摘要:

VEGEI'ABLE PHYSIOLOGY AND AGRICULTURE. 21.5 Chemistry of Vegetable Physiology and Agriculture. Further Studies on Putrefaction. LEO F. RETTGER ( J . Biol. Chenh. 1908 4 45-56).-Real putrefaction is the work of anaErobes. Bacillus tetani has little or no putrefactive action on native proteins. B. aZrogenes capsdatus attacks proteins slightly but the change is not genuine putrefaction. B. putrijcus and B. ndigni edemcctis are present in normal faxes in small amount and probably in spore form only. As spores they are able to resist the unfavourable conditions of the human intestine. W. D. H. Fermentation of Formic Acid by Proteus vulgaris. HARTWIG PRANZEN and GEORG ERAUN (Biochem. Zeitsch. 1908 8 29-39).- The same amount of formic acid is fermented in a given time and a t a given concentration whether the acid is present as potassium or as sodium salt. The velocity of the reaction is increased by increasing the concentration of the formate.G. B. Sugar Formation and other Fermentative Processes in Yeast. ERNST SALKOWSKI (Zeitsch. physiol. Chern. 1908,54,398-405. Compare Abstr. 1 S89 1027).-On autolysis of yeast in chloroform water a fermentable sugar is formed from the carbohydrate material of the cells. The fluid however is lavorotatory but this action is not necessarily due to the fermentable sugar for the fluid contains a mixture of numerous substances such as gum dextrin pentoses purine bases tyrosine lysine leucine peptone and sometimes succinic acid. The sug:tr was identified as dextrose by separating it as a diphenylhydrazone compound. W.D. H.216 ABSTRACTS OF CHEMICBL PAPERS Constitution of Aqueous Solutions and the Influence of Salts on Alcoholic Fermentation. ALBERT J. J. VANDEVELDE (Chem. Zentr. 1907 ii 1435 ; from BuZl. Assoc. Aizciens EZhes del' Imt. Brasserie Gand 13 83-94).-The velocity of the fermentation of sugar in presence of vayious inorganic salts has been followed gravi- metrically and the results are expressed in tables in terms of the number of hours requiibed for the decomposition of three-fourths of the sugar termed the '' fermentation energy." Within concentrations of 2-1 0% barium &lor ide ammonium sulphate magnesium sulphate and zinc sulphate appear to be without influence on the velocity of the fermentation but the numerous other inorganic salts investigated retard the fermentation in some cases to a n extent approximately proportional to the increase in the osmotic pressure of the solution.G. P. Influence of Micro-organisms on the U t i l i s a t i o n of the Insoluble Phosphates by Higher Plants. SANTE DE GRAZIA and A. CERZA (Bied. Ze75tr.) 1908,37 85-86 ; froin Xtacz. spev. agrar. ital. 1906 39 8 17).-Xxperiments with Aspei*giZlus nige?. Penicilliunz. glaucum and P. brevicaule showed t h a t the moulds ha1-e a dissolving action on tricalcium phosphate. N. 13. J. 31. Chemistry of the Higher Fungi. I. Tranietes suaveolens. JULIUS ZELLNER (Monmtsh. 1908 29 45-54. Compare Abstr. 1904 ii 679; 1905 ii 550 ; 1906 ii 572).-1n continuation of his in- vestigations into t h e chemistry of the fungi the author has under- taken the study of some parasitic fungi and now gives a n account of the results obtained with T'rumetes suaveoleias.The fungus was gathered from ~v11lows in February and ATarch when full of sap but still free from spores. The freshly-gathered fungus contains 65-670/ the air-dried material 7-9% of water. When incinerated the completely dried substance yields 2.9.h of ash consisting chiefly of potassium and calcium sulphates and carbonates with smaller amounts of magnesium phosphoiic acid and silica and traces of sodium iron aluminium and chlorine. The crude fat is yellow deposits a crystalline substance and gives the acid number 32-29-29.40 and the hydrolysis number 175.2-172.0 ; the small amount of fatty acid obtained has the acid number 186-1 and consists chieffy of oleic acid; the very small amount of solid fatty acids obtained has m.p. 74". It is shown that the powdered fungus contains a lipolytic ferment. The soap from the crude fat on extraction with ether yields a substance m. p. 158-167" closely resembling the ergosterol obtained from fly agaric (Abstr. 1905 ii 550) ; i t is a mix- ture of two substances of which the less soluble in alcohol has m. p. 165--1G'i0. The alcohol extract yields mycose and dextrose but not mannose or trehalase (Bourquelot and Hdrissey Abstr. 1905 ii 193). The resin from the alcoholic extract gives coloured precipitates with metallic acetates and a brown coloration with ferric chloride. The light petroleum extract amonnts only to 0.8%. C,,H,,O,H$AThe aqueous extract 1 S-SOy& contains dextrin or gum-like sub- stances pentosans in sufficient amount to give a strong furfuraldehyde reaction a ferment which hydrolyses glucosides a diastatic arid probably an inverting ferment and traces of proteins.The fungus contains also amanitol previously found in fly agaric and when distilled with very dilute sodium hydroxide yields traces of ammonia and probably trimethylazmine. The skeleton of the fungns does not give the lignin reactions. The grey colouring matter in old Supposed Extracellular Photosynthesis of Carbon Dioxide by Chlorophyll. ALFRED J-. KFVART (Proc. Roy. Soc. 1908 80 23 30-36).-A severe criticism of the work of Usher and Priestley (Abstr. 1906 ii 299 881). All forms of commercial gelatin turn pink in the presence of decolorised rosaniline ; i t is on this reaction that Usher and Priestley mainly depended for the detection of formaldehyde in their gelatin chlorophyll films.Moreover chlorophyll itself when exposed t o light yields formaldehyde as a decomposition product whether in the presence or absence of carbon dioxide. There is no conclusive evidence that living plant cells ever contain hydrogen peroxide the other product of this supposed photosynthesis ; i t is probably always destroyed by catalase. The author has also failed to detect the evolution of oxygen from gelatin chlorophyll films and from dead cells of Elodea and VaZlisne?*in as described by Usher and Priestley. The simultaneous production of formaldehyde and of hydrogen peroxide in a gelatin film appears to be improbable from the experiments of Geisow (Abstr.1904 i 289) who found that these substances interact with the formation of carbon dioxide water and hydrogen. G. B. Hydrogen Cyanide and the Assimilation of Nitrogen in Green Plants. CIRO RATENNA and ARRIGO PELI (Gazzettu 1907 37 ii 586-600).-The formation of hydrogen cyanide in Sorglizcna vulgare is traced to the indirect simultaneous action of nitrates and carbo- hydrates and when these are removed the proportion of the acid present diminishes rapidly. Light favours the formation of hydrogen cyanide provided that the functions of the chlorophyll are riot impaired. The acid seems to be the simplest substancc which can be detected as taking part in the synthesis of proteins. Production and Physiological R81e of Pentosans in Plants.G. A. CALABRESI (Bied. Zentr. 1908 37 93-96; from Stax. s p w . ngrccr. itnl. 1906 39 69).-Deterniinations of pentosans were made in the different parts of maize beet and beans a t different periods of growth. K. H. J. 31. Constant Composition of Vegetable Juices Obtained by Successive Extractions. GUSTAVE ANDR~ (Compt. rerzd. 1907 145 1349-1 352).-Experiments made with leaves of Valei*iucnelln olito7ia and carrots (roots) showed that the composition of the extracts as indicated by the ratios N extract and ash extract remained almost the same whatever the pressure employed. plants is insoluble. G. Y. T. H. P. N. H. J. 35. VOL. XCIV. ii. 15218 ABSTRACTS OF CHEMICAL PAPERS. Nitrate-reducing Enzyme in Green Plants. ANNIE A. IRVING and RITA HANKINSON (Bio-Chena.J. 1908 3 87-96).-The presence of a reducing enzyme in green plants is considered to be established. Asparagine is regarded as a stage in protein synthesis but the centres for nitrate reduction and protein formation may be distinct. I n ensilage the loss of nitrogen may be i n part due to evolution of gaseous nitrogen owing to the distribution of the enzyme becoming less localised. Normally the only conditions necessary for nitrate reduction are the presence of the enzyme and a suitable carbohydrate. The latter condition suggests the leaf as the centre for reduction and this agrees with the distribution of nitrates in the plant. Any hexose or polysaccharide is suitable for the supply of energy for nitrate reduction not as in later stages of protein synthesis where dextrose is the only carbohydrate which together with asparagine can provide the necessary basis for protein construction.[Composition of] the Pulp of Parkia Biglobosa ‘‘ Farine de Nett&” A. GORIS and L. C R ~ T ~ (Compt. rend. 1908 146 187-189). -The substance is produced in the fruits of Pccrkia and a t the period of maturity is dry and friable. The percentage composition was found to be as follows water 4.90; N 0.624; ash 4.96 ; P,O 0.383 ; soluble in water alcohol and carbon disulphide 72.00 56.67 and 1.30 respectively. The pulp contains more sugar than any other known substance the amount being sucrose 25% dextrose and laevulose 20.5%. W. D. H. N. H. J. M. Vegetable Phosphatides 11. ERNST WINTERSTEIN and 0. HIESSTAND (Zeitsch. physiol. Chenz,.1908 54 288-330. Compare Abstr. 1906 i 478).-The phosphorus compounds soluble in absolute alcohol and ether (phosphatides) obtained from the following plants have been examined. Cereals Avena sativa Lupinus albus L. Euteus Vicia sativa Pinus cembra Yicea excelsa Boletus edulis Cantharellus cibccrius also from the leaves of Aesculus hppocastanunz pollen of Alnus siridis Pinus montana and polato. The products obtained from all these sources with the exception of P i m s cernbra? when hydrolysed gave carbohydrates. The actual amount of reducing carbohydrate varied with the differeut sources ; thus Triticum uulgare gave IS% Lupinus albus 13% and L. Zuteus only 1%. Even t h e same material gave varying amounts. Lecithins were also isolated in addition to phosphatides. It is possible t h a t the phosphatides which gave only small amounts of reducing sugars contained these in an adsorbed state.Galactose has been isolated from cereal phosphatide and the presence of dextrose has been proved but it has not been settled whether these exist as such in the molecule or are derived from di- and poly- saccharides. These phosphatides probably contain other nitrogenous residues i n addition to choline. The ratio N P in the phosphatides is practically the same as in lecithins. Bio-chemistry of Barley. I. Amylase of Resting Barley. JOHN S. FORD and JOHN M. GUTHRIE ( J . Inst. Brewing 1908 14 61-85).-l’he diastatic activity of a barley extract is largely increased J. J. S.VEGEl’ABLE PHYSIOLOGY AND AGRICtXYY.JRE. 219 when the digestion of the barley with water is carried out in presence of (1) a salt such as sodium or potassium chloride potassium sulphate potassium dihydrogen phosphate or calcium sulphnte ; (2) glycine aeparagine or a-ahnine or (3) a proteolytic enzyme such as bromelin animal trypsin or active or inactive papain.These substances apparently bring about the dissolution of an insoluble partially occluded enzyme whilst in the case of papain with which the increase in diastatic activity is especially marked the amphoteric proteins present tend to prevent the destruction of amylase which takes place under other conditions of extraction. It is further found that considerable increase of amylolytic activity is exhibited by the filtered extract of barley digested for twenty hours with water containing an antiseptic a t 30-35’ instead of for one hour at 18O as in the ordinary aqueous extraction; this increased activity the authors term “ autodigestion activity.” The ‘‘ aqueous extraction ” and “ autodigestion ” values represent the algebraic sum of solution and destruction of the enzjme under the conditions employed and are not a measure of the amylase but rather of other substances in the barley.Various unsuccessful attempts have been made to produce a marked increase in the activity of barley extracts but the results are insufficient to disprove the existence of a zymogenic or inactive soluble variety of translocation diastase. By far the greater part of the amylase obtained by treatment of barley with active papain is derived from the endosperm the embryos containing an in significant quantity.The enzyme apparently permeates the entire amyliferous tissue but its concentration is far greater in the peripheral zone and aleurone layer than in the inner- most parts. The distribution of soluble salts in the barley corn is also irregular the relative amounts estimated by measuring the con- ductivity of their solutions in equal weights of the various parts being endosperm including the aleurone layer 1 embryo 4 and husks 3. Further the salts in the different parts vary in character since in many barleys the husks are distinctly alkaline to rosolic acid whilst the reactions of the embryos and endosperms tend towards faint acidity When an aqueous extract of barley is shaken with solid starch a portion of the translocation amylase present is adsorbed by the starch the filtered extract exhibiting diminished diastatic activity.The amylolytic activity of barley does not appear to be connected with the hordein or edestin contained in the barley. T. H. P. Importance of Sodium for Sugar Beet. K. ANDRLfK and JOSEF URBAN (Zeitsch. Zuckerind. Bohnz. 1908 32 208-216).-The percentage of sugar in the roots is high when the roots contain high arnounts both of potassium and nitrogen t o one of sodium. High amounts of potassium alone in relation to one of sodium are also generally coincident with high percentages of sugar ; the relation of potassium to sodium however varies during growth. After sixty-six days roots were found to contain less potassium than sodium whilst after one hundred and seventy days the relation of potassium to sodium was 1 a 8 2 1.15-2220 ABSTRACTS OF CaEMfCAL PAPERS. The presence of large amounts of sodium in roots is coincident with lower amounts of sugar; i t is however not established that the greater assimilation of sodium is the cause of diminished sugar production. N. H. J. M. Nutritive Value of Non-Proteins in Hay. OSCAR KELLNER (J. Lmdw. 1908 56 49-52).-A criticism of Mar; Muller’s results and conclusions (Bbstr. 1907 ii 645). N. H. J. M. Humous Carbonate Soils and t h e i r Conversion into Grey Sand Soils. A. F. LEBEDEFF (Uied. Zenlr. 1908 37 60-61 ; from J. exper. Lm2dw. 1906 2 591).-Analyses are given of (I) humus- carbonate soils and (11) transition soils from humus-carbonate t o grey sand characterised by the complete washing out of the carbonates and by low amounts of humus KC1 HLIIT~US.RaC1. CaO. AlgO. A1,03. Pe,O,. SiO,. (30,. 1. 6 7 1 0.87 32.91 - 4.56 1-33 27-13 22.87 I. 2. 3.25 0.68 45-37 0 . 6 4 4.11 1.23 14.01 32-47 3. - 0.38 50.85 0.65 2.11 0‘65 4.80 40.26 (4. 1-18 2-58 0.90 1.93 10.44 80.96 0.0 0.49 0.85 3.17 1.27 9Om04 0.0 i ‘I.15. 2-10 1.67 N. H. J. M. Action of Calcium Cyanamide on Different Kinds of Soils. THEODOR REMY (Bied. Zentr. 1908 37 91-93 ; from Lccndw. Jahrb. 35 i%g.-bd. iv. 114).-In pot experiments 0.07 gram of nitrogen as calcium cyanamide per kilo. of soil was injurious to vegetation and as little as 0.03 gram was temporarily injurious. I n the field a top dressing of 30 kilos. per hectare mas distinctly injurious.The manure acts most favourably on clayey soils and is then almost equal to sodium nitrate ; even considerable amounts are without injurious effect on clay soils. On sandy soils the manure may be injurious to seeds and its action is both slow and incomplete comparable with that of blood meal. Calcium cyanamide was found t o be without action on the bacteria of heavy soils whilst on light soils the manure was decidedly injurious. N. H. J. M. Calcium Cyanamide. CAMILLE ASCHMANN and J. P. ARENU (Bied. Zentv. 1908 3’7 62-63 ; from Landw. 1906 No. 23j.- Experiments with maagolds and barley showed that calcium cyanamide had no poisonous action and that it acts most quickly on light soils. N. H. J. A!t. Decomposition of’ Calcium Cyanamide. F. LOHKIS and A. SABASCHNTKOFF (Centr. Bakt. Pa?.. 1908 ii 20 322-332. Compare Abstr. 1905 ii 412).-Experiments on the decomposition of the two forms of the manure (:‘ Kalks tickstoff ” and “ Stickstoff kdk ”) under different conditions gave almost identical resulta. The presence ofA N A LY TI C A L C H E M 1 ST R Y 221 calcium chloride (in ( I Stickstoffkalk ”) has liowevei- Eome influence on the number of bacteria other than those which produce ammonia. Reiny’s results indicating that calcium cyanamide has no retarding action on nitrification were confirmed. N. H. J. 3r.

ISSN:0368-1769    

DOI:10.1039/CA9089405215

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

A N A LY TI C A r C H E M 1 ST R Y . 221 Analytical Chemistry. An Accurate Form of G a s Analysis Apparatus for Com- mercial and other Purposes. J ~ I L L I A M A. BONE and RICHARD V. WHEELER (J. SOC. Chem Incl. 1908 27 10-ll).-A modification of Bone’s apparatus (Proc. 1898 14 131). The appsratus consists of a water-jacketed combination of measuring and pressure tubes communi- cating with a mercury reservoir an absorption vessel standing over mercury in a mahogany trough and a n explosion tube fitted with wires and connected with a separate mercury reservoir. The connexions between the parts of the apparatus are of capillary bore glass taps being provided where necessary. The principle of measurement adopted is that recommended by Regnault namely the measurement of the pressure of the gas under constant volume and the length of the pressure tube provides for the proper dilution of the ‘‘ explosive mixture ” in an explosion analysis.The absorptions are carried out over mercury in the vessel provided fresh quantities of the reagents being used for each analysis and the reagents are removed from the vessel by means of an exhaust pump in connexion with the top of the vessel The apparatus is particularly adapted to the analysis of mixtures of oxygen with hydrocarbons and of producer gas water gas oil gas coal gas ctc. w. P. s. A Problem of Gas Analysis. P. ANEIIA and CHARLES &I. VAN DEVENTER (Chem. Weekblud 1908 5 65-74).-Examples of deter- ininate and indeterminate problems in gas analysis are cited. A. J. W. Preparation of Normal Hydrochloric Acid with Gaseous Hydrochloric Acid.H. REBENSTORFF (Chenz. Zeit. 1908 32 99-100).-This is based on Moody’s method (Trans. 1898 73 658). Hydrogen chloride is evolved from ammonium chloride in lumps and sulphuric acid and after the air has been expelled the dry gas is passed into a weighed flask containing an exact weight of water. The flask is placed in water and when sufficient gas has been absorbed it sinks to a certain mark which indicates that an approximately correct N-acid has been obtained. The Aask is then re-weighed and the increase equals the exact amount of hydrogen chloride absorbed. It is then brought to exact normal strength by suitable dilution. L. DE K.222 ABSTRACTS OF CHEMICAL PAPERY. Estimation of Ghlorates Bromates Iodates and Periodatee by means of Formaldehyde Silver Nitrate and Potassium Persulphate.HEINRICH BWNNER and RUDOLF MELLET (J. pr. Chem. 1908 [ii] 7’7 3 3-43).-Griitzner’s method of estimating chlorates and bromates by heating the salts with formaldehyde nitric acid and silver nitrate (Abstr. 1897 ii 166) is extended to the estimation of iodates and periodates by ad(1ing potassium persulphate to the reaction mixture. This addition has the advantage i n all cases that it prevents the evolution of free halogen and hence removes the necessity of working in closed vessels. The analyses quoted show the method t o give satisfactory results. A number of experiments are described showing that chlorates iodates and periodates are not reduced by the persulphate in absence of formaldehyde and that neither hydrogen peroxide nor potassium hydrogen sulphate can be employed in place of the persulphate.Contrary t o Griitzner’s statement iodates and periodates are reduced only more slowly than chlorates or bromides by formaldehyde alone. G. Y. Estimation of Bromic and Iodic Acids by means of Thiosulphuric Acid. ANGELO CASOLARI (Gnxxetta 1907 37 ii 609-618. Compare this vol. ii 173).-Bromic and iodic acids can be estimated in acid solutions with great exactness by means of sodium thiosulphate the excess of which is determined by titration with iodine. This method may be applied to the determination of the titre of solutions of sodium thiosulphate and iodine starting from that of potassium bromate or iodate solution of decinormsl strength with reference to its oxidising power; i t can also be used generally in the volumetric estimation of substances readily redticible in the cold.I n the reaction which occtirs tetrathionic acid is formed in almost theoretical proportion ; hydrogen sulphide is also evolved as is the case when other oxidising agents are used. A polythionate containing nz atoms of sulphur in the molecule generates m molecules of sulphuric acid when treated with hydrogen peroxide and sodium hydroxide ; polythionates may be estimated by determining the amount of sulphuric acid formed in this way. T. H. P. Rapid Estimation of Water in Articles of Food &c. WTLHELN THORNER (Zeitsch. anyew. Chem. 1908 21 148-1 50).-Ten t o twenty-five grams of the substance are placed into a round-bottomed distilling flask fitted with a thermometer and connected with a small condenser in turn connected with a vertical narrow graduated cylinder.Fifty C.C. of petroleum are added and a few pieces of pumice stone are introduced ; also in the case of milk butter and cream a little dry tannic acid. The whole is now distilled and when about 18 C.C. of petroleum have passed over all the water has been expelled and the volume may then be read off in the bottom part of the graduated tube. L. DE K. Detection of Ozone Nitrogen Peroxide and Hydrogen Peroxide in Gas Mixtures. EDWARD H. KETSER and LEROY MCMASTER (Ai~zer. Chem. J. 1908 39 96-104).-A method isANALYTICAL CHEMISTRY. 223 described for detecting ozone nitrogen peroxide and hydrogen peroxide in presence of one another in mixtures of gases.If the gas is led through a solution of potassium permanganate the nitrogen peroxide and hydrogen peroxide are destroyed whilst the ozone passes through and can be detected by means of potassium iodide and starch. The presence of nitrogen peroxide can be ascertained by passing the gas through a tube containing manganese dioxide ozone and hydrogen peroxide being decomposed by this reagent whilst the nitrogen peroxide is not affected and can be detected by means of very dilute permanganate or by passing it into a solution of pure sodium hydroxide and testing for nitrites by the sulphanilic acid and a-naphthylamine method. The presence of hydrogen peroxide can be proved by passing the gas into a solution of potassium ferricyanide and ferric chloride the solution being rendered first blue and then green by the action of the hydrogen peroxide.It has been found that when hydrogen is burnt in air ozone and nitrogen peroxide are produced together with a very small quantity of hydrogen peroxide. If pure dry air or oxygen is passed through a Siemens’ ozoniser the ozonised gas does not contain either nitrogen peroxide or hydrogen peroxide. The gas produced by the action of strong sulphuric acid on barium dioxide contains ozone but not hydrogen peroxide or nitrogen peroxide. Ozone and nitrogen peroxide are formed by the slow oxidation of phosphorus in moist air but hydrogen peroxide is not produced. By the action of the flaming electric arc on air nitrogen peroxide a little hydrogen peroxide and traces of ozone are formed.A sample of ordinary air which was examined WAS found to contain ozone but neither nitrogen peroxide nor hydrogen peroxide was present. Estimation of Sulphur in Iron and Steel. EMILE JABOULAY (Chent. Zentr. 1907 ii 1444-1445 ; from Bev. gen. chim. pure. uppl. 1907 10 193-195).-Five grams of the metal are dissolved in 100 C.C. of dilute hydrochloric acid (1 1) in a current of hydrogen and the gas evolved is burnt in a mixture of air and oxygen. The sulphur dioxide formed is absorbed i n a cylinder containing a known amount of hydrogen peroxide and the excess of this may then be titrated with permanganate or the sulphuric acid formed may be estimated gravi- metrically The hydrogen peroxide may be preserved by adding 20 C.C. of nitric acid to one litre of its 12% solution.For exact details and figure of the apparatus the original communi- E. G. cation should be consulted. L. DE K. Colorimetric Estimation of Nitrogen in Soils the Nessler Test. D. CHOUCHAK and ISIDORE POUGET (Bull. Xoc. chim. 1908 [iv] 1 1173-1180).-0*2-0*6 Gram of the carefully prepared sample is mixed with 0*02-0*03 gram of dried oxalic acid and burnt in the ordinary way with soda-lime in a tube 25-30 cm. long and 0*8-0*1 em. in diameter. The gases evolved are passed through a kind of small Peligot tube containing 2-3 C.C. of dilute hydrochloric acid. The liquid is then diluted t o 50 c.c. and in 5 C.C. of this the ammonia is Nesslerised as usual.224 ABSTRACTS OF CHEMICAL PAPERS. The Kjeldahl process may be employed instead ; 5 C.C.of sulphnric acid are used with additions of a small drop of mercury or preferably n few decigrams of reduced copper. When cold the liquid is diluted to 50 C.C. ; 5 C.C. are taken diluted with 20 C.C. of water and if mercury has been employed boiled with n little rednced copper. When cold a sufficiency of aqueous sodium hydroxide is added and the ammonia is distilled off the distilliLte being received in n tube containing a few C.C. of water. The ammonia is then Nesslerised. In this process extreme care should be taken to ensure the complete nbsence of ammonia from any of the reagents also the absence of nitrates from the soda-lime. L. DE K. Microchemical Detection of Traces of Arsenic Antimony and Phosphorus. BOUWH SJOLLEMA (Chem. WeekbZad 1908 5 11-15>. -A modification of Gutzeit's test is described the silver nitrate solution (1 1) being placed on a microscope slide held over t h s test- t'uhe the reducing action of the filter-paper being thereby eliminated.With arsenic three forms of lemon-yellow crystals are obtained 0.005 mg. of As,Os being recognisable. The results for antimony and phosphorus are also characteristic. Mercuric chloride can be sub- stitutecl f o r silver nitrate. A. J. W. Estimation of Arsenic Hydride in Gaseous Mixtures. HANS RECKLEBEX and GEORG LOCKEMANN (Zeitsch. a n d Chem. 1908 47 126-1 32).-Gccsometiic Methods.-These can be applied only to mixtures cont,aining a large percentage of arsenic hydride. The gas is carefully measured before and after treatment with suitable absoxbents (compare this vol.ii 36). I n the presence of methane for instance silver nitrate iodic acid or hypochlorite solutions may be nsed ; i n t b e presence of ethylene silver nitrate or iodic acid should be employed whilst in presence of acetylene hypochlorite or iodic acid must be used. In presence of saturated and unsaturated hydrocarbons iodic acid only must be employed. G'ravirnetric Methods.-The gaseous mixture is treated with silver nitrate which is then heated with excess of ammonia The precipitated metallic silver may then be weighed or better still the solution which now contains the arsenic as ammonium arsenate may be used for estimating the same by the well-known grltvimetric methods. Rohmer's distillation process with hydrocarbons and sulphurous acids (Abstr.1901 ii 194) is recommended as R preliminary step. Volumetric Methods.-The most satisfactory plan is t o titrate the arsenious acid obtained by the distillation process by means of standard iodine after removing the sulphur dioxide present by means of a current of carbon dioxide. Traces of arsenic hydxide are estimated by pasking a measured volume of gas through bromine covered with water. The arsenic is then finally estimated with the Marsh apparatus. L. DE K. Detection of Arsenic in Sodium Fluoride by means of the Gutzeit and Fluckiger Reaction and the Marsh Apparatus. WILLEM VAN RYN (Pharm. Feekblud 1908,45 98-101).-Experiments showing that sodium fluoride may prevent completely the formation ofAN h LY TT C A T CFIE R.1 IST R T. 325 arsenical mirrors in the Marsh apparatus although the hydrogen evolved may show positively the presence of arsenic by the Fliickiger (mercuric chloride) test or by the Gutzeit (silrer nitrate) reaction.Estimation of Carbon. ISIDORE POUGET and D. CnOUCIIAK (Bull. Xoc. chim 1908 [iv] 3 75-80).-The authors state that in the ordinary method of estimating carbon by complete combustion in a current of air or oxygen in presence of an inorgnnic oxidising agent the substitution of a volumetric method of determining the amount of carbon dioxide produced makes it possible to use much smaller quanti- ties of the organic substance and generally to simplify the operation (compare Loges Abstr. 1883 247 830). The disposition of apparatus is similar to that usually employed except that the tube is drawn out to tt point a t one end and that t h e carbon dioxide is collected in a modified form of Winkler’s aspirator containing a standard solution of baryta and suitably connected to a reservoir of mercury so that the pressure can be adjusted during the progress of the combustion.When the whole of the carbon dioxide has been evolved the pointed end of the tube is connected t o a wash- bottle containing a concen trnted solution of potassium hydroxide the point is broken and air is drawn through the apparatus to sweep the last traces of carbon dioxide into the aspirator. Finally the baryta solution in the aspirator is titrated with 1V/50 sulphuric acid. Full detaiIs of the method of conducting the combustion are given in the original. The method is regarded as particularly suitable for tho estimation of carbon in soils.Estimation of Ash in Graphite. SAMUEL S. SADTLER (Chem. Zentr. 1907 ii 1445 ; from J. Frankliia Inst. 1907 144 201-203). -The powdered sample is placed into a platinum crucible the top diameter of which is a little smaller than the bottom one. A sinall accurately-weighed quantity of ignited magnesium oxide is added and the mixture is ignited gradually over the blowpipe in a slow current of oxygen. The addition of magnesium oxide serves to prevent the fusion and agglomeration of the ash The crucible should be placed a t Rapid Estimation of Carbon Dioxide in Mineral Waters. J. STR~~NSKP (Chena. Zeit. 1908 32 100-101).-The sample is collected by means of a capillary tnbe in a cylinder containing some ether and the carbon dioxide is titrated as usual with i N / l O potass- ium hydroxide with phenolphthalein as in- dicator. The capillary tube attached t o the burette dips into the aqueous layer. Escape of carbon dioxide is thus prevented.Soda-lime Apparatus for Organic Ana- lysis and Carbon Dioxide Estimation. MAX DENNSTEDT (Chew,. Zeit. 1905 32 77).- The apparatus will be readily understood from tho accompanying illustration. It may be made of thin glass and its weight when empty need not exceed 50 grams. It is loosely filled with about 50 grams of granulated soda- L. DE K. T. A. H. an angle of 30’. L. DE K. L. DE K.226 ABSTRACTS OF CHEMICAL PAPERS. lime which if too dry should be moistened with a few C.C. of Estimation of Carbon Disulphide in Benzene. ISIDORE BAY (Conapt.rend. 1908 146 132).-The white crystalline precipitate of phenylhgdraxine phenylthiocarbazate CS,(NHPh*NH,) obtained by addition of phenylhydrazine to carbon disulphide is sufficiently stable to allow i t to be employed aa the basis of a method of estimating carbon disulphide. The precipitate is collected on a double tared filter waehed with benzene and dried in a vacuum desiccator. The method gives very accurate results when estimating carbon disulphide in benzene the greatest error observed being less than 0.5% of the amount determined the values being always too high. E. H. water. L. DE K. The precipitation is complete in two to three hours. Use of Borax Bc. Beads in Analysis. OSCAR LUTZ (Zeitsch. anal. Chem. 1908 47 1-36).-The author has compared the colora- tions produced by various elements when the latter are fused in the ordinary way on borax and phosphate beads and finds that borax beads are only suitable for use in the case of basic elements such as chromium manganese iron coball nickel copper tin and cerium.For acid-forming elements such as titanium vanadium molybdenum tungsten and uranium phosphate beads give the better results. The bead reactions are a t best only confirmatory tests and in most cases better tests are available. w. P. s. Electrolytic Analysis. ALEXANDER CLASSEN (Zaitsch. Elcktroohem. 1908 14 33-34). ARTEUR FISCHER (ibid. 34-36).-Claims for priority in reference t o several methods recently brought forward in papers dealing with this subject. Volumetric Estimation of Zinc according to Schaffner.V. HASSREIDTER (Zeitsch. angew. Chem. 1908 21 66-69).-A criticism of Scbaffner’s zinc titration process with sodium sulphide. The retention of zinc by the. ferric hydroxide may be much lessened by mashing the precipitate with dilute ammonia instead of water. Excess of ammonia has been supposed to have an injurious effect when applying the spot-test on lead-paper but the author thinks this is caused by too high a temperature of the solution also by a large excess of ammonium salts. The analysis of the ore and the checking of the sodium sulphide solution should be carried out simultaneously with the aid of two separate burettes It also appears that the richer the ore the less chance there is of discrepancies in duplicate commercial Electrolytic Separation of Silver and Copper.HORACE W. GILLETT (J. Physical Chem. 1908 12 26-87).-Silver may be determined satisfactorily in presence of copper if the following conditions are observed total silver and copper about 0.25 gram in the form of nitrates 7 grams of tartaric acid 25 C.C. of ammonia T. E. analyses. L. DE K.ANALYTICAL CHEMISTRT. 227 D 0.9 water up to 120 c.c. voltage 1-1.35. The electrolysis may be carried out either at 70'or ZOO but at the lower temperature a very rapid rotation of the anode is necessary so as to get a firmly adhering deposit. From the liquid the copper may be precipitated as sulphide which is then redissolved in nitric acid and deposited by electrolysin in the usual way. 1,. DE K. Electrolytic Estimation of Minute Quantities of Copper.E. E. FREE ( J . Phyeical Chent. 1908 19 28-29).-The author states that i t is possible to estimate fractions of a milligram of copper with accuracy by electrolysis if care is taken to work with a small electrode weighing about 0.3 gram and with the aid of a delicate assay-balance. The electrode is weighed after the copper has been deposited and then again after its removal by means of nitric acid. Good results are obtained by using 25 C.C. of copper solution acidified with 2-4% of nitric acid and a few drops of sulphuric acid. The electrolysis should last overnight with a current of about 1.8 volts and Volumetric Estimation of Mercury in its Ores. JOSEPH A. MULLER (Bull. SOC. chin?. 1908 [iv] 1 1169-1173).-A quantity of the powdered ore representing about 1 gram of metal is dissolved .in nitro-hydrochloric acid a t a gentle heat and then evaporated t o dryness a t 50'.The residue is dissolved in hot water 50 C.C. of 20% potassium iodide are added and then a solution of sodium carbonate so long as a precipitate is formed. After adding a slight excess of 20% aqueous sodium hydroxide the liquid is filtered the residue is again extracted a few times with alkaline potassium iodide solution and finally well- washed with hot water ; when cold the solution is made up to 100 C.C. Ten C.C. of the solution are then placed i n ,a stoppered flask 20 C.C. of 20% aqueous sodium hydroxide are added also 20 c.c.,of 35% formaldehyde and the whole is kept for twenty hours a t 25'. This causes the precipitation of metallic mercury which is carefully washed with alcohol and dissolved in a knomn measure of standard iodine solution.The excess of iodine is titrated with standard thio- sulphete. Gold or platinum should be absent as they are also reduced by Volumetric Estimation of Lead [a. Sulphide]. Huao KOCR (Cham. Zeit. 1908 39 124-125).-Lead may be estimated with sufficient accuracy by titrating the dilute solution with standard sodium sulphide until no further precipitate is formed. Addition of carbon tetrachloride causes a rapid separation of the precipitate leaving the aqueous layer quite colourless. Lead sulphate should be dissolved in solution of ammonium acetate. 0.01 ampere. The usual precautions are taken L. DE K. formaldehyde. L. DE K. Sodium sulphide solution keeps well in an atmosphere of coal-gas.L. DE K. Red Leads and their Examination. ALFHED PARTHEIL (Arch. Pharm. 1907 245 683).-The author's results (this vol. ii 69) have,228 ABSTRACTS OF CHEMICAL EAPERS. for the most part already been obtained by Reinsch (-4poth.-Zeit. 1907 195). G. B. JULIUS F. SACHER (Chern. Zeit. 1908 32 62-63).-The sample is digested with water and a sufficiency of nitric acid with addition of formaldehyde until the lead peroxide is decom- posed ; hydrogen peroxide mny also be used but mgar oxalic acid alcohol and lactic acid cannot be recommended ns they may lead to the formation of insoluble lead oxalate. ‘1he solution is then evaporated to dryness the lead nitrate is dissolved in water and the ERNST PIESZCZEK (Phawn. Zeit. 1908 53 87-88).-A criticism of Sacher’s process (preceding abstract).The author cannot recommend the reduction by means of formaldehyde as the action is too violent. Hydrogen peroxide causes no such incon- venience and it is not necessary as recommended by Sacher to remove the excess of nitric acid by evaporation 8s red lead is not likely to contain lead sulphate. . The solution should be tested also for calcium. Assay of Red Lead. insoluble matter is collected and weighed. L. DE K. Assay of Red Lead. L. DE K. Volumetric Estimation of Manganese in Steel. LUIGI SACERDOTI (Chen7. Zentr. 1907 ii 1448 ; from L’Industria Chimice 1907 7 258-259).-A modification of Deshay’s process. 0-2 Gram of borings is boiled with 45 C.C. of nitric acid 1-18 until no more nitrous frimes are evolved 40 C.C.of water are added and after heating to boiling 1-5-2 grams of lead peroxide are added. After boiling for another two minutes the liquid is rapidly cooled diluted to exactly 100 c.c. and filtered through asbestos Fifty C.C. of the filtrate are then diluted with 50 C.C. of water and the permanganate present is titrated with standard solution of sodium arsenite which has been checked by means of a steel containing an accurately known percentage Titration with Permanganate in Presence of Hydrochloric Acid. THOMAS W. HARRISON and F. MOLLWO PERKIN (Analyst 1908 33 43-47).-0wing to the reducing action of hydrochloric acid on permanganate the authors find that the latter cannot be used for the titration of solutions of ferrous salts containing even small quantitie8 of this acid.The addition of substances such as potassium sulphate magnesium sulphnte borax sodium acetate mercuric sulphate mangmous sulphate and phosphoric acid some of which have been stated to have a retarding action on the rednction due to the hydro- chloric acid had no effect on the results except in the case of manganous sulphate. This salt appeared to have a distinct retarding action but owing to the yellow colour of the solution the end point Volumetric Estimation of Iron in Ferric Compounds. M. M. PATTISON MUIR (Chem. A’ews 1908 97 BO).-The process iu based on the fact that addition of mercuric chloride to a mixture of zirlc and dilute sulphuric acid stops the evolution of hydrogen. of manganese. L. DE K. of the titration was distinguished with difficulty.w. P. s.ANALYTICAL CHEMISTRY 229 The iron solution is placed in a flask fitted with a cork carrying B glass tube narrowed at its upper end. Two hundred C.C. of dilute sulphuric acid and 20 grams of iron-free granulated zinc are introduced the liquid is warmed until there is a brisk evolution of hydrogen and the flask is shaken from time to time until the reduction is complete. One hundred C.C. of strong mercuric chloride solution are now added and after shaking for a few minutes the contents are cooled rapidly Application of Sodium Hyposulphite in Volumetric Analysis. HERMANN ROLLEKBACH (Clma. Zeitsch. 1908 33 146-148).-Sodiup hyposulphite now obtainable in a fairly pure solid condition has already been used in volumetric estimations. The author gives another instance where i t may be successfully applied. Estimation of Fervic Iron.-The dilute iron solution the temperature of which should not exceed 30° is acidified with dilute sulphuric acid until the yellow colour has disappeared.After adding a few drops of potassium thiocyanate the standardised hyposulphite is added until the red colour has nearly vanished. A few drops of indigo solution are then added and the titration continued until the liquid is colourless. No notice should be taken of the fact that the solution soon turns blue again. The hyposulphite solution which may vary in strength from 2.5 to 30 grams per litre is checked with a solution of ferrous-ammonium sulphate previously oxidised by means of permanganate. During the titration the nozzle of the burette should dip into the liquid.A burette arrangement is described in which the hyposulphite is kept in a reservoir in an atmosphere of either hydrogen coal-gas or carbon Separation and Estimation of Cobalt and Nickel. 31. EMMANUEL POZZI-ESCOT ( A n n . Chim. anal. 1908 13 66-67).-In the method proposed the nickel is separated as ammonium-nickel molybdate. The solution containing the nickel and cobalt is rendered faintly acid an excess of saturated ammonium molybdate solution is added and then a quantit*y of ammonium chloride. The mixture is heated to a temperature of 80° next cooled to Oo and the precipitate consisting of ammonium-nickel molybdate is collected on a filter and washed with cold saturated ammonium chloride solution. The double salt is then dissolved in hot water the solution is boiled after the addition of sodium hydroxide to remove the ammonia and the nickel is precipi- tated by the addition of bromine.The hydrated nickel sesquioxide obtained may be weighed or dissolved in a suitable acid and the nickel deposited electrolytically The cobalt in the filtrate from the double salt is also precipitated by the addition of bromine in the presence of sodium hydroxide. The results obtained by the method are stated Detection and Estimation of Nickel in Presence of Cobalt Iron arid Manganese. M. EMMANUEL POZZI-ESCOT (Compt. rend. 1907 145 1334-1335). -The neutralised solution freed from and a t once titrated with standard permanganate. L. DE K. dioxide. L. DE K. to be trustworthy. w. P. 8.230 ABSTRACTS OF CHEMICAL PAPERS.alkaline earths by addition of ammonium sulphate is mixed with a large excess of ammonium chloride and a saturated solution of ammonium molybdate which on heating at 80-OOo for a few minutes completely precipitates the nickel and practically all the iron a8 double molybdates whilst cobalt and manganese are not precipitated. The precipitate is well washed with saturated ammonium chloride solution and the filter is theu placed in a beaker containing water. This is heated to boiling and ammonium chloride and ammonia are added. The iron is precipitated and the nickel is completely dissolved and may at once be estimated colorimetrically ; or the metal may be precipitated by boiling with excess of potassium hydroxide and then adding bromine The sesquioxide is then redissolved and the nickel precipitated by electrolysis.L. DE K. Detection of Nickel. HERMAN GROSSMANN and BERNARD SCH~CK (Bull. Sob chim. 1908 [iv] 3 14-15).-The reaction described by Pod-Escot (Abstr. 1907 ii 818) for the detection of nickel in presence of cobalt is not new since Markwald (Inaug. UGs. Berlin) has already observed that nickel molybdate is less soluble than cobalt molybdate and that the latter is precipitated much more rapidly than the former especially in presence of excess of ammonium molybdate. The reaction is however unwitable for the detection of nickel in presence of cobalt since salts of the latter when warmed with excess of ammonium molybdate yield a precipitate of the anhydrous violet molybdate. The reaction is therefore less delicate as a test for nickel than those described by the authors (Abstr.1906 ii 903) Tschugaeff (Abstr. 1907 ii 989) and Brunck (ibid.) Volumetric Estimation of Nickel. H. CANTONI and M. ROSENSTEIN (BUZZ. Xoc. chim. 1908 [iv] 1 1163-1169).-Nickel may be con- veniently titrated with potassium ferrocyanide or ferricyanide using ferric chloride (or uranium acetate) or ferrous sulphate as indicator. The end reaction is determined by placing a drop of the solution on a piece of folded filter paper and applying the spot-test on the paper below. The best results are obtained with ferricyanide in solutions faintly acidified with acetic acid. The ferro- or ferri-cyanide solution should be checked with a known weight of electrolytically-deposited metal under the same conditions as in the analysis of the Fample.Tables are given showing the influence of acetic acid sodium acetate ammonium acetate sodium sulphate potassium sulphate and ammonium sulphate. WILLIAM BETTEL (Chem. New4 1908 97 40)-The solution to be tested is evaporated nearly to dryness carefully neutralised with nitric or sulphuric acid and mixed with hydrogen peroxide solution. If this should give a yellow coloration a drop uf dilute ammonia is added when should molybdenum be present a browrlish-red colour will appear. The colour however is discharged on dilution and by adding excess of alkali. Accurate quantitative colorimetric results cannot be obtained by this process. T. A. H. ' L. DE K. New Colour Test for Molybdenum. L. DE K.ANALYTICAL CHEMISTRY. 231 Separation of Tungstic Acid From Phosphoric Acid.GEORQ VON KNORRE (Zeitsch. a w l . Chem. 1908 47 37-57).-Tungstic acid may be separated almost quantitatively from phosphoric acid by precipitation with benzidine hydrochloride (compare Abstr. 1906 ii 286). The solution containing the phosphotungstate is diluted to a volume of about 400 c.c. 3 C.C. of hydrochloric acid D 1.12 are added the mixture is boiled and a sufficient quantity of benzidine hydrochloride is introduced. When cold the precipitate is collected on a filter washed with dilute benzidine hydrochloride solution and then boiled with 200 C.C. of water in order to remove remaining traces of benzidine phosphate. After again cooling. the precipitate is collected washed as before ignited in a platinum crucible and weighed as tungsten trioxide.Benzidine phosphates are not very soluble in water and for this reason tolidine hydrochloride may be used for the above separation ; tolidine phosphates are readily soluble so that the precipitate of tolidine tungstate does not need to be boiled with water. I n other respects the process is carried out as described for use with benzidine hydrochloride. Should it be desired to remove any traces of phosphate which may remain in the pre- cipitate the ignited residue is fused with alkali and the tungsten then w. P. s. Detection of Ruthenium in Platinum Alloys. N. A. ORLOFF (Chem Zeit. 1908 33 77).-A portiou of the alloy is fused with lead the regulus is extracted with nitric acid and the residue ignited in contact with the air to remove any osmium.The mass consisting of platinum iridium rhodium and ruthenium is fused with potassium hydroxide and nitrate dissolved in water and treated with nitric acid in excess When this operation is carried out in an Erlenmeyer flask or simply a test-glass covered with a piece of filter paper this will gradually (12-24 hours) darken owing to the formation of RuO vapours. The paper may then be ignited the ash fused with potassium hydroxide and nitrate and the orange-coloured ruthenate extracted MAX ROLOFF (Zeitsch. bfentl. them. 1908 14 53-58).-The author protests against the use of an undue number of decimals in recording the results of analyses of mineral waters. H e instances a case in which the total amount of mineral matter in a litre of water is given to six decimal places.I n the light of modern knowledge the practice of combining the bases and acids found on the analysis of a water to show that re-precipitated with tolidine hydrochloride. with water. L. DE K. Analyak of Natural Mineral Waters. certain salts are present in the water is also open to objection. w. P. s. Improved Method for Estimating the Acidity of Soils. H. SOCHTINQ (Zeitrrch. angew. Chem. 1908 31 151-153).-Ten to fifty grams of the soil are mixed with a little water contained in a flask an accurately weighed quantity (about 0.4 gram) of calcium carbonate is added and the carbon dioxide evolved is removed by means of a current of hydrogen with constant stirring of the mass.292 ASYTSACTB 0% CHEMICAL PAPERS. The carbon dioxide is absorbed and titrated- (Pettenkofer's process) but this may as a rule be omitted.Dilate hydrochloric acid is now added and the carbon dioxide evolved determined as before The difference between the result and the figures calculated from the calcium carbonate added equals the carbon dioxide expelled by the acids from the soil. If the sum of the carbon dioxide found by the two processes exceeds that of the amount added the excess is due t o carbon dioxide formed by decomposition of organic matters I n accurate analysis this should A New Dephlegmator for the Fractionation of Naphtha. V. F. HERR (Chem. Zed. 1908 32,148-145).-The apparatus consists of a tube or column which may be conveniently made from the outer jacket of a Liebig's condenser (300-1000 mm.) by removing the water-inlet tube ; the outlet tube is then connected with a condenser.After placing a disc of wire gauze a t the bottom the column is filled with shot and a thermometer is fixed in with its bulb just opposite the outlet tube. The whole is held in podion by means of a ring lined with asbestos and a round-bottomed short-necked dist,illation flask is attached. The column is isolated by means of cotton-wool filter paper and asbestos. If fractions above 130' bhould have to be collected the 1000 mm. column should be surrounded by a thin asbestos covering only and then be placed in a jacket made of strong sheet copper which is heated by means of four burners to the desired temperature. be allowed for. L. DE I(. L. DE I(. Observations on the Analysis of Lavender Oile PAUL JEANCARD and CONRAD SATIE (Bull.SOC. china. 1908 [iv] 3 155-159).-This work has been in progress since 1900 to ascertain how the percentage of esters in lavender oils is affected by (1) the altitude a t which the plants are grown and (2) the conditions under which the distillation is conducted. The results confirm the observations recorded previously (Abstr. 1900 i 510) and show in addition that the most important factors in ascertaining the value and freedom from sophistication of a lavender oil are (a) the acid number ( b ) specific gravity (0.880 to 0*890) (c) rotatory power ( - 6' t o - 10' in a 100 mm. tube) and ( d ) saponifica- tion number after acetylation (above 160). The addition of spike oil increases the second and diminishes the third and fourth of these constants.The principal constants of lavender oils produced in (1) the higher Alps and ( 2 ) in the Italian Alps in recent years are tabulated in the original. Estimation of Esters in Wine. G ~ Z A AUSTICRWEIL and PAUL YACOTTET (Chem. Zeit. 1908 32 112-113).-0ne hundred to two hundred and fifty C.C. of the carefully-nentralised wine are distilled in a special apparatus a t the temperature of boiling ether or ethyl bromide under reduced pressure until about one-third of the liquid has passed over. The distillate is then boiled in a reflux apparatus for one hour with 10 C.C. of NjlO potassium hydroxide when the excess of T. A. H.ANALYTICAL CHEMIB'I'RY. 233 alkali is titrated with N/10 sulphuric acid. in ethyl acetate. The result is expressed One C.C.of N/10 alkali =0*0088 gram of the same. Evaluation of Picric Acid. FRANZ U t e (Zeiteitsch. anal. Chem. 1908 47 140-144).-0~1 Gram of thesample is heated in a flask with 5 C.C. of 30% aqueous sodium hydroxide and 10 C.C. of 3% hydrogen peroxide for twenty to thirty minutes. The water evaporated is replaced from time t o time and a few drops of hydrogen peroxide are also added occasionally. I n this manner the nitrogen is converted into nitrite; 40 C.C. of water and 100 C.C. of 3% hydrogen peroxide are now added the temperature is raised to BOO and 40 C.C. of 5% sulphuric acid are introduced by means of a pipette reaching to the bottom of the flask. After heating once more t o SO% 12 C.C. of 10% solution of nitron in 5% acetic acid are added and on cooling the nitric acid formed is precipitated as nitron nitrate.After placing the flask for an hour in iced water the precipitate is collected by aid of a filter pump washed with 10-12 C.C. of iced water dried a t 1 0 5 O and Estimation of m-Cresol in Cresol Mixtures. FRITZ RASCHIQ (Pham. Zeit. 1908,53 99-100).-A reply to Herzog who seems not Q have followed the author's directions (Abstr. 1900 ii 694) and has in consequence obtained incorrect results with high-grade cresols. The process consists in converting the m-cresol into insoluble trinitro-m-cresol and oxidising the 0- and p-cresol with formation of JOHANNES HERZOQ (Pharm. Zeit. 1908 53 14l).-The method of estimating m-cresol in mixtures of cresols described by Raschig (preceding abstract) is not considered by the author t o be a suitable one for use by pharmacists.A good fume- cupboard is required in which t o carry out the process and the results w. P. 5. OTTO WIEQAND and M. LEHYANN (Chem. Zeit. 1908 33 109-110).-The process described previously by the authors is now applied t o the fraction passing over between 170-180". Ten C.C. of the distillate are ahaken vigorously as directed with excess of 50yA resorcinol solu- tion and the amount of cineol absorbed may thus be read off and calculated on the origins1 quantity taken for analysis. Colour Reaction of Cholesterol on Oxidation. ISAAC L I F s c a l f T z (Ber. 1908 41 252-255).-The recognition of oxycho- lesterol in bone fat blood (Abatr 1907 ii 899) brain and pancreatic fat has led to the study of its colour reactions.When a few grains of benzoyl peroxide are added t o an acetic acid solution of a few mg. of cholesterol the whole warmed then cooled and four drops of sulphuric acid added to the mixture a beautiful green or violet-red colour changing to green iB developed. The sensitiveness of this reaction is 1 in 10,000 in layers of 12-15 mm. Although less sensitive than L. DE I(. weighed. One gram = 0,037406 gram of nitrogen. L. DE K. oxalic acid and other soluble substances L. DE K. Analysis of Crude Cresols. obtained do not appear to be always trustworthy. Estimation of Cineol (Eucalyptol) in Eucalyptus Oils. L. DE K. VOL. XCLV. ii 16234 ABSTRACTS OF CHEMICAL PAPERS. Liebermann’s reaction (Abstr. 1888 1075) it has the advantage that the absorption bands are situated between the lines C and d whereas in the other the bands are situated near 6 and resinification caused by the acetic anhydride may mask the colour.The colourfi are due to oxgcholesterol or the ether (Abstr. 1907 i 315 and Zoc. cit.) ; oxy- cholesterol is best prepared by using benzoyl peroxide. A combination of the above test for oxycholesterol and Liebermann’s test for cholesterol is made by first adding sulphuric acid to an acetic acid solution ; the green colour produced by oxycholesterol is destroyed by acetic anhydride and if cholesterol is present the characteristic colour due to this substance is developed. Titration of Formaldehyde in Highly-Goloured Solutions. SOREN P. L. SORENSEN and H. JESSEN-HANSEN (Biochem. Zeitsch. 1908 7 407-420).-Formaldehyde may be titrated with alkali and phenol- phthalein as indicator even if the liquid should be coloured yellow or yellowish-brown but in such case it is advisable to make a check experiment using water judiciously coloured with tropaeolin and Bismarck-brown (ihid.1907 64). But even this device fails when the solution is too dark coloured as in the case of protein decomposition products. I n this case the authors operate as follows 20 C.C. of the solution are acidified with say 5 C.C. of N/2 hydrochloric acid (if there is already excess of acid it may be advisable t o add N/2 sodium hydroxide instead) 4 C.C. of 2N barium chloride are added and then with constant shaking 20 C.C. of N/3 silver nitrate ; the silver chloride formed precipitates most of the colouring matter After making up the volume to 50 C.C.and adding four drops more water the liquid is filtered and ttn aliquot part is used for the usual titration allowance being made for acid or alkali added. HANS KREIS (Chew. Zeit. 1908 32 149)-When applying Komarowskg’s test for amyl alcohol in spirits i t is necessary to make sure as t o the purity of the salicylaldehyde employed. If alcohol free from fuse1 oil is available it is easy t o make a practical test but if not the following test is recommended three drops of the sample are mixed with ten drops of sulphuric acid. Pure salicylaldehyde turns a clear orange-red whilst unsuitable preparations give more or less dark brownish-red colora- tions. If now 5 C.C. of 95% alcohol are added the pure substance gives a colourless solution whilst the impure samples give red solutions Use of p-Nitrophenylhydrazine in the Identiflcation of AX- phatio Ketones and Aldehydes HENRY D.DAKIN (J. Biol. Chsrn. 1908,4,235-238).-1n the identification of small quantities of simple aldehydes and ketones p-nitrophenylhydrazine is of great service ; it gives compounds which are insoluble in water and easily crystallisable. The melting points of the phenylhydrazones of the following substances are given thus formaldehyde 181-182O ; acetaldehyde 126-128-5’ ; propaldehyde 123-124O ; n-butaldehyde 91-92’ ; isobutaldehyde 131.5-132’; isovaleraldehyde 109-1 10’ ; glyoxylic acid about 200° j W. R. L. DE K. Testing the Purity of Salicylaldehyde. of varying intensity. L. DE I(.ANALYTICAT CHEMISTRY 235 acetone 1 4 9 O ; methyl ethyl ketone 128-129’ ; methyl isopropyl ketone 108-109O ; methyl n-nonyl ketone 90-91O.GUNNAR HEIEEL (Chem. Zeit. 1908 32 75-76).-Eoth Messinger’s process (titration with iodine in alkaline solution) and Denigh’s mercuric sulphate method give concordant results. Should a serious difference be noticed the acetone contains subfitances which interfere with the tests. I n the case of almost pure acetone the mercury precipitate is yellowish-white but with inferior HENRI PELLET (Ann. Chim. ccnnl. 1908 13 56-57).-The author thinks that the iise of the special tubes recommended by Rousset (this vol ii 73) would tend t o lead to confusion and require alterations in some of the instru- ADOLB JOLLES (ZeitscA. anal. CAena. 1907 46 764-771).-The urine is freed from interfering volatile substances by boiling with a few drops of acetic acid and if necessary concentrated.One hundred C.C. of the sample are mixed with 150 C.C. of hydrochloric acid D 1-06 and distilled in a current of steam until the distillate measures say 1 litre. One hundred C.C. of the distillate are then over neutralised with 20% #odium hydroxide solution using methyl-orange as indicator and N/2 hydrochloric acid i a again added until the red colour is permanent. The furfuraldehyde which represents the pentose is then estimated in the usual way by titration with sodium hydrogen sulphit,e and Barfoed’s Acid Cupric Acetate Solution as a Means of Distinguishing Dextrose from Maltose Lactose and Sucrose. F. C. HINKEL and HENRY C. SHERMAN (J.Amev. Chem. Xoc. 1907,29 1744-1747).-Barfoed’s copper solution is made by dissolving 45 grams of crystallised copper acetate in 900 C.C. of water 1-2 C.C. of 50% acetic acid is added and the whole is diluted to a litre. Five C.C. of the reagent are then placed in a test-tube 5 C.C. of the sugar solution are added and the tube is placed in boiling water for ten minutes The author has investigated this method but states that in order to get trustworthy results the amount of dextrose should not exceed 2 mg. as otherwise the reduction is incomplete. The filtrate may then be tested for the W. D. H. Estimation of Acetone. samples it is yellowish-brown or nearly brown L. DE K Normal Tubes for Saccharimeters. rnents now employed. w. P s. Estimation of Pentoses in Urine.standard iodine solution. L. DE K. Any reduction is due to dextrose only. other sugars. L. DE K. Estimation of Sugar in Blood IVAR BANQ (Biochem. Zeitsch. 1908 7 327-328).-Blood is received from the animal into excess of alcohol ; the coaguluni is broken up and then separated by repeated centrifugalisation with alcohol. The alcoholic extracts are mixed concentrated shaken with a little kaolin and filtered. The sugar is estimated in the clear filtrate (compare Rona and Michaelis this vol. ii 117). W. D. H. 16-2236 ABSTRACTS OF CHEMICAL PAPERS. Estimation of Lactose in Milk. CYRILLE CARREZ (Ann. Chim. anal. 1908 13 17-22).-When using the author's process i t is not necessary to know the volume occupied by the coagulum. Fifty C.C. of milk aremixed with 5 C.C. of potassium ferrocyanide solution (150 grams per litre) and then with 5 C.C. of zinc acetate solution (300 grams per litre) and the clear filtrate is then examined polarimetrically.The operation is repeated three times addition of 10 25 and 50 C.C. respectively of water being made to the milk. Formuls are given explaining the calculation of the % of lactose. L. DE K. The Polarinietric Determination of Sucrose. The Effect of Clariflcation with Basic Lead Acetate on the Optical Activity and Copper Reducing Power of Sugar Solutions. FRANCIS WATTS aud HAROLD A. TENPANY (J. SOC. Chern. I n d - 1908,2'7 53-51). -The authors find that the use of excessive amounts of basic lead acetate has an appreciable effect on the optical activity and reducing power of solutions of invert-sugar. When such an excess is avoided clarification by means of dry anhydrous basic lead acetate-involves no such error (compare Abstr.1907 ii 656). In the case of low grade products such as molasses trustworthy results are obtained by clarification with dry anhydrous basic lead acetate followed by treatment with sulphur dioxide ; this especially applies to estimations by Fehling's method. The authors consider that it appears to be unnecessary t o search for more complicated methods of clarification since the use of dry anhydrous basic lead acetate gives results which are well within the limits of acciiracy of ordinary methods of analysis. w. P. 8. Detection of Rice Starch in Wheat Flour. PELTRISOT ( A m . Chim. anal. 1908 13 50-53).-The method described by Qastine (Abstr. 1907 ii 137) is considered t o be of value in the detection of rice starch in wheat flour ; the appearance of the hilum of the starch grairi i R characteristic. As however a few other starch grains notably those of darnel may be mistaken for rice care should be taken to avoid an error of judgment.Whenever possible the character of the pericarp should be taken into consideration. Estimation of Crude Fibre and Separation of Cellulose Lignin and Cutin. JOSEF Kdsra (nw. 19OS 41 46-49. Compare Abstr. 1906 ii SOB).-Polemical. A reply t o Matthes and Streit- berger (Abstr. 1907 ii 991). HEHJIANN MATTIIES (Be?.. 1908 41 400-403. Compare Matthes and Streitberger Abstr. 1907 ii 991).-Polemical. w. P. 8. W. H. G . Estimation of Crude Cacao Fibre. A reply to Konig (preceding abstract).G. Y. WILLIAM €1. ENERSON (J Arne?.. Chem. Soc. 1907 29 1750-1756).-In carrying out some estimations of stearic acid by Hehner and Mitchell's method (Abstr. 1897 ii 289) difficulty was experienced in obtaining a definite saturated solution of the acid and a study has therefore Solubility of Stearic Acid in Ethyl Alcohol at Oo.ANALYTICAL CHEMISTRY. 237 been made of its solubility in alcohol a t 0'. It hits been found that the solubility is practically constant when not less than 0-7 gram is used with 100 C.C. of alcohol or not less than 0-5 gram with 50 c.c. but that if smaller quantities of the acid are employed highly supersaturated solutions are produced. The bolubility a t Ooof the acid in 100 C.C. has been found to be 0,1246 gram in alcohol of 95.7% strength 0.1223 gram in 95.5% alcohol 0.1139 in 95*1% 0.1035 in 94*5% and 0.0996 in 94.3% alcohol.When an alcoholic solution of stearic acid is evaporated on the water-bath small quantities of ethyl stearate are produced and the solubility of the acid therefore appears greater than i t actually is. Thus on evaporating a solution in 99% alcohol 1.26% of the acid was converted into the stearate. F. GRANSTH~M (Beitv. G. A. LE ROY (Compt. r e d . 1907 145 1285; Ann. Chiin. anal. 1906 13 16-17).-An intense violet coloration is produced when tartaric acid or a tartrate is heated with from 10 to 20 times its weight of a 10% solution of resorcinol or pyrogallol in concentrated sulphuric acid. Under the same conditions citric acid does not give a coloration and malic and lactic acids yield-yellow colorations.For the detection of tartaric acid or its salts in cider the test is applied as follows the cider is nentralised and treated with an excess of basic lead acetate solution the precipitate is collected on a filter washed with cold water and then decomposed with hydrogen sulphide. The lead sulphide is separated by filtration the filtrate is heated to expel the hydrogen sulphide an excess of sodium hydrogen carbonate is then added and the solution is evaporated to dryness. The resulting residue is dissolved in a quantity of the resorcinol or pyrogallol solution and the mixture is heated. If tartaric E. G. Detection of Qlyoxylic Acid in Urine Detection of Tartaric Acid i n Cider. chem. Plysiol. Path.1908 11 132-142).-See this vol. ii 122. arid is present a violet coloration will be produced. w. P. s. Goldenberg Method for the Estimation of Tartaric Acid in Wine Dregs Tartar and other Crude Materials. CHEMISCHE FABRIK. voRw GOLDENBERG GEROMONT & co. (Zeitsch. wnal. Chem. 1908 47 57-59).-The following manner of carrying out this process is given Six grams of the sample containing more than 45% of total tartaric acid or 12 grams if the tartaric acid content is less than 45% are digested for ten minutes with 18 C.C. of hydrochloric acid D 1-10. The mixture is then diluted with water to B volume of 200 c.c. mixed and the solution is passed through a dry filter. One hundred C.C. of the filtrate are transferred t o a beaker of 300 C.C. capacity in which have been placed previously 10 C.C.of 66% potassium carbonate solution and the solution is boiled for twenty minntes. The solution together with the precipitated calcium carbonate is then rinsed into a 200 C.C. flask diluted with water to the mark mixed and filtered through a dry filter. One hundred C.C. of the filtrate are evaporated in a porcelain basin on the water-bath t o a volume of 15 c.c. 3.5 C.C. of glacial acetic acid are now added and the mixture is stirred f o r five minutes After ten minutes 100 C.C. of 95% nlcohol are added the238 ABSTRACTS OF CHEMICAL PAPERS. stirring ,is continued for five minutes and a t the end of a further ten minutes the precipitate is collected on a filter and washed with alcohol. The filter and precipitate are next placed in a basin treated with 200 C.C.of hot water and the solution is titrated with N/5 sodium hydroxide solution using litmus paper as indicator. The sodium hydroxide solution is standardised with pure potassium hydro- gen tartrate. A correctlion is made for the volume of the insoluble constituents of the crude material ; in the case of samples containing less than 45% of tartaric acid 0.80% is subtracted from the result obtained ; for samples containing from 45-60% the correction is 0.30% and 0.20% for those with from 60-'70%. No correction need be applied to the results obtained with samples containing more than Estimation of Non-volatile Organic Acids in Tobacco. JULES T ~ T H (Rev. intem. Fulsq 1907 20 165-166).-Furtber results are given of the estimation of oxalic malic and citric acids in tobacco (Abstr.1907 ii 513). The quantities found were oxalic acid from 0-42 to 257% ; citric acid from 0.92 to 4.56% ; malic acid from 1-56 t o 7.81%. It is found that by estimating the acids separately and calculating the results into oxalic acid a value was obtained which was sometimes more and sometimes less than the value obtained by estimating the acids directly by titration and expressing the result as oxalic acid. The differences were probably due to the 70% of tartaric acid. w. P. s. influence of the volatile acids present in the tobacco. w. P. s. Estimation of Fat in Milk. D. SIDERSKY ( A m . Chim. unal. 1908 13 22-24).-The author recommends the process of Soxhlet as modified by Timpe. T'o 100 C.C. of milk are added slowly and with gentle shaking 50 C.C.of sulphuric acid ; 50 C.C. of water are then added and when cooled to 15O 60 C.C. of ether are introduced and the whole is well shaken to extract the butter fat. The ether before use is well shaken with dilute sulphuric acid (1 3). The percentage of fat is now found by taking the sp. gr. of the ethereal solution and reference to a table. L. DE K. Estimation of Fat. ELLY A. BOUDANOFF (J. Lamdw. 1908 53 53-87).-See this vol. ii 206. Estimation of the Caprylic [Octoic] Acid Value of Butter- Fat. R. K. DONS (Zeitsch. Nahr. Genussna. 1908 15 75-79).-The process is a modification of that described previously by the author (Abstr. 1907 ii 824). Five grams of the butter fat are saponified in the usual way the soap is dissolved in 100 C.C.of hot water and the fatty acids are liberated by the addition of 50 C.C. of dilute sulphuric acid. After cooling the aqueous portion is removed and the solid cake of fatty acids is extracted twice with 150 C.C. of hot water. After this treatment the cake of fatty acids is placed in a flask 20 grams of glycerol 5 grams of sodium sulphate and R few pieces of pumice stone are added and the mixture is distilled until 110 C.C. of distillate have been collected. One hundred C.C. of thisANALYTICAL CHEMISTRY. 289 distillate are neutralised as in the usual Reichert-Meissl process. The acidity of the distillate is due almost entirely to caprylic [octoic] acid and this is precipitated by the addition of iVjl0 silver nitrate solution The quantity of the lat’ter required expressed as C.C.of NjlO solution multiplied by 1.1 give6 the ‘‘ caprylic acid” value of the fat. A correction is applied for the solubility of the silver salt in the volume of solution and that of the water used for mashing the precipitate (20 c.c.); this correction is 0.4 c.c. which is added to the result obtained. Pure butter-fat gives a value of from 1.6 t o 2.0 ; butter containing 10% of cocoanut oil from 2.7 to 3.0 and pure cocoanut oil 5 -3. w. P. s. RICHARD KRZIZAN (Chem. Rev. Fett-Ham- Ind. 1908 15 7-9 29-3C)).-Blackberry seeds yield about 12.6% of a drying oil having the following chemical and physical constants D15 0.9256 j saponification number 189.5 ; iodine number 147.8 ; acid number 2.03 ; insoluble fatty acids 96.3%. The liquid fatty acids contain about 80% of linolic acid 17% of oleic acid and 3% of linolenic and isolinolenic acids and amount to about 91% reckoned on the oil whilst the solid acids chiefly palmitic acid are about 4.7%.Volatile acids are not present in the oil. The unsaponifiable portion of the oil contains 0.6% of phgtosterol. Tbe drying properties of the oil are somewhat inferior to those of raspberry-seed oil (Abstr. 1907 i 821). VLADTMIR STBN~K (Zeituch. phy8iol. Chem. 1908 54 354).-In reply to Kiesel (Abstr. 1907 ii 994) i t is pointed out that most of his observations have been made previously by the author. Indicators in the Titration of Cinchona Bases. ERWIN RUPP and K. SEEGERS (Chem. Zentr. 1907 ii 1363 ; from Apoth. Zeit. 1907 22 743-750).-Hsematoxylin may be advantageously replaced as an indicator for cinchona alkaloids by dinitrophenolphthalein or better still by p-nitrophenol in ail cases where the solution is colourless or nearly so.I n cases of strongly-coloured liquids tetrachlorotetra- bromophenolphthalein may render good service. The indicators are used in the form of 1% alcoholic solutions ten to twenty drops of the first or twenty to thirty drops of the latter solution. The liquids must be diluted with sufficient alcohol to prevent separation of free alkaloid. Both indicators turn yellow in presence of alkali and the cinchona alkaloids behave toyards them as monobasic compounds. Blackberry-seed Oil. w. P. 8. Stangk’s Method for Estimating Choline. J. J. 8. r,. DE K. Estimation of Ecgonine in Java Coca. ANNE W. K. DE JOKG (Phorm.Weekblad 1908,45,42-43. Compare Abstr. 1005 ii 778)- A criticism of Greshoff’s process (Abstr. 1907 ii 914). The ecgoniae hydrochloride obtained is not always pure but may be contaminated with sodium and sometimes ammonium chloride. To prevent this the ‘ g acid-alkaloid ” is dissolved in ether and shaken a few times with water the ether is removed by distillation and the residue treated240 ARSTRACTS OF CHEMICAL PAPERS. according to Greshoff’s method. The aqueous solution may still retain some ecgonine ; it is therefore boiled if necessary with a slight excess of sodium hydroxide to expel the ammonia. It is then acidified with hydrochloric acid and evaporated to dryness ; the result after allowing for sodium chloride represents ecgonine hydrochloride.acid-alkaloid ” cannot be calculated as stated by Greshoff from the ecgonine hydrochloride RS it is in reality composed of three alkaloids namely cocaine cinnamylcocaine and Control and Estimation of Atomic Complexes in Drugs. Pro LAYI (Boll. chim. farm. 1907 46 826-833).-Methorls are given for the examination of protargol heroine (diacetoxymorphine) meso- tan (acetylmethyl salicylate OH-C,H,.CO,-CH,-COMe) aspirin (0-acetoxybenzoic acid) aristochin (quinine carbonate The composition of the isoatropylcocaine. L. DE K. T. H. P. Estimation of Tannins in White Wines. MAX KOEBNER (Chem. Zeit. 1908 32 77)-Ten C.C. of wine are placed in a stoppered cylinder 10 C.C. of tartaric acid solution (1 10) are added then three drops of ferric chloride (1 l o ) ammonia in exceFs and water up to 50 C.C. A clear solution is oltainedwhich owes its darkcolourto R certain amount of iron tannate. The solution is then compared with one made in 8 similar manner using a solution of 1 gram of tannin and 50 C.C. of hydrochloric acid made up to 1 litre as a standard comparison fluid. L. DE K. The Polariscopic Method f o r the Estimation of Gliadin. G. W. SHAW (J. Amaar. Chena. SOC. 1907 29 1747-1750).-Snyder1s process (Abstr. 1904 ii 524) is recommended. If care is taken to make two polarimetric determinations the first in the original solution and the second after precipitating the protein with mercuric nitrate the results compare favourably with the usual chemical methods. L. D E K . The Aloin Test f o r Hemoglobin. A. BOLLAND (Bull. Acad. Sci. Cvacow 1907 441-448. Compare Schaer Abstr. 1903 ii 344).- The blood stain is extracted for twenty-four hours with 1 C.C. of con- centrated ammonia the ammonia is allowed to evaporate and the residue is dissolved in 3-4 C.C. of water. After concentration and acidification with 2.6 C.C. of a 0.06% solution of citric acid 1 C.C. of a 0.1% aloin solution and 1 C.C. of oil of turpentine are added. If hzemo- globin is present a red coloration is produced in ten to fifteen seconds. As in the case of the analogous guaiacum test citric acid should be added t o exclude ferrous compounds which may produce a coloration similar to that given by hsmoglobin. G. B.

