摘要:

MINERALOGICAL CHEMISTRY. Mineralogical Chemistry. 107 Origin of the Freiberg Mineral Veins. By ALFRED W. STELZNER (Zed. prakt. Geol., 1896, 377--412).-Sandberger has found the mica from the gneisses carrying the Freiberg lead veins to contain small quantities of heavy metals, and OQ this he founded his theory of lateral secretion to explain the origin of mineral veins. The108 ABSTRACTS OF CHEMICAL PAPERS. present author gives the results of numerous analyses made on large quantities of fresh mica from the Freiberg gneiss and from the gneisses and granites of the Black Forest, but these do not confirm Sandberger's results. None of these micas show the presence of heavy metals (lend, silver, &c.) other than small quantities of cobalt, nickel, copper, and zinc, and since sulphur was also found these probably exist as sulphides mechanically enclosed in the mica, rather than as silicates entering into the constitution of the mica, as was supposed to be the case by Sandberger.Several other arguments are brought against the theory of lateral secretion. The material of the veins has more probably been brought up from great depths by mineral waters, and only a small amount leached out of the rocks surrounding the veins, L. J. S. Copper, Bornite, and Petalite from the Caucasus. By PAVEL V. VON JEREM~EFF (Zeit. Krysl. Bin,, 1898, 30, 388 ; from Verb. kais. PUSS. min. Ges., 1896, 34, 55).-Distorted crystals of native copper and cubes of erubescite (= bornite) with convex faces are described. Petalite from the Amanaus glacier, Batalpaschinsk district, gave, on analysis by J.A. Antipom, Loss on SiO,. A1,0,. FeO. CaO. MnO. Na,@,K,O. Li,O. ignition. L. J. S. 77-28 14.82 1-08 0.58 trace 2.07 1-97 0.45 Diaphorite from Washington and Mexico. By LEONARD J. SPENCER (Amer. J. Xci., 1898, [I iv], 6, 316).-Orthorhombic crystals of the rare mineral diaphorite are noted from two new localities: (1) Lake Chelan district, Okanogan Go., Washington ; associated with stephanite and pyrargyrite; (2) Santa Maria de Catorce, San Luis Potosi, Mexico ; with miargyrite. The three minerals, andorite (Abstr., 1898, ii, 120), diaphorite, and freieslebenite, are strikingly similar in appearance, and between them there is the same kind of morphotropic relation as that which exists between the members of the humite group (Abstr., 1894, ii, 241).Andorite ... ... ...... 0.9846 : 1 : 0.6584 5.35 (Pb,Ag,)S,Sb,S, Diaphorite ... ... , .. 0.9839 : 1 : 0.7345 5.9 5(Pb,Ag,)S,2Sb2S, Freieslebenite ... 0.9786 : 1 : 0.9277 6.3 5(Pb,Ag2)S,2Sb2S, a b c Sp. gr. Chem. comp. B = 87" 46'. Since, in diaphorite, the vertical axis c and the sp. gr. fall between those of andorite and freieslebenite, it is to be expected that it should also be intermediate in composition. Brongniardite, which has sush an intermediate formula, namely, 2(Pb,Ag,)S,Sb,S,, agrees in sp. gr. and external characters with diaphorite ; it therefore seems very probable that brongniardite and diaphorite are identical. (The so- called cubic crystals of brongniardite are identical with stanniferous argyrodite, Abstr., 1898, ii, 436.) Cubanite from Butte, Montana.By HORACE V. WINCHELL (American Geologist, 1898, 22, 245).-A brass-yellow mineral, now being mined as a copper ore at Butte, gave, on analysis by S. J. Gormly, L. J. S.MINERALOGICAL CHEMISTRY, 109 cu. Fe. S. SiO,. 43 An. 25.04 34-26 39.90 0-77 0-96 oz. trace Other determinations of the copper gave 25.35, 19.8, and 23.6 per The excess of copper over that required by the cubanite cent, formula, CuFe,S,, is probably due to the presence of bornite. L. J. S. Lonchidite from Olkusch. By J. A. ANTIPOW (Zeit. Xryst. Min., 1898, 30, 388; from Verh. kais. rzcas. min. Ges., 1896, 34, 24)-A spheroidal concretion of marcasite with fibrous structure was found to contain As, 5 ; Te, 0.3 per cent. By WILLET G. MILLER (Rept. Brit. ASSOC., 1898 [For 18971, 6’7, 660-661).-Samples of ore from the larger deposits of titaniferous magnetite in eastern Ontario have been found to contain nickel (and cobalt) to the extent of 0.8 per cent.No nickel has been found in the non-titaniferous magnetites of the district. The former are considered to be of igneous origin, and the latter of aqueous or mechanical origin. The high quality of iron extracted from the titaniferous ores may be due t o the presence of nickel. L. J. S. Interaction of Calcium Hydrogen Carbonate and Alkali Sulphate: Formation of Alkali Carbonates in Nature. By HEINRICH VATER (Zeit. Kryst. g i n . , 1898, 30, 373-386).-Hilgard and Tanatar have determined the amount of alkali carbonate which, with gypsum, is formed when carbonic anhydride is passed through a solution of alkali sulphate in contact with an excess of calcium carbonate, and they have explained the natural formation of alkali carbonates by this reaction (Abstr., 1893, ii, 165; 1896, ii, 419; lS97, ii, 58).The present author adversely criticises these results, and considers that alkali carbonates in the solid form cannot be obtained in this manner. The alkaline reaction of the solution he attributes to calcium carbonate. From solutions not in contact with solid calcium carbonate, there is a separation of calcium carbonate or of the double salt, K2S0,,CaS04,H,0, but not of gypsum or alkali carbonate. L. 6. S. By FRANK W. CLARKE (J. Amer. Chm. Xoc., 1898, 20, 739-742).-The author describes experiments on the decomposing action of pure water on various natural silicates.For this purpose, the finely-powdered mineral was shaken with water to which a minute quantity of phenolphthalein had been added, the alkalinity of the water, as measured by the depth of colour imparted to it in the presence of the phenolphthalein, being taken as a measure of the susceptibility t o decomposition by water of the mineral in question, Amongst the micas, muscovite and lepidolite are only very slightly affected by water, whereas phlogopite, a magnesium mica, is readily attacked ; similarly, orthoclase is but slightly acted on, oligoclase more readily, albite still more readily. These observations are in accord with the observed susceptibility to weathering of the minerals in question. L. J. 5. Nickeliferous Magnetites.Alkaline Reaction of some Natural Silicates. VOL. LXXVI. ii 8110 ABSTRACTS OF CREMICAL PAPERS. Leucite, nephelite, spodumene, scapolite, laumontite, stilbite, chabazite, and thomsonite gave very little coloration ; henlandite and analcite stronger colorations ; cancrinite, sodalite, natrolite, pectolite, apophyllite, zgirite still stronger colorations. G. W. F. H. [Baddeckite, Tennantite, &c., from Canada.] By C. CHRISTIAN HOFFMANN (Awn. Rept. [1896], Geol. Survey Canada, 1898, 9, R, 1-53).-The name baddeclnite is given t o a micnceous mineral occurring as minute scales and scaly aggregations in clay at Baddeck, Victoria Co., Nova Scotia. It is copper-red and gives a tile-red streak; before the blowpipe, it fuses to a black, magnetic glass, and it is decomposed by strong hydrochloric acid, with separation of gelatinous silica.SiO,. A1,0,. Fe,O,. CaO. MgO. K,O. Na,O. H,O. Total. Sp. gr. 48.96 13.85 25.82 1.17 2.65 3.47 0.22 3.78 99.92 3.252 Formula, 2H2O,(Ca,Mg,K,,Na,)O,3(A1,Fe),O,,8Si0,. The mineral is, therefore, considered to be a variety of muscovite (hydromuscovite) with alumina largely replaced by ferric oxide. (Also in Arner. J. Xci., 1898, 6, 274). Tennantite occurs near the Bonaparte River, Lillooet district, British Columbia; it is usually massive, but rarely in tetrahedra, Colour, dark greyish-black ; thin splinters are translucent and deep ruby-red by transmitted light ; streak, cherry-red. It contains 41.51 Cu and 0.2385 Ag per cent. ; besides much arsenic and sulphur, there are also small quantities of Sb, Pb, Zn, and Fe.Chalcanthite, in fine specimens, results from the alteration of this tennantite. A straw-yellow, crystalline incrustation on limestone in the A1 berta district, North-west Territory, is readily soluble in water, and gave on analysis by Johnston, SO,. Fe,O,. FeO. A1,0,. MgO. H,O. Insol. Total. 36.43 13.15 0.93 5.57 5.92 36.98 0.48 99.46 This corresponds with a mixture of epsomite and a hydrated basic ferric sulphate, possibly fibroferrite. Xenotime, in masses weighing up to 312 gra,ms, occurs in a granite vein at Calvin, Ontario ; sp. gr. = 4.395. The report also includes various other mineralogical notes (with partial analyses and sp. gr. determinations), also analyses of coals, rocks, waters, nickel and cobalt ores, and the results of numerous gold and silver assays.By PETR A. ZEMJAT- SCHENSKY (Zeds. Kryst. &?in., 1898,30,389; from Trav. Xoc. Naturalistes, &'t. Petersbourg, 1896,1-322).--Kaolinite from various Russian locali- ties is described from geological and chemical points of view, The follow- ing formulze are given. 2A1,03,5Si0, ( = Al,0s,3Si0, + Al,03,2Si0,) ; A1,03,2Si0, ; A120,,3Si0,; 2Al20,,7Si0, ( = A120,,2Si0, + A1,03,5Si0,); A1,03,5Si0, ; 3A120,,20Si0, ; 8A1,0,,1 5Si0,. Water begins to be given off at 300O; between 300-400°, a small portion is expelled, and complete dehydration is effected at 700-770". Kaolinite has an acid character, in that the hydrogen, or a part of it, is easily replaced by a Analysis by R. A. A. Johnston gave, L. J. S. Kaolinite Deposits of South Russia.MINERALOGICAL CHEMISTRY.111 metal. With haloid compounds of the alkalis, it gives a product allied to muscovite, and with sulphur compounds it gives hydrogen sulphide. With ferrous sulphate at a high temperature and pressure, sillimanite, or a product resembling chlorite, is formed. Norites [ Hypersthene, Diallage, Enstatite, and Anortho - clase] from the Transvaal. By J. A. LEO HENDERSON (Inaug.-diss. Leipxig (London), 1898, pp. 1-56).-The following analyses by Rohrig are given of minerals separated by heavy liquids from some of the South African rocks described in this thesis. Diallage- norite (sp. gr. = 3.01) from the Zwaartkoppies range is composed of basic plagioclase (sp. gr. = 2*7), hypersthene, diallage, and a colourless to pale-green pyroxene resembling salite.The hypersthene (anal. I) is strongly pleochroic, and the diallage (II), with extinction angle 46O, contains numerous acicular enclosures, possibly of rutile ; the hypers- thene and diallage form very intimate regular intergrowths, and it was not possible to obtain absolutely pure material for analysis. The analyses give the formula RO,SiO,, with some MgO,(Fe,A1),0,,4SiO,. Hypersthene, in a similar rock (sp. gr. := 2.87) from the same locality, gave 111. Hypersthene-norite (sp. gr. = 2.93), From the Hex River near Rustenburg, consists of plagioclase (sp. gr. = 2.7 1) and pleochroic hypersthene (IV) ; the latter encloses numerous small, colourless plates, probably of plagioclase, arranged parallel to the pinacoid faces. A finely crystalline quartz-norite (sp.gr. = 2-97), from the Marico district, is composed of felspar, hypersthene, diallage, quartz, and biotite ; the hypersthene (V, also alkalis 2-17 ; MnO, 0.67 per cent., and Cr203, trace) is only very slightly pleochroic, and the material analysed enclosed plates of biotite arranged parallel to the pinacoid faces. The quartz in this rock forms micropegmatitic intergrowths with the fel- spar. These norites, which have been previously described as gabbros, contain no olivine. An enstatite-pyroxenite, from the Marico district, composed entirely of 'granules of green enstatite, gave anal. VI. The enstatite, however, encloses numerous minute plates of anorthite, as shown by the analysis, to the extent of 4.5 per cent. Si02. TiO,. AhO,. Fe,O,. FeO. MgO.CaO. H20. Total. Sp.gr. L. J. S. I. 51'64 0'34 1.32 4-41 18-62 14-74 6-46 1-50 99-03 3-50 11. 52.54 0.21 0.24 5-12 12'46 12-02 17-12 - 99-71 3'36 111. 54.49 - trace 21'84 19.21 4'40 - 99.94 3'38 IV. 50'28 0'24 1'49 9.79 7-82 23'00 7'33 0*16 100-11 3'36 V. 53-35 0.36 4'50 5.12 13'32 16.15 4'42 0.40 100-46 3'366 VI. 55.23 0'44 2'08 3'94 6-25 29.29 1-68 1-12 100'03 3.297 Amphibole-pyroxene-syenite (hatherlite), from Hatherley near Pre- toria, is composed of anorthoclase, hornblende, pyroxene, and biotite, with very little quartz. The large anorthoclase crystals have an angle of optical extinction on c(OO1) of 9-12'; they consist of a core of white felspar (anal. VII) surrounded by a zone of red felspar (VIII). Large porphyritic crystals of dark-red anortboclase in porphyry (pilan- dite) from the Pilandsberge gave IX ; the ground-mass of this rock consists of red felspar and amphibole, with very little quartz.From these analyses, small quantities of Fe203, MgO, and H,O have been eliminated. These rocks, to which the new names hatherlite and -+ 8-2112 ABSTRACTS OF CHEMICAL PAPERS. pilandite are given, are considered to be the plutonic and porphyritic equivalents respectively of the volcanic anorthoclnse-bearing rock pan tellarite. SiO,. AI20,. CaO. Na,O. K20. Total. Sp. gr. VII. 61.81 24-68 2.71 7.53 3-37 100*10 2.65 VIII. 64.06 22-68 1-87 7.53 4.50 99.66 2.56 IX. 66.31 20.60 0.48 7.54 4.92 99.85 2.60 L. J. S. Origin, Composition, and Alteration of Glauconite. By KONSTANTIN D. GLINKA (Zeit. Xryst. Min., 1898, 30, 390-391 ; St.Petersburg, 1896, pp. 114. Compare Abstr., 1896, ii, 568; 189'7, ii, 54).-Ten analyses are given of glauconite isolated from Russian sandstones, and one limestone; the extreme amounts of each consti- tuent are quoted below. The dark-green grains have sp. gr. = 2-7-2.8, and the yellowish green 2*4--2*5. SiO,. Al,O,. Fe,Og. FeO. CaO. MgO. K20. N%O. at 100". ignition. Sp. gr. 41.02 5-84 s w 1-32 - 0-69 5'74 0'30 2.42 4.45 2'400 52-96 22'19 23'43 5.95 8.37 4.11 9-54 0'98 7.79 7'88 2'867 Glauconite and celadonite, when heated with potassium carbonate solution, take up potassium ; solutions of various chlorides have no action, L. J. 5. Granitic Rocks of the Riesengebirge. By LUDWIG MILCH (Jcl/rhb.f. Nin,, 1898, Beil. Bd. 12, 115-237).-1n this petrographical paper, the following analyses of biotite are given by W.Herz. I. Biotite from biotite-granite of the Schneekoppe ; the rock itself gave anal. 111. 11. Biotite from a basic streak in biotite-granite from Arnsdorf ; the streak gave anal. IV., and the biotite-granite gave V. Twenty-one other rock analyses are given. SiO,. Al,03. Fe,O,. FeO. CaO. MgO. K,O. Na20. H20. Total. I. 40'38 15-40 5-26 7-73 - 19.87 7-11 1'80 1'68 99-23 I1 39'66 14.26 4.01 8-10 - 2048 7'99 2.60 2'04 99-14 111. 73'81 15'22 1'88 1-40 2-77 1-10 1-54 2'10 1-66 100'48 IV. 63-06 18'01 2'48 1'91 2.72 4 5 5 3'88 2'01 2'20 100'22 V. 74.65 12-64 2-26 0-85 2-12 1-01 2.37 3-41 1'14 100.45 Dunite in Massachusetts. By G. C. MARTIN (Amer. J. Xci., 1898, [iv], 6, 244-248).--8 boss of dunite is intrusive into the gneisses near Chester, in the Green Mountain region of western Massachusetts.It is in part altered to serpentine. The pale green olivine isolated from the altered rock gave, on analysis, H20 H,Oon L. J. S. SiO,. A1,Og. FeO. MgO. CaO. H,O. Total. Sp. gr. 40.07 1.94 4.84 51-41 - 1.03 99.29 3-27 L. J. S. Vanadium and Molybdenum in Rocks of the United States. By WILLIAM F. HILLEBRAND (Amer. J. Xci., 1898, [iv], 6, 209-216; and Chem. News, 1898, 78, 216-219).-Vanadium has long been known to occur in small quantities in various rocks and minerals. Quantitative determinations of the vanadium present in 64 rocksMINERALOGICAL CHEMISTBY. 113 from the United States show that it occurs in appreciable amounts in the more basic igneous and metamorphic rocks (up to 0.08 per cent.of V,O,), but that it is absent, or nearly so, in the highly siliceous rocks. The existence of the vanadium mica, roscoelite, suggests that this element is present as V,O, rather than as V,O,, and that it occurs in the heavier aluminous silicates biotite, pyroxene, and amphi- bole. Determinations of the amount of vanadium in these minerals are given ; for example, in biotite (0.127 per cent. V203), isolated from pyroxenic gneiss (0,083, V,O,) from Calaveras Go., California ; am- phibole (0.037, V,O,) from Californian amphibole-gabbro (0.02, V,O,). Molybdenum was found in only a few of the rocks, and then only as traces in the more acid ones. Full details are given of the methods and precautions used in the analyses. The determinations were made on 5 grams of material.L. J. 5. Meteoric Iron from Beaconsfield. By EMIL W. COHEN (Xitx.- ber. Akad. Berlin, 1898, 306-307. Compare Abstr., 1898, ii, 171). -In the previous description of this iron, i t was stated that carbon having the appearance of anthracite was present; this was found after dissolving the meteoric iron in dilute hydrochloric acid, and treating the residue with cupric ammonium chloride in order to sepa- rate the tsnite and cohenite from the schreibersite and rhabdite. It is now found that this anthracitic carbon is not an original consti- tuent of the iron, but is formed by the action of the cupric ammonium chloride on the cohenite. Although cohenite, Fe,C, contains only about 6& per cent. of carbon, this carbonaceous residue is compact and shining.The crystals of cohenite from the Toluca and Beaconsfteld irons give homogeneous solid pieces, whilst the crystalline aggregates of cohenite from the Niakornak iron give finely granular carbon possessing little cohesion. It is suggested that some anthracites, for example that of mineral veins, may have been formed by the alteration of carbides, which are now known to be of terrestrial origin (Abstr., 1898, ii, 83, 232). L. Ji S. Meteoric Iron from San Cristobal, Chili. By EMIL W. COHEN (Sitx.-ber. Akad. Berlin, 1898, 607--608).-Four fragments of this iron were brought to Europe in 1896 from the San Cristobal gold- mining district near Antofagasta in Chili ; one of the fragments weighs 60 grams. Troilite nodules are surrounded by a zone of schreibersite, and this again by a zone of dark nickel-iron, The main mass of the iron shows an intricate structure on the surface; this appears to be due to minute lamellae, which are much bent and twisted. Putting aside the Oktibbeha Co. and Santa Catharina irons as being doubtfully meteoric, this iron differs from all other meteorites in the high per- centage of nickel and in its peculiar structure ; it is, therefore, placed in a special class of the ataxites. Analysis by 0. Sjostrom gave P. Total. Sp. gr. 73.72 25-60 1-00 0.18 100*50 7.8593 Fe. Ni. co. L. J. S.114 ABSTRACTS OF CH EMlCAIA PAPERS. Mineral Water from Selters, Nassau. By HEINRICH FRESENIUS (Jahrb. Nassau Per. Natuyk., 1898, 51, 1-23).-Water from a new boring at Selters, near Weilburg, on the Lahn, is clear and has a tem- perature of 13' ; sp. gr. = 1.004182 at 20'. It contains in 1000 parts : Na,CO,, 0.200786 ; Li,CO,, 0.010135 ; (NH4)2C03, 0.0036'33 ; K,SO,, 0.028505 ; KCl, 0*015267 ; NaCl, 1*889081 ; NaBr, 0.000854; NaI, 0*000017 ; Na,HP04, 0*000302 ; CaCO,, 0-779638 ; MgCO,, 0,359795 ; FeCO,, 0.008784 ; MnCO,, 0*003115 ; SO,, 0.020180 = 3,320152 ; CO, in bicarbonates, 0.627025 ; free CO,, 2.58583. Also traces of barium, strontium, alumina, and boric acid. It is an acid water containing much sodium chloride and carbonates of calcium, &c. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA8997605107

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

114 ABSTRACTS OF CH EMlCAI, PAPERS. P h y si 01 og i c a1 Chemistry. Relation of the Blood to the Automaticity and Sequence of the Heart-beat. By WILLIAM H, HOWELL (Amer. J. PhysioZ., 1898, 2, 47-81).-A strip of vena cava from the terrapin’s heart may be kept in rhythmic action for 2 days or more, when immersed in a bath containing only sodium chloride, potassium chloride, and calcium chloride ; this fact renders improbable Kronecker’s theory, that the cardiac tissue beats only so long as serum-albumin is supplied to it. The energy is evidently derived from material within the cardiac tissue, and if supplied with an adequate stimulus, the beat will continue until this is consumed. The normal stimulus is dependent on calcium compounds, but for rhythm, potassium salts are also necessary.The proportion of the three salts necessary is that which occurs in the blood, andithe sodium chloride must be isotonic with the blood, and is ‘essential only to preserve the normal osmotic relations between the tissues and the surrounding liquid. Such a liquid will not keep the ventricle of frog or terrapin in action, although it mill that of the cardiac tissue at the venous end of the heart. The normal heart’s rhythm is, therefore, started at the venous end, because that part of the hea(rt is alone susceptible to the salts of the blood. W. D. H. Relation of the Inorganic Salts of the Blood to the Auto- matic Activity of Ventricular Muscle, By CHARLES WILSON GREENE (8mer. J. PhysioZ., 1898, 2, 82--126).-Normal serum will not keep a strip of the apex of the terrapin’s heart in contraction, although it remains alive for several days. Regular contractions may, however, be produced by increasing the amount of calcium chloride in the serum.The same is true for a solution of the blood salts (like Ringer’s fluid) similar to those used by Howell (see preceding abstract). Sodium chloride will sustain contractions only for a short time, and these present the appearance of fatigue owing to the removalPHYSIOLOGICAL CHEMIS'I'MY. 115 of the inorganic salt necessary for contraction. Calcium salts in isotonic solutions of sodium chloride stimulate the strip to increased rhythm and final contracture. Potassium chloride in a similar solu- tion produces relaxation. Cane-sugar and urea in isotonic solutions do not produce rhythmic contractions in the isolated strip ; dextrose increases muscular tone and may produce an imperfect series of contractions.By F. BLUM (Zeit. phpiol. Chem., 1898, 26, 160--174).-The paper is largely critical. The author believes the thyroid is an excretory organ removing poisonous substances from the blood, and that the iodine formed there originates in that way. He regards the iodine as in organic union with proteid material, and iodothyrin as an artificial product. W. D. H. Functions of the Thyroid Gland. W. D. H. Active Physiological Substance of the Suprarend Cap- sules. By OTTO VON FURTH (Zeit. phgsiol. Chem., 1898, 26, 15-47). -Various methods are described in which an attempt was made to isolate the active substance in extracts of the suprarenal capsules.Although the author still continues to speak of the material as catechol- like, he admits t h a t Moore is right when he places the substances among the derivatives of pyridine. He suggests with reserve that it is a hydrogenised dihydroxypyridine. By ARTHUR BOWER GRIFFITHS (Compt. 9-end., 1898, 127, 448--449).-The cellules of ~oZosornc~ tenelwarurn contain a green pigment which has a respiratory function. It dissolves in acids, form- ing a green solution which is coloured purple by alkalis, but changed back again to green by excess of acid. It also dissolves in turpentine. The solutions of the pigment show no definite absorption bands. BoLosmin exists in two forms, aeolosomin and oxyzeolosomin ; the empirical composition of the former is C,,oH,,oN,,3FeS'20,,,.W. D. H. A2olosomin. C. H 6. Human Milk. By VANDERPOEL ADRIANCE and JOHN S. ADRIANCE. -This pamphlet records analyses of 200 specimens of human milk obtained by the breast pump. These are arranged according to the time after parturition. The fat is variabIe, and shows no constant change. The lactose on the second day of lactation is low, but then rises rapidly; this increase continues more slowly until the end of lactation; the proteids and salts pursue a reverse course. I n the later months of lactation, the total solids decrease steadily. The colostrum period has low carbohydrate with a tendency to increase rapidly, and high proteids and salts with a tendency to decrease rapidly. I n cases of abnormal milk, excessive fats or proteids, especially during the colostrum period, cause gastro-intestinal symptoms in the child.The excess in the milk may be reduced by diminishing the proteid food, and increasing the exercise of the mother. Deterioration in the milk is marked by reduction in proteids and total solids, or in116 ABSTRACTS OF CHEMICAL PAPERS, the proteids alone. and indicates that additions to the infant’s diet are necessary. Such deterioration is normal in the later months, W. D. H. Supposed Existence of Iodine in Organic Combination in the Urine a f t e r the Administration of Potassium Iodide. By DIOSCORIDE VITALI (L’O~osi, 1898, 21, 145--153).-The urine ex- creted by subjects to whom pure potassium iodide had been adminis- tered was treated with baryta water to remove phosphates and urates, the chlorides and iodides precipitated by silver nitrate, the excess of the latter removed by means of sodium chloride, and the filtered liquid mixed with caustic potash and potassium nitrate and evaporated to dryness.No iodine could be detected in the fused residue until after reduction with sulphurous acid, the whole of the ‘ I organic iodine ” having been converted into iodate by the large excess of nitrate. Chlorides, under the same conditions, are partially converted into chlorates, and this fact may account for the discrepancies between the statements made by different observers as to the existence of “organic chlorine ” in urine. Experiments were made to ascertain whether the ‘‘ organic iodine ” was present as iodoleic acid, by extracting the con- centrated and acidified urine with ether.By this process, organic compounds containing iodine were certainly obtained, but they were formed during the extraction, since similar results were obtained with normal urine to which potassium iodide had been added. The author concludes that, although organic iodine compounds may, perhaps, be formed in certain organs and tissues of the body, yet the iodine contained therein passes into the urine in the form of alkali iodides which may subsequently, after excretion, undergo decomposition with Organic Phosphorus in Urine. By HORST OERTEL (Zeit. physiol. Chem., 1898, 26, 123-1 30)-Several previous observers have realised that all the phosphorus in the urine is not combined as phosphoric acid, but that there are organic compounds like glycero- phosphates present.The total phosphorus may be estimated as phosphate after fusing the dry residue of the urine with potassium hydroxide and nitrate. The organic phosphorus may be similarly estimated after precipitating the inorganic phosphates with calcium chloride and ammonia. If the total phosphates in the day’s urine amount to 2 grams, 0.05 gram comes from the organic phosphorus compounds ; this varies, however, with nitrogenous metabolism ; muscular exercise has no effect on it. Uric Acid and the Acidity of Urine. By W. J. SMITH JEROME (J. Physiol., 1898, 23, 315-324).-The urine in healthy persons may be made to deposit uric acid by the ingestion of a sufficient quantity of food rich in nuclein. Some urines after an ordinary diet have an abnormal tendency to the precipitation of uric acid; this tendency is not always due either t o a high degree of acidity, or to a high percentage of uric acid in the urine, or to the CO- existence of these two conditions, however much such conditions may favour the precipitation, the formation of organic compounds of iodine.N. L. W. D. H. W. D. H.PHYSIOLOGICAL CHEMISTRY. 117 Uric Acid and Diet. By E. GOWLAND HOPKINS and W. B. HOPE (J. Physiol., 1898, 23, 271-295).-Experiments on seven persons confirm Mares’ statement that, during the period of increased nitrogen excretion that follows a meal, the rise i n uric acid has a shorter duration than that of urea, and occurs in the earlier hours of this period. This is difficult to reconcile with the view that the acid originates from the nuclein of the diet, on which the earlier stages of digestion have only a minimal effect.The chief evidence in favour of the view that nucleins play a r8Ze as precursors of uric acid is based upon the results of thymus feeding. The present experiments show that extracts may be prepared from this gland which contain only traces of nuclein and nucleic acid, but when injected they produce a large excretion of uric acid. It there- fore appears that some more soluble constituent of the diet acts either as a direct precursor or as a factor in a synthetic process. W. D. H. Dichlorothymolglycuronic Acid. By K. KATSIJYAMA and S. HATA (Ber., 1898, 31, 2583--2585).-Rabbits were fed with thymol and their urine treated with hydrochloric acid and sodium hypochlorite (Blum, Zeit.physiol. Chent., 1895, 16, 514). I n this way, a product was eventually obtained which was identical with Blum’s dichlorothy- molglycuronic acid, except that it melted at 1 1 8 O instead of 125-126”. Its bcvriuwz salt, (C,6H,,C1208)2Ba, was prepared and analysed ; when boiled with dilute sulphuric acid, the acid gave glycuronic acid and a substance containing chlorine. Rabbits, then, like men and unlike dogs, excrete thymolglycuronic acid; they are able to bring about a combination of thymol with the glycuronic acid of their bodies. C. F. B. Excretion of Kynurenic Acid. By LAFAYETTE B. MENDEL and HOLMES C. JACKSON (8me!r. J. Physiol., 1898, 2, 1--28).-The experi- ments made on dogs, which are recorded, gave the following results. Kynurenic acid is a direct product of proteid katabolism, and as Baumann indicated, it does not originate as the result of putrefaction in the intestines.Its amount in the urine rises with proteid katabolism, whether this is produced by starvation, excess of proteid food, or the drugs borax and phloridzin; gelatin and carbohydrates do not act in this way. In conditions of nitrogenous equilibrium, or under the influence of proteid-sparing foods, the excretion of the acid is diminished or absent. Uric acid and kynurenic acid may occur together in dog’s urine, as Solomin found. K.ynurenic acid was not found in the urine of cats and rabbits. The observations suggest the presence of a quinoline-like radicle in the proteid molecule; the existence of a large carbohydrate group is also confirmed. W. D. H. Modification of Rigor Mortis by Fatigue. By CAROLINE W. LATIMER (Amer. J. Physiol., 1898, 2, 29--46).-After prolonge d fatigue from electrical stimulation, the muscles of cold-blooded animal s118 ABSTRACTS OF CHEMICAL PAPERS. enter into rigor much earlier, and shorten much less than when not fatigued. This is not due to increase of lactic acid, of carbonic anhydride, or other fatigue products, or to the abstraction of calcium salts, .but to the exhaustion of the glycogen normally present in muscle, for the circulation through the exhausted muscle of a liquid containing dextrose in the proportion normally present in the blood effects a more or less complete restoration of the normal rigor. W. H. D.

