摘要:

ii. 1 1 6 ABSTRACTS OF CENMICAL PAPXRS. Mineralogical Chemistry. Composition of Seleniferous Sulphur. GLENN V. BROWN (Amer. M k . 1917 2 116-117. Compare A. 1916 ii 531).- Examination of further specimens of so-called selen-sulphur from various localities (Sicily Lipari and New Ze'aland) by the method of W. Smith (A. 1915 ii 839) shows the presence of only small amounts of selenium (trace-O*298%). The depth of colour of the material bears no relation to the amount of selenium praent; pale yellow specimens may contain more of this elemeptl than deep brown ones. L. J. S. Epiboulangerite from Montana. FARL V. SHANNON (Amer. Mila. 1917 2 131-132).-Bunches of stee'l-grey needles and fibrous masses occur with quartz and granular blende in the Iron Mountain mine near Superior Montasa.Small grains and needles are also scattzred through the blende Associated mineralsMINERALOGICAL CHXMTSTRY. ii. 117 in small amounts are chalybite pyrites and sericite. The fibres are moderately brittle and break across a t right' angles; the streak is blackish lead-grey. D 6.303. A partial analysis gave Yb 52.74 Sb 20.85%. From these characters the mineral is provisionally identified as epiboulangerite. L. J. S . Mullaaite a .New Member of the Jamesonite Group from Two Localities. EARL V. SHANNON (Amer. J. Scz. 1918 [iv] 45 66-70).-1n the Iron Mountain mins near Superior Montana the new mineral occurs with epiboulangerite (preceding abstract) from which i t is indistinguishable in appearance; but' it is readily distinguished by its brownish-black streak that of the epi- boulangerite being greyish-black.It here forms long parallel steel-grey fibres around and enclosed in a crystal of quartz. I n the Gold Hunter mine near Mullan in Idaho forty miles W.N.W. of the former locality the mineral occurs with quartz and chalybite as fine matted wool-like masses of dark grey fibres and as a compact steel-grey fibrous material. The needles are' usually flattened and are deeply striated longitudinally ; they are termin- ated by the basal plane and are' probably orthorhombic ( a b = 1 :0*835) with the three pinacoidal cleavages. The thinner fibres are very flexible whilst the thicker ones are quite brittle. Analysis I mean of two of material from the Iron Mountain mine and 11 from the Gold Hunter mine agree with the formula 5PbS,2Sb,S3 corresponding with the silver-lead diaphorite.Sb. As Pb. Ag. Cu. Fe. S. Total. Sp. fir. 1. 25.Tl 0.25 55-05 nil nil trace 18.82 99.83 6.274* 11. 24.67 0.64 53-33 nil nil 1.47-i- 18.11 98.22 6407 * Probably low. 1 Representing chalybite 3-40,; present as impurity. L. J. S. Occurrence of Chalmersite CuFe,S in the Ore Deposits of Prince of Wales Sound Alaska. BERTRAND I;. JOHNSON (Econ. Geol. 1917 la 519-525) .-This mineral previously known only as minute crystals from Brazil (A. 1902 ii 267; 1906 ii 553) has been found in considerable quantities a t eight different localities in the Ellamar district and on Knight Island in Prince of Wales Sound where itl has been mined as an ore of copper. It is iiiassive very pale yellow and shows a conspicuous cleavage with a satiny sheen.It is strongly magnetic and this property enables i t to be separated from the copper-pyrites with which it is intim- ately intergrown. Analyses by E. T. ALLEN agree with the formula Cu Fe&. cu. Fe. S. Sp. gr. 22.87-23.83 40.70-41.92 35.09-35.30 4.04 L. J. S. Chalcedony Mistaken for an Iron Sulphate Mineral. EDGAR T. WHERRY and MILTIADES L. GLENN (Amer. Min. 1917 2 6-7) .-Two specimens of orange-brown botryoidal material hadii. 118 ABSTRACTS OF CHEMICAL PAPERS. been for many years labelled as glockerite in the U.S. National Museum. I is from Pinos Altos New Mexico and I1 from Black Hawk Colorado. When examined they were found to be chalce- dony and this is confirmed by analyses I and 11. The ferric sulphate is not present as visible enclosures nor is i t extracted by acids ; it must be present as sub-microscopic inclusions. SiO,.Fe,O,]. SO,. H,O t110'. H20> 110". Total. Sp. gr. n. I. 94.37 3-10" 1.47 trace 1-86 100.80 2.57 1.530 11. 93.94 1.58 1-00 0.65 2.59 99.76 2.55 1.525 * Including a minute amount of pyrites. For pure chalcedony D-2.60 and n=1*637; as shown above with increasing water there is a corresponding decrease in the values Massicot and Litharge the Two Modifications of Lead Monoxide. ESPER S. LARSEN (Amer. Mzn. 1917 2 18-19).- Natural specimens of 'mas~icot' from Austria and from Kern Co. and San Bernardino CP. California consist of minute brownish-red scales built up of two minerals with distinct optical properties. The central portion of tl-e plates consists of the yellow orthorhombic modification (nearly colourless under the microscope optically biaxial and positive /3 = 2-61 birefringence very strong) and the borders of the red tetragonal modification (yellowish- orange under the microscope optically uniaxial and negative o = 2.64 birefringence very strong).It is proposed to restrict the name litharge to the former and massicot to the latter. The border of massicot is probably an inversion product of the litharge. (Coin- pare A. 1915 ii 59). L. J. s. Nomenclature of the Lead Monoxide Minerals. E. T. ~VIIERHY ( A I I I P T . M ~ I L . 1917 2 19).-The mineralogical tern1 inassicotite for a mineral Corresponding with the artificial product iizassicot was used by D'Acliiardi in 1883. Now that the ortho- rhoiiibic modification of lead monoxide has been recognised as a miiieral (see preceding abstract) the name Zithargit e is suggested for the second species.Xanthosiderite from Schendlegg Lower Austria Formation of Brown dl Glaskopf.' ' H. LEITJIEIER and M. GOLDSCHLAG (Centr. Mi?z. 1917 473-477).-Near the foot of the Raxalp in Lower Austria are deposits of iron ore consisting of chalybite carrying small amounts of copper-pyrites. I n the level of the Schendlegg mine the walls are coated with a reddish- brown unctuous colloidal material of recent formation. After drying in the air for a few weeks this shows a concentric shelly structure and brown colour ; the streak is yellowish-brown. Under the microscope i t showed thin scales of brownish-yellow amorphous material. It then contained 19.70% H,O corresponding with Fe,03 2H2O-the formula for xanthosiderite.Of this water 3'93% is lost' over sulphuric acid and 8'16% a t looo. The same for the density and refractive index. L. J. 8. L. J. S.MINERALOGICAL CHEMISTRY. ii. 11‘3 material after exposure to the air for two years still contained the same quantity of water (H,O 19-11 Fe,O 80.02 SiO 0*47%) but it had by that time acquired a dark blackish-brown colour with metallic lustre on the surface and a dark brown streak. Under the microscope the material was now seen t o have a distinct granular structure and to be crystalline. The colloidal material has thus become gradually converted t o the crystalline brown “ Glaskopf .” Columnar Manganocalcite from Franklin Furnace New Jersey. WALLACE GOOLD LEVISON (Avter.Mzn. 1916 1 5).-This is pinkish-white with a marked columnar structure. It is tough and less brittle than ordinary calcite and is soluble in cold acid. Analysis gave CaO. MnO. FeO. ZnO. MgO. CO,. Insol. Total. Sp.gr. L. J. S. 38.58 11.94 0.22 0.29 4-33 39.70 4.60 99.66 2.81 L. J. S. Proof that Priceite is a Distinct Mineral Species. ESPER S. LARSEN (Anzer. Mi?%. 1917 2 1-3).-The friable chalky priceite from Curry Co. Oregon and the compact nodular pander- mite from Asia Minor have often been regarded as impure massive varieties of colemanite. A determination of the optical constants of these minerals proves that pandermite is identical with priceite (a=1’572 p=1*592 y=1.594) and that the latter is distinct from colemanite (a= 1.586 /3== 1.592 y = 1.614).Priceite is triclinic 5Ca0,6B20,,9H,O and colemanite monoclinic 2Ca0,3Bz0,15H,0. On the other hand fine-grained specimens (labelled priceite) of hydrous calcium borate from Californian localities were found to be howlite. L. J. S. Vivianite from the Land Pebble Phosphate Deposits of Florida. ’THOMAS L. VATS SON and STAPLETON D. GOOCH (J. Il-ashitzgtot~ d cad. Sci. 1918 43 82-88).-An exainiiiatioii of a sample of vivianite occurring in a ferruginous or dark yellow ochreous iiiatrix in a deposit’ of Florida pebble phosphate. The mineral 0ccurre.d as light to pale green crystals D 2.693 an optical examination of which gave the following results optically (+ ) ; 2V large; dispersion not strong; X is normal to 010; 2 makes an angle of 28°30’f10 with c .The refractive indices are a=1*580+ 0.003; p=1*598+0*003; y=1*627+0*003. Analysis gave H20 H,O FeO. Fe,O,. CaO. MnO. P,O,. TiO,. SiO,. (c 105 ). (=- 105”). Total. 32.64 9.43 0.02 0.25 29.99 trace 0.12 11.86 15.84 100.15 The presence of ferric oxide in blue vivianite is due to oxida- tion and not to inversion. Oxidation takes place rapidly on fine grinding. The matrix in which the vivianite occurs is not a clay but an earth compsed of the hydroxides of iron and aluminium chiefly the former phosphates of calcium iron and aluminium and some free quartz. W. G.Mirabilite from the Isle Royale Mine Michigan. ALBERT B. PECH (,4me9-. illin. 1917 2 63-63).-The matbrial from the Isle Royale copper minel a t Houghton consists of a clear colour- less mass of interlocking fibres with a little clayey matter enclosed.On exposure to the air it soon crumbles to a white powder. All the water is expelled a t 130O. Deducting 5.69% insoluble the following analysis agrees with the usual formula Na,S0,,10H20. Mean refractive index 1.437. Na20. K,O. CaO. SO,. c1. H,O. 19.02 0.77 trace 25.37 trace 54.84 L. J. S. Gilpinite a Mew Uranium Mineral from Colorado. ESPER S. LARSEN and GLRNN V. BROWN (Amer. Min. 1917 2 75-79) .-The mineral occurs as pale greenish-yellow to canary- yellow aggregates of minute lath-shaped crystals intermixed with gypsum on pitchblende and copper ore from Gilpin Co. Colorado. The crystals are monaclinic and show two sets of polysynthetic twin-lamellz. The optical coastlants are compared with those of zippeite and uranopilite. The mineral is readily soluble in dilute acids; it is difficultly fusible and becomes black on heating.D > 3.32. The1 following analysis (19.64% gangue mainly pitch- blende deducted) gives the formula R0,U03,S0,,4H,0 where R=Cu Fe Na,. H,O H,O SO,. UOs. CuO. FeO. PbO. Na,O. K,O. a t 105'. at 200". 13.45 56.72 5.80 4.77 0.82 1.93 0.70 1.66 12.15 A specimen labelled uranopilite from Cornwall was found to have optical characters identical with those of the Colorado mineral and it is also regarded as gilpinite. L. J. S . The Probable Identity of Uranothallite and Liebigite. ESPER S. LARSEN (Amer. Min. 1917 2 87).-Optical examination of three specimens labelled liebigite from Schneeberg Saxony and Joachimsthal Bohemia and of two specimens labelled urano- thallite from the latter locality gave the following results optic- ally positive 2 3 = 6 5 O j 3 O 2 V = 4 2 O f 2O p>v a = 1.500 p-11.503 -y=1*537k0*003 cleavage normal to a.The single analysis of liebigite (for which the formula was deduced as Ca0,U0,,2C02,20H,0) was made in duplicate on only 65 and 85 mg. of material and although this name has priority it is rejected in favour of the name uranothallite which was applied to more completely deter- mined material and analysed by three authors with the result 2Ca0,U0,,3C0,,10H20. It is however remarked that the original material described as liebigite was not available for optical examination and it is possible that those examined may really have been uranothallite incorrectly labelled liebigite. L. J. S.MINERALOGICAL UHXMISTRY.ii. 121 Pectolite Pseudomorphous after Quartz from West Paterson N.J. MILTIADES L. GLENN (Amer. Xiu. 1917 2 43-45) .-A small group of crystals collected from a basalt quarry a t West Paterson New Jersey shows the forms of sharply-developed crystals of quartz each about # inch in diameter. They however consist entirely of a compact fibrous material with the optical char- acters of pectolite. Analysis of the material gave SiO,. Al,O,+Fe,O,. CaO. MgO. N q O . H,O. To t t d . 7.45 3.77 100.14 53.42 0.52 32.63 9.35 L. J. S. A New Occurrence of Stevensite a Magnesium-bearing Alteration-product of Pectolite. MILTTADES L. GLENN (Anzer. Mzz~L. 1916 1 44-46).-The Hartshorn quarry a t Springfield Essex Co. New Jersey is in a somewhat altered basalt containing in cavities secondary anorthoclase quartz calcite zeolites datolite and pecto- lite. Some of the pectolite is of the usual type as silky radiations of fine needles but much of it is altered the colour becoming pinker and.the lustre morel waxy towards the ends of the fibres. I n the most altered material the colour is white to pink lustre waxy translucent; the structure is compact and the material optically isotropic and amorphous n about 1-50; D 2.15-2.20 H 24. It is easily fusible to a white enamel and is decomposed by hydrochloric acid with separation of granular silica. Analysis I is of partly altered material still retaining the pectolite structure but impreg- nated by waxy material; a n . I1 of the most altered waxy material apparently homogeneous although still perhaps containing a few fibres of unaltered pectolite SO,.Al,O,+Fe,O,. MnO. CaO. MgO. Na,O. H,O( > 110"). Total. I. 53-84 1.18 0.13 22.59 9.81 5.59 6.76 99.90 11. 58.03 0-37 0.03 1.61 27.66 3.73 8.45 99.88 These analyses when arranged in a series with other analyses of altered pectolit-es (' walkerite ' from Corstorphine Hill Edinburgh and ' magnesium pektolith ' from Burg Herborn Germany) show a gradual passage from the monohydrate of pectolite HNaCa2( SiO,) + H,O to the monohydrate of talc H2Mg3(Si03)q + H,O. They show a pro- gressive increase in magnesium and water and a decrease in calcium and sodium. Th0 latter formula t o which anal. I1 approximates is given as the composition of stevensite. The alteration has no doubt been brought about by the action of magnesium-bearing solu- tions derived from the weathering of the basalt.A Review of Amorphous Minerals. AUSTIN F. ROGERS ( J . Geol. Chicago 1917 25 51 5-541).-The amorphous equiva- lents of crystalline minerals should be recognised as separate mineral species and given distinctive names. About twenty of the more prominent and well-defined amorphous minerals (for example opal psilomelane collophane halloysite etc.) are discussed. The amor- L. J. S. VOL. CXIV. ii. 8ii. 122 ABSTRACTS OF CHEMICAL PAPERS. phous cadmium sulphide probably with adsorbed water CdS,sH,O which occurs as a thin powdery yellow coating on zinc-blende is separated from the hexagonal greenockite and named xuntho- chroite. Intimately associated with the chrysocolla (a microcrystalline or crystallised mineral) of several localties is the amorphous equivalent t o which the name cornuite is applied.Cornuite from Copper Mountain Prince of Wales Island Alaska occurs as a banded crust of bluish-green transparent glassy material with refractive index 1.549. It is more readily soluble in hydrochloric acid than chryso- colla and is also somewhat softer. Analysis by G . S. BOHART gave CUO. Al,O,. SiO,. H@* 42-61 0.3 1 34.13 23.11 Here the ratios of both silica and water are somewhat in excess over those required by the chrysocolla formula H4CuSi0 and cornuite is probably a solid solution of cupric oxide silica and water mCu0,nSiOz,zH20. The natural hydrocarbons and glasses are discussed under the term mineraloids. L. J. S. Nature of the Water in Zeolites.GEORG STOKLOSSA (Uiss. Bresluu 1917 64 pp.; from Cltem Zeittr. 1917 ii 420-421). -The author has investigated the following seven minerals and has found in all cases that the water contained in them is in chemi- cal combination (1) heulandite from Teigarhorn in Iceland ; (2) skolezite from Iceland; (3) natrolite from Bohemia; (4) harmo- tome from Strontian ; (5) chabasite from Nova Scotia ; (6) analcime from the Seiseralp; (7) apophyllite from the Seiseralp. Analyses gave SiO,. 1. 59.66 2. 46-71 3. 46.95 4. 48.51 5. 48-12 6. 54.74 7. 53.87 Al,O,. BaO CaO. 16.37 - 6.33 25.90 - 13.70 27.06 - 0.27 16.44 20.19 - 19.27 - 9.63 23.64 - 0.32 - - 23.85 MgO. K20. NqO. H,O. 2.36 0.42 14-90 13.64 15.97 9-58 1-59 - 13.79 2-45 3-02 - 16.11 18-71 8.58 4.81 - 16.24 - - - - - - - - - - Total.100.03 99-95 99.73 100.52 98.59 100.96 99.47 R. V. S. A New Occurrence of Ptilolite. LOUIS H. Koc~r (AwY. Min. 1917 2,143-144).-This species previously known only from Colorado is described from Challis Idaho. The material consists of a soft fluffy mass of minute fibres coating a layer of chalcedonic silica on a weathered basic igneous rock. Analysis gave SO,. A1,0,. CaO. MgO. K,0,Na20. H,O. Total. I. 81.5 8.2 1.7 0-3 1.0 7.3 100.0 11. 72.3 12.3 2.6 0.4 1.6 10.9 - The high value for silica is due to the presence of microscopic spindle-shaped crystals of quartz t o the extent of 31pX,; deductingii. 123 ANALYTICAL C1-f ZMISTRY . this the results are as under 11 Under the microscope the material is seen to consist of well-defined transparest needles with straight optical extinction ; biaxial with large angle and optically negative ; refractive indices a == 1.475 p = 1.477 y = 1.478.J) 2.30. 1,. J . S. E. JV. HILGARD (Yroc. National d c a d . Sci. I;.S.L4 . 1916 2 8-12).-The material examined consisted of soil samples from certain unproduc- tive tracts of land on the hacienda S'anta Lucia. It has the appear- ance of a dark grey clay adheres strongly t o the tongue and becomes very plastic with a little water. D 2.25. When immersed in water it swells u p t o many times (for one sample as much as tliirty-two times) its original volume forming a coherent gelatinous mass. The larger part of the material is colloidal but there are also minute inseparable grains of calcium and magnesium carbonates SiO,. A1,0,. Fe,O,. CaO. MgO. Ign. Insol. Na,SO,. Na&O,. NaCl. Total. 43.00 3.48 1.76 9.06 17.11 19.60 1.83 1-74 0.74 0.12 98.44 A Peculiar Clay from near the City of Mexico. A partial analysis gave The material is thus mainly a hydrated magnesium silicate allied to saponite or wpiolite but it differs from these in being very readily deco'mposed by acids even by dilute acetic acid and in its exceptionally high absorptive power f o r water. The name Zucianite is suggested for this new type of magnesian clay. L. J. s..

ISSN:0368-1769    

DOI:10.1039/CA9181405116

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

ANALYTICAL CHZMISTRY. ii. 123 Andyticd Chemistry. Filtering Tube. N 7 ~ ~ ~ ~ ~ ~ 1 M. THORNTON Jun. (J. Ind. Eng. Chem. 1918 10 132).-The stem of a carbon filter tube is pro- vided with a glass tap and the top of the tube is closed by a rubber stopper through which pass the stem of a holder for a filter crucible and an exit tube connected with a pump. The carbon tube serves as a small filter flask; the filtrate collected in this tube is discharged by opening the tap and admitting air through a side-tube on the exit tube. The apparatus is convenient for use in dealing with Preparation of N/100 Permanganate Solutions. J. 0. HALVERSON and OLAF BERGEIM ( J . Ind. Eng. Chem. 1918 10 119-120).-To prepared permanent N / 100-permanganate solution 0.40 gram of potassium permanganate is dissolved in 1 litre of re-distilled water and the solution is heated nearly a t boiling point f o r thirty-six hours under a reflux apparatus.The solution is then cooled kept overnight filtered through asbestos and after three days standardised against Bj50-oxalic acid solution (0,1261 gram of crystallised oxalic acid per 100 c.c.). The strength. of the solution does not vary more than 0.1Yh per week. [See further Ind. 1 9 3 ~ . ] small quantities of liquid. w. P. s. w. P. s. 8"ii. 124 ABSTRACTS OF CHEMTCAL PAPERS. Suggestions on some Common Precipitations. GEORGE H. BROTHER ( J . Ind. Eng. Chem. 1918 10 129-130).-The fol- lowing directions are given for obtaining precipitates which are retained by filter paper of moderately close texture. I n the case of hariuni sulphate the sulphate solution should contain about 1 C.C.of hydrochloric acid (D 1.2) per 200 c.c.; i t should bae heated t o boil- ing treated with about one-half the required quantity of barium chloride solution added drop by drop and the remainder of the barium chloride is added after the lapse of five minutes. The mix- ture is ready for filtration after a further fifteen minutes’ digestioi:. Calcium oxalate is readily obtained in a crystalline state by treating the boiling solution of the calcium salt with an excess of ammonium oxalate dissolving the precipitate by adding a very slight excess of hydrochloric acid then adding ammonia drop by drop until the precipitate has formed again and keeping the mix- ture hot for thirty minutes. For the precipitation of ammonium phosphomolybdate the phosphate solution is rendered ammoniacal then acidified with nitric acid heated to boiling and treated a t this temperature with ammonium molybdate solution.When a phos- phate is precipitated with magnesia mixture the precipitate should be dissolved by the addition of hydrochloric acid the solution heated t o boiling and ammonia then added slowly until a distinctly crystalline precipitate has formed; the mixture is now cooled one- fifth of its volume of ammonia (D 0.9) is added and after fifteen Reagents for Use in Gas Analysis. 371. The Absorption of Hydrogen by Sodium Oleate. R. P. ANDERSON and M. H. KATZ ( J . Znd. Eng. Chem. 1918 10 23-24. Compare A. 1917 ii 39).-The spdium oleate reagent containing nickel in suspension recommended by Bosshard and Fischli for the absorption of hydro- gen (A.1915 ii 788) is of little use. Amongst the objections to the reagent may be mentioned the time and trouble required for the preparation of the catalyst and the readiness with which it oxidises the bad keeping properties of the reagent itself and the slowness of the absorption of the hydrogen. [See further Znd. Detection and Estimation of Small Quantities of Free Hydrochloric Acid in the Presence of Chlorides and other Mineral or Organic Acids. M. ENTAT ( A m . China. anal. 1918 23 5-7) .-Hydrochloric acid may be determined by the electro- metric titration method previously described (A. 1917 ii 268). N-Silver nitrate solution is used for titration and the hydrochloric acid solution should contain 2% of nitric acid.Titration of Chlorides by Volhard’s Method. J. M. KOLTHOFF (Zeitsch. anal. Chenz. 1917 56 568-576).-Trust worthy results may be obtained in this method if as recommended by Schoorl the titration is interrupted a t the first change in colour minutes the precipitate is collected on a filter. w. P. s. 8 2 A . l w. P. s. T. F. B.ANALITICAL CHEMISTRY. ii. 125 of the indicator the mixture then stirred thoroughly and the titra- tion completed. Rothmund's modification (A. 1909 ii 932) is less trustworthy. The author finds that i t is best to dilute the solution containing the chloride and an excess of silver nitrate to a definite volume shake the mixture thoroughly allow the precipitate to settle and titrate an aliquot portion of the clear solution with thio- cyanate. As the silver chloride absorbs about 0.7% equivalent of silver a corresponding correction of 0.7% must be made on the quantity of chloride found.Chlorides may be detected and esti- mated in the presence of thiocyanates if the latter be oxidisecl by treatmeiit with sodium peroxide in sulphuric acid solution (if hydrogen peroxide is used i t should be tested previously for the Estimation of Chlorates and Hypochlorites. E. RUPP (Zeitsch. anal. Chem. 1917 56 580-586)-Ten C.C. of a solution containing about 0.5% of potassium chlorate and calcium hypo- chlorite are placed in a stoppered litre flask diluted to 100 c.c. 2 grams of potassium iodide are added the mixture is acidified with dilute acetic acid and after five minutes i t is titrated with iV/lO- thiosulphate solution ; this titration gives the quantity of hypo- chlorite present.Another portion of 10 C.C. of the solution is also placed in a large stoppered flask and 1 gram of potassium bromide and 30 C.C. of concentrated hydrochloric acid are added. After fifteen minutes the mixture is treated with 150 C.C. of 1% potassium iodide solution shaken and titrated with AT/ 10-thiosulphate solu- tion. The difference between the two titrations corresponds with the amount of chlorate in the solution. presence of chlorides). w. P. s. w. P. s. Action of Sodium Sulphide on Iodine and the Use of the Reaction in Analysis. JOSEF EHRLICI-I (Zeitsch. n m l . Chewh. 1918 57 21-22) .-Pure sodium sulphide solution reacts with free iodine to form sodium iodide; sulphur is liberated a t the same time but re-dissolves in the excess of sodium sulphide added.The iodine in an iodide solution also containing other substances may be estimated by liberating the iodine with potassium permanganate adding an excess of sodium sulphide separating the manganese sulphide etc. by filtration removing the excess of sulphide in the filtrate by treatment with zinc sulphate and then precipitating the iodine as silver iodide. w. P. s. Estimation of Hypobromite and Bromate or Hypo- iodite and Iodate in Mixtures of the Same. E. RUPP (Zeitsch. anal. Chenz. 1918 57 16-19).-The method is based on the reaction between hypobromites or hy oiodites and hydrogen peroxide according to the equation 8aBrO + H,O,= NaBr + H,O + 0,. The solution containing hypobromite and bromate is treated with a mixture of hydrogen peroxide and sodium hydroxide solution the excess of the hydrogen peroxide is then removed by boiling potassium iodide and sulphuric acid are added and the iodine liberated by the bromate is titrated with thiosulphate solu- 8"-2ii.126 ABSTRACTS OF CHEMICAL PAPERS. tioii. Another portion of the solution is treated directly with potassium iodide and sulphuric acid and titrated with thiosulphate solution. This titration is a measure of the hypobromite and bromate together and the quantity of hypobromite present is obtained from the difference in the two titrations. A mixture of hypoiodite atld iodate is analysed in the same way. W. P. S. Estimation of Iodates in the Presence of Bromates.E. RUPP (Zeitsch. mrl. Chem. 1918 57 19-21).-Bromates when treated with dilute hydrochloric acid are decomposed gradu- ally with the formation of hydrobromic and hypochlorous acids whilst iodates are not affected by this treatment. To estimate the two salts when contained in the same solution a portion of the latter is treated with potassium iodide and sulphuric acid and titrahd after a few minutes with thiosulphate solution. Another portion of the solution is diluted with water to 50 c.c. 20 C.C. of 12.5% hydrochloric acid are added and after one hour the mix- ture is treated with 25 C.C. of 3% hydrogen peroxide solution and 15 C.C. of 15% sodium hydroxide solution boiled for ten minutes cooled and titrated with thiosulphate solution after the addition of potassium iodide and sulphuric acid.The first titration gives the quantities of bromate and iodate together and the difference between the two titrations corresponds with the quantity of bromate present. w. P. s. Estimation of Sulphur in Pyrites. Z . KARAOGLANOW [with P. and M. DIMITROW] ( Z e i t s c h . a d . (%em. 1917 56 561-568). -After the sulphur has been oxidised t o sulphuric acid by heat- ing with a mixture of nitric and hydrochloric acids or by fusion with sodium carbonate and potassium nit.rate the sulphuric acid may be precipitated directly from the hydrochloric acid solution obtained after separating the silica previous removal of t,he iron being unnecessary if the precipitation is carried out under the following conditions. The solution (from 0.5 gram of pyrites) which should contain from 30 to 50 C.C.of 6N-hydrochloric acid (free) is diluted to 700 c.c. heat'ed to boiling and 40 C.C. of hot 10% barium chloride solution diluted previously with 100 C.C. of hot water are added gradually while the mixture is stirred. The precipitated barium sulphate is collected after fifteen hours washed first with water containing hydrochloric acid and barium chloride then with hot water dried ignited and weighed. w. P. s. Gravimetric Estimation of Sulphuric Acid and Barium as Barium Sulphate. 11. 2. KARAOGLANOW (Zeitsch. anal. Ghem. 1917 56 487-498. Compare this vol. ii 47).-In the estimation of barium the presence of nitric acid or a large quantity of hydrochloric acid causes the results obtained to be Goo low; potassium salts and ferric chloride have the opposite effect.Under equal conditions the errors in the gravimetric estimation of barium are less than in the estimation of sulphuric acid w. P. s.ANALYTICAL CHEMISTRY. ii. 127 Detection of Selenium in Sulphuric Acid. LUCIANO P. J. PALET (Anal. SOC. Quim. Argentina 1917 5 121-123).- Sulphuric acid containing selenium gives an intense violet colora- tion with aspidospermine. The pure acid does not give this reac- tion but in presence of an oxidiser such as potassium chlorate or lead peroxide it develops a rose-red coloration. [Compare I d . 147A.J A. J. W. Estimation of Nitrogen in Calcium Cyanamide. (MLLE.) RRONISLAVA TURKUS (L41~u. Chim. mml. 1918 23 3-5).-ln the estimation of nitrogen in cyanamide by Kjeldahl's method only thirty minutes' digestion with sulphuric acid is required for the complete decomposition of the cyanamide if the sulphuric acid used is diluted previously with onefourth of its volume of water; for 1 gram of the sample 40 C.C.of coiiceiitrated sulphuric acid mixed with 10 C.C. of water are required. The digestion must be pro- longed for more than thirty minutes if the acid used is weaker or w. P. s. The Microchemical Estimation of Nitrogen. B. S.JOLLEMA and C. W. G . HESSERSCHY (Biochem. Zeitsch. 1917,84 359-4370). -A critical examination of the methods of Bang and of Folin and Denis with some suggested minor alterations of the details. s. B. s. stronger than the concentration given. Simple Rapid Method of Estimating the Filtrate Nitrogen in Small Quantities of Blood and of other Body Fluids.R. DONALD (Quart. J . Med. 1917 11. 19-29).-One C.C. of blood is mixed with 1 c.c. of a saturated solutioii of sodium chloride in a mixture of nine parts of 6% sulphuric acid and one part of 6% phosphoric acid. It is centrifugalised and 1 C.C. of the clear liquid is then transferred to a second centrifugal tube mixed with 0.1 C.C. of 10% phosphomolybdic acid and again centrifugalised. Of the final clear protein-free liquid 1 C.C. is injected into a solu- tion of sodium hypobromite contained in a Doremus ureometer and the nitrogen evolved is transferred to a calibrated narrow measuring tube and its volume measured. Attention is directed to the necessity of rapping the ureometer prior to the removal of the nitrogen to the measuring tube in order to liberate a con- siderable proportion of the gas which otherwise remains in the gas- supersaturated hypobromite solution.The result is obtained in about forty-five minutes from the commencement of the operations and is stated t o be sufficiently accurate for clinical purposes. FI. W. B. Estimation of Amino-acid Nitrogen in the Blood. SEIZABURO OKADA ( J . BioZ. Chern. 1918 33 325-331).-The chief point in the new method is the removal of the proteins of the blood by hating with dilute acetic acid the last traces of protein being removed by shaking with kaolin. The use of alcohol as a iwecipitant is shown to be undesirable' (compare Back. A . . 1917 ii 159). H W. B.ii. 128 ABSTRACTS OF CHEMICAL PAPERS. The Estimation of Residual Nitrogen of the Blood.B. SJOLLEMA and C. W. G . HESSERSCHY (Biochem. Zeitsch. 1917 84 371-377) .-Different results are obtained according to whether phosphomolybdic acid metaphosphoric acid or t'richloroacetic acid is used as precipitant of the proteins. Still-head for Use in the Distillation of Ammonia. A. HUTIN (Ann. Chim. aizal. 1917 22 242-244).-The apparatus consists of a bulb with a lower tube which enters the neck of the distillation flask and an upper tube connected with a receiver; this upper tube extends into the bulb the portion inside the bulb being constricted and bent. upwards. If desired a wide tube filled with glass beads may be placed between the lower tube of the still- head and the distillation flask. The whole apparatus is made of sheet tin and its purpose is to prevent any spray from the dis- Use of Diphenylamine- Sulphuric Acid for Colorimetric Estimations.J. TILLMANS (,Zeitsch. rriznl. Cher12. 1917 5 6 509-511).-A reply to L. Smith (A. 1917 ii 217). The use of diphenylamine for the colorimetric estimation of nitric acid is trustworthy if the test solution and the standards are treated in S. B. S. tillation flask passing over into the receiver. w. P. s. exactly t h i same way particularly as regards shaking or stirring. w. P. s. Estimation of Phosphorous Hypophosphoric and Phos- phoric Acids in Mixtures. K. G. VAN NAME and WILBERT J. HUFF ( A m e r . J . Sci. 1918 [iv]. 45 91-102).-The estimation of phosphorous acid in presence of hypophosphoric and phosphoric acids may be effected by the absorption of iodine in presence of disodium hydrogen phosphate. The same method may be used for the estimation of hypophos- phoric acid if this is hydrolysed in presence of hydrochloric acid as catalyst producing thereby equimolecular quantities of phos- phorous and phosphoric acids in accordance with the equation H,P,O + H,O = H,PO + H,PO,.A mixture of phosphorous hypophosphoric and phosphoric acids inay be analysed by estimating the phosphorous acid before and after hydrolysis by {he iodometric method and also determining the total phosphoric acid in the solution after oxidation. [See further Ind. 147~.] The Precipitation of Phosphoric Acid in the State of Ammonium Phosphomolybdate. Estimation of Phosphoric Acid by a Simple Azotometric Method. J. CLARENS (Compt. rend. 1918 166 259-262).-If the phosphate is precipitated by ammonium molybdate in the presence of sufficient ammonium nitrate the resultant precipitate contains phosphoric acid and ammonia in the proportions requisite to form triammonium phos- phate.The proportions to use should be 0.1 gram of phosphoric anhydride and 100 C.C. of ammonium molybdate containing 15-20 grams of ammonium nitrate. The precipitate is washed with dis- H. M. D.ANALYTICAL CHEMISTRY. ii. 129 tilled water and the ammonia present estimated by one of the usual methods such as distillation with potassium hydroxide. W. G. Estimation of Phosphoric Acid. A Modification of the Citrate Method. J. GROSSFELD (Zeitsch. aml. Chenz. 1918 57 28-33).-To avoid the intermediate precipitation of phosphoric acid by molybdic acid the author proposes a method for the analysis of fertilisers ashes etc.in which the calcium is precipi- tated as oxalate from an acetic acid solution and after the removal of the calcium oxalate the phosphoric acid is precipitated in the usual way as ammonium magnesium phosphate citric acid being added t o prevent precipitation of iron and aluminium. The hydro- chloric acid solution (or other solution) of the substance under examination is treated with a few drops of methyl-orange solution and an excess of ammonium oxalate solution and saturated ammonium acetate or sodium acetate solution is added until the colour of the indicator changes from red to yellow; the mixture is then diluted t o 100 c.c. mixed and filtered through a kiesel- guhr filter.An aliquot portion of the filtrate is mixed with 5 C.C. of 20% citric acid solution and the phosphoric acid precipi- w. P. s. Estimation of Phosphoric Acid particularly in Super- phosphate. G VORTMANN (Zeitsch. m a l . Chent. 1917 56 465-487).-For the direct estimation of phosphoric acid in super- phosphate the most trustworthy method consists in precipitation as ammonium magnesium phosphate after the calcium has been removed as oxalate and the iron as sulphide; the presence of ammonium oxalate ammonium molybdate and ammonium sulphide does not interfere with the precipitation. If aluminium salts are present the quantity of magnesia mixture used should be increased. When the phosphoric acid is precipitated with molybdic acid solution before it is converted into ammonium magnesium phosphate the precipitation may be made equally well from a nitric hydrochloric or sulphuric acid solution.Molybdic acid solution containing pyridine is a very sensitive reagent for the detection of traces of phosphoric acid; i t will detect 0.01 mg. of P,O in 10 C.C. of solution whilst the limit' for molybdic acid containing nitric acid is about 0.1 mg. of P,O in 10 C.C. The phosphoric acid in superphosphate can also be precipitated as a basic mercury com- pound by means of yellow mercuric oxide; this compound is then decomposed with sodium sulphide and the phosphoric acid pre- cipitated as ammonium magnesium phosphate. Precipitation as calcium triphosphate is untrustworthy. tated with magnesia mixture. [See also Ind. 1608.1 w. P. s. Use of Textile Fibres in Microscopic Qualitative Chemi- cal Analysis.11. Detection of Boron by means of Turmeric Viscose Silk Fibres. 111. Detection of the Heavy Metals by means of Zinc Sulpbide Wool Fibres. E. 31. CEIAMOT and H. I. COLE ( J . Znd. Eng. Chem. 1918 10 48-50. Compare A. 1917 ii 57$).-Viscose silk fibres dyed with turmeric areii. 130 ABSTRACTS OF CHEMICAL YWERS. useful for the detection of very small quantities of boric acid; a reaction may be obtained with one drop of solution containing 0*000025 mg. of boron. Wool fibres free from fat and treated with sodium sulphide’ and zinc acetate are suitable for the detection of heavy metals the coloration obtained indicating the metal Rapid Organic Combustion. P. A. LEVENE and F. I%*. BIEBER ( J . Amer. C‘hern.Soc. 1918 40 460-462).-The pro- cedure adopted in the authors’ laboratory is fully described with diagrams. Cerium dioxide is used as a catalyst and from the first weighings to the final ones the combustion requires only about forty-five minutes. Micro-analysis of Organic Substances. J. V. DUBSKY (Ber. 1917 50 1709--1713).-An account of recent experiences and improvements of micro-methods of combustion made in the university laboratory at Zurich where all analyses are now per- formed with small quantities of material. For the combustion of halogeno-nitro-compounds the tube contains a 5 cm. layer of pieces of fine silver wire then a 16 em. layer of a mixture of copper oxide and lead chromate then another short layer of silver and finally the boat. The preliminary decomposition is carried out with the oxygen supply cut off and if the compound is very poor in hydrogen (for example trichlorodinitrobenzene) it is found best to adopt Benedict’s method (A.1900 ii 439) and place before the boat another boat containing a weighed amount of pure benzoic acid naphthalene or sugar in order t o reduce some of the copper oxide. (See also Ind. April.] J. C. W. Electrical Combustion Furnaces for Micro-analyses. J. V. DUBSKY (Ber. 1917 50 1713-1717).-A description of a platinum resistance and a chromium-nickel resistance furnace designed a t the author’s instigation for use with silica combustion tubes. [See Znd. April.] J. C. W. The Eggertz Test for Combined Carbon in Steel. J. H. WHITELEY (Zron Steel Inst. Carnegie Schol. Mem. 1917 0 1-101) .-Small quantities of carbon dioxide may be accurately estimated by absorbing in an ammoniacal solution of barium chloride (McFarlane and Gregory A.1906 ii 802) and an apparatus is described by the use of which the carbon in steel may be estimated by wet combustion or the weight of carbon dioxide evolved during the Eggertz colour test may be determined. This gas is given off a t a decreasing rate during several hours’ heat- ing and the quantity obtained in a given time is closely propor- tional to the carbon content of the steel irrespective of its heat treatment the only exceptions being austenitic steels. The other volatile products of the reaction include hydrogen cyanide and hydrocarbons the ‘ missing ’ carbon remaining in solution as shown by oxidatiori with permanganate.A 1% carbon steel yields in the present. [See further Znd. 75A.l w. P. s. J. C . W.ANALYTICAL CHEMISTRY. ii. 131 first ten minutes' boiling with nitric acid 22% of its carbon as carbon dioxide 5-10% as hydrogen cyanide and 2-3% as hydro- carbons. When steel is dissolved in nitric acid kept cool by water a black pre- cipitate forms in all cases in which carbide particles are visible in the section etched with sodium picrate. This precipitate becomes brown later especially on warming and later this changes to a brown solution. The particles first formed have the form of the carbide. Quenched steels yield the solution directly. On dialysis a substance passes through the membrane,. which has an orange colour in concentrated solution but becomes green on dilu- tion.The colour is not merely that' of the organic substances present but depends on the reaction of these with iron. With further heating the green substance changes to a colourless or only slightly coloured substance. The proportions of the coloured products depend on the electro-chemical conditions of solution and cold-worked steeIs give 8 deeper colour. The tints given by different steels are more easily matched if sulphuric acid be added. For 0-5 gram of steel 10 C.C. of nitric acid (1.2) are used and after boiling for fift?een minutes 15 C.C. of sulphuric acid (1 3 by volume) are added. [See further Ind. 1917 1097.1 C. H. D. Gravimetric Estimation of Potassium by Sodium Cobalti- nitrite. C. V. GAROLA and V. BRAUN (Ann. Falszf. 1917 10 572-575).-The reagent used consists of 28.6 grams of cobalt nitrate and 50 C.C.of glacial acetic acid dissolved in 500 C.C. of water and 180 grams of sodium nitrite also dissolved in 500 C.C. of water; these two solutions are mixed twenty-four hours before use and then filtered. The mixed reagent keeps for a few days only. Twenty-five C.C. of the potassium salt solution (containing about 0.250 gram of potassium chloride and free from other bases except sodium) are treated in a stoppered flask with 25 C.C. of the reagent and after about eighteen hours the precipitate is collected on an asbestos filter washed with 10% acetic acid then once with 95% alcohol dried a t looo and weighed. The precipitate con- tains 20.74% of K,O. The method is trustworthy for the estima- tion of potassium in fertilisers soils wines etc.Ammonium salts should be removed previously by ignition and other bases by treat- ment with sodium carbonate and filtration. [See also Ind. 168~.1 Estimation of Potassium and Sodium as Chlorides through the use of the Refractometer. €3. A. SHIPPY and G. H. BURROWS (J. Amer. Ghern. SOC. 1918 40 185-187).-The refractive index a t 25O of a 20% sodium chloride solution is 1.36829 whilst that of a 20% potassium chloride solution is 1.35992. If therefore the refractive index of a 20% solution of the mixed chlorides be determined the approximate quantities of the two saltis can be foiind by a simple calculation. [See also Tnd. 168~.1 The colouring matter of the brown solution is colloidal. w. P. s. w. P. s.ii.132 ABSTRACTS OF CHEMICAL PAPERS. A Proximate Method for the Estimation of Rubidium and Caesium in Plant Ash. W. 0. ROBINSON ( J . Ind. Eny. Chern. 1918 10 50-51).-After removal of phosphoric acid calcium magnesium etc . the mixed alkali chlorides are fraction- ally precipitated with platinum chloride. The potassium rubidium and czesium platinichlorides are collected reduced in hydrogen and the resulting chlorides treated with concentrated hydrochloric acid. The solution thus obtained containing all of the rubidium and czesium chlorides and a large amount of potassium chloride is then compared spectroscopically with standard solutions containing known amounts of rubidium czesium and potassium chlorides and prepared under the condi- Colloido-chemical Methods for Estimating the Hardness of Water.1,. BERCZELLER (Biocheiiz. Zeitsch. 1917,84 149-155). -The surf ace tension of soap solutions is diminished considerably by addition of small amounts of alkali hydroxides but the addition to such alkaline solutions of small amounts of calcium or mag- nesium salts increases the surface tension. These facts might. form a basis f o r a method for determining the hardness of water. tions given. [See further Znc?. 7 6 ~ . 1 w. P. s. S. B. S. Estimation of Zinc by Schaff ner’s Method. lT. HASSREIDTER (Zeitsch. anal. Chem. 1917 56 506-509. Compare A. 1917 ii 509).-In any of the modifications of this method the precipita- tion of the iron (whether it be a single double or treble precipita- tion) should be carried out under conditions which will minimise the retention of zinc.It is advisable t o make a comparison pre- cipitat’ion a t the same time using a definite quantity of iron and zinc. The iron precipitate should be tlest~ed for the presence of 0. BAUER (Stahl ‘zt. Eisen 1915 734; from Ann. Chim. anal. 1918 23 21).-A measured and weighed piece of the metallic sheet is treated with a solution containing 2 grams of sulphuric acid and 2 grams of arsenic trioxide per litre ; this solution dissolves the zinc readily b u t does not attack the iron. When evolution of hydrogen ceases the remaining sheet of iron is removed from the solution washed dried and re-weighed. This method can be used only with galvanised iron prepared electrolytically; when i t is made by the hot dipping process an iron-zinc alloy is formed between the layers of iron and zinc and this alloy dissolves in the reagent.The presence of iron in the solution indicates that the galvanised iron Estimation of Lead as Phosphate and its Separation from Antimony. G. VORTMANN and A. BADER (Zeitsch. anal. Chem. 1917 56 577-580).-The solution containing about 0.5 gram of lead nitrate is treated with 5 grams of tartaric acid then rendered zinc. [See also I d . 168~.] w. P. s. Estimation of Zinc on Galvanised Iron. had been made by the hot process. w. P. s.ANALYTICAL CHEMISTRY. ii. 133 slightly ammoniacal heated a t 80° and 100 C.C. of 10% ammonium phosphate solution are added. The mixture is kept at 70-80° for sixteen hours then cooled the precipitate collected washed with dilute ammonium nitrate solution dried ignited at a low temperature and weighed.If antimony is present the quantity of tartaric acid used is correspondingly increased; antimony is not precipitated under these conditions and may be estimated as sulphide in the filtrate from the lead phosphate precipitate. The method yields trustworthy results and is useful for the analysis of (‘ hardened ” lead. Separation of the Copper Group from the Arsenic GrQup with Especial Reference to the Identification of Arsenic. M.. CANNON SNEED ( J . Amer. Chem. Soc. 1918 40 187-191).- The method depends on the solubility of mercury arsenic anti- mony and tin sulphides in a solution prepared by saturating a 12% sodium hydroxide solution with hydrogen sulphide and add- ing to each litre 400 C.C. of 40% sodium hydroxide solution.Lead bismuth cropper and cadmium sulphides remain insoluble. The solution containing the soluble sulphides is treated with ammonium carbonate to precipitate the mercury ; arsenic antimony and tin sulphides are precipitated by hydrochloric acid and the antimony and tin sulphides are separated by solution in warm concentrated hydrochloric acid. The arsenic sulphide is dissolved in ammonia oxidised with nitric acid and the solution a t 80° treated with an excess of ammonium molybdate. The latter yields a yellow yre- cipitate with the arsenic and will detect as little as 1 part of arsenic in 225,000 parts of water. [See further Znd. April.] ?V. P. s. w. P. s. New Methods for the Estimation of Copper Zinc Cadmium Nickel and Cobalt. ADOLPHE CARNOT (Comrzpt.rend. 1918 166 245-251).-To a solution containing any one of these metals sodium carbonate in slight excess is added in the cold until i t is just alkaline. The precipitate formed is then re- dissolved by the addition of just sufficient ammonium hydroxide or in some cases ammonium carbonate and the liquid is boiled usually for five minutes until precipitation is complete. The pre- cipitate is washed dried and ignited and weighed as the oxide or reduced and weighed as t.he metal. If the amount of precipitate obtained is very small it is dissolved in a little nitric acid the solution evaporated to dryness with a little sulphuric acid and the metal weighed in the form of its anhydrous sulphate. I n every case it is essential to ensure the absence of all ammonium salts prior t o the precipitation with sodium carbonate.New Separations of the Five Metals of the Group Soluble in Ammonia. 1 4 ~ ~ ~ ~ ~ ~ CARNOT (Conzpt. Tend. 1918 166 329-333. Compare preceding abstract).-If copper and zinc are pressnt together in solution they are precipitated and weighed as their combined oxides (Zoc. c i t . ) and these are then heated in a current of hydrogen. The zinc volatilises as formed and the W. G .ii. 134 ABSTRACTS OF CHEMICAL PAPERS. residual copper is weighed. With a mixture containing copper nickel and zinc the copper is first precipitated from the boiling acid solution by the addition of sodium thiosulphate and weighed as its sulphide. From the filtrate the nickel and zinc are pre- cipitated and weighed as the mixed oxides these being then reduced in hydrogen and the nickel weighed.For an alloy of zinc and cadmium the metal is dissolved in nitric acid and the solution evaporated nearly to dryness and then diluted to 150-200 C.C. Sodium carbonate is added until the liquid is alkaline and then ammonium sesquicarbonate and a little ammonia the liquid being heated to just1 below 100° until it no longer smells of ammonia. The cadmium carbonate is washed by decantation with ammonium carbonate solution until free from zinc and then ignited and weighed as cadmium oxide. The zinc is estimated in the filtrate by Meunier's method (compare A. 1897 ii 464). Cobalt may be semparated from nickel when in solution with it by precipitation with ammonium sulphide in the presence of an alkali oxalate.The nickel passes through in solution on filter- ing and is precipitated from the filtrate as nickel sulphide by boi7ing i t witlh acetic acid. This method also applies to the separa- tion of copper and nickel if an alkali sulphide is used in place of ammonium sulphide. By a combination of these methods the five metals if present in solution together may be separated and estimated. The Examination of Mercury Fulminate and the Analysis of Mixtures for Percussion Caps. PAUL NICOLARDOT and JEAN BOUDET (Compt. rend. 1918 166 258-259).-Free mercury may be detected in the fulminate by shaking 1 gram of the latter with 100 C.C. of a 5% solution of ammonium thiosulphate. All the fulminate dissolves and leaves the mercury as a grey powder or in metalIic globules which can if necessary be weighed.For the examination of detonating mixtures the percussion caps are treated first in the cold for two hours and then at' 60° for one hour with yellow ammonium sulphide. The mercury fulminate is converted into mercury sulphide which is filtered off along with any powdered glass present. To the filtrate ammonium sulphite is added and the antimony sulDhide which separates is collected and weighed. In the filtrate the alkali metals are estimated in the usual way. Any chlorate or nitrate in the mixture is extracted with cold water and estimated in the usual manner. Any copper present owing to the attack of the metal of the caps will come down with the antimony sulphide and may be estimated electro- lytically after calcining the sulphides and extracting them wit7h nitric acid.W. G. W. G. Estimation of Manganese in Steel in the Presence of Chromium and Vanadium by Electrometric Titration. G. L. KELLEY 34. G . SPENCER C. B. ILLINGivoR'rH and T. GRAY (?7. Tnd. Eng. Chern. 1918 10 19-23).-The manganese isANALYTICAL CHEMISTRY. ii. 135 oxidised to permanganate by sodium bismuthate or ammonium per- sulphate and the permanganate then titrated with mercurous nitrate solution. The solution to be titrated should contain about 50 C.C. of sulphuric acid (D 1-58> per 200 C.C. of water and t.he temperature should be 20°. The end-point of the titration as observed on the electrometric apparatus is sharp and is not affected by the presence of chromates or vanadates. [See further Zmct. Analysies of Tin Ores.T. F. GOLICK (Eng. Mzn. J. 1916 827; from Ann. Clzim. anal. 1917 22 248).-The ore is fused with a mixture of potassium carbonate and sulphur the mass when cold is extracted with hot water and the solution filtered. The filtrate is then evaporated with the addition of sulphuric acid and heated until sulphuric acid fumes are evolved the residue treated with hydrochloric acid and hydrogen peroxide to insure camplete conversion of the tin intlo stannic chloride and the tin precipitated as sulphide. After the precipitated sulphide has been collected and washed it is treated with a known quantity of potassium iodate in the presence of concentrated hydrochloric acid and the excess is titrated with potassium iodide solution; the reac- tion proceeds according to the equation SnS + KIO + 6HC1= Detection of Small Quantities of Vanadium in Water.VICTOR L. MEAURIO (Anal. SOC. Quim. Argentina 1917 5 185-189).-A solution of 0.2 gram of diphenylamine in 100 C.C. of water in presence of hydrochloric acid gives' a violet coloration with aqueous solutions of vanadium compounds. The coloration is unaffected by the presence of nitrates iron or titanates and the test will detect the presence of vanadates in solutions of 0.0002% strength. [Compare Id. April.] A. J. W. The Estimation of Vanadium in the Presence of Molyb- denum by means of Titanous Chloride. A. TRAVERS (Compt. Tend. 1918 166 289-290. Compare A. 1917 ii 545).-In using the method previously described (Zoc. cit.) it is now noted that if the indicator pobassium thiocyanate is added before the titonous chloride the vanadic acid is reduced first and when this action is complete the molybdic acid is reduced.Thus vanadium and molybdenum in steels may be estimated by carrying out the method for the two together as already described (Zoc. cit.) and then in another portion estimating the vanadium alone by adding the thiocyanate first and running in the titanous chloride from a burette until an end-point is reached. Antimony Dioxide. JULIUS VON SZILBGYI (Zeitsch. anal. Chem. 1918 57 23-28).-Antimony dioxide may be prepared by heat- ing the pentoxide a t bright redness or by oxidising antimony with concentrated nitric acid and heating the resulting oxide a t dull redness iintil constant in weight When heated with concentrated 92A.l w.P. s. SnCl + S + KCl + ICl + 3H,O. w. P. s. W. G .ii. 1.36 ABSTRACTS OF CHEMICATA PAPERS. hydrochloric acid and potassium iodide antimony dioxide liberates iodine; the reaction proceeds according to the equation 2Sb0 + 6HCl+ 2HI = 2SbC1 + 4H20 + I,. The iodine may be separated by distilling the mixture; if the distillate is collected in a receiver containing potassiuiii iodide solution titration with thiosulphate solution will give the quantity of antimony dioxide present. Meta- stannic acid does not liberate iodine from potassium iodide under the above conditions but the reaction is of little practical use for the estimation of antimony in the presence of tin since alloys of these two metals usually contain other metals which interfere. w. P. s. Colorimetric Estimation of Bismuth (in Copper).H. A. B. NOTHERWELL (Eng. and Min. J. 1917 104 1091-1092; from J . soc. Chem. Znd. 1918 37 92~).-The copper is dissolved in nitric acid and the cold diluted solution treated with sodium carbonate until a small quantity of the copper is precipitated; this precipitate will also contain all the bismuth. After six hours the precipitate is collected dissolved in hydrochloric acid the copper and bismuth are separated as sulphides and these are dissolved in nitric acid. To the solution are added 5 C.C. of lead nitrate solution (13.5 grams per litre) the mixture is nearly neutralised with ammonia treated with an excess of ammonium carbonate boiled cooled the precipitate collected and dissolved in nitric acid and the precipitation is repeated.If much copper is still present dilate potassium cyanide solution must be added until the colora- tion has nearly disappeared and the precipitate is then washed until free from copper. The precipitate is dissolved in a small quantity of nitric acid the solution evaporated the residue dis- solved in three drops of nitric acid and 5 c . ~ . of water the solution diluted to 25 c.c. and made up to 50 C.C. with 1.7% potassium iodide solution. The coloration obtained is a t once compared with that given by a known amount .of bismuth under the same conditions and in the presence of 5 C.C. of the lead nitrate solution. w. P. s. The Estimation of Humus by means of a Simplified Procedure of Elementary Analysis. A. JAKOBSEN (Zhzu. Optyit. Agron. 1916 17 93-98; E x p t .Stat. Rec. 36 614; from Physiol. Abstr. 1918 2 629-630).-The humus in soils is estimated by a combustion method using platinised asbestos as a catalyst. From 1 to 25 grams of material may be used and the oxidation is complete in thirty minutes. It is claimed that the method is as satisfactory as the more complex one of Gustavson. w. G . Determination of the Concentration of the Hydrogen Ions in Acid Liquids. Application to Wines. MARCEL DUBOUX ( J . Chim. Phys. 1917 15 473-5Ol).-Two methods are described namely a graphic method and a method of calculation the latter giving the more precise resulte.ANAIAYTIC7AL CIIEMISTRY. i i . 137 I n the first' method a iieutralisation curve is drawn plottiiig the conductivity of the solution against the volume of standard alkali added the wine being previously diluted with water in the pro- portion of 1 4 or 3:97 by volume according as the amount of alkali required to neutralise 1 litre of it as determined volumetric- ally is less or greater than 110 C.C.N-sodium hydroxide. The tangent to the curve at the neutralisation point is drawn and the tlist,ance x from its point of intersection with the ordinate axis (conductivity) to the curve along the axis is measured. Then LH'] = x/0*291 or ~ / 0 * 1 5 7 according to the dilution used. I n the method of calculation it is necessary to determine (1) the volume of N-sodium hydroxide required t o neutralise 5-5-2 C.C. of the wine; (2) the percentage of alcohol by volume.in a mixture of 1 C.C. of wine to 4 C.C. of water; (3) the specific conductivity of the wine before and after the addition of the volume of alkali as determined in (1).Formula are given for the calculation of the hydrogen ion concentration from these data. W. G. Volumetric Estimation of Formic Acid in the Presence of Hydroxides Carbonates Oxalates and Acetates. F. TSIRO PINAS ( J . Znd. Eng. Chenz. 1917 9 1110-llll).-The solution containing from 2.5 to 5 grams of formic acid together with carbonates oxalates and acetates is boiled for a few minutes rendered alkaline with sodium hydroxide and treated with a quantity of calcium chloride sufficient to precipi~ate the carbonates and oxalates. The mixture is filtered the filtrate diluted to 250 c.c. and 50 C.C. are acidified with sulphuric acid and boiled in a flask with 400 C.C.of chromic acid solution (50 grams of sodium dichromate 80 C.C. of concentrated sulphuric acid and 500 C.C. of water) for fifteen minutes the flask being connected through a reflux apparatus with a gas-measuring tube filled with water. When carbon dioxide ceases to collect in the measuring tube the volume of the gas is observed and its weight calculated into formic acid. Acetates if present do not interfere as they are not oxidised by chromic acid. With pure sodium formate the method yields 99.6% of the formic acid present. w. P. s. Estimation of Acetic Propionic and Butyric Acids. R. D. CROWELL (J-. Amer. Chem. SOC. 1918 40 453-460).- Various principles underlying possible methods for separating the lower aliphatic acids are discussed and a procedure is described which depends essentially on the fact' that most of the butyric acid and some propionic acid can be extracted by means of light petroleum (b.p. 150-3OOO) after saturating the solution under examination with calcium chloride and a little potassium chloride. The total acidity and weight of sodium salts dried a t 200° are first determined and then the acidity and salt weight of the light petroleum extract. The first salt weight minus the sodium acetate equivalent gives the total weight of -cR,. groups and the second minus the sodium propionate equivalent gives the weight of -CH groups present as butyric acid. A correction for the solubility ofii. 138 ABSTRACTS OF CHEMICAL PAPERS. butyric acid in the calcium chloride solution etc. also requires t o be made.[See furt.her Ind. April.] J. C. W. G. DENIG~S (Ann. Chim. anal. 1918 23 27-31).-Five C.C. of a butyric acid solution are mixed with 5 C.C. of hydrogen peroxide solution (0.01 vol. for each 0.01 gram of butyric acid per litre) and 1 C.C. of ammonium ferrous sulphate solution (5 grams of ammonium ferrous sulphate and 10 C.C. of 10% sulphuric acid per 100 c.c.). The mixture is heated at 70° for five minutes then treated with six drops of sodium hydroxide solution cooled filtered and 5 C.C. of the filtrate are mixed with three drops of sodium hydroxide solu- tion three drops of 5% sodium nitroprusside solution and a slight excess (0.5 C.C. or more) of acetic acid. A red coloration develops its intensity depending on the quantity of butyric acid present. The amount of the acid in the solution may be estimated colori- metrically by comparison with standards under the same condi- tions.The method may be applied to the estimation of butyric acid in mixtures organic fluids etc. after the acid has been Estimation of Lactic Acid in the Presence of other Organic Acids. P. SZEBERENYI (Zeitsch. anal. Chem. 1917 56 505-506) .-Lactic acid when heated with chromium trioxide and sulphuric acid yields acetic acid carbon dioxide and water; if the oxidised mixture is then distilled the quantity of acetic acid in the distillate is a measure of the lactic acid present. The results obtained are slightly too low since about 3% of the lactic acid is converted directly into carbon dioxide and water. Under the above conditions tartaric acid malic acid citric acid and oxalic acid are oxidised directly to carbon dioxide.Volatile acids alcohol acetone and esters must be removed previously by distilla- tion. A small portion of the lactic acid also distils over and this quantity may be estimated approximately from the acidity and the molecular weights of the acids in the distillate. [See also Ind. Detection and Estimation of Small Quantities of Hydro- cyaaic Acid. J. M. KOLTHOPF (Zeitsch. ana2. Chem. 1918 57 1-15).-0f the varieus reactions used for the detection of hydro- cyanic acid that depending on the formation of ferrocyanide is the only one which is characteristic and trustworthy. In using this reaction for t h O colorimetric estimation of small quantities of hydrocyanic acid it is important to have exactly the same quanti- ties of reagents in both the test and comparison solutions.The thiocyanate reaction (compare A. 1916 ii 455) may be used for the purpose if it is remembered that certain body fluids (saliva stomach contents etc.) may already contain thiocyanate; in such cases the hydrocyanic acid may be separated by the aeration-dis- tillation method The picric acid guaiacum phenolphthalein silver and iodine-starch reactions arel untrustworthy since many Detection and Estimation of Butyric Acid. 'separated by distillation or extraction. w. P. s. 1654.3 w. P. s.ANALYTICAL CHEMISTRY. ii. 139 substances other t,han hydrocyanic acid give similar reactions. In dealing with pure hgdrocyanic acid the sensitiveness of the tests (expressed in mg. of CN per litre) is as follows ferrocyanide 2 ; thiocyanate 0.1 ; picric acid 1 ; guaiacum 0.004 ; phenolphthalein 0.05 ; silver 0.03 ; iodine-starch 0.1.w. P. s. Detection of Picric Acid by Ferrous Tartrate Reagent. RUPEAU (Ann. Chim. anal. 1918 23 15-16).-The author claims to have been the first to use ferrous sulphate-tartaric acid solution often called Le Mithouard's reagent for the detection of picric Detection of the Poisons which can be Extracted with Ether from the Acid Aqueous Solution in the Stas-Otto Process (Picric Acid Picrotoxin Antipyrin). 0. TUNMANN (Apoth. Zeit. 1917 32 4 4 1 4 4 3 447-448; from Chem. Zentr. 1917 ii 499-501. Compare A. 1917 ii 551).-This is a con- tinuation of the papers referred to. Picric acid.-The sublimates are homogeneous colourless or even yellow.Typical crystals can- not be reckoned on even after recrystallisation from water or alcohol. Hydriodic acid dissolves the sublimate at' once but no crystals are formed. Zinc chloroiodide dissolves rich sublimates only on warming; on cooling large yellow prisms and flat pris- matic crystals are deposited ; they show strong pleochroism and extinction parallel to the long axis. Bromine-potassium bromide solution acts similarly but the prisms are less regular and not pleochroic. On the whole reactions like the isopurpuric acid reaction the picramic acid reaction and the dyeing of wool are most satisfactory for these microchemical purposes. Picrotoxin.-The picrotoxin sublimes a t 215-225O for the most part. The sublimate exhibits no crystals but only drops and crystallisation could not be brought about.Zinc chloroiodide and hydriodic acid yield no reaction products Nitric acid dissolves the sublimate but produces no coloration. Rich sublimates yield good crystals of picrotoxin when treated with hydrochloric acid but it is better to apply 5% ferric chloride solution for this pur- pose because this distinguishes picrotoxin sublimates from those of antipyrin. The sublimate and the solution are heated under a cover glass until bubbles appear ; on cooling typical pentagonal tablets can be observed. They are colourless the large ones polarise in variegated shades and show oblique extinction. If the sublimate under the cover glass is treated with a drop of bromine- potassium bromide solution and heated colourless prisms of bromo- picrotoxinin are formed on cooling.These crystals are monoclinic and can also be obtained by the action of bromine water. Antipyrin.-The residues from the ethereal extraction of the acid solution yield only traces of antipyrin because the greater quantity of this substance is extracted only when the solution is alkaline. The sublimates a t first consist of drops which eventually form groups of radially arranged flat prismatic crystals which polarise strongly. These antipyrin deposits yield deep red drops acid (compare A 1917 ii 158). w. P. s.ii. 140 ABSTRACTS OF CHEMlCAL PAPERS. with hydrogen iodide shining droplets with zinc chloroiodide and droplets also with bromine-potassium bromide solution. The colour reactions ordinarily used are evident even with the smallest quantities without the aid of a microscope.Two antipyrin reac- tions which yield decisive crystalline precipitates are to be found in the formation of nitrosoantipyrin and f erripyrin respectively. I n the former case the sublimate is dissolved in a drop of water and treated successively with a drop of 10% sodium nitrite solution and a drop of acetic acid. The green solution deposits doubly refractive dichroic crystals or if it is heated long yellow prisms. The ferripyrin reaction is carried out by heating the sublimate with a drop of 5% ferric chloride solut.ion under a cover glass until bubbles are formed ; on cooling orange-yellow crystals are deposited mostly 30-5Op (sometimes S o p ) long which show yellow shades in polarised light.The reaction distinguishes antipyrin from sali- pyrin. I n the case of salipyrin the sublimate consists of groups of bent needles. Addition of ferric chloride produces a violet solu- tion which remains on heating and no crystals are- deposited unless too high a temperature has been used for the sublimation. In this case a mixture of crystals of ferripyrin and salicylic acid may be observed. R. v. s. L. VAN ITALLIE and J. VAN TOORENBURG (Pharm. TVeekbZad 1918 55 169-178). -An account of t'ests applicable to the alkaloids pseuda-morphine protopine tritopine cryptopine laudanine laudanidine and laudanosine. [See further Znd. April.] A. J. W. Modification of the Ehrlich Indole Reaction in Bacterial Cultures. W. NOWICKI (Wien. klzn. Woch. 1917 30 983; from Chem. Zentr. 1917 ii 498).-The culture which should contain 8-10 C.C. of peptone water is treated with 1 C.C. of Ehrlich's reagent and two drops of 40% formaldehyde solution. On shaking 8 reddish-violet colorat'ion appears and by addition of alcohol the solution may be made suitable for colorimetric examination. Microchemistry of some Opium Alkaloids. R. V. S. Analysis of Blood and Urine. 0. I. LEE (S't. Luke's H Q S ~ . Med. and Surg. Rep. 1917 4; from Physiol. Abstr. 1918 2 587). -A mixture prepared by adding three parts of amyl alcohol to seven parts of phenyl ether is advocated for the prevention of foaming in analytical work. A colorimetric method for the estimation of iron in urine is described the iron being precipi- tated with ammonium persulphate and ammonia incinerated and the ash moistened with potassium thiocyanate. The iron content of normal urine varies from 0.06 to 0012%. For the estimation of chlorine in blood the proteills are coagu- lated by the addition bf acetic acid and heating the mixture. After filtration potassium alum and sodium carbonate are added and the mixture is boiled and filtered and the yellow filtrate is titrated with standard silver nitrate until a permaaent red colour is obtained. W. G.