ISSN:0368-1769    

DOI:10.1039/CA9089405221

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

241 General and Physical' Chemistry Index of Refraction of Mixtures of Alcohol and Water. A. G. DOROSCHEWSEY and 8. V. DVORSCHAN,ISCHIK ( J . Russ. Ph98. Chem. Soc. 1908 40 101-125).-The experimrnts were carried out in a similar manner to those of Wagner and Schultze (Abytr. 1907 ii 821) althcugh quite independently and it is pointed out that the results of these iuvestigators are vitiated by the employment of an inaccurate method of reading the temperature. Tables and curves are given showing (1) the change in refractive index for lo rise in temperature for various compositions. (2) The change in this quantity with change in composition. (3) The refractive index of vnrious mixturrs a t certain temperatures as observed and also as calculated from the results of experiment. Employing the values of the refractive indices obtained by experiment the composition of the mix- tures is calculated bythe formuls (a - l ) / d (a2 - l ) / d (n2 - l)/(n2+ 2)/d; the first formula gives the best results but all three yield fairly satisfactory results for weak solutions of alcohol in water or vice versa but not for solutions of medium strength.Contrary to Kiegler's statement (Abstr. 1896 ii 224) it is shown that the addition of water t o a concentrated solution of alcohol at first greatly raises the index of refraction and then the effect diminishes until a t the coniposition 60% water i t is zero and further addition lowers the index; it is also shown that C in Pulfrich's formule (Zeitsch. physikal. Chem. 1889 3 561) (D - Dl)/D = C.(iV1- N)/N is not a constant.The refractive index method cannot be employed for the accurate determination of the constitution of concentrated solutions of alcohol in water but for dilute solutions it yields very satisfactory results. Z. K. The Swan Spectrum. KARL VON WESENDONE (Physikal. Zeitsch. 1908 9 151-154).-The flame of a hydrocarbon burning in an atmosphere of chlorine shows the Swan spectrum which would indicate that the latter is due to carbon and not to carbon monoxide. T. E. Some Infra-red Spectra. W. J. H. MOLL (Arch AVerZand. 1908 [ii] 13 lUO-l34)-An automatic spectrometer was employed having silvered concave mirrors in place of lenses. The radiation was measured by Rubens' method using an iron-constantan couple and an automatic arrangement was employed for making the photographic record of the galvanometer readings.The rotation of the prism being intermittent the curve on the drum was traced as a series of separate poiuts. The arc spsctra of sodium potassium rubidium and casium are tabulated and illustrated by curves the wave-lengths studied being from 0 . 5 5 ~ to 4p. The spectrum of mercury was examined as far as lop but beyond 1'7p -emission could not be detected. The absorption VOL. X C ~ V . ii. 17242 ABSTRAC'TB OF CHEMICAL PAPERS bands of atmospheric air were measured by examining the spectrum aE a Nernst lamp. C. H. D. Ifltra-red Emission Spectra of the Alkali [Metals]. A. BERG- MANN (Zeitsch. wiss. Photogmph. Photophysik. Photochem. 1908 6 113-13U).-By a conibination of the phosphorographic and photo- graphic methods the author has examined the ultra-red emimion spectra of the alkali metals.Phosphorescent screeus were prepared from zinc sulphide obtained by dissolving ziuc chloride in water adding excess of ammonia precipitating with hydrogen sulphide and heating the dried product to a moderate white heat. The phosphorescent plates were rendered active by exposing them for one of two minutes to an arc light placed on the further side of a cupriammonium sulphate solution or by exposing them for a few seconds t o diffused daylight. They were then subjected to the actiou of the ultra-red radiation for a few minutes and then immediately brought into contact with photographic plated. After au exposure of about two hours the plates were developed. As bource of light an arc lamp mas used the carbons being axially perforated arid filled with the auhydrous chlorides of the alkali metals.The objectives of the collimator and of the camera were specially designed t o enable meisurements of wave-lengths up to 2OOOpp t o be effected. Spectral lines in the ultra-red region were obtained as follows the numbers representing wave-lengths i n terms of p p sodium 1144.4 ; potassium 1177.6 and 1349.4; rubidium 1322.9 1344.2 and 1366.8; cssium 1359.0 H. M. D. Speotrum of Magnesium and of the so-called Magnesium Hydride as Obtained by Spark Discharges under Reduced Pressure. E. E. BROOKS (Pvoc. Roy. Soc. 1008 80 A 21S-228).- The spark spectrum of magnesium in hydrogen shows among other features a complex system of bands and flutings extending over a con- siderable part of the visible spectrum (compare Liveing and Dewar Abstr.1881 957 ; 1882 254 255; 1883 2 ; 1889 89) aud these lines and flutings have been provisionally ascribed to the presence of magnesium hydride. The author has investigated the spectra obtained with magnesium electrodes in hydrogen and other gases under reduced pressure but has not succeeded in elucidating the origin of the so-called hydride spectrum. Discharges of high frequeucy (with Leyden jars) and of low frequency with alternating currents have been used and the results are described in detail. I n certain circumstances with the high frequency discharge the tube is filled with a green flame the so-called high frequency flame the current being then carried by magnesium ions.The hydride spectrum appears always to be obtained with the high frequency flame in hydrogen even when the gas is dried with phosphoric oxide but is not obtained with other gases in the absence of water vapour. In the low frequency flame however the hydride spectrum is not obtained in perfectly dry hydrogen although underGENERAL AND PHYSICAL CHEMISTRY. 243 the same conditions in the presence of water vapour it shows dis- tinctly. The spark spectrum of magnesium in air nitrogen and other gases has also been invehtigated. In a note appended t o the paper it is mentioned that Fowler has recently obaerved the ‘L hydride ” bands and flutings in the spectra of Zeeman Effect for the Helium Lines. ~ I L H E L M LOHMAN~~ (Physikol. Zeitsch. 1908 9 145-148. Compare this vol.ii 152).- All the lines of the helium spectrum are converted into triplets when the glowing gas is placed in a magnetic field and examined a t right angles t o the lines of force. The distance between the side lines divided by the wave-length squared is the eame for all the lines. This is the simplest case foreseen by Lorenz’s theory and it has not been observed in any other substahce j it indicates a very simple structure for the helium atom. ART~X kAKowsKI (Zeitech. w k . Photogvcbph. Photop?~ylsik. Photochenz. 1908 6 73-100).-Five cerium preparations purified by different methods were found to give identical spectra. A complete table of the lines in the arc spectrum of cerium from A 2576 to h 5003 is given together with identificatioiis of a large number of lines with lines in the solar spectrum.sun-spots. c. 8. T. E. The Arc Spectrum of Cerium. 0. H. D. Some Phopphorescent Spectra;. HENRI BECQUEREL (Con@. rend. 1908 146 440-446).-A comparison of the phosphorescent spectra of two specimens of fluorspar (chlorophane and a Buorapar fiom Titlis) shows that whilst the two spectra have band8 in common these are not the most characteristic bands in either spectia but the flame spectrum of fluorspar from any source is always the same. In view of these facts the author is of opinion that the bands cannot be wholly attributed to the presence of rare earths as stated by Urbain (Abstr. 1907 ii 3). The phosphorescent spectra of apatite and scheelite are almost identical and it would appear therefore that neither the phosphorus in the one nor the tungsten in the other mineral plays any part in the phosphorescent phenomenon which is due to the constituents common to the two minerals namely the calcium and the rare earths.Absorption S p e c t r a of the Vapours of Benzene and it0 Homo- logues at Different Temperatures a n d Pressures and also of Solutions ofBenzene. W.NOEL HABTLEY (Pvoc.Roy. Xoc. 1908,80,A 162-165. Compare Friederichs ALstr. 1905 ii 782).-Vaxiations in the vapour-spectra of benzene at different temperatures ahd pi essures are due t o the fact that t h e are two kinds of absorption (a) general absorption (due to encounters between the molecules) which is broadened and extended towards the less xefrangible rays by rise of temperature ; ( b ) selective absorption (due t o atomic vibrations) which includes all the individual bands and groups of bands which are not widened or displaced by rise of temperature. The selective absorption can be studied most advantageously by raising the general absorption M.A. W. 17-2244 ABBTRACTS OF CHEMICAL PAPERS. to r~ maximum (at looo) and studying the spectra produced by reduction of pressure. The bands of the benzene spectrum between 12-7O and 2 5 O may be resolved into four spectra which partially overlap ; two are composed of strong bands of which there are 64 (27 in each spectrum) and the other two of about 30 weak bands. The intensities of the bands are much the same a t loo0 and a t lower temperatures. The similar groups of bands in the spectra of benzene and its homologues show that the mode of vibration within the nucleus is not greatly affected by the side-chain substitution.The influence of the position of the sub- stituted hydrogens on the number and position of the bands in the spectra of its homologues is clearly shown. The relationships between vapour-spectra and solution-spectra are discussed It is shown that up to nine bands may be recognised in the solution spectsa of benzene six of which aie similarly constituted and four of these are almost exactly similar in all respects. Thefie four correspond with t h e four groups of vaponr-bands already mentioned and occur where these bands overlap to the greatest extent. The view of Baly and Collie (Trans. 1905 87 1333) that benzene has seven and no more than seven solution-bands is shown t o be incompatible with the facts.G. 8. Absorption S p e c t r a of Collidine and Nonachlorocollidine. JOHN E. PURVIS and W. H. FOSTER (Pvoc. Camb. Phil. Soc. 1908 14 381-381.),-The character of the absorption band of collidine is similar t o that of pyridine (Hartley Trans. 1885 47 685) and of lutidine (Baker and Baly Trans. 1907 91 1122) except that it is moved a little more towards the red end of the fipectrum. Jn the case of nonachlorocollidine there is a much greater shift towards the red end and also a slight decrease i n the persistence of ihe band From this the conclusion is drawn that the nine chlorine atoms have replaced tho nine atoms of hydrogen in the methyl groups and have not entered the nucleus Anomaloue Magnetic Rotary Disperaion of Neodymium ROBERT W.WOOD (Physikul. Zeitsch. 1908 9 148-151).-1n geueral the magnetic rotation of the plane of polarisation is greater for short wave-lengths than for longer ones For neodymium nitrate however the rotation is smallest in the blue it increases gradually in the green and then very rapidly as the absorption band in the yellow is approached. No marked increase or decrease on the red side of the band could be observed. The anomaly is thus the same as that observed a t the B lines in sodium vnpour. Does Beer’s Law Hold for Colloidal Solutions? OSCARRN SCARPA (Zeitsch. Chena. Im3. Kolloide 1908 2 Supt. 11 60-52).- The dependence of the absorption of light on the concentration and the thickness of the solution has been examined in the case of colloidal solutions of platinum silver nickel cobalt and copper prepared by the electrical method.Deviations from Beer’s law amounting to 10% were observed. P. H. T. E.GENERAL AND PHYSICAL CHEMISTRY. 245 With increasing dilution t h e absorption in t h e violet region diminishes i n all cases whereas i n some cases t h e effect of dilution is to increase t h e absorption at t h e red end of the spectrum. Chemically- prepared colloidal solutions of ferric hydroxide basic ferric acetate arsenious sulphide and silver obtained according t o Schneider’s method by reduction of silver nitrate also exhibited deviations from t h e requirements of Beer’s law accompanied by increased absorption i n t h e violet region as the dilution of the solutions was increased. H. M. D. The Reduction [of the Photographic Image] with Persulphate and according t o Farmer.JOIIANNES PINNOW (Zeitsch. wiss. Pfbotogrcqh. PJLotophysik. Photochern. 1908 6 130-135).-The mode of action of ammonium persulphate as a photographic reducing [weakening] agent has been 6xamined. The change of colour from black to a brownish-black which is sometimes observed on treatment with ammonium persulphate is evidence of the formation of a new solid substance. This is shown t o contain sulphuric acid and t h e author supposes that t h e substance is either silver sulphate or a com- pound of this with gelatin. The reducing action of persulphate is accelerated by silver salts a fact which is utilised t o explain the mode of action of the persulphate. Two different views are suggested.According t o t h e first reaction takes place between the finely- divided Eilver and the persulphate as represented by the equations (NH,),S,O,i+ 2Ag = Ag,SO + (NH4),S04; (NH,),S,08 + Ag,SO,+ 2H,O = 2Ag0+(NH4),S04 + 2H,S04. The silver peroxide then reacts with a further quantity of silver and sulphuric acid to give silver siilphate which decomposes further persulphate according t o the second equation. According t o the second view tife small amounts of Caro’s acid which are present in t h e persulphate are supposed t o play a part. The liberation of ozone from Caro’s acid takes place very rapidly i n presence of silver salts which act catalytically. The formation of silver sulphate according to the first equation furnishes the requisite catalytic agent and t h e ozone liberated reacts with silver to form peroxide which with the finely-divided silver and sulphuric acid yields a further quantity of the sulphate and thus t h e reaction pro- gresses with gradually increasing velocity.The catalytic activity of the silver salts explains t h e difliculty of obtiining good results when ordinary tap-water is used i n reducing by means of persulphate. The formation of silver salts must be prevented by using chlorine-free distilled water. H. M. D. What is Radium? The Composition of Metals Calculated and Established. R. FAUST (Chem. Zelztr. 1907 ii 1963 ; from a pam- phlet Dresden 1907 1-15).-A theoretical paper in which t h e con- clusions of Ramsay (Trans. 1907 91 1593) are criticised and tha suggestion put forward that t h e alkali metals a r e composed of a metal with radium emanation t h e latter having a negative atomic weight ( - 88.5). An example given is (+Cu),Ra = K = 39.J. V. E.246 ABSTRACTS OF CHEMICAL PAPERS. Phosphorescence Produced by C a n a l Rays. JOHN TROWBRIDQE (Amer. J. Sci. 1908 25 141-142).-Wheii canal rays fall on lithium chloride a red phosphorescence is prodnced whereas cathode rays usually give a faint blne colour. The author shows that this difference is due to t h e greater energy containnd in the canal rays for a cathode stream if sufficiently intense induces the red phosphorescence. I n order t o obt,ain this result the cathode stream is concentrated to a focus on the lithium chloride by passing i t through the longitudinal magnetic field produced by a solenoid.JOHN JOLY (Phil. Mag. 1908 [vi] 15 385-393. Compare Strutt Abstr. 1906 ii 716).-The author has measured the radioactivity of sea-water taken from different parts of the Atlantic and a190 from the Arabian Sea. The emanation was usually distilled OE and estimated by t h e electroscopic method. I t was found t h a t trustworthy results could he obtained when t h e water was acidified with a few C.C. of purified hydrochloric acid per litre in order to liberate tho emanation from Ruspended particles and to prevent t h e formation of a preripitate during boiling. The average activity of fonr samples collected off the West of Ireland and one from the Isle of Man mas equivalent to 0.0344 x 10-'2 grams of radium per gram of water. A sample from t8he ArRbian Sea gave 0,0278 x 10-12 arid five samples collected between Madeira and the Bay of Riscay gave t h e valiie 0*0173 x 10-'2 grams radium per gram whereas Eve (Phil.Mag. 1907 [vi] 13 348) obtained only 0.0003 x 10-12 grams of radium per gram of water from mid- Atlantic. These figures point to an increase i n radioactive material near tho land. The author supposes t h a t much of the radioactive matter reaches the sea in very fine BUS ension and ultimately finds its way into t h e sediments everywhere co 17 lecting. MLLE. ELLEN GLEDITSCH (Compt. rend. 1908 146 331-333).-1n continuation of her inves- tigation of radioactive minerals for the presence of copper and lithium (this vol. ii 9) the author has estimated t h e copper (as coprous sulphide) and the lithium (by fipectroscopic comparison of the residues remaining after the elimination of all the other metals except those of t h e alkalis with artificial mixtures of sodium and lithium chloride) in come radioactive minerals and has obtained the following results R.J. C. The Radioactivity of Sea- Water. K. J. C. The Lithium in Radioactive Minerals. Radioactivity compared Copper. IAthium. with uranium. QJoachimsthsl pitchblende ............... 1.2X0 0*00017% 1.5 Colorado pitchblende .................... 0.15A 0'00034% 1.75 Chalcolite (from Cornwall) ........... 6.54% O~OOOil% 2.0 Thorite ...................................... trace 0'0033 Carnotite .................................. 0'15% 0'030% 0.52 Autunite ..................................... o 0 * 0 0 0 8 ~ 1.48 o,59 The gangue accompanying the chalcolite contained 0.01 2% and that with the autunite 0*0033% of lithium.It is t o be noted t h a t carnotite contains much lithium with b u t little copper whilst t h e reverse is theGENERAL AND PHYSICAL CHEMISTRY. 247 case in thorite. Autunite like gummite (McCoy Natuve Nov. 28th 1907) contains lithium but no copper. I n the latter cases the copper may have been trsnsformpd into lithium but this is not very probable since 'chalcolite contains so much copper and very little lithiurn. Owing t o t h e sensitiveness of the spectroscopic reaction of lithium i t is difficult in some cages t o determine whether this metal is present i n the mineral itself or in the accompanying gangue. The results whilst not invalidating Ramsay's theory ('rims.1907 91 1593) are not favourable t o i t ; they prove that no simple relation exists between the copper and lithium i n radioactive minerals. Lithium in R a d i o a c t i v e Minerals. SIR WILLIAM RANSAY and ALEXANDER CAMERON (Compt. rend. 1908 146 456-457).-The detection of lithium in certain radioactive minerals has not the exclusive significance attributed to i t by McCoy (Nature Nov. 28th 1907) and by Mlle. Cleditsch (this vol. ii 9 and preceding abstract). The authors have shown (Trans. 1907 91 1593) t h a t lithium is one of the products of the action of rddium emanation on copper salts hut i t is probable t h a t other alkali metals are also produced as the alkali residue obtained from the s i l t after treatment with radium emanation was greater than before and a spectroscopic examination showed t h e presence of both sodium and potassium ; experimonts now in progress involving the use of silica vessels will decide whether t h e presence of these metals in the residue is drie t o the use of glass vessels.The proportions of the degradation products appear t o depend on conditions at present unknown for whilst helium is the ordinary degradation product of radium emanation neon is formed in the presence of water and argon in t h e presence of a copper salt. E. H. M. 'A. w. S c a t t e r i n g of P-Rays from Uranium by M a t t e r . J. ARNOLD CROWTKER (Proc. Roy. SOC. 1908 80 A 186-206)-The scattering of the /3-rays from uranium by matter has been investigated by compar- ing the intensity of a parallel pencil of the radiation traversing a fixed cross-section when a thin plate is interposed between the source and the cross-section at some distance from t h e latter with t h a t in t h e absence of the plate.Very thin plates of mica aluminium copper silver and gold were used. As the gource of t h e rays uranium-X waa employed. P-Rays are completely scattered in a thickness of material much less than t h a t required t o absorb them ; scattering is complete after they have traversed a thickness of material varying from 0.015 cm. for aluminium t o 0.0002 cm. for gold. The scattering after correcting for absorption may be represented by an equation of the form I / l o = e - - o d where d is the thickness of material traversed u is the coeificient of scattering and Ib and I are the respective inteneities of t h e radiation passing t,he cross-section referred t o above i n the absence and presence of the thin plate.The ratio of the coefficient of scattering t o the coefficient of absorption (Abstr. 1906 ii 720) is approximately constaiit for all the subotances examined its average value being about 13. G. S.248 ABBTRACTS OF CEEMICAL PAPERS. Preeence of Thorium in the Soil at Rome. GUN A. BLANC ( A t t i R. Accad. Lincri 1908 [v] 17 i 101-106).-By collecting on a negatively charged metallic wire the whole of the thorium products A B and C resulting from the thorium emauatiori librrated from a definite area of the soil a t Rome under normal coifditions and deter- mining the rate of discharge of a sensitive electroscope under the influence of the wire the author finds that the soil contains a quantity of thorium capable of generating the same emanation as it would do if i t contained 0-00166% of thorium hydroxide If the thorium is present in the soil in a form other than hydroxide the proportion of thorium compound must be considerably greater than that given above.T. H. P. Wehnelt Cathode in High Vacuum. J. E LILIENFELD (Physikal. Zeitsch. 1908 8 193),-The author takes exception to the opinion of Soddy (this vol. ii 81) that the Wehnelt cathode ceases to be active a t very high degrees of exhaustion. The phenomena observed in highly exhausted discharge tubes are due t o the large increase in the fall of potential of the positive column which is independent of the nature of the electrodes as the author has shown in experiments published previously.H. M. D. Aluminium in the Potential Series. JOBANNEB J. VAN LAAR A reply to van (Chem. Weekblad 1908 5 124-127).-Polemical. Deventer and van Lummel (this vol. ii 12). A. J. W. Electro-chemistry of Lead. ALEXANDER C. GUMMING (Trans. liai*aday Soc. 1907 2 199-213).-The object of the research is to determine the affinity of the change Pb""= Pb"+2F which (at 25') is expressed in volts by e = P + 0.059 l/nlogl0[Pb""]/[Pb"] where P is a constant which is characteristic of the reaction and the bracketed quantities are the concentrations of the qnadri- and bi- valent lead ions in a solution. Suitable solutions were made by saturating nitric acid with lead peroxide. The solubility of lead peroxide in nitric acid (in milligram-molecules per litre) is 5.3N acid 0.104; 7*5N acid 0.415 ; 9-2N acid 0.8 and l l .5 N acid 1-54. The effect of the concentration of the acid on the solubility is given by the expression [Pb""]/[H']4[HaO]z = constant and the values found agree with this; i t is therefore probable that the lead dissolves as quadrivalent ions The potentials of platinum electrodes coated with lead peroxide in nitric acid solutions of quadri- and bi-valent lead ions were measured against a calomel electrode the diffusion potential being eliminated by means of a strong solution of ammonium nitrate The mean value of P (referred to the hydrogen electrode) found is 1-83 volts assuming in the calculation that the ionic concentrations vary in the same way as those of the total lead salts dissolved Measure- ments of concentration cells containing lead electrodes in solutions of lead nitrate in nitric acid show that this assumption icl not true for tbe bivalent ions ePpecially in the more concentrated acids The solubility of lead nitrate in nitric acid a t 26' is found to beGENERAL AND PHYSICAL CHEMISTRY. 249 (gram-mols.per litre) i n water 1.62 ; i n 2.02N acid 0.536 ; i n 4 4 4 N acid 0.185 j i n 8.77117 acid 0,042 and in 14.35N acid 0 00 I?. The effect on the ionisation of a 0.1 molar solution of lead nitrato of the addition of alkali nitrates was investigated by means of con- centration cells. Equal quantities of sodium potwsium and am- monium nitrates diminish t h e ionisation to very different extents Lead nitrate is less soluble in nitric acid or sodium nitrate than i t is in water but more soluble in potassium nitrate showing t h a t complex ions are formed; hence no information about the dissociation i n nitric acid can be obtained from experiments with alkali nitrates.A few measurements of t h e concentration of plumbous ions i n alkaline solution were made and the solubility of lead monoxide i n water was found to be 3.8 x 10-8 gram-mols. per litre. WLADIMIR KISTIAKOW- SKY (Zeitsch. Elektrochem 1908 14 113-121).-The potential diflerenco between a metal and a solution is affected by the quantity of oxygen dissolved i n the latter. The author has observed as much as 0.2 volt difference between a copper electrode touching the surfdce of a solution of potassium cyanide and one dipping nnder t h e surface ; henre i t is better to eliminate oxygen by working in a closed ' apparatus.The effect of local galvanic actions between different parts of the electrode surface is avoided by polishing t h e surface and exnmin- iog i t microscopically for inequalities and by rotating the electrode rapidly and measuring t h e B.M B' during and after the rotation ; the two measurements should give the same result. A number of examples are given in which electrodes of zinc and magnesium are used. T. E M e a s u r e m e n t of Electrode Potentials. T. E. Anomalous A n o d i c P o l a r i s a t i o n by Nitrio Acid. H. W. HUQO SCHELLHAASS (Zeitsch. EZekti*ochem. 1908 14 121-1 27).-The anode potential at a platinum anode and the yield of active oxygen a r e measured in mixtures of sulphuric and nitric acids. The anode potential is a maximum i n a'mixture of 70 mols.sulphuric acid and 30 mols. nitric acid of normal strength ; i n 4 N acid t h e maximum is at 90 mols. H,SO and i n 10Nacid at about 98 mols. H,SO,. These results a r e true for a current density of 0-05 ampere per sq. om. ; at higher current densities tho maximum is much closer t o the sulphuric acid end of the curve. The quantity of oxygen fixed at t h e anode rises and falls with the anode potential. Even i n pure nitric acid some oxygen is fixed which may be due t o t h e formation of a pernitric acid. T. E. RICIIARD LORENZ and M. KATAYAMA (Zeitsch. physikol. Chem. 1908 63 11 9-128).-A theoretical supplement to Kntayama's experimental work (this vol.ii 145). It is shown t h a t the Gibbs-Helmholtz formula is applicable to the cells which were investigated. EUGEN VON BIRON and B. P. APHANASSIEFF (J. Buss. Phys. Chem. SOC. 1908 40 70-78).-With the view of determining whether the r61e of the alkali halides in the formation of double salts is merely the furnishing of Thermodynamics OF Cells with Solid Substances. J. C. P. Alkali Double Salts of Cadmium Chloride.250 ABSTRACTS OF CHEMICAL PAPERS. halogen ions by their dicsocintion concentration cells of the type Ag.AgC1 1 N/lMCl 1 sat.MC1 1 N/lMCdCl I AgC1.Ag have been in- vestigated (where M equals an alkali metal). The concentration of C1’ ions is the same for potassium and ammoninm since the degree of dissociation of potassium and am- monium chloride is the same at both concentrations N/1 and N/2 b u t t h e lowei ing of concentration of Cl’ taking place partly owing t o the formation of CdCI,4’ is greater for KCdCI than for NH,CdUI ;.it is thus evident t h a t t h e elementary dissociation of the alkali salts is not the only cauw of the formation of double salts in solution the process being prob%bly far more complex. If S16 = lowering of concentration of Cl’ for solutions NjlMCl + N/lCldCI and N/lMCL + N/2CJCl2 respectively then for potassium and ammonium S,>6,/p but for lithium and sodium which form most probably the salts bl,CdCI or M,Cd,CI7 6,<6,/2. Concentration Cells. 11. EUUEN VON BIRON (J. Russ. PAys. Chem. Suc. 1908 40 79-95 Compare this vol. ii 145).-When working with cadmium electrodes a white or prey deposit is always obtained which on examination proves t o be a n oxychloride of cadmium mixed with a little metallic cadmium.The formation of this layer can onlx he avoided when the air is wholly removed from t h e reacting solution and vessel but in t h a t caqe there seems t o occur a slight distillation of the cadmium which appears as thin layers here and there on the surface of the cathode. Experiments were made with electrodes which had been ( I ) untreated ( 2 ) polished (3) polished more thoroughly with t h e following results. ( u ) Electrodes of equal surface display a greater difference when they have been variously trefited than when they have undergone the same treatment ( h ) I n N/1 o r more concentrated solutions the more highly polished electrode always foimms the + pole of t h e element.(c) With removal of air the difference between the electrodes diminishes but the more polished electrode becomes the cathode even i n very dilute solutions. ( d ) The difference i n potential diminishes with time and the more rspidly the more thoroughly evacuated the solution. In any case this difference is more marked for dilute than for conrentrated solutions and cannot be orercome even by vigorous stirring. From these and other experiments in a specially constructed vacuum app iratus the conclusion is drawn t h a t cadmium forms good electrodes only in a vacuum that the electrodes should always undergo t h e same treatment and that all the anomalies observed by various investigntors when working with cadmium electrodes are due to the formation of cadmium oxychloride hy the intcriction of the enclosed air and the cadmium chloride solution.Z. K. Z. K. A Silver Micro-voltameter. EMIL ROSE and F. CONRAT (Zeitsch. Elekwochern. 1908 14 86-8S).-The silver nitrate solution is con- tained i n a U-tube one limb of which contains the anode consisting of R small piece of silver fused to t h e end of a platinum wire and t h e other limb t h e cathode This is a piece of platinum wire 0.06 t oGENERAL AND PHYSICAL CHEMISTRY. 251 0.1 mm. diameter atid 1.5 to 2.5 cm long which is hung on a platinum hook so t h a t it dips into the solution about 1 cm. It is weighed on a Nernst micro-balance. The currents used varied from about 0.003 t o 0.1 milliampere and the quantities of silver deposited from 0.5 t o 2 mg.the accuracy being 0.35 to 0.5%. Experiments in which the electrolyte was a solution of silver nitrate treated with excess of metallic silver at 95* gave deposits about 2% heavier than those obtained from a cold solution with the same current. This result is attributed to the presence of Ag,' ions which would also explain the irregularities of the silver voltatneter. T. E. Electrical Conductivity and Internal Friction. N. LENCKE (J. Buss. Phys. Chem. Soc. 1905 37 1134-1138).-1n order t o determine whether the regularities regarding the internal friction of sodium chloride solutions were also applicable t o other salts glycerol and aqueous solutions of potassium chloride and bromide were examined by the method employed previously (Pissarjewsky and Jdemcke Abstr.1905 ii 684) with the following results (1) the degree of dissociation of potassium chloride is greater in a mixture of glycerol and water than in pnre water. (2) k.=ysc .vx =about 151 both for potassium chloride and bromide and IS independent of the solvent. (3) A s in the case of sodium chloride so with potassium chloride the internal friction changes periodically with the increase in volume of the solvent. Z. K. Electrical Conductivity in Mixtures of Acid or Base and Water. G. BOIZARD (Ann. Chim. Phys. 1908 [viii] 13 289-361. Compare Abstr. 1906 ii 419).-'Che paper commences with a rdsnmd of the work done on this subject during the past twenty years. This is followed by a detailed description of the two methods of measurement emplojed ; (1) Lippmann's (Compt.rend. 1876 83) modified by Routy (Ann. Chim. Phys. 1884 [vi] 3) and (2) Kohlrausch's in which the solution and the solvent t o be compared form two arms of the Wheatstone bridge and by a discussion of their causes of error. The work described in the present paper relates only to sulphiiric acid as a solvent and ammonium sodium potassium and potassium hydrogen sulphates acetic acid and potassium acetate as solutes. The sulphuric acid is used in concentrations of 0.25%. 0*50/ l% 2% 3% 5% lo% 15% 20% 30% 45% 60% 73% 84.50/ 88% 92% 97*5% and 100%. The ratios ( I ) of the differences between the conductivities of solutions of the above salts at varying concentrations in these solvents and the conductivities of the solvents compared with the latter are given in tabular form and also plotted against the concentrations i n gram- molecules per litre (m) of solution in the form of curves.The latter are shown t o be of five distinct types. The results show t h a t for all the above salts there are two concentrations of srilphuric acid one very high and the other very low,between which addition of the salt lowers the conductivity of the acid A t concentrations of sulphuric acid above the higher and below the lesser of these limits addition of solute has the normal effect of increasing the conductivity. The curves show t h a t in 0*25% 0 ~ 5 % ~ and 1% acids Bouty's law (compare Abstr. 1884,252 ABSTRACTS OF CHEMICAL PAPERS. 881 1241 ; 1886 653,839 ; 1887 758 877 882) holds for ammonium and potassium sulphates a t concentrations up to half a gram-molecule per litre and if allowance is made for the water set free by secondary changes of other salts the conclusion is drawn that the law holds generally for sulphuric acid as a solvent considering always the acid of minimum conductivity.I n many cases i t is observed that the solutions in acid are better conductors than the aqueous solutions of t h e same salts showing that sulphuric acid is a more highly dissociating solvent than water. The conductivity of 20% acid is not altered by addition of potassium hydrogen sulphate at concentrations up to a half gram-molecule per litre; the same phenomenon is observed with the sodium salt in 15% acid. I n acids of concentrations from 20 to 90% the molecular variation of the conductivity of ammonium sulphate remains constant at concentrations up to 1 gram-molecule per litre.Determinations of the solubility of this salt in sulphuric acid of varying strengths show that 60% acid has the least dissolving power. Similarly sodium and potassium sulphate have a minimum solubility in 60% acid The ratio I varies slightly with the temperature atcord- ing to the equation &=ZI8[l + k ( t - IS)] L being positive or negative and generally independent of the concentration. A table of the observed values of Jc for different salts is given. I n the case of solutions whirh according to their concentration are a t tirst less and then more highly conducting than the solvent in the neighbowhood of the concentration of equal Conductivity the tempera- ture effect is t~o change the sign of the variation of conductivity.But at very high or very iow concentrations rise in temperature produces an increase in the variation. I n the case of the acid sulphates and acetic acid k is negative for all the solvents studied. At high temperatures the temperature effect for ammonium sulphate tends towards zero. The author finds that an acid more nearly 100% than that indicated either by Kohlrausch (Abstr. 1883 413 769) or by Knietsch has the minimum conductivity 70.6 x 10-4 instead of the value SO x given by Bohlrausch. E. H. Electrolysis of Solutions of Pure Hydrogen Chloride. EMMANUEL DOUMER (Compt. rend. 1908 146 329-331).-During the electrolysis of hydrochloric acid pure hydrogen is collected at the cathode but the chlorine collected simultaneously at the anode is never pure being always mixed with varying quantities of oxygen.The volume. of oxygen evolved varies with the strength of the solution increasing considerably as the concentration of hydrogen chloride diminishes. I n a series of experiments in which solutions of hydrogen chloride containing 14.5-0.72 grams per litre were electrolysed between platinum mires 0.5 mm. thick and 6 cm. long by currents of about the same intensity in each cage the ratio (v/V) of the volume of oxygen (v) t o that of the hydrogen ( Y ) evolved increased from 0.034 to 0.212. To determine whether the oxygen is formed by the action of the nascent chlorine on the water or from actual electrolysis of the water an experiment was made using a silver anode to combine with the chlorine set free.I n this case a larger volume of oxygen masGENERBL AND PHYSICAL CHEMISTRY. 253 produced fro& which it is deduced that the latter explanation is correct. The deficit of oxygen with the platinum anode is probably due to the formationof oxides of chlorine. If all the oxygen evolved could be measiired the ratio of the number of ions produced from the water to the tot’al number of ions could be determined. The con- clusion is drawn that in the electrolysis of hydrochloric acid part of the current is used in decomposing the water and it is therefore necessary to take this into account when determining the transport numbers of H and C1 or the conductivity of hydrogen chloride solutions.E. H. + - Strong Electrolytes. ALEXANDER C. CUMMING (Trans. Paraday Soc. 1907 2 213-221).-In order to eliminate the potential difference a t the contact of two dissimilar solutions a strong solution of potassium chloride has been interposed between the solutions. The author studies the effect of solutions of potassium and ammonium nitrates. A 1 O N solution of the latter salt completely eliminates the diffusion potential between solutions of hydrochloric acid and of lithium chloride. A saturated solution of potassium nitrate is not sufficiently concentrated to do so. Solutions of salts the ions of which have very different mobilities are quiet ineffective as the theory requires. Tho above result was applied to the measurement of the E.Jl.F.’s of cells containing silver electrodes in solutions of silver nitrate directly connected or separated by a 10N solution of ammonium nitrate.Using N/lO and N/lOO silver nitrate directly connected the E.M.F. is 0.0590 volt whilst when connected through ammonium nitrate it is 0.0556; the difference between these numbers is the eliminated diffusion potential which is calculated from Nernst’p formula to be 0.0033 volt in close agreement with the experimental result.. The &.&I. F. of the concenfkation cell apart from the diffusion potential may be calculated from the ratio of the concentrations of the silver ions i n the two solutions ; taking the conductivities as a measure of these concentrations the E.M.3’. comes out a t 0-0557 volt. I n ct similar way the author finds for O.UlhTand 0-001N solutions the E.M.3’.to be 0.0579 volt (0.0580 calculated) and for 0.1N and 05Nsolutions 0.029 volt (0*0292 calculated). H e considers that conductivity is a true measure of ionisation. T. E. Decomposition Curves of Lithium Chloride in Pyridine and in Acetone. The Effect of Water. HARKISON E. PATTEN and WILLIAN R. MOTT (J. Physical Chem. 1908 12 49-74. Compare Abstr. 1904 ii 379).-Lithium can be deposited on a smooth platinum cathode a t 25” from an anhydrous saturated solution of its chloride in pyridine or in acetone a t a current density of 0.001 amp./cm2. The cathode polarisation due to deposited lithium is + 2.60 volts both in pyridine and in acetone as comparod with about 2-45 volts for water (“ absolute ” potentials according to Ostwald) although the heats of solution of the chloride in the respective solvents are very different being equivalent to 0.254 0,371 and 0.613 volt in acetone water,254 Al3STRACTS OF CHEMICAL PAPERY. and pyridine respectively.The total polarisation of the cell is about 4 volts in pyridine and 4-15 volts in acetone. When a little water is added to the solution of lithium chloride in pyridine the current rapidly diminishes almost t o zero owing t o the formation of an insulating film on the cathode. The effect on the conductivity of the gradual addition of water and lithium chloride respectively t o pyridine has been determined. For solutions containing more than 0.5% of lithium chloride the increase of specific conductivity with further increase in the proportion of salt is very slow.The conductivity of a pyridine solution of lithium chloride is greatly increased at first by adding a little water 0.5% of the latter doubling the conductivity of a N / 3 solution of the chloride ; the effect of adding water to the aeetone solution is much less. Tile current efficiency (estimated by measuring the gas liberated at the cathode) for the deposition of lithium from a pyridine solution at a current density of 0.1 amp./cm2 is 23.3% ; from itxi acetone solution at a current density of 0.001 amp./cm.2 38 5% and from a n amyl alcohol solution at a current density of 0*0012 amp./cm.g 44.S%. G. 5. Validity of Faraday's Law in the Electrolysis of Hot Porcelain. FRHZ HABER [with A. R I ~ ~ F F and P. VOGT] (Zeitsch. aworg. Chem. 1908 57 154-173.Compare Abstx. 19Oi ii 6 66 67).-As electrolyte unglazed porcelain (a Rose's crucible) was used. The current was conveyed by graphite rods dipping in melted tin the latter making contact both outside and inside with the crucible the t i n inside the crucible forming the cathode. Tile E.M.P. was so ad- justed that 3-4.5 milliamperes per sq. cm. passed from the anode to the cathode t i n through the crucible at the lower temperatures and the current was measured with a silver voltameter. The whole arrange- ment was kept at a n approximately constant temperature (at intervals between 800' and 1250') in a n electric furnace access of oxygen to the cathode compartment being carefully prevented. After the electrolysis the amounts of different metals which had passed into the cathocle tin were determined by analysis.Porcelain is a conductor from 300' upwarcls. The cathode compartment was fcund to contain aluminium (very little at lower temperatures) iron calcium magne.ium potasbium a i d sodium. There is reason to suppose that the conductivity at the lower temperatures is mainly due t o alkalis and t h a t aluminium silicate the chief constituent of porcelain becomes to some exteiit a conductor at higher temperatures. On this view the relatively large proportions of magnesium and calcium in the cathode liquid are a little surprising and some evidence has been obtained that the liberated alkali metals react in a secondary manner wit)h the porcelain libetating magnesium and calciurn. The results were checked by analysis of the porcelain before arid after electrolysis.Comparison of the quantity of electricity which passes with the amounts of the different metals liberated iu the electrolysis show that within the limits of experimental error (which is naturally somewhat large) Frtraday 's law is valid for porcelain as electrolyte 0. 8.GENERAL AND PHYSICAL @HENISTRY 2.55 Thermo-electric Power of Lithium and Sodium. ARCIEI~O BERNINI (Nzcovo Cinz. 1908 [v] 15 29-42. Compare Matthiessen Ann. Plzys. Chenz. 1858 103; Naccari and Bellati Nuozilo Cinz. 1876).-The author has investigated the thermo-electric properties of lithium and sodium at various temperatures le'id being used as the second metal of the couples used. I n the eahe of lithiuu the constarits b aiid c of Avenarius's formula e = (tl - t ) [ b + ~ ( t + t } ] are fouud to have the mean values 0.0000128 1 and 0*000000~1905 respectively for the temperature interval 10-1'73'. The temperature of inversion given by the quotieut - b/c is - 674.2' and the neutral point - 332.1".These rehults mliich were obtained by means of a Latimer Clark potentiometer were very nearly confirmed by measureme tits made with a Dolezalek electrometer. Sodiuiri differs from lithium in being negatively thermo-electric towards lead. The values of b and c for sodium are 0*000004339 aiid O*OOOOOOO 1 13 respectively these holding with close approximation up to temperatures higher than the melting point of sodium ; the neutral point is here - 192'. Naccari and Bellati (Zoc. cit.) were led to the conclnsion that in the neighbourhood of the melting point of sodium the c<,urde of the curve connecting the E.&t.F.of the sodium- lead couple with the temperature cannot be well represented by a parabola of the second degree but the author finds no such irregularity. Taking the thermo-electric power P as being b + 2ct and 8 = 273 + t the following eqaations are obtained P = 1.26 + 0.040 for lithiurn and P = - 1.63 + Om0258 €or sodium the results being in microvolts. T. H. P. Quantitative Invevtigations on the Electrical Synthesis of Colloids. 11. THE SVEDBERG (Zeitsch. CheJm. I9zd. XuZZoide 1908 2 Supt. 11 39-44).-Tiie influence of changes in the arrangement of the electrical circuit on the production of a colloidal solution of cad- mium in ethyl ether has beeu studied.The extent to which the electrodes are disintegrated and the medium decomposed is the same whether the induction coil is connected directly with the condenser or with the electrodes. The yield of colloid is unchanged wiiether a mercury or a WehneIt alternator is used. By altering the constants of the discharge circuit within wide limits the effect of varying the unsymmetrical distribution of potential was studied and under all conditions the 1 0 s of weight of the two electrodes was found to be the same. H. 31. D. Relation between the Ignition Temperature and the Vapour Pressure of Inflammable Liquids of Low Boiling Point. K. W. CIIARITSCHKOF'P (J. Rus~.. Phys. Clienz. Xoc. 1908 40 138-140).- Various fractions of naphtha and of light petroleurn have been inves- tigated aud the close dependence of the ignition ternpeiature on the boiling point and vapoui pressure of the substance is shown i n tnbuldr for In.2. K. ETIENNE REXGADE (Bull. Soc. dk. 1908 [iv] 3 188-190).-A niodified form of Mahler's bomb Modified Bomb Calorimeter.256 ABSTRACTS OF CHEMICAL PAPERS. calorimeter is described and figured which is suitable for investigating the heat relations of such actions as the solution of the alkali metals in water. The wiring arrangement for electric firing of the bomb is done away with and is replaced by a steel piston passing through a pressure- stopper in the cover of the bomb and terminating (1) outside in a pulley by means of which the b tmb can be rotated in alternate directions and (2) inside in a disc which can be used to br.e.tk a fragile vessel containing a weighed quantity of the alkali metal.A stoppered outlet in the cover of the bomb is provided for the escape of gases at the end of the operation. A glass rod is placed diagonally inbide so that when the bomb is rotated the liquid is mechanically stirred by the rod. The precautions necessary in using the bomb and the corrections which must be applied to results obtained by its use Rre given. T. A. H. The N e u t r a l Alkali and Alkali-earth Carbonates. ROBERT DE FORCRAND (Conapt. rend. 1908 146 511-515) -The whole of the thermochemical ditta necesary for comparison with experiments on the decomposition by heat of the alkali and alkali-earth carbonates has not hitherto been known. The thermochemical cycles concerned are M,O(solid) + CO,(ga.) = i\12C0,(solid) + x ; M,CO,(solid) +Aq = A ; M,O(solid) + Aq = B ; COJgas) + Aq = 543) Gal.; M,O(diss.) + C02(diss.) =M,CO,(diss.)+C (in all of which ill represents two atoms of an alkali or one atom of an alkali-eaith metal).The values of A for sodium and potassium carbonates of B for lime and of C for sodium potassium calcium strontium and barium oxides have long been known. The values of A for calcium strontium and barium carbonates are zero; for lithium rubidium and cmiuni carbonates a t 1 5 O the author finds + 3.06 + 8.75 and + 11.84 Cd. respectively. Rengade (Abstr. 1907 ii 737; this vol. ii 155) has determined the heats of dissolution ( B ) of sodium potassium rubidium and czesium oxides ; for lithiurn strontium and barium oxides the author has obtained the values + 31.2 + Y0.8 and + 35.64 Cal.respectively,whilst for the heats of neutralisation (by dissolved carbon dioxide) of lithia rubidium and caesia he finds the values + 20.57 + 20.57 and + 213.49 Cal. From these data are calculated the heats of combination of the solid oxides with gaseous carbon dioxide (Na,O,CO,) + 76.S8 Gal. (K,O,CO,) + 94.26 Gal. (Rb,O,CO,) + 97.42 Cal. (Cs,O,CO,) + 97.53 Cal. (CaO,W,) -t- 43.3 Cal. (amorphous) + 42.0 Cal. (calc. spar.) + 42.6 Cal. (aragonite) (Li,O,CO,) + 54-23 Cal. (SrO,CO,) + 57.3 Gal. (orthorhombic) (BaO,CO,) + 63.44 Cal. The first numbers in the serie.; are not in accordance with Lebeau’s results (Abstr. 1903 ii 4 7 7 ; 1904 ii 121)’ according t o which cmsiurn carbonate would be wore easily dissociated than rubidium carbonate and the latter more so than potassium carbonate.From the author’s general relation Q/T = 30 the tempet attires of dissociation are calculated to be calcium carbonate (aragonite) + 1160° lithium car- bonate 1536” strontium carbonate (orthomombiv) 1637O and barium carbonate 1842O although the relation is not rigorously applicable since the carbonates fuse below these temperatures. Experimentally it i s known that lithium carbonate loses all its carbon dioxide at 800’GENERAL A N D PHYSICAL CHEMISTRY. 257 in a current of hydrogen; Zavrieff (Abstr. 1907 ii 768) has found the temperature 910' for the dissociation of calcium carbonate and Herzfeld and Stiepel have found 1250' for strontium carbonate and 1450' (approx.) for barium carbonate.The author considers that the discrepancies between the calculated temperatures are explained by a decrease in the heats of formation of the carbonates a t high tempera- tures. I n support of this a concordant series of numbers having the mem + 34.76 Gal. is calculated by application of Clapeyron's formula to Zavrieff's curve between 800' and 900". With this value for calcium carbonate and values for lithium strontium and barium carbonates obtained by applying similar reductions to those a t the ordinary tem- perature the temperatures 886O 1200° 1284'' and 1 4503 are obtained for the dissociation of the several carbonates. These (excekt that for lithium carbonate) agree with the observed values. E. H. Heat of Formation of Antimony Hydride.ALFRED STOCE and FRANZ WREDE ( B e y . 1908 41 540-543).-The earlier deter- minations of Berthelot and Petit (Abstr. 1889 666) by decomposing antimony hydride by bromine according to the equation SbH + 4Br2 = SbBrs+3HBr cannot be accurate. The gas used contained only a small percentage of the hpdride and the greater portion of the antimony existed as tribromide so that in addition to the large amount of gas required the method involved the knowledge of the heats of formation of hydrogen bromide and antimony tri- and penta- bromides as well as the heat of solution of bromine in potassium bromide. A bimpler method was therefore desirable and this was carried out by decomposing antimony hydride quantitatively into its elements by the electric spark in a stout cylindrical glass vessel of 300 C.C.capacity provided with a capillary tube in which a small bulb was blown fitted with platinum wires and closed with a glass rod. At the other end of the cylinder a bent capillary tube wv:zs fused for the admission of the gas. The quantity of gas introduced was 0.8 gram and a correction was made for the departure from the gas lams (com- pare Abstr. 1907 ii 180). The cnlorimeter contained 4 litres of water and the temperature was measured by a platinum resistance thermometer. The mean of three determinations gave Sb(meta1) + 3H = SbH - 33.98 Cal. at constant pressure and - 34-27 Cal. a t constant volume The earlier determinations gave - 86.8 Gal. and a comparison of Berthelot's determinations of the heats of formation of the hydrides of phosphorus and arsenic with that of antimony renders their re-investigation a necessity.W. R. Heat of Vaporisation of Propionic Acid. A. FAUCON (Cowpt. rend. 1908 146 470-473).-Preliminary to the determination of the heat of vaporisation of propionic acid by Bertbelot's method the author has redetermined the corresponding constant in the cases of benzene and formic and acetic acidfi with the following results For benzene L=93*62 Gal. [Schiff found 93.40 Gal. (Abstr. 1887 9); Luginin 92.97 Gal (Abstr. 1899 ii 269); Miss Marshall 94.4 Cal. (Abstr. 1896 ii 349)]; for formic acid L = 121.03 Gal. [Fsvre and VOL. XCIV. ii. 18258 ABSTRACTS OF CHEMICAL PAPERS. Silbermann 120.7 Cal.; Miss Marshall 120.36 Cal. (Abstr. 1896 ii 589); Raoult 120.9 Gal.] ; and for acetic acid L = 97.37 Cal.[Miss Marshall found 97 Gal. (Abstr. 1896 ii 349) ; Raoult 97.4 Cal. ; Favre and Silbermann 101.9 Cal. and Berthelot 120.8 Cal.]. The propionic acid employed was purified by repeated crystallisations and had b. p. 139*8'/761.2 mm. and m. p. 19.3'; the value of df/dt using Schiff's number 0.536 for the specific heat (Zoc. cit.) was found to be 23.61 mm. and the heat of vaporisation 90.43 Cal. I n common with acetic and formic acids propionic acid does not obey Trouton's law the value of MS/T being 16.20 instead of 20.21. M. A. W. Application of Low Temperatures to Some Chemical Problems (1) Use of Charcoal in Vapour Density Deter- minations ; (2) Rotatory Power of Organic Substances. SIR JAMES DEWAR and HUMPHREY 0. JONES (Proc. Roy. Xoc. 1908 80 A 229-238).-Barkla and Sadler (Abstr.1907 ii 731) on the basis of certain experiments depending on the use of Kontgen rays have recently suggested that the accepted atomic weight of nickel is much too low. To test this point the authors have redetermined the density of nickel carbonyl at 0" and low pressures by a method depending on the use of low temperatures and condensation with charcoal. A vessel measuring over two litres and surrounded by melting ice was connected to a manometer and to an absorption tube containing charcoal which could be detached and weighed. The apparatus was first exhausted by a Fleuss pump and finally by subsidiary tubes con- taining charcoal and immersed in liquid air ; the vessel was then filled with nickel carbonyl at a definite pressure and after equilibrium was attained the carbonyl was absorbed in the tube for that purpose immersed in liquid air the tube being finally removed and weighed. It is shown that the method is fairly accurate.The density of nickel carbonyl at 0" and 16-47 mm. pressure is 84.67- 84-79 in satisfactory accordance with the accepted atomic weight. The optical rotatory power of certain organic compounds dissolved in alcohol and in light petroleum has been measured a t very lorn temperatures in a jacketed metal polarimeter with ends of thick glass the cooling agent being poured into the space between the tube proper and the outer jacket. The negative rotation of nicotine in alcohol diminishes regularly with temperature down to -120° just as it does at temperatures above Oo and that of bitter orange oil increases regularly down to - 95O also in accordance with its behaviour at higher temperatures.In both cases the curve showing the relation between rotation and temperature is approximately a straight line and extrapolation indicates that the rotation in both cases would be considerable a t the absolute zero. G. S. Anomalous Viscosity at the Clearing Point of so-called Crystalline Liquids. EMIL EOSE and F. CONRAT (PlAysikuZ. Zeitsch 1908 9 169-173).-The viscosity of anisaldazine is measuredGENERAL AND PHYSICAL CHEMISTRY. 259 between 170' and 190'. The sample used changed from a turbid to a clear liquid a t 182.S'. The viscosity of the turbid liquid diminishes as the temperature rises up to 180° ; it then begins to increase rapidly reaching a maximum a t the clearing temperature ; above this tempera- ture the viscosity of the clear liquid diminishes again in the usual way.The change of viscosity in passing from the turbid to the clear liquid is thus not isothermal but is spread over an interval of t w o to three degrees. T. E. Conductivity and Viscosity of Solutions of Certain Salts in Water Methyl Alcohol Ethyl Alcohol Acetone and Binary Mixtures of these Solvents. VII. HARRY C. JONES and W. R. VEAZEY (Zeitsch. physikal. Chena. 1908 61 641-697).- The conductivity of cupric chloride in water methyl alcohol ethyl alcohol and in binary mixtures of these solvents has been determined as also the conductivity of potassium thiocyanate in all the four so!- vents mentioned in the title and their binary mixtures. The viscosities of these solvents of their mixtures and of the potassium thiocyanate solutions have been measured.In some cases a minimum of conductivity has been observed; even where a real minimum does not occur the values found for the con- ductivity in the mixed solvent are in many cases considerably below the values calculated by the mixture rule. To these cases of virtual minima as well as t o the cases of actual minima the theory of Jones and Lindsay (see Abstr. 1902 ii 55 ; also Jones and Murray Abstr. 1902 ii 637 ; Jones and Veazey Abstr. 1907 ii 438) is applied. ' A conductivity maximum has been observed for solutions of potass- ium thiocyanate in mixtures of acetone with methyl and ethyl alcohols and i t is shown that the fluidity also of the mixed solvent is at a maximum a t the same composition.The explanation of such conductivity maxima adopted by Jones and Bingham (Abstr. 1906 ii 66) is extended and the phenomenon is referred ultimately to an aggregation of the two kinds of solvent molecules. Whereas the conductivity of cupric chloride is greater than that of potassium thiocyanate at a corresponding concentration in water the reverse is the case when the solvent is methyl alcohol ethyl alcohol or acetone. It is suggested that ternary electrolytes although yield- ing three ions in water dissociate into only two ions in organic solvents. The temperature-coefficient of conductivity is found to be greatest for those mixtures of water and organic solvent which contain 25% of the latter.It is accordingly supposed that in these mixtures more complex aggregates between the solute and solvent are formed than in any other mixture of the same two liquids. The conductivity of potassium thiocyanate is higher in acetone than in water; this is shown to be due t o the greater fluidity of acetone and the consequent higher speed of the ions; further as shown by the difference between the temperature-coefficients of conductivity in the two solvents the aggregates present in the water solution are much more complex than those in the acetone solution. J. C. P. 18-2260 ABSTRACTS OF CHEMICAL PAPERS. Conductivity and Viscosity of Tetraethylammonium Iodide in Water Methyl Alcohol Ethyl Alcohol Nitrobenzene and Binary Mixtures of these Solvents. VIII.HARRY C. JONES and W'. R. VEAZEY (ZeitscA. physiknl. Chem. 19OS 62 44-58. Compare preceding abstract). -The conductivity of tetraethylaminonium iodide in water and methyl alcohol exhibits a minimum for the 50% mixture both a t 0' and 25'. A minimum conductivity not so well marked is observed also in water and ethyl alcohol. I n mixtures of the two alcohols and in mixtures of nitrobenzene and methyl alcohol no minimum conductivity is observed only a slight falling below the values calculatled by the mixture rule. Both a t 0' and 2 5 O the conductivity of tetraethylammonium iodide in mixtures of ethyl alcohol and nitro- benzene exhibits a slightly marked maximuin noticeable for all dilutions. A mixture of t,hese two solvents containing 25% of nitro- benzene has both at Oo and 2 5 O a greater fluidity than either of the constituents.The various observations recorded in this paper are interpreted on the lines already described (Eoc. cit.). In connexion with viscosity the authors consider that the very marked influence of slight impurities accounts for the different values found by various observers for the viscosity of a given liquid. J. C. P. Viscosities of Binary Mixtures of Organic Compounds. Formation of Molecular Compounds in the Liquid State. I. Mixtures of ( a ) Acetone and Chloroform and Ib) nz-Cresol with (1) Aniline and (2) o-Toluidine. 11. Mixtures of Pgridine with (1) Acetic Acid and (2) Butyric Acid. D. I$. TSAI~ALOTOS (Bull. Xoc. clhirn. 1908 [iv] 3 234-242 243-247).-The previous work of Poiseuille (Anit. Chinh.Phys. 1843 50; 1847 76) Graham (P?d. Tq-ans. 1861 373) Thorpe and Rodger (Trans. 1897 71 360) Vateune and Godefroy (Abstr. 1904 i 2) arid Dunstan (Trans. 1907 91 83 1728) has shown that viscosity curves of liquid binary mixtures may be (1) normal (equal or only slig\;tly below those calculated from the viscosities of the two components) ( 3 ) negative [much below the calculated due according to Dunstan (loc. c i t . ) to breaking down of associated molecules of the components] (3) positive (much above the calculated) and showing one or more maxima probably corresponding with the formation of molecular compounds. The object of the present investigation is to us8 viscosity determinations as a method of investigating the formation of such molecular compounds between liquids.The figures quoted are molecular concentrations per cent For the two systems m-cresol and aniline and m-mesol and o-toluidine (at 25') a maximum occurs at m-cresol 65 and not 50 as niight be expected. The deviation is probably due to partial decomposition of the molecular compound in each case. With chloroform and acetone the curve for "time of flow " at 0' shows a maximum a t chloroform 50 but the inaxima of the viscosity curves at 0 20 and 40 for this mixture ale displaced beyond that point The viscosity curves of mixtures of (1) pgridine All the mixtures studied gave positive curves."JENERAI AND PHVSICAJ CHEMTSTRT. 261 and acetic acid and (2) pyridine and butyric acid show well-marked maxima a t acetic acid 77.9 and butyric acid 74.4 respectively. The conclusion is drawn that in the f i r k t three mixtures the com- pounds formed contain 1 mol.of each component and in the last two 2 mols. of pyridine combined with 3 mols. of the acid. The acetone- chloroform compound may have the constitution CNe2:O:CHCl and the pyt idine-fatty acid compounds the constitution H Py*O.Pg H 0 -0 . T. A. H. \\/ \/ \ R Simple Apparatus for Demonstrating the Dissociation Pressure of Solid and Liquid Substances. JAN YON ZAWIDZKI (Chem. Zeit. 19OS 32 lS6-187).-A glais tube 15-18 em. long and 10 mm. external diameter closed a t one end is filled to about I /S to l / i of its length with a substance which readily dissociates such as 2AgC1,3NH3 CaC1,,4NH3 or ZnC1,,4NH3 ; it plug of glass wool is then inserted and the open end drawn out and fused on to a capillary tube 6 60-70 em.long and about 2 mm. internal diameter. By means of a very fine thin-walled capillary tube a thread of mercury about 1 cm. long is introduced into the capillary tube b some 10 em. from the junction with the large tube after which the end of the tube b is sealed off. The length of the tube bettvesn the mercury and the sealed end is divided into divisions representing pressures of 1 2 3 4 &c. atmospheres in the large tube by meins of small indiarubber rings. By preparing several tubes cont'aining varying quantities of the same or different substances it is possible by placing the tubes i n a n oil-bath to shorn that the pressure is (1) independent of the quantity of substance taken and (2) varies with different substances. W.H. G. Adsorption Compounds. GUNNER J~RGENSEN (Zeitsch. anorg. Chenz. 1908 5'7 353-358. Compare Abstr. 1902 ii .%).-The absorptive power of metastannic acid for nitric acid has been inves- tigated by extraction of mixtures of the two acids with successive quantities of water for three or four months a t room temperature and a t 36* the removal of the nitric acid been then practically complete. The ratios of the distribution of the nitric acid between the water and metastannic acid are tabulated. Similar experiments have been made with hydrochloric acid. Fibre-like Developed Alumina (Fibre-alumina) and its Surface Actions (Adsorption). HANS WISLICENUS (Zeitsch. Chem. Id. Kolloide 1908 2 Supt. 11 11-20.-In cont,act with mercury and moist air aluminium oxidises with the formation of aluminium bydroxide of fibrous character.This resembles in many respects the natural fibres of plants and animals. It i s doubly refracting and when examined through a plate of gypsum it shows exactly the s ~ m e colour distribution as the eccentric portion of a starch granule The G. 5.262 ABSTRACTS OF CHEMICAL PAPERS. cause of the double refracting power is t o be found in the lamellar structure ; the double refraction disappears when the aluminium hydroxide is immersed in water or in xylene. The micro-structure and the optical properties remain unchanged when the hydroxide is converted into oxide by heating. The fibrous aluminium hydroxide has very strongly developed adsorptive properties. The adsorptive power apparently increases when the hydroxide is converted into oxide but if equal molecular quantities are compared the adsorptive powers are about the same.The adsorptive properties have been studied in detail by experiments with aqueous solutions of a large number of different substances and comparative measurements have also been made on tannin solutions with other adsorbing materials. From these it is evident that the adsorptive power of fibrous alumina is approximately equal to t h a t of hide powder and is much greater than that of other adsorbents such as kieselguhr meerschaum and animal bone and wood charcoal. The removal of substances from solution is shown t o be due chiefly t o surface action and not to the formation of chemical compounds; in general the quantities taken up from concentrated solutions are relatively smaller than the quantities removed from dilute solutions of the adsorbed substance.An apparatus is described for ‘‘ adsorption analysis,” in which fibrous alumina is used as the active adsorbing material. This may be applied in the examination of all kinds of colloidal extracts including tannin- plant- colour- and drug-extracts. H. M. D. Changes in Tanning [Processes]. REGINALD 0. HERZOG and J. ADLER (Zeitsch. Chem. Ind. KoEZoide 1908 2 Supt. 11 3-ll).- The adsorption of various substances from aqueous solution by lightly chromated hide powder has been investigated. The experiments were made at 2 5 O 5 grams of hide powder being shaken up with 100 C.C. of the solution for four hours when the adsorption was found t o be complete.Phenol catechol resorcinol and pyrogallol solutions of various concentrations were used and for comparison the adsorption of the two first substances by animal charcoal was examined. The experimental data are discussed in reference to the equation c = K.am in which c denotes the concentration of the aqueous solution a the quantity of substance adsorbed by the hide powder and K and m are constants. When logn is plotted as a junction of logc the experi- mental data should be represented by a straight line if the above equa- tion is satisfied. This is the case for the adsorption of phenol and cate- chol by animal charcoal and of resorcinol and pyrogallol by hide powder but the data for phenol and catechol adsorbed by hide powder correspond with curves which are convex t o the logc axis.A study of the influence exerted by mineral substances in N/10 solutions on the adsorption of phenol has shown that this is diminished by hydrochloric acid and still more by potassium hydroxide. A smaller but similar effect is produced by ammonium chloride whereas salts of the alkaline-earth metals are without influence and salts of the alkali metals slightly increase the adsorption.GENERAL AND PHYSICAL CHEMISTRY. 263 Measurements of i h e adsorption of a number of acids mineral salts sugars carbamide acetone colloidal substances and colouring matters are also recorded. I n general the adsorption cannot be a t all accur- ately represented by the equation c = 1 i . c ~ . Attempts were made to measure the rate of adsorption of phenol but the process was found to be too rapid both a t 25' and at 0'.The fact that the adsorption from a 0-025N phenol solution was the same as that from a 0.05N solution after the hide powder in the second case had been treated with an equal volume of water is considered to be evidence in favour of a reversible process in the adsorption phenomena. H. M. D. Time-law of the Capillary Rise of Liquids and the Relation- ship of Velocity to the Chemical Constitution. WOLFGANG OSTWALD and F. QOPPELSROEDER (Zeitsch. Chem. I n d . KoZEoide 1908 2 Supt. 11 20-39).-The author finds that the experimental data obtained by F. Goppelsroeder (Verh. der Naturforsch. Ges. Basel 1907 19) in his investigations of the rate of rise of liquids in filter paper can be represented by the exponential equation s= K.tm in which s denotes the distance through which the liquid rises in time t and K and m are constants depending on the nature of the liquid the fibrous character of the filter paper the temperature and other factors which in comparative experiments may readily be kept con- stant.The constant K varies from 2.21 to 15.10 and 772 from 0.04 to 0.49. The view is put forward that the rnta of rise of a liquid is deter- mined by the magnitude of the capillary forces and t h e viscosity of the liquid. The fact that the vaIues of the maximum capillary rise of different liquids in filter paper are not all proportional t o the values obtained in glass tubes is attributed to differences in the '' wetting power" of the various liquids for filter paper on the one hand and glass on the other.I n the comparable series of monohydric fatty alcohols the velocity constants K are shown to be related t o the viscosity values. Examples of stoicheiometric relationships between the values of m and the chemical nature of the various liquids are also quoted. H. I\I. D. The Crystalline State as a General Property OP Matter. P. P. VON WEINARN (J. Russ. Phys. Chem. SOC. 1908 40 27-64. Compare this vol. ii 90).-A theoretical resume is given of the experi- mental work performed by the author and other investigators on the crystalline and colloidal states of matter. It is claimed that the conclusions arrived a t regarding the dis- continuity and crystalline structure of all forms of matter whether liquid solid or gaseous and the non-existence of amorphous substances are based on purely experimental evidence.It is incorrect to say that since chemically-pure colloids are unknown therefore they are complexes of the suspended substance with the solvent for any inorganic colloid can be obtained in a pure state by recrystallisation from a solvent which dissolves i t appreciably ; on the other hand any crystalline substance can be obtained i n such264 .IRSTRACTS OF CHEMICAL PAPERS. minute crystals as to render it difficult to free it from the remnants of water or other matter absorbed by it. Z. K. Physico-chemical Investigations on Soaps Considered as Colloids. A N D R ~ MAYEH GEOEGES SCHAEFFER and E. F. TERROINE (Comnpt. rend. 1908 146 484-487).-An examination of the optical properties of solutions of soaps of the fatty acid series shows that the acetate propionate butyrate and valerate form homogeneous solu- tions in acid alkaline or neutral aqueous or in alcoholic alkaline solution ; the hexoate octoate laurate palmitate oleate and stearate yield colloidal solutions o r jellies according t o the complexity of the molecule and t,he nature of the medium These colloidal solutions are caused by the hydrolysis of the salts and partial or complete precipi- tation of the fatty acid.The viscosity of solutions of the lower members of the series is only slightly altered by the addition of acids but increased by the addition of bases; but in the case of the hexoate and the higher members of the series the viscosity of the solution is increased either by the addition of an acid or a base and the minimum point on the viscosity curve is a critical point coinciding with the first appearance of ultra- microscopical granules i n the solution.31. A. W. The Process of Gelatinisation. IV. S. A. LEVITES (Zeitsch. Chenz. Ind. Kolloide 1908 2 237-241 ; see this vol. ii 161).-A solution of gelatin in dilute formaldehyde gelatinises owing to the conversion of the gelatin into an insoluble substance. The change is very slow at low temperatures. Salts of univalent ions and non- electrolytes retard the change about equally ; salts of bivalent ions have a greater effect. Hydrogen ions retard the change very much and hydroxyl ions accelerate i t enormously. By prolonged boiling with water glutin sodium a-t hymus-nucleates and agar-agar are con- verted into substances which do not set.The change is accompanied by a diminution of the viscosity of the solution whicb is measured and reproduced in curves. T. E. The Equilibrium 2Au(metal) + Au'" Z 3Au'. EMIL BOSE (Zeitsch. Elektrochem. 1908 14 SS-SS).-By means of the apparatus described previously (Abstr. 1907 ii 735) it is shown that the equilibrium in question exists (this had already been proved by Woldwill Abstr. 1899 ii 105) and that it is displaced in the direction of aurous ions by rise of temperature. T. E. Temperature-coefficients of Ionic Mobilities in Water as a Function of the Mobilities. FRIEDRICH KOHLRAUSCR (Zeitsch. Elektrochem. 1908 14 129-133).-The formula proposed by Rasch and Hinrichsen (this vol. ii 148 149) u=A/logl where a is the temperature-coefficient and l the mobility requires another constant owing to the fact that I is really the product of a number and the dimensions of the unit of conductivity.If I is expressed in C.G.X. units the original formnla gives impossible results. By plotting all known temperature-coefficients against the corre-GENERAL AND PHYSICAL CHEMISTRY. 265 sponding mobilities i t is seen that the ions formed of univalent elements lie on a smooth curve whilst univalent compound ions (except OH and NH,) lie below the curve and bivalent ions lie above it. For the univalent elementary ions four formuke are tried (1) a= 0,0136 + 0.67/( 18.5 + I ) ; ( 2 ) a = 0.01341 + 0*640/1- 6*94/P ; (3) a= O.O3481/logZ - 0.207; (4) a=0*0391/logl.The first three agree with the experi- mental results within the limits of error and the fourth gives a system- atic deviation. The first formula (which was used by the author in 1901) is the only one which gives probable values for. a when I becomes very large or very small. The ions probably carry with them an envelope of water molecules the size of which depends on the nature of the ion; the arguments for this view are summarised. Reactivity of Undissociated Electrolytes. RUDOLF WEG- SCHEIDER (&its&. EZektTochern. 1908 14 133).-Referring t o Meyer and Trutzer's work on the decomposition of ammonium nitrite (this vol. ii lsl) the author points out that it is impossible to decide from measurements of the velocity of reaction whether undissociated mole- cules or ions react the result being the same so long as the two are in equilibrium The same applies to the change of trichloroacetic acid into chloroform and carbon dioxide studied by Timofkeff and Koboseff (Abstr.1904 i 470). JULIUS MEYER (Zeitsch. physikal. Chem. 1908 62 59-88).-In view of the birotation of dextrose and laevulose the inversion of sucrose by dilute acids cannot be a simple unimolecular reaction ; i t is to be regarded as a reaction completed in several stages which may be represented by the scheme T. E. T. E. Theory of the Inversion of Sucrose. E:3 Ic5 a-Dextrose p-Dextrose. \ k.5 Sucrose f k* Ic a-Lzlevulose P-Lzevulose. k2 On this basis a general formula is deduced which permits the calculation of the angle of rotation of a solution a t any moment from the reaction constants and the specific rotatory powers of the com- ponents and which gives aIso the concentration of each constituent a t any given time.I n order to study the various separate changes involved in the inversion of sucrose the author has investigated the mutarotation of dextrose at 18' and 25' i n water and in dilute hydrochloric acid solution. For a-dextrose the mean value of [a] is 109.575'; for P-dextrose 20*460° and for the equilibrium mixture 52,335'. The value of k3+k4 has been determined experimentally and the separate values of k and k4 which follow from these data are given below Temperature. k,. 18" 0.00747 25 0.01513 k** 0'00415 o.oo844 1 in water 0.00638 o.01452 ) in 0.028 HC~ 18 0'01147 25 0 *02609266 ABSTRACTS OF CHEMICAL PAPERS.The equilibrium between a- and P-dextrose is not noticeably displaced either by the presence of acid or by rise of temperature. I n the case of a- and p-lzevulose the sum (k,+k,) only of the velocity coeficients of the opposing reactions has been determined. On rise of temperature the eqrii1it)rium is shifted in the direction of p-le-evulose. I n its very earliest stages as careful experiments have shown the inversion of sucrose is not a simple nnimolecular reaction ; the velocity coefficient calculated on Lthe supposition that it is such a reaction diminishes as inversion proceeds. Only after inversion has taken place to the extent of 4-5% does its course correspond with that required for a unimoleculnr reaction. When the curve obtained by plotting the inversion coefficient against time is extrapolated t o zero time an approximate value is obtained for k the true inversion constant. When this value of L is inserted in the general formula already mentioned the latter can be considerably simplified and ultimately reduced to the unimolecular form.For the inversion of a n 8% sucrose solution by 0.02N HCI the value of k is found to be 0.000050 at 1S0 and 0.000150 at 25'. The temperature-coefficient is 4.5 for an interval of 10'. A formula representing the change of rotation of a solution con- taining dextrose and laevulose is deduced and tested by experiment with satisfactory results J. C. P. A New Method for Studying Intramolecular Change. THOMAS 8. PATTERSON and ANDREW MCMILLAN (Be?*. 1907 40 2564-2573).-1n continuation of work previously published (Trans.1907 91 504) the authors have determined the rate of change of anis-sp.-aldoxime into the crnti-isomeride when dissolved in various esters by observing the change in t'he rotatory power of the ester. The following values have been obtained for l O O O k in methyl tartrate 3.0 ; ethyl tartrate 1.8 ; n-propyl tartrate 1 0 ; methyl malate 5.0 ; ethyl malate 6.7 ; n-propyl malate 8.4. The value for k diminishes with increasing mol. weight of the tartrate but increases with increasing mol. weight of the malate. The high value lOOOk= 3-9 previously observed for anis-syn.-aldoxime in ethyl tartrate solu- tion (Zoc. cit.) is ascribed to the use of a n impure oxime. The rotatory power of a solution of m-nitrobenz-syiz.-aldoxime in rz-propyl tartrate containing 6 05% of the aldoxime changes from a (100 mm.) +18*14O to C$ (100 mm.) +14*68O; 1000k=0.5.An ethyl tartrate solution containing 5.04% of m-nitrobenz-anti-aldoxime has (100 mm.) + 14.68' (compare Ciamician and Silber Abstr. 1904 i 161 ; Goldschmidt Abstr. 1904 i 250; Ciusa Abstr. 1907 Catalytic Reactions at High Temperatures and Pressures. XVI. Function of Oxides in Catalysis. WLADIMIR N. IPATIEFF (J. Russ. Phys. Chem. Soc. 1908 40 1-27. Compare Abstr. 1907 i 5 6 457 S27 828).-T0 determine the rBle of the catalyst nickel oxide in hydration and dehydration processes it is necessary in the first place to study i t s hehaviour on reduction a t ordinary and at i 137). G. Y.GEKERAL AND PHYSICAL CHEMISTRY. 267 high pressures. The conclusions arrived a t by Moissan regarding the reduction of this oxide (Abstr.1881 77) are mostly inaccurate owing to the fact that he did not analyse the original material. Pure commercial nickel oxide contains far more nickel than that necessary for the formula Ni,O is not always of constant composition and contains about 6% water which it commences to lose a t 120' but loses the last traces only above 300'. It is probable that the main con- stituent is really the lower oxide NiO. The best reagent €or detecting even very minute quantities of nickel produced by the reduction of the oxides is nitric acid D 1 *38-1*40 which whilst producing no effect on the oxides evolves oxides of nitrogen in the presence of nickel and i t is even possible t o estimate the latter by the appearance of the reacting mixture.At the ordinary pressure nickelic oxide is reduced by hydrogen at 1 70-190° forming metallic nickel and lower oxides mostly NiO but it is improbable that the oxide Ni,O,is formed. Nickelous oxide NiO only commences to be reduced above 200° and cannot be oxidised either with dry or moist oxygen even a t 480'. At high pressures nickelic oxide is reduced a t lSO" and at 210Opure nickel is produced ; nickelous oxide under the same conditions yields almost pure nickel at 172". I n all cases the reduction of the oxides is either prevented or greatly retarded when any water is removed by previous heating. The temperature of reoxidation of the reduced nickel depends on the tem- perature at which it was produced and is lower when moist oxygen or air is employed ; in any case only nickelous oxide is formed. When the reduction of benzene is performed at high pressures in the presence of nickelic oxide both the organic substance and the oxide are only very slowly reduced unless precautions are taken not to wet the oxide with the liquid. Employing nickelous oxide both the benzene and the oxide are readily reduced at 172O but not if the oxide has been previously well dried.Comparing the velocity of reduction of benzene in the presence of nickelic oxide nickelous oxide and reduced nickel ( 8 p p l 8 ~ ) ~ ~ ~ ~ . is found to be greatest for the first and least for the last. It is thus evident that the oxides form the most important part of the catalyst in these reactions the traces of water always present in the oxides employed being as important in these cases as they are in catalytic processes of oxidation.Thus in presence of reduced nickel which always contains the oxides and water hydrogen under pressure reduces the oxide forming the metal and water which in their nascent state react on one another reproducing the oxide and nascent hydrogen which hydrogen- ates rapidly tho organic compound. The current ideas regarding catalytic reactions require modification in the light of the facts disclosed by the study of heterogeneous catalysis at high temperatures and pressures. Thus it is probably not true that a catalyst merely increases the speed of a reaction which otherwise proceeds a t a slow rate; firstly the catalyst often alters the limits of a reaction and secondly it seems more probable that it acts as a transformer of heat into chemical energy.To understand the diff orent catalytic actions displayed by various268 ABSTRACTS OF CHEMlCAL PAPERS. metals i t is necessary to study their chemical properties and also those of their oxides. Z. K. Kinetics of the Elimination of Carbon Dioxide from Cam- phorcarboxylic Acid. GEORG BREDIG and R. TV. BALcoif (Bey. 1908 41 740-751).-In aqueous solution the decomposition of d-camphorcarboxylic acid when heated follows rz mass action law of the first order. Substitiition of dilute hydrochloric acid for water led to no increase in the rate of change. The sodium salt decomposes very much less rapidly than the free acid and the rate of change of the salt is only slightly depressed by excess of alkaline hydroxide.The temperature-coefficient is large being 3.15 for loo. I n benzene solution it is 3.0. The decomposition obeys a similar mass action law in benzene aniline alcohol phenetole or ether ; in heptane and acetone solution this is not the case and the velocity constant increases as the reaction proceeds. I n ethyl alcohol a simultaneous esterification and elimina- tion of carbon dioxide takes place. The influence of the solvent on the rate of change is very large the change being particularly rapid in aniline and alcohol. The decompositions of both d- and I-camphorcarboxylic acids in d- and I-limonene solutions do not follow mass action laws of the first or second order but the four reaction curves when plotted appear to be identical within the limits of error.This is not apparently a suitable case for the detection of stereochemical differences in the catalytic action of the solvent (see following abstract). GEORG BREDIG and K. FAJANS (Bey. 1908 41 752-763).-The decomposition of the optically active camphorcarboxylic acids is studied not in an indifferent optically active medium as formerly (see preceding abstract) but i n presence of an optically active pronounced base such as nicotine used either alone as solvent or diluted with an indifferent substance. Under these conditions the elimination of carbon dioxide follows a unimolecular reaction of the first order. I n nicotine solution the d-acid decomposes about 13% more quickly than the Z-acid ; in nitrobenzene solution con- taining !5% of nicotine the d-acid is decomposed 8% more rapidly than its isorneride and nine times as quickly as when no nicotine IS present showing the powerful catalytic activity of the base.In acetoplienone solution containing 10% of nicotine the d-acid is attacked 17% more quickly than the I-acid. The stereochemical conditions of the catalysis of optically active substances by optically active catalysts are thus very similar to those in the case of enzyme action and adopting the analogy from enzymes it is considered that there is an intermediate temporary formation of an additive compound between catalyst and substrate. The results are parallel to Dakin's (Abstr. 1904 i 1071 ; 1905 i 556) observations on the hydrolysis of mandelic acid esters by lipase.The Relationship between the Strength of Acids and their Capacity to Preserve Neutrality. LAWRENCE J. HEKDERSON (Amer. J. Pl~ysiol. 1908 21 173-179).-Acids the ionisation E. F. A . Stereochemistry of Catalysis. E. F. A.GRNERAL AND PHYSICAL CHEMISTRY. 269 constant of which is nearly equal to the hydrogen ionisation a t neutrality possess with the help of their snlt,s a great capacity for preserving neutrality in simple solution whilst other acids in like concentration have relatively little effect in this direction. IV. D. H. Constitution of Indicators used in Acidimetry. JOHN T. HEWTT (A77aIyst 1908 33 85-89. Compare Hewitt and Mitchell Trans. 1937 91 1251),-1n order that a substance may act as an indicator it must be a weak acid or a weak base and the complex ion which it forms must have a different constitution to the parent substance.Weakly acidic indicators are present in solution in a state of equilibrium represented thus X,H X,H X, + H' where X and X are isomeric complex radicles. I n the case of phenolphthalein for example X and X are respectively since X, is the stabre configuration and <hexsubstance is a very weak acid X,H and its ions are only present to an exceedingly small extent in neutral solution and the absorpt,ion due to X is observed (with phenolphthalein this is in the ultra-violet and the substance is colourless). Addition of bases removes the hydrogen ions the equilibrium is disturbed towards the right and the colour due to X makes its appearance. I n the case of methyl-orange the aqueous solution will contain the internal salt the real dimethylamino- nzoberizenesulphonic acid and the ions of the latter in a state of equilibrium thus 4 Red N~~e,'C,H,*N:N*C,H,*SO,' + H Yellow Addition of a weak base results in the removal of hydrogen ions and the solution becomes yellow. It is stated in conclusion that extremely sharp results are ob- tained by using l-nitro-2-sulphobenzene-4-azo-a-naphthol as an indicator.The acid and its monobasic salts are yellow; addition of excess of alkali turns the yellow solution sharply to a purple; the purple colour is not discharged by an excess of alkali hot or cold neither is it affected by alcohol even in strongly alkaline solutions. W. H. G. Symmetry in t h e Law of Atomic Weights. N. DELAUNAY (Chem. ATews 1908 97 99.Compare Abstr. 1908 ii 97).-The elements are arranged on a set of curves with the numbers 0 1 2 3 ; 3 2 1 0 successively as ordinates and the atomic weights commencing with helium as abscissze. The curve obtained for each period of eight elements is ,completely symmetrical ; in other words t4he elements of each period fall into pairs the sum of the atomic weights of which is constant. Thus i n the first two periods I I e + F = L i + O = B e + N = B +C =23 Ne + Cl= Nn t S = Mg + P= A1 + Si = 55.3. K. J. C.270 ABSTRACTS OF CHEMICAL PAPERS. Demonstration of the Formation of Ammonium Amalgam by Electrolysis of Ammonium Chloride. JOHANNES SCHROEDER (J. pr. Chenz. 1908 [ii] 77 271-2$2).-The author describes and figures two simple pieces of apparatus designed to enable a large audience to observe the formation of ammonium amalgam by electro- lysis of ammonium chloride with a mercury cathode.Three Lecture Experiments. EIMIUND KNECHT (Ber 1908 41 498-499).-1. Synthesis of Calcium Carbide.-Sm,zll quantities of calcium carbide are readily prepared by igniting a piece of calcium about the size of a pea placed on wood-charcoal by means of a small blowpipe flame ; the metal burns for a moment with an intense orange- yellow flame and then sinks into the charcoal. The calcium carb:de formed is readily obtained by breaking the piece of charcoal. 2. A Visible Atitoxidation.-An approximately N/10 potassiuin per- manganate solution acidified with sulphuric acid is divided into two portions. One portion is kept for comparison; small quantities of titanous sulphate are added from time to time to the other portion the blood-red colour of which gradually changes through scarlet to orange-yellow. 3. Precipitation of Metallic Copper by Titanow 8ulphnte.-About 1 C.C. of a 10% copper sulphate solution is added to a 1-2 litre glass cylinder nearly full of water; about 5 C.C. of a solution of titanous sulphate is then stirred into the solution from which metallic copper separates in a few minutes. The precipitate is so fine that most of it passes through a filter paper and the solution which appears copper-coloured by reflected light is blue by transmitted light. The reaction may be employed as a test for copper since it is visible in t h e presence of 1 part of copper per 1,000,000 parts of solution. G. Y. Excess of the salt decolorises the solution. W. H. G. New Pressure Cylinder. BALTHASAR PFYL and BR LINNE (Chem. Zeit. 19OS 32 205).-The pressure cylinder previously described by the authors (Abstr. 1905 ii 770) has been in use for more than two years and continues to act in a satisfactory manner. FREDERICH 31. G. JOHNSON and K. BUCH (Beg-. 1908 41 640-641).-An apparatus to regulate the pressure of a gas current has been designed on the principle of the electromagnetic thermo-regulator and is here described and figured G. Y. T. H. P. Gas Current Pressure Regulator. A Laboratory Pump. ROBERT LUTHER (Chem. Zeit. 1908 32 267-268).-The pump which is driven by an electro-motor is designed for driving a continuous stream of water through thermostats or condensers. It consists of four tubes arranged in the form of a cross which rotates about a vertical axis in a metal box. The water enters the cross from below by a pipe at the centre of the cross and passing through the bottom of the metal box the rotation of the cross draws the water up and forces it out into the metal box from which it passes out by a side tube. P. H.