ISSN:0368-1769    

DOI:10.1039/CA8997605114

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

118 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Action of Oxygen on Beer Yeast. By JEAN EFFRONT (Gompt. ?*end., 1898, 127, 386--327).-When pressed beer yeast is exposed to the air, it absorbs oxygen with considerable development of heat, and with 2 kilos, of yeast in layers 37 cm. high, the temperature rises from 20' to 563. This fact m y be utilised for the detection of oxygen in a mixture of gases; the gas to be examined is passed very slowly through a mixture of yeast and pumice in yhich a thermometer is embedded, and the presence of oxygen is indicated by a rise of temperature. The phenomenon is due to the presence in the cellulss of an oxidising enzyme, which will be described subsequently. Poisonous Effects of Cupric Salts on Higher Plants.By HENRI COUPIN (Compt. rend., 1898, 127, 400-401).-Experiments on young wheat plants lead to the following toxic equivalents, which represent the minimum quantity of the salt that must be dissolved in 100 parts of water in order t o kill the plants : cupric bromide, 0.004875 ; chloride, 0.005000 ; sulphate, 0.005555 ; acetate, 0-005714; nitrate, 0.006102, It seems clear that the toxic effect is due to the copper ion, and that the electronegative radicle is practically without influence. It follows from these results that the use of solutions of cupric salt's as germicides is attended with considerable risk. C. H. B. Composition and Feeding Value of Millet. By BALLAND (Compt. rsnd., 1898, 127, 239-240).-The term miUet is applied commercially to grains derived from several different plants.Common or panicdated millet forms brilliant, ovoid, white, yellow, red, or black grains, which weigh from 4.60 to 5.90 grams per 1000. It has been grown from pre-historic times in middle Europe, Egypt, and Asia. Awmed millet, or panic millet, which is sometimes erroneously described as Panicumitalicum, forms small, round, straw-coloured grains, 1000 of which weigh about 2.65 grams. Like common millet, it has been grown in temperate climates and used as human food since pre- historic times. Long millet forms elongated, greyish-yellow grains, with a smooth, highly lustrous envelope; they are much larger than the grains of common millet, and 1000 weigh 7.0 to 8.2 grams, C. H. B.VEGETABLE PHYSLOLOCY AND AGRICULTURE. 119 Like maize, millet is rich in fat and nitrogen, and is physiologically a more complete food than wheat ; whilst millet contains less cellulose than African millets, and the latter contain more nitrogen.A number of millets from Africa, France, Italy, and Turkey were found to show the following extremes of composition. Water, 1 O o l O to 13.00 ; nitrogenous compounds, 8.98 to 15-04 ; fats, 2.20 to '7.30 ; sugar and starches, 57.06 to 66.33 ; cellulose, 3.00 to 10.23; ash, 1.40 to 6.00 per cent. ; acidity, 0.055 to 0.098 per cent. Phosphoric Acid dissolved by the Water in Soils. Ey TH. SCHLOESING, Jun. (Compt. rend., 1898, 127, 236-239 and 32?-329).-The quantity of phosphoric acid dissolved in the water impregnating soils is usually about 1 milligram per litre, but some- times is as much as 2 or 3 milligrams.Estimation of the phosphoric acid in the water displaced from various soils by the method of Schloesing, sen., shows that the proportion of phosphoric acid in solution depends on the nature of the soil, but is independent of the proportion of water in the soil, The quantity of phosphoric acid that remains in solution is the result of equilibrium between complex reactions, some of which tend t o withdraw the acid from the solution, and, in most cases, the quantity dissolved is very small compared with the total quantity in the soil. It follows that, as fast as the dissolved acid is removed by vegetation, a corresponding quantity passes into solution from the soil, and hence, although the quantity dissolved at any particular instant is small, the total quantity brought to the roots of a plant during its life-time may be considerable.The method of displacement involves the use of large quantities of soil and has other inconveniences, and in most cases the quantity of dissolved phosphoric acid can be estimated more quickly and easily. Agitation with water for 10 hours is quite sufficient to ensure the dissolution of the maximum proportion of phosphoric acid, and it is not advisable to agitate for a longer time, because secondary reactions may cause the reprecipitation of part of the acid. Further, although the proportion of acid dissolved increases with the ratio of soil to water, the increase is practically negligible if the proportion of dry soil is not less than 300 grams to 1300 C.C.of water, It is advisable, therefore, to take soil and water in these proportions. Carbonic anhydride has no influence on the result, provided that it is not in excess with respect to the calcium carbonate present. C. H. B. By GUSTAVE ANDRI~ (Compt. rend., 1898, 127, 414--41'7).-The author has sub- jected various soils to the action of dilute acids and alkalis, with a view to throw light on the constitution of the nitrogenous organic matter that they contain. The soils were a cultivated soil, moorland soil, leaf-mould, and peat, and they were heated a t looo for 15 hours with potassium hydroxide or bydrochloric acid in quantity equal to twenty times the weight of the total nitrogen present, the acid or alkali being diluted with thirty times its weight of water.The nitrogenous matter insoluble in the alkali was afterwards treated with the acid, and vice verslt. I n the case of the alkali, the author estimated the nitrogen in four distinct forms, (1) evolved as C. H. B. Constitution of Natural Humoid Substances.120 ABSTRACTS OF CHEMICAL PAPERS. ammonia, (2) insoluble in alkali, (3) soluble in alkali and not pre- cipitated by acids, (4) soluble in alkali and reprecipitated by acids. After treatment with the acid, he estimated the nitrogen (1) insoluble in acid, (2) existing as ammonia, (3) existing as amides. The results are given in tabular form. The peat and the cultivated soil, when treated with alkali: yield a larger proportion of their nitrogen in the form of ammonia than the moorland soil or vegetable mould.The percentage of total nitrogen rendered soluble by the alkali is : peat, 79.19 ; cultivated soil, 76.92 ; moorland soil, 74.84 ; leaf-mould, 72-95, but the soluble nitrogen not precipitated by acid is higher in the cultivated soil and leaf-mould than in the other two. On the other hand, the percentage of total nitrogen rendered soluble by hydrochloric acid is : cultivated soil, 61.52 ; moorland soil, 61-70 ; peat, 53.91 ; leaf-mould, 39.34 ; and the proportion of ammoniacal nitrogen obtained is lower than when treated with alkali. The different order in which the soils arrange themselves when treated by different reagents indicates that their nitrogenous matters differ in constitution. Action of Calcium Oxide and Carbonate on certain Humoid Substances.By GUSTAVE ANDRI~ (Compt. Tend., 1898, 12'7, 446--448).-The four soils used in experiments with dilute acid and alkali (preceding abstract) were heated a t 100' for 15 hours with calcium oxide, calcium carbonate, or water only, and the nitrogen volatilised and the nitrogen rendered soluble were determined. The soils were also allowed t o remain in contact with calcium oxide at the ordinary temperature for 82 days, with occasional agitation. The results are stmated in the form of a table. The quantity of ammonia liberated by the action of calcium oxide a t looo is considerable, but is lower than that liberated by potassium hydroxide. Calcium carbonate, and even water alone, cause the liberation of ammonia from all the soils, and in the case of the cultivated soil and peat the quantity is not negligible.The culti- vated soil is more completely attacked than the other three by calcium oxide at looo, and this is trne also of calcium carbonate at 100'. The quantity of nitrogen converted into ammoniacal nitrogen by the action of calcium oxide at the ordinary temperature amounts to from 5 to 6 per cent. of the total nitrogen in all four cases, and this indicates that the nitrogen of the amides in the soil is partially con- verted into ammoniacal nitrogen under the conditions specified, what- ever may be the nature of the original nitrogenous matter. C. H. B. C. H. B. Nitrogenous Substances accompanying Humic Acid in the Soil. By FAUSTO SESTJNI (L'Orosi, 1898, 21, 1-6).--The humic acid extracted from soil always contains notable quantities of nitro- genous substances, other than ammonia, which are more or less com- pletely removed when the crude substance is purified by repeated dis- solution in alkalis and reprecipitation with hydrochloric acid. These impurities are readily decomposed by concentrated alkalis, but on boiling crude humic acid with 2 per cent.sodium hydroxide solutionANALYTICAL CHEMISTRY. 121 for 134 hours little more than half the nitrogen is expelled as ammonia. Dilute hydrochloric acid effects no sensible decomposition, and only a relatively small amount of ammonia i s formed by boiling with 10 per cent. hydrochloric acid for 24 hours. It is concluded from these results that the nitrogen accompanying humic acid does not exist, to any large extent, in the form of amides. Experiments on the action of nitrous acid indicate the presence of appreciable amounts of amido-acids, but this question is reserved for further study. Previous observations by the author on the production of furfuraldehyde by the action of hydrochloric acid on humic acid have led him to suppose that the nitrogenous substances accompanying the latter might contain a pentosan residue. It is now found that furfuraldehyde is yielded, not only by crude humic acid, but also by the purified product, and, although to a less extent, by the humous substances formed by the action of mineral acids on pure sugar. N. L.

ISSN:0368-1769    

DOI:10.1039/CA8997605118

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 121 Analytical Chemistry. nearly free from alcohol and measure about 600 c.c., is introduced into the detached cylinder A , 300 C.C. of ether is added, the stoppers are put in, and the whole is thoroughly shaken. When the two layers have separated, the stoppers are removed and well rinsed with ether ; the top part of the cylinder is also rinsed. The other parts of the apparatus are then connected. B is a distilling flask of 200-300 C.C. capacity, partially filled with ether, and furnished with a cork having two perforations, the flask being heated by hot water. The ether vapour passes through the tube a into b, and when condensed in C runs through E Extraction of Liquids. By OTTO FOERSTER (Chm. Zed,, 1898, 22, 421--422).-The apparatus is intended for the extraction of unsaponifiable matter from soapy liquids.The soap solution, which should be b to nearly the bottom of A, and th& ascending, gradually increases the volume of ether until it overflows into the flask B by means of the syphon tube c. The extraction is complete within 4 hours. As soap is not quite insoluble i n ether, this must be afterwards shaken four times in succession with a little122 ABSTRACTS OF CAEMICAT, PAPERS. water to remove the soap. In order to ascertain the accuracy of the process, 1 gram of cholesterol was added to a solution of soap previously extracted with ether and 0.9997 gram was recovered. L. DE K. A New Form of Crucible. The Tube Crucible. By ERNST MURMANN (Monatsh., 1898, 19, 403).-The bottom (b) of this crucible is perforated and furnished with a straight ( c ) or bent (c,) tube, which serves the twofold purpose of conducting away a liquid from a precipitate '- or allowing the passage of a gas over the preci- pitate while the crucible is heated.The retention of the precipitate is provided for by placing a layer of asbestos between the bottom of the crucible and a sieve-plate which is of somewhat smaller size. The crucible may be used in the estimation of many metals, and is of especial advantage in the case of the estimation of zinc or manganese as sulphide (see this vol., ii, 126). By RALPH S. SWINTON (Plmrm. J., 1898, 59, 562--564).-The amount of iodine in any mixture of soluble haloid salts is determined by successively adding to an aqueous solution, containing a known quantity of the mixture, strong sulphuric acid, phenol, aud bromine water.The mixture is thoroughly agitated and then extracted with chloroform, which removes the liberated iodine. This treatment is repeated in order to decompose all the iodide present; in each case, the excess of bromine combines with the phenol to form tribromophenol. The chloroform extract is mixed with water, and titrated with sodium thiosulphate in the usual manner. I n the absence of iodides, the amount of bromine present in a mixture is obtained by agitating its solution in cold sulphuric acid with potassium permanganate and chloroform. The solution of bromine in chloroform is added to alcoholic potassium iodide; the amount of iodine set free and estimated by thiosulphate is a measure of the bromine originally present in the solution.Three determinations are required in order to ascertain the amount of chlorine, bromine, and iodine in a mixture of the haloid salts. The iodine is determined in one portion by the method described above. From another portion, the iodine is liberated by means of the calculated amount of N/2 potassium permanganate and extracted by chloroform ; the bromine is then liberated by the addition of excess of permanganate, and its solution in chloroform mixed with alcoholic potassium iodide, to which the chloroform extract of iodine is sub- sequently added, and the whole diluted with water and titrated with thiosulphate. Lastly, a portion of the original mixture is titrated with standard silver nitrate solution, using potassium chromate as indicator. These three determinations furnish sufficient data for the estimation of the halogens in any mixture of their salts.y A. L. Quantitative Separation of Halogens. G. T. M.ANALYTICAL CHEMISTRY. 123 Quantitative Electrolytic Separation of Chlorine, Bromine, and Iodine. By H. SPECKETER (Zeit. Elektrochem., 1898, 4, 539).- When a normal solution of hyciriodic acid is electrolysed with a silver anode and a platinum cathode, silver iodide is formed, and hydrogen eliminated with an E.M.F. of - 0.06 volt, hydrobromic acid requires +0.15 volt, and hydrochloric acid 0.3 volt. More dilute solutions require greater E.M.F.’s. Oxygen must be absent otherwise the combination develops an E.M.F. of more than 1 volt, and all the halogens separate out.The silver employed must be pure. In practice, a solution in normal sulphuric acid is used and an anode of pure silver gauze, the electrolysis being conducted in a current of hydrogen. With 0.1 3 volt, the iodine is almost completely separated as silver iodide which adheres firmly to the anode, and may be washed aud weighed together with it; 0.35 volt separates bromine in the same way, the chlorine remaining being titrated as usual. The greater part of the results given are accurate to within 0.5 per cent. T. E. Application of Phloroglucin-vanillin for the Detection of Sulphur and Nitrogen in Organic Compounds. By P. N. RAIKOW (Chem. Zeit., 1898, 3,2, 377--379).-The author (this vol., ii, 52) finds that an ethereal solution of phloroglucinol-vanillin not only readily detects halogens in organic compounds, but that it is also an excellent reagent for the detection of organic sulphur and some forms of organic nitrogen.To detect sulphur in commercial oils, an open glass tube is bent a t right angles near one end, a few drops of the oil are introduced at the bend,awick of long-fibre asbestos is then introduced,.and theoil is burnt, oils which give off much soot being diluted with alcohol or ether; the products of combustion are allowed to act on a porcelain crucible lid moistened with the reagent. I n the presence of sulphur, sulphuric acid is formed which gives a characteristic red spot. A yellow spot is obtained by the combustion of amines, hydrazines, and similar nitro- genous compounds, and if halogens or sulphur should also be present, both kinds of spots are visible.This is the case with such substances as wool, hair, goose-feathers, casein, and artificial products such as t hiocarbamide, sulphanilic acid, magenta, methyl-violet, &c. L. I)E K. Colour Reaction of Anhydrosulphuric Acid. By ETIENNE BARRAL (Bull. Xoc. Chim., 1897, [ iii], 17, 744-’745).-Hexachloro- benzene paradichloride slowly dissolves in sulphuric acid containing anhydrosulphuric acid, with the production of a fine, red-violet colora- tion. The reaction is not given by dry sulphuric anhydride, but, on exposure to a moist atmosphere, the coloration quickly appears, and is finally destroyed when sufficient water or dilute sulphuric acid is added to convert the whole of the sulphuric anhydride present into ordinary sulphuric acid.The colour changes are sufficiently sharp to admit of the volumetric estimation of anhydrosulphuric acid by titra- tion with dilute sulphuric acid of known strength, In the case, how- ever, of commercial Nordhnusen sulphuric acid, which is usually more124 ABSTRACTS OF CHEMICAL PAPERS. or less coloured, the end-point is somewhat obscure, and the results Detection of Sulphides, Sulphites, Sulphates, and Thiosul- phates in the presence of each other. By PHILIP E. BROWNING and ERNEST HOWE (Anae,; J. ti'&, 1898, [iv], 6, 317-322 ; and Zeit. tcnovg. Chem., 18, 371-377).--This is a modification of the scheme recommended by Greig Smith (Abstr., 1896, ii, 71). To about 0.1 gram of the mixture, dissolved in 10 C.C. of water, ammonia is added until distinctly alkaline, the sulphide is then precipitated with zinc acetate, and the precipitate is further examined.The filtrate is slightly acidified with acetic acid, any sulphate is precipitated by barium chloride, the solution filtered, and the tiltrate mixed with a very slight excess of iodine; stannous chloride is added until the colour of the iodine disappears, and then a few drops of hydrochloric acid; a precipitate proves the presence of a sulphite. The filtrate from this is mixed with excess of bromine water, and stannous chloride is added until the liquid is decolorised; a precipitate indicates the By ALBERT ATTERBERQ (Chem. Zeit., 1898, 22, 505-506).-The author heats 0.5 gram of the nitrogenous compound with 20 C.C. of strong sulphuric acid and a drop of mercury, and, when frothing has ceased, 15 to 18 grams of potas- sium sulphate is added; the liquid is generally colourless after 30 minutes boiling, but i t is advisable to boil for another 15 minutes.Treated in hhis manner, even quinine yields the whole of its nitrogen in the form of ammonia. Attempts t o replace the mercury by other metals or oxides were not quite successful. Phosphoric anhydride has no advantage over potassium sulphate. Molybdic acid acts energetically, but, on account of the blue colour of the solution, it is difficult to observe the end Estimation of Arsenic in Antimony and in Metals. By 0. DUCRU (Compt. rend., 1898, 127, 227-229).-About 5 grams of the coarsely powdered substance is distilled with 100 C.C. of ferric chloride solution and 200 C.C.of concentrated hydrochloric acid until 100 C.C. has passed over. A further quantity of 100 C.C. of hydrochloric acid is then added, and a second 100 C.C. distilled off, after which the same treatment is repeated, so that the total volume of the distillate is 300 C.C. The end of the condenser tube should dip into the distillate, and aboiit 50 C.C. of water should be placed in the receiver at the beginning of the operation. The distillate contains a little antimony, and must therefore be redistilled until about 300 C.C. has passed over. If 50 to 100 C.C. of concentrated sulphuric acid is added before redistilling, it is usually sufficient to collect 150 C.C. The arsenic in the final distillate is precipitated with hydrogen sulphide in the usual way.The ferric chloride solution is prepared by allowing 2000 C.C. of hydrochloric acid and 2000 C.C. of water to act on 800 grams of French nails, and, after all action has ceased, the liquid is saturated are wanting in accuracy. N. L. presence of a thiosulphate. L. DE I(. Modifications of Kj eldahl's Process. reaction. L. DE K.ANALYTICAL CHEMISTRY. 125 with hydrogen eulphide and filtered. The excess of hydrogen sulphide is expelled by boiling, and a current of chlorine is passed into the liquid until all the iron is oxidised. The excess of chlorine is after- wards expelled by means of a current of air, and the liquid is diluted to 5000 C.C. by adding concentrated hydrochloric acid. The solution should be examined for arsenic by distilling some of it, after adding 15 grams of ferrous sulphate free from arsenic.The method is applicable to many metals, such as iron, steel, lead, tin, zinc, and alloys, as well as to antimony. Methods for Estimating Potassium, and the Best Precipi- tants of Platinum. By ALBERT ATTERBERG (Chern. Zeit., 1898,22, 522-523 j 538-539).-1t is admitted that, instead of weighing the potassium platinochloride, it is better to dissolve the compound in boiling water and to reduce the platinum by suitable means; the metal is then collected, weighed, and calculated to potassium. For this purpose, the author prefers using magnesium ribbon, the excess of which may be readily removed by hydrochloric acid. If the amount of platinum is very small, thioacetic acid is recommended. When potassium is separated from sodium, the latter is left in the alcoholic filtrate containing also the excess of platinum chloride.If it be desired to directly estimate the sodium, the author recommends removing the platinum by means of metallic mercury a t the boiling temperature. The liquid then contains some mercuric chloride, which is readily separated from the sodium chloride by heating the dry residue. To avoid the tedious separation of iron or aluminium before treating the sample with platinum chloride, the author recommends adding some citric acid ; the acid citrates of iron and aluminiuni are readily Electrolytic Deposition of Silver from Solutions in Nitric Acid.-By FRIEDRICH W. K~STER and H. VON. STEINWEHR (Zeit. Ekktrochem., 1898,4, 451).-The authors have experienced great diffi- culty in obtaining a smooth deposit of silver from solutions of the nitrate by the processes hitherto prescribed; a spongy deposit was almost invariably formed after some time.I n all these cases, they attempted to work with the prescribed constant current, the result being that, as the amount of silver in the solution diminished, the E.M.F. required increased. A very large number of experiments mere then carried out in which the E.M.F. was kept constant and the current allowed to vary. The formation of silver peroxide is easily prevented by the addition of a little alcohol. The result finally arrived at is that a perfect deposit of silver may be obtained with certainty by adding 1 to 2 C.C. of nitric acid of sp. gr. = 1.4 and 5 C.C. of alcohol to the solution, and electrolysing a t 85" to 60" with a constant E.M.F.of 1.35 t o 1-38 volts. With 2.4 volts or more, the deposit becomes spongy, even when the other precautions are taken. As much as 2 grams of silver may be deposited. The constant E.M.F. was obtained by short-circuiting a Gulcher thermo-battery by a resistance small enough to reduce its E.M.F. to the desired value. The terminals of the electrolytic cell are then connected to those of the battery. The usual plan of putting a resistance in series with the electrolytic C. H. B. removed by washing with alcohol. L. DE I(. VOL. LXXVI. ii. 9126 ABSTRACTS OF CHEMICAL PAPERS. cell so as to reduce the E.M.F. between the electrodes to the desired value is unsuitable because, as the electrolysis progresses, the resistance of the cell increases, and with it the E.M.F.Test analyses of a silver coin carried out by the method described, gave results varying from 89-75 to 89.83 per cent. of silver, the mean, 89.79, being practically identical with the mean of two very careful gravimetric determine- tions (899'89). T. E. Estimation of Zinc and Manganese as Sulphides. By ERNST MURMANN (Miat&., 1898, 19, 404--405).-The estimation of zinc and manganese as sulphides is not in general use, owing to the diffi- culty of obtaining a clear filtrate and the lengthy washing which is necessary. The author avoids these difficulties by precipitating the sulphides in presence of mercuric chloride, when the mercuric sulphide which is formed largely increases the bulk and conspicuousness of the precipitate and renders it more easy to filter and wash.The precipi- tate is collected in a ' I tube-crucible I' (see this vol., ii, p, 122) and heated in a stream of hydrogen as usual, when the mercuric sulphide is com- pletely volatilised. The same method may be employed in the case of stannic hydrate, and is probably applicable to other precipitates, NOTE.-LOW~ has shown that there is no difficulty in the filtration of zinc sulphide if the precipitation is effected with the proper pre- cautions (Abstr., 1893, ii, 302). EDITOIGS. Electrolytic Separation of Cadmium and Iron. By WILLEM STORTENBEKER (Zeit. Ehktrochem., 1898, 4, 409).-The mixture of cadmium and iron salts is dissolved in 100 C.C. of water, and, if more than a trace of ferric salt is present, reduced by adding about five times the requisite quantity of sodium sulphite to the slightly acid solu- tion and warming.Two or three grams of pure potassium cyanide are now added, and the solution warmed until it takes the yellow colour of potassium ferrocyanide j it is then diluted to 200-250 c.c., and electrolysed overnight a t the ordinary temperature with 0.05 to 0.1 ampere per sq. dcm. A. L. The results are excellent. T. E. Electrolytic Separation of Copper from Silver, Mercury, and Arsenic. By N. REVAY (Zeit. EZektrocbn., 1898, 4, 313 and 329).--Coppr a d SiZuer.-In order to decompose a solution of silver nitrate, an E.M.F. of about 0-9 volt is needed, whilst for copper nitrate the value is approximately 1.4 volts ; when a solution con- taining silver and copper nitrates is eIectrolysed at about 70" with from 1.3 to 1.4 volts, the silver is deposited, the copper remaining in solution.The deposit obtained is not quite smooth, but adheres sufficiently well to the platinum dish to allow of its being washed ; a t lower temperatures, this is not the case. The solution must be strongly acidified with nitric acid in order to prevent the formation of silver peroxide. In presence of potassium cyanide, the cathodic polarisation, both of silver and copper, is much higher than in acid solution, owing to the smaller number of ions present. It also in- creases as the concentration of the metal diminishes, so that, fromANALYTICAL CHEMISTRY. 127 solutions containing much copper and little silver, the former may be more readily deposited than the latter.At 45-60', however, with 1.65-1-8 volts, the author obtains very satisfactory results, the deposit of silver being smooth and adherent. Copper and Mercury.-The E.M.F. required to deposit mercury is almost the same as that required for silver under similar circum- stances. From acid solutions of copper sulphate and mercuric chloride, deposits of mercury, apparently contaminated with mercurous salts, were thrown down, and no results of value were obtained with solutions of mercurous nitrate in presence of nitric acid. In solutions containing potassium cyanide, mercury behaves in much the same way as silver. When the concentration of the mercury falls below about 1/384 normal, potassium is more easily separated a t the cathode than mercury, and hydrogen is therefore evolved, When the concentration of the copper is not too great, however, a satisfactory separation is possible, using 1-8-1.95 volts at the ordinary temperature.In the experiments quoted, 0.5 to 0.6 gram of crystallised copper sulphate was mixed with 3 grams of potassium cyanide, and from 0.25 to 1.0 gram of mercuric chloride; themercuryfoundwas 0.1 to 0.2 per cent, too low. Copper and Arsenic.-From solutions of copper sulphate and potas- sium arsenate acidified with sulphuric acid, the copper is readily deposited in a pure state by 1-6 to 1.8 volts in 16 to 24 hours. The separation is also a good one in ammoniacal solution, 9 to 20 hours being required with 1.65 to 1.8 volts. Separation of Nickel from Cobalt by Hydrogen Chloride.By FRANKE S. HAVENS (Zeit. anorg. Chrn., 1898, 18, 378-381).