ISSN:0368-1769    

DOI:10.1039/CA9181405123

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

i. 136 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemist rg. Applications of Gas Analysis. 111. Apparatus for the Study of the Respiratory Exchange in Small Animals. A. L. PRINCE (J. Biol. Chem. 1917 32 333-336).-The apparatus described is suitable for the study of the respiratory exchange in rats and similar animals and for teaching purposes. Applications of Gas Analysis. VI. Respiratory Exchange and Indirect Calorimetry. YANDELL HENDERSON ( J . BjLo1. Clicrn. 1918 33 47-53).-A simple spirometer is described which permits the measurement of the expired air and the analysis of a sample of i t by the methods previously detailed (see this vol. ii 81). Directions for the calculation of the respiratory quotient and exchange are appended. Applications of Gas Analysis. 11. Carbon Dioxide Tension of the Venous Blood and the Circulation Rate.YANDELL HENDERSON and A. L. PRINCE (J. Biol. Chem. 1917 32 325-331. Compare A. 1917 ii 506).-The authors describe a simple method for estimating the carbon dioxide tension of venous blood. The subject makes the deepest possible expiration into an empty rubber bag. After a few minutes the expired air is inhaled and after being retained for ten seconds in the lungs is again expired into the bag. This procedure is repeated a t iiitervals five or six times and then the estimation of the percentage of carbon dioxide gives the required carbon dioxide tension of the venous blood of the patient. Relationship between Cholesterol and Cholesterol Esters in the Blood during Fat Absorption. ARTHUR KNUDSON (J.Bid. Chem. 1917 32 337-346. Compare Bloor A. 1916 i 450; Bloor and Knudson A. 1917 i 236).-During fat absorp- tion in dogs the cholesterol in the blood remains unchanged but the amount of cholesterol esters in both plasma and corpuscles increases the increase being most marked in the corpuscles. dimilar changes are1 observed in the lecithin and total fatty acids of the plasma and corpuscles; indeed a fairly constant relationship between lecithin cholesterol esters and total fatty acids in the blood is noted. The blood corpuscles evidently play a very important part in f a t metsbolism. H. W. B. H. W. B. H. W. B. H. W. B.PRY SIOLOGICAL CHEMISTRY. i. 137 The Amount and the Distribution of Creatine and Creatinine in Normal Human Blood. ANDREW HUNTER and WALTER R.CAMPBELL ( J . Biol. Chem. 1918 33 169-191).-The amount of creatinine in normal human blood plasma ranges under different conditions from 0.7 t o 1.3 mg. per 100 c.c. average 1 mg. and it is practically certain that it is distributed through corpuscles and plasma in uniform concentration. It is apt to be lower in the female than in the male and lower in sedentary than in active subjects. Creatine is chiefly coiicentrated in the corpuscles ; roughly it may be said that corpuscles contain G to 9 mg. per 100 c.c. whilst plasma contains but 0-4 t o 0.6 rng. The blood as a whole seems on an average to contain about 3 mg. per 100 C.C. There seems to be more in the blood of females than in that of males. There is a distinct correspondence between increase of plasma creatine and the appearance of creatine in the urine.Amino-nitrogen and Dextrose in Lymph and Blood before and after the Injection of Nutrient Solutions in the Intestine. BYRON M. HENDRIX and JOSHUA E. SWEET ( J . Biol. Chem. 1917 32 299-307).-In a fasting dog the thoracic lymph contains less amino-nitrogen but more dextrose than the blood. After the injection of milk peptone or amino-acid solutions into the intestine the amino-nitrogen in both the blood and the lymph increases but the amount in the lymph is greater than in the blood. The intro- duction of sugar solutions into the intestine is followed similarly by a large increase in the dextrose content of the lymph and a smaller rise of the dextrose in the blood of the general circulation. I n some cases the dextrose in the lymph approximates in amount to that present in the mesenteric veins.The authors suggest that. absorption of dextrose and amino-acids takes place into both lymph and blood but as the volume and rate of flow of the blood are so much greater than those of the lymph the concentration of dextrose and amino-acid attained in the former is correspondingly less than in the latter fluid. A. J. G . H. W. B. Use of Indicators €or the Colorimetric Determination of the Hydrogen-ion Concentration of Sera. ANNIE HOMER (Biochem. J. 1917 11 283-291).-Six out of fifteen indicators examined can be applied to the colorimetric determination of hydrion concentration in sera using the Il7alpole colorimeter. Neutral red gives accurate results over the range y,=5'9-7.6 whilst dibromoeo-cresolsulphonephthalein is satisfactory for pH = 5.2-5-4 and tetrabromophenolsulphonephthalein for p = 3.0.a-Naphtholphthalein phenolsulphonephthalein and dibromo- thymolsulphonephthalein the respective ranges of which are pH= 7-6-8.5. 6.5-8.4 and 6.0-7-6 in pure solutions indicate consistently low values of pH (that is high acidities) when used with sera but as the differences are fairly constant for sera con- taining 4-10% of protein and as a rule do not exceed one unit these indicators can be employed in routine work if suitable correc-i. 138 ABSTRACTS OF CHEMICAL PAPERS. tions are made. Each operator should determine the necessary corrections by making comparative determinations of pi on the same sera colorirnetrically and electrometrically.By the colori- metric method i t is possible to determine rapidly the amount of acid or alkali required to adjust the reaction of a serum t o any given value within the useful raiige of any of the indicators men- tioned and also by interpolation t o certain intermediate values not amenable to direct colorimetric observation. J. H. L. Influence of the Heat Denaturation of +-Globulin and Albumin on the Nature of the Protein appearing in Con- centrated Sera. ANNIE HOMER (Biochem. J. 1917 11,292-306). -The extent of the denaturatioii of the proteins in antitoxic sera a t 57-5O (compare A. 1916 i 614; 1917 i 497) as measured by their increased precipitability by ammonium sulphate a t 30% of saturation attains its maximum after four hours’ heating when the reaction of the liquid is alkaline but after only one hour when the reaction is acid; the nature of the changes involved appears to be different in the two cases.Tables and curves are given showing the influeiice of hydrion concentrations between p = 9.5 and 4.5 011 the denaturation of albumin and $-globulin when their aqueous solutions are heated for six hours a t 57.5O. Further tables show the precipitating power of various concentrations of ammonium sulphate with respect to solutions of albumin and $-globulin of reaction pH=8 before and after heating for six hours a t 57.5O. From the observations made it is concluded that in the concentration of antitoxic sera by methods involving thermal denaturation of the proteins the preliminary heating a t 57.5O should be continued for four to five hours if the reaction of the serum is on the alkaline side of prr=7.By employing ammonium sulphate a t 44% instead of 50% of saturation for the precipita- tion of the second fraction from thermally denaturated sera com- plete precipitation of the $-globulin (and therefore of the anti- toxin) is attained whilst the proportion of albumin appearing in the second fraction is considerably reduced. The final product is thereby rendered lighter in d o u r and more potent. The Formation of Lactose from Starch by the d l Loosened” Ferments of Sucrose Serum. F. ROHMANN (BiocTzenz. Zeitsch. 7 917 84. 399-401).-The parenteral injection of siicrose into rabbits gives rise t o special ferments in the serum ( ‘ f hervorgelockte Fermente”). The extract of the liver of a rabbit thus treated acts on soluble starch causing degradation and producing ainoiigst other products lactose.Occurrence of Lichenase in the Digestive Tract of In- vertebrates. MINNA E. JEWELL and HOWARD B. LEWIS (J. Biol. Chem. 1918 33 161-167).-Lichenii1 the complex carbohydrate in Iceland moss is readily hydrolysed by the enzyme lichenase which is found iii various invertebrates but not in vertebrates. The enzyme occurs usually in the pancreas but in smaller animals J . H. T,. S. B. S.PHYSIOLOGICAL CHEMISTRY. i. 139 the aliment'ary tract may be taken as a whole for the preparation of the enzymic extract. The behaviour of t.he pancreatic extract to lichenin constitutes therefore a chemical method of differentiating between vertebrate and invertebrate animals.H. W. B. The Inter relation of the Surviving Heart and Pancreas of the Dog in Sugar Metabolism. A. H. CLARK ( J . Exp. lvetl. 1917 26 721-724; from Physiol. Abstr. 1918 2 678-679).- When the pancreas of a dog is perfused aseptically with Locke's solution containing physiological concentration of dextrose the optical rotation of the perfusate is diminished but its reducing power is unaltered. Similar results are obtained when a mixture of dextrose and sugar-free pancreatic perf usate is incubated and the osBzones from these perfusates have lower m. p.'s than glucos- azone. When a pancreatic perfusate containing dextrose is circu- lated through the living heart the above changes occur and in addition the reducing properties of the perfuqate are altered.These phenomena are believed to be due to an enzyme or enzymes obtained from the perfused pancre'as. It is suggested that these enzymes have a specific action on dextrose lzvulose being un- changed when perfused and that they are responsible for the pre- paration of that sugar for normal utilisation. Nothing definite can be stated as to the degree of condensation produced or the nature of the polysaccharides formed. Influence of Thyroid-€ceding on Carbohydrate Metabolism. I. Storage and Mobilisation of the Liver Glycogen in Thyroid-fed Animals. 11. Amount of Adrenaline in the Adrenals of Thyroid-fed Rats. 111. Acidosis in Experi- mental Hyperthyroidism and its Relation to Adrenaline in the Blood and the Decrease of Liver Glycogen. SHIGENOBU KURIYAMA (J.Biol. Chem. 1918 33 193-205 207-213 215-227).-Feeding an animal with thyroid gland causes a rapid disappearance of glycogen from the liver. The author now shows that a formation of glycogen in the liver of an animal fed on thyroid gland and carbohydrate occurs only when the amount of carbohydrate administered is exceedingly large. The increased diastatic activity of the liver which these results indicate may be due to the acidosis which is likewise induced by feeding with thyroid gland although the simultaneous administration of sodium hydrogen carbonate fails to depress the diastatic activity as it does in the normal animal. There does not seem t o be any connexion betweeii hyperthyroidism and excessive activity of the adrenals. The amount of adrenaline in the adreiials of animals fed with thyroid gland is riot greater than in those of normal animals; the glands are also not increased in size.Nutritive Factors in Animal Tissues. I. THOMAS B. OSBORNE and LAFAYETTE B. MENDEL [with EDNA L. FERRY and Preparations of niuscle (meat extract meat powder etc.) contain W. G. H. W. B. ALFRED J. WAKEMAN] ( J . B i d . Chem. 1917 32 309-323).-i. 140 ABSTRACTS OF CHEMICAL PAPERS. protein suitable for nutritional purposes but are unable to pro- mote the growth of rats owing t.0 a lack of the water-soluble vitamine. Dried pig’s liver contains both protein and vitamine and charts are given which depict the rapid growth which occurs when this material is the sole soiirce of protein in the diet. H. W. B. Composition and Digestive Activity of Different Fractions of the Pancreas.K. A. NELSON and J. H. LONG (J. Amw. C’hem. Suc. 1917 39 1766-1778. Compare A. 1915 i 1025) -A more complete account of the distribution of the enzymes in the three layers into which mimed pancreas can be separated by centrifugation at a very high speed. Amylopsin is mostly found in the middle liquid layer which is more active than the non-centri- fuged pancress; trypsin is found in all the fractions but chiefly in the solid ones; lipase and esterase are mainly present in the solid layers. The pancreas of the hog compared with that of the ox or sheep is chiefly remarkable for the enormous amylolytic activity of its liquid layer whilst i t also exceeds these in lipolytic power. The proportions of fatty liquid and protein layers in the three cases are also recorded and analyses given of the soluble solids found in the liquid layer.11. J. C. W. The Physical Chemistry of Cell Membranes. L. BERCZELLER (Hiochem. Zeitsch. 1917 84 59--74).-The tendency of sub- stances t o accumulate a t the surface of cells is discussed in con- iiexion with the surface tension of solutions. Stalagmometric measurements of extracts of organs are given. S. B. S. The Action of Animal Tissue on Methylene-blue. T. THUNBERG (Skand. Arch. Phgsiol. 1917 35 163-195 ; from Physiol. Abstr. 1918 2 655).-A detailed study of the dehydro- genation of succinic acid by ‘‘ dehydrogenase ” and methylene-blue and a full theoretical discussion of the reaction (compare this vol. ii 87). W G . C. XEUBERG and K. SCHWARZ (Berlin.KZin. Tl’ocA. 1917 54 84-87; from Yhysiol. A b s f r. 1918 2 584) .-The non-photosensitive substances of animal and plant tissue become photosensitive in the presence of certain inorganic salts particularly those of iron. These salts act as photocatalysts taking oxygen from the air and passing it on to the organic light receptors. Under these conditions leuco- compounds and quinol pass into the quinonoid forin the change being reversible. Proteins are 21so affected. This photosensitivity is increased by the application of mineral waters containing heavy metals. Theory of the Biochemical Action of Light. W. G . The Possible Origin of the Toxicity of Ultra-violet Light. F. I. HARRIS and H. S. HOYT (Science 1917 46 318-330; from Physiol *4 bstr. 1918 2 656).-Paramoecia were experimentedPHY SIOLOGTCAL CHEMISTRY.i. 141 with. Ultra-violet rays are detosicatecl by passage through solu- tions of gelatin peptone amiiiobenzoic acid cystine tyrosine and leucine the protective action of tyrosine being exceptionally marked in alkaline solution. Solutions of other substances investigated had no appreciable effect. These results agree with the view that the susceptibility of protoplasm to ultra-violet light is conditioned by the selective absorption of the toxic rays by the aromatic amino- acid racticles of the protoplasm. Proteins of Cow's Milk. Taow~s B. OSBORNE and ALFRED J. WAKEMAN [with CHARLES S. LEAVENWORTH and OIWEN L. NOLAN] (.I. Biol. C'J2u1n. 1918 33 7-17).-After the caseinogen has been removed from skim milk by precipitation with dilute sulphuric acid the rerriainiiig proteins are thrown out by saturation with ammonium sulphate and subsequently separated by treatment with magnesium sulphate.Lactoglobulin is insoluble in saturated magnesium sulphate solution and contains 2.2% of phosphorus. Wheii it is digested with alcohol a phosphatide appears to be split off and the remaining coagulated lactoglobulin now contains only 0.24% of phosphorus. A similar cleavage of phosphatide from vitellin occurs when it is treated with alcohol and the authors suggest' that' these so-called globulins are really lecithalbumins or mistures of proteins. Lactalbumin is soluble in saturated mag- nesium sulphate solution and is practically free from phosphorus. Although traces of proteoses can always be isolated from cow's milk it is uncertain whether these substances are present as such in the fresh milk or are formed from the proteins by the reagents employed for their isolation.The " nucleon " described by Sieg- fried (A. 1897 ii 219) is shown by the authors to consist probably of a mixture of uncoagulable protein and a still unidentified organic substance which yields phosphoric acid on hydrolysis. By extraction of precipitated caseinogen with alcohol a new protrin is obtained which resembles the gliadin of wheat in its solubility in 50 to 80% alcohol. [See also J . Soc. Chem. Znd. 19 18 March .] The Excretion of Substances Foreign to the Organism in the Urine. L. BERCZELLER (Biochem. Zcitsch. 1917 84 75-79).-Attention is directed to the fact that in the case of foreign substances excreted as conjugated or otherwise altered derivatives the surface tensions of the latter in aqueous solution are greater than that of those of the former.Examples benzoic acid aiid hippuric acid menthol and menthol glycuronate phenol and phenolsulphonic acid phenol catechol and quinol. IV. G . H. W. B. S. B. S. Citric Acid in Urine. S. AMBERG and W. B. MCCLURE (Awe?.. J. Physiol. 1917 44 453-462; from Physiol. Abstr. 1918 2 683).-Citric acid can be detected in human urine by Kunz's pentabromoacetone method or by Salant and Wise's method a modification of DenigGs's reaction. Preliminary experimentsi. 142 ABSTRACTS OF CHEMICAL PAPERS. indicate thak about 500 ing. of citric acid are voided daily in the urine. w. a. Salicylates .IX. Question of Salicyluric Acid in Salicyl Urines. PAUL J. HANZLLK (J. Pharm. &per. Ther. 1917 10 461-490).-The author has been unable to isolate any salicyluric acid from urines after administration of salicylic acid although all the methods for its isolation which have been published have been employed. I n each case only impure salicylic acid containing no glycine has been obtained. It appears improbable therefore that salicylates are converted into salicyluric acid in the human or animal organism. €1. W. B. Acidosis. IX. Relationship between AIkali Retention and Alkali Reserve in Normal and Pathological Individuals. WALTER W. PALMER and DONALD. VAN SLYKE (J. Biol. Chem. 1917 32 499-507. Compare A 1917 i 523).-Iii normal persons the urine becomes more alkaline than the blood (pH=7-4) when the carbon dioxide present as hydrogen carbonate in the plasma exceeds 71 +5 volumes per cent.In most pathological cases the urine does not become more alkaline than the blood until a higher level of hydrogen carbonate has been reached than in normal individuals. If therefore the administration of sodium hydrogen carbonate to a patient is continued until the urine turns alkaline unnecessarily large aiid perhaps iiijurious quantities of hydrogen carbonate may be given. The therapeutic use of sodium hydrogen carbonate should theref ore be controlled by estimations of the hydrogen carbonate in the plasma. The alkali retention test (feeding with sodium hydrogen carbonate until the urine shows an alkalinity of pH =.7*4) indicates a greater acidosis than actually exists.If a positive result is obtained it" should be confirmed by blood analysis before being accepted . H. W. B. The Nitrogenous Extractives of Tumours. JACK CECIL DRUMMOND (Biochenz. J. 1917 11 246-254).-Four kinds of tuniours of human and avian origin were extracted with boiling water and after treatment with basic lead acetate the extracts were investigated in respect of their nitrogenous constituents. I n general the purine fraction was largest; adenine was found in all cases and guanine xanthine and hypoxanthine in some. Small quantities of histidine carnosine and (probably) arginine were isolated from the avian tumour (Rous chicken sarcoma). Tyrosine and creatinine were present in all and leucine in most cases (com- pare A.1916 i 866). Formation of Creatine. Effects on the Excretion of Creatine in the Bird produced by Paraformaldehyde and Hexamethylenetetramine given separately and combined with Arginine Carbonate and other Substances. WILLTAM HENRY THOMPSON (Biochem. J. 1917 11 307-318).-1t is sug- gested that formaldehyde which probably takes part in the pro- J. H. L.\%GET-4BLE PHYSIOLOGY AND AGRICULTURE. i. 143 ductiou of rnethylatecl coinpouiids such as betaine in plants and in the muscles of invertebrates is formed also in the muscle tissue of vertebrates and is disposed of by combination with a guanidine nucleus to form creatine. The increased excretion of creatine following the administration of arginine to ducks with their food (A. 1917 i 673) becomes greater if parsformaldehyde is administered a t the same time although the latter alone has no effect. Paraformaldehyde ingested together with glycine sarcosine or guanidine carbonate also increases the production of creatine.Very much larger increases (in some cases six to eight times the normal amount) are produced by subcutaneous injection of para- formaldehyde alone or with arginine . Hexamethylemtetramine produces similar effects. The mechanism of the formation of creatine from arginine and formaldehyde in vivo is represented as involving conversion of the arginine into glycocyamine (compare Baumann and Hines A. 1917 i 677) methylation of the amino- group of the latter by interaction with two molecules of form- aldehyde (compare Werner T. 1917 111 844) and isomeric change of the product into creatine by migration of the methyl group. J. H. L. Lacquer Poisoning. I. TOYAMA and T. KAYABA (Hzf ukicci Ifitsi~?i.yokiliuw Za.sslii 1916 16 No. 7 7-10; from Physiol. -1 bstr. 1918 2 693).-Lacquer poisoning may be produced in susceptible individuals by passing iiear a lacquer tree or through a store containing lacquered articles. The poisoning is probably not due to a volatile constituent. The chief constituent of lacquer is urushiol the chief poison having the composition C,,H,,*C,€X,(OH),. Lacquer also contains a hydrated and a methylated urushiol which are toxic and a dimethylated and a hydro-dimethylated urushiol which are non-toxic (compare Majima A. 1908 i 437; 1909 i 402 945; 1912 i 883). Surface Tension of Solutions of Alkaloids. L. BERCZELLER and 111. SEINER (Bioch en2. Zeitsch. 1917 84 80-105) .-Stalagmo- metric measurements of solutions of salts of alkaloids with addi- tions of varying amounts of alkali carried out with the object of illustrating T r y be’s theory of the connexioii between surface tensions of solutions and troxic action. ?V. G. S. B. S.