ISSN:0368-1769    

DOI:10.1039/CA9089405241

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 271 Inorganic Chemistry. Purification of Hydrogen from Arsenic. IIAKS RECKLEBEN and GEORG LOCKE~CIANN (Zeitsclh. angew. Chern. 1908 21 433-436).- The absorption of arsine when mixed with hydrogen has been studied previously (this vol. ii 176 224) by shaking the mixed gases with various reagents. An account is now given of the results obtained on passing the mixed gases through most of the reagents previously employed and in addition mercuric chloride and silver nitrate solu- tions and a mixture of cupric and cuprous oxides (Lionet- Abstr. 1880 2). For the purification of hydrogen i n the laboratory it is recommended to pass the gas through a saturated solution of potsssiuin permanganate and finally to test the purity of the gas through a 5-10% solution of silver nitrate when the presence of traces of arsenic is shown by the formation of a precipitate.Mercuric chloride solution can be employed only so long as the precipitate formed is yellowilh- white. Copper oxide forms the best solid absorbent ; iodine may be used if the hydrogen is afterwards passed through a wash-liljuid to retain hydrogen iodide and traces of iodine vapour. Only potassium hypochlorite solution dropped on to pumice stone or bleaching powder kept thoroughly moistened with water is suitable for use on the technical scale. I t is recoinniended to employ bromine when traces of arsine h ~ v e to be removed from large volumes of hydrogen. G. Y. Decomposition of Hydrogen Peroxide in the Presence of Various Substances. EDUARDO FILIPPI (Chem. Zentr.1907 ii 1S90 ; from Arch. Farm. sperim. 1907 6 363-395).-The author finds that all inert powders decompose hydrogen peroxide the velocity of decomposition being proportional to the exposed surface of the added powder and independent of the concentration of the hydrogen peroxide. V:trious ferment-containing organic substances which give the guaiacum reaction and also ferment-free organic substances which cannot give this reaction decompose hydrogen peroxide. Therefore the conclusion is drawn that these tests are insufficient to establish the nature OF the ferment present in a substance. J. V. E. Atomic Weights of Nitrogen Oxygen and Carbon. ANATOLE LEDUC (Compt. ?*end. 1908 146 399-400).-The value N = 14.01 adopted by the International Committee on Atomic Weights and based on Guye’s recent determinations is greater than the value N = 14.005 obtained by the author (Abstr.1897 ii 549). Using the value N = 14.01 and the ratio of the densities of carbon monoxide and nitrogen determined by Lord Rayleigh (Abstr. 1895 ii 444 ; 1898 ii 290) and the author (Abstr. 1893 ii 165; 1S97 ii 140) the atomic weight of carbon lies between 12.011 and 12-16 ; whilst taking C = 12.000 the atomic weight of nitrogen lies between 14-002 and 14.004. M. A. W.272 ABSTRACTS OF CHEMICAL PAPERS. Formation of Oxides of Nitrogen in the Ozone Generator. WILHELN MANCHOT (Uer. 1908 41 471-472).-1n connexion with the study of the action of ozone on alkalis (Alanchot and Kamp*chulte this vol. ii l O l ) i t has been observed that on prolonged exposure t o a current. of ozone prepared from 98% oxygen the coloured compounds at first formed with alkalis are decolorised and converted into nitrates (Warburg and Leithaiiser Abstr.1906 ii 743). The presence of nitric oxide in ozone prepared from 99.3% oxygen has been deter- mined in the same manner. On passing 10% ozone slowly through 15% potassium hydroxide the concentration falls to 4%; the resulting gas which is free from nitric oxide has not a n acid reaction and does not increase the conductivity of water but behaves towards organic and inorganic bases as described previously (Zoc. cit.). Hence contrary to Baeyer and Villiger’s view (Abstr. 1902 ii 650) ozone is not a n acid anhydride. Irregularities in the Combination of Nitric Oxide and Oxygen. ALFRED MANDL and FRANZ Russ (Zeitsch. ccngew.Chern. 1908 21 486-491).-1t is usually assumed that nitric oxide and oxygen when mixed in the proportion of 2 vols. t o 1 vol. undergo complete combination. This is found t o be not always the case the reaction often coming to an end whilst considerable amounts of nitric oxide and oxygen are still uncombined. The results of experiments quoted show t h a t the extent to which the combination takes place depends on the genesis of the oxygen about 97% of the nitric oxide combining with oxygen prepared from air by Linde’s method about 95% with oxygen obtained by electrolysis of water and passed over heated palladium asbestos but only about 40% with oxygen prepared by the action of potassium dichrornate and sulphuric acid on barium peroxide.As the reaction takes place also to a much smaller extent with oxygen prepared by electrolysis of water but not passed over palladium asbestos the retardation might result from the presence of hydrogen peroxide. This could not be tried but comparative experi- ments with Linde’s oxygen and the same oxygen after ozonisation show that the combination is markedly retarded by the presence of ozone. This retardation inay be a direct action of the ozone or may result fiorn the destruction by the ozone of some catalyst necessary t o the reaction. G. P. G. Y. Nitrogen Sulphide. HANS W~LBLING (Zeitsclh. anoyg. Chenz. 1908 57 281-289).-Certain compounds of nitrogen sulphide N4S with the higher halogen derivatives of certain elements have been prepared and a reduction product of nitrogen sulphide has been obtained by the action of stannous chloride in alcoholic solution on the sulphide. Unless ot lierwise mentioned the compounds were obtained by interaction of the components dissolved in carbon tetrachloride.The compound N,S,,TiCI occurs as a n amorphous brownish-red precipitate insoluble in most solvents ; i t decomposes in moist air reacts very vigorously with water and with alkali :ind is split u p into i t s components by hydrochloric acid and by alcohol. The coinpound N,S,,SbC15 occurs as a scarlet amorphous powder which is very stable,273 iNORCxANJC CHEMISTRY. not being attacked by water by hydrochloric or by nitric acid in the cold ; it yields ammonia on heating with potassium hydroxide. The cornpou~~d 2hT,S4,S~c'l4 occurs as an amorphous insoluble Bordeaux-red powder which behaves towards reagents like the antimony compound ; it decomposes when heated above 160'.The compound N,S4C1 (compare Muthmaon and Seither Abstr. 1897 ii 255) can be prepared conveniently by heating nitrogen sulphide with the theoretical amount of sulphur dichloride S,Cl in carbon tetrachloride solution for two hours in a reflux apparatus. The corresponding bronaide N3S4Br appears to be obtained by interaction of nitrogen sulphide and sulphur dibromide S2Br2 dissolved in carbon tetrachloride but in carbon disulphide solution only the compound N4S,Br was obtained. Nitrogen sulphide and selenium dichloride Se,Cl react in boiling carbon tetrachloride to form a green insoluble amorphous compound probably N,S4,Se2C12 which has not been obtained pure. This compound is not affected by water or hydrochloric acid but is decomposed immediately by nitric acid and by potassium hydroxide.By the action of bydrogen sulphide on nitrogen sulphide dissolved in benzene and in alcohol precipitates of ammonium polgsulphides and of ammonium thiosulphate respectively were obtained. Stannous chloride does not combine directly with nitrogen sulphide but in warm benzene solution the latter compound is reduced and a compound of the empirical formula NSH separates in yellow lustrous leaflets which after recrjstallisation from pyridine have m. p. (decomp.) 152'. The new compound is not combustible or explosive is not acted on by cold potassium hydroxide but gives off ammonia when heated ; with hydrochloric acid sulphur dioxide is given off and i t reacts vigorously with nitric acid.Its constitution has not yet been deter- mined. G. S. The Essentially Chemical Causes of the Allotropic Trans- formation of Phosphorus Dissolved in Oil of Turpentine. ALBERT COLSON (Co~npt. retzd. 1908 146 401-403).-The graduaI and irreversible change to the red modification that phosphorus dis- solved in oil of turpentine undergoes a t 250' (this vol. ii 35; 176) is due to the formation of small quantities of hydrogen yhosphide and its subsequent decomposition into red phosphorus and hydrogen the latter reacting with the dissolved phosphorus to form a further ynantity of hydrogen phosphide. A 2% solution of phosphorus in oil of turpentine was sealed in a tube with hydrogen phosphide and enctosed in a tube containing a further qimntity of the solution.After heating a t 240' for four hours the inner tube contained a copious depo+it of red phosphorus whilst the contents of the outer tube remained clear even after twelve hours at 250'. The red phosphorus formed under these conditions has D 2.095 and contains small quantities of the phosphides of hydrogen which are eliminated on distillrttion in a vacuum. Phosphorus dissolved in an oxygenated solvent such as ethyl benzoate does nut undergo any allotropic transformatmion even when the solution is heated at 305-310' for twenty-five hours M. A. W. VOL. XCIV. ii. 19274 ABSTRACTS OF CHEMICAT PAPERS. Hittorf's Phosphorus. ALFRED STOCK (Ber. 1908 41 764).- The crystallographic determinations cited in tho previous communics- tion (this vol.ii 176) were made by I?. von iVolt'f. 33. F. A. Phosphoryl Bromide. ERNEST BERUER (Conzpt. rend. 1908 146 400-401 ).-A convenient method of preparing phosphoryl bromide consists in gently heating a mixture of phosphorus pentabromide and phosphoric oxide until traces of bromine vapour appear ; after four to five hours the liquid product is distilled over a little phosphoric oxide ; the reaction is represented by the equation 3PBr + P,O = 5POBr and the yield amounts t o 85% of that theoretically possible. Phosphoryl bromide forms colourless crystals m. p. 55-56O b. p. lS9*5*/774 mm. and the heat of formation as determined by decom- posing the compound with water is 75900 C d . (compare Ogier Abstr. 1881 21s).31. A. W. Sulphides of Phosphorus. 11. Phosphorus Pentasulphide. ALFRED STOCK and WILHELM SCHARFENBERG (Bey. 1908,41,558-564. Compare Abstr. 1905 ii 703).-By the distillation of phosphorus pentasulphide-in a high vacuum Stock and Thiel (Abstr. 1905 ii 703) observed the formation of another substance in addition to pure phosphorus pentasulphide m. p. 276". A special apparatus is now described in detail which enabled the distillation of larger quantities in a high vacuum and rapid cooling of the vapour. This had in particular the advantage that the phosphorus pentasulphide distilled a t a much lower temperature than formerly and the distillate con- tained but little else than pentasulphide. When superheated even in a high vacuum phosphorus pentasulphide decomposes ; the density is normal at 630° but rapidly becomes less above this temperature. Phosphorus pentasulphide when distilled or sublimed decomposes somewhat at atmospheric pressure decomposes more in a high vacuum or in a stream of carbon dioxide and still more when the vapours are superheated.E. F. A. Sulphides of Phosphorus. 111. Vapour Densities of the Compounds P,S P,S and P,S,. ALFRED STOCK and HEINRICH VON REZOLD (Bey. 1908 41 657-660. Compare Abstr. 1905 ii 703 ; this vol. ii 176).-The existence of only three P,S P,S and P2S5 of the numerous compounds of phosphorus ahd sulphur described in the literature can be considered as established. The vapour density determinations made with these three substances by various authors have given normal results but in no case is the temperature of.the determination recorded.The present authors have therefore deter- mined the vapour densities of the three compounds a t temperatures up t o 1000". A Victor hleyer's apparatus made of glazed porcelain filled with nitrogen and heated in R Heriius's resistance-oven was employed. The temperatures were recorded by means of a thermo- element. The results are tabulated and expressed in the form of curves. All three compounds decompose at a red heat ; the compound P,S commences to decompose immediately above its b. p. whereas P,S and P,S7 give normal results a t temperatures considerably aboveINORGANIC CHEMISTRY. 2'75 their b.p.'s. Hence these two compounds can be distilled under the ordinary pressure only P,S uudergoing slight decomposition (Mai and Schaffer Abstr.19@3 ii 363). Remarkable is the rapid fall in the vapour density of P,S7 between 760' and SOOO. HUGO ERDMANN (Ber. 19OS 41 521-523).- Many of the results published by Linck in his paper on the poly- morphous modifications of the phosphorus-arsenic group (this vol. ii 176) were communicated to him by the author and Reppert who intend to publish their own work the more so as Linck's statements G. Y. Yellow Arsenic. as to it are frequently incorrect. c. s. Solubility of Graphite in Iron. CARL BENEDICKS (Metullurgie 1908 5 41-45).-A sample of iron containing 3.9% carbon and 0.75% silicon was repeatedly heated rapidly to SOOO and then slowly cooled. By this treatment the whole of the carbide was decomposed the mass consisting only of ferrite and graphite. This iron mas then heated for two hours a t 940'and quenched.The microscopic examina- tion then showed the presence of martensite troostite sorbite and perlite This indicates a considerable solubility of graphite in iron a t 940° amounting to about l?& a fact in accordance with the older views as to the stable iron-carbon system and not with the theories of Heyn and Ruer. Conversion of Diamond into Coke in High Vacuum by Cathode Rays. CHARLES A. PARSONS aiid A. A. CAMPBELL SWINTON (Proc. Roy. Xoc. 1908,80 A 184-185).-The vacuum tabe employed was provided with two concave aluminium electrodes so arranged as to focus the rays on the diamond which rested on an iridium support. Two diamonds each about 0.2 in. in diameter were employed and an alternating current was used.With an E.H.F. of 8000 volts and a ciirrent of 44 milliamperes the diamond began to throw off small sparks ; at 9600 vults and 45.5 milliamperes it commenced to blacken and a t 11,200 volts and 48 milliamperes appeared to be converted completely into coke. The temperature a t which disintegration took place as measured by an optical pyrometer was 1890". It was not found possible to determine whether the gas pumped off from the tube during the experiment originated from the diamond or from the rest of the appamtns neither could a marked difference be detected in specimens of gas removed from the vacuum tube just before and just after conversion. Action of Alkali Salts of a Fixed Base on the Combustion of Gases and Combustible Powders.DAUTRICHE (Compt. rend. 1908 146 535-538).-The author has detonated cartridges made of explosives either alone or mixed with small proportions of certain salts in a large vessel full of air and determined the proportion of the evolved gases (hydrogen and carbon monoxide) burnt by measurement of the heat developed. A decanitrated cotton developed less than half as much heat when mixed with 3% of potassium sulphate as when detonated alone. One to two per cent. of sodium hydrogen carbonate or 2% of potassium nitrate effects a slightly less reduction in the amount C. H. I>. G. 8. 19-2276 ABSTRACTS OF CHEMICAL PAPERS. of heat developed whilst calcium and magnesium carbonates and lead nitrate have only about one-half the effect. With a nonanitrated cotton the heat developed is reduced about 60% by addition of 10% of sodium hydrogen carbonate.Trinitrotoluene when mixed with 5% of potassium nitrate develops only one-fourth as much heat as when detonated alone ; the effect of barium nitrate is only one-third as great. These results show that the combustion of the products of detonation of explosives can be prevented by addition of small amounts of sodium or potassium salts and that such an addition should be made to explosives used in mines containing fire-damp. It is shown that addition of 3% of sodium hydrogen carbonate t o a mixture of a decanitrated cotton (30%) with ammonium nitrate (70%) prevents inflammation when detonated. Potassium nitrate has a similar effect on a mixture of trinitrotoluene and ammonium nitrate.The con- clusion is drawn that a cloud formed of the powder of any sodium or potassium salt whatever tends to prevent the combustion of gases and combustible powders whilst salts of the alkaline-earth metals have only a secondary action. E. H. Combustion without Flame and the Inflammation of Gases at the End of a Metallic Rod. JEAN MEUNIER (C0771~)t. vend. 1908 146 539-540).-An interesting experiment with an alcohol- fed incandescent burner is described. The burner has the form of an aolipile supported on four tubes through which cotton wicks pass supplying the alcohol. The eolipile has an annular form the flame rising from a central cylinder which is covered with a convex disc perforated with closely occurring holes. An iron stern 8 cm. long supporting the mantle rises from the centre of the disc.It is observed that after continued use the light becomes less bright and that the darkening of the mantle commences a t the moment that the disk reddens. After removal of the mantle the author succeeded in getting the disk to redden without production of a flame. Once the disk is red hot its incandescence increases with the supply of alcohol vapour. It is impossible to ignite either a pad moistened with alcohol a wick soaked in light petroleum or a wooden match by bringing them near the hot disc although the wood of the match is charred. This flameless combustion occurring on the surface of the disk is to be explained by the retention of either the combustible gas or the oxygen on this surface as suggested by Couriot and Meunier (this vo1 ii 11) in the case of the non-explosion of a n explosive mixture by an incan- descent filament.Application of a lighted match to the upper end of the metallic stem results in the production of a flame at this point which continues to burn so long as it is protected from draughts showing that the oxygen is retained by the disk and that the excess of combustible gas rises around the stem without mixing with the sur- rounding air and without igniting although the stem is at a fairly high temperature. The shape of the flame is altered by varying the form of the upper extremity of the metallic rod. The experiment besides its important bearing on the mechanism of combustion by incandescence seems to show that gases have a certain amount of cohesion.E. H.INORGANlC CHEMISTRY. 277 [Preparation of Silicon Monoxide.] HENRY N. POTTER (D.R.-P. 189833).-When silica is heated electrically in an inert atmosphere with sufficient reducing agent (carbon or silicon carbide) to remove half its oxygen it is converted into avery voluminous brown powder which contains 91.28% of silicon monoxide SiO. This oxide which has D 2.24 is much less soluble than silica in hydrofluoric acid hut dissolves more readily in aqueous alkali hydroxides; it is a bad conductor of heat or electricity. The monoxide exists in the vitreous condition. G. T. 11. Tschermak’s Method of Preparing Silicic Acids from Natural Silicates. OTTO MCGGE (Centr. Him 1908 129-134. Compare abstr. 1906 ii,77 I ; Ann. Rep.,2,273; 3,303).-Tschermak’srnethod is criticised und the determinations are repeated for natrolite.The position of the break in the drying.curve is found to vary greatly with the temperature at which the silica jelly dries at 9* corresponding with 33*5-46% H,O and at 33.3O with 20% H,O. Further the break i n the curve is never very sharply defined and its position cannot be accurately estimated to within 1 or 2 per cent. and some of the complex silicic acids assumed by Tschermak do not differ from one another by more than this amount. L. J. S. Rare Gases of Thermal Waters. Gaseous Outputs of Some Springe. CHARLES MOUREU and ROBERT BIQUAHD (Compt. rend. 19OS 146 435-437. Compare Moureu Abstr. 1896 ii 298; 1903 ii 222 ; 3905 ii 5 ; 1906 ii 126 442 ; Moureu and Riquard Abstr. 1906 ii 685).-The authors have conducted a series of experiments on the gases evolved from thermal springs and from the results have calculated the total gaseous output of the spring and the percentage of rare gases and of helium.The volume of gas evolved varies from 4891 to 560,640 litres per annum.; the proportion of rare gases varies from 1.24 to 6.39 per cent. and of helium from 0.097 to 5.36 per cent. ; the Bourbon-Lancy spring evolves annually 16,614 litres of rare gases of which 10,074 litres are helium. I n conclusion the authors draw attention to the close connexion existing between the results obtained by them on the rare gases from thermal waters all more or less radioactive and those obtained by Sir W. Ramsay and Cameron (Trans. 1907,91,1266) on the chemical properties of radium emanation. Solubility of Potassium Chloride in Aqueous Pyridine at 10’.JOHANNES SCHROEDER (J. pr. Chem. 1908 [ii] 77 267-268. Compare Abstr. 1905 ii 306).-Potassium chloride is not appreciably soluble in anhydrous pyridine but dissolves in aqueous pyridine the solubility increasing with the proportion of the water. The results of t w o series of determinations are given in tables. More com- plicated phenomena are observed at higher temperatures and with other. salts; two layers are formed the composition of which is readily affected by changes of temperature. G. Y. Electrochemical Behaviour of Silver and its Oxides. ROBERT LUTHER and F. PoKoRNii (Zeitsch. anorg. Chem. 1908,57 290-310). -When silver is oxidised a t the anode in alkaline solution (normal M.A . W.sodium hydroxide) with small current-density silver oxide Ag,O is at fir.,t foriiied quantitatively and reversibly ; on farther oxidation it is changed quantitatively aud reversibly to ft higher oxide Ago. The change Ag -+ Ag,O takes place a t + 1.172 volts (taking the hydrogen electrode as zero) the change Ag,O -+ Ago a t + 1.40 volts both at 2 5 O and no higher peroxide coiild be obt'ained in alkaline solution Wohler (1868) has described the preparation of a silver peroxide by electrolytic oxidation of a silver anode in siilpliuric acid and Illnlder (Abstr. 1897 ii 551 he) has described a '' peroxynitrate " and ot'her salts of silver prepared by electrolysis of neutral solutions of silver salts. By electrolytic reduction experiments the authors now show that Wohler's peroxide aiid Mulder's salts consist essentially of tlie peroxide Ag,O (in the latter case with occluded or adsorbed silver salts); in alkaline solution the change Ag,O -+ Ago takes place at + 1-57 volts.I n acid solut'ion the componnd Ag,O is decomposed directly into silver on electrolytic reduction and conversely silver can be oxidised directly to Ag,O,. From the potential of the electrode Ag/Ag,O in sodium hydroxide (1 -1 72 volts) tlie E. X.F. of the hydrogen-oxygen cell is calculated at 1.221 volts in fair agreement with the valu0 1,217 volts recently obtained by Lewis (Abstr. 1906 ii 262) by a less direct method. G. S. Alloys of Calcium with Zinc Cadmium Aluminium Thallium Lead Tin Bismuth Antimony and Copper. L. D O ~ K I (Zeitsch.anoyq. Chem. 1908 57 185-2 I9).-Froni a n investigation of these alloys by Tammanu's method of thermal analysis controlled by microscopic observations evidence has been obtained of the existence of the following compounds CaZnl CilZn Ca2ZnR CaZn(?) Ca,Zn ; CaCd CaCd Ca,Cd,(l) ; OaAl? ; Ca'L'l CaTl(?) ; Cnl'b C'aSn,. In only two cases does tlie compositlon correspond with the ordinary salt vnlencieP and the frequent occurrence of the forrnuh C a l l is remarkable. The experiments were greatly interfered with by oxidation of the calcium and in many cases it was not found possible t o investigate alloys rich in tlie latter metal. Z~~C-CCCICZ'UI~E Alloys.-The freezing-point curve shows two maxima at 71 7" and 5.7% calcium and 68s' and 297A of calcium corresponding with the compounds CnZn and Cn2Zn3 respectively a break at 680" arid 12.8% calcium corresponding with the compound CaZn which possibly melts without decomposition and two eutectic points at 635" and 17% and 420' and 57% of calcium respectively.Between 29% and 56% of calcium the compound Ca2Zn reacts with the fused mass st' 431" to form a fourth compound the cornposjtion of which could not be accnrately determined but may be CnZn At 385" between 52% and 847; of calcium a fifth compound Ca4Zn is produced by reaction of the compound of unknown composition with calciui~i. Alloys containing 1113 to 6yh of cnlciuru are rather harder t'han zinc and are fairly stable in air and towards water but with increasingINORGANIC CHEMISTRY. 279 proportion of calcium they darken in the air and act more vigorously on water. The brittleness increases up to 30% of calcium and then diminishes.Cadmium-Calcium Alloys.-The f reezing-point curve of these metals does not show any maxima but there are two eutectic points at 319' and 1% of calcium (components calcium and CaCd,) and 415' and 71% calcium (components CnCd and mixed crystals rich in calcium). Between 12% and 64(5/0 of calcium the alloy forms two layers which react at 685' with formation of the compound CaCd; the latter has R transition point a t 635'. A t 615" the compound CaCd reacts with the fused mass rich in cadmium to form a second compound CaCd,. A further break in the cooling curve a t 510" appears t o indicate ;L reaction betmeen CaCd and the fused mass to form a third compound the formula of which may be Ca2Cd,.Alloys containing up to 10% OF calcium are stable in the air and scarcely act on water ; beyond that point the action on water increases with increase in the proportion of calcium. The brittleness increases rapidly between 10% and 40% of calcium and beyond that point diminishes. Aluminium-Cdciurn AEZoys.-In this case special precautions which are described in detail had to be employed to diminish oxidation. The freezing-point curve shows two eutectic points at 610' and 8.1% (components aluminium and CaAl,) and 550' and 75% (components calcium and CaAI,) of calcium respectively. Between 16% and 43% of calcium the alloys separate into two liquid layers which react at 692" to form the compound CnAl,. Alloys containing 0-80/ of calcium are the colour of aluminium and somewhat harder than that metal.Those containing a moderate amount of calcium are brittle and porous and those rich in the latter metal are less brittle and are unstable in the air. Thallium- Culcium riZZoys.-Only alloys containing up to 15% of calcium could be investigated. The eutectic temperature lies about 6' higher than the melting point of thallium from which the conclusion is drawn that mixed crystals rich in calcium are present ; at the eutectic temperature these are in equilibrium with the compound CaTI and the fused mass. Between 6% and 16% of calcium the compound CaTl (needles) separates ; at 534' this compound reacts with the fused mass to form CaTl (bluish crystals) which separate primarily from about 0.5-6% of calcium.The nlloys are harder than tballium brittle and oxidise rapidly in the air. Those containing more than 6% of calcium do not decompose water a t the ordinary temperature. Lead-Calcium AZloys,-Only alloys up t o 12% of calcium mere examined. The freezing-point curve rises steeply from the melting point of lead to a maximum at 648O and 6% of calcium corresponding with the compound CaPb and then falls to a eutectic point a t 625' and 9.776 of calcium. Alloys containing up to 4% of calcium are harder than lead and not brittle ; those containing a higher proportion of calcium are brittle. Alloys containing up t o 6% of calcium are not markedly decompoced even by hot water,280 ABSTRACTS OF CHEMICAL PAPERS. Tin-Calcium At2oys.-Only alloys u p to 187; of calcium were examined.The freezing-point curve rises steeply from the melting point of tin to a msximrini at 623Oand 10.1% of calcium corresponding with the compound CaSn3 and then falls to a cutectic point at 603Oancl 14.9% of calcium. Alloys containing u p to 4% of calcium are harder than tin and fairly tough ; with further increase of calcium they become brittle. Those containing 2% of calcium are acted on by cold water. Calcium-Bismuth AZZops.-Only alloys up t o 10% of calcium could be investigated. The freezing point of bismuth is lowered about 5" by the addition of calcium ; the eutectic mixture contains much less hhan 17; of the latter metal. From the eutectic point the freezing-point curve rises to 500" and 4.5% of cdcium and then runs 1iorizont:illy as far as it could be followed.The metals form a compound (needles) the formula of which could not be determined ; it decomposes rapidly in moist air and even in a vacnum over sulphuric acid. Antimony-Calcium Alloys.-On1 y alloys up t o 9% of calcium mem investigated. The freezing point of antimony is lowered to 585O by the addition of calcium the eutectic mixture containing 8% of tho latter metal. The alloys containing a small proportion of calcium are less brittle than antimony; the alloy containing 9% of calcium is brittle and porous. Those containing up to 6$& of calcium are not acted on even by hot water. Copper-Ccclcium AZZoys.-On account of the high melting point of copper these alloys could not bs investigated satisfactorily. The melting point of copper is lowered 74" hy the addition of 5% of calcium.The alloy containing 1% of calcium is acted on by cold water. (2. s. Preparation of Dry Calcium Hypochlorite. CnEmscrIe chlorite in a dry stable condition can be obtained by saturating milk of lime with chlorine filtering the solution of hypochlorite and evaporating this down as rapidly as possible under reduced pressure. Crystalline calcium hypochlorite is precipitated in t h e concentrated solution and thus freed from calcium chloride. As t h e instability of the crystalline salt is due t o the presence of water this is removed by drying the compound i n a vacuum until all the moisture and a portion of t,he water of crystallisation has been removed. The final product does not deliquesce in air owing t o i t s freedom from calcium chloride ; i t dissolves i n water to a clear solution and on treatment with hydro- chloric acid evolves SO% t o 90% of i t s weight of chlorine.Monoxides and Monosulphides of the Elements of the Second Group of the Periodic System. JAKOB UECKENKANP (Zeitsch. Kvpt. Hk. 1908 44 239-263).-A discussion of the dimorphic relations and the crystalline structure of the oxides and siilpliides of gincinum magnesium? calcium zinc kc. many of which cerystallise ia both the cubic and the rlioniboliedral systems with very pearly the same angles ic'ABR1K GRIESHETM-ELEKTRON (D.R.-P. 188524).-Cn~ciiim h9~0- G. T. 31. L J. S.INORGANIC CHEMISTRY. 251 Mixturm of Zinc Sulphide with Other Sulphides. I<. FRIEDRICH [with P. SCHOEN] (Metallurgie 1908 5 114-1 28).- Mixtures of zinc sulpbide with other metallic sulphides were submitted to thermal and microscopic examination.Mixtures with lead sulphide show a eutectic point a t 1045' and 6% ZnS ; there is no indication of the formation of a double sulphide or of mixed crystals. The eutectic structure is well marked in the solidified mixtures. Mixtlures of cuprous sulphide with zinc sulphide on the other hand do not show any eutectic structure and only a single branch of the freezing-point ciirve could be observed the eutectic point if preFent lying close to the freezing point of cuprous sulphide. Mixtures of the sulphides of silver and zinc form a eutectic con- taining 3% ZnS and solidifying a t $00'. Zinc sulphide and ferrous sulphide also form an eutectic containing 5% ZnS and solidifying a t about 1 1 7 5 O .Pure zinc sulphide appears to melt at about 1660'. Zinc sulphide is somewhat volatile a t high temperatures. C. H. D. Atomic Weight of Lead. I. Analysis of Lead Chloride. GREGORY P. BAXTER and JOHN HUNT WILSON (Zeitsch. anorg. Chenz. 1908 57 174-184; J. Amsr. Chem. SOC. 1908 30 187-195).- The amount of silver (in the form of nitrate) required for the complete precipitation of a known weight of lead chloride was determined and the weight of silver chloride produced was also estimated. Two samples of the chloride mere prepared by different methods and crystallised several times in platinum vessels. When however the samples were finally heated in a current of hydrogen chloride they darkened a little and on dissolving in water left a dark residue showing that some impurity was present.This difficulty is ascribed to a reaction between the salt and filter paper. A sample which remained colourless on heating and formed a clear solution with water was finally obtained by repeated crystallisation in platinum from solutions containing excess of hydrochloric acid. The pure chloride was melted in a stream of dry hydrogen chloride in a platinum vessel before weighing ; the precautions taken are fully described. The determination of the ratios PbC1 2Ag (with the help of the nephelorneter) and PbCI 2AgC1 were carried out a s described in previous papers. As a mean OF nine concordant experirnenk from the ratio PbC1 2Ag the value P b = 207.188 was obtained and from six deterrniaations of the ratio I'bC1 2AgC1 the value 207.193.The most probable value is the mean of the two series Pb = 207-190 [Ag = 107.93 ; Cl= 35.4731. G. S. The Sulpbides of Lead Copper Silver and Iron. I(. FRIED- RICH [with P. SCHOEN] (Metalluryie 19O8,5 23-27,50-58. Compare Abstr. 1907 ii 68'7 95 1).-The experimental difficulties encountered in determining the freezing point of metallic siilphides and mixtnres of sulphides are discused. By examining mixtures containing both more and less siilphur than is required to form the pure sulphide fairly accurate values for the freezing point of the latter may be obtained.282 ABSTRACTS OF CHEMICAL PAPERS. The most probable values :we PbS 1120'; Cu,S 1135" ; As& 812" ; PeS 1171'; in each case with an accuracy of & 10" only.Solidification takes place in all these cases over an interval of temperature which however is possibly due merely t o the low conductivity of the mass for heat and to the low velocity of crystal- lisation. When a further quantity of sulphur is added the freezing point of lead silver and iron sulphides is raised and that of cuprous sulphide is depressed. c. 11. I). Electrolytic Extraction of Copper from its Ores. LUCIEN JUMAN (D.R.-P. 189643 and 189974).-The roasted copper ores when treated with an ammoniacal solution of ammonium sulphite or sulphate furnish a solution containing 7% of the metal ; this solution when freed from uncombined ammonia by evaporation is treated with sulphur dioxide whereby a precipitate of cuprosocupric sulphite (Cu2SOa,CuS0,) is obtained which is dissolved in an ammoniacal solution of ammonium sulphite or sulphate and the metal precipitated by electrolysis with 0.5 ampere per sq decimetre and 0.3 t o 0-4 volt.The ammonia and ammonium salts can be again utilised in subsequent extractions of the roasted ore. By treating ammoniacal solutions of copper with sulphurous acid or rz normal or hydrogen sulphite a precipitate of cuprous sulplrite cuprosocupric sulphite or copper ammonium sulphite or a mixture of these three salts is obtained. Tho solut.ion is used for t h e extraction of more copper ores and the precipitate is treated with a n acid such as sulphuric acid which only gives rise to a cupric salt so that a portion of the copper is pre- cipitated Cu,SO + H,XO = Cu + CuSO + SO + H,O and then sub- jected to electrolytic refining.Q. T. M. Conditions of Formation of Natural Copper Carbonates. PEDERICO MILLOSEVICH (Atti R. Accad. Lincei 1907 [v] 1'7 i 82-45. Compare Bend. Accad. Lincei 1906 [v] 15 ii 732).-Fi.Om the results of experiments in which carbon dioxide was passed through copper sulphate solution placed i n a tall cylinder and containing powdered marble in suspension the author draws the following conclusions (1) The necessary condition for the formation of the less basic of the two natural copper carbonates namely azurite is the presence of calcium carbonate in large excess compared with the copper sulphate. (2) The presence of carbon dioxide which dissolves the calcium carbonate accelerates the formation of both malachite and azurite and is possibly indispensable for the formation of the latter mineral since only by i t s aid can a sufficiently large amount of calcium carbonate be brought into solution.T H. P. Determination of Atomic Weight of Europium. GUSTAV JANTSCH (Contpt 7*end. 1908 146 473-475).-Owing t o the ciis- arepancies existing between the values for the atomic weight of europium (Demarpy Eu= 151 Abstr. 1900 ii 481 ; Urbain and Lacombe Eu = 151.99 Abstr. 1904 ii 340 and Feit and Przibylla Eu= 163.57 Ahst,r. 1006 ii 745) the author bas at Urbain's1 N 0 RG A N 1 C CHEMISTRY . 283 suggestion undertaken a redetermination of the constant. The method employed was the one used by Urbain and Lacombe (Zoc. cit.) and consisted in preparing the octnhydrated sulphate from a nitric acid solution of the pure oxide and weighing the anhydrous sulphate and the oxide obtained on ignition of the same.The purity of the oxide used was tested by photographing its spectrum obtained by the electric arc (Griner and Urbain this vol. ii lOS) on the same plate as the similarly obtained spectra of gadolinium and samarium ; t,he only lines common to the three spectra were those of iron silicon and magnesium due to traces of these elements as impurities in the carbon electrodes. The mean value of four determinations gives Eu = 152.03 with an error of t 0.02 when 0 = 16 H = 1.008 S = 32.06. n1. -4. w. Fluorides of Gadolinium Neodymium and Praseodymium. JOAN Popovrc~ (Ber. 1908 41 634-635).-Gnclolinium Juoritle UdF is obtained as st white gelatinons precipitate when a solution of the sulphate is mixed with concentrated hydrofluoric acid.The precipitate becomes granular when heated on the water-bath; it is insoluble in water but somewhat solubIe in hot hydrofluoric acid. Gelatinous precipitates of the fluorides of neodymium NdF and praseoil ymium are formed when concentrated hydrofluoric acid is added t o solutions of the nitrat’es. When warmed the neodymium precipitate fornis a pale lilac-coloured crystalline powder and the praseodymium fluoride a mass of yellow glistening crystals. J. J. S . Lutecium and Neoytterbium. GEORGES URBAIN (Compt. rend. 1908 146 406-408).-In a previous communication (Abstr. 1907 ii 956) the author has described the resolution of Marignac’s ytterbium into the two elements lutecium. and neoytterbium which were characterised by their spark spectra; in the present paper tho results of the atomic weight determinations are recorded.The crude ytterbium was isolated from the xenotime earths by first eliminating the earths of the cerium gadolinium terbium dysprosium and holmium group by fractional crystallisation of the ethyl sulphates ; the mother liquors which contained the yttrium erbium thulium and y tterbiums were then submitted to repented fractional crystallisations of the nitrates (Abstr. 1907 ii 956) involving in all 15,000 successive crgstallisations. The atomic weight of the ytterbium? determined by analysis of the octahydrated sulphates of sixteen successive fractions varied from 1’70.66 in the first fractions to 174.01 in the Iatter fractions.From the ytterbium sulphate corresponding with atomic weight of 173.5 the base mas fractionally precipitated by dilute sodium hydroxide and each fraction converted into the sulphate ; the atomic weight of the element yielding the weaker base (lutecium) was found to be 173.82 and that of the stronger (neoytterbiuul) 171.70. The magnetic siisceptibilities of the oxides of the two elements were determined by means of Curie and Chdneveau’ s magnetic balance ; neoytterbia is much more para-magnetic t h m lutecia the ratio between the two values being represented by the fraction 53/13.284 ABSTRACTS OF CHEMICAL PAPERS. I n conclusion the author claims priority against Auer von Welsbach [Sitxungsber. K. Akad. T~sP. JTien. (Uath. Natur. Klnsse) 1907 4681 on the ground that the two eIements aldebarnnium and cassiopeiurn isolated by him from ytterbium are identical with lutecium and neo- ytterbium respectively.3%. A. W. An Isomeric Modification of Hydrated Hypovanadic Acid. GUSTAVE GAIN (Compt. rend. 1907 146 403-405).-Hydrated hypo- vanadic acid V,0,,2H20 (Abstr. 1307 ii 32) when kept out of contact with the moisture of the air loses its red colour and changes into an olive-green isomeric form. Each isomeride loses H,O at 1 40-150° forming the bluish-black monohydrate V,O,,H,O or when heated in hydrogen at 200-250° is converted into the black tetroxide V,O,. The red hydrated hypovanadic acid dissolves in sulphuric acid to form an azure-blue solution containing the sulpbate V20,.,2SO ; the green isomeride under similar conditions gives a green solution the heats of solution in the two cases being 12.62 Cal.and 10.89 Cal. respectively and each solution on neutralisation with po tassium hydroxide becomes colourless. The heat of neutralisation of the blue solution is 16.92 Cal. and that of the green solution 18.56 Cal. It follows therefore that the loss of energy involved in the change from the unstable red modification of hydrated hypovanadic acid to the stable green isomeride is equivalent to 1.64 Gal. Hardness of Aluminium Zinc Alloys. A. V. SAPOSCHNIKOFF (J. Izuss. Phys. C?Lem. Soc. 1908 40 95-100. Compare this vol. ii 294).-Here as in the case of tin and lead the close relation existing between the structure and hardness of an alloy is very evident from the resemblance between the curves representing the relation between the composition of a n alloy and its solidifying point and hardness respectively. The hardest alloy is one containing 30% zinc which very much resembles the alloy of composition 72% aluminium 24% zinc 4% copper.The d o y s containing 20-25% of zinc have a fitrong tendency to combine with iron forming probably a definite chemical componnd with great development of heat. The composition and limit of elasticity curve does not altogether correspond with the other curves the variation of elasticity depending chiefly on the formation of solid solutions but the hardest alloy has also the highest limit of elasticity. Z . K. Alloys of Aluminium with Copper Iron Nickel Cobalt Lead and Cadmium. ALFRED G. C. GWYER (Zeitsch. anorg.Chem. 1908 57 1 13-1 53).-From an investigation of these alloys by Tammann’s method of thermal analysis controlled by microscopic observations evidence has been obtained of the existence of the following compounds CuAl CuAI Cu,Al; FeAl,; Nihl NiAl X A l ; Co3AlI3 Co2A15 coA1. Lead and csdminm do not enter into chemical combination wikh alum ilium. A4ost of the coolitig cui-ves wera taken in an atmosphere of riitrogon in order to avoid oxidation. Cop~~er-AZurrzi~aiunz AZZoys. (Compare Campbell Abstr. 1904 ii 820 ; Guillet hbstr. 1905 ii 712 ; Carpenter and Edwards Eighth M. A. W.INORGANIC CHEMISTRY. 255 Rep. Alloys Research Committee 1907).-The freezing-point curve of these alloys shows a maximum at 1050" and 87.6% copper corre- sponding with the compound Cu3A1 two breaks a t 625' and 5676 and at 590" and 45% of copper respectively a minimum at 88.5% of copper and a eutectic point a t 545' and 325% of copper the components of the mixture being the compound CuAlz and mixed crystals containing 4% of copper.Three series of mixed crystals contain 0-4% 71-88*5% and 91.5-100% of copper respectively. From 88*5-91*5% of copper the alloys consist of the two saturated mixed crystals but although the curve shows a minimum a t t'he point there is no true eutectic. At 625' the saturated mixed crystal containing 71% of copper reacts with the fused mass to form the compound CuA1; at 590" the latter reacts with the fused mass containing 44% of copper to form a third compound CuAlY The work of Guillet (Zoc. cit.) is adversely criticised and the author's results differ from those of Carpenter and Edwards (loc.cit.) inasmuch as the latter observers suggest the formation of a compound Cu,Al but did not detect the well-defined compound CuAI. Iron-AZuminium AZlogs. (Compare Guillet Abstr. 1902 ii 21 ; Roberts-Austen Engineering 1895 59 744).-The freezing-point curve falls fairly rapidly from l00-50% of iron shows a distinct break a t the latter point fdls slowly from 50-30% of iron and then rapidly to the melting point of aluminium. Two series of mixed crystals contain 40-48% and 66-100% of iron respectively ; the end member of the first series may be the compound FeAl (40.7% of iron). Alloys containing 60-65% of iron show eutectic breaks in the cooling curve at 1087' but the breaks occur a t higher temperatures from 50-57.5% of aluminium ; alloys containing 52-65% contain a eutectic of the same structure but the latter appears to differ in structure from the eutectic i n 50% iron.Several points in the behaviour of alloys containing 48 -66% iron remain unexplained. Only alloys containing more than 70% of iron are magnetic and the temperature a t which the magnetic permeability disappears on heating is gradually lowered as the proportion of aluminium increases. Nickel-Aluminium AZZoys.-These metals combine almost explosively when heated a t 1300". The cooling curve mas taken in magnesia tubes. The freezing-point ciirve shows a maximum a t 1628' and 68.4% of nickel corresponding with the compound NiA1 two breaks a t 830' and 27% and 1130' and 42% of nickel respectively a minimum a t 87% nickel and a eutectic point (Al-NiAl,) a t 630" and 6% of nickel.Two series of mixed crystals contain 68-4-81% and S75-100% of nickel respectively a t 1370" but the limits of saturation are considerably displaced on change of temperature. For example the alloy containing 85% of nickel becomes homogeneous on prolonged heating at 1050". The explanation of the minimum in the curve is the same as in the case of the iron-aluminium alloys to which these alloys bear a close resemblance. At 1130° NiAl reacts with the fused mass to form the compound NiAl and at 830' the latter reacts with tho fused mass to form a third compound NiAl (long needles). Only alloys containing more than 85% of nickel are magnetic and the magnetic power falls off rapidly with decrease in the proportion of286 ABSTRACTS OF CHEMICAL PAPERS. nickel.The temperature a t which the magnetic permeability disap- pears is greatly lowered by the presence of aluminium. Cobalt- AZuntinium Alloys.-The freezing-point curve of these alloys shows a maximum of 162SO and 68.5% of cobalt correaponding with the compound CoAl two breaks a t 1165' and 3S0/ and 940' and 20% of cobalt and a minimum a t 90% of cobalt. Two series of mixed crystals contain 68*5-800/ and 90.5 -100% of cobalt respectively. Alloys containing 82-90% of cobalt did not become homogeneous on heating for three hours a t 1250-12'70°. At 1165O the compound CoS1 reacts with the fused mass t o form the compound Co,A15 ; at 940° the latter reacts with the fused mass to form a third compound Co,All,.Only alloys containing more than 68.5% of cobalt are magnetic and ttie temperature at which the magnetic power disappears on heating is progressively lowered by the addition of aluminium. (Compare Heycock and Neville Trans. 1892 61 SSS).-These metals are not miscible in the fused state. Alloys containing up t o 5% of lead solidify without separatiug into two layers forming a sort of emulsion. Alumiiziunt-Cccdmium Alloys.-These metals are also not miscible in the fused state. Separation into two layers only takes place when the alloy contains more than 10% of cadmium. Alum~inium-Lead Alloys. The paper is illustrated by twenty-two photomicrographs. G. 8. Preparation of Hydrosols of Metallic Hydroxides from Hydrogels. ARTHUR MWLLEB (Zeitsclb.anorg. Chem. 1908 57 3 ll-322).-Colloidal solutions of certain metallic hydroxides have been prepared by dissolving the precipitated washed hydroxides (hydrogels) in dilute mineral acids or in strongly hydrolysed solutions of t.he corresponding metallic salts. The hydroxide is shaken up in a flask with water and the acid or salt solution added in successive portions until a clear solution is obtained the mixture being well boiled after each addition of electrolyte. The preparation by the above method and the properties of colloidal solutions of the hydroxides of aluminium thorium yttrium cobalt and iron are described. The solutions show the usual pro- perties of colloidal solutions the particles being positively charged. There is no definite relation between the quantity of electrolyte used and the amount of hydroxide brought into solution the amount of electrolyte required depending on the age and previous treatment of the colloidal hydroxide.G. 8. . The Decarburisation of Iron. FRIEDRICH Wu ST (Metnllurgie 1908 5 7-1 2).-In the conversion of cast-iron into malleable-iron by beating in contact with iron oxide the removal of carbon only begins after a decomposition of the carbide (cementite) into ferrite and carbon (temper-carbon) has takensplace. By experiments with a cast-iron containing 4.15% of carbon 3.4574 of which was in the form of temper-carbon it was found t o be immaterial whether the iron was in contact with the ferric oxide or not. By exhausting the apparatus and analysing the gases formed from time to time it was found thatINORGANIC CHEMISTRY.287 the oxidising agent is oxygen evolved by the ferric oxide at 1000° and upwards. This oxygen diffuses into the iron forming carbon dioxide which then diffuses fnrther being converted into carbon monoxide by the temper-carbon in the interior. This carbon monoxide is reoxidised by the ferric oxide ferrous oxide and metallic iron being produced. Should the quantity of iron oxide be insufficient the pressure of carbon dioxide may rise to such an extent that the process is reversed the outer layers of iron being carburised by the de- composition of the carbon dioxide. This explanation of the process is confirmed by the microscopic examination of the outer and inner layers of the mass of iron. C. H. D. Influence of Phosphorus on the System Iron-Carbon.FRIEDRICH WUST (Metalluvgie 1408 5 73 -87).-The temperature at which saturated iron-carbon alloys begin to solidify is lowered by the addition of phosphorus 1% of phosphorus causing a depression of 37". When the proportion of phosphorus exceeds 6.7% the freezing point again rises. The ternary eutectic melts at 950° and contains 6.7% P 2.0%' C and 91.3% Fe. The eutectic disappears a t a phosphorus content of 15% corresponding with the phosphide Fe,P. Alloys containing between 6.7% and 15% of phosphorus show crystals of the phosphide. The solubility of carbon in iron is reduced by the addition of phosphorus but the temperature of formation of the eutectoid perlite is not influenced by the presence of the phosphide. The paper is illustrated with photomicrographs in some of which the oxidation-tints of the constituents are reproduced by colour- photography. C.H. D. Different Coloura of Ferric Oxide an Effect of the Size of the Grains. LOTHAR WOHLER and C. CONDREA (Zeilsch. cungew. Chem. 1908 21 481-486).-A study of the conditions of the formation of differently coloured ferric oxides. The violet substance formed by heating yellowish-red ferric oxide with sodium chloride in It is prepared also by heating yellow ferric oxide with other salts such as calcium chloride sodium sulphate potassiiim chloride and borax. The shade varies from brown to violet with the temperature and with the amount and nature of the salt added the deepest shades being obtained when the added salt is not less than 6% of the weight of the ferric oxide.The amount of salt which must be added diminishes as the temperature is raised; the reaction does not take place below the m. p. of the salt. The rate of cooling is without influence on the shade at least with small quantities. A t low temperatures the presence of water is found to affect the shade in the same manner as that of salts at high temperatures. These results point to the size of the grains as determining the colour of the ferric oxide. In agree- ment with this brown or violet ferric oxide is converted into the yelloRish-red variety by alternate grinding and washing. G. Y . iron crucible over the blowpipe flame is pure ferric oxide.288 ABSTRACTS OF CHEMlCAL PAPERS. Ferronitrososulphides. LIVIO CAMBI ( A t t i a.Accud. Lincei 1908 [v] 17 i 202-207. Compare this vol. ii 41).-The author discusses previous work on the constitution of Koussin’s salts and describes further experiments bearing on this question. An excess of silver sulphate together with dilute sulphuric acid was treated with potassium ferronitrososulphide in an atmosphere of carbon dioxide. Subsequent titration with permanganate showed that in this reaction the iron is reduced quantitatively to the ferrous state. I n some cases when the temperature and acidity are chosen so as to cause the reaction t o proceed very rapidly the iron may undergo only partial reduction a large proportion of the nitroso-groups not being oxidised but yielding hyponitrous acid. The reducing action of the nitroso-groups here manifest is demonstrated even more clearly by treating excess of ferric sulphate and silver sulphate in presence of sulphuric acid with potassium ferronitrososulphide ; in this reaction 7 mols.of nitric oxide and 7 atoms of ferrous iron are obtained per mol. of ferronitrososulphide. The act ion of potassium ferronitrososulphide on silver sulphate yields silver nitrate and silver hyponitrite the gas evolved under the action of sulphuric acid consisting of nitric oxide and nitrous oxide ; the latter owes i t s formation to the deficit of ferric iron The production of 7 mols. of nitric oxide per mol. of ferronitrososulphide is hence necessarily connected with the foi mation of seven ferrous ions. The reaction in presence of ferric salt may be represented by the equation Seven IX~OIF.of nitric oxide are also liberated from potassium nitrososulphide by the action of copper sulphate which acts as an oxidising agent and passes into the cuprous form. These results lead to the conclusion that Roussin’s salts do not coiitain the residue of hyponitrous acid (0N:NO)”. These salts contain a univalent group NO‘ capable of acting in two ways firstly giving hyponi trous acid and secondly of yielding nitric oxide under the action of various oxidising agents. [ Fe,S,”(NO),]’ + 3Fe”’ = 7Fe” + 7 N 0 + 35”. T. H . P. Hydrolysis of Ferric Chloride. Effect of the Valency of the Negative Ions. G. MALF~TANO and LEOPOLD MICHEL (Conzpd. rend. 1908 146 338-341. Compare this vol. ii 11 l).-It is known that the precipitation of ferric colloids by anions diminishes ns the valency of the latter increases.It is now shown that the anions act according to the same rule in preventing the formation of colloid. The authors have iiieasured the increase in the conductivity at 50” of N/150 solutions of ferric chloride containing nitric oxalic hydro- chloric sulphuric arsenic and phosphoric acids a t concentrations N / l O O O N/250 and N/100 as a function of the time and have illus- trated the results by curves. The activity of the acids in retarding the progress of the irreversible hydrolysis (indicated by the increase in conductivity with the time) is shown to be partly dependent on their degree of ionisation but the influence of the anion is shown by the difference in activity betwaen equally ionised acids such as hydrochloric and nitric acids and particularly by the activity of oxalic acid which is much higher thanI S 0 RG A S I C CZ T E M I ST R I'.289 woulcl be expsctecl froin its ionisation coefficient. As the concentrs- tion of the acids diminishes the influence of the hpclrogen ions become; negligihle ant1 that of the anions wheu multivalsnt preponderant probably tlirongh the rep1 icetnent of cl~loi~iim in ferric chloride and formation of less c1issoci;it)le molecules. Curves are given shotvhg the increase with time of the conductivity of N/150 ferric chloride holutions containing varying quantities of phosphori acid. The increase is least when the concentration of the acid i q fV/250 ; at lower concentrations the hydrolysis and formation of colloid are only slackened and a t higher concentrations the forma- tion of colloid is definitely prevented.the conductivity meanwhile increasing with time. This can oiily be explained by the quantity of free hydrogen chloride displaced by the phosphoric acid. The phenomenon becomes more evident at 100° ; solutions of ferric chloritle coEtaining an equivalent of phosphoric acid when heated at this temperature give a white positive colloid containing iron and phos- phoric acid which tends to disappear on cooling the more easily the greater the concentration of the ferric chloride. The forination of the hydroxide colloid is prevented when the ratio Fe/PO reaches the values 1/6000 at 1 8 O 1/200 at SO0 and 1/16 at looo increase in temperature and dilution affecting only the irreversible not the reversible hydrolysi;. The authors conclude that the ferric ions become less apt to form complex ions (Fe[Fe(OH),],) as the vslency of the accompanying anions increases and the micro-cells conceived as complex iom of llrge dimensions (n being very great) protect the molecules of the hydroxide from the hydrochloric acid.Consequently if these complex ions cannot be formed t h e irreversible hydrolysis is impeded. E. 11. Thermal Diesociation of the Anhydrous Sulphates of Iron. GUSTAV KEPPELEI~ and JEAN D'ANs (Zeitsch. physiKaZ. Chenz. 1908 62 89-1 1 S).-The authors have studied some problems bearing ou the ferric oxide contact process for the inanufitcture of sulyhuric acid (compare Lunge and Pollitt Abstr. 1903 ii 70; Lunge and Meinliardt Abstr.1904 ii 724). TheIanhydrous sulphtttes investigated were ferric snlphate basic ferric sulphate Fe,O(SO,) and ferroi1.r sulphate; details of the preparation of these substsnces are given in the puper. A current of air or nitrogen was passed throngh a tube containing the anhydrous sulphate and heated to a definite temperature ; the proportion of sulphur dioxide and sulphur trioxide in the issuing g.ts w7as then determined analytically. The equilibrium between ferric sulphate a n d sulphur trxioxide is represented as Fe,(SO,) Zr F P ? ~ + ~ S O ~ . The change of the SO tension with temperature i n this system is given adequately between 500' and $00" by the formula logp = 11.8626 - 44720/1*5812'. 1 n the gaseous phase the equilibrium SSO 230 I- 0 is established,.ancl the equilibrium constants foiind for this reaction are in good a!.reement with the values given by Bodenstein and Pohl (hbstr. 1905 11 581).The tension of sulphur trioxide over basic ferric sulphate is greater than over normal ferric sulphate at the same temperaturt. and the VOL. XCIV. ii. 20290 ABSTRACTS OF CHEMICAL PAPERS former is accordingly regarded as a labile compound. It was observed that in the gaseous phase at the lower temperatures the expected equilibrium was not reached ; in all cases too much sulphur dioxide was found. The behaviour of fei rous sulphate is best represented by the equation 2FeS0 (Fe,O,,SO,) +SO the sulphate on the right hand side of this equation being the normal one. I n the gaseous phase above ferrous sulphate a t a high temperature there is a constant ratio between the partial pressures of sulphur dioxide and sulphur trioxide.lndications were obtained that a t 640' ferric oxide undergoes an allotropic change. It was a t this temperature that Lunge and Reinhardt (Zoc. cit.) found a maximum yield of sulphur trioxide from gases containing 2.1% of the dioxide. A t this temperature also the observed tension of sulphur trioxide is the same as that of ferric sulphate. Above 640° the velocity of the catalytic combination of sulphur dioxide and oxygen is greater than the velocity of formation of ferric sulphate. New Method for Determining the Tension of Sulphates. LOTHAR WOHLER W. PL~DDEMANN and P. WOELER (Be?. 1908 41 703-717).-This investigation was undertaken as the knowledge of the partial pressures of sulphur trioxide from sulphates is necessary for the interpretation of the contact process.The tension of the sulphates was determined by a statical method which had to satisfy the following conditions (1) sulphur trioxide should not condense (2) the gas ought not to come in contact with the mercury in the manometer (3) the equilibrium 280 2S0 + 0 must be accom- plished in the shortest possible time (4) sufficient substance should be taken in order to carry out a series of determinations and ( 5 ) no india-rubber connexions or greased cocks should be employed. The apparatus consisted of a porcelain tube which contained the sulphate placed in a platinum tube on the t o p of which a piece of platinum gauze was placed and then some spongy platinum.The tube heated in a HerLus vertical tube furnace is connected to a condenser heated by steam by means of a ground-joint smeared with deliquesced phosphoric oxide and sealed with mercqry. The manometer is connected t o the condenser by a T-piece through a tube containing sodium hydroxide and calcium chloride the other end of the T-piece being connected to the pump. The equilibrium pressure was determined by closing the tube heated to the desired temperature and allowing air into the evacuated apparatus a t a known pressure opening momentarily the connecting stopcock and if the pressure did not change the equilibrium pressure was reached. With ferric sulphate for example at 599O the pressure observed was 53.0 mm.; at 630' it was 102.5 mm. To ascertain whether ferric sulphate was decomposed direct into oxide and sulphur trioxide the basic material Fe,O,,SO was heated and the tension found at three different temperatures agreed with thoee found for Fe20,,3S0 thus showing that a basic sulphate of iron is not formed and that there is no evidence for the formation of a solid solution of oxide and J.0. P.sulphate. I n this way it was found that aluniiniurrl and thorium sulphates also decompose directly to oxide. ,is the normal chromium and titanium sulphates could riot be obtained the water-free basic sulphates Clr,03,2X03 2Cr,03,3S0 mere prepared the first by heating in a stream of carbon dioxide to 280° and the second by heating to 450-460’ in a crucible. With the latter basic sulphate the tensions observed are lower than with the more acid sulphate.A material of composition 7Cr,03,2S03 showed the same tensions as the sulphate 2Cr203,3S0,. Similar results were obtained with the basic titanium sulp h ates TiO SO 2Ti02 S 0,. Copper sulphate is shf,wn to form in addition to the normal sulphate only the basic oxide 2Cu0,S03. Cerium sulphate by heating loses oxygen and passes into cerous sulphate. The method of calculating the partial pressure of sulphur trioxide from the total pressure is given and the heat of dissociation of Fe20,,3503 A1,0,,3S03 Cr,0,,2S03 Th02,2S0 Cu0,S03 and Zn0,S03 found to be 27 17 22 21 13 and 36 calories respectively A method has been devised for the quantitative separation of iron and zinc by means of their different tensions. At 680° the tension for ferric sulphate is nesrly 1 atmos.whereas for zinc sulphate it is only 6 mm. so that by heating the mixture of sulphates a t that temperature until constant in weight the ferric oxide remains mixed with the unchanged zinc sulphate. Other separations can be effected but in general metals of similar chemical characteristics cannot be separated in this way for example iron and aluminium. W. R. Metallic Silicates. I. Preparation of Metallic Silicates by Wet Methods. EDUARD JORDIS (J. pr. Chenz. 1908 Lii] 7’7 226 -237. Compare this vol. ii 103)-A discussion of the conditions which must be observed in the study of the formation of silicates of the heavy metals in the wet way and a criticism of Grijger’s investiga- tion of copper carbonate (Abstr. 1900 ii 542). G. Y. Metallic Silicates. 11.Interactions of Sodium Silicate and Metallic Salt Solutions. EDUARD JORDIS AND w. HENNIS (J. pr. Chem. 19OS [ii] 77 238-26 I).-The reactions of copper sulphate ferrous sulphatc and ferric chloride with sodium silicate in aqueous solution do not take place according to the equations which can be written for them. I€ the reagents are mixed in equivalent amounts m acid liquid is obtained which contains silicic acid in considerable amount from the ferric chloride reaction. The amount of the metal found in the filtrate varies independently of the reaction of the liquid and is especially large with ferric chloride. I n presence of much alkali the metal dissolves together with silicic acid. If an excess of either reagent is added the portion which passes into the filtrate increases with the excess from a minimuin.The course of the reaction is especially complicated in the case of ferric chloride. The acid filtrate requires considerable amounts of alkali for neutralisation and thereafter combines with still larger amounts of alkali before becoming alkaline This reaction is taken part in not only by the precipitate but also by dissolved substances. 20-2292 ABSTRACTS OF CTIEhIICAT PAPERS. The amount of alkali neutralised is approximately proportional to the total amount of silicic acid present. Precipitates of varying composi- tion are obtained from the clear filtrate by addition of hydrochloric acid by the action of heat' and on neutralisation. Permanent changes are produced by heating. I n many cases tho reaction especially between the precipitate and the mother liquor takes place slowly.The precipitates are soluble in acids only when freshly formed. Clear filtrates am obtained from the turbid reaction mixture only when a colloidal layer has h n formed on the surface of the filter. Pure ferrous silicates are bluish-green and on oxidation become yellow passing through green or brown intermediate stages. The copper silicates are blue or when anhydrous green ; precipitates formed Kith an excess of copper sulphate are more or less green in con- sequence of the formation of crystalline basic copper sulphate. The silicate precipitates remain unchanged when boiled with their mother liquors whereas under the same conditions a partly oxidised ferrous hydroxide becomes black ; this blackening however does not take place if the precipitate is ground with colloidal silica before being boiled.Solutions of Na,Si,O or ZNaHSiO which analytically are identical react in the same manner as solutions of Na,SiO,. I t is probable that they contain the ion Si,O,". G. Y. Freezing-point Curve of the Nickel Sulphides. K. BORNE- MANR (L$letnlh.wgie 1908 5 13-1 9).-Mixtures containing from 0% to 31% sulphur were examined mixtures richer in sulphur being unstable under atmospheric pressure The components are completely miscible in the liquid state The equilibrium diagram is complicated five series of mixed crystals separating from the fused mass. The freezing- point curve up to 31% sulphur consists of five branches with eutectic points at 21.4% and 30 6% sulphur and 644' and 81.2' respectively.The only compound capable of existence in contact with the melt is Ni,S melting a t 7 8 7 O . A number of transformations take place in the solid state the existence of the compounds NiS Ni,S and NiS being proved by Tammann's method. All these dissociate below the melting .point. The compound Ni,S has no existence mixtures of that composition having a eutectic structure. The existence of Ni,S is highly probable but mixtures of this composition lose sulphur on fusion. The curves representing the thermal transformations in the solid state have been completely studied there being a well-marked eutectoid point a t 29.7% sulphur and 520". The results of the thermal analysis are fully confirmed by a comparative study of the density and microscopic structure of mixtures allowed to cool slowly and rapidly quenched.C. H. D. The Constitution of Nickel Matte. K. BORNEYANN (iVetcd- Zurgie 1908 5 61-68. Compare preceding abstract).-The thermal and microscopic examination of mixtures of ferrous sulphide with the stable nickel sulphide Ni,S shows the existence of a compound 2FeS,Ni,S2 which melts at 840" and dissociates considerably onINORGANIC CHEMISTRY. 293 fusion. The compound forms mixed crystals in all proportions with Ni,S but ferrous sulphide only dissolves it to a very small extent in the solid state. A t lower temperatures transformations occur which i t has not been possible to determine accurately. When the mixtures are prepared with a nickel sulphide of the composition Ni,S a more complicated thermal diagram is obtained. This compound although incapable of separate existence forms stable compounds with ferrous sulphide.The only compound which is st'nble in contact with the fused ma=s is 2FeS,Ni,S which melts at 8 8 6 O but breaks up on cooling to 575" into FeS and 3FeS,2Ni2S. A t a still lower temperature this compound combines with FeS to form 4FeS,Ni,S but the change is not accompanied by development of heat and could only be detected by microscopic examination and by determinations of density. C. H. D. Molecular Weight of the Greyish-blue Hydrate of Chromic Chloride. I. Neutralisation of the Salt by Sodium Hydroxide. JULIUS SAND and F. GRANMLING (Zeitsch. physikd. Chew. 1908 62 1-27. Compare Werner and Gubser Abstr.1901 ii 453 ; Bjerrum Abstr. 1907 ii 554 663).-If sodium hydroxide is gradually added to a solution of the greyish-blue chromic chloride the colour assumes more and more a green tinge but remains peifectly clear until 1 molecule of sodium hydroxide has been added for every atom of chromium present ; further addition of the alkali produces an opalescence and finally when two or more molecules of sodium hydroxide have been added for every atom of chromium a precipitate is formed. The gradual neutralisation of the greyish- blue salt by sodium hjdroxide in the first stage and the consequent removal of the hydrogen ions have been followed by the electrochemical method already employed (Sand and Eisenlohr Abstr. 1907 ii 178). Two formult-c showing the relation between the 3.M.K of a hydrogen electrode immersed in a partly neutralised solution of the chloride and the amount of sodium hydroxide added are deduced ; these are respectively based ( I ) on the supposition that the chromium ion is Cr' and (2) on the supposition that it is Cr2:::.The experimental figures are in good agreement with the second formulz and the greyish-blue salt is accordingly formulated as Cr2(H20)12C16 and it is regarded as probable that the two chromium atoms in this compound are connected with each other through an oxygen atom. The reaction which takes place on the first addition of sodium hydroxide is re- presented by the equation Cr,(H,O),,CJ + 2NaOH = 2Cr[OH(H20),]C12 + 2NaC1+ (12 - Zx)H,O. At this stage of the neutralisation the concentration of the hydrogen ions will be determined by the hydrolytic equilibrium Cr2:: + 2H20 t 2CrOH" + 2H'.The green chromic chloride on the basis of similar electrcchemical measurements is found to be unimolecular. The addition of sodium hydroxide to a solution of this salt leads to simultaneous hydrolysis in two directions (1) CrCI,' + H20 ~2 CrOH" + H' + 2Cl'. (2) CrCl,' + H,O CrO' + 2H' + 2C1'. J. C. P.294 A BS'I'R A CTS 0 F C H E M I C A I PA YE RS . Molecular Weight of the Greyish-blue Hydrate of Chromic Chloride. 11. Hydrolysis of the Salt by Potassium Iodide and Iodate. JUI.IUS SAND and F. GRAIIMLIKG (Zeitsch. physikal. Chem. 1908 62 28-43. Compare preceding abstract).-The velocity with which solutions of the greyish-blue hydrate of chromic chloride libel-ate iodine from a mixture of potassium iodide and iodate has been determined and from theso measurements the proportion of hydrogen ions in solutions of the hydrate has been deduced (compare Sand and Eisenlohr Abstr.1907 ii 179). On the basis of the supposition t h a t the hydrolytic equilibrium involved is Cr2:: + 2H,O z2 2CrOH' + 2H' formul3e are deduced for the rate of liberation of iodine from the iodide-iodate mixture which are in good agreement with the experimental figures. On the other hand there is no agreement between the experimental figures and the values of the velocity-coefficient based on the supposition t h a t chromic chloride has the unimolecular formula Cr(H,0)6CI,. Tho evidence therefore goes to show that this formula must be doubled and t h a t the molecule of the greyish-blue hydrate contains two chromium atoms linked together.J. C. P. Chromates. NICOLA PARRAVANO and A. PASTA. (Zeitsch. anorg. Chern. 1907 57 240. Compare Abstr. 1907 i 961).-A claim for priority against Briggs (this vol. ii 113) with reference t o the preparation of compounds of certain dichromates with pyridine. G. S. Sulphate of Tervalent Uranium ARTHUR ROSENIIEIM and HEINRICH LOEBEL (Zeitsch. nnorg. Chem. 1908 5'7 234-239).- A solution of uranium trichloride UC1 (Peligot 1842) in a large excess of hydrochloric acid was obtained by the electrolytic reduction of the trioxide UO dissolved in hydrochloric acid (U 1.12) in a special apparatus in which a layer of mercury was used as the cathode. To complete the reduction the solution had t o be cooled to 0' towards the end of the experiment.I n the presence of traces OF dissolved mercury or of platinum the reduction stops at quadrivalent uranium probably because these substances facilitate the liberation of hydrogen. The great majority of reagents even water decompose the acid solution of uranium trichloride with formation of quadrivalent uranium compounds bnt when the solution is mixed with fairly concentrated sulphuric acid both previously cooled to Oo deep brown leaflets of the compound UH(SO,) separate. Before analysis the crystals were washed with anhydrous acetic acid but owing t o the difficulty of removing all the sulphuric acid t h e formula of the compound is not regarded as being conclusively established. G. S. Hardness of Tin and Lead Alloys.A . V. SAPOSCHNIKOFF (J. Buss. Phys. Chem. Soc. 1908 40 92-95).-Tin and lead do not form chemical compounds but solid solut,ions are formed by t i n in lead up to ths composition 10-'5?; tin. As t i n is added to lead the hardness of t h e ~ l l o y increases until 400A tin is present when itI NORGX NI C C H EM I STllY . 295 decreases but at the composition 66% tiu the hardness attains a inaximum. Since this point coincides wit,h the eutectic point of the alloy it confirms the view previously expressed that the hardness of alloys is very closely related to their structure. Z. K. Stannichlorides of the Type M2’SnC16 1\l”SnCI,. 111. Hydro- lysis of Stannic chloride. EUGEN VON BIRON (J. Russ. Phys. Chem. Soc. 1905,37 963-993. Compare hbstr. 1905 ii 40).-The first pro- ducts of the hydrolysis of stannic chloride are oxychlorides intermediate in nature between meta- and parr-chlorostannic acids and it is these oxychlorides which yield the colour reaction with stannous chloride before p-stannic acid has been formed either as a hydrosol in solution or as a precipitate.The latter occurs the more rapidly the more dilute the solution ; a t higher concentrations however p-stannic acid is not precipitated but undergoes condensation forming oxychlorides with a smaller proportion of chlorine thus leaving more free hydro- chloric acid in solution and the quantity of the latter determined by measuring the electric conductivity of the solution is taken as a measure of t,he extent of hydrolysis of the stsnnic chloride (compare Foster Phys.Beview 1899 9 41 ; Kowalewski Abstr. 1900 ii 256 ; Kohlrausch Abstr. 1900 ii 408 ; Van Bemmelen and Xlobbie dbstr.. 1900 ii 338). The increase in the initial electrical conduc- tivity on dilution proceeds more rapidly than is the caw for ordinary electrolytes and the acidity of the solution in spite of the fact that SnCl itself is not an electrolyte and the analogy of SnCI with TiC1 and SiCI leads to tbe conclusion that i t decomposes in water thus :&SnCI + (1.3 + 2)fI,O SnO,,nH,O + 4HC1 and side by side with this the following reaction probably also occiirs SnC1 + nzSnO,,nH,O = SnCl,,~~zSinO,,nH~00rSnC1~ + nzSn0,,nH20 = (m + l)[SnO,,xHICl,yH,O] but the main reaction being instsntaueous is not applicable to the slow hydrolysis of stannic chloride.Although all aqueous solutions of stsnnic chloride are electrolytes when freshly prepared only those solutions give the reaction with stannous chloride the electric con- ductivity of which changes with time. It is thus evident that the change in electric conductivity is a consequence of the formation of the derivatives of ,8-stannic acid the P-oxychlorides of tin being formed by the gradual condensation of the stannic acid contained in the indefinite oxychlorides of tin termed a-oxychlorides the hydrochloride thus disengaged causing a rise in the electric conductivity. The slow hydrolysis of stannic chloride may therefore be expressed thus a-SnO,,zHCl,yH,O = /3-Sn0,,zHCl,sH20. I n concentrated solutions part of the stsnnic chloride decomposes forming stannic acid which with undecomposed chloride forms a-oxy- chlorides containing a high percentage of chlorine which prevents the condensation of its constituent stannic acid thus hindering the occurrence of slow hydrolysis.I n such solutions there is also present undecomposed stannic chloride either in the form OF hydrates or as chlorostannic acid. If at the very commencement of a reaction hydrochloric acid is added to a dilute solution undergoing slow hydrolysis the latter cannot proceed since the condensation of stannic acid is prevented ; when however the solution is too dilute the a-oxy-296 ABSTRACTS OF CHEMICAL PAPERS. clilorides contain too little chlorine consequently instead of forming /3-oxychlorides they are converted into p-stannic acid which is precipi- tated in a more or less condensed form depending on the time intervening between the prepar,ation of the solation and the precipita- tion of the acid.Z. K. Stannichlorides of the Type M’SnCl ISI’’SnC1,. IV. Dissocia- tion of Stannichlorides in Aqueous Solutions. EUGEN VON BIRON (J. Russ. Php. Chenz. Soc. 1905 37 994-1036. Compare preceding abstract).- Sodium chloride retards the formation of p-oxy- chlorides in concentrated solutions of stannic chloride ; a s the solutions are diluted this effect becomes less and in very dilute solutions (0.01 part SnCl! per litre) i t considerably accelerates the separation of stannic acid. Probably in concentrated solutions it is the sodium staimichloride which exerts most influence whereas in dilute solutions the free sodium chloride affects the rate of the reaction.Investiga- tion o€ the electrical conductivity of such solutions confirms theso results and shows that as the concentration of sodium chloride is in- creased the change in specific conductivity Ax becomes less and finally becoines constant. The same is true for magnesium chloride but the action of cadmium chloride is quite different its 1og.time-sp. con- ductivity curve being very similar to t b a t for piwe stannic chloride. The following reasons l e d to the conclusion that the metallic stsnnichlorides are only partly dissociated in solution ( I ) the possi- bility of crystallising thein from solutions containing an excess of t i n chloride. (2) Ax varies in the same may in experiments with an excess of tin chloride as with an excess of sodium chloride and since the latter does not influence Ax merely as such the variation of Ax must depend on the formation in tho solution of a stannichloride.(3) The influence of sodium chloride on the slow hydrolysis of stannic chloride is 430 times as great as that on tin metachloride. (4) The addition of sodium chloride reduces the electrical conductivity to below that of a eolut’ion of sodium chloride and this can of course only be due to the presence of a complex compound. (5) Ax continually diminishes with time in the case of pure stannic chloride whereas in the presence of :L metallic chloride it remains constant f o r considerable intervals and although the hydrolysis is of the same character with or without the metallic chloride the stannichloride formed i n the presence of the latter acts as a reserve for the continual supply of more ions for preserving equilibrium.(6) The impossibility of obtaining cadmium stannichloride agrees with its abnormal behaviour mentioned above. A large number of experiments with various stannichlorides (0.5 part per litre) shows that except for zinc and cadmium Ax is comtant for ten days and does not depend on the degree of dissociation of the metallic chloride or on the initial conductivity of the solution but the latter depends on the mobility of the cation. These and other experiments also point t o the fact that Ax is a true measure of the degree of dissociation of the given stannichloride. In the case of t h e alkaline earths in dilute solutions Ax is practically identical for each but as the concentration of the flee metallic chloride increases ha becomes least for calcium and highest for barium this probably depending on the formation of hydrates of the metallic chlorides.INORGANIC CHEMISTRY 207 Thus whilst the quantity of the chIoride is small and the active mass of water lai-ge the formation of these hydrates cannot influence the course of thg reaction and Ax therefore indicates the degree of dissociation of the stannichloride but when the concentration of the chloride is high the foimntion of hjdrates diminishes the active mass of water; Ax therefore diminishes and the extent of this diminution will depend on the degree of hydration of the chloride.This is also observed to a less extent in the case of the other metals.Z. K. Stannichlorides of the Type i\l,’SnC16 i\l”SnC16. V. Partition of Stannic Chloride between Two Metallic Chlorides. EUGEN YON RIRON (J. Russ. Phys. Chenz. SOC. 1905,37 1036 - 1063. Coiiipni-c preceding abstract).-The conclusions arrived a t in the preceding abstracts are confirmed by a spectrophotoi-netric method. As stannic chloride is added to a solution of cobalt chloride the absorption region of the latter spreads out towards the red end of the spec- trum and at the same time there is increasing absorption a t the violet end. By thus investigating the absorption spectra of solu- tions of stannic chloride cobalt chloride and some other transparent chloride i t is possible t o calculate tho partition of the stannic chloride between the two metallic chloricles. Staiinic chloride itself does not absorb light and the absorption which after a certain concentration of stannie chloride becomes constant must thus be due to the formation in solution of cobalt stannichloride which has a greater absorption-coefficient than cobalt chloride.The quantity of stanni- chloride i n solutions in which i t is appreciably dissociated csn be calculated by a series of calculations by means of t’he formula ct = A(c - x) + A’z ( c = quantity of CoCI x = CoSnC‘l formed A’ = frac- tional-coefficient of absorption of cobalt stannichloride and A = similar coefficient for cobalt cliloride ; the values so obtained agreeing well with the experimental results). The equilibrium constant k = C,C,/C (C = concentration of cobalt chloride C = concentration of tin Chloride and Ccs = concentration of cobalt stannichloride).Calculating in this way the values Co 11 (31 =any metal) in relation t o the affiriity of their chlorides for stannic chloride and compsring them with tho values l / A x for the corresponding metals there is a striking siniilarity bet n-een the two constants. The following conclusions are also drawn (1) the affinity constants K of the motallic chlorides for stannic chloride are comparable with the affinity of anhydrides for oxides. (2) I n the first and second groups of the elements in the periodic system K increases .with increasing atomic weight in the even series and decreases in the odd series. (3) K is greater for tho50 chlorides which have the greatest tendency to hydration (4) The metallic chlorides which form complex anions have little affinity for stannic chloride. Various theories regarding the formation of double salts are criticised and i t is pointed out that Wells’ classification of the halogen double salts rests on their comparison under really non- corn parable conditions.Z. K. Application to Thoria of a General Method of Synthesis of Fluorides and Silicates. ANDRJ~ G. DUBOIN (Compt. rend. 1908 146 489-491).-The double fluoride K F,ThF obtained by298 ABSTRACTS OF CHEMICAL PAPERS. dissolving thoria in fused potassium hydrogen fluoride yields thallium fluoride ThF in the form of brilliant crystals on fusion with excess of potassium chloride or bromide (Abstr. 1895 ii 351). The crystals belong t o the cubic system elongated in the direction of one of the axes as in certain specimens of cuprite they melt a t a red heat are not attacked by Concentrated sulphnric acid are slowly decomposed by the dilute acid or by hydrochloric acid and on fusion with sodium carbonate yield transparent cimystals of thoria which closely resemble the crystals of the original fluoride.Potassium i?Lorium silicate K2O,ThO,,2SiO Do 4.44 prepared by the general method already described (Abstr. 1897 ii 96) forms highly doubly-refracting crystals belonging to the monoclinic or to the orthorhombic system. 31. A. W. Fluorides and Oxides of Quinquevalent Bismuth. Omo RUFF [with &tAX I<WOCEI and ;JULIAN ZEDNEB] (Zeitsch. ccnorg. Chem. 1908 37 220-233. Compare Weinlsnd and Lavenstein Abstr.1899 ii 370).-Bismuth trifluoride does not combine directly with fluorine but traces of a higher fluoride appear t o be formed by the action of fluorine on bismuth trichloride at - 809 When “ bismuthic acid ” is added to concentrated hydroflnoric acid a colourless very unstable solution is obtained which appears t o contain mainly bismuth oxytrifluoride BiOF,. On evaporating this solution in a vacuum the oxyflooride suff wed partial decomposition ; on addition of potassium fluoride (1 mol.) befoie evaporation the con2pound (or mixture) Bi,04F?,3KF was obtained in small yellow crystals and with 3 mols. oi potassium fluoride the cornpoui~d BiO F 3K F in well-formed colourless prismatic crystals which become yellow and decompose rapidly in moist air. I n order to thyow light on the nature of ‘‘ bismuthic acid ” and “ alkali bisinuthates,” on the existence of which doubt has been thrown by Gutbier and Buuz (Abstr.1906 ii 174 234 551 678) the solution of the trioxyfluoride was decomposed by water and nitric acid and by alkali respectively and nearly pure bismuthic acid and sodium bismuthate isolated. I n order to obtain the latter a solution of the pentoxide in 60% hydrochloric acid was cooled to Oo and added drop hy drop to N-sodium hydroxide also at 0’; the yellow precipitate rapidly mashed and partially dried on n porous plate contained 95-9S% of its bismuth in the quinquevalent form and 1 mol. of &odium hydroxide. On further washing sodium bismuthate loses alkali and darkens in colour ; it does not lose much oxygen even on heating t o boiling when excess of alkali is present. From this bismuthate by treating with ice cold 15% nitric acid to neutral reaction and washing rapidly by decantation a reddish-brown precipitate containing up t o 93% of bismuth pentoxide is obtained.On treating the fresh pentoxide with 15% sodium hydroxide it slowly changes t o yellow bismuthate so that the statement of Gutbier and Biinz (loc. cit.) t h a t the higher oxides of bismuth have no acidic properties is incorrect. G. S.INORCANIC CHEMISTRY. 299 Physico-chemical Researches on the '' Explosive " Platinum Metals. ERNST COHEN and TH. STRENGERS (Zeitsch. physikal. Chem. 1908 61 698-752).-lt has been long known that some a t least of the inetals of the platinum group are explosive under certain conditions and the authors have set themselves the task of determining exactly the conditions utider which the phenomenon is observed and the cause to which i t is due.To prepare the '' explosive " metal the metal in the ordinary form is alloyed with a large excess of zinc and the alloy is treated with hydrochloric acid. The residue from this treatment explodes when heated in the case of rhodium iridium and ruthenium ; from palladium and osmium no explosive residues have been obtained ; the platinum residue is sometimes explosive sometimes not and the factors which determine this result have not been definitely ascertained. Explosive rhodium is obtained also when cadmium is used instead of zinc in its preparation. With zinc the rhodium appears to form a solid solution and it is not possible to extract all the zinc with hydrochloric acid.When the rhodium residue is kept a t 100" o r 200' for a few days i t is no longer explosive. It is shown that explosive rhodium contains hydrogen and oxygen and that when the utmost precautions are taken t o exclude air during the preparation of the residue the latter is not explosive. A similar remark applies to iridium. Ruthenium on the other hand yields ;tn explosive product ever1 when the grestest care has been taken to exclude air. When rhodium is alloyed with lead and the alloy is treated with nitric acid a residue is obtained con- t'aining oxides of nitrogen; this residue explodes when heated even although air is excluded. The amount of heat developed by the explosion of t h s '' explosive " rhodium is of the same order of magnitude as that calculated on the basis of the view that t h e explosion is due to the combination of hydrogen and oxygen which have been occluded i n the rhodium.This view in conjunction with the fact established by the author's experi- ments that rhodium becomes passive on contact with nitric acid gives a satisfactory explanation of all observations made by earlier workers. It is therefore unnecessary to suppose as Bunsen and Dehray did that the explosion affords evidence of an allotropic_change. It is possible however that this is the correct explanation in the case of ruthenium. J. C. P. The Oxidisability of Platinum CHARLES MARIE (Compt. vend. 1908 146 475-477).-When plates of platinum or platinum-iridium are placed in an alkaline solution of potassium permanganate at the ordinary temperature for twenty-four hours the metal becomes super- ficially oxidised for on treatment with a dilute solution of pot,assium iodide and hydrochloric acid they yield red soliitions containing platinum (Bbstr.1907 ii 698) from which the sulphide is precipitated by hydrogen sulphide. Similar results are obtained when the alkaline permanganate solution is replaced by a n acid solution of potassium persulphate dichromate chlorate or permanganate or by a n alkaline300 ABSTRACTS OF CHEMICAL PAPERS. solution of potassium ferricyanide or by warm concentrated nitric acid whilst an acid solution of ferric chloride or an acid or alkaline ~olution of hydrogen peroxide has no oxidising action on platinum. The total loss of weight of a platinum plate 5 cm.x 2.5 cm. after several treatments with a n oxidising solution amounts to 0.3 mg. and pure platinum is more readilF oxidised than platinum containing 20% of iridium. I t appears therefore that platinum is more readily oxidised a t the ordinary temperature than is usually admitted and the solubility of the oxide thus obtained makes i t an easy matter t o introduce traces of platinum i n chemical o r physico-chemical experiments in which platinum is employed. M. A. W. Freezing-point Diagrams of the Binary Systems Platinum- A r s e n i c and Bismuth-Arsenic. K. FHIEDRICII and A. LEROUX (,I/etrcZturyie 1908 5 14~-149).-Pl~tinum and arsenic form a eutectic containing 137; arsenic and solidifying a t 597'.By plotting the times of eutectic solidification the probable existence of a compound Pt,As is indicated but it is not possible to study the solidification of mixtures containing more than 28% arsenic. Rismuth and nrsetiic :ire only slightly miscible in the molten state and separate completely on solidific a t' 1011. C. H. D. Oxides of Iridium. IJoTIIAR WOHLER and W. WITZMANN (Zeitsch. m 0 ~ 3 . Chenz. 1908 57 323-352).-The methods of preparation and properties of the three oxides of iridium h,O Ir02 and Ir03 have been investigated syst~ematically. The oxide IrO also mentioned in tho literature does not seem to exist under ordinary conditions. Iridium dioxide Ir02 is best prepared by a modification OF Claus's method (1846) by the action of alkali on a hot solution of sodium iridichloride Na,IrC16 the sesquioxido first formed being oxidisetl to dioxide by passing a current of oxygen through t'he solution.The precipitated dioxide can be obtained practicdy pure by drying a t 400' in carbon dioxide and then boiling with alkali and subsequently with sulphuric acid. The solution obtained by the action of potassium hydroxide on sodium iridichloride in the cold ultim.ttely becomes violet in colour and contains the dioxide in colloidal solution ; after a time a violet modification of the dioxide separates. On boiling the violet solution becomes blue due probably to a n aggregation of tho colloidal particles ; the latter are positively charged. The blue and green solutions obtained by dissolving the dioxide in hydrochloric acid also contain the dioxide in colloidal solution.The colour of the dioxide depends greatly on the proportion of water present. When dried in a desiccator over sulphuric acid it contains approximately 2H,O! and is black; the water can only be driven off completely by heating a t 760'. The anhydrous dioxide is also black. The freshly-precipitated dioxide is much more soluble in acids and allralis than when dried. Iridium sesquioxide Ir203 is obtained in an impure form by mixing air-free hot solutions of sodium iridium sesquichloride dr2C16,6NaC1,24H:,0 and potassium hydroxide in a current of carbondioxide and evnporating to dryness. The residue is then heated to redness in a current of carbon dioxide and then further purified by boiling successively with sodium hydroxide and sulphuric acitl.f n the dry way as used by Claw (1546) the above method Fields only a mixture of iridium and the clioxitle. When heated above 4003 the s~squioxide decomposes into the dioxide and iridium a IittIe oxygen being liberated simultaneously. As in the case of the dioxide the properties of the sesquioxide depend on the proportion of water present. With hydrochloric acid it forms a colloidal so1 u t ion. Attempts to obtain the lower oxide IrO by decomposition of a corresponding double sulphite IrS0,,M2S0,,nH,0 with alkali were unsuccessful. The methods of preparation by fusing finely-divided iridium with potassium nitrate and alkali and with sodium peroxide as well as by the anodic oxidation of an alkaline solution of the dioxide yield products con- taining considerably less than the theoretical proportion of oxygen. Oxygen is also absorbed when the dioxide mixed with alkali is heated in oxygen but not in the amount required to form the trioxide. I n the absence of alkali the dioxide does not absorb oxygen from which the conclusion is drawn that a trioxide free from alkali is unstable and that the comparative stability in the presence of alkali depends on the adsorption of the trioxide by the alkali. Iridium trioxide Ir03 has not been obtained pure. G. S. Solid Solutions in the Dissociation of Iridium Oxides. I>oTHAR WijHLER and 'cv. WITZMANN (Zeitsch. Is'lektrochem. 1908 14 97-107).-The dissociation of iridium dioxide is studied in the same way as that of t'he oxides of co2per and palladium (8bstr. 1907 ii 33). Undecomposed iridium dioxide gives the highest dissociation pressures. At a constant temperature the dissociation pressure falls as oxygen is removed from the system but after about n quarter of the oxygen has been pumped out the pressure becomes independent of the composition of the solid ph-tse. There are no discontinuities in the curve connecting pressure and composition at the points corre- sponding with iridium sesquioxide and monoxide. The sesquioxide when heated gives higher pressures than the dioxide but they are not equilibrium pressures; the oxygen is reabsorbed slowly and the final pressure is the same as that observed when oxygen is removed from the dioxide. The author considers that the dioxide when heated decomposes into oxygen and the metal. The dioxide and the metal are mutually sduble to a limited extent YO t h a t after a certain amount of decomposition has occurred the solid consists of two saturated solutions and therefore gives a constant dissociation pressure. Iridium i j most rapidly oxidisecl to the dioxide by oxygen gas at 1070". The reaction 1rO2 = Ir + 0 absorbs about 5000 cals. one gram of iridium heated in oxygen a t 775' loses 0.33 mg. per hour and a t 10@Oo about 0.5 mg. per hour. The volatilo substance ii possibly a tetroxide which being endothermic decomposes on cooling depositing the oxide. T. E.