- The method described by E. Piiieriia (Abstr., 1897, ii, 38'7) which is based on the insolubility of nickel chloride in ether saturated with hydrogen chloride is not accurate. Pifierha precipitates the nickel chloride in a mixture of equal parts of concentrated hydrochloric acid and dry ether saturated with hydrogen chloride, but the author finds that 14 C.C. of such a solution contains 0.002 gram of metallic nickel. An accurate separation of nickel and cobalt chlorides can be effected by a modification of this method, provided that only a few centigrams of cobalt chloride are present, but when more cobalt chloride is present, the nickel chloride always carries down with it an appreciable quantity of cobalt which cannot be washed out of the precipitate with ether saturated with hydrogen chloride.The separation is carried out as follows, The solution of the chlorides is evaporated to dryness, dissolved in the smallest possible quantity of water (about 1 c.c.) 10-15 C.C. of dry ether added, and the cooled solution saturated with hydrogen chloride. The precipitate formed is washed with ether saturated with hydrogen chloride, and the nickel in the precipitate and the cobalt in the filtrate are then estimated by electrolysis. It is probable that, in the presence of larger quantities of cobalt, a complete separation could be obtained by repeated precipitation of the nickel chloride. T. E. E. C. R. Electrolytic Separation of Cobalt and Nickel. By ALFRED COEHN (Zeit. Elektrochem., 1898, 4, 501).-The author shows that electro-stenolysis occurs in the following cases : (a) t h o negative 0 -2128 ABSTRACTS OF CHEMICAL PAPERS.radicle separated at the anode does not act on the metal deposited at the cathode ; (6) insoluble compounds such as peroxides are formed a t the anode ; (c) the radicle separated a t the anode combines with the solution, as, for example, in a solution of cuprous chloride. He has observed that the cobalt salts exhibit stenolysis, whilst those of nickel do not ; the difference is due to the deposition of cobaltic oxide a t the anode, nickel salts giving no such deposit ; this behaviour may be utilised for the separation of the metals. The electrolysis is carried out in neutral solution, copper sulphate being added in order to prevent the deposition of part of the cobalt at the cathode. Estimation of Manganese as Pyrophosphate.By FRANK A. GOOCH and MARTHAUSTIN (Amer. J. Xci., 1898, 6, 233-243, and Zeit. amorg. Chem., 18, 339-351).-The accuracy of this procoss depends a good deal on the amount of ammonium salts and free ammonia present, and the authors, after a lengthy investigation, now propose the following process. The liquid, which should be slightly acid and contain an amount of maganese not exceeding that which would produce 0*4 gram of pyrophosphate, is diluted to 200 c.c., and 20 grams of ammonium chloride and 10 C.C. of a cold saturated solu- tion of sodium ammonium phosphate are added. After adding dilute ammonia in very slight excess, the mixture is heated until the precipi- tate which is formed becomes silky and crystalline ; after being allowed to cool for half an hour, the precipitate is collected on a Gooch’s crucible, washed with slightly ammoniacal water, dried, ignited, and Estimation of Oxide of Iron and Alumina, in Phosphates.By N. BLATTNER and J. BRASSEUR (Bull. SOC. Chim., 1897, [iii], 17, 760--761).-A critical examination of the methods commonly employed for the estimation of oxide of iron and alumina in phosphates has led the authors to the following conclusions, The acetic method, as modified by Maret and Delattre, should be rejected as giving low results, since a portion of the alumina always remains in solution. Glaser’s method is rapid, easy of execution, and gives sufficiently accurate results in the case of phosphates free from manganese.The msthod involving the use of caustic soda gives very accurate results when all the precautions described by Lasne are duly observed. The results obtained by Gruber’s method, a simplification of the preceding, are inexact. Gladding’s method only differs in detail from that of Lasne, caustic potash being substituted for caustic soda. The method of direct precipitation by ammonia, as carried out by Thomson, gives variable results, according to the nature of the phosphate under examination, and the precipitate always contains lime. N. L. By H. BAUCKE (Zeit. anal. Chen?., 1898, 37, 668--679).-The ferruginous pigments prepared by roasting ochres exhibit a gradation of shades ranging from yellowish-brown to deep purple, the depth of colour increasing with the temperature and duration of the roasting.Even in the most strongly heated specimens, the ferric oxide is practically all T. E. weighed as pyrophosphate. L. DE K, Technical Examination of Ferruginous Pigments.ANALYTICAL CHEMISTRY 129 soluble in concentrated hydrochloric acid, and digestion with that acid furnishes the most convenient means of dissolving the iron for esti- mation. The specific gravity of the substance increases with the depth of colour, being 3.484 in those most feebly roasted, and 4.462 in those most strongly heated ; the passage from pale brown to red is accompanied by the most marked increase in specific gravity. AS these pigments are largely used for painting iron-work, especially on railways, the degree in which they resist the action of the acids in coal smoke is of importance.The degree of resistance increases with the t.emperature of roasting, and comparative experiments on this point may conveniently be made by boiling the samples with excess of 1 per cent. sulphuric acid for a determined time (1 hour). The percentage of the total iron dissolved by this method is quite independent of the size of the particles, fractions exhibiting, under the microscope, diameters of 4-10 p, giving up to the acid the same percentage as those of 30 p and higher. M. J. S. Analysis of Molybdenum Compounds. By HARRY BBEARLEY (Chem. News, 1898, 78, 203--205).--Chatard's process for the estima- tion of molybdenum by precipitation with lead acetate is accurate in neutral solution, but even if the solution is faintly alkaline decompo- sition of any excess of lead acetate ensues with deleterious effects ; in the presence of 2 C.C.of free 33 per cent. acetic acid per 250 c.c., the results again are accurate, whereas with more free acid the precipitate loses its granular character, becomes powdery, and liable to pass through the filter. Excess of lead acetate may be detrimental in neutral or alkaline solutions, but is not so in acid solutions; in fact, water slightly acidified with acetic acid and holding, per litre, 2 C.C. of a solution of lead acetate (containing 7.896 grams per litre) may be used towards the end of a washing with pure hot water to prevent the formation of opalescent filtrates. To ignite the precipitate, it need not be removed from the paper, but the wholemay be folded wet and dried in a crucible in the front of a muffle ; ignition should be started at as low a temperature as possible to prevent the formation of imperfectly decarbonised patches that would require a dangerously high tempera- ture to burn away; lead molybdate may, however, be exposed for hours at a temperature between 850" and 900° without suffering a greater loss than 1 per cent.The result is, moreover, either not affected at all, or, at any rate, not beyond + or - 1 per cent., by the presence of 0.1 or 0.2 gram of the following substances: sodium chloride or nitrate ; ammonium chloride, nitrate, or acetate ; manganese ; copper ; cobalt ; nickel ; zinc ; magnesium ; mercuric mercury ; but uranium causes a difference of 1.7 or 1.5 per cent.The presence of ammonium acetate makes the precipitate powdery ; copper and manganese darken the ignited precipitate, although the colour can be nearly removed by treatment with nitric acid and lead peroxide. Cobalt renders the ignited precipitate greyish, and on dissolving in hydrochloric acid imparts a greer, colour to the solution which disappears on dilution ; 0.00005 gram of cobalt can be detected by this reaction, which, more- over, may probably prove useful in colorimetrically indicating the mount of oobalt present in the grey precipitate of lead molybdate.230 ABSTBAC'TM OF CHEMICAL PAPERS. I n this and some other instances, redissolving the ignited lead molyb- date precipitate in dilute hydrochloric acid, neutralising with ammonia, acidifying with acetic acid, and treating with a few additional drops of lead acetate, suffices to furnish a practically pure precipitate of lead molybdate.I n the presence of zinc, molybdenum causes a cloudiness in the neutralised solution, which may be disregarded where it forms a mere opalescence on adding the excess of acetic acid, otherwise, when neutralising the hydrochloric acid, the final portions should be got rid of by means of ammonium acetate. Nickel exhibits this clouding effect to a lesser degree, mercury and uranium to a more marked ex- tent; but in these cases, too, the warm, acidified solution may be cleared by adding ammonium acetate. Uranium colours the ignited precipitate yellowish-brown, and although it dissolves in hydrochloric acid, it needs repeated reprecipitations to remove the last traces of uranium from the lead molybdate.Molybdenum may be estimated volumetrically by adding an excess of lead acetate, filtering off the lead molybdate, and determining the lead in the filtrate, or by Schindler's process, in which lead acetate is added to an acidified solution of a molybdate, until the latter ceases t o give any coloration when mixed with tannin in a white cupped tile. This process is rapid, and gives approximate results; it may, however, be advantageously supplemented by filtering some of the liquid after the completion of the tannin reaction, and testing it, first with lead acetate, and, if necessary, with sodium molybdate ; the intensity of any cloudiness indicates approximately the quantity of any unprecipitated molybdate or excess of lead, as the case may be, inasmuch as lead acetate gives a distinct cloudiness in solutions faintly but decidedly acid with acetic acid if they contain even as little as 1 part of molybdenum per 4,000,000.D. A, L. By P. N. RAIKOW (Chem. Zeit., 1898,22, 523-534).-The author, in reply to Dietze (Suddeutsche Apoth. Zeit., 1898, 174), states that the Saponification number of the oil is but in- significantly increased when the sample has been previously filtered a t 18'. As regards the solidifying point, he asks whether Dietze regards 15' or 20' as the limit of temperature. An analysis is given of a sample which was undoubtedly genuine, but wbich would not satisfy Dietze's requirements : sp.gr. 0.855 at 27"/17-5'. Solidifying point, 20.5'; optical activity in a 100 mm. tube, 2' 45' at 25' ; acidity figure, 1.1 ; saponification number, 15.5 ; ether number, 14.4 ; and relation figure (Verhaltnisszahl), 13. Testing Otto of Roses. L. DE K. Detection and Estimation of Methylic Alcobol in Ethylic Alcohol. By AUGUSTE TRILLAT (Compt. rend., 1898,127, 232-234). -When ethylic alcohol is oxidised with chromic mixture, it yields aldehyde, acetic acid, and acetal, whereas methylic alcohol, under the same conditions,, yields acetic acid and met hylal. When condensed with dimethylanilme, acetal yields the compound CHMe(CcH,*NMe)2, which bas not previously been described, and methylal yields tetra- methyldiamidodiphenylmethane, CH2(C,H4*NMe2)2, and this, when oxidised, gives an intense blue coloration, permanent when the liquidANALYTICAL CHEMISTRY.131 is heated. The acetal derivative, under the same conditions, yields an unstable blue compound which is decomposed on heating. When applying these facts to the detection of methylic alcohol in ethylic alcohol, precautions are necessary, because dimethylaniline often con- tains small quantities of methylic alcohol, and even of the base derived from methane, and also, when heated with certain acids in presence of air, it develops a blue coloration. Twenty C.C. of the alcohol to be examined is diluted with 300 C.C. of water containing 30 grams of potassium dichromate in solution, and 100 C.C. of dilute sulphuric acid (1 : 5) is added. After standing for an hour at the ordinary temperature, the liquid is distilled, the first portions of the distillate being rejected, and the distillate is exactly neutralised with sodium hydroxide and redistilled almost to dryness.The second distillate is diluted to 400 c.c., and 100 C.C. is mixed with 2 C.C. of pure dimethylaniline and 1 C.C. of dilute sulphuric acid (1 : 10) and heated a t 65-70' for 5 hours out of contact with the air. The liquid is made alkaline, the excess of dimethylaniline expelled by means of a current of steam, and the liquid, or part of it, acidified with acetic acid and mixed with lead peroxide suspended in water. The intensity of the blue colour produced is compared with that obtained with alcohol containing known percentages of methylic alcohol. It is well to make a blank experiment with pure ethylic alcohol.C. H. B. Estimation of Glycerol in Sweet Wines. By GUIDO FABRIS (r/'Orosi, 1897, 20, 260--267).-The estimation of glycerol in wines containing much sugar presents special difficulties, and in the methods generally employed there is a loss of glycerol, which is not com- pensated for by the traces of sugar, colouring matter, &c., which are weighed with the latter. The German official method and that of Lecco, both of which involve the use of lime, give satisfactory results when certain precautions are observed ; the following method of procedure is recommended. Fifty C.C. of the wine is mixed with 5 grams of sand and 8-10 grams of calcium hydroxide, and the mixture evaporated to the consistency of a thin paste, which is then ground in a mortar and repeatedly extracted with hot alcohol of 96', using 30-40 C.C.a t each extraction. The filtered extract, which should amount to about 200 c.c., is evaporated to a syrupy consistence, and 10 C.C. of absolute alcohol and 15 C.C. of anhydrous ether gradually added; when the precipitate has subsided, the liquid is filtered, the filter washed with a mixture of alcohol and ether (2 : 3 vols.), the filtrate evaporated, and the residue dried for 1 hour at 100' and weighed. I f the residue appears to be impure, it is redissolved in a mixture of 5 C.C. of alcohol with 7.5 C.C. of ether, filtered, evaporated, dried for half an hour a t looo, and weighed. Should more than 0.5 per cent. of glycerol be found, it is well to repeat the analysis with a smaller amount of the wine, so that the glycerol finally weighed may not exceed 0.3 gram.The isolation of larger quantities of glycerol is foiind to be accompanied by a more than proportionately greater loss. N. L.132 ABSTRACTS OF CHEMICAL PAPERS. Nitration of Glycerol with Nitrous Acids. By R. AUZENAT (Chem. News, 1898, 78, 258--259).-Glycerol, of sp. gr. = 1.262, was treated with 97 per cent. sulphuric acid and 94 per cent. nitric acid containing varying proportions of nitric peroxide, The nitroglycerols obtained were washed in the ordinary way with water, and, in addition, twice at 60' with equal volumes of a 4 per cent. solution of sodium carbonate, the alkali being finally removed with dis- tilled water. These products were filtered and submitted to the heat test, and i t was found that nitroglycerol satisfying this test can be pre- pared with nitric acid containing as much as 3 per cent.of nitric peroxide, although decomposition during the nitration frequently occurs with anything above 2 per cent. The presence of free sulphuric acid is not detected by the heat-test, although it is dangerous if the explosive has to be stored, but the test is effective in rejecting any nitroglycerol containing more than 0.003 per cent. of free nitric acid. Washing with sodium carbonate at a high temperature increases the stability. D. A. L. Detection of Acetone. By PASQUALE MALERBA (Zeit. anal. Chem., 1898, 37, 690; from Ann. Chirn. Parm., 21, 14)-On adding, drop by drop, a 1-2 per cent. solution of dimethylparaphenylenediamine to the suspected liquid, a red coloration gradually appears, and in- creases in intensity after some hours.Both alkalis and strong mineral acids change this colour to a bright violet. M. J. S. Estimation of Formic Acid in the Presence of Acetic Acid and of Easily Oxidisable Substances. By ALEXANDER LEYS (Chem. News, 1898, 78, 245-246).- When acetic acid containing formic acid is mixed with mercuric acetate, crystalline mercurous acetate forms in proportions exactly corresponding to the quantity of formic acid present. Dilute, 1 per cent., solutions are best for the reaction, which takes place a t the ordinary temperature, but is expe- dited by heating, and is complete at the boiling point ; it is, moreover, not affected by the presence of alcohol, acetic acid, or aldehyde.To estimate formic acid, the total acidity of the solution is first ascer- tained, and if much acetic acid is present, the solution is diluted to 20 or 30 per cent.; if, however, the proportion of formic acid to acetic acid is 1 to 20, o r greater, the solution is diluted to 2 per cent. acidity. Ten C.C. of this is mixed with 20-30 C.C. of a 20 per cent. solution of mercuric acetate, and made up to 100; i t is heated during 7 or 8 minutes up to the boiling point and allowed to cool overnight. The precipitate is collected on a glass wool filter, washed 4 or 5 times with alcohol of 95' containing 2 per cent. of glacial acetic acid, then 2 or 3 times with neutral alcohol of 95O, finally with dry ether to remove the alcohol. It is dried in the air or in a vacuum, dissolved in nitric acid diluted with an equal volume of water, mixed with sodium chloride and the mercurous chloride filtered, washed, dried at looo, and weighed ; the number obtained, multiplied by 0,0976, gives the corresponding weight of formic acid.In mixtures of formic acid and alcohol, or of formic acid, alcoholANALYTICAL CHEMISTRY. 133 and acetic acid in which the latter is not present in sufficient quantity, 2 C.C. of glacial acetic acid is added before the mercuric acetate, D. A. L. Estimation of Potassium Bydrogen Tartrate in Wines. By HENRY JAY (BUZZ, Soc, Chim., 1897, [iii], 17, 626-629).-The author has examined both Berthelot and de Fleurieu’s and Reboul’s methods for estimating potassium hydrogen tartrate in wines. The former, which depends on the precipitation of the salt by the aid of alcohol, gives num- bers somewhat too low, but may be rendered more accurate by suitable corrections. The results obtained by Reboul’s method, which depends on evaporating down the wine and crystallising the salt, are much too high, as malates, &c., are also carried down with the tartrate.J. J. S. Microchemical Reactions. By CONSTANTIN SAINT-HILAIRE (Zeit. physiol. Chem., 1898,26, 102--109).-1n order to test microchemically for uric acid, the sections obtained from organs hardened in alcohol, and embedded in celloidin, are placed in a 5 to 10 per cent. solution of copper sulphate for some hours ; the compound which uric acid forms with copper is then reduced by placing the sections for a few minutes in a boiling saturated solution of sodium hydrogen sulphite ; after wash- ing, the sections are finally treated with potassium ferrocyanide ; con- cretions of uric acid are by this means coloured red.In some preparations, the chromatin network of the nuclei was observed to be somewhat similarly stained, and it was found that the alloxuric bases, histon and protamine, are similarly affected. The constituent of the nucleus which gives the reaction is believed to be histon, combined as nucleo-histon. Examination of Beeswax. By KARL DIETERICH (Zeit. anal. Chem., 1898, 37, 699-700; from Helfenberger Anmlem, 1897, 218), and by CEORU BUCHNER (ibid., 700 ; from Zed. o.$snt. Chem,, 1897,3, 570).- For the estimation of the “saponification number” of a glyceride, it is recommended by Henriques t o dissolve 3-4 grams of the substance in 25 C.C.of light petroleum, add an excess of alcoholic soda, and allow to remain in the cold until the next day ; saponification is com- plete, and the results of this ‘‘ cold saponification process ” agree absolutely with those of saponification by heat, whilst, in some cases, such as mixtures of beeswax and ceresin, cold saponification is even more satisfactory than the usual method, provided that a petroleum is selected in which the substance is perfectly soluble. The author maintains that, with beeswax, cold saponification gives lower values than the hot method, and that the saponification number is more affected than the acid number. BUCHNER ascribes these differences to the use of a petroleum having too low a boiling point (55-75’ instead of 100-150O).New Colour Reaction for Phenylhydrazine. By LOUIS SIMON (Compt. rend., 1898, 126, 483-485).-The addition of a few drops of an aqueous solution of sodium nitroprusside to a warm solu- tion of phenylhydrasine and trimethylamine develops a blue W. D. H. 116. J. 8.134 ABSTRACT8 OF CHEMICAL PAPERS. coloration, the intensity o€ which is increased by subsequently adding a concentrated solution of potash. The coloration, although fugitive, is very intense, and serves to detect 1 part of phenyl- hydrazine in 50,000. The presence of alcohol, ether, or ammonia, is not detrimental, but chloroform, benzene, and acids hinder the production of the colour, whilst acetone gives its own characteristic red coloration.This reaction is limited to phenylhydrazine and to those derivatives which, like orthotolylhydrazine and 1 : 4-bromophenylhydrazine, are substituted in the aromatic nucleus ; alkylic and acidyl derivatives of phenylhydrazine, hydrazones, semicarbazide, and hydrazine hydrate, under similar conditions, give no colour reactions of this nature. G. T. M. Estimation of Caffeine in Coffee. By E. TASSILLY (Bull. Xoc. Chzm., 1897, [ iii], 1’7, 761-766 and 766-768).-The methods employed for the estimation of caffeine in coffee may be classed in three groups. 1. The coffee, with or without the addition of lime, magnesia, or ammonia, is extracted with warm chloroform. 2. The coffee is extracted with hot water and the solution shaken with chloro- form, either directly or after evaporation with magnesia.3. The coffee, with or without the addition of an alkali, is treated with a solution of sodium benzoate (Herlant) or salicylate (Gorges) and the liquid then extracted with chloroform, The methods of the first group give uncertain results, with the exception of that of Grandval and Lajoux, in which ammonia and ether are employed. Of the methods of the second group, those of Dvorkovitch and of Domergue and Nicolas give satisfactory results, and may be employed when time does not allow the use of the more accurate, but tedious, processes of Herlant and Gorges. Since the complete desiccation of hydrated caffeine is somewhat troublesome,it is always preferable to weigh it after crystallisation from chloroform. i n order to obtain a pure product, it is necessary to use an alkali in the extraction, and magnesia is to be preferred to lime, since the latter, in presence of water at looo, causes decomposition of caffeine with liberation of ammonia.Some other slight modifications in the working of the various processes are suggested. In the second paper, the authm describes a new process, which is carried out as follows. Ten grams of the powdered sample is extracted five times with boiling water, 200 C.C. of the latter being used for each extraction, Half of the liquid thus obtained is evaporated to dryness, the residue made into a paste with 1-2 C.C. of 10 per cent. sulphuric acid, and thoroughly extracted with boiling water. The aqueous extract is then either (1) evaporated to dryness with 20 grams of sand and 2 grams of magnesia, and the caffeine extracted by digestion with warm chloroform, or (2) made alkaline with ammonia and repeatedly agitated with chloroform in the cold.The best results are obtained by the second mode of procedure, and the test analyses quoted are very satisfactory, By GIULIO MOBPURGO (L’Orosi, 1897, 20, 397--403).-With the object of improving its appearance, coffee is frequently subjected t o the processes of (1) washing with N. L. Artacid Coloration of Coffee,ANALYTICAL CHEMISTRY. 136 water to which antiseptics, such as boric acid, are often added; (2) colouring with mixtures of various substances, of which the most com- monly used are graphite, bone black, soot, ultramarine, Berlin blue, lead chromate, iron tannate, yellow ochre, chalk, talc, and various aniline colours; (3) polishing with resin, wax, sandarach, talc, and similar substances.The colour of the sample and its appearance when examined with a lens often afford indications of the treatment to which it has been subjected. The presence of resin is shown by the turbidity produced on adding water to the cold alcoholic extract. Wax may be extracted by heating with alcohol to which a little ether has been added. For the detection of colouring matters, 50 grams of the coffee is boiled for half an hour, first with alcohol alone, and then with alcohol rendered slightly alkaline with potash, and after the filtrates have been allowed to stand for some hours, the sediment is examined by micro- chemical methods. The treatment with alkaline alcohol removes those colouring matters, such as carbon and lead chromate, which adhere more closely to the seed.The lighter particles of vegetable matter may be separated by treating the sediment with chloroform Method for Testing Natural and Artiflcial Organic Colours. By A. G. ROTA (Chem. Zed., 1898, ii, 437-442).-The author has tabulated a scheme for the detection of organic dyes and separation of the same. The chief reagent used is stannous chloride containing free hydro- chloric acid, which reduces some colouring matters, but does not affect others. The separation of the colours is effected by ether, either in acid, neutral, or alkaline solution. Wool is also used to By ITALO CEPPELLINI (L’orosi, 1898, 21,47-48).-About 1 gram of the suspected extract is dissolved in 6 C.C.of water acidified with 30 drops of concentrated sulphuric acid, and the solution vigorously shaken with 10 C.C. of oil of turpentine; after half an hour, it is again shaken and passed through a filter previously moistened with oil of turpentine. If the extract is pure, the aqueous layer acquires the colour of sherry, whilst the oily layer remains colourless. If, however, not less than 10 per cent. of elderberry juice is present, the oil of turpentine acquires a more or less intense yellowish-green tint, and the aqueous By LEO VIGNON (Compt, rend.,: 1808, 12’7, 369--372).-Silk free from gum absorbs tannin readily and completely from solutions of tanning materials at 50°, but does not absorb gallic acid, glucose, &c. About 5 grams of silk is neceslsary for 0.1 gram of tannin dissolved in 100 cx.of water. The tannin may be estimated by (a) the increase in the weight of the silk, ( 6 ) the difference in the proportion of solid matter in the solution before and after the treatment with silk, ( c ) by titration with permanganate. The last method is the most exact, but b is simple and expeditious, and gives results sufficiently exact for practical purposes. and allowing the liquid to stand for 24 hours. N. L. separate basic colours from acid compounds. 1,. DE I(. Detection of Elderberry Juice in Extract of Ergot. layer is of a fuller wine-red colour. N. L. Estimation of Tannin.136 ABSTRACTS OF CHEMICAL PAPERS, The silk is prepared by boiling 20 grams of raw silk for 30 minutes with a solution of 50 grams of white soap dissolved in 500 C.C. of water, this treatment being repeated and the silk then well washed. The tannin solution is prepared by treating in the usual way from 10 to 20 grams of the tanning material. One thousand C.C. of the solution should contain about 3 grams of tannin, Twenty-five C.C. of this solution is diluted to 250 c.c., and 100 C.C. of the diluted liquid is heated at 50’ for 5 hours, but not more, with 5 grams of the prepared silk. Tit.ration with permanganate and indigo, before and after the treatment with silk, is conducted in the usual way. The results with sumach and oak galls are practically identical with those obtained by precipitating the tannin with cat-gut or ammoniacal zinc acetate, and the method is more expeditious. The special reagent (silk) is very readily prepared and is practically constant in composi- tion. C. H. B. A New Proteid Reaction. By J. H. ELLIOTT (J. Physiol., 1898, 23, 296--300).-Dilute fsulphuric acid (1 to 5 of water) acting on protoids produces a bluish-violet coloration when allowed to con- centrate slowly. When the proteid matter is digested, the colour passes into the liquid; this shows a wide absorption band reaching from C to E or b. The colour disappears from sections when they are transferred from acid to water, alcohol, or saline solutions, and returns on placing th’em (even after 3 weeks) again in the acid, or in strong solutions of nitric or hydrochloric acids. Deposits of lardacein are shown very distinctly by this method. The test may be employed microchemically. W. D. H. Separation of Albumosee from Peptone. By PAUL M~LLER (Zeit. physiol. Chem., 1898, 26,48--55).-The method suggested, which is stated to have advantages over Kiihne’s ammonium sulphate process, is a modification of that originally introduced by Schmid t-Nulheim. To the solution, an equal volume of 30 per cent. ferric chloride solu- tion is added, and then alkali until the reaction is only feebly acid. The voluminous precipitate is filtered off, and to the filtrate a pinch or two of zinc carbonate is added, the mixture shaken and again filtered. The final filtrate is free from albumoses. If leucine and tyrosine are present, small quantities of these sub- stances are carried down with the precipitate. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8997605121