ISSN:0368-1769    

DOI:10.1039/CA9181400136

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

G. 141 General and Physical Chemistry. Determination of the Carrier in the Emission of the Continuous Spectrum by the Hydrogen Canal Rays. J. STARK M. GORCKE and M. ARNDT (Ann. Physz'k 1917 [iv] 54 81-110. Compare A. 1917 ii 281).-The conditions under which the ultra-violet continuous spectrum is emitted by hydrogen canal rays have been investigated and an attempt is made to identify the entities which are directly responsible for this radiation. The intensity of the continuous spectrum increases as the wave- length diminishes from A400 to h240 and the increase is particu- larly marked in the region from A280 to h240. The distribution of the intensity is independent of the velocity of the hydrogen canal rays. The continuous spectrum is emitted by the hydrogen canal rays in oxygen and the intensity of this spectrum as well as the dis- tribution of the intensity are the same as for the spectrum emitted by the canal rays in hydrogen.A continuous spectrum is also emitted by nitrogen canal rays in nitrogen and by oxygen canal rays in oxygen but for cathode falls of potential varying from SO0 to 8000 volts the intensity of this spectrum is less than one-tenth of the intensity of the continuous spectrum emitted by the hydrogen canal rays. Nitrogen canal rags in hydrogen give rise to the emission of the hydrogen series lines in considerable intensity but' there is no appreciable continuous radiation even when tho cathode fall of potential reaches 8500 volts. From these observations the conclusion is drawn that the emission of the continuous spectrum in question is characteristic of hydrogen.The facts suggest that the radiating entity is neither the hydrogen ion nor the neutral hydrogen atom but that the continuous spectrum is due to an intermediate type in which the hydrogen ion is combined or associated with an electron the com- bination representing a transition phase in the reversible change H+@= H. H. M. D. Experimental Facts and Bohr's Theory of the Hydrogen Spectra. J. STARK ( A m . Physik 1917 Liv] 54 111-116).-A theoretical paper in which the author discusses recent observations on the continuous ultra-violet hydrogen spectrum in relation to Bohr's theory. The experimental evidence adduced in support of the view that the entities responsible for the emission of the con- tinuous spectrum contain a single atom of hydrogen (compare pre- ceding abstract) is considered to prove the untenability of Bohr's theory in its present form.Bohr's model of the hydrogen mole- cule is also incapable of affording an account of the facts which VOL. CXIV. ii. 9ii. 142 ABSTRACTS OF CHEMICAL PAPERS. have led the author to the opinion that the many-lined spectrum is attributable to diatomic combinations carrying a single positive charge. H. M. D. Measurements in the Spectrum of Molybdenum accord- ing to International Normals. MARTHA PUIILMANN (Zeitsch. wiss. Photochem. 1917 17 97-131) .-Measurements of the wave- lengths of lines in the arc spectrum of molybdenum have been made with the aid of a large concave grating. The results obtained for the region A2420 to A4888 are recorded and compared with those given by Exner and Haschek.It has been suggested by Paulson that certain pairs of lines exhibit constant frequency differences but the existence of this relation is not supported by the author's measurements. H. M. D. The Arc Spectrum of Tungsten according to Inter- national Units. MARIA BELKE (Zeitsclt. wiss. Photochen~. 1917 l a 132-142 145-168) .-Wavelength measurements of the lines in the arc spectrum of tungsten between A2249 and A6984 are recorded and compared with the results previously obtained by Exner and Haschek. The existence of pairs of lines with constant differences of frequency is not indicated by the measurements. . H. M. D. Colour of Inorganic Compounds. F. RUSSELL VON BICHOWSKY (2 Amer. Chem. SOC.1918 40 500-508).-A theoretical paper in which an attempt is made to connect the colour of inorganic substances with the valence electrons and the stability of the electron grouping round the positive nucleus. The Polymorphism of certain Substances (Liquid Crys- tals and Sphaerolites with Helicoidal Winding). PAUL GAUBERT (Bull. SOC. franq. Min. 40 5; from Chem. Zentr. 1917 ii 806-807. Compare A. 1916 ii 604; 1917 ii 113).-Amy1 cyanobenzylideneaminocinnamate has been found to exist in four different crystalline modifications. The stable &form is biaxial optically negative and has a high rotatory power; it is obtained by crystallisation of the fused substance or by evaporation of solutions. The P- and y-forms are sphzerolitic and distinguished by differences in rotatory power; they are obtained by the rapid evaporation of solutions.The fourth modification is that described byvorlander and Huth (A.) 1911 ii 165). Anisylideneaminoazotoluene exists in five different crystalline forms which are all biaxial. The stable a-form is monoclinic or triclinic and the other four are probably rhombic. There are also two liquid anisotropic forms of this substance one of which is optically positive and the other negative. The cholest'eryl esters of low freezing point readily form liquid crystals when their solutions are evaporated. A difference in the tendency t o form solid crystals has been observed according to the optical charact'er of the liquid phase. H. M. D. R. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 143 The Photolysis of Uranium Salts.E. BAUER (Schzoeix. Cherri. Zeit. 1918 2 40-41).-\Vhen light is absorbed by a solu- tion of a uranium salt the uranyl ion undergoes a reversible change from the ‘‘ dark ” condition into the “light ” condition ; when the reverse action takes place the light energy absorbed is given off again in the form of fluorescence. The addition of certain substances such as chlorine or iodine ions ferric and vanadyl salts vanadic acid and quadrivalent uranium salts extinguishes the fluorescence. The same substances also destroy the Becquerel effect. I n the “light” condition the uranium is resolved into a higher (octavalent) and a lower (tervalent) stage of valency and the two reunite to the sexavalent form in revert- ing to the “dark ” condition. When an inhibiting substance is added the formation of the intermediate products is prevented because they are immediately taken u p by the substance for example iodine to form the sexavalent ion.Under the influence of light uranyl formate ,is decomposed with liberation of carbon dioxide and hydrogen a reaction in which the octavalent uranyl ion plays a part. The reaction dies down again through the accumulation of the sexavalent ion which acts as an extinguisher. Another instance of photolysis is the decomposition of oxalic acid by uranyl sulphate under the action of light’. I n this case the octavalent ,intermediate ion produces carbon dioxide and the ter- valent ion carbon monoxide whilst the sexavalent ion is recon- stituted Analogous processes of simultaneous oxidation and reduction are held to account for the photosensitising effects of other fluorescent compounds such as eosin.J. F. B. The Photolysis of Uranyl Formate. E. C. HATT (Zeitsclz. physikal. Chem. 1918 92 513-562).-The decomposition of solutions of uranyl formate under the influence of light has been further examined with a view to the determination of the influence of the concentration of the uranyl salt the intensity of the light and the presence of foreign substances. The experiments with varying concentration indicate that. the photolysis is retarded by the uranous salt which is one of the pro- ducts of the light reaction. For widely varying light intensities the initial velocity of the reaction is proportional to the intensity of the light but a t later stages the velocity increases less rapidly than the intensity of the acting light.Potassium chloride potassium iodide ferric chloride vanadyl sulphate and vanadic acid retard the reaction but potassium sulphite appears to produce no change in the velocity of the reaction. The view that uranium compounds of higher and lower valency are formed is rendered probable by the factl that the insolated solutions have an oxidising action on potassium iodide and a reducing action on potassium permanganate. I n terms of the oxidation and reduction products i t is possible to explain a number of facts which have been estab- lished in this and previous investigations of the photochemical decomposition of uranyl formate (compare A. 1916 ii 9). 9-2ii. 1.44 ABSTRACTS OF CHEMICAL PAPERS.A method for the estimation of uranous salts in presence of iormic acid is described. The uranium solution 'acidified with sulphuric acid is added to a solution containing ammonium acetate and sodium phosphate placed in a cylindrical separating funnel connected below with a suction pump through a filter bottle. The funnel is provided with a Gooch filter and with an attachment by which the air in the funnel can be replaced by hydrogen. The mixture of uranyl ammonium phosphate and uranous phosphate which is precipitated is filtered by suction in the hydrogen atmo- sphere the precipitate washed with ammonium acetate solution and then dissolved in sulphuric acid (1 :4) the solution thus obtained being titrated with standard permanganate. This method of estimating uranous salts has been found to give quite satisfactory results in the investigation of the insolated uranyl formate solutions.H. M. D. The Scattering of a-Rags as Evidence on the Parson Magneton Hypothesis. DAVID L. WEBSTER (J. Amer. Chenz. SOC. 1918 40 375-379).-The large-angle scatt.ering of a-rays is generally considered to prove the untenability of theories of atomic structure which postulate large diffuse spheres of positive elec- tricity. The magneton hypothesis put forward by Parson (Smith- sonian Jliscellaneous Collections 1915 65 No. 1 l) postulates such a structure but the author contends that this is not really an essential feature and thatl the a-ray scattering cannot be accepted as valid evidence against the magneton theory. H. 31. D. Absorption Laws €or R6ntgen Rays.K. GLOCKER (Pl~ysilcnl. Zeitsch. 1918 19 66-72).-This paper contains a discussion of the laws expressing the absorption coefficient of X-rays as a func- tion of the wave-length and atomic number of the absorbing element and contains tables of the various constants involved in the formulze for ten elements and six compounds The data are of practical and theoretical importance but the paper cannot be suitably abstracted. F. S. X-Ray Spectra and the Constitution of the Atom. L. VEGARD (PI&?. Mag. 1918 [vi] 35 293-326).-An account of work previously described (compare this vol. ii 93 94). The periodic variation of the electric conductivity of the elements (Benedicks Jahrb. Radioalctiu. Elektronik 1916 13 362) is con- sidered to afford support f o r the configurations which are put for- ward by the author.H. M. D. Solubility of Pure Radium Sulphate. S. C. LIND J. E. UNDERWOOD and C. F. WHITTEMORE (,7. Amer. Chem. Soc. 1918 40 465-472).-1f a solution containing a mixture of radium and barium salts is partly precipitated by the additdon of a sulphate the ratio of radium to barium in the precipitat'e is the same as in the original solution. The behaviour resembles that which is metGENERAL AND PRY SICAL CHEMISTRY. ii. 145 with in the case of the isotopic elements and has not yet been satisfactorily explained. With the object of providing data which may serve t o elucidate the nature of the phenomenon the authors have determined the solubility of pure radium sulphate in water and in sulphuric acid solutions. The measurements were made by dissolving the salt and also by precipitating it from solution.The mean value obtained f o r the solubility in water a t 2 5 O is 2.1 x 10-8 grafn per c.c. which is about onehundredth of the solubility of barium sulphate. The presence of sulphuric acid up to 50% has no appreciable influence on the solubility. A t higher acid concentrations the solubility increases rapidly the data obtained showing that the solubility is more than twelve times as great in 70% acid as in 60% acid. I n dilute acid solutions the solubility increases about 50% when the temperature is raised frdm 25O to 35O and the same increase is found when the temperature is raised to 4 5 O . .The observed value of the solubility of radium sulphate is in ageement with that expected from a comparison of the solubilities of the sulphates of calcium strontium and barium.The term pseudo-isotopy is given to the phenomenon which is exhibited by radium and barium sulphates. H. M. D. Radioactivity of the Lake of Rockange. (MISS) H. J. FOLMER and A. €1. BLAAUW (Proc. K . Akad. TVetensch. Amsterdam 1918 20 714-735)=-A detailed account is given of the investi- gation of the radioactivity of samples of mud obtained by borings to different depths from the floor of the lake of Rockange (Hook of Holland). I n contradiction to certain previous observations the authors’ results lead to the conclusion that the alluvial mud of the lake possesses no radioactivity of importance. The figures obtained correspond with an average value of the order of 10-12 gram of radium per gram.With regard to the origin of this i t is suggested that the radioactive substance in the mud is for the most part brought down by the rivers and does not come from the dunes. H. M. D. Electrical Conductance of Solutions in Bromine. EDWARD H. DARBY ( J . Anzer. Chenz. Soc. 1918 40 347-356).-Trimethyl- ammonium chloride is readily soluble in liquid bromine producing solutions of a yellow colour the viscosity of which increases very rapidly with the concentration. The electrical conductivity of these solutions has been measured a t 1 8 O with results which show that the equivalent conductance of the salt. increases from 0.3186 a t c = 0.09076 gram-equivalents per litre to 11.49 atl c = 1.2356. The variation of the conductance with the concentration is in agreement with the equation of Kraus and Bray.The constants have values which are comparable with those obtained for electrolytes in other solvents. The conductance of trimethylammonium chloride is much greater than that obtained for iodine and phosphorus pentabromide,ii. 146 ABSTRACTS OF CHEMICAL PAPERS. the conductance of which in liquid bromine has been previously examined by Plotnikov and Rokotjan (A. 1913 ii 378). H. M. D. The Influence of some Hydroxy-acids on the Electrical Conductivity of Boric Acid. J. BOESEKEN and H. KALSHOVEN (Eec. trav. clzim . 1918 37 130-143).-1n continuation of previous work (compare-A. 1916 ii 73 209) the authors have examined the influence of glycollic a-hydroxy-P-phenylpropionic P-hydroxy-P-phenylpropionic and diglycollic acids on t h s electrical conductivity of boric acid.Glycollic acid gave an increase in the conductivity but the substitution of a group *O*CR,*CO,R for the hydrosyl group changed the' influence from positive t o negative as shown by the results with diglycollic acid. 6-Hydroxy- P-phenylpropionic acid is similar t o P-hydroxybutyric acid (Zoc. c i t . ) in its influence. The influence of a-hydroxy-P-phenylpropionic acid is positive and almost equal to that of lactic acid (Zoc. c i t . ) . W. G. The Influence of some Derivatives of Nitrogen on the Electrical Conductivity of Boric Acid. J. BOESEKEN [with W. STURM and G. GOETTSCH] ( R e c . trav. chim. 1918 37 144-1 61) .-The nitrogenous compounds examined were carbamide biuret alloxan alloxantin glgcino glutamic cyanuric and dialuric acids.dihydroquinazoline (quinoxaline) and the glycol of uric acid. The results indicate t h a t the presence of the group *NH*CO- has no influence on the electrical conductivity of boric acid and t h a t substances containing this group do not form com- plexes with boric acid. The results obtained with quinoxaline NH*?o for this compound. NH*CO favour the htonic formula C,H,< Glycine forms a complex boric acid derivative which is however dissociated t o a large extent judging from the slight increase in conductivity obtained. Alloxan in aqueous solution has X (5 x 10-9 and it does not form a complex with boric acid. Dialuric acid does not form a complex with boric acid. It has K = 6 x 10-5 the value diminishing rapidly probably owing t o oxidation.Alloxantin dissociates in aqueous solution into dialuric acid and alloxan. The glycol of uric acid slightly increases the T h e Influence of Boric Acid on the Electrical Conduc- tivity of Diacetyl. J. BOESEKEN [with G. VAN DER HOEH OSTENDE] ( R P c . frau. chim. 1918 37 162-164).-The results obtained althoiigh incomplete indicate that in concentrated solution diacetyl is dihydrated. It has an acid reaction in aqueous solu- tion halving I<= +4 x 10-7. The Influence of some Hydroxy-acids on the Electrical Conductivity of Boric Acid. J. ROESEKEN [with (MLLE.) J. WEISFELT (MLLE.) J. VAN DEE SPEK CHR. VAN LOON and G. GOETTSCH~ ( R e c . trnu. chim. 1918 37 165-178. Compare pre- ceding abstract) .-Four acids were studied.a-Hydroxyoctoic acid conductivity of boric acid. w. G. W. G .GENERAL AND PHYSICAL CHEMISTRY. ii. 147 like other a-hydroxy-acids gives with boric acid a complex having a high conductivity. Glyceric acid behaves like an a-hydroxy-acid the P-hydroxyl group having no influence on the conductivity. Dihydroxymaleic acid behaves in aqueous solution like a di-a- hydroxy-acid. Its decomposition is retarded by boric acid. With gluconic acid the increase in the conductivity is greater than that with the other a-hydroxy-acids the1 group :C(OH)*CO,H exerting its influence in addition to that of the four other hydroxyl groups. The opening of the lactonic ring may be followed by the’ regular change in the conductivity which increases with increase in the concentration of the hydrogen ions.W. G. The Influence of Boric Acid on the Conductivity of some Optically Active a-Hydroxy-acids and on that of their Racemates. J. BOESEKEN and L. A. VAN DER ENT (Rec. tmv. chim. 1918 37 179-183) .-Measurements of the electrical con- ductivity of T- and d-amygdalic acids and r- and d-tartaric acids in the presence of boric acid show that the influence of a racemic acid on the electrical conductivity of boric acid is equal to that of its active component. W. G. Free Energy of Dilution of Sulphuric Acid. MERLE RANDALL and 0. E. CUSHMAN ( J . Amer. Chem. SOC. 1918 40 393-397).- The E.M.F. of cells of the type H2 I H,SO I Hg,SO I Eg has been measured for widely varying sulphuric acid concentrations. From the results the authors have calculated the free energy of the reaction H + Rg,SO = H,SO + 2Hg for acids of different concen- tration.I n combination with previous data (compare A. 1914 ii 521) these results also give the free energy of formation of sulphuric acid from 1N hydrogen and sulphate ions. The numbers obtained are t’a bula t ed. H. M. D. Electromotive Force and Free Energy of Dilution of Lithium Chloride in Aqueous and Alcoholic Solutions. J. N. PEARCE and F. S. MORTIMER ( J . Amer. Chem. SOC. 1918 40 509-523).-Ths influence of the solvent on the E.U.F. of concentration cells has been systematically examined in experi- ments with solutions of lithium chloride in water and the five lowest alcohols of the series beginning with methyl alcohol. The concentration ratio was in all cases 10 1 the absolute concentra- tion of the stronger solution varying from 1-0 to 0.05 mol.of lithium chloride per litre. The data recorded are those obtained with cells of two types. I n the case of cells involving transference the E.M.F. increases with increasing dilution in water and the three lower alcohols but decreases with dilution in n-butyl and isoamyl alcohols. For cells arranged so that there is no transference the observed E.M.F. decreases with increase in the dilution in all the solvents examined. These relations indicate that the ionisation of lithium chloride is abnormal in all these solvents.ii. 148 ABSTRACTS OF CHEMICAL PAPERS. The transport number of the lithium ion the free energy of dilution and the activity ratios for both the ions and the non- ionised molecules have been calculated.The tramport number increases with the dilution whilst the fre9 energy of dilution and the activity ratios decrease with the dilution in all the solvents examined. An a,ttempt is made to account for these relations by the assunip- tion of effects due to hydration polymerisation and change in the dielectric capacity of the solvent#. H. ni. D. Effect of Interionic Force in Electrolytes. 11. S. R. MILNER (Phil. Nag. 1918 [vi] 35 352-364. Compare this vol. ii 54). -The author's view that the decrease in the molecular conduc- tivity of electrolytes with increasing concentration is to be attributed mainly to a reduction in the mobilities of the ions and not to a reduction in their number by their combination to form molecules is discussed further by reference t o the influence of interionic forces on the elect'rical conductivity and on the osmotic pressure.The theoretical investigation of this influence leads to the conclusion that a change in the concentration will produce identical variations in the conductivity and in the osmotic pressure of the free ions that is to say the ions which momentarily have no mutual energy with other ions. 'This result when applied t o strong electrolytes suggests that the observed changes in the conductivity and osmotic pressure of strong electrolytes with the concentration may be explained by a modification of the usual view. Interionic forces produce an increase in the frequency of occurrence of ions in an associated state and the result of this is a reduction in the osmotic pressure of the free ions.The average mobility of an ion taken over a period sufficiently long to include it in the free and associated state is reduced in the same ratio and the experimental facts are thus account'ed for. If this view is correct the ions of sttong electrolvtes are not associated into molecules but pairs of oppositely charged ions which are temporarily in closest proximity will behave iu a certain number of cases as if they were bound together. H. M. D. Alternating Current Electrolysis with Mercury Elec- trodes. HARRY B. WEISER ( J . Physical Chem. 1918 22 78-94). -When solutions of sodium thiosulphate are subjected to the action of an alternating current between metallic electrodes metallic sulphides are precipitated in quantities which increase as ths frequency of alternation decreases.The extent to which the electrodes are thereby corroded varies considerably with the nature of the electrode surface and reproducible results capnot be obtained with solid metals. When mercury electrodes are used the changes in the surface tension give rise to a rhythmical vibration of the mercury surface which maintains the electrode in its original condition and servesGENERAL AND PHYSICAL CHEIXISTRY. ii. 149 to agitate the solution in the immediat'e neighbourhood of the electrode. I n these circumstances reproducible results are obtained and experiments have been made in which the same frequency of alternation was used (72000 alternations per minute) but in which changes were made in the current density the temperature and the concentration of the sodium thiosulphate solution.The corrosion o€ the mercury electrodes increases with the current density but not in direct proportion. The departure from proportionality is greater in the more dilute solutions. The corrosion also increases with the concentration of the thiosulphate solution the two quantities being approximately proportional. When the concentration reaches a certain limit a film of sulphide is formed over the mercury surface and this greatly reduces the corrosion. The corrosion increases with rise of temperature and is increased by mechanical stirring. Under like conditions zinc electrodes are corroded t o a much smaller extent and although i t is probable that the above factors affect the deqree of corrosion as in the case of mercury variations in the electrode surface have a much greater influence on the actual result.H. M. D. Thermal Leakage and Calorimeter Design. WALTER P. WHITE ( J . Amer. Chem. SOC. 1918 40 379-393).-The factors wliich play a part in the interchange of heat between a calorimeter and its environment are considered more particularly with refer- ence to the influence of the surrounding air. The convection currents in this air are of considerable importance in that the thermal leakage due to convection is approximately proportional to the square of the difference between the temperatures of the calorimeter and its environment. The influence of convection may be diminished by reducing the width of the air gap round the calorimeter.It is shown that gaps of from 10 to 17 mrn. are most suitable for ordinary calorimeters but larger gaps may be used in the case of large calorimeters in which smaller temperature differences are involved. Thin reflecting shields may be advantageously employed to diminish the effect of conduction. H. M. D. Specific Heats at Low Temperatures of Sodium Potassium. Magnesium and Calcium Metals and of Lead Sulphide. E. D. EASTMAN and W. H. RODEBUSH (J. Amer. Chem. Soc. 1918 40 489-500).-On the assumption that C,=3R is the normal higher limit for the atomic heat of an element it would seem that the strongly electropositive metals have exceptionally large atomic heat capacities and in order to obtain further in- formation on this point measurements have been made of the specific heats of sodium potassium magnesium and calcium between 65O and 300° (abs.).The method used consisted in measnring the rise of temperature 9"j i . 150 ABSTRACTS OF CHEMICAL PAPERS. produced by a known quantity of electrical eiiergy supplied to the metal suspended in a vacuum the change of temperature being measured by means of a carefully calibrated copper-constantan thermocouple. From the values of G' derived from the experi- mental data the values of C were obtained by calculation accord- ing t o methods previously described. The results obtained show that the value of C becomes con- siderably greater than 3R=5*97 cal. over the higher portion of the range of temperatures examined. According to Lewis and Gibson ( J . Amer. Chem. SOC. 1917 39 2554) the curve which is obtained by plotting C; against the logarithm of the absolute temperature is a general curve which can be made t o fit the data for any one of a large number of elements by simple horizontal displacement. When the data obtained by the authors are examined in reference to this general curve i t is found that the points for sodium magnesium and calcium lie on the curve at lower temperatures but are situated above it at the higher temperatures.I n the case of potassium the values of C lie above the curve a t all temperatures examined. The deviations from the normal curve are considered to be due t o the heat capacities of the electrons the energy absorption of which is supposed t o depend on the degree of constraint t o which they are subjected in the atom.This constraint diminishes with increase in the electropositive chaxacter of the met,al. H. M. D. Boundaries of Existence of the Liquid State. W. HERZ (Zeitsch. Elektrochem. 1918 24 48-50) .-The author has collected and tabulated the melting points and critical tempera- tures of a number of elements halogen derivatives of non-metals and some organic compounds. It is shown on comparison that in the case of metals the region of existence of the liquid decreases with increasing atomic weight in a given group of the periodic system whilst for non-metals the region of existence increases. The same regularity holds for the halogen derivatives of the non- metals. I n the case of organic compounds the region of existence of the liquid increases with increasing molecular weight.The quotient critical temperature/melting point is approximately a constant for analogous groups of sitb&mces (see also Clarke A m w . Chem. J . 1896 18 618). J. F. S. The Cryoscopic Constant of Asymmetric Heptachloro- propane CCl,~CCl,-CHCl,. J. BOESEKEN and J. BENEDICTUS (Rec. trav. chim. 1918 37 121-129).-Determinations have been made with a large number of different substances and the results show that the heptachloropropane has a cryoscopic constant just under 120 but the solubility in it of hydroxy-compounds and acids is not' very great. Acids are strongly associated in this solvent even acids of high molecular weight giving values equal t o twice the theoretical molecular weight. Alcohols a t great dilu- tions give almost normal molecular weights but as the concentra-GENERAL AND PHYSICAL CREMISTRY.ii. 151 tion increases they become associated. Hydrocarbons chloro-com- pounds amines and esters behave normally. Formula giving the Saturated Vapour Pressure of a Diatomic Liquid. E. ARIBS (Compt. rend. 1918 166 417-450. Compare this vol. ii 61).-The author deduces the formula II = T ’ ’ ’ ~ ~ / X where x = [1+ { (1 - ;-)(O*S6 - ~))!(0*353~‘ + 0*642)].ri and shows that the calculated results agree with the observed results in the cases of chlorine and carbon monoxide. w. G. The Anomalies which the Saturated Vapour Pressures of certain Diatomic Liquids Show. E. A R I ~ S (Conzpt. yend. 1918 166 553-556).-The formula previously deduced from a study of chlorine and carbon monoxide (preceding abstract) applies also to hydrogen chloride and hydrogen iodide but in the cases of oxygen nitrogen and nitric oxide certain anomalies occur between the values as calculated and observed.W. G. TV. G. Thickness and Structure of the Capillary Layer of a Liquid in Contact with its Saturated Vapour. G . EAKKER (Ann. PJ~ysd. 1917 [iv] 54 245-295).-By making use or“ the Laplacian theory of capillarity and certain thermodyiiamic argu- ments it Ts shown that the number of molecules in the surface layer increases from about three a t the freezing point of the liquid to a very much larger number in the neighbourhood of the critical temperature. I n the case of carbon dioxide a t the reduced temperature 0*999O the number obtained lies between 300 arid 1800. Thermodynamic reasoning leads to the conclusion that the fhickness of the surface layer is about 1 .5 ~ ~ at the reduced temperature 0*9O whilst in the immediate neighbourhood of the critical temperature the thickness increases to a value represented approximately by half the wave-length of violet light. The thermodynamic method gives results which agree with those previously mentioned in so. far as the number of molecules in the surf ace layer is concerned. Since the number of molecules in the surface layer is very limited if the temperature is not in the neighbourhood of the critical temperature it follows that the radius of action of the attractive forces does not extend beyond the limits of the nearest molecules. This deduction is not compatible with the assumptions iiivolved in the original theory of Laplace.The Law of Thsrmochemical Processes (Summary) and of Photochemical Processes. MAX TRAUTZ (Zeitsck. anoq Chem. 1918 102 81-1 29) .-According t o the author’s theory reactions in gases take place only between molecules which are in an ‘‘ activated ” condition. A species of thermal isomerism of the molecule is assumed and the heat energy necessary to transform the inactive into the active modification is termed the “heat of activation.” I n the mass-action equations developed from thernlo- dynamic principles for reactions of the firstl and second orders the H. M. D. 9*-25. 152 ABSTRACTS OF CHEMICAL PAPERS. factor representing the heat of activation appears as an ex- ponential function and from two determinations of the velocity constant of a reaction at two different temperatures it is possible to calculate the heat of activation. The heat of activation is a fraction of the total heat of decomposition into atoms and this fraction can be calculated from the heat of reaction and the heat of activation.I n the case of the reaction H,+& F 2H1 for instance the fraction is between one-fourth and one-third. According to the author’s theory the time of contact between two “activated” molecules is of so short duration that the chance of simultaneous contact with a third activated atom is very smaI1 indeed. Reactions of a higher order than the second are therefore held t o bs impossible (compare A. 1915 ii 338 623 828; 1916 ii 304 422). The theory is applied t o photochemical reactions and equations are given for reactions of the first and second orders.The rela- tion of the heatl of activation to the frequency of the aclinic radia- tion is considered with special reference t o Planck’s radiation law which is deduced in a novel manner. Just as the course of a thermochemical reaction is determined by the smallest heat of activation to the exclusion of those reactions requiring greater heats of activation so a photochemical reaction is determined by the smallest radiation frequency to which the substance is resonant. The relation between heat of activation and radiation frequency is expressed by an equation q= RPu where- q is the heat of activa- tion and v is the frequency proper to the r’eaction. This frequency should be found in the spectrum of the reacting substances and ths possibility arises of determininq heats of reaction and heats of activation spectroscopically. The theory is examined in its’ relation t o Bunsen and ROSCO~S law and the law of photochemical equivalents.E. H. R. The Energy Theory of Matter. H. STANLEY REDGROVE (Cken2. News 1918 117 145-146. Compare A. 1917 ii 411). -In a recent paper (A 1917 ii 164) Thornton pointed o u t that a constant is obtained if the molecular heats of combustion of saturated hydrocarbons are divided by the corresponding numbers of oxygen atoms which are required for the complete combustion of the hydrocarbons. An attempt has been made (Vliet this vol. ii 98) to utilise this relation in the calculation of the contribution of the carbon and hydrogen at’oms and the valency bonds towards the heats of combustion of their conipounds.It is shown that t’he equation thus introduced is deducible from the equations given by the author and thus affords no additional basis for the calcula- tions in question. The author criticises the siqnificance of the relation indicated by Thornton and contends that. it is not generally applicable to diff ereiit groups of organic compounds. The advantages of the author’s theory as a basis for the com- putation of additive or partly additive properties are discussed in relation to other underlying hypotheses. H. M. D.GENERA& AND PHYSICAL CHEMISTRY. ii. 153 Equilibria Involving Cyanogen Iodide. The Free Energy of Formation Of Cyanogen. GILBERT N. LEWIS and DONALD B. KEYES ( J .Amer. Chem. Soc. 1918 $0 472-47$).-Tho reversible reactions represented by 2CNI (CN) + I and CNI+HI HCN+I have been examined and from the equil- ibrium data the free energy of formation of cyanogen has been calculated. The partial pressure of iodine in the saturated cyanogen iodide vapour was determined colorimetrically by comparison of this with the vapour given off by pure solid iodine the temperature of which was adjusted until the colours in the tu7o comparison tubes were equal. The partial pressure obtained in this way increases from 3-42 mm. at 90-Oo to 56.7 mm. a t 123.0O. From these partial pressures the equilibrium constant is calculated and the logarithms of these numbers when pIotted against the reciprocal of the absolute temperature fall very nearly on a straight line from the slope of which the heat absorbed in the dissociation is found to be 48,000 cal.By extrapolation the value of the equil- ibrium constant a t 2 5 O is obtained and this leads t o AF9,,=14,950 for the free energy of the reaction represented by 2CNI(solid)= When a mixture of solid cyanogen iodide and iodine is treated with a dilute solution of hydriodic acid the equilibrium repre- sented by CNI + H' +I' ;2 HC" + I is quickly established and methods are described by which the authors have found it possible to obtain the concentrations of the hydrogen and iodine ions and that of the hydrocyanic acid for a series of hydriodic acid solutions of varying strength. The values obtained for Ii = [HCN] /[H'][I'] are not very constant but by taking the mean value IT=13 the free energy of the reaction CNI(solid) + H' + I/= HCN(gas) + I,(solid) is found to be AF, = - 1520.Measurements of the partial pressure of hydrogen cyanide for aqueous solutions of varying concentration gave Plm =0.096 at 25O where P is the pressure in atmospheres and m the concentration in mols. per 1000 grams of water. From this ratio of distribution the value AF,,,=1390 is obtained for the reaction HCN(aq.)= RCN(gas). By combining these with values previouslv obtained the free enerqy of formation of cyanogen iodide according to t h s equation C(gas) + +IT2 + I(so1id) = CNI(so1id) is found t o be Combining this result with the equations for the free energy of dissociation of cyanogen iodide (see above) and the formation of iodine vapour from solid iodine the free energy of formation of cyanogen gas accordinq to the equation 26(gas) + N = (CN),(g;as) is found to be AF2,s=57,580.The Oxidising Power of Cyanates and the Free Energy of Formation of Cyanides. GILBERT N. LEWIS and THOMAS B. BRIGHTON ( J . arner. Ckem. Soc. 1918 40 482489).-Tha ex- periments described were undertaken with the object of providing data for the calculation of the free energy of formation of hydrogen (CN,)+I,(gas). AFq,,=38,635. 33. M. D.ii. 154 ABSTRACTS OF CHEMICBL PAPERS. cyanide a substance which is of considerable importance in con- nexion with the determination of the free energy changes associated with many different types of organic reactions. Fused pot’assium cyanide is oxidised by carbon dioxide and the fused cyanate is reduced by carbon monoxide.The equilibrium condition resulting from these opposed reactions has been examined by determining the value of K=[C02]/[CO] for the gas mixture in equilibrium with the eutectic mixture of potassium cyanide and potassium cyanate a t various temperatures between 7 2 1 O and 847O (abs.). Preliminary experiments showed that the eutectic tempera- ture is 555O (abs.) and that the mixture contains 14.6% of potassium cyanide. When the values of K are plotted against 1/T a straight line is obtained and by extrapolation to the temperature of the eutectdc point this gives R=0-89. From this value of I< the free energy of the reaction KCNO(solid)+ CO(gas) =KCN(solid) +- C02(gas) is found to be AF,,,= 126. This in combination with the value for the heat of the reaction a t the ordinary temperature AH =4300 cal.gives hF,,,= 2060 for the free energy of the reaction a t 2 5 O . From solubility and freezing-point data the free energy change msociated with the conversion of the solid salts into the corre- sponding ions in normal concentration has been found to be hFZg8= -2130 for potassium cyanide and AF298= -1440 for potassium cyanate. By combination of these results with the previous one the free energy of the change CNO’+ CO(gas) = CN’ + CQ2(gas) is found to be hFzs8= 1370. From this and free energy values previously derived it follows that for the reaction C(gas) + 4N -I- 0 = CN’ AF298=35,277 and since the free energy of formation of the hydrogen ion is taken as zero we have for &Ho + @(gas) + &N = H’ + CN’ = 35,277.This result in combination with AFQ,,=11,S56 for the free energy of the reaction HCN(aq.) =He + CN’ gives for the free energy of formation of hydrogen cyanide in accordance with the equation $H2 -+ C(,aac;) + JN2 = HCN(aq.) the value AF,,,=23,421. H. M. D. Gas Dilatometer for ascertaining Decomposition Points. W. C. MOORE and J. B. DAVIES ( M e t . and Chem. Eng. 1918 18 301-304).-The substance examined is heated in a vacuous glass test-tube placed vertically in a paraffin bath. Distillation products pass into a horizontal pipette-shaped air condenser sealed on to the test-tube and closed a t the other end by a U-shaped manometer filled with mercury. The pressure in the apparatus is plotted as the temperature rises. A discontinuity in the curve due to the rapid evolution of permanent’ gas is taken as the decom- position point.The results are influenced by rate of heating but when this was lo per minute up t o 150° and then slower the follow- ing results were obtained sucrose 178O dextrose 1 7 7 O and soluble starch 2 1 4 O whilst with cellulose (filter paper) a slow decomposi- tion commenced at 143O with further points a t 1 8 5 O and 204O. B. J. H.GENERAL AND PHYSICAL CHEMISTRY. ii. 155 Compressibility and Dilatability of Gases. A. LEDUC ( A m . Physique 1918 [ix] 9 5-28).-A detailed description of a piezo- meter which can be used to observe the gases succsssively a t pressures of 1 2.8 and 5 atmos. which has been used for neon and argon. The following are the values of the constants found for neon coefficient of departure from Mariotte's law -6*10-6 per cm.of mercury a t 1 7 O between 1 and 5 atmos.; molecular volume at Oo and 760 mm. 1.0004; atomic weight 20-15; coefficient of dilatation p=3664. 10-6 between 5O and 30°. For argon the values are coefficient of departure from Mariott'e's law 10.2. 10-6 between 1 and 5 atmos.; molecular volume 0.9990 atl Oo and 760 mm.; atomic weight 39*91+0*01; coefficient of dilata- tion p=3669.10-6 between 8 O and 3 2 O . W. G . Fluidity and Specific Volume of Aqueous Solutions. W. HERZ (Zeitsch. anorg. Chenz. 1918 102 173-176. Compare R. 1917 ii 361).-Curves are given showing that for aqueous solutions of a number of acids for example sulphuric and acetic alkalis such as sodium and potassium hydroxides hydrolysed salts such as sodium carbonate and ferric chloride and neutral sub- stances such as sucrose there is a direct! proportionality between the fluidity expressed in C.G.S.units and the specific volume. Even in the cBse of mixed solutions. for examde. a solution con- taining sodium and copper sulphates,' the propokiona1it.v holds. E. H. R. Soap Solutions. 111. VICTOR LENHER and GEORGE H. BISHOP ( J . Physical Chem. 1918 22 95-98).-The adsorption of sodium oleate by Ceylon graphite willow charcoal and animal charcoal has been examined by filtering a N/lO-solution through 30 cm. columns of the principal materials. Successivel fractions of the filtered liquid were analysed and the process continued until no further adsorption occurred. The results show that animal char- coal has a much greater adsorbent capacity than wood charcoal which in turn adsorbs sodium oleate more readily than graphite.H. M. D. Theory of Dyeing. H. R. KRUYT and (MISS) J. E. H. VAN DEE MADE (Proc. R. Aknd. TVetensch. Amsterdam 1918 20 636-641). -The observations recorded by Reinders (A. 1913 ii 836) have led the authors to investigate further the influence of various salts on the distribution of dyes between water and isobutyl alcohol. Experiments made with crystal-violet magenta and methylene- blue and the sodium salts of different acids show that the sequence of the anions when arranged according t o their influence on the distribution of the basic dye is identical with the lyotropic series. This sequence is no longer found when acid dyes are substituted for the basic dyes.The influence of salts on the ndsorntion of dyes bv blood char- coal has also been examined. In the case of methylene-bllle-Eii. 156 ABSTRACTS OF CHEMICAL PAPERS. extra and auramine-0 the order is not that of the lyotmpic series and it' is supposed that the electrical charges of the ions have a preponderating influence. With crystal-violet on t'hhe other hand ths sequence of the sodium salts is that of the lyotropic series. [See further Znd. 238~.] R. M. D. A New Method for the Measurement of the Coefficient of Diffusion of Electrolytes. ST. PROCOPIU ( A m . Physique 1918 [ix] 9 96-112).-1n a broad vertical tube are superposed two layers of different concentration of the same electrolyte and the variation of a physical or chemical property at a given distance from the surface of contact with the time is estimated.I n this case the E.iI1.F. bet'ween an electrode of the metal contained in the electrolyte and a similar electrode a t a much greater distance is studied and the time taken for it t o reach its maximum is determined. Then D=x2/28 where D is the coefficient of diffusion x is the dist'ancei of the first' electrode from the surface of contact and 6 is the time taken for the E.M.F. and consequently the con- centration a t x to attain its maximum. W. G. Experiments on the Manifestation of Osmotic Pressure with Membranes of Chemically Inert Materials. S. L. BIGELOW and C. S. ROBINSON ( J . Physical Chem. 1918 22 99-127).-The experiments described were made with the object of ascertaining whether osmotic effects are exhibited under con- ditions which seem to preclude the possibility of chemical reaction between the membrane and the solvent.For this purpose mem- branes were constructed from silica graphite amorphous carbon copper silver and gold in a very finely divided state. These materials were compressed into the form of disks which served to separate the solvent and solution. A special type of osmotic cell was devised which appeared t o be adapted to the use of membranes of this type. Preliminary results obtained for sucrose solutions (0.5 to 2 molar) are recorded which show that small osmotic effects are exhibited with these chemicallv inert membranes. By varying tho degree of compression of the disks the diameter of the pores could be altered and it has been found that such variations are accom- panied by a chanqe in the osmotic effect iii the Fense that this increises with diminution in the size of the pores.With copper membranes negative osmotic effects have been observed. Similar results have been previously recorded for kaolin membranes. H. M. D. Crystal Structure of the Alums and the Rdle of the Water of Crystallisation. L. VEGARD and H. SCHJELDERUP (Ann. Pltysik 1917 [ii] 54 146-164).-Bragg's method has been applied in the investigation of the crystal structure of the alums by observations on crystals of potassium alum ammonium alum iron ammonium alum and chrome alum. Using the rhodium lineGENERAL AND PHYSICAL CHEMISTRY. ii. 157 A=0*607 x 16-8 cm. the authors measured the relative int'ensities of the spectra of different orders obtained by reflection from the (loo) (110) and (111) planes and from the results have deduced the probable arrangement of the metal sulphur and oxygen atoms in the space-lattice system.For a description of the rather com- plicated structure the original paper must be consult<ed. The crystal model divides the twenty-four molecules of water into six groups which groups are cubically disposed with reference to tho four tetrahedrally arranged atoms of sulphur. The model makes no distinction between the water of crystallisation and the other constituents of the alum. Any hypothesis which would dis- tinguish the water of crystallisation from water of constitution could not be reconciled with the observed relations between the high-frequency reflection spectra.The removal of the wa,ter of crystallisation is necessarily accompanied by the destruction of that structure which is characteristic of the hydrated salt. The zeolites obviously present an attractive material for in- vestigation in regard to the influence of the water content on the crystalline structure and observations of a preliminary character have been made on chabasite crystals of which were dehydrated by heating a t 200-300° and examined before and after dehydra- tion by the X-ray method. The results show that the relative intensities of the spectra of different orders are not appreciably altered by the loss of water. The dehydration is however accom- panied by a diminution in the absolute' intensities and more par- ticularly by a decrease in the sharpness of the maxima.'The assumption that the water rnoleculm do not form an essential part of the space lattice of the zeolite is held t o be in- admissible. The facts can be accounted for by the hypothesis that the weakened reflection of th2 partly dehydrated cryst'als is due t o crystal elements which have not lost water and retain therefore their original configuration. Crystal elements which have lost water and from which new structures have been formed are pre- sumably orientated in all possible directions and for this reason phy a minor part in the effective reflection of the X-rays. H. M. D. In- Uni- and Bi-variant Equilibria. XVIII. F. A H. SCHREINEMAKER s (Proc. K . d had. TV e t ensc h. ,4 mst erdam 1918 20 659-667.Compare A. 1917 ii 454).-A..further discussion of the equilibrium relations in systems of n-components with n-phases a t constant temperature with varying pressure. The properties of such systems are very similar to those which have already been described for conditions in which the pressure is constant and the temperature variable. H. M. D. One-sided Chemical Equilibria. E. BAUR (Scliweix. Chem Z e i t . 1918 ii 25-26).-When salicylic acid is heated a t 200° it volatilises and the vapour undergoes partial dissociation into phenol and carbon dioxide. The degree of dissociation is dependentii. 158 ABSTRACTS OF CHEMICAL PAPERS. on the pressure and follows the law of mass action P . a21 1 - a2= K=254-9 where P is the pressure in cm. of mercury and a is the measured degree of dissociation.Although the dissociation is correctly described as an equilibrium yet no synthesis of salicylic acid from phenol and carbon dioxide can take place in the gaseous condition. Hence the reaction being irreversible is a " one-sided " equilibrium. Another instance of a similar phenomenon has been observed in the formation and decomposition of phloroglucinol- carboxylic acid. Phloroglucinol and potassium hydrogen carbonate in aqueous solution give a partial formation of potassium phloro- glucinolcarboxylate. A t 50° the equilibrium is adjustable from both sides and follows the law of mass action. When the velocity of the changes on the one hand the formation and on the other the decomposition of the carboxylate is studied in solutions satu- rated with phloroglucinol it is found that for the expression V=R(C-C,) where C is the momentary and Cl the equilibrium concentration of the carboxylate the value of K is about one- fourth in the formation of its value in the decomposition.This is explained on the ground that the decomposition of the carb- oxylate may take place in two ways directly and by way of an intermediate ester salt' potassium phloroglucinol carbonate whereas the formation of the carboxylate can only take place in one way namely through this intermediate stage. I f this way through the est,er salt did not exist the carboxylate could decompose but not re-form yet the limit of the decomposition must be the same as it actually is where both ways are available. Reversible Reactions of Sulphur Compounds.GILBERT N. LEWIS MERLE RANDALL and F. RUSSELL VON BICHOWSKY (1. Amer. Chenx. SOC. 1918 40 356-362).-An account is given of preliminary experiments which were undertaken with the object of finding reversible reactions suitable for the investigation of the free energy changes of sulphur compounds. Towards aqueous solutions of various salts sulphur begins to exhibit considerable reactivity when the mixtures are heated a t 150° t o 2 0 0 O . Mercuric ferric and stannic salts are quantitatively reduced and mercurous cupric bismuth and lead salts are slowly but quantitatively precipitated as sulphides. Nitrate per- manganate iodate and bromate ions are reduced to nitric oxide manganese dioxide iodine and bromine respectively. Chlorates appear to be reduced very slowly but sulphates periodates and perchlorates are not acted on a t 1 8 0 O .The reactjons in question are probably due t o the reversible change 2H,O + 3S= 2H2S + SO the sulphur dioxide being the active reducing agent. Solid sulphates are reduced by hydrogen at moderate tempera- tures and the sulphate ion is reducible a t about 150° by mild reducing agents. The investigation of the decomposition of silver sulphite on hea,t- ing shows thatl the reaction does not occur in accordance with the equation Ag,SO,=Ag,O + SO but that the solid product of the reaction is either a basic salt or a solid solution. In presence of 5. F. B.GENERAL AND PHYSICAL CHEMISTRY. ii. 159 water reaction takes place more rapidly in accordance with the equation 2Ag2S0 = 2Ag + Ag,SO + SO this reaction being cata- lyscd by the water.Sulphuric acid is then produced in consequence of the further reaction represented by Ag,SO + SO + 2H,O = 2Ag + 2H,SO,. The potent'ial of the sulphur dioxide electrode has also been examined by measuring the E.M.F. of the cell Pt I SO [ H,SO I Hg,SO I Hg for varying concentrations of the sulphuric acid and varying partial pressures of the sulphur dioxide. It has not been possible t o find a satisfactory interpretation of the results obtained. H. M. D. Equilibrium in the Reaction between Water and Sulphur at the Boiling Point of Sulphur. GILBERT N. LEWIS and MERLE RANDALL ( J . Amer. Chem. SOC. 1918 40 362-367).-The equilibrium in the system 2H,O + 3 s = 2H,S + SO has been examined a t the boiling point of sulphur.The experiments were made in the presence of an excess of sulphur and in these circum- stances the partial pressure of this compound was constant. A weighed quantity of water enclosed in a thin-walled se'aled tube was introduced into the reaction chamber consisting of a glass bulb of known capacity which was heated in the vapour of boiling sulphur. The formation of hydrogen sulphide and sulphur dioxide is accompanied by an increase in the pressure when the volume of the reaction mixture is kept constant and the pressures required to maintain this condition were measured in a series of experiments in which varying quantities of water were introduced into the reaction bulb. From these pressures it is possible to calculate thel partial pressures of the hydrogen sulphide sulphur dioxide and water in the reacting mixture.Some difficulties were metl with by reason of the fact that the water adsorbed by the surface of the glass is partly given off a t the temperature of the experiments but suitable allowance was made for the effect thereby produced. ThO results obtaine'd in six experiments gave values of K =[H2S]2[S0,]/[H,0]2 varying from 0.00088 to 0.00232. The differences between these results are not considered excessive when the multiplication of errors which the formula involves is taken into account. Tho mean value ll=O*O0154 may be used in the calculation of the free energy of formation of sulphur dioxide. H. M. D. Equilibrium in the Reaction between Water and Sulphur at High Temperatures.The Dissociation of Hydrogen Sulphide. MERLE RANDALL and F. RUSSELL VON BICHOWSKY ( J . Amer. Chem. SOC. 1918 40 368-375. Compare preceding abstract) .-The equiliSrium in question has been further investi- gated at? higher temperatures where free hydrogen is formed by the dissociation of the hydrogen sulphide. The equilibrium mix- ture contains therefore the five gases water sulphur hydrogenii. 160 AqSTRACTS OF CHEMICAL PAPERS. sulphide sulphur dioxide and hydrogen. I f the dissociation constant of hydrogen sulphide is known the composition of the equilibrium mixture of the five gases can be calculated if t,he original composition of the mixture the total pressure and the partial pressure of one of the five gases are determined. The partial pressure of the hydrogen has been measured by the use of an evacuated platinum bulb inserted into the reaction chamber into which the hydrogen diffused until the pressure in the bulb became equal to the partial pressure of the hydrogen in the gas mixture.This apparatus was used in the extension of previous measurements of the dissociation of hydrogen sulphide to higher temperatures. The values obtained for ICp = [H2S]/[H2][S2]i when the pressures a10 measured in atmospheres decrease from 7.98 a t 1362O (abs.) t o 1-81 a t 1667O (abs.). These results agree with the observationg of Preuner and Schupp (A. 1909 ii 977) whose measurements extended to 1405O (ah.). I n the investigation of the more complex equilibrium a mix- ture of gases of known composition was obtained by electrolysing a 10% solution of potassium hydroxide in two separate vepsels the oxygen from one or both of which could be passed over boiling sulphur and converted into sulphur dioxide. The currents pass- ing through the electrolysers which were placed in parallel were accurately measured and afforded the data for the calculation of the composition of the original mixture.Since the experiments were made a t atmospheric pressure the further quantity required was readily obtained. The results obtained in experiments a t temperatures ranging from 1 1 6 0 O (abs.) to 1645O (abs.) are used in the calculation of f he logarithm of the equilibrium constant K = rH20I2rH?S] 1 rH9I3[SOo] corresponding with the equation 3H + SO = 2H,O + H,S. The value of log K (partial pressures being measured in atmospheres) decreases from 5.93 a t 1160O to 2-56 at 1645O (abs.).Studies in Esterification. X. The Esterification of Benzoic and the Toluic Acids by Methyl Ethyl and Propyl Alcohols. RAYMOND FREAS and E. EninmT REID (J. Amer. Chenz. Soc. 1918 40 569-578).-A r-xamination of the position of equilibrium attained by various mixtures of methyl ethyl o r propyl alcohol with benzoic or one of the toluic acids or by mix- tures of the esters with water. The biEary mixture of known composition was in each case sealed in a glass tube and heated for four or eight days a t 200° the proportion of acid in the final mixture being then estimated and the percentage of equivalent amounts esterified or hydrolysed a t equilibrium calculated by the formula given by Faber and Reid (A.1917 i 626). Under these conditions it is found that with mixtures of any pair of the above alcohols and acids or of one of the esters-with water in varying proportions the position of equilibrium accords closely although not exactly with the law of mass action this result agreeing with that of Berthelot and Pean de St. Gilles. Of the toluic acids the R. It. I).GENERAL AND PHYSICAL CHEMISTRY. ii. 161 ortho-compound shows the least and the para-compound the highest est'erification limit towards methyl alcohol but the reverse is true of the esterification limits towards ethyl and propyl alcohols; the esterification limit of any one of the four acids is lower towards ethyl alcohol than towards propyl or methyl alcohol the latter giving the highest value with each of the acids.D. F. T. The Hydrolysis of Methyl Sulphate and Ethyl Sulphate with Sodium Methoxide or Ethoxide. J . POLLAK and A. BAAR (Monntsh. 1918 38 501-523) .-Methyl sulphate undergoes hydrolysis by water more rapidly than ethyl sulphate (Claesson A. 1879 775; Kremann A. 1907 ii 241) but in the presence of potassium hydroxide the ratio of the reaction velocities is very different from that observed for the hydrolysis by water only. With 0.5AT-potassium hydroxide a t 25O the unimolecular constant for methyl sulphate is forty-five tinzes as great as for the ethyl ester whereas with water only the ratio is approximately 5 1. I n order to decide whether the difference is due t o the difference in the solubility of the two esters in water and t o avoid the possibility of such a disturbing factor it is desirable1 to examine the rate of reaction in a homogeneous system. Kremann (A.1907 ii 157) has already observed that with methyl and ethyl alcohol. the rate of reaction of methyl sulphate is three to four times that of ethyl sulphate. With an alcoholic solution of sodium ethoxide however at 25O methyl sulphate reacts approximately twentv-five times as rapidly as ethyl sulphate whilst a t Oo the ratio is 5 8 l . The reaction in each case proceeds as far as the corresponding alkyl hydrogen sulphate or its sodium salt any further hydrolysis being negligible. These results demonstrate that the great difference in the velocities of reaction of alkali on the two alkyl sulphates is not mainly due to any difference of solu- bility on the part of the sulphates because a similar difference is observed in homogeneous and in heterogeneous systems. The difference is therefore presumablv to be attributed to the different character of the reactions the alkali hydrolysis yielding the alkali salt of the alkyl hydrogen sulphate whilst the free alkyl hydrogen sulphate is produced by the action of water or of alcohol.Examination of the reaction velocity of ethyl and methyl sulphates with alcohol in the presence of a graduallv increasing proportion of water-shows that the former ester is distinctlp less soluble in water and that the difference in the solubility of the two esters may exert an appreciable influence on the relative apparent reactivity of the two esters towards alkali hydroxide in the heterogeneous aqueous system.Methyl alcohol reacts with the two alkyl sulphates more rapidly than does ethyl alcohol and although it was found that as expected sodium methoxide affects the methyl ester much more rapidly than the ethyl ester the surprising result was obtained that sodium methoxide in methyl- alcoholic solution is less reactive than an ethyl-alcoholic solution of sodium ethoxide,. A similar observation t o this has alreadyii. 162 ABSTRACTS OF CHEMICAL PAPERS. been made in certain cases for example by Lobry de Bruyn and Steger (A. 1899 i 745 849) Steger (A. 1889 i 745) and Kremann (A 1905 ii 307) but the suggestion of the last-named that the difference is due to the presence of traces of water which cause a greater proportion of hydrolysis in the sodium ethoxide is discredited and the suggestion is made that the ex- planation may be found in the possible occurrence of the reaction between the alkyl sulphate and the undissociated portion of the sodium dkoxide (compare Wegscheider and Amann A.1915 ii 757). D. F. T. The Velocity of Formation of Nitrosyl Bromide 2NO+ Br = 2NOBr. NAX TRAUTZ and VASANJI P. DALAL (Zeitsch. anoyg. Ckem. 1918 102 149-172. Compare A. 1916 ii 304 and this vol. ii 151).--The investigation of this reaction was limited to temperatures between -150 and +15O to bromine pressures of 11-26 mm. and nitric oxide pressures of 11-12 mm. At greater temperatures or pressures nitrosyl bromide decomposes and at lower temperatures the bromine condenses on the glass of the vessel.I n presence of excess of bromine the resction appears to be of the third order the velocity constants found lying between 0.9 and 1.6. 1O1O. Probably however there are two superimposed reactions the first NO+Br2 NOBr coming to equilibrium very quickly whilst the second NOBr?+ NO 2NOBr is measurable. The temperature coefficient is very small apparently slightly greater than unity and could not be determined with certainty. On the supposition that the reaction bakes place in the above two stages the “ heat of activation” is calculated and is found to be 3076 cal. The velocitv constants calculated from this number agree substantially with the observed valnes and support the authors’ theory of thermochemical processes. E. B. R. Velocity of Dissolution of the Metals in Acids.111. Velocity of Dissolution of Alloys of Zinc with Arsenic Lead Cadmium Nickel Platinum and Gold. M. CENTNER- SZWER (Zeitsch. physikal. Ghem. 1918 92 563-580. Compare A. 1914 ii 550; 1915 ii 158).-The observations previously made on the rate a t which hydrogen is evolved from solutions of hydro- chloric acid by zinc-copper alloys have been extended to alloys of zinc with other metals. The results obtained show that arsenic lead and cadmium produce no increase in the rate of dissolution of the zinc. The contrary observations recorded by previous observers are attributed to the presence of traces of other metals- probably iron o r copper. The facts established by the author’s experiments are difficult to reconcile with the theory of local elements.Very small quantities of nickel platinum and gold of the order of 0.01% produce an appreciable increase in the rate of dissolution of zinc. The results obtained lead to the conclusion that pure zinc isGENERAL AND PHYSICAL CHEMISTRY. ii. 163 riot acted on by either hydrochloric or sulphuric acid i f the con- centration is less than about 0.5 to 1N. H. M. D. Method for the Carrying Out of Catalytic Reactions. JOHANN WALTER (D.R.-P. 295507; from Ghem. Zeiztr. 191'7 i 291).-Thorough exposure of the catalyst to the reagents is achieved by electromagnetic means. The catalyst itself may be magnetic and if desired spread on a non-magnetic material or a non-magnetic catalyst may be deposited on a magnetic substance and parts of the apparatus such as baffle plates or gauze in a gas tube or mechanical agitators are made magnetic or magnetisable.During the reaction or during the removal of the products mag- netic fields are established and broken by electrical means so that the catalyst is kept moving but near the exit of the apparatus a permanent field is maintained to prevent loss of the agent as dust. Examples given in the original specification include the hydro- genation of train oil the preparation of methane from carbon monoxide and the reduction of cinnamaldchyde to P-phenylprop- aldehyde and P-phenylpropyl alcohol lzvulose to mannitol and quinine t o di- and tetra-hydroquinine. J. C. TV. Some Problems of Atomic Stability. J. W. NICHOLSON (Proc. Physical SOC. London 1918 30 65-82) .-The author has investigated the dynamical stability of model atoms of pyramidal form consisting for example of a nucleus a ring of electrons in tho form of a circle the axis of which passes through the nucleus and a single stationary electron oil this axis.It is shown that no positively charged or neutral atom can exist in this form. Such structures are incompatible with a steady rotation of the ring electrons and cannot well form part of any molecular structure. The results appear to vitiate completely the molecular structures which have been formulated by Stark. H. 31. D. Molecular Frequency and Molecular Number. H. STANLEY ALLEN (Phil. Mag. 1918 [vi] 35 338-349).-1n a previous paper (compare this vol. ii 14) it has been shown that the atomic number of an element is related to its characteristic frequency.Similar considerations have been applied t o compounds and it is shown that the formukc N v = 1211 and Nv = (n + Q)vA represent the relations between the molecular number N and the characteristic frequency v calculated from the specific heat at low temperatures or from Lindemann's formula. I n these formulz .n is an integer and v the fundamental atomic frequency= 21 x 1012(sec.-l). The molecular number N of a compound A,BbC is given by the equation N = a N + bNb+ cn in which N Nb and N are the atomic numbers of the component elements. Evidence in support of the above formulze connecting N and v has been obtained by reference t o the data for both inorganic and organic compounds. The agreement is such that the relations cannot be regarded as fortuitous.ii. 164 ABSTRACTS OF CHEMICAL PAPERS. It is suggested that the integer n (the frequency number) is related to the number of valency electrons which are concerned in imparting t o the solid its crystalline structure. 13. M. D. Glauber’s Period in Amsterdam. W. P. JORISSEN (Chenz. WeeEblad 1918 15 268-271).-The register of the Western Church a t Amsterdam records that “ Johan Rudolph Glaubar ” was interred on March 10th) 1670 proving t’he inaccuracy of the statement made by Goossen van Vreeswyck (“ Silvere Rivier,” The Hague 1684 p. 117) that’ his death occurred 011 March 19th 1670. A. J . W . Berend Coenders Van Helpen ; a Groningen Alchemist of the Seventeenth Century. F. M. JAEGER (Chem. Weckblad 1918 15 285-302).-An account of the life work and family of the alchemist Berend Coenders van Relpen a typical landed proprietor of the seventeenth century who was born a t Groningen in June’ 1601 and died a t Copenhagen on January 3rd 1678. A. J. W. Willem Homberg. F. M. JAEGER (Clzem. TVcekhZcLd 1918 15 316-337).-Aii account of the life and a list of the publications of Willem Homberg who was born in Batavia on Jannary 8th 1652 and died in Paris on September 24th 1715. Arrangement €or Illuminating a Chemical Balance. B. D. PORRITT ( J . SOC. Chem. Znd. 1918 37 85~).-A “tubo- lite” metallic filament lamp of 16 candle-power and 8.5 inches long is fitted on the top of the balance case; the lamp is enclosed in a semi-circular aluminium reflector which serves t o direct the light through the glass top of the case on to the beam and to screen the lamp from the eyes of the person using the balance. A. J. W. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9181405141