ISSN:0368-1769    

DOI:10.1039/CA9089405271

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

302 XRSTRACTS OF CHEMICAL PAI’EKY.; M i n e r a l o g i c a l Chcnni iitry Proximate Constituents of Coal. PETER P. BEDSOX (J. SOC. Chem. I92d. 1908 2’7 147-150. Conipare Abstr. 1900 ii 20; Anderson J. SOC. CI~en2. Ind. 1902 22 242).-A r6sumtl of the work of various authors on the action of solvents on difierent classes of ccals and on the proximate analysis of coal and a preliminary notice of a study of coals from the Busly seam Boitley County Durham. Pyridine dissolves 19.38% of the “hright coal” from this seam; a number of products are obtained by treating the residue from the pyricline extract with various solvents including a red crystalline substance m. p. 65” soluble in light petroleum and volatile with steam will be described later. The “ d a n t ” from the same seam resembles anthracite containing 9.92% of voltxtile matter and dis- solving in pyridirie only t o the exteut of less than 1%.The proximate analyses quoted for a number of gas coals agree in general with the resnlts obtained i n the gas works. Proximate analyses of four “ cannel ” coals and a n oil shale are given for Comparison. G Y. Polymorphous Substances. J. WEBEE (Zeitsch. Kryst. Mi?2. 1908 44 212-238).-The literature of the following pairs of dimor- phous minerals is recapitulated and some new observations confirin those of previous authors blende and wurtzite metacinnabarite and cinnabar senarmontite and valentinite. Several analyses of blende and of wurtzite were made to determine the ratio of zinc t o sulphur ; in blende there is a slight excess of sulphur (0.98-1*07%) over that required by the formula ZnX whilst i n wurtzite there is a deficiency of sulphur (0*21-1.59%).L. J. S. Change of State in Quartz at 570”. OTTO Mumm (Jcthb. JIi7&. 1907 Pestband 181-1 96).-When heated t o 570” quartz suddenly becomes more strongly circulai.ly polarising and birefringent and on cooling i t returns t o its original rondition. These two modifications of quartz are distinguished as a-quartz (stable below 570’) and p-quartz (stable above 570’) ;. both are tetartohedrnl-hexagonal but as indicated by etching experiments they probably represent different ty1)es of tetartoheclrisrn. I J. S. Formation of Dolomite and the Chemical Precipitation of Calcium Carbonate from Sea-water. E. PHrrmPI (Jcclwb. Xin. 1907 Pestband 397-445).-A general discussion of previous work (compare Abstr.1899 ii 306 ; 1904 ii 351 ; 1907 ii 480). L. J. S. Chemical Constitution of a North American Monazite Sand. G. P. TsCHERNrK (Bull. Acad. Sci. St. Petemburg 1908 243-254).- The sample from Carolina contained 7S.39./; of monazite the rest being chiefly quartz gdtr.net corundum zircon titmiferoiis iron mngnetite,c hromite and colurnbite of which the columbite garnet titaniferous iron and magnetite were analgsed and described fully. The monazite consists of more 01- less perfectly formed crystals with rounded edges of a dark co,)per-yellow colonr hut occasionally light yellow or green. Some of the crystals also show distinct signs of efllorescence and corrosion. The powdered normal dark yellow crystals are decomposed readily by a1 kalis a1 kaline carbonates acid sulphates and mineral acids.SiOl. CI,,O,,T,L~O,. %to,. I'29j. Tho,. Cp203. (Ln,Pr,Ntl),O,. \720j. 1 .GO 4 1 2 :J'25 2.3'18 1 - 2 2 4.5.40 6**-i6 2.07 JIiiO. Yf>,O,. FcO. Al,O,. Total. Anzl-ysii.; gave El Inca Meteoric Iron. FRITZ RIKNE and H. E. BOEKE (Jcdwb. M i ? z . 1907 Festbctnd 227-255).-This meteoric iron weighing 320 kilos was found in 1903 i n the nitrate works i n the Pampa de Tamwugal near Iquique in Chile. Analysis by Halbsch gave Fe. Xi CO. P. S. C. Cr. Sp. gr. The structure is octahedral and large nodules of troilite are present When the meteoric iron is heated for some hours to 1300" slight differences in the structure become apparent indicating that there has been a partial recrystailisation of the material while still in the solid condition. When iron sulphide and iron are fused together mixed crystals con- taining 93% FeS and 7"/;;Fe were obtained ; these undergo a change in state a t 138". 90'734 8200 0220 0.234 0.001 0,243 0.345 7'64 L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9089405302

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

Physiological Chemistry Gaseous Metabolism in Uramic Dogs. S. LA FRANCA (Biochenz. Zeitsch. 1908,8 180-1 98).-The gaseous metabolism and respiratory quotient was investigated i n dogs before and after removal of the kidneys or ligature of the ureters. The respiratory quotient rises immediately after the operation and this is probably due to reabsorption of urinary constituents; i t then falls nearly to the normal level and rises again with tbe onset of death. The quantities of oxygen absorbed and carbon dioxide given out increase after the operation and fall considerably when the animal is near death. Compiete analytical records of Lutneiwus experiments are given. W. 2>. H.304 .msrR.wrs OF CHEMICAL PAPERS. Increase in Osmotic Concentration of the Blood during AnEsthesia AN'roN J.CARLSOX and A. U. LucKmRwr (Amev-. J . PhysioZ 1908 21 168-1 6S).-Duriug chloroform and ether nnmthesia tlie osmotic concentration of the blood ri.jes. This varies with the depth but not with the duration of the anmthesia. The main factor in this is the ether or chloroform itself di4solved in the blood but there are other fastors diicussed a t length which cannot be altogether excluded. W. D. H. The Influence of Intestinal Ex tract on Blood-coagulation. F. CZUBALSKI (PfEiiger's Archiv 1908 121 395-403).-Exbracts of tlie intestine intravascularly injected produce the same effect in delaying the coagulation of the blood as is produced by injecbion of Witte's peptone. It is probable that the active substance is not peculiar to the intestine but can be also obtained from other tissues for inahance the brain.W. D. H. Relative Hamolytic Power of Serum and Lymph under Various Conditions of Lymph Formation. W. T. HUGHES and ANTOX J. CARLSON (d~ner. J. Physiot. 19OS 21 236-847).-The concentration of hzinolysins for rabbits' corpuscles in the norinal body-fluids of dog cat and horse exhibits the following descending series serum lymph from thoracic duct neck lymph lymph from limbs thyroid and salivary glands pericardial fluid aqueous humor The cerebro-spinal fluid contains none. The large retro-pharyngedl lymph glands do not influence the htemolytic power of the lymph which passes through them. Immunisation against typhoid baciUi increases the hzemolytic power of the serum and lymph of the dog. Lymphagogues (peptone salt sugar) may increase the 1rEmolytic properties of lymph from the thoracic duct but not of that from the neck.This may be accompanied by loss of such power in the serum. The action of peptone on serum i s probably due to its action on the liver ; this organ probably produces antilysins. Alkalescence and Acidosis of the Blood. Part 11. On the Influence of Alkalis on the Alkalescence of Normal Blood and of Blood in Cases of Endogenous Acidosis. ANASTAZY LANDAU (A7.d. exp. Puth. Plmm. 1908 58 207-220).-The analyses were performed by the methods described in the first comniunication (Abstr. 1905 ii 330). Experiments were c.trried out to determine the in- fluence of sodium carbonate (both subcutaneous and per 0s) on the alkalinity of tho blood both in normal animals and in animals with experiinentnl acidosis.The latter condition was produced by two methods starvation and phosphorus poisoning. In the cme of nornlal animals (rabbits) both mineral and organic alkalinity of the blood plasma is increased; this increase is however of short duration and rapidly comes to a n end through the excretiou of the excess of alkali by the kidneys. The alkalinity of the whole blood is not increased in spite of the increased alkalinity of the pla.ima; this is due to hydrmnia and since norm illy the blood corpuscles contain lnrger quantities of alkali than the plasma the diminished number in a given volume tends t o W. D. H.PHYSI OT,OG ICAL CHEMISTRY. 305 counteract the increased alkalinity due to the plasma. I n the case of starving animals the effect of alkali is to diminish the acidity due to starvation; on the other hand in animals poisoned by phosphorus there is no tendency to increased alkalinity from the injection of sodium carbonate.The difference between the two cases is due to the funda- mental difference in the methods of acid production. I n starving animals the acid production is limited and is due entirely t o the break- down of the fats and proteins to meet the energy needs of the organism ; as soon as these needs have been met the acid production ceases and the acids can be neutralised by the increased alkali in the blood. I n the case of phosphorus poisoning the acid production goes on continu- ally; the alkali is excreted by the kidneys before i t is able to reach the cells where the acid is produced ; the urine is consequently alkaline and the acid products subsequently reach the blood.The alkali can in this case have only a very temporary effect in diminishing the acidity and for this reason the injection in cases of diabetic coma is often without result-a toxic acidosis is being dealt with. s. B. s. Proteoses in Blood E m L ABDERHALDEN (Biochem. Zeitsch. 1908 8 360-375).-Polemical against Freund (this vol. ii 117). His methods and the conclusion that proteoses exist in normal blood- plasma are criticised. GEORGE SENTER (Proc. physiol. SOC. 1907 xxxiii-xxxv ;* J. Physiol. 36).-The guaiiicum reaction is obtained from boiled blood although it is not so intense as that given by fresh blood. It is probable that there is a substance of non-enzymatic nature in blood responsible for the reaction; i t is certainly greater than that which could be produced by the liberation of chlorine from its sodium chloride.W. D. H. W. D. H. Guaiacum Reaction of Blood. Isotonic and Isosmotic Solutions. YVES DELAGE (Compt. rend. 1908 146 319-321).-Comparison of the author’s results on parthenogenesis in Echinoderms wihh those of Loeb. The author accepts Loeb’s explanation horn if a saline and a sucrose solution are isotonic and the saline solution is ibosmotic with an egg the sucrose solution is not ; this is due to sucrose diffu.ing more slowly through the egg-membrane than the s d t s which the eggcmtains. - G. B. The Work of Digestion. ERNST HEILNER (Zeitd. Biol. 1908 50 488-503).-.The author reaffirms his original contention that digestive work in Zuntz’s sense does not exist or rather that the increase of work in the digestive organs during digestion is so small as to be negligible in the study of general metabolism.Rubner’s ‘‘ specific dynamic action ” of foud-stuffs is on the other hmd the important factor. W. D. H. Action of the Amylase of Pancreatic Juice and it8 Activation by Gastric Juice. H. BIERRY (Conapt. rend. 1908 146 417-419).-The alkalinity of pancrea-tic juice obtained by a VOL. XCIV. ii. 21306 ABSTRACTS OF CHEMICAL PAPERS. temporary fistula and injection of secretin is equivalent to N/8 sodium carbonate (helianthin as indicator). Pancreatic juice hydrolyses starch t o maltose but onIy very slowly to dextrose unless the juice is partially neutralised.The best yield of dextrose is obhined by reducing the alkalinity to one-fifth of the original. The action of gastric juice in accelerating the production of dextrose by pancreatic juice is wholly due to t,he hydrochloric acid and occurs normally in digestion when the acid contents of the stomach passing through the pylorus partially neutralise the pancreatic juice. Metabolism of Calcium Magnesium and Phosphorus during Inanition. 0. WELLNANN (PJiigeq.’s Archiv 1908 121 508-533). -Proofs are adduced that some of the calcium magnesium and phosphorus which leave the body during inanition come from the bones I n rabbits the bones lose about 14% of their weight and more than half of this falls on the fat. G. B. W. D. H. Parenteral Utilisation of Carbohydrates.LAFAYETTE B. MENDEL (Proc. Amer. physiol. Soc. 1907-8 xii-xiii ; Amer. J. Physiol. 21).-If sucrose is introduced parenterally over 90% reappears in the urine. Starch similarly administered appears only i n p w t in the urine as dextrin-like substances. The retention is greatest after subcutaneous injection less after intraperitoneal and least after intravenous injection. Tissue amylases are doubtless concerned in the utilisation of the carbohydrate. Moscati claimed to have found complete utilisation but this was not confirmed. W. D. H. Influence of Carbohydrates on Protein Metabolism. JOHN R. MARLIN (PYOC. Arne?.. physiol. sbc. 1907.43 xxi-xxii ; Amer. J. Physiol. 21).-Sucrose added t o the diet of a well-nourished dog produced no change in the total urinary nitrogen.I n emaciated or pregnant dogs it caused a marked reduction of the nitrogen excreted. I n the f a t dog the ammonia eliminated was much increased and in all cases the crestinino output was raised. I n pregnant animals creatine also passed into the urine on the days on which sugar mas given. W. D. H. Feeding and Other Experiment8 on Dogs with an Eck Fistula. PHILIP B. HAWK (Anzer. J. PhysioZ. 1908 21 959-281). -After an Eck’s fistula has been made a diet rich in meat may cause toxic symptoms ; these however are frequently absent and may then be induced by giving Liebig’s extract. The symptoms include anzsthesia ataxia catalepsy tetanus and loss of sight and hearing ; there is usually a fatal termination. If the diet is meat-free no toxic signs result even if Liebig’s extract is given.Sodium csrbamate produces no poisonous effects The animals waste after the operation but glycosuria and albuminuria are absent. Composition and Energy-Value of the Food of the Soldier. MARCUS S. PEMBREY and L. E. L. PARKER (PTOC. physid. Soc. 1908 xlix-1; J. Physiol. 36).-The tables given show that the minimum W. D. H.PHYSIOLOGICAL CHEMISTRY. 307 diet of the British soldier is above 100 grams of protein 100 grams of fat and 400 grams of carbohydrate and possesses nu energy value of about 3000 Calories. W. D. H. Importance of Glutamic and Aspartic Acids as Food- stuffs. KARL AKDRL~K and K. VELICH (Zeitsch. Zuckwisad. Bohna 1908 32 313-348).-The subject is of importance in connexion with the food-value of (beet) molasses now extensively used as food for cattle.Molasses contain 1.5-2% of nitrogen which is distributed as follows proteins and peptones lo% betaine 35-40% ainino- acids 40% purine bases 5-7%. For betaine i t has already been shown (Abstr. 1903 ii 228; 1905 ii 266) that it is completely absorbed by fierbivora; in carnivora some passes into the urine. For the present research a sheep which mas approximately in nitrogenous equilibrium was given daily 20 grams of glutamic OF aspartic acid as the sodium salt; 96% of the former and 98% of the latter acid was absorbed. A portion of the psrt absorbed (modi in the case of the aspartic acid) mas used up in protein synthesis; the rest was oxidised to urea but no acid appeared as such in the urine. The faxes contained protein 92-94% of which was not digestible by pepsin.G. B. Composition of Human Brain at Different Ages. WALDEMAI~ KOCH and SIDNEY A. MANN (Proc. physiol. Soc. 1907 xxxvi-xxxviii ; J. Physiol. 36).-Three brains were examined one at the age of six weeks one a t two years and the third at nineteen years. With the growth of the brain a decrease in moisture proteins extractives and ash occurs whilst there is an increase in cerebrins lipoid sulphur and cholesterol that is of substances which predominate i n the white matter W. D. H. The Smallest Molecule from which the Liver can make Glycogen. KARL GRUBE (Zyiiger’s A d & 1008 121 636-640).- By perfusion of the tortoise’s liver with a weak (O*Ol-O*OZ%) solution of formaldehyde it was found that the liver was able to form glycogen from it.w. n. H. The Capacity of the Liver to Reverse the Optical Action of Sugars. EDUARD PFLUGER (PJZiiger’s Archiv 1908 121 559-571). -The administration of Izvulose leads to the formation of glycogen in the liver but the glycogen formed is not laworotatory ; the liver cells have therefore the power to transform the sugar given into dextrose and it is this from which the glycogen is formed. W. D. H. Changes in Uric Acid in Animals and Men. ALFRED C. CROFTAN (Pjuyer’s Archiv 19OS 121 377-394).-Uric acid was mixed with minced organs and tissues or their extracts and the loss in the amount of uric acid estimated; the human liver has greater power in this direction than the livers of other animals; the same is true for the kidneys; the muscles however surpass all other tissues in this power.The power of the human spleen on the other hand i s 21-2308 ABSTRACTS OF CHEMICAL PAPERS. relatively small and that of the blood almost negligible. Neither nucleo-protein nor a proteoee separated from the extracts destroys uric acid but a mixture of the two does so. The proteose does not decompose hydrogen peroxide. As to what happens to the uric acid nothing very definite was discorered; a small increase in urea and oxalic acid was noticed but little or no formation of allantoin. W. D. H. The Influence of Colloids on Ferments. LUDWIG PINCUSSOIIN (Biochenz. Zeitsch. 19OS 8 387-398).-Ascoli and Izar (this vol. ii 121) have shown that small quantities of colloidal silver gold and platinum have a distinct action in increasing the rate of action of the autolytic enzyme of the liver.Experiments were made to determine the influence of colloids on pepsin digestion. I n no case was the rate of action increased. S. B. S. Leucomaines of Cod-liver Oil. PHJLIP B. HAWK (PTOC. Atner. physiol. Soc. 1907-8 xxii-xxiii ; Amel.. J . Yhysiol. 21).- The total amount of leucomaines isolated by the method of Gautier and Monrgues from oils of different t i n t varied from 1-06 to 1-11 grams per kilogram of cod-liver oil. By fractional distillation but’ylamine amylamine hexylamine and dihydrolutidine mere separa- ted. From the non-volatile portion morrhuine was identified but not the aselIine of Gautier and Mourgues. Refractory Period of the Frog’B Sartorius. H. C. BAZETT (J. Physiol. 1908 30,414-430).-The refractory period is lengthened by fatigue injury or normal saline solution.A lowering of tem- perature acts in the same way and the lengthening obeys Arrhenius’ lam of the velocity of chemical reactions. Potassium salts lengthen and calcium salts shorten the refractory period. Chloral hydrate after a short initial effect in lessening it increases the length of the period. W. D. H. Relative Resistance of Cardiac Muscle and Nerve to Drugs. WALTER J. MEEK ( Anzer. J. Physiol. 1908 21 230-235). -Alkaloids anqthetics and other chemical substances produce paralysis of the Linzzchs heart tissues in the following order; (1) ganglion (2) motor nerve plexus and (3) muscle. EDWARD MELLANBY (J. Physiol. 1908 36 447-487).-Among the many contradictory statements relating t o the proportion of creatine to creatinine in muscle that of Monari who says that the latter increases a t the expense of the former when muscle becomes active has usually been regarded as most trustworthy. It is now shown that Monari’s technique afforded a n opportunity for the change t o occur and moreover his precipitates were impure; and it is shown that creatiniue is never present in muscle at all even after prolonged muscular work ; the original amount of creatine remains unaltered after work and also in frog’s muscle after survival for three days.When the muscle becomes mptic all the creutine disappears Aseptic or antiseptic autolysis causes no change in creatine or TV. D. H. W. D. H. Creatine and Creatinine.PHYSIOJ,OGTCAL CHEMISTRY. 309 crentinine.Gottlieb and Stangassinger’s statements (Abstr. 1907 ii 637) regarding numerous tissue enzymes which affect these substances were in no single respect confirmed. Creatine and creatinine feeding has no effect on the creatine of muscle after the muscle has reached a certain saturation point. I n one set of chickens only the muscular creatine was slightly increased by glycocyamine feeding but this is not universal. I n early life also creatine feeding and possibly creatinine feeding increase the muscular creatine but the normal differences in chickens are unknown and this factor has to be eliminated before the fact can be established. Creatinine feeding leaves the muscles still free from that substance. Before the twelfth day of incubation in the chick creatine is absent from the muscles; after this date the liver and the muscular creatine develop pnri pccssu.After hatching the liver still continues to grow rapidly creatine formation increases also but muscular gromth is slow. Invertebrate musde even when striated does not contain creatine. The invertebrate ‘‘ gIand of the mid-gut ” has no morphological o r physiological connexion with the vertebrate liver. The sinall amount of creatinine excreted in hepatic disease gives support to the view that the liver is responsible for the formation of creatinine. The excretion of creatine in cancer of the liver makes it probable that where muscle cells break down creatine is liberated without conversion into creatinine before excretion. Creatinine after the earlier period of life is an excretion product of metabolism; creatine has no influence on muscular contraction or on the passage of nervous impulses into muscle.Tho general conclusion reached is that the liver is continuously forming creatinine from substances carried to i t by the blood from other organs and that in the developing muscle this is changed to creatine and then when the muscle is saturated with creatine creatinine is continuously excreted. If creatine (an innocuous neutral substance) was converted by the muscles into creatinine (a strongly basic substance) it would be contrary to all that is known of the chemical changes which occur in the body. W. D. H. Chemical Processes in the Earth-Worm. EI~NST J. LESSER. The Ferments of the Earth-Worm. ERNST J. LEESE~~ and ERNST TN.TASCHENBERG (Zeitsch. Biol. 1908 50 42 1-445 446 -455).-During inanition the respiratory quotient of the earth- worm sinks. I n the early stages fat and glycogen are used up but later as glycogen disappears its decomposition is relatively small. The output of nitrogen remains constant between 2 and 4 mg. per fifteen animals per day. Products of incomplete carbohydrate break- clown are not contained in the excretions. Ammonia is present which is not the case in Ascaris and the leech. The hydrolysing ferments present are those which act on protein starch and glycogen also invertase and lipase. Catalase and alde- hyd ise (2) are present. Lactase inulinase cytase tyrosinase and a ferment mhicb renders guaiacum blue are absent. W. D. a,310 ABSTRACTS OF CHEMICAL PAPERS.The Organic Substance of the Skeletal Tissues of Anthozoa. 11. CARL TII. MORNEK. (Zeitsch. phgsiol. Che~n 1908 55 77-83).- The previous work (Abstr. 1907 ii 2S3) was undertaken with the skeletal tissue of the Govgonacea. The investigations have now been extended t o the Pennatulacea the Alcyonacea and the A~ztipathidea. The following general results have been arrived at. I n all cases the halogens are in organic Combination ; iodine is present in all cases (from traces up to 7%) also bromine (in quantities of 0.25 to 4%) with the exception of two Antipathiden and chlorine (generally only about 0.2%)). The variations are independent of climate composition of sea-water age ckc. and also of the physical properties of the skeletal substance. The organic substance of the PennatuZacea?z skeleton provisionally called Penszatulin differs from that of the other Anthozoa by i t s solubility in pepsin-hydrochloric acid.The amount of sulphur in the skeletons of allcmembers of the group is so low that the organic substance cannot be regarded as a keratin. It is probable that halogens are far more widely distributed in the tissues of marine organisms than has hitherto been considered probable. S. B. S. The R61e of Calcium Salts in the Mechanical Inhibition of the Ctenophore Swimming-plate. RALPH 8. LILLIE (Amer. J . Phpiol. 1908 21 200-220).-RIechanical stimulation arrests the activity of the swimming-plate ; this susceptibility is dependent on the presence of calcium salts. Strontium and barium cannot take the place of calcium.The essential action of the calcium consists in decreasing the permeability of the contractile tissue to ions. Mechanical stimulation favours the entrance of calcium ions into the fibrils. W D. H. The N i t r i t e s of the Saliva and their Origin. JULES VILLE and W MESTREZAT (BUZZ. SOC. chim. 1908 [iv] 3 212-217).- Schijnbein observed in 1862 that saliva contains nitrites as shown by its action when acidified on potassium iodide and starch. The authors show ttiat saliva when obtained pure by the catheterisation of the ducts of the parotid and sub-maxillary glands does not contain nitrites ; i t does however contain nitrates in quantities varying from 10-300 mg. per litre in different individuals. The quantities increase considerably after ingestion of nitrates in the food.The nitrites in the saliva are stated to be due to the reducing action of R certain species of bacteria on the nitrates in the buccal cavity. These bacteria when inoculated in Winogradski’s medium containing nitrates (0.1 gram per litre) can reduce as much as 50% in twenty-four hours. S. B. S. Action of Lymphagogues on the Concentration of Agglutinins in S e r u m and Lymph. B. BRAUDE and ANTON J. CARLSON (Amer. J. Physiol. 1908 21 221-229).-Xerum thoracic lymph neck lymph and pericardial fluid of dogs contain agglutinins for typhoid bacilli. Aqueous humor and cmebro-spinal fluid contain no agglutinin. The agglutinating action runs parallel to the hsemolytic power of tbe fluids. I n cats on tbe The order named is the order of activity.PHYS IOLOCTI C A T C H EM I ST RT .311. other hand agglutinins are usually nbsetit from all the fluids but aftel* immunisation against the typhoid bacillus the fluid-; have an agglutinating action ancl the relative concentration in the different fluids is the same as in dogs. Lymphagogues (strawberry-extract 10% peptone 10% sucyose 574 sodium chloride) have no effect on the concentration of agglutinins. W. D. H. Behaviour of Rennet and Acid tr> Human Milk. ERNST FULD ancl JULIUS WOHLGENUTH (Biochem. Zeitsch. 1908 8 376-377. Compare Abstr. 1907 ii 797).-The authors disagree with Bienen- feld’s conclusion (this vol. ii 121) that human milk cannot be curdled by rennet on several grounds one of which is that if the amount of calcium chloride in the milk is increased curdling occurs in the usual way.W. D. H Excretion of S u g a r i n Healthy Men and the Estimation of S m a l l Q u a n t i t i e s of Sugar in Urine. BERNIIARD SCH~NDORFF (PJZiiger’s Archiv 1908 121 572-603).-Using large quantities of urine it is possible to detect sugar in many healthy people by the Worm-Miiiler reaction and even if this test is negative i t is still possible in many cases by concentrating the acidified filtrate after precipitation by mercuric nitrate ; the sugar can then be estimated by the Fehling-Soxhlet method. Quantities varying from 0.005% upwards can be detected. I n the urines of over three hundred soldiers 95% con- tained sugar and in few cases as much was found as in diabetes. This is attributed to diet; in civilians who did not take so milch carbo- hydrate 85% secreted a sugar-free urine.The sugar was identified as dextrose by means of its osazone W. D. H. Metabolism in a Case of Coma under Rectal Feeding. P. P. LAIDLAW and JOHN H. RYFFEL (Proc. physiol. Xoc. 1908 xlvii-xlix ; J. Physiol. 36).-Details are given of the composition of urine and faxes of a man in a state of coma who was fed peq* rectum. The nitrogen excretion is low and roughly equal to that obtained in the later stages of fasting. Uro- rosein was present; this disappeared on the resumption of mouth feeding. The absence of stercobilin in the faxes suggests that a prolonged stay of bile pigments in the intestine is favourable to the production of urorosein. Zawidzky obtained a substance apparently identical with urorosein by oxidising pure urobilin.Creatine was absent from the urine. W. D. H. Action of Therapeutic Agents on the Gastric Secretion. 111. Action of Iodine in the Promotion of Secretory Activity. JOHANN FEIGL (Bioclzem. Zeitsch. 1908 8 667-5 19).-Experiments were made to determine the rate of secretion of gastric juice in dogs with a Pawloff fistula after the ingestion of iodine and various iodine compounds. Water was first administered and the gastric juice collected and measured the quantity excreted in each half-hour being noted. As soon as the excretion had stopped the same quantity of water containing iodine or the iodine compound was administered and the amounts of secretion measured a t half-hourly intervals. The312 ABSTRACTS OF CHEBIICAL PAPERS. administration of iodine and iodides caused conqiderable increase in the amount of secretion ; iodine itself mas particularly powerful ; 200 O.C.of water caused a secretion of 4.8 C.C. of gastric juice the secretion of which ceased after two hours ; the same quantity of water containing 0.05 gram of iodine caused a secretion of 22.5 C.C. of juice which ceased t o be secreted only after four hours. Potassium iodate had also a powerful action. Experiments were also made with iodised fats and proteins. The f a t derivatives acted in varying ways some acting like the iodides others having but little action. As a general result it mas found that the iodine compound in all cases when ions could be formed caused considerable secretory activity. S. B. 8. Biochemistry of Colloids. JOHANN FEECL and ADOLF ROLLET (Biochem.Zeitsch. 1908,8 145-1 79).-Vttrious colloid prepa.rations of metals and metallic compounds prepared chiefly by Paal's method such as the commercial preparations collargol lysargin (silver colloid) hygrol (mercury colloid) &c. were administered t o a dog with a Pawloff gastric fistula. In all cases there was a considerably increased secretion of gastric juice as compared with t h a t obtained by the administration of the same quantity of water without t h e colloid. The colloidal condition has some specific action therefore of promoting gastric secretion which is not possessed by the metals when administered in the form of ordinary ionisable salts. S. B. S. Antagonistic Act,ion of Calcium and Magnesium SAMUEL J. MELTZER and JOHN AUER (Proc.Amer. pl~ysiol. Soc. 1907-8 x i ; Arnev. J. Physiol 21).-The paralysls and anasthesia prodnced in an animal by the injection of a magnesium salt disappear about one minute after the injection of a calcium salt. I n plant life also the cure for too much magnesium in the soil is '' liming." W. D. H. Action of Hydrocyanic Acid on Protein Katabolism. ADOLF LOEWY CHARLES G. L. WOLF and EMIL OSTERBERG (Biochem. Zeitsch. 1908 8 132-144).-Three experiments on dogs which were given respectively small medium and large doses of hydrocyanic acid are described. I n all there was a rise of nitrogenous katabolism ; the amount of urea is also increased so that the proportion of urea t o total nitrogen does not sink. The ammonia excretion is very slightly lessened ; the amount of urinary creatinine sinks markedly but creatine appears also in the urine ; the residual nitrogen is increased.The relation of sulphates to total sulphur is lessened and the total phosphorus rises. W. I>. H. Action of Benzidine on the Animal Body. OSCAR ADLER (Arch. exp. Path. Pharm.. 1908 58 167-1 97).-Symptoms of intoxi- cation are produced in a dog by doses of 1 t o 3 grams of benzidine as such. or as a salt suspended or dissolved in water or alcohol ; they are the same whether the drug is given by stomach-tube or by subcutaneous injection. Vornit'iug first hets in followed by symptoms indicating excessive excitement of the motor centres and analogous $0 those produced by cocaine poisolring. A ootidition of fatigue andPHPSIOLOGTCAT CHEMTSTRT'. 31 3 somnolency follows and the animal dies generally after a period of several days ; recovery is however possible.These symptoms were accompanied by gl ycosuria and in the case of rabbits blood-corpuscles appeared in the urine containing a changed blood-pigment which is insoluble in water and in the case both of rabbits and dogs an abnorrrial urinary pigment mas formed. Very little if any unchanged benzidine is recovered in the urine but a substance has been isolated melting between 130' and 138' of the formula C,,H,(OH),(NH,) which is presumably 4 4'-diaminodihydroxydiphenyl. s. B. s. Purgative Action of Phenolphthalein and of its Disodium Derivative. C. FLEIG (Compt. rend. 1908 146 367-370).-The action which is much more marked on man than on animals is due to increased secretion and not to incressed peristalsis.The disodium derivative is soluble in water and is more active than the parent substance ; it can be given hypodermically. G. B. Effect of Strychnina on Muscular Work. P. C. VAERIER-JONES (J. Physiol. 1908 36 435-446),-Ergographic experiments on man show that small doses of strychnine produce a n immediate increase in the power to do work especially if the drug is taken early in the day. A fall then follows and the capRcity remains subnormal for hours. The effect of successive doses is cumulative. It is suggested that the effects are produced by a diminution of the resistance of the spinal cord to the entry of sensory impulses and the after effect may be due either to Bhe-poisonous a-ction-of the drug or to pure fatigue.W. D. H. Chemistry of the Infundibular Portion of the Pituitary Body. THOMAS B. ALDRICH (Proc. Amer. physiol. Soc. 1907-8 xxiii-xxiv ; Bsmer. J. PTLYs~oZ. 21).-A crystalline picrate of the substance which raises blood-pressure was prepared from the extract of the infundibulum which had previously been freed from protein. The sulphate was prepared from the picrate. Both these salts raise blood-pressure. Platinum cliloride also gives a double salt. W. D. H. The Sensory Nerves of the Heart and Vessels as a Factor in Determining the Action of Drugs. D. E. JACKSON and SAMUEL A. MATTHEWS (Amer. J. Plzysiol. 1908 21 255-258).- The fall of blood-pressure in e ~ l y stages of aconitine poisoning is too great to be accounted for by the cardiac weakness and the vaso- motor nerves respond well on stimulation. Some experiments recorded seem to confirm the suggestion that the alkaloid acts on the termina- tions of the depressor nerve and there are indicatiocs that other sensory nerve-endings may be affected. W. D. H. The Action of Cobra Venom in Destroying Complement. JULIUS MOILGENROTH and R. KAYA (Biochenz. Zeitsch. 1908 8 378-382).-The disappearance of complement from serum under the influence of snake poison is due either t o the action of a ferment in31 4 SBSTRAC'TS OF CHRMICAT PAPERS. the latter which destroys the former or to a combination between the amboceptor of the venom arid the coniplement of the serum t o forni an inactive compound. W. D. II.