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

137 General and Physical Chemistry. Dissociation-spectra of Fused Chlorides, Bromides, and Iodides. By ARNAUD DE GRAMONT (Bull. Soc. Chim., 1897, [iii], 17, 897-898,899-900,900-901).-The author has examined the spark- spectra of the chlorides of sodium, lithium, potassium, rubidium, cadmium, and zinc, the bromides of sodium, potassium, calcium, and zinc, and the iodides of sodium, potassium, and cadmium, and finds that they exhibit the chief lines of the spark-spectrum of the halogen present ; detailed measurements are given in the paper, and the method can be used for the detection of minute traces of the halogens. T. M. L. Single Differences of Potential. By HECTOR R. CARVETH (J. Physical Chem., 1898, 2, 289--321).-Tbe author has determined a number of single differences of potential by the dropping mercury method, attention being directed more especially t o the measurement of metals in solutions of their salts ; i n opposition t o the results of Paschen, i t would appear that both anion and cation have an effect.With different concentrations of the same electrolyte, the values obtained apparently follow in regular order. Cases in which the dropping electrode gives values corresponding with the polarisation method have been observed, as well as cases in which a difference in the values occurs. The solution pressure formula of Nernst was tesked, and found to hold approximately in a few cases, whilst in the great majority of cases it failed. The author concludes that the values given by the drop electrodes are not true single differences of potential.H. C . By DOUGLAS MCINTOSH (J. Physical Chem., 1898,2, 273--288).-The author, after attempting to determine the transference numbers for hydrogen in different acids by the Helmholtz method, using gas electrodes, comes to the conclu- sion that the method is not applicable to gas cells. It is probable that the source of error is to be found in the solubility of the electrode in the electrolytic solution. The results indicate that the transference number for hydrogen in hydrochloric acid does not change with the dilution between normal and thousandth-normal solutions. Transference Number for Hydrogen. H. C. Influence of Pressure on the Electrical Conductivity of Solutions. By A. BOGOJAWLENSKY and GUSTAV TAMMANN (Zeit. physikal. Clbem., 1898, 27, 457-473).-The influence of pressure is due t o the changes produced in (1) volume, (2) viscosity, (3) degree of dis- sociation, (4) dissociation of the solvent, and is given by the equation I / X x dX/dp = 112) x dvldp + l / v x dvldp -I- l / a x daJdp i- X,/Xa, x da,ldp.The last term may be neglected if the number of ions of the solute far exceeds that of the solvent ions. The volume changes of aqueous s o h tions have been calculated in previous papers, and the first partial value is obtainable. From Cohen’s determinations of the effect of pressure on VOL. LXXVI. ii. 10138 ABSTRACTS OF CHEMICAL PAPERS. viscosity, the values l/q x dv/cZp are also obtainable for sodium chloride solutions. The effect of pressure on the dissociation constant is given by the expression d log.ii/dp= - Av/lOOORT, where hv is the volume change (which must be expressed as a function of the pressure) conse- quent on the dissociation of a gram-molecule of the solute. The values l / a x da/dp are hence obtained, and from the sum of the three partial values the total pressure effects are calculated for pressures of 100, 200, 300, 400, and 500 atmospheres. The variation of the pressure effect with varying degrees of dissociation is seen in the case of the chlorinated acetic acids; the valuesfor l / X x dh/dp decrease with incrsase of dissociation, and are in all cases in good accord with the values found. I n the cases of aqueous solutions of ammonia and water, the volume changes consequent on dissociation are unusually great, hence also the conductivity change due to pressure; in the case of ammo- niacal solutions the found and calculated values are compared, with fair agreement.For very dilute solutions, the dissociation of the solvent becomes important, and this is allowed for in the case of dilute solutions (u = 500 to v = 50,000) of hydrogen and sodium chlorides ; the pressure effect is found to increase rapidly with dilution, but not as rapidly as calculated. The apparatus employed for the determination of conductivity at high pressures is described, and the results oE the determinations are given, the compounds examined being solutions of acetic, monochloracetic, dichloracetic, trichloracetic, phosphoric, citric, tartaric, benzenesulphonic, and hydroferrocyanic acids, sodium phos- phate, tartrate, and chloride, potassium citrate and ferrocyanide, and ammonia.L. M. J. Thermal Equilibrium in Electrolysis. By DONATO TOMMASI (J. Physical Chem., 1898, 2, 229--232).-A compound capable of being oxidised or reduced is submitted to the simultaneous action of an oxidising and a reducing agent. This is eEected by making use of the mixture of hydrogen and oxygen obtained by the electrolysis of water containing in solution the compound under examination. The platinum electrodes are brought as closely together as possible, the liquid is frequently stirred, and the current reversed occasionally. The following results were obtained. Initial compound. Nitric acid. Potassium nitrate. Sodium nitrate. Potassium nitrite. Potassium chlorate. Arsenic acid. Potassium arsena te.Arsenious acid. Potassium arsenite. Ferrous sulphate. Ferric sulphate. Final compound. Ammonia and nitrite. 9 9 ?¶ 9 9 Y, Ammonia. Perchlorate. No change. Arsenic acid. Arsenate. Partial oxidation. Partial reduction. 7 9 9 , From these experiments, the author deduces the following laws. 1. When a substance is submitted to two equal and contraryGENERAL AND PHYSICAL CHEMISTRY. 139 chemical actions, the reaction which develops the most heat will take place in preference, provided always that it can begin. 2. Of two chemical actions, that which requires less heat t o start it will always take place in preference, even if it develops less heat than the other action. H. C. Magnetic Rotation in Salt Solutions. By S. OPPENHEIMEB (Zeit. physikal. Chem., 1898, 27, 447--456).-1t has been shown by Perkin (Trans., 1889, 680; 1894, 20) and by Schonrock (Abstr., 1895, ii, 196) that the magnetic rotation of solutions of hydrogen chloride decreases with increase of concentration, and the author, therefore, endeavoured to determine whether the same effect could be observed with salt solutions if sufficiently sensitive instruments were used.The half-shadow apparatus used by Schonrock with a polarisa- tion tube 80 cm. long was employed, and solutions of sodium and potassium chlorides and bromides, cadmium chloride, and acetic acid were examined, but i n no case was any effect of concentration apparent. L. M. J. Constant Temperature Device. By HAMILTON P. CADY (J. Physical CJLern., 1598, 2, 242-244).-1n order to keep a constant temperature in an apparatus which cannot be immersed in a bath, water having a constant temperature may be circulated round the apparatus by the device illustrated in the cut.A is an ordinary ~b-mm. glass funnel mounted on a glass rod and running in the bearings of a Witt stirrer. F is a large water-bath kept a t the desired tempera- ture. C is the appa- ratus through which - - - - - _ - - - - - - - - . . ._._#::.:-I:- ~ ~ ~ e w a $ ~ s s ! ~ h ~ ~ ~ kiy 1 - - ~ - . ~ ~ ~ . .. . - -f connects C and F, so that the water comes to the same level in both vessels. A is ad- iusted so that the top hf the funnel comes just at the surface of the water in F. The siphon E connects the interior of the funnel with C, so that when equilibrium is reached the level of the liquid in A, F, and C is the same.If A is caused to rotate, the water in A mill be thrown out, and the level of the liquid will be lower than that in C. This will cause water to flow through E from C to A, and back again through D fromF to C. This will set up a circulation of water through C which will continue as long as A is rotated. Experimenting at Low Temperatures. By WALTEIER HEMPEL (Bev., 1898, 31, 2993-2997).-A test-tube 4 cm. wide was placed in a beaker 13 cm. wide, and the intermediate space packed with some H. C. 10-2240 ABSTRACTS OF CHEMICAL PAPERS. non-conducting material. This apparatus was compared with a Dewar's tube, of which the inner vessel had the same dimensions as the test-tube ; equal quantities of solid carbonic anhydride and ether were placed in each, and the temperature read a t intervals by means of an electropyrometer.It was found that, with a packing either of eider-down or of pure wool dried a t 100°, cooling was prevented almost as well as with the best-exhausted Dewar's tubes, and better than with the ordinary commercial ones. A packing of dry wool should, then, be placed round vessels in which ice or a freezing-mixture is kept, and filters in which it is desired to filter at a low tempera- ture should be similarly packed; the filter may be a double one, with the space between filled with solid carbonic anhydride and ether. For collecting solid carbonic anhydride, a cardboard funnel is re- commended, with a very short neck closed with a cork, and an annular strip of linen fastened round the edge of the funnel so as t o form a bag.The cylinder of liquid anhydride is placed mouth downwards in a slanting position; the linen bag is grasped with the gloved hand and gathered round the mouth of the cylinder, which is then opened ; solid anhydride collects in the bag, and may be shaken down through the neck into a suitable receptacle. From 1 kilo. of the liquid anhydride, 270-300 grams of the solid can be obtained ; at the prices current in Germany for the liquid, the solid thus costs 2s. per kilo. The lowest temperature (about -79") is attained by mixing the solid anhydride with so much ether that not too stiff a magma is formed; the temperature then remains constant so long as solid particles are still present. C. F. B. By E. F. THAYER (J. PhysicaE Chem., 1898, 2, 382-384).-The following table gives the percentage of benzene in the solutions examined, the boiling points, and the corresponding barometric readings in millimetres of Boiling Point Curve for Benzene and Alcohol.mercury. Benzene. Temp. Bar. 1 oo*oo 79.5O 736.9 95.18 70.8 728.5 93-87 69.6 728.5 92.64 68.8 728-5 85.28 67.6 736.3 76.00 67.1 736.0 Benzene. Temp. Bar. 67-15 66.9" 735.8 59.21 67.1 735.3 44.45 67.5 732.9 35.1 1 68.4 732.9 27.14 69.8 732.9 15.86 72-1 732.9 The first addition of alcohol to benzene lowers the boiling point a great deal ; then comes a nearly horizontal curve followed by a rise at the alcohol end which is somewhat less steep than at the benzene end. Boiling Point of Mixed Solutions. I. By THEODORE W. RICHARDS and WENTWORTH LEWIS HARRINGTON (Zeit.phylsihE. Chem., 1898,27, 421-425).-By the addition of a gram-molecule of cadmium oxnlate to 10 litres of water containing a slight excess of hydrogen chloride, the boiling point is depressed to the extent of 0*101". This is explained by the formation of two almost undissociaked molecules, psmely, cadmium chloride and oxalic acid, thus 2H' + 2C1' + CdC,O = H. C.GENERAL AND PHYSICAL CHEMISTRY. 141 LiNO, 47 34 30 - CdCl, + H,C20,. From the known dissociation of the hydrochloric acid, on the assumption that there is no dissociation in the products, the number of molecules removed is calculated as 1.6, hence the depres- sion = 0.083', whilst from the known effects of hydrochloric acid, cadmium chloride, and oxalic acid on the boiling point of water, the depression is calculated as 0*093', both results being lower than t h a t actually obtained.Analogous results were obtained by the use of cadmium citrate, the calculated depression being 0.364', whilst the value found was 0.434'. By CLARENCE M. C. GORDON, L. J. HENDERSON, and W. L. HARRINGITON (ibid., 4%-428).-Experiments similar t o the pre- ceding were made with sodium chloride and cadmium sulphate ; in this case, also, a depression of the boiling point occurs, owing to the dissociation of sodium sulphate being less than that of sodium chloride. The greatest possible decrease of molecular groups is given by CdSO, + 2( 1 - a)NaCI+ 2aNa' + 2aCl' = CdCl, + Na,SO,, that is, = 2a. From the known dissociation of sodium chloride, the maximum depressions (that is, for undissociated sodium sulphate) in the cases examined are 0.081' and O*OSS', whilst those found were 0.093' and 0.060'.From this, it appears that either the accepted dissociation values are incorrect, or that even in dilute solutions of cadmium salts double molecules occur. 11. L. M. J. NaNO, KNOy 53 66 45'5 54 -5 14 56 - - Study of a Three-Component System. By HECTOR R. CARVETH (J. Phpsicatl Chern., 1898, 2, 209--22S).-Numerous determinations were made of the freezing points of mixtures of the nitrates of lithium, sodium, and potassium, the results being plotted on the triangular diagram (Abstr., 1893, ii, 65). The composition and melting points of the three binary and the ternary eutectic mixtures are approxi- mately as follows. M. p. 204' 129 218 120 H.C. Thermochemistry of Sodium Suboxide and Peroxide. By ROBERT DE FORCRAND (Compt. ?-end., 1898, 127, 5 14-5 16).-The reaction Na30 sol. + 2H,O liq. + Aq = 3NaOH diss. + H gas develops + 97.78 Cal., hence Na, sol. + 0 gas = Na30 sol. deveidps + 101.57 Cal. or +67.62 Gal. for Na,. The reaction, Na,O, sol. + 2HC1 diss. = 2NaCl diss. + H,O, diss. develops + 41 -81 Cal., hence Na, sol. + 0, gas = Na,O, sol. develops +119*79 Cal. The heat of formation of the monoxide is about 100 Cal. The rapidity of the action of water and other reagents on tha142 ABSTRACTS OF C!HEMICAL PAPERS. suboxide is partly attributable t o the large area of its surface resulting from its porous character. Heats of Formation of Cyanic Acid and Carbamide. By MARCELLIN P. E.BERTHELOT (Ann. Chim. Phys., 1897, [vii], 11, 145--149).-This paper gives details of thermochemical determina- tions previously recorded (Abstr., 1897, ii, '7). Thermochemistry of Formaldehyde. By MARCEL DEL~PINE (Bull. Xoc. Chim., 1897, [ iii], 17, 849-859. Compare Abstr., 1897, ii, 359).-The author recognises two polymeric modifications of formalde- hyde, namely,trioxymethylene or metaformaldehyde, (CH,O),, produced by the polymerisation of anhydrous formaldehyde, and by the action of dehydrating agents on the concentrated aqueous solution ; and para- formaldehyde produced OD evaporating the aqueous solution. Para- formaldehyde is distinguished from metaformaldehyde by its solubility in water ; it is invariably hydrated (compare Losekann, Abstr., 1892, 423), and is regarded by the author as containing a number of com- pounds of the series (CR,O),,H,O, of which methylene glycol is the first member.It is now shown that the heat of formation of metaform- aldehyde is identical with that of formaldehyde in aqueous solution, namely, 40.4 Gal. ; as the heat of formation of the anhydrous substance is only 25.4 Cal. there is a development of heat = 15.0 Cal. in the poly- merisation, which is, therefore, a strongly exothermic action. The dis- solution of metaformaldehyde, which takes place when it is heated with water a t 130' in sealed tubes, is a n isothermic action, but two exothermic changes also occur, 2CH20 aq. + H20 liq. = CH,, OH aq. + HGOOH aq. + 2 x 8.1 Cal. 3CH,O aq. + H20 liq. = 2CH3,0H aq. + CO, gas for this reason, formaldehyde is a methylating agent of greater power than methylic aleohol.The heat of formation of a specimen of para- formaldehyde, of the composition CH,O,QH,O was found t o be 42.5 Cnl. ; this value is 2 units greater than that of metaformaldebyde, and serves t o explain the fact that the latter is only produced from the aqueous solution in presence of dehydrating agents. The action of potash on aqueous formaldehyde does not lead t o the production of any definite compound, although heat is developed, especially in concentrated solution. The development of heat depends only on the final, and not on the initial, concentration of the solution ; thus, for molecular proportions, CH,O aq. ( 500 c.c.)+KOH aq. ( 500 c.c.) gave +3.10 Cal. CH,O aq. ( 100 c.c.)+KOH aq.( 900 c.c.) ,, +3*13 ,, CH,O aq. (1000 c.c.) + KOH aq. (1000 c.c.) ,, + 2-54 ,, CH,O aq. ( 100 c.c.) + KOH aq. (1900 c.c.) ,, + 2-61 ,, C. H. B. G. T. M. + 2 x 11.0 ,, { { The heat of dilution of the potash solution is insignificant, and that of the formaldehyde must, therefore, be equally small ; as, however, a sudden development of heat occurs on diluting a concentrated solution, the slow absorption of heat which follows must be of equal magnitude ; for the first phase, CH20 aq. (100 c.c.) + H,O (900 c.c.) gave +0*45 Cnl. The slow absorption of heat corresponds with theGENERAL AND PHYSICAL CHEMISTRY. 143 slow decrease of molecular weight observed by Grossman and Esche- weiler (Abstr., 1890, 1092), and, in the opinion of the author, is due t o the gradual dissociation of the paraformaldehyde in the solution.The first development of heat he regards as due to the hydration of monomolecular formaldehyde, and by cooling a 30 per cent. solution t o -4O", he was able to separate a solid hydrate, which melted between - 30" and - 254 and had approximately the composition, CHZO + 3HzO. Thermochemistry of Isoamylmalonic Acid. By GUSTATE MASSOL (Compt. rend., 1898, 127, 526-528).-Isoamylmalonic acid, prepared by the action of isoamylic iodide on ethylic sodiomalonate and crystallised from ether, forms anhydrous crystals which melt a t 98' ; heat of dissolution, - 2-50 Cal. ; heat of neutralisation by potas- sium hydroxide, 1st equivalent + 13-90 Gal.; 2nd equivalent + 13-95 ; total + 27.85 Cal. Heat of dissolution of the anhydrous potassium salt + 6-44 Cal., hence C,H,,O, sol.+ 2KOH sol. 1 C,H,,O,K sol. + 2H,O sol. develops + 46.69 Gal. The corres- ponding value for suberic acid is + 44.76 Cal., hence the value of the acidic function is higher for isoamylmalonic acid than for suberic acid, a result which affords additional evidence in support of the conclusion previously arrived at that in the oxalic series the thermal value of the acidic function of the normal acid is lower than the corresponding value for its isomerides, and is always related to the degree of separation of the two carboxyl groups. C. H. B. Solution of Solids and Liquids in Gases. By P. VILLARD (Chem. News, 1898, '78, 297-298, 309-310. Compare Hannay and Hogarth, Abstr., 1880, 210; Pictet, 1895, ii, 201, and Villard, ibid., 255)-At a temperature of 17", gasesunder pressure take up considerable quantities of liquids and solids.Oxygen under 4 atmospheres absorbs an increased amount of bromine, which is still more marked at 50,100, or 200 atmospheres. A t 100 atmospheres, the density of the sus- pended bromine appears to be almost three times that of a saturated bromine atmosphere in a vacuum ; the colour of the atmosphere under pressure is deeper than when no compression is employed, and when the pressure is released the bromine is deposited, Iodine also volati- lises in compressed oxygen, but to a less extent than bromine, whilst air and hydrogen under pressure also sustain increased quantities of bromine. Methane is very active in thisdirection; ethylic chloride at 180 atmospheres dissolves in 5 or 6 times its volume of methane, whilst at 200 atmospheres the two become miscible in any proportion and the surface of separation between the gas and the liquid disappears.The same phenomenon takes place with carbon bisulphide under about 550 atmospheres at the ordinary temperature, and under 250 atmospheres at 150'. Iodine, camphor, and paraffin also volatilise in Compressed methane, and on releasing the pressure the iodine and camphor crystal- lise onthe inside of the tube, and the paraffin falls out in brilliant flakes. Ethylene under 300 atmospheres pressure takes up sufficient iodine t o colour it a very deep violet, but in time the colour disappears as combination ensues. Compressed ethylene also dissolves paraffin, T. M. L.144 ABSTRACTS OF CHEMICAL PAPERS.stenric acid, and camphor ; the latter volatilises readily under small pressure, and when the pressure is increased to 150 atmospheres, the unvolatilised camphor becomes liquid, but continues volatilising as the pressure is further increased ; on releasing the pressure, the same phenomena ensue, but in the reverse order. Compressed nitrous oxide takes up bromine t o the same extent a t 20 atmospheres as oxygen at 40 and compressed carbonic anhydride takes up iodine, but the pressures that can be obtained are limited by the liquefaction of the gas. Critical point phenomena are observed in these experiments either when the temperature is raised and the pressure kept constant or vice uersd. It is suggested that these observations may find applica- tion for the distillation of substances that are decomposed by heat ; when taking up under pressure in a suitable gaseous medium and redepositing by relieving the pressure might in some cases prove more advantageous than distilling in a vacuum.Solution Pressure of some Haloid Salts. By PAUL ROHLAND (Zeit. ccnorg. Chem., 1898, 18, 327-330.)-The solubility of the haloid salts of the alkali metals in alcohols decreases with rising molecular weight of the alcohol, and increases with rising molecular weight of the salt, the chlorides having the lowest and the iodides the greatest solubilities. In the case of the haloid salts of cadmium, copper, silver, mercury, and lead, the solubility also decreases with the rising molecular weight of the alcohol, but the iodides in these cases have the smallest and the chlorides the greatest solubilities.D. A. L. H. C. Some Reactions in Methylic Alcohol and Acetone. By PAUL ROHLAND (Zeit. onorg. Chem., 1898, 18, 322-326).-Methglic alcohol occupies a position, as a solvent, between that of water and ethylic alcohol. Ionisation takes place to a greater extent than in ethylic alcohol, and is in some cases even equal to that in water; reactions, therefore, usually take place in methylic alcohol as in water. I n acetone, ionisation does not take place to the same extent., and the reactions are, therefore, frequently modified. Mercuric iodide is far more soluble in acetone than in water, and potassium chloride is much less soluble ; consequently, in dilute solution in acetone, potass- ium iodide and mercuric chloride give a precipitate of potassium chloride.For similar reasons, potassium iodide and cadmium bromide Benzene, Acetic Acid, and Water. By JOHN WADDELL (J. Physical Chem., 1898, 2, 233--241).-The distribution ratio of acetic acid in benzene and water as solvents was studied; an exponential formula of the general form x$n=const., where x and y refer to the amounts of benzene and water in a constant quantity of acetic acid, is only found to give an approximate representation of the results. The ratio of acetic acid in water to acetic acid in benzene increases indefinitely with increasing dilution. The percentage of acetic acid in the aqueous phase passes through a maximum. The ratio of benzene to water in the more dense phase is greater than nnity over a portion of the isothermal, even when the concentrations are expressed in reacting weights. H.C. give a precipitate of potassium bromide. H. c.GENERAL AND PHYSICAL CHEMISTRY. 145 Equilibria of Stereoisomerides. By WILDER D. BANCROFT (J. Physical Chem., 1898, 2, 143-158, and 245--255).--The theory of permanent changes developed by Duhem (Abstr., 1897, ii, 439), and applied by him to explain the behaviour of supercooled sulphur, is extended by the author to organic compounds which exist in isomeric modifications, such as stilbene dichlorido, acetaldoxime, benzaldoxime, and others. In general, we have in these cases two modifications in equilibrium in the liquid phase, the presence of the one lowering the freezing point of the other.If we take into account the element of time, equilibrium may be reached practically instantaneously, or in a measurable length of time, or the system will appear to contain two components provided we act rapidly enough, and one component provided we act slowly. If a solid substance melts at one temperature and freezes at another, this is proof positive of the existence of two liquid modifications, provided no decomposition takes place. If the more fusible of two solid modifications is the more stable, we are also justified in deducing the existence of two liquid modifications, although the converse is not necessarily true, and if the less fusible of two solid modifications is the more stable, it does not follow that only one liquid modification is possible.A discussion is also given of the conditions under which a reversal of stability does and does not take place, on adding another component which forms no compounds with the two modifications. By PAUL CALAME (Zed. physikal. Chem., 1898,27, 401--420).-The degrees of dissociation of a number of metallic salts of organic acids were determined a t various dilutions, the ratio of the actual to thenormal molecular depression being given. For formates and acetates, the values are almost identical; in the cases of zinc formate and acetate, and of lead acetate, the increase of dissociation with dilution is greater than for the other salts, so that the curves for these three compounds cut other curves. In the case of the acetates of calcium, strontium, and barium there is an apparent increase of dissociation with increase of concentration from N/&o N/2.For copper malate, the ratio is less than unity so that, probably, complex molecules are present. The concentrations of the copper ionsjn solutions of copper malate, citrate, glycerate, and salicylate were also calculated by the determination of the E.M.F. of copper chains containing these salts ; the existence of complex molecules was indicated in the case of the three first salts, but not in the case of the salicylate,results in accord with the cryoscopic observations (Kahlenberg, Abstr., 1896, ii, 6). Magnesium fumarate was found t o be more highly dissociated than magnesium maleate, a result which is in accord with Ostwald’s law concerning the dissocia- tion of dibasic acids (Abstr., 1892, 1145).Molecular Weights of Liquids. By CLARENCE L. SPEYERS ( J . Physical Chem., 1898, 2, 347-361 and 362-363).-The author applies the equation nl/(.n2 + nl) = ( p -p’)/p, in which nl is the number of molecules of one constituent of a homogeneous mixture, m2, the number of molecules of the other constituent, p , the vapour pressure in the pure state of that constituent to which .n2 refers, aud p‘, the H. C. Dissociation of Polyvalent Salts. L. M. J.146 ABSTRACTS OF CHEMICAL PAPERS. vapo~ur pressure of the same constituent after the other constituent has been mixed with it, to the experimental results obtained by Linebnrger and Raoult. H e concludes that where discrepancies al*ise, these can be accounted for by association or dissociation of the constituents as given by the fundamental equation.H e also shows that when two liquids are not miscible in all proportions, the separa- tion of a second phase shows the sudden formation of more complex molecules on the part of one constituent. By ALEXIUS VON SIGMOND (Zeit. physikal. Chcm., 1898, 27, 385-400).-The velocity of hydrolysis of maltose was determined, hydrochloric acid being employed as the hydrolytic agent ; the reaction was found to be of the first order, as i n the case of sugar inversion, but the velocity increases slightly with the maltose concentration. The effect of rise of temperature was examined, and it was found that the ex- ponential formula of Arrhenius (Abstr., 1889, 1103) applies here also, but the constant A of the formula being greater for maltose than for cane-sugar, the temperature effect is more marked in this case.The catalytic effects of hydrochloric, sulphuric, and oxalic acids were found to be in the ratio 100 : 40.5 : 14.1, whilst for cane- sugar the values are 100 : 53.7 : 18.2, so that, although the order is the same, yet the velocity is dependent, not only on the acid, but also on the sugar employed. The velocity-constants for the hydrolysis of cane-sugar and maltose by acetic acid were compared at 69*24O, the ratio being found to be 1133, but, owing to the different effects of temperature, this ratio would not remain constant for different temperatures. L. M. J. Catalytic Action of Platinum Black. By ALEXANDER DE HEMPTINNE (Zeit. physikal. C'hem. , 1898, 27, 429-441).-Mond7 Ramsay, and Shields (Abstr., 1898, ii, 599) have shown that the formation of a compound of platinum and hydrogen during the occlusion of the gas is very doubtful, and the author hoped to solve the question by the examination of the phenomena of occlusion at very low temperatures, since it seems probable that, if due t o the formation of a compound, the occlusion would then be greatly diminished.The absorption of hydrogen by carbon, which appears to be purely mechanical, was found to be far greater at -78' than a t +15O, but in the case of platinum the reverse obtained, the absorption i n all the experiments being greater at the higher tem- perature, whilst, if the absorption tube is allowed t o slowly regain the higher temperature, a marked absorption of the gas occurs at about -40'.Freshly prepared platinum black possesses a very great absorptive power, even at the temperature of liquid air, so t h a t at - l Y O o it induces the combination of oxygen and hydrogen. The absorption of carbonic oxide is completely analogous to that of hydrogen, and, according to Harbeck and Lunge, a definite compound of platinum and the gas exists (Abstr., 1898, ii, 166). For palladium and hydrogen, different results were obtained, the absorption being greater at the low temperature, although with carbonic oxide the results are similar t o those obtained in the case of platinum. It was H. C. Velocity of Hydrolysis of Maltose.GENERAL AND PHYSICAT, CHEMISTRY. 147 here noticed, also, that palladium which has been in equilibrium with carbonic oxide is in some respects altered, and has lost its power of absorbing hydrogen until a temperature of about -20' is reached, when a sudden, great absorption occurs, The explanation of the phenomena must be deferred, but in the case of platinum and hydrogen, the formation of a compound appears t o be indicated.Catalytic Action in the Oxidation of Iodide by Bromic Acid. By NIKOLAI SCHILOPF (Zeit. physikal. Chem., 1898, 27, 51 3-518).- Catalytic actions in the above reaction were investigated for a large number of acids, salts, and organic compounds; acids usually cause acceleration, salts either acceleration or retardation, whilst neutral organic compounds have no effect. The greatest accelerative effects were those of potassium chromate and dichromate, ferrous and ferric salts, and pyrogallol, whilst sodium phosphite and snlphite, nitro- benzene, and resorcinol produced the greatest retardation.If the acceleration be measured by the expression l / t , - l/t,,, where tz and to are the times required for the same amount of oxidation in the pre- sence and absence respectively of the catalytic agent, it is found that in the case of potassium molybdate and chromate, the acceleration is a linear function of the concentration for very low concentrations only. Reaction between Potassium Persulphate and Potassium Iodide ; Catalysis in the same Reaction. By THOMAS S. PRICE (Zeit. physikal. Chem., 1898, 27, 474-512).-The reaction may be represented thus : S,O," + 21' = 250," + I,, and hence appears t o be of the third order.The velocity constants as calculated for reactions of both second and third order were obtained; those for the second order are slightly more constant, but the results obtained thus are un- trustworthy. The order may, however, be calculated by the expression n, = log(dc,/d~,~dc,/d6,)/logcl/c2, where dc/d6 is the rate of change of concentration at the concentration c; the value n = 2.4 is so obtained, again an uncertain result. If the time necessary for any given frac- tional change be found for any initial concentration A, then in a reaction of the first order t = constant, for the second order At =constant, &c. The values of t, At, and,A2t are, therefore, compared for a fractional change of one-fourth, and it is seen that the values At increase and those of A2t decrease with dilution, so that definite results are not obtained.If the reaction is of the second order, however, equivalent changes in the concentration of both compounds should produce equal effects, and this being found to be the case, the author considers the reaction to be of the second order. This result may indicate the molecular formula KSO,, which is not in accord with former work (Abstr., 1893, ii, 572), or that the order of the reaction depends, not on the number of mole- cules, but of compounds reacting. The author does not, however, discuss either these or any other possible explanations. Various salts were found t o have a catalytic effect on the reaction, that of disso- ciated iron and copper salts being very marked, I n the case of ferrous and copper sulphates, the acceleration (measured by the quantity l / t n - l/to) was found to be proportional to the concentration. Salts of nickel and cobalt cause a slight acceleration, but chromic acid, L.M. J. L. M. J.148 ABSTRACTS OF CHEMICAL PAPERS. potassium dichromate, manganese sulphate, sodium nitrite, zinc sul- phate, magnesium sulphate, and potassium sulphate were inactive. Mixtures of ferrous and copper sulphates were found to cause an acceleration almost double of that calculated additively, so that the catalytic effect of each is increased by the presence of the other. Inactive compounds, such as zinc sulphate, have no effect on the catalysis caused by copper sulphate, but decrease the influence of ferrous sulphate. The addition of acid, at first causes a decrease in the catalytic effect of copper sulphate, but a constant value is soon reached.L. M. J. Atomic Weight of Tellurium in Relation to the Multiple Proportions of the Atomic Weights of other Simple Sub- stances. By HENRY WILDE (Compt. rend., 1898, 127, 613-616).- This paper is largely controversial, and does not lend itself to abstraction. W. A. D. Position of Tellurium and Iodine in the Periodic System. By HENRY WILDE (Compt. rend., 1898, 127, 616-618).-Metzner (Abstr., 1898, ii, 572) has recently obtained results which indicate that the atomic weight of tellurium (128) is greater than that of iodine; this, it is maintained, necessitates a change in position of these elements in the periodic system, and involves a contradiction of the accuracy of the latter. It is contended that if the order of the atomic weights of the elements is exactly followed, the law of period- icity of their properties ceases to be valid ; also, that MendelBefi’s success in predicting the existence of gallium, scandium, and germanium was simply a consequence of Dumas’ classification of the elements in families and to the relations shown to exist between the ‘‘ equivalents ” of the elements of a family. Boron, judging from its properties, should belong to the group containing phosphorus and vanadium (compare Etard, Abstr., 1881, 20), and should not be considered as the analogue of aluminium and gallium, as required by Mendelheff’s classification, whilst the position of gold, mercury, and lead is also looked on as abnormal. W. A. D. By UARL PULFRICH (Chem. Centr., 1898, i, 763 ; from Zeit. Instrumentk., 18, No. 2)-In this apparatus, a round sheet of asbestos is held horizontally above a Bunsen burner by means of a clamp, which slides on a vertical rod attached t o the burner. The sheet can be rotated so that the flame of the burner passes through one of several round holes, about 1 cm. wide, which are cut near the periphery of the sheet. By heaping the illuminating salt, preferably sodium nitrate, on account of its low melting point, or sodium bromide, which gives a more brilliant light, round the hole, a luminous flame may be maintained for a long time. The shape of the flame may be altered by changing the form of the hole. The apparatus, fitted also with a detachable carrier for platinum wires, is made by C. Desaga, in Heidelberg. Laboratory Sodium Burner. E. W. W.