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

\%GET-4BLE PHYSIOLOGY AND AGRICULTURE. i. 143 Chemistry of Vegetable Physiology and Agriculture. Enzymes concerned in the Decomposition of Dextrose and Mannitol by Bacillus coli communis. 11. Experiments of Short Duration with an Emulsion of the Organisms. EGERTON CHARLES GREY (Proc. Roy. SOC. 1918 [B] 90 75-92. Compare A. 1914 i 1034).-An emulsion of B. coli commzcnisi. 144 ABSTRACTS OF CHEMICAL PAPERS. in saline solution containing an amount of bacteria which would weigh when dry 1 gram is sufficient completely to ferment 40 grams of dextrose in forty-eight hoursh the presence of ealcium carbonate. The author describes an ingenious device to prevent the settling of the latter during the experiment. The calcium carbonate is sewn up in small sacks of cloth in each of which is placed also a small cork the weights being- so adjusted that the sacks just sink to the bottom of the flask when they are first introduced.During the course of the fermentation the acid did- engagead penetrates the sacks and they become swollen with gas and rise to the top of the solution. During this movement up and down the calcium carbonate contained in the sacks becomes gradu- ally liberated so that the solution is always turbid with calcium carbonate without being mechanically agitated from without. At the end of the experiment the products of fermentation namely alcohol carbon dioxide formic acetic lactic and succinic acids are estimated in the solution. The actual amount of any of the products obtained is dependent on the concentration of salt and the temperature of fermentation.By comparison of the various amounts produced in different experiments it is found that succinic acid and acetic acid are complementary as regards the extent of their formation and are therefore probably produced from a common parent substance. Acetic acid and alcohol and alcohol and succinic acid are similarly related to one another so that it would appear that the three substances alcohol acetic acid and succinic acid are formed from a common intermediate substance by the action of the same enzyme. The formation of lactic acid appears to be quite independent of that of the other products of fermentation and its production is therefore due to a separate enzyme. The addition of peptone to the culture medium contain- ing dextrose leads t o the production of a greater proportion of lactic acid and a lesser proportion of alcohol acetic acid and succinic acid.The products of the bacterial decomposition of mannitol closely resemble in amount those obtained from dextrose which is in har- mony with the author's view that' the fermentation of various carbohydrates and allied substances by bacteria is effected by a single set of enzymes the action of which is common t o all such casm of fermentation. The first step in the degradation of a particular molecular structure may require a special enzyme to pro- duce the common intermediate substance but the subsequent changes 81-0 always similar being due t o the action of the standard series of bacterial enzymes. [See also J . SOC. Gitem. Ind. 1918 103~.] H.W. B. Enzymes concerned in the Decomposition of Dextrose and Mannitol by Bacillus coli communis. 111. Various Phases in the Decomposition of Dextrose by an Emulsion Qf the Organisms. EGERTON CHARLES GREY CProc. Roy. Soc 1918 [ B ] 90 92-106. Compare preceding abstract,).-By exam- ining portions of a fermenting solution containing dextrose and bac-\‘EGE’L‘ABLE P H YSIOLOQP AND AGRICULTURE. i. 145 teria a t the end of twelve twenty-four forty-eight and seventy-two hours respectively it is found that during the first twelve-hour period the number of living bacteria diminishes very rapidly whilst during the second period a still more rapid growth of bacteria sets in so that a t its close the number present greatly exceeds that a t the commencement of the experiment.Corresponding with these changes there is a cessation in the production of lactic acid in the first period the chief products being carbon dioxide alcohol and acetic and succinic acids whilst subsequently in the third period when the number of bacteria is at a maximum the production of lactic acid is so much accelerated that i t forms 70% of the fermented sugar. The period of exalted bacterial growth is associated with the transformation of a large proportion of the dextrose into a complex carbohydrate which only reduces Fehling’s solution after hydrolysis. The extent of the synthesis during this period is quan- titatively of the same order as the degradation which ensues in the following period. A synthesis of fat was also observed on one occasion in circumstances which could not be again realised.Since the amount of sugar decomposed during the first period in which the rapid diininution in the number of living cells occurs is as great as during the third period in which the number of living cells both at the start and a t the finish is enormously greater the author draws the conclusion that the fermentation is brought about not by the cells as such but by enzymes in the cells. This conclusion is confirmed by the fact that different conditions result in variations in the- amounts of the products of fermentation due presumably t o the varied influence of the altered conditions on the operation of the different enzymes present. [See also J . SOC. Chem. Illd. 1918 103A.I H. W. B. Influence of Conditions of Bacterial Cleavage of Proteins on the Cleavage Products.TAKAOKI SASAKI (J. Biol. Chem. 1917 32 527-532).-When I-tyrosine is acted on by Bacillus coli comnzzcnis or B. proteus vulgaris the chief product obtained depends on the composition of the medium employed. I n the presence of lactose p-hydroxyphenylethylamine is produced whilst if the lac- tose is replaced by Henderson’s phosphate mixture the same bac- teria. form d-p-hydroxyphenyllactic acid without any trace of the amine. H. W. B. Stereochemistry of the Bacterial Decomposition of Albumin. TAKAOKI SASAKI and ICHIRO OTSUKA ( J . Bzol. Chern. 1917 32 533-538).-When B . p o t e u s vulgaris or B . coli com- mwis acts on d-tyrosine d-p-hydroxyphenyllactic acid is formed. If now B. subtilis is substituted for either of the above bacilli the product is 1-p-hydroxyphenyllactic acid.The author suggests that an intermediate substance probably of a ketonic nature is first formed which is then completely converted into one or other of the two possible asymmetric products. H. W. B. VOL. CXIV. i. ii. 146 ABSTRACTS oli' CHEMICAL PAPERS. Biochemical Study of Proteus vulgaris Hauser. Com- parison of the Properties of a Pathogenic Race and of a Saprophytic Race. F. G. VALLE MIRANDA (Con@. rend. 1918 166 184-187).-A comparison by ponderal methods of the bio- chemical properties of a Yroteus isolated in a case of acute infan- tile gastro-enteritis. and of another found in putrefying meat. These have been compared with respect to their behaviour towards carbohydrates glycerol gelatin amino-acids and tryptophan and the results indicats that despite their different origin the two Proteus examined constitute two races of PTotezis vuZgnris and not cwo distinct species.W. G . Biochemistry of Pathogenic Anaerobes. 11. The Acid Production of Bacillus Welchii (B . perfringens) and Bacillus sporogenes (Metchnikoff). CHARLES GEORGE LEWIS WOLF and STEPHEN VEITCH TELFER (Biochenz. J. 1917 11 197-212).- Dyer's method (A 1917 ii 157) was applied to the investigation of the volatile acids formed by 3. perfringens and B. sporogenes under anzrobic conditions in milk and in peptone broth contain- ing 2% of dextrose. It was found that for the identification of the constituents of an unknown mixture of volatile acids the method must be applied not only to the original mixture but also t o certain distillation fractions or even to secondary fractions.By this means useful comparative data may be obtained in the in- vestigation of a number of mixtures especially if the curves plotted are compared with those corresponding with mixtures of known composition ; but very tedious fractionation would be required to obtain quantitative results or even to detect such an acid as pro- pionic in presence of acetic and butyric acids. The colour tests recommended by Dyer cannot be depended on until the acids have been separated. The results of the present investigation indicate that in milk B. sporogenes forms acetic butyric valeric and hexoic acids prob- ably in the approximate proportions 25 17 16 41 whilst B. per- fringens forms only acetic and butyric acids in the proportions 2 3. I n the dextrose-peptone broth both organisms produce only acetic and butyric acids in the proportions 3:2.These figures are given with great reserve ; considerable amounts of propionic .acid may have been present in all cases without being detected. For both organisms in milk the volatile acids constituted 68-69% of the total acids produced (both expressed in terms of alkali); for 13. sporogenes and B. perfringens in dextrose-peptone the corre- sponding values were 55% and 50% respectively. Biochemistry of Pathogenic Anaerobes. 111. The Effect of Acids on the Growth of Bacillus Welchii (B. perfringens) and Bacillus sporogenes (Metchnikoff). CHARLES (3. L. WOLF and JOHN EDMUND GUY HARRIS (Biochem. J.1917 11 213-245). -After an investigation of the effect of addition of different quanti- ties of various acids on the reaction of peptone broth containing 2% of dextrose the authors studied the influence of the initial reaction J. H. L.VEGETABLE PHYSIOLOGY AND AQRICULTCRE. i. 147 of the medium adjusted to various values between pH=6.6 and 4.5 by addition of acid on the anzrobic fermentation of B. perfi.ingens and B . sprogencs. The acids employed were hydrochloric formic acetic butyric lactic malic and succinic. The main conclu- sions drawn may be summarised as follows. The higher the initial hydrion concentration in the medium the longer is the latent period of growth i.e. the time elapsing between inoculation and the first visible signs of growth; and i f the initial hydrion concentration exceeds a certain critical value (about p,=4*8 for B .yer1ringens and pH=4.9 for R. sporogenes) no fermentation occurs. Where fermentation takes place the final reaction attained is not a ‘. physiological constant,” but varies within comparatively narrow limits (pH =4*2-4*8 for B . per- fringens and %=4*9-5*5 for B. sporogenes) according to the initial reaction of the medium. Moreover the form of the curve representing the dependence of final on initial reactions designated the “reaction resultant,” is to a certain extent characteristic of the particular acid to which the initial reaction is due. The change in the value of p during fermentation is not a measure of the amount of acids produced. I n the case of B. perfringens the pro- duction of acids and carbon dioxide is practically independent of the initial reaction when the latter is due to hydrochloric acid.With feebly dissociated acids 011 the other hand much larger amounts are required to produce the same initial hydrion concen- trations and these acids appear to exert an inhibitive influence on fermentation apart from that due t o their cations. B. sporogenes differs from B. pPrfrinyejis in that in media of which the initial reaction is near the critical point the final reaction may be less acid than the initial. This is attributed to the production of large amounts of basic and amphoteric substances which reduce the acidity and act as buffers. Cessation of growth is probably clue almost entirely to accumulation of metabolites.It is suggested that by treatment of gas gangrene infections by means of highly buffered solutions with hydrion concentrations slightly above the critical value growth might be inhibited. J. H. L. Ptomaines and War Wounds. ALBERT BERTHELOT (Compt. rend. 1918 166 187-189).-The author has endeavoured t o show that toxic ptomaines may be formed by the action on the blood of proteolytic and amino-acid splitting microbes likely t o be found in wounds and considers that his experimental results support thie idea. W. G . The Autolysis of Yeast and the Influence of its Products of Proteolysis on the Development of Yeast and of Lactic Bacteria. PAUL VANSTEENBERGE (Ann. Inst. Pastew 191 7 3 1 601-630).-After death the yeast-cell loses its cell water and diminishes in size.If the enzvmes present have not been destroyed after a time varying with the temperature liquefaction of the yeast occurs. For the endotryptase the optimum temperature isi. 148 ABSTRACTS OF CHEMICATI PAPERS. 45-50° and the maximup temperature 5 3 O . For autolysis of yeast in the living state the optimum temperature is 48-50°. The progress and completion of the autolysis are best shown by an increase in the acidity to a certain maximum and the separation of tyrosine in a crystalline state from the autolysate. When yeast is boiled with water the extract only contains one-third of the total nitrogen but if the boiling is precsded by an autolysis at 48O lasting twenty-three hours the whole of the nitrogen is obtained in a form soluble in water and not coagulated by heat.An extract of autolysed yeast is much more nutritive for yeast and for lactic bacteria than an extract of fresh yeast and the nitrogen is con- verted by the autolysis into a form more readily assimilable by these organisms. I n an extract of autolysed yeast of a strength equivalent t o 20 grams of yeast per 100 c.c. there are certain products unfavour- able to the development of yeast but this injurious action disap- pears on dilution. Such products are tyrosine and leucine of which the former is injurious a t conceiitrations over 0.05% and the latter a t concentrations above O*OS0,6. At the concentrations a t which these substances are present in autolysed yeast they inhibit the development of yeast but do not exert any unfavourable influence on lactic bacteria.[See also J. S o r . Ckem. Ind. 1918 103A.I W. G. The Action of Arsenic Salts on Yeast. F. Boas (Zeitsch. Garzcmgsphysiol. 1917 6 1-12 ; from Physiol. Abstr. 1918 2 631) .-Sodium metarsenite retards fermentation by living yeast. Fermentation is a t first arrested by alkali arsenates but in the presence of soluble nitrogen it is promoted after five to seven hours. Although in nitrogen-free solutions the inhibiting action is very strong yet in some cases after twenty-four hours fermenta- tion had proceeded under these conditions. Owing to different physiological conditions of the yeast considerable variation in the results was noticeable. W. G. The Water-soluble Accessory Growth-promoting Sub - stance in Yeast. JACK CECIL DHUMMOND (Biochem. J. 1917 11 255-271).-The opinion of McCollum and Kennedy (A.1916 i 451) that the “ water-soluble growth-promoting factor B ” is identical with the antineuritic vitamine is confirmed inasmuch as i t is now shown by feeding experiments with rats that the water- soluble factor in yeast possesses many of the properties of the anti- neuritic principle such as insolubility in ether or absolute alcohol and relative insensitiveness towards heat dilute acids and alkalis. Unsuccessful attempts to isolate the active substance from yeast are described. The water-soluble factor is not identical with adenine nucleic acid or any of the constituents of commercial meat extract. [See also J. SOC. Chtem. I n d . 1918 134~.1 J. H. L.VEGETABLE PHYSIOLOGY ASD AaRICt7LTURE. i. 149 Intermediary Reactions in Alcoholic Fermentation.€3. EULER HJ. OHLSEN and D. JOHANSSON (Biochem. Zeitseh. 1917 84 402-40G).-A Swedish beer-yeast was dried ab 40° and ex- tracted with water. Such an extract contains a phosphatase which acts directly on Izvulose. Dextrose is not however acted on by it unless previously treated with fresh yeast.. A Swedish yeast weakened by being kept for six weeks in a solution containing sodium chloride sugar but no nitrogen could esterify lmmiose but not dextrose. The results confirm Harden's view (compare A. 1908 i 590) that the hexose phosphate is a derivative either of laevulose or of a closely allied sugar and that the dextrose must be converted into this in order to form the phosphate ester. S. B. S. Is Lactic Acid an Intermediate Product of Alcoholic Fermentation ? ALESANDRE LEREUEV (Biochem.J. 1917 11 189-196).-The balance of experimental evidence is considered to be unfavourable to the view that lactic acid is an intermediate product of fermentation. The conclusions of Palladin and Sabinin on this subject (A. 1916 i 620) are criticised. In the decomposi- tion of lactic acid by yeast-reductase in presence of methylene-blue the quantity of acetaldehyde formed is much smaller than corre- sponds with the equation given (Zoc. v i f . ) and when pyruvic acid is substituted for niethylene-blue very little alcohol is formed in comparison with the amount of carbon dioxide. Pyruvaldehyde is a more probable intermediate product of fermentaticn than lactic acid for a t very low concentrations it is decomposed by yeast into practically equivalent amounts of alcohol and carbon dioxide but on the other hand it is fermented only very slowly and is toxic towards yeast enzymes.The evidence regarding the possible formation of pyruvic acid in the course of alcoholic fermentation is incoiiclnsive. J. H. L. Influence of Metallic Salts on Germination in the Presence of C d C i U r n . L. M-AQUENNE and E. I)EMOUSSY (C'omnpt. reiid. 1918 166 89-92).-A continuation of previous work (compare A. 1917 i 530) the peas being germinated in water containing the various salts examined either with or without the addition of calcium in the form of its sulphate or chloride. The root measure- ments show that the presence of any salt in amount approaching the toxic quantity in pure water lessens or prevents the favour- able action exerted by calcium when present alone.Thus the different metals whether toxic or alimentary function as antagon- ists to calcium in germination in the same way as calcium behaves as an anti-toxic towards them. The physiological action of a mix- ture is thus not equal to the sun1 of the actions of its constituents. W. G. Action of Acids on Plants. 1. ONODERA (Be?.. Ohara Imt. LnncFuT. Porsch. 1916 1 53-100; from Physiol. Abstr. 1918; 2,i. 150 ABSTRACTS OF CHEMICAL YAPEKS. 70%).-In geueral plant growth was considerably stimulated by rruderately concentrated acids and in particular by nitric acid in the form of carbamide nitrate containing 0.05 gram per litre. The acids investigated arranged in descending order of toxicity were hydrochloric sdphuric formic butyric acetic nitric and a-hydroxypropionic .Plants grown in an acid cukure develop abnormally in height their root development being quiclrly arrested but the growth of the foliage is continuous. The Effect of certain Organic Compounds on Plant Growth. M. J. FUNCHESS ( A l(cbnmg ifyric. Ex@. Stat. Hull. 1916 191 103-132 ; from Ph~siol. d bstr. 1918 2 707-708).-Pot experiments were conducted to deterniiiie the effect of coumarin vanillin pyridine quinoline dihydroxystearic acid and pyrogallol on $ant growth in the case of oats and wheat grown on red clay or a sandy soil. Yyridine and quinoline were found to be bene- ficial in the soils used. The compounds used in mall amounts were not found to be harmful to growth. Vanillin applied a t the rate of 5-10 parts per 10,000 was quite harmful to oats grown on the sandy soil in the presence or abPence of complete fertilisers but there was no residual harmful effect.Similar results were obtained with coumarin. The conclusion is drawn that rapid chemical or biochemical transformation of these compounds into inert' forms occurs in unsterilised soils under the above experimental condi- tions and that the results obtained with soil cdtures do not agree with those obtained with solution cultures. W. G . W. G. Action of Various Fertilisers especially Manganese Sulphate on the Growth of Oats. L. HILTNER and G. KORYE' (Prakt. Blutt. P$ccnsertbau R. P@anze?zschutz 1911 15 549-556 ; from Bied. ZeiLtr. 1918 47 15-19).-The authors describe pot experiments in which oats were grown in various types of soils some of which were treated with iron copper or manganese sulphates or with sulphur and all received guano.The addition of manganese suIphatle caused in each case an increase in the size of the plant and in the total number of oat-grains especially in s d s cont'aining much humus. I n peaty soils the yield of oat- grains was seventy times as great in the presence of manganese sulphate as in its absence. It is suggested that these remarkable results are largely due to the accelerating action of manganese on the oxidation of the guano added t o the soil. The other sulphates and the sulphur experimented with produced similar but not such marked results. [See also ,7. Soc. Phcm. Tad. 1918 March.1 H.W. B. The Necessity for an Acceptor of JHydrogen and an Acceptor of Oxygen for the Manifestation of the Processes of Oxido-reduction in Organic Liquids of Animal and Vegetable Origin. J. E. RBELOUS and J. ALOY (Compt. rend. 1918 168. 130-132).-It has been shown by Bach (compare A. 1917 i 375 431) that the presence of a readiIy oxidisable sub-I’EGETABEE PHYSIOLOGY AND AGRICULTURE. i. 151 stance is necessary for the reduction of alkali iiitratev by milk or potato juice and the authors now show that the presence of a readily reducible substance is essential for oxidation under similar conditions. w. Q. The Relationship between the Osmotic Concentration of Leaf Sap and Height of Leaf Insertion in Trees. J. ARTHUR HARRIS Ross AIKEN GORTNER and JOHN V. LAWRENCE (Bull.Torrey Bot. CEub 1917 44 26‘7-286 [reprint]).-Measurements have been made on leaves gathered from different heights on twenty- six trees belonging to twelve species. The results indicate that the osmotic concentration of the leaf sap as determined by the freezing-point lowering method increases from lower to higher levels. The specific electrical conductivity K shows a tendency to decrease from lower to higher levels but the results obtained are not very regular. The ratio Z<]A where A is the lowering of the freezing point however shows a regular decrease from lower to higher levels. The authors have endeavoured t o establish a formula showing the relationship between the increase in osmotic concentration and the difference in heights of insertion of the leaves plus the resistance to the passage of water nioving at ths rate of the transpiration stream opposed by conducting tracts equal in length to the differences in the heights of insertion. The value for the latter factor is.however not yet definitely established. W. G . Genesis of Inulin in Plants. H. COLIN (Compt. rend. 1918 166 224-227) .-Estimations of the total sugar reducing sugar sucrose starch and inulin in the various organs of the plant in the case of chicory dahlias and Jerusalem artichokes show that there can be no question of the immediate elaboration of inulin by the leaf and of i t d migration as such to the subterranean organs. The leaves only deliver to the plant the sugars the condensation of which takes placfi in the stein or only in the tubercles or the roots.The Constituents of Wood which give Colour Reactions. 11. 1% WICIJELHAUS and NARTIN LAKGE (Ber. 1917 50 1683-1685. Compare A. 1916 i 874).-About 98 litres of distillate have been collected from 1200 grams of pine or fir wood by the passage of a current of steam a t 180-200° and separated by a second distilla- tion into two fractions. The first t.wo-thirds gave a green precipi- tate with phloroglucinol and hydrochloric acid whilst the last third gave the typical cherry-red precipitate and also formed a brick- red subdaoice CI8Hl80,NF with p-nitrophenylhydrazine. The latter is a parently a condensation product of a ketofurfuraldehyde C,H,O lerived from a hexose as follows C6Hl2O6 - H,O + 0 = C,H,O,+H,O. W. G . [See also J . SOC. Chem.Ind. 1918 March.] J. C. W. The Constituents of the Bark of the Hymenodyctyon excelsum. CHARLES STANLEY GIBSOY and JOHN LIomr SIMONI~ENi. 152 ABSTRACTS OF CILEMICAL PAPERS. ( J . I'roc. Asiatic SOC. Benyal 1916 [N.S.] 12 161 [reprint]).- The authors have confirmed Broughton's Fork (1870) in that they were able t o isolate mculin and scopoletin from the bark of the Rymenodyctyon ezcelsum but they were unable to find any traces of an alkaloid (compare Naylor A . 1583 1141; 1885 565). W. G. The LQganberry and the Acid Content of its Juice. MILO REASON DAUGHTERS ( J . I d . Eng. Chem. 1918 10 30).- Analyses are given of the loganberry and of its juice. The chief acid in the fruit is citric; tartaric and volatile acids are pre- sent in traces; inalic acid is absent.[See also J . "?oc. Chem. Id. 1918 March.] 1,. A. C. Soil Acidity and the Hydrolytic Ratio in Soils. C. H. SPURWAY (J. Agric. Research 1917 11 659-672).-The examina- tion of a number of soils from glacial formations indicates that the Peaction of these soils is probably determined chiefly by the hydro- lytic ratio between salts of the alkaline e x t h metals on the one hand and those of iron and aluminium on the other when these are in equilibrium; the hydrolytic ratio depending on the concen- tration and degree of hydrolysis of ezch salt in the presence of the other when equilibrium is reached. [See also J . SOC. Chem. Znd. 1918 132A.l W. G. Isolation of 23-Hydroxybenzoic Acid from Soil. E. H. WALTERS ( J . Amer. Chem. SOC. 1917 39 1778-1784).- p-Hydroxybenzoic acid and benzoic acid have been isolatled from a soil' in the orange groves of Florida. The soil is largely composed of quartz sand mixed with organic matter which can be almost entirely removed by washing with dilute sodium hydroxide. The actual quantities of the pure acids obtained correspond with about 21.6 parts of p-hydroxybenzoic acid and 1.7 parts of benzoic acid per million. J. C. W. Alkali Soils Biochemical Factors in their Reclamation. J. H. BARNES and B. ALI (Agric. J. India 1917 12 368-380; from Phyaiol. A b s t ~ . 1918 2 712).-Ordinary alkali land con- tains all the organic life associated with soil fertility but in a more or less dormant state. I n the more saline soils of long duration the vitality of these organisms is somewhat impaired. Nitrifying organisms are thus dormant in alkali soils so long as the saline matter is in excess but washing of such soils is followed by increased nitrification and this will commence before the soil is sufficie'ntly washed to admit of the growth of crops as nitrifying organisms can exist in a solution of higher osmotic pressure than can the higher plants. Ammonifying organisms are still more hardy than the nitrifying organisms t o saline matter. There is ail indication that the activity of nitrogen-fixing bacteria of the Azotohcter type is increased after. washing. W. 0.