ISSN:0368-1769    

DOI:10.1039/CA9089405303

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

305 Organic Chemistry. 8 tructural Changes in Organic Chemistry. MARC TIFFENEAU (Chem. Zentr. 1908 i 112-113; from Keu. g%n. Sci. pur. appZ. 1907 18 583-594).-A theoretical paper dealing with the changes in the ‘‘ carbon skeleton ” through the wandering of a carbon radicle. Such structural transformations are divided into two groups as taking place in a stable or in an unstable molecule. I n the first group are placed those changes which involve the formation of a more stable molecule; for instance the change of a carbylamine into a primary amine. The second group is considered to be due to the setting free of valencies caused by the interaction of one or more elements in the molecule ; the freed valencies only being satisfied through a molecular rearrangement. This last group is subdivided into two classes (a) carbon wandering owing to the setting free of two valencies on the same element ; an example being the change of diphenylchloroethylene into tolane and the Beckmann intramolecular change.( b ) Carbon wandering due to the setting free of two valencies on two neighbouring or distant elements ; for instance the pinacolin transformation and t’he Auwers transformation. The author points out that the wandering OF an aryl radicle only takes place when the compound contains an OH group attached to the same carbon atom as the wandering group which is not split off during the change R.CPh(OH)*CHI*R’ - HI = R*CO*CHPh*R. I 4 J. V. E. Applications of Grign ard‘s Reaction. ALEXANDER MCKENZIE (Brit. Assoc. Report 1907 77 273-298).-A detailed account of the reactions to which Grignard’s reagent is applicable and of the theoretical considerations underlying these reactions.T. H. P. Boiling Point of isoButane. WILLIAM A. NOYES (J. Amer. Chem. h‘uc. 1908 30 142-143) .-isoEutane prepared by the reduction of isobutyl iodide with zinc and dilute alcohol has b. p. - 11*5°/760 mm. !rhe hydrocarbon (b. p. 0”) obtained by Mabery from American petroleum (Abstr. 1897 i 389) and regarded by him as isobutane was not this substance but probably n-butane. E. G. Relative Volatility of Certain Groups of Mixed Carbon Compounds. LOUIS HENRY (Bull. Acad. voy. Bdg 1907 842-855. Compare Abstr. 1907 i 1102).-The boiling points of series of &substituted ethane compounds represented by the general formuls CH,R*CH,R CH,R*CH,R and CH,R’*CH,R’ are compared.I n certain cases the boiling point of the mixed compound is the arithmetic mean of the boiling points of the corresponding simple compoundg. This is the case whm R and R’ represent chlorine and VOL. XCIV. i. Y306 ABSTRACTS OF CHEMICAL PAPERS. bromine fatty acid radicles of similar structure isomeric fatty acid radicles methoxy - and e thoxy-groups or bromine and the ethoxy -group. The boiling point of the mixed compound is higher than the mean of the boiling points of the simple compounds when R and R' represent the hydroxyl and amino-group or chlorine and the acetyl group. Finally the boiling point of the mixed compound is lower than the mean of the boiling points of the simple compounds when R and R' represent bromine and hydroxyl hydroxyl and ethoxyl or ethoxyl and the amino-group.The differences between the three groups of comparable compounds are attributed to the circumstance that certain substituting groups do not appreciably alter the degree of association in the liquid state whilst other groups exert a marked effect the extent of the influence varying considerably from one substituting group to another. H. &!I. D. Chloroform and Acetone. DAVID B. DOTT (J. Xoc. Chem. I d 1908 27 6 271).-The formation of chloroform from ethyl alcohol is shown t o be best indicated by 3C2H,0 + 8Ca(OCl) = 2CHC1 + 3CaC0 + CO + 8H,O + 5C!aC1 and the equation generally given for the formation of chloroform from acetone 2CO(CHI,) + 3CaOC1 = BCHCI + (CH,*CO,),Ca + 2Ca(OH) agrees well with results found.The observation of Finnemore and Wade (Trans. 1904 86 938) that R small proportion of ethyl chloride is formed in preparing chloroform from ethyl alcohol is confirmed. When purifying acetone it is advisable to avoid treatment with mineral acids or other methods likely to cause formation of condensation products such as mesityl oxide phorone or mesitylene which although shown by about 7% distilling above 5So do not affect the iodoform or other methods of estimation. A rise of temperature 11.7' is observed when two molecular proportions of chloroform are mixed with one molecular proportion of acetone and the resulting mixture distils for the most part abo1.e the b. p. of either constituent. Oxidation of Ethyl Propyl isoButy1 and Amy1 Alcohol by a Contact Process.E. I. OXLOFP (.I. 12uss. Phys. Chem. Xoc. 1908 40 203-215. Compare this vol. i '77).-A stream of dry air is saturated with the vapour of the given alcohol and then passed through a heated tube containing freshly-reduced copper gauze. As in the case of methyl alcohol c2.c1/2r2 is a constant and for ethyl alcohol = 0.0003-0*00024 ; for isobutyl alcohol = 0,0004-0.00045 ; for nmyl alcohol = 0*0005-0.00048 ; for propyl alcohol = 0*00107. The pro- ducts of oxidation are carbon mon- and di-oxides both saturated and unsaturated hydrocarbons aldehydes (chiefly) and very small quantities of acids and ketones. I n the case of propyl alcohol when the conditions are such that the copper is heated without the application of external energy an almost exactly theoretical quantity of air is needed for the oxidation but with ethyl isobutyl and amyl alcohols a n excess of air must be employed.When however in all these cases the concentration of the alcohol is near the theoretical there is no spontaneous rise in the temperature of the copper; this J. IT. E.ORGANIC CHEMISTRY. 307 being due to the fact that side by side with the exothermic reaction of oxidation there is also an endothermic reaction of decomposition (very slight in the case of propyl alcohol) of the alcohol into water and unsaturated hydrocarbons and in order t o maintain the exothermic character of the reaction it is necessary to have an excess of air which oxidises the carbon monoxide with development of heat. Detailed tables of the products obtained for each of the alcohols are given.z. K. Action of Organo-magnesium Haloids on Ethylidene- acetone. A. GRY (Bull. Xoc. chirn. 1908 [iv] 3 377-381).-This work was undertaken with the view of synthesising and investigating tertiary alcohols containing an ethylenic linking. The results have 'been in part anticipated by those of Kohler (Abstr. 1907 i lOSO) but t h e latter author by using excess of the Grignard reagent obtained as the principal products the corresponding saturated ketones whereas when the quantities of ethylideneacetone and organo- imagnesium haloid used are equilnolecular the principal product is the corresponding tertiary olefinic alcohol. These alcohols undergo dehydration when treated with the ordinary acetylating reagents and l;he hydrocarbons described below were obtained in this way.These itre colourless resemble light petroleum in odour and give precipi- tates with aqueous solutions of mercuric chloride. Dimetliylisoallylcarbinol CH Rle CH C Me,*OH b. p. 7 9 - SO3/ 145 mm. Do 0.8154 D'! 0.8347 YL 1.4302 obtained by the action of magnesium methyl iodide on ethylideneacetone is a. colourless mobile liquid (compare Pawlowsky Abstr. 1872 1093) and on dehydration yields a hydrocarbon which may be identicdl with Ipatieff's trimethylallene CHRle:C:CMe,. &Methyi?-A~-hexene-S-oZ (met hy Ze t h y Zisoul Z y Zca r b inoZ) C H Me C H C $1 e E t 0 H b . p . 7 2 - 7 so/ 60 mm. DO 0.8471 Dt2'5 0.8360 ng5 1.4268 is a colourless liquid with a pleasant fruity odour. On dehydration it yields a diethylanic hydrocarbon b.p. 107-1093 which may have the formula CEl Me C CMe- C2H5 (meth y liso butyliso taZZyZcarbiwoZ) UHh!te:CH*CMe(OH)*CH2*CHMe2 b. p. 68-69'/ 117 mm. DO 0.13105 0.8281 n 1.4285 similarly obtained is a pleasant- smelling liquid. 8y-DimethyZ-A~-octene-6-ol (7netr'LyZiso~~~yliso- cdl ytccwbinol) CHNe CH* C Me(0 H)*CH,*C H,* CHMe b. p. S7-SS0/ :18 mm. (decomp.) Do 0.8443 D:"'" 0.8330 n 1.4368 is a liquid of insipidly sweet odour. a[- Dimethyl-As-heptene-8-01 T. A. H. Action of Alkalis on Alkylene Glycol-chlorohydrin Ethers. Compare Houben and A reply to the criticisms of ~JOSEF HOUBEN (Ber. 1908 41 1027-1029. Eiihrer this vol. i 73).-Polemical. Hoering (this vol. i 119). W. H. G. Density Refractive Index S u r f a c e Tension and Viscosity of Various Mixtures of Glycerol and Water at 18'.PABLO MART~NEZ-STRONG ( A n d Fis. Quim. 1908 6 75-77).-The following t,able shows the results of the measurements Y 2308 ABSTRACTS OF CHEMICAL PAPERS. Rcla tivo Composition. density. Water .................. 1'0000 10 per cent. glycerol 1'0295 1.0681 20 7 7 1 *0860 30 Y 7 40 $ 7 7 ) 1.1094 50 7 7 7 ) 1.1340 60 9 ) 7 ) 1.1602 70 > 9 7 7 1.1860 80 $ 1 7 1 2.2142 90 9 9 7 7 1.2330 7 ) 7 7 Glycerol .............. 1 *2599 Refractive index. 1.3277 1 -3390 1 -3528 1.3650 1'3787 1.3891 1.4020 1.4129 1-4386 1'4529 1 *4650 Surface tension number of drops. 102 106 110 114 119 124 130 136 147 158 172 Viscosity. - No. of seconds. p. 105 1'0000 134 1.3137 170 1,7197 245 2.534 345 3'6451 476 5 4108 640 7.0716 1258 14.2094 4165 48.1632 6900 81.0256 64800 777'5382 The surface tension was determined by means of a Duclaux pipette which when filled with water at 15O delivered 100 drops.The viscosity was measured by an Ostwald viscosimeter. p is the coefficient of viscosity. W. A. D. Derivatives of Epichlorohydrin. EMANUALE PAT ERN^ and MASANIELLO CINGOLANT (Gaxxetta 1908 38 i 243-247 ; Atti R. Accad. Lincei 1908 [v] 17 i 237-241).-The authors have investi- gated the properties and derivatives of epichlorohydrin cyanate (compare Thomsen Abstr. 1879 217) which can be obtained by the action of either cyanic acid or potassium cyanate on epichlorohydrin. When potassium cyanate is employed it is probable that an additive compound is formed which is hydrolysed immediately yielding potass- ium hydroxide ; the latter then acts on some of the epichlorohydrin giving potassium chloride and glycerol so that half of the epichloro- hydrin is destroyed.The maximum yield of epichlorohydrin cyanate obtained is about 37% of the theoretical amount. With fuming nitric acid epichlorohydrin cyanate yields a nitro- derivative C,H,O,N,Cl which crystallises from water in shining needles m. p. 70° and is a nitroamine as it gives a hydrazine on reduction. The hydrazine could not be isolated but i t gives a benxyzidene derivative CON*C,H,CIO*N:CHPh which crystallises from alcohol in yellow plates m. p. 191'. Epichlorohydrin cyanate yields an oily nitroso-derivative whilst it gives isopropylamine when reduced with sodium in alcoholic solution From these results it is concluded that epichlorohydrin cyanate CH,C1* SH*NH CH,-0 T.H. P. y o . possesses the structure Organic Polysulphides. BROR HOLMBERB (Alznalen 1908 359 81 -99).-Whilst the organic hydrosulphides sulphides and di- sulphides have been investigated repeatedly little is known as to the methods of formation or the properties of ths organic polysulphides. The author therefore has made these the object of a systematic study and now describes the results obtained including a method for the pi eparation of organic trisulphides hitherto formed only with great difficulty.ORa ANIC CHEMISTRY. 309 Whilst alkali sulphides unite with sulphur forming polysulphides alkali mercaptides are oxidised by sulphur or alkali polysulphides in aqueous solution at the ordinary temperature. Thus potassium ethyl- mercaptide when shaken with sulphur in aqueous solution yields ethyl disulphide and only Fmall amounts of polysulphides a result obtained also by treating the mereaptide with potassium disulphide Potassium phenyl sulphide on the other hand although oxidised in the same manner by sulphur forming phenyl disulphide is not attacked by potassium di- or tri-sulphide and is oxidised only slowly by potassium tetrasulphide.Previous authors (Muller J . p Chem. 1871 [ii] 4 40; Klason ibid. 1877 [ii] 15 216; BGttger Abstr. 1884 1282) have found that ethyl sulphide disulphide and tetrasulphide form higher poly- sulphides when heated with sulphur at 150-180'. It is now shown that ethyl disulphide unites with sulphur in absolute alcoholic solution if saturated with anhydrous ammonia a t the ordinary temperature.Ethyl dithioglycollate under the same conditions forms a brownish-red solution from which the unchanged ester and sulphur are recovered on evaporation. When shaken with aqueous potassium hydroxide potassium sulphide and sulphur ethyl bromide forms an oil consisting chiefly of ethyl disulphide together with ethyl sulphide and poly- sulphides (Spring and Demarteau Abstr. 1889 1110). It is con- cluded that such reactions the mechanism of which is discussed do not throw any light on the constitution of the polysulphides. Mercaptans react with sulphur dichloride prepared by passing chlorine into an ethereal solution of disulphur dichloride forming mixtures of several productp chiefly di- and tetra-sulphidee. This is in agreement with Aten's observation (Abstr.1906 ii 157) that sulphur dichloride is partly dissociated even a t low temperatures. The action of thionyl chloride on mercaptans in cooled ethereal solution takes place almost quantitatively according to the equation 4R*SH + SOCI = R,S + R2S3 + H,O + 2HC1. The di- and tri-sulphides are separated by fractional distillation. Ethyl trisulphide S,Et2 is a yellow strongly refracting oil b. p. 84-85'/15 mm. and has the characteristic odour of the organic sulphides. A short r h m 6 is given of other methods of forming polysulphides described by previous authors. Frithiodincetic acid S,(CH,*CO,H) formed together with the disulphide from thioacetic acid crystallises from water in white leaflets m. p. 123*5-124O and has the electrical conductivity R= 0.104 ; the lead and silver salts are described.The tetrasulphide of acetic acid S,(CH,*CO,K) prepared by the action of disulphur dichloride on thiolacetic acid in ethereal solution crystallises in prismatic needles m. p. 112*5-113° is partly decomposed with separation of sulphur on titration with alkalis and yields the disulphide when boiled with water. The silver and lead salts are described. Reduction of the tetrasulphide with zinc and sulphuric acid leads to the formation of hydrogen sulphide and thiol- acetic acid ; on oxidation with bromine in aqueous solution the tetra- sulphide yields sulphuric and sulphoacetic acids. The ethyl ester is obtained as an oil G. Y.310 ABSTRACTS OF CHEMICAI PAPERS. Action of Magnesium on Ethyl Bromoacetate.ROBERT STOLLE (Ber. 1908 41 954-955).-The reaction between ethyl bromoacetate and magnesium in ethereal solution leads t o the formation of ethyl acetoacetate and of ethyl y-bromoacetoacetate (compare Zeltner this vol. i 243). c. s. Vapour Density of Propionic Acid. A. FAUCON (Compt. rend. 1908 146 691-694. Compqre this vol. ii 257).-Like the lower homologues of the fatty acids propionic acid has an abnormal rapour density at its boiling point t h e values obtained using Dumas' method being 3.75 and 3.80 at 14S0 3.58 and 3.60 a t 152" 3-39 at 160° 2.98 at 162' 2.96 a t 170° 2.77 at 180° 2.70 a t 190" and 2.57 at 210") the theoretical value calculated from B = M/28-95 being 2.55. The vnpour density of the acid a t its boiling point (140°) obtained by extrapolation is 4.0; it follows therefore t h a t the molecular com- plexity a t t h a t temperature is 4/2.55 or 1.56.Knowing the value of the vapour density of propionic acid a t its boiling point the author has calciilated its heat of vaporisation by two mothods using Clapeyron's formula L = 7'/425.(u' - u).dp/dT and Raoult's formula L = 1*988.T2/(M.d'/d;f ).clf/dT; the values obtaimcl a r e 90.9 Cal. and 91.2 Cul. respectively and these are in close agree- ment with the experimental value 90.43 Cal. (loc. cit.). The factor (u' - u) in Clapeyron's formula represents the difference between the volumes occupied by one gram of the saturated vapour and one gram of the liquid acid; in order to calculate the value of u the specific gravity and coefficient of expansion of the liquid acid at 130' were determined and found t o be 0.8567 and 040153 respec- tivel y.M. A. W. Z- and d-Hexoic Acids. CARL NEUBERG and B. REWALD (Biochena. Zeitsch. 1908 9 405-413).-Neuberg and Rosenberg have shown t h a t the hexoic acids obtained from the putrefaction products of egg- white contain about 50% of an optically active acid which is by reason of its origin presumably P-methylvaleric acid. The racemic form of the acid has been synthesised by van Romburgh. This sub- stance was prepared by a modification of van Romburgh's method and separated into its antipodes by means of the brucine salt. The Z-form was obtained pure and gave [u] - 8.98". S. B. S . Preparation of the Alkyl Esters of the Higher Iodated Fatty Acids. FARBENFARRIKEN VORM. FRIEDR.BAYER & Go. (D.R.-P. 188434).-Ethyll iodobehenccte thin prisms m. p. 290° obtained by boil- ing together iodobehenic acid alcohol and concentrated sulphuric acid crystallises from light petroleum. Ethyl iodostearate prepared in a similar manner is a pale yellow oil of faintly fruity odour. Preparation of Diacyl Ulycerides of the Higher Fatty Acids. FERDINAND ULZER J. BATIK and RUDOLF SOMMER (D.R.-P. 189839).-The diglycerides of the higher fatty acids (CI6-C2J are readily prepared by heating a mixture of the acid with excess of G. T. M.ORGANIC CHEMISTRY. 311 glycerol a t 170’ under 10 mm. pressure. After four to six hours the diglyceride is separated from the glycerol by extraction with light petroleum. G. T. M. Catalytic Reactions of Oxidation and Reduction of Un- mturated Organic Compounds.SERGIUS FOKIN ( J . Russ. IT)FVy8. Chem. Soc. 1908 40 276-321. Compare Abstr. 1907 i SSO).- The oxidation of such substlances as linseed oil is probably a process of molecular autoxidation accompanied by the decomposition of the products of the reaction into more volatile compounds as well as by more complex reactions The absorption of oxygen by unsaturated compounds can be accomplished without any formation of decomposition products if metallic oxides are employed as catalysts the explanation of their action being similar to that given previously but the formation of unstable intermediate oxygen compounds must also be assumed The results obtained in the absorption of oxygen by thin layers of drying oil and by passing oxygen into solutions of various unpaturated oils are similar in character.Tho reaction takes place in two stages for which the equations x = k,.t and k = l/tlogn/a - x are proposed ; OstwaId’s formulE for autocatalysis do not yield satisfactory results but Nernst’s theory connecting the influence of diffusion arid the chemical action itself should be taken into account here; thus in accordance with this theory the first (linear) stage is prolonged a s the quantity of catalyst is diminished; again the results of Geste’s experiments with ultra- violet light agree far better with the equation dx/dt = l/tloga/(a - x) than with dx/dt = (k + k,x)(a - x) which shows that no autocatalyst can be present. Experiments with linseed oil cod liver oil almond oil some fatty acids and mulberry oil are dewribed ; in the case of the latter i t is possible that autocatalysis does occur.Moisture retards the absorption of oxygen by drying oils but to a less extent than is usually assumed. Light considerably hastens the process even in the presence of strong catalysts. Rise of temperature hastens the process. The absorption tends to become proportional to the pressure OF the oxygen ; for pressures of 15-20 atmos. at the same time the colour changes but on removal of the high pressure the substance regains the original colour. A simple and convenient apparatus is described for carrying out reduction experiments. The process of reduction is a unimolecular reaction and is not autocatalytic the shqpe of the reduction curve depending on the diffusion of the gaseous particles the condition of the surface of the catalyst and the possibility of the decreasing effect of the latter owing to fatigue or poisoning.Unsaturated compounds containing a closed-chain do not react under the conditions of the ex- periments although this inertness can probably be overcome under certain conditions of temperature even without the application of high pressures. Unsaturated compounds with low b. p. change but slightly. The stereo-isomeric forms of a substance react identically. The number of electro-negative groups the occurrence of double link-312 ABSTRACTS OF CHEMICAL PAPERS. ings in close proximity to these groups and the size of the molecule all influence the rate and limits of the catalytic reduction of the sub- stance.The catalytic properties of solid molecular platinum are almost identical with those of colloidal solutions of platinum. The rate of the reaction with 2% platinum is already sufficiently great to furnish a method for detecting various impurities by the estimation of the quantity of hydrogen absorbed. Palladium acts as a far weaker catalyst than platinum. z. K. The Carrying Down of Soluble Oxalates by Oxalates of the Rare Earths. GREGORY P. BAXTER and HERBERT WILKENS DAUDT (J. Amer. Chem. SOC. 1908 30 563-572).-An investigation on the effect of conditions on the quantity of alkali oxalates carried down by the oxalates of neodymium lanthanum samarium and yttrium. I n general it is found that (1) the oxalates of the rare earths show a marked but varying tendency to carry down the oxalates of alkalis and ammonium which increases with an increase in temperature and in the concentration of t'he molecular alkali oxalate a t the moment of precipitation ; (\2) potassium and ammonium oxalates are occluded t o a much greater extent than sodium oxalate.Precipitation with the latter gives in most cases precipitates only slightly contaminated with this salt ; (3) by conducting the precipitation in the presence of a quantity of a strong acid considerably more than equivalent to the alkali oxalate the occlusion is in many cases wholly prevented ; in the case of yttrium the diminution is however slight; (4) in order to obtain a precipitate of a rare earth oxalate as pure as possible by means of an alkali or ammonium oxalate precipitation should be con- ducted in cold dilute solution in the presence of a quantity of strong acid considerably more than equivalent to the oxalate added.The following table gives the molecular ratio of occluded oxalate to rare earth oxalate when precipitated from neutral and acid solutions Na,C204. K&,O.p (NH,),C,O,. +- - 7- Acid. Neutral. Acid. Neutral. Acid. Neutral. N$(C,O,) ............ 0.02 0.02 0.01 0.79 0.01 0.71 L%( C20,) ............ 0 -04 0 -02 0.00 0.09 0.01 0.27 Sm,(C,O,) ............ 0 .OO 0-30 0.00 0.94 0.00 0'32 Y,(C204)3 ............ 0.04 0'04 0.69 0.73 0.65 0.82 W. H. G. New Drugs. IV. [Derivatives of Malonic Acid.] ALFRED EINHORN [and in part HEINRICH VON DIESBACH RICHARD FEIBELMANN and CARL LADISCH] (Annalen 1908 359,145-187. Compare Abstr.1901 i 439 493 ; 1903 i 257).-A study of the influence of sub- stituting groups on the reactions of derivatives of malonic acid Various authors have observed that diethylmalonic acid and its derivatives undergo abnormal reactions. Thus whilst the action of ammonia on methyl dimethylmalonate and methylethylmalonate leads to the formation of the corresponding amides methyl diethylmalonate does not form an amide under the same conditions (Fischer and Dilthey Abstr 1902 i 269 ; Meyer Abstr 1906 i 137). Tafel andORGANIC CHEMISTRY. 313 Thompson (this vol. i 58) found that on electrolytic reduction barbituric acid yields hydrouracil and trimethylenecarbamide whilst ti-ethylbarbituric acid is reduced similarly to 5-ethylhydrouracil (I) and 4-ethylirimethylenecarbamide (11) but that 5 5-diethylbarbituric acid forms 4 6-diketo-5 5-diethylhexahydropyrimidine (111) H'CH2>CH Et NH*CP CO<&rH.C&>CHEt C0<2JI-I.CH2 (11.) (I*' NH*CO (111.) Again the action of phosphoryl chloride and carbamide on diethyl- rnalonic acid leads to the formation of diethylacetylcarbamide (Fischer and Dilthey Abstr.1905 i 35) whereas barbituric acid and 5 5-dimethylbarbituric acid are formed by the action of these reagents on malonic and dimethylmalonic acids respectively. It is evident therefore that the abnormal reactions result from the presence of the two ethyl groups. In agreement with Fischer and Dilthey's view (Zoc. cit.) that the first stage in the action of phosphoryl chloride and carbamide on diethylmalonic acid leads to the formation of diethylmalonuric acid NH,*CO*NH*CO*CEt2*C0,H i t is now found that this acid is formed by the action of carbamide on diethylmalonyl chloride in cold pyridine solution and subsequent addition of dilute hydrochloric acid but that if the reaction mixture is heated on the water-bath and the pyridine removed by distillation in a current of steam before the acidification t be product obtained is 5 5-ditthylbarbituric acid. It is assumed that in these reactions an intermediate udditive compound of dietbyl- malonuryl chloride and pyridine NH2*CO*NH*CO*CEt,~C?O*NC5H5Cl is formed. The action of carbonyl chloride on diethylmalonic acid and carbamide in pyridine solution on the other hand leads to the formation of diethyl- acetylcarbamide (compare Einhorn and Hollandt Abstr.1898 i 577). The first stage of this reaction probably leads t o the formation of the monochloride C02H*CEt2*COCI which must decompose at low tem- peratures forming hydrogen chloride and the anhydride of diethyl- malonic acid since it is found that the action of aqueous pyridine on diethylmalonyl chloride leads to the formation of this anhydride (Abstr. 1906 i 398). As it has been generally considered that anhydrides of the malonic acid series are incapable of existence it was of special interest to study the action of aqueous pyridine on other malonyl chlorides. It is found tohat such anhydrides are obtained only from disubstituted malonyl chlorides and that the stability increases with the size of the substitut- ing groups. Thus dimethylmalonyl chloride yields a duodeci-molecular anhydride which is more easily hy drolysed than the diethyl-anhydride but ethylmalonyl and malonyl chlorides yield substances which are probably mixtures cannot be purified and do not yield pure decom- position products.The influence of the two ethyl groups on the reactions of malonic acid derivatives has been studied also i n the action of sodium amalgam CH,<NH GO>C Et,.314 ABSTRACTS OF CHEMICAL PAPERS. on the thiobarbituric acids. Whereas thiobarbitnric and 5-ethyl- barbituric acids react with sodium amalgam and water only with great difficulty and yield oily decomposition prodt~ct~s 5 5-diethyl- thiobarbituric acid is rapidly converted in the oold into chiefly diethylmalonamide formic acid and hydrogen sulphide 4 6-diketo- 5 5-diethylhexahydropyrimidine (Tafel and Thompson Zoc.cit.) and bisdiethylmalonylt etrs-aminoethane (2- bisdeoxyveronyl) which has the annexed constitlution being formed as by-products. I n explanation of these reactions the transient formation of yo-yH :=-yo the bivalent group CEt,2<o0.NH CO*NH>C. . is as- CEt2 cK-CH CE' sumed. I n agreement with this,it is found that I ~ 0 - k ~ AH-& the sulphur atom of diethylthiobarbituric acid is readily displaced by the action of aniline and phenylb ydrazine with formation of diethylmalonylphenylguanidine C E t < ~ ~ ~ ~ > C N P h and diethylmalonylphenylaminogusnidine,CEt~<~~:~~>C:~*~HPh whilst the thio-acid is converted into diethyl barbituric acid when boiled with mineral or organic acids.Molecular weight determinations with the higher polyrneride of di- ethylmalonic acid (Abstr. 1906 i 398) in benzene and in ethylene dibromide agree with the formula (C1H100R)12 but in nitrobenzene with the formula (C7HlOOJ8. This anhydride is hydrolysed slowly by aqueous potassium hydroxide at; the ordinary temperature ; when heated with a limited amount of sodium othoxide in alcoholic solution i t yields ethyl diethylacetate and diethylmnlonate and ethyl hydrogen diethyl- 9nnaZonate which is obtained as an oil decomposes a t 150° forming car- bon dioxide and diethylacotic acid is soluble in alkalis and on evapora- tion with aqueous sodium carbonate yields sodium diethylmalonate (compare Brown and Walker Abstr. 1893 i 394). Tables are given showing the amounts of die thylmalonamide diethylmalonic acid and diethylmalonamic acid formed by the action of ammonia and of di- ethylacetyldiethylamide diethylmalondiethylamic acid and diothyl- malonic acid formed by the action of diethylamine on the anhydride under varying conditions as to solvent molecular proportions and temperature.The duodeci-molecular mzhydride of dimethylmalonic acid is obtained as a white amorphous powder m. p. 145-148O (dscomp.) cannot be converted into a quadrimolecular modification is readily hydrolysed by moisture forming dimethylmalonic acid and when heated with aqueous ammonia yields dimethylmalonamide and dimethyl- malonic acid. The action of aqueous pyridine on ethylmalonyl chloride leads to the formation of a yellow oil which mostly contains ethylmalonic acid and chlorine and sometimes pyridine.The product obtained similarly from malonyl chloride is a yellowish-brown powder m. p. 190-195" (decomp.).ORGANIC CHEMISTRY. 315 CO-NH 5-Et~yZtlzio~u~bilur~c acid CHEt<CO.NH>CS prepared by heating ethyl sodioethylmalonate with thiocarbamide in alcoholic solution crystallises in yellow needles m. p. 192'. 5 5-DimethyltAioburbituric acid C,H,O,N,S prepared from thiocarb- amide and ethyl sodiodimethylmalonate crystallises in yellow needles ni. p. 2 1 6 O and on treatment with sodium amalgam and water is con- verted partly into dimethylmalonamide. ~isdietiiylmcclonyltetra-aminoethane C,,H,,0,N4,2H20 crystallises in whiteprisms loses 2H20 at l l O o m. p. 340° is soluble in aqueous sodium carbonate being reprecipitated on acidification and is stable towards oxidising agents.4 6-Diketo-5 5-diethylhexahydropyrimidine m. p. 293' (292' Tafel and Thompson Zoc. cit.) has feeble basic properties is stable towards oxidising agents and does not condense with benzaldehyde in presence of zinc chloride ; the rnercui.ichZoyide C,€€,,02N,,HgC12 long needles m. p. 215-218'. 5 5-Dipl'opylthiobr;cr.bituric acid C,,H,,O,N,S prepared by heating dipropylmalonyl chloride with thiocarbamide or by condensation of ethyl dipropylmalonate with thiocarbamide i n presence of sodium ethoxide crystallises in yellow needles m. p. 1 5 4 O and on treatment with sodium amalgam and water at the ordinary temperature yields dipropylmalonamide and a small amount of a substance which is pro- ba bly bisdip ropy 1 malon y 1 tetra-aminoet han e.Diethylnzalonylphenylg.uccrLidine (2 phenylimilzodiethyl6ar6ituric acid) CIl,H170,N prepared by heating diethylthiobarbituric acid with aniline at 120-130° crystallises from alcohol in white needles m. p. 2 5 3 O and is readily soluble in dilute alkalis. DiethylmaZony~p?~en~lamino- guanidine (2-phen ylhyclraxinodiet~ylbar6ituric acid) C,,H,,O,N formed from diethylthiobarbitoric acid and phenylhydrazine a t 120-1 30° crystallises in yellow needles m. p. 2 1 5 O and yields a bluesodium salt which forms a red solution in much water. These two malonyl- guanidines are decomposed by boiling mineral acids forming diethyl- barbituric acid and the bases from which they are prepared. When heated at 100-1 30' with as-dimethylcarbamide diethyl- malonyl chloride forms the diethylmalonyl derivative CEt,(CO*NH*CO*NMe,) which separates from hot water in rhombic crystals m.p. 1 5 8 O and is soluble in aqueous alkalis. The diethylrnalonyl derivatives of as-di- ethylcarbamide C17H,,0,N4 white needles m. p. 125O and as-phenyl- methylcarbamide C,,H,,O,N white needles m. p. 172' are formed in the same manner. These diethylmalonylcarbamides are hydrolysed formiDg diethylbarbituric acid when heated with a mixture of concen- trated and fuming sulphuric acids. Diethyl- and dipropyl-barbituric acids are formed when the corre- sponding malonamides are heated with phenyl carbonate at 200-2 15'. The diethylmalonuts of glycollnmide CF t2( C0.U CH,* CO *N H,) formed by heating sodium diethylmdonate and chloroncetamide with a a smallamount of sodium iodide a t 110-120° separates from water in white crystals rn. p.126O. CE ta( CO.0 CH,*CH2* NE t,) niethylaminoeth y l diet?$ ylmalotbate,316 ABSTRACTS OF CHEMICAL PAPERS. prepared by the action of diethylmalonyl chloride on cooled diethyl- aminoethyl alcohol is obtained as a yellow oil which decomposes partly on distillation ; the citrate Cl,H,,0,N,,2C,H,07 was analysed. Bietl~ytmalonyllt ydrazide CEtz<Co.+H prepared from bydrazine hydrate and diethylmalonyl chloride in aqueous solution cry stallises in prisms m. p. 256'. CO*NH * The diethylmaEonyl clerivative of anthranilamide CEt,(CO*N€I.C,H4*CO*NH,)2 prepared by the action of diethylmalonyl chloride on anthranilarnide in cooled pyridine solution crystallises i n microscopic prisms m.p. 215'. G. Y. R e f r a c t o m e t r i c Evidence for the Constitution of Carbon Suboxide. ARTHUR MICHAEL (Bey. 1908 41 925-928).-The conclusion drawn by Diels and Blumberg (this vol. ii 103) from the determinations of the molecular refraction and dispersion that the author's representation of i t as P-hydroxypropiolic lactone (Abstr. 1906 ii 442) is incorrect is controverted. The calculated Falues given for this formula are not accepted as Moureu (Abstr. 1906 ii 1) has shown that Briihl's numbers for the acetylenic linking in hexyl- propiolic acid ale too low 2.22 and 0.19 instead of 3.60 and 0.455 and therefore this optical method cannot decide between the two formulse at present. W. R. Action of Zinc or Magnesium on Mixtures of Esters of Oxalic and of a-Brominated Fatty Acids.New Syntheses of as-Dialkylmalic a n d Dialkyloxalacetic Esters. BERTHOLD RASSOW and R. BAUER (Ber. 1908 41 963-965).-The reaction between ethyl oxalate and ethyl bromoisobutyiate in the pre>ence of zinc a t 60-65' leads t o the formation of ethyl as-dimethylnialonate whilst the same two substances in ethereal solution react with magnesium to form ultimately ethyl dimethyloxalacetate the semi- carbaxone of which Cl,H,905N3 has m. p. 96". Ethyl oxalate and ethyl bromodiethylncetate react in a similar manner under the latter conditions yielding the substance CI2H2"O5 b. p. 135-136"/12 mm. c. s. Behaviour of Cholic Acid towards Ozone. KURT LANGHELD (Ber. 1908 41 1023-1025. Compare this vol. ii 21 I).-Cholic acid resembles cholesterol to which it is generally assumed to be chemically related in its stability towards oxidising agents which i f sufficiently powerful to attack the molecule break it down to simple acids. Hence although cholic acid has formed the subject of many investigations its conetitution has been elucidated only so far t h a t it is known to be a monocarboxylic acid containiug two primary and one secondary carbinol groupingp. With the object of throwing further light on the constitution of cholic acid the author has now studied its behaviour towards ozone.When treated with 10% ozone in presence of chloroform cholic acidORGANIC CHEMISTRY. 317 combines with 4 atoms of oxygen forming a solid oxonide C24H400Q which when boiled with water is partly decomposed yielding hydrogen peroxide and a reducing substance. The ozonide decomposes at 120-130° in a vacuum forming aldehydes which have an aromatic odour ciin be distilled and react with phenylhydrazine and semi- carbazide.This behaviour of cholic acid towards ozone is analogous to that which has been observed with unsaturated acids and with hydroaromatic substances (Harries Abstr. 1906 i 225). Cholesterol when treated in the same manner with ozone forms an o.aonide which contains two or more 0,-groups and decomposes on distillation in a vacuum. G. Y. Formation of Acetaldehyde in Alcoholic Fermentation. J. AUGUSTE TRILLAT (Compt rend. 1908 146 645-647. Compare Abstr. 1903 ii 231 ; 1907 ii 492).-Contrary to the observations of Iloeser (Ann. Inst. Pasteur 1893,41) the author finds that in alcoholic fermentation the production of aldehyde is only a concomitant phenomenon and does not occur in the absence of oxygen.Compar- ative experiments were made in which nutrient liquids containing lactose were sown with yeasts obtained from cheese in the first case allowing free access of air and in the second case expelling all the oxy- gen both from the nutrient liquid and the space above it by a current of hydrogen or ctrbon dioxide. The aldehyde was estimated colori- metrically by means of rosaniline hydrogen sulphite the precaution being taken in the second series of experiments to distil off the alcohol in the absence of air. The results show that no aldehyde is produced in an atmosphere of hydrogen or carbon dioxide that introduction of a small amount of air caused the production of 2-10 mg.of aldehyde per litre and that 50 mg. per litre are produceJ with free access of air. E. H. Formation of Acetaldehyde in Alcoholic Fermentation. 13. KAYSER and A. DEMOLON (Compt. rend. 1908 146 783-784).- Trillat’s conclusion (preceding abstract) relative t o the origin of acetaldehyde in alcoholic fermentation had already been arrived at by the authors (Abstr. 1907 ii 714). Production of acetaldehyde is intimately connected with the presence of a living aerobic yeast on the surface. Addition of antiseptics capable of killing the yeast considerahly reduces the proportion of aldehyde and aseptic addition of yeast afterwards killed by heat has no action on the aldehyde production. The magnitude of the differences observed leads the authors to conclude that living yeast is an essential agent of the phenomenon.E. H. Molecular Dispersion of Succindialdehyde. CARL D. HARRIES (BeT. 1908 41 909-910 Compare this vol. i 133).-A correction. The dispersion was calculated for the F-C lines and not for the G’-C as Bruhl’s figures require. A redetermination of these constants shows the molecular dispersion t o be 0.52 a result in close agreement with that calculated for the dialdehyde namely 0.55. W. R318 ABSTRACTS OF CHEMICAL PAPERS. Formation of Aldehydes or Ketones during Acetic Fer- mentation. K. FARNSTEINXR (Zeitsch. Nahr. Genussnz. 1908 15 321-326).-An investigation showed that all liquids which have undergone more or less complete acetic fermentation contain a neutral volatile substance which reduces Fehling's solution (compare Abstr.1901 i 625). The substance is similar to acetol in its physical properties and in its behaviour t o Fehling's solution and sulphurous acid ; when treated with phenylhydrazine however it yields an osazone m. p. 2 4 3 O and also an oily product. 'cv. Y. 8. Formation of Thio-aldehydes. LUDWIG VANINO (J. p ~ . Chena. 1908 [ii] 77 367-368. Compare Abstr. 1902 i 744; Schmidt ibid. 1906 i 711 ; 1907 i 282).-Trithioformaldehyde is readily formed when sodium thiosulphatc crystals are fused mixed with an equal weight of 40% formaldehyde solution and this mixture poured into half its weight of 38% hydrochloric acid. The crystalline thioaldehyde is deposited almost immediately and is removed washed with water and recrystallised from benzene.Other aldehydes react in u similar manner. J. J. S. Keten. NORMAN T. 11\11. WILSNORE and ALFRED W. STEWART (Ber. 1908 41 1025-1027. Cornpare Abstr. 1907 i 478; Wilsmore Trans. 1907 91 1938).-Polemical A clainl for priority over Staudinger and Klever (this vol. i 246). W. H. G. Ketens.' VII. Classification. HERMANN STAUDINGER and H. W. KLEVER (Bey. 1908,41 906-909. Compare this vol. i 246).- Dilute ethereal solutions of methyl- arid ethyl-keten are obtained when zinc reacts with ethereal solutions of u-bromopropionyl bromide and a-bromobutyryl bromide and the products are distilled. The yields are poor and the solutions react with aniline forming the anilidea of propionic azld butyric acids. Carbon suboxide (Diels Abstr.1906 ii 227) is also a keten and may be obtained by the action of zinc on dibromonialonpl byonaide which is an oil b. p. 91-92'/13 mm. The ketens are divided into the following groups 1. Keten its monoalkyl derivatives and carbon suboxide. They are colourless and not capable of autoxidation. They are polymerised by pyridine or quinoline and do not form additive compounds with substances containing the C:N or C:O groups. These are coloured and readily undergo autoxidation. They yield keten bases with pyridine and quinoline arid form additive compounds with benzylideneaniline (C:N group) and quinone (C:O group). Both groups readily combine with water alcohols or amines and also with bromine or chlorine. 2. Dialkylatod ketens. The first groups are termed abdo-ketens and the second keto-ketens. J.J. S. P-Hydroxy-aa-dialkyl Ketones. Migration under the In- fluence of Alkalis. EDMOND E. BLAISE and I. HERUAN (Compt. rend. 1908 146 700-702).-The unsaturated C? ketone obtained asORGANIC CHEMISTRY 319 one of the products of the action of potassium hydroxide solution on ethyl hydroxytevt.-butyl ketone (this vol. i 248) is isopropyl methylvinyl ketone CHMe,*CO*CMe:CH for it is identical with the synthetical product obtained from ethyl a-bromopropionate by the method described by Blaise and Maire (Abstr. 1907 i 749) and involving the following series of reactions CHMeBr-CO,Et + CH,O + Zn -+ OH*CH,-CHMe*CO,Et -+ OAc*CH,*CHMe*CO,H -+ OAc%H,*CHMe*COCl + CHllle,ZnI -+ oAc*CH,*CHMe*CO*CHMe -+ CH,:CMe*CO*CHMe,.isoPropylmethylviny1 ketone has b. p. 55-56'/60 mm. the semi- carbaxone has m. p. 90*5O and the p-~~~tro~~~enylh?clraaone has m. p. 89" and its formation from ethyl hydr0xytes.t.-butyl ketone is probably the result of an intramolecular change involving the migration of the carbinol group -CH,*OH and subsequent dehydration of the hydroxy- ketone formed OH*CH,*CMe,*CO*C H,Me -+ CHMe,* CO*CHMe*CH,* OH -+ CH&€e,*CO*CMe:CH (compare Blaise and Courtot Abstr. 1905 i 853). The author discusses and rejects two other possible explanations of the course of the reaction. I n addition t o isopropyl methylvinyl ketone a hydroxy-ketone is o'btained in small quantity by the action of potassium hydroxide solution on ethyl hydroxy-tevt.-butyl ketone ; it is an isomeride of the original ketone has b.p. 62-63*/15 mm. yields a phenylurethsne derivative and a p-nitrophenylhydrazone and is converted into isopropyl methylvinyl ketone by the dehydrating action of 50% sulphuric acid ; it probably has the constitution represented by the formula C HMe,*CO*CAle,*OH. Ill. A. W. Behaviour of Dextrose LEevulose and Galactose towards 1)ilute Sodium Hydroxide JAKOB & l E I s E N m i b i E i t ( B e y . 1908 41 1009-1019).-Buchuer Meisenheimer and Schade (Abstr. 1907 i 17) fouud that the action of hydrogen peroxide on Izevulose in alkaIine solution leads t o the formation of formic and glycollic acids and a bydroxy-acid having the composition of el ythritic acid. The identity of the last is now doubtful as the supposed i-erythritylphenylhydr- azide obtained from it has since been found to be acetylphenylhydrazide (compare Lespieau Abstr.1907 i 173 ; Nef this vol. i 5) and i t niay have been a mixture of polyhydroxy-acids having the composition of erythritic acid. The present author has now studied the behaviour of hexoses towards dilute sodium hydroxide in absence of an oxidising agent as this also is of interest in connexion with the problem of a,icoholic fermentation. Dextrose and lzevulose behave similarly yielding af ter some months in dilute sodium hydroxide a t the ordinary temperature 50-60% of i-lactic acid 30-50% of a mixture of polyhydroxy-acids 0*5-2% of formic acid and a small amount of a brown amorphous substance whilst about 1% of the hexose forms carbon dioxide and alcohol. Under the same conditions,.galactose yields less than 20% of lactic acid but about 70% of the mixture of polyhydroxy-acids together with traces of formic acid. The mixture of polyhydroxy-acids Forms a,320 ABSTRACTS OF CHEMICAL PAPERS. calcium salt which on analysis gives results corresponding with an acid (CH,O),.S ; hence the polyhydroxy-acids are not all saccharinic acids C,H,,O as assumed by Nef (Zoc.cit.). On prolonged extraction with ether the mixture of acids yields small amounts of dihydroxybutyric acid. The presence of sodium sulphite or of potassium cyanide does not prevent the coloration of sugar solutions by alkalis (compare Schtlde Abstr. 1906 i 931); the decomposition of the sugar is only slightly if at all retarded by the sulphite. G. Y. A Grystallised Lzsvulose Tetra-acetate.D. H. BRAUNS (Proc. K. Akad. Wetensch. Amsterdam 1908 10 563-566).-L~vulose reacts with an excem of acetyl bromide at - 15O and the yellow product after removal of the acetyl bromide under lorn pressure dissolution in alcohol and evaporation in a desiccator yields colourless crystals. Laevulose penta-acetate has m. p. 131-132" D15 1.388 and has a bitter taste. Crystals monoclinic; a:b:c=1*3463:1 :1.5733 /3=52*12. I n chloroform solution it has [a]2Dq - 9 1 ~ 3 8 ~ . C. H. D. Condensation of Formaldehyde and Lactose. PAUL ROSENBERG (D.K. -P. 18 903 6).-FormccZ~ehyde-Zactose Cl,H,,01,,5CH,0 H,O is obtained by heating lactose with 40% formaldehyde solution at 65O in a vacuum and finally evaporating the solution t o dryness. The product is soluble in water alcohol or acetone On warming its alcoholic solution a t 60-70" the compound decomposes regenerating lactose.G. T. M. Formula of Polysaccharides. HEINRICH KILIANI (Chem. Zeit. 1908 32 366).-The formula for starch or cellulose should not be ( CsHloO5) the correct general formula €or a polysaccharide being (C,H,,O,),,H,O or Cs,,HIOn + 205n + 1. This is proved by the author's previously published analyses of the three anhydrous trisaccharides raffinose melezitose and mannasaccharide all of which pointed to the formula C18H82016. Similarly the analysis of inulin led to the formula C,,H,,O,,. Although Brown and Morris (Trans. 1889 55 463) from molecular weight determinations are in favour of doubling t h e formula for inulin it is a t l e u t doubtful whether the ordinary methods of determination yield trustworthy results in the case of substances of such high molecular weight.P. H. Composition of Starch Grains. Z. GATIN-GRUZEWSKA (Compt. rend. 1908 146 5 10-542).-The separation of starch into amylopectin and amylose (Maquenne and Roux) can be effected by placing the grains in very dilute sodium carbonate until their envelope of amylopectin is burst ; by subsequent neutralisation the envelope contracts again and can be separated the amylose remaining in solution. G. B. Composition of Starch Grains. L ~ O N MAQUENNE (Compt. rend. 1908 146 542-545).-Amylose (compare preceding abstract) gives a pure blue colour with iodine and amylopectin a violet colour j these substances are probably related and intermediate substances mayORGANIC CHEMISTRY.321 exist. Starch paste which has not been superheated is not a true colloid but contains amylose in a state of true solution together with prtrticles of the grain envelope (amylopectin) which are to some extent organised and are much larger than ordinary colloid particles. Amylopectin can also be separated from amylose by boiling wit,h salt solutions. G. B. The Influence of the Alternating Current on the Rate of Hydrolysis of Starch by Diastase and Mineral Acids. 8.. LEBEDEFF (Biochem. Zeitsch. 1908 9 392-402).-Alternating currents of weak strength (0*013-0*015 ampere) increase the rate of formation oE sugar by diastase ; stronger currents act in a similar way at first but afterwards the enzyme loses its activity. Weak currents also increase the rate of starch hydrolysis by acids.Various hypotheses are suggested t o account for these facts; the author is inched t o regard the change in the surface tension of the colloidal particles as the most likely cause. S. B. S. Cellulose and its Derivatives. CARL G. SCHWALBE (Chem. Zeit. 1908 32 287-288).-Polemical. A reply to Grandmougin (this vol. i 250). P. H. Preparation of Formyl Esters of Cellulose. J. P. BEMBER~ (13.R.-P. 189836 and 189837).-Formic acid in the presence of sulphuric acid reacts with cellulose yielding a formate. Cotton wool (1.5 parts) is added to 100 parts of 9S% formic acid containing 3-10 p:mts of concentrated sulphuric acid. After several hours a colourless syrupy solution of cellulose formate is obtained which is precipitated by water as a white mass. Instead of cellulose hydrocellulose cellulose hydrate and mercerised cellulose may be employed.Formic acid alone does not condense in this way but the sulphuric acid may be replaced by 2% to 4% of hydrogen chloride. G. T. M. Acetylstion. DOUGLAS J. LAW (Chem. &it. 1908 32 365-366). -The author has investigated the action of the new acetylating agent recommended by Cross Bevan and Briggs which is obtained by adding 100 grams of acetic anhydride to a solution of 50 grams of zinc chloride in 100 grams of glacial acetic acid. With cellulose it gives a triacetate but with starch it does not react at all; it converts sucrose into the octa-acetyl derivative and dextrose into a tetra-acetyl compound indefinite crystals m. p. 98'. Added in slight excess to benzaldehyde a violent reaction takes place; after some time the fluorescent solution is poured into cold water when crystals of a.dincetate C,H,*CH( OAc) are obtained ; this substance crystallises from alcohol and has m. p. 43' and b. p. 225-230'. When furfuraldehyde dissolved in glacial acetic acid is treated with an excess of the reagent and the mixture is cooled i n a freezing mixture a dark solution is obtained. On pouring into water after half an hour an oil separates out which gradually crystallises ; this substance which is also a dicccetyl derivative C,OH,*CH(OAc) crystallkes from alcohol and has m. p. 45' and b. p. 220". If the reagent VOL. xciv. i 2322 ABSTRACTS OF CHEMICAL PAPERS. is allowed to react with furfuraldehyde at the ordinary temperature a black substance is obtained which is not attacked by acids or a1 kalis.P. H. Constitution of pAmmonium Bases. 11. JOHANNES GADAMER (Arch. Pliurw2. 1908 246 89-90).-An introduction t o the paper dealt with in the next abstract; this paper brings experimental evidence to support (ladarner's view as to the three tautomeric forms of +ammonium bases (Abstr 3905 i 368). Chloral Alcoholates. Connexion with the Constitution of $-Ammonium Bases. F. KUNTZE (Arch. Phurm. 1908 246 91-1 11. Compare preceding abstract).-The conversion of R chloral alcoholate into that of another alcohol by evaporation of its solution in an excess of this second alcohol is due t o mass action and t o the dissociation of the alcoholate as supposed by Gadamer. This is proved by the polarimetric investigation of the equilibrium in chloroform solution between I-amyl alcohol chloral I-amyl alcoholate and an inactive alcohol with its chloral compound a t a temperature of 20". The equili- brium was approached from both sides for instance by mixing equal molecular proportions of chloral Z-amyl alcoholate [a]? i- 1-1 go and ethyl alcohol and of chloral ethyl alcoholate and I-amyl alcohol.I n the case of ethyl and of propyl alcohol the equilibrium is reached when about 60% of chloral I-amyl alcoholate and 70% of I-amyl alcohol are present. With secondary alcohols the proportion of I-amyl alcohol is smaller and with tertiary alcohols i t falls to less than 10%. Two molecular proportions of ethyl alcohol added to one of chloral I-amyl alcoholate raised the proportion of liberated Z-amyl alcohol t o 50% and 8 molecules to 84%.One molecule of I-amyl alcohol added t o chloral hydrate dissolved in chloroform liberates water and forms 98% of Z-amyl alcoholate. With cotarnine in benzene solution similar results were obtained indicating the existence of an (unstable) alcoholate. Fourteen chloral alcoholates of the type CCI,*CH(OH)*OR were prepared ; the following were obtained crystalline and were analysed from methyl alcohol m. p. 38" ; from ethyl alcohol m. p. 50" ; from isopropyl alcohol m p. 45" ; from rz-butyl alcohol m. p. 4 9 O ; from trimethylcarbinol m p. 43* and from cinnamyl alcohol m. p. 42". G. B. G. B. Preparation of Hexamethylenetetramine Borate. AKTIEN- GESELLSCHAFT FOR ANILTN-FABRIKATION (D.R.-P.188815).-When one two and three molecular proportions of boric acid are mixed with hexamethylenetetramine (1 mol.) one two and three molecular proportions of water are eliminated respectively on drying a t 70-80". The residues consist OF the three borates of hexamethylenetetramine HBO,,C,H,,N ZHBO,,C,H 2N4 and 3HB02,C,H,,N,. These salts which also separate from the alcoholic solutions of their generators are neutral or feebly acid crystalline powders soluble in water and having useful antiseptic properties. Reduction of Amino-acids to Amino-aldehydes. CARL NEUBERB (Be,.. 1908 41 956-963).-Fixcher's method in the sugar series of G. T. M.ORGANIC CHEMISTRY. 323 reducing lactones to aldehydes led the author to attempt the reduction of amino-acids in a similar manner with negative results.When however the esters of a-amino-acids or their hydrochlorides are reduced by sodium amalgam in a well-cooled aqueous or alcoholic solution which is kept always acid by the addition of hydrochloric acid when necessary amino-aldebydes are obtained the amount of which is determined by isolating the amino-aldehyde in the form of the phenylosazone or of the p-nitrophenylosazone (ammonia and hydrogen being eliminated) or by converting it into the pyrazine derivative by means of alkaline mercuric chloride I n this way the reduction of the esters of glycine alanine aminobutyric acid leucine aspartic acid anilinoacetic acid tyrosine diaminopropionic acid serine isoserine cystine glycyl glycine and hippuric acid has been detected. The hydrochlorides of the esters of P-amino-acids also undergo reduction but the resulting solutions whilst reducing a1 kaline solutions of silver salts are not affected by Fehling's solution ; this affords therefore a method of differentiating between a and p-amino- acids.The phenylosazocne C,,H,,N obtained from aminoacetaldehyde forms yellow crystals and has m. p. 176-1'77". The p-niti*opltenyZ- osaxone C,,H,,O,NG! m. p. 277' (decomp.) from a-amiuopropaldehyde Physico-chemical Study of the Complex Copper-Glycine Sulphates. J. T. BARKER (Trans. Fa~uday Soc. 1908 3 188- 204). -Measurements of the relative concentrations of cupric ions in solutions containing copper sulphate and glycine (by means of the E.M.F. of concentration cells) lead to the conclusion that complex ions are formed containing 4 molecules of glycine to each atom of copper The freezing point of a glycine solution is raised by addition of copper sulphate and the results are in harmony with the view that the complex anions above meutioned are partly dissociated in solutions which do not contain a very large excess of glycine.The electrical conductivity of a copper sulphate solution increases when glycine is added to it until 10 molecules of glycine have been added for each ni.olecule of copper sulphate; further additions result in a decrease of conductivity. It is suggested that this is due to disturbance of the hydrolytic dissociation equilibrium in the copper sulphate solution the cupric hydroxide combining with the glycine and so giving rise to the production of more free sulphuric acid.Zinc sulphate behaves iu the same way. Measurements of the 3.M.F. of a hydrogen electrode in zinc sulphate-glycine solutions and of the rate of inversion of sucrose by copper sulphate-glycine solutions show that the con- centration of hydrogen ions is actually increased by the addition of glycine. By crystallisation of copper sulphate-glycine solutions products mere obtained consisting of mixtures of copper glycine (NH,* CH,*CO,),Cu and basic glycine sulphate is a scarlet crystalline powder. c. 8. (NH,*~H,*CO2H),H2SO4. T. E. Reduction of Glycine Ethyl Ester EMIL FISCHER (Ber. 1908 4X 1019-1023).-EthyI oxdate differs from other esters of aliphatic 2 2324 ABSTRAOTS OF CHEMICAL PAPERS. and aromatic acids in that it can be reduced by sodium amalgam (Traube this vol.i 75). This behaviour results evidently from the direct union of the two strongly negative cnrbethoxy-groups. A similar although more feeble effect was observed previously as resulting from the accumulation of hydroxyl groups in the dibasic acids of the sugar group (Fischer Abstr. 1890 597). As an amino-group in the a-position has an influence similar to that of hydroxyl on the carboxylic group it was to be expected that the esters of a-amino-acids would be capable of being reduced by sodium amalgim. This is now found t o be the case with glycine ethyl ester which when treated with sodium amalgam in neutral or slightly acid solution yields a liquid which reduces Fehling's solution and must contain aminoacetaldehyde or its semiacetal NH,*CH,*CH(OH)*OEt. The reducing power of the solution shows that the ester is reduced to the extent of about 25%.On addition of hydrochloric acid to the reaction solution evaporation almost to dryness under 10-15 mm. pressure and treatment of the residue with hydrogen chloride in alcoholic solution a t O' most of the unchanged glycine ester separates as the hydrochloride whilst the reduction product is converted into aminoacetal which is stable towards alkalis and hence is readily separated from the remainder of the ester. a. Y. Walden's Inversion. 11. EMIL FISCHER and HELMUTH SCHEIBLER (Bey. 1908 41 889-893. Compare Abstr. 1907 i 192).- Fa-Aminoisovaleric acid (2-valin) reacts with nitrosyl bromide yielding an active a-bromoisovaleric acid which with ammonia yields the original valin and not its optical isorneride.This forms another example of the abnormal manner in which compounds containing an isopropyl group react (Fischer and Dilthey Abstr. 1905 i 35 ; Annalen 1904 334). The a-bromoisowaleric acid crystallises from well-cooled light petroleum' in colourless prisms m. p. 43.5'. In benzene solution it bas [a] + 22.6'. It is only sparingly soluble in cold water and has [ G X ] ~ +9.03. Synthesis of Polypeptides. XXIII. EMIL FISCHER (Be?*. 1908 41 850-S64).-Fischer and Abderhalden (Abstr. 1907 i 737,990) by the hydrolysis of silk obtained a soluble tetrapeptide which is precipitated by ammonium sulphate and is composed of two molecules of glycine and one each of d-alanine and I-tyrosine. Attempts have now been made to synthesise this compound in the first place by the com- bination of tyrosine ester with chloroacetyl-d-alanylglycine which led to a tetrapeptide differing from the above in being precipitated by am- monium sulphate with difficulty.I n the second place it was proposed t o couple a- bromopropionylglycylglycine with tyrosine but it was not found possible to obtain the chloride of this tripeptide in a pure state. d l - Alanyldiglycylglycine was obtained by coupling the raw product with glycine ester. d-Byomopropionylglycina prepared by coupling glycine with d-bromo- propionyl chloride crystallises from toluene in long needles or from water in thin prisms m. p. 122-123O (corr.) to a colourless liquid. Aqueous ammonia converts i t into d-alanylglycine NH,*CH.Me* CO NH CH,* CO,H J.J. S.ORGANIC CHEMISTRY 325 identical with that previously prepared (Abstr. 1905 i 864). C'hloroacetyl-d-alanytgkycine crystallises in microscopic globular ag- gregates of minute needles rn. p. 118' (corr. decomp.) and has [ (113 - 53.4'. Glycyl-d-alanylglycine NH,*CH,*CO*N H*CHMe*CO*NH-CH,*CO,H crystallises in very minute needles which darken at 220° m. p. 245" (corr. decomp.) and has [a] - 64.3" ; it is sparingly soluble in water and is not precipitated by phosphotungstic aoid. Chloi.oacetyl-d-alanylglycyl chlpride is obtained by the action of phos- pliorus pentachloride and acetyl chloride on the finely-divided substance as a yellow powder. It couples with tyrosine methyl ester in acetone solution to form clr,loroacetyZ-d-alany~glycyl-l-tyrosine methyl ester which crystallisea in faintly yellow laucet-shaped plates m.p. 163-164.5' (corr.). The corresponding acid obtained by hydrolysis of t tie ester with sodium hydroxide crystallises in colourless microscopic needles or thin prisms m. p. 206-207' (corr.); it has an acid reaction and gives a red coloration with hlillon's reagent. G lycyl-d-akan ylgl yc y l-1-t prosine NH,*CH,~CO*NH*CHMe*CO*NH*CH2*CO*NH*~H~C02H is obtained by the action of ammonia on the above as a colourless amorphous powder which decomposes a t 229' (corr,) without meltiag. It has [a] + 4.0' and shows the biutet coloration and the red colora- tion with Millon's reagent. It is precipitated by phosphotungstic acid or by tannin b u t only with difficulty by ammonium sulphate; i t is rapidly hydrolysed by fresh pancreas extract yielding tyrosine.C~loroacetyl-d-alanylglycylglycine ester forms very minute matted needles m. p. 165-1 67' (corr.). d-a-Eromopropionytglycylglycine pre- pared in the same manner as the antipode (Fischer and Warburg Abstr. 1905 i 692) has m. p. 172' (corr.) + 29.7'. d-dtanyl- glycylglycine darkens at 206O m. p. 220' (corr. decomp.) ; the antipode behaves similarly and the m. p. 240' (corr.) previously given (Zoc. eit.) is an error. The tripeptide has [ a] + 31.3' and is easily soluble in water. a-Broinopropion yldiglycylglycine ethyl ester prepared by coupling a-bromopropionylglycylglycyl chloride with glycine ethyl ester crystal- lises in very minute needles decomposing a t 189' (corr.). On hydro- lysis it yields dl-a-bromopropionyldiglycylglyci.ne CHBrhle*CO*[NH*CH,*CO],* NH*CH,*CO,H which has m.p. 176' (cori-.). This acid is more conveniently prepared by coupling digljcylgly cine with a-bromopropionyl bromide when it has m p. 180' (corr.). OH*CGH,*CH2 9 dl-Alanyldiglycylglycine NH CHMe*CO*[NH* CH,*CO] *NH CH,* CO,H formed on treating the above substance with ammonia becomes brown at 220° m. p. 242' (corr.). Conversion of I-Serine into the Natural Optically Active Cyatine. EMIL FISCHER and KARL RASKE (Ber. 1908,41 893-4397) -dZ-Cystine is obtained when dl-P-chloro-a-aminopropionic acid hydro- chloride is heated with water and barium hydrosulphide at 100' for one E. P. A.326 ABSTRACTS OF CHEMICAL PAPERS. and a-half hours in sealed tubes and the resulting product oxidised by atmospheric oxygen in the presence of ammonia (Erlenmeyer A bstr.1903 i 792). When the optically active natural serine is used an active cystine is obtained which is identical with the cystine from natural sources The conclusion is drawn that natural cystine serine and alanine belong to the Sam2 genetic group. The configurations previously suggested for the laat two compounds (Abstr. 1907 i 393) cannot be regarded as rigidly established Full details for the preparation of barium hydrosulphide are given. J. J. 5. Preparations of Sodium Glycocholate. WILLIAM C. M. LEWIS (Bio-Chem. J. 1908,3 119-1 28).-Strecker’s formula f o r sodium glyco- cholate is confirmed. The ordinary methods of extraction of mixed bile salts do not yield a product consisting entirely of sodium glycocholate and taurocholate but there is in addition a varying amount of sodium salts of fatty acids of much smaller molecular weight.This admixture may amount to as much as 50% of the total product. It is suggested that sodium myristate is the principal component of this admixture. W D. H. A New Method of Forming isoCyanaters [Carbimides]. I. RICHARD ANSCHUTZ (Annalen 1908 350 202-216. Compare Freund and Asbrand Abstr. 1895 i 576).-An application of ‘Hofmann’s synthesis of thiocarbimides from carbon disulphide and primary amines to the formation of carbimides from carbonyl sulphide. The action of primary amines on carbonyl sulphide leads to the formation of alkylammonium alkylthiolcarbamates NHR*CO*S* NH,R which react with metallic salts in aqueous or aqueous-acetone solution forming the metallic alkylthiocarbamates. As Hofmann’s method of decomposing the metallic alkyldithiocarbamates in aqueous solution is inapplicable to the formation of carbimides which react with water forming carbon dioxide and s-dialkylcarbamides the author has studied the action of heat on the metallic salts of alkyldithio- and alkylthio- carbamates and finds that whilst mercuric ethyldithiocarbamate decomposes at 150-160O forming only small amounts of ethyl thio- carbimide together with carbon disulphide s-diethylcarbamide and considerable quantities of mercuric sulphide mercuric alkylthiol- carbamates (NHR*CO*S),Hg when heated yield mercuric sulphide carbonyl sulphide and s-dialkylcarbamides together with small amounts of the carbimides but the chloromercuric salts NHR CO S Hg C1 decompose chiefly into mercuric siilphide hydrogen chloride and alkyl- carbimides the formation of carbonyl sulphide and the s-dialkyl- carbamide taking place in this case to only a small extent.The decomposition of the mercuric nlkylthiolcarbamates is considered to take place probably in two stages the first leading to the formation of mercuric sulphide and the intermediate product S(CO*NHR),. Ethglammoniuna ethylthioZcarbamate C5,H140N,S prepared by passing carbonyl sulphide into an ethereal solution of ethylamme crystallises in white needles m. p. 88-49’ is hygroscopic decomposes in contactORQANIC CHEMISTRY. 327 with water forming hydrogen sulphide and an oil and yields the mercuric and chloromercuric salts as white precipitates on addition of the calculated quantities of mercuric chloride to its concentrated aqueous solution.Mercuric ethylthiolcarbamccte (C,HGONS),Hg has an odour of ethyl carbimide when moist or after drying; it commences to decompose at 90° evolving carbonyl sulphide and at 156-160° yields red mercuric sulphide s-diethylcarbamide and small amounts of ethylcarbimide. The chloromercuric salt C,H,ONClHg has an odour of ethylcarbimide yields s-diethylcarbarnide when boiled with water and forms ethylcarbimide when heated. The silver copper and bad salts of ethylthiolcarbamic acid were also prepared. isoButylammonizcrn iso6utyZthiolcarbc~m~te C,H,,ON,S crystallises in glistening leaflets m. p. 102O and is more stable than the ethyl compound.The mercuric and chloromercuric salts behave in the same manner as those of the ethyl compound. isoButylcarbimide (Brauner Abstr. 1880 228) is a colourless liquid b. p. 101*5O/760 mm. has an odoixr resembling that of e thylcarbimide and reacts with isobutylamine forming s-diisobutylcarbamide. The copper C,oH200,N2S,Cu and cadmium C,oH200,N2S,Cd salts were analysed ; when heated these salts yield s-diisob u tylcarbamide. G. Y. Nitroacetonitrile. 111. WILHELM STEINKOPF and LUDWIU BOHRMANN (Ber. 1908 41 1044-1052).-After many unsuccessful a,ttempts (compare Abstr. 1907 i 490) nitroacetonitrile has at last been prepared by treating methazonic acid with thionyl chloride in ether. That the compound so obtained is nitroacetonitrile follows from the fact that it yields a-nitroethenylamino-oxime with hydroxyl- amine andgives the nitrolic acid reaction and Konowaloff's reaction Its formation from methazonic acid 'proves the correctness of the formula assigned to this substance by Meister (Abstr.1907 i 885). Further since the compound obtained by Steiner (Trans. 1876 ii 288) from fulminuric acid and described by him as nitroacetonitrile is not identical with nitroacetonitrile this author's formulation of fulminuric acid ae nitrocyanoacetamide becomes doubtful. Attempts are being made to prepare ni trocyanoacetarnide. Nitroacetonitrile NO,.CH,.CN is obtained as a fairly stable yellow limpid oil ; when pure it may be distilled under reduced pressure b. p. 96"/14 mm.; it is not explosive neither is the ammonium salt which crystallises in slender yellowish-white needles decomposing at 130-135' ; the silver salt obtained as a brown pre- cipitlnte is however very explosive.An aqueous solution of the ammonium salt when treated with a solution of diazobenzene nitrate yields nitrocyanoformaldehydephenylhydraxone CN-C(N0,) N*NHPh ; if; forms glistening reddish-brown crystals decomposing at 108" and is soluble in dilute alkalis. a-Nitroethenylamino-oxime NO,*CH,*C( NH,) NOH obtained by the action of hydroxylamine on nitroacetonitrile forms yellow crystals and decomposes suddenly a t 108'. NO,* CBr,.CN prepared by adding bromine to an aqueous solution of ammonium Dibromonitroacetonitrile,328 ABSTRACTS OF CHEMICAL PAPERS. nitroacetonitrile is a pale yellow oil b. p. 57-58'/12 mm.with an unpleasant odour ; it solidifies to a crystalline mass at about - 30'. When nitroacetamide or its ammonium salt is warmed with thionyl chloride it is converted into a compound which is probably nitro- acetimide chloride NO,*CH,*CCl:NH ; it crystallises from water in white crystals with H20; the anhydrous substance has m. p. 157-158O. When boiled with water for some time i t is converted into a substance C,H,OBN decomposing violently at 121O. The nature of this compound is under investigation. W. H. G. Metallic Acetylene Compounds. OSKAR MAKOWKA (Ber. 1908 41 824-829. Compare Abstr. 1907 ii 399 403).-The copper acetylene compound obtained by the precipitation of a cuprous salt by acetylene is of constant composition C,H,OCu whether derived from chloride nitrate sulphate or acetate or by precipitation in acetone solution. When oxidised with hydrogen peroxide volatil6 products showing an aldehyde reaction are formed.I n view of this the compound is regarded as dicuproacetaldehyde of the constitution y u > ~ ~ * ~ ~ ~ . c u The so-called palladium acetylene has the formula C,H,OClPd. It is non-explosive and yields palladium when ignited When heated with water or alkali hydroxides butyraldehyde is produced and on fusion with potassium hydroxide butyric acid and possibly also higher fatty acids are formed. The compound is considered to be pallado- CH*CH CCI*CHO' chlorobutyraldehyde Pd< I E. F. A. The Study of Hydro-aromatic Substances. EDWARD DIVERS ARTHUR W. CROSSLEY WILLIAM H. PERKIN MARTIN 0. FORSTER and HENRY R.LE SUEUR (Byit. BYSOC. Report 1907 77 104-115).-This report deals with the action of reducing agents on 5-chloro-3-keto-1 1- dimethyl-A4-tetrahydrobenzene ; the action of alcoholic potassium hydroxide on 3-bromo-1 l-dimethylhexahydrobenzene ; recent work on hydroaromatic hydrocarbons alcohols ketones and acids ; steric hindrance in the formation of rings; optical influence of conjugated unsaturated groups and velocity of chemical change in the poly- methylene series. T. H. P. Products of tbe Action of Aluminium Chloride and Hydrogen Chloride on Benzene ; Phenylmethylcyclopentane. GABRIEL GUSTAVSON (Compt. rend. 1908 146 640-642).-When a mixture of benzene and aluminium chloride saturated with hydrogen chloride is heated for some hours in hermetically sealed flasks on a water-bath a dark brown liquid gradually separates which on decomposition by water gives a mixture of benzene hydrocarbons b.p. up to 360° and a resinous residue (J. Russ. Phys. Chena. Xoc. 1878 1 0 390). By treating the fraction b. p. 230-240' with fuming sulphuric acid and heating the sulphonic acid isolated through its barium salt with hydrochloric acid in sealed tubes at 180-200" the author has obtained a hydrocarbon Cl2Hi6 b. p. 230-232O,ORGANIC CHEMISTRY. 329 wi6 1.5210 apparently identical with the 3-phenyl-1-methylcyc20- pentane described by Borsche and Menz (this vol. i 149). It is not :attacked by bromine and not immediately by potassium permanganate solution. On oxidation by the latter or by chromic acid a t looo benzoic and acetic acids are formed.When the dark brown liquid is extracted with light petroleum a substance remains which will again combine with benzene and the product on saturation with hydrogen chloride gives more phenylmethylcyclopentane mixed with more highly ,phenylated cyclic hydrocarbons. Amongst the latter Kursanoff's IdiphenylcycZohexane (Abstr. 1902 i 20) hss been detected. Probably the cyclohexane is transformed into the methylcyclopentane and t h e toluene observed by Friedel and Crafts arises from a transposition of the latter. E. H. Transformations and New Nitrogenous Derivatives of Vinyltrimethylene. NICOLAUS J. D E i w A N o m (Ber. 1908 41 9 15-920).-The constitution of Gustavson's vinyltrimethylene not having yet been finally established (compare Abstr. 1896 i 699 ; Fecht Abstr.1907 i 906) the action of nitrogen trioxide on the hydrocarbon was investigated and by the reduction OF the additive product so obtained cyclobutanone was formed. The nitrosite C5H,O3N2 separates from an ethereal solution a t 0' when the gas from arseuious oxide and nitric acid (D 1.36) is passed through it and forms colourless glisten- ing leaflets m. p. 145' to a deep blue liquid. A good yield of succinic acid is obtained by its oxidation with concentrated nitric acid. I t is shown to be a +-nitrosite by its conversion into the weak base NO;C,H,.NHPh by aniline nitrous oxide being liberated ; this forms yellow leaflets m. p. 9s' ; the hydrochloride CllH1502N2CI is crystal- line. Reduction of the nitrosite with tin and hydrochloric acid as well as of the liquid product obtained simultaneously with the nitrosite leads to the formation of a diamine a colourless liquid b.p. 180-1 85". The di7zydrochZoride C,H,(NH:,,HCl) foi ms coloui-less prisms ; the ,ptcctinichZoride C5Hl,N2 H2PtC1,,3H20 orange-red prisms ; the auri- chlmide C,H,,N,,2 HAuC14 H,O yellow leaflets and the picrate C5H,(NH2\,,2@,H2(NO2),*C)H needle.. These results show that in the nitrosite and liquid product the nitrogen atoms are directly united t o carbon. In addition to the diamino a nentral product was obtained possessing aldehydic properties b. p. 98-101' ; the semi- carbazone has m. p. 201-203' and it is therefore identified as cyclo- butanone the formation of which is most easily explained by assuming the hydrocarbon to be methylene-cyclobutane CH, C<Z2>CH2 but the question requires further investigation.W. R. Action of Nitric Acid on Saturated Hydrocarbons. S. S. NAMETKIN (J. Buss. Pi~ys. Chern. Soc. 1908,40 184-192. Compare Konowaloff Abstr. 1907 i l).-The formation of nitro-compounds is only the first stage in the action of nitric acid on hydrocarbons and consequently the mass of the nitric acid employed influences greatly the final products obtained; thus if the quantity of acid is small only330 ABSTRACTS OF CHEMICAL PAPERS. nitro-compounds are obtained but i f the acid is increased oxidation products are formed and the proportion of the nitro-compounds is diminished. The nitration of hexahydro-$-cumene b. p. 142-144' can be curried out with equally good results and more conveniently in open vessels than in sealed tubes if 75-150 C.C.of nitric acid D 1 *3 are used for 100 C.C. of the hydrocarbon the chief products being mononitro- derivatives. Z K. The Study of Isomorphous Derivatives of Benaenesulphonic Acid. HENRY A. MIERS HENRY E. ARMSTRONG W. PALMER WYNNE and WILLIAM J. POPE (Brit. Assoc. Report 1907 77 272).-A11 the possible isomeric sulphonic chIorides and sulphonic bromides of the isomeric dichloro- the isomeric dibromo- and the isomeric chloro- brornobenzenes are to be prepared and examined crystallographically so as t o determine the extent of variation in the series of closely- related compounds. T. H. P. Catalytic Reactions at High Temperatures and Pressures. XV. Reduction of Anthracene and Phenanthrene in Presence of Nickel Oxide WLADIMIR N.IPATIEFF W. JAKOWIEFF and L. RAKITIN ( B e y . 1908 41 996-1000. Compare Godchot Abstr. 1904 i 987 ; 1906 i 76 ; Schmidt and Mezger Abstr. 1907 i 1022). -When repeatedly heated with hydrogen in presence of nickel oxide at 260-270'/100-125 atmospheres for ten to fifteen hours anthracene is reduced in three stages. The product of the first heating consists chiefly of tetrahydroanthracene ; this is reduced in the second stage to decahydroanthracene CI4Hg0 which crystallises in odourless plates m. p. 73-74' (52-53' Lucas Abstr. 1888 lZOl) and when again reduced yields a mixture of perhydroanthracene and a substance m. p. - 3" having apparently the same composition. The yields are not quantitative as part of the anthracene decomposes forming carbon and methane.The reduction of phenanthrene takes place in three stages in the same manner but at higher temperatures. The reduction products are obtained in quantitative yields as even at 400' carbon and methane are not formed. The product of the first stage is a mixture of dihydro- and tetrahydro-phenanthrene and yields two picrates m. p. 135-137" and orange-red needles m. p. 105-106' respectively. The second reaction product m. I>. -4' to -5" is octahydrophen- anthrene perhaps containing other hydrocarbons. The final reduction product consists of perhydrophenanthrene C14H24 which is a colour- less liquid b. p. 266-276' has an odour resembling caoutchouc becomes slightly yellow on prolonged exposure to light and is not attacked by nitric acid bromine or potassium permanganate a t the ordinary temperature G.Y. Derivatives of Dihydroanthracene. LATHAnI CLARKE (Bey. 1908 41 935-936).-The reaction between anthraquinone and magnesium ethyl bromide in ethereal solution leads to the formationORGANIC CHEMISTRY. 332 of a substance C1,H,,O m. p. 159' and of dihydroxydiethyldihydro- anthracene C 6 H 4 < ~ ~ ~ [ ~ ~ { > C 6 H 4 m. p. 175O which separates from ether in large greenish-white needles containing I mol. of ether and from alcohol in thick white plates which also contain alcohol of crystallisation which is rapidly lost by exposure to the air. C. S. Fluorene Perhydride. LEOPOLD SPIEGEL (Ber. 1908 41 884-886). -A repetition of the experiments of the author and Liebermann (Abstr. 1889 719) shows that contrary to the statement of Schmidt and Mezger (this vol. i 16) fluorene psrhydride C13H22 is actually existent.c. s. Attempt t o Prepare Hexaphenylethane. RICHARD ANBCHUTZ (Annaleqh 1908 359 196-20l).-It mas observed previously (Trans 1885 47 898 S99) that phenyl fumarate when heated decomposes in two stages into carbon dioxide and stilbene the intermediate product being phenyl cinnamate. Recently Tschitschibabin has drawn at- tention to the instability of carboxyl and cyano-groups when attached to the same carbon atom as other negative groups (Abstr. 1907 i 27). These facts together with the long-known formation of triphenylmethane by the decomposition of triphenylacetic acid induced the author to study the action of heat on triphenylmethyl triphenylacetate CPh,* CO,*CPh triphenylmethyl fumarate CPh,* CO,*CH :CH*CO,*CPh and phenyl triphenylacetate CPh,*C02Ph as these might be expected in analogy with the formation of stilbene and triphenyImethane to yield hexaphenylethane s-bistriphenylmethylethylene and tetra- phenylethane respectively.Only in the case of the first of these esters however has any indication of the formation of such a product been obtained. Triphenylrnethyl triphenyhcetate C,,H,,O? prepared by the action of triphenylmethyl chloride on silver triphenylacetate in boiling benzene solution crystallises in needles m. p. 184-185' is readily hydrolysed by alkalis forming triphenylcarbinol and triphenylacetic acid and when heated at 185-200' in a vacuum loses carbon dioxide and yields triphenylmethane a white crystalline substance soluble i n chloroform a product m.p. about ZlO' insoluble in chloroform but soluble in benzene and a n amorphous residue m. p. about 300° which dissolves in boiling ethylene dibromide and may be hexaphenyl- ethane C,,H,,. Phenyl trzphenylacetate C26H2002 prepared from sodium phenoxide and triphenylacetyl chloride crystallises in small needles m. p. 1 2 2 O and when heated above its m. p. loses carbon dioxide and forms triphenylmethane and phenol. Tkiphenylmethyl furnarate C,2H3'704 prepared from triphenylmethyl chloride and silver f umarate crystallises from carbon tetrachloride in needles containing CCl which is lost a t 100'; m. p. 152-153". A t 200° the ester loses carbon dioxide forming a mixture from which a pure product has not yet been obtained.G. Y.332 ABSTRACTS OF CHEMICAL PAPERS. Catalytic Reactions at High Temperatures and Pressures. XIII. Reduction of Aromatic Amines and Quinoline in Presence of Nickel Oxide. WLADIMIR N. IPATIEFF (Ber. 1908 41 991-993. Compare Abstr. 1907 i 828).-Whilst the action of hydrogen on aromatic amines in presence of nickel oxide under the atmospheric pressure leads to the formation of large amounts of abnormal products sometimes as i n the case of quinoline even to the complete suppression of the normal reduction product (Padoa and Carughi Abstr. 1906 i 765) the reduction by means of hydrogen i n presence of nickel oxide a t high temperatures and under high pressures takes place more simply. When heated with hydrogen in presence of nickel oxide a t 220-230°/115-120 atmospheres for forty t o fifty hours aniline forms aminocyclohexane in a 40-50% .yield together with dicyclohexylamirle and phenylcyclohexylamine in 10%.yields. Under himilar conditions diphenylamine yields dicyclohexylamine and traces of c yclohexylamine whilst quinoline is reduced almost quantitatively to decahydroquinoline or on less prolonged heating to tetrahydroquinoline. G . Y. The Transformation of Aromatic Nitroamines and Allied Substances and its Relation to Substitution in Benzene Derivatives. FREDEHIC S. KIPPING KENNEDY J. Y. ORTON SIEGFRIED RUHEMANN ARTHUR LAPWORTH and JOHN T. HEWITT (Brit. Assoc. Report 1907 77 101-103). -A detailed study of the conditions governing the transformation of 2 4-dichloro-1-nitroamino- benzene into the isomeric 2 4-dichloro-6-nitroaniline and a study of the wandering of bromine in the chlorination OF bromo-anilines.T. H. P. Preparation of p-Toluidine from Mixed Toluidines by means of p-Toluidine Hydrate. RICHARD J. FRISWELL (J. SOC. Chern. I ? z d 1908 27 258).-Referring to the recent publication of WalkerandBeveridge( Trans. 1907,91,1797) the author calls attention t o the fact that in 1889 he devised the mode of sepsratingy-toluidine from mixed toluidines by means of p-toluidine hydrate and 6uccess- fully carried it out on a large scale. Technical details are given in the original. J. V. E. Condensation of Chloral with Primary Aromatic Amines. 11. ALVIN S. WHEELER (J. Arner. Chem. Xoc. 1908 30 136-142).- In an earlier paper (Wheeler and Weller Abstr. 1903 i 246) it was stated that chloral condenses with 0- and p-nitroanilines t o form trichloroethylidenedi-o- and pnitro-anilines.An account is now given of the behaviour of chloral with other primary ary lamines. The products crystallise well and are decomposed by strong mineral acids with regeneration of the amine. They react readily with bromine a t the ordinary temperature to form bromo-derivatives in which the bromine atom probably replaces the hydrogen of the chloral residue. [ with c. W. M~~~~~.]-~richloroet?iy~idenedi-p-brornoaniline m. p. 140° forms colourless needles and decomposes a t 2 0 5 O . CCI,*CH(NH-C,H,Br) TheORGANIC CHEMISTRY. 333 bronzo-derivative m. p. 2 0 3 O cryst'allises in colourless plates and the ehlo~o-derivative m. p. 93O in long needles.[With W. S. ~~~~~~~.]-Tr~ch~oroelhyl~dened~-o-methoxyphe?zy~(TCl,.CH(NH*C,H,*OMe) m. p. 1 21° forms large pale yellow rhombohedra or long slender prisms and is soluble in 100 C.C. of alcohol t o the extent of 7 grams at the b. p. and 2.5 grams at 25'. The bvomo-derivative crystallises in clusters of needles arid decomposes at about 230O. ~richZoroetA?/lidenedi-~-met~oxyphenyZarraine m. p. 1 18-1 20° forms lirilliant pink scales and decomposes at 158'. By the action OF bromine a compound is obtained which blackens a t about 198'. [With W. S. I)rc~so~.]-Trichloroethjrlidene-o-aminobenzoic acid (chloral-anthranilic acid) (Niementowski and Orzechowski Abstr. :L896 i 187) m. p. 152" yields a bromo-derivative decomposing at 2 3 7". When trichloroe t h ylidenedi-o-amino benzoic acid (chloral- tlianthranilic acid) (Niementowski Abstr.1903 i 91) is boiled with acetic anhydride o-acetylaminobenzoic acid is produced. The bromo- derivative of chloral-dianthranilic acid has m. p. 236' (decomp.). [With STROWD Jolt~a~.]-Trich~oroethylidenedi-o-toly~amine CCJ,*C H(N H*C,H,Me) m. p. 80° forms silky needles and yields a bromo-derivative m. p. about 26SO. Physiologically the compound produces a numbing effect. E. G. Condensation Products of Dibromo-p-hydroxybeneyl Bromide with Aromatic Bases. KARL AUWERS and ALFRED DOMBROWSKI (Ber. 1908 41 1053-1058).-A further contri- bution to the study of the influence of the position of the methyl group on the chemical properties of benzenoid compounds (compare Auwers Abstr. 1906 i 258). Although derivatives of dibromo-p-bydroxy-$-cumylaniline are readily obtained by the action of dibromo-p-hydroxy-$-cumyl bromide on an aromatic base in ethereal solution (compare Auwers and Dombrowski Abstr. 1906 i 380) it is found that when dibromo-p- hydroxybenzyl bromide acts on aniline p-toluidine or m-toluidine instead of the expected substituted benzylaniline the corresponding benzylidene derivative is obtained.However the normal reaction product is obtained when o-toluidine q-cumidine p-xylidine or as-m- xylidine is employed. It is therefore evident that the presence of the methyl group ortho to the amino-group prevents the oxidation of the substituted benzylaniline t o the corresponding benzylidene derivative ; further since benzylidene derivatives have never been obtained when dibromo-p-hydroxy-$-cumyl bromide is employed it follows that the same protective influence against oxidation is exerted by the methyl group when ortho t o the -CH,Br group.The nature of the solvent employed also influences the coiirse of the reaction. Only in ethereal solution does the reaction take place in the manner above described ; when benzene is used the chief product formed for example by the action of dibromo-p-hydroxybenzyl bromide on p-toluidine is the di-derivative C,H,Me*N(CH,*C,H,Br,.OH),.334 ABSTRACTS OF CHEMICAL PAPERS. The benzylidene derivatives obtained by the action of dibromop- hydroxybenzyl bromide on aniline and p-toluidine were identical with those described by P a d and Kromschriider (Abstr 1896 i 225) ; the m.p. of the p-toluidine derivative OH* C,H2Br2*CH:N*C6H4n/Ie,Et10H was found to be 187' and not 157' as stated by these authors. The following new compounds were prepared dibrorno-p-hydroxy- benxylidene-m-toluidifie C,,H,,ONBr a dark red crystalline powder m. p 155.5-1 57" ; dibronzca-p-ilydroxybenxyl-o-toZ~idine C14H,,0NBr2 a white crystalline powder m. p. 11 7'5-1 19" ; the N-acetate forms needle-shaped crystals ; dzbromo-p-hydroxybewyl-as-m-xylidine N-acetate C17H1702NBr2 crystallises in very small leaflets m p. 175' ; the isomeric p-xylidine compound forms colourless crystals m. p. 240-2 4 1 O ; di bromo-p-hy droxy benx ylidene-as-m-xylidine C15Hl ?ON Br is a red powder m. p. 1 G 1' ; dibromo-p-hydroxybenxyl-+-cumtdwae crystallises in slender needles m. p. 123-125'; the N-acetate has m.p. 205' ; bisdibromo-p-lzydrox?jbenxyl-p-toluidine C,H,Dle*N( CH,*C6H2Br2 OH) has m. p. 134-1 35' ; tet.rctbronzo-p-hydroxybenxylaniZine C1,H,ONBr crystallises in small glistening pearly leaflets m. p. 126-127' ; when its alcoholic solution is boiled for some time it is partly converted into bistetl.abromo-p-~ydroxybenxylanile C,H,*N(CH,*C,Br,-OH)2 a fine powder m. p. 212O. C,,Hl5?2NBr2? C,,H,pNBr,? W. H. G. Asymmetric Nitrogen. XXXII. Dependence of the Velocity of Racemisation of Optically Active Ammonium Salts on the Nature of the Anion EDGAR WEDEKIND OTTO WEDEKIMD and F. PASCHKE (Bey. 1908 41 1029-1035. Compare E. Wedekind Abstr. 1906 i 161 419).-The velocities with which d-phenylbenzylmethylpropylammonium iodide bromide and chloride undergo autoracemisation in chloroform solution at 35' have been measured the velocity constants obtained being for the iodide K=0.0065 for tho bromide K=0*0013 and for the chloride K= OA0O027 that is in the ratio G I Br I = 1 5 25.The rate of change of the bromide in bromoform solution was found t o be the same as in chloroform solution. Similar comparative measurements were made with d-phenylbenzyl- methylallylammonium bromide and iodide in chloroform solution a t 25') 3 5 O and 4 5 O the K values obtained being for the iodide 0.0012 and 0*0040 a t 25' and 35' respectively and for the bromide 0*00061 arid 0-0024 a t 35" and 4 5 O respectively. From these values it is seen that (1) the iodide undergoes racemisation about six times more rapidly than the bromide at the same temperature (35'); (2) the allylammonium salts are more stable than the corresponding propyl salts.The effect of an increase in temperature on the rate of change is in several cases quite abnormal ; for example the K values for d-phenyl-ORGANIC CHEMISTRY. 335 henzylmethylpropylammonium iodide at 25' and 35' are respectively 0-0013 and 0-0065. 1- P~~enylbenxylmethylpro~ylammonizcm chloride has been prepared ; it forms small colourless crystals decomposing at 174-1 7 5 O Ila] - 143.8' (in chloroform). Phenyl Mesaconates. ROSALIND CLARKE (Annulen 1908 359 188-1 95)-The esters described in this paper were prepared in amplification of Anschutz's study of derivatives of meeaconic acid (Abstr. 1907 i 468). Phenyl memconate CO,Ph*CH:CRle*CO,Ph prepared by the action of mesaconyl chloride on sodium phenoxide in boiliiig toluene solution csrystallises from carbon disulphide in yellow leaflets m.p. 66-67" ; :it resembles phenyl fumarate in that i t evolves carbon dioxide when heated a t high temperatures. On hydrolysis with 1 mol. of potassium .hydroxide in boiling aqueous-acetone solution it yields a-phenyl hydrogen mesuconnte CO,Ph*CH CMe*CO,H which crystallises from light petroleum in needles m. p. 9 9 O . a-Phenyl /3-methyl mesaconccta C0,Ph*CH:CMe*C02Me m. p 45-46") b. p. 166'/13 mm. is obtained by gently heating sodium phenoxide with P-methyl mesaconyl a-chloride in ethereal solution. /3-Phenyl hydrogen mesaconate could not be obtained by partial esterification of the acid but the P-phenyl a-methyl ester CO,Me*CH:CMe*CO,Ph m.p. 23-25') b. p. 176'/20 mm. is formed from sodium phenoxide :and a-methyl mesaconyl P-chloride. a-Phenyl nzesaconyl P-chzoride CO,Ph*CH:CMe*COCl obtained as a crystalline mass on treatment of the a-phenyl hydrogen ester with phosphorus pentachloride in chloroform solution and distillation of the phosphoryl chloride and the solvent in a vacuum yields t h e following three substances when treated with the corresponding bases in ethereal isolut ion. a-Yhen yl mesucon-p-amate C0,Ph. CH C Me C 0 NH crystal - lises from ether in white needles m. p. 114-1 15'. a-PhenyZ mescwo?z- j3-anilute CO,Ph*CH:CMe*CO*NHPh white needles m. p. 121'. a-Phenyl mesacon-P-p-tolztidute CO,Ph*CH CMe* CO*NH* C,H,Me yellow needles m. p. 129-130'. P-Phenyl nzesacon-a-anilate white crystals m.p. 1 14-1 15' and the corresponding a-p-toluidate yellow needles m. p. 1 2 2 O are prepared by the action of mesacon-a-anilyl and mesacon-a-p-toluidyl chlorides on sodium phenoxide. Whilst the P-alkyl mesacon-a-anilates and -a-p-toluidates melt at the same temperatures as or at higher temperatures than the corre- sponding ,f3-anilates and P-p-toluidates the a-phenyl mesacon-p-anilate (and /3-p-toluidate melt 7' higher than their isomerides. W. H. G G. Y. 2 4 6-Trichlorophenol and its Transformation into Chlori- nated Benxoquinones. EUGENE LEGEB (Compt. wnd. 1908 146 694-697).-2 4 6-Trichlorophenol can be prepared readily and i n quantity when concentrated eau de Javel is used instead of the dilute solution of hypochlorite employed by Chandelon (Abstr.1883 1108). It has M. p. 66-67' (corr.) [Chandelon (Zoc. cit.) gives 54'1,336 ABSTRACTS OF CHEMICAL PAPERS. By the action of nitric acid D 1.41 containing a small quantity of hydrochloric acid trichlorophenol is converted into a mixture of tri- and tetra-chlorobenzoquinones which can be separated by fractional crystallisation from alcohol ; trichlorobenzosuinone softens at 166' and melts at 168' (corr.) (Graebe gives 164-16& Annalen 1868 146 1). M. A. W. Basic Tri-iodophenoxide of Bismuth. ORESTE CARRASCO (Boll. china. farm. 19OS 47 109-112).-The author gives an improved method for preparing 2 4 6-tri-iodophenol (compare Brenans Abstr. 1901 i 322) from which he obtains a basic bismuth derivative possessed of therapeutic value. By adding a potassium iodide solution of rather more iodine than is required by the equation C,H,*OH + 3KHO + 61 = C,H,T,*OH + 3KI + 3H20 gradually to a solution of phenol in a large excess of potassium hydroxide (8 mols.) solution a theoretical yield of 2 4 6-tri-iodophenol free from di- or mono-iodophenol is obtained.Monohydrated bisrnuthyl 2 4 6-tri-iodop~~enoxide C,H2T,*O* Bi(OH) prepared by treating a. solution of 2 4 6-tri-iodophenol (1 mol.) in alkali with a solution of bismuth nitrate (rather less than 1 mol.) in 45% aqueous glycerol is obtained as a heavy yellow amorphous powder. The corresponding anhgdrous derivative C,H,Iq.O*BiO to which the name ' neoform ' is given is a yellow powder having a faint odour recalling that of xeroform a similar compound containing bromine in place of iodine ; i t begins to decompose a t 170-180'.T. H. P. Quinonoid Sulpho-derivatives. THEODOR ZINCKE and R. BRUNE (Ber. 1908 41 902-905).-An acetone solution of 2 6-dibromo- phenol-4-sulphonyl chloride (Abstr. 1907 i 698) becomes deep yellow when shaken with sodium acetate solution. Hydrogen chloride is eliminated and probably a qzcinonoid compound 0 c<g;:g>c:so2 is formed. This compound has not been isolated as the solution rapidly becomes colourless and deposits a colourless crystalline com- pound having tbe same composition and probably representing the polymeric compound U,H,Br,<~~~~>C,H,Br,. This behaviour is analogous to that of various +-bromides (Abstr. 1907 i 125). The polymeride readily reacts with methyl o r ethyl alcohol and also with aniline yielding the same derivatives as are formed when these sub- stances react with the original sulphonyl chloride.The polymeride is practically insoluble in the ordinary organic solvents crystallises from hot nitrobenzene in rhombic plates and prisms and is not readily oxidised. Methyl 2 6-dibromophenoE-4-sulphonate OH* CGH,Br,*SO,* OMe crystallises from benzene in rhombic plates m. p. 196-197O which dissolve readily in alkalis. The corresponding ethyl ester CSH804SBr2,ORGANIC CHEMISTRY. 337 crystallises in prisms m. p. 146-147". crystallises in colourless plates m. p. 177". The sdphanilide OH*CGH2Br2*S02*NHPh J. J. S. 4-Hydroxy-l 4-dimethyl - 1 - trichloromethyldihydrobenzene. Zincke and Suhl's ketone C,H?OUI (Abstr.1907 i 37) reacts readily with magnesium methyl iodide yielding 4-hydroxy- 1 4-dimethgl- P-tricl~Zoromet2iyZcyclohexcldiene OH*CMe<CH:'CH>CMe*CCl~ CH'CH which crystallises from light petroleum in slender needles or plates m. p. B31-132°. It is extremely unstable and when kept rapidly gives iip water yielding 1 -methyZ-4-P-tric?~loroetlt,glbenxene C6H,Me' CH,*CC1 which crystallises from methyl alcohol in slender plates m p. 31-339 When oxidised t h i s compound yields terephthalic acid and when heated with alcoholic potash gives l-methyl-4-P-dic~loroviny~b~~~xene CGH %&f e c H c c I colourless plates m. p. 40-41 . The carbinol reacts with a chloroform solution of bromine yielding bromo-derivatives which probably have the following constitution (:H2:C,H2Br,<CCl~ CH m.p. 90-9 1' ; CH $>C6H,Br2<g3 m. p. 'FHEODOR ZINCKE and FR. SCHWABE (Ber. 1908 41 897-902).- ' 0 u 0 106-107° (decomp.) and CH2~~>C6H2Br,<~$ m. p. 133' (de- camp.). derivative. J. J. S. The latter two readily lose bromine y:elding the dibromo- Action of Chlorine on Dithymol. HENRI COUSIN (Cornpt. rend. 1908,146 636-637. Compare this vol. i 84 162).-When dithymol (1 mol.) suspended in chloroform is treated with slightly more than the theoretical quantity (2 mols. ) of chlorine dicldorodithymol C~,oH,,O,Cl is formed as brilliant slightly yellow prismatic crystals m. p. 152-153' (corr.). By the continued action of chlorine or bettor by the action of bromine (1 mol.) on its chloro- form solution dichlorodithymol is oxidised t o dichlorodithymo- p i n o n e C,,H,,O,CI which forms radiating groups of deep garnet- red prismatic needles m.p. 130-132' (corr. decomp.) insoluble in alkalis and giving an intense blue colour with tincture of guaiacnm. Dithymol suspended in chloroform is converted by the prolonged action of chlorine into dichlorodit~~ymoquinone dichloride a substance forming small prismatic crystals of a sulphur-yellow colour m. p. 176-178' (corr. decomp.) insoluble in alkalis. The la,tter substance on reduction gives dichlorodithymol. C,,H,,O2C1,? E. H. Styrene Oxide. MARC TIFFENEAU and ERNEST FOURNEAU (Compt. rend. 1908 146 697-699).-Styrene oxide obtained in a yield of 50% by the action of powdered potassium hydroxide on an ethereal solution of styrene iodohydrin (Abstr. 1905 i 591 ; this vol.i 19) VOL. XCIV. i. r X Q338 ABSTRACTS OF CHEMICAL PAPERS. has b. p. 191-192' (corr.) or 84-8€i0/15 mm. DO 1.0633 D*6'4 1.0523 ; it is not appreciably changed when heated in a sealed tube above its boiling point and is only slowly converted into the isomeric phenyl- acetaldehyde on boiling with dilute mineral acids (Abstr 1907 i 404). Styrene oxide is reduced by sodium and water to benzyl alcohol and combines with halogen acids to form halohydrins (Abstr. 1907 i 404) ; when heated in a sealed tube with hydrocyanic acid it yields the cyanohydrin of phenylacetaldehyde which is converted into a mixture of ethyl phenylhydracrylateand ethyl cinnamate by the action of an alcoholic solution of hydrogen chloride. Styrene oxide condenses with organo- magnesium derivatives to form the corresponding substituted benzyl- carbinol CH,Ph*CHR*OH and not the alcohol CH,R*CHPh*OH as previously stated (Abstr.1907 i 8 IS) and is converted quantitatively into the corresponding amino-alcohol when heated in a sealed tube with amines (compare Krassusky this vol. i 139). RI. A. w. Oxidation of m-Nitrobenzoylcarbinol. WILLIAM L. EVANS and BENJAMIN T. BROOKS (J. Amer. Chem. Xoc. 1908 30 404-412).-1n an earlier paper (Evans Abstr. 1906 i 269) an account has been given of the behaviour of benzoylcarbinol towards oxidising agents. Further work is being carried out with the object of ascertaining whether the substituted benzoylcarbinols follow the same general course of reaction and of determining the effect of substitution on the behaviour of these substances.The present paper deals with the oxidation of rn-nitrobenzoylcabinol. An improved method is described for the preparation of bromo-m- nitroacetophenone. m-Nitroacetophenone acetate has m. p. 51'. On hydrolysis it yields m-nitrobenxoylc~rbinol m. p. 92*5-93' which forms pale yellow crystals and when heated with a mixture of glacial acetic acid and acetyl chloride is reconverted into m-nitroticeto- phenone acetate. Aqueous solutions of the carbinol reduce ammoniacal silver nitrate and Fehling's solution. When the carbinol is treated with freshly -precipitated mercuric oxide freshly-precipitated silver oxide or potassium permanganate either alone or in presence of alkali hydroxide it yields oniy m-nitro- benzoic acid and carbon dioxide.By the action of cupric hydroxide and alkali hydroxide on the carbinol it is converted into m-nitro- mandelic acid whilst if treated with potassium ferricyanide and potassium hydroxide it yields both m-nitrobenzoic and m-nitro- mandelic acids. E. G. Preparation of Eugenyl 0- and nz-Aminobenzoates. J. D. RIEDEL (D.K.-P. 189333).-Eugeny/E o-nitrobenxoate pale yellow prisms m. p. 60-62' and eugenyl m-wits-obenzoate well-defined yellow prisms m. p. 71-79' are obtained by the action of the respective nitrobenzoyl chlorides on eugenol in the presence of aqueous sodium hydroxide. The corresponding amino-esters are produced on reducing the foregoing nitro-compounds with tin and hydrochloric acid or zinc and acetic acid ; eugenyl o-aminobenxoate yellowish-white lustrous plates m.p. 98-99' ; ncetyl derivative yellowish-white needles m. p.ORGANIC CHEMISTRY 339 1 02-103' ; eugenyl m-aminobenxoate yellow lustrous prisms m. p. 72-73' ; hydrochloride yellowish-white flakes m. p. 160-162' ; acetyl derivative colourless plates m. p. 102'. 0. T. M. Benzoylaminoisobutyrolactjmone. ERNST MOHR and THEODOR GEIS (Ber. 1908 41 798-799).-&Iohr and Kohler obtained an anhydride termed a lactimone by heating o-aminobenzoylanthranilic acid with acetic anhydride (Abstr. 1907 i 414). A similar anhydride CMe,<FGXph which contains the typical lactime and lactone group- ings *O*C:N- and *C*CO*O.C* and is therefore a lactimone has now been obtained in the same manner from a-benaovlaminoisobutyric acid. - The lactimone group includes also such sub,&ances as tge yellow lactimide of benzylidenehippuric acid CHPh:C<N=Yph (Eden- coo0 - meyer jan. Abstr.1899 i 759),and the acylanthranils C,H,<:&SR (Anschiitz Schmidt and Greiffenberg Abstr. 1903 i 57). a-~ensoylrtmilaoisobut~ric acid NHBz*CMe,* CO,H prepared in a 60-65% yield by the action of benzoyl chloride and potassium hydro- gen carbonate on a-aminoisobutyric acid in cold concentrated aqueous solution crystallises in colourless plates m. p. 198' decomp. above 220'. The lactimone C,,HI,O,K crystallises in colourless plates xu p. 34O b. p. 123'19 rnm. and when treated with cold saturated adcoholic ammonia forms a-bensoylaminoisobutyrccmide NHBz-CMe,-CO* NH mhich crystallises in white needles m. p. 201O. When boiled with a.queous sodium hydroxide the amide evolves small amounts of N=$?Ph CO-NH (?) crystallising in ammonia and yields the Zactum CMe,< in white needles m.p. 202'. G. Y. Preparation of the Urethane of nz-Amino-p-ethoxybeneoic Acid. AKTIEN~ESELLBCHAFT FUR ANILIN-FABRIKATION (D.R.-E. 189838).-The ui*ethane CQ,Et *NH* C,H,( OEt) CO,H of 3-amino-4- ethoxybenzoic acid is produced by dissolving the hydrochloride of this amino-acid in aqueous sodium carbonate and adding ethyl chloro- carbonate j it crystallises from alcohol in needles m. p. 21 1-212' and has a very soluble sodium salt. G. T. M. 4-Methylcoumarin. F. PETERS and HUGO SIMONIS (Bey. 1908 4:1 830-837).-The synthesis of methylcoumarin from ethyl aceto- acetate and phenol by von Pechmann's method (Abstr. 1884 66 1331) gives poor yields owing probably to the concentrated sulphuric acid used acting rather to sulphonate the phenol than to cause condensa- tion.Using a less concentrated acid (73% H,SO,) which no longer acts as a sulphonating agent and less phenol and stirring the mixture rapidly a more satisfactory yield is obtained. The proof of the constitution of 4-methylcoumarin is given by conversion into methyl- coumltrilic acid (Hantesch and Lang Abstr. 1886 706). A number cc a 2340 ABSTRACTS OF CHEMICAL PAPERS. of halogen derivatives are now described. 4-Methylcoumarin CMe:CH CBR4<0-&) 9 forms long colourlees needles m. p. 90'; the dibromide is unstable and forms minute red needles which lose hydrogen bromide on drying CMe:CBr giving 3-bromo-4-methylcoumccrin C6H,<o-~o This crystallises in colourless prisms m.p. 114'; when heated with concentrated potassium hydroxide it forms the potassium salt of 2-methylcoumarilic acid crystallising in silky glistening needles ; the acid forms feather- like prisms m. p. 18s" (compare Hantzsch Zoc. cit.); the copper salt forms green needles containing 3H,O and the methyl ester long glistening needles m. p. 70'. 4-Methyldihydrocoumarin crystallises in colourless monoclinic prisms m. p. 278'. CMe:CBr 3 6-Dibromo-4-methylco~~ar~n C6H,Br<o-bo prepared by the action of bromine in carbon disulphide solution in sealed tubes a t 140") crystallises in yellow needles m. p. 167". Alkali converts it into 4-bromo-2-metl~ylcoumari~ic acid separating from benzene in aggregates of yellow needles m. p.155O and forming a copper salt ( +2H20) bright green needles and a potassium salt ( + 2H,O) silky glistening needles. 3 6 8-~ribromo-4-nzet?~ylcoumccrin prepared by heating with bromine under pressure at 175" separates in colourless prisms m. p. 196". It yields when heated with potassium hydroxide 4 6-dihomo- 2-methy~coumuri~ic acid C,I~,B~,<?~>C*CO~H a yellow flocculent precipitate rn. p. 96'; the copper salt (+2H,O) forms green microscopic needles. * CMe:UH 6-Bromo-4-me~hyEcoumccrilz C6H,Br<0 -b0 I prepared from p- bromophenol and ethyl acetoacetate forms colourless needles M. p. 187". It yields a mixture of 3 6- and 6 8-dibromomethylcoumarins when brominated and the 3 6 8-tribromomethylcoumarin on further bromination. This last compound when oxidised with permanganate in alkaline solution gives 3 5-dibromosalicylic acid thereby fixing the position of the bromine atom 3.CMe ?Me 0-co 3 ; 4-DimethyZcoumarin C6H,< prepared by condensing ethyl methyl acetoacetate with phenol has m. p. 115' and is isomeric with von Pechaann's 4 6-dimethylcoumarin (Abstr. 1885 56). E. F. A. Comparative Study of the Dehydration of Atrolactic and p-Methoxyatrolactic Acids. p-Methoxyatropic and Di-p- methoxyatropic Acids. 6. BOUGAULT (Compt. rend. 1908 146 766-769. Compare Abstr. 1902 i 452).--Methoxyatrolactic acidORGANIC CHEMISTRY. 341 is markedly different from atrolactic acid in its relation t o dehydrating agents. Ladenburg found (Abstr. 1883 670) that atrolactic acid is dehydrated by prolonged boiling with dilute hydrochloric acid giving atropic acid and a little of Fittig's isoatropic acid ; the author obtains the same transformation by heating for thirty minutes with concen- trated hydrochloric acid on a boiling water-bath.By the very prolonged action (five to six months) of cold hydrochloric acid however P-chlorohydratropic acid CH,Cl-CHPh*CO,H is the chief product together with a small quantity of isoatropic acid. Atrolactic acid does not give appreciable quantities of atropic acid when boiled with acetic or very dilute mineral acids. On the other band p-methoxy- atrolactic acid is rapidly dehydrated by boiling with these acids giving good yields of p-methoxyatropic acid OMe*C,H,*C(CO,H):CH shining spangles m. p. 119-120' which forms a dibromide m. p. 142'. When p-methoxyntrolactic acid is left in contact with cold concentrated hydrochloric acid for forty-eight hours the product is a mixture in almost equal parts of p-methoxyatropic acid and a dimolecular condensation derivative of this called by the author his-p-methoxy- atropic acid (C~oE€~,,03)2.At the temperature of the water-bath the latter acid is the sole product and the reaction is complete in fifteen to twenty minutes. Bis-p-methoxyatropic acid has m. p. 2 1 5 O and by titration with standard alkali its molecular weight is found to be 356 (calculated as a monobasic acid). Re-titration after boiling with slight excess of alkali gives the result 178 (also calculated as a monobasic acid) indicating that the substance is a lactonic acid. Fittig (Abstr. 1881 425) proposed the formula (I) for isoatropic acid from which the formula (11) would be deduced for bis-p-methoxyatropic acid The author however considers that a direct combination of the *CH,* groups is improbable and prefers the formula (111) for the new acid and accordingly represents Fittig's <boatropic acid by (IV) which explains more easily than (I) its oxidation to anthraquinone.E. H. Tyrosine. JULES ALOY and CHARLES RABAUT (Bull. Soc. chim. 1908 [iv] 3 391-393).-A study of the action of various reagents on tyrosine. The hydrobromide and hydriodids of the base which are both crystalline are described. Bromine vapour converts the base into dibromotyrosine hydrobromide but with excess of bromine water an unstable yellow perbromide is obtained which is soluble in alkalis rand most organic solvents.Dry chlorine has no action on the base but in presence of moisture a yellow unstable perchlorinated product is formed which blackens on exposure342 ABSTRACTS OF CHEMICAL PAPERS. t o air. No definite derivatives can be obtained by the action of iodine vapour on tyrosine. Tyrosine suspended in water or dissolved in hydrochloric acid gives on addition of chlorine water followed by ammonia solution a fine red colour. Bromine water may be used in place of ohlorine water but the colour formed is then less intense. Leucine does not give this reaction. T. A. H. Catalytic Reactions at High Temperatures and Pressures. XVI. Reduction of Aromatic Ethers Eaters and Acids in Presence of Nickel Oxide. WLADINIR N. IPATIEFF and 0. PHILIPOFF (Be?..1908 41 1001-1007).-Phenyl ether is reduced by hydrogen in presence of nickel oxide at 230°/100 atmospheres in twelve hours forming cyclohexane cyclohexanol and cyclohezgl ether O(C,HI,) which is formed also together with cyclohexanol by reduction of phenol in the same manner and is obtained as a viscid oil b. p. 275-277O/760 mm. Ethyl phthalate when heated with hydrogen and nickel oxide under high pressures yields methane carbon dioxide o-toluic acid phthalic acid and small amounts of benzoic acid. Potassium phthalate remains unchanged when mixed with nickel oxide and heated in a current of hydrogen at 300° or if heated with hydrogen alone under pressure but if heated with hydrogen and nickel oxide under pressure a t 300° it is reduced to trans-cyclohexane-1 2- dicarboxylic acid together with small amounts of benzoic acid and metbane ; the amount of these by-products increases rapidly with the temperature of the reaction.This reduction is recommended as the most convenient method of preparing the ti.cclz~-cyclohexanedicarboxylic acid. Under the same conditions potassium benzoate is reduced in nine hours to the extent of 40-50% yielding potassium cyclohexane- carboxylate ; at temperatures above 320° the yield decreases in consequence of increased formation of methane. The yclohexane- carboxylic acid is best prepared by heating sodium benzoate which is more easily reduced than the potassium salt with hydrogen and nickel oxide under pressure a t 300" for two periods of four hours each. G. Y. Phthalides a n d Meconines.ERIC MERMOD and HUGO STMONIS (Ber. 1908 41 98%-985).