ISSN:0368-1769    

DOI:10.1039/CA8997605137

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 149 Inorganic Chemistry. Presence of Free Hydrogen in the Atmosphere, By ARMAND GAUTIER (Compt. rend., 1898, 127, 693--694).-The air in the neigh- bourhood of towns contains variable quantities of combustible carbon compounds, only minute traces of which can be detected in the atmo- sphere of mountainous regions, and in sea air. On the other hand, pure air contains a small amount of free hydrogen, the proportion varying from 11 to 18 C.C. per 100 litres. Decomposition of Hydrogen Peroxide by Silver Oxide. By MARCELLIN P. E. BERTHELOT (Ann. Clzim. Phys., 1897, [vii] 11, 217-222).-An indefinite amount of hydrogen peroxide may be decomposed by a small quantity of silver oxide, the whole of the oxygen evolved being furnished by the peroxide, whilst the silver oxide is itself changed into the sesquioxide, Ag40,, and free silver. If, however, the silver oxide is in excess, or if the solutions employed are not sufficiently dilute, or if excess of free alkali is present, then some oxygen is given up by the silver sesquioxide.I n employing this reaction for the estimation of hydrogen peroxide, i t is preferable to employ dilute solutions, to prepare the silver oxide beforehand, and to avoid excess of this reagent ; if the oxide be formed in the presence of the hydrogen peroxide by the action of caustic potash on silver nitrate, the heat evolved in this reaction promotes the decomposition of silver sesquioxide, which then gives off oxygen. G. T. M. G. T. M. Decomposition of Hydrogen Peroxide by Ammoniacal Silver Oxide.By MARCELLIN P. E. BERTRELOT (Ann. Chim. Phgs., 1897, [vii], 11, 223-230. Compare preceding abstract).-When hydrogen per- oxide is added to a suspension of ammoniacal silver oxide in water, a portion of the latter is reduced to metallic silver, and in so doing evolves oxygen ; with excess of peroxide, the reduction is almost com- plete, When a solution of ammoniacal silver nitrate is added t o hydrogen peroxide, the latter is decomposed, but only a slight reduc- tion of silver oxide takes place; when the peroxide is added t o the ammoniacal silver nitrate, four-fifths of the silver is precipitated in a crystalline form. When a solution of silver nitrate and hydrogen peroxide is added to ammonia, or vice versd, more or less silver is always precipitated, the amount depending on the order of mixing and the strength of the solutions.Noappreciable quantity of silver sesquioxide appears t o be formed when ammoniacal solutions are employed (compare previous abstract). Ammoniacal silver nitrate (1 mol.) rapidly decomposes excess of hydrogen peroxide (30 mols.), but with a smaller proportion the reaction is slow and incomplete. Alkaline solutions of potassium silver cyanide and sodium silver thiosulphate have no action on hydrogen peroxide ; ammoniacal silver150 ABSTRACTS OF CHEMICAL PAPERS. chloride causes a slow evolution of oxygen, which becomes more rapid when caustic potash is added, crystalline silver being deposited. G. T. M. By F. UIETZE (Chem. Centr,, 1898, i, 1094; from Pharm. Zed., 43, 290).- According to the author, when iodine is shaken with water at 15O, 1 part dissolves in 3750 parts of water, whilst by heating water and iodine together and then cooling to 1 5 O , 1 part of iodine is obtained in solution i n 3500 parts of water.The solubility of iodine increases with the temperature, and at 30° 1 part dissolves in 2200 parts of water. The German pharmacopain gives the solubility of iodine in water as 1 part in 5000, and that of bromine as 1 part in 30 parts of water. The latter, according to the author, is correct. Preparation of Hydrogen Chloride, Bromide, and Iodide for Laboratory Purposes. By AD. VANDENBERUHE (Chena. Centr., 1893, i, 916-917 ; from Mc&andbZ. naturw., 22, 35-36).-When concentrated sulphuric acid'is added drop by drop to strong hydro- chloric acid, the liberated gas usually contains free chlorine and ferric chloride which are derived from impurities in the hydrochloric acid ; according t o the author, the gas may be purified by adding ferrous sulphate to the hydrochloric acid, whereby the chlorine is retained and the ferric chloride reduced to ferrous chloride.In order t o test for free chlorine by means of starch paper, a solution of the gas must be used, as gaseous hydrogen chloride with starch paper always produces a blue coloration owing to oxidation of the acid. Pure hydrogen bromide and hydrogen iodide may be obtained in a constant stream by allowing a solution of the acid, prepared by means of phosphorus, to drop on to phosphoric anhydride. In the case of hydrogen iodide, the first portions of the gas contain free iodine, which can be removed by passing it through a solution of calcium iodide.The gases are dried by means of phosphoric anhydride. When prepared from organic substances, the gases always contain volatile organic compounds. Density and Molecular Weight of Ozone. By WILHELM STAEDEL (Bey., 1898, 31, 3143--3144).-The author points out that the assumption recently made by Ladenburg (this vol., ii, 18, 89) in his attempt to determine the density of ozone, that 1 molecule of iodine is liberatsd by 1 molecule of ozone is purely empirical, and in reality assumes the very quantity which is to be determined. The molecule of ozone may be expressed by the formula 0, + no, so that each molecule of ozone liberates n, molecules of iodine. Without independent information as to the value of n, it is impossible to deduce the density of ozone from the density of a mixture of this gas with oxygen, and an estimation of the amount of iodine liberated per unit volume of this mixture.By MAX GROUER (Ber., 1899, 31, 3174--3176).-In a recent paper by Ladenburg (this vol., ii, 18, 89) the density of a specimen of ozonised oxygen is given, and also the weight of iodine liberated by the gas when in Solubility of Iodine and Bromine in Water. E. W. W. E. W. W. A. H. Density and Molecular Weight of Ozone.INORGANIC CHEMISTRY. 151 contact with potassium iodide, and by means of these numbers, taken in conjunction with the fact that the gas undergoes no alteration in volume during the action referred to, an attempt is made to prove that the molecule of ozone is triatomic. The argument employed is fallacious, as the excess of the density of the ozonised gas over that of pure oxygen represents the weight of oxygen available for the liberation of the iodine, and the amount of the latter set free may be at once calculated if that excess be known, whatever be the molecular weight of the ozone concerned.By P. VILLARD (Ann. Chirn. Phys., 1897, [vii], 11, 289-394).-The author gives full details of the apparatus employed by him in obtaining the hydrates of the following gases, nitrous oxide, carbonic anhydride, acetylene, ethylene, methylic chloride, and sulphurous anhydride, and in investigating their physical properties (compare Abstr., 1888, 1020, 1241 ; 1890, 1386; 1895, i, 635; ii, 44, 497).The preparation of the hydrates of the following liquids, methylic iodide, ethylic chloride, bromide and iodide, methylenic chloride, chloroform, carbon tetrachloride, ethylidenic chloride, chlorethylene ethylenic chloride, and carbon bisulphide is described, and their pro- perties are compared with those of the hydrates of the gases. The influence of inert gases under pressure on the dissociation of these hydrates is fully discussed, Action of Sodammonium on Arsenic. By C. HUGOT (Compt. rend., 1898, 127, 553--555).-Whereas different products are ob- tained by the action of sodammonium on phosphorus in presence of liquefied ammonia, according as the phosphorus is present; in small quantity only or in excess (Abstr., 1896, ii, 20, and 1898, ii, 573), arsenic gives rise to only one deriuatiwe, AsNa,,NH,, under all con- ditions.I n the experiments described, both the arsenic and sodium were carefully purified by distillation, and were allowed to interact under the same conditions a6 were employed formerly i n the case of phosphorus (Zoc. cit.). A brick-red product was obtained, which con- tained traces of sodamide, and dissolved only sparingly in liquid ammonia; from the latter solution, small crystals of the compound were obtained. W. A. D. A. L. Hydrates of Gases. G. T. M. Compounds of Carbonic Anhydride with Water, Ethylic Ether, and Alcohols. By WALTHER HEMPEL and JOHANNES SEIDEL (Bey., 1898, 31, 299'7-3001).--8 weighed quantity of water was sealed in a tube with solid carbonic anhydride; at the ordinary temperature, the liquid formed two layers, the water underneath ; on cooling the tube slowly, crystals formed; these began to melt at about 8'.The tube was then cooled to -79", opened, furnished with a delivery tube dipping under mercury, and then allowed to rise in temperature ; carbonic anhydride was evolved furiously at first, but ceased t o come off at - 25" ; at - 2O, the evolution of gas again corn- menced, and the volume that came off between this temperature and + 20" corresponded with a composition of CO, + 8H,O for hhe crystals ; another experiment gave results corresponding with CO, + 9H,O.152 ABSTRACTS OF CHEMICAL PAPERS. Aqueous ether was saturated with solid carbonic anhydride, and the solid that formed was collected on a cooled filter; the loss of weight which it underwent up to 0" was taken as carbonic anhydride, and that a t 0-37" as ether, the rest being wator ; the error of such a n estimation is 2-3 per cent.It was found that the composition of the solid varied with the temperature a t which it had been collected. At a very low temperature, little else but carbonic anhydride was present; the amount of ether, and still more that of the water, increased with the temperature of isolation ; at - 50" the composition corresponded approximately to CO, + 4H,O + Et,O. With aqueous ethylic alcohol, a compound 1700, + 3EtOH +H,O was obtained. Monocarbonates of alkyl radicles, ROH + CO,, were obtained by weighing a quantity of the alcohol into a tube, distilling into it excess of liquid carbonic anhydride, and then allowing the excess t o evaporate and cooling the tube.The methyl, ethyl, tertiavy butyl, and amyl compounds melt at - 57 to - 60", - 61 to - 57", - 15 to - lo", and - 60" ; the mixture withpropylic alcohol separates, on cooling, into two layers which melt at - 56" and - 50" respectively. 0. F. B. Examination of Sodium Phosphate for Sodium Carbonate, and Reaction of Sodium Phosphate with Phenolphthalein. By BRUNNER [Wetzlar] (Zeit. anal. Chem., 1898, 37, 740-741)- The author cannot confirm Geissler's statement (Abstr , 1898, 458) that pure disodium hydrogen phosphate does not give a pink colour with phenolphthalein. The purest salt obtainable, recrystallised from a solution, which, after being strongly acidified with phosphoric acid, has been boiled for a long time to ensure the complete decomposition of carbonate, exhibits an alkaline reaction with both litmus and phenolphthalein even when its immediate mother liquor is feebly acid.M. J. S. Preparation of Lithium and Calcium Ammonias and Corresponding Amides. By HENRI MOISSAN (Conzpt. rerzd., 1898, 127, 685-693).-Dry ammonia gas combines with potassium, sodium, lithium, and calcium, and the superior limit of temperature at which this reaction occurs is - 20" for sodium, - 2" for potassium, 20' for calcium, and 70"for lithium; solid ammonia a t - 80" is without action on these metals. The sodium and potassium ammonias decompose at -20" and -2" respectively, whereas the calcium and lithium compounds are stable at ordinary temperatures. Lithium ammonia, Li,NH,, is obtained as a brownish-red solid when the liquid produced by the action of dry ammonia gas on lithium a t ordinary temperatures is rapidly heated t o 70"; if produced at lower temperatures, i t always contains more ammonia than that demanded by the above formula.When allowed t o remain for any length of time at the ordinary temperature, a solution of lithium ammonia in liquid ammonia yields lustrous, transparent crystals of lithamide. This reaction proceeds more rapidly at 65-80", and appears to be indepen- dent of the pressure. If solid lithium ammonia heated at 50" or 60" is exposed to the rapid action of the vacuum pump, ammonia is evolved and crystalline lithium is obtained ; i f the exhaustion is effected moreINORGANIC CHEMISTRY. 153 slowly at ordinary temperatures hydrogen is also evolved, and the residue consists of lithium and lithamide.Calcium ammonicc, Ca, 4NH,, is obtained as a broF nish-yellow solid with a bronzy reflex when crystallised calcium is treated with dry ammonia at ltjo-2O0; it evolves ammonia and hydrogen at ordinary temperatures, and is slowly converted into calcamide, Ca(NH,),. Both the lithium and calcium compounds take fire when exposed to air, and are far less soluble in liquid ammonia than the corresponding sodium compound. These substances are being investigated both by the author and by Giintz, the latter having independently examined the action of ammonia on calcium obtained from lime by reduction with magnesium. G.T. M. Properties of Calcium. By HENRI MOISSAN (Compt. rend., 1898, 127, 584--590).-Pure calcium, prepared by the author's method (Abstr., 1898, ii, 578), separates from fused sodium in hexagonal crystals, which have a sp.gr. = 1-85, and melt, in a vacuum, at 760' ; after solidifying, the metal is less malleable than sodium or potassium, and is somewhat brittle, showing a crystalline fracture. When free from nitride, its surface is brilliant, and silver white in colour. When exposed at a dull, red heat to a stream of hydrogen, the crystalline hgdride, CaHz, is formed, Contrary to Matthiessen's statement (Annalen, 1855, 93, 277), calcium is not acted on by chlorine at the ordinary temperature, but at 400' vigorous action occurs, calcium chloride being formed ; chlorine, however, readily combines at the ordinary temperature with calcium containing nitride, a fact which explains Matthiessen's result.The metal is not acted on by bromine or iodine at the ordinary temperature, but burns vigorouslywhen heated in the vapours of these elements. It ignites in oxygen at 300°, and burns brilliantly, the oxide formed being partially fused and volatilised. When calcium is gently warmed in air, it burns with brilliant scintil- lations ; at a dull red heat, a partially fused mass is obtained, which is decomposed by water, giving ammonia and calcium hydroxide; no peroxide appears to be formed. A t 400°, calcium and sulphur com- bine with incandescence, the sulphide obtained being a white powder, which dissolves in dilute hydrochloric acid without depositing sulphur. With selenium and tellurium, calcium also combines, whilst it burns with incandescence in the vapour of phosphorus, giving a product which decomposes water to form spontaneously inflammable hydrogen phosphide.Arsenic, at the temperature at which it sublimes, gives, with calcium, a dark-coloured, fused mass, which decomposes water, forming hydrogen arsenide and a black, insoluble powder ; calcium antimonide, however, prepared similarly, does not yield hydrogen antimonide when decomposed by water or dilute hydrochloric acid, but only a black, insoluble powder, and the same is true of the compounds of calcium and bismuth, although here hydrogen is also evolved. At a red heat, calcium combines vigorously with lamp-black, yielding only one carbide, CaC,, whatever proportions are employed ; calcium silicide, prepared by strongly heating a mixture of its constituent elements, is not decomposed by water, but dissolves in hydrochloric VOL.LXXVI. i. 11.154 ABSTRACTS OF CHEMICAL PAPERS. acid, slowly at the ordinary temperature, rapidly when heated, giving hydrogen, silicon hydride, and a large quantity of silicon, Calcium does not readily dissolve in potassium, but yields somewhat brittle alloys with magnesium, zinc, and nickel ; with tin, a crystalline alloy is obtained, which contains 3-82 per cent. of calcium, has a sp. gr. = 6.70, and decomposes water very slowly. With mercury, cal- cium combines a t the ordinary temperature to form a crystalline amalgam, heat being evolved ; although no calcium hydride is formed when this is distilled in an atmosphere of hydrogen a t 400°, the amal- gam is rapidly decomposed by nitrogen, under similar conditions, giving calcium nitride, and blackens when exposed to air at the ordi- nary temperature, owing to the fixation of both oxygen and nitrogen.At a red heat, calcium liberates the alkali metal from potassium or sodium chloride ; the corresponding iodides are, however, not affected. When calcium is fused with calcium iodide, a subiodide appears to be formed, which is also obtained in the form of red, transparent crystals, when calcium iodide is decomposed electrolytically ; calcium chloride, under the like conditions, behaves in a similar manner. Calcium is only slowly acted on by pure water at the ordinary tem- perature, hydrogen being evolved ; when heated in sulphurous anhy- dride, i t becomes incandescent, a complex change taking place. In nitric oxide, it burns brilliantly, giving rise to calcium oxide only, no nitride being formed.At a red heat, calcium combines with phos- phoric anhydride with exploRive violence; a t 600°, it reduces boric anhydride to boron, without the production of calcium boride (Moissan and Williams, Abstr., 1898, ii, 116), and a t a red heat decomposes silica, giving calcium silicide and a small quantity of silicon. When slowly heated in carbonic anhydride, it is only partially acted on, carbon, calcium oxide, and a small quantity of calcium carbide being formed ; when, however, the heating is rapid, the whole of the metal is converted into oxide and carbide. With carbonic oxide, the action is always incomplete, some carbon being liberated.Uranium sesqui- oxide, and titanic and vanadic acids are reduced, when heated with calcium, to lower oxides. Fuming nitric acid acts only very slowly on pure calcium ; when very slightly diluted, however, the action is rapid. Cold fuming sulphuric acid is immediately reduced by the metal, sulphur and sulphurous anhydride being formed, whilst sulphuric monhgdrate gives rise, in addition, to hydrogen sulphide. Both hydrochloric and acetic acids dissolve calcium with evolution of hydrogen. When heated in gaseous hydrogen chloride, the metal becomes incandescent and is converted into chloride ; hydrogen sulphide, under similar con- ditions, produces calcium sulphide. Calcium is not acted on by ammonia gas in the cold, but at a dull, red heat it is converted into a mixture of hydride and nitride; with liquefied ammonia at - 409 calcium gives rise to calcium ammonia, a reddish-brown solid, the study of which is being continued.Calcium decomposes boron bromide a t a dull red heat, giving calcium boride and boron; the latter is also obtained on heating a mixture of cal- cium and boron nitride, calcium nitride being formed. At a dullINORGANIC CHEMISTRY. 155 red heat, calcium is only partially acted on by acetylene, ethylene, and methane, a crust of carbon, carbide, and nitride being formed, which prevents further action. Calcium Amalgam. By JULES FEREE (Compt. rend., 1898, 127, 618--620).-When a well cooled 50 per cent. aqueous solution of calcium chloride is decomposed electrolytically, using a mercury electrode and a porous diaphragm, so arranged that the chlorine generated cannot act on the calcium amalgam formed, the latter is found to be much richer in calcium than the amalgam obtained by Mayuenne (Bull.Xoc. Chim., 1893, 366) ; when submitted to distilla- tion in a vacuum, 1-2 per cent. of a compound, Ca3Hg,, is left. The amalgam is a porous, whitish-green substance, which rapidly oxidises in air, and readily decomposes water. When heated in an atmosphere of hydrogen, it loses mercury, but does not form calcium hydridc. Its remaining properties are identical with those given by Moissan (preceding abstract). In conclusion, the author confirms the formula Ca.,N2 for calcium nitride, by analyses based on its conversion by dilute sulphuric acid into calcium and ammonium sulphates.Preparation and Properties of Calcium Nitride, W. A. D. W. A. D. By HENRI MOISSAN (Compt. rend., 1898, 127, 497--501).-Calcium at a dull red heat combines with nitrogen with incandescence to form a nitride, Ca3N2. The calcium is best placed in nickel dishes in a nickel tube. The nitride forms transparent, brownish-yellow, microscopic crystals, which are deeper in colour if they contain unaltered calcium; sp.. gr. = 2.63 at 17". It is attacked by hydrogen below dull redness, with formation of the hydride and ammonia ; by chlorine and bromine, with incandescence in the cold, or on very gently beating, and by iodine at dull redness; by oxygen, below a red heat, with incan- descence ; by sulphur, at about 500°, and by phosphorus vapour a t a cherry-red heat, but not by boron or silicon at 100OO.Carbon has no action on the nitride at 800°, but completely decomposes it in a few minutes in the electric furnace; at 1200°, small quantities of cyanide are formed. Sodium, potassium, and magnesium have no action on the nitride at a red heat; nitric oxide attacks it slowly below dull redness and violently, with incandescence, at a higher temperature. Dilute acids dissolve the nitride, but no action takes place in complete absence of water. Alcohol gradually decomposes it at the ordinary temperature, with production of ammonia and calcium ethoxide ; ethylic chloride attacks it at a dull red heat, with production of methane, ammonium chloride, and calcium chloride. When calcium can be prepared on a large scale, it can readily be made t o combine with nitrogen separated from the air, and the nitrogen can be converted into ammonia by the action of steam on the nitride.C. H. B. Action of Water on Calcium Carbide. By ERNEST CHUARD (Bull. Xoc. Chhn., 1897, [iii], 1'7, 678--679).-The gas evolved when water acts on calcium carbide contains 0*03-0*06 per cent. of 11-2156 ABSTRACTS OF CHEMICAL PAPERS ammonia, produced by the action of water on the calcium nitride, which is always present. Ammonia is also found in the residnes, and is derived from the action of water on calcium cyanate. The presence of hydrogen sulphide and phosphine in the acetylene has also been proved. The latter impurity forms 0*018-0.032 per cent. of the gas, and its presence accounts for the insecticidal properties of acetylene prepared in this manner.By introducing calcium phosphate into the material used in preparing the calcium carbide, the relative amount of phosphine in the gas, and therefore the insecticidal power, is greatly augmented, and it is hoped that it may find an application in the treatment of phylloxera-infested vines. A. L. Simple and Complex Magnesium Pyrophosphates. By MARCELLIN P. BERTHELOT and GUSTAVE ANDRE (Ann. Chim. Phys., 1897, [vii], 11, 190--197).-The precipitate obtained, either from sodium pyrophosphate in the estimation of pyrophosphoric acid (Abstr., 1897, ii, 140), or from sodium metaphosphate under similar conditions, consists of the double salt Mg,(NH,)2(P,07)2 + nH,O mixed with Mg,Na2(P207), in the proportion of three of the former to one of the latter; it also contains a small quantity of an alkali acetate.The double salt retains the whole of its ammonia, even when heated to l l O o , or when repeatedly mashed with dilute acetic acid; the latter treatment removes some of the magnesium, but the quantity of phosphoric acid thereby rendered soluble is inconsiderable, and only amounts to 0.1 per cent. Excess of ammonium salts is necessary to ensure the complete precipitation of pyrophosphoric acid. A boiling solution of sodium pyrophosphate, treated with a mixture of magnesium chloride and acetic acid, yields a precipitate of the simple pyrophosphate, Mg2P,07 ; but the filtrate still contains nearly one-third of the total phosphorus. Artiflcial Boraoites containing Iodine, By H.ALLAIRE (Compt. rend., 1898, 127, 555-557).-The author describes several substances containing iodine, which are analogous with natural boracite in composition and crystalline habit. The magmesium- boracite, 6Mg0,8B20,,Mg12, is obtained only with difficulty by Pam- ing the vapour of magnesium iodide over heated magnesium borate ; it is also formed, but in an impure state, by the action of iodine on a mixture of magnesium and its borate heated in an atmosphere of hydrogen; it forms colourless cubes and tetrahedra. The zinc bui*acite, 6Zn0,8B203,Zn12, is, however, readily prepared by passing a stream of carbonic anhydride laden with iodine vapour over a heated mixture of zinc and zinc borate; the cadmium compound, 6Cd0,8B20,,Cd121 and the manganese and iron compounds of corre- sponding composition, are prepared similarly, and closely resemble the zinc derivative, but the nickel compound, 6Ni0,8B,0,,Ni12, is yellow, and the cobalt compound, 6C00,8B20,,CoI,, violet in colour.A better method of preparing boracites containing chlorine than has been hitherto given (compare Rousseau and Allaire, Abstr., 1893, ii, 468, and 1894, ii, 413) consists in passing hydrogen chloride G. T. M.INORGANIC CHEMISTRY. 157 over the corresponding amorphous borate at a dull red heat; the product is well crystallised and pure. Several of the artificial boracites which contain iodine can be prepared by fusing molecular proportions of the iodides of sodium and of the metal chosen with boric acid and a small quantity of borax, in a steel crucible on to which is fitted a cover furnished with a small iron exit-tube ; this is necessary in order to prevent aqueous vapour from the furnace coming into contact with the contents of the crucible.By LEON BOURGEOIS (Bull. Soc. frang. Min., 1898, 21, 170--176).-Crystals of cupric chlorate, Cu(ClO,), + 6H,O, fuse a t 65" in their water of crystallisation to a blue, syrupy liquid ; decomposition commences at loo", and takes place rapidly at 110-140" with evolution of gas and formation of the basic salt Cu(C10J2,Cu(OH),. Bluish-green crystals, 1-2 mm. across, of this basic salt are obtained when the heating is effected in a flask on a sand-bath. Smaller crystals are obtained by heating a solution of cupric chlorate with fragments of marble or with carbamide in a sealed tube at 1 30°.The crystals have a sp. gr. = 3-55 ; they are monosymmetric, and are isomorphous with the corresponding nitrate, CU(NO,)~,CU(OH),. When cupric nitrate is heated in the same manner, orthorhombic crystals of the mineral gerhardtite, a dimorphous form of CU(NO,),,CU(OH)~, are formed. Cupric bromate yields a greenish blue, crystalline powder of basic bromate. New Hydrate of the Saline Oxide of Chromium [Cr,O,] By GEORGES BAUGE (Compt. rend., 1898, 12'7, 551-553).-When chromous sodium carbonate (Abstr., 1898, ii, 294), or, better, the corresponding potassium compound (ibid., 598), is boiled with water i n an atmosphere of carbonic anhydride, a somewhat unstable, brick-red powder is precipitated, having apparently the compositionCr30j + 4H20; when dried in a vacuum at lOO", it gives rise to a yellowish brown compound, Cr30, + 3H,O,.which bas a sp. gr. = 3.49, and is converted into chromium sesquioxide by the action at 250' of water-vapour, hydrogen chloride, or an inert gas, hydrogen being evolved ; it is also decomposed by chlorine at a dull red heat, giving chromyl chloride, water, and hydrogen chloride. Although stable in dry air at the ordinary temperature, it is rapidly oxidised to chromium sesquioxide in presence of water or when heated; by hydrogen sulphide, it is converted a t a somehat elevated temperature into a crystalline sulphide, whilst it rapidly reduces dilute sulphuric acid at 40°, hydrogen sulphide being evolved if a large quantity of the oxide is employed. When the latter is dissolved in concentrated hydrochloric acid, a mixture of chromous and chromic chlorides is obtained.All attempts t o convert the oxide Cr,O, + 3H20 into the compound Cr304 + H,O described by Peligot (Ann. Chim. phys., [iii], 1844, 12, 539) failed. Iron Chromium Carbide and Iron Molybdenum Carbide. By PEREY WILLIAMS (Compt. rend., 1898,12'7,483-484).--li.on chromium carbide, 3Fe3C,2Cr3C,, intermediate between the carbides 3Fe,C,Cr,C2 and Fe3C,3Cr3C, described by Carnot and Goutal, is obtained by heating a mixture of chromic oxide, 200 grams; iron, 2OOgrams; andpetroleum W. A. D. Crystallised Basic Cupric Chlorate. L. J. S. W. A. D.158 ABSTRAC'I'S OF CHEMICAL PAPERS. coke, 70 grams, in a carbon crucible for 5 minutes with an arc from a current of 45 volts and 900 amperes. The crystalline ingot thus obtained, which resembles ferrochrome in appearance, is treated with aqua regia a t loo', and any graphite that remains is removed by levigation with bromoform.The carbide forms very brittle needles with a metallic lustre and the colour of nickel ; sp. gr. = 7.22 at 19' ; hardness between glass and rock crystal. It is attacked by chlorine at a red heat, and also, although more slowly, by bromine and iodine; by oxygen and water vapour a t about 500', and by gaseous or dissolved hydracids, but not by nitric acid or aqua regia. Iron molybdenum carbide, Fe,C,Mo2C, is prepared in an exactly similar way from a mixture of molybdenum dioxide (prepared by heating ammonium molybdate), 130 grams; iron, 300 grams; and petro- leum coke, 50 grams.The ingot is treated with hydrochloric acid instead of aqua regia, and the insoluble residue is separated into two parts by means of a magnet, The non-magnetic part consists of graphite, which is separated by means of bromoform or methylenic iodide, and the iron molybdenum carbide, which consists of a grey powder of microscopic, arborescent crystals resembling those of anti- mony; sp. gr. = 7-47 at 18". The carbide is attacked by chlorine, bromine, iodine, or the gaseous or dissolved hydracids when heated, but is most readily dissolved by dilute nitric acid. In the preparation of these and similar carbides there is always a relation between the proportions of carbide and of graphite respec- tively in the ingot obtained ; the one seems to vary inversely as the other, and the manner of cooling exercises a considerable influence on the proportions.C. H. B. Preparation of Tungsten, Molybdenum, Chromium, and Manganese Silicides. By HENRY N: WARREN (Chem. News, 1898, 78, 318--319).-When aluminium is added to a well fused mixture of 2 parts of cryolite with 1 part of sodium silicate, reaction pro- ceeds tranquilly, which is not the case when potassium silicofluoride is employed. A mass of graphitoidal silicon mixed with aluminium is obtained, fromwhich thelatter isremoved by means of hydrochloric acid. Mcmgmese silicide is obtained when any oiide of manganese is reduced at a full white heat in presence of excess of silicon; it contains 30 to 40 per cent. of silicon, has a white, metallic lustre, is fusible, brittle, and hard enough to scratch glass.Chromium silicide resembles the manganese compound, but is less fusible, harder, and offers greater resistance to reagents. Twngsten and molybdenum silicides require the full heat of an oxy- hydrogen furnace for their preparation, and when the reaction is properly conducted, they form well fused masses; they are crystal- line and very hard, in some cases scratching quartz, tungsten silicide being the harder. All these silicides are decomposed readily by hydro- fluoric acid and by chlorine at a red heat ; other acids, however, only act on them with difficulty. By L. A. HALLOPEAU (Compt. rend., 1898, 127, 755-756. Compare Moissan, Abstr., 1896, ii, 606, and this vol., ii, 3Z).-Lithium paratungstate D. A. L. Electrolytic Production of Crystalline Tungsten.INORGANIC GHEMISTRY.159 heated to 1000° is submitted for 3 hours to the action of an electric current of 3 a.mperes with an E.M.F. of 15 volts. The product, after extraction with hot water, concentrated hydrochloric acid, and lithium hydroxide solution, consists of crystalline tungsten, which is con- taminated with more or less platinum derived from the electrodes. The tungsten thus obtained forms opaque prismatic crystals with a metallic lustre, and having an acicular habit like those of silicon. G. T. M. Tungsten Tetriodide. By ED. DEFACQZ (Compt. rend., 1897,127, 510--512).-Tungstel.~ tetriodide, WI,, obtained by the action of an excess of liquid hydrogen iodide on tungsten hexachloride at l l O o , is a black, crystalline substance of sp.gr. 5-2 at 1 8 O , insoluble in water, ether, chloroform, and turpentine, but soluble in absolute alcohol ; it does not melt, and does not sublime without decomposing. Hydrogen reduces it below a red heat, chlorine displaces the iodine at the ordinary temperature, and bromine displaces it at 100'. Water de- composes it slowly in the cold, and rapidly on boiling, and it is readily attacked by dilute hydrochloric and sulphuric acids, and by nitric acid and aqua regia, which convert it into tungstic acid. Alkali hydroxides and carbonates, whether in solution or fused, and fused potassium hydrogen sulphate also readily decompose the tetriodide (compare Abstr., 1898, ii, 521). C. E. B. Crystallised Tungsten Dioxide and a Tungstolithium Tungs- tate. By L.A. HALLOPEAU (Compt. r e d . , 1898, 12'7, 512-514)- Whenlithium paratungstate is heated in a current of hydrogen at about the melting point of glass for 45 minutes, it is completely reduced to tungsten dioxide, which is obtained as an opaque, brown, microcrystalline powder with a coppery lustre, by treating the product of reduction successively with boiling water, concentrated hydrochloric acid, and lithium hydroxide solution (20 : loo), and finally mashing thoroughly with warm water. The dioxide thus prepared is of con- stant composition ; it is not attacked by hydrochloric and sulphuric acids, or by concentrated solutions of the alkalis either a t the ordinary temperature or on heating. Nitric acid oxidises it to tungstic acid, and when heated in oxygen it burns and yields pure microcrystalline tungstic anhydride. If the paratungstate is fused with a fragment of tin for about an hour, and the product is treated in the same way as the product of reduction in hydrogen, it yields a very deep blue powder consisting of microscopic prisms of the '' tungsten bronze," Li,W,O,, or Li,O,WO, + WO2,3W0,, analogous to the sodium compound prepared in the same way.C. H. B. Action of Metallic Sulphates on Potassium Paratungstate. By L. A. HALLOPEAU (Compt. rend., 1898, 121, 620-621. Compare von Knorre, Abstr., 1885,1184, and 1886,597).-0n mixing solutions of potassium paratungstate and magnesium sulphate in molecular pro- portion, and concentrating the product, the double salt, 12WOa,5(#K,0 + +MgO) + 24H,O,160 ABSTRACTS OF CHEMICAL PAPERS.separates in hexagonal prisms ; it is almost insoluble in cold water, but dissolves more readily in hot, and loses 17H20 at 100'. When solutions of potassium paratungstate and manganese sulphate are mixed, the salt, 12W0,,3K20,2Mn0 + 16H20, is immediately precipi- tated as a colourless, crystalline powder, which loses 10H20 when dried at looo. The zinc double salt is crystalline, but cannot be obtained pure, whilst the cadmium and most other double salts are amorphous. W. A. D. By LEON BOURGEOIS (Bull. SOC. Philomatiqzce, Paris, 1897,9,125-130 ; and Bull. Xoc. fray. Min., 1898, 21, 32--39).-From a solution of precipitated uranium phos- phate in hot water acidified with hydrochloric acid, yellow crystals, 2-3 mm across, of H(U02)P04 + 4H20 are deposited after some time.These have the sp. gr. 3.03, and are square, tetragonal plates with angles closely related to those of the minerals cupro-uranite, Cu(UO,),(PO,), + 8H20, and calco-uranite, Ca(U02)2(P04)2 + 8H20, &c. Crystallised cupro-uranite has often been prepared by the actlon of copper phos- phate on uranium nitrate, but attempts to obtain calco-uranite always result in the formation of H( U02jP0, + 4H20. Pure Platinum Metals of Commerce. By FRANZ MYLIUS and RUDOLF DIETZ (Rev., 1899, 31, 3187-3193).-A number of ingots of purified platinum metal supplied by the firm of Hereaus of Hanau were analysed with the object of ascertaining the degree of purity attained in the commercial processes of purification. Platinum was not perceptibly impure. Palladium contained a t least 99.9 per cent. of pure metal, 0.05 per cent. of platinum being also present. Iridium contained not more than 0.3 per cent. of impurities, of which a trace was ruthenium and 0.15 per cent, platinum. Rhodium was less pure, containing scarcely 98.4 per cent. of the pure metal ; impurities were : 1.5 per cent. of iridium, 0-1 per cent. of ruthenium, and a trace of platinum; another specimen, however, contained only 0.4 per cent. of iridium and a third, only 0.05 per cent. of platinum. The persistence with which iridium adheres to rhodiumfinds its explanation in the fact that iridium forms a pentammine chloride, isomorphous with rhodiumpentammine chloride, which is the compound used for the purification of the metal in question ; the two compounds are only separable, therefore, by frequently repeated crystallisation, that of iridium being the more soluble of the two, The colour of the solution serves as a criterion of the purity of the rhodium compound, as it is colourless when free from iridium; moreover, the impure compound is comparatively readily soluble, Osmium, hitherto believed to be infusible, may be melted with the help of the electric furnace, The existence of volatile oxides of osmium and ruthenium renders it easy to obtain these metals in a pure state. Perosmic acid, as sold, is practically pure ; perruthenic acid is not sold owing to the readiness with wbich it undergoes decomposition, but the dioxide may be obtained and converted by fusion with potash and nitre into potassium ruthenate (K2Ru0,) and the solution of the latter, after treatment with chlorine, yields the pure tetroxide on distillation. Crystallised Uranium Phosphate. L. J. S.MINERALOGICAL CHEMISTRY. 161 The paper concludes with the description of a method for the detection of the platinum metals when mixed together in presence of others, including gold and mercury ; the method, however, is lengthy, and does not lend itself to abstraction. A. L.

ISSN:0368-1769    

DOI:10.1039/CA8997605149

出版商:RSC    

年代:1899

数据来源: RSC

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MINERALOGICAL CHEMISTRY. Miner a 1 o gi c a1 Chemistry , 161 Generalisations on Humous Coal. By C. EG. BERTRAKD (Compt. rend., 1898, 127, 767--769).-The author puts forward a number of generalisations deduced from the microscopic study of specimens of oil shales and bituminous coal. Salt on Shore of Lake Ruszanda. By ALEXANDER VON KALEC- SINSZKY (Foldtad Riixlony, 1898,28, 234-236,283-285).-The water of the Lake Ruszanda, Com. Torontal, Hungary, is yellowish, and has an alkaline taste and a soapy odour ; it is used for baths. On the shore of the lake there is a deposit of whitish salt, a sample of which contained 53.32 per cent. of insoluble matter, mainly sand ; the soluble portion contained Na. I(. Cs. Mg. Fe,Al. SO,. COP C1. SiO,. 100". ignition. Total. 31.744 0.228 0.100 0.055 traces 60'804 2.490 2.828 0.009 0-338 1-441 100'037 This corresponds with 86-86 per cent.of sodium sulphate, 4.07 of sodium carbonate, and 4.66 of sodium chloride. In efflorescences of this kind from other localities, there is usually much more sodium car- bonate. An analysis is quoted of the water of the lake, in which sodium sulphate, carbonate, and chloride are present in about equal amounts. L. J. S. G. T. M. H,O at H,O on Artificial Production of Lautarite. By AUGUST B. DE SCHULTEN (Bull. SOC. franc. Min., 1898, 21, 144--145).-The mineral lautarite, Ca( 103)2, occurs in the Chilian nitrate deposits (Abstr., 1892, 124). It is prepared artificially by saturating molten sodium nitrate with amorphous calcium iodate, Ca(10,)2 + H20. The latter is prepared by heating precipitated Ca(IO,), + 6H20 at 100'.The fused mass contains brilliant, monosymmetric crystals of the com- position Ca(IO,),, which are slightly soluble in water, and have the 8ame habit and angles as the natural mineral ; sp. gr. = 4.591. L. J. S. Artificial Production of Lanarkite. By AUGUST B. DE SCRULTEN (Bull. SOC. franc. Min., 1898, 21, 142--144).-Lanarkite is produced by the action of basic lead acetate, Pb(C,H,O),,PbO, on sodium sulphate; when sodium hydroxide is added t o a solution of normal lead acetate and the filtrate added to a hot solution of sodium162 ABSTRACTS OF CHEMICAL PAPERS. sulphate, a crystalline precipitate having the composition BPbO,SO,, is formed ; sp. gr. = 6.923. By diffusion, larger crystals, several milli- metres in length, can be obtained, together with crystals of anglesite.The colourless, monosymmetric crystals are elongated in the direction of the axis of symmetry, and have the same habit and angles as the natural crystals. L. J. S. Cobalt Deposits at Port Macquarie, New South Wales. By JOHN B. JAQUET (Ann. Rept. [1897] Dept. Mines, New South Wales, 1898, 177-1 80).-Earthy cobaltiferous wad (asbolite) occurs at Port Macquarie in considerable amount in nests and pockets in serpentine and scattered throughout the red clays which result from the decomposi- tion of the serpentine. It is black to bluish-black (the latter con- taining more cobalt), with a more or less spongy texture, and a rudely laminated or botryoidal structure, Analysis by H. P. White of a picked sample of ore gave SiO,. A1,0,.Fe20,. MnO,. COO. NiO. Cr20,. CuO. CaO. MgO. 6-40 9.97 16.85 36-50 7'03 2.39 0.40 0.12 1'20 0.83 P,O,. CO,. H,O at 100". H20 combined. Total. 0.14 0.22 6 '38 12.24 99-67 This mode of occurrence is similar to that of the cobalt ores of New Caledonia. The material has probably been segregated during the processes of decomposition of the serpentine. By E . VON SEYFRIED (Inaug.-l)iss. Strassburg ; and Jahrb. h. peuss. geol. Landesalzst. [for 18961, 1897, 1-38). The Triassic volcanic rocks of this district in Bavaria are described. Analysis I is of augite (after deducting 4.06 per cent. of magnetite and calculating to 100) taken from tephrite, which gave anal. XI. SiO,. TiO,. A1,0,. Fe20, FeO. CaO. MgO. K20. N%O. ignition. Total. Sp.gr.144.15 - 12'11 - 9-16 20'50 9-80 0.85 3'43 - loomoo 3'46 1153.26 0.31 16-63 8-29 3'21 7.30 1-10 3'54 531 1'43 100'38 2.871 Analyses are also given of nephelite-basalt, basanite, and felspar- basalt. L. J. S. Differentiation in Igneous Magmas as a Result of Progres- sive Crystallisation. By J. J. HARRIS TEALL (Rept. Brit. ASSOC., [for 18971, 1898, 67, 661-662 ; and Quart. J. Geol. Xoc., 1897, 53, 482--48S).-Crystal building in a homogeneous igneous magna necessarily produces differentiation into portions of different chemical composition. Usually iron ores are the first, and quartz the last, to crystallise out ; but in the basalts of Franz Josef Land, the magnetite is the last to separate, and the mother liquor remaining after the labradorite and augite have crystallised is, therefore, more basic. Analysis of the palagonite representing this basic residue gave SiO,.Al,O,. Fe203. FeO. CaO. MgO. N%O. K,O. H20. Total. 35-48 8-30 1230 14.60 1-04 7.10 3.92 trace 16.80 99.5 Chrome iron ore is associated with the wad in places. L. J. S. [Augite] from Kreuzberg, Rhon Mtns. Loss on The progressive cry stallisation has here given rise to a concentrationPHYSIOLOGICAL CHEMISTRY. 163 of iron and of magnesia and a reduction of silica, alumina, and lime in the mother liquor ; and in dykes the more basic portion would be in the centre instead of at the margins, as is more usually the case. The palagonite results from the alteration of brown glass; it is interstitial between the labradorite (sp. gr. = 2.7) and augite, and also fills amygdales in the vesicular basalts, It is a soft, black or greenish-black substance, sp.gr. = 2.4, and is readily attacked by hydrochloric acid, leaving a white, siliceous skeleton. Under the microscope, in very thin sections, it is doubly refracting and appears to be formed of minute interlacing fibres or scales of a brown, or rarely green, substance. In composition, i t differs from hullite and other palagonites, in that much of the iron is ferrous. By E. TULLEY NEWTON^^^ J. J. HARRIS TEALL (&ZM;Grt. J. G'eol. Xoc., 1898, 54, 646-651. Com- pare preceding abstract).-The common type of basalt of wide dis- tribution in Franz Josef Land consists of labradorite, augite, magne- tite, rarely olivine, together with interstitial matter and various secondary products. SiO,. TiO,. A120,. Fe,O,. FeO. MnO. CaO. MgO. K20. Na20. H,O. Total. 47-28 1-48 13'24 4'44 10.50 0'40 11'04 5.94 0'31 2'62 2'00 99.25 L. J. S. Rocks from Franz Josef Land. Analysis by Teal1 gave This agrees very closely with analyses of basalt from Iceland. L. J. s. Water of the Illyes Lake, Hungary. By BELA LENGYEL (Foldtani Riixliiny, 1898, 28, 229-234, 280-282).-Three lakes in the salt district near Szovata, Com. Maros-Torda, Transylvania, were formed in 1875-9 by subsidences consequent on the removal by springs of material from the salt-bearing strata. The water in these lakes is used for baths ; it is very heavy, and has a temperature of 60° a t a depth of 3-4 metres. On the surface is a layer of cold, fresh water brought in by streams. 1000 grams of water from the Illyes Lake contains : Na, 91.23003 ; Ca, 0.60061 ; Mg, 0.07109 ; Fe, 0.00622 ; C1, 140.70685 ; Br, 0.00759 ; SO,, 1.01750; GO,, 0.09800 ; SiO,, 0.009. Total : 37233.74726 grams. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA8997605161