ISSN:0368-1769    

DOI:10.1039/CA9181400143

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

Organic Chemistry. Solubility of Lead Acetate in Water. YUKICHI OSAKA and REIJIRO HARA ( M e r n . CoZZ. Sci. Kyoto 1917 2 14'7-150).- Measurements have been made of the solubility of lead acetate in 0.025 0.05 and O'1N-acetic acid a t 25O 3 5 O and 4 5 O . The quan- tity of salt dissolved per 100 grams $of water increases slightly with the acidity of the solution the relation being linear. By extra- polation the solubility in pure water is found t o be 54.38 parts per 100 of water a t 25O 87.77 a t 3 5 O and 154.25 a t 45O. These extra- polated values are based on the assumption that the salt is not 11 ydrol ysed. H. M. D. Physical Properties of a Number of Pure Esters. J . HOWARD MATTHEWS and KATHARINE E. FAVILLE (J. Physical Chern. 1918 22 1-21).-The esters ,obtained from Kahlbaum were purified by chemical treatment according to the method described by Young and Thomas (T.1893 63 1191) and then subjected t o fractional distillation in an apparatus devised t o give a constant pressure of 760 mm. I n accordance with the results obtained by most of the previous observers the boiling p i n t s of the esters were found t o extend over an appreciable range. The physical properties measured were the boiling point density vis- coBity specific inductive capacity and refractive index the values bleing recorded in the table. B. p. isoAmy1 formato ... 123.46'-123*56" isoButyl formate ... 98-15 - 98.25 Propyl acetate . . . 101.57 -101.77 Ethyl propionate . . . 99-12 - 99-22 Propyl propionate . . . 121.0 -121.25 Ethyl butyrate ... 120.0 -120.5 isoButyl valerate ...167.0 -168.5 q? 0.8773 0-8832 0.8869 0-8904 0.8809 0.8784 0.8544 vmo. (2r)". 0.789 4.98 0.638 5.93 0.585 8.10 0.545 5.75 0.674 4.66 0.665 5-91 1.118 8-21 n,. 1.39772 1.38568 1.38422 1.38414 1.39325 1.40002 1.40569 The boiling points of the esters a t various pressures were also determined and the results applied in testing the deductions. made by van der Waals in reference to the theory of corresponding states. For ethyl propionate ethyl butyrate and isobutyl formate critical data have been previously determined and by making use of these a comparison is made of the values of the ratios of the absolute temperatures a t corresponding pressures to the absolute critical temperatures. Fur a given pressure the temperature ratio varies appreciably with the nature of the ester but the deviations from constancy are less than those found by Young and Tho'mas in their investigation of a series of ten esters.H. M. D. Relation between the Minity Values bf the Aliphatic Acids of the Mono- and Di-basic Series. GERVAIS LE BAS (Chem. A'ews 1918 117 121-122).-Tables ,of the affinity values (k x 104) VOL. CXIV. i. 7i:i. 154 ABSTRACTS OF CHEMICAL YAPERS. of monobasic fatty acids starting with formic acid and of dibasic fatty acids starting with succinic acid are given. The latter form a nearly arithmetical series that is the values for n(k x lo*) where n represents the position in the series are very nearly the same. If the numbers for the members of the dicarboxylic acid series be divided by the numbers for the members of the monooarboxylic acid series a series of numbers is obtained which when plotted against successive integers gives a curve resembling a rectangular hyperbola. The free enarrgy due t o the carboxylic group in the monobasic acid series diminishes with the increase in the length of the hydrocarbon chain.When two such groups are present in the same molecule the ratio between the affinity values varies inversely with the number of carbon atoms between the groups except in the case of oxalic and succinic acids the ratio of which sliows a greater increase. In the dicarboxylic acid series the two carboxylic groups are mutually active the one increasing the tencl- ency of the other to be active or possess residual affinity but the latter function varies inversely with the number of interposed methylene groups.The following formula for the dioarboxylic acids in which these facts have been noted is suggested e. CH,-CH,-CO,H v C. A. M. Method of Preparing Acetaldehyde. UNION CARBIDE Co. (U.S.-P. 1247270 1917; from J . SOC. Chem. Znd. 1918 37 74~).-Acetylene is combined with the elements of water in an acid bath containing a mercury compound. The bath is maintained a t such a temperature that the acetaldehyde distils continuously and the mixture of acetaldehyde and acetylene is conducted into a series of baths similar to1 the first bath. w. P. s. The Wagner-Saytzeff Reaction with Mesityl Oxide. C. J. ENKLAAR (Chem. Weeliblad 1918 15 188-190).-The liquid obtained by the action of zinc mesityl oxide and ally1 bromide in preseiice of anhydrous ether yields on distillation two fractions in addition to unchanged products.The first fraction has b. p. 71°/ 20 mm. and consists of @-dimethyl-A~'-heptadien-8-d mixed with a smaller proportion of a ketone C,H,,O probably a dimethyl- heptenone. The second fraction has b. p. 140-142*/3 mm. and its coiistitu- ents have not been identified. Influence of different Compounds on the Destruction of Monosaccharides by Sodium Hydroxide and on the Inver- sion of Sucrose by Hydrochloric Acid. 1x1. Constitutional Formula of the Hydroxybenzoic Acids and of Sulphanilic Acid. H. P. WATERMAR (Proc. K. A knd. Wetansch. Amsterdam 1918 20 581-589. Compare A. 1917 i 631; this vol. i lOl).- Salicylic aoid behaves in alkaline solution as a monobasic acid in A.J. W.ORGANIC CHEMISTRY. i. 155 CH WC/\C:O HC\)CH*CO,H CH retarding the destruction of dextrose whereas 732- and p-hydroxybenzoic acids behave as dibasic acids. The author considers that these results support the constitutional formula (annexed) assigned t o salicylic acid by Brunner (compare Hollernan " Die direkte Einfiihrung voii Substituenten in den Benzolkern," Leipzig 1910). Sulphsnilic and hippuric acids behave as inoiiobasic acids in alkaline solutions and are neutral in their influence on the inver- sion of sucrose by hydrochloric acid. On these grounds the author assigns the constitution I to sulphanilic acid in alkaline solution and constitution I1 in acid solution. S H NHi3 \// f)'o 0 S0;OH SO. [See also Id. 189A."] \I-. c:. Lactose. 11.A. SMITS and J . GILLIS (I'roc. Ii. ,4kcrt7. it2tcicscii Amsterdam 1918 20 573-580. Compare this vol. i l O l ) . - From a study of the results previously given (Zoc. cit.) coupled with those obtained by Hudson (compare A. 1909 ii 131; 1910 i 220) the authors consider that mutarotation is not due t o a slow dehydration process in the sugar series as was assumed by Hudson but t o the slow establishment of an internal equilibrium between two stereo-isomeric f oms. Further that for the unsubstituted aldoses such as dextrose galactose lactose etc. the presence of water of hydration does not change anything in the structure of the asymmetric terminal carbon atom. The pseudo-ternary T- ~ t figure of the system water-a-lactose-p-lactose is given and the surface of equilibrium lying in it is shown.The Reduction of the Group 9CH.J attached to Nitrogen. AMAND VALEUR and EMILE LUCE (Compt. rend. 1918 166 392-394. Compare this vol. i 102) .-Dirnetliyliodometliyl-6-iodo- iziiiylaininonium iodide CHMeI.CH,*CH,.CH,*Nl\lle,I.CH,I wheii reduced by zinc in alcohol or in dilute acetic acid gave trimethyl- aniylarrimoniuin iodide CH2Me=CH,*CH,*CH,=Nie31 together with a m a l l aiiiouiit of an unsaturated methiodide. Methylene-des- dimethylpiperidiiie iodide when similarly reduced gave desdi- inethylpipmidine methiodide [trimethyl - As - pentenylammonium iodide] m. p. 227-229O giving an aurichloride m. p. 1 0 7 O . Di- methyliodomethyl-lly-penteinylammonium iodide CHMe:CH*CH,*CH,*NMe21*CH,I wllen reduced gave a mixture of two isomeric unsaturated nzeth- iodides C8Hi,NI giving two awichlorides having m.p.,s 1 l G o (decomp.) and 89-91O respectively. Trimethyliodometliylammon- W. G . * In cross references to abstracts I n d . will be uscd in place of J. SOC Chem. In&. 1918,37.i. 156 ABSTRACTS 03 CHEMlCAL PAPERS. ium iodide when reduced by zinc and acetic acid yielded tetrrt- methylammonium iodide. W. G . Isethionic Acid Deriwtives of some Aliphatic Amino- acids. E. SALKOWSKI ( Z a t s c h . physiol. Chein. 1917 101 1-14 Compare A. 1916 i 815) .-A mixture of equimolecular quantities of the amino-acid ancl isethionic acid is dissolved in water heated on the water-bath and finally a t 140-1433 for three and a-half t o four hours. The cooled mass is dissolved in water,,and the product of tlie reaction precipitated by alcohol.It is then recrystallised from dilute alcohol with the aid of animal charcoal. Isethionyl- ylycine C0,H*CH,*NH*S02*C2H,*OH does not melt below 260° ; i t gives a crystalline copper salt. Isethionylalanine C,H,,O,NS has m. p. 2 4 2 O (decomp.) and isethionyllezicine C8H170,NS m. p. 260° (decomp.). The three compounds have several properties in com- mon; the aqueous solution is acid t o litmus but neut,ral t o Congo- red unless the solution is very concentrated. Phosp'notungstic aci(1 does n o t produce a precipitate but only a turbidity which dis- appears 011 warming ancl reappears on cooling. They reduce ammoniacal silver nitrate and when heated give off sulphur dioxide and a gas of which the odour resembles that of mercaptan. A similar compound appears to be formed between isethionic acid and aspartic acid but it could not be isolated in a crystalline condition.H. W. B. Action of Formaldehyde on Glycine and its Metallic Salts. HUGO KRAUSE (Ber. 1918 51 136-150).-The use of formalde- hyde in the titration of glycine is now a matter of common know- ledge but 110 definite work has yet appeared on the nature of the reaction between these compounds or on the behaviour of the iiietallic salts of glycine. It is now shown t h a t the salts react like the free amino-acid and that the products which may be iso- lated in all cases correspond with a condensation product of tlie foriiiula C,HI4O,N,. Allowing C,H,O,N for two glycine residues i l follows that this product can only be written as OH*CH(CH,*NH*CEC,*CO2H)Z. From a imasnrement of the amount of formaldehyde whicli takes part in the reaction the very puzzling discovery is made that oiily one molecule of the aldehyde is required f o r one of the acid- This is explained by the fact that the methyl alcohol present in the formalin used also enters into the process.If pure formaldehyde solution is used very little of the compound is formed relatively much more formaldehyde disappears and a considerable amount of formic acid is produced. It can be proved moreover by a rough quantitative method that methyl alcohol disappears. The normal reaction is therefore expressed in the equation 2NH,*CH,-CO,H + 2CH20 + CH,*OH = C;.H,,0,N2 + 2H,O whilst the pure aldehyde reacts according to the equation 2NH2*CH2-C0,H + 4CH20 = C,H,,O,N + H*CO,H + H20.The existence of the -CH*OH group in tlie molecule is proved by the facts that methyl and ethyl alcohoIs are formed on 'heatingORGANIC CHEMISTRY. i 167 the product t h a t the compound yields an acetate and t h a t acetone is formed in traces by oxidation with chromic acid. A full account of the isolatioh of the products is given and also of the application of the barium salt to the settlement of the above questions. Free P-hydrozytrimethylenediglycine is a deliquescenb white powder which decomposes a t above 75O restores the colour of Schiff’s reagent and decomposes alkali carbonates with vigorous effervescence and its acetate is also white. The sodium salt lH20 and calcium salt 2H,O are deliquescent powders with alkaline reac- tions; the barium salt 3H20 crystallises in Rat rods or leaflets is not hygroscopic and is only soluble in 22 parts of water a t 18O; the mn~nesiutn salt 3H20 and an acid salt C7R1205N2Mg ,025 C,€II40,N2 2.5H20 are somewhat hygroscopic ; copper glycine gives a fairly insoluble deep blue salt of the formula C7HI20,N,Cu,3H*CHO ; with silver glycine a white precipitate probably of the normal salt is formed momentarily b u t this soon changes into a yellow salt according t o the equation C,H,,O,N,Ag + 2H,O = 20H*CH2*NH*CH,*C02Ag + CH,*OH.J. C. W. Action of Ethyl Oxalate on Ethyl P-Aminocrotonate. WILHELM WISLICENUS and KARL SCHOLLKOPF (J. pr. Chem. 1917 rii] 96 174-179).-The interactior of ethyl oxalate and ethyl P-aminocrotonate i n the presence of alcoholic-ethereal potassium ethoxide follows the course stated by Benary Reiter and Svenderop (A.1917 i 252) the product being the yellow potassium deriv- ative C02Et*C(OK):N*CMe:CH-C02Et of ethyl N-ethoxalylamino- crotonatle from which the free ester is liberated on acidifying. I n the presence of water the potassium derivative readily undergoes partial hydrolysis with formation of ethyl P-osalylaminocrotonate prisms which after dehydration have m. p. 106-1OSo. If ethyl amiiiocrotonate is allowed t o react with a bimolecular proportion of ethyl oxalate and of potassium a deep yellow dipot,assium com- pound C,,H,,O,NK is obtained probably a cyclic derivative of ethyl A’-C-diethoxalyl-P-aminocrotonate ; on treatment with dilute mineral acid thel aqueous solution of this dipotassium compound deposits yellow needles of a compound C,,H,,O,NR containing only one atom of potassium. The Nitrogenous Pigments of Molasses.H. FRIEDRICH (Zeitsch. Zuckerinct. Bijkm. 1917 41 769-771). VL. STAN~K (ihid. 771-773).-Polemical. Friedrich’s reply to Stanhk’s criticism (A. 1917 i 545) and a rejoinder. The Pseudo-system Methyl Thiocyanate Methylthio- carbimide and Trimethyl Trithiocyanate. J. GILLIS (CJim. IJ”eekbZad 1917 15 48-78) .-An investigation of the curves of solidification and ebullition of mixtures of methyl thiocyanate and methylthiocarbimide. A . J. W. Organo-Cadmium Compounds. I. Simple Cadmium Alkyls. ERICEI KRAUSE (Re?.. 1917 50 I S13-~8~?J).-Cadminni dialkyls can be readily obtained by adding finely powdered dry D. F. T. J. C. W.i.158 ABS'L'RAC!TS 05' C'HRMTCAT PAP ERS . cadmium bromide to ethereal solutions of the magnesium alkyl bromides and distilling the product in a high vacuum. The pure compounds are colourless highly refractive oils with very un- pleasant odours and irritating action on the mucous membrane. The lower members are remarkably volatile especially in ether vapour and i t is also interesting that the boiling points range higher than those of the corresponding mercury dialkyls. The oils are permanent if stored i n tubes filled with pure nitrogen in the dark but with traces of air and moisture they soon become steely-blue especially in the light. Cadmium dimethyl merely gets coated with a white crust of the methoxide on exposure to the air but the others are vigorously oxidised and even inflame if allowed t o fall in drops.The oils sink in water add then if shaken begin t o decompose with a crackling noise which proceeds for hours. They are mostly stable in an indifferent atmosphere up to about 180° when they decompose so. vigorously that part of the liberated metal melts to brilliant drops and another part is deposited as a mirror. The atomic refraction and dispersion of cadmium in these alkyls rise steadily with the molecular weights but taking averages they are remarkably high compared with the const'ants for mercury and zinc. Cadmium cliiurthyl hag in. p. - 4.5" b. p. 1O5.ri0/758 nini. D'\9 1.9546 IL 1.57766 i z l 1.58488 i z H P 1.60381 izTTy 1.62053 at 1 7 . 9 O . Cadrniiinz clieth!jl has m. p. - 21° b. p. 64O119.5 mm..D'Hq" 1.6564 ii, 1.56512 12 1.56798 1.58447 nHr 1.59887 at 1S.l". Cadmium di-n-pmpyl has m. p. - S 3 O b. p. S4O/21-5 mni. 17.6". Ccd77~iiim di-n-but?yl has ni. p - M0 lo. p. 103*5°/15*5 mn. I)'!' 1.3056 IZ, 1.51100 72 1*5154G? ?zIr6 1.52762 IZ, 1.53793 at 1 9 . 5 O . Cnd?zi2m diisobz&jl has 111. p. - 3 7 O b. p. 90.5°/S0 U ~ J I I . D' 1.2693 ii 1.49528 1 2 1.49966 nil 1.51160 IL 1.52173 atj 18". Cad~niwn diisortnayl has m. p. - 11.5O b. p. 121*Eio/15 mm. TlY 1.3210 1.4201 ;zHn 1.53412 I t 1..53906 71Hp 1.5426'7 IZ, 1.55452 st 1.49967 72 1.50339 I!,, 1.51470 7 l H 7 1e.52412 at 19'. All densities are i~cducecl to racnum standard. Some mixed Tin Tetra-alkyls and Tin Trialkyl Haloids. GERHARD GR~TTNER and ERICH KRAUSE (Ber. 1917 go 1802-1807).-The physical constants of some twenty known organo-tin compounds are tabulated and an account is given of about twenty new compounds of the same nature. The material is being gathered for an investigation on the atomic refraction af tin and for studies on compounds containing tin chains (compare following abstract).Mixed tin tetra-alkyls are prepared by heating tin trialkyl bromides with three times the theoretical quantity of magnesium alkyl haloids first in ether and then at looo and they are con- verted into the tin trialkyl bromides by the action of bromine a t - 40° to - 30° the rule being that the lightest alkyl group is dis- placed (compare lead; A. 1917 i 256). The chlorides are made from the bromides by shaking their ethereal solutions with 33% J . C. W.ORGAWIC CHAEMTSTRY.i. 159 sodium hydroxide (or silver hydroxide in the case of the methyl compounds) and then adding hydrochloric acid to the ethereal extract of the tin trialkyl hydroxide. Tin triethylisobzityl has b. p. 96.5'117 mm. 1.1390 nII 1.46977 12 1 *47304 I Z ~ 1.48132; ?lH 1.48836 a t 20.3'. Tin dimethyldiiso- 7mtyl has b. p. 85'/16.5 mm.. D:o'l 1.1179 n 1.46037 nD 1.46354 p i I t p 1.47165 7 z H y 1.47851 at 20*lo. Tin triethylisomzyl has b. p. 1 11'/18*5 mni. Dyl 1.1203 'lZ 1.46917 72 1.47243 9zH 1.48050 ~ i ~ ~ 1.45739 at 2 0 . 1 O . Tin ethyltri-n-propyl has b. p. 117.5/23*5 mm. DY' 1.1235 n 1.47053 n 1.47374 izHB 1,48197 nHy 1.48590 a t 31.S'. Tin dzethyldiisobutyl has b. p. 108.2'/13 mm. D;O4 1.1030 72 1.47036 1 1 1.47361 izHp 1.48167 i i H y 1.45846 a t 20.4'.Tii~ ti.i-n-p1,o~ylisobzityl has b. p. 12So/1S mm. DY'l 1.0841 ?z 1.46929 11 1.47245 nHp 1.48042 nHy 1.48711 at 34.1'. Tin diethyldzisoamyl has b. p. 131'/13.5 mm. Dig 1.0725 n 1.46957 12 1.47268 I Z ~ 1*48040 nHY 1.48694 at 19'. Tin ethyltriisobutyl has b. p. 125'/16 mm. D:' 1.0779 nHR 1.47053 n 1.47371 ?zHp 1.48167 7zH 1.48830 at 21'. Tin ethyl-n-propylcliisoamyl has b. p. 141-142'/ 17 mni. DY.' 1.0654 I Z ~ 1,46902 n 1,47214 ?z,? 1.47996 7zHy 1.48653 at 21.9'. Tin tetraisobutyl has m. p. - 1 3 O b. p. 143O/16*5 mm. D 1.0540 nH 1.47112 n 1.47423 nHp 1.48206 YZ 1.48863 at 23'. Tin triisobzitylisoamyl has b. p. 152.9O/16-5 mm. I)? 1 *0356 IZ 1.46851 ?L 1.47174; 1~~~ 1.47984 ?z 1.48575 at 26.8'. Tin diethyl-n-propyl chloride has b. p. 10S0/17 min. DF" 1.3848 n 1.50807 11 1.50580 nHp 1.51534 nHy 1.52322 at 15.7'.Tin (7iethylisonn~yl chloride has b. p. 125-5-126*5O/13 mm. Digg 1.2994 nzin 1.49443 32 1.49806 ?zHP 1.50687 n 1.51443 at 19.9'. T k dieth?yZ-n-propyl b?-omicle has b. p. 112*2O/16 mni. DY 1.5910 n, 1.51759 iz 1.52177 nHF 1.53232 nH 1.54129 at 21'- Tin dieth;jZisob2ifyl byonzide has b. p. 122'117 mm. D;O 1.5108 nH 1.51194 77 1.51586 ?zHp 1.52609 nHy 1.53464 at 20'. Tzn diethylisoarrzyl hronLide has b. p. 137.Fio/17 mm. Di7 1.4881 nEa 1.51252 n 1'51651 H ~ 1.52653 nHY 1.53503 at 1 7 O . Tzn ethyldiisobutyl bromide has b. p. 130*6O/13 mm. D:"'5 1.4085 nH 1.50452 n 1.50837 7zHp 1.51799 nHy 1.52607 at 19.5'. Tin ethyldzisoamyl h O m i d e has b. p. 1.54-155/16 mm. 1.3650 n 1.50263 n 1-50631 nITR 1-51562 i i I f y 1*52$47 at 30' All densities we reduced to vacuum standard and optical constants at higher temperatures are also recorded in one or two instances.J . C. W Hexa-alkyldistannanes. Atomic Linking of Tin. GERHARD GRUTTNER (Ber. 1917 50 18O8-1813) .-Hexa-alkyldistannanes R,Sn*SnR are prepared by heating tin trialkyl bromides diluted wit'h an equal volume of ether with sodium powder a t 1 2 0 O . They are colourless highly refractive and dispersive liquids with very unpleasant penetrating odours. They are stable towards heat and are only slowly oxidised on exposure t o the air. Hexuethyldistaia72nIze has b. p. 161-1 6 2 O Dli 1 *3795 nRn 1.53224 YL 1.53738 i t H p 1.55065 nEy 1.56210 at 1 7 ~ 8 ~ . Hexn-n- propyldistanizctneze has b. p. 143.6OJ15 mm. DY'j 1.2436 n 1.58122,i. 160 ABSTRACTS OF CHEMICAL PAPERS.n 1.52583 ?z.,,~ 1.53773 i ~ ~ 1.54806 at 19.5O. Flexnisobutyl- distannane has b. p. 179'13.5 inm. ni. p. 43*8' DTI 1.1330 i i H 1049706 n 1.50128 ?I, 1.51191 nHY 1.52120 at 59'. s.-Tetra- ethyldi-n-propyldistaItnuIze Sn2Et.iPrR2 has b. p. 165*8'/15 mm. s.-Tetraet7zyldarsobzltyldistalziznlze has b. p. 179°/15.5 mm. 1.2919 nHn 1.53108 n 1.52571 nHn 1.53772 nIIy 1.54815 at 19.8'. Densities are reduced to vacuum standard J. C. W. D:' 1.3313 11,~~..1.53042 71 1.53541 ?aHp 1.54822 ?I, 1.55945 at 15.3'. Side-chain Chlorine Derivatives of Toluene (Benzyl. and Benzylidene Chlorides and Benzotrichloride) . H. D. GIBBS and G . A. GEIGER (U.S.-P. 1246739 1917; from J . SOC. Clzenz. 7nd. 1918 37 5 2 ~ ) .-Gaseous toluene and chlorine are introduced into a suitable reaction chamber in which they are subjected t o the action of ultra-violet rays.One mol. of toluene with one two or three mols. of chlorine produces benzyl chloride benzylidene chloride and benzotrichloride respectively. w. P. s. Bromination of p-Nitrotoluene. J. F. BREWSTER (J. Amel.. Chem. Soc. 1918 40 406-407).-In view of the usefulness of p-nitrobenzyl bromide in the characterisation of acids and phenols (see Reid A 1917 i 333) it is of interest to know that satis- factory yields of the reagent can be obtained by gradually adding bromine dissolved in carbon tetrachloride to a boiling solution of pnitrotoluene containing a trace of iodine and exposed t o sun- light. [See also Inn. April.] J. C. W. Sulphonation of Aromatic Hydrocarbons or their Derivatives.H. BULL (U.S.-P. 1347499 1917; from J. SOC. Chem. Ind. 1918 37 52a).-The sulphonation is carried out in the presence1 of an organic solvent of lower specific gravity than sulphuric acid in which the hydrocarbon and sulphonated sub- stance are soluble. The solution of the sulphonated product is removed and if this is done continuously the process may be made continuous. The solvent may consist' of an excess of the aromatic hydrocarbon. w. 9. s. Tolane Chlorides from Calcium Carbide Chlorine and Benzene. CLINTON DAVIDSON ( J . Amer. Clzenz Soc. 1918 40 397-400).-If powdered calcium carbide free from iron is added to cold benzene saturated with chlorine a reaction slowly sets in the mixture becomes warm and hydrogen chloride is evolved.After a time the action subsides even while much chlorine still remains. I f the solution is then chilled i t deposits a mixture of the stable and labile forms of tolane dichloride but if it is heated for several days until the b. p. rises to looo it will then give much tolane tetrachloride. Toluene reacts somewhat' more readily and apparently in the same way. The mechanism of the process is indicated as follows CaC,+ C12 + CCliCCl;ORGANIC CHEMISTRY. i. 161 this + 2C6H6 -+ CPhiCPh and this + C1 -+ CPhCKCPhCl and CPhCl,*CPhCl,. [See also Ind. April.) J. C. W. Coloured Condensation Products of Fluorene and Alde- hydes. LUIS GUGLIALMELLI and ANGELES DELMON (Anal. SOC. Qzcim. Argeiitiiin 1917 5 124-130. Compare following abstract). -An account of colorations obtained by the action of fluorene in chloroform solution on aliphatic and cyclic aldehydes.A. J. W. Chromatic Reactions of Fluorene and Carbohydrates. LUIS GUGLIALMELLI and ANGELES DELMON (Anal. SOC. Quirn. Argentina 1917 5 169-176. Compare preceding abstract).- Solut’ions of fluorens in chloroform and in alcohol give character- istic colour reactions with moqoses polyoses polyhydric alcohols and glucosides. A. J. W. Addition of Ethyl Sodioacetoacetate to the Aromatic Mustard Oils [Thiocarbimides]. DAVID E. WORRALL ( J . Anzer. Chem. SOC. 1918 40 415-423) .-Ethyl sodioacetoaoetate reacts readily with phenyl- the three tolyl- pbromophenyl- and P-naphthyl-thiocarbimides according t o the equation Na*CHAc*CO,Et + R*N:C:S = CH,*CO*CH(CO,Et)*C(SNa):NR.The products change into thioanilides NHR*CS*CRAc*CO,Et 011 acidifying with hydrochloric acid. I n the case of the phenyl para-su bsti t u t ed phenyl and nap h thy1 compounds these compounds suffer “ acid hydrolysis ” even with dilute alkali hydroxides giving the fragmente NHR*CS*CH,*CO,H AcOH and EtOH but the 0- and m-t olyl compounds undergo “ ketonic hydrolysis,” yielding alcohol carbon dioxide and the substances CH,Ac*CS*NH*C,R,Me. Ethyl and benzyl derivatives of ethyl sodioacetoacetate react with phenylthiocarbimide less readily and the products are more stable towards alkalis. Ethyl sodioacetoacetate obviously prepared in a non-hydroxylic solvent (ether) and phenylthiocarbimide yield ethyl acetyltbion- nzalonanilate NIIPh*CS*CHAc*CO,Et which crystallises in pale yellow prismatic needles m.p. 82-83O yields hydrogen sulphide ethyl acetate and aniline hydrochloride when boiled with concen- trated hydrochloric acid and silver sulphicle and acetaldehyde with warm silver nitrate and changes into malonthionanilic acid NHPh*CS*CH,*CO,H (Ruhemann T. 1908 93 624) on warming with sodium hydroxide. o-Tolylthiocarbimide yields such an &stable primary product that it cannot be isolated. Ketonic hydrolysis takes place so readily that the product is acetothionaceto-o-toluidide CO Me*CH,* CS-NH C,H,Me which crystallises in nearly colourless needles m. p. 73-75O and is hydrolysed by concentrated hydrochloric acid to acetic acid and Wallach’s thionaceto-o-toluidide CH,*CS*NH*C6H,Me (the m. p. ip k+i. 162 ABSTRACTS OF CHEMICAL PAPERS.now given as 91-92O instead of 67-68O). Acetothioizaceto-m- toluidide has m. p. 83-44". p-Tolylthiocarbimide gives ethyl acetylthionmalon-p-tohidate glistening diamond-shaped tablets m. p. 8 1 O (the primary sodium derivative has m. p. 61-62O) and this yields thionmalo?z-p-toluidk acid on hydrolpis in long flat needles which melt at 97O and change thereby into thionaceto-p- toluidide m. p. 129*5-130'5° (Wallach). E t h y l acetylthionmaloit-p-Bronaoanilate has m. p. 81-83O ; thionnzcslon-p-b?*onzoanilic acid forms cream-coloured flat needles and plates and changes at 150° into ~bl.on.2othionacetn.nilide which cryst'allises in narrow hexagonal plates m. p. 153O. E f hyl acetybt hionmalon-B-naph th ylamate C,,R,*CS*CHAc*CO,Et (not purified) yields thionmalon-j3-naphthylam,ic acid in pale yellow plates m.p. 87-89O (dscomp.). Ethyl sodio-a-ethylacetoacetate gives ethyl a-acetyl-a-ethyl- thiommalon-anilate as an oil which is much more stable towards acids and alkalis than the above analogues. Ethyl sodio-a-benzyl- acetoacetate reacts very sluggishly with phenylthiocarbimide and the only product' described is a polynzeride of apparently P-phenyl- thionpropionanilide CH,Ph*CH,*CS*NHPh having m. p. 222- 223O (decornp.). J. C. W. Unsaturated Groups in Chemical and Pharmacological Connexions. I. J. VON BRAUN and Z. KOIILER (Bey. 1916 5 1 79-96) .-That the unsaturated radicle allyl differs in many respects from aliphatic radicles is well known. Chemically the most striking differences are to be found in its weaker attachmerits t o nitrogen (compare Collie and Schryver T.1890 57 767; von Braun A. 1900 i 641; Komatsu A. 1913 i 39) halogens (Clarke T. 1910 97 416; von Braun A. 1912 i 433) and oxygen (Claisen and Eisleb A. 191 3 i 11 75). Pharmacologically itl is a striking fact that by the replacement of an N-methyl group by allyl in choline or codeine bases are obtained which are ant'agonistic to the parent bases (A. 1917 i 254; 1916 i 665). The question naturally arises are thes9 effects peculiar to ally1 or are they reproduoed by other unsaturated 'radicles and i f so is the position of the ethylene linking of moment? The problem has therefore been attacked and so far the chemical influences of t'he cinnamyl -CH,*@H:CHPh the 2-furfuryl -CH2*C<CH.-!lr. and As -pentenyl -CM2=CH,-CH,*CH:CH groups have been' ex- amined.It is found that the last resembles saturated radicles in its attachments whilst the first two resemble allyl. An ethylene linking between the P- and y-carbon atoms is therefore one factor of importance. 1. THE CINNAMIIPL RADICLE .-Cinnamyl bromido is conveniently prepared by helating cinnamyl alcohol with three times its weight of hydrobromic acid (D 1.48). The halogen is so loosely combined that it is quickly removed by warm water alone. The bromide 0-C HORGANIC OHEMISTRY. i. 163 combines most readily with tertiary bases; for its behaviour with pyridine see Clarke (Zoc. cit .) ; wit'h trimethylamine it forms cinnamyltrimethylammonium bromide in silvery leaflets m. p. 165O. It reacts vigorously with magnesium thO bromine being removed and a<-diphenyl-A.6-hexadiene formed.With magnesium ethyl iodide it yields this diphenylhexadiene and also a-p henyl- Aa-pentene b. p. 202-205O Dy 0-8782 ni' 1.51575. It condenses with dimethylamine to. form ciniZQ;~yZdimetFYylamilZ.e NMe,. CH,* CH CHPh as a colourless liquid witlh strong basic odour b. p. 100-lO1°/ 7 mm. which forms a picrate m. p. l l O o . 11. THE ~-FURFURYL RADIcLE.-FurfuraIdehyde is converted by Schwabbauer's method (A. 1902 i 230) into 2-furfurylmethyl- amine b. D. 59-60°125 mm.. which forms a b e n z o d derivative I b. p. 180-185O/5 mm. and' reacts with ethyl ioYdide to give 2- f UT ficrylm e t kyle thyla mine NMeE t,* CH2; C<' -gH This is a CH*CH' colourless base which smells strongly like ammonia has b. p.69-70°/23 mm. forms a picrate m. p. 9l0 a jdatinichloride m. p. 147O and a methiodide m. p. lolo and reacts very vigorously with cyanogen bromide to give some di-2-f2crfurylmethylethyl- ammonium bromide (C,H30*CH2),NMeEtBr in. p. 151° a little met,hylethylcyanamide CN-NMeEt but also in 80% yield the desired 2-furfuryl bromide. This is a very unstable oil which severely attacks the mucous membrane the skin rubber and cork is quickly hydrolysed by warm water and energetically combines with tertiary arnines. 2-FurfuryZtrimetkylammonium platini- chloride m. p. 146-148O (decomp.) is mentioned in this con- nexion. 2-Furfurylmethylamine combines with ethylene oxide a t 50° to form 2-furfu~ylmet hyl-fl- h ydroxyet h ylamine C,H,0*CH2*NMe*CH,*CH~*O~ as a glycerol-like liquid b.p. 105O/6 mm. which yields a picrate m. p. 68-70° a very soluble aurichloride a platinichloride decomp. 133O and a methiodide m. p. 77-80O. 111. THE As -PENTENYL RADrcLE.-The parent substance in this series is t'he dimethylpentenylamine CH,:CM*rCH,],*NMe which is obtained by the Hofmann degradation of piperidine. This reacts very vigorously with cyanogen bromide about half of the base being converted into its methobromide and the remainder into met hyZ-As-pent en ylcyanamid e CH, CH*C3H,*NMe* CN b . p . 96-98O/7 mm. This is hydrolysed by boiling with 25% sulphuric acid to methyl-A'-pentenylamine a mobile liquid b. p. 107-109° which fumes in the air and forms a pZatinichZoride m. p. 1 5 8 O a picrate m. p. 150° and a benaoyl derivative b. p. 164-167O/ 7 mm.This amide CH,JCH-C,H,-NMeBz gives the desired A'-pentepyl haloids on fusion with phosphorus pentahaloids but the yields are very small. Another attempt to prepare the haloids was therefore made. A solution of sodium arnyloxide is cautiously warmed \vitlh I,.* 2i. 164 ABSTRACTS OF CHEMICAL PAPERS. as-dichlorope~itaiie when the di-ether C,H,,(O*C,H,,) (Hamonet A. 1904 i 705) and E-chlorodiamyl ether C,Hi1*O*C5H,,C1 are formed the yield of the latter being 40%. This ether is a colour- less pleasantrsmelling liquid b. p. 100-105°/8 mm. which reacts with dimethylainine t o form dimetkylanzyloxyamylami~ae as a limpid liquid with penetrating odour b. p. 99-103O/7 mm. [The amyloxy-residua in these compounds is derived from ordinary amyl alcohol ; the prefix " g.- " is proposed from GSrung =fermentation to signify this.] The tertiary amine is h'ydrolysed by means of concentrated hydrochloric acid to ~~nzetJiyl-~-chloroumylamine hydrochloride which is snow-white and may be converted into the auriclzloride m.p. 64-65O. The free base is stable enough to be transfornied into the nzethiodide C,H,,C1-NMe31 m. p 134O but this loses some chlorine as well as the iodine on treatment with silver oxide so that on distilling the quaternary ammonium hydr- oxide oiily an impure specimen of the desired pentenyl chloride can be obtained. The purest specimen of A*-pmnteiT,?/Z bl*omicZe so far obtained had b. p. l l O o . It has a sweet odour does not att'ack the eyes is not readily attacked by water does notl combine easily with tertiary amines but reacts fairly completely with magnesium in all these respects differing from ally1 bromide.Not sufficieiit magnesium A'-pentenyl bromide could be obtained in this way for any experi- ments but the coinporind mas prepared from a&-tribromopentane as follows. e-Phenoxyarnyl iodide is treated with trimethylamine tho quaternary iodide is converted. into the hydroxide and this is dis- tilled when a 40% yield of e-phenosyha-pentene is obtained as a pleasant-smelling limpid liquid b. p. 109-111°/13 mm. DT 0.9464 n?,n 1.50. The dib~oniide of this b. p. 190-205°/ 12 rum. is hydrolysed by prolonged boiling with fuming hydro- l~romic acid t o as€-trihrontopentaiz~ which is a heavy oil b. p. 128-132°/11 mm. with spicy odour. This beheves like other tri- bromides which contain two bromine atoms attached t o neighbour- iiic carbon a,torns when treated with niagnesinm (A.1911 i 701 938) the chief product being magnesium As -pentenyl bromide CW&CH*C,€I,*MgBr. This is proved by the fact that As-hexenoic acid CH,:CH*C,FI,*CO,K is produced from it by the action of carhon dioxide (compare Fichter and Langgut'h A. 1897 i 590). J C. W. Dicyclohexylamine . Solid Hydrate and Alcoholate. GUSTAVE FOUQUE (Compt. rend. 1918 166 394-395).-DicycZo- hexylamine when poured on to water a t below 2 3 O gave a crystal- line kydrate NH(C;3H,,)2,H20 m. p. 23O. The solubility of the arnine in water and of water in the amine diminished as the temperature rose above 2 3 O . An equimolecular mixture of dicycZo- hexylamine and ethyl alcohol a t the ordinary temperature gave the aZcohoZate NH(C,H,,),,EtOH in.p. 2 8 O which dissociated in the air. W. G.ORfl ANTC! CHEMISTRY. i . 1G5 Oxalyl Chloride as a Reagent in Organic Chemistry. 11. Preparation of Aromatic Anhydrides. Reaction with Alcohols. ROGER ADAXS W. V. WIRTH and 11. E. F R m c x I ( J . Amer. Chenz. Soc. 1918 40 424-431. Compare A. 1916 i 140; 1917 i 4).-When slightly more than one molecular pro- portion of oxalyl chloride is added t o a boiling solution of two parts of an aromatic acid in benzene very good yields of the acid anhydride are obtained. The reaction apparently proceeds in two stages thus 2R*CO.,H + C,OLCl = 2RC1+ (R*CO*O),C,O and this = (R*CO),O + CO + CO for m-nitro- 2 4- and 3 5-dinitro-benzoic acids yield the intermediate mixed anhydrides (probably owing to the .insolubility of these in benzene) which decompose in the indicated way on heating or on treatment with cold pyridine.The advantages of the method are obvious. The following anhydrides have been prepared in this way benzoic; the three toluic; o-chlorob enzoic white prismatic needles m. p. 78-79O ; m-chlorobenzoic short white needles m. p. 95O ; p-chlorobenzoic ; m-iodobenzoic plates m. p. 134O ; o-nitrobenzoic ; m-nitrobensoic oznlic an h y&ide (NO,*C,R,*CO O),C,O pale yellow decomposing a t 1 5 7 O into m-nitrobenaoic ankydride ni. p. 163O [Autenrieth's anhydride m. p. 47O (A. 1901 i 186) was really Greene's m-nitro- benzoic acetic anhydride Ac*O*CO*C,H,*NO (A. 1890 53)] ; 3 5-dinitrobenzoic oxalic anhydride decomp.175O and 3 5-dinitro- henzoic anhydride m. p. logo; 2 4-dinitrobenzoic oxalic anhydride in. p. 205-209O (decomp.) and 2 4-dinitrobenzoic nnlzydridP ni. p. 160O. Just as phenols react with oxalyl chloride in the presence of pyridine a t Oo t o form oxalates so primary and secondary alcohols give these esters in 5004 yield on an average. Tertiary alcohols usually do not react a t all. The following oxalates have been pre- pared by this method be??zhydml m. p. 142-143O; phenyl-o- fo7ylcnrbii~i/l (CHPh*C,H,Me)2C,0 m. p. 86-87O ; benzoin o mlnte (COPh*CHPh)2C901 m. p. 243-245O ; piperonoin ozalate C,,H,,O m. p. 225-226O; bornyl ; menthyl; isopropyl; and dg phen?/lmetTLylcnrbi?yl omdate (CMePh,)?C,O pyramids decomp. 1?0-185O (yield very small). [See also Znd.. April.] J.C. W. Preparation Of SOlUtiOIlS Of Glycol Esters. FARBENFABRIKEN VORM. FRIEDX. BAYER & CO. (D.R.-P. 298185 1915; from Cheni. Z ~ f 2 t r . 1917 ii 145).-Ethylene glycol monobenzoate m. p. 45O can be dissolved in almost any proportion in solutions of the alkali salts of benzoic toluic salicylic or cresotic acid ; in' place of the lienzoyl derivative of ethylene glvcol the corresponding m- and 11-toluoyl o-chlorobenzoyl or salicyl compound may be used. D. F. T. Preparation- of Acyl Derivatives of Aromatic Amides. MENDEL PERELSTEIN and EMIL BURGI (D.R.-P. 297875 1915; from (YhPni. Z m t ~ . 1917 ii 144-145).-By introducing the isovaleryl radicle into the amino-group of aromatic amides compounds arei. 166 ABSTRAaTS OF CHEMICAL PAPERS. obtained possessing the soporific power of the amides but much less poisonous.The method of preparation is by the direct interaction of the isovaleryl haloid with the acid amide either in the molten condition or dissolved in an organic solvent in the presence of a dehydrating agent. By brominating the isovaleryl-substituted amide or by using an a-bromoisovaleryl haloid for the first reac- tion it is possible t o produce compounds of especial therapeutic value. The following substances were obtained cinjnamoyl-a- 7,romoisovccZe?.yTnmide colourless needles m. p. 118O (dibromide crystals m. p. 1 4 5 O with reddening) ; benzoyl-u-bromoisovaZevl- cimide colourless needles m. p. 142-143O ; b~.S-OE-bromoisovaIeryl- salicylnmide [a-hromoisovaleroxyben~oyl-a-bro~noisovaleryla~ide~ needles in.p. 1 1 9 O ; benzoylisovalerylamide needles m. p. 89O; cinnnnzoylisoz?/cle?.?/lamide needles m. p. 103O (dibromide m. p. 1 6 5 O ) . D. F. T. The Walden Inversion. VI. Influence of the Solvent on the Sign of the Product in the Conversion of Phenylbromo- acetic Acid into Phenylaminoacetic Acid. GEORGE SENTER and STANLEY HORWOOD TUCKER (T. 1918 113 140-151; corn- pare A. 1915 i 535; 1916 i 815; 1917 ii 301).-It was found in the first experiments of this series that the sign of the amino-acid obtained by the action of ammonia on active phenylchloroacetic acid depends on the nature of the solvent employed and it appeared Go be of interest t o examine this phenomenon in other cases. Experiments on the displacement of bromine by the amino-group in the case of I-phenylbromoacetic acid have given the following results (a) in aqueous solution or in the higher alcohols (n-butyl trimethylcarbinol n-heptyl) the amino-acid obtained is opposite in sign which agrees with the behaviour of phenylchlosoacetic acid ; ( b ) in the lower alcohols (methyl ethyl n- and iso-propyl) the pro- duct is also' opposite in sign whereas the amino-acid obtained from phenylchloroacetic acid in these solvents has the same sign as the parent lialogeno-acid ; ( c ) in acetonitrile or liquid ammonia the product has the same sign as in the earlier case; ( d ) considerable racemisation takes place in the lower alcohols but not in the higher; (e) the presence of ammonium bromide has little racemis- ing influence in aqueous solution but considerable in liquid am- monia ; (f) small quantities of iminodiphenyldiacetic acid of high activity opposite in sign to the original acid are formed in all solvents.The mechanism of the formatioa of the imino-acid is discussed. It is probable that it is formed by the direct action of ammconia on two molecules of the halogeno-acid rather than by the inter- action of the halogeno-acid with the amino-acid. The Walden Inversion. VIP. Influence of the Solvent on the Sign of the Product in the Conversion of a-Bromo- P-phenglpropionic Acid to a-Amino-P-phenylpropionic Acid (Phenyldanine) . Iminodiphenyldipropionic Acid. GEORGE SEWTER HARRY DUGALD KEITH DREW and GERALD HARGRAVE MARTIN (T. 191 8 1 13 15 1- -I 63) ,-tr-Bromo-B-phenylpropionio J. C. W.ORGAMIC CHEMISTRY. i. 1G7 acid has been examined in this series as the phenyl group is removed from the asymmetric carbon atom and consequently different results might perhaps be anticipated.It is found that in all the solvents tried water alcohols and even acetonitrile and liquid ammonia the amino-acid has the opposite sign t o the parent active acid although very considerable racemisation occurs in the last two media. The most remarkable difference between this case and the earlier ones is however that ammonium bromide actually lessens racemisation when the reaction is carried out in liquid ammonia. a-~mino-PP-diplteiayldipro~'o?l~c acid NH[CH(CH,Ph) *CO,H] is formed in small amounts in all the solvents with the same sign as the bromo-acid. The perplexing differences observed in the three cases (papers V.VI. and VII.) are perhaps best accounted for on the assump- tion that the action of ammonia on the halogeno-acids proceeds as two simultaneous reactions the formation of both d- and Z-amino- acids. Which of these reactions predominates depends on the nature of the acid the nature of the solvent and other factors. [For experimental details see the original. J J. C. W. Preparation of a Solid isovaleric Acid Compound Soluble in Water. HUGO VOSWIXCKEL (D.E.-P. 294877 1914 ; from Chem. Zentr. 1917 ii 144).-By warming a mixture of iso- valeryl chloride and mandelic acid in benzene solution isovnlery1- rttandelic [a-isoualer~loxyph.eizylaceticl acid C,R,*CO*O * CHPh*CO,H hard crystals m. p. 71° is obtained the1 calcium salt of which is a granular solid soluble in water.Pbthalic Acid Derivatives Constitution and Colour. V. Some Derivatives of Tetrachloro- and Tetraiodo-phthal- irrtides. DAVID S. PRATT and GRANVILLE 9. PERKINS (J. Amer. Chenz. SOC. 1918 40 198-214. Compare A. 1914 i 415; 1915 i 686 692).-In the hope of obtaining a dearer insight into the relation- ship between the' absorption bands shown by various members of the same family and a more exact knowledge of the origin of each band investigation is being made of the absorption spectra of a large number of compounds related to phthalic acid each differing only slightly from its neighbours. The present paper only deals with the preparation of phthalic acid derivatives in which halogen is substituted into the benzene ring or in which the anhydride oxygen is replaced.Tetrachlorophthalic anhydride prepared by the action of chlorine on a hot solution of phthalic anhydride in fuming sul- phuric acid in the presence of iodine gives unstable deeply coloured additive compounds wit.& certain amines ; with dimethylaniline and dimethyl-p-toluidine the additive compounds were isolated as red prisms C,O,Cl,,NPhMe and almost purple crystals reswctively but the formation of similar compounds with diethyl- ar)line methylaniline and the two' naphthylamines could only ho D. F. T. C,O3ai,C:H,*NM%,i. 1C,8 ABSTRACTS OF CHEMICAL PAPERS. detected by the red colour of mixtures of the anliydride and the respective bases dissolved in xylene if necessary ; diplienylaini tie and aniline yielded yellow solutions whilst no coilour change was observed with pyridine and triethylamine ; the presence of chlorine is not essential t o this reaction because 3-nitrophthalic anhydride and other substituted phthalic anhydrides including indeed even phthalic anhydride itself are capable of similar belzaviour the effect being so general as to suggest that the formation of such additive compounds is an essential first stage in the condensation of phthalic anhydride and its nuclear substituted derivatives with aromatic amines.In these rtdditive coinpounds it is believed that the attachment between the two molecules occurs by means of residual valency a t the anhydride oxygen atom and the nitrogen atom of tlie amine; with a tertiary amine no further change is possible but with a secondary amine rearrangement sub- sequently occurs with formation of the colourless salt whilst with a primary amine such as aniline the formation of the aniline phthalanilate can be succeeded by loss of aniline and production of tlie anil. I n accordance with this view the yellow solution of tetra- chlorophthalic anhydride and aniline in benzene gradually deposits aniline tetrachloropht halanilate C2,H,40,N,Cl a colourless crystal- line powder m.p. 271-273O (corr.) which readily undergoes fur- ther condensation to tetrachlorophtlialanil m. p. 274-275O (corr.). When tetrachlorophthalic anhydride is heated with aniline prefer- ably in an inactive atmosphere the reaction goes still further with production of 3-andko-4 5 6-tm'clzlorophthaZaizil C,,H,,O,N,Cl mange blades m. p. 1 79.5-180*6° (corr.) and a dianilinodichboro- phtlzalanil C,H,,O,N,Cl bright scarlet blades m.p. 182*5-183*5O (corr.). Tetrachlorophthal-ortoZz'Z C,,H70,NC14 colourless rhombic leaflets m. p. 232-236.5O (corr.) also its metaisomeride m. p. 245'5-246'5O (corr.) and para-isomeride were obtained by 'heating a solution of tetrachlorophthalic anhydride and the corresponding toluidine in acetic acid. Tetrachlorophthal-o-tolil exhibits dimorpli- ism separating from acetic acid o r alcohol in colourless hexagonal leaflets which a t 207O (corr.) soften and become yellow with forma- tion of a coloured modification m. p. 214-214'5° (corr.); this is stable only above l1S0 and can also be obtained in long hair-like crystaIs by seeding the warm solution of the ordinary form in acetic acid or alcohol with a little of the yellow form.I n accord- ance with the probability that the yellow form below its transition point must possess more free energy than the colourless modifica- tion it is found that the former yields coloured additive colmpounds with benzene (3 o r 4C,,H70,NCl4,C,H long yellow hair-like crystals) m-xylene (4C,,H,0,NCl,,C,H,Re2) nitrobenzene yellow blades) and dimethylaniline (5C,,H,O,NCl,,NMe,Ph scarlet needles) whereas the colourless variety shows no such tendency. The following anils were obtained by heating together the corre- sponding base and tetrachloroplithalic anhydride in acetic acid solution t P trnch loroph t hnl-o-nitro0 17 il C,,H40,N,CI colourl ess (~c,~H,o,Nc~~,c,H,=No~,ORGANIC CHEMISTRY. i. 169 leaflets m.1). 272--273O (corr.) ; tetracJilol.ol~?i~?ic~I-m-~litl.oaniI colourless blades In. p. 300-301’5° (corr.) ; tetrncJi2o.roplitliaZ-p- nitroanil fine colourless needles m. p. 292-297O (corr.) ; tetra- chloropht hnl-p-hydroxyanil C,,H,O,NCl bright yellow needles m . p. 3 05-307O (corr .) ; t e trachl oroph t hal-p-a ce t ylamin oanil pale yellow nodules or colourless needles m. p. near 339O (corr.). F o r the preparation of tetrachlorophtlialimide m. p. 338-339O (corr.) Graeble’s method (AiLncrlen 1887 238 332) is less conveni- ent than one employing formamide in place of animonia a warm solution of the tetraclilorophthalic anhydride in the former rapidly depositing the imide. 11; a similar manner tetra-iodophthalic anhy- dride reacts with formamide giving tetrcriodop~~t7inlirni(~e7 C,HO,NI fine yellow needles in.p. 370-380° (decoinp.) whilst condensation of the anhydride with the various aromatic amines in nitrobenzene solution gives tetmiodopJL thalnni! C14H502N14 yellow blades m. p. 314-315O (corr.) ; t~traiodoy/iLthal-o-tolil C15H702N14 minute yellow crystals m. p. 314-315O (corr.) ; tetrniodophthal-m- tolil yellow blades m. p. 325-326O ; tetraiodophthal-p-tolil yellow blades m. p. 317-318O (corr.) ; tetraiodophthal-m-nitroanil Cl,H,0,N21 yellow matted needles in. p. 318-319O (corr.) ; tetra- iodophthal-phydroxyanil C14H,03N14 fine yellow needles m. p. 330-336O (corr.) and tetraiodophthal-p-ncetylanzinoaizib minute yellow blades m. p. 339O (corr. tlecomp.). D. F. T. Phthalic Acid Derivatives Constitution and Colour.VI. Action of Amines on Dichlorophthalic Anhydrides DAVID S. PRATT and GRANVILLE A. PERKINS ( J . Amer. Chem. SOC. 1918 40 214-218. Compare preceding abstract).-3 4-Dichloro- phthalic acid reacts with aniline in boiling acetic acid solution yielding 3 4dichloropht halaizil C1,H7O2NCl2 which usually crys- tallises in very pale yellow silky needles m. p. 174O (corr.) but on account of the readiness of transformation into a second modifica- tion colourless prisms m. p. 182-182.5O (corr.) the lower m. p. can be observed only by sudden immersion of a small quantity of the needles in a bath near 174O. When heated with an excess of aniline in an inert atmosphere the dichlorophthalic acid undergoes further conversion into 3-anilino-4-chlorophthalaizi1 C,,H,30,N2Cl orange leaflets m.p. 159.5-160O. I n a similar manner 3:6-di- chlorophthalic acid is convertible into 3 6-dichlorophthalanil m. p. 197-198O (corr.) and 3-anilino-6-chlorophthalani17 C20H1,02N,C1 which exhibits dimorphism the crystals commonly obtained from alcohol forming orange needles which on rapid heating have m. p. 141O (corr.) whereas on slow heating or on being kept in contact with the solvent the substance beconies changed into a second form small orange prisms m. p. I 60-1 60.5O. 4 5-Dichloaophthalic an- hydride reacts with aniline in boiling acetic acid yielding 4 5-di- chloroplithalnnil colourless. rhombic leaflets m. p. 212’5-213O (corr.) but shows no tendency t o the further replacemeiit of chlorine hy the anilino-group. T). F. T.i. 190 AUYTR.AOT9 O F CHEMICAL PAPXRS.Phthalic Acid Derivatives Constitution and Colowr. VII. Di-iodo- Tri-iodo- and Dichloroiodo-phthalic Acids. DAVID S. PRATT and GRANVILLE A. PERKING ( J . Amer. ChenL. SOC. 1918 40 219-236. Compare preceding abstracts).-In extensiou of the investigation in which chlorine in halogenated phthalanils was observed t o be replaceable by the anilino-group various iodo- phthalic acids were prepared for interaction with aniline. When phthalic anhydride dissolved in fuming sulphuric acid is treated with iodine the composition of the product is dependent on the temperature; prolonged heating a t 75O gives rise t o nearly equal amounts of the 3:4- and 3:6-di-iodo-acid-s with much smaller quantities of 4 5-di-iodophthalic acid and 3 4 6-tri-iodophthalic anhydride whereas the product obtained on rapid heating t o 200° contains approximately the same amount of the 4 5-di-iodo-acid with a larger amount of the 3 4-di-iodo-acid and the tri-iodo-anhy- dride a t the expense of the 3:6-di-iodo-acid.Traces of 4-iodo- phthalic acid and tetra-iodophthalic anhydride were also observed. A partial separation of the products is posdble by esterification only the 4 5-di-iodo-acid and part of the 3 4-di-iodo-acid forming normal esters with alcohol ahd hydrogen chloride. Separation was finally effected 'however by fractional precipitation from a solution of the disadium salts with acetic acid causing deposition of the monosodium salts in the order 4 5-di-iodo-acid7 tri-iodo-acid and 3 4-di-iodo-acid the salt of the 3 6-di-iodo-acid remaining in solm- tion aided by the knowledge t h a t on recrystallisation from acetic aeid the 3 4- and 4 5-di-iodo-acids separate unchanged whereas the 3 6-di-iodo-acid and the tri-iodo-acid become converted into the corresponding anhydrides which are very soluble in benzene.The structure of the various acids was determined by heating with sodium hydroxide solution and examination of the resulting hydroxy-acids. The dichlorophthalic anhydrides can be iodinated in a similar manner t o the parent phthalic anhydride. 3 4-Di-iodophtholic acid C,H,0,12 colourless leaflets m. p. 212-213O (corr.) when heated with acetic anhydride in benzene solution yields the corresponding anhydride CsHz031e almost colourless prisms m. p. 198-198.5O (ctxr.) is slowly hydrolped by sodium hydroxide solution with formation of 3 4-dihydroxybenzoic acid and reacts with aniline in bailing acetic acid forming an unit C14H,09N12 very pale yellow prisms m.p. 270-271O (corr.). 3 6-Di-iodophthalic acid forms colourless leaflets which undergo gradual dehydration even below looo with formation of the anhy- dride colourless prisms m. p. 234.5-235.5O (corn.). When heated with aqueous sodium hydroxide 3-hydroxyphthalic acid is produced with much tarry matter but no 3 6-dihydraxy-acid ; however by boiling a solution of the anhydride with aqueous pyridine and silver sulphate it Is pmsible t o obtain 6-iodo-3-lz?ldro,r?/phthaZic an h?ydride (ucetate C,,H,O,I square crvsta'ls m. p. 148*5-152*5° corr.). which is hydrolysable with concentrated sodium hydroxide solution t o 3 6-dihydroxyphthalic acid.3-Hydroxyphthalic acid C,H,O colourless prisms m. p. 161-163O (corr. ; decomp.) readily passes into the anhydride orange-yellow crystals m. p. 198-1990 (corr. ;ORGANIC CHEMISTRY. i. 171 Jacobsen A. 1883 1124 gives 145-148') the acetate of which crystallises in colourless leaflets m. p. 113*5-115*5O (con.) and the benzoate in leaflets m. p. 147.5-148O (corr.). 3 6-Di-iodophthal- anil prepared similarly t o its 3 4-isomeride forms colourless rect- angular plates m. p. 233*5-234O (corr.). 4 5-Di-iodophthnlic acid colourless needles (probably with acetic acid 'of crystallisation) or leaflets m. p. 221-222O (corr. ; decomp.) on dehydration with acetic anhydride or by mere heating is con- verted into the anhydride colourless prisms m.p. 216.5-217O (corr.) ; hydrolysis of the acid with sodium hydroxide yields 4 5-di- hydroxyphthalic acid and perhaps a little 3 4 5-tri'hydroxyphthalic acid. 4 5-Diiodophthalani1 prepared by 'heating the acid with acetic anhydride and aniline in acetic acid solution exhibits dimorphism separating from acetic acid or xyl'ene in pale yellow needles which on rapid heating have m. p. 231-5-233O (corr.) but on gradual heating undergo transformation into a modification m. p. 241.5-243O (corr.) the latter being also obtained in the form of pale yellow hexagonal leaflets from the molten ahil on very slow cooling. 3 4 6-Tri-iodophthalic anhydride C8H0,13 bright yellow rhombic pyramids m. p. 230-231O (corr.) yields an and C,,H,O,NI light yellow microscopic needles m.p. 254.5-255-5O (corr.) and o'n hydrolysis with sodium hydroxide gives a mixture of 3 6-dihydroxyphthalic acid with other substances probably including a little 3 5-dihydroxybenzoic acid. 3 4-Dichloro-5 6-di-iodopht italic anhydride C80,Cl,12 yellow prisms m. p. 229.5-230'5O (corr.) obtained by the interaction of 3 4-dichlmophthalic anhydride and iodine in heated fuming sul- phuric acid yields an anil ~,4H,02NC1,1 pale yellow needles m p. 242*5-243.5" (Cory.). 3 6-Dzchloro-4 5-di-iodbphthnlic mi- hydrdde yellow prisms m. p. 258-258'5O (corr.) obtained in a similar manner yields an anil pale yellow needles m. p. 232-232'5O (corr.). 4 5-Dichloro-3 6-di-iodophthalic anhydride yelltow blades m. p. 232-233'5O (con-.) forms an a d very pale yellow needles m.p. 282'5-284O (corr.) and when heated with excess of aniline f o r twenty-four hours a t 130° undergoes further conversion into 4 5-dichloro-3 6-dianilinophthalanil orange-red crystals m. p. 181'5-185O (corn.) quite distinct from the isomeric product obtained by the action of aniline on tetra- chlorophthalanil (this vol. i 168). CkK iO,N,C' 7 D. F. T. Phthalic Acid Derivatives. Constitution and Coloui. XII. Tetrachlorophthaloxime and some of its Derivatives. DAVID S. PRATT and CHARLOTTE H MILLER ( J . Amer. Chem. SOC. 1918 40 407-412. Compare preceding abstracts).-Unsubsti- tuted phthaloxime exists in two chromoisomeric forms (A. 1912 i 190) but only one colour has been observed with the tetrachloro- and tetraiodo-phthaloximes and their ethers and est'ers.The ethers of tetrachlorophthaloxime however often exist in two modifications,lisiially coLton like III~SSC:; 311(1 stat)le HtOilt prisins whirl1 are inter- changeable and this dimorphism 'tin:; n o t been olise~vcd in the other series. Tetrachlorophthaloxiine (A. 1913 i 100) forms a red silver salt from which the following colourless ethers may be prepared methgl blades in. p. 206O; ethyl m. p. 1 6 0 O ; isoprop?/l very thin glistening plates or clusters of stout prisms m. p. 146O; isoam?/1/ in. p. 244O; nllyZ m. p. 186O; and benzyl filaments only m. p. 1 9 2 O . The acetat,e (ibid.) and benzoutt. pearly diamond-shaped plates or stout prisms m. p. 21O0 are also obtained froin the* silver salt. Te t r n chl o ~ o p h t k a7 i c n I I h ydr ide @ e 7 ~ ~ 1 hytTr'~t z o n c from the anhydride phenylhydrazine and glacial acetic acid crystallises in yellow plates which rapidly pass into orange needles m.p. 2 8 7 O . All in. p.'s are " corrected." [See also I d . April.] J. C. V7. Phthalic Acid Derivatives. Constitution and Colour . XIII. Tetra-iodophthaloxime and some of its Derivatives DAVID S. PRATT and THOMAS B. DOTVNEY ( J . Amer. Chem. SOC. 1918 40 412-415) .-Tetra-iodophthalic anhydride (this vol . i 177) has been converted into tetra-iocloplzthrrloxini e I /co- 6 4 'q:r;.(+@y which exists in only one form long lemon-yellow needles of no definite m. p. From the red silver salt the methyl ethyl n-propjl isop~opyl ii-bzbtyl isoamyl n-octyl allyl and benzyl ethers and the cccetate and benzoate have been obtained.These all crystal- lise in more or less palei yellow needles arid also decompose with- out melting. [See also Znd. April.] J. C. W. A. TY. I<. DE JOXG (Prnc. R. Aknd. Wetensch. Anwterdanz 1918 20 590-596).-From a consideration of their properties their inter-conversion and their preparation from cinnamic acids the author has assigned spacial formulae t o the a- P- y- 6- and s-truxillic acids and t o P-cocaic acid on the assumption that these acids contain a tetrarnethylene New Synthesis of Digallic Acid and Migration of Acyl in the Partial Hydrolysis of Acylated Phenolcarboxylic Acids. RMIL FIScrIER ~ I A X BERGMANN and J J T ~ ~ ~ ~ ~ h P s c H I T z (Bw. 1918 51 45-79).-Two syntheses have already been described which were expected to lead to p-digallic acid lint yielded The Structure of Truxillic Acids.ring. w. G.ORGANIC CHEMISTRY. i. 173 m-digallic acid instead (A. 1908 i 893; 1911 i 875; 1913 i 479). A third method is now described. 3 5-Diacetylgallic acid is con- densed with triacetylgalloyl chloride giving penta-acetyl-p-digallic acid and this is cautiously hydrolysed by cold dilute ammonia solution. Again the surprising discovery has been made that the product is m-digallic acid. Similarly if 3 5-diacetylgallic acid is benzoylat'ed and the acetyl groups are removed by hydrolysis the product is not para- but* m-benzoylgallic acid and when 4-benzoyloxy-3-acetoxybenzoic acid is partly hydrolysed the product is 3-benzoylprotocatechuic acid. All these unexpected products are therefore due to the wander- ing of one acyl group into the position vacated on hydrolysis by another attached t o a neighbouring carbon atom.Thus CO,H C0,H CO,H /\ /A /\ \/ OAJ lOAc OH1 lOBz \/ 0 H OBz (111.) A trausference of an acyl group has often been reported before b u t only irom carbon to oxygen or nitrogen and vice versa or from nitrogen in a side-chain to nitrogen in the ring numerous references to which are quoted but this is tthe first record of such a migration from one phenolic group t o another. The intermediate compound (111) might perhaps be formed. ' DERIVATIVES OF GALLIC AcID.-Triacetylgallic acid is con- veniently obtained by adding granulated zinc chloride (50 grams) to a mixture of gallic acid (500) and acetic anhydride (2500).If too much zinc chloride is used considerable quantities of triacetyl- p ~ l l i c [3 4 5-triacetoxybe?aaoic] anhydride m. p. 175-176O (corr.) are formed as well. Pyridine and acetic anhydride may also be used. The acid has m. p. 171-172O (corr.) crystallises well and fornis a sparingly soluble silver salt' and dark blue copper salt. The chloride is obtained in well-developed prisms m. p. 106-107° (corr.) by the action of phosphorus pentachloride. The acid is hydrolysed to 3 5-diaceiylgallic [3 5 - ~ ' i c t c e t o x ~ / - 4 - h ~ ~ ~ ~ o ~ ~ ~ ~ ~ ctcicl C,,Hlo07,11,0 stout spikelets m. p. 174-175O (corr.) by dis- solving it in the required quantity of concentrated potassium hydrogen carbonate solution and slowly adding cold 2N-sodium hydroxide (16 mds.) the mixture being kept below Oo and well stirred and hydrogen being passed through without interruption.Soiiie gallic acid and a rnonoacetylgnllic [acetoxydihydroxybenzoic] acid m. p. 225O (decomp.) are also formed and a good deal of the triacetate escapes hydrolysis. The diacetate is methylated by means of diazomethane the product being methyl 3 54iacetoxy- 4-methozybenxoate7 elongated tablets or prisms m. p. 68-69O which may be hydrolysed by cold dilute sodium hydroxide in a current of hyclrogen to the known 3 5-dihydroxy-4-methoxybenzoici. 174 ABSTRACTS OP CHEMICAL PAPERS. acid (gallic acid 4-methyl ether) (A. 1912 i 559). This provea the constitution of the diacetate. Yenta-acetyl-pdigallic acid [4-(31 4/ 5l-triacet osybenaoyloxy)- 3 5-diacetoxybenaoic acid] is prepared by the interaction of tri- acetylgalloyl dhloride and 3 5-diacetylgallic acid in cold aqueous acetone in the presence of just sufficient dilute sodium hydroxide or potassium hydrogen carbonate.It forms thin needles m. p. 202-203° (corr.) yields a methyl ester rn. p. 192-193O (corr.) and a chloride m. p. 164-167O (corr.) and is hydrolysed by shaking with 5N-ammonia (8-9 mols.) in the cold and in the absence of air to m-digallic acid. This yields the methyl pentamethyl-mdigallate of definih constitution and may also be shown not to be a para- derivative by the fact that on acetylation it yields a different penta- acetate. Penta-acetyl-m-digallic acid crystallises in stout prisms m. p. 204-205O (corr.) (given in A. 1913 i 479 as 193-194O) and forms a methyl ester m.p. 167-168O (corr.). Similarly the above methyl penta-acetyl-p-digallate yields methyl m-digallate lH,O m. p. 175O when cautiously hydralysed by ammonia. This gives a bluish-black coloration with ferric chloride and yields pre- cipitates with pyridine quinoline brucine and quinine salts ; it may also be obtained by the action of. dilute ammonia on methyl penta-acetyl-m-digallate or converted into this by acetylation . 3 5-Diacetylgallic acid is benzoylated under the same conditions as observed in the above acylation. . A small amount; of a benzoyl- ox;yaceto.xybenxoic mid OH*C,H,AcBz*C02H m. p. 174-176O (corr.) is formed but the main product is the desired 4-be?izoyZ- 3 5-diacetylgallic [4-henzo$osy-3 5-&acetozybenzoic] ncid (I). This crystallises in well-developed tablets or prisms m.p. 183-184O (corr.) forms a methyl ester m. p. 138-139O (corr.) and may be hydrolysed by means of 5N-hydrochloric acid in acetic acid a t 85-90° or by ammonia a t Oo or by warming with sodium acetate the first being the best method to 3-benzoyZgalZic [3-benzoylozy- 4 5-dihydroxybenzoicJ acid (11) which has m. p. 240-242O (corr.) and gives a bluish-green colour with ferric chloride and a deep red with potassium cyanide. When treated with diazo- methane this yields methyl 3-benxoqloxy-4 5dimethoxybenzoate in stout tablets m. p. 91-92O which may be hydrolysed to the known 3-hydroxy-4 5-dimethoxybenzoic acid (3 4-dimethylgallic acid) m. p. 197-198O (corr.). Similarly the above methyl 4-benzoyI-3 5-diacetylgallate may be converted into meth?yl 3-benzoyZox?/-4 5-dih?/~ro.-~.~benzoate stout plates or prisms m.p. 173-175O (corr.) and this into the above ester m. p. 91-92O o r into methyl 3-benzoyZoq/-4 5-dincetcxyh eii =oat e elongated flat hexagonal tablets m. p. l l O - l l l o . 3-Benzoylgallic acid may also be reaeetylated by means of pyridine and acetic anhydride yield- ing the isomeric 3-ben,zo?/7ory-4 5-clincrlor?ybenaoic acid which crystallises in thin curved needles in. I). 177-178O (corr.) atid may be esterified t o the same ester as above (m. p. l l O - l l l o ) or hydrolysed again to 3-benzoylgallic acid. 4 5-Carbonylogallic acid (A. 1913 i 479) yields 3-benzoyloay-ORGANIC CHEMISTRY. i. 175 4 5-carbonyldioxybenzoic acid (annexed formula) when shaken with benzoyl chloride GO< and pyridine.This crystallises in thin hexagonal tablets m. p. 207-210° (corr.) and is hydrolysed to 3-benzoylgallic acid by boiling with acetone and water. DERIVATIVES OF PROTOCATECHUIC Acm.-Protocatechuic acid is most conveniently acetylated by the method used in the case of gallic acid. The diacetylprotocatechuic acid [3 4-diacetoxybenzoic acid] m. p. 157-158O (corr.) is partly hydrolysed also by the method applied to triacetylgallic acid the product being 3-acetyl- protocatechuic acid m. p. 202-203O (corr.) apparently identical with an acid described by Ciamician and Silbelr in 1892. The constitution is proved by the fact that it is converted by diazo- methane into methyl 3-acetosy4-methoxybenzoate m. p. 87-88O which may be hydrolysed to 3-hydroxy-4-methoxybenzoic acid (isovanillic acid).4-Benzoyloxy-3-acetoxyb enzoic acid is obtained by benzoylation in whet-stone forms m. p. 154-155O (corr.). This yields a methyl ester m. p. 102-103° (corr.) and may be hydro- lysed by means of 5N-hydrochloric acid mixed with aoetio acid a t looo to 3-benzoyloxy4-hydTozyb eizzoic acid. This crystallises in microscopic needles m. p. 225-227O (corr.) and forms methyl 3- b enzoyloxy-4-methoxyb enzoate m. p. 101-102° when treated with diazomethane this being also obtained by benzoylating methyl isovanillate. Similarly the above methyl 4-benzoyloxy-3-acetoxy- benzoate may be hydrolysed by ammonia to methyl 3-be?moy~oxy- 4-hycFroxybenzoate hexagonal tablets m. p. 153'5-155O (corr.) which yields methyl 3-henzoylo~y-4-acetoxybenzoate in long thin prisms m.p. 54-55O on acetylation. Phthalic Acid Derivatives. Constitution and Colour . VIII. Tetraiodofluorescein and some of its Derivatives. DAVID S. PRATT and ARTHUR B. COLEMAN ( J . Amer. @hem. SOC. 1918 40 236-245. Compare this vol. i 168 169 170).-Tetraiodo- flzcoresceiiz CzoH80514 obtainable from tetraiodophthalic anhydride and sesorcinol by 'heating with zinc chloride exists at the ordinary temperature as 3,n unstable mixture of the beiizenoid and quinonoicl modifications. I t s solutions in dilute aqueous alkali possess a yel- lowish-red colour and a vivid green fluorescence and on acidifica- tion deposit a golden-yellow hydrnte ; this when freshly precipi- tated appears to contain loosely combined water bnt after drying a t the ordinary temperature in the air for a few days ret-ains only approximately one molecule of water for the removal of which a temperature of 120° is necessary ; the first dehydration process does nof affect the colour but the passage into the anhydrous compound is accompanied by a chaiige to reddisli-brown clue to a partial conversion oC the beiizeiioid into the yuinonoid form ; the hydrate is believed to be of the benzeiioid Ptmcture.The application of 8 d r o p of acetone alcohol or ethyl acetate to the reddish-brown allhydrous compound causes an immediate change of colour to a clear canary-yellow due to rearrangement into the mare stable benzenoid o/\uo,a \/ OBZ J. C. W.i. 176 ABSTRACTS OF CHEMICAL PAF'ERS. modification. This behaviour is in marked contrast t o that of fluorescein wliicli has never been isolated in the benzenoid condi- tion.Treatment of the freshly precipitated tetraiodofluorescein with a little methyl or ethyl alcohol immediately converts i t into the very pale yellow cwbinol-carlsoxylic acid the structural change being represented by the difference between formuh I and 11. The anhydrous tetraiodofluorescein was also converted into the red- dish-orange potassium salt deep red diammonium salt red silver salt amorphous bright red methyl ether C,,H,,O,I decornp. near 25 lo diacetate C2,HI2O,I4 yellow crystals and dibenzoate C,,H,,O,I pale yellow crystals m. p. 2 8 8 O (corr.). D. F. T. Phthalic Acid Derivatives. Constitution and Colour . IX. Tetraiodoeosin and some of its Derivatives.DAVID S. PRATT slid ARTHUR B. COLEMAN ( J . Amer. Chern. SOC. 1918 40 245-249. Compare preceding abstract).