-The condensation of organo-magnesium compounds with phthalaldehydic acid and opianic acid has been con- tinued (compare Abstr. 1906 i 32 303). a-Ethylphthalide (compare Gottlieb Abstr. 1899 i 512) and a-phenyl- phthalide (Graebe and Juillard Abstr. 1888 1095) have been prepared from phthalaldehydic acid. Anhgdro - aa' - climethylh?/dropl~t?~alide C6H4<:k&:50 or CMe CMe C,H4< I >0 obtained by the action of magnesium methyl iodide on an ethereal solution of a-methylphthalide (Abstr. 1906 i 32) crystallises from dilute alcohol in colourless needles m. p. 153' (decomp.) after sintering at 140".ORGANIC CHEMISTRY. 343 a-Yhenylmeconine C H ( O M e ) < ~ ~ ~ ~ > O crystallises from alcohol in glistening prisms m.p. 112'. When warmed with alkalis the ring is ruptured but closes again on the addition of acid The meconine dissolves in cold concentrated sulphuric acid to a colourless solution which assumes a purple coIour when warmed. Magnesium alkyl or aryl bromides do not react with phthal- aldehydic or opianic acid. Bromonlkylmeconines can be obtained either by the condensation of Grignard's compound with bromo-opianic acid or by the bromination of the alkylmeconines. Bromo-a-msthyE meconine C,HBr(OMe),<CHMe>O forms colourless plates rn. p. 77* and the corresponding ethyl compound has m. p. 79'. - co- Nitro-a-etJiylmeconi~ze N0,*C,H(OiMe)2<C'KEt>0 -co- obtained by the action of fuming nitric acid on ethylmeconine crystallises from alcohol in yellow plates m.p. 103.5'. When reduced it yields amino-a-ethyl- meconine C,,H,,O,N in the form of colourless prisms m. p. 158'. The hydrochZoride C',,H,SO,N,HCl forms sparingly soluble glistening needles m. p. 1 9 6 O (decomp.). The plcctinichlorids forms a brown precipitate which decomposes at 172O and the aurichloride a dark green precipitate decomposing at 200'. J. J. S. Synthesis of Certain Aromatic Succinic Acide. SAMUEL AVERY and FRED W. UPSON (J. Amer. CAem. Soc. 1908,30,600-604). -In order to compare the up-diphenylglutaric acid obtained by Avery and McDole (compare following abstract) with its isomeride a-phenyl- p-benzylsuccinic acid CO,H*CHPh* CH( CH,Ph)*CO,H the latter was prepared by the condensation of ethyl sodiobenzylmalonate with ethyl bromophenylacetate ; it crystallises in slender whito needles m.p. 176'; the silver salt is a white amorphous precipitate. The in- vestigation was then extended to see if sodium benzyl cyanide could be made to conderise with aldehyde cyanohydrins in the same way as ethyl sodiocyanoacetate as described by Higson and Thorpe (Trans. 1906,89 1455). This was found to be the case; thus the nitrile of up-diphenyl- succinic acid (compare Chalaney and Knoevenagel Abstr. 1892 61 9) was obtained from sodium benzyl cyanide and benzaldehyde cyano- hydrin. I n some cases one of the cyano-groups undergoes saponi- fication during the reaction. This seems to depend on the nature of the adjacent groups ; for example /I-cyccno-p-phenyl-a-isopropyZpropionic acid CN*CHPh*CHPrp*CO,H is formed by condensing sodium benzyl cyanide with isobutaldehyda cyanohydrin ; it forms white feathery crystals m.p. 126' and when heated with strong hydrochloric acid under pressure is converted into p-phenyl-a-isopropylguccinic acid CO,~*CHPrs*CHPh*COzH crystallising i n colourless microscopic plates m. p. 17s". Action of Sodium Benzyl Cyanide with Cinnamic Ester. SAMUEL AVERY and GUY R. MCDOLE (J. Amer. Chern. SOC. 1908 30 595-600).-The action of benzyl cyanide on ethyl cinnamate was studied with the object of preparing certain aryl glutaric acids. It W. H. G.344 ABSTRACTS OF CHEMICAL PAPERS. was thought probable that the reaction would take place in a manner similar to that observed by Michael (Abstr. 1887 6'72) in the action of ethyl sodioacetoacetate on the esters of unsaturated acids namely in the formation of a compound having the constitution CN*CHPh*CHPh- CHNa*CO,R.It was found however that the ester had undergone saponifkation the two principal products formed being sodium y-cyano-by-diphenyl- butyrate and a compound to which is provisionally given the formula O<CO* Co*CH2'CHPh>CPh*CN CH * C H P h ; this formula is in harmony with the observed facts except in the following the compound appears to be unchanged when boiled with sodium carbonate or ammonia in aqueous or alcoholic solution and although it is converted into a salt when boiled with alcoholic potassium hydroxide the acid liberated from the salt has resisted all attempts to reconvert it into an anhydride. y-Cyano-by-diphenylbutyric acid CN*CHPh*CHPh-CH,*CO,H pre- pared by the interaction of benzyl cyanide and ethyl cinnamate in the presence of solid sodium methoxide crystallises in glistening white needles m.p. 161.5'. When heated with strong hydrochloric acid in a sealed tube a t 150' for three hours it is converted into ap-diphemyL glutaric acid CO,H*CHPh*CHPh*CH,*CO,H crystallising in needles m. p. 223-224'; the silver salt CI7Hl40pAg2 was prepared The anhydride could not be obtained ; the anzlzde C2sH2103N crystallises in flat needles with a pearly lustre m. p. 230-232'. The substance CN*CPh(CHPh*CH,*CO),O (?) is obtained when a mixture of benzyl cyanide and dry sodium methoxide heated to 140' is added to hot ethyl cinnamate the whole being kept at 140' for ten minutes. It crystallises in long obliquely pointed plates m.p. 231-232' ; when heated with a strong alcoholic potassium hydroxide solution it is converted into the potasaium salt of an acid ; the free acid C2,H2,04N crystallises in rectangular plates m. p. 213'; the silver salt is a white insoluble powder W. H. G . HENRY M. GORDIN (J. Amer. Chern. Soc. 1908 30 2 65-2 7 1 ).-Marrubiin the bitter constituent of horehound (Mar- rubiurn uulgare) was first investigated by Harms and later by Kromayer Hertel Morrison and Matusow. Marrubiin C2,H,,04 has m. p. 1545-155*5" b. p. 297-299'/ 15 mm. [ a] + 45-68" and when crystallised slowly from alcohol forms large monoclinic prisms [a b c = 1.5551 1 0.885 ; p= 61'17'1 but when crystallised rapidly forms flat tabular prisms which also belong to the monoclinic system.The compound does not contain any methoxyl groups and does not decolorise bromine solution. It has a bitter taste a neutral reaction and does not contain hydroxyl or carbonyl groups. When boiled with alcoholic potassium hydroxide it is converted into potassium marrubate. Marrubic acid C,,H290,*C0,H m. p. 1'73-174' and [a] + 7-86' forms long white silky needles and when heated a t 190-200° under 15 mm. pressure is reconverted into marrubiin The same change can be brought about by heating the acid a t 50° with acetic anhydride containing a trace of zinc chloride or by boiling it with alcoholic Marrubiin.ORGANIC CHEMISTRY. 345 hydrochloric acid. The acid reduces ammoniacal silver nitrate and Fehling's solution. The barium salt is described.The eth$ ester m. p. 87' forms lustrous scales and when heated at 100' under 28 mm. pressure is converted into marrubiin. The results of the investigation indicate that marrubiin is a lactone O < ~ ~ H 2 s 0 2 behaving like a y-lactone in taking up a molecule of water to form a hydroxy-acid marrubic acid OH*CzoHz80,-C02H. E. G. Synthesis of Optically Active Dibenzylaspartic and Dibenzylmalamic Acids. OSCAR LUTZ (Bey. 1908 41 841-847). -Fischer and Baske (Abstr. 1907 i 381) have shown that under certain conditions d-aspartic acid is formed from I-bromosuccinic acid ; the chief product however is malamic acid. I t appears on further study of this reaction that in addition to the influence of temperature the strength and constitutiou of the base employed have also t o be taken into account. By the action of dibenzylamine a weaker base on I-chloro- or -bromo-succinic acid d-dibenzylaspurtic acid is formed t o the extent of 65-70% and 1-dibenxylmalamic acid to the extent of 8-1 5%.The former N(C?H,),*CH( CO,H)-CB,* CO,H forms thread- like matted needles m. p. 152-153" is relatively stable towards heat and barium hydroxide and forms a siher salt C18H1704NAg2. I n ethylalcohol [a] = 0"; in sodium bjdroxide Eolution [a] = + 23.2' ; in presence of benzylamine it has [a] + 43.8" in ethyl alcohol +4' in methyl alcohol - loo in acetone aad - 5.2" in acetic acid. 1-Dibenzylmcdamic acid CO,H-CH(OH)*CX,*CO*N(C,H,) forms minute prisms m. p. 169-170° (decomp.) ; it loses water when heated and forms an optically inactive unsaturated compound.It has [.ID - 61.6' in ethyl aliohol or - 26.4" in presence ofbenzylsmine. E. F. A. Action of Ozone on Santonin. GUIDO BARGELLINE and CESARE GIALDINO ( A t t i R. Accad. Lincei 1908 [v] 17 i 248-849).-The action of ozone on a chloroform solution of santonin or on a faintly alkaline solution of sodium santoninate yields an acid apparently identical with the ketonic acid C1,H,,07 obtained by Angeli and Marino (Abstr 1907 i 321) by the oxidation of santonic acid with potassium permnnganate. T. H. P. Preparation of Coumarincarboxylic Acid. HAARMANN and REIMER (D.R.-P. 189252).-Cournarin-3-carbox~~Zic acid m. p. 187-188" mas obtained by condLnsing cyanoacetic acid and salicylaldehyde in alkaline solution to o-hydroxybenzylidenecyano- acetic acid and hydrolysing this intermediate product with steam and concentrated hydrochloric acid.Coffee. 11. I<. GORTER (Annalen 1908 359 217-244. Compare this vol. i 186).-In continuation of his investigation of the con- stituents of coffee extract the author has studied the decomposition G . T. M.346 ABSTRACTS OF CHEMICAL PAPERS. products of chlorogenic acid and describes some further new substances obtained from the coffee beans. When treated with aqueous potassium hydroxide at the ordinary temperature chlorogenic acid yields caffeic and quinic acids but if boiled with dilute mineral acids decomposes t o the extent of 70% forming carbon dioxide and a product which is reddish-violet with blue fluorescence in solution and to the extent of 30% is hydrolysed to caffeic and quinic acids.The colour reactions of these two acids and the zinc ( CtH,,O,),Zn and calcium (C7H,,0,)2CYa,10H20 salts of quinic acid are described. The action of acetic anhydride containing small amounts of sulphuric acid on chlorogenic acid a t the ordinary temperature leads to the formation of pe~tta-acetyZhe1ltic7t7o~ogenic mid C,,H,,O Ac5 which crystallises from dilute alcohol in white needles m. p. 180.5-181° and has a bitter taste; the aniline salt C,,H,,0,Ac5,NH2Ph white crystals m. p. 142-143'. On hydrolysis with acids or alkalis the penta-acetyl compound yields hemichlovogenic acid ; this is isolated as the aniline salt C,,H,,OS,NH,Ph crystallising in white needles m. p. 173'. A mixture of this salt with the aniline salt of chlorogenic acid C,,H,,01,,2NH,Ph m.p. 174' has m. p. 165-166O. The Oenxidine salt needles m. p. 161° is more readily soluble than the corresponding chlorogenate. The consideration of these facts leads to the formulation of the annexed constitutions for chlorogenic acid (I) and hemichlorogenic acid (11) I 0 I Addition of alcohol to the first extract of Liberian or Arabian coffee beans precipitates a pectin substuncs [a] + 15O which has a feeble acid reaction dissolves slowly in water when heated with dilute mineral acids yields galactose and a pentose and on oxidation with nitric acid forms mucic acid. Cofaliu acid C34H54015 is obtained on evaporation of the mother liquor from the preparation of potassium-caff eine chlorogenate ; it crystallises in colourless rhombic prisms m. p. 255O has a sweet taste forms precipitates with silver nitrate copper sulphate and lead acetate and ammonia and on hydrolysis with alkalis or acids yields isovaleric acid and an amorphous substunce which commences to soften at 160° m.p. about 2559 Liberian coffee beans contain an oxydase which gives yellow changing to yellowish-green and reddish-brown coloration with potassium caffeine chlorogenate and is therefore the cause of the colour gradually acquired by the colourless beans after plucking ; the oxydase is destroyed at 70° and gives a coloration with guaiacol solu- tions resembling but less intense than that given by laccase.ORGANIC CHEMISTRY. 347 The caffetannic acid described by previous authors is a mixture of ahlorogenic and coff alic acids with other substances G.Y. Preliminary Note on the Constitution of Gdlotannic Acid and of Tannins in General. STEWART J. LLOYD (Chem. News 1908 97 133).-From molecular weight determinations of crystalline com- pounds of gallotannic acid notably the penta-acetyl derivative it is concluded that natural gallotannic acid is composed of three digallic acid groups united to each other through three oxygen atoms to form a six-membered ring of the type CXY<E:g$g>O in which X= OH CO,H /-\OH and Y = 0- (-\* analogous t o that -/ OH OH -\-/ OH found in trithio-ketones and trithio-aldehydes. Such a configuration admits of an inactive cis-form as well as the active trans-form which is assigned to natural gallotanriic acid. P H. Catalytic Reactions at High Temperatures and Pressures. XIV.Reduction of Benzaldehyde and Benzyl Alcohol in Presence of Iron. WLADIMIR N IPATIEFF (Ber. 1908 41 993-995. Compare Abstr. 1907 i 5 827).-It was shown previously that aliphatic aldehydes and ketones are reduced to the corresponding alcohols by hydrogen in presence of iron at high temperatures and pressures and that on the other hand aromatic alcohols aldehydes and ketones under similar conditions but in presence of nickel oxide yield cycbpolymethylenes. It is now found that when heated with hydrogen in an iron tube for twelve hours at 280"/100 atmospheres benzaldehyde yields water toluene dibenzyl and resins. It is considered that the reduction must lead in the first place to the formation of benzyl alcohol; part of this is reduced directly to toluene whilst another part forms water and benzyl ether whioh on further reduction yields toluene and dibenzyl.I n agree- ment with this view it is found that benzyl alcohol under similar conditions yields toluene benzaldehyde and dibenzyl. Moreover whilst reduction of the alcohol in a copper tube leads t o the formation of toluene and small amounts of dibenzyl benzaldehyde which as previously shown does not form benzyl alcohol when heated with hydrogen in presence of copper under these conditions also does not yield dibenzyl. I n the absence of hydrogen benzyl alcohol decom- poses when heated in an iron tube at 400° forming hydrogen and benzaldehyde which partly decomposes further t o benzene and carbon monoxide and partly is reduced by the hydrogen forming toluene and dibenzyl.G. Y. Reaction between Potassium Cyanide and o-Nitrobenz- aldehyde. S. EKECRANTZ and A. AHLQVIST (Ber. 1908 41 878-881).-The authors have examined the action of potassium cyanide on o-nitrobenzaldehyde under Popovici's conditions (Abstr. 1907 i 628) and conclude that her so-called 2 2'-dinitrobenzoin348 ABSTRACTS OF CHEMICAL PAPERS. consists of o-nitrosobenzoic acid and o-azoxybenzoic acid and thRt her 2 2'-dinitrobenzil is o-nitrobenzoic acid. c. 8. Action of Grignard Compounds on o-Phthalaldehyde. F. NELKEN and HUGO SIMONIS (Bey. 1908 41 986-989).-o-Phthal- aldehyde condenses with an excess of magnesium alkyl iodides yielding o-dihydroxyalkylhenzenes which when distilled form alkyl derivatives of isocoumaran or 1 3-dialkylphthalans (compare Ludwig Abstr.1907 i 702) Di-a- iiydi.ox?/-o-diethyZbenzene C,H,(CHMe*OH) is a yellow viscid oil which solidifies when placed in a freezing mixture. It dissolves readily in practically all solvents and when distilled under reduced pressure yields 1 3-dimethylphthalan as a pale yellow oil b. p. 122O/50 m.m. Di-a-hydroxy-o-dipropyZbenxene CGH,(CHEt*OH) is an oil and the corresponding 1 3-diethy/phtl,ccZccn has b. p. 137O/50 mm. 1 3-DiphenyZphthaZccn has b. p. 240*/14 mm. and forms a limpid yellowish-red oil. J. J S. [Preparation of Vanillin from Guaiacol.] A. ROESLER (D.R.-P. lS9037).-The formation of an aldimide compound does not occur with guaincol hydrogen cyanide and hydrochloric acid except when the reagents are brought together in the capillary interstices of infusorial earth.This earth is mixed with aqueous zinc chloride and heated to dryness then treated with a benzene solution of guaiacol and hydrogen cyanide and saturated with hydrogen chloride. The intermediate aldimide hydrochloride OMe*C,H,(O€I)*UH:NH,HCl is decomposed with water and the vanillin extracted with ether and purified by means of its bisulphite compound. G. T. M. Synthesis of Trimethylgallaldehyde. FERDINAND MAUTHNER (Bey. 1908 41 920-925).-The close relationships existing between gallaldehydes and some natural products suggested the above synthesis. Trimethylgall yl chloride (Perkin and Weizmann Trans. 1906 89 1655) was first condensed with hydrogen cyanide in ethereal solution in tbe presence of pyridine to form 3 4 5-trimethoxybenzoyl cyanide C1,Hl,O,N which crystallises in yellow needles from light petroleum ; m.p. 136-137'. It is hydrolysed on warming with dilute acids or alkalis to trimethylgallic acid but the cyanide and hydrochloric acid (D 1.19) a t the ordinary temperature after ten days yield a mixture of (1) trimethoxyphernylglyoxyhmide C,H,(OMe),*CO*CO*NH in small amount crystallising from benzene in colourless needles m. p. 149-150° which on heating with acids or alkalis give trimethyl- gallic acid ammonia and carbon monoxide and (2) a good yield of trimethoxyphenylglyoxylic acid CllH,,OG separating from benzene in colourless needles m. p. 155-156" ; the phenylhydraxone CI7Hl8O5N2 forms yellow needles m. p. 213-214". Bouveault's method of converting this a-ketocarboxylic acid into the aldehyde by heating with aniline and then hydrolysing the anilORGANIC CHEMISTRY.349 (Abstr. 1896 i 649) was used. (rrinzethyZgallaEdehyde C,,H,,O crystallises from light petroleum in colourless leaflets m p. 74-75'. It has all the usual properties of an aldehyde; its p-fiit?-ophengZ- hydruxone CleHl7O5N3 forms red needles m. p. 201-202O and the semicarbuxone C,,H,,O,N crystallises from water in colourless needles m. p. 219-2204 W. R. Formation of Mixtures of Isomerides of Constant Melting Point in Friedel and Crafts' Reaction. GUSTAVE PERRIER and H. CAILLE (Compt. rend. 19OS 146 769-770).-0ne of the authors (Perrier 2'/&5se Paris 1896) has described previously a method of separating the mixtures of isomeric ketones obtained by Friedel and Crafts' reaction based on the differences in stability and solubility i n carbon disulphide of their additive compounds with aluminium chloride. To effect a good separation by this method the crystals first deposited must be collected separately and when decomposed with water these give one isomeride in a pure state.If in the preparation of the phenyl naphthyl ketones this precaution is not observed the product consists not of the P-isomeride but of a substance m. p. 54' (sharp) also resulting from Friedel and Grafts' reaction as ordinarily carried out. This substance by (1) recrystallisation from light petroleum and mechanical separation of the crystals de- posited and (2) preparation of the picrates can be separated into the U- (m. p. 75") and the P-isomerides (m. p. SZ') and appears to be a eutectic mixture of the two.E. H. isoOrcacetophenone Dimethyl Ether. JOSEF TAMBOR [and in part ST. BARAROWSKI A. COMITESSE and W. Tom] (Ber. 1908 41 793-79s. Compare this vol. i 358).-A substance obtained occasionally as a by-product in the preparation of orcacetophenone dimethyl ether is now found to be an isorneride. When heated with methyl benzoate m-methoxybenzoate or veratrate and sodium it forms substituted benzoylacetophenones which are isomeric with those obtained under the same conditions from orcacetophenone dimethyl ether and are converted in the same manner into substituted methyl- flavones. Hence the isoorcacetophenone dimetiw2 ether must have the constitution C(*Me):CH*flMe- I It is preiared by the action of CH:C(ONe)*C*COMe' \ acetyl chloride and aluminium chloride on orcinol dimethyl ether in presence of small amounts of glacial acetic acid or of acetic anhydride and aluminium chloride on cooled orcinol dimethyl ether ; it crystallises on evaporation of the light petroleum filtrate from orcacetophenone dimethyl ether in white needles m.p. 48'. iso0rcacetophenone monomethyl ether formed together with the dimethyl ether must be a product of the hydrolysis of this having the constitution C(OMe):CH-;C;Me 6 ~ C(OH)-C*COM~ since in substituted acetophenones a methoxyl group in the ortho position is always more easily hydrolpsed than one in the para position The monomethyl ether crystallises in white needles m. p. 79" and is350 ABSTRACTS OF CHEMICAL PAPERS. converted into the dimethyl ether by tho action of methyl sulphnte and a1 kalis.2 4-Dimethoxy-6-nzethylbenxoylacetophenone C,H2Me(OMe),*CO*CH2-COPh crystallises in white needles m. p. 76-77' and when boiled with concentrated hydriodic acid yields ( a ) 7-methoxy-5-methylJEavone OMe=C,H,O,PhMe which crystallises in colourless needles m. p. 115' and is insoluble in a1 kalis and (b) 7-hydroxy-5 -methyZ~'$avone OH* CSH302PhMo which forms white needles rn. p. 297' dissolves in dilute sodium hydroxide to a slightly ysllotv or in concentrated sulphuric acid to a colourless solution with blue fluorescence and is converted by methyl sulphate and alkalis into 7-methoxy-5-methglflavone. 7-Acetoxy-5-methyZJZavone CigHI4O4 forms colourless needles m. p. 147'. 2 4 3'-Trimethoxy-6-methyEbenxoylacetophenone C,H,Me( OMe),*CO*CH,*CO*C,H,*OMe prepared from isoorcacetophenone dimethyl ether and me thy1 m-methoxybenzoate crystallises in colourless prisms m p.107". 7 3'-Bihydroxy-5-methyIJEccvone OH*C,H,O,Me*C,H,*OH colourless needles m. p. 260*. 2 4 ; 3' 4'-Tetrccmethoxy-6 -methyEbenxoylncetophenone C20H22?6 pre- pared from the isodimethyl ether and methyl veratrate crystallises in white needles,m. p. 134'. 7 3' 4'-Trihydroxy-5-methyZjavone C,,H,,9 greenish-yellow needles m. p. 258'. The tyiacetate C,,H,,08 white needles m. p. 188". The di- tri- and tetra-methoxymethylbenzoylacetophenones give red colorations with alcoholic ferric chloride. The di- and tri- hydroxymethylflavones form yellow or greenish-yellow solutions in concentrated sulphuric acid G. Y. Preparation of Aldehydes and Quinones.WALTIIER LANQ (D.R.-P. 189 178).-Mccnganous ammonium eulphate 2MnS04,(NH,),S0 is obtained from a hot acid solution containing excess of ammonium sulphate; it forms yellow anhydrous crystals and is decomposed by water into the double salt MnSO,,(NH,),SO and ammonium sulphate. The new double salt dissolved in dilute sulphuric acid is electrolysed into manganic ammonium alum a lead-lined electrolytic cell serving as the anode. When benzene and toluene are oxidised with this manganic salt at 50° p-benzoquinone and benzaldehyde are produced whilst naphthalene anthracene and phenanthrene yield their respective quinones. G. T. M. Trimethyl Ethers of Emodin from Frangula and from Aloes. OTTO A. OESTERLE and ED. TISZA (Arch. Pharm. 1908 246,112-1 16).-The above emodins have been methylated (with methyl sulphate in aqueous solution) with a view to determining whether any of the hydroxyl groups are in the a-position to a carbonyl group and thus resist methylation (as found by Kostanecki and Drehe. Frangula- emodin readily gives a trimethgl ether C15H702(OMe)3 yellow needles m. p. 2 2 5 O and since this emodin is derived from P-methylanthraceneORGANIC CHEMISTRY. 351 (according t o Iiebermann) it appears t o be a 3 6 7-trihydroxy- 2-methylanthraquinone HO/\ HO( )zc0- C O - O M e ,OH. The isomeric tvirnethyl ethey of emodin 'from aloes forms orange- coloured needles m. p. 1 6 3 O and is only formed very slowly ; from this and from the tinctorial properties it is deduced that two at least of the hydroxyl groups are in a-positions.The substance thus appears to be connected with chrysazin. G. B. Preparation of Dimenthyl Dimethylene Ether. K. A. LINGNER (D.R.-P. 189331).-Dimenthyl dimethylene ether O(CH,*O*C,,H,,) formerly obtained from menthol formaldehyde and a mineral acid at low temperatures has now been prepared by adding 8-dichloromethyl ether to a toluene solution of sodium menthyl oxide the yield being 76% of the calculated. 42. T. M. Preparation of Bornyl Borate. VEREINIGTE CHININFABRIKEN ZIMMER & Co. (D.R.-P. 188703).-BonzyZ borate B(OC,,,Hl7) a white tasteless powder is prepared by heating borneol with boric acid or anhydride in xylene or by melting together at 250" boryl acetic anhydride and borneol. G. T. M. Preparation of isoBornyl Esters of the Fatty Acids from Pinene Hydrochloride or Hydrobromide.CHEMISCHE FABRIK VON HEYDEN (D.R.-P. 189261).-isoBornyl acetate results from the heating together of pinene hydrochloride acetic acid zinc chloride and aluminium hydroxide or magnesium oxide. The presence of zinc chloride is essential ; in its absence a portion of the pinene derivative remains unchanged. G. T. &I. Dynamic Isomerism. HENRY E. ARMSTRONG THOMAS M. LOWRY SYDNEY YOUNG JAMES J. DOBBIE ARTHUR LAPWOBTH MARTIN 0. FORSTER and CECIL H. DESCH (Brit. Assoc. Report 1907 77 270-272).-Tbis report deals mainly with the influence of impurities on the velocity of mutarotation of nitrocamphor. T. H. P. An Isomeride of Dipheaylcamphorylmethane and the Con- ditions of its Formation. ALBIN HALLER and E.BAUER (Contpt. rend. 1908 146 71 8-722).-When diphenylcamphorylmethylene is reduced by sodium amalgam in acid-alcoholic solution diphenyl- camphorylmethane m. p. 106-107° is formed (Abstr. 1906 i 441) but if the reduction i s carried out in alkaline alcoholic solution an $someride m. p. 136* is obtained. The compound described previously is moreover transformed into its isomeride when boiled with alcoholic potash or when heated with sodamide in the presence of toluene. The product of the action of magnesium phenyl bromide on benzyl- idenecamphor reacts with benzoyl chloride as has been described fop352 ABSTRACTS OF CHEMICAL PAPERS. the benzylideneacetophenone derivative (Kohler Abstr. 1904 i 595) thus C:CHPh -t PhMgBr = CsH14<eOMgBr C*CHPh C8Hl C-CXPh cg1314<' C*CHPh2 I + PhCOCl= CgH14<8.0.c0ph + MgCIBr C*OlIaBr v forming d~p?~enylctc~~~~horyZmeth~~e benzoate. The latter compound whether hydrolysed by boiling alcoholic potash by cold sodium ethoxide solution by ammonia at 180° or by concentrated hydro- chloric acid at 150° invariably gives rise to the isomeride m.p. 136-137O. But the benzoyl derivative cannot be prepared by the direct action of benzoyl chloride on either of the modifications of diphen ylcamphorylmethane. The observed molecular refractive powers of the isomerides m.. p. 106-101° and 136-137O are 98.39 and 98.87 respectively whilst the values calculated for the ketonic (I) and enolic (11) forms of C*CHPb *OH I* C8H14<&) CH*CHPh2 11. CgH14<Z dipheoylcamphorylmethane are 97.35 and 98.29.But although the observed values approximate to the latter figure it cannot be deduced that the isomerides have the euolic form since it has been shown (Haller and Muller Abstr. 1900 i 182) that introduction of aromatic groups into the camphor molecule increases the molecular refractive power by as much as one unit. It is stated in conclusion that hitherto no reaction or phpical measurement has elucidated the constitution of these two isomeric compounds. E. H. Preparation .of Normal Alkyl Camphorates. J. D. RrEDEL (D.R.-P. 189840).-The methods hitherto employed have not given a satisfactory yield of dislkyl camphorates as the normal ester was always mixed with the acid ester. It has now been found that the use of alkyl sulphates or aryl sulphonates readily leads to the normal ester.Methyl d-camphorate was obtaiued by adding methyl sulphate to an alkaline solution of d-camphoric acid. Ethyl d-camphorate was prepared either by adding ethyl sulphate to d-camphoric acid dissolved in alcoholic sodium ethoxide or by mix- i n g together ethyl benzenesulphonate and an aqueous solution of potassium d-camphora te. G T. 3%. Dimethylcampholide. GUSTAV KOMYPA (Ber. 1908 41 1039-1044).-This investigation had as its object the preparation of aa-dimethylcamphor in order that the properties of this compound might be contrasted with those of fenchone. If the latter compound has the constitution assigned to it by Semmler then the two sub- stances should closely resemble one another in chemical properties I n order to obtain the dimethylcamphor dirnethylcarnpholide was first prepared ; it was then thought possible that by treating this withORGANIC CHEMISTRY. 353 potassium cyanide and hydrolysing the cyanide formed that dimethyl- homocamphoric acid would be obtained from which dimethylcamphor could be prepared by the dry distillation of the calcium salt.This however could not be realised since dimethylcampholide when heated with potassium cyanide yields an acid isomeric with dimethyl- campholide instead of the desired cyanide. CH,*C H - C Me Dimet JA ylcumpholide I >CMe >0 is prepared by treating with dilute sulphuric acid the additive product formed by acting on camphoric anhydride with magnesium methyl iodide in ether; it crystallises in slender white needles m. p. 835-85O. When heated alone in a sealed tube at 285-300° or with potassium cyanide at 275 -290° or with 50% aqueous potassium hydroxide solution under pressure a t 285-295O it is converted into an unsaturated monobasic acid which probshly has the formula I >CMe or CH,*(J=== CMe CH,*CMe- co CH,-CH- CMe:CH OH CMe-- CO,H I >CMe CH,*CMe--CO,H ; it crystallises in bent needles m. p.68.5-70.5"; the Lmmonium s i l t crystallises in glistening white leaflets. The acid decolorises bromine water and potassium permanganate solution and is reconverted into diniethylcampholide by passing dry hydrogen chloride into its solution in absolute ether. W. H. G. sesquiterpene from Oleurn Cadinurn. :WAN SCIITNDELMEISER (J. Russ. Phys. Chem. SOC. 1908,40,1$1-184. Compare Lepeschkin this vol.i 27$).-The sesquiterpene described by Lepeschkin is considered to be a mixture of a sesquiterpene described by Troger and Feldmann (Abstr. 1899 i 376) with considerable quantities of cadinene ; and the isomeric sesquiterpene obtained by treating Lepeschkin's subst6nce with hydrogen iodide is not identical with humulene but consists of a mixture of tetrahydrocadinene cadinene and an optically inactive sesquiterpene. Sesquiterpenes. 11. ERNST DEUSSEN and ARNOLD LEWINSOHN (Annaleln 1908 359 245-261. Compare Abstr. 1907 i 945).- 1. CuryophyZZene ,Series.-It is now found that on repeated distilla- tion caryophyllene yields two hydrocarbons one of which has b. p. 132-134"/16 mm. [a] - 4-67" D20 0,90346 rz 1-4997.3 and yields 20.8% of nitrosochloride and 8.2% of blue nitrosite whilst the other has b.p. 128-128*5°/17 mm. [a]" - 23*57O Dl70.91034 ng 1.49899 and yields only traces of nitrosochloride and 0.5% of nitrosite. This hydrocarbon is not identical with the sesquiterpene b. p. 123-124*/14 mm. previously described (Zoc. cit.) as that forms 25% of nitrosochloride. A further fraction obtained from caryophylleqe has [a]. - 8" to - 9*6" and gives 4*5-4.0% of nitrosochloride and 19*5-22% of nitrosite. The conclusion is drawn that the caryo- phyllenes described in the literature are mixtures of inactive caryo- phyllene with considerable amounts of a leevorotatory hydrocarbon. YOL. XCIV. i. b b Z . K.354 ABSTRACTS OF CHEMICAL PAPERS a-Caryophyllene nitrosobromide Ci,H,40NBr prepared by the action of ethereal hydrogen bromide on a mixture of caryophyllene ethyl nitrite ethyl acetate and alcohol a t - 20° separates from chloroform in crystals m.p. 144-145' (decomp.) is optically inactive and when heated with sodium methoxide yields i-a-nitrosocaryophyllene m. p. 116'. With bromine in carbon tetrachloride solution this forms a n additive compound which on recrystallisation from boiling alcohol is converted into the optically inactive bromo-ethoxy-compound C,,H,,Br(NO)*OEt zrystallising in colourless needles m. p. 185-1 86' (decomp.). Cnrgophyllene nitrosate m. p. 130.5' is now found to be optically active having [.ID + 56.91'. It is formed together with a substance crystallising in rosettes in. p. 156-157' by the action of chromic acid equivalent t o three atoins of oxygen on the blue nitrosite in glacial acetic acid solution.When boiled with alcohol the blue nitrosite yields a dicyclic hydrocarbon Cl6K2* b. p. 125-125*5"/14*5 mm. DI9 0439941 [u]E - 26*1'74" 7%; 1.49665 which is identical with the sesquiterpene b. p. 123-124'/14*5 mm. previously described (Zoc. cit.) and forms two isomeric nitrosochlorides ; the one of these has ni. p. 122' [ u ] ~ + 14-71' and the other m. p. 146' [a] - 33.69'. Both nitrosochlorides react with benzylarnine forming /3-caryophyllenenitrol- benzylamine m. p. 172-173'. When the hydrocarbon b. p. 123-124O/14.5 mm. is treated with nitrosyl chloride the filtrate From the resulting nitrosochloride contains a tricyclic hydrocarbon C,,H24 b. p. 132-134"/15 mm. DlS 0.9310 [alD - 22*28O 7%:" 1*50035. This forms a white crystalline mitrosite m.p. 175". Clovenq prepared by Wallach and Walker's method (Abatr. 1893 i 102) for the purpose of comparison with the preceding hydrocarbon is obtained in two fractions b. I>. 131-139"/15.5 mm. DI9 0,92223 a +1*30° (100 mm. tube) ng 1.4740 and b. p. 139-143O/15.5 mm. DID 0.92786 a +2.75' (100 mm. tube) cng 1.50085 respectively It does not form a nitrosite and is probably a mixture. When oxidised with an amount of potassium permanganate equi- valent to four atoms of oxygen in dilute aqueous solution caryophyllene [u] - 143 obtained from clove oil yields a substance Cl,R2,04 which crystallises in needles and leaflets rn. p. 120*5" is strongly lmorotatory has a persistent bitter taste and appears to be derived from the lzvo- rotatory hydrocarbon.11. Cadinene.-If a current of chlorine is passed through a cooled solution of I-cadinene dihydrochloride exposed t o sunlight hydrogen chloride is evolved and on evaporation of the product a white sandy powdw C,,H,,CI or C,,H,,CI m. p. 65-70° is obtained. This is probably a mixture of chloro-compounds which cannot crystallise i n presence of each other (compare Gladstone and Hibbert Abstr. 1889 1207). The action of bromine on cadinene dihydrobromide in presence of a small amount of mercuric chloride leads to the formation of a grey amorphous powder Ci5H23B~- m. p. about 100' (evolving hydrogen bromide). G. Y.ORGANIC CHEMISTRP. 355 Long Leaf Pine Oil. JOHN E. TEEPLE (J.'Amer. Chern. Xoc. 1908 30 412-414).-Long leaf pine oil obtained by the distillation of lightwood (Pirzus palustris) with steam has a faint yellow colour D'5'5 0.935-0.947 [.ID about - 1 lo and wD 1.483.When heated it begins to distil at about 206-210"; 75% collects between 211' and 218O and 50% between 213" and 21'7". The sp. gr. of the distillate increases regularly as the temperature rises and becomes steady at about 0.947 a t 2 1 7 O . The oil consists essentially of terpineol probably the 2-modification of a-terpineol [A1-p-menthenol-(8)] of b. p. 217-2189 E. G. Constituents of Essential Oils. Derivatives of Santene Santene Glycol and the Unsaturated Ketone C,H1,O derived from the Diketone C,H,,O,. FRIEDRICH CV. SEXIMLER and KONRAD BARTELT (Ber. 19OS 41 866-871. Compare Abstr. 1907 i 1062; this vol. i 38 194 195).-When the unsaturated dicyclic hydrocarbon santen~ 11 QHz 1 dissolved in diluted acetone is oxidised by potassium permanganate it yields a glycol OH .CMe*QH*CH m.p. 193" b. p. 135'/10 mm. which is very stable OH*Cllle*CH*OH towards dehydrating agents and is converted by boiling dilute sulphuric acid into a ketone C,H1,O b. p. 76-80°/10 mm. DZo 0.988 n 1.47980 which is not identical with camphenilone. Oxidation of the glycol yields the saturated ketone C,H1,O described previously from which the unsaturated ketone C,H120 formerly obtained by the action of sodium ethoxide is prepared in very much better yield by the action of alcoholic ammonia at 170". This unsaturated ketone b. p. 104-105°/10 mm. Dao 1.029 nD 1.51390 is not a derivative of dicyclo-2 2 2-octane as stated previously but is 1-methyldicyclo-1 2 3-A1-octsne-3-one CMe*Q€I*CH CMe*CH* CH2 I QH2 I FO--Q H C H CMe- CH=CH2 fp QH21 By oxidation with potassium permanganate it yields the ketonic acid CH,*yH*CO,H 1,150 ?q) 1.47936 the CH,*CH*COMe semicarbaxone of which has ma p.182'. The constitution of the ketonic acid is proved by its oxidation by sodium hypobromite to cis- cyclopentane-1 3-dicarboxylic acid I b p. 173-175°/'10 mm 1 YH2 CH2*QH*C0,H 7H2 CH CH* CO,H The dioxime of the ketone CQHI4O2 is reduced by sodium and alcohol to a bccse C,H17N b. p. 78-SOo/10 mm. D" 0*953 ?aD 1,49856 the picrate of which has m pa 192". c. s. b b 2356 ABSTRACTS OF CHEMICAL PAPERS. Resin Oil. WILLI SCHULTZE (AnmaZen 1908,359,129-144).-The crude oil obtained in a yield of about 60% on further distillation of American colophony after the resin essence which forms about 5% of the resin and the light oil amounting to about lo% have been removed has been investigated by a number of authors who have disagreed as to vvhether it is a simple substance o r a mixture of hydrocarbons. A refined resin oil obtained in a 60% yield on fractional distillation of the crude oil is now found to be a mixture of saturated and unsaturated hydrocarbons. It is a wine-yellow liquid having n strong violet fluorescence b.p. about 300-350° D15 0.9693 a -39.96" (100 mm. tube) has the ignition temperature 112O the tenacity factor 6.97 and Engler's viscosity factor 2.12 at 50". A t - 20° i t forms a viscid syrup solidifies to a vitreous mass in a carbon dioxide-ether mixture and distils unchanged under 12 mm.pressure but evolves gas on prolonged boiling in a reflux apparatus. A pure substance could not be obtained by fractional distillation or solidification. On treatment of the refined oil with concentrated sulphuric acid and repeated distillation of the product over sodium a mixture of saturated hydrocarbons is obtained in a 36% yield as a transparent liquid which has an odour faintly resembling petroleum is not fluorescent is stable towards a1 kaline perrnanganate or bromine water and on distillation yields four fractions b. p. 152-179"/10 mm. D15 0.9486 a - 3.23" (100 mm. tube) ; b. p. 178.5-189"/10 mm. D15 0,9550 U - 4.14O ; b. p. 191-194"/13-5mm.,D150~9590,~o - 10*66°~andb.p.196-202"/13~5 mm. D150.9780,a - 20*22",respectively. A fraction b.p. 195-197*5O/19 mm. gave on analysis figures agreeing only approximately with those required by octahydroretene. When boiled with manganese dioxide and dilute sulphuric acid the saturated oil yields trimellitic acid and a saturated hydrocarbon b. p. 198*5-200°/18*5-20 mm. which is volatile with steam and is not attacked by fuming sulyhuric acid. The action of sulphur on the saturated oil b. p. 178-210"/11-12 mm. leads to the formation of retene m. 1'. 98*5-99' and a substance C,,H,,S which is formed also by heating retene with sulphur at 230-240'. It crystallises in white leaflets m. p. 225*5-286' and gives-an intense indigo-blue coloration with a mixture of fuming and Concentrated siilphuric acids. Trimellitic acid is best prepared by oxidation of $-cumene with potassium permanganate in boiling aqueous sodium hydroxide solution ; the anhydride has m.p. 162.5-163" (157-158" Baeyer this Journ. 1873 756). G. Y. Arbutin and Some of its Derivatives considered with Regard to *their Rotatory Power and their Hydrolysis by Emulsin. EMILE BOURQUELOT and HENRI HERISSEY (Compt. vend. 1908 146 764-766*).-Pur.e arbutin that is a glucoside which on hydrolysis gives one molecule of dextrose and one molecule of quinol has not yet been obtained. According to Schiff and others commercial arbutin is a mixture of arbutin (as above defined) and methylarbutin whilst Hnbermann holds that arbutin is a complex glucoside C,,H,,O, containing the elements dextrose quinol and quinol methyl ether. By a cryoscopic determination the authors have found * and J.Pharm. China. 1908 27 421-427.ORGANIC CHEMISTRY. 357 the value 268 for the molecular weight of the commercial glucoside which is so nearly in accordance with the number 272 required by OH*C6H,*O*C,Hl,0 as to render Habermann's theory untenable. Undried commercial arbutin has uD - 61-76" which becomes - 61.3' after purification. The purified glucoside loses 5.15% of water when dried at 120-125' from which the value an - 64.7" is deduced for the dry substance. Arbutin methyl ether prepared according t o Schiff's directions has m. p. 1'75-176' (corr.) and uD - 63m433. Since the latter is very close to the value for purified arbutin the specific rotatory power of true arbutin must approximate to -65" and thus the glucoside is lsvorotatory.Arbutin benzyl ether CH2Ph~O*C6H,*O*C,Hl,0 has m. p. 161-162O and a; - 44*47'(in alcohol). Dinitroarbutin OH*C6H2(N02),*O*C,Hl105 is lsvorotatory. The compounds arbutin methyl and benzyl ethers and dinitroarbutin are hydrolysed by emulsin. The conclusion is drawn that arbutin and its three derivatives follow the rule laid down by the authors that "all glucosides hydrolysed by emulsin are lsvorotatory and are derived from dextrose." E. H. Simple Method of Preparation of Phylloporphyrin. LEON MARCHLEWSKI [with PIASECKI] (Ber. 1908,41,84'7-849*).-To prepare phylloporphyrin i t is no longer first necessary to isolate phyllotaonin ; the following method renders the former compound one of the easiest chlorophyll derivatives to prepare. A slight excess of barium hydroxide is added to an extract of dried acacia leaves.The precipitate is separated washed suspended in 96% alcohol and carefully decomposed with concentrated sulphuric acid. The slightly acid solution is concentrated and heated with 10% alcoholic potash in a n autoclave at 200'. The product is neutralised with acetic acid and warmed with alcohol whereon phylloporphyrin dissolves leaving a brown residue The alcohol is evaporated water added and the phy lloporphyrin and other chlorophyll derivatives extracted with ether. The ethereal solution is shaken with 5% hydrochloric acid and the phylloporphyrin precipitated from this in the form of a reddish-brown mud by sodium acetate. This is dissolved in ether and the above process repeated using 1% hydrochloric acid. The product is recrystallised twice from alcohol and obtained as bright brown narrow rhombic plates pointed a t both ends.E. F. A. An Attempt to Synthesise 1 2Gournaran. MAXIXILIAN HELBIa (J pr. Chem. 1908 [ii] 77 364-366).-The sodium derivative of salicylaldehyde is most readily prepared by adding the theoretical amount of sodium ethoxide solution gradually to the aldehyde dissolved in three times its weight of absolute alcohol When the sodium derivative is heaked with bromosuccinic acid hydrogen bromide is eliminated and fumaric acid formed. The sodium derivative condenses with ethylene dibromide at 130-1 40° yielding the 6romoethyZ ether of salicylaldehyde CH2Br*CH2*O*C6H,*CH0. * Bull. Acad. Sci. Cracow 1908 3 127-129.358 ABSTRACTS OF CHEMICAL PAPERS. It has m.p. 5 2 O b. p. 184'/11-12 mm. and gives a red coloration with ferric chloride. The pherzylhydraxone C15H150N2Br crystallises in yellow needles m. p. 114O. Further condensntion to the coumaran does not occur. J. J. S. The Flavone Group. JOSEF TAMBOR [and in part B. ARONSTAMM ST. BARANOWSKI ST. CUKIER and w. TOMI] (Bey. 1908,41 787-792). -Tambor and Ludwinowsky found that orcacetophenone dimethyl ether condenses with ethyl benzoate forming 2 6-dirnethoxy-4-methyl- benzoylacetophenone (Abstr. 1907 i 75)) which when boiled with hydriodic acid D 2.00 yields 1-hydroxy-3-methylflavone. This reaction has now been extended t o the condensation of orcacetophenone with the three methyl methoxybenzoates and with methyl veratrate which form the corresponding 2 6-dimethoxy-4-methylbenzoyl-methoxy- acetophenones CGH,Me(Oll.le),*CO*CH2*CO*C6H4*OMe and -di- met hoxyacetophenone C,H,Me( On/re),* CO*CH,*CO *C,H,(OMe),.These are converted by treatment with hydriodic acid D 2.00 into the 0-C*C H *OH dihydroxy- OH*U,H2Ma<C0 uH ' and trihydroxy-7-methyl- 0-C*C H (OH) flavones OH*C,H2Me<C0.~H 2 respectively. When these are heated with potassium hydroxide and methyl iodide the hydroxyl in position 5 remains unchanged but the hydroxyls in the phenyl group are etherified the resulting ethers having the constitution OH*C6H,Me< 0 - g o C,H,* OMe CO*CH or The results of the work now published confirm the view of Tambor and Ludwinowsky (Zoc. cit.) as to the constitution of orcacetophenone. Orcacetophenone dimethyl ether crystallises in rhornbic plates 2 6 2'- Trimethoxy-4-meth$benxoylacetophenone C,,H,,O prepared from methyl methylsalicylate crystallises in rose-coloured needles m.p. l l t ; O and gives a blood-red coloration with ferric chloride. 5 2'-Dihydrox~-7-rnethylJlavo.lze C,,H,,O forms greenish-yellow needles m. p. 300-301° ; the diacetate CY,,H,,O white prisms m. p. 108". 5-Iiydrox~-2'-met1oxy-7-.172ethy~~~uo~~e C,fH,,O crystal- lises in yellow needles m. p. 1 5 6 O and forms a sparingly soluble yellow sodium salt. prepared from methyl m-methoxybenzoate crystallises in light brown prisms m. p. 9 8 O . 5 3'-Dihydroxy-7-methyljZavone forms colourless needles m. p. 227O and forms a yellow solution in concentrated sulphuric acid but does not dye mordanted threads ; the diacetata crystallises in yellow rhombic prisms ni.p. 13 7". 5 -Hydroxy-3'-methoxy-7-methy~auone forms yellow needles m. p. 146O yields a sparingly soluble yellow sodium salt and gives a yellow coloration with concentrated sulphuric acid. [GC b c = 0.7522 1 0.39321. 2 6 3'-Trimet?~oxy - 4 - riaethylbenxoyluce€op~enone,OllGANIC CHEMISTHY. 359 2 6 4'-~~imethoxy-4-methylbenxoylacetophenone prepared from methyl anisate crystallises in colourless needles m. p. 97-98'. 5 4'-Dj hydroxy-7-methylflavone crystallises from alcohol in yellow needles m. p. 295O; the diacetate white needles m. p. 148-149'. 5-~ydroxy-4'-methoxy-'I-naethyl~%6uone crystalhses in yellow needles m. p. 274O and forms an insoluble yellow sodium salt. 2 6 3' 4'-Tetr~cmethoxy-4-metl~ylbenxoyZacetophenone C,,H2,06 from methyl veratrate crystallises in white needles m.p. 11 2'. 5 3' 4'-Tri~ydroxy-'I-metl~yZJEavoize C16H1,05 yellow needles rn. p. 270° gives with concentrated sulphuric acid a light yellow or with sodium hydroxide solution an intense yellow coloration and alumina mordant dyes a greenish-yellow. The triacetate C22HlS08 forms white needles m. p. 169". 6-Hydroxy-3' 4'-dimethoxy-7-methyIfEavons C,,H,,O crystallises in yellow needles m. p. 147" forms an insoluble yellow sodium salt and gives B yellow coloration with concentrated sulphuric acid. G. Y. Two Monohydroxy-a-naphthafhvonols. STANISLAUS VON Kos- 1908 41 783-786).-1n connexion with Bigler and Kostanecki's investigation of 3' 4'-dihydroxy-~-naphthaflavonol (Abstr. 1907 i 76) 3'- and 4'-hydroxy-a-naphthatlavonols have been prepared and are now described. TANECKI [and in part J.w. ENGELSOIIN and 81. WURZELMANN] (Ber. by boiling 2-anisylideneacetyl-1-naphthol (Abstr 1899 i 524) with hydrochloric acid in alcoholic solution crystallises in white needles crys- m. p. 148'. The isonitroso-derivative C,,H,< tallises from benzene in yellow needles m. p. 169-170° (decomp.) and dyes orange with cobalt bnt yellow with uranium cadmium and lead mordants. When boiled with 10% sulphuric acid in glacial acetic acid solution the isonitroso-derivative is converted into 4'-methoxy- a-napht haflavonol C H < ~ ~ ~ ?2*OMe which cry st a1 lises in yellow needles m. p. 249* dyes light yellow with alumina mordants dissolves in concentrated sulphuric acid to a solution with intense light green fluorescence and forms an insoluble yelIow sodium salt.The acetate OMe*C,SH1,O,*OAc forms white needles m. p. 196". 0-E* C,H,* OH 4 ' - ~ ~ d r o x y - a - n ~ ~ ~ ~ t h ~ ~ a u o n o l C,,H,< CO*C*OH prepared by boiling the 4'-methoxy-compound with concentrated hydriodic acid crystallises in yellow plates m. p. 293O dyes light yellow with alumina mordants and dissolves in concentrated sulphuric acid or dilute sodium hydroxide to yellow solutions with green fluorescence. The diacetate C11,H,,0,(OAc)2 forms white needles m. p. 181'. The members of the isomeric seriee are prepared in the same manner starting from 2-m- metliox y benx y Iidemacet y I - 1 -naphtha I OH *C,,H,*CO*CH CH *C6H,*OMe which is prepared by condensation of m-methoxybenzaldehyde with O-FH*C,H,*OMe CO*C:N*OH360 ABSTRACTS OF CHEMICAL PAPERS.2-acetyl-l-naphthol in the usual way. It crystallises in orange-red needles m. p. 1 1 5 O and gives a red coloration with concentrated sulphuric acid. The isonitroso-derivative is a yellow crystalline powder m. p. 15 1' (decornp.) which dyes orange with cobalt mordants. 3'-M'ethoxy-a-naphtha$uvonol yellow needles m. p. 185* dyes light yellow with alumina mordants and forms a yellow sodium salt ; the acetate white needles m. p. 165'. 3'-Hydroxy-a-nuphth~$avonol crystallises from alcohol in yellow prismatic needles containing C,H,O m. p. 248O dyes light yellow with alumina mordants and forms yellow solutions with green fluor- escence in concentrated sulphuric acid or very dilute alkalis; the sodium salt forms yellow needles.3'-Methoxy-a-naphtha$avanone forms white needles m. p. 130'. G. Y. Some Derivatives of Thiophen. VICTOR THOMAS (Compt. rend. 1908,146,642-645).-1n the presence of anhydrous ether magnesium dissolves in 1-iodothiophen giving magnssium thiophen iodide which in general behaves like the corresponding pbenyl derivative. With the aliphatic ketones acetone methyl ethyl ketone methyl amyl ketone and butyrone it reacts normally giving tertiary alcohols but the latter are difficult t o isolate in a pure state owing to the readiness with which they undergo dehydration forming ethylenic hydrocarbons. Since the carbinol formed from acetophenone readily loses water whilst the compound derived from benzophenone is remarkably stable this dehydration is probably to be represented thus C,SH,*UR(OH)*CH -+ C,SH,*CR:CH2 R signifying an aliphatic or aromatic radicle.Acetone condenses with magnesium thiophen iodide giving a mixture of thienyldi- methylcnrbinol C,SH,*CMe,*OH needles m. p. 3 3 O which after a time liquefy t o a viscous substance with a piquant odour and P-thienylpropylene C,SH,* CMe CH a colourless agreeably smelling liquid b. p. 166-167"/727 mm. which is easily polymerised when kept finally giving a solid black mass. Methyl ethyl ketone gives a mixture of alcohol and hydrocarbon which could not be separated. The chief product of the action of methyl amyl ketone on magnesium thiophen iodide is P-thienylheptylene C,H,,.C(C,SH,):CH a somewhat oily liquid b. p. 165-1 68'/62 mm. Butyrone gives thienyldipropyl- curbird C,SH,*CPr,*OH a n agreeably smelling liquid b.p. 160-163'/45-46 mm. which on distillation at ordinary pressure decomposes into the hydrocarbon and water. Acetophenone forms a-phenyl-a-thienylmeth ylcarhinol C,SH3-CPhMe. OH needles m. p. 5 Oo which gradually undergo partial liquefaction probably forming the hydrocarbon. Dip~LenyltTLienylcarbinoZ C1,SH;CPh2*OH hexagonal crystals m. p. 1 2 5 O is formed from benzophenone ; whilst yielding colourless solutions in neutral solvents i t resembles triphenylcarbinol in giving intensely yellow solutions in acids. E. H. Preparation of SHydroxy-( 1)-thionaphthen. KALLE & Co. (D.R.-P. 18S702).-1t was formerly shown that phenylthioglycol-o- cszrboxylic acid when heated with sodium hydroxide gave S-hydroxy- (l)-thionaphthen-2-carboxylic acid wh.ich subsequently furnishedORGANIC CHEMISTRY. 361 3-hydroxy-( 1)-thionaphtben It it now found that the two reactions can be effected in one stage by heating phenylthioglycol-o-carboxylic acid a t 230".G. T. M. Acid Properties of Amino-ketones. PAUL RABE and WILHELM SCHNEIDER (Ber. 1908 41 873-878. Compare Willstatter and Bode Abstr. 1900 i 245 ; Miller and Rohde Abstr. 1901 i 95 ; Rabe Abstr. 1907 i 954; this vol. i 100).-The amphoteric character of the u- /3- and E-amino-ketones cinchoninone piperidylacetophenone dimethylaminocamphor tropinone and cinchotoxine is manifested not only by the greater solubility (and the change of colour) in dilute sodium hydroxide than in water but also in the formation of 0-benzoyl derivatives. The two criteria are more pronounced in the methiodides than in the amino-ketones themselves.The sodium s d t of cinchoninone C,,H,,ON,Na is obtained in clusters of yellowish-red crystals by the addition of ether to cinchon- inone dissolved in a normal solution of sodium ethoxide; the sodium salt of cinchoninone methiodide C,,H,,ON,INa obtained in a similar manner forms deep yellow crystals. [With FRITZ B~~~sc~.]-Piperidylacetophenone (compare Schmidt and van Ark Abstr. 1900 i 686) b. p. 180-181"/26 mm. is a colourless oil with a pronounced basic odour ; the hydrochloride C13Hl~ON,€ICl has m. p. 223". Piperidylacetophenone (2 mols.) and benzoyl chloride (1 mol.) in benzene solution deposit after fourteen days nearly the theoretical quantity of the hydrochloride ; the 0-benzoyl derivative obtained as an oil after evaporation of the solvent yields by hydrolysis benzoic acid and the products of the decomposition of piperidylacetophenone. Piperidylacetophenone methiodide by treatment with benzoyl chloride and normal sodium hydroxide yields the colourless bennxoyl derivative C,,H,,O,NI m.p. 146" (decomp.). Dimethylaminocamphor methiodide by the Schotten-Baumann method yields a benxoyl derivative C,,H,,O,NI. Tropinone methiodide m. p. 273-275" (Willstatter gives m. p. 263-265') forms a benxop? derivative Cl6H2,O2N1 m. p. 263-265" which separates from alcohol in rhombic leaflets. Methylcinchotoxine is more soluble in water than in normal sodium hydroxide. Methylcinchotoxine methiodide is not appreciably more soluble in dilute alkali than in water but the change of colour in thealkaline solution is an indication of salt formation.It forms a benxoyl derivative C,sH3,0,N,T. c. s. Morphine. XVIII. Hydrolytic Products of a- and P-Chloro- codide. LUDWIG KNORR and HEINRICH HORLEIW (Ber. 1908 41 969-975. Compare Schryver and Lees Trans. 1900 77 1024; 1901 79 563 ; Lees and Tutin Proc. 1906 22 253 ; Lees Trans. 1907 91 1408 ; Knorr and Horlein this vol. i 41).-The following constants for the halogen derivatives of morphine and codeine are given a-Chloromorphide m. p. 204' (decomp.) ; [a] - 375". P-Chloro- morphide m. p. 188'; [.ID - 5 O a-Chlorocodide m. p. 152-153';362 ABSTRACTS OF CHEMlCAL PAPERS. [a] - 380O. Bromo- morphide m. p. 169-170'; [.-ID + 6 6 O .Bromocodide m. p. 162'; [a]= +56". When hydrolysed by boiling with dilute acetic acid the two chloro- codides yield the same products but in different proportions. a-Chloro- codide gives $-codeine 45% ; do-+-codeine (P-isocodeine) 15% and isocodeine 25% whereas P-chlorocodide gives +-codeine 10% ; allo- $-codeine 20% and isocodeine 55%. P-Chlorocodide m. p. 152-153' ; [a]? - 10". J. J. 5. Hydrolytic Products of a-Chloromorphide. ALFRED O P P ~ (Bey. 1908 41 975-981. Compare Schryver and Lees Trans. 1900 77 1024; 1901,79 563 ; Lees 1907 91 563; Knorr and Horlein preceding abstract).-a- p- and y-isomorphines are obtained by the hydrolysis of a-chloromorphide with dilute acetic acid. y-isoMorphine (neoisomorphine) is readily separated from the p-iso- meride by extraction with boiling acetone in which the y-compound is very sparingly soluble.It separates from acetone in compact crystals and has m. p. 2 7 8 O (decomp.) and [a] - 94'. The hydrochloride has m. p 314' (decomp.) and [a]? - 76' (Lees - 79.1O). The hydro- 6rornzde C17H?,0,NBr decomposes a t 298O and has [a] - 71". Its acetyl derivative is oily but yields a ntethioclide C,,H,,O,NI which crystallises in needles m. p. 267O (decomp.) and [a] - 24". The ntethioclide of diacetylinorphine crystallises in needles decom- poses a t 252" and has [a]:; - 107". When methylated y-isomorphine yields $-codeine and from this c-methylmorphirnethine (Knorr and Horlein Abstr. 1907 i 151) has been obtained. J. J. S. Action of Ammonia on Methyl Ethyl Ketone. WILHELM TRAUBE (Bey. 1908 41 777-782).-Sokoloff and Latschinoff (this Journ.1875 353) found that acetone reacts with ammonia forming diacetoneamine together with small amounts of triacetoneamine. The present author has studied the action of ammonia on the first homologue of acetone methyl ethyl ketone. This absorbs ammonia in only very small amounts but if an alcoholic solution of the ketone is saturated with ammonia and allowed t o remain a t the ordinary temperature for two or three weeks 4-keto-2 3 6-trimethyl-2 6-dielh&ipe~idine ?H2.CMeEtg~H is formed in a 25% yield and can be isolated as CO*CHRle-C MeEt' the oxalate. The free base is a colourless liquid b. p. 157-159O/ 30 mm. or 24Y0/760 mm. and has a characteristic odour. The nitrate C,,H2,ON,HNO crystallises in colourlesa needles M.p. 169-172O (decomp.). Reduction of the keto-base by alternate additions of sodium amalgam and dilute hydrochloric acid to the oxalate leads t o the formation of 4-hydroxg-2 3 ; 6-trimethyl-2 6-dieth~Z~i~eridine ~H2*C'1eEt-~H which is obtained as a colonrless oil b. p. CH( OH)*CHhle* C MeEt' 140°/20 nim. This is a mixture of two isomerides which can be separated by means of the difference in the solubilities of their oxalates. The more sparingly soluble ozalate C,,H,,ON,C,H,O m. p. 208O (decomp.) when heated with benzoyl chloride at 160'ORGANIC CHEMISTRY'. 363 yields the hydrochloride of the benzoate C1,H2g02N,HCl m. p. 230° ; the benzoate C1,H2902N forms a colourless oil which is partially decomposed on distillation in a vacuum and forms in addition to the preceding salt a second highly soluble hydrochloride obtained as a brittle mass on evaporation of the aqueous solution.The base corresponding with the more soluble oxalate is converted into the benzoate hydrochloride m. p. 230° when heated with benzoyl chloride. G. Y. Nitrosopyrroles. E. M-ORELLI and GUERRIERO MARGHETTI ( A t t i R. Accad. Lincei 1908 [v] 17 i 250-254).-The authors have studied the reactions of the trioxime NOH :CMe*CH,*C(NOH)*CMe:NOH obtained by Angeli and Marchetti (Abstr. 1907 i 436) by the action of hydroxylamine on 3-nitroso-2 5-dimethylpyrrole or 3-nitroso-1-oxy- 2 5-dimethylpyrrole. The trioxime readily loses 1 H,O giving a furazan derivative and this when boiled with dilute sulphuric O<N C Me N:y* CH,*CMe:NOH which N $l*CH,*COMe N CMe acid yields hydroxylamine and the ketone O< crystallises from ether in white needles m.p. 1 9 O gives iodoform when treated with potassium hydroxide and iodine and yields a semicarbaxone C,H,ON,:N,H*CO*NH m. p. 188'. When reduced by means of sodium in alcoholic solution the trioxime yields 3-arnimo- 2 5-dimethylpyrrolidine NH< CHMe*yH2 which forms a picrate C,H14N,,2C,H,07N m. p. 242' (decomp.). CHMe*CH*NH T. H. P. Action of Hydrazine Hydrate on Dinitrophenylpiperidine. LEOPOLD SPIEGEL (Ber. 1908 41 886-888).-Hydrazine hydrate in boiling alcoholic solution hg drolyses 2 4-dinitrophenylpiperidine the product,s being a piperidine salt and a substance C,H,O,N m,- p. 206' (decomp.) crystallising in yellowish-brown glistening prisms which is identical with Curtius and Mayer's 6-nitro-1-hydroxy- 1 2 3-benzotriazole (this vol.i 53). c. s. Bx-Quinoline Mercaptans. ALBERT EDINGER (Ber. 1908 41 937-943).-Quinoline-8-mercaptans have been prepared by the reduction of the corresponding quinolinesulphonyl chlorides with stannous chloride and hydrochloric acid. QztinoZine-8-sulphon yE chloride C,NH,*SO,Cl m. p. 122" prepared from phosphorus pentachloride and the siilphonic acid or its sodium salt a t 136-140° is reduced by stannous chloride and hydrochloric acid yielding a doubZe salt of tin and the mercaptan which crystallises in stout yellow prisms and decomposes a t 270'. A cold alkaline solution of the double salt with benzoyl chloride yields the benxoyl derivative C,NH,*S*COPh m. p. l l O o whilst benxyl chloride gives the benzyl derivative Cl,Hl,NS m.p. 112'. By hydrolysis with hot moderately concentrated hydrochloric acid and subsequent neu tralisation at Oo,364 ABSTRACTS OF CHEMICAL PAPERS. the benzoyl derivative yields the mercaptam C,NH,*SH,BH,O m. p. 58-59" which crystallises in glistening red needles. By prolonged exposure t o the air or by oxidation with alkaline potassium ferricyanide the mercaptan yields the disulphide C,,H,,N,S m. p. 206O which separates from alcohol or glacial acetic acid in yellow prisms. 8-Thiocyanopuinoline C,NH,*SCN m. p. S9O prepared from the mercaptan sodium methoxide and cyanogen iodide in methyl-alcoholic solution separates from dilute alcohol in white needles and by warming with aniline forms a substance C,,H,,N,S m.p. 142". The ethyl thio-ether C,NH,*SEt m. p. 5 lo crystallises i n colourless needles. 5-BromoquinoIine when heated at 130-140' with fuming sulphuric acid (40% SO,) yields 5-bromoquinoline-8-sulphonic acid the chloride of which m. p. 1 2 4 O yields by reduction a tin double salt from which a benzoyl derivative C,NH5Br*S*COPh m. p. 115" is obtained. The corresponding mercaptan C,NH,Br*SH m. p. 69O crystallises in yellow needles. The disulphide has m. p. 193'. c. s. Partial Racemism. VII. ALBERT LADENBURG and W. HERRMANN (Ber. 1908 41 966-969. Compare Abstr. 1894 i 208)-When quinaldine and a n aqueous solution of tartaric acid are mixed a t 60-63' a crystalline acid tartrate is deposited which yields an inactive base when decomposed with alkalis. The crystalline salt is not a mixture of d- and Z-hydroquinaldine hydrogen tartrates but a partially racemic salt.The pure Z-tetrahydroquinnldine was isolated in the form of the Z-tartrate by the addition of Z-tartaric acid to the mother liquor from the d-tetrahydroquinaldine d-tartrate. The following data for the salts have been determined Water of M.p. DIp5. crystallisation. 1.-Tetrahydroquinaldine hydrogen tartrate.. . 72-73' 1.310 1 -5H20 d-Tetrahydroquinaldine ... 90-91" 1.344 1H20 I- Te trah y droquinaldine ... 62-63" 1.314 1.5H2O The transition temperature is 59O. J. J. 5. Quinoline Derivatives. 111. Phenyl Quinolyl Ketone. PERCY REMFRY and HERMAN DECKER (Ber. 1908 41 1007-1009. Compare Abstr. 1905 i 828; 1906 i 984).-The action of magnesium phenyl bromide on ethyl cinchonate has been studied partly in connexion with the investigations of quinoline derivatives already published and partly with a view to determining the applicability of carboxylic esters of the pyridine series to Grignard's synthesis.. It is found that the action of 1 mol. of magnesium phenyl bromide on 2 mols. of ethyl cinchonate leads to the formation of dipbenyl-y-quinolylcarbinol together with considerable amounts of phenyl y-quinolyl ketone but that only traces of the ketone are obtained when 3 mols. of the organo-magnesium compound are added to 1 mol. of the ester. <C(COPh):FH N===CH' separates from Pheny Z y-guinoly I ketone,ORGANIC CHEMISTRY. 365 alcohol in crystalline aggregates m. p. 294' and is soluble in mineral acids. D iphenyl- y - qu inol y lca,rbinol U,H,N* CP h OH separates from alcohol in small white crystals m.p. 247*5O is soluble in dilute mineral acids and gives with concentrated sulphuric acid a red coloration which disappears on dilution with water. The hydrochloride yellow crystals m. p. 223'; the carbinol forms two crystalline picrntes the more soluble of which has m. p. 142-144' whilst the other decomposes at high temperatures. The methiodide forms yellow crystals becoming reddish-brown when dried m. p. 159' and gives with sodium carbonate in aqueous solution a white precipitate which becomes violet on exposure to air can be extracted by ether and on evaporation of the ethereal solution is obtained as a violet residue m. p. 234'. G. Y. Preparation of Quinoline Derivatives of the Anthraquinone Series.FARBWERKE VORM. MEISTER Lucrus & BRUITING (D.R. -P. yellow crystals m. p. 1 6 9 O is obtained by condensing 1-aminoanthra- quinone and glycerol in the presence of concentrated sulphuric acid and nitrobenzenesulphonic acid. AntJwaquinonyZ- 1 5 -diquinoline is an almost colourless base m. p. 342' ; the nitrate C2,H,,H,0,,2HN0 is produced iu a similar manner from 1 5-diaminoanthraquinone. G. T. M. Derivatives of Tetra- and Hexa-hydrocarbazolea and a New Synthesis of Carbazole. WALTHEH. BORSCHE [with A. WITTE and W. BOTIIE] (Annalen 1908 359 49-80).-It was shown by Dreschel (Abstr. 1888 1276) that when heated with dilate mineral acids the phenylhydrazone of cyclohexanone yields only small amounts of pheny lhydrazine and cyclohexanone undergoing for the most part a reaction analogous to Fischer's synthesis of indole from the phenylhydrazones of aldehydes and ketones in which it loses ammonia and forms tetrahydrocarbazola (compare Baeyer Abstr.1894 i 174). The present authors undertook the study of t h i s little known reaction because it has become of importance in consequence of the ease with which cycloketones may now be obtained and on the other hand of the increased interest attached to the hydrocarbazoles in connexion with their possible relation t o the alkaloids of the strychnine series. The results obtained show that substituting groups in the meta- or para-position in the benzene nucleus of the phenylhydrazine do not a t least markedly affect the reaction but that tetracarbazoles are formed only from phenylhydrazones of simple saturated cycloketones such as cyclohexanone d-l-mebhyl-3-cycZohexanone and I-menthone and not from those of substances such as 1 3-dimethyl-Ae-cyclohexene-5-one pulegone d-carvone and d- camphor.366 ABSTRACTS OF CHEMICAL PAPERS.The tetracarbazoles are readily reduced by tin and hydrochloric acid forming hexahydrocarbazoles (compare Graebe and Glaser this Journ. 1872 302) and in so far as they are volatile are converted into carbazoles by distillation over finely-divided lead oxide which must be heated but not too highly. The annexed scheme has been adopted in the first part of this paper for the numbering of the positions in carbazole as the usual method is insufficient for the naming of the new compounds now described. \/ y/' The hydrazones mere for the most part not purified but heated in the crude state with dilute sulphuric acid on the water - bat h.The action of bromine on tetracarbazole in glacial acetic acid solution leads t o the formation of a hexabromo-derivative C,,H7NBr or C1,H,NBrG obtained as a yellow crystalline powder unchanged at 300' or on prolonged heating with alcoholic potassium hydroxide or digestion with zinc dust and alcoholic hydrochloric acid together with a more soluble tetrabronzo-compound C1,H,NBr4 m. p. 230". 4-~ethyl-A1(')-tetrc6~~ydrocar~~~o~e C,,H,,N from phenylhydrazine and l-methyl-3-cyclohexanone9 separates from alcohol in crystals m. p. 94' ; the picrate C19H1807N4 brownish-red leaflets m. p. 155'. 9-Met?~yZ-A-1(")-tetrahydrocai.baxoZe C,,H1,N from p-tolylhydrazine and cydohexanone crystallises from light petroleum in white needles m.p. 141-142'. 4 9-Dinaetl~~Z-A1(6)-tets.c6hydrocarbaxole C,,H17N from p - tolyl- hydrazine and l-methyl-3-cycZohexanone separates from methyl alcohol in transparent plates m. p. 1 4 6 O ; the picrate dark red leaflets m p. 1 2 9 O . The phenyl?qdmxone from menthone and phenylhydrazine forms unstable needles m p. 5 3 O and yields 2-methyl-5-i~opro~yZ-A'~~~-tetru- hydrocarbaxole C16H21N which crystallises from dilute methyl alcohol in transparent prisms m. p. 114*5O b. p. about 150-200°/15 mm. The a-naphthylh ydraxone of cyclohexanone colourless needles yields A'@)- t etrahydrobenxo- a-naph thindole C6H,< gFCR>CH white needles m p. 1S9-14Oo. A1(6)-Tetrahydrobenzo-P-naphthindoZe ~,€€,<NH'~-CH>CH from P-naphthylhydrazine and cyclohexanone forms white crystals m.p. 152'. 9-Methoxy-A'(ti)'-tetrahydrocar6axoZe C,,H,,ON from p-methoxy- phenylhydrazine aud cyclohexanone crystallises in colourless needles m. p. 94-95". The 9-etlhoxy-compound C,,H170N prepared in the same manner from p e t hoxyphenylhydrazine forms colourless needles m. p. 87-88". 1 l-ChZoro-A'(')-tetrchyd~~ocarbazoZe colourless prisms ma p. 56-5 6 O 9-chZoro-A1(6)-tetrahydrocarbaxole C,,H,,NCl needles m. p. 54-65' and 9-br0mo-A'(~~-tetrahydrocarbaxoZe colourless plates m. p. 15 3O are prepared from cyclohexanone and o-chloro- p-chloro- and p-bromo- phenylhydrazines respectively. (yNH\$$ \ z / NH C C,H4 C* C6H4ORGANIC CHEMISTRY. 367 cycloHexanorte-p-nitrop~~enyZh~d~a~one Cl2Hl,O2W3 forms yellow needles m.p. 146-1 47". 9-Nitro-A1(6)-tetrahydrocarbasoZe C12H,,0,N2 brownish-red crystals m. p. 174'. cycloHexanone-o-nitrophenylhydrazone golden-brown needles m. p. 7 4'. 11 -Nitro- A1(6)-tetra~ydrocar~axoZe yellowish-brown leaflo t s m. p. 148-149'. cyclollexanone-m-nitrophenyZhydrazom red needles m. p.'102-103'. 1 O-Nitro-A1(6)-tetrahydrocarbazole red crystals m. p. 151-1 52'. 1 -illethyl-3-cyclokexano~ze-m-nitrop?~enylJ~y~raxone Cl3H1TO2N3 sepa- rates from alcohol in crystals m. p. go" and is unstable 10-Nitro- 4-methyl-A1(p)-tetracl~ydrocarbaxoZe C13H1,0,N2 forms reddish-brown crystals m. p. 147-148O. The m-nitrophenylhydraxone8 of 1 3-dimethyl-A6-hexene-5-one red prisms m. p. 140° and d-carvone orange-red needles m.p. 105-106' and the p-nitrophenylhydracxone of d-carvoae reddish-brown needles m p. 174-1 75" are described. Pulegone and rn-nitrophenylhydrazine form a viscid condensution product. 4-Methythexah~drocarb~zola prepared by reduction of the tetra- hydrocarbazole with tin and alcoholic hydrochloric acid crystallises in colourless prisms m. p. 11 lo j the nitroso-derivative C,,H,,N*NO needles m. p. 62' ; the carbainyl derivative C13H16N*CO*NH2 colour- less crystals m. p. 153-154" ; the benxo$ derivative ClSHIBNBz colourless prisms m. p. 89'. 2-~~ethyl-5-isopropythexa7~ydrocccrbaxole Cl6HI3N obtained by reduc- tion of the tetrahydrocarbazole crystallises in white needles m. p. 71" ; the nitroso-derivative ClAH220N2 yellow prisms m. p. 140-141' ; the curbamyt derivative C16H22N*CO-NH2 colourless needles m.p. S7-58'. Carbazole is formed when tetrahydrocarbazole or 9-chloro- or 1 I-chloro-tetrahydrocarbazole is distilled over lead oxide. The following new substituted carbazoles have been prepared in the same manner from their tetrahydro-compounds. The positions occupied by the substituting groups are numbered in the usual manner 2-Methylcarbaxole C13HllN from 4-methyl-A1(@-tetrahydrocarbazole crystallises in colourless leaflets m p. 259"; the picnxte red needles m. p. 167'. This methylcarbazole is formed also from 6-nitro-3-acetyl- aminotoluene by conversion of this successively into 4-nitro-m- toluidine 4-nitro-3-anilinotoZuene and l-phenyt-6-methylben~otrinxoZe N<N-->C,H,Me which on distillation yields the 2-methylcarbazole.2 6-DimethyZcarbaxole is obtained as a white crystalline powder m. p. 208-209'; the picvate light red needles m. p. 153". 1 3 7-Trimethylcarbazole C,,H15N crystallises in white leaflets m. p. 119' ; the picrate m. p. 177". 1 3 4 7-2"etramethylcarbaxole C1,Hl7N prepared from $-cumyl- hydrazine and d-1-met hyl-3-cyclohexanone by way of the tetrahydro- carbazole crystallises in nacreous leaflets m. p. 153' ; the picrate dark red needles m. p. 146-147". 4-MethyZ-l-isopropytcarba~oZe C16H,$ is obtained as a colourless oil solidifying to a mass of leaflets m p 86'; the picrate light red needles m. p. 152'. NPh368 ABSTRACTS OF CHEMICAL PAPERS. 3-MethoxycarbaxoZe C,,H,,ON crystallises in colourless needles m. p. 138-139'; thepicrate m. p. 143'.Some Derivatives of Phenylisooxazolone. ANDRE WAHL and ANDRE MEYER (Compt. rend. 1908 146 638-640).-Schiff and his pupils have shown (Abstr. 1896 i 83; 1897 i 444 493) that hydroxylamine ehydrochlot ide and an aldehyde condense with ethyl acetoacetate in the presence of aniline producing solid substances which are formed by the condensation of the aldehyde with the methyliso- oxazolone first formed. The authors find that pheoylisooxazolone undergoes a similar reaction. Phenylisooxazolone which is best prepared separately condenses with most aromatic aldehydes on boiling in alcoholic solutions and in the other cases piperidine is effective as a condensing agent. P?~enyZbenxyEideneisooxaxolone C,O,NPh CHPh forms bright yellow shining spangles m. p. 191' (decomp.).~henylcii~namyZidneisooxGcxolone crystallises from acetic acid in orange leaflets m. p. 160' (decomp.). f'heny/furyEideneisooxGcaolone forms brown tablets m. p. 132-1 33' (decornp.). I'henyl-p-dimethylamino- benxylideneisooxa%olone C,O,NPh CH- C,H;NMe crystallises in brick- red phining spangles m. p. 184'; i t has a slight affinity for wool and cotton mordanted with tannin. The derivatives phenyl-o-hydroxy benxyliclsneisooxaxolone yellow needles m. p. 1 87' phen yE- p-hy drox y- benxylidemeisooxaxolone yellow needles m. p. 206-207" phenpl- 4 -11 ydroxy - 3 -met~oxybenxylicle?zeisooxccxolo?ze golden-yellow needles m. p. 2 13' and phenyl-P-hydroxyn~~~t~~?/Zideneisooxaxolone m. p. 223' which dissolve in alkalis to orange-red solutions could not be examined for their tinctorial power since their solutions lose t.heir colour through hydrolysis.The readiness with which phenyliso- oxazolone condenses with aromatic aldehydes indicates that it probably contains a methylene group and that the above reaction should be represented by the equation G. Y. CO*qH CO.Q:CHR + R*CHO = O< + H,O. O<r,T=CPl N=-CPh This is supported by the fact that phenylisooxazolone condenses with nitrosodirnethylaniline (Sachs Abstr. 1900 i 362 ; 1901 i 229) giving pi~enyl-4-diniethy~amino;uhe~~ylimi~aoisooxaxolone CO- $XN*C,H,*NMe *<N=CPh 7 violet-black needles m. p. 184" (decomp.). Relying on its formation by the action of hydroxylamine on ethyl ethoxycinnamate or on phenylpropiolamide Moureu and Lazennec (Abstr. 1907 i 716) have proposed the formula O< phenylisooxazolone.The present work and the preparation by Rabe (Abstr. 1897 i 568) of two isomeric benzoyl derivatives of phenyl- isooxnzolone indicate that the latter substance also reacts in the tautomeric methylene form. E. H. Coloured Salts of Schiffs Bases. Colour as Related t o Chemical Constitution. FORRIB J. A~OORE and R. D. GALE (J. Arner. Chem. Xoc. 1908 30 394-404).-In studying the corn- 'O.EH for NH*CPhORGANIC CHEMISTRY. 369 pound C!H,:0,:C6H,*CH N*C6H4*NMe2 obtained by the condensation of p-aminodimethylaniline with piperonal it was observed that on treating it with hydrogen chloride a deep blood-red hydrochloride was formed at first and was afterwards converted into a bright lemon- yellow dihydrochloride. It has now been found that p-benzylideneaminodimethglaniline (Calm Abstr.1885 38'7) and the corresponding cinnttmylidene salicylidene and anisylidene derivatives (Nuth Abstr. 1885 784) behave in a similar manner except that the last-mentioned compound absorbs nearly 3 mols. of hydrogen chloride instead of 2. The 'mono- and di-hydrochlorides of these bases are described and their possible constitution is discussed. Pipe~o.iLylidene-p-toluidi~e m. p. 98O forms cream-coloured prisms. Pipel.ony2idene-p-chloroccniline has m. p. 78". Ethyl piperonylidene-p- ccminobenxoate has m. p. 109'. Piperonal condenses with m-nitro- aniline and p-bromoaniline with formation of substances of m. p. 119' and 109' respectively. All these compounds and piperonylidene- aniline form only monohydrochlorides which are of a yellow colour.On treating piperonal with p-phenylenediamine and with benzidine compounds m. p. 216' and 241' respectively are obtained which are formed by the condensation of 1 mol. of the diamine with 2 mols. of piperonal ; these substances form yellow scales with a bronze lustre. E. G. Substitution Products of p-Diaminodiphenylmethane and of p-Diaminodiphenyl. THEODOR NEUM~LLER (J. pr. Chem. 1908 [ii] 77 353-363).-p-Diaminodiphenylmethane and its 3 3'-dinitro- derivative readily condense with monochloroacetic acid in the presence of sodium acetate yielding diglycine derivatives. 4 4'-Diphenyl- methanediglycine CH,( C,H,*NH*CH,*CO,H) separates from water or dilute alcohol as a flocculent crystalline mass m. p. 175". 3 3'- Dinitro - 4 4'- dip?m&nethane diglycine crgstallises in lemon-yellow needles m.p. 164' (decomp.). CH,[C,H,(NO,)*NH*CH,*CO,H] NH,*C,H,*C,H,( NO,)*NH* Coo GO,€€ is readily formed when 4'-aminodiphenyl-4-oxamic acid (D.R.-P. 95060) is nitrated a t - 5' to - 10' with the theoretical amount of potassium nitrate dissolved in concentrated sulphuric acid. It crystallises from alcohol in small chrome-red aggregates which melt above 250'. I t s lccetyl derivative C16H1806N3~ forms orange-red crystals which also melt above 2 5 0 O . The position of the nitro-group in the nitrated oxamic acid follows from the fact that on hydrolysis it yields o-nitro- benzidine and on reduction yields a diamine which with nitrous acid gives a diazonium salt and not an azimino-compound as would be expected if the two amino-groups were in the ortho-positions.3-Nitro-4'-amimodiphenyl-4-oxamic acid 4'-Acetyla~~zinodiphe~ay~-4-oxamic acid NHAc*C,H,~CGH,*NHoCOoCO,H crystallises from dilute acetic acid in colourlem needles m. p. above 2509 The calcium salt C,,H2,OsN,Ca crystallises from dilute alcohol in slender needlea. When nitrated the acid yields 3'-nitro-4'-acatyl- VOL. XCIV. i. c c870 ABSTRACTS OF CREMTCAT PAPERS ccn~inodiphen y I - 4-0xccq~~ic acid N H A c *C,H,( NO,) * C H,*NH * CO* CC' [ I which separates from water as a pale orange-red crystalline mass m. p. 155O. When boiled with concentrated ammonia it yields S'-nitro- 4'-amirzodipheiiyI-4-oxccmic acid in the form of slender needles m. p. 206". The fact that the nitro- and acetylamino-groups are in ortho- positions with respect t o one another follows from the readiness with which the acetyl group is eliminated.Preparation of 5 5 Dialkylbarbituric Acids from the Corre- sponding Dialkylrnalonylguanidines. CHEMISCHE FABRIK AUF AKTIEN (VORM. E. SCHERING) (D.R.-P. 189076).-The 5 5-dialkyl- barbituric acids are obtained in good yield (90-100~~) by treating with nitrous acid the dialkylmalonylguanidines produced by condensing the ethyl dialkylmalonates with guanidine or by condensing the ethyl alkylmalonx tes with guanidine and alkylating the intermediate product. P. AUBOUY (Bull. Xoc. chim. 1908 [iv] 3,388-390).-These two salts have been prepared in extemion of previous work on the preparation of the salts of pyramidone with mineral acids (Abstr. 1906 i 989). Both were obtained by the addition of the respective acids t o antipyrine dissolved in alcohol.Antippine p h s p h t e [C,,H,,0N2]2,H,P04 m. p. 158-1 60" forms colourless crystals and is soluble in water or alcohol and insoluble in ether. Antipyine arsenccte [CY/11H120N2]2,H3As04 has m. p. 1 46-148" and otherwise resembles the phosphate. Aqueous solutions of either salt are acid t o test paper and the colour reactions of such solutions with various reagents are recorded. J. J. S. G. T. M. Antipyrine Phosphate and Arsenate. T. A. H. 3-Hydroxy-1 2-dihydroquinoxaline and its Derivatives. SIGMUND MOTYLEWSKI (Ber. 1908 41 800-805).-3-Hydroxy- 1 2-dihydroquinoxaline although not formed by the action of o-phenyl- enediamine on ethyl chloroacetate may nevertheless be prepared by the condensation of o-phenylenediamine with chloroacetic acid ; it crystallises from water in slender colourless needles m.p. 96 -97" containing 1 mol. H,O ; the anhydrous substance has m. p. 132-133" ; the fers*ocyaicide CsHsON,,H,Fe(CN) crystallises in silvery leaflets. KH-(?H2 crystallises in o r C,H4< The acetate C,H,< ,- colourless needles m. p. 166' ; the benzoate CsH,N2=OBz crystallises in microscopic white needles m. p. 210-211". The p u e n t substance is converted by nitrous acid into 1 -nitroso-3-I'Lydroxy-~ 2 - d i k ~ d r o p i ~ ~ - N(No)'(?H2 crystallising in yellow prismatic needles ; C*OH' omlim C,H4< Jy-- i t melts and paitly decomposes a t 164' forming tt white mass which becomes transp:trent at 2 1 Oo. Hydrated 3-hydroxy-1 2-dihydroyuinoxaline mhen heated at; 125" loses i t s water of crystallisation together with 2 atoms of hydrogen b ~ i i i g converted into a yellow amorphous substccnce N*$XI or EL p.264' (decomp.); it probably has the formula c! H < I N-CO NAc*CO ' NH-YH h- C*C>AcORGANIC CHEMISTRY. 37 1 %H4<& .;.OH9 A substc6me C,H,ON isomeric with the latter corn- pound is obtained by the oxidation of 3-hydroxy-1 2-dihydroquin- oxaline with potassium permanganate ; it crystallises in colourless needles m. p. 269O and forms a white amorphous silver salt and a green copper salt Cl6Hl0O4N4Cu5~ Oxidation of 3-hydroxy- 1 2-dihydroquinoxaline with chromic acid leads to tho formation of o-phenyleneoxamide m. p. 41 0’ (compare Seeliger and Meyer Abstr. 1897 i 45).The silver salt (C,,Hlp05N4Ag4)2r4+H20 and copper salt CI6H1,,O7N4Cu4 were prepared. The substance C,H,0N2 obtained by the oxidation with potassium permanganate and o-phenylene- oxamide are converted by phosphorus pentachloride into 2 3-dichloro- quinoxaline C,H,<N ccl crystallising in colourless needles ni. p. 149-150O”. Preparation of Indoxyl and its Homologues and Deriv- atives. BADISCHE ANILIN- & SODA-FABEIK (D.R.-P. 188436). -The acylarylgly cines when condensed with aluminium halides give rise to indoxyl derivatives. Acetylphenylglycine its potassium salt o r its ethyl ester when heated with aluminium chloride either in a vacuum or in a current of inert gas a t 220-250’ furnishes indoxyl which is isolated in the form of indigotin. Acetyltolylglycine gives rise to the methyl homologua of indigo tin.G. T. M. LEON LILIEN- FELD (D.R.-P. 189021).-It is found that the yield of indoxyl or indigotin obtained by heating phenylglycine with alkali hydroxides in presence of an alkali metal is greatly increased by carrying out this operation under reduced pressure. The potassium salt of phenylglycine potassium or sodium hydroxide and sodium when heated in a good vacuum at 200-%0° furnish S0-90% of indigotin. Indigoid Dyes. PAUL FRIEDLANDER (Ber. 1908 41 772-777. Compare Abstr. 1907 i 334).-The author applies the term “indigoid” to dyes which are related to indigotin in that the irnino-groups of the latter are substituted by a sulphur or other bivalent atom or group. In continuation of the investigation of thioindigotin now termed bisthionaphthenindigotin i n conformity with Jacobson’s system of nomenclature (Abstr.1906 i 378) it has been found that asymmetric as well as symmetric indigoid dyes can be prepared by condensation of substances such as in- cloxyl thioindoxyl 1 3-diketohydrindene a- and @-naphthols and the more reactive phenols of the benzene series which contain the grouping *CO*CH,* or *C(OH):(TH* with cyclic a-diketones such as isatin a-keto-halogen compounds such as isatin chloride or dibromo-oxy- thionaphthen C kI,(g>CBr2 and reactive anilinoketones and alkyl- oxyketones such as the a-anilide and a-methyl ether of isatin. The C16H1005N4Ag3 N:FCl W. H. G. Preparation of Indoxyl and its Homologues. G. T. M. co c c 2372 ABSTRACTS OF CHEMICAL PAPERS. products are all coloured orange-red to greenish-blue.They vary in stability and in their behaviour towards alkalis with the nature of the two cyclic nuclei of which they are composed but are in general stable towards acids and on treatment with alkaline reducing agents yield colourless products mostly easily oxidised by the atmospheric oxygen with formation of the original dye. The following two new indigoid dves are described. Y co-c==y-F)O CH:~H NH-C,H prepared Naphthalene-indole-indigotim C,H,< by the action of isatin chloride on a-naphthol in beizeie solution crystallises in copper-coloured prisms or needles m. p. about 240° and forms at higher temperatures a reddish-violet vapour which condenses to woolly needles It is more easily soluble than indigotin and is sulphonated with difficulty yielding a product which is loss stable towards alkalis than is indigo-carmine.When boiled with sodium carbonate solution the indigotin forms a greenish-yellow soluble sodium compound readily decomposed by acids and when boiled with sodium hydroxide dissolves and is rapidly decomposed. The solution obtained on reduction with alkaline hyposulphite is yellow. - - 2-Thionaphthen-2-indole-indigotin C,H,(s->C CO C<NH)C,H co pre- pared by heating indoxyl with dibromo-oxythionaphthen in glacial acetic acid solution crystallises from nitrobenzene in reddish-violet needles does not melt a t 300° sublimes at higher temperatures and forms a slightly yellow reduction product which dyes textile fibres bluish-violet. The suZp'honic acid is blue and becomes yellow on addition of an excess of alkali.The absorption spectra of thioindigotin and of the two new indigoid dyes are described. G. Y. Behaviour of Indigoid Dyes and Indigotin towards Alkalis. PAUL FRIEDLANDER (Ber. 1908 41 1035-1039. Compare preced- ing abstract).-Binz has shown (Abstr. 1906 i 749) that indigotin forms an additive product with sodium hydroxide having the com- position C,,H1,O,N,,NaOH in which he supposed the sodium hydroxide ONa to be attached to a carbonyl group thus >C<oH . Since indigotin and quinones contain the group -CO*C:C*CO- which on the addition of acetic acid changes into -C(OH):CH*C€€(OAc)*CO- or -C (OH) CH C (OAc) C( OH)- the author considers it probable that the sodium hydroxide would combine in a similar manner. This view receives support from the fact that 2-naphthalene-2-indoleindigotin is decomposed by sodium hydroxide yielding anthranilic acid and 1 -hydroxy-2-naphthaldehyde9 the reaction being represented thus YGH4 * Wo>C:C<~H>C,H -+ I I PO- CHZCHORGANIC CHEMISTRY.373 1 -Bydroxy-2-naphthaZdehyde7 CllH802 crystallises in long pale greenish-yellow needles m. p. 59' ; it is very similar to salicylaldehyde gives a crystalline hydraxone and when treated with methyl sulphate in alkaline solution yields l-rnethoxy-2-naphthaZdehyde crystallising in white compact prisms m. p. 47'. 2-Hydroxy- 1 -naphthaldehyde has been obtained by warming 1- naphthalene-%indoleindigotin with 10% aqueous sodium hydroxide solution. Similarly 1 -hydrox y-4-rnethoxy2-naphthaldeh yde lemon- yellow crystals m.p. 1 OOO and 2-hydi*oxy-3-thionaphthenat?dehyde C,H4<c(cFo)>C*OH m. p. 130° have been prepared from 4- methoxy-2-naphthalene-Z-indoleindigotin and 3-thionaphthen-2-indole- indigotin respectively. The p-quinonoid compounds which are formed together with the indigoid dyes by the condensation of isatin chloride with certain phenols and naphthols are also decomposed by alkali yielding hydroxy-aldehydes ; for example 2 - c h Z o r o - 4 - ~ ~ d r o x y - ~ - ~ ~ ~ ~ t aldehyde C 6 H 4 < ~ ~ ~ ~ ~ ) ~ - m. p. about 220' (decomp.) is obtained from the product 'which results on condensing isatin chloride with 2 - chloro-a-naphthol. Action of Halogens on Aromatic Amines and their Use in the Synthesis of Certain Dyes. ADRIANO OSTROGOVICH and T.SILBERMANN (Chem. Zentr. 1908 i 2 6 6 ; from BuZ. Xoc. Stiinte Bucuresci 1907 16 120-1 26).-lodine bromine and chlorine react with aniline at 140-180° giving dyes of the induline class. If a mixture of aniline hydrochloride and a-naphthylamine is subjected to the action of iodine in presence of aniline a substance of the nature of a rosinduline is produced. p-Toluidine when heated at 140-1 80' with aniline and iodine gives p-rosaniline hydriodide. Oxidation of Aniline by Halogen Acids. ADRIANO OSTROGOVICR and T. SILBERMANN (Chem. Zentr. 1908 i 266; from BuE. SOC. Xtiinte Bucwre8ci 1907 16 127-133).-1n the presence of mineral acids chloric bromic and iodic acids oxidise aniline to aniline- black. I n presence of acetic acid aniline is scarcely attacked by chloric acid ; with bromic acid it yields dianilinoquinoneanil and with iodic acid azophenine.When dianilinoquinoneanil is melted with aniline hydrochloride and aniline a blue induline dye is obtained ; by using p-phenylenediamine in place of aniline a bluish-violet induline dye is obtained ; o-aminophenol p-aminophenol and p-phenyl- enediamine react in this respect like aniline. Explanation of the Formation of Induline. ADRIANO OSTROGOVICH andT. SILBERMANN (Chem. Zentr. 1908 i 266-267 ; from BuZ. SOC. Stiinte Bucuresci 1907 16 133-1 41).-When aniline-black is heated a t 180' with excess of an aniline salt induline is quanti- tatively formed ; from this and other observations the author concludes that aniline-black is an intermediate product in the oxidation of aniline to induline.J. V. E. W. H. G. J. V. E. J. V. E. Glycine as a Product of Uricolysis. LYMAN B. STOOKEY (Proc. A ~ w . Xoc. Bid. Chew& 1907-8 xxx. ; J. Biol. Chem. 4),-Although374 ABS'TRACTS OF CHEMICAL PAPERS in vitro uric acid may be readily degraded to glycine it is unsettled whet,her glycine is an intermediary product in uricolgsis. Minced liver and kidney were incubated with uric acid and benzoic acid ; the greater portion of the uric acid was destroyed but there was no corresponding increase of hippuric acid ; hencsglycine WRS not formed. W. D. H. Azoxy-compounds TH. KOTARSKI (Rev. 1908,41 865-866).- The liquid crystalline modifications of azoxybenzene m-azoxytoluene m-axoxyanisole and p-azoxyphenetole are reduced in acid solution to amino-compounds and in alkaline solution or by distillation with iron to azo-compounds but differ from the solid forms in the following respects (1) They respond to Lieberrnnnn's nitroso-reaction. (2) The solution in b o i h g glacial acetic acid is coloured red by hydro- chloric acid D 1-19.(3) The yellow colour is unchanged by sunlight. (4) Sulphuric acid does not convert them into hydroxyazo-compounds. (5) The additive compound with bromine formed in chloroform solution loses hydrogen bromide when melted. The temperature at which the turbid liquid crystals become clear is unchanged by crystallisation or distillation. m-Axoxyanisole m. p. 5 lo obtained from m-nitroanisole and sodium methoxide becomes red on exposure to light and by distillation with iron filings yields rn-axoanisole m.p. 73-74'. c. s. Constitution of the Acetylated Condensation Products from Benzeneazo - u - naphthol and Tetramethyldiamino- benzhydrol. RICHARD MOHLAU (Bey. 1908,41,989-990. Compare Mohlau and Kegel Abstr. 1900 i 56).-The author confirms Auwers and Eisenlohr's statement (this vol i 229) that when the acetylated condensation product is reduced acetanilide is not formed but aniline ; hence the argument for the hydrazone constitution for the condensation product is no longer valid. J. J. S. Chloroamine Reaction of the Proteins. CHARLES F. CROSS EDWARD J. BEVAN and JOHN F. BRTCWS (J. SOC. Chem. Ind. 1908 27 6 260).-The reaction of chlorine and hypochlorites on nitrogenous colloids to form chloroamine derivatives is shown to take place in constant and characteristic quantitative proportions the derivatives being formed without destructive actions.The bearing of the fixation of '' active " chloroamine chlorine on bleaching processes and the application of chloroamine reactions to histological investigations are dealt with in detail. J. V. E. Hydrolysis of Different Proteins in Pepsin-Acid Solutions. WILLIAM N. BERG (Pvoc. Amer. Xoc. Biol. Chem. 1907-8 xlv.; J. BioZ. Chena. 4).-Various proteins and various acids of strength equiva- lent to 0.2% hydrochloric acid were employed. Edestin digests most rapidly then follow in the order given alkali-albumin acid-albumin fibrin egg-albumin nucleo-protein and elastin. The order of the acids in efficiency is hydrochloric nitric oxalic phosphoric sulphuric tartaric lactic citric acetic and boric.W. D. H.ORGANIC CHEMISTRY. 375 The Preparation of Goleuoine from the Hydrolysis Product8 of Proteins. PHCEBUS A. LEVENE and WALTER A. JACOBS (Biochem. Zeitsch. 1908 9 231-232).-The principal difficulty which has existed hitherto in the preparation of pure leucine and its isomeride consists in the separation of valine from the leucines. This can be best accomplished by precipitation of the latter substances by normal lead acetate and ammonia. The leucines were prepared from casein in the following way. The casein was hydrolpsed with 33% sulphuric acid and the latter separated by ba,rium hydroxide. On evaporation of the filtrate from barium sulphate a mixture of tyrosine and leucine separated. On addition of bromine the bromo-compound of the former substance was obtained and could be dissolved out with amyl alcohol On further evaporation of the liquid after this treatment the leucine-valine mixture separated.This was redissolved and the crude leucine precipitated by lead acetate and ammonia. On de- composing the lead precipitate with hydrogen sulphide a mixture of leucine and isoleucine was obtained from which the constituents could be readily separated by treatment of the copper salts with methyl nlco hol. S. B. S. Influence of Electrolytes on the Coagulation-temperature of Egg-albumin. WOLFGANG OSTWALD (Chem. Zentr. 1908 i 89 ; from Zeitsch. Chem. Ind. Kolloide 1907 2 108-113).-By using the figures of Bonamartini and Pauli (Abstr. 1907 i SOZ) the dependence of the coagulation-temperature of various solutions of egg- albumin on the concentration of an added salt such as NaCl or NH,Cl is represented with great accuracy by the equation l / t = Kcm where t = coagulation-temperafure c = salt concentration and K and m = constants.By altering the coagulation-temperature to 1 Go and a salt concentration from 1% to 20% sn only varies between 0.08 and 0.21. The similarity of the above equation to the general adsorp- tion equation apparently shows a connexion between the temperature of coagulation of egg-albumin in presence of electrolytes and adsorption phenomena in solution. The attempt of Freundlich (Abstr. 1907 ii 939) to connect the phenomena of coagulation with ion adsorption is criticised. J. V. E. Adsorption of Acid8 by Casein. LUCIUS L. VAN SLYKE and DONALD D.VAN SLYKE (J. Biol. Chem. 1908,4 259-266).-In spite of criticisms by T. B. Robertson (this vol. ii 89) the authors main- tain that the relationship between casein and acids is one of adsorption rather than chemical combination. W. D. H. Preparation and Some Properties of the Oxyhaemocyanin Crystallised from the Snail. C. D~RB (Compt. rend. 1908 146 784-786).-When snail’s blood is dialysed in a collodion bag in the presence of distilled water renewed morning and evening at the temperature of melting snow it remains perfectly limpid during the first seven days. I n the course of the eighth day the blood becomes cloudy and soon depogits an abundant precipitate of oxyhaemo- cymin the azure colour of the liquid becoming paler. Microscopic376 ABSTRACTS OF CHEMICAL PAPERS.examination of the deposit shows t h a t it consists entirely of crystals in the form of six-pointed stars which are not birefringent. After sixteen days the supernatant liquid has become practically colourless and is not altered by agitation with air. If after seven days the dialysed blood is subjected to the action of a continuous current of 0.1 milliampere at 120 volts the oxyhzemocyanin is deposited at the anode whilst the liquid surrounding the cathode becomes colourless but on shaking the whole liquid the crystals of oxyhzemocyanin re- dissolve to a blue-coloured solution. Oxyhzemocyanin after calcination leaves a small quantity of a black residue which dissolves in nitric acid and contains copper. It dissolves in water containing R trace of acetic acid.The absorption spectrum given by a layer 3 mm. thick of a solution containing 7.59 grams of oxyhzemocyanin per litre presents a band in the ultra- violet between X 292.6 and X 262.8. On increasing the thickness of the layer a fresh band appears and a t 10 mm. extends from X 364.0 to X 328.2. The latter band seems to be characteristic; the most refrangible band is common to all albuminous substances. E. H. Soluble Silver Compounds of Nucleic Acids and their Derivatives. FARBENFABRIKEN VORM. FRTEDR. BAYER & Go. (D.R.-P. 188435).-The silver compound of sodium nucleate from yeast is obtained as a thick paste by adding aqueous silver nitrate to a strong solution of the nucleate in water. A saturated solution of sodium chloride is added until the precipitate has redissolved when the compound is reprecipitated with alcohol.The product is a yellowish-white powder containing 22% to 23% of silver. Sodium nucleate from the thymus gland gives a similar derivative as do also the formaldehyde derivatives of these acids. Pyrimidine Derivatives in Nucleic Acid. THOMAS B. OSBORNE and FREDERICK W. HEYL (Amer. J. Physiol. 1908 21 157-161).- The question has arisen whether or no the pyrimidine derivatives of nucleic acid originate from the purine substances in the presence of carbohydrates. I n the present research the purines were first removed by mild hydrolysis ; severe hydrolysis then liberated the pyrimidine compounds. The fact that the mild hydrolysis completely removed the purine is shown by no ammonia being liberated during the severe hydrolysis for each molecule of pyrimidine which is formed from the purines involves the production of two molecules of ammonia The further conclusion is drawn that uracil is not derived from cytosine for this also involves the production of ammonia.The Origin of Cytosine obtained by the Hydrolysis of Nucleic Acids of Animal Origin. PH~BUS A. LEVENE and JOHN A. MANDEL (Biochem. Zeitsch. 1908 9 233-239).-The estimation of cytosine obtained in different stages of partial and also in complete hydrolysis of nucleic acid of spleen was carried out. The results lead to no definite conclusion as to whether the cytosine is of secondary origin or not that is whether it is derived from the hydrolysis of G. T. M. W. D. H. puFine compounds or directly from the original nucloic acid molecule.5. B. S.ORGANIC CHEMISTRY. 377 Reducing Action of Animal Fibres. GUSTAV ULRICH [and in part THEODOR SCHMIDT] (Zeitsch. physiol. Chem. 1908 55,25-41).- These investigations were carried out with the object of determining the action of wool on the mixture of chromium trioxide and formic acid as employed in mordanting processes The direct reducing action of the formic acid on the chromium trioxide appears t o be but small. The formic acid acts on the fibres with the production of substances which bring about the reduction of chromium trioxide. 8. B. 8. Behaviour of Gelatin Solutions Towards Naphthols or Mixtures of Naphthols with Formaldehyde. ARTHUR WEIN- SCHENE (Chem. Zeit. 1908 32 266-267).-A reply to Stiasny’s statements concerning the author’s observations on the tanning of hides by means of naphthols in the presence of aldehydes.The addition of formaldehyde to a solution obtained by adding P-napht4hol dissolved in glycerol to a strong aqueous solution of gelatin produces a thick flaky precipitate which is quite insoluble in water whereas no such precipitate is formed in the absence of /3-naphthol. P. H. Some Oxides as Tanning Material. LUPPO-CRAMER (Chem. Zentr. 1908 i 93-94; from Zeitsch. Chern. Ind. Kolloide 1907 2 171-173).-The author found previously (Abstr. 1907 i 1098) that gelatin absorbs soluble salts without becoming tanned whereas colloidal silver oxide acts as a typical tanning material. Silver peroxide prepared from silver nitrate and ammonium persulphate is now shown to be a far more powerful tanning agent.The silver peroxide compound of gelatin is insoluble in boiling water and un- changed by sodium hydroxide ammonia sodium thiosulphate or dilute sulphuric acid but is decomposed when warmed with strong acids. Metol-soda developer darkens the yellow colour partly reduces the peroxide to silver and does not destroy the tanning. A photographic negative desilverised by ammonium persulphate behaves in a similar manner and since a 10% potassium cyanide solution removes the image but does not destroy the tanning the photobromide remaining in the negative plays no part in the tanning. Silver peroxide itself coagulates conceritrated solutions of gum nrabic. Mercury and copper oxides tan gelatin rendering it insoluble.The HgO-gelatin shows unusual hardness and like Ag,O-gelatin when warmed in water becomes intensely white. CuO-gelatin is green and by washing out excess of salt the tanning is not destroyed. I n the coagulation of egg-albumin by silver nitrate solution adsorption compounds of silver oxide with egg-albumin are formed which are not attacked by thiosulphates. I n all albumin papers therefore after fixing and washing there remains some silver oxide which may cause the paper to become yellow. J. V. E. Lipoids. SIGMUND FRANHEL (Biochem. Zeitsch. 1908 9 44-53). Part I. Neottine a Triaminophosphatide. CARLO BOLAFFIO. - Two substances have been prepared from egg-yolks containing nitrogen378 ABSTRACTS OF CHEMICAL PAPERS. and phosphorus the one:with the element in the ratio 8N lP and the other a triaminophosphatide designated neottine.The former WQS prepared by extracting egg-yolks with acetone filtering distilling off the acetone and again extracting the residue left with ether. On distilling off the latter solvent crystals were deposited and were separated from the liquid fats by aid of a porous tile. They were only partly soluble in acetone ; the solution in this solvent gave a precipitate with cadmium chloride in alcoholic solution which was soluble in hot benzene and could be recrystallised from boiling 95% alcohol. The cadmium compound thus obtained was crystalline and readily darkened on exposure to air and was therefore probably an unsaturated compound. The second compound neottine C,,Hl7,O1,~,Y was obtained by extracting dried egg-yolks with acetone until a white residue was obtained; this was digested for two hours a t 45' with double its weight of 95% alcohol.The filtered extract on evaporation in a vacuum gave a white residue which showed little change on exposure to air ; the subsequent alcoholic extract of the residue darkened however. The substance from the first extract was recrystallised several times from hot alcohol and a white substance was finally obtained which could be readily powdered; the powder consisted of a fine network of microscopic needles m. p. 91'. The molecular weight was confirmed cryoscopically. The substance absorbs but a small quantity of iodine the Hub1 number being only 16.2 and is optically inactive. It was found by the Herzig and Mayer method that only one-third of the nitrogen is combined with methyl groups (that is in the form of choline).On hydrolysis with barium hydroxide three acids were obtained presumably cerebronic scearic and palmitic acids. It contained 1.84% N and 0.51% P. S. B. X. Synthetic Tryptophan and Some of its Derivatives. ALEX- ANDER ELLINGER a i d CLAUDE FLAMAND (Zeitsch. physiol. Chem. 1908 55 S-24).-By the reduction of a-bei.Lxoylaminoindolylcccryl~c acid C,H,N*CH:C:(NHBz)-CO,H with sodium and alcohol racemic trypto- phan has been obtained (Abstr. 1907 i 737). For identification and comparison with the natural dextrorotatory substance the benzene- sulyhonyltr~ptophans C,H,N.CH,*CH(NH.S02Bz)*C0,H the corre- sponding p-naphthaleneszcl~honyttryptoph~ns and the tryptophan- Izaphthplcarbinzides were prepared.The derivatives from the natural dextrorotatory substance and the racemic synthetical compound had identical melting points (1 85O 180° 15S0). The naphthylcarbimide compound is very sensitive to light. The paper gives in addition the details OF the preparation of the synthetical substance. S. B. S. Optical Behevicur of Tryptophan. H. FISCHE~~ (Zeitsch. physiol. Chern. 1908 55 74-76).-Tryptophsn and its hydrochloride are laevorotatory whilst the sodium salt is dextrorotatory. The rotation in aqueous solutions shows considerable variations wliich cannot be accounted for by polymerisation. There is no reason to alter the origiual designation of Hopkins and Cole of I- into d-tryptophan. 8. B. S.OKGANlC CHEMISl'KP.379 Union of Carbon Dioxide with Amphoteric Amino-corn- pounds. 111. MAX SIEGFRIED and C. NEUMANN (Zeitsch. physiol. Chevn. 1908 54 423-436. Compare Abstr. 1905 ii 332; 1906 i 324).-The amount of carbon dioxide absorbed in the formation of carbaniic acids from amino-compounds is determined by adding to 0*1-0.5 gram of the substance dissolved in 50 C.C. of ice-cold water a few drops of phenolphthalein in lime-water and then about 10 C.C. of milk of lime containing 20% of calcium hydroxide. Carbon dioxide is passed in until the indicator is almost decolorised while the solution is gently shaken. The addition ol milk of lime and its neutralisation by carbon dioxide is repeated three to four times. The solution of the calcium carbamate is filtered clear and boiled ; the calcium carbonate which is thus precipitated is weighed and the nitrogen in the filtrate is determined by Kjeldahl's method.A number of amino-acids and other substances have been examined and the molecular ratio of ammonia to carbon dioxide approximates in nearly all cases rather closely to a whole number (in accordance with the theory). The reaction has been applied fractionally to R gluco-albumose first obtained by Pick. The purity of the substance is deduced from the constancy of the nitrogen content of the fractions. G. B. Union of Carbon Dioxide with Amphoteric Amino-corn- pounds. IV. NAX SIEGFRIED and HANS LIEBERMANN (Zeitsch physiol. Chem. 1908 54 437-447).-The method described in the preceding abstract has been applied to polypeptides. I n the case of glycyl- glycine the ratio N/CO is 1.79 ; this seems t o be due to the formation of the anzmonium salt of glycylglycine-carboxylic acid m.p. 206" (almost identical with that of the acid itself). Glycylglycine-carboxylic acid does not unite with carbon dioxide in the presence of lime. For a number of dipeptides the ratio N/CO was 1%3-la79 ; for tripeptides 2-57 ; for a tetrapeptide 3.29 ; for trypsin-fibrin-peptone-a and -/3 (Abstr. 1903 i 782) it was 2-14-2.46. Since these peptones cannot be as simple as di- or tri-peptides the explanation of the low value (2.1 4-2-46) is sought in the possible presence of hydroxyl groups; in the peptones ; small quantities of alcohol when present in the reaction mixture (for instance as alcoholic phenolphthalein) lower the ratio very considerably. G. B. Serum Containing Anti-amylase. C. GESSARD and JULES WOLPF (Compt. rend. 190S 146 414-416).-As was shown by Gessard (Comnpt. rend. Soc. Biol. 1906 01 425) a serum can be prepared inhibiting the action of malt-extract on starch. I n the present experiment the greatest degree of inhibition is 70% as deter- ruined by the amount of maltose produced. At 50" the inhibitory effect is only half as great as at 2 0 O . G. B. Tyrosinase and Raoemic Tyrosine. GABILLEL BERT~AND arid 1111. ROSENBLATT (Compt. rend. 1908 146 304-306 ; Bull. Soc. c h h ~ 1908 [iv] 3,394-398).-The oxidation of d-tyrosine and of I-tyrosine380 ABSTRACTS OF CHEMICAL PAPERS. and of dZ-tyrosine by tyrosinase (from 12ussuZc) takes place at the same rate. Accordingly there is only one ferment for both antipodes. G. B. The Go-enzyme of Expressed Yeast in Juice. EDUARD BUCHNER and FRITZ KLATTE (Biochem. Zeitsch. 1908 8 520-557).-- Previous researches have shown that the fermentative activity of yeast is due to two substances the zymase which is destroyed by boiling the expressed juice and a co-enzyme which is not so destroyed; the latter only can dialyse through parchment and can also be separated from the former by filtration through a Martin gelatin filter. Further experiments have been carried out with a view of throwing light on the chemical nature of these substances. Considerable differences were noted in their activity in yeasts of different origin ; the juice from Berlin yeast for example could be better regenerated by the addition of boiled juice after it had lost its activity than could that from Munich yeast. This fact may account for some of the dis- crepancies in the observations of different observers. This regeneration could be accomplished in some cases as many as six or seven times and the zymase was still active even after twenty- seven days. These facts indicate that the co-enzyme is much more readily destroyed than the zymase. Yeast juice which has become inactive by keeping without sugar cannot be regenerated ; neither can a co-enzyme be prepared from it. It is known that the proteoclastic enzyme contained in yeast can destroy the zymase and experiments were carried out t o determine whether it exerted a similar action on the co-enzyme. It was found that the co-enzyme lost but little of its activity after treatment with trypsin ; it is improbable therefore that the tryptic enzyme of the yeast is responsible for the destruction; furthermore on mixing the co- enzyme (boiled yeast juice) with fresh juice without sugar it rapidly loses its activity. If however the juice is six months old it exerts no destructive action on a co-enzyme even although it retains its proteo- elastic activity The tryptic enzyme presumably destroys the substance which acts on the co-enzyme. Boiled juice however on treatment with lipase from castor-oil seeds rapidly loses its co-enzymic activity and this fact leads to the supposition that the co-enzyme is of the nature of a phosphoric ester. It was found in fact that sodium glycerophosphate has considerable power in regenerating the inactivated zymase. S. B. 8. The Chemical Changes in Adrenaline produced by Enzymes. CARL NEUBERG (Biochem. Zeitsch. 19OS 8 383-386).-The extract from the ink bag of Sepk8 o$ici.naZis has the power of producing a black pigment from adrenaliiie which is insoluble in alcohol but partly soluble in alkalis ; i t is an oxidation product. Other substances from the animal organism which yield colours were investigated but only tryptophan and tyrosine yielded pigments. The action is due t o an enzyme as the boiled extract has no action. s. B. s.