出版商:RSC    

年代:1899

数据来源: RSC

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PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. 163 Temperature of the Human Body. By MARCUS S. PEMBREY and B. A. NICOL (J. Physiol., 1898, 23, 386--406).-A large number of observations on two healthy men are given. The temperature was usually taken of the stream of urine, which is a trustworthy indica- tion of the internal temperature ; the mouth and axilla are not so. The observations show the diurnal variations of the temperature, but the most prominent feature is the very considerable rise of body temperature that occurs as the result of muscular exercise. Food only causes a slight rise, Mental work has little or no effect. A simple flat bulb mercurial thermometer gives results which corn-164 ABSTRACTS OF CHEMICAL PAPERS. pare favourably with those given by thermo-electric methods of deter- mining the temperature of the skin.Influence of Antiseptics on the Artificial Gastric Digestion of Fibrin. By CHARLES F. MABERY and LEO GOLDSMITH ( J . Amer. Chem. Xoc., 1897, 19, 889-894).-The substances tested were alum, cream of tartar, boric acid, and formalin. Alum alone exhibits a marked effect i n retarding digestion. Action of Certain Substances on Digestive Ferments. By FRANK D. SIMONS (J. Amer. Chem. Soc., 1897, 19, 744-754).-!I'he following substances retard the artificial gastric digestion of proteids : picric acid, tropsolin 000, metanil-yellow. The following retard artificial pancreatic digestion of proteids : bismarck brown, oil of cinnamon, and formol. Gastric digestion ensues only after prolonged treatment if salicylic acid or oil of winter-green is added to the mixture.Both gastric and pancreatic digestion progress normally i n the presence of oil of peppermint, chrysoidine, safranino, and methylene-blue, W. D. H. By FRTEDRICH KR~GER (Zeit. Biol., 1898, 37, 229--260).-The bulk of the present paper is occupied with references to past work on the subject of the action of the juice of the small intestine. The remainder describes experiments which confirm the results already well known to physi- ologists in this country, namely, that the juice does not act on proteids or fats ; that i t is able to saccharify cooked starch ; that it inverts cane- sugar, and has no reverting properties. Glycocine as an Intermediate Product of Metabolism. By HUGO WIENER (Chm. Celztr., 1898, i, 626-627 ; from Arch.Exp. Path. Pharm., 40, 313--325).-1f more than 0.7-0.8 gram of beiizoic acid per kilo. of body weight is given by the mouth to rabbits, the excess is not excreted as hippuric acid, but as free benzoic acid; the maximum amount of glycocine available for the formation of hippuric acid is, therefore, 0.32-0.34 gram per kilo. of the rabbit's body weight. 1.7 gram of benzoic acid per kilo. is fatal; but if glycocine is injected at the same time, this amount can be considerably exceeded without untoward results. Alanine and asparagine do not act in this way, but leucine does; this amido-acid, therefore, yields glycocine as an intermediate product. Feeding with uric acid increases the amount of urea, and also the hippuric acid excreted. Halogen Metabolism.By F. BLUM (Chem. Centr., 1898, i, 992-993 ; from Munch. med. Woch., 45, 231-233. Compare Abstr., 1898, i, 287).--Iodothyrin is regarded as an artifkial product ; it does not occur free in the thyroid. The non-coagulable iodine-containing proteid of that gland is termed thyrogen ; formaldehyde converts it into a non-coagulable variety called thyrogen f. Synthetically pre- pared iodine compounds of albumin, on treatment with dilute alkalis, or on gastric digestion, yield a product of which the properties are similar to those of iodothyrin. After feeding on the iodine-containing substance of the thyroid, potassium iodide appears in the urine ; this W. D. H. W. D. H. Ferment Actions of the Succus Entericus. W. D. H. W. D. H.PHYSIOLOGICAL CHEMISTRY.165 is supposed to be formed by oxidation in the body leading to the appearance of nascent iodine. Formation of Urea from Oxamic Acid in the Organism. By LEO SCHWARZ (Chem Cento.., 1898, i, 951; from Arch. Exp. Path. Phccrm., 1898, 41, 60--73).-0nly a small part of the oxamic acid given passes from the body as urea, and there is no formation of oxalic acid ; the greater part of the oxamic acid passes unchanged into the urine. Alinced liver has not the power to change oxamic acid into urea. W. D. H. By LEON ASHER (Zed. BioZ., 1898, 37, 261-306. Compare Abstr., 1898, ii, 239)- Intravenous injection of bile increases the activity of the liver, and causes an increased flow of concentrated lymph from the thoracic duct; this confirms the views previously expressed by the author.After a time, this lymph contains hzemoglobin, but the fluids in the serous cavities and the urine contain no hsmoglobin. This is in favour of the view that the fluids in the serous cavities are not the same as tissue-lymph ; possibly they are secretions. Urea which does not plasmolyse blood-corpuscles, like sugar and sodium chloride which do, causes an increase of lymph. Sometimes the intravenous injection of small quantities of crystal- loid materials causes a noteworthy rise i n tho percentage of solids in the lymph; this cannot be a mechanical result, but is due to the increase in metabolism which is thus set on Poot. Choline causes no increase in bile formation ; the lymph also is not more concentrated ; but the amount of lymph in the neck and thoracic lymphatics is increased, which corresponds with the fact that choline stimulates secretion in glands.Muscarine behaves in the same may. Simultaneous injection of crystalloid substances and choline causes little or no lessening of the concentration of the lymph. The results of the intravenous injection of crystalloid substances are thus partly due t o physical, partly to physiological factors. W. D. H. Properties and Formation of Lymph. W. D. H. Action of the Cells of Frog's Lymph on Bacilli. By W. B. HARDY (J. Physiol., 1898, 23, 359-375).-Measurements show that contact with an oxyphile cell of frog's lymph retards or stops the growth of a chain of Bacillus filamentosus. Below 19O, growth is arrested, whilst between 20' and 25' it is only retarded. The cells exert the action by coating the chain with a slime derived from the oxyphile granules.Contact with a hyaline cell, on the other hand, does not necessarily have any effect on the growth of the bacilli, but if the bacillus gets enclosed within vacuoles developed in the cell-substance, then retardation of growth occurs. W. D. H. Thiocyanic Acid in Human Saliva. By FRIEDRICH KRUGER (Zed. Biol., 1898, 37, 6--24).-The quantity of saliva secreted by a man in the 24 hours varies between 250 and 300 c.c., and is not influenced to any important degree by cigarette smoking.166 ABSTRACTS OF CHEMICAL PAPERS, Thiocyanic acid is a normal constituent of the saliva, and is not produced by putrefactive processes, nor by foreign admixture due to smoking. The amount present is independent of age, sex, health, or disease ; the saliva of smokers, however, contains two or three times as much as that of non-smokers. The Number of Red and Colourless Corpuscles and Amount of Haemoglobin a t Different Ages in Man.By WILHELM SCHWINGE (PJZCger’s Amkiu., 1898, 73, 299--338).-After birth, the quantity of red corpuscles and of hzemoglobin are at their maximum ; these two values soon sink to a minimum, rise during growth, and during adult life shorn periodic alterations, finally sinking once more towards the end of life. The number of colourless corpuscles behaves in the reverse manner, sinking during growth and adolescence, and rising afterwards. The two sexes differ in that, during puberty, the numbers for the female sex are smaller than those for the male.The differences noted are believed to be parallel to differences in metabolic activity, and correspond with the amount of interchange between blood and tissues. The high percentage of leucocytes in youth illustrates the formation of new formed elements at that period oflife. Comparative Physiology of Digestion. 11. Presence of an Enzyme which Dissolves Cellulose in the Secretion of the Liver of the Snail (Helix pomatia). By WILHELM BIEDERMANN and P. MORITZ (Pfluqer’s Arciiiv , 1898, 73, 219-287. Compare Abstr., 1898, ii, 614).-That cellulose is digested in the alimentary canal of many animals is an undoubted fact ; in most instances, this is believed to be due t o the action of micro-organisms, and although the existence of an enzyme which has the same power has been mooted by several observers, their results can hardly be considered as definite ; on the other hand, in the vegetable world, the existence of a ‘ cytase ’ appears in many cases to be have been satisfactorily proved.The first part of the present paper is occupied with a lengthy critical discussion of these results. The secretion of the so-called liver of the snail, Helix pomatia, is remarkably rich in proteid material ; it converts starch into dextrose, but its most marked characteristic is the possession of a very active cytase, which acts, not only on the more soluble constituents of the cell wall, like the hemicelluloses, but on the more insoluble materials also which have not undergone actual conversion into woody fibre. The products of action on the hemicelluloses are the same as those which are produced by the action of dilute mineral acids on those substances.The secretion was collected from the intestinal canal of the animals ; extracts of the liver have no action on cellulose ; doubtless, the cytase is preceded in the liver cells by a zymogen, which is not converted into the enzyme during the process of extraction. The ferment resembles that described in the secretion of the crab’s ‘ liver ’ by acting at a low temperature. The reaction of the juice has been described by some previous observers as markedly acid ; this is not so, the acid reaction which can be demonstrated with some indicators is slight, and is due to acid salts ; the juice is alkaline t o litmus and to lacmoid. The juice has no action on proteids; numerous proteids of both W.D. H. W. D. H.PHYSIOLOGICAL CHEMISTRY. 167’ animal and vegetable origin were tried ; the observations were made between April and September, but it is possible t h a t at other periods of the year its action may be different. By SCHURIG (Chem. Centr,, 1898, i, 951 ; from Arch. Exp. Path. Pharm., 1898, 41,29-59). -Injection of 0-5 gram of haemoglobin per kilo. of body weight in rabbits for 17 days does not lead to haemoglobinuria, but this condition appears in 6 days after a daily injection of 1 gram. Hemoglobin is also found in the bile. The urine is dark, but does not contain bile pigment. After the injection, the connective tissues are rich in iron ; part of the haemoglobin is changed into bilirubin by the liver, and part is found in the spleen and bone-marrow as iron compounds, which can be detected microc hemicall y.Action of Arsenic on Bone Marrow and Blood. By RALPH STOCKMAN and E. D. W. GREIQ (J. Physiol., 1898,23, 376--382).-1n healthy animals, arsenic does not increase the number of blood corpuscles nor the amount of haemoglobin. In pernicious anaemia, it acts favourably by stimulating the red-marrow ; it does not, however, affect the real cause of the disease, and is simply a symptomatic method of treatment. W. D. 13. Fate of Hzemoglobin in the Organism. W. D. H. W. D. H. Action of Copper on the Animal Organism. By HERM. BAUM and RICHARD SEELIGER (Chem. Centr., 1898, i, 852 ; from Zed. bfentl. Chem., 4, 181--210).-Different preparations of copper have different degrees of toxicity, copper oleate being by far the most poisonous of the compounds investigated ; then follow in order, copper acetate, copper sulphate, and ‘‘ cupro-haemol ” ; the last-named has little or no harmhl action.The toxic action is mainly on the brain and on metabolism. W. D. H. Physiological Action of Alkalis and Acids when greatly Diluted. By JACQUES LOEB (PJuger’s Archiw., 1898, 73,422-426).- It is well known that the activity of spermatozoa and cilia is increased by dilute alkalis; to say that the alkali acts as a stimulus is no real explanation of this fact. Investigations were undertaken to discover whether the stimulus acts by increasing oxidation processes in the living cilia. The infusorian Param~cium was selected for experi- ment.These animals were divided into three sets-one in distilled water, one in distilled water t o which a little akali was added, and the third in distilled water t o which a little acid was added ; all were placed in an Engelmann’s chamber, and a stream of pure hydrogen passed through it. Those in the alkaline solution lived longest ; the dilution of the sodium hydroxide employed must be from i2DG t o per cent.; greater dilution gives a negative result, less dilution hastens the death of the Paramowium. Acids in every degree of dilution are very fatal. In fever, the alkalinity of the blood decreases ; whether this is related t o the metabolic activity of the febrile state is uncertain, but it is cer- tainly the case that Paramoecium lives and moves longer at a tempera- ture of 40’ in an alkaline than it does in a neutral or acid solution.168 ABSTRACTS OF CHEMICAL PAPERS. Potassium cyanide kills by preventing the assimilation of oxygen (C.Bernard and Geppert); a trace of alkali, however, added to a fatal solution of this salt prolongs the life of the Paranmcium con- siderably. The same is true for atropine, but veratrine and strychnine are equally fatal in acid, neutral, and alkaline solutions. Another series of experiments were performed with the larvae of the sea-urchin. According to Hoppe-Seyler, free oxygen is necessary for embryonic development ; in the present research, dilute alkali mas added to see if the development and growth of the larvae were hastened; this was found to be so in a marvellous degree. From such experiments it is inferred that dilute alkalis favour, dilute acids impede, oxidation in the living organism.It is recommended that in transfusion, after severe haemorrhage, a dilute alkaline solution should be used. Another practical issue appears to be the desirability of administering alkalis in fevers. Chloride Metabolism in Pneumonia and Acute Fevers, By ROBERT HUTCHISON (J. Pathol. und Bacterial., 1898, 5, 406-442).- The research confirms the old statement that during an attack of croupous pneumonia the chlorides of the urine are greatly diminished, or may even entirely disappear. There is a true retention of about 2 grams per diem within the body. This lasts until one or two days after the crisis, and is succeeded by an excessive secretion of chlorides.The degree of diminution varies, but has no relation to the intensity of the fever, lung trouble, or to concomitant albuminuria. The phosphates, sulphates, and urea are increased. Decrease of chlorides may occur in other fevers, such as typhus and acute rheumatism, whilst in malaria the chlorides are increased. The presence of abundant chlorides would negative the diagnosis of pneumonia, but diminution of chlorides is not pathognomonic of that disease. The absorption of chlorides goes on normally in acute fevers, and no vicarious excretion occurs; there is, however, some increase of these salts in the sputum and in the inflammatory exudation. There is no functional disability of the kidneys to explain the decrease in the urine. The chlorides of the blood are lessened, but there is an in- crease in all the organs and fixed tissues in general, not in any one in particular.Attempts to produce chloride retention in pyrexia by in- jection of the pneumococcus failed. Views on the cause of the re- tention of the chlorides are merely speculative, but are discussed fully ; it does not appear to be the result of a retention of water. The increased secretion of chlorides in malaria is due to increase of arterial pressure in the kidney during the pyrexial stage of that disease. W. D. H. Influence of Experimental Jaundice on the Glycogen of Liver and Muscles. By FRIEDRICH VON REUSZ (Chem. Centr., 1898, i, 950-951 ; from Arch. exp. Path. Pharm., 41, 19--2S).-By feeding rabbits on sugar after ligature of the bile ducts, it is found that the sugar is badly absorbed, and, post mortem, much is found in the sub- cutaneous tissues ; nevertheless, there are considerable quantities of glycogen in the liver and muscles.Slight diuresis and glgcosuria generally occur, Diabetic puncture in these animals causes only slight W. D. H.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 169 glycosuria. There is a good deal of fermentative change in the sugar i n the alimentary tract. I n dogs, ligature of some branches of the bile duct leads to a n increase of water, but only to a slight lessening of the glycogen in the icteric portions of the liver. Chemico-physiological Studies on Phloridzin. By MAX CREMER (Zeit. Biol., 1898, 37, 59-81. Compare Abstr., 1898, ii, 243).-Of all theories on phloridzia diabetes, the original one of von Mering is the most probable; still a true secretory activity has also to be taken into account. There is no evidence of any increased new formation of dextrose molecules, and it is possible, but not proved, that the rise in the sugar of the blood is due to the dextrose molecules preformed in glycogen. Phloridzin has no special influence on the cells of the mammary gland, in spite of what Cornevin (Compt. rend., 116, 263) says to the contrary. By OSCAR LOEW (Zeit. Biol., 1898, 37, 222--22S).--According to Nef, the substance obtained by the action of iodine on silver acetylide is not di-iodacetylene, but the isomeric di-iodacetylidene, C:CI,. In keeping with this view, the experiments recorded show the intensely poisonous character of this substance t o all kinds of animal and vegetable life. A solution of 1 part in 20,000 kills bacteria, moulds, and yeasts. Solutions of 1 in 100,000 kill algae in a few hourw, of 1 in 1,000,000 in a few days. Similar results mere obtained in other cases; the amount of dilution necessary varies, but is always very high ; these cases include infusoria, flagellata, copepods, nematodes, rotifers, &c. I n vertebrate animals, the substance was breathed in the form of vapour, or injected under the skin ; here again the small toxic dose is equally remarkable. W. D. H. W. D. H. Di-iodacetylidene its a Poison. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8997605163

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 169 Chemistry of Vegetable Physiology and Agriculture. Importance of Stereo-chemistry in Physiology, By EMIL FISCHER (Zeit. physiol. Chem., 1898, 26, 60--87).-The object of this paper is to bring before physiologists the bearing of the author's work, especially on the carbohydrates. Such importance is indicated by the way in which isomerides are affected by micro-organisms and fungi, some being destroyed, and other substances, with a different optical action, being unaffected. Relation of Oxygen to the Activity of Living Yeast-cells. By HANS BUCHNER and RUDOLPH RAPP (Zeit. B i d , 1898, 37, 82--142).-An abundant oxygen supply has no really favourable influence on the fermentative activity, as such, of yeast-cells ; it leads t o a n increase in their number, but the gas is as indifferent as hydrogen or nitrogen is towards the ferment-process as such, that is, towards the formation of zymase. Only in pure surface cultures (on sugar-gelatin) is there an increased respiratory decomposition of W.D. H. VOL. LXXVI. ii. 12170 ABSTRACTS OF CHEMICAL PAPERS. the sugar by the yeast-cells, accompanied by increased fermentative activity. Mechanical shaking of the yeast-cells beyond a certain point has a harmful influence on them. Zymase is the only active agent in the chemical changes produced by yeast. Composition of Buchner's Yeast Extract, By AUGUSTIN WROBLEWSKI (Bep., 1898, 31, 3218--3225).-The proteid substances include invertase and a proteolytic ferment (Abstr., 1898, ii, 246), both of which are probably contained in the same precipitates from the extract as are the proteoses. No ferment capable of decomposing starch could be detected, and the presence of oxydases has not been established with any certainty.The presence of several coagulable proteids has been established by the process of partial coagulation ; these separate at 40°, 51', 56", 59", 6 2 O , and 68' respectively. The first proteid is also coagulated by ether a t 35', and does not pass through a Chamberland filter ; it seems to be the one which most readily under- goes alteration when the extract is kept. Attempts at fractional salting out with concentrated ammonium sulphate (3.8 C.C. of extract to 6.2 C.C. of sulphate solution) indicate thah the proteids which coagulate above 60" are precipitated, whilst the others remain in solu- tion.A complex carbohydrate, small amounts of proteoses, and larger quantities of peptone, and a substance with reducing properties have also been isolated. Tyrosin, leucine, glutamic and other amido-acids, together W. D. H. with glycerol, are contained in the alcoholic filtrate from the peptones. J. J. S. Action of the Sorbose Bacterium on Aldoses. By GABRIEL BERTRAND (Compt. rend., 1898, 127, 728-730. Compare Abstr., 1898, i, 530 and 536, and this vol., ii, 44).-When the sorbose bacterium is cultivated in a yeast decoction containing an aldose, it is found that after a time a portion of the sugar has disappeared, whilst a corresponding amount of a monobasic acid has been produced. Three solutions containing 5 grams of arabinose, dextrose, and galactose yielded, after 25 days, 0.74 gram of arabonic acid, 1.27 grams of gluconic acid, and 3.62 grams of galactonic acid respectively.Action of Ammonium Salts on Aspergillus Niger. By CHARLES TANRET (Bull. Xoc. Chim., 1897, [iii], 17,914-921. Compare Abstr., 1897, ii, 154 and 338).-The author has already shown that when AspergiZZus &ye. is sown i n a nutrient solution containing an excess of ammonium nitrate, the mycelium can be made to grow con- tinuously without the formation of spores during as long a period as a month, provided the solution is renewed every day; if, horn- ever, this liberal diet is curtailed, or if the temperature is allowed to fall much below 30°, fructification at once sets in. It is now shown that a similar effect is produced by ammonium sulphate and ammonium chloride ; on the other hand, ammonium phosphate appears to favour the production of spores.The growth of the mycelium, of which 200 grams can be obtained in 10 days from 400 sq. em. of surface, is accompanied by the liberation of mineral acids, the ammonia only of the ammonium salts being absorbed by the fixngus; the author, G. T. M.VEGETABLE PN YSIOLOGY AND AGRICULTURE. 171 therefore, suggests that the large excess of mineral bases in the ash of plants is due to a similar absorption of the bases of the neutral salts, whilst the acids are excreted. Starch is formed in considerable quantities under the conditions described, although it does not appear in ordinary cultures ; the quantity, estimated by a colorimetric method, was found t o be nearly 5 per cent.of the weight of the mycelium under favourable conditions ; traces of starch were also found in the nutrient liquors, together with larger quantities of dextrin and dextrose. When rendered soluble by the action of acids and purified by precipitation with baryta, the starch from A. niger gave [a),,= + 177", whilst ordinary starch gave [a]== + 185'; its identity was further established by conversion into dextrose. When nourished with racemic inositol instead of cane-sugar, the mycelium growth of A . lziger did not effect the resolution of the optical isornerides, but in ordinary cultures the dextrorotatory form was consumed more rapidly, the liquid in which fructification had taken place becoming laevorotatory.By CHARLES TANRET (Bull. SOC. Chim., 1897, [iii], 17, 921--927).-When AspergilZus lziger is macerated successively with water, alcohol,ether, and 5 per cent. caustic soda, and then digested with dilute sulphuric acid a t 100' for several hours, an insoluble residue of "fungin" remains. By treating this product a second time with caustic soda (2 per cent.), the author has obtained a residue of pure chitin ; the identity of this substance was established by analysis (C = 46.28, H = 6-63, N = 6-30), and also by the formation of glucos- amine on heating with hydrochloric ?cid at looo, and of chitosan on heating with potash at 1'70'. Other fungi gave similar results, but in no case was a residue of pure chitin obtained; thus, the chitin of the crab and that from A .lziger gave 82.5 per cent. of glucosamine hydrochloride, but the residue from Claviceps purpurea gave only 47-0 per cent., that from Polyporus o$icinaZis gave 40.8 per cent,, and that from Boletus edulis 39.5 per cent.; yeast, on similar treatment, gave only a minute quantity of insoluble residue, and may, therefore, be regarded as practically free from chitin. The author applies the name fulzgose to that part of the crude fungin which is soluble in soda; these substances approximate to cellulose in composition, but contain a small and variable percentage of nitrogen ; they do not, however, dissolve in Schweitzer's reagent, and give no blue coloration with iodine after treatment with sulphuric acid. Like cellulose, they dissolve slowly in 90 per cent. sulphuric acid and are converted into glucose ([a], = + 50') ; by the action of acetic anhydride and sodium acetate, they give di- and tri-acetates which are laevorotatory, whilst the salts are dextrorotatory ; they are insoluble in ammonia.The author has examined the fungoses from A . niger, C. purpureu, P . o$icinaZiS, and also that from Saecharomyces ceyevisia which has been previously mistaken for cellulose. T. M. L. Fungi. T. M. L. Change in Composition of Oleaginous Seeds during Germina- tion. By L ~ O N MaQUENNE (Compt. rend., 1898, 127, 625-628),- It is well known that the germination of many oleaginous seeds is 12-217s ABSTRACTS OF CHEMICAL PAPERS. accompanied by an increase in the amount of sugar present, and a decrease in that of the fats ; in order to determine whether sugar is elaborated, during this change, from the acid radicle of the fat, and, if so, whether the nature of the latter influences the result, the be- haviour, during germination, of seeds of Arachis (earth nut) and Ricinzcs (castor oil seed) was studied.The former contains the saturated fatty acid, arachidic acid, whilst the latter contains the unsaturated ricin- oleic acid. The seeds were grown in sand a t 20-25’, complete analyses being made at different stages of the plant’s growth. The results obtained indicate that the amount of oil decreases in both kinds of seed during the whole period of germination ; the maximum increase of total carbohydrates present, including ‘‘ cellulose,” occurs after 18 days in the case of Arachis, and after 10 days in that of Ricinus.I n the first case, the increase is 5.6 per cent., and in the second 16 per cent. ; the former appears entirely attributable to the glycerol of the oil being transformed into sugar, but the latter involves a transforma- tion of the ricinoleic acid into carbohydrates. The term ‘‘ cellulose ” used by the author denotes that portion of the plant which remains after successive treatment with light petroleum, dilute sulphuric acid, and 10 per cent. caustic potash; it contains, in addition to true cellulose, insoluble substances richer in carbon, which are sometimes nitrogenous. The sugar formed appears t o consist principally of glucose, associated, perhaps, with levulose. I n the case of Arachis, there is an initial decrease in its amount, with a subsequent increase, whilst in the case of Ricinus, a very rapid increase first occurs, followed by an equally rapid decrease; in the former case, the increase of “cellulose” is continuous, whilst in the latter it is preceded by B de- crease.Generalising from his results, the author considers that the fatty acids are less readily transformed into sugars than acids of the oleic series, and probably take part only in respiratory functions. The change of unsaturated acids, and especially of ricinoleic acid, into sugar, probably depends on the presence in the centre of the acid chain of the ally1 grouping, CH:CH*CH,; this is liberated by the progres- sive combustion of the ends, and gives rise, initially, to glycerol, which subsequently undergoes polymerisation. The amount of nitrogen present undergoes little change.W. A. D. Absorption of Haloid Potassium Salts by Plants. By E. DEMOUSSY (Compt. rend., 1898, 127, 771-774).-Terrestrial plants whose roots are immersed in solutions of potassium nitrate or potas- sium chloride absorb these salts at equal rates (compare Abstr., 1896, ii, 128), and the nitrate or chloride, when once absorbed, is retained by the living protoplasm, so that it cannot be extracted with cold water. Boiling water removes the salt, and the same result is obtained by first killing the plant with ether and then extracting with cold water. Potassium chloride is of far less importance to the plant than potassium nitrate, yet each is absorbed with equal readiness ; potassium bromide, which is never found in terrestrial plants, is also taken up by them in a precisely similar manner, when their roots are immersed in its solution.I n the case of these three salts, the amount removed from solution by the plant is far greater than that which would haveVEGETABLE PHYSIOLOGY AND AGRICULTURE. 173 been absorbed owing t o transpiration. With potassium iodide, the result is quite different; absorption keeps pace exactly with tran- spiration, and the salt exerts a toxic effect on the plant. The be- haviour of the terrestrial plant towards iodine is contrasted with that of the marine flora, in which this element is an essential constituent of the vegetable tissues. G. T. M. Absorption of Carbohydrates by Roots of Plants. By JULES LAURENT (Compt. rend., 1898, 127, 786-'78'7).-Seedlings of maize, when surrounded by an atmosphere deprived of carbonic anhydride, and cultivated in sterilised solutions containing glucose, continue t o grow, and after a few weeks exhibit a considerable increase in the weight of dry matter ; a duplicate culture, made without glucose and placed under the same bell-jar, shows no appreciable change in weight.The presence of sunlight is beneficial, the increase of weight being less when the plant in the glucose solution is cultivated in the dark. Other carbohydrates, such as cane sugar, dextrin, or starch can be utilised by the plant ; the roots have a powerful inverting action on the former, whereas the absorption of dextrin or starch is very slow. The seedlings of various plants, developed in distilled water until their reserve material is exhausted, and deprived of starch by cultiva- tion i n the dark, are immersed in glucose solutions surrounded by an atmosphere free from carbonic anhydride, and allowed to remain in sunlight during 5 or 6 hours at a temperature of 20-25' ; at the end of the time, the leaves are found to contain a notable amount of starch.These experiments indicate that the glucose absorbed by the roots is utilised by the plant in the synthesis of starch, and that green plants assimilate carbon, not only by the agency of chlorophyll, but also by the absorption of certain Carbohydrates by their roots. G. T. M. Assimilation of Nitrogen as Ammonia and Nitrites by the Higher Plants. By LAURENT, EM. MARCHAL, and CARPIAUX (Bied. C'entr., 1898, 27, 821-823; from Bul.Acad. Belg., 1896, 32, 815-865, and Bot. Centr., 1897, 70, 232).-The object of the experiments was to ascertain whether, in the case of higher plants, the presence of light is necessary to enable ammonia and nitric nitrogen t o be assimilated. Various plants were kept, with and without light, in distilled water, and in ordinary nutritive solutions containing ammonium sulphate and potassium nitrate respectively, and pure saccharose (4 per cent.). The organic nitrogen, and the nitrogen as ammonia and as nitrates, were determined after several days. It was found that assimilation only takes place in presence of light. Leaves free from chlorophyll assimilate ammonia vigorously, but not nitrates to any extent ; with chorophyllous leaves, the reverse is the case.Assimilation of nitrogen depends entirely, or almost entirely, on the ultra-violet rays ; when the light passed through a 0.2 per aent. solution of quinine sulphate, assimilation of nitrogen ceased. N. H. J. M.174 ABSTRACTS OF CHEMICAL PAPERS. Degeneration of Cattleya. By ALEXANDRE H~BERT and GEORGES TRUFFAUT (Bull, Xoc. Chim., 1897, [iii], 3.7, 712-718) -Cattleya, when grown under the usual artificial conditions, quickly becomes less vigorous, and in the course of a few years no longer affords saleable blossoms. The authors have compared the composition of plants grown under natural and tinder artificial conditions, before and after flowering, as well as that of the blossoms themselves. The cause of the degeneration seems to lie in the fact that the flowers contain a higher proportion of nitrogen, phosphorus, calcium, and magnesium than does the rest of the plant, and, in consequence of this, the necee- sary amount of these constituents in the plant diminishes rapidly with the successive flowering, as they are not supplied by the sphagnum and polypody on which the orchid is usually grown. Phosphoric Acid in Barley and Malt : Presence of Organic Acids in Malt.By CHARLES G. MATTHEWS and G. H. WOOLCOTT (J. Fed. Inst. Brew., 1898, 4, 6--20).-The authors find that there is a rough relationship between the soluble phosphates of malt and the acidity of the extract, a high acidity as arule accompanying a high percentage of soluble phosphates ; for the estimation of the latter, the malt extract is evaporated to dryness with some lime, the residue charred, and the phosphoric acid determined by the molybdate method.I n determining the acidity of malt worts, rosolic acid and litmus give practically the same results, but phenolphthalein gives values which are often four or fives times as high, since it is not affected by the secondary phosphates, which are alkaline to rosolic acid ; phenol- phthalein is, therefore, to be preferred. The authors confirm Prior’s statement that there is no connection between the acidity of malt and the total phosphoric acid. Numbers are given showing the percen- tages of calcium andmagnesium in cold-water extracts of malt and in worts. By extracting malt with alcohol, the authors only obtained 0.024 per cent. fixed acidity and 0.0054 per cent.volatile acidity,calculated in both cases as lactic acid. Butyric, lactic, and succinic acids were identified in the extract. There can, therefore, be no doubt that the acidity of malt is almost entirely due to the presence of acid salts, as Fernbach and others have suggested. Carbohydrates of Barley and Malt with special reference to the Pentosans. By BERNHARD TOLLENS (J. Red. Inst. Brew., 1898, 4, 438-454).-The author reviews the present state of knowledge in connection with the nature of those carbohydrates of barley and malt which yield pentoses and furfuraldehyde on boiling with dilute acid. He is of opinion that in addition to pentosans, the furfuraldehyde- yielding substances of malt contain other compounds which are more susceptible of fermentation than arabinose and xylose, and which dc not contain the methylene group, as suggested by Cross and Bevan, since they do not give the characteristic reaction with phloroglucinol and hydrochloric acid.Composition and Feeding Value of French Haricots. By BALLAND (Compt. rend., 1898, 127, 532--534).-The author has A. L. A. C. C. A. 0. C.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 175 analysed haricots grown in sixteen departments of France i n the year 1897. The mean weight of 100 beans varied from 23.80 to 98.70 grams, and the percentage of husk varied between 6.2 and 9-2. The extremes of composition in the natural state were : water, 9.00 to 14*40; nitrogenous matter, 17.02 to 22.70 ; fat, 1.10 to 1.90; sugar and starch, 52-22 to 62-56 ; cellulose, 2-15 to 6.65 ; ash, 2.25 to 6.65 ; or in the dry state, nitrogenous matter, 19.61 to 25-50; fat, 1.26 to 2-16 ; sugar and starch, 61.00 to 71.52 ; cellulose, 2.50 to 7.57 ; ash, 2.61 to 7.77.If the haricot,s are to be kept for a long time, they must not contain more than 12 to 14 per cent. of water when gathered, and must only be harvested during dry weather. The smaller varieties are generally more nitrogenous, and lose their excess of water more quickly, than the larger beans. C. H. B. Nitric Nitrogen produced by the Pea. By JASPER L. BEESON (J. Amer. Chem. Xoc., 1898, 20, 793-795).-Samples of soil were taken from small plots, on which various plants were growing, at the end of September, after about six weeks of dry weather, and the nitric nitrogen determined. The following amounts of nitrogen per million of soil were found.Fallow. Peas (I). Peas (2). Peas (3). peas. Maize. Cotton. Sorghum. 1.01 3.33 8.67 10.51 7-50 0-34 0.42 0.33 Maize and Peas (1) had pods nearly grown, (2) had pods nearly ripe, and (3) had been dead two or three weeks. The cotton and sorghum were still growing, but not the maize. It is concluded that the nodule bacteria assimilate more nitrogen than the plant requires, and that peas growing with another crop would tend to increase the yield of that crop, provided that they were not too thick to check the root development, or use up too much soil moisture. It is suggested t h a t the nodule bacteria may possibly continue t o assimilate nitrogen after the death of the plant as long as there are any juices left in the plant.The soil was a very productive, rich bottom land. N. H. J. M. Nitriftcation in Soils. By TH. SCHL~SING, gun. (Compt. rend., 1897, 125, 824--827).-Whilst the fact that nitrification is less vigorous in heavy than in light soils is usually attributed to insufficient aeration, the author's experiments indicate that, in many cases, at any rate, it is not a deficiency of air but of water which retards nitrification. Artificial soils, to which ammonium sulphate was added, wore kept in flasks for 2h-34 months, and the nitric nitrogen determined. The sand and clay together amounted in each case to 100 grams. In the following summary, the amount of sand is given (in grams), and the percentage amounts of nitrogen which was nitrified. The chalk which was added mas 0.5 gram (Nos.1-5 and 12-15), and 1.0 gram (6-11). Flasks 1-5 had 0.05 ; 6-11,O.l ; and 12--15,0.0666 gram of ammonium sylphate.1'16 ABSTJZACTS OF CHEMICAL PAPERS, - Grams. 100 90 80 75 70 No. - 1. 2. 3. 4. 5. I-------- -1- Per 1 Per Grams. cent. Grams. Grams. cent. 10.0 83.0 1 6. 100 9-5 63-0 10'0 94-0 7. 90 9.5 66'0 10.0 89-0 8. 85 9.5 94.0 10'0 56.0 ~ 9. 80 9.5 100.0 10.0 10.0 10. 75 9.5 21.0 1 11. 70 9.5 2.7 Sand. Water. nizfied No. Sand. Water. No. I I ll ! I I N !I Grams, 70 70 70 70 Grams. 10'6 11'5 13.2 14.0 __ 12. 13. 14. 15. I I Sand. I W ater. -- N. iitrified Per cent. 80.0 100 -0 100.0 100 '0 - I n Nos. 1 and 6,-nitrification was incomplete, nitrous acid being present; 9.5 to 10 per cent. of water is probably too much for pure sand, and by occupying too much space hindered aeration.The very incomplete nitrification in Nos. 4, 5, 10 and 11 could not have been owing to want of air, as the soils were, in each case, quite permeable ; moreover, in Nos. 13-15, which contained 30 per cent. of clay, and more water, the whole of the ammonia was nitrified, The failure in the cases mentioned must therefore be ascribed to in- sufficient water in presence of 25-30 per cent. of clay. With regard to the remarkable effect brought about by a slight increase in water or a slight decrease in clay, it is suggested that the conditions under which nitrification was diminished were owing to the limit having been exceeded, below which the capillary attraction, which retains the water and dissolved substances on the soil, become, nearly everywhere, superior t o the osmose which caused the water to penetrate the cells of the microbes, and thus rendered them unable to obtain food from the soil.The results have an important bearing on the question of nitrification in heavy soils. By E. F. LADD (J. Amer. Chem. Xoc., 1898, 20, 861--867).-The following summary gives the lowest, highest, and average percentage results obtained with 24 North Dakota soils. N. H. J. M. Humates and Boil Fertility. In soil (total). In Humus. 'F P Humus. ates. N. K,O. CaO. P20,. N K20. CaO. P205 Lowest ...... 3'84 1.56 0.180 0-18 trace trace 0.041 0.075 0 0'086 Highest ..... 15.26 7.90 0'456 0.73 2.70 0-40 0.362 0.233 1'03 0.199 Average ..... 9'15 4.77 0'292 0'409 0'944 0'269 0'163 0'153 0.436 0,138 Assuming the weight of an acre of soil to the depth of 1 foot t o be 2,225,0001bs., the total nitrogen will amount, on the average, t o 6,497 lbs., the nitrogen in humus to 3,627 lbs., and the phosphoric acid to 5,985 and 3,061 lbs.As regards the effect of continuous cropping on soils, ordinary analyses of new, unbroken prairie soil and the soil of an adjoining field which had been cropped 17 years (chiefly wheat) gave very little indication as to the cause of the marked decrease in produce which was observed. The amount of humus was found to be unusually low for North Ddkota (2.53 per cent.), and by continuous cropping i t had been reduced by 39 per cent, f l Hum-VEGETABLE PHYSIOLOGY AND AGRICULTURE. 177 A field which had been cropped continuously for 15 years (wheat) was afterwards rendered more fertile by a system of crop rotation.During 8 years of rotation, the humus increased 46.9 per cent., whilst the phosphoric acid in the form of humates increased 48 per cent. N. H. J. M. Efficacy of Various Manures. By H. STEFFECE and MAX MAERCKER (Jahr6. agrik.-chem. Versuchs-Stat. Halle a-S., 1896, 2, 105--131).-The Nitrogen and Phosphoric Acid of Fish Guano.-Two different Norwegian fish guanos were employed for the experiments, containing N = 11.81 and 9.27, and P,O,, 4.51 and 12.06 per cent. re- spectively. With both barley and oats, the more nitrogenous guano gave much the best results. I n the case of barley, the yield was almost as great as when the same amount of nitrogen in the form of nitrate was given, whilst the barley produced was less nitrogenous.The low percentage of fat in the guano (19"7-1*84 per cent.) was favourable. As regards the effect of the phosphoric acid, it was found to be about equal to 60-70 per cent. of phosphoric acid soluble in water for the first crop. Ammonium ccnd Potassium Phosphates.-As a nitrogenous manure, ammonium phosphate acted in a manner quite similar to ammonium sulphate with both oats and barley, both as regards yield and nitrogen- content of the grain. The effect of the ammonium salt as a phosphate corresponded with only 88.33 per cent, of that of phosphoric acid soluble in water, whilst potassium phosphate was exactly equivalent t o a super-phosphate. Bone Meal.-The bone meal was treated with only sufficient sulphuric acid to combine with the calcium present as carbonate, and to form di- calcium phosphate.As a manure, the product equalled, the first year, phosphoric acid soluble in water, and the after effect was greater than that of basic slag. It is thus possible to obtain an excellent manure from bone meal at a slight expense. Four manufactured products contained total P?O,, 19.17-24-25 ; P,05 soluble in water, 2.10-5.44 ; P,O, soluble in citrate (excluding soluble in water), 9.80-20-25 per cent. Stone Meal.-The phosphoric acid of stone meal mas found to be entirely without effect. The potash is quite insufficient for a crop, even with an application of 100 cwt. per hectare, whilst smaller amounts are injurious, as they induce a certain amount of development in the plants which cannot be maintained.Efect of Extracting the Rat fi.om various Nitrogen Manums.-The manures were meat meal, fish meal, and poudrette. I n the case of meat meal, the result of removing the fat was to increase the manurial effect by 17.1 per cent., whilst 16.3 per cent. more nitrogen was taken up by the plants (white mustard). With fish meal, the effect was almost as great as regards the increased amount of nitrogen assimi- lated. I n the case of poudrette, the yield was raised only 5.7 per cent., and 'the nitrogen taken up mas increased by 7-2 per cent. Fish meal, freed from fat, was found to be equivalent t o 81.6 per cent. of the value of nitrate, and meat meal to 73.1 per cent. of nitrate. The effect of the residue on the second crop was very slight. V&rious Nitrogenous Manui*es.-A process has been proposed forI78 ABSTRACTS OF CHEMICAL PAPERS. converting nitrogenous refuse, such as hair, leather, and wool, &c., into a satisfactory manure, by heating 500 parts with a solution of potash (50 parts) containing lime (50 parts) in thin layers, first in a current of carbonic anhydride and afterwards in steam, Slaughter- house refuse thus treated gave very satisfactory results with oats, and especially with barley, whilst refuse from tanned skins gave still better results. Leather refuse was unsatisfactory. Experiments made with some new guanos are also described. Proteids of Cream. N. H. J. M. By E. F. LADD (J. Amea. Chem. Soc., 1898, 20,855-860).--Casein was precipitated by adding a saturated solution of alum (3 c.c.) to 10 grams of cream diluted with water (80 c.c.); after 10 minutes, the solution was filtered, and the precipitate washed with water. The albumin was next separated by heating the filtrate to boiling, and filtering after a few minutes. The filtrate from the albumin was evaporated to about 50-60 c.c., and the albumoses pre- cipitated by saturating with zinc sulphate. After 10-12 hours, it was filtered, the precipitate well washed, and the nitrogen determined. The peptones were determined in the filtrate by evaporating to a small bulk, when R portion of the zinc salt separated, and then adding absolute alcohol to 80 per cent. of the volume ; after 12 hours, it was collected, washed with alcohol, and the nitrogen determined. As a check, the total nitrogen of the cream was also determined. The following percentage results, obtained with (1) fresh cream and (2) ripened cream, are given. N in N in N in N in N in casein. albumin. albumoses. peptones. Total. cream. 1. 0.237 0-035 0.031 0.023 0.326 0.335 2. 0.249 0.027 0.033 0.032 0.341 0.344 The results show that the method adopted involves no great losses, and that there is no very marked change in the proteids of cream during ripening. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA8997605169