-Tetraiodofluorescein is readily brominated in acetic acid solution with formation of tetra- iodoeosiit C2,H,0,Br41 canary-yellow crystals which show no tendency t o pass into a highly coloured quinonoid form and are therefore presumably of benzenoid constitution. It dissolves in aqueous alkalis yielding deep red solutions with faint green fluorescence from which dilute hydrochloric acid precipitates a pink amorphous hydrate 3C2,H,0,Bs,I,,H20. Ammonia converts the solid tetraiodoeosin into a red dimnmonium salt whilst the siliver salt C,,€I3O,Br4I,Ag obtained by precipitation is reddish-purple. Te trazodoeosin inethyl ether C,,H,O,Br,I ob- tained by the action of methyl sulpliate in the presence of alkali is a red amorphous powder whilst the diacetate C,,H,O,Br,P and dihenzmte CS4H,B07Brjf.i form pale yellow crystals m.p. 270-280° and near 261O respectively with liberation of iodine in both cases. D. F. T. C,,,H,O,Br,I WH Phthalic Acid Derivatives. Constitution and Colour. X. Tetraiodoerythrosin (Octaiodofluorescein) and some of its Derivatives. DAVID S. PRATT and ARTHUR B. COLENAN ( J . Anzer. Ghent. Soc. 1918 40 249-254. Compare preceding abstracts).- Octaiodo~~ioresceirz C2,H,0,1 is most conveniently obtained by heating tetraiodofluorescein with iodine and iodic acid in alcoholic solution for twelve hours. When free from combined solvent the compound forms clear yellow crystals but a t 140° it becomes dark red probably due t o a transformation from the beiizenoid t o the quinonoid constitution.With acetone i t forms a yellow ndditi7)c. compound C20H405T8,C,H,0 wliich i s decomposed into its con-ORGANTC CHEMISTRY. i. 177 stituents a t 1 ZOO. Gaseous aniinonia coiiverts the solid octaiodo- fluorescein into a red tetram nzoniu m salt C,oH+?518,4NH3 whilst the silver salt C,,,H,O,I,Ag obtained by precipitation is violet. The methyl ether C2113G0518 prepared by the action of methyl sulphate is an unstable dark red non-crystalline substance whilst the diacetate @2iHs0,1s and the dibenzoate C34€1120718 form yellow crystals decomp. above 200° and m. I). near 300° respec- tivel y. D. F. T. Phthalic Acid Derivatives. Constitution and Colour. XI. Phenoltetraiodophthalein and some of its Derivatives.DAVID S. PRATT and ASHER F. SHUPP ( J . Amer:Chem. SOC. 1918 48 254-264. Compare preceding abstracts).-Tetraiodophthalic anhydride yellow needles In. p. 320-325O (corr.) obtained by heat- ing phthalic anhydride and iodine with fuming sulphuric acid when heated with an excess of phenol with the gradual addition of sulphuric acid undergoes condensation with formation of phenol- tetraiodophthalein yellow crystals m. p. 239-245O (compare Rupp A. 1911 i 301) which give a deep red solution in aqueous alkali. The phthaleiii is probably of benzenoid constitution the yellow colour being attributed t o the influence of the iodine atoms in bringing the absorption into the visible spectram. It yields a dincetate C241<,40614 pale yellow crystals m.p. 230° (corr.) a dibenzoate C34H7RO&4 pale yellow needles m. p. 236O (corr.) a dimethyl ether C2,H140414 yellow crystals m. p. 221O (corr.) a dinitro-derivative C,,H,0,N,14 yellow needles m. p. 31 1-312O (corr.) (diacetate C,4H,,01,,N,14 deep yellow crystals m. p. 281° corr.) a tetmnitro-derivative C,,H60,,N,14 yellow crystals decomp. near 31 lo (corr.) and a tetrabromo-derivative yellow crystals m. p. 311-31Z0 (mrr.) (diacetate C?,H,,Q),Br,I yellow crystals m. p. 285O corr. ; dibemoate C34H,406Br414 yellow crystals m. p. 21 3-215O corr. ; dimethyl ether C,2H,,0,Br,T yellow crystals m. p. 255O corr.). By treatment in cold aqueous alkalilie solution with a solution of iodine in potassium iodide it is possible t o convert phenoltetraiodophthalein into tetmiodopfi enol- tetraiodophthalein C20H60J8 deep yellow crystals m.p. 285O (corr. with decornp.) ; this forms a diacetate C,,H,,O,T pals yellow crystals m. p. 288O (corr.) a dibenzoate C,,H,,0,T8 pale yellow crystals m. p. 202-203° (corr.) and a clinzeth?/Z ether CsH,,O,Ts pale yellow crystals decomp. a t 295-297O (corr.). C20H604Br414 D. F. T. Laurent’s Benzimide (Benzylidenebenzaldehydecyan- hydrin-acetal). MARIA SAVELSEERG ( J . 211’. Chem. 1917 [iil 96 186. Compare A. 1916 i 728).-An acknowledgment of the priority of Stolle (A. 1902 i 468) in the observation of the forma- tion of an acetal compound by the coildensation of mandelonitrile and benzaldehyde. D. F. T.i. 1'78 ABSTRA(!TS UB CTFTEMTCJAL PAPERS. Derivatives of Veratrole. ADOLF KAUPMANN and HERMANN MULLER (Ber.1918 51 123-130).-I. DERIVATIVES OF 0-VERATR- ALDEHYDE.-^ 3-Dimethoxyb~nzyl alcohol (0-veratryl alcohol) is ob- tained by reducing the aldehyde with hydrogen and platinum- black ; it crystallises in very long massive transparent rectangular columns m. p . 50° and is converted into the chloride b. p. 128.5-129°/11 mm. by means of thicmyl chloride. The chloride rather easily loses hydrogen chloride 011 distillation under higher pressures suffering condensation to an anthraoene derivative. It also combines with methylnorhydrastinine but the normal quatern- ary chloride (I) cannot be isolated neither can the corresponding base. The solution howev'ar gives precipitates of a perchlorate and a @crate m.-p. 223-225O whilst a beilzoyl derivative m.I>. 146O probably of the formula 11 may be obtained by t h e Schotten- Balimann method. CH 1x3 O/\/\FHp CtR2<()I \/\ NBx*CH;C €J3(OMe)2 COMe ( 11. ) Veratraldeliyde and homopiperonylamine condense to form o-vercitrylideizeho?no~~eronylanLi?ae white needles m. p. 59-60° which may be hydrogenated in the presence of palladium-black t o o-veratryEhomo23.perolzylarnine (2 3-di.nzet~~oxybene?/I-P-3 4-methpl- erbedioxyphenylet hylambze) CH,:O,:C,H,*CH,*CH,*NH*CH,*C,H,(OMe) a viscous oil which forins a h?ydrochloridr 1H,O. 11. p-DERIVATIVE s OF VERATRom.-p-Homoveratronitrile (3 4- rrlir,zeth~xyphenylacetonitrz'le) is obtained in long colourless needles in. p. 64-65O b. p. 1T1-178°/10 mm. by heating the correspond- ing aldoxime with acetic anhydride. o - Bromoacetoveratrone [3 4 - diixethoxyphenyl bromomethyl ketone] (Mannich and Hahn A.1911 i 649) reacts with potassium acetate in boiling alcohol to form the acetate (glistening tablets m. p. 91-92O) of p-veratroylcarbind (3 4-dimethoxybenzoylmethyl alcohol) which separates in transparent crystals m. p. 86-87O. with pheiiylacetyl chloride under the influence of aluminium chloride to form 3 4 - d z n z e t ~ ~ o x y d e o ~ ? / F ~ ~ ~ ~ ~ n (3 4ddmethoxyphelzyl benzyE ketone) iri white needles m. p . 8 8 O . A bromide pale yellow crystals m. p. 116-117° is produced when the required quantity of bromine is carried by a stream of carbon dioxide into a solution of this ifi carbon disulphids and ptoluenesulphomethyIamide reacts 111. DERIVATIVES O F ~IMETHOXYBENZOIN.-veratrO~e condensesORGANIC CXT li'MTSTRY.i. 179 with this bromide t o form 3 4-diinethosypJbenyl a-p-tolueitesul- pJzonylmethylamiizobensy1 ketone C,€14Me. S O,*NMe-CHP h- C0*C,IrI3( OMe) in white crystals m. p. 180°. J. C. W. The Beckmann Rearrangement. VIII. MITSURU KUEIARA NAOMICHI AGATSUBIA and KIUKICHI ARAKI (Mem. CoZZ. Sci. Kyoto Imp. Univ. 1917 111 (l) Repr'nt 16 pp.).-Kuhara and his ccl- leagues have already shown that the esters of oximes derived from strong acids for example benzenesulphonates spontaneously suffer the Beckmann rearrangement whereas the addition of an acid like hydrochloric acid is necessary in order to bring about the change in esters of weak acids like acetates. It is now suggested that the function of hydrochloric acid is to expel the weak acid giving the oxime chloride which is immediately rearranged.Thus in the case of diphenylketoxime acetate the reaction is represented as follows CPh,:N*OAc + HC1+ MeC02H + CPh,:NCI + CPhCKNPh. It is impossible to isolate these chlorine derivatives as the reaction pro- ceeds further t o the production of benzanilide but if the acetate is heated with benzenesulphonic acid a t 95-97O an analogous pro- duct phenylbenziininobenzenesulphonate (A. 1915 i 144) may be recovered thus CPh,:N*OAc + OH*SO,Ph -+ MeC0,H + CPli,:N*O*X'O,Ph -f NPh:CPh*O*SO,Ph. The same idea may be applied in explaining the rearrangement of the hydrochlorides of oximes under the influence of dehydrating agents. The bydrochloride of diphenylketoxime changes instantly into benzanilide when heated a t 128O quickly when heated with zinc chloride or chloral a t 90° and within a day or two a t 2 5 O when mixed with chloral.The change is formulated thus CPh,:N*OH,HCl- H,O + CPh,:NCl+ CPhC1:NPh 5% NHPh*COPh. I n the case of the methyl ether hydrochloride CPh,:N*OMe,HCl methyl chloride is lost a t above 45O and no! trace of the oxime suffers rearrangement owing to the absence of the necessary :NC1 group. The same interpretation is given to the rearrangement of diphenylketoxime by phosphorus pentachloride. If this agent is gradually added to an ethereal solution of the oxime it first dis- appears then the white hydrochloride of the oxime se arates and finally when an equivalent has been added a yellow c K lorine corn- pound is formed which changes into benzanilide on adding water +PCI CPh,:NCl and this -+ NPh:CPhCl.What a t first sight is a weak point in Kuhara's argument is the fact that chloroiminodiphenylmethane CPh,:NCl when prepared by the action of hypochlorous acid on iminodiphenylmethane resists the transforming influence of a large variety of agents (com- pare Stieglitz and Stagner A. 1917 i 22). I f howsverj the thus 2CPh,:N*OH + PCl ++ CPh,:NC1+ CPh,:N*OH,RClchloro-imine is fused with potassium hydroxide the rearrangement takes place with almost explosive violence aniline and benzo- phenone being formed. The unsubstituted imine and also di- phenylketoxime and its acetate do not yield aniline under the same treatment. The authors' explanation is that the chlorine atom in the stable chloro-imine is positively charged and requires t o be negatively charged belore spontaneous rearrangement can take place which alteration is brought about by the molten alkali thus CPh,:NClf Eo$ CPh,:NCl- -+ NPh:C'PhCl-. Evidence is also giveii t o show that the ease with which the oxime esters undergo rearrangement is mutually dependent on the nature of the acid radicle and the hydrocarbon residues.Thus the follow- ing benzenesulphonates suffer rearrangement at different tempera- tures CPh2:NX 6 2 O ; (CH,Ph),C:NX 74O; CMe,:NX 130° ; OEt* EP" 95-96O; whilst the following CMePh:NX 81-82O ; esters of diphenylketoxime vary in stability according to tlie strength of the acid CPh,:N*O*SO,Ph 6 2 O ; CPh,~N*O*S0,*C,H~l=N02(m) 24O ; CPh,:N*O*CO*CH,Cl above 195O ; and CPh,:N*OAc which does not change on heating.It appears therefore that the exchange of groups in the rearrangement is simultaneous. Uibe?z,zyllzetoxime benseneszdphonate (above) forms colourless crystals m. p. 64O; the acetate has m. p. 33-34O and the benzoate ni. p. 60'5O. Dipheitylketoxime m-lzitrobesazene.c~clphonate (above) has in. p. 24O and the ch7oroacetnte (above) also has m. p. 24O. NX ' J. C. W. Preparation of Dihydroxyanthraquinones and their Derivatives. FARBENFABRIKEN vom. FRIEDR. BAYER & Co. (D.R.-Y. 298345 1916; from Cliem. Zentr. 1917 ii 256).-It is possible t o effect the condensation of phenols naphthols hydroxyanthracenes and similar substances with phtlhalic anhydride under the influence of aluminium chloride with production of anthraquinone deriv- atives in one operation if tlie reaction mixture is heated at approxi- mately 180-250O; it is advantageous to use an excess of phthalic anhydride to act as solvent.I n this way catechol gives liystazarin free from alizarin in considerably greater yield than when sul- phuric acid is used ; a-naphthol yields pure hydroxynaphthacene- quinone whilst &naphthol gives hydroxynaphthanthraquinone yellow needles. Hydroxyanthracenes and hydroxyantliraquinones reduced a t the ketonic groups for example leucoquinizarin and deoxyalizarin can also be condensed to hydroxyanthraquinone com- pounds. Pyrogalbl yields anthragallol yellow needles. The patelzt also refers to the formation of condensation products of phthalic anhydride with 1- and 2-liydroxyanthraquinones 1 4 9 10-tetra- hydroxyanthracene deoxyalizarin and 2 7-dihydroxynaphthalene the product in the last case crystallising in yellow needles.3 6-Di- chlorophthalic acid and a-naphthol undergo condensation withORGANIC CHEMISTRY. i. 181 iormation of a compound crystallising in brown needles and soluble in sulphuric acid to a violet solution. D. F. T. 1 4 6-Trihydroxyanthraquinone. M. L. CROSSLEY ( J . A?mr. Chem. Soc. 1918 40 404-406).-4-Aminophthalic anhydride (Bogert and others A. 1902 i 98; 1906 i 510) condenses with quinol in concentrated sulphuric acid a t 170-190° to form some 6-amino-1 4-dihydroxyanthraquinone ( ?) but chiefly 1 4 G-tri- I~ydroxyaitthrapu/ino-ne which is a reddish-brown powder not molten a t 300° and gives bluish-violet solutions in alkali hydr- oxides.It has no particular value as a mordant dye. [See also Znd. April.] J. C. W. Hydrogenation of Olefinic Terpene Alcohols Aldehydes and Acids. CARL PAAL (D.R.-P. 298193 1913 ; from Chcm. gentr. 1917 ii 145-146).-Under suitable conditions it is possible to re- duce alcohols aldehydes and acids of the terpene group by hydrogen and palladium or platinum the ethylenic linking becoming bydro- genated and two ethylenic linkings if present being capable of successive hydrogenation without affecting the alcoholic aldehydic or acidic group. It is thus possible to reduce citral successively into citronella1 and dihyd.rocitronella1; geraniol successively into citronellol and dihydrocitronellol ; linalool successively into its dihydro- and tetrahydro-derivatives and geranic acid successively into dihydrogeranic acid (r-citronellic acid) and tetrahydrogeranic acid.The palladium o r platinum catalyst niay be used in the colloidal condition but for the present purpose the palladous or platinous hydroxide or the metals themselves deposited on powders free from any anti-catalytic effect are especially suited. A deposit OF palladium or platinum may be formed on magnesium nickel or cobalt by immersing these i2ietals in a solution of a palladium or platinum salt o r by treating precipitated magnesium oxide or carbonate o r calcium ca-rbonate with a solntioii of bivalent palla- dium or platinum it is possible t o coat these powders with palladous o r platinous hydroxide. Another inetliod is to soak an indifferent powder such as barium sulphate iiif usorial earth carbon and cellu- loss powder with a solutioii ol palladous or platinous salt and then t o precipitate the hydroxide of the rare metal on the powder by treating with sodium carbonate solution.With palladium or palla- dous hydroxide a convenient proportion of catalyst t o carrier is 0*5-1% whilst with platinum and its hydroxide it is 1-2%. D. F. T. The Colouring Matters of Camwood Barwood and Sanderswood. PAULINE O’NEILL and ARTHUR GEORGE PERKIN (T. 1918 113 125-140).-The well-known red dye-woods sanderswood barwood caliaturwood and camwood are very similar in tinctorial properties. I n fact the first three might well con- tain the same pigment but camwood dyes mordanted wool some what bluer tones and is more readily extracted by water.A chemical comparison of the camwood pigment with the sant’alin ofi. 182 ABSTRACTS OF OHEMICAL PAPERS. sanderswoad recently investigated by Cain and Simonsen (T. 1912 101 1061) appeared t o be desirable and a preliminary account of a research in this connexion is now given. ThO chief more insoluble colouring matter of calplwood is found to be an isomeride of santaliii designated isosanfaliiL. It decorn- poses a t a higher temperature than santalin (250-28O0 as against 250-260O) and dyes bluer shades. For many reasons both pig- ments are best expressed as c2,H,,06(OMe) instead of C,,H,,Q,(OMe). Both woods contain more soluble dyes which are again isomeric. For these the names deoxysantalin and deoxpisa- wntalin and the formula C2&Il6 * O,(OMe) are proposed.Not much can be said as t o the relation between the santalins and the deoxysantalins except that the results of acetylation do not indicate that the former possess one 11101-43 hydroxyl group than the latter. The deoxysantalins are the better pigments. The first pigment to be isolated from sanderswood was that obtained by Meier (1 848) which is apparently deoxysantalin rather than santalin although the present authors were not so successful in obtaining a crystalline specimen. I n 1870 Weidel also obtained from sanderswood santal which is now written as C,,HSO,*OMe and a bright red substance which is now designated santalone and is possibly deoxysant alin monomethyl ether C,H,,O,(OMe),. These are difficult to obtain from sanderswood but they have now been extracted from barwood which contains santalin as well.Santal crystallises in large colourless leaflets m. p. 222-223O and yields santol flat needles m. p. 270-273O on demethylation by Zeisel’s method. Elantalone forms glistening red leaflets m. p. 300O. The colowing matter in the flower of St. John’s wort is v quercetlin and not gossypetin as Kegan suggested (A. 1915 i 758). For experimental deltails seel the original. J. C. W. The Mechanism of the Formation of certain Isomerides of Cinchonine and of their Hydrohaloid Derivatives. E. L~GER (Compt. Tend. 1918 166 255-258. Compare this vol. i 121).-Admittiiig for cinchonine the constit,ution (formula J) and for cinchonigine and cinchoniline the constitu- CH,:CH.C1,,H,7N,:CH(OH)- CHMe*[C16H17N2:CH] I I (1.) (11.1 tion (formula II) and for apocinchonine CHMe:C,,H,6N?I:CH*OH this latter being formed from cinchonine by the addition and subsequent removal of the elements of water it is easy to see that the fixation of hydrogen bromide will in all four cases give the same hydrobrornocinebonine. But the four compounds are optic- ally active and it must be supposed that the fixation of hydrogen bromide is preceded in certain cases by stereoisomeric changes.It is probable that cinehonine and cinchoniline have the sameORGANIC CHEMISTRY. i. 183 steric arrangement) t)heir isomerism being due to differences of structure. In thO caws of cinchonigine and apocinchoaine there is a formation of their normal hydrobromo-derivatives and a t the same time a partial transformation into cinchoniline which then yields hydrobromocinchonine. W.G. A Synthesis of 2 6-Dimethylcinchomeronic Acid and 2 6-Lutidine. OTTO MUMN and HUGO KUXEKE (Be).. 1917 50 1568-1584).-Some years ago Mumm and Bergell found that the ammonium salt of aoetylpyruvic acid gradually loses water to form 3-acetyl-4-rnethylpyridine-2 6dicarboxylic acid and this was explained on the assumption that the ammonium salt changes partly into an acid of the formula CH,-CO*CH:C(NH2)*C0,H which condenses with a further portion of the salt (A. 1912 i 936). If this view is correct it should be possible to effect such a pyridine synthesis using other compounds of the type of acetyl- py.ruvic acid on the one hand and the above unsaturated amino- acid on the other. It is now shown that ethyl acetylpyruvate and ethyl /3-aminocrotonate react vigorously a t Oo to form ethyl 2:6- dimethylcinchomeronic acid the constitution of which is revealed by the facts that the corresponding potassium salt yields 2:6- lutidine on distillation with lime and that the1 free acid gives an anhydride.Ethyl acetylpyruvate which is obtained by Claisen's method from ethyl oxalate and acetone reacts equally well with ethyl P-aminocrotonate a t Oo whether undiluted or mixed with alcohol or ether giving a 90% yield of ethyl 2 6-dimethylpyridine-3 4- dicarboxylate which is a pale yellow viscous oil b. p. 163O/ 13 mm. m. p. 16O and gives a hydrochloyide quadratic tablets m. p. 121° a picrate clusters of stout needles rn. p. lolo and a platinichlorz'de yellow needles.I f burnt in the ordinary way the ester apparently forms a nitrogenous compound which escapes combustion so nitrogen was determined by Kjeldahl's method and carbon and hydrogen by Dennstedt's process. If the mixture is not cooled the water liberated during the condensation may cause two other reactions with the parent substances thus NH,*CMe:CH*CO,Et + 1120 = CH,Ac*CO,Et + NH and CH,Ac*CO*CO,Et + NHB = C"H,Ac*@(:NH)J.CO,Et + H,O. That is ethyl acetoacetate and ethyl a-iminolaevzclate (" a-imide of ethyl acetylpyruvate" in the earlier paper) may be formed. The latter crystallises in thin prisms m. p. 39O b. ~ . . 1 1 5 ~ / 1 3 mm. The free 2 6-~~methyllryridi?ae-3 44icarboxyZzc aczd (2 6di- methylcinchonzeronic acid) crystallises by spontaneous evaporation of aqueous solutions in short\ rhombic prisms m.p. 275O (sealed capillary; deconip.). It is almost insoluble in most solvents. The potassium salt forms silky needles and gives a 91% yield of 2 6-dimethylpyridine (2 6-lutidine) b. p. 14Z0 when distilled with calcium hydroxide this being a t present the most convenient method f o r making the pure lutidine. The acid also yields an ucnhydride needles m. p. lolo when heated a t 220°/vac. or with acetici. 154 ABSTRACTS 0%' CHEMICAL PAPERS. anhydride. It may be that Collie and Wilsmore were correct in a tentative suggestion that they had obtained the same acid by the oxidation of 8-hydroxy-1 3 6-ttrimethylisoquinoline (T. 1896 69 295). If the diethyl ester is left with one equivalent of alcoholic potassium hydroxide i t is partly hydrolysed to CO,H the 3-ethyl hydrogen ester (annexed formula) small needles m.p. 161° whilst the anhydride ( \ I C o 2 E t dissolves in alcohol to form the 4-ethyl hydrogen ester short flat prisms m. p. 151O. On heating the ammonium salt of the acid a t 2 30° sublimes The diethyl ester reacts with alcoholic ammonia a t 120° to forin the diarnide slender needles m. p. 220° (heab CO,H ing very rapidly; vigorous decomp.). The 3-amic acid (annexed formula) crystallising /'Co*NH2 with 2€I,O in rhombic leaflets is formed by dis- solving the imide in 4N-sodium hydroxide whilst the 4-amic acid 2H,O long needles m. p. 115O is obtained by saturating a benzene Me\/'1e N 2 6-dime t ?a y lcin chom er onimide in very long needles m. p 230O. A d hf3 solution of the acid anhydride with ammonia.\/ N J. c. w. Synthesis of some Pyridine-polycasboxylic Acids. OTTO MUMM and HUGO HUNEKE (Ber. 1918 51 150-164).-The synthesis of 2 6-dimethylcinchomeronic acid (preceding abstract) opens up a convenient way to prepare tri- and tetra-carboxylic acids of pyridine. Oxidation of the acid with alkaline permanganate sufficient for one methyl group gives rise to a 67% yield of t'wo methylpyridine- tricarboxylic acids. The chief product is 2-nzethylberberonic acitl (~-112.~tT~~12r~?.idiize-3 4 6-tricarb oxylic acid) which crystallises from water in stout short rhombic prisms with 3H,O decomp. 226O (anhydrous) and the lesser product) is 6-1??,ethylpyridiiic- 2 3 4-tricarbozylic acid which forms long thin prisms or some- 1 jnies hexagonal tablets and carbonises without obvious evolution of gas a t 230-280O.The two acids differ in a remarkable1 way in their copper salts; the former gives a precipitate with cupric acetate in hot solutions which dissolves on cooling but the latter gives a precipitate in the cold which dissolves on heating. 2-Methylberberonic acid loses carbon dioxide on heating with glacial acetic acid for some days yielding 2-methyZpyridine-3 4- dicarboxyZic acid in very long thin prisms m p. 250-255O which gives an anJLydricZe m. p. 9 2 O when boiled with acetic anhydridel this being also formed when the tricarboxylic acid is heated at 230° in a vacuum. The new dicarboxylic acid may be oxidised by alkaline permanganate to pyridine-2 3 4-tricarboxylic acid which crystallises in thin rectangular leaflets 1*5H20 m.p. 249O and is identical with the acid obtained by the oxidation of cinchonine (Camps A. 1902 i 824).ORGANIC CHEMISTRY. i. 185 Both methyl groups in the original acid msy be oxidised if twice as much permanganate is used. The product is pyridine- 2 3 4 6-tetracarboxylic acid which crystallises from water in narrow tablets 3H20 m. p. 235O and is identical with the acid prepared by Fischer and Tguber from flavenol (A. 1885 400). When this is boiled with glacial acetic acid i t loses carbon dioxide and gives a tricarboxylic acid which is not identical with any pyridinetricarboxylic acid of definite constitation such as the above 2 3 4-acid and can theredore only be pyridine-3 4 6-tri- carboxylic acid.It is however crystallographically and chem- ically identical with berberoiiic acid obtained from berberine and this synthesis confirms the structure already assigned to this acid. The acid crystallises wit'h 2H,O which it does not lose on exposure to the air and has m. p. 243O (decornp.). J. C. W. The Relative Stability of Cyclic Bases. V. J. VON BRAUN (Ber. 1918 51 96-100. Compare A. 1909 i 604; 1911 i 563; 1917 i 168 169).-Two very different methods have been worked out for effecting the rupture of cyclic systems containing nitrogen namely the Hofmann reaction and treatment with cyanogen bromide but i t has recently been shown that the gradations of stability exhibited by many of these bases are the same whichever teeet is applied. One exception seems to be dihydroindole which proves to be one of the most stable systems in the Hofmann degradation but one of the weakest towards cyanogen bromide.l-Methyl-2 3-dihydroindole reacts with cyanogen bromide in the cold according to the scheme C,H4<~~{>CH2+BrCN -+ quaternary salts of (1) with (2) and (4) being formed as well the yields being about 27% of (3) and 70% of (Z) of which only 40% escapes the secondary reaction resulting .in the quaternary salt. The quaternary salts are removed by ether as an insoluble red oil from which a small quantity of the methobromide of l-methyl- dihydroindole m. p. 195-197O (decornp.) may be recovered. The other bromide cannot be purified. The base (2) is charac terised by warming the soluble products with dimethylamine dis solved in benzene when it is converted into cyanomethyl-o-j.3- dimethytaminoethylaniline NMe2*C,H,*C,H4*Ni\ne*CN.This may be extractled from the benzene by dilute sulphuric acid; it is a pale yellow oil b. p. 175-178O/16 mm. which exhibits pale green fluorescence in alcoholic solution forms a picrate m. p. 1 4 2 O a flatinichloride m. p. 144O a methiodide m. p. 170° and may be hydrolysed by means of concentrated hydrochloric acid a t 150° to me thyl-&dirn e t hy laminoe t h ylaniline N~e,*CH2=CH,*C,II,.NHMe. VOL. CXJV. i. 1i. 186 ABSTRACTS OF CHEMICAL PAPERS. This base is a pa10 yellow oil b. p. 138-139O/15 mm. which forms a picrate m. p. 165-166O a platinichloride 2H20 m. p. 218O a thiocarbamide m. p. l l O o and a p'crate of its nitroso- derivative m. p. 139O.The remaining product 1-cyano-2 3- dihydroindole (3 j is recovered from the above benzene solution as a yellow liquid b. p. 164-168O/23 mm. J. C. W. Hydroxy-bases and Homologous Cholines. 11. J. VON BRAUN and Z. KOHLER (Ber. 1918 51 100-108 Compare A. 1916 i 631).-2-Methyltetrahydroisoquinoline forms an ethiodide m. p. 132-134O which may be converted into the hydroxide. When this is distilled under reduced pressure the chief product is o-vinylbencylmethylethylamine which has b. p. 105-107°/ 17 mm. and forms a platinichloyide m. p. 134O and a methiodidp in. p. 166-167O. The reaction illustrates once more the instability of the tetrahydroisoquinoline system (A. 1917 i 169). N-Methyldihydroisoindole is formed in small quantities by the interaction of o-xylylene dibromide and niethylamine.It has b. p. 81-82O/13 mm. and forms a trihydrate m. p. 45-46O. Other derivatives were described by Frankel (A. 1901 i 44). The ethiodide (Scholtz A. 1898 i 568) may be converted into methylethyldihydroisoindylium hydroxide which suffers decom- position in two ways on heating. The main product is AT-methyl- dihydroisoindole which is best removed by triturating the dis- tillate with water when the above trihydrate is formed but o-hydroxyrnethylbenzylmethylethylamine is obtained as well as a colourless viscous oil b. p. 145-150°/ 16 mm. which darkens on exposure to the air and gives a deep red ylnti,Lichloride m.. 1). 1 70°. The corresponding dimethyldihydroisoindylium bromide m. p. 238-240° from o-xylylene dibromide and dimethylamine yields a hydroxide which behaves similarly on distillation.More than half of the product is o-hydrox?/ineth?llbencyldinzethylamine 1). p. 130-132°/13 mm. the reaction being represented thus The new hydroxy-base forms an oily picrate a platinichloride m. p. 168O and an oily benzoate which yields a @crate rn p. 159-160° and i t changes on heating with hydrochloric acid into dimethyldihydroisoindyli,~im chloride m. p. 198-20O0. The hydroxy-base may also be converted through the mPthiodide rn. p. 148-149° into o-hydroxymethylbenzyltri-ORGANIC CHEMISTRY. i. 187 nzetlLylumi/Lonizcnz chloride OH.CH,*C,H,*CH,.NMe,CL m. p. 189O which has exactly the same physiological activity as choline and forms a ylati~ticldoride m. p. 216O and an uurichloride m. p. 1 2 7 O . The corresponding allyliodide m.p. 123O y+elds a chloride which like allylhomocholine is antagonistic to choline. These new h y dr oxy- b ases and 0-h y dr ox ymet h yl b eiiz ylpiperidin e (A. 1917 i 170) differ very characteristically from tertiary amino- benzyl alcohols of the type OH*CH,*C,€I,*NMe (A. 1916 i 473 etc.). The former are colourless the latter yellow and whilst the latter are oxidised by formaldehyde in acid solutions the former are quite stable towards this agent. J. C. W. Synthesis of Cinchonic Acids. ADOLE' KAUFMANN (h'er. 1918 51 116-122).-The cinchonic acids or their nitriles or esters seem to be the most favourable material from which to build up synthetic alkaloids of the cinchona group. Consequently the synthesis of these acids from quinolines is a matter of importance and therefore some new notes on the method originated by Kauf- mann in 1909 (A.1909 i 958) are of interest. The conversion of quaternary salts of the quinolines int'o 4-cyano- 1-alkyl-1 4-dihydroquinolines by means of cold aqueous potassium cyanide is best' carried out in the presence of ether which removes the unstable nitrile as fast as it is formed either by dissolving it or by causing it to crystallise out. Quinoline itself gives a 75% yield but substituted bases give better results. Thus the methosulphate of 6-methoxyquinoline gives a very high yield of 4-cyano-6-meth- oxy-1-methyl-1 4-dihydro uinoline m. p. 8 2 O (A. 1912 i 651). With the methiodides 01 various nitroquinolines extremely fine crystals of the nitrile are deposited in a-very short time; 5kit7'0- CH(CN)*C H k y a n o - 1 -methyl- 1 4-di hydro pu in olin e NO,*C,H <r; Me--jH separates in large pale yellow cubes or columns m. p.7 8 O (decomp.) ; the 6-nitro-compound is a pale yellow crystalline powder m. p. 108O (decomp.); and the 8-nitro-compound forms large yellow prisms decomp. 90-92O; they all have the odour of hydrogen cyanide and are very easily osidised even decomposing with violence sometimes when brought' from a de.siccator into the air. These nitriles may be oxidised by iodine to the methiodides of 4cyanoquinoline (A. 1911 i 749 750). This is best carried out by dissolving the nitrile in pyridine and adding the solution quickly t o an alcoholic solution of iodine (1 mol.). The yield of the quaternary salt varies from 90% for the unsubstituted quinoline product t o 74% for the 6-methoxy-compound and 65% for the 6-ethoxy-derivative.The corresponding nitrile from hydrastinine and the above nitro-compounds react in a different way being deprived of the cyano-group and reconverted into the parent met hiodides. The 4-cyanoquinoline methiodides are best converted into the 4-cyanoquinolines by heating alone (4-cyanoquinoline itself is E 2i. 188 ABSTRACTS OF CHEMICAL PAPERS. obtained in 90% yield) or with ethyl benzoate the latter being the best treatment of the alkyloxy-derivatives. J . C. W. The Diketopiperazines. IV. Attempts to Prepare 2 3.Diketo- 1 -phenylpiperazine. J . V. DUBSRY and Chi. GRANACHER (Be?.. 1917 50 1686-1692. Compare A. 1916 i 635 672).-When an aqueous solution of I-nitro-3 5-diketopiper- azine (“niC.roiminodiacetirnide,” A.1912 i 753) is boiled it de- posits ‘ an indigo-blue amorphous’ com&&d ’probably ’of the >CO. This dissolves in N H-Go >CC<$* -NH formula “O<(liJ,.N 111. I (NO)*CHi sodium hydroxid; to give a dark r~ddisl;-brown solution which is bleached by sodium liypwulphite. I n order to obtain soluble sulphonic acids related to this in- soluble product the authors have made many attempts described in this and in following abstracts to prepare 2 3-diketo-l-phenyl- piperazine but so far without success. I n the first’ place dichlorodiacetanilide C,H,*N(CO* CH,Cl) was required. All attempts to prepare this from aniline and chloro- acetyl chloride or chloroacetic anhydride resulted in the formation af the monochloroacetanilide whilst a condensation of phenylcarb- imide with chloroacetic anhydride a t 160-180° gave the same pro- duct mixed with 2 4-diketo-3-phenyltetrahydrothiazole m.p. 148O. J. C. W. The Diketopiperaaines. V. Action of Aniline on Methyl Iminodiacetate. J. V. DUBSKY and CH. GRANACHER (Be?.. 1917 50 1692-1701).-1n another attempt t o prepare 2 S-diketo-l- phenylpiperazine the authors have heated methyl iminodiacetate o r its hyd-rochloride wihh aniline in the hope of realising the reaction represented by equation (a). As a matter of fact the reactions ( b ) and ( c ) are found t o run concurrently. (a) NTI(cH,=COiMe) + NH,Ph = NH<CH2.CO>NPh CR *co + 2MeOH. 0 L ( h ) NH(CH,*CO,Me) + 2NH,Ph = ( c ) ZNH(CEE,*CO,Me) + 2NH,Ph= NH(CH,*CO*NHPh) + 2MeQH.4MeOH + N H P h * C O * C B * N < ~ ~ ~ ~ ~ ~ N * C H * C O N H P h Iminodiacetonitrile (from hexarnethylenetetramine and hydrogen cyanide) can be converted into methyl iminodiacetate hydrochloride in one operation (compare Jongkees A. 1908 i 959). 2 :&Diketo- piperazine-k 4diacetaniZide (equation c ) is not particularly soluble except in gIaciaI acetic acid from which it cryskllises in pale grey silky leaflets m. p. 310-320° (decomp.). On hydrolysis it yields the known I 4-diacetic acid (;bid.). Zrninodiacetanilide ( b ) is ex- tracted from the product of the reaction by means of boiling water,ORGANIC CHEMISTRY. i. 189 the iuixturs beiilg slightly acidified by hydrochloric acid. It crystal- lisees in glistening long snowy leaflets in.p. 138-139O the hydro- chlorid forms leaflets m. p. 242O (decomp) and the nitrate stout needles m. p. 182-183O. The salts are completely dissociated in water but can be precipitated by the addition uf the free acids or metallic salts in excess. The compound also reacts with acetic anhydride to give acet?/lirninod~acetct?tilide m. p. 223-224O and with absolute nitric acid to form ndtroiminodiacetotetranitroaniZ.ide N0,*N[CH,*C0.NHgC,H,(N02)~]2 which forms sulphur-yellow leaflets m. p. 214-215O (decomp.) and dissolves in concentrated potassium hydroxide with blood-red colour. The Diketopiperazhes. VI. Action of Bromoacetamide OR Glycineanilide. J. V. DURSKY and CH. G R ~ A C H E F . (Ber. 191 7 50 1701-1 709).-Glycineanilide NH,*CH2*C'O-NRPh,2H,O is conveniently prepared by saturating a solution of chloroacet- anilide in alcohol (50 grams to 500 c.c.) with ammonia a t a low temperature heating the mixture in an autoclave at 50-60° for twelve to fifteen hours and carefully concentrating the product.The yield is much poorer if smaller quantities are employed. Bromoacet yZglycineuniZ& from bromoacetyl bromide and glycineanilide forms slender needles m. p. 170-172O (decomp.). It does not yield 2 5diketo-1-phenylpiprazine when heated. Reaction gradually sets in when equimolecular quantities of glycineanilide and bromoacetamide are mixed and left a t 20°. The product is tm'glycinediamddeanilide NHPh*CO*CH,*N( CH,*CO -NN,) which crystallises in stout platelets rn. p. 227O (decomp.) and is not soluble in organic media.The hydrochlom'dc! m. p. 200-202° is hydrdysed by water. When heated a t 200-210°/vac. the com- Dound loses ammonia and chanpes into 3 5-diket~lri.nerazine-l-ac~t- J. C. W. v L L an ilide ) NH<::"c> N CH2* CO NHP h which crys t alli,ses in glistening leaflets m. p. 189-190° and forms a readily dissociated hydrochloride lH,O leaflets and nitrate 0'5H20 m. p. 124O (vio- lent decomposition) whilst absolute nitric acid gives 3 5-diketo- ~~erazine-l-opdinitroacetanilide very pale yellow needles m. p. 225-226O (decomp.). If the original glycineanilide contains iminodiacetanilide which is usually the case triglycineamidedianilide NH2*CO*CH2*N(CH,*C0-NHPh) is formed as well in the reaction with bromoacetamide. This com- pound is freely soluble in alcohol and so may be extracted from the product.Tt ctystnllises in long filaments 111. p. 1 6 5 O . J. C. W. Dyes of the Anthraquinone-2 1-acridone Series. FRITZ ULLMANN and PERCY DOOTSON (Ber. 1918 61 9-24),-- Ullmann and Billig have already dwribed the influence on the tinctorial properties of anthraquinone-2 1 -acridone exerted by sub-i. 190 ABSTRACTS OF CHEMICAL PAPERS. stituents in the half of the acridine system to which the anthra- quinone residue is attached (A. 1911 i 489 490). The present communicatioln is an outcome of an inquiry into the influence of aubstituents in the other part of the acridine system. The new derivatives are generally prepared by condensing l-aminoanthra- quinone with the methyl ester of a substituted 0-chlorobenzoic acid and then treating the corresponding free o-anthraquinonylamino- benzoic acid with concentrated sulphuric acid.X e t h y l o-an tkmquinoizyl-1-aminobenzoate is prepared by boiling I -aminoanthraquinone with methyl o-chlorobenzoate potassium acetate and a trace of copper acetate in naphthalene soldtion the yield being 92%; i t crystallises in red needles m. p. 205O (corr.) is hydrolysed by alcoholic sodium hydroxide to the sodium salt and is converted by warming with concentrated sulphuric acid or with sodium hydroxide and hyposulphite a t 40-50° into anthraquinone- 2 1 -acridone. Similarly 1 5-diaminoanthraquinone yields cli- methyl o o'-anthrapuinonyl-l 5-diaminodibenzoa f e in brownish-violet glistening crystals m. p. 2 6 2 O (corr. decomp.) which may be converted into the corresponding acid and di-acridone Methyl 2-chloro-5-nitrobenzoate also condenses readily giving aE 87% yield of methyl 5f-nitro-2'-anthraq~~inmyl-laminob enzoate which crystallises in blackish-red needles m.p. 310° (corr.) and may be hydrolysed by A7-sodium methoxicle solution to the free acid orange needles m. p. 340O. This resists condensation to an acridone derivative but the corresponding 5'-nmino-2r-anthra- quinonyl-1-aminob enzoic acid which is obtained in dark violet crystals m. p. 300° (decomp.) by reduction with sodium sulphide may he condensed by fuming sul- phuric acid (15% SO3) to 2famino- anthraquinone-2 1-acridone (annexed 1 I formula). This crystallises in bluish- \/ violet tablets decomp. 340° and dyes NH cotton in the vat the same shade whereas the unsubstituted anthra- quinoneacridone gives reddish-violet shades. Methyl 2-chloro-5-methoxybenzoate does not react so rapidly but gives nnzeth yl Zr-ant h raquinonyl-I -amino-5'-metltozyb en zoate in the normal way.This crystallises in reddish-violet needles m. p. 215" (corr.) whilst the free acid forms a felted mass of violet needles m. p. 290° (decomp.) and may be converted into the chloride by boiling with phosphorus pentachloride and benzene and then by boiling with nitrobenzene into 2~-rnethoxyanthraqzcinone-Z 1- izcridone. This forms small violet leaflets m. p. 308O (corn.) and gives a hyposulphite vat of the same colour. For the preparation of the 3'-methoxy-compound pmethoxy- anthranilic acid seemed to be the best starting material.This is synthesised as follows p-toluidine is converted into 2-nitro-ptolu- (ibid.). NH- co I l l ' \/\/\/ coORGANIC CHEMISTRY. i. 1191 idine sulphate tlieii into 2-nitro-pcresol ; this is methylated by means of methyl sulphate and the ether is oxidised by boiling with permanganate solution t o 2-nitro-4-methoxybenzoic acid which is reduced by means of stannous chloride. 4-Methoxyanthranilic acid (see also Friedlander A. 1912 i 318) is boiled with l-chloroanthra- quinone potassium carbonate and copper acetate in amyl alcohol and so converted into 2~-anthmqz~it~onyl-l-ctrnino-4~-~netho~ybenzoic crcid which crystallises in violet needles m. p. 2 7 2 O (decomp.) and may be transformed through its chloride into 31-methoxganthra- cyitinoize-2 lacridone. This forms a wine-red mass of felted needles m.y. 350° (corr.) gives a red vat and dyes cotton red. The influ- ence of the substibuent in the para-position with regard to the carbonyl group is therefore of the same order as Friedlander observed in the case of indigotins and ‘‘ thioindigos ” (Zoc. cit.) and as has been found in the case of 3~-chloroanthraquinone-2:1- acridone (D.R.-P. 245875) namely that the shade is modified in the direction of red. X e t h y l 3-chloro-2-~1npJ~t?~octte in. p. 58O (for the acid see Stroh- bach A. 1902 i 149) condenses with 1-aminoanthraquinone t o form methyl 3f-anthrapuinonyl- 1 - amino - 2’- naphthocrte violet needles m. p. 277O the corresponding acid crystallising in violet tablets m. p. 322O. When the ester is shaken with alkaline sodium hyposulphite a t 40-50° in the absence of air it gives a vat from which air precipitates ctnthrrr- \/\ one (annexed formula) (for the method see D.R.-P.246966). This crystallises in dark violet needles m. p. 360° and gives a green vat from which cotton may be dyea bluish-violet. The isomeric 2 1 1’ 21-anthraquinonenaphthacridone of A. 1916 i 484 and indanthrene-red B.N. extra of D.R.-P. 237236 dye red shades. [See also Ind. 178~.] Preparation of Nitrogenous Condensation Products of the Anthraqwinone Series. FARBWERKE VORM. MEISTER LUCIUS C% BRUNING (D.R.-P. 298706 1913; from Chem. Zentr. 1917 ii 347).-Iminazole compounds of the general formula d C N > C R where ,4 represents an anthraquinone group pos- sibly containing other substituents R an aryl or alkyl radicle and R’ an aryl radicle can be obtained in good yield with simultaneous formation of water and halogen liydracid by treating o-halogen substituted acylaminoanthraquinones with primary aromatic amines in the presence of neutralising agents and catalysts such as copper salts.The products are of value for the production of dyes. 3-Bromo-1-N-phenyl-C-phen yl-l 2-anthraqwhoneiminazole pre- pared by heating 1 3-dibromo-2-benzoylaminoanthraquinone with aniline potassium acetate and copper acetate forms yellow needles gives an orange-red solution in sulphuric acid and on reduction NH-- CO - /\ /\ /\--co-- /\ I I I quino~ze-2 1 21 3/-naph>thacrid- I \/A/\/ co \/ J. C. W. NR’with hyposulphite gives a vat dyeing cotton pale yellow; by warm- ing with fuming sulphuric acid it can be converted into a sulphonic acid.l-N.-p-Tolyl- C - methyl-l %an thraquinoneiminazole yellow needles m. p. 2 3 6 O obtained similarly from 1-chloro-2-acetylamino- anthraquinone and ptoluidine gives a yellow solution in sulphuric acid and a ’hyposulphite vat which dyes wool yellow. D. F. T. Chromoisomerisrn and Salt Formation of Iminovioluric Acids. I. I. LIPSCHITZ and I%oN KRITZWANN (Bey. 1917 50 1719-1738) .-The bearing of residual affinity on questions of chromoisomerism and polychromism is now generally recognised and therefore the’study of a compound whicb can exist in tauto- meric forms and also give various internal salts by the exercise of subsidiary valencies is of special interest. Such a compound is iminovioluric acid which can exist theoretically in the following forms - OH trans.cis. . I Ni troso-enol. Ni troso-amino. The isomerism in the cases of the cis-modification and the nitroso- amino-form would be influenced by the possibility of internal salt f m a t i o n . Iminovioluric acid is an amphoteric substance which forms colourless salts with mineral acids and pink or red salts with the alkalis and alkaline-earths. Spectrographically ths metallic salts are identical with those of the simple violurates which indicates that the nitroso-group is modified and involved in the establishment of a ‘‘ residual affinity ring.” The salts with mineral acids are opti- cally identical with violuric acid itself and therefore contain no residual affinity rings. The silver salt exists in a pink and a bluish- violet form the former being most probably a salt of the above trans-modification with the metallic atom linked by residual affinity to the carbonyl group whilst the latter may be derived from the cis-acid with a subsidiary valency uniting the metal and the imino-group. The free iminovioluric acid has been isolated in three forms.The commonest is red and spectrographically like its alkali salts; that is it is the internally-complex form of the &-modification. Another is yellowish-orange and is t o be regarded as the trana- isomeride whilst the third is blue and is most probably ail internally-complex form of tho nitroso-amino-type. Some salts of iminovioluric acid were prepared by Traube in his synthesis of uric acid (A. 1900 i 416) but the following schemeORGANIC CHl4MlSTK.Y.i. 1!13 represeiits aii iiiiprovecl nietliod CO(NH,) + C:N*CH,*CO,H (with Ac,O) + NH,*CO*NH-CO-CH,*CN. This and this + NaNO + HC1+ sodium hydrogen salt of iminovioluric acid or the normal salt according to the conditions of the reaction. Sodium iminoviolurate C,H,O,N,Na crystallises in silky pink threads and the acid salt C,H70,N,Na,2*5H,0 is reddish-violet. The potassium salts obtained by similar methods using potassium nitrite are also pink and reddish-violet but the acid salt has only 1H20. From the sodium salt the following new salts have been prepared magnesium MgX2,6H,0 a yellow microcrystalline powder and MgX a bright brick-red powder; barium BaX2,R20 red and Ba,X,,5H28 pale pink; c u p r k CuX2,2H,0 pale green and CuX almost black; silver AgX,H,O pink AgX bluish- violet and Ag,X,ccH,O yellow ; strychnine blue ; brucine BX,2*5H20 yellow BX red BX,1*5H20 blue; sulphate (C,H,O,N,),,H,SO colourless m.p. 140° (loss of water) ; kydro- chloride C,H,O,N,,HCl,H,O unstable in the air. For the details of the conditions under which the various salts are formed the original should be consulted. Two dimethyl esters have also been obtained by treating tho sodium salt with methyl sulphate; one is pale yellow and givm a yellow solution in d i u m hydroxide the other is orange-yellow and gives a red solution. Different ethyl esters are also formed when the different silver salts are treated with ethyl iodide. The three forms of the free iminoviolum'c acid are obtained thus yellowish-orange by covering the sodium salt with 2- to 3-N-mineral acids ; violet-tinted red by exactly neutralising the sodium salt ; bluish-violet by boiling the others with water.If the sodium salt is reduced with ferrous sulpbte or the free acid with iron a very dark blue solution is obtained. I n concen- trated solutions the new product may be obtained as a precipitate which is a dark blue po;wder with coppery lustre. The compound gives a colourless solution in dilute acetic acid from which it may be precipitated again by alkalis and i t may be represented by the formula N H *CH-O\ ,o-- CH*NH CO' >C NOTFe*O*Fe.+lN:C< \ C@,4H20. \N H C==NH. .. NH==c--NH/ J. C. W. Various Observations on Phenylhydrarones Semi- carbazones and Anils. K. VON AUWERS (Rer. 1917 60 1585-1614.A . PHENYLHYDRAZONES .-Equimolecular proportions of 4-methyl- coumaran-2-one and pnitrophenylhydrazine hydrochloride react in aqueous-alcoholic solutions in the cold to form the normal p-nitm- 1111 enylhydrnzone (I) which crystallises in red leaflets with metallic Compare this vol. i 27).i. 194 ABSTRACTS O F CHEMICAL PAPERS. green reflex m. p. 200-204°. With an excess of the basic reagelit in boiling solutions t,he coumaranone ring is opened and the di-p- iaitrophenylhydrazone of 4-hydro.xy-rn-tolylgl?y~~al (11) is formed in dark reddish-violet leaflets m. p. 2 7 6 O . 1 4-Dimethylcoumaran-2-one and p-bromophenylhydrazine com- bine without the elimination of water the product being most probably the p-bromophenylhydrazone of 1-hydroxy-1 44imeth?yl- coumaran-2-on,e since it is a pale yellow powder which is not soluble in sodium hydroxide.With lethoxy-1 4-dimethylcoumaranone and the same base in boiling alcohol rupture of the ring takes place to a certain extent for the di-p-bromophenylhydrazone of 4-hydroxy-m-tolyl methyl diketone pale yellow flat needles m. p. 148-149O is formed as a by-product’ (compare formula I1 or IV). The reaction between 1 4-dimethylcoumaran-2-one and p-nitro- phenylhydrazine is somewhat complicated. I n the main the ring is opened and an osazone is formed but the mother liquors from this contain the p-nitrophenylhydracone of 1-hydroxy-1 4- dimethylcoumaran-%one (111) which forms rosettes of orange- yellow needles m. p. 171-172O. The osazone 4-hydroxy-m-tolyl methyl dike tone di-pnit roph enyl h ydrax one (IV) is produced from 1 4-dimethylcoumaranone or 1-hydroxy- or l-ethoxy-1 4-dimethyl- coumaranone by heating with pnitrophenylhydrazine hydrochloride in glacial acetic acid.It crystallises in flat needles of the appear- ance of chromic oxide m. p. 255-265O (according to the rate of heating). C N*NH*C,H,*NO JH*C,H,*N02 If a solution of this osazone in acetone is diluted with water or allowed to evaporate a salmon-coloured precipitate which looks like clean copper in the mass is formed. This is a “hydrate,” the elements of water being attached at on0 of the -C:N- groups; itl has m. p. 273-274O and loses water again if boiled with aromatic hydrocarbons or glacial acetic acid but! not’ by heating alone at 130O. A different ‘( hydrate” is formed if the reaction between 1 4-dimethylcoumaranone and pnitrophenylhydrazine is carried outl in cold or boiling alcohol or if 1-hydroxy-1 4-dimethyl- coumaranone is treated with the base in boiling alcohol; this isomeride is of a bright brick-red colour has m.p. 265-270° and may be dehydrated more readily. A pale brick-red dihydrate ”ORGANIC CHEMISTRY. i . 195 is also formed from 1-hydroxy-1 4-dimethylcoumaranone in the cold. The colour and stability of these (‘hydrates” seem to depend considerably on the mode of preparation. From the analytical data i t appears that the osazone has a tendency to hold water and aromatic hydrocarbons more or less firmly not only in chemical butl also in mechanical union. It is remarkable that of all the coumaranones only the 1 $-dimethyl- (and 1-hydroxy-1 4-di- methyl-) compound yields these hydrates of osazones. 1-Hydroxy- 1 4-dimethylcoumaran-2-one can also be converted into a normal p-bromop~enylhy~razone golden-yellow prisms or brilliant sulphur- yellow needles m.p. 149O and a normal pnitrophenylhydrazone slender sulphur-yellow needles or amber-coloured stout prisms m. p. 176-177O. I n other cases normal hydrazones are formed or osazones after opening of the ring but it frequently happens that the latter are dimorphic. Thus 4-methyl-1-ethylcoumaran-2-one gives the di-p- nit roph enylhydrnz one of 4-hydroxy-m- t olyl ethyl diket one in orange-red needles with blue reflex m. p. 248-249O ; occasionally chromic oxide coloured leaflets or flat needles possibly a (( hydra&,” ‘were obtained.4-Methyl-1-isopropylcoumaranone yields the di-p- nitrophenyl hydra> one of 4-h ydro,-cy-m-t olyl isopropyl diket one ; deep orangered crystals from much methyl alcohol and stout yellow prisms from glacial acetlic acid m. p. 254-255O. The difference in colour between the osazones of the ethyl and isopropyl tolyl diketones is remarkable. 1 3 5-Trimethylcoumaran-2-one forms a normal p-nitrophenyZhydrazone in orangered needles and scales m. p. 214-215O;when treated with the base in cold alcohol and the di-p-nitrophenylhydrazone of 5-hydroxy-m-xylyZ-4-met hyl diketone (annexed formula) deep ruby-red needles m. p. The p-nitrophenylhydrazone of benzaldehyde yields an acetyl derivative CH C:N-NH*C,H;NO /\/\ CM~:N,NH,C,H,.NO 2810 in hot solutions.CHJ\,O” 1 CRPh:N*NAc*C,B4*NO2 small pale yellow needles m. p. 174-175O when treated with acetyl chloride and the t rincetate OAc*CRPh*NAc*NAc*C,H4*N02 colourless scales m. p. 154-155O when warmed with acetic anhydride and a trace of concentrated sulphuric acid. B. SEJ.IICARBAzoNES.-In this section some cases of “hydrates” of semicarbazones are described. 1 4-Dimethylcoumaran-2-one suffers rupture of the ring when warmed with semicarbazide a t 40-50° the product being 4 -h?yc?rolt.y-m-t olyl a-semicar barid c t h yl ketone semicnrb nzone (I) C:N*NH*CO*XH C,H ,Me*OH I M e / \ / \ c H ~ ~ * ~ ~ ~ N H = c o ~ ~ H ~ C(OH)-NH~NH*CO-NH I ‘\ // IOH hHIke*NH*N€€*CO*NH (1.1 (11.1i. 196 ABSTRACTS OF CHEMICAL PAPXRS. m. p. 2 2 7 O . Izydrate” (11) ni. p.2 2 7 O if its alkaline solutions are acidified. 1-Hydroxy-1 4-dimethylcoumaranone yields products M. p. 207-210° and 227-228O which give analytical results between the values for the true disemicarbazone of 4-hydroxy-m-tdyl methyl diketone and its monohydrate. 4-Methyl-1-ethylcoumaranone gives 4-h ydrom-m-t oly 1 atsemicar6 azidopropyl ketone semicarb - uzone glassy flat needles and rhombic plates m. p. 230° (quickly heabd; compare also this vol. i 29) and its (‘hydrate,” m. p. 1 60°. Phenyl methyl diketone forms a normal disemicarbazone m. p. 229-232O. C. ANILs.-Whilst anils show little tendency to combine with water to form “hydrates” of the type OH*CHR*NHR’ they do sometimes unite with acetic acid to form compounds of the type OH-CHReNAcR’. 5-Nitrosalicylaldehyde yields 5-nitrosalicylideneaniline yellow needles m. p.133O which reacts with boiling acetic anhydride to form the compound OAc*c6H,(N0,)*CH (OH)*NPhAc cdourless needles m. p. 145O. 5-Nitro-4-ltydroxy-m-tolylidene- aniline orange-red flat needles m. p. 133*5-134*5O forms an aniline salt stout ruby-red prisms and reacts with acetic anhydride to give the compound OAc*C6H,Me(N0,)*CH(OH)*NPhAc white platelets m . p. 16 7O. &Nit ro-2-rtl ydrolcy-m- t 01 ylideneandine golden-yellow needles m. p. 176-177O forms a &acetate isomeric with the last in glistening scales in. p. 153-154O. Diaryl-substituted Hydrazidinecarboxylic Esters and their Hydrolytic Products. Degradation of Ethyl Acetoacetate to Derivatives of Formic Acid. CARr BULOW and RICHARD Huss (Ber.1918 51 24-42).-The hydrolytic degradation and other reactions of the hydrazidinecarboxylates derived from ethyl acetoacetab (this vd. i 42) have been studied in order to confirm the constitution assigned to them. Ethyl a-o-toluidinoglyoxylate 2 4-dichlorophenylhydrazone C,H,Cl,*NH-N:C( NH*C,E4Me) CO,Et has been chosen for the purpose as the possible products offer few difficulties in the way of identifying them. I . Proof of the CarbethoxyZ Group-The ester is converted by contact with alcoholic ammonia into a-o-toluidinoglyoxylrnide 2 4-dichlorophenylhydraaone C,H,Cl,-NH-N C( NH*C,E,Mel) *CO*NH which crystallises in small needles M. p. 1 5 2 O dissolves without change in concentrated sulphuric acid and changes into a golden- yellow solid with evolution of gas if heated above its m.p. The same amide may be1 formed by mellting the 2:kdichlorophenyl- hydrazone of a-chloroglyoxylamide (A. 1913 i 911) with o-tduidine. The ester may also be converted into the 2:4-dichlorop7~en?/7- I) yclmzon e of a-o-t oluidinoglyoxylhydraaide This is precipitated as a Some new examples are now given. J. C. W. C,H,Cl,*NH*N C(NIP*C,H,Me)*CO *NH *NH,,ORGANIC CHEMISTRY. i. 197 which crystallises in prisms m . p. 145O and condenses with aldehydes and ketones in the normal way. The isopropjlidene compound C,H,cl,*NH*N:C (NH* C,H,Me) *CO*NHoN CMe from acetone forms slender needles m. p. 202O and reacts with chlorine in cold alcoholic suspension to give 2 4dichlorophenyldiazoniurn chloride which later on suffers decomposition in some inexplicable manner.The b enz ylidene compound crystallises in glistening needles m. p. 176O and also gives 2 4-dichlorophenyldiazonium chloride when treated with chlorine the product yielding a crystal- line yellowish-red dye with &naphthol. The o-chlorobenzylidene compound has m. p. 198O and apparently does not give a diazonium salt if treated with chlorine in ethereal suspension. The sdicylidene compound forms glistening yellow needles m. p. 1 8 6 O and is not attacked by chlorine in light petroleum. The m-nitro- b enuylidene compound forms glistening pale golden-yellow needles m. p. 229O. Ethyl diacetylsuccinate also condenses with the hydrazide giving the 2 4-dichlorophenylhydrazone of ethyl 1 -a-o-toluidinogZyoxylamido-2 ; 5-dimethyipyrrole-3 ; 4-dicarboayTnt P in white needles m.p. 225O which yields a diazonium salt with chlorine. 11. Action of Acetic Althydride.-The compound readily yields an acetyl derivative C19H1903N3C12 in colourless plates m. p. 115O which is also converted into a diazonium salt by chlorine. III. Degradation to the Hydrazidine of Formic Acid.-The ester is wetted with alcohol and warmed with 20% potassium hydroxide a t 95O for a few minutes when a new potassium salt separates which is dissolved in warm water and mixed with hydrochloric acid. Free a-toluidiiLoglyoxylic acid 2 4-dichlorophenylhydrazon P separates as a lemon-yellow mass which becomes dark brown in time even in a well-closed bottle and gives golden-yellow solutions in most solvents. It has m. p. 98O but i f kept a t this temperature in an evacuated vessel it soon loses carbon dioxide and changes int80 o-toluidinoformaldehyde 2 4-dichlo~opJzenylhycFrcrzone C,H,Me*NH*CH:N.NH*C,H~Cl~ which forms white needles m.p. 9 1 O . IV. Complete Disruption.-The ester is decomposed by warming with zinc dust and glacial acetic acid into 2 4-dichloroaniline and o-toluidine this being identified by removing the solid base as far as possible and converting the oil into o-tolueneazo-&naphthol. The ester may be recovered almost entirely unchanged after boiling with water for a week but it is hydrolysed by boiling hydrochloric acid yielding 2 4-dichlorophenylhydrazine m. p. 90° oxalic acid and o-toluidine. J. C. W. Hydrazides and h i d e s of Sulphocarboxylic Acids. ERNST SCHRADER ( J . p. Chem. 1917 [ii] 96 180-185).-When hydrazine and o-cyanobenzenesulphonyl chloride react in benzene solution the product is a heterocyclic compound o-sulphohgdrazido-i.198 ABSTRACTS OF CHEMICAL PAPERS be?uoWrazide anhydride SO,<gEf>C*NH*NH iieedles 111. 1). 154' (dmomp.) which with benzaldehyde yields a benzylideiie derivative CI4I3,,O,N4S prisms m. p. 179O. With aqueous sodium azide an ethereal solution of o-cyanobenzenesulphonyl chloride slowly reacts with formation of o-cyaliob enxenesulp~~or~7,/Zaazidr CN-C,H,*SO,*N non-explosive rhombohedra m. 11. 40°. 6 4 D. F. T. Compounds Derived from Proteins by Energetic Treat- ment with Nitric Acid. VI. CARL TH. MORNER (Zeitscli. physiol. Chem. 1917 101 15-24. Compare A 1917 i 711).- The ethereal extract of the products of the action of nitric acid on proteins yields on fractional crystallisation from hot water henzoic and m-nitrobenzoic acids both of which are probably formed from the aromatic amino-acids in the protein.From the aqueous extract of the precipitate formed by the addi- tion of barium hydroxide and alcohol to the hydrolysed protein solution (compare A. 1915 i 324) shining yellow prisms separate after some days from which on treatment with dilute nitric acid an acid substance C4H304N3 is liberated which melts at about 300O. During the extraction of the products of the action of nitric acid on hzemoglobin by ether. a yellow powder gradually settles out from the originally clear liquid. On recrystallisation an acid substance is obtained in small colourless polygonal crystals C,H,O,N m.p. about 300O. Among the products of the combined action of hydrochloric and nitric acids on gluten a substance was isolated which crystallised in slender nee'dles but appeared nevertheless t o be a mixture of chlorinated benzoic acids. Effects of Electrolytes on Gelatin and their Biological Significance. I. Effects of Acids and Salts on the Pre- cipitation of Gelatin by Alcohol. W. 0. FENN ( J . Bid. C'hem. 1918 33 279-294).-The author finds that the quantity of alcohol required to precipitate a fixed amount of gelatin from its solution is dependent on the nature and number of ions present i n the gelatin solution. The method consists essentially in adding 95% alcohol to 5 C.C. of the gelatin-electrolyte mixture in a test- tube until such an opacity is produced that a pencil held behind the test-tube caii 110 longer be seen.The number of C.C. of alcohol added constitutes the '' alcohol number." The results show that acids alkalis and salts hinder the pre- cipitation of gelatin by alcohol. I n the case of strong acids and alkalis this effect rapidly increases passes through a sharp maxi- mum and then decreases as the concentration of the electrolyte is increased. Thus when the conditions above described are observed the quantity of alcohol required t o precipitate the gelatin rapidly increases as the concentration of hydrochloric acid in the gelatin solution is raised from 0 t o 0-024M. From 0.024 t o 0*095M y e - ' cipitation does not occur however much alcohol is added whilst It appears t o be a derivative of glyoxaline.H. W. €3.ORGANIC CHEMISTRY. i. 199 beyond this limit the amount of alcohol required slowly diminishes. When salts are added the precipitation of the gelatin is also hindered and the effect becomes more marked as the concentration of the salt is increased. Tervalent ions are more effective thaii bivalent and bivalent than univalent in this respect. Certain salts such as aluminium and copper chlorides which are very effective in hiiidering precipitation by alcohol resemble the strong acids in that their effect passes through a maximum and .then decreases. Others such as manganese sulphate containing bivalent cations and anions are exceptions to the general rule and either assist or only very slightly hinder the precipitation of gelatin by alcohol.The effect of the sulphates citrates and tartrates of the alkali metals decreases in high concentrations due to their strong ‘ I salting out ” or dehydrating powers. Eventually a point is reached where the salt itself precipitates the gelatin without any addition of alcohol being required. The discussion of the theoretical significance of these results is reserved for a future communication. H. W. B. Action of Diazomethane on Haemin. ~VILLIAN KusrER [with OTTO GEERING and 0. KUSCH] (Zeitsch. phylsioE. Chem. 1917 10.1 25-32. Compare A. 1915 i 853).-It has been stated (loc. cit .) that whereas bilirubin and hEmatoporphyrin are readily esterified by diazomethaiie hzemin is only esterified with difficulty or not a t all. Further experiments have shown that only a very small percentage of a-chlorohaemin is esterified by diazomethane whilst a-bromohaernin is quite unattacked.On the other hand some P-hzmin derivatives have been found to be readily methylated by this reagent. P-Bromoethylhaemin is converted into @-methyl- ethylhaemin and P-chlorohEmin into 8-chloromethylhzemin ; but B-chloromethylhzmin is unattacked and in mixtures containing P-chlorohzmin and the methyl mono-ester only the 0-chlorohaemin undergoes methylation. The methylation of the second carboxyl in P-haemin can therefore only occur through the agency of diazo- methane wheii the first carboxyl has been esterified by the ethyl radicle and hence it follows that the carboxyl esterified by ethyl alcohol is different from that esterified by methyl alcohol.These results furnish new evidence for the view that the carboxyl radicles in haeniin are affected in different ways by the neighbouring basic and iron-cont.aining groups (compare A. 1912 i 670) one beiiig in closer relation to the basic group than the other. This is illus- trated by the scheme \ \ // C0,Rlo / CO,H \ \ \ 4. / C0,H C0,Me / COO-NH + MeUIT --+ CL) 3-N H not niethylated IJY diaxomethanc COO*NH + EtOH -+ C‘0O.NEt niethylated forming COO-XE; CO,Ri. 200 ABSTRACTS OF CHEMICAL PAPERS. P-B7.omoet?L~lhLletltili C,,,N:,,O,N,BrFe prepared by Moruer s Ilke?thOd when suspended in chloroform and treated with diazo- methane yields P-bromome f ltylct hyllznp nciti C37H,,0,N,BrFc which is insoluble i n 5‘g Podiurn carbonate solution. Esterification and Empirical Composition of Haemin.WILLIAM K~STER (Zeitsch. physiol. Chena. 1917 101 33-42. Compare preceding abstract) .-Haemin prepared by Morxier’s method using pure ethyl alcohol consists of a mixture of a-hzemin and monoethylhaemin whilst when methyl alcohol is employed the products consist of &haemin monomethyl- and dimethyl-hkmin. When a mixture of ethyl.and methyl alcohols is used methylhzmin is first formed which then interacts with the ethyl alcohol to form ethylhemin. Since it has been shown (Zoc. cit.) that ethyl and methyl alcohols become attached to different carboxyl groups it follows that the ethylhzmin formed by the direct action of ethyl alcohol on haemin should be isomeric with that formed by the action of the mixture of alcohols in which the ethylhzmin is produced from the primary methylhzmin.Experiments carried out on these lines have notl been so far successful in isolating two isomeric ethyl- limnins only mixtures of mono- and clialkyI-hzmins being obtained. The analyses of the alkyl- and halogen-hzmins prepared in various ways are all in harmony with the empirical formula C,H,O,N,Cl(Br)Fe for haemin. Action of Aniline on Haernin and its Transformation by the Acetic Acid Method. WILLIAM K~STER [with in part pare A 1914 i 887 and preceding abstracts).-The product of the actdon of aniline on hzmin consisb of a mixture of three sub- stances. One of these hydroxyhEmin is formed from chloro- or brome-hzmin by the probable intermediate production of an addi- tive compound of the haemin with aniline which subsequently undergoes hydrolysis. It acts as a base forming salts with acids and has the hydroxyl group at’tached directly to the iron atom in the hzmin molecule. The other two products are two dehydro- halogenohzemins in one of which the iron atom is attached to oxygen and in the other to nitrogen. The latter N-detrivative is more stable than the 0-derivative and therefore does not so readily undergo transformation into a true hzmin. By the action of aniline on fl-chloromethylhzrrlin N-dehydrochlorohzmin and hydroxyhEmin are formed of which only the latter yields crystal- line fl-dimethylhaemin when esterified by means of methyl alcohol and hydrogen chloride. Two a-dehydrobromohaemins are similarly produced by the action of aniline on a-bromohaemin and can be separated by treating with a pyridine-chlorof orm mixture. Part dissolves but the solution does not yield hzmin when poured into acetic acid containing sodium chloride. The insoluble portion dissolves in alcoholic ammonia and is readily converted into crystallised hzmin. I n the first case the iron atom is attached to nitrogen whilst in the 13. W. R . H. W. B. LOBMILLER] (.&itsch. PhYSiOZ. Chem. 1917 101 43-76. Corn-PHYSIOLOGICAL CHEMISTRY. i. 201 second the less stable iron-oxygen compound is present which is therefore transformable int,o hizmin. I n some cases the failure to re-form a crystalline hizmin from a methylated hzemin is ascribed to the intermediate production of a “pseudohaemin,” in which salt formation with one of the basic nitrogen atoms is assumed to occur. H. W. B. The Influence of Neutral Salts on the Action of Urease. J. TEMMINCK GROLL (Proc. I . . Akad. IVetensch. Amsterdam 1918 20 559-565) .-The cations exert a preponderating influence on the decomposition of carbamide by urease the anions having coni- paratively little influence. The cations and the anions in so far as the influence of the latter can be observed arrange themselves. as regards their retarding action on urease in much the same order as they do in regard t o their influence on various colloidal phenomena. W. G .