ISSN:0368-1769    

DOI:10.1039/CA9089400305

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

31 4 SBSTRAC‘TS OF CHRfiIICAT PAPERS. Chemistry of Vegetable Physiology and Agriculture. Law8 of Disinfection. HARRIETTE CHICK (J. Eygie~e 19OS 8 92-158).-1n anthrax spores the disinfection process obeys the equation for a nnimolecular reaction if ‘‘ concentration of reacting substance ” is replaced by ‘‘ numbers of surviving bacteria.” I n B. paratyp?~osus this law does not hold for the younger bacteria are more resistant than the others. The process is influenced by tempera- tur.e and the equation of Arrhenius can be applied ; from this follows the advantage of using warm solutions in practical disinfection. I n the case of some metallic disinfectants the metallic ion appears to be the active agent. I n disinfection with mercuric chloride a toxic compoimd is formed between the metal and the substance of the bacterial cell.This compound prevents further growth but vitality can be restored by a large excess of soluble sulphide. 7M. D. H. Relative Efficiency of Filters. WILLIAM I3 LJLLOCH J. A. CRAW and E. E. ATKIN. Grain of Filters and Growth of Bacteria through Them. J. A. CRAW (J. Hygiene 1908 8 63-69 70-74).-0f the filters tested the Doulton filters alone prevented the direct transmission of micro-organisms. Berkefold filters and Slade and Brownlow filters gave contaminated filtrates within fifteen minutes of the commencement of filtration. Striking photomicro- graphs of the size of t,he pores in the filters show that this is inversely proportional to the eaciency of the filters. W. D. H. Micro-organisms Oxidising Hydrogen.11. BRONISLAW NIKLEWSKI (Cent?.. Bakt. Pa?’. 1908 20 ii 469-473. Compare Abstr. 1907 ii SSO).-The condensation of hydrogen and oxygen by the soil is due to two organisms living symbiotically and together constituting the membrane formed on mineral solutions in an oxygen- hydrogen atmosphere. The fact that neither organism when grown by itself can oxidise hydrogen and that morphologically they greatly resemble each other accounts for the diEculties of obtaining a pure culture. The author doubts the identification of Kaserer’s organism (Abstr. 1906 ii 113 697) with Bucillws oligocnrbophilus ; in his own cultures he never observed nitrification nor did growth take place in a carbon monoxide atmosphere as described by Kaserer. In spite of these differences the author regards his organism as probably identical with th:at of Kaserer and probably also with that of Nubokich arid Lebedeil’ (Abstr.1907 ii 43). G. B.VEGETABLE PHYSIO1,OCfY AND AGRICULTURE. 31 5 Survival of Bacillus Typhosus in Soil. W. MAIR (J. Hygiene 1908 8 37-4’7).-The typhoid bacillus survives in soil for seventy t o eighty days but there is no evidence that i t multiplies and leads a saprophytic existence there. If the soil has been sterilised previously by steani under pressure the bacillus dies out more rapidly (eleven days) but this does not obtain in all cases. Sterilisation apparently produces bactericidal s u b tances. TV. D. 1%. Chemical Constitution and Biological Properties of the Protoplasm of Koch’s Bacillus. JULES AUCLAIR and LOUIS PARIS (Conaljt.rend. 1908 146 301- 303).-Tubercle bacilli were freed from soluble proteins and from the fatty wax and then extracted a t 80’ with concentrated acetic acid ; on almost completely ceutrdising the extract with sodium hydroxide flakes are precipitated which resemble a nucleo-casein. When injected in dosea of 1 mg. this bacillo-casein produces small tumours in t,he rabbit and the guinea-pig. It and the fat,ty wax are the essential poisons of tubercle bacilli. G. €3. Nitrification. LESLIE C. COLENAN (Centr. Baht. Pcir. 19@S ii 20 401-420 484-5 13).-1n accordance with Bazarewski’s results it mas found tlist nitrification in non-sterilised soil uiny be considerably in- creased by small amounts of dextrose (to 0.5%). The greatest effect is produced i n the second and third weeks; subsequently the effect diminishes whilst denitrification due to organic ma ttm increases. Sucrose glycerol and lactose in small amounts seem to have a favourable effect ; no effect was detected in the case of calcium butyrnte whilst calcium acetate seenis to retard nitrification.Peptone aiid urea (0.5% and 0.75% respectively) greatly retard nitrification. Nitrification in a loam was most active i n presence of 16% of water and mas much retarded when the amount of water was reduced to 10% or increased to 26%; in presence of an excess of water dextrose is injurious instead of beneficial. Approximately pure cultures of nitrate and nitrite organisms in sterilised sand or soil are rendered more active by 0 02-0 05% of dextrose ; under similar conditions pure cultures of the nitrate organism seem to acquire increased activity in presence of 0.05% of dextrose. A supply of carbon dioxide is necessary in presence as in the absence of dextrose. Carbon disulphide has a t first a very decided retarding action on nitrification ; sobsequently nitrification is increased owing no doubt to a stimulating action.N. H. J. 31. Carbohydrates of Yeast. WILHELM MEIGEN and A . SPREKG (Zeitsch. physiol. Chenz. 1908 55 4S-73).-Tmo carbohydrates can be obtained from the cell membrane of yeast ‘‘ yeast gum ” and ‘‘ penst ceZEuZose.” Ths yeast gum has been prepared in different ways such as by boiling the yeast with water (Nageli and Low Bkhamp and Schiitzenberger) by boiling with chalk (Hessenland) and by boiling with dilute potassium hydroxide and precipitation of the poIy- saccharide with E’ehling’s solution (Salkomski).The preparations so316 ABSTRACTS O F CHEMICAL PAPERS. obtained show different specific rotations varying from 47.6’ to 989’. This is due to the fact that the “yeast gum ” obtained by different processes contains admixtures of other substances such as proteins glycogen and hemicell dose. Salkowski’s method gives the purest prepar‘ttion (with aD 91.1’). Hydrolysis with 351/0 sulphuric acid gives a mixture of mannose and dextrose in the molecular proportions of 2 1. Pentoses seem to be absent. Two other carbohydrates were prepared from the yeast in the following way. The yeast was treated for six months with 0.25% potassium hydroxide which was changed a t intervals.The residue was re- peatedly treated with alcohol until t,he water was removed and then dried. This preparation gave a brown colour with iodine and sulphuric acid and also with iodine dissolved in potassium iodide; it was insoluble in ammoniacal copper hydroxide solution. On treatment with 3% sulphuric acid (20 times the quantity for ten hours) or with 15% sodium hydroxide (for four hours) two-thirds of the quantity went into solution ; on evaporation of the solution and addition of alcohol a carbohydrate mas precipitated which after purification had a rotatory power of + 113’ ; i t gave no precipitate with Fehling’s solution but a precipitate with lead acetate and bttryta water. It differs therefore from the yeast gum. On hydrolysis it yields only dextrose. This substance is then yeast dextrose and seems to be identical with Salkowski’s erythro-cellulose.The insoluble residue from the hydrolysis with 3% sulphuric acid or 15% sodium hydroxide is another hydrocarbon yeast ceElulose ; on hydrolysis in the cold with SO% sulphuric acid it yields mannose and dextrose in approximately equal molecular proportions ; i t seems to be identical with Salkowski’s achroo-cellulose. It does not give however the typical cellulose reactions and is not present in the yeast cell in this form but is produced from the original hydrocarbons by hydrolysis. S. B. S. The Influence of the Chemical Constitution of the Nitro- genous Nutriment on the Fermentative Action and Growth of Certain Fungi. 11. HANS PRINGSHEIM (Biochenz. Zeitsch. 1908 8 119-12i.Compare Abstr. 1907 ii 44).-As in the case of yeast the capability of producing the alcoholic fermentation being due t o the presence of amino-acid groups is true also for the fungi Rhixopus tonkirzensis Mucor racemosus and Toruta I but is not the case for Atlescheric6 Guyonii or Z’oruta K As was found also by Czapek for Aspergillus niger this source of nitrogen favours the growth of R. tonkinensis M. vacemosus and I’orukc V but not of A. Gayonii. W. D. H. Formation of Fuse1 Oil by Certain Fungi. HANS PRINGSI-IEIRI (Biochenz. Zeitsch. 1908 8 128-13l).-Various fungi which produce the alcoholic fermentation were investigated. All of these possess the power of converting leucine into amyl alcohol and the smaller the amount of ethyl alcohol formed t,be richer it is in fuse1 oil.w. D. €3.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 317 Fixation of Zinc by Sterigmatocystis nigra. MAURICE JAVILLIER (Conzpt. rend. 1908 146 365-367).-The growth of this mould { = Aspergillus) is stimulated by minute traces of zinc up to 1 part in 10,000,000 parts of the culture fluid. A t higher concentra- tions up t o 1 in 250,000 growth is not accelerated any further but the fungus assimilates nevertheless the whole of the zinc which no doubt is useful. From concentrations of 1/250,000 to 1/25,000 a portion of the zinc is absorbed the excess being harmless. I n solutions containing more than 1 part in 25,000 the Aspergillus no longer attains its normal weight. Although :the beneficial effect of traces of zinc (and of other poisonous metals) is well known the direct proof of the fixation of the zinc is now given for the first time.G. B. Active Principles of the Fruit of an African Strychnos. ALEXANDRE HBBERT (J. Pharna. Chim. 1908 [vi] 27 151-155).- The fruit of Sts.yclmos aculeata from the Ivory coast of Africa contains neither strychnine nor curarine :but traces of brucine. It contains in addition an active principle which is non-volatile with steam and is toxic to fish but not to mammals. It exerts this toxic action in doses corresponding with 1 part of the fruit in 10,000 parts of water. s. B 8. Chemical and Bacteriological Effects of Liming. EDWAKD 13. VOORHEES JACOB G. LTPrvrm and PERCY E. BROWN {f!‘ew Je~sey Agric. Expes.. Stat. Bul. 1907 2lOj.-Experiments on the effect of burnt lime and calcium carbonate on oats and crimson clover grown in boxes containing 50 lb.of a market garden soil somewhat sandy and of a red shale arable soil respectively. I n many cases the application of lime reduced the yield of dry matter and increased the yield of nitrogen; magnesian lime caused a greater depression in the yield of rJry matter than non-magnesian lime. On the other hand ammonification and nitrification were promoted by liming and more by magnesian than by non-magnesian lime. The amounts of lime applied were not sufficient seriously to affect the CaO/NgO ratio. The diminished yield of dry matter under the influence of lime is attributed to a decreased supply of available phosphoric acid accumulation of injurious substances due to bacterial activity being increased by the lime or to the utilisation of pla.nt-food by the increased numbers of soil organisms Actual countings by the plate method and by Hiltner and Stormer’s dilution method showed an enormous increase of soil organisms under the influence of soil treatment. N. H. J. M. Proteins of Rice. OTTO ROSENHEIM and S. KAJIURA (Proc. physiol. Xoc. 1908 liv-Iv; J. Physiol. 36).-Rice yields 7% of total protein of which 0*14”,! is a globulin 0.04% an albumin and the remainder a protein which like the glutenin of wheat is soluble only in dilute alkali; the name oryzenin is suggested for it. It gives all the usual protein colour reactions. The almost complete absence of a gliadin318 ABSTRACTS OF CHEMICAL PAPERS. (or alcohol-soluble protein) explains why rice is unsuitable for making dough and bread. The addition of barley t o rice diet prevents outbreaks of Beri-beri. It is suggested that the increased supply of glutainic acid in hordein (the alcohol-soluble! protein of barley) may partly explain this. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9089405314