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

I78 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Hydrogen Sulphide as a Reagent. By CARL GRAEBE (Ber., 18 98, 31, 298 1-2 982) .-In the author’s laboratory, precipitations with hydrogen sulphide are always carried out in closed vessels; for this purpose, small bottles are employed, into which the gas is passed by a, tube, an expansion on which is ground into the neck of the bottle thus preventing all escape of gas into the air. The vessel is not closed until the air above the liquid has become displaced by hydrogen sulphide. The precipitation is accelerated by shaking, J. J. 8. [Estimation of Hydrogen Peroxide.] B.y MARCELLIN P. E. See this BERTHELOT (Ann. Chim. PAYS., 1897, [vii], 11, 217-222. vol., ii, 149).ANALYTICAL CHEMISTBY. 179 Estimation of Perchlorate in Chili Saltpetre.By FR. FREYTAG (Chem. Centr., 1898, i, 1203; from Zeit. ofentl. Chem., 4, 321-323). -Ten grams of the sample is heated in a covered porcelain crucible until effervescence has nearly ceased, and the crust formed on the cover is removed and put back into the crucible, which is again heated for 10 minutes. The contents are then dissolved in water, the solution acidified with pure nitric acid, boiled for 10 minutes, and the total chlorine estimated by Volhard’s process. From this is deducted the chlorine present as chloride estimated in 10 grams of the sample by Volhard’s process, and the difference is then calculated t o Dotassium Derchlorate. Allowance should be made for A A traces of iodate, if present. Estimation of [Dissolved] Oxygen in Water. By A.FLORENCE Chem. Centr., 1898, i, 474; from Rdp. Pharm., 1897, 385).-The round-bottomed flask B is filled with the sample of water and at once closed with a perforated indiarubber cork, fitted with a three-way stop- cock, R. By means of the latter, B is con- nected at will with a graduated burette, furnished with a stopcock R’, or, by means of an indiarubber tube, with the cylinder M, filled with mercury. By lifting M and opening R the burette is filled witb mercury. R’ is then closed and M is lowered, which causes a vacuum in the burette. By turning R, the communication between the burette and M is intercepted, and established with B instead ; the dissolved gas is now given off, and this may be accelerated by gentle warming. When no more gas is given off, the burette is again connected with M, the mercury in the two tubes is levelled, and the volume of gas is read off.After removing any carbonic anhydride by means of aqueous potash, the volume of oxygen is determined as usual by absorption with alkaline pyrogallol. By means of this apparatus, estimations may be made in a very short time; this is very important, as the amount of dissolved oxygen may rapidly diminish owing to the ac- tion of bacteria. L. DE E(. L. DE K. Distinction between Ozone and Nitrous Acid or Hy- drogen Peroxide. By G. ERLWEIN and THEODOR WEYL (Ber., 1898, 31, 3158--3159).-0zone produces a wine-red coloration with a solution of metaphenylenediamine, both in presence of acids and alkalis. Since neither nitrous acid nor hydrogen peroxide produces any coloration with the diamine in presence of caustic soda, this re- agent may be employed for distinguishing between ozone, on the one hand, and nitrous acid and hydrogen peroxide on the other.A freshly prepared solution of 0.1 -0.2 gram of metaphenylenediamine180 ABSTRACTS OF CHEMICAL PAPERS. hydrochloride and 10 C.C. of 5 per cent. aqueous soda, made up to 100 c.c., is recommended as a suitable reagent, 25 C.C. of this giving a yellowish-brown coloration with 0.08 milligram of ozone in 5 seconds. Similar colours are produced with the corresponding ortho- and para-diamines. The authors propose to examine the atmosphere, and a number of animal and vegetable organs, and liquids, for ozone. A. H. Estimation of Sulphuric Acid. By F~LIX MARBOUTIN and ADRIEN P~COUL (Bull.SOC. Chirn., 1897, [ iii], 17,880-881).-The estimation of sulphuric acid as ammonium sulphate gives accurate results when the evaporation is carried out at 65', but an increase of weight occurs when the residue is further heated on a water-bath at a temperature of 85-100' ; above this temperature, the weight decreases again, and becomes normal at 120'. The authors regard this increase of weight as due to loss of ammonia and consequent absorption of water by the residual sulphuric acid ; in support of this view, they show that the residue, after heating to 85', has a marked acid reaction. T. M. L. NoTE.-According to Watson Smith (Abstr., 1898,ii, 575),ammonium sulphate is dissociated, on heating, into the acid sulphate and ammonia, and not into sulphuric acid and ammonia.T. M. L. Delicate Test for Ammonia and Nitrogenous Compounds which readily yield Ammonia. By E. RIEULEB (Chem. Celztr., 1898, i, 272-273; from Bull. Soc. Xci. Bucuresci, 1897, 6, 335)- One gram of paranitraniline is dissolved in 20 C.C. of hot water and 2 C.C. of hydrochloric acid ; 160 C.C. of water is added, the mixture well shaken, and when cold mixed with 20 C.C. of a 2.5 per cent. solution of sodium nitrite. Should the solution become turbid, it must be filtered. Ten C.C. of the solution to be tested for ammonia, or compounds, like proteids, &c., which readily yield ammonia under the influence of strong alkalis, is mixed with 10-15 drops of the reagent and 10 per cent. aqueous soda is added drop by drop. I n the presence of ammonia, reddish-yellow clouds appear, and, on shaking, the liquid turns yellow, or even red.If now excess of sulphuric acid is added, the colour vanishes, but on the surface of the liquid microscopic, yellow needles appear, which are soluble in alcohol, the solution giving an intense reddish-violet colour with aqueous soda. L. DE I(. Phosphorised Oil, By H. EEROOS (Arch. Pharm., 1898, 236, 6 2 7-6 35).-Bo t h D usart-Blondlot's met hod and the bromine method for the estimation of elementary phosphorus in phosphorised oil give results which are about 50 per cent. too low. Phosphorised oil contains a portion of the dissolved phosphorus in the elementary condition, and a portion in the combined state, which is only slightly oxidised by bromine or nitric acid, is not volatile with steam, and of which the amount increases with the length of time t h e oil is kept.It seems probable that the phosphorus is combined with the fatty acids of the oil, but this could not be definitely proved. A. W. C.ANALYTICAL CHEMISTRY. 181 Detection of Phosphorus in Insoluble Substances by Sterelectrolysis. By FRANQOIS MAYEN~ON (Chem. Centr., 1898, i, 904 ; from Rev. Techn., 1897, 398).-The process, which is applicable to phos- phides and insoluble phosphates, is based on the liberation of phos- phorus by the galvanic current, a sheet of platinum, zinc, or silver servingas anode. The substance is put on a piece of filter paper covering the anode, moistened with water or brine, and connected for a short time with the cathode ; the liquid will then give the reac- tions for phosphoric acid.Or the substance may be moistened on a platinum foil with a few drops of molybdenum solution; the foil is then connected with the positive pole, and when the circuit is closed a Detection of Arsenic in Coal-Tar Colours. By ALFRED ORTMANN (Chem. Centr., 1898, i, 998-999 ; from Zeit. Ncchrungsnz. Hyg. Waccr., 12, 85--91).-Five grams of the dried colour is intro- duced into a tubulated retort, 5 C.C. of strong ferrous chloride added, and a current of pure hydrogen chloride is passed through the gently heated mixture; the vapours evolved are passed first through a Liebig’s condenser, and then through a receiver containing water, After an hour’s action, the distillate is introduced into the Narsh’s apparatus, b u t should i t contain sulphurous anydride this is first oxidised by potassium chlorate and the excess of chlorine expelled by heating on the water-bath. Or 5 grams of the sample is heated i n a Kjeldahl flask with fuming nitric acid and evaporated to dryness ; a mixture of 1 part of potassium sulphate and 2 parts of sulphuric acid is added, and the whole boiled until nearly colourless. When cold, the mass is dissolved in a little Volumetric Estimation of Boric Acid.By H. COPAUX (Compt. rend., 1898, 127, 756-759).--8 known quantity of a soluble borate dissolved in a few C.C. of water is titrated with standard sulphuric or hydrochloric acid, using methyl-orange as indicator ; the amount of acid required is a measure of the base combined with the boric acid; twovolumes of an alcoholic solution of glycerol are now added, and the solution is titrated with N/4 caustic soda (free from carbonate) in the presence of phenolphthalein. The latter titration is repeated, under similar conditions, with a solution of pure boric acid and glycerol; the amount of boric acid in the soluble borate is deter- mined from a comparison of the results.Solutions of soda and boric acid in ethylic alcohol may he employed, and the author applies the method to the estimation of boric acid i n its alkylic salts ; methylic alcohol, however, must be absent, as it interferes with the end-point. yellow spot will make its appearance. L. DE K. water, and then tested i n the Marsh’s apparatus. L. DE K. G. T. M. By HENRYK WDOWISZEWSKI (Zeit. anal. Chem., 1898, 37, 742).-The dissolution of iron in cuprammonium chloride and the subsequent dissolution of the precipitated copper are tedious operations if allowed t o proceed in repose, but by vigorous skaking they can be greatly accelerated.The author employs a conical flask oE 250-300 C.C. capacity, with a well Estimation of Carbon in Cast Iron and Steel.182 ABSTRACTS OF CHEMICAL PAPERS. fitting stopper held down by a clip. I n this is placed the weighed metal with 50 C.C. of copper solution for each gram of iron present, and the stoppered flask is immediately shaken in a shaking apparatus ; the operation is complete in 5-8 minutes, and the carbon is obtained in a condition in which it can readily be collected and washed. M. J. 5. Estimation of the Alkaline Earths without previous Separa- tion.By JOHANNES KNOBLOCH (Zeit. anacl. Chem., 1898,37,733-740). -Jn consequence of the unsatisfactory character of all methods which depend on the complete separation of the three alkaline earths from one another, the author re-advocates the method of indirect estimation, and gives the preference to that form in which the mixed carbonates are weighed and then converted into oxides. This is effected by fusing the carbonates with borax which has first been heated t o a constant weight in a platinum crucible (employing a Buneen flame and a fire-clay crucible-jacket). Puttingp for the weight of the carbonates,and n for that of theoxides. 2-00652915p-2*58283141n = the CaO present when the other metal is barium. 2.77369366~ - 3.9526343% = the CaO present when the other metal is strontium.7-2546326p-9'33816773n = the SrO present when the other metal is barium. If the three metals occur together, the indirect method requires to be supplemented by the direct estimation of the barium; the solution containing the neutral chlorides of the three metals is divided into two portions, in one of which the barium is precipitated as chromate with the precautions laid down by Fresenius (Abstr., 1891, 110, 500; 1893, 436); in the other, the three metals are thrown down as car- bonates, and the values p and n, (calculated on the total original solution) ascertained as above. Then putting T for the weight of the barium chromate (also in the total solution), CaO = 2 ~77369366~- 3.95263432n + 0.23080504~. BaO = 0.60367371~.SrO = n - BaO - CaO. The test analyses communicated show that fairly close results are obtainable. M. J. S. Detection of Cadmium in Presence of Copper by Adsorp- tion. By HEINRICH TREY (Zeit. anal. Chem., 1898, 37, 743-74.7)- The author has devised a simple piece of apparatus, for the applica- tion of the principle first studied by Schonbein in 1861, that when a dilute solution containing several soluble substances is allowed to rise by capillarity in a piece of filter paper dipped into the liquid, the soluble substances are not only withdrawn by the paper from the water, but are arrested at different distances from the surface of the liquid. A narrow piece of glass-tube has one end widened into a funnel, and the other drawn out t o a capillary point; the tube is then bent into a U form, and fixed with its open ends upwards.The solution can then be introduced by the funnel, and when it reaches the capillary point a disc of filter paper can be brought in contactANALYTICAL CHEMISTRY 183 with the point, by resting it on a light wire frame, and allowed to remain until it has absorbed enough of the solution t o form a wetted spot of any desired diameter. Solutions containing copper and cadmium are treated with excess of ammonia, and then diluted until the blue colour is scarcely visible. One of Schleicher’s ash-free filters is allowed t o absorb enough of the solution to wet the paper t o a distance of 2.5 cm. from the capillary tube, and is then exposed to the vapour of ammonium sulphide, when the central black spot will be surrounded by a yellow ring of cadmium sulphide, the width and intensity of which will depend on the amount of cadmium present.Detection and Estimation of Lead in Tin-plate and Tinned Foods. By P. CARLES (Chern. Centr., 1898, i, 798; from Bull. SOC. Phurm. Bordeaux). -For the estimation of lead in tin-plate, Riche’s method is recommended, in which the lead is obtained as dioxide by electrolysis; this process is not interfered with by the presence of copper, but is rendered irregular by the presence of 5 per cent. of iron, and should more than 10 per cent. be present, the solu- tion retains ferric stannate. To detect lead in foods, these are burnt in a muffle, the charred mass is powdered and extracted with water t o remove chlorides and alkali phosphates, and then burnt, with addition of sulphuric acid.The ash is treated with a mixture of 6 C.C. of nitric acid and 30 C.C. of sulphuric acid in 264 C.C. of water, and the solution submitted t o Volumetric Estimation of Mercury by Sodium A-rsenite. By C. REICHARD (Zeit. and. Chem., 1898, 3’7, 749-751).-The oxides of mercury are reduced to metal when heated with an excess of solution of sodium arsenite in excess of sodium hydroxide, with conversion of a corresponding amount of arsenite into arsenate ; the unreduced arsenite is then titrated by iodine or permnnganate, after filtering hot and washing. The method seems capable of some degree of accuracy. M. J. 5. Alkalimetric Estimation of Metals. Estimation of Mercury. By HENRI LESCGUR (Bull. Xoc. Chim., 1897, [iii], 1’7, 706-712.Compare Abstr., 1898, ii, 455).-Mercuric chloride may be estimated by titration with N/10 alkali, phenolphthalein being used as an indi- cator ; it is necessary that the precipitated mercuric oxide should be separated by filtration, in order to minimise the disturbing influence of the mercuric oxide on the dissolved potassium chloride, a condition which is also attained by employing an alkali of N/100 strength. The use of heliant hin leads to unsatisfactory results in this particular instance. I n the cases of mercuric sulphate and nitrate, which are only soluble in presence of excess of acid, the estimation of the metal may be accomplished by making two distinct titrations of the solution, one with helianthin in presence of common salt, which gives the amount of free acid, and the second with phenolphthalein alone, which gives the sum of the free acid and that of the mercuric salt itself.M. J. S. electrolysis. L. DE I(.184 ABSTRACTS OF CHEMICAL PAPERS. Mercurous chloride, when boiled with alkalis, is decomposed in accord- ance with the equation Hg,CI, -t- 2KOH = Hg + HgO + 2KCI-t- H,O, a reaction which may be taken advantage of in estimating mercurous salts. The authors recommend the same method for estimating chlorides in certain liquids, mercurous nitrate being used to precipitate the halogen as calomel. For practical details, the original paper must be consulted. A. L. Volumetric Estimation of Osmium Tetroxide. By EDUARD A. KLOBBIE (Chem. Centr., 1898, ii, 65-66 ; from Kon. Akud. Wetensch. Amsterdam).-Osmium tetroxide may be estimated to 0.01 per cent.by treating its solution in dilute sulphuric acid with potassium iodide solution and titrating the liberated iodine with sodium thiosulphate ; four atoms of iodine are liberated by each molecule of osmium tetroxide, osmium dioxide, potassium sulphate, and water being formed. The solution becomes dark green, and, even after remaining for days, no further reduction takes place ; osmium dioxide is feebly basic, and probably the green coloration is due to the intermingling of the blue solution of this oxide in sulphuric acid with the solution of iodine. E. W. W. Estimation of Organic Matter in Water by Potassium Permanganate. By FELIX MARBOUTIN and MICHEL FRANCE (BzcZZ. Soc. Chim., 1897, [ iii], 17,888--890).-The authors show that Lhy’s method in use in France gives results twice, or even thrice, as great as those obtained by the modified Forchammer method used in England ; the French standard, however, allows twice as much organic matter, and the classification of the waters is consequently the same in both countries.T. M. L. By G. MEILLBRE (Chem. Centr., 1898, ii, 140 ; from AnuZ. Chim. Anul. AppZ., 3, 153--154).-0ne gram of the sample is introduced into a flask, or if a solution has to be tested, a suitable quantity is evaporated to dryness in the flask ; to this, 25 C.C. of pure nitric acid is added and then 1.7 gram of silver nitrate. The flask, connected with a Liebig’s bulb apparatus containing a little silver solution to serve as a trap, is now heated, gently at first, but more strongly towards the end ; when no more nitrous fumes are evolved, the liquid in the flask is diluted to 150 C.C.and heated until quite clear. If the liquid in the bulbs is turbid, it must be added to the main bulk of liquid. The silver iodide is collected on a weighed filter, Analysis of Aqueous Alcohol. By CHESI’ER B. CURTIS (J. PhysicaZ Chem., 1898, 2, 371-375).-1f a definite quantity of aqueous alcohol is taken, the amount of toluene that must be added in order to produce a cloudiness increases as the amount of water in the alcohol decreases. The percentage purity of alcohols containing water may, therefore, be determined by titration with toluene. The method of operating suggested by the author for determining the percentage of alcohol (above 85 per cent.) in a mixture containing water, is to pipette off 10 C.C.of the solution, dilute with 1 c,c. water, and add toluene until the mixture clouds and clears at 09 The following Assay of Iodoform. dried a t looo, and weighed. L. DE K.ANALYTICAL CHEMISTRY. 185 table gives the number of C.C. of toluene required for alcohols differing by one-half per cent. from 85 to 100. Per cent. alcohol. 85.0 85.5 86-0 86 -5 87-0 87'5 88.0 88.5 C.C. toluene. 3.40 3-49 3.58 3'70 3.90 4.05 4'25 4 48 Per cent. alcohol. 89.0 89'5 90.0 90.5 91 '0 91 *5 92 '0 92.5 Per cent. C.C. 1 to*uone* alcohol. / I 4'70 I / 93'0 4'95 93.5 5'20 11 94.0 5 '40 94-5 5-80 1' 95'0 6'15 /I 95-5 6.55 96'0 7.00 11 96.5 C.C. toluene. 7.50 8 *lo 8 -70 9.55 10-60 11 *70 12-90 14-25 Per I a E t i _- 97.0 97'5 L8'0 98.5 99'0 99 *5 100'0 - c.c. toluene. 15.75 17'45 19'40 21 5 0 23.70 25.85 28'00 - It is obvious that the accuracy of the method is greater as the purity Detection of Glucose in Urine by Means of Methylene- Blue. By ALFRED FROHLICH (Chem. Centy., 1898, ii, 66-67; from Centr. inn. Med., 1898, No. 4).-Ten C.C. of the urine is first freed from reducing colouring matters by mixing i t with 5 C.C. of solution of lead acetate (3-lo), and, then, after shaking, with 5 C.C. of basic lead acetate. The filtrate which, if not colourless, should be diluted with an equal bulk of water and treated with a little more solid lead acetate, is then tested for sugar as follows : 5 C.C. is mixed with 5 C.C. of a solu- tion of methylene-blue (1 : 300) and 1 C.C.of 10 per cent. aqueous potash and boiled. If the colour of the mixture fades, sugar is present. of the alcohol increases. H. C. As little as 0.04 per cent. may thus be detected. L. DE K. Estimation of Sugar in Urine. By W. SCHLOSSER (Chem. Centr., 1898, i, 1209-1210 ; from Phwm. Centr.-HalZe, 39, 259-261).-0ne hundred C.C. of the sample of urine is fermented with 4 grams of yeast in a long-necked flask closed with cotton wool, the fermentation being started by placing the flask in water of 35-40'; the whole is then kept for 12 hours at a temperature of 20'. After making sure that all the sugar has disappeared, the yeast is allowed to subside, the liquid poured off, the carbonic anhydride removed by agitating the liquid, and the sp. gr. is then carefully taken (Dl).Another 100 C.C. of the sample is mixed with 2 C.C. of a 1.6 per cent. solution of salt, which the author calculates will introduce the satme error in sp. gr. as the amount of added yeast does, and the sp. gr. is taken (P). The difference D1 - 0 2 is then multiplied by ( V2 : V1).229 or (102 : l00).229 = 233, in which formulze Vl and V2 represent the respective volumes of the samples, and 229 the factor proposed by Roberts for calculating the amount of sugar from the loss in sp. gr. I f D1 and 0 2 are taken at different temperatures, a correction must be made. If tl is the temperature of the urine and salt, t2 the temperature after fermentation, the difference $1 - t 2 should be multi- plied by 0.0002, and the product added to D1- 0 2 when the tempera VOL. LXXVI.ii. 13186 ABSTRACTS OF CHEMICAL PAPERS. ture lies between 15"and 20". For temperatures between 20" and 25", Estimation of Diabetic Sugars by the Polarimeter, by the Reducing Power, and by Fermentation. By F R ~ D ~ R I C LANDOLPH (Compt. ?*end., 1898, 127, 765-767. Compare Abstr., 1897, ii, 512, and 1898, ii, 148).-The author's investigations on the reducing power, fermentation, and thermo-optical properties of diabetic sugars, and on the appearance of their solutions when viewed through the polaristroborneter render it possible t o divide these sugars into three classes which may be useful in the diagnosis of various glycosuric and diabetic affections. G. T. M. Estimation of Sugar in Meat and Urine. By EDUARD POLENSKE (Chem. Centr., 1898, i, 1071-1072; from Arbb.Kais. Ges. A., 14, 149--152).-Two hundred grams of finely comminuted meat, after being soaked for half an hour in 600 C.C. of cold water containing a little acetic acid, is heated to boiling, and when cold the mass is pressed through flannel, and then extracted twice more. The sugar is estimated in the united extracts by means of Peska's ammoniacal copper solution. Treatment with lead acetate is not advisable, as this might cause loss of sugar ; precipitation by means of alcohol also is unadvisable. The extract is first filtered through paper, animal charcoal is added, and the whole evaporated on the water-bath until about 250 C.C. is left; it is then filtered, the charcoal well washed, and the filtrate again concentrated t o 250 C.C. To the liquid, ammonia is added in slight excess, the whole diluted to 300 c.c., and after 15 minutes filtered and neutralised with acetic acid.It is then colourless and well adapted for the titration; it must, however, be borne in mind that urine, and more particularly meat, contains small proportions of reducing substances which in the analysis count as sugar. It is more difficult to prove the presence of cane sugar, as this becomes partly inverted, whilst some components of the meat extract also suffer inversion when treated with acids. The author has, how- ever, found that this may be reduced to a minimum by using 5 drops of hydrochloric acid for 100 C.C. of liquid, and heating for half an hour only; the extractive compounds, such as glycogen, are then but little affected, whilst the sugar is completely inverted.The author also recommends Peska's process for the testing of diabetic urine; this should be diluted so as to contain about 0.5 per By R. FRUHLING (Chem. Ceatr., 1898, ii, 305; from Zeit. o$entZ. Chem., 4, 410-412).-The author calls attention to the fact that solutions of honey, when freshly prepared in the cold, show a very abnormal polarisation, caused by birotation. After the lapse of 5-6 hours, the polarisation is normal. The error caused by this birotation is sometimes very large, and may amount to as much as - 14'. The author found that the normal polarisation is at once restored by adding to the liquid about 0.1 per cent. of ammonia ; basic lead acetate should not be added, but the liquid should be clarified by means of alumina cream.It is also the factor 0*0003 should be used. L. DE K. cent. of sugar. L. DE K. Polarisation of Honey,ANALYTICAL CHEMISTRY. 1 ss advisable to dissolve the honey first in a little boiling water, as a high temperature destroys birotation. By R. WOY (Chem. Celntr., 1898, i, S61 ; from Zeit. o f e d . Chew%., 4, 224-226).-The process recommended by de Koningh (Abstr., 1898, ii, 314) is accurate, bat rather slow, when applied to chocolate, unless the sample is first deprived of its fat, The author now proposes the following process, based on Scheibler's principle of double dilution. A 100 and a 200 C.C. flask are taken; half the normal weight of powdered chocolate (13.024 grams) is introduced into each, moistened with alcohol, and treated with water at 50'; after thoroughly shaking to dissolve the sugar, 4 C.C.of basic lead acetate solution is added, and, when cold, the liquids are made up to the mark and again shaken. The filtrates are now polarised in the 200 mm. tube. If a represents the polarisation of the 100 C.C. liquid, b that of the 200 C.C. liquid, and x the volume of the insoluble matter, including the lead precipitate, then the sugar in the 100 C.C. flask is dissolved in 100 - x and the other in 200 - x C.C. of By GEORGE H. MORRIS (J. lied. [rat. Brew.,1898,4,162--176).-1t is pointed out that, both in commer- cial glucoses and invert'sugars, there is a certain amount of unferment- able matter which reduces Fehling's solution and is optically active. In the method of analysis proposed by the author, a correction is applied for this, and the true percentages of the fermentable sugars (dextrose, levulose, and maltose) are obtained.Details of the analytical methods adopted are given, as well as tables of optical constants and cupric- reducing power. A. C. C. The Correction for Unfermentable Reducing Substances in Sugar Analysis. By TOM A. GLENDINNING (L lied. Ilzst. Brew., 1898, 4, 363-365).--The author points out that raw cane sugars usually contain unfermentable Fehling-reducing substances, and that this may account partly for the presence of these substances in com- mercial invert sugars. Analyses are given in which the percentage varies from 0.47 per cent. to 2.64 per cent. This unfermentable matter was slightly dextrorotatory, and had a cupric-reducing power of about 30.Malt. I. The Ready-formed Sugars of Malt, and the Action of Diastase on Barley Starch. By ARTHUR E. LING (J. Fed. Inst. Brew., 1898, 4, 187--202).