ISSN:0368-1769    

DOI:10.1039/CA9181400153

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

ii. 164 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Production of Oxygen Free or almost Free from Chlorine. CHEMISUHE FABRIK GRUNAU LANDSHOFF & MEYER EMIL FRANKE and FRIEDRICH SCHMIEDT (D.R.-P. 299505 1915 ; from Cheem. Zentr. 1917 ii 508).-By the addition of B small quantity of nickel or cobalt in the form of metal oxide or salt the “first period ” of development of oxygen from chlorates or perchlorates is prolonged; cerium dioxide also can be used as catalyst. The last traces of chlorine can be removed from the gas by passing this through a filter of magnesium oxide whiting or anhydrous sodium carbonate which may be distributed over some inert material such as glass wool or asbestos. D. F. T.INORGSNIC CHEMISTRY. ii. 165 A Hydrogen Sulphide Generator. L.SATTLER (J. Ind. a i d Eng. Chem. 1918 10 ,").-The main generator consists of a large aspirator bottle the bottom tubulure of which is fitted with a straight stop-cock connected with one of the tubulures of a three-neck Woulfe bottle. Through the central orifice of the latter a tube passes t o the bottom of the bottle and is connected by a rubber tube to an aspirator bottle placed a t a higher level which governs the pressure under which the apparat'us works. The third orifice of the Woulfe bottle serves for t h s passage of a siphon tube with stop-cock through which the waste acid can be discharged. The upper tubulure of ths main generator carries a T-piece on0 branch of which is connected with a tube dipping under mercury forming a safetv-valve seal against excessive pressure.The other branch of the T-piece leads the generated gas through a stop- cock to a lead pipe terminating in a perforated coil submerged in a washing bottle through which the washed gas is delivered for use. The main generator is charged with about 23 kilos. of iron sulphide and the high-level acid reservoir with about 14 litres of hydrochloric acid diluted 1 :1 by volume. On opening the stop- cocks leading t o and from the main generator the three-neck mixing bottle should be filled with acid and about 7.5 cm. of the acid should remain in the reservoir. J. F. B. Synthesis of Arnmonia at High Temperatures. EDWARD BRADFORD MAXTED (T. 1918 113 168-172).-From a rough calculation of the equilibrium between nitrogen hydrogen and ammonia made by extending Haber's f orinuke t o temperatures above 1000° abs.it appears that increaqe of temperature leads a t first to a rapid decrease in the proportion of ammonia until a minimum is reached after which further increases cause the yield of ammonia to rise with increasing velocity. It should be possible therefore to realise a fair production of ammonia by heating mixtures of hydrogen and nitrogen to high temperatures and suddenly cooling the hot gases. The subject has been examined experimentally by igniting mix- tures of nitrogen hydrogen and oxygen in a tube (a) under water so that the hot gases were cooled by the water itself or ( b ) cooled externally by being made the tube of a Liebig's condenser. The direct cooling (a) proved to be far more efficient and with a mix- ture of gases in the proDortions N H 0 = 1 43 20 giving a flame with temperature 2580O abs.the yield of ammonia was as much as 1.23% a t atmospheric pressures. For experimental details see the original. Preparation of Carbon Monoxide. BERTRAM BLOUNT (9nnZyst 1918 43 88).-Fairly pure carbon monoxide free from carbon dioxide may be obtained by heating a mixture of calcium oxalate and calcium oxide. The gas usually contains some sulphur dioxide if it is prepared from potassium ferrocyanide and sulphuric acid or carbon dioxide if made from oxalic acid and J . C. W. sulphuric acid. w. P. s.ii. 166 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Argon in the Laboratory. MAX BODENSTEIN and LILI WACHENHEIM (Ber. 1918 51 265-270).-Samples of oxygen prepared from the air usually contain argon occasionally as much as 3%.The' commercial product' can t h e d o r e be used as a source of argon the oxygen being removed by combination with hydrogen. For this purpose the authors have designed an apparatus which is described and figured in the text. The con- trol of the process requires a certain amount of manipulative skill but even on the laboratory scale it' only takes about two hours t o prepare a litre of argon. The hydrogen and oxygen supplied from cylinders with good valves are led into a small quartz combustion chamber through gas current manometers the water is then trapped in two con- densers and the issuing gas made t o pass through a sensitive gas current manometer. If this records minimum rate of flow it indi- cates that neither oxygen nor hydrogen is being supplied in excess; i f not the gases are regulated accordingly. After this manometer are placed a hot tube containing copper oxide and copper to trap any traces of uncombined gases then another condenser for the water and finally an iron gas-washing tube containing calcium turnings heated electrically to 600O.This serves to absorb any nitrogen that may be present. The process is based on a method described by the Griesheim- Elektron Co. D.R.-P. 295572 of 1913. J. C. W. Production of Mono- Di- and Tri-metallic Alkali Per- phosphates and Perarsenates. S. ASCHKENASI (D.R.-P. 299300 1914; from Chenz. Zentr 1917 ii 438).-By the addition of the necessary quantity of alkali to a solution of barium peroxide in aqueoris arsenic or phosphoric acid barium arsenate or phosphate is precipitated and the filtrate containing the per-salt is then evaporated with slight warming and under reduced pressure; an aqueous solution of a mixture of sodium peroxide with the primarv or secondary alkali salts can also be submitted to evaporation.If a solution of an arsenate phosphate or borate in dilute hydrogen Iieroxide is evaporated to dryness with gentle warming and under reduced pressure the corresponding per-salt for example sodium pcrborate can be obtained with scarcely any loss of oxygen. D. F. T. Influence of Calcium Sulphate on the Corrosive Ac- tion of Water on Iron. P. MEDINGER (Bey. 1918 51 270-271). -The fact that gas and water mains suffer corrosion particularly severely in heavy clays which contain calcium sulphate is explained as follows through the ionisation of the sulphate the proportion of calcium ions in solution becomes so great that the dissociation of the calcium hydrogen carbonate is depressed and consequently the production of H and HCO ions from the free carbonic acid is not so much hindered.The enhanced acidity of EL solution con- taining free carbonic acid and calcium hydrogen carbonate con-INORGANIC CHEMISTRY. ii. 167 sequent on the addition of calcium sulphate may be demonstrated by means of litmus. J. C. W. Iron Trisulphide. WERNER MECKLENBURG and V. RODT (Zeitsch. nnorg. Chenz. 1918 102 130-148).-The work of previous investigators has left undecided the question of the existence of ferric sulphide. The authors have studied the action of hydrogen sulphide on ferric hydroxide of allrali sulphides on ferric salts and of alkali polysulphides on ferrous salts.When hydrogen sulphide is passed for a long time (about twelve hours) through an aqueous suspension of freshly prepared ferric hydroxide at; the ordinary temperatnre in absence of air the colour of the hydr- oxide gradually becomes black and when the reaction is 'fiaished the1 composition of the precipitate corresponds with Fe,S ag. The precipitate contains no sulphiir soluble in carbon disulphide and is completely decomposed by dilute hydrochloric acid forming ferrous chloride hydrogen sulphide and sulphur. Treatment with carbon disulphide however changes the character of the t'ri- sulphide rendering it partly insoluble in dilute hydrochloric acid.The hydrated trisulphide is rapidly decomposed by air and in absence of air it undergoes spontaneous decomposition into ferrous sulphide and iron disulphide. It can be completely dried in a vacuum over phosphoric oxide. The anhydrous trisulphide is pyrophoric if suddenly brought into contact with air but if spontaneous ignition is prevented it is quite stable. By addition of a solution of a ferric salt t o excess of sodium sulphide solution. a precipitate is produced having the composition Fe,S3,Na,S and the same compound is formed by the action of excess of sodium polysulphide solution on a solntion of a ferrous salt. The alkali sulphoferrites form diIute aqueous colloidal solln- tions having a deep 'green colour. E. H. R. Reactions in Non-aqueous Solvents.11. The Action of Chromyl Chloride on Phosphorus Haloids . HARRY SHIPLEY PRY and JOSEPH I,. DONNELLY ( J . A m ~ r . Chem. SOP. 1918 40. 478-482).-The action of chromyl chloride on phosphorus cli- iodide tri-iodide. pentachloride and pentabromide in anhgdroiis carloon tetrachloride has been. examined. With phosph oriis di-iodide a brown-coloured additive compound Cr02Cl,,PI,. is precipitated. It is readily decomposed by water with liberation of iodine and the formation of a solution contain- ing phosphate chromic chloride and iodide ions. Phosphorus tri-iodide also yields an additive compound CrO,Cl,,PI which when dry consists of a purplish-red povder. It is decomposed by water in accordance with the equat'ion 2Cr0,C1,,P13 + 4H20 = 4BC1 -l- 4HI + 2CrP0 + I,.With phosphorus pentachloride the additive compound CrO,Cl,,PCl is produced in the form of a yellowish-red powder readily decomposed by water. It has been previously found (A. 1916 ii 626) that phosphorusii. 168 ABSTRACTS OF CHEMICAL PAPERS. tribromide reacts according to the equation 2Cr0,C12 -t 3PBr = 2CrOCI,POBr3 + PBr,Cl and the product obtained by interaction of chromyl chloride with phosphorus pentabrom:de appears to be a mixture of CrOCl,POBr and the additive compound CrO2C1,,PBr,. The formation of these substances is presumably connected with the fact that phosphorus pentabromide is measur- ably dissociated into the tribromide in carbon tetrachloride solu- tion. H. &I. D. The Reaction between Antimony and Solutions of Sodium in Liquid Ammonia.EDWARD B. PECK ( J . AirLet.. Chem. SOC. 1918 40 335-347) .-Metallic antimony dissolves when brought into contact with a solution of sodium in liquid ammonia. 'The atomic ratio of antimony to sodium in the saturated solution increases from about 1.2 for a solution con- taining 0.005 gram atom of sodium per litre to about 2.3 for a solution containing 0.4 gram atom of sodium per litre. For more concentrated solutions the ratio diminishes slightly. The diminu- tion may be due to the failure to reach equilibrium in the more concentrated solutions which are highly viscous o r it may possibly be accounted for by the fact that tho solution was assumed to have the same volume as the ammonia which it contained. The observed facts suggest that there are a t least two com- pounds formed in one of which the ratio Sb :Na is greater than two whilst in the other this ratio is less than two.The electrolytic behaviour of these solutions when subjected to the action of a current bettween a platinum anode and an antimony cathode has also been examined but the quantitative data do not permit of any definite conclusion. The results show however thst antimony is present in the solutions as anion and that more than on0 atom of antimony is associated with each negative charge. €1. M. D. A New Metastable Form of Antimony Tri-iodide. A. C . VOURNASOS (Compt. rend. 1918 166 526-528).-Antimony tri- iodide regarded as trimorphous may be obtained in a fourth form by cooling a hot saturated solution of the red iodide in glycerol. It is thus obt>ained as an amorphous yellow powder m. p. 1 7 2 O a t which temperature it steadily passes into the red variety form- ing hexagonal crystals. This metastable; amorphous form may also be obtained from the red form by warming it' on a water- bath with fifteen times its weight of acetic acid and a little potassium acetate. The solution on cooling deposits the yellow amorphous iodide. It may also be prepared from antimony tri- oxide and potassium iodide by heating them a t looo with an excess of anhydrous acetic acid. The last niethod also applies to the pre- paration of arsenic antimony and bismuth tribrornides and arsenic and bismuth tri-iodides. W. G.

ISSN:0368-1769    

DOI:10.1039/CA9181405164

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

MINERALOCICAL CHEMISTRY. Mineralogical Chemistry. ii. 169 The Gyrohedral Character of Rock Salt. R. GROSZ (Celzti.. Nin. 1918 l-l9).-The crystal structure deduced by W. H. and W. L. Bragg for sodium chloride and other similar salts is stated not to be satisfactory. On the one hand it is a holohedral structure whilst there is abundant evidence that the structure of sylvine is gyrohedral hemihedral and that other salts of the same series are certainly not holohedral; on the other hand no account is taken of the chemical bonds between individual atoms. By symmetrically displacing the centres of gravity of selected atoms in the Bragg structure a number of new structures can be produced having gyrohedral or tetartohedral symmetry and it is claimed that these cannot be distinguished by X-ray analysis from the holohedral form.If rock salt were tetartohedral irregularities might be ex- pected t o appear in the Laue radiogram but- such irregularities the author has failed to discover. It has been shown by Smits and Scheffer (A. 1917 ii 78) that it is possible t o couple symmetrically the atomic valencies in a cubic structure of atoms of two kinds. The coupling leads to the formation of cubic aggTegates of different sizes according to the disposition of the planes of atoms and these aggregates may be regarded as crystal molecules. The structure derived by the association of such aggFegates affords an explanation of the cubic cleavage of .rock salt since at regular intervals there occur in the series of (100) planes pairs of planes between which no chemical bonds are active.A crystal cleaved along these planes of zero affinity would contain no excess of uncombined atoms of either kind whereas in other crystal models the “ideal” crystal always contains an excess of atoms of one kind. The hemihedral charactler of the crystals of rock salt may also be accounted for by making certain assumptions regarding the axis and direction of rotation of the valence electrons about the individual atoms. E. H. R. Algodonite and Whitneyite. L. H. BORGSTROM (Geol. FGY. F o ~ h . 1916 38 95-100; from Jalwb. Min. 1918 Ref. 11-13). -Analyses of algodonite and whitneyite from the Mohawk mine Michigan gave Cu 84.1 and 87.2% respectively. Melting-point determinations in capillary tubes showed a wide interval sintering beginning a t 695O but fusion was complete only a t looo higher.Thess minerals are therefore decomposed before fusion takes place. The cooling curves of the fused materials show in each case a pronounced break at 6 8 8 O that is near the freezing point (685O) of the eutectic Cu,As-Cu. Polished plates of the natural minerals and of the fused products were etched with nit,ric acid and ex- amined under the microscope. Algodonite was seen to consist of almost homogeneous crystalline material with very little metallicii. 170 ABSTRACTS OF CHEMICAL PAPERS. copper whilst whitneyite contains 3-4% of metallic copper and thus consists of a mixture of algodonite and copper. The fused pro- ducts in each case consist of a mixture of light grey Cu,As and copper. The electrical resistance in ohms for rods 1000 mm.long and 1 sq. mm. cross-section is for whitneyite 0.341 and 0.335 for algodonite 0.415 and for the fused materials 0.469 and 0.634 respectively. Although not indicated on the cooling diagrams of copper-arsenic fusions the copper arsenide CusAs (algodonit,e) therefore exists but is only stable below the point of fusion. On the other hand the arsenide Cu,As (whitneyite) has no existence. L. J. S. Spectral Investigation of the Composition of Goyazite. A. DE GRAMONT (Bull. Soc. fmnq. Min. 40 2 6 ; from Chem. Zentr. 1917 ii 825) .-According to spectral observatbons calcium strontium and probably aluminium are characteristic constituents of goyazite. R. &I. D. Meerschaum from Kraubat Styria. H. LEITMAIER (Sitzungsber. K .A k a d . ?Viss. Wim Math.-iVat. Kl. Abt. I 1915 124 163-180 ; from Jalarb. &fin. 1918 Ref. 21-22).-The8 meer- schaum occurs as bands 1 mm. to 20 dcm. thick in mzssive magne- site. It is white yellow or green and either earthy (being then mixed with magnesite) or compact with large-conchoidal fracture. Analysis of the latter variety gives the formula 2Mg0,3Si0,,4H20 About half of this water is lost over sulphuric acid a t 20° and is reabsorbed from a moist atmosphere to the extent of 37.56% H,O after 144 hours. At looo the loss is 9-72% and a t 450° it is 18.17%. Since 2H,O is more closely held the formula is written 2Mg073Si0,,2H,0 any extra water present depending on the vapour tension of the surrounding atmosphere. The meerschaum and magnesite have probably originated by the action of carbonated waters on serpentine.When fused the meerschaum gives rise to an eiistatite containing an excess of silica (MgQ SiO,= 7 9) which is probably held in solid solution. L. J. S. The Identity of Shattuckite and Plancheite. F. ZAMBONINI (Compt. rend. 1918 166 495-497).-The mineral shattuckite as described by Schaller ( J . TVashingtom Acud. Sci. 1915 5 7) and the mineral plancheite as described by Lacroix (A. 1908 ii 508) possess the same optical and crystallographic properties although differing slightly in their chemical analyses. As a result of the examination of a specimen of plancheite the author has obtained analytical data in agreement with those for shattuckite and for the composition 2CuSiO,,H,O and he considers that these two minerals are identical and that the older name plancheite should be retained.W. G. Gedrite from the Tatra Mountains Hungary. W. PAWLICA (Bull. Acad. Sci. Cracow Cl. Sc. Math. e t Nat. Ser. A 1915 18-25; from J a l ~ r b . Min. 1918 Ref. 19-20).-Analysis I is of aANALYTICAL CHEMISTRY. ii. 171 gedrite-gneiss froin the Gewont peak containing quartz (41.3 mol. y;) plagioclase (a basic oligoclase Ab,,An28 35*3) gedrite ( 1 3 ~ 0 ) ~ biotite (5.1) ilmenite (1.3). The gedrite (anal. 11 mean of three) forms black orthorhombic prisms 8-3 cm. long and 0.1 mrn. thick with distinct pleochroism bluish-green to pale green. The high percentage of fluorine and water is not accounted for by the ordinary formula but' in Penfield's amphibole formula it figures in the molecule (F,HO),Nlg(Al,Fe~'~)SiO which is here present to the extent of 39*G% with the metasilicate molecules MgSiO (36*6) FeSiO (25*7) CaSiO (7-2) and Na,Si03 (0.9:L).SiO,. TiO,. P,O,. A1,0,. Fe,O,. FeO. MnO. CaO. MgO. 1. 69-82 1.24 0.18 12.70 2.32 2.78 0.12 2-96 2-47 11. 41-59 0.97 0.16 12-81 5.90 14.81 trace 3-65 15-13 H,O H,O Totalless K,O. Na20. F. <105". >105". 0 for F. Sp. gr. I. 0.40 3.27 0-17 0.23 1.30 99.89 3.240 11. 0.12 0.43 2.34 0.86 1.68 99-42 2.701 L. J. S. Iron Silicate Ores of the Diabase and Schalstein Zone between Sternberg (Moravia) and Bennisch (Austrian Silesia). FRANZ KRETSCHMER (Jalzrb. Alzn. 1918 19-48).-A detailed account is given of the characters of these ores as seen in inicro-sections an account of their chemical characters having been sent for publication in Arch.Lagerstattenforsch. Berlin. The dense chloritic minerals of which these ores are composed include thuringite and rnoravite (A. 1906 ii 458) and two new species viridite and mackensite differing from the former in con- taining more iron (respectively ferrous and ferric) and correspond- ingly less alumina. I'zridite contains only 4.49% A1203 and approx- imates to the end-rnember 4Fe0,2Si0,,31-120. It is a compact leek- green ore D 2.89 H 3-34 and under the microscope is seen t o consist of minute needles and scales with pearly micaceous cleavage. iwackensite cont,ains 6.14% Al,03 (in part due to the presence of admixed thuringite) and approximates t o the end-member Fe203,Si0,,2H,0 of the thuringite series. It is compact iron- black to greenish-black D 4-89 H 3-34 and under the rnicro- scope shows colourless or brownish-green needles surrounding shreds of thuringite and grains of calcite and magnetite. Locally the magnetite is present in greater relative amount but ores of this character are not abundant. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9181405169