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

318 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Detection of Free Hydrochloric Acid in the Stomach Contents. F. A. STEENSMA (Biochem. Zeitsch. 1908 8 210-2 11). -The following modification of the Gunzberg solution is recom- mended phloridzin 2 grams vanillin 1 gram absolute alcohol 30 C.C. To carry out the test the inverted cover of a crucible is placed on a water-bath and warmed. When hot a drop of the reagent is added ; the alcohol evaporates and leaves a faint yellow ring. I n the middle of this ring where there is no reagent one or two drops of the liquid under investigation are placed. If hydrochloric acid is present a bright red edge will form on the inside of the yellow ring on evapora- tion ; if only small quantities. of hydrochloric acid are present only a thin red line will be formed.The reagent will not keep long and should be freshly made for the test especially if methyl alcohol is employeci instead of ethyl alcohol. Fluorine in CEnological Products. P. CARLES (Ann. Clzim. anal. 1908 13 102-104).-The author calls attention to the fact that traces of fluorine compounds may be introduced into wines by the use of animal charcoal gome kinds of tannins (China galls) clarifying agents (gelatins) to which hydrofluosilicic acid has been 5. B. S. added as a preservative &c. L. DE K. Detection of Hydrogen Peroxide in Milk. E. FEDER (Zeitsch. N d r . Genussm. 1908 15 234-236).-The presence of 0.01% of hydrogen peroxide in milk may be detected by heating 5 C.C. of the milk 5 C.C. of hydrochloric acid D 1.19 and 1 drop of dilute formaldehyde solution to n temperature of about 60" for three or four minutes.If hydrogen peroxide is present a violet coloration is obtained. Fresh milk treated in the same way gives a yellow coloration. Other substances however besides hydrogen peroxide give a violet coloration when heated with milk and hydrochloric acid in the presence of formaldehyde. Of these nitric and nitrous acids may be mentioned Milk containing added water may give a coloration indicating the presence of hydrogen peroxide but in reality due to the nitrous acid (nitrite) introduced along with the water. In testing watered milk the presence or absence of nitrous acid should therefore be established by means of other tests. w. P. s.Estimation of Small Quantities of Oxygen and Carbon Dioxide in Small Volumes of Saline Solutions.THOMAS G. BRODIE and WINIFRED C. CULLIS (J. Physiol. 1908 36 405-413).- A simple method is described of boiling off and collecting the gases from small amounts of oxygenated Ringer's solution used to perfuse surviving organs. The gas bubble is t l o n introduced into n carefully- calibrated capillary tube and its length measured ; potassiuni hydroxide is then introduced t o absorb the carbon dioxide m d an alkaline solution of pyrogallol acid to absorb the oxygen ; the diminution of the length of the bubble is a measure in each case of the amount of gas absorbed ; the final residue is nitrogen. Differential Method of Blood-Gas Analysis. JosEPrx BARCROFT (Yroc. physiol. Soc. 1908 lii ; J. YhysioE. 36).-Equal quantities of venous and arterial blood in separate bottles are connected to the manometer of the Barcroft-Haldane apparatus.The blood is then laked as usual potassium ferricyanide added and the oxygen liberated The difference of the levels in the fluid in the manometer is a measure of the amounts of oxygen in the two fluids. The carbon dioxide can then be liberated by tartaric acid and another reading taken. For oxygen estimation the ferricyanide may be omitted and the two samples of laked blood simply shaken with the air ; both samples will then saturate themselves with oxygen and the same difference of level will be produced. Estimation of Gases in Human Blood by the Chemical Method. JOSEPH BARCROFT and P. MORAWITZ (Proc. physiol. Xoc. 19OS lvi; J. Physiol.3B).-Doubt has been expressed as to whether the ferricyaride method is eflicient for human blood. The present series of experiments on five persons shows that it is. W. D. H. New Procees for the Estimation of Sulphur in Organic Substances. ~SIDOHE BAY (Comp. rend. 19OS 14G 333-334).- The substance is heated in a tube with sodium carbonate and mag- nesia; a current of oxygen is passed through the tube during the combustion and the sulphuric acid formed is estimated subsequently by dissolving the contents of the tube in dilute hydrochloric acid and precipitating with barium chloride. The combustion tube may be filled as follows firstly a plug of asbestos 3 cm. in length ; then 10 em. of a mixture consisting of equal weights of sodium carbonate and magnesia ; next the substance to be analysed mixed with sodium car- bonate and magnesia and finally,another layer of the mixture of sodium carbonate and magnesia about 20 cm.in length a second plug of asbestos being employed t o close this end of t'he tube. The exit end of the tube may be connected with a Liebig bulb containing sodium hydroxide and bromine to prevent any loss of. volatile sulphur corn- pounds. The quantity if any of sulphuric acid yielded by the sodium carbonate and magnesia must be estimated separately and deducted from the result obtained. The process is suitable for the estimation of sulphur in mercsptans ethyl sulphide allylthiocarbimide t hiophen &c. Ln the case of liquids the substance is introduced into the com- W. D. H. W. D. H. bustion tube in a small glass tube.\v. P. s.320 ABSTRACTS OF CHEMICAL PAPERS Detection of Sodium Sulphite in the Presence of Sulphate and Thiosulphate. FRANK E. WESTON and C. TIV. JEFFREYS (Chem. News 1908 97 85).-Tlie solution is precipitated by means of lead nitrate or acetate the precipitate is washed by decantation and treated with N-thiosulphate. The lead sulphate and thiosulphate dissolve whilst lead sulphite is insoluble. The precipitate is washed and then treated with a little dilute sulphuric acid. The solution now contains sulphur dioxide which is tested for in the usual may by the odour or by means of perman- A. RONCHBSE (J. P?umt. Chinz. 1908 27 [vi] 231-235 ; Bull. Soc. china. 1908 [iv] 3 362-366).-The method described previously (Abstr. 1907 ii 651) may be applied to the estimation of ammonia in water. From 250 C.C.to 1 litre of the water are acidified with sulphuric acid and evaporated to a volume of about 40 C.C. ; the solution is then neutralised using phenolphthalein as indicator and 4 C.C. of a neutral 20% formaldehyde solution are added. The solution is next titrated with N/lOO sodium hydroxide solution until the pink coloration reappears. Owing to the influence of the ammonium salts on the indicator a correction is applied to the number of C.C. of alkali required for the titration 0.1 C.C. being added for every 3 C.C. of N j l O O sodium hydroxide used. ganate &c. L. DE K. Estimation of Ammonia in Water. TV. P. s. Nitrates Nitrites and Ammonia in Sea-water. WILH~LM E. RINGER and MEJ. I. N. P KLINCEN (Chem.Weekblad 1908 5 147-1 68).-The authors review the methods employed in the estima- tion of nitrates nitrites and ammonia in sea-water basing their criticisms on the results of experiments carried out with artificial solutions of known strength and with numerous samples of sea-water from various places on the coast of Holland. Volumetric Estimation of Phosphoric Oxide by Uranium FERNAND REPITON (Chem. Zentr. 1907 ii 2078; from Non. Xci. 1907 [iv] 21 ii 753-754).-A modification of Malot’s cochineal process. Tincture of cochineal is prepared by boiling powdered cochineal with 100 C.C. of water for an hour replacing the loss by evaporation and heating again to boiling. When cold 50 C.C. of alcohol are added nud the solution is filtered. The phosphate solution to be tested is mixed with 5 C.C.of sodium acetate solution diluted to 100 c.c. heated to boiling and mixed with a few drops of the indicator Uranium solution is then run in until the solution after first turning dark and then brick-red changes suddenly t o dull green. I n order to make the necessary correction an experiment is made by titrating under the same conditions a suspension of uranyl phosphate when about 0.2-0.3 C.C. of uranium solution will be required to effect Estimation of Carbon in Irons. LUCIEN L. DE KONINCK and E. VON WINIWARTER (Bull. Soc. d i m . Rely. 1908 22 104-105).- It is proposed to burn the iron with lead borate in a current of A. J. W. the change in colour. L. DE K.ANALYTICAL CHEMISTRY. 381 oxygen and to estimate the carbon dioxide formed by any suitable means.L. DE K. New Experiences in the Simplified Method of Elementary Analysis. MAX DENNSTEDT (Ber. 1908 41 600-604. Compare Abstr. 1907 ii 986).-The author gives a detailed account of the precautions t o be taken in the analysis of difficultly combustible substances of substances containing halogens o r sulphur and in the use of commercial calcium chloride and soda-lime. c. s. Estimation of Potassium by the Perchloric Acid Method in Manures Dung Soils and Vegetable Substances &c. VINCENT SCHENKE (Lnndw. Versuchs. Stat. 1908 68 61-65. Compare Abstr. 1907 ii 910)-The acid solution to which sulphuric acid should be added if not already present is evaporated and ignited a t a low red heat and the cold residue repeatedly rubbed and then digested with hot water and 2-3 C.C.of 5% hydrogen chloride. It is then washed into a measuring flask heated and treated with a very slight excess of 10% barium chloride. When the amount of barium sulphate is small as in the case of straws and grain filtration is unnecessary ; phenolphthalein is added and then milk of lime until strongly reddened to precipitate phosphates &c. After half an hour an aliquot portion is acidified with hydrochloric acid evaporated to a smaller volume and treated with a suitable amount (5 C.C. or more) of 20% perchloric acid. A number of determinations made by the above method are given as well as by the less expeditious modification in which ammonia and ammonium carbonate are employed. Concordant results were obtained by the two methods those by the lime precipitation method being as a rule slightly higher It is important to avoid adding more than a very slight excess of 10% barium chloride and to employ only about 2 C.C.of 57; hydro- chloric acid to dissolve the ignited substance. N. H. J. M. Separation of Silver Chloride from Silver Iodide. HENRI BAUBIGNY (Compt. Tend. 1908 146 335-336).-Whilst the method described by Hager (Zeitscl,. ccnctl. Chem. 1871 10 341) for the separation of silver chloride iodide and bromide from each other yields only approximately accurate results the author finds that a modification of the method gives trustworthy figures if the chloride and iodide alone are present. The precipitate consisting of the two silver salts (chloride and iodide) is treated for a few minutes a t a temperature of 70' to 80' with about 100 C.C.of a solution containing 100 grams of ammonium sesquicarbonate and 20 C.C. of 20% ammonia per litre. The mixture is then cooled the clear solution is decanted on to a filter and the residue is once more extracted with the ammoniacal solution. The residue which now consists solely of silver iodide is poured on the filter washed with the ammoniacal solution diluted with an equal volume of water dried and weighed. The silver chloride is separated from the filtrate by the addition of nitric acid and estimated in the usual manner. w. P. s. VOL. XCIV. ii. 22322 AIZSTRACTS OF CHEMICAL PAPERS. Barium Arsenite and Arsenate. LEOPOLD ROSENTHALER (Chem. Zeiztr. 1907 ii 2078 ; from Apot?~. Zeit. 1907 22 982)- Eai ium may be precipitated quantitatively by arsenious acid in the presence of aminonia but not by arsenic acid unless sodium hydroxide is substituted for the ammonia.Conversely arsenious and arsenic acids may be precipitated quan- titatively by barium chloride with addition of ammonia or of sodium hydroxide respectively. L. DE K. Electrolytic Analysis. FRITZ FOERSTER (Zeitsch. EZeAtroclLem. 1908 14 90-93).-A reply to Classen and t o Fischer (this vol. ii 226). T. E. New Method of Qualitative Analysis of the Metals of the Second Group without using Hydrogen Sulphide or Ammonium Sulphide. ETTORE SELVATICI (Boll. chim. fcwm. 1908 47 73-74. Compare Tarugi and Schiff Abstr. 1845 ii 84).-The precipitation of the metals of the second group by means of hydrogen sulphide in presence of hydrochloric acid is only complete under certain conditions of acidity temperature and concentration which cannot always be determined exactly.Further cupric sulphide dissolves to some extent in ammonium sulphide solution and mercuric and tin sulphides combine giving a compound soluble in water and partly soluble in ammonium sulphide. In order to obviate these and other difkulties the author recommends the following procedure which involves the use of neither hydrogen sulphide nor ammonium sulphide. The acid filtrate separated from the insoluble chlorides of the first group is treated with thioacetic acid heated almost to boiling allowed to cool and filtered. After being washed on the filter the precipitate is heated with concentrated nitric acid which dissolves the sulphides of arsenic lead (partly) bismuth copper and cadmiurn and converts stannic and antimony sulphides into insoluble metastannic and antimonic acids and lead sulphide partly into sulphate.After filtra- tion the liquid is freed from excess of nitric acid by heating and treated with excess of Concentrated sodium hydroxide solution which precipitates bismuth copper and cadmium as hydroxides arsenic and lead remaining in solution ; this precipit,ate is washed and dissolved in nitric acid the bismuth being then precipitated as hydroxide by the addition of excess of ammonium hydroxide; the copper may be separated from the cadmium in the ammoniacal solution by means of hydrochloric acid arid potassium thiocyanate or of potassium cyanide and hydrogen sulphide.The addition of dilute sulphuric acid to the sodium hydroxide solution containing the arsenic and lead precipitates the latter the arsenic remaining in solution. The metastannic and antimonic acids mercuric sulphide and lead sulphate are treated with alkaline ammonium tartrate to dissolve the lead sulphate the insoluble residue being washed and dissolved in hot nitro-hydrochloric acid. The solution is then freed from excess of acid and of chlorine and treated with hydrazine hydrochloride or sulphate to precipitate metallic mercury The addition of zinc to the filtrate causes the precipitationANALYTICAL CHEMISTRP. 323 of antimany and tin the latter being separated by its Polubility in hydrochloric acid. T. H. P. JTJLIUS LOEVY (Chen2. Zeit. 1908 32 220).-The Belgian method of fusing the sulpbide in a n iron crucible yields from SS-lOO% of the amount of lead regulus obtainable whereas the English or German method fusing with metallic iron in a Hessian crucible yields from 92-95% only.Any eventual loss in silver is not caused by evaporation during the cupelling prochess but is due simply to the lead being deficient. When ores contain much zinc low results are obtained even wit’h the Belgian Dry Lead and Silver Assays in Ores. met hod. L. DE I<. Estimation of Copper in Pyrites. G. REMONDINI (Chem. Z e ~ z t ~ . 1907 ii 2082 ; from Mon. Sci. 1907 [iv] 21 ii ‘754).-Pive grams of the sample are heated until the sidphur has been completely burnt arid the residue is boiled for fifteen t o twenty minutes with 50-35 C.C.of iiitric acid I) 1.4 the solution is diluted with water t o 250 c.c. and 200 C.C. of the filtrate are neutralised with ammonia. After again acidifying with 5 C.C. of nitric acid the copper is deposited electro- Technical Assay of Amorphous Carborundum. GmRwr CIIESNEAU ( A n 7 ~ . Chin?. anal. 19OS 13 85-S9),-One gram of the finely-powdered sample is heated in a platinum crucible to redness for two hours in a muffle. This burns off the free carbon and the residue is treated with 20 C.C. of pure hydrofluoric acid and I C.C. of sulphuric acid and slowly evaporated on a sand-bath. The mass is then boiled with hydrochloric acid and after adding some hot water the undissolved ixatter is waahed by decantation with hot acid water and finally collected on the filter and washed with hot water.It consists of pure carborundum (amorphous and crystalline) which is ignited and Volumetric Estimation of Manganese in Iron and Steel. EDG. KAYNOND (BUZZ. SOC. chi7.12. Uelg. 1908 22 75-80).-The author again recommends a process published by him in 1883 and independently worked out by Hampe in 1885 based on the fact t h a t nianganese is precipitated as dioxide when its solution in nitric acid is heated with potassium chlorate. The dioxide is then estimated by dissolving i t in an acid solution of ferrous ammonium sulphate and titrating the excess of the latter with standard permanganate. When dissolving pig-iron in nitric acid €or the purpose of a man- ganese estimation it is advisable to remove the bulk of the silicon by means of a little hydrofluoric acid.The filtrate is then concen- trated and boiled with potassium chlordte and nitric acid as usual. I yt icall y . L. DE K. weighed. L. DE I<. L. DE K. Estimation of Ferrous Iron. NICHOLAS KNIGHT (Chem. iVews 1908 97 122).-As has been stated by Mauzelius when assaying native ferrous carbonate such as siderite by the Berzelius-Bunsen process (separation of the ferric from the ferrous iron by means of 22-2324 ABSTRACTS OF CHEMICAL PAPERS. barium carbonate) i t is of great importance lhat the mineral should be merely coarsely powdered. If reduced to a fine state of division a not inconsiderable portion of the ferrous iron is oxidised to the ferric state; this is due i n part to the heat generated by the friction and also to the larger surface exposed.L. DE K. Electrolytic Separation of Nickel and Zinc. FRITZ FOERSTER and W. TREADWELL jun. (Zeitsch. Elektrochem. 1908 14 89).-ln the separat’ion of nickel and zinc from an ammoniacal solution containing sodium sulphite the nickel deposited contains sulphur ; the error due to this is usually between 1% and 2% of the weight of the nickel (compare Thiel and Windelechmidt Abstr. 1907 ii 601 1137 and Foerster Zeitsch. Elektyochem. 1907 13 563). T. E Rapid Electrolytic Separation of Nickel from Zinc. ARTHUR FISCHER (Chenz. Zeit. 1908 32 185-186).-The author has acceler- ated the electrolytic deposition of nickel from ammoniacal solution by addition of sodium sulphite. The solution should contain about 0.15 gram of nickel and zine (as sulphates). As electrolytes are added 5 grams of ammonium su1phat.e 1-3 grams of sodium sulphite and 30 C.C.of ammonia D 0.91 ; the whole is then diluted t o 250-300 C.C. The nickel may be deposited in twenty minutes if the following conditions are observed; as electrodes are employed t F o concentric cylindrical diaphragm-cathodes. Temperature 90-92’. The strength of the current to begin with is 1 ampere which is gradually reduced to 0.1 ampere according t o the potential ; this is controlled by the author’s c cmrensation process described previously. The zinc may be recovered by oxidising the solution with hydrogen peroxide expelling the ammonia by heating and adding 2-3 grams of tartaric acid and excess of alkali The separation is complete in forty-five minutes when using a current of 3.5 amperes.L. DE K. Estimation of Nickel in the Presence of a very large Excess of Cobalt. ill. EMNANUEL POZZI-ESCOT (Ann. Chim. aizaZ. 1908 13 89-91).-When applying the author’s molybdate process (Abstr. 1907 ii 818) to mixtures containing say 1 part of nickel to 20,000 parts of cobalt it is necessary to remove first of all the bulk of the cobalt and then test for thenickel. To the solution containing about 20 grams of the cebalt nitrate is added ammonium chloride and ammonia and also a n excess of hydrogen peroxide. The liquid is now neutralised with acetic acid and a saturated solution dof ammonium molybdate is added slowly until most of the cobalt is precipitated. The filtrate is evaporated t o dryness and the residue is moistened with nitric acid and heated t o expel most of the ammonium salts; it is then dissolved in R few drops of nitric acid and the nickel precipitated by means of a n excess of ammonium molybdate as described in the previous article.L. DE K.ANALYTICAL CHEMISTRY. 325 Rapid Estimation of Potassium Dichromate in Milks. GOUBRE (Compt. rend. 1908 146 291-292).-The ash from 10 C.C. of the sample is treated with 3 C.C. of 10% potassium iodide solution and 5 C.C. of hydrochloric acid and the iodine liberated is titrated with sodium thiosulphate (5.06 grams per litre ; 1 C.C. = 0*001 gram of potassium dichromate). No indicator is used. L. DE K. Volumetric Estimation of Titanium. H. D. NEWTON (Amer. J . Sci. 1908 [iv] 130-132).-The solution which should contain not less than 10% of sulphuric acid is placed in a flask fitted with a rubber cork through which pass a delivery tube and a small separating funnel A sufficiency of pure zinc is added and the whole is heated gently while a current of hydrogen is passed over the surfa.ce of the liquid.When the zinc has completely dissolved the liquid is allowed to cool in the current of hydrogen a sufficiency of ferric snlphate is poured through the funnel and then sufficient air-free water to nearly fill the flask. The contents are transferred to a larger flask containing more air-free water and the liquid is a t once titrated with hT/10 permanganate. One at. of iron=1 at. of titanium. If the zinc is not free from iron this should be allowed for. L. DE K. Estimation of Small Quantities of Bismuth.HERBERT W. ROWELL (J. Soc. Chent. Ind. 19OS 27 102-104).-1n the process described the bismuthisobtainedin solution free from largequantities of lead copper tin antimony gold and silver then precipitated as oxy- chloride and finally estimated colorirnetrically as iodide in sulphuric acid solution. In the case of ores mattes Ssc. the sample is treated with hydrochloric and nitric acids the silica is separated in the usual way and the solution is evaporated with sulphuric acid t o remove the hydrochloric acid and lead before being used for the estimation of the bismuth. For the estimation of bismuth in copper 10 grams of the sample are dissolved in 60 C.C. of nitric acid (1 l) the solution is diluted with 150 C.C. of water and saturated sodium carbonate solution is added until a slight permanent precipitate forms.One C.C. of the carbonate is then added in excess the mixture is boiled for five minutes and the precipitate consisting of the mhole,of the bismuth and a little copper is allowed to settle. The precipitate is then collected on a filter washed dissolved in hydrochloric acid and precipitated as basic chloride. I n the case of lead base bullion &c. 10 grams of the sample are dissolved in 20 C.C. of nitric acid D 1.42 and SO C.C. of water the solution is boiled to precipitate most of the tin and antimony and a little sodium chloride is added to precipitate the silver. The lead is precipitated by adding sulphuric acid t o the boiling solution and after cooling for one hour the lead sulphate is collected on a filter.The filtrate is treated with 5 C.C. of concen- trated hydrochloric acid a slight excess of ammonia is added and then dilute hydrochloric acid until the solution is faintly acid in reaction towards methyl-orange. The solution is boiled kept in a warm place for one hour and the precipitate is collected on a filter and washed twice. The filtrate is tested with potassium iodide to326 ABSTRACTS OF CEEMICAL PAPERS. ascertain whether it is free from bismuth. The filter and precipitate are now pulped with 10 C.C. of sulphriric acid (1 3) 30 C.C. of \.v;ttor ai'e added the mixture is boiled cooled to sepnritte any lead sulphate and filtered the residue being washed with dilute sulphuric acid. The whole or a suit'able portion of the filtrate containing possibly antimony arsenic tellurium iron and traces of lead copper o r silver and not more than 2 or 3 mg.of bismuth is ti.ea,ted with 5 C.C. of sulphuric acid (1 3) 5 C.C. of 20% potassium iodide solution and ten drops of sulphuIous acid. The coloration obtained is compared KODOLFO NAMIAS (Chenz. Zentr. 1907 ii 2079-2080; from Mon. Sci. 1907 [iv] 21 ii 75 1 -752).-Estinzcttion of Uisnzuth in Complex Slccgs.-Tit o grams of the slag are fused with 10 grams of potassium hydroxide for twenty hours the fused mass is dissolved in water acidified with nitric acid and evaporated to dryness. The mass is taken up with nitric acid D 1.3 and filtered off from the undissolved t i n and antimony oxides and silica. The solution is t'hen repeatedly evaporated with hydrochloric acid to expel the nitric acid and the filtrate now free from silver and the bulk of the lead am treated with hydrogen sulphide.The precipitate after being washed with wtrm ammonium sulphide is redissolved in hot dilute nitric acid and the lead is precipitated by adding 15% sulphuric acid up to 200 C.C. An aliquot part of the filtrate is then precipitated with ammonia and the bismuth oxide collected washed with ammoniacal w;tter ignited with the usual precaution$ and weighed. The same process may be applied also to aZZoys although traces of bismuth are frequeiitly retained by the tin-antimony precipitab from which they may be recovered by a second fusion with potassium hydroxide and subsequent treatment with nitric acid. Estimation of Antimony in SZngs.-The slags are fused with a mixture of 2 parts of potassium carbonate and 1 part of sulphur.The mass is dissolved in hot water and the filtrate is boiled with liydrochloric acid and potassium chlorate ; any undissolved matter should be fused again with the sulphur mixture. The antimony is then precipitated as usual by means of metallic iron. Estimation of Tin another portion of the slag is fused with potassium hydroxide and then boiled repeatedly wihh nitric acid ; the joint oxides of t i n and antimony aye collected ignited and weighed. Estimation o f Antimony in Alloys.-In the case of type metal and similar alloys the finely cut up nietal is boiled with dilute hydrochloric acid (1 1) and some potassium iodide which dissolves the t i n and lead and leaves the antimony undissolved.Estintation of Tin the alloy is treated with nitric acid and the joiut amount of tin arid antimony oxides is thus obtained. Estimation o f Fin in Slctys and Ashes (Ash of Dj*essed Silk).-The sample is fused with potassium hydroxide and treated repeatedly with nitric acid ; the result is tin oxide and silica and the latter is then estimated in the usual way by fusion with alkali and evaporation with that produced by known amounts of bismuth. w. P. 8. Analyses of some Alloys and Slags. with acid. L. DE K.ANALYTICAL CHEMISTRY. 327 Estimation of Gold by means of Sucrose cr Dextrose. P. LEEDLER (Chenz. Zentr. 1907 ii 1867-1868 ; froin Zeitsch Chenz. Ind. Koltoids 1907 2 10S).-Gold may be precipitated quantitatively by heating the solution on the water-hth w i t h aclditicn of siicrose or dextrose.Lzctosa c:tnnot be used on account of the very finely- divided state of the precipitate. I n the Rut1iol”s liandq the process gave satisfactory results with aut ic chloride ai,d hydrogen auri- chloiide but not with sodium :turichlorid(> Platinum solutions tire not affected. Silver s d t s yield c olloicLil solutions. L. DE K. Method for the Complete Analysis of Vegetable Substances. JACQUES 31. ALBAHAHY ( C U Y ) I ~ ~ . r e d . 1908 146 336-338).-A Iloi-tion of the substance is dried ftt 1003 t o obtain tlie quantity of voldtile 111 d t e r (water &c.) arid is then incinerated to give the amount of total ash. A second poition of the sample is extracted with alcohol; the alcoholic extract is distilled a t a low temperature and the distiIlate is collected in a receiver containing a kno A n volume of standard eodinm hydroxide solution arid siirronncled by a freezing mixture. On titrating b x k the excess of sodium hydroxide tlie qu.intity of volatile acids is obtained and this added t o the weight of tlie raiclue remniriing in the distillation -8:xsk gives the weight of the alcohol-soluble subxtmees. Tlie sum of the substances soluble and insoluble in alcohol siibtracted from the weight of the original material gives the actud amount of miter present.The dried substance is utilised f o r the estiwntion of the fnt coloriring matters cholesterol and lecithin. The portion of the +ubst;ince insoluble in alcohol is next digested for two days in alcohol acidified tvit!i hydro- chloric acid. The solution is then poured tlirongh a filter and the residue is watalied with d ~ o l i o l .The filtritte and wiisllings :ire evaporated the residue is weighed extracted with ether to remove organic acid< aud then dissolved in water. Portions of the so1nt:on are used for the estimntiou of t’,o reducing sugnt s mineral acids nitrogen aspnragine sulphur and ash. In the poytion insoluble in acid-nlcohol are estimated the tot:tl protein nuclein albumin starch cellulose C ~ C . w. P. s. Estimation of Phenolic Hydroxyl Groups. JOHANSES HERZOG and V. HSsc.u (Ber. 1908 41 633-639).-The number of liydroxyl groups present in a phenol can be determined by condensing the phenol with diphenylcLwb;tmy1 chloride (Herzog hbstr. 1907 i 51 a) hytlrolysing the uretliane thus formed and weighing t’he amount of diphenylnmine formed.The hydroljsis is accomplished by heating 1 gram of the phenolic urethane with 8 C.C. of alcohol and :in excels of pot‘issium hydroxide in a pressure flask for oiie hour at 100’. The product is transferred to a flask and steam-distilled until the distillate is clear. Any diphenylamine which remains in t!ie condenser tube is driven over by removing the water from the condenser and passing steam through the inner tube. After one or two days the diplieiiyl- amine is collected on a dry filter paper dried at 30° and weighed. The results are mostly 1% too high.328 ABSTRACT8 OF CHEMICAL PAPERS. Fairly good results were obtained with phenol resorcinol pyro- gallol eugenol and o-nitrophenol. J. J.S. Commercial Carbolic Acid and Disinfecting Powders. MEREDITH W. BLYTH (J. Hygiene 1908 8 83-91).-Phenol solutions used as a standard in the bacteriological testing of disinfectants should be made from freshly-distilled phenol. The actual quantity of phenols and cresols present in commercial carbolic acids and carbolic powders may be estimated by extracting the oils and testing their germicidal power. The comparative germicidal valiie of disinfectant powders may be estimated by keeping the powder and organism in contact by mechanical means during the whole period of the experi- ment. W. D. H. Estimation of Picric Acid. MAX Buscm and G. RLUME (Zeiisch. ccngew. Chem. 1908 21 354-356).-The process is based on the practical insolubility of nitron picrate in water.One hundred and fifty C.C. of the solution containing about 0.3 gram of any picrate are mixed with 1-2 C.C. of dilute sulphnric acid and heated just to boiling. Ten C.C. of nitron acetate (10:h solution of nitron in 5% acetic acid) are added and when cold the precipitate is collected on a Neubauer crucible washed with 50-100 C.C. of cold water dried for an hour a t l l O o and weighed. Bromides iodides chlorides chlorates perchlormtes nitrites nitrates The weight x 229/541= picric acid. and chromates should be absent. L. DE K. Differentiation bet ween Arbutin and Quinol. P. LEMAIRE (Ann. Chim. anccl. 1908 13 105-107).-When heated with am- moniacal silver nitrate arbutin gives a beautiful silver mirror whilst quinol is reduced rapidly in the cold. When heated with a solution of sodium hypobromite arbutin gives a precipitate whilst with quinol a passing blue coloration is noticed in the cold aud also a precipitate which forms rapidly.A mixture of equal volumes of arbutin solution and sulphuric acid turns green on adding a few drops of 10% potassium dichromate solution but quinol causes a brownish-black coloration Rrbutin gives a blue colour with ferric chloride whilst quinol turns yellowish-brown finally yielding a black crystalline precipitate. When boiled with an equal volume of mercuric sulphate solution (5 grams of mercuric oxide 20 C.C. of sulphuric acid 200 C.C. of water) the liquid turns pale yellow and on cooling gives a deposit ; in the case of quinol a yellowish-brown coloration is noticed. A mixture of arbutin solution with an equal volume of sodium hydroxide gives no coloration in the cold whilst quinol turns yellowish-brown.An alkaline solution of arbutin turns pale yellow with sodium persulphate New Reactions for Cholesterol and Oxycholesterol. L. GOLODETZ (Chem. Zeit. 190S 32 160).-Solid cholesterol turns blackish-brown when moistened with 1-2 drops of a mixture of 5 parts of sulphuric acid and 3 parts of 30% formaldehyde. Cholesterol turns blue when treated with a drop of liquefied whilst quinol turns reddish-brown. L. DE K.ANALYTICAL CHEMISTRY. 329 trichlcroacetic acid and a drop of 30% formaldehyde. Oxycholesterol when treated with a fern drops of liquefied trichloroacetic acid turns at once green and shows in the spectrum a dark band in the red. 1,. DE K.The Sugar in Blood. LEONOR MICHAELIS and PETE& RONA (Biochem. Zeitsch. 1908 8 356-359).-Parallel determinations mere made of the sugar in the blood using the electronegative kaolin and the electropositive ferric hydroxide for adsorption of the proteins. The results with the former substance were somewhat higher than those with the latter and this has been shown to be due to the fact that the kaolin contained small quantities of a magnesium salt which was precipitated as oxide with the cuprous oxide. With the polarimeter the same results were obtained with kaolin as with ferric hydroxide. s. B. s. Use of Potassium Ferrocyanide and Zinc Acetate as Defecating Agents in Urine Analysis. CYRILLE CARREZ (Ann. Chim. ctnnl. 1908 13 97-101).-A solution is prepared containing 150 grams of pot,assium ferrocyanide per litre and another one containing 300 grams of zinc acetate per litre.When a urine has to be tested for sugar with Fehling’s solution or when the amount has to be determined polarimetrically 50 C.C. of the sample are mixed first with 5 C.C. of the ferrocyanide and then with 5 c. c. of the zinc solution and the fi1t.rate is then tested as usual. When the polariscope is employed a second portion of 50c.c. is treated in the same manner but with a further addition of 25 C.C. of water. From the result of the two readings the amount of dextrose is calculated as usual. L. DE K. Estimation of Lactose in Milk. GABRIEL GU~RIN (J. Pllarm. Chin& 1908 27 [vi] 236).-Ten C.C. of the milk are treated with 92 C.C. of a solution containing 5 mg.of mercuric acetate and 2 mg. of glacial acetic acid. The mixture is poured on a filter and the filtrate is shaken for a few moments with an excess of zinc dust and again filtered The lactose in this filtrate is then estimated volumetrically with Fehling’s solution. A correction is applied to the result obtained if the milk has undergone any decomposition; the acidity is estimated and any excess over 165 C.C. of N/10 alkali solution per litre of milk is calculated into lactose and added to the quantity found previously. One C.C. of 3 / 1 0 alkali is equivalent to 0*0088 EDUARD PFLUGER (PJiigev’s Archiv 1908 121 641-643).-Certain precautions in the method of filtering after the precipitation of glycogen by alcohol are described the most important being that the supernatant fluid should have become quite clear before filtration is attempted -otherwise the finely-divided glycogen may pass through the filter.WILHELM GREBE (PJziiger’s A?-cJki~ 1908 121 604-635).-The statement of gram of anhydrous lactose. w. P s. Precipitation of Glycogen. W. D. H. Estimation of Glycogen by Inversion with Acids.330 ABSTRACTS OF CHEMICAL PAPERS Nerking and Gatin-Gruiewska is confirmed thilt by inversion with 2.2% hydrochloric acid and b>i!ing for tliree hours the maximum yield of sugar is reached. A Colour Test for Formaldehyde and Benzoyl Peroxide. L. GOLODETZ (Cl~en2. %kit. 1908 32 245).-If n few particles of benzoyl peroxide are dissolved in 10-12 drops of sulphuric acid a strong reaction takes plwe accompanied by white fumes having the odour of benzophenone or fluorenone.If now a drop of dilute form- a1dehg.de is added the acid turns a permanent blood-red; this colour however is destroyed on adding xater. l h e test is a very delicate one Estimation of Citral in Essence of Lemon. P. BRUPLANTS (Ann. Cl~in2. ctnal. 19OS 13 91-97).-The process is based on the fact that if alcoholic citral solution is added in suficient quantity tr :t mixture of defibrinated (pig's) blood ant1 yellow ammonium sulphide the spectroscopic examinat ion shows t8hnt the two bands of oxygenated h~moglobin bcgin to fade and that a third band appears in the centre. A nnmber of experiments have sliown that t h e time this takes to form is inversely proportional to the amount of aldehyde p~eseiit. It is therefore sufficient t o prepare standard solutions of citr a1 in lemon oil previously deprived of aldehyde by fractiorinl distillation.W. D. I€. and serves for the detection of either compound. L D E K . Before use these are dissolved in aldehyde-free alcohol. L. DE K. Detection of Formic Acid. HENRY J. H FENTON and I€. A . S r s s o ~ (Proc. Ca~zb. PItiZ. ~Soc. 1908 14 386).-See this vol. i 243. Estimation of the Acidity of Wine. GABRIEL G U ~ H I N (J. Pharnz. Chiin. 1908 27 [vi] 237).-The method described previously (Abstr. 1907 ii 512) by the author gives results which are too low owing to the fact that certain acid constituents of the wine are precipitated by the mercuric acetate employed. For instance the number 1 I *4 found by the method corresponds with the number 12.5 of Gautier's alcohol-acid scale.w. Y. s. JULIUS T ~ T H (Chem. Zeit. 1908,32 242-244. Compare this vol. ii 238).-The distillation process gives unsatisfactory re5ults. When tartaric acid is used the distillate is actually alkaline. The following process gives good results; i t is based on the fact that small quantities of oxalic acid are decomposed and expelled on repeated evaporation with water. Three grams of the powdered sample are moistened with 3 C.C. of dilute sulphuric acid (1 5) and enough plaster of Paris is added to form a dry mass mliich is then placed in a stoppered cylinder and kept in contact for forty-eight hours with 150 C.C. of anhydrous ether with frequent shaking so as to dissolve all the organic acids. Fifty C.C. of the ether are then withdrawn and after adding 20 t o 40 C.C.of water titrated with N/2 sodium hydroxide using phenolphtbalein as indicator ; in the aqueous solution the oxtilic acid is then estimated. Auother 50 C.C. of ether are taken and evaporated to dryness; the Estimation of Volatile Organic Acids in Tobacco.ANALYTICAL CHEMISTRY. 331 residue is then evaporated thrice with addition of 50 C.C. of water. It is then dissolved in a little water and titrated with N/2 sodium hydroxide when the loss in acidity mill represent the volatile acidity (acetic acid &c.) including the oxalic acid. L. DE K. Estimation of Fat and Unsaponifiable Matter in Tissues together with a Critical Examination of the Methods now in Use. MUNEO KUMAGAWA and KENZO SUTO (Bioclwm. Zeitsch.1908,8 212-347).-The various methods in use for the estimation of fat (see later) produce when tested on the same material very varying results and they have been subjected to a critical experimental examination. I n all cases the material employed was a specially prepared dried meat powder. When the fat has been estimated by weighing the amount extracted by a given solvent varying results have been obtained depending on the solvent or solvents employed. An examination of the extractive power of different organic liquids was made and i t was shown that ethyl alcohol can produce the largest amount of extract. Putting the amount which can be. extracted by this solvent as 100 the amounts extracted by other solvents can be represented by the following numbers methyl alcohol 99 ; ethyl acetate 77 ; chloroform 72 ; acetone 62; benzene 5 3 ; ethyl ether 46; light petroleum 45. The examinat'ion of the alcoholic extract after it had been purified by solution in ether and filtration showed that besides fats considerable quantities of other products were present and the nitrogen in one case amounted to as much as 4.3%; the extract also contained phosphorus (compare Abstr.1207 i 371). Various methods were attempted for the separation of other substances extracted but without success. It is found however that the higher fatty acids produced by hydrolysis can be readily obtained nearly pure by solution i n light petroleum in which the accompanying substances are insoluble. The true fats can therefore be estimated by weighing the fatty acids thus purified which are produced by the hydrolysis of the alcoholic extract.It is found that a considerable part of the aliphatic acid produced by hydrolysis that is not soluble in light petroleum is lactic acid. The residue of the meat powder after extraction with alcohol yields on hydrolysis a certain quantity of higher fatty acid which can also be purified by solution in light petroleum. It is proposed therefore to estimate the fat in tissues by determining the quantity of fatty acids obtainable by hydrolysis of the whole substance as follows. Two to five grams of the dry tissue powder are warmed on the water- bath for two hours with 25 C.C. of 5AT-sodium hydroxide (20 per cent.). The tissue readily dissolves. The mixture is then washed into a separating funnel and acidified with 30 C.C.of a 20% hydrochloric acid. The separated fatty acids are t,aken up with 50-1UO C.C. of ether. The ethereal solution is filtered through asbestos and the ether evaporated off a t 50°. The residue thus obtained contains in addition to fatty acids colouring matters lactic acid and other substances. After thoroughly drying at 50° for some hours 20-30 C.C. of light petroleum are added when the impurities separate in a resinous form. The light petroleum solution is then filtered through asbestos the332 ABSTRACTS OF CHEMICAL PAPERS. solvent distilled off a t 50° and the residue dried a t this temperature to constant weight. Analysis shows t h a t it consists of almost pure fatty sicids and that i t is practically free from phosphorus and nitrogen.Comparisons were made of this method with those of Rosenfeld (extraction with alcohol and then with chloroform and weighing the combined extracts) of Dormeyer (digestion with pepsin extraction of the digestl with ether and weighing ethereal extract) of Glikin (extraction with light petrolenm) and of von Liebermann-Szekely (hydrolysis of tissue with sodium hydroxide acidification extraction of acids with light petroleum and titration of a n aliquot part of extract with sodium hydroxide). Rosenfeld's method gives results which are I7.4-46% too high in spite of the fact that the residue of tissue after extraction with organic solvents st'ill yields appreciable quantities ' of higher fatty acids on hydrolysis. The Pfliiger-Dorrneyer method gives results which are 16-7-40% too high.The Glikin method shows smaller inaccuracies whilst in the von Liebermann-Szekely method the principle of which is somewhat similar t o the newly-proposed method other than the higher fatty acids are estimated and there are besides various minor inaccuracies. It is claimed finally that it is not possible to estimate fats in tissues with absolute accuracy. The fatty acid number obtained by this method gives results however which compare favourably i n accurxcy with other indirect determinations such as t h a t of the proteins in tissues determined by the nitrogen values and the carbohydrates determined by the copper reduction method. The non-saponifiable matter can be determined by treating the fatty acids in petroleum solution with sodium hydroxide dissolved in absolute alcohol and estimating the amount of substance remaining BRUNO BARDACH (Zeitsch. physiol. Chem. 1908 54 355-35S).-If iodine is dissolved in an albumin solution in the presence of small quantities of acetone the formation of iodoform is hindered and instend of the usual plates and stars a precipitate of yellow needles is deposited after a varying lapse of time. The same reaction is given by various proteins but its delicacy varies in different members of the group. Physiological Assay of Digitalis Leaves. C. FOCKE (Arch. PIiurm. 1908 245 646-656. Compai e Ziegenbein Abstr. 1903 ii 118 ; Barger and Shaw Abstr. 1904 ii 793).-A 10% infusion of the powdered leaves is injected into the femoral lymph sac of R a m temporaria; the dose should be 1/50 of the body weight. The activity of the drug is then regarded as being inversely proportional to the average time required t o stop the heart's action permanently in a series of frogs ; this period should be seven t o fifteen minutes. *The frogs employed should weigh 2 0 4 5 grams and during the experiment they should be cooled (down to 17") in very hot weather or warmed (up t o 22.) in winter so as to secure the optimum pulse rate of 48-60 per minute. It is only in this manner t h a t uniform results can be obtained throughout the pear. in the organic solvent after addition of water. s. 13. s. A New Reaction of Proteins. W. z). H. G. B.

ISSN:0368-1769    

DOI:10.1039/CA9089405318

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

General a n d Physical Chemistry. Refractive Indices of Alcohol-Water Mixtures. LAUHCELOT W. ANDREWS (J. Anzer. Chenz. SOL 1908 30 353-360).-Leach and Lythgoe (Abstr. 1905 ii 655) have made determinations OF the refractive powers of aqueous solutions of methyl and ethyl alcohols in which the concentrations were probably deduced from the densities. I n the case of very strong alcohols the refractometric and density constants bear such a relation to each other that the concentration may be much more accurately inferred from the former than from the latter and it was therefore considered;of importance that the refractive constants shoiild be fixed independently of density measurements. The author has prepared absolute alcohol and made the required solutions by diluting it with known weights of water.The absolute alcohol was prepared in three ways (1) the usual calcium oxide z e t h d (2) by means of calcium and (3) with magnesium amalgam. All these methods gave a product of the same density refractive index and critical solution-temperat ure. Crismer's observation that the critical solution-temperature of alcohol in petroleum is the best criterion of its dryness is confirmed. Absolute alcohol has Up 0.78510 k 0.00001 refractive index p against air 1.35941 +_0.00001 at 25" on the hydrogen scale and refractive powers (76 - l ) / d 0.45833 and (p - l ) / d 0.45779. The refractive indices against air are recorded for alcohol containing from 0% to 30% of water and the approximate temperature-coefficients of refraction are given throughout the same range.A maximum refractive index 1.363315 at 2 5 O has been found for the mixture containing 20-7:L of water which corresponds closely with 3C,H,*O€€ 28,O. E. G . Refractive Power of Helium. KARL SCHEEL and RUDOLF SCHMIDT (Ber. dezct. physikal. Ges. 1908 6 207-210. Compare Abstr. 1907 ii 145).-The refractive index of helium has been measured for a series of wavelengths by the interference method previously described. The dispersive power of helium is very small and the index of refraction of heliuni at 14Ofor wave-lengths within the limits of the visible spectrum is found to be 1.0000340. This is appreciably smaller than the value given by Ramsay and Travers (1.0000362). H. M. D. Refraction and Dispersion of Helium. KURT HEBBMANN (Ber. deut. physikal.G'es. 1908 6 21 1-216. Compare preceding abstract).-The refraction and dispersion of air hydrogen and helium has been measured by the interference method. As the source of VOL. xc1v. ii. 23334 ABSTRACTS OF CHEMICAL PAPERS. light a mercury arc lamp was used and the followingvalues are given for the refractive index of helium Wave-length. 0 '57 6p ,j 0.546 1 p 0 . 4 3 5 9 ~ 0.5 7 9p\ Refractive jiidex. 1.000034384 1 *00003 45 2 5 1.000035335. H. M. D. Abn orrnal Dispersion of Metallic Vapou rs. FRANZ SCHON (Chem. Zerztr. 1908 i 332 ; from Zeitsch. wiss. Plhotograph. Photo- physik. Photochenz. 1907 5 349-372 397-436).-The vapour of alkali and alkaline-earth metals thallium gold silver and copper are shown to exhibit abnormal dispersion. The salts examined mere vaporised i n a carbon arc a cold iron plate being introduced whereby the flame was bent out and the typical anomalous dispersion observed.With the alkali metals abnormal dispersion was only noticed with the lines of the principal series the same being the case with copper silver and gold. The alkaline-earth metals show anomalous dispersion only in the case of a few lines wbilst magnesium zinc cadmium and aluminium give normal dispersion. The calculated results confirm a formula derived from the electromagnetic theory of light. Concerning this however also the relation between the values of the constants found and the atomic weight of the metal the original must be con- sulted. J. V. E. Wave-length Tables of the Spectra of the Elements and Compounds. SIR HENRY E.ROSCOE MARSHALL WATTS SIR W. NORXAN LOCKYER SIR JAMES DEWAR GEORGE D. LIVEING ARTHUR SCHUSTEL~ W. NOEL HARTLEY WOLCOTT GIBBS SIR WILLTAM DE W. ABNEY and WALTER E. ADENEY (Brit Assoc. lieport 1907 77 11 6-270).-A table of standard lines and wave-length tables of the arc and spark spectra of iridium osmium and rhodium. T. H. P. A Phenomenon Attributable t o Positive Electrons in the Spark Spectra of Yttrium. JEAN BECQUEREL (Compt. rend. 1908 146 683-685. Compare Abstr. 1906 ii 317 421 ; 1907 ii 147; this vol. ii 3 78 ; Diifour this vol. ii 138).-The variation of the absorption bands in a magnetic field observed by the author in the cases of crystals and solutions at low temperatures of the rare earths and by Dufour (Zoc. cit.) in the flame spectra of alkali-earth chlorides and fluorides is also exhibited in the spark spectrum of yttrium.If as is probable the phenomenon is due to the presence of positive electrons it follows that although the positive electrons are so closely associated with the atom that they cannot be separated either by electric discharges or by radio-active phenomenon they acquire sufficient mobility t o manifest themselves in optical phenomena. M. A. W. Presence of Spark Lines in Arc Spectra. CHARLES FABRY and HENRI BUISSON (Cowyt. rend. 1908 146 751-754).-SpectroscopicGENERAL AND PHYSICAL CHEMISTRY. 335 examination of the arc between iron poles has shown (C'ompt. rend. 1907 144 1155) that this emits all the spark lines but onIy from some parts of the arc. The arc produced between two vertical iron rods 7 mm.in diameter on visual examination appears to be formed of two flames one proceeding from each electrode. The negative flame is much the more brilliant and the difference is the greater for the radiations of the longer wave-length ; thus through a red glass the positive flame is almost invisible. I n the ultra-violet the lines given by the negative flame are widened and a great many undergo reversal but none of the lines are reversed by the positive flame. The flames seem to originate a t a brilliant pcint situated on the fused drop of iron terniinat- ing each electrode. These brilliant points enlit all the spark lines but an anastigmatic spectroscope is required to distinguish their origin. For the smallest wave-lengths of the extreme ultra-violet the arc spectrum and the spark spectrum are very different.The lines 2493,2664 and 2684 are emitted only by the electrodes ; the flame gives the lines 2679 2689 and 2735 which are not strengthened a t the poles whilst 2395 2413 and 2563 common to both are strengthened a t the electrodes. The above properties are not peculiar to the iron arc but are observed also with nickel and copper electrodes ; the phenomenon has also been observed by Hartniann (Astrophysical Joumal 1903 17 270) with magnesium. Lockyer considers that the production of spark knes in arc spectra is due to the very high temperature but the authors believe that it is more probably the result of the rapid fall of potential occurring in the neighbourhood of the electrodes and suggest that the essential condition for the emission of these rays is the existence of very rapid vibrations caused in the present case by the electric field and in other case3 due to a thermal effect.The emission of spark lines by the brilliant points on the electrodes explains their predominance when the conditions are such (immersion of the arc in water) that the intensity and length of the flames of the arc are diminished. The arc between iron poles can also take another form in which the brilliant point is observed only on the cathode and the anode flame has vanished. A considerable increase in the difference of potential between the electrodes occurs on passing from the first form of arc to the second. E. H. Change in the Hydrogen Spectrum under t h e Prolonged Action of Strong Electric Discharges E.KOGOVSKY (J. Russ. P h p Chern. Soc. 1908 40 37-41 Phys.).-After passing a strong discharge through a tube of hydrogen for several hours the lines Ha Hp and Ha disappear from its spectrum many new lines and bands making their appearance whilst the colour of the discharge changes from pink to light lilac. When a tube through which a strong discharge has been passed is kept a t rest for four months the red and blue lines X1.656.3 and 486.1 pp together with many other lines in the red orange and green have disappeared from the spectrum whilst some of the other lines in the blue which had at first disappeared now reappear. The 23-2336 ABSTRACTS OF CHEMICAL PAPERS. photograph of the latter spectrum is given and is compared with a n ordinary hydrogen spectrum.The hydrogen spectra here described differ entirely from the secondary spectrum described by Dufour (Abstr. 1907 ii 1). More probably they are the spectra t o be expected for hydrogen from Goldstein’s results for some of the alkali metals (Abstr. 1907 ii 725). Z. K. Band Spectrum of Calcium Fluoride. B. WALTER (PI~ysikc~Z. Zcitsch. 1908 9 233-234. Compare Dufour this vol. ii 138).- Spectral observations with a Bremer arc lamp the carbons of which contain calcium fluoride show that the individual lines in several of the bands due to this substance are reversed. This is the case for the bands the centres of which are represented by the wave-lengths 6036-96 6050*81 and 6064-49 whilst the band with its centre a t 6087.24 is not reversed. These four bands are all of the same type but reversion is also exhibited by the band with its centre at the wave- length 5290.94 which is of a different type.H. M. D. Spectroscopic Study of Flames of Various Kinds. GUSTAVE A. HEMSALECH and CHARLES DE WATTEVILLE (Compt. rend. 1908,146 748-75 l).-The method of studying flame spectra previously described (Compt. rend. 1907 144 1338; 145 1266) has been applied t o the hydrogen flame. If the hydrogen before burning traverses an arc between iron rods or better between an iron and a carbon electrode the flame emits light but is not uniformly luminous. The matter detached from the electrodes forms a cylindrical column composed of threads of incandescent particles which gives a continuous spectrum. I n the latter the ray 3860.03 of iron occurs very feebly the three 4030.54 4033.1 6 and 403459 of manganese are just visible and the calcium ray 4226.9 appears extremely feebly. These rays probably proceed from impurities in the hydrogen.The external envelope of the flame emits only the calcium ray. If the arc is produced between calcium electrodes the entire hydrogen flame takes an orange coloration and besides the above rays the green and red calcium bands are observed in its spectrum. The fact that in the case of iron the internal luminous column of the flame furnishes only a continuous spectrum seems to support the theory that flame spectra are the result of chemical reactions. When the iron is present only in traces as impurities in the burning hydrogen addition of oxygen causes the appearance of some supplementary rays.This spectrum is probably composed of de Gramont’s ‘‘ ultimate rays ” (Abstr. 1907 ii 517). The authors have compared their spectrum with t h a t of the star a-Cygni (Lockyer 1902) giving a table showing the comparative intensities of the various lines in the two spectra which show a certain resemblance. E. H. Ultra-red Emission Spectra of the Alkali [Metals]. A. BERGMANN (Zeitsch. wiss. Photograph. Photophysik. Photochem. 1908 6 145-169. Compare this vol. ii 242).-In this concluding part of the author’s paper an account is given of relative measurements in theGENERAL ASD PHYSICAL CHEMISTRY. 337 ultra-red prismatic spectrum. It has been found that the majority of the lines are too weak for accurate determinations of the wave-lengths t o be obtained from the diffraction spectrum and the wave-length values have been obtained from observations on the prismatic spectrum using an interpolation formula of the form X = A + B / ( D - C) - KD2 in which h is the wave-length B the angular reading and A 13 C and K are constants.The numbers of new lines which have been measured in the ultra- red region are for lithium 2 ; sodium 1 ; potassium 9 ; rubidium 8 ; cssium 10. With the exception of one cmium line (A- 1377 pp) all the new lines fall into series and for potassium rubidium and cmium the existence of a new secondary series of lines is established. These new series exhibit relationships which are opposite in character to those of the series previously known in that with increasing atomic weight of the alkali metal the new series lines are shifted towards the blue end of the spectrum. H.M. D. Modifled Spectroscopic Apparatus. GREGORY P. BAXTER (J. Anzer. Chenz. SOC. 1908 30 577-578).-1. I n the examination of absorption spectra of dilute solutions in long tubes the faintness of the spectra is often a great disadvantage. This difficulty is partly obviated by the use of a container made from a T of glass tubing of suitable diameter. The light passes through the tube B lengthwise and is focussed upon the slit 5' by the solution in the tube A which acts as a cylindrical lens thus increasing the in- tensity of the light 2. A simple fulgurator is readily con- structed by fusing together in a nearly parallel posit'ion by means of a small piece of glass rod two glass tubes into one end of each of which platinum wires have been sealed.One of the wires is bent in the form of a U so that the end is directly below and parallel to the wire in the other tube. The end oE the lower mire may be covered with a glass capillary in the usual way. The apparatus is dipped into the solution to be examined until the capillary is filled with solution. This system can be readily transferred from one solution to another and can easily be rinsed into the vessel in which it has been used. 41- W. H. G. Influence of Temperature and Magnetisation on Selective Absorption Spectra. HENRI E. J. G. DU Bors and G. J. ELIAS (Proc. K. Akad. JV&ensch. Amsterdam 1908 10 578-588).-The absorption spectra in the visible region of solid compounds of chromium uranium neodymium and erbium and of natural crystals of ruby and emerald were examined a t 18' and at - 193'.The bands become narrower at the temperature of liquid air in some cases becoming as sharp as the lines of sodium vapour. The effect of magnetisation in resolving the sharper lines mas examined. C. H. D.338 ABSTRACTS OF CHEMICAL PAPERS. Absorption Spectra of Crystals of the Rare Earths and the Changes which they Undergo in a Magnetic Field at the Temperatures of Liquefaction and Solidification of Hydrogen. JEAN BECQUEREL and H. KANERLISGH ONNES (Compt. rend. 19OS 146 625-628. Coinpare this vol. ii 78).-Previous observations relating to the influence of temperature on the absorption bands of tysonite and xenotime have been extended by measurements a t - 253" and - 85'3". The conclusion drawn from measurements between + 100" and - 190" that the width of certain bands of tysonite is proportional to the square root of the absolute temperature is found not t o hold for temperatures between - 190' and - 259O.I n this region the width of the bands decreases much less rapidly than would be the case if the above ielationship held good. I n the case of xenotime two of the bands examined are wider a t -259' than a t - 253" and the widt,li appears to have passed through a minimum at an intermediate temperature. This 11 henomenon is supposed to repre- sent the general influence of temperature there being for all bands a certain temperature for which the width uf the band is a minimum. Observations relating to the influence of temperature on the absorption bands observed in circularly polarised light are also recorded and interpreted in terms of the electron theory.H. M. D. Infra-red Reflection Spectra. W. W. COBLENTZ (Jahrb. Radio- aktiv. Elektvowik. 1908 5 1-14).-A number of minerals have been studied by measuring the rays from a Nernst lamp reflected from a cleavage surface and comparing them with those reflected by a silver mirror. The radiation was measured by means of a Rubens thermo- couple. Molybdenite pyrrhotite chalcocit e and covellite and also magnetite hzematite chromite and? zincitu give continuous reflection. On the other hand scheellite wulfenite rutile and corundum show selective reflection as do the silicates. Quartz both in the crystalline and in the glassy form shows selective reflection which is different for the two modifications.In the absence of more definite knowledge re- specting the constitution of the silicates it is not possible t o draw any conclusions as to the relation of the spectra to the structure of the silicic acids. C. E. D. Examination of Liquid Crystals in Convergent Polarised Light. ERNST SOMJIERFELDT ( f ' h p i k d . Zeitsch. 1 908 9 234-235. Compare Vorlander Abstr. 1907 ii 441 442).-To demonstrate the pseudo-isotropic character of liquid crystals at the ordinary temperature ammonium and potassium oleate may conveniently be used. The double refraction exhibited by the ammonium salt is about the same as that of the felspars. On account of the turbidity of potassium oleate it could not be examined alone but when mixed with the ammonium salt the double refraction observed with the latter was considerably increased and it was possible to obtain a complete interference ring in the field of view with a mixture of the two oleates.H. M. D.GENERAL AND PHYSICAL CHEMISTRY. 339 Rotatory Polarisation in C r y s t a l s which are not Enantio- morphous Methyl Mesityloxidoxalate. ERNST SONMERFELDT (Jahrb. Min. 1908 i 58-62).-Crystals of the polpmeride of methyl mesityloxidoxalate ([C9HI2O4]J (Federlin Abstr. 1907 i l O U 6 ) are hemihedral-monoclinic possessing a plane of symmetry but no axis of symmetry. The optic axial plane is parallel to the plane of symmetry and the axial angle is wide. The interference-figure shown in convergent polarised light in the position when the vibration- directions of the plate coincide with those of the nicols differs from a normal biaxial interference-figure in the absence of the dark bar perpendicular to the axial plane. Sohncke in his theory of crystal structure connected the rotatory polarisation of crystals with their enantiomorphous forms but i t has since been proved theoretically t h a t certain classes of crystals which are not enantiomorphous may be circularly polarising.L. J. S. The Mathematical Treatment of Photochemical Reactions on Thermodynamical a n d Electrochemical Basis. ALFRED BYK (Zeitsch. physikal. Chent. 1908,62 454-492).-1n this theoretical paper the author deals with photochemical reactions in homogeneous systems and develops the conception of a photochemical ptocess as a special case of electrolysis by alternating current.This conception is based on the electromagnetic theory of light and leads t o formulz. which are in general harmony with what is known of photochemical processes both in respect of reaction velocity and of equilibrium (see Luther and Weigert Abstr. 1905 ii 785) and do not presuppose the formation of intermediate compounds. In 1 eversible photochemical reactions according to the author’s views the change which takes place in the dark takes place all the same when the system is exposed to light; i t is to be regarded as an electrically neutral process; on exposure to light an extra reaction is induced which is simply supeqosed on the former and is to be regarded as of an electrolytic character.J. C. P. Photochemistry. MAX TRAUTZ (Zeitsch. wiss. Photograph. Photophysik. Plbotochent. 1908 6 169-194>.-A theoretical paper in which photochemical change is considered from the standpoint of thermodynamics. It is shown that all the chief photochemical regularities can be deduced by the aid of the second law of thermodynamics. 13. &I. D. Phototropy of the Fulgides and other Substances. HANS STOBBE (An?~aZen 1908 359 1-48. Compare Abstr. 1905 i 857 ; 1906 i 96O).-Fulgides containing aromatic substituting groups undergo change of colour when exposed t o light. Thus triphenyl- fulgide which forms pleochroic orange-red monoclinic crystals becomes dark brown when exposed to sunlight o r the rays of an arc lamp changing again to its original colour in the dark.The brown and orange modifications are chemically identical and differ only in the solid state. Such phenomena have been termed by Dlarckwald (Abstr. 1900 i 2) phototropy. If this phototropic change is frequently340 ABSTRACTS OF CHEMICAL PAPERS repeated the difference between the shades of the two forms becomes gradually less a chemical change taking place which leads finally to the complete conversion of the fulgide into a new substance the photo-anhydride. This slow photochemical reaction which accom- panies t,he phototropic change is not reversible. The structure of the photo-anhydride will be discussed in a future communication. The present paper is a study of the nature of the phototropic change and the conditions under which it takes place.To study the action of light waves of different lengths the fulgide is exposed in a thin layer between two glass plates in a special spec- trographic apparatus. Orange-yellow triphenylfulgide when exposed to the light of the spectrum after two minutes shows a broad brown band between the spectrum lines E and G which on prolonged ex- posure gradually extends towards the ultra-violet. If the whole layer of fulgide is first exposed to light under a cobalt or bluish-violet Jena glass light filter it change's to blackish-brown and on exposure to the spectrum light becomes orange-yellow between the lines E and B but brown from E towards the ultra-violet. Hence the yellow modification is sensitive to blue and violet light rays but the blackish- brown form which is intermediate between the yellow and brown modifications is sensitive to yellow and red rays.The portion of the spectrum which causes the phototropic change from the yellow into the brown modification is termed the zone of stimulation (Erregungs- zone). The behaviour of a number of di- and tri-arylfulgides towards light rays of different wave-lengths has .been studied in this manner and the results obtained of which those described for triphenylfulgide are typical are tabulated and expressed graphically. Phototropic change has been observed only with the lemon-yellow to orange-red diaryl- and the orange-red to dark red triaryl-fulgides ; the colourless alphyl- greenish-yellow t o yellow-monoaryl- and red purple-red or brown or tetra-aryl-fulgides are not phototropic.The modifications of a phototropic substance can exist in the pure state only when exposed to light rays of the wave-length under the influence of which they are formed. Under all other conditions the substance is a mixture or solid solution of the one form in the other. The phototropic change is caused by the light rays which are absorbed by the modification undergoing the change. Hence the brown form of tripheaylfulgide must be in reality blue the brown appearance resulting from its state of granulation. The equilibrium between the two modifications in a mixture depends on the wave-lengths of the light to which it is exposed. It follows that the parts of the spectrum which produce the phototropic change depend on the colour of the fulgide the zone of stimulation lying the more towards the violet the deeper the normal shade of the substance whilst the lighter the shade the further towards the ultra-red does the portion of the spectrum causing the reverse change extend and that the amount of change in the colour of a phototropic fulgide not only increases with diminishing wave-lengths of the light rays and with increasing intensity of illumination but diminishes with increasing temperature itnd depends further on the number and nature of the substituting groups being greatest with diphenyl-o-methoxyphenyl- diphenyl-GENERAL AND PHkSICAL CHEMISTRY.341 piperonylallo- and diphenyl-o-nitrophenyl-fulgides less with diphenyl- p-methoxyphenylfulgide and least with the diaryl-fulgides. The f uryl-f ulgid es resemble the phenyl compounds.The phototropy of the fulgides is shown to be analogous to a number of other reversible reactions which take place under the influence of light and is compared with the phenomena of fluorescence. As the phototropic modifications of the f ulgides undergo the reverse change spontaneously in the dark the energy of the light rays of short wave- length absorbed during the phototropic change might appear during the formation of the original form as heat or fluorescence. This how- ever has not yet been observed. The phototropy of other substances bas been studied in a similar manner. The zone of stimulation for colourless P-tetrachloro-a-keto- naphthalene (Marckwald Zoc. cit.) lies in the ultra-violet whilst the reverse change is caused by yellowish-green or yellow rays.Red and blue rays have no action. Phenylbenzylidenehydrazine which forms light yellow crystals or a white powder becomes red on exposure to violet or ultra-violet rays becoming again colourless when ,exposed to yellow o r green light. Phenylankylidene- and phenglcuminylidene-hydr azines behave in the same manner as do also osmones of the b e n d series (Biltz and Wienands Abstr. 1899 i 91 0). Tetraphenyldibydrotriazine (Walther Abstr. 1903 i 582) and ethyl oxalisobutyrate (Wislicenus and Kiesemetter Abstr. 1898 i 240) have also been observed t o exhi bit phc totropy. Simple Gas Burner Contrivance f o r Showing Various Flame Reactions Combustion Phenomena and Flame Colorations. WILHELM THORNER (Zeitsch. cmgew. Chern. 1908 21 6'73-677).- The ring by means of which the air supply of an ordinary Bunsen burner is regulated is replaced by a brass cylinder to which is fixed at right angles a brass tube A.The air supply of the burner passes through this tube consequently if a U-tube or other suitable vessel be attached containing a volatile liquid such as carbon disulphide or chloroform or in which a gas such as hydrogen sulphide or hydrogen cyanide is being evolved the combustion of these liquids or gases can be demonstrated. By making use of the methods of Riesenfeld and Wohlers (Abstr. 1906 ii 593) or Beckmann (Abstr. 1907 ii ZOS) the flame colorations of various substances can also be shown. A list of experiments which may be shown by means of this apparatus is given. W. H. G. H. STARKE (Ber.deut. physikcd. Ges. 1908 6 267-284).-It is found that y-rays are not produced when the P-rays of radium are allowed to fall on substances such as lead aluminium and paraffin. The y-rays of radium cannot therefore be considered as a type of Rontgen radiation resulting from the action of the P-rays on the substance of the radium. Absorp- tion measurements which have been carried out with the secondary rays emitted by the action of /3-rays on different substances indicate that these are very heterogeneous and that some of the component. rays are much more readily absorbed than are the primary P-rays. G. Y. Experiments on the Secondary Rays of Radium.342 ABSTRACTS OF CHEMICAL PAPERS. The secondary rays from paraffin are very easily absorbed; those from aluminium are less penetrating than the secondary rays from lead.The most absorbable rays both in the reflected and transmitted radiation originate in layers of the material which are very close to the surface. I n consequence of this the transmitted radiation has a maximum intensity for a certain thickness oE the material placed in the path of the P-raps this thickness depending on the nature of the material. The secondary rays which originate from the action of the /3-rays on air are in all probability very readily absorbed. Extraction of Polonium and its Properties. FRIEDRICH GIESEL (Bey. 1908 41 1039-1062).-The lead chloride obtained from pitch- blende is dissolved in water and to the solution is added a little sulphuric acid to remove radium and then ammonia. Tbe precipitate is digested with a large excsss of hydrochloric acid the acid solution filtered off and the lead chloride extracted four or five times with hydrochloric acid.Each extract is reduced to a small bulk the lead chloride which crystallises out being removed ; hydrogen sulphide precipitates a mixture of the sulphides of arsenic lead bismuth copper and mercury from the first extracts whilst almost pure copper sulphide is obtained from the later extracts. The mixture of sulphides after treatment with ammonium sulphide is boiled with hydrochloric acid ; the radium-E accompanies the bismuth whilst the polonium remains with the* copper sulphide. The latter is digested with nitric acid and excess of ammonia added to the solution; the polonium separates as a slight white flocculent precipitate which when collected and dried on a filter is obtained as a yellowish-grey film.This precipitate is far more active than any film of polonium hitherto obtained as it deposit on metal; it ozonises the air which a t the same time is seen to phosphoresce and induces a beautiful phosphorescence on a zinc sulphide screen. The solut'ion of the precipitate in 2 or 3 drops of hydrochloride acid is yellowish-brown ; this colour which is dis- charged on the addition of hydrogen peroxide or nitric acid is not due to the polonium but is probably connected with the presence of radium-D. No indication of the formation of helium from polonium during a period of two years was obtained. W. H. G. Heating Effects produced by Rontgen Rays in Lead and Zinc.HENEY A. BC'NSTESD (Phil. fh'ag. 1908 [vi] 15 432-437.* Compare Abstr. 1906 ii 141).-The iesult previously obtained by the author (ZOC. cit.) that the quantities OF heat produced in lead and zinc by Rontgen rays is as 2 1 is not confirmed by further experiments which indicate that the quantities of heat are equal with an uncertainty of from 5% to 10%. The source of error in the previous experiments is traced to t h e imperfect heat insulation of the metals. New experiments are described which show that the secondary rays emitted by lead exposed to the action of R6ntgen rays are incapable of producing scintillations in a zinc-blende screen. Rays of the a-type are therefore absent. H. 31. D. * Amr. J. Sci. 1908 [iv] 25 299-304.GENERAL AND PHYSICAL CHEMISTRY.343 Other experiments show that the rate of change of the active deposit from thoriu-m emanation is not altered by exposure to Rontgen raFs. H. M. D. Anode Rays. V. E. GEHRCKE and 0. REICHENHEIN (Ber. deut. physihl. Ges. 1908 6 217-225. Compare Abstr. 1907 ii 421).- In continuation of previous investigations of anode rays the authors have examined most closely the so-called ‘ striction anode rays.” Experiments with different forms of discharge tubes have shown the conditions under which such rays make their appearance. A convenient form consists of two bulbs of 10 cm. diameter with aluminium electrodes sealed through the walls at right angles to the axis joining the centres of the bulbs these being connected by a tube which protrudes into each bulb to the extent of 2 em.“Striction cathode rays” are at once seen when such a discharge tube filled with air or hydrogen is evacuated. If a trace of iodine vapour is added “ striction anode rays” also make their appearance. These anode rays are not influenced by a magnet. Bromine hydrogen chloride bromiae and iodide vapours also favour the formation of “striction anode rays,” although the effect is much smaller than that observed when iodineisadmitted to the tube containing hydrogen. The rays are not only produced in hydrogen and air but also in oxygen and helium whereas in nitrogen no positive results were obtained. Measurements of the fall of potential at various points betweeii the anode and cathode when “striction anode rays” are being produced indicate that the potential gradient iu the anode ray region is very steep.These facts indicate that the phenomena of discharge at the anode are very similar to the more closely-studied effects observable a t the cathode. H. 31. D. Anomalous Behaviour of Selenium. CHR. RIES (I’hysikal. Zeitseh. 1908 8 228-233).-The anomalous behaviour of crystalline selenium in regard to its electrical properties can be explained on the assumption that there are two different forms. The one form (a) obtained by heating amorphous selenium at temperatures below ZOOo for a considerable time and cooling rapidly has a negative temperature- coefficient of electrical resistance. The temperature-coefficient of the second form (p) is within certain temperature limits positive and this crystalline form of selenium is influenced by light in the opposite direction to that which characterises the u form.The /3 modification is obtained byi heating amorphous selenium at temperatures above 2 0 0 O . The product obtained by the various methods described for the preparation of crystalline selenium j s characterised in terms of the author’s theory. H. 35. D. Contact Potential Differences Determined by means of Null Solutions. S. W. J. SMITH and H. Moss { P i d . Mug. 1908 [vi] 15 478-497).-Palmaer’s conclusion from the results of experi- ments with drop electrodes (Abstr. 1907 ii 424) that the true344 ABSTRACTS OF CHEMICAL PAPERS. contact potential difference between mercury and 0*1N KC1 solution is about 0.57 volt is shown to be of doubtful validity. Several so-called null solutions for which the potential difference between still and dropping mercury electrodes in contact with the solution is zero have been examined.A 0 . 2 6 3 solution of potassium cyanide possesses this property and 0.1 N solutions of potassium chloride iodide and hydroxide are convertible into null solutions by the addition of definite small quantities of sodium sulphide. The potential differences between diEerent null solutions and mercury are not the same. This is proved by measuring each potential difference against the potential difference Hg/O*lN KC1 and also by measuring one null solution against another. If the null solution potential differences are assumed to be zero the values obtained for the potential difference Hg/O*lN KC1 vary from about 0.53 to 0.79 volt.Assuming that the potential difference corresponding with maximum surface tension is most likely to be zero when the maximum is not depressed it is probable that the potential difference Hg/O*lN KCI does not exceed 0.53 volt. The equality between the polarising electromotive force required to produce the maximum surface tension between mercuryand a given electrolyte and the electromotive force of the corresponding dropping electrode circuit no longer exists when the chemical action at the dropping electrode due to atmospheric oxygen becomes appreciable. On the addition of small quantities of sodium sulphide to the solution the potential difference between the dropping mercury electrode and 0 . 1 3 KCI remains unchanged although the natural potential difference is thereby altered by more than 0.5 volt.The variation of the natural potential difference with increasing con- centration of sodium sulphide is not uniform but a t a certain critical concentration the potential difference varies with extreme rapidity. H. M. D. [Condition of Air which has been passed between Sparking Electrodes.] M. DE BROGLIE (Gompt. rend. 1908 146 624-625).- The fact that flames fed with air which has passed over metal electrodes between which a spark discharge is taking place exhibit spectra of the metals has led the author to examine the condition of such air. It contains (1) ions of small mobility (2) neutral centres which are converted into ions by the action of radium or Rontgen rays and (3) attenuated solid particles which can be seen in the beam of an arc light.The cloud of solid particles is very densa in the case of sodium thallium and bismuth The particles obtained from thallium electrodes have been found to show Brownian motion. These particles are the cause of the spectral reactions ; some of them are electrically charged. H. M. D. Hydrogen Peroxide Cell. HOWARD T. BARNES and G. W. SHEARER (J. P?t,ysicuZ Chem. 1908 12 155-162).-In a previous paper (Trans. Amer. Electrochem. Soc. 1907 12 54) it was shown that a cell with magnesium and aluminium electrodes in contact with water containing dissolved air gives an E.M.F. which slowly rises to aboutGENERAL AND PHYSICAL CHEMISTRY. 345 1 volt although the metals are close together in the potential series. This is now shown to be due to the formation of hydrogen peroxide by the action of water containing dissolved air on aluminium; the peroxide is detected by the potassium iodide starch test.When free hydrogen peroxide is added to the aluminium compartment of the cell the E.X.F. rises to about 2 volts but falls gradually as the peroxide is decomposed. I n some of the experiments a solution of aluminium sulphate was used as electrolyte. The rate of change of the &.MJ'. and current of the magnesium- aluminium cell after a time and the effect of adding hydrogen peroxide are described and the effect of rise of temperature on the behaviour of the cell with and without the addition of peroxide has also been investigated. Some other metals show a similar behaviour to that of aluminium in the above respect but the effect is much smaller and hydrogen peroxide cannot be detected. G.S. Conductivity of Gaseous Mixtures at the Moment of Explosion. R. DE MUYNCK (Bull. Acad. ~ o y . Belg. 1907 901-928).-The electrical conductivity of mixtures of carbon monoxide and air or oxygen at the moment of explosion has been measured. The explosion vessel consisted of a cylindrical brass tube in the axis of which a copper wire was supported this being insulated from the tube by ebonite. The tube and wire were connected through a galvano- meter with the opposite poles of a battery of small cells by means of which the conducting power of the gaseous mixture when exploded by means of a spark was determined. For a given electrometric force the galvanometer deflection mas found to be much greater when carbon monoxide and oxygen are mixed in the proportion in which they combine than when the gaseous mixtures contain excess of oxygen.The conductivity is uni-polar in character being considerably greater when the axial copper wire is connected with the positive pole of the battery than when the connex- ions are reversed. The galvanometer deflection for a given mixture increases with the pressure but does not appear to depend much on the hygroscopic condition of the gases. An influence of the electrodes is apparent from the fact that larger deflections are obtained in the first explosion after the electrodes have not been used for some time than are met with in subsequent explosions. With increase in the applied difference of potential the galvanometer deflection increases and the relationship between deflection and voltage can be expressed by a linear equation.When the temperature of t h e explosion tube is raised the conductivity of the explosion mixture increases considerably. The experimental results are utilised i n a discussion of the question as to whether the electrical conductivity is a direct result of the chemical action or is a secondary effect due to the development of heat which accompanies the explosion. It is calculated that one ion is produced for every 200 million molecules of carbon dioxide which are formed. This result favours the view that the conducting power of the exploded mixture is to be attributed to the heat liberated in the change. H. 31. D.346 ABSTRACT8 OF CHEMICA'I PAPERS.Electrical Conductivity of Mixtures of Acid or Base and Water. G. BOIZARD (Ann. Chim. Pltys. 190S [viii] 13 433-479. Compare this vol. ii 251).-The author has studied the changes of conductivity viscosity and freezing point accompanying the addition of good or weak electrolytes to mixtures of good elect,rolytes with water With mixtures of good electiolytes with water there are two concentrations one high and the other low between which tlie addition of a strong or weak electrolyte produces a diminution in the con- ductivity. These points of inversion depend on the temperature and in certain cases on the amount of electrolyte added. With good electrolytes without action on the solvent mixture a condition of isoconductivity obtains a t the points of inversion the solution having the same conductivity as the solvent mixture.The increases or diminutions of conductivity produced in this way are referred t o five principal types the transition from one of these t o another generally taking place in a perfectly definite order ; these variations are functions of the temperature and are not related t o the corresponding variations of the viscosity and of the depression of freezing point. Solutions of electrolytes in mixtures of sulphuric acid with water are stable and the chemical equilibria attained are not functions of the time and undergo reversible variations when the temperature is changed. Further the equilibrium depends only on the relative amounts of the ions present and not on the form in which these are introduced into the solutions.On the basis of a simple theory concerning chemical or ionic equilibria in the solutions formulae are derived which lead to results agreeing with the experimental observations. The changes taking place when sulphates bisulphates or acetates are added to mixtures of sulphuric acid and water are considered in detail T. H. P. The results are briefly as follows. Equivalent Conductivity of the Hydrogen Ion derived from Transference Experiments with Nitric Acid. ARTHUR A. NOYES and YOGORO KATO (J. Anzer. C'hem. Soc. 1908 30 318-334).-1n a paper by Noyes and Sammet (Abstr. 1903 ii 126) an account was given of transference determinations made with 3/20 AT/60 and N/80 hydrochloric acid solutions a t loo 20° and 30". The results when combined with the equivalent conductivity of the chloride ion gave a much higher equivalent for the hydrogen ion than that derived from the conductivity of acids at high dilutions.I n order t o ascertain the cause of this divergence transference experiments have now been made with nitric acid a t 20" with the following results Equivalent of Transference Equivalent. con- o*ocs 155.7 350-3 0.0154 159'6 340'2 0.0067 160-0 339-1 0.0022 '162.8 332'2 0'0000 166'0 324'6 IINO per litre. number x '10". ductivity of hydrogen ion.GENERAL Ah'D PHYSICAL CHEMISTRY. 343 These valnes for the equivalent conductivity of the hydrogen ion except a t the highest concentration agree closely with those obtained in the experiments with hydrochloric acid and show that the value for the concentration intervals between 0-018N and 0.006N is nearly 5% greater than that derived from conductivity measurements at extreme clilut,ion.This divergence has also been observed by Noyes and Samrnet (Zoc. c i t . ) and has been confirmed by the conductivity determinations of Goodwin and Haskell and by the transference experiments of Jahn Joachim and Wolff. The conclusion is drawn that the transference number of the anion of acid$ and therefore the ratio of the velocity of the anions to that of the hydrogen ion is considerably greater at very low concentrations (O*OOIN or less) than at moderate concentrations (0~05-0*005N). l t is considered probable that this change of the transference number is due chiefly if not entirely to a retardation of the hydrogen ion at very high dilution.The nearly constant values of the equivalent conductivity of the hydrogen ion between concentrations of 0.006N and O*OlSN are regarded as normal whilst the variation at lower concentrations is t'hought to be due to sonie secondary effect of a general character. I n view of these results it is suggested that in calculating tbe ionisation values of acids which are largely ionised at moderate concentrations the observed equivalent conductivity of the acid should be divided by a A value obtained by adding t o the equivalent conductivity of the anion that of the hydrogen ion obtained by the transference experiments a t the given concentration. On the other hand in the case of an acid solution in which the ion concentration is less than 0*001N the older value (324 a t 20' or 315 a t 18") for the hydrogen ion is to be preferred.E. G. Conductivity and Ionisation of Salts Acids and Bases in Aqueous Solutions at High Temperatures. ARTHUR A. NOYES [with A. C. MELCHEH H. C. COOPER G. W. EASTMAN and YOGORO KATO] (J. Anzer. Cl~en2. Soc. 1908 30 335-S53).-Noyes and Coolidge (Abstr. 1904 ii 226) have described an apparatus for determining the electrical conductivity of aqueous solutions at high temperatures and have recorded measurements ma,de wi t,h solutions of sodium and potassium chlorides. The investigation has now been extended to other di-ionic salts namely silver nitrate magnesium sulphate sodium acetate ammonium chloride and ammonium acetate t o two tri-ionic salts barium nitrate and potassium sulphate and also t o potassium hydrogen sul phat e hydrochloric nitric sulp huric phosphoric and acetic acids and sodium barium and ammonium hydroxides.I n most cases the measurements have been made a t four or more different concentrations between 0*1N and 0.002i'VT and at temperatures ranging from 18" to 306'. I n the case of the di-ionic substances the values of the equivalant conductivity for complete ionisation become more nearly equal as the temperature rises and approach equality rapidly between 18" and 2 1 8 O but comparatively slowly at higher temperatures. Thus the specific migration velocities of the ions are more nearly equal the higher the348 ABSTRACTS OF CHEMICAL PAPERS. temperature. Complete equality is not reached however even a t 306O but the divergonce only exceeds 5% in the cases of hydrochloric acid sodium hydroxide and sodium acetate The equivalent conductivity of the tri-ionic salts increases steadily with the temperature and attains values which are much greater than those for any di-ionic salt with univalent ions.Thus at 306' the value for potassium sulphate is 1.5 times that for potassium chloride. The rate of increase in conductivity with all the neutral di-ionic salts is greater between 100' and 156" than between 1s" and 100° or between 156O and 218" so that the temperature-conductivity curve is first convex later concave and then again convex towards the temperature axis with two intermediate points of inflexion. With acids and bases however and therefore with the hydrogen and hydroxyl ions the rate of increase of the equivalent conductivity steadily decreases as the temperature rises and the curve is consequently always concave towards the temperature axis.I n the case of the tri-ionic salts the rate of increase steadily grows owing to the great increase in the equivalent conductivity of the bivalent ion and hence the curve is always convex towards the temperaiure axis. With regard to the variation of the equivalent conductivity A with the concentration C of solutions between O * l N and 0.002 or O.OOOSiV the results for all temperatures with all the salts both di- and tri-ionic and also with hydrochloric acid nitric acid and sodium hydroxide can be expressed by the function C(h - A) = K(CA)'& if to 16 is assigned a value (varying with different substances) between 1.40 and 1.55.It is evident that if the conductivity ratio A/A can be taken as a measure of the ionisation y the latter changes with t-he concentration in accordance with the function (Cy)'L/C(l - y ) = a constant in which n has values varying between 1.40 and 1.55. It has been pointed out previously (Noyes Congress. Arts. Sci. St. Louis Exhibition 1904,4 317) that at the ordinary temperature the form of the functional relation between ionisation and concentration is the same for salts of different ionic types The present results show that this is true also at high temperatures and that even the large variation of temperature and the consequent change in the character of the solvent affect very slightly if a t all the value of the exponent in this empirical relation. This affords a confirmation of the view that the form of the concentration function is independent of the number of ions into which the salt dissociates and shows that chemical mass action has not any appreciable influence in determining the equilibrium between the ions and the non-ionised part of largely dissociated substances.The functions A,- - A = KC; and A - A = K(CA)i also express the results with potassium chloride sodium chloride hydrochloric acid and sodium hydroxide up to 2 1 So between OglN and 0.002 or 0*0005iV. The equivalent conductivity and ionisation of acetic acid and ammonium hydroxide cbange with the concentration at all temperatures even up to 3064 in accordance with the law of mass action. Phos- phoric acid has intermediate values of (1.8-1.9) which approach more nearly to the theoretical value (2.0) than to the empiricalGENERAL AND PHYSICAL CHEMISTRY.349 value. I n general the ionisation decreases steadily with rise of temperature in the case of every substance investigated and the decrease is nearly the same for all largely ionised salts of t h e same ionic type. I t is shown that the effect of temperature on the ionisation of salts is comparable with its effect on the dielectric constant of water. Neutral salts of the same ionic type are ionised to nearly the same extent in all cases. Hydrochloric acid (up to 1 5 6 O ) nitric acid and barium and sodium hydroxides also conform to this principle although their ionisation is somewhat greater than that of the corresponding salts.The rough proportionality which exists st the ordinary temperature between the non-ionised part of a salt and the product of the valencies of its ions has now been proved to persist up to high temperatures. The ionisation constant for ammonium hydroxide increases considerably from 0" t o lSo then remains nearly constant to 50° and afterwards rapidly decreases until a t 306" its value is only 1/200 of that a t 1 8 O . The values for acetic acid are similar to those of ammonium hydroxide at all temperatures. Phosphoric acid has a much greater ionisation constant which decreases steadily and rapidly with rising temperature. From these results the conclusions are drawn that the ionisation of salts strong acids and bases is primarily determined not by specific chemical affinities but by electrical forces arising from the charges on the ions; that t h i s is not affected except in a secondary degree by chemical mass action but is regulated by general comparatively simple laws ; and that in most respects the phenomenon differs from that of the dissociation ordinarily exhibited by chemical substances including that of the ionisation of weak acids and bases.E. G. Determination of Ionisation Factor of Water in Hydro- chloric Acid Solutions. EXNANUEL DOUMER (Conzpt. rend. 1908 146 657-690. Compare this vol. ii 252).-1n a n earlier paper the author has defined the ionisation factor of water in solutions of hydro- chloric acid as the ratio 2v/V where v and P represent the volumes of oxygen and hydrogen respectively obtained during the electrolysis of the solution ; and in the present paper methods are described whereby the value of v can be determined accurately.For this purpose electrodes of silver or mercury are used ; in the former case after the anode has become coated with brown silver oxide i t absorbs all the chlorine and all the electrolytic oxygen is evolved and in the latter case the mercury anode absorbs both the oxygen and the chlorine and from the increase in weight of the mercury and the volume of hydrogen liberated a t the cathode the weight of electrolytic oxygen and of chlorine can be calculated after making the necessary correction for the trace of mercury oxide dissolved by the solution. The results of the experiments tabulated in the original show that the ionisation factor of water in hydrochloric acid solutions is a constant and independent of the intensity of the current of the strength of the solution and pro- bably also of the nature of the anode; the factor is equal t o 0.662 whence it follows that in the electrolysis of solutions of hydrochloric VOL.XCIV ii. 24350 ABSTRACTS OF CHEMICAL PAPERS. acid about two-thirds of the hydrogen evolved comes from the electrolysis of the water and the remaining one-third from the hydro- chloric acid. M. A. W. Apparatus for the Quantitative Electrolysis of Hydro- chloric Acid. J. B. LEWIS (J. Amer. Chenz. h'oc. 1908 30 II 6 15-6 16).-The apparatus con- sists of (1) a glass cylinder (2) a porous pot (3) a carbon anode (4) a cathode of sheet platinum fitted together as shown in the sketch.The chlorine delivery tube is connected to the bottom of the tall cylinder (6) the top of which is provided with an air outlet j a loose plug of cotton wool (7) is placed in 6 to retard the mingling of chlorine and air. A two-way stopcock is interposed as shown at 5. The air (or chlorine) and hydro- gen evolved during the electro- lysis may be collected over water in inverted burettes. To start the apparatus the anolyte is saturated with chlorine by add- ing a few crystals of potassium chlorate to it. The mixture may then be used immediately ; ele& trolysis need only be cairied on a minute or two during which time the chlorine is allowed to escape by means of the stopcock 5 and then the apparatus is reedy for the demonstration. W.H. G. Electrolytic Valve Action of Columbium and a Classifha- tion of the Behaviour of Electrolytic Anodes. GejNTIIER SCHULZE (Am% Physik. I9OS [iv] 25 775-782).-The electrolytic valve action of columbium is studied in the same way as that of tantalum (ibid. 1907 [iv] 23 226. The results obtained with the two metals are very similar. A classification of anodes is given according to whether they are attacked or not and whether the product of reaction is soluble insoluble a conductor or not forms an adherent film &c. The anodes which exhibit vdve action are supposed to belong t o the class in which a non-condncting porous skin is formed and simultaneously gas is evolved ; the gas film retained in the poresof the skin is the non-conductor t o which the valve action is due.T. E. Electrolytic Reduction of Solutions of Titanic Sulphate B. DIETHELM and FRITZ FOERBTER (Xeitsch. physikal. Chem. 19OS 62 129-1 77),-The only result of the electrolytic reduction of titanic sulphate in sulphuric acid solution is t o reduce the metal from the Compare also Abstr. 1907 ii 842).GENERAL AND PHYSICAL CHEMISTRY. 351 quadrivalent to the tervalent condition (compare Knecht's experiments on the chloride Abstr. 1903 ii 217). The course of the reduction varies with different electrodes the current efficiency being consider- ably higher with a lead or a copper electrode than with one of bright platinum. In all these cases the reduction goes on until it is complete. With an electrode of platinised platinum whilst the current efficiency is high the reduction may be incomplete.It appears from a study of the potentials at an electrode immersed in a solution containing titanium in both stages of oxidation that such a solution is in equilibrium with hydrogen a t atmospheric pressure. I n contact with platinised platinum,the equilibriumTi"" + H z T i " ' + H' is reached from either side. The cathode potentials and the may in which they vary with the current density have been studied in detail for the reduction which takes place without the evolution of hydrogen. Here again the influence of the material of the cathode is very evident. The velocity of the reduction of titanium sulphate is much smaller a t a bright platinum cathode than a t a platinised platinum cathode. The effective reducing agent at lead cathodes is electrolytically separated finely-divided lead and at copper cathodes apparently a n alloy of copper and hydrogen.The influence of the cathode material recorded in this paper is analogous to that observed by Chilesotti in the electrolytic reduction of molybdic acid (Abstr. 1906 ii 263 365) and to that observed by Haber and Russ in the reduction of organic substances (Abstr. 1904 ii 309). Electrolytic reductions which involve a change of valency appear t o depend on the secondary action of the hydrogen which is primarily separated at the cathode surface or of the electrolytically separated metal. &(nLl)+ + - "l+ does not correspond with what usually happens. Such a direct loss of charge as represented by J. C. P. Thermal Conductivity of Mixtures of Argon and Relium. JOHANNES WACHSMUTH (Physikal.Zeitsch. 1908 0 235 -340).-The thermal conductivity of various mixtures of argon and helium has been measured according to the method of Schleiermacher. The experimental data are discussed in reference to the formula k= f r].C in which k denotes the thermal conductivity 71 the coefficient of viscosity and C the specific heat a t constant volume. Previous experiments have shown that the value of f for argon and helium is 2.5 in accordance with the Maxwell-Boltzmann theory. For mixtures of these two gases the value off is however not constant and the curve which represents f as a function of the composition of the gas mixture exhibits a maximum for the mixture containing 60% helium. This corresponds with the results of previous measuremants of the thermal conductivity of hydrogen-oxygen mixtures the maximum value of f in this case being obtained for the mixture containing 60% of hydrogen.The variation in the value of the factor f in the gas mixtures is attributed to the alteration in the mean free path of the molecules of a gas which takes place when this is mixed with a second 24-2352 ARSTRACTS OF CHEMICAL PAPERS. gas. An interpolation formula is deduced by taking account of this alteration in the mean free path from which the thermal conductivities of mixtures of argon and helium can be calculated in good agreement with the observed values. H. AT. I). Speciflc Heat and Dissociation of Chlorine. NATHIAS PIER (Zeitsch. physikal. Chenz. 1908 62 385-41 9)-The molecular specific heat of chlorine according to the work of earlier investigators is about 2 cal.greater than that of most diatomic gases. This might be connected with the abnormal density of chlorine and accordingly the author has studied the bshaviour of this gas a t various tempera- tures and pressures. I f the value 2-49 (air= 1) is taken as the correct density a t O@ and 1 atmosphere pressure (see Moissan Abstr. 1904 ii 114) then under the same pressure the densities at higher tempera- tures are as follow 50*24O 3.4688 ; 100*4O 3.4601 ; 150.7" 2.4554 ; 184.0° 2,4538. When the pressure is reduced to about 0.1 atmosphere the theoretical value of the density namely 2.4494 is reached; the variation of density with pressure at 13.5' is shown by the following figures the first number given in each case being the pressure in atmospheres ; 1.00 3-4820 ; 0466 2.4640 ; 0.294 2.4584 ; 0.195 2.4543 ; 0.123 2.4518; 0,0569 2.4494.As to the influence of the abnormal density of chlorine on its specific heat the assuniption is made that there is a partial association to C1 molecules. On this assumption a formula is based which gives the variation of density (A) with the pressure (P atmospheres) and with the absolute temperature. With this formula which runs log(A - 2.4494) = 463*11/T- 0,6415 - logy+ IogP it is possible to calculate the density of chlorine in very good agreement with the values actually found a t various pressures and temperatures. From the foregoing formula the author calculates also the correction which must be applied to the molecular specific heat of chlorine to get the value for the ideal undissociated gas ; the correction however amounts even at the ordinary temperature only to 0.3-0-5 cal.and hence the exceptionally high value of the specific heat of chlorine cannot be attributed to its abnormal density. The degree of association of chlorine is practically zero at 300° and from this temperature up to 1450O the density is normal. This is shown by a study of the specific heat. Hydrogen and chlorine were exploded in a bomb (1) with an excess of chlorine and (2) with an equivalent excess of hydrogen. From the maximum pressure pro- duced by the explosion the maximum temperature reached was calculated and from the data obtained in the two cases the specific heat of chlorine mas compared with that of hydrogen.Regnault's value for the specific heat of chlorine is distinctly too high and the author finds that up t o 1450O the experimental values are satisfactorily given by the formula C = 5.431 + 0.0005T. The values so obtained however are still greater than those of most diatomic gases for which the formula G = 4.327 + 0*00051' is valid. Above 1450° the experimental values for the specific heat of chlorine are considerably greater than those calculated by the fore- going formula. On the basis of the