-Attention is called to the fact that in the estimation of the ready-formed sugars of malt by the method pro- posed by Moritx and Morris, the results are vitiated by the diastatic action taking place during the process of extraction. Experiments are described, showing that diastase does act appreciably on ungelatin- ised barley starch in the cold, but that this action can be entirely arrested by the presence of 0.0073 per cent. of free hydrochloric acid. Owing t o the decomposition of organic salts by hydrochloric acid, this reagent cannot be used in the extraction of the sugars from malt. Results of experiments are given, showing that there is no formation of maltose when a solution containing 0.0168 per cent.of potassium L. DE K. Estimation of Sugar in Chocolate. water. Then cc(100 - x) = b(200 - 2). L. DE K. Analysis of Brewing Sugars. A. C. C. 13-2188 ABSTRACTS OF CHEMICAL PAPERS. hydroxide is used for the extraction, and it is suggested that this might well serve as the basis of a method for the estimation of the sugars existing ready-formed in malt. Exact Estimation of Total Carbohydrates in Acid Hydro- lysed Starch Products. By GEORGE W. ROLFE and W. A. FAXON (J. Arne?.. Chem. Xoc., 1897, 19, 69S-703).-The authors have deter- mined the exact amount of carbohydrate present in solutions of com- mercial glucose, the specific rotatory power of the samples employed varying from [a]3.86 = 70.5' to [a] D3.86 = 164'.The solutions mere evaporated, and the residues dried a t 100-120' in a vacuum apparatus, which is a modification of that of Lobry de Bruyn and Van Leent (compare Brown, Morris and Millar, Trans,, 1897, 79). When the specific gravity factors (that is, the excess of the specific gravity of a solution containing 1 gram of dry matter in 100 c.c.) are plotted as ordinates against the specific rotatory powers as abscissae, a straight line is obtained. The authors conclude that, for solutions of acid hydrolysed starch products of sp. gr. varying from 1.035 to 1.045 at 15*5", the sp. gr. factor (2) may be calculated by the equation A. C. C. ~=0*004023 - 0.000001329 (195 - [ U ] D ~ , ~ ~ ) . A. R.L. Testing Formaldehyde. By CARL E. SMITH (Chem. Cent?.., 1598, i, 798-799 ; from Amer. J. Pha!rm., 70, S6-94).-The author pro- poses the following tests for the purity and identity of the '' formalin U.S.P." It should contain 35-40 per cent. of formaldehyde, to be estimated by Legler's ammonia process ; it should be colourless, trans- parent, neutral or very faintly acid, and have a pungent odour and caustic taste. The sp. gr. should be about 1.08, and it should be miscible in all proportions with water and alcohol. When heated with ammoniacal silver nitrate or Pehling's solution, a deposit of metallic silver or cuprous oxide is obtained. If 2 C.C. is heated with 2 C.C. of aqueous potash and 0.5 gram of resorcinol, a red colour is developed. If 5 C.C. of sulphuric acid, containing a little salicylic acid, is added to 2 drops of the sample, a permanent dark-red coloration is obtained.If 1 C.C. of the solution is mixed with 5 C.C. of ammonia and eva- porated t o dryness on the water-bath, a white, crystalline residue is left, which, when heated with dilute sulphuric acid, gives the original pungent odour. One c.c., mixed with 10 C.C. of iodine solution and a sufficiency of aqueous potash, should give no iodoform reaction, show- ing the absence of acetone. The sample should also be quite free Estimation of Formaldehyde. By OSRAR BLANK and H. PINKENBEINER (Bey., 1898, 31, 2979--298l).--Three grams of the formaldehyde solution, or 1 gram of '' solid formaldehyde," is dissolved in 25 C.C. of 2N sodium hydroxide; if the formaldehyde solution is stronger than 45 per cent., then 30 C.C.of alkali is employed. The mixture is placed in a tall Erlenmeyer flask and 50 C.C. of pure hydrogen peroxide free from acid (2.5-3 per cent.) run in through a funnel during the course of three minutes; the funnel is then washed out with distilled water, and the excess of alkali in the from any mineral matters. L. DE K.ANALYTICAL CHEMISTRY. 189 flask titrated with 2N sulphuric acid, using litmus as an indicator. If the aldehyde solution contains less than 30 per cent. of formaldehyde, the mixture must be allowed to remain 10 minutes after the hydrogen peroxide has been run in, The number of C.C. of alkali which have been used up in converting the aldehyde into sodium formate, when multiplied by two, gives the percentage of formaldehyde in the original solution.The results agree with those obtained by other methods employed in commercial analysis, but give higher values (about 1.5 per cent.) than the ammonia method. J. J. S. Volumetric Estimation of Acetaldehyde. By XAVIER ROCQUES (Cow@. vend., 1898, 127, 524-526).-The author has modified the method described by Rieter (Abstr., 189'7, ii, 606). H e finds that alcoholic solutions of sulphurous acids and sulphites are much more stable than aqueous solutions ; that alcoholic solutions of alkali- hydrogen sulphites are most suitable for the estimationof aldehyde; that in dilute solutions a t least 12 hours is required to ensure complete combination ; and that unless the proportion of aldehyde is very small, the sulphite compound is not completely decomposed by potassium hydroxide.The sulphite solution is prepared by dissolving 12.6 grams of anhydrous sodium sulphite in 400 C.C. of water, adding 100 C.C. of normal sulphuric acid, diluting to 1000 C.C. with alcohol of 96', and filtering after 24 hours. Ten C.C. of the alcoholic solution of aldehyde to be examined is placed in a 100 C.C. flask, mixed with 50 C.C. of the sulphite solution and made up to 100 C.C. with alcohol of 50'. A second quantity of 50 C.C. of the sulphite solution is placed in a similar flask, and made up to 100 C.C. with the samealcohol. After at least 12 hours, 50 C.C. is withdrawn from each flask, and the sulphurous acid estimated by means of decinormal iodine solution ; the difference is the quantity of sulphurous acid that is in combination with the aldehyde ; 1 C.C.of N/10 iodine= 0.0022 gram of aldehyde. If the liquid to be examined contains less than 1 per cent. of aldehyde, the sulphite solution must be diluted ; for 0.5 per cent., it should be diluted with an equal volume of alcohol of 50°, and N/20 iodine should be used ; for 0.1 per cent., the sulphite should be diluted with alcohol of 50' to 10 times its ordinary volume, and centinormal iodine solution should be used. C. H. B. Volumetric Estimation of Acetaldehyde. By XAVIER ROCQUES (Compt. rend., 1898, 127, 764-765. Compare preceding abstract).-The action of alkali hydrogen sulphites on acetalde- hyde, when carried out at 15", is not complete after 48 hours. The solution to be examined should be mixed with a knownvolume of alcoholic bisulphite solution, made up to 100 C.C.with 50 per cent. alcohol in a stoppered flask, and heated for 4 hours at 50'; a blank experiment should also be performed in another flask containing similar quantities of bisulphite and alcohol, and a t the end OF the time both solutions should be titrated with iodine in the manner previously indicated. G. T. M.190 ABSTRACTS OF CHEMICAL PAPERS. Detection of Acetone in Urine. By B. STUDER (Chem. Centv., 1898, i, 1152 ; from Sc7Lweix. Woc?~. P?Larm., 36, 149--151).-The author combines the methods proposed by Legal, and Lieben and Dragendorff; 50 C.C. of the sample of urine is mixed with 5 C.C. of dilute sizlphuric acid and submitted to distillation, the distillate being collected in a test-tube placed in cold water.When 3 C.C. has passed over, 6 to 10 drops of a freshly-prepared 10 per cent. solution of sodium nitroprusside, and 1-2 drops of aqueous soda are added ; if acetone is present, a purple-red coloration is produced. If the reaction is not decided enough, i t may be advisable to add 6 to 8 drops of acetic acid, when a claret colour will prove the presence of acetone. The reaction is interfered with by hydrogen sulphide, which is occa- Soap Analysis. By RUDOLF HEFELMANN and ERNST STEINER (CIAern. Centr., 1898, ii, 142-143; from Zeit. bfentl. Chern., 4, 389--396).-The estimation of the fatty acids in soaps made from Ceylon oil is attended with some inaccuracies which are avoided by using the authors' process. The fatty acids and other fatty matters are liberated by a mineral acid, and extracted by ether ; this solution is neutralised by N/3 potash, using phenolphthalein as indicator, and the whole is dried over a weighed quantity of sand at 100".The amount of fatty acids and neutral fats may then be easily calculated, Equally accurate results are obtained by evaporating the ether and drying the residue at 55" ; a t a higher temperature, some of the fatty acids volatilise. Light petroleum should not be used, as i t does not dissolve the acids completely. Relation between the Sp. Gr. and the Insoluble Fatty Acids of Butter and other Fats. By NORMAN LEONARD (Analyst, 1898,23, 282--283).-It is well known that animal fats used for making butter substitutes have a much lower sp. gr. than butter-fat itself, and the author states that the relation between the sp.gr. a t 100' F. and the percentage of insoluble fatty acids yielded by the sample may be approximately represented by the formula y = k( 1 - z), where y is the percentage of insoluble acids, and x the sp. gr. of the melted fat a t 100" F., water at 60" F. being taken as unity. k is a constant which may be taken as = 951 on an average. When the butter mixture contains animal fats, the percentage of fatty acids actuallyfound will a t the most differ by 1.4 per cent. from that calculated by the formula. But when vegetable oils such as cotton-seed oil, cocoa nut oil, or sesame oil have been used, the formula Chemistry of Drying Oils : Examination of Linseed Oil. By OTTO HEHNER and CHARLES A. MITCHELL (AnaZyst, 1898,23,3 10-3 18).-The paper is chiefly devoted to a criticism of the work done by Hazura and Grussner (Abstr., 1888, 817; 1270). Their results are, on the whole, verified by the authors. By dissolving 1-2 grams of linseed oil in 40 C.C. of ether and a fern C.C. of glacial acetic acid, cooling the mixture in ice, and adding sionally present in stale urines. L. DEK. L. DEK. mill no longer agree. L. DE K.ANALYTICAL CHEMISTRY. 191 bromine, a precipitate is obtained which may be collected, washed with cold ether, and finally dried in a water-oven until the weight becomes constant. The process seems a valuable one for the assay of commercial raw linseed oil, as the pure article yields from 24-25 per cent. of brominated deposit, whilst common adulterants such as cotton-seed oil either yield no deposit at all, or but a trifling quantity, as in the case of walnut oil, forjnstance.Marine animal oils, however, also yield abundant precipitates, and cannot be detected by the bromine By JOSEPH NERKING (PfEiiger's Archiv., 1898, '73, 172-183. Compare Abstr., 1898, 413).-This paper is a defence of the method introduced by Dormeyer, who subjects meat, &c., to gastric digestion before extract- ing it with ether. A new piece of apparatus for performing the extraction is described and figured. Hydrochloric acid has no dele- terious action on fatty acids. Analysis of Bone Fats. By AL. A. SRUKOFF and 9. J. SCHESTAKOFF (Cheaa. Centr., 1898, i, 864-4365 ; from Clhern. Rev. Pett. u. Harx-Ind., 5,5--8).--Moisture is estimated by drying 5 grams of the sample in a, current of air, or carbonic anhydride, at 100-110'. Foreign admixtures are found by treating the dried fat with light petroleum, which, however, also dissolves any lime soaps.The ash is obtained by burning the fat, and it is then tested for lime with standard acid. To make a direct estimation of the fatty matter, 10 grams of the sample is mixed with 3-5 drops of strong hydrochloric acid to decompose the lime soaps, and the fatty matter is extracted by means of light petroleum; any insoluble matter is collected on a weighed filter, which is then well washed and the bulk of the light petroleum being distilled off, the remainder is removed by drying the fat as before in a current of carbonic anhydride at 100-110'. The unsaponifiable matter is estimated by evaporating 5 grams of the fatty matter to dryness with 25 C.C.of 8 per cent. alcoholic soda in a porcelain dish ; the soap is dissolved in 80 C.C. of water, and three times extracted with 80 C.C. of ether ; if the layers will not separate readily, this may be accelerated by adding a little alcohol. The ethereal solution is evaporated to dryness, and the residue treated with a little aqueous soda and then with light petroleum ; the latter, on evaporation, leaves the unsaponifiable matter in a state of purity. The solidifying point is taken according to Dalican's directions. test. L. DE K. Estimation of Fat in Animal Tissues and Fluids. W. D. H. L. DE K. Analysis of Fats : Preparation and Crystallisation of Cholesterol and Phytosferol.By A. BOMER (Chem. Centr., 1898, i, 466-467 ; from Zeit. Onters. Ncchr. u. Genussm., 1898, 21-49).- The author proposes a modification of Salkowski's process. Fifty grams of the fat, melted in an Erlenmeyer flask fitted to a reflux condenser, is saponified with 100 C.C. of 20 per cent. alcoholic potash, the soap introduced into a separating funnel, 200 C.C. of water added, and the whole extracted by shaking with 500 C.C. of pure ether ; after remov- ing the ether, the extraction is twice repeated, using 250 C.C. of ether192 ABSTRACTS OF CHEMICAL PAPERS. each time. The ether is then distilled off from the mixed extracts, and the residue again saponified with 10 C.C. of the alcoholic potash ; 20 C.C. of water is added, and the shaking repeated with 100 C.C.of ether. This, after being freed from traces of soap by washing thrice with 10 C.C. of water, is left to evaporate spontaneously; the residual cholesterol or phytosterol must then be recrystallised from boiling absoliite alcohol. It appears that the microscopical appearance of the two substances depends on various circumstances, but, as a rule, cholesterol forms thin, rhombic tablets, whilst phytosterol yields thin needles. In doubt- ful cases, the melting point should be taken. If both are present, a kind of mixed crystal is obtained, which looks either somewhat like Analysis of Fats : Melting Points of Cholesterol and Phy- tosterol; Amount of Unsaponifiable Matter in Fats. By A. BOMER (Chm. Centr., 1898, i, 638-639 ; from Zed. Unters. Nab. u. Genzcssm., 1898, 81-9G).-The author estimated the amount of cholesterol in la,rd and butter-fat by his process (preceding abstract), and obtained, on an average, 0.1774 per cent.of crude cholesterol from lard and 0.3512 per cent. from butter. These figures are higher than those obtained by Salkowski. Cholesterol melts a t 146-14S0, whilst phytosterol melts a t 135.5-141O. Mixtures of the two have a melting point varying but slightly from the calculated figure. The phytosterol test enables the presence of commercial margarine in butter, or of cotton-seed oil in lard, to be detected with certainty if the chemical analysis of these articles leaves any doubt. It is, however, not so easy to detect small percentages of animal fats in By EDWARD KREMERS and MARTHA M. JAMES (Chem.Centr., 1898, i, 1070; from Pi~tcma. Rev., 16, 130--133).-The authors have slightly modified the method proposed by Ewing, and now boil a weighed quantity of the substance with a known volume of normal alkali for 5 minutes. The excess of alkali is then titrated with normal acid, and the alkali consumed, multiplied by 0-152, represents the number of grams of methylic salicylate. The method proposed by Messinger and Vortmann is also recom- mended. Five grams of the sample is saponified with excess of alkali, and when cold diluted to 500 C.C. ; 10 C.C. of this is heated, 50 C.C. of N/10 iodine solution added, and the liquid diluted to 500 c.c; in 100 C.C. of this, the excess of iodine is estimated by means of N/10 sodium thiosulphate. One C.C. of iodine solution absorbed, when multi- plied by 0.631 825, represents the amount of methylic salicylate, as cholesterol or phytosterol.L. DE T(. vegetable oils. L. DE K. Volumetric Estimation of Methylic Salicylate. 1 mol. of the ethereal salt absorbs '7 mols. of iodine. L. DE I(. Detection of a-Naphthol in /3-Naphthol. By A. DUBOSC (Chem. Centr., 1898, i, 800 ; from Bull. SOC. Ind. Rouen, 1897, 434).-If a solution of a-naphthol is mixed with a few drops of sodium hypobromite solutiop (30 C.C. aqueous soda of sp. gr. = 1.33, 100 C.C. of water, and 5 C.C. of bromine), a dirty violet coloration is produced, but P-naphtholANALYTICAL CHEMISTRY. 193 only gives a pale yellow colour. The author now proposes to use this reaction for testing commercial samples of P-naphthol which, should they contain even as little as 3 per cent.of the a-compound, are useless By NORMAN LEONARD and H. METCALFE SMITH (Analyst, 23, 281--282).-Thie drug being often deficient in camphor, the authors ascertain the amount present by drying 3 or 5 grams of the sample for 2 hours at 120" in a flat- bottomed dish. The loss, after adding 0.15 per cent. t o compensate for the gain in weight caused by the oxidation of the olive oil, should amount to 21-45 per cent. Assuming the sp. gr. of the olive oil t o have been 009164, the amount of camphor may be calculated from the sp. gr. of the sample, each per cent. of camphor raising the density by 0.00045. Mineral oil is sometimes employed instead of olive oil, but this fraud is readily detected by the insolubility of the sample in hot alcoholic potash.for preparing dyes. L. DE K. Examination of Camphor Liniment. L. DE K. Action of Iodine on Antipyrine. Estimation of Antipyrine or of Iodine. By J. BOUGAULT (Chem. Centr., 1898, i, S58; from J. Pliarm., [vi], 7, 161--163).-The author has found that 1 mol. of antipyrine dissolved in alcohol containing mercuric chloride absorbs exactly 1 mol. of iodine ; or 1 gram of antipyrine = 1.351 grams of iodine. To estimate antipyrine, 20 C.C. of a 1 per cent. alcoholic solution is mixed with 20 c,c. of a 2.5 per cent. alcoholic solution of mercuric chloride and an alcoholic solution of iodine containing 1.351 grams of iodine in 100 C.C. of 95 per cent. alcohol is added until a permanent, yellowish coloration is noticed. If the antipyrine is pure, it will con- sume exactly 20 C.C.of iodine solution; if not, it will take propor- tionally less. An iodine solution may, in turn, be estimated by Reactions of Alkaloids with Benzaldehyde and Sulphuric Acid. By HERM. MELZER (Zeit. anal. Chem., 1898, 37, 74'7-74S).- Besides picrotoxin (Abstr., 1898, ii, 651), only a few other alkaloids and poisons produce colours with benealdehyde and sulphuric acid. It is best t o use a 20 per cent. solution of benzaldehyde in absolute alcohol, a drop of this solution being added t o a trace of the alkaloid in a watch-glass, and then a single drop of concentrated sulphuric acid without any stirring. Digitalin gives brown streaks ; veratrine, a red coloration ; codeine, a yellow to blood-red ; thebaine, a dark brown; delphinine, reddish-brown streaks ; morphine, red to yellowish-red streaks ; whilst colchicine, cantharidin, coniine, nicotine, brucine, strychnine, aconitine, papaverine, narcotine, hyoscyamine, emetine, apomorphine, and narceine give no characteristic colours.Estimation of Nicotine in Tobacco. By C. C. KELLER (Chem. Centr., 1898, ii, 388-389 ; from Ber. Deutsch. Plkwm. Ges., 8, 145--15S).-The author recommends the following process : 6 grams of tobacco dried over quicklime is powdered and treated in a stoppered bottle with 60 grams of ether, 60 grams of light petroleum, means of a standard solution of antipyrine. L. DE K. M. J. S.194 ABSTRACTS OF CHEMICAL PAPERS, and 10 C.C. of 30 per cent. aqueous potash ; the mixture is well shaken forhalf an hour, then left for 3 or 4 hours, and 100 grams of the ethereal liquid is collected in a 200 C.C.bottle; after a strong current of air has been passed through to expel any ammonia present, 10 C.C. of alcohol, one drop of a 10 per cent. solution of iodeosin, and 10 C.C. of water are added, and the whole is well shaken, which causes the iodeosin and the nicotine to pass into the aqueous liquid. N/lO hydro- chloric acid is now added until the liquid is colourless, and the slight excess of acid is titrated by meam of N/10 ammonia. One C.C. of acid = 0.0162 gram of nicotine. Analyses are given showing the amoiint of nicotine in various brands of tobacco and cigars, from which it appears that so-called strong tobaccos do not necessarily contain a high percentage of Estimation of Morphine in Opium.By HERMANN THOMS (Chem. Centr., 1898, ii, 136 ; from Ber. Deutsch. Pharnb. Gesell., 8, 124-125).--The author condemns the so-called brine method pro- posed by Montemartini and Trasciatti for the assay of opium (Abstr., 1898, ii, 270) as being too tedious, and giving results which are too Action of Sulphuric Acid on Strychnine when separating this Alkaloid from Organic Matters. By EDGAR H. S . BAILEY and WM. LANGE (Chem. Centr., 1898, i, 478; from Amer. J. Phwrm., ’70, 18-21).--The authors find that the treatment with sulphuric acid so modifies the strychnine that it requires more than four times the usual amount to get a satisfactory reaction with the potassium dichromate test. Matters are even worse, if, after the acid treat- ment, the alkaloid is extracted by means of aqueous potash and chloroform.Minute traces of the alkaloid may, therefore, escape By ALBERT BRY- LINSKI (Chern. Centr., 1898, i, 1041 ; from Bull. Soc. Ind. Mulhouse, 1898, 33--39).-Tbe extraction of indigotin by means of boiling aniline is attended by two serious sources of error; if the extraction is continued for 3-4 hours, about 30-40 per cent. of the indigo may be decomposed; on the other hand, the indigotin crystals retain about 20 per cent. of aniline. As, however, in Brandt’s process the boiling only lasts for half an hour, the two errors fairly well com- pensate one another, so that the result is technically accurate. The acetic acid process gives almost theoretically correct results. The sample is extracted in a Soxhlet’s apparatus with boiling glacial acetic acid until the acid runs off colourless; on diluting the extract with four times its bulk of water, the indigotin is completely pre- cipitated and may be collected on a weighed filter.It is washed first with hot water, and then with alcohol and ether to free it from certain impurities extracted from the paper filter by the strong acid. nicotine. L. DE I(. low. L. DE K. detection altogether. L. DE I(. Estimation of Indigo : Brandt’s Method. L. DE I(. Heller’s Test for Detecting Blood in Urine. By V. ARNOLD (Chem. Centr., 1898, i, 1002 ; from Rev. Klifi. Wochschr., 35, 283-285).-This well-known test is based on the fact that aqueousANALYTICAL CHEMISTRY 195 potash, on warming, precipitates the earthy phosphates from urine, which, in the presence of blood, assume a ruby-red colour ; the test does not depend on the formation of hzematin, but of haemochromogen. As, however, the reaction may be also due to the presence of melanin or urobilin, the author advises not to trust t o Heller’s test alone, but always to confirm the result by means of the spectroscope.Blood spots may be dissolved in aqueous potash, and urine may then be added ; the addition of ammonium sulphide becomes superfluous. L. DE K. Guaiacol Test for Blood, By EDUARD SCHAER (Arch. Pl~arrn., 1898, 236, 572-579).-The author finds that a 65-80 per cent. solution of chloral hydrate is an excellent solvent for blood, and proposes to modify the guaiacol test in the following manner. The blood stain, after moistening with glacial acetic acid, is treated with a concentrated solution of chloral hydrate.To a small portion of the extract, guaiacol is then added, and either hydrogen peroxide or Hiinefeld’s reagent, when the blue colour is produced with remarkable delicacy. A. W. C. By ERNST FREUND (Chem. Centr., 1898, i, 637 ; from Wien. Klin. Rundsch., 1898, 37).- The urine is freed from nucleo-albumins, albumin, and protalbumoses by means of a 10 per cent. solution of lead acetate, two drops being generally sufficient for 10 C.C. of urine. Should, however, the urine contain from 0.1 to 3 per cent. of albumin, this must be first removed by coagulation with a few drops of dilute acetic acid at the boiling heat, The filtrate is then carefully neutralised with soda before adding the lead solution.The second filtrate, which should not give any reaction with acetic acid and potassium ferrocyanide, showing absence of excess of lead, is now used for the biuret test. One part of peptone may thus be detected in 12,000 parts of urine. Simplified Test for Peptone in Urine. L. DE K. Precipitation of Albumoses by Zinc Sulphate. By K. BAUMANN and A. BOMER (Chenz. Centr., 1898, i, 640 ; from Zeit. Unters. Nahr. ii. Genussnr., 1898, 102--126).-The authors state that zinc sulphate may be advantageously used instead of the ammonium salt in the analysis of meat extracts, &c. The solution, which must be free from coagulable albumin and contain about 1 gram of solid matter in 50 c.c., is acidified with 1 C.C. of dilute sulphuric acid (1 : 4) and gradually saturated with zinc sulphate, using very finely-powdered salt towards the finish. The liquid is filtered after being kept over- night, and the precipitate washed with a slightly acidified saturated solution of zinc sulphate.The amount of albumose is then found by treating the precipitate by Kjeldahl’s process. In the filtrate, the peptones, meat-bases, and ammonia are precipitated by the ordinary solution of phosphotungstic acid to which half its volume of dilute sulphuric acid (1 : 8) has been previously added. After being first kept for some time a t 60-65*, the mixture is allowed to remain for 24 hours in a cool place ; it is then filtered, and the precipitate, after being masheci with dilute sulphuric acid (1 : 6), is treated by Kjeldahl’s process.196 ABSTRACTS OF CHEMICAL PAPERS. Ammonia may be estimated in a second phosphotungstic precipitate by distillation with magnesia, and must be allowed for when calcu- lating the amount of peptones and meat-bases from the result of the Detection of Dextrin, Gelatin, and Gum in Desiccated Albumin. By A. A. BONNENA (Chem. Centr., 1898, ii, 386; from Pharm Centr.-HcdZe, 39, 424-425).-Ten grams of the powdered white of egg is well stirred with water, boiled to coagulate the albumin, and after a few minutes the liquid is filtered and a portion of the filtrate put aside to cool at a low temperature for 24 hours; if it turns to a jelly, gelatin is present. Another portion is mixed with alcohol in excess, and if a permanent precipitate is obtained, gelatin, dextrin, or gum is present; the former precipitate disappears on adding a little nitric acid. Dextrin may be identified in the filtrate by the red coloration produced with iodine, and gum by the precipitate given with basic lead acetate. Dieterich's iodine absorption test for the purity of albumin is not recommended by the author. nitrogen estimation. L. DE E(. L. DE K. Estimation of Gelatin in Gums and Food Materials. By AUGUSTE TBILLAT (Compt. rend., 1898, 127, 724-725).-1n estimating the amount of gelatin present in a sample of gum arnbic, the sub- stance is dissolved in water, filtered if necessary, evaporated to a syrupy consistency, treated with excess of formaldehyde solution, and the evaporation continued until the mixture becomes pasty; it is then extracted with water to remove the gum and the gelatin rendered insoluble by the aldehyde, is dried at 100' and weighed. The results obtained agree to 1 per cent., and the method serves t o distinguish between artificial jellies containing gelatin and those derived from vegetable sources. The increase in weight of the gelatin due t o the fixation of formaldehyde is inappreciable, owing to the great difference between their molecular weights. If the sample to be analysed con- tains proteid substances coagulated by heat, these are first removed by warming the solution ; the filtrate should be concentrated before the addition of formaldehyde, as no precipitate is produced in dilute solutions. G. T. M.

ISSN:0368-1769    

DOI:10.1039/CA8997605178

出版商:RSC    

年代:1899

数据来源: RSC