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. Analytical Chemistry. ii. 171 Increasing the Delicacy of Delivery of Burettes. EWART H. MERRITT (Analyst 1918 43 138).-Both the inside and the outside of the jet of the burette are coated with a thin film ofii. 172 ABSTRACTS OF CHEMICAL PAPERS. paraffin (m. p. about 550); the number of drops per C.C. delivered by the burette may be thus increased from twenty to forty. w. P. s. RLBERTO BETIM PAES LEME (Compt. rend. 1918 166 465-467).-The method is a spectrographic one using a screen having a narrow horizontal opening and travelling with a constant velocity in a vertical direc- tion during the vaporisation of a known weight of the mineral containing the element' to be estimated. The width of the open- ing and the velocity of the screen are equal. A given ray for the element is adopted once and for all and the time duriEg which it is visible is determined.An example is given aluminium being the metal to be estimated. A New Process of Quantitative Analysis. W. G. Detection of Small Quantities of Chlorine in Iodine. J. PINKHOF (Pharm. Weekhlad 1918 65 23G).-The presence of chlorine in iodine between Q% and 2yA can be detected by neutral- isation with thiosulphate and precipitation with barium nitrate Estimation of Chlorides in Blood. MARCEL DUGARDIN (An&. Chim. a?zal. 1918 23 59).-Ten C.C. of the serum are mixed with 10 C.C. of 20% trichloroacetic acid solution the mixture is filtered and 10 C.C. of the filtrate are diluted with 25 C.C. of water then acidified with 5 C.C. of nitric acid and the chloride is [Estimation of Sulphur in Ores etc.] F.G. HAWLEY ( 8 n g . arnd Min. J. 1918 105 385-386).-A method is described for estimating sulphur gravimetrically in ores and furnace products by oxidation to sulphate and precipitation as barium sulphate which avoids the difficulties usually experienced in oxidising mattes and calcines or ores containing much copper or zinc sulphide. The oxidising mixture employed is a ZOYL solution of sodium chlorate to which is added a small quantity of a mixture of equal parts of bromine1 and glacial acetic acid followed by an equal volume of nitric acid nearly saturated with potassium chlorate. [For details see Ind. May.] Some Limitations of the Kjeldahl Method. HARVEY C. BRILL and FRANCISCO AGCAOILI (Yhilippke J . Sci. 1917 ~ Z A 261-265) ,-The Kjeldahl method yields low results when applied to the estimation of nitrogen in pyridine piperidine quinoline isoquinoline hydroxyquinoline pyrrole and sometimes in nicotine ; this is possibly due to the formation of sulphonic derivatives which re& decomposition.I n the case of pyridine the Gunning-Arnold method gives trustworthy results if the heating is prolonged for a considerable period (four hours) after the solution has become clear. Low results are always obtained when sodium sulphate is used in place of potassium sulphate for raising the boiling point of the sulphate formed. A. J. w. titrated by Volhard's method. w. P. s. W. F. F. of the mixture. [See further Znd. 2 2 5 ~ . ] m7. P. s.kNALY TICAL Cax MISTRY. ii. 173 Kjeldahl's Method for the Estimation of Nitrogen.EDUARD SALM and SIEGFRIED YBAGER (Chem. Z e i t . 1918 42 104-105).-The addition of zinc dust is necessary in the distilla- tion of the ammonia obtained by digesting a nitrogenous substance with sulphuric acid and mercury or with sulphuric acid phos- phoric oxide and mercury i f potassium sulphide is not added to the sodium hydroxide. If potassium sulphide is used zinc turnings may be used in place of zinc dust. The results obtained are too low if the zinc is omitted or replaced by aluminium. [See Foam Inhibitor in the Van Slyke Arnino-nitrogen Method. 13. H. MITCHELL and H. C. ECKSTEIN (,7. Biol. Chem. 1918 33 373-375).-The formation of foam during the liberation of nitrogen in the Van Slyke apparatus is prevented by the addition of two or more drops of diphenyl ether which is readily synthesised from bromobenzene and potassium phenoxide (Ullmann and Sponagel A.1905 i 644). Alkalimetric Estimation of Phosphorus in Iron and Steel. NIKOLAUS CZAKO (Chem. Zeit. 1918 42 53-54).-When the vellow ammonium phosphomolybdate precipitate is dissolved in a known excess of sodium hydroxide solution and the excess then titrated with standardised nitric acid it is recommended that the latter be standsrdised against potassium hydrogen carbonate. The pot'assiurn hydrogen carbonate value of the acid is then multiplied Separation of Phosphorus from Vanadium. ALFRED KROPF (Chem. Zeit. 1917 41 877-878 890-891).-0ne gram of the alloy containing phosphorus and vanadium is dissolved in aqua regia the solution evaporated to dryness the residue heated gently t)hen cooled boiled with the addition of 20 C.C.of hydrochloric acid (D 1*12) diluted to 60 c.c. and filtered to separate silica. The filtrate is treated with 15 C.C. of ammonium citrate solution (prepared by neutralising 1 kilo. of citric acid with ammonia and diluting the solution to 5 litres) and boiled for three minutes to reduce the vanadic acid; after the addition of 30 C.C. of 40% ammonium nitrate solution and 10 C.C. of nitric acid (D 1-18> the phosphoric acid is precipitated with molybdic acid reagent. I n the case of ores the sample is fused with a mixture of sodium and potassium carbonates or sodium carbonate and pot'assium nitrate the mass dissolved in water filtered and the filtrate treated as described.If arsenic is present it may be separated from the vanadium and phosphorus by treatment with hydrogen sulphide or the phosphorus together with some of the vanadium may be precipitated as hydrated aluminium phosphate and thus separated from the arsenic. w. P. s. A. DE GRAMONT (Compt. rend. 1918 166 477-480).-Boron may be readily detected if further Ind. May.] w. P. 8. H. W. B. by 0.013481 to obtain the phosphorus value. w. P. s. Spectroscopic Detection of Boron. CXIV. ii. 10ii 174 ABSTRACTS OF CHEMICAL PAPEEGS. present to the extent of 1 in 10,000 by means of the ray h3451.2 and the doublets h2497.82 and 2496.87 shown in t,he condensed spark spectrum. W. G . Gasometric Estimation of combined Carbon Dioxide. W. MESTREZAT (Ann. Chim. anal. 1918 23 45-47).-A method for the estimation of carbon dioxide in a mixture containing a carbonate and a hypochlorite consists in treating a portion of the sample with sulphuric acid and measuring the volume of the liberated carbon dioxide after tho chlorine has been absorbed by oil of turpentine. The estimation is carried out in an ordinary calcimeter but a tube containing a plug of cotton wool impregnated with oil of turpentine is placed between the reaction flask and the gas-measuring burette.[See further Znd. May.] W. P. S. Estimation of Potassium. BERTRAM BLOUNT (Analyst 1918 43 117-120) .-For tthe estimation of potassium in siliceous rocks clays etc. the material is decomposed with hydrofluoric and sulphuric acids iron aluminium manganese and calcium are removed from the solution in the usual way sulphuric acid is separated by treatment with barium hydroxide and the solution is evaporated to obtain the mixed sodium and potassium chlorides.The quantity of potassium is then estimated by the platinum chloride or perchlorate method. w. P. s. Calcium in Man. I. Estimation of Calcium in the Blood. W. H. JANSEN (Zeitsch. physiol. Chem. 1918 181 176-192).- The blood (10 c.c.) is dried and incinerated. The ash is dissolved in hydrochloric acid nearly neutralised with ammonia and the iron and phosphorus removed by boiling with ammonium acetate. The calcium is subsequently precipitated as oxalate from the care- fully neutralised filtrate. The precipitate is collected and after ignition in the usual way the residual calcium oxide is estimated by dissolving in a known volume of N/lOO-hydrochloric acid and titrating the excess with alkali or by dissolving in 15 C.C.of N/100- hydrochloric acid adding 25 C.C. of water 2 C.C. of a 10% pobassium iodide solution 4 drops of a 4% potassium iodate solution and 2 drops of a 1% starch solution in 20% potassium chloride solution and then titrating with N / 100-thiosulphate solutlion until the blue colour just disappears. H. W. B. Estimation of Hardness of Water by the Method of Wartha-Pfeiffer. WAGNER (Zeitsch. ofentl. Chem. 191 7 23 375-379. Compare A. 1914 ii 490).-'This method yields more trustworthy results particularly in the case of waters containing relatively large quantities of magnesium salts if the amounts of sodium carbonate and sodium hydroxide in the reagent are increased to 14.5 grams and 8.01 grams per litre respectively.w. P. s.ANALYTICAL CHEMISTRY. ii. 175 Estimation of Sulphur and Copper Oxide. C. G. MAIER (En,g. and ruin. J . 1918 105 372-373).-For estimating the proportions of copper sulphide and (‘ oxide ” or soluble copper in a sample of copper ore especially for use in flotation processes the ore is heated with 4% sulphuric acid a t 80-90° the mixture cooled and clean mercury added and mixed thoroughly with the residue so that it amalgamates with the metallic copper present or reduced from cuprous oxide. The solution is filtered and the copper determined separately in the filtrate and residue preferably by the iodide method. The copper in the residue represents the sulphide and that in the solution the “oxide” or soluble copper.[See further Znd. May.] Copper Dicyanodiamide and its Use in Analysis. H. GROSS- MANN and J. MANNHEIM (Chem. Z e i t . 1918 42 17-19).-Copper may be precipitated by treating a solution of one of its salts m t h concentrated dicyanodiamide sulphate solution rendering the mix- ture slightly ammoniacal heating it t o boiling and then adding sodium hydroxide solution until the blc e colour changes to reddish- violet. After cooling the red precipitate is collected washed with cold water and dried a t 1 2 0 O ; it contains 23.92% of copper. As the precipitate is slightly soluble in water all the solution used should be concentrated. Nickel may be precipit-ated in a similar way (compare A. 1907 ii 819) and the method may be used for the separation of copper and nickel from zinc aluminium chromium arsenic lead and antimony.I n exceptional cases where the introduction of alkali into the solution is not desired dimethylamine may be used in place of sodium hydroxide to pre- Analysis of Aluminium Alloys. BERNARD COLLITT and WILLIAM REGAN ( J . SOC. Chem. Incl. 1918 37 91-94~).- Methods are given for the estimation of copper iron nickel man- ganese zinc magnesium and silicon in aluminium alloys such as are used in the construction of aircraft and other engines of war- fare. I n cases where the alloy contains only copper (10 to 15%) and manganese (1%) in addition t o aluminium the copper may be estimated volumetrically by the iodide method; in other alloys it is estimated gravimetrically by precipitation as sulphide by thio- sulphate the sulphide being subsequently ignited and weighed as oxide.The original should be consulted for the details of the methods recommended for the estimation of the other constituents. Volumetric Estimation of Manganese by means of Sodium Arsenite. FRED IBBOTSON (Chenz. News 1918 1 17 157-158).- When permanganate solution containing nitric acid is titrated with sodium arsenite solution the latter has a reducing value about 33% in excess of the valne it has when used against potassium per- manganate solution alone. This appears to be due to the forma- tion of manganic compounds in the presence of nitric acid. [See W. F. F. cipitate the copper and nickel compounds. w. p. s. w. P. s. further Ind. May.] w P. s.ii.176 ABSTRACTS OF OHEMICAL PAPERS. Estimation of Manganese in Aluminium Alloys and Dust. J. E. CLENNELL (Eng. and Min. J . 1918 105 407-410).-Two methods are described for estimating manganese in dust made from aluminium-manganese allop. Several known methods were in- vestigated but the following much simpler methods are preferred 1 Gram of the sample is carefully heated with 50 C.C. of 50% nitric acid and finally boiled to expel oxides of nitrogen. The solution is filtered the residue washed placed in a nickel crucible dried ignited and the ash covered with sodium peroxide. 'The mixture is fused and the product' dissolved in water and added to the previous nitric acid solution. The mixture is boiled and about 1 C.C. of standard silver nitrate solution added to remove chlorides.0.1 Gram of lead peroxide is added for each estimated 0.1 gram of manganese present the mixture boiled cooled made up to 100 c.c.. and filtered. Fifty C.C. of the filtrate are titrated with standard sodium arsenite which has been standardised against a manganese salt. Another method is described in which ammonium prsulphate is substituted for lead peroxide but this was not so trust'worthy owing t o the variability in the quality of thel per- sulphate. [For details see I n d . May.] W. F. F. Gravimetric Estimation of Chromates and Dichromates. L. W. WINKLER (Zeitsch. angew. Chern. 1918 31 46-48).- I. A s Barium Chromate.-One hundred C.C. of a neutral solution containing about 0.2% of an alkali chromate are treated with 1 C.C. of N/lO-acetic acid and 1 gram of sodium chloride heated to boil- ing and 5 C.C.of 10% barium chloride arel added slowly while the mixture is stirred. The mixture is kept boiling for three minutes then cooled and after eighteen hours the precipitate is collected washed with 50 C.C. of cold water dried at 1 3 2 O and weighed. When the precipitate weighs less than 0.1 gram the weight found is about 1 mg. too low. If the precipitate is ignited before being weighed it loses 0.25% in weight. The presence of ammonium potassium magnesium and calcium chlorides does not interfere but nitrates chlorates and acetates cause the results t o be too high. Dichromates are estimated in a similar way after their solu- tiQn has been boiled with the addition of calcium carbonate and filtered. 11. A s Silver Clzromate.-This method must be used i€ the chromate solution contains sulphate; in any case it is more trustworthy than the barium chromate method but cannot be used in the presence of chlorides. One hundred C.C.of the chromate solution (or dichromate solution after treatment with calcium carbonate) are boiled and 5 C.C. of 10% silver nitrate solution are added. After eighteen hours the precipitate is collected washed with 50 C.C. of water saturated previously with silver chromate dried at 1 3 2 O and weighed. The results are notl affected by the presence of nitrates chlorates or acetates butl sulphates cause the A. TRAVERS (Compt. rend. 1918 166 416).-For this method using titanous chloride results to be too high. w. P. s. Colorimetric Estimation of Tungsten.ANALYTICAL CHEMISTRY.E. 177 (compare A. 1917 ii 545) the tungsten solution should not con- tain more than 0.1 gram of the metal in 100 c.c. and the acidity of the solution should not exceed N/10. The estimation cannot be performed in the presence of vanadium phosphorus or molyb- denum. W. G . [Estimation of Uranous Salts in Presence of Formic Acid.] E. C. HATT (Zeitsch,. pkysikal. Chem. 1918 92 513-562).-Com- pare this vol. ii 144. Oxidimetric Estimation of Thorium Precipitated as the Oxalate. F. A. GOOCH and MATSUSUKE KOBAYASHI (Amer. J. Sci. 1918 [iv] 45 227-230).-'The following conditions are given for the estimation of thorium by titration with permanganate of its oxalate or of the excess of oxalic acid used for the precipitation. The oxalate is precipitated by adding the thorium solution to an excess of cold oxalic acid solution; the reverse procedure is less trustworthy owing to the formation of basic compounds especially in hot solutions.After thirty minutes the precipitate is collected on an asbestos filter washed with cold water containing one drop of concentrated sulphuric acid in each 25 c.c. the filter and pre- cipitate are then transferred to a beaker containing 100 C.C. of water the' mixture is heated a t 8 5 O 5 C.C. of sulphuric acid (1 1) are added and the solution is titrated with 1V/lO-permanganat.e solution until t*he greater part of the malate# has been oxidised; the solution is then heated aqain a t 85O and the titration completed. I f a known excess of oxalic acid has been used the filtrate from the oxalate precipitate may be heated at 8 5 O acidified with sulphuric acid and titrated with permanqanate.I n this case there is no need t o reheat the titration mixture. The precipitated thorium oxalate has the composition Th(C,O&. w. P. s. The Estimation of Tantalum in its Alloys with Iron. A. TRAVERS (Compt. rend.. 1918 166 494--495).-1n the estima- tion of tantalum the precipitate of tantalic acid usually contains some silica and if this is removed by means of hydrofluoric acid some of the tantalic acid is also lost. The tantaljc acid may how- ever be volatilised in a current of hydrogen chloride a t 900°. The silica which is left is weighed. and the weight' deducted from that of the original precipitate. For details of application t o steels etc.see 711~7. 2 4 4 ~ . W. G. Detection and Estimation of Methyl Alcohol its Presence in Various Foodstuffs and the Behaviour of Foodstuffs containing Methyl Alcohol in the Organism. TH. VON FELLENBERG (Riochem. Zeitsch. 1918 85 45-117. Compare A.. 1917 i 616).-A detailed account is given of the modification of DenigBs's method for estimat'ing methyl alcohol. The essential process consists in the oxidation of the liquid (which generally con-ii. 178 ABSTRACTS OF CHEMICAL PAPERS. taiiis ethyl alcohol) with permanganate and the colorimetric estimatlion of the formaldehyde thus obtained by oxidation under standard conditions by magenta-sulphurous acid solutions. A new method is also given for determining the preeence of methyl alcohol when i t is only present in small quantities The essential process consists in the fractional separation of the mixed methyl and ethyl alcohols by potassium carbonate.The alcohol separated first by incomplete1 saturation with the carbonate con- tains scarcely any methyl alcohol. After separation of fractions containing only minute amounts of methyl alcohol the residue is distilled. The distillate is fractionated and the first fractions are redistilled. These fractions are again redistilled the earlier frac- tions only being retained. A fraction is finally obtained which is rich in methyl alcohol and this after drying over calcium oxide is converted into iodides from which a fraction rich in methyl iodide can be separated. It is shown that the methyl alcohol in certain spirits is derived chiefly from the pectin substances from which 10-11% of methyl alcohol can be separated by treating with dilute sodium hydroxide.The lignins of wood also yield methyl alcohol but this is not eliminated so readily as that of pectins. It can be obtained in various fractions by treating the wood first with sodium hydroxide to eliminate the pectin alcohol and then with graded strengths of sulphuric acid. Each filtrate obtained in this way is then treated with 70% sulphuric acid and the methyl alcohol in the distillate is estimated as well as the methyl alcohol in the distillate before treatment with the 70% acid. The methyl alcohol of the pectins and lignins was determined in ,z large number of different kinds of woods etc. An investigation was also made of the effect of ingestion of sub- stances containing pectins.The ingestion of pectin-containing sub- stances caused a small increase in the excretion of methyl alcohol in the urine which was much more marked when ethyl alcohol was ingested a t the same time. It' was suggested that certain symptoms found in the drinkers of spirits may be due to the methyl alcohol contained therein. [See also Znd. May.] s. €3. s. Estimation of Glycerol by Wagenaar's Method. J. H. M. BECKERS and I. M. KOLTHOPF (Phurm. WeekbZuct 1918 55 272-281) .-Wagenaar's method of estimating gfycerol (A 1911 ii 663) gives results dependent on the composition and tempera- ture of the liquid. Methyl alcohol is without influence on the reaction but the pi-esence of ethyl alcohol haloids nitrates and to a less degree sulphates is deleterious.With fats it is best to saponify with methyl-alcoholic potash and remove the fatty acids wit8h the minimum quantity of sulphuric acid. I. M. KOLTHOFF (Pknrm. Weekblad 1918 55 304-307) .-An account of a method of est'imating the percentage of water in glycerol by observing the temperature range of complete miscibility of mixtures A. J. W. Estimation of the Amount of Water in Glycerol.ANALYTICAL CHEMISTRY. ii. 179 of the sample and aniline. percentages of water is given. A t'able showing the corresponding A. J. W. Methylene-blue a Sensitive Reagent for the Detection of Picric Acid in Urine. ROZIER (Bzd2. Sci. Phawnacol. 1917 ; from Anm. Chirn. anal. 1918 23 63).-The urine is treated with normal lead acetate and filtered; 4 C.C.of the filtrate are placed in a test-tube one drop of 0.5% methylene-blue solution is added and the mixture is shaken with 1 C.C. of chloroform. After separation the chloroform layer has a green colour if picric acid or picraniic acid is present in the urine; in their absence the chloroform is coloured blue. The test will detect the presence of 2 mg. of picric acid per litre of urine. TV. P. s. Colorimetric Estimation of Ficric Acid and its Derivatives in Body Fluids. X. LAPORTE (Bull. SOC. Pharm. Bo-l.deaax 1917 No. 3; from Ann. Chim. anal. 1918 23 64).-A definite volume of the fluid (which should be diluted or concentrated so that it contains about 0.01 gram of picric acid per litre) is neutralised and treated with 0.5 C.C. of ferrous sulphate-tartaric acid reagent (compare A.1917 ii 158) and 1-5 C.C. of ammonia; these quanti- ties of reagents are required for each 10 C.C. of the sample. The coloration obtained is compared with that produced by a known amount of picric acid under the same conditions. w. P. s. Estimation of Cholesterol. I. LIFSCH~TZ (Zeitsch. physiol. Chem. 1918 101 89-98).-The author finds thatl the method described by Windaus (A 1909 i 172) f o r recovering the cholesterol or similar component f rom the digitonin-cholesterol complex is unsatbsfactory. By the following procedure a quanti- tative separation is effected. About 0.5 gram of the anhydrous complex is weighed out and boiled with 5 C.C. of acetic anhydride for t'wenty to thirty minutes under a reflux condenser. The hot liquid is poured into about 80 C.C.of water. After t.he product of the reaction has solidified it is collected washed and dried in a vacuum. It is now removed as completely as possible from the filter paper transferred to a small flask dissolved in 10 C.C. of 90% alcohol and mixed with 10 C.C. of 1% aqueous sodium hydr- oxide. The resulting emulsion is boiled for two and a-half to three minutes cooled dilut'ed with water acidified and extracted with ether. The cholesteryl acetate dissolves in the ether whilst the digitonin remains in the dilute alcohol. After evaporation of the ether the cholesteryl acetate is hydrolysed with alcoholic potassium hydroxide and the free cholesterol or similar compound extracted by ether weighed and subsequently identified in the usual way. H. W.B. Detection of Acetone in Urine. HANS TRUNREL (Phamz. Z e i t . 1918 63 104-105).-Legal's nitroprusside test is trust- worthy and gives the best results when applied as a ring test. Twoii. 180 ABSTRACTS OF CHEMICAL PAPERS. C.C. of the urine are mixed with ten drops of 20% sodium nitro- prusside solution and 1 C.C. of acetic acid and 2 C.C. of ammonia are poured on the surface of the mixture; if acetone is present a violet-red zone appears a t the junction of the two liquids. Reichardt's test (A. 1916 ii 119) in which the acetic acid of the Legal test is replaced by ammonium chloride is less trustworthy since a feeble coloration is obtained in the absence of acetone. It' is not necessary for the nitroprusside solution employed to be freshly prepared; the solution i f made with the pure salt keeps Estimation of Pyridine Bases in Ammonia and its Salts.T. F. HARVEY and C. F. SPARKS (J. SOC. Ckem. Znd. 1918 37 41-43~) .-The pyridine is precipitated as periodide from a sulphuric acid solution of the sample (ammonia ammonium carbonate or other salt) in the presence of sodium chloride the periodide is converted into sulphate and the latter titrated with alkali solution. When sufficient sodium chloride is added 1 mg. of pyridine in 200 C.C. of N/2-sulphuric acid is precipitated com- pletely as periodide. The method in detail is as follows Fifty C.C. of the sample of ammonia (D about 0.885) is treated in a separating funnel provided with a plug of cotton wool above the tap with 100 C.C. of 1ON-sulphuric acid the mixture being cooled during the addition of the acid. Fifty grams of sodium chloride are then dissolved in the mixture and 10 C.C. of iodine solution (iodine 13 grams and potassium iodide 13 grams per 100 c.c.) are added. The mixture is shaken and after fifteen minutes the liquid por- tion is forced through the cotton wool filter; the precipitate is washed with 20 C.C. of a mixture of lOA'-sulphuric acid 10 c.c. water 190 c.c. and iodine solution (see above) 10 c.c. then decom- posed by a slight excess of saturated thiosulphate solution diluted t o about 20 c.c. and neutralised with N/1-sodium hydroxide solu- tion using methyl-orange as indicator. Phenolphthalein is then added and the pyridine sulphate titrated with N/lO-sodium hydr- oxide solution; 1 C.C. of the latter is equivalent to 0.0079 grain of pyridine. The solution employed for washing the periodide pre- cipitate should be made about eighteen hours before using and be almost indefinitely. w. P. s. filtered if necessary. w. P. s. Colour Reactions in the Chemico-legal Examination of Bloodstains. LUCIANO P. J. PALET and AMANCIO FERNANDEZ (Anal. BOG. Qziim. 9ryentinu 1917 5. 177-184).-A review of the various colour tests proposed for t,he identification of blood- stains. A. J. W.

ISSN:0368-1769    

DOI:10.1039/CA9181405171

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

General and Physical- Chemistry. The Optics of Disperse Systems. I. I. LIFSCHITZ (KaZZoid Zeds&. 1918 22 53-57).-A general discussion of the optical properties of disperse systems including the absorptive power the refractivity and the rotatory power of optically active colloids. H. M. D. The Relation between the Degree of Supersaturation the Refractive Index and the Temperature of Sugar Solutions. E. V. MILLER and F. P. WORLEY (J. SOC. Chem. Iizd. 1918 37 98-103~) .-Measurements have been made of the refractive index of supersaturated solutions of sucrose with the object of deter- mining the influence of temperature and concentration on the refractive index between 30° and 75O and between 72% and 81% of sucrose which range of concentration is of technical impedance. The results obtained show that the refractive index in its depend- ence on the temperature t and the percentage concentration 21 can be satisfactorily represented by the equation r= 1,28534 - 0*0001241t + (0.00263 - 0.000001267t)p. This equation may be written in an alternative form in which r is represented as a func- tion of the temperature and the degree of supersaturation s the relation between p and s being given by y = lOO(S + s)/ 100 + S+ s in which S represents the number of parts of sucrose pes 100 of water in the saturated solution. A table is given showing the values of the refractive indices of solutions for s=O to s=110 and for temperatures ranging from 43-3O to 76'6O.H. M. D. The Arc Spectrum of Europium and a New Element Eurosamarium between'Europium and Samarium.JOSEF MARIA EDER (Sitzungsber. K.K. Akad. W i s s . TViem 1917 IIA 126 473-531 ; from Ckem. Zentr. 1918 i 70-71).-Europium imparts a fine red colour to the electric arc and its characteristic groups of lines are very bright and easily distinguished. The author has examined the photograph of the spect'rum of one of Urbain's preparations which proved to be remarkably pure and has also tested two samples supplied by Auer the one being a europium fraction related to gadolinium and the other a specimen akin to samarium. In these he has measured 1171. europium lines between 7370 and 2373. The lines which were obtained with the material quite free from samarium iscluded some which are ascribed to a new element eurosamarium and these are tabulated in the original. Atomic Weights of the Elements in Nebulae.J. W. NICHOLSON (Month. N o t . Roy. Astr. SOC. 1918 78 349-362).- A theoretical paper in which equations are derived for the periods J. C. W. CXIV. ii. 11ii. 182 ABSTRACTS OF CHEMICAL PAPERS. of vibration of atoms with a single ring of electrons. These equa- tions in combination with the wave-lengths of the principal lines in the spectrum of nebulium give for m/iM the value 0*000415 in which m is the mass of an electron and M the mass of the atom. Assuming that for hydrogen m/H =0*000545 the atomic weight of nebulium is found to be 1.31 with a possible error of one unit in the second decimal place. The Shifting of Radioactive Equilibria under the Influence of Fluorescein. H. ZWAARDEMAHER (Proc. K. Akad.Wetensch. Amsterdam 1918 20 768-772. Compare A. 1917 i 241).-The antagonism between potassium and uranium in their influence on the pulsation of the frog's heart is found to be appreci- ably affected by the addition of fluorescein in the sense that a larger quantity of potassium is required to antagonise a given quantity of uranium if fluorescein is added t80 the solution. The displacement produced by fluorescein is in the same direction as that which according to observations on summer and winter frogs is produced by a rise of temperature. H. M. D. H. M. D. Radioactivity of Waters of the Mountainous Region of Northern Luzon (Philippines). GEORGE W. HEISE (Philippzm J. Sci. 1917 12 [A] 293-307).-In continuation of previous work (Wright and Heise A. 1917 ii 560) the author has examined the waters of a number of springs and wells in northern Luzon.The region shows evidence of recent vulcanism. The data are n o t yet numerous enough to warrant general conclusions but they d o not confirm the usual observation that radioactivity is most com-moii among waters from volcanic regions or a t least among thermal springs. Of the numerous salt springs and hot springs examined none showed high radioactivity. The most active waters were rich in calcium and magnesium indicathg an origin in calcareous material. High activity was found only in waters from a small district (Ifugao) and was probably due t o the presence of local deposits of radioactive material. J. H. L. Constancy in the Radioactivity of certain Philippine Waters. GEORGE W.HEISE (PhiZippzne J. Sci. 1917 12 LA] 309-31 1) .-Measurements of the radioactivity of the water of a Philippine spring a t different periods of the year showed no appreci- able changes in spite of great variations in the rate of flow of the spring. The composition of the water is substantially the same as in 1890. J. H. L. Extrapolation of Conductivity Data to Zero Concentration. JAMES KENDALL ( J . Amer. Chem. Soc. 1918 40 622-623).- Polemical in which the author claims priority over Washburn (this vol. ii 55) in the method employed by the latter for the calculation of the1 zero concentration values of conductivity data. [See T. 1912 101 1279 1291.3 J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 183 Electrolytic Dissociation in Solvents with LOW Dielectric Constants.V. A. PLOTNIKOV (Reprint).-From theoretical considerations and the results of conductivity measurements on various solutions the following conclusions ar0 drawn. Solvents with low dielectric constlants are capable of forming solutions show- ing high electrical conductivity. The conductivity of a solution depends to. as great an extent on the solute as on the solvent; these two must be in peculiar electrochemical correspondence in order that they may yield a conducting solution. The phenomenon of electrical conductivity in a solution cannot be explained by any definite property of the solvent conditioning its dissociating capacity; electrochemical investigation of a solution has to deal with a conducting " couple.:' Electrochemical correspondence is explained as due to the resonance of the movement of the solvent molecules with the ionic vibrations of the electrolyte.Electrochemical Potential and the Periodic Law. J. C. THOMLINSON (Chem. News 1918 117 l76).-The relation between electrochemical potlential and the position of the elements in the periodic system is demonstrated by means of a curve. I n this curve starting with the most electropositive element cmium the elements follow the order czesium to lithium (as in group I) barium to magnesium (as in group II) aluminium chromium manganese zinc cadmium iron cobalt nickel hydrogen. The non-metals then continue the curve and these after silicon carbon and boron all occupy positions in the upper right-hand corner of the periodic table. The Passivity of Chromium.A. H. W. ATEN (PTOC. K. dkad. TVetensch. Bnzsterdam 1918 20 812-823).-The values recorded in the literature for the potential of the chromium elec- trode are very divergent and this is supposed to be connected with the tendency of the metal to assume the passive condition. Elec- trodes were prepared from chromium obtained by Goldschmidt's method by the electrolysis of solutions containing a mixture of chromic sulphate and chromic acid and by the electrolysis of solu- tions of chromic chloride. These were brought into contact with a 0.3 molar solution of chromous sulphate and combined with a normal calomel electrode. The results obtained indicate that the potential of chromium in contact with chromous sulphate solution is about -0.75 volt or -0.47 volt when referred t o the hydrogen electrode.This active potential value is only attained when hydrogen is present in the metal in sufficient quantity. The hydrogen appears t o act as a catalyst in promoting the establishment of the electrode equilibrium. H. M. D. Potential Measurements on the Copper-Nickel Series of Alloys and some observations on Brasses. NEwm T. GORDON and DONALD I?. SMITH (J. Physical Chem. 1918 22 194-215).-A study of the factors affecting the potential differ- T. 13. P. J. I?. S. 11-22. 184 ABSTRACTS OF CHEMICAL PAPERS. ence between a binary (solid) alloy and an electrolyte containing the corresponding ions (see A. 1916 ii 214). With copper-zinc alloys no treatment employed was sufficient t o ensure reproduci- bility or constancy in the " steady " potential finally attained but copper-nickel alloys are shown to be very regular in electrochemical conduct and the potential values are reproducible and constant for many hours.Six ingots of copper-nickel alloys containing 6.8 10.9 65.5 74-3 83-4 and 94.7% of Cu were carefully prepared and a small testrpiece 2 x 2 x2g mm. cut from each the end surface of each bar forming a portion of a horizontal plane passing through the middle of the ingot and this was the part exposed afterwards to the electrolyte Each piece was annealed in an atmosphere of nitrogen the first tlwo a t 218O and the others a t 600O. The electro- lytes employed were all N/1-solutions of copper and nickel sulphates combined and some contained in addition N / 1-sodium sulphate. All potentials were measured a t 2 5 O against a normal calomel electrode by means of a potentiometer and a galvanometer.For some time after immersion the potential changes rapidly but after some hours a steady value is reached which afterwards remains constant within 3 millivolts during the period of observation. It is found that carefully annealed specimens give the most constant results and although there are no regular differences between the steady potentials of surfaces annealed and treated with emery yet the latter exhibit greater accidental variations. Polished surfaces have a greater tendency to give ions to the solution. With alloys from a given ingot and also with ingots of a similar composition it was found that the steady potential is definitely determined by the composition of the electrolyte.The potential differences ex- hibited are expressible by a relation which is linear both with respect to alloy composition and to the. logarithm of elect.ro1yte composition. It is shown that copper sulphate concentration may be employed without any sacrifice of accuracy in the representation of the empirical results in place of the cupric ion concentration required by Nernst's thermodynamic theory provided the constants of the equation are altered. B. N. The Lead Electrode. 11. FREDERICK H. GETMAN (J. Amer. Chem. SOC. 1918 40 611-619).-Since the publication of the previous paper (A. 1916 ii 287) the question of the possible allotropy of lead has arisen. The present work was undertaken t o furnish an answer to this question. The E.M.F.of cells of the type P b IO.ldlKC1 sat'. with PbCl 11 O-lMKC?l,Hg2C1 1 Hg has been measured at 2 5 O using lead electrodes from various sources and treated in different ways. It is shown that the value of the E.M.F. obtained with different specimens of lead cast into sticks with electrolytically deposited lead and with lead amalgams was the same in all cases The normal electrode potential of lead was calculated from the results to be 0-4121 volt referred to theUENERAL AND PHYSICAL CHEMISTRY. ii. 185 it‘-caloiiiel electrode and 0.1293 volt against the N-hydrogen efec- trode. The values of the E.M.F. of cells containing electrodes which had been immersed for varying periods of time in Heller’s solution (400 grams lead nitrate 1000 C.C. water and 100 C.C.nitric acid [D 1-16]) were found to be about 8 millivolts higher than the values obtained with cells containing electrodes which had not been subjected to this treatment. The ternppature coefficient of the cell was found to be 0.00022. The heat of the reaction Pb + Hg,Cl,=PbCl,+ 2Hg was calculated and found to be 21,840 cal. and the heat of formation 84,440 cal. The heat of reaction Tr0 and the maximum work A23-10were calculated by means of the Nernst-Lindemann equation and the value of the E.M.F. at 234O A computed. The values Uo=24.035 cal. A =24,041 cal. were obtained and the value of the B.2Cf.F. was in close agreement with the experimental value. J. F. S. The Quantum Theory of Paramagnetism. FRITZ REICHE (Ann. Physik 1917 [ivl 54 401-436) .-A mathematical paper in which the quantum hypothesis is applied in the development of a theory of paramagnetism.The formula derived for the relation between the magnetic susceptibility and the temperature is tested by reference t o the available data for ferrous sulphate auci man- ganous sulphate and found to be quite satisfactory. Investigations on the Thermal Conductivity of Gases. I. and If. SOPHUS WEBER (Aim. Physik 1917 [ivl 54 325-356 437-462).-The sources of error involved in the deter- mination of the thermal conductivity of gases by Schleiermacher’s method are subjected to a critical analysis and a modified form of apparatus is described in which the errors due t o convection are greatly reduced With this improved form of apparatus measure- ments have been made of the thermal conductivity of a number of gases.The following values are recorded hydrogen. 4.165 x 10-4; neon 1.089 x 10-4; helium 3.438 x 10-4; argon 3.850 x 10-5; nitrogen 5.660 x 10-5; oxygen 5.768 x 10-5; methane 7.200 x 10-5; carbon dioxide 3.393 x 10-5; nitrous oxide 3.530 x 10-5. The results are discussed in reference to certain aspects of the theory of the con- ductivity of gases. B. M. D. The Course of the Values of cn and b for Hydrogen at Different Temperatures and Volumes. J. J. VAN LAAR (Proc. R. Akad. Wetensch. Amsterdam 1918 20 750-767).- A theoretical paper in which the author discusses the influence of temperature and volume on the constants n and 6 of the van der Waals’s equation. It has been suggested by van der Waals that CG varies with the volume i f the temperature is lower than the critical temperature hut the author’s arguments lead to the con- clusion that a depends only on the temperature whether this is above or below the critical temperature.On the other hand 7) appears t o be a function of both temperature and volume. €I. M D. H. M. D.ii. 186 ABSTRACTS OF CHEMICAL PAPERS. The Saturated Vapour Pressures of Triatomic Liquids. E. A R I ~ S (Compt. rend. 1918 166 668-672. Compare this vol. 11 61).-Using the known physical constants for carbon dioxide the author deduces tho. formula II = T ~ ' / ' Z / ~ where x = [1+ (1 - ~)(0*88 - ~)/0*40(72 + l)]~"'" for the saturated vapour pressures of triatomic liquids. The observed results are in fairly close agreement with those calculated by this formula in the cases of sulphur dioxide and nitrous oxide but this is not true for hydrogen sulphide and water.The Adsorption of Sodium Gold Chloride by Charcoal. The Estimation of Gold in Sea-water. HELLMUTH KOCEI (KoZFooi'd Zeitsch. 1918 22 1-22).-The adsorption of gold from very dilute solutions of gold chloride in 3% sodium chloride by various forms of carbon has been examined with a view t o the application of the adsorption process in the estimation of gold in sea-water. Measurements of the rate of the adsorption show that this takes place fairly rapidly but the attainment of a con- dition of equilibrium is prevented by the fact that the adsorbed gold saltl is slowly reduced and in consequence of this there is a continuous fall in the concentration of the gold in the aqueous solution.The concentration time curve consists accordingly of two branches of very different slopes the intersection of which affords a sufficiently accurate measure of the adsorption effect. The results obtained for solutions of varying concentration are satisfactorily represented by means of the ordinary adsorption equation. Finely divided wood charcoal was found to be the most satisfactory adsorbent and this material was used in experiments on sea-water three samples of which gave results indicating the presence of 2.5 to 4 mg. of gold per cubic metre. These values for the quantity of gold in sea-water are in agreement with the results obtained by some earlier observers although much larger values have been recorded. The literature of the subject is discussed in detail.[Compare J . Soc. Chem. Z n d . June.] H. M. D. Influence of Neutral Salts on the Dissociation Constants of Indicators. J. M. KOLTHOFF (Chenz. TVeekblad 1918 15 394-400) .-The dissociation constants of phenol aniline and colorimetric indicators are increased by addition of neutral salts. This fact explains the development of the alkaline tint on addition of a neutral salt t o an acid indicator and the corresponding development of the acid tint of an alkaline indicator. The effect is very marked in the case of azolitmin. [Diffusion of Gases through Indiarubber. J SIR JAMES DEWAR (Proc. Roy. Znst. 1918 21 813-826).-An appendix to a lecture on (' Problems of Hydrogen and the Rare Gases " (compare ;bid. 543). An account is given of apparatus which has been used by the author in the investigation of the diffusion of gases through thin rubber membranes at varying prsssures and ftempratures. ..7 N . G. A. J. W.GENERAL AND PHYSICAL CHEMISTRY. ii. 157 With a membrane about 0.01 mm. thick the rates observed for different gases a t atmospheric pressure and 1 5 O in C.C. per day per ern-2 were air 2-0 ; nitrogen 1.38 ; carbon monoxide 1-88 ; helium 3.5; argon 2.56; oxygen 4.0; hydrogen 11.2; carbon dioxide 28.0. The order in which the gases are arranged accord- ing to their diffusibility does not appear to be directly related to any chemical or physical property of the gases concerned. The rate of diffusion increases rapidly with rise of temperature and when the logarithm of the rate is plotted against the tempera- ture straight line graphs are obtained.These lines all show a distinct break a t Oo which suggests that water is in some way involved. I n the case of carbon dioxide a much more pronounced break is found a t -37O. The composition of the gaseous mixture resulting from the diffusion of air through rubber has been examined by ordinary chemical analysis and also by the spectroscopic investigation of the residue obtained after subjecting the mixture to the action of charcoal cooled in liquid air. By this means i t has been found that ths hydrogen and helium in air diffuse at' nearly the same rate whilst the rates of diffusion of helium and neon are as 9 to 1. Observations were also made on the diffusion of gases through rubber membranes immersed in different liquids such as water salt solutions ethyl alcohol and glycerol.H. M. D. Diffusion in Anisotropic Liquids. THE. SVEDBERG (Kolloid Zeitsch. 1918 22 68-71).-1n view of the necessity of main- taining a constant temperature in the diffusion experiments the author has made use of an equimolecular mixture of pazoxy- anisole and p-azoxyphenetole. This mixture which melts at 95O and becomes isotropic a t 150° is convenient for the observations in that the diffusion measurements may be made a t 1000. The rate of diffusion of m-nitrophenol in the anisotropic liquid was measured ( a ) in the absence of an external magnetic field ( b ) in a longitudinal magnetic field and (c) in a transverse magnetic field. The results obtained show that the rate of diffusion is increased by the application of the longitudinal field alld diminished when the direction of the field is transverse to that in which diffusion takes place.H. M. D. Kinetic Theory of Osmotic Pressure and of Raoult's Law. 11. G . J~GER (Ann. Physilc 1917 [iv] 54 463-480. Compare A. 1913 ii 762).-A theoretical paper devoted to the consideration of the kinetic interpretation of osmotic pressure and of Raoult's vapour pressure law. Manifestation of Osmotic Pressure with Membranes of Chemically Inert Materials. S. L. BIGELOW and C. S. ROBINSON ( J . Physical Ckem. 1918 22 153-183).-A method and apparatus have been devised for the study of osmotic pheno- mena with membranes of powdered materials such as silica €3 M. D.ii. 188 ABSTRACTS OF CHEMICAL PAPERS amorphous carbon graphite metallic copper gold and silver.The membranes were prepared by alternately pressing the purified material under a high pressure and clogging the pores by sucking a fine material in suspension through the membranes. Thus in the case of pure silica a pressure of 350 kilos. per cm. was used and the largest pores in two membranes were reduced to 1-4823 and 0.3488 microns respectively. Amorphous carbon was pre- pared by ignition of a pure sucrose compressed and clogged as above but the pore diameters in this and in flaky graphite washed with acid and similarly treated had t o be considerably reduced to produce osmosis. Reduced copper and silver powders had to be pressed for several days a t 350-450 kilos. per cm. t o reduce the diameters and the results show generally that the magnitude of osmotic effects increases with a decrease in the diameters of th0 pores of the membrane.It appears t o be fairly obvious that the various examples of osmosis are not due to one but to a variety of causes and according to the various theories osmosis may take place (1) through capillary spaces in the mem- brane (2) by solution of the solvent in the membrane (3) by the formation of a labile chemical compound between the membrane and the solventl. The present work has demonstrated that osmotic pressure can be produced through the agency of capillary forces alone without the aid of solution processes or chemical reactions. B. N. Theory of Solutions. Solubility Studies in Ternary Mixtures of Liquids. JOHN HOLMES (T. 1918 113 263-275 Compare T.1913 103 2147).-In the further investigation of the theory that the miscibility of liquids is determined by the possibility of the closepacking of the diff erent kinds of molecules and is therefore depelndent on the relative molecular radii the author has examined a number of t'hree-component systems. The theory indicates that these liquids should be miscible in all proportions if the molecular radii are equal. If the molecules are of different sizes the dimensions of the interspaces will decrease as the ratios between the several radii increase until a point is reached atl which close packing is a maximum. I n the case of an equi- molecular mixture this occurs when the radii are as 1.682 1.466 1. If the respective ratios are greater than these limiting values which correspond with the border line between complete and partial miscibility separate layers are formed.So long as the radial ratio of the two smaller molecules is not greater than 1.618 and the corresponding ratio for the extreme molecules exceeds 1.682 but is less than (1*618)2 the mixture should separate into two layers only. I f the ratios are greater than these values three separate layers are to be expecM. I n the expectation that the higher paraffin hydrocarbons would afford liquids for which the molecular radii compared with water are greater than (1-618)2 the author has examined the miscibility of various binary mixtures of petroleum and water with a thirdGENERAL AND PHYSICAL CHEMISTRY. ii. 189 substance. Threelayer systems were obtained with aniline phenol nicotine and nitrobenzene and the behaviour of these mixtures is described.Three liquid layers were also found in the case of mixtures of petroleum glycerol and nitrobenzene. H. M. D. Condition of Substances in Solution in Absolute Sulphuric Acid. VIII. G. ODDO [with A. CASALINO]. (Gaxettn 1918 48 i 17-44).-The author uses t,he results of his previous measurements some of which have now been repeated and confirmed to refute tbe criticisms of Hantzsch (ibid. 1911 41 i 645). T. H. P. Flocculation. SPENCER UMFREVILLE PICKERING (Proc. Roy. SOC. 1918 [ A ] 94 315-325).-Experiments have been made to determine the effect of freezing on the sedimentation of certain voluminous precipitates such as basic copper sulphate cupric hydroxide ferric hydroxide and aluminium hydroxide and also on clay and kaolin.I n all cases sedimentation takes place more rapidly after freezing and the volume of the sediment from the liquids which have been frozen is considerably smaller than that from liquids which have not been subjected to this treatment. The shrinkage observed varies from 40 to 90% and is probably due to dehydration. The flocculation of suspensions of kaolin on the addition of various substances has been examined with results which show that the process is accompanied by a considerable increase in the volume of the particles. The increase in the volume of the sedi- ment when acids o r salts are used as the flocculating agents is closely related to the quantity of kaolin remaining in suspension the latter becoming nil when the former reaches a maximum.When the added substance produces no flocculation there is n o increase in the volume of the sediment. I n explanation of these relatiuns it is suggested that the kaolin combines with the flocculant. H. M. D. Jellies Formed by Dyes. R. HALLER (Kolloid Zeitsch. 1918 22 49-57).-1t has been observed that hot concentrated solut'ions of substantive dyes produce jellies when tho solutions are allowed to cool. Experiments made with benzopurpurin 4 B and chrysophenin B show that the formation of these jellies is dependent on the presence of small quantities of electrolytes in the dyes. If a 1% solution of either of the dyes is subjected to dialysis the electrolytes are removed and t h s contents of the dialyser separate into two parts one of which is liquid and the other of gelatinous consistency.The latter does not dissolve even when heated to looo and it seems probable that the colloidal dye has been rendered insoluble by the removal of the electrolytes. If the dialysed substance is dried and powdered the product is markedly different from the original dys in its small solubility 11"ii. 190 ABSTRSCTS OF CHEMICAL PAPERS. in water. The purified substance dissolves quite readily liowewr if sodium chloride is added to thel water. The structure of the benzopurpurin 4 B jellies has been ex- amined and found to be very similar to that of the soap jellies described by Zsigmondy and Bachmann (A. 1912 ii 1149). [See further J . SOC. Chem. Znd. June.] H. 35. D. The Quaternary System AgN0s-NH4*NOs-Ba(N03)2- Water at 30°.(MISS) W. C. DE BAAT (Chem. Weekblad 191S 15 463468).-An application of Schreinemakers’s graphic method t o aqueous solutions of the nitrates of silver ammonium and barium a t 30°. A. J. W. A Method of Obtaining General Reaction-Velocity Curves for Complete Homogeneous Gas Reactions at Constant Pressure. GEORGE W. TODD (Phil. Mag. 1918 [vi] 35 435-444. Compare this vol. ii 102).-Th0 method previously described for the derivation of curves representing the progress of homogeneous reachions a t constant volume has been extended to the case of binary gas reactions taking place a t constant pressure. For a bimolecular reaction of the type A +B+ in which a gram mols. of A react with b gram mols. of B v is the total volume of reactants and resultants and x the number of gram mols.transformed in time t the equation for the velocity of the reaction when B is in excess may be written in the form d X / d t = k . a / v o . (1-X)@-X) where X = x / a p = b / a and vo is the original value of v. Since the right-hand side of this equa- tion does not involve the constant which in a particular case is determined by the ratio between the numbers of mols. of reactants and resultants it follows thatl the general curves previously given will be applicable to the case of bimolecular reactions a t constant pressure as well as a t constant volume. Termolecular reactions of the type 2A + B-+ with A and B in excess are also considered and general equations devised for these. The curves which are plotted from these equations show the change of X with t for different values of p = b / a and two sets of diagrams are given corresponding with the case where the volume of the resultants is 2/3 and 1/3 respectively of the volume of the reactants. This volume change is expressed in the general equation for the velocity by means of a quantity a in terms of which if B is present in excess v = vo(3a(l + ax) + ( b - a ) ) / 3a+ ( b - a ) and if A is presentl in excess v = u0(3b(l + ax) + 2(a - b)} /3b + 2(a - b ) .H. M. D. Periodic System of the Elements. P. V. WELLS (J. Washington Acad. Sci. 1918 8 232-234).-The author has redrawn the spiral pe’riodic table of Stoney and others as revised by Harkins and Hall and has given it a period of 8 instead of 16. The distance from the centre of the spiral to anGENERAL AND PHYSICAL CHEMLYTEY.ii. 191 eleruaiit represents the atomic weight and the eleineiits arc arranged in angular order of atomic number each group being placed radially with the sub-groups slightly displaced. The metals of positive valence are sharply separated from the non-metals of negative valence. The proposed arrangement is much simpler than the double helix and has all its advantages; it overcomes the artificiality of the 16-period table and brings the main groups and sub-groups together. The new table is particularly adapted to illustrating the electron theory. The possibility of two forms of neon is indicated. A. B. S. Characteristic Frequency and Atomic Number. H. STANLEY ALLEN (Yroc. Roy. SOC. 1917 [ A ] 94 100-111.Compare this vol. ii 14 15 163).-The relation between the atomic number and the characteristic frequency of an element is considereld with refer- ence to the theory of probability and it is shown that the chance of the relation being accidental is very small. According to Rydberg there are two unknown elements between hydrogen and lithium and the atomic number of lithium should be taken as 5 instead of 3 which is the value assigned by Moseley. The relation Nv=nv fits the results of observation more closely however when Moseley's numbers are used f o r iV. With regard to the physical significance of the relation it is supposed that the energy of the nucleus is an integral multiple of a certain quantity of energy characteristic of that condition of the atomic system which corresponds with the liiniting frequency.The similar relation connecting the atomic number and the electronic frequency is supposed to indicate that in the limiting conditions which are associated with the maximum of the photo- electric effect the ionisation potential and the thermionic potential we are dealing with a minimum value of the energy of the atomic system. H. M.D. Molecular Frequency and Molecular Number. 11. The Frequency of the Longer Residual Rays. H. STANLEY ALLEN (Phil. Mag. 1918 [vi] 35 404-409. Compare this vol. ii 14 163).-According to the results previously communicated it would seem that the product of atomic number and atomic fre- quency in the case of an element' or of molecular number and molecular frequency in the case of a compound is an integral multiple of a fundamental frequency which is approximately equal t o 21 x 1012 see.-1 I n order to obtain the frequency of vibration of the atoms in compounds recourse may be had to the residual rays which are obtained by repeated reflections from the surfaces of solids and have been investigated by Rubens (compare A 1910 ii 172; 1913 ii 648; 1914 ii 236).By reference to the avail- able data for the wavelengths of the residual rays for various inorganic compounds further evidence is obtained in support of t*he above relation between the molecular number and the niole- cular frequency. 11*-2E. 192 ABSTRACTS OF CHEMICAL PAPERS. The results obtained in this and the preceding papelrs suggest that the forces binding the atoms in the molecule are similar in character to those which bind the molecules of a solid.To account for the integral relations it must be assumed that there is some- thing of a discrete character in the nature of these forces and the suggestion is made that the linking between the atoms are con- stituted by Faraday tubes of force which would then be regarded as physical entities. Device for Preventing Back-flow in Water Pumps. MESTREZAT (Ann.. Chim. anal. 1918 23 84-85).-An ordinary bicycle valve suitably fitted in the pipe connecting t*he pump with the vessel from which the air is to be exhausted prevents water Modification of the Soxhlet Extractor. J. W. V C 7 ~ 1 ~ ( J . Lab. and Clin. Med. St. Lou.is 1917 3 204; from Physiol. Abstr. 1918 3 4).-A modification for use in the extraction of liquids is described and figured in the1 original. New and Simple Ultra-filters. WOLFGANG OSTWALD (Kolloid Zeitsch. 1918 22 72-76) .-Ultra-filters of simple construction for the filtration of colloidal solutions are described. Itl has been found that an efficient apparatus may be obtained by the use of either an ordinary or a Buchner funnel and filter paper which has been treated in situ with a 2% collodion solution. The best results were obtained however by the use of a Schleicher and Schull Filtrierhut N577 treated in the same way with the colloidal solu- tion. The results obtained by subjecting a number of colloidal solutions of different kinds t o ultra-filtration in this apparatus are described. H. M. D. H. M. D. passing into the latter. w. P. s. W7. G .

ISSN:0368-1769    

DOI:10.1039/CA9181405181

出版商:RSC    

年代:1918

数据来源: RSC