prepared in a closed electric furnace from calcium phosphate and iron silica being added as a flux. Iron pyrites may be employed as a reducing agent instead of the carbon hitherto uked 4Ca,P,08 + 12Si0 + 5FeS2 + 1 1 Fe = 8Fe2P + 12CaSi0 + 1 OSO ; or 5Ca,P20 + l'5Si0 + 10 FeS + 5Fe,O = 10Fe,P + 15CaSi0 + 20S0,. The temperature required is slightly above the melting point of iron. Several arcs each with ft tension of 25 to 30 volts enter the same crucible and the energy consumed amounts to 50-60 volts per sy. cm. of electrode surface. Acid calcium phosphates may be em- ployed to economise flux. Some free phosphorus is formed by secondary reactions and is absorbed in a chamber containing iron borings.C. H. D. Alloys of Cobalt and Nickel. W. GUERTLER and GUSTAV TAMMANN (Zeit. anorg. Chenz. 1904,42 353-362).-The authors have studied the melting-point curve of alloys of cobalt and nickel to deter- mine whether a compound of these metals is formed or whether both metals separate completely or incompletely from the molten mass.INORGANIC CHEMIS'l'ltY. 93 When cobalt is heated i t is like nickel converted into a stable non- magnetic variety. I n the curve represented where the abscissz indicate the coinposition of the mixture and the ordinates the melting points observed the melting-point curve is represented by a straight line the course of which is expressed by the formula Ato = 0.35p where p indicates the percentage of cobalt and At the rise of melting point.Thevariation of each individual melting point from this straight line amounts to only + 5". Nickel and cobalt accordingly separate from their molten masses in mixed crystals. Cobalt is transformed into the non-magnetic variety at IlliO" whereas nickel is transformed at 333". The equilibrium curve of the magnetic and non-magnetic crystal forms of nickel cobalt and their alloys mas studied. The transition temperature of alloys containing 10 per cent. of cobalt rises from 100" to 60° from which the conclusion is drawn that the concentration of the single crops of mixed crystals which separate from the same molten mass cannot differ from one another by more than 2 to 3 per cent. Various mixtures of nickeland cobalt were taken and the lowest temperature determined a t which those mixtures became non-magnetic ; the temperatures were also noted a t which the mixtures again became magnetic after having been cooled.The melting point of gold is 1044'. I n the concentration-temperature diagram sketched in the paper the melting-point curve separates the field of the molten mass from the field of non-magnetic crystals whilst the transition curve separates the latter from the field of magnetic crystals. At the temperatures of the melting-point curve from the melting point of pure nickel 1484" to the melting point of pure cobalt 152S0 the composition of the molten mass and of the mixed crystals which separate is approximately identical. A t the temperatures of the transition curve the magnetic mixed crystals are in equilibrium with the non-msxgnetic mixed crystals.A. McK. Triamminecobalt Salts. A New Case of Hydrate Isomerism. ALFRED WERNER and ADOLF GRUN (Be?*. 1902 37 4700-4706).- CAZorodiaquotriccmmineco balt nitrate [ CoCl( N H3)J *NO,,. formed by the addition of a freshly-prepared solution of chlorodiaquotri- amminecobalt chloride to nitric acid of sp. gr. 1-4 separates in bluish- violet needles. The corresponding bromide CoCl(OH,),( NH3)SBr2 prepared by the addition of the chloride to hydrobromic acid of sp. gr. 1-49 cryatallises in dark blue needles. It is very unstable and in a moist atmosphere forms c ~ l o r o b r o r n o a p u o t r i m ~ i i ~ ~ e c o b a l t bromide [CoClBr(OH,)(NH,),!Br a green salt from which the original bromide may be regenerated in small amount by suspending it in alcohol and gradually adding water. The solution of chlorodiaquotriamminecobalt bromide in water is blue and when heated becomes red.When hydrobromic acid is added t o the blue solution the isomeric chZorobromoapuotriamn.LinecobaZt bromide [CoClBr( OH,)(N H,),]Br,H,O separates in brown needles even at temperatures below 0". It is more stable than the blue iso-94 ABSTRACTS OF CHEMICAL PAPERS. meride and is converted into the green chlorobromoaquotriammine- cobalt sulphate by the action of concentrated sulphuric acid. It may also be prepared by the action of hydrobromic acid on dichloro- aquotriamminecobalt chloride when it separates in glistening chocolate-coloured leaflets. Below 0' it forms a green solution with water at the ordinary temperature a bluish violet and at higher temperatures a red solution. When chlorodiaquotriainminccobalt sulphate is triturated with fuming hydrobromic acid anhydrous chlorobromoaquottriamminecobalt bromide separates in olive-green crystals.The structural relationship between the three bromides described is expressed as follows [clCo&2k]Br2 (blue bromide) Br,H20 (brown bromide) A. McK Existence of a Normal Green Chromic Sulphate. ALBERT COLSON (Compt. rend. 1905 140 42-44).-When the green solution obtained by reducing chromic acid by means of sulphur dioxide a t 0' is completely evaporated in a vacuum an amorphous green hygroscopic substance of the composition Cr2(S0,!,,10H,0 is obtained. The sub- stance appears to be a normal chromiuin sulphate; its aqueous solu- tions do not contain free sulphuric acid and the green colour of the solutions is permanent.On addition of barium chloride a considerable proportion of snlphuric acid is precipitated. It differs from the green sdphate described by Kecoura (Abstr. 1892 i 411) for the green colour of solutions of this soon changes to violet and barium sulphate is not precipitated on addition of barium chloride. On boiling t'he aqueous solution a change takes place which is repre- sented by the equation 2Cr,(S0,)3 + H20 = Cr,O(SO,) + H,SO,. The density of the solution is smaller after boiling and the heat development on addition of barium hydroxide indicates the presence of one molecule of free acid in the boiled solution for every two mole- cules of the original salt.The freezing point of the solution is un- altered by the change which takes place. The salt is supposed to have the constitut'ion SO,< I Cr:SO Cr:RO H. M. D. Uranyl Selenide and Potassium Chromic Selenide. JAR. MILBAUER (Zeit. unorg. Chem. 1904 42 450-452).-17ranyl selenide U02Se prepared by heating a mixture of selenium potassium cyanide and uranium oxide (prepared from uranyl acetate) a t a low red heat forms black hexagonal prisms with a metallic lustre and closely resembling uranyl sulphide. When cold hydrochloric acid is added to it hydrogen selenide is evolved and uranyl chloride produced. It is acted on very vigorously by nitric acid selenium a t first separating and then gradually oxidising.INORGANIC CHEMISTRY 95 Potassium chwmic seleizide K2Cr2Se4 prepared by heating a mixture of seleninm potassium cyanide and chromium sesquioxide a t a red heat forms dark green hexagonal crystals which are readily soluble in nitric acid but; insoluble in hydrochloric acid.A. McK. Action of Sodium Hyposulphite on Metallic Salts. 11. OTTO BRUNCK (Annalen 1904 336 281-298. Compare Abstr. 1903 ii 481).-On addition of a solution of sodium hyposulphite to solutions of metallic salts mostly one of three reactions takes place ( a ) the pre- cipitation of a sulphide ( b ) reduction to the salt of a lower oxide or ( c ) complete reduction to the metal. The following reactions with sodium hyposulphite are described. Thallium salts a t the ordinary temperature and indium salts on boiling yield the sulphides but incompletely owing to the action of sulphurous acid formed.I n a neutral solution stannous chloride forms a precipitate of stannous hyposulphite which dissolves in an excess of the reagent but in presence of an excess of acid stannous sulphide is formed ; solutions of stannic chloride are completely precipitated as the sulphide. I n neutral solutions lead salts are completely precipi- tated as the yellow hyposulphite which changes into the black sulphide. Molybdic acid forms the sulphide in neutral solutions whilst tungstic is reduced in slightly acid solution. Nickel and cobalt salts form the sulphides quantitatively in neutral ammoniacal or weak acetic acid solutions. Titanium tetrachloride is reduced in neutral solution to the tri- chloride but not in alkaline solution as the action is reversed; similarly chromates are reduced to chromium oxide permanganates to manganese salts ferric to ferrous salts and on heating to ferrous sulphide and platinic to plntinous chloride with precipitation of sulphur.Salts of palladium selenates and tellurates are reduced in neutral! solutions completely to palladium selenium and tellurium respectively. Similarly arsenic is obtained from its oxygen compounds as a brown powder which if the reduction takes place in a strongly acid solution contains arsenic trisulphide and sulphur. The behaviour of salts of antimony and of bismuth is similar to that of the salts of copper. Solutions of salts of germanium are apparently unaffected at the ordinary temperature but on warming sulphur is precipitated. G. Y. Inactive Thorium. CHARLES BASKERVILLE and FRITZ ZERBAN (J Amer. C h n . Xoc. 1904 26 1642-1644).-1t has been shown by Hofmann and Zerban (Abstr. 1903 ii 732) that inactive thorium can be obtained from certain minerals which do not contain any radioactive constituent. A new source of inactive thorium has been found in a rock from South America which is of a greyish-slate colour consists chiefly of barium carbonate containing a very small percentage of thorium and exhibits no radioactivity. E. G.96 ABSTRACTS O F CHEMICAL PAPERS. Decomposition of Antimony Hydride. ALFRED STOCK (Zeit pJLysiknZ. C'hem. 1904 50 11 1-1 12).-A continuation of a discussion with Bodenstein (see Bodenstein Abstr. 1904 ii 245 719 ; Stock and Guttmann ibid. 489). J. C. P. Purification of Tantalum. SIEMENS & HALSKE AKTIENGES. (D.11.-P. 155548).-Crude tantalun1,obtained by reduction with sodium always contains oxide which may be removed by fusion in a closed exhausted electric furnace. The crude tantalum compressed into a crucible of thoria or magnesia forms the anode; the cathode con- sists of a rod of pure tantalum or silver which is movable from the outside of the enclosing vessel. An arc is started and is then caused t o travel over the whole anode surface when fusion to tt homogen- eous non-porous mass occurs. C H. D.

ISSN:0368-1769    

DOI:10.1039/CA9058805081

出版商:RSC    

年代:1905

数据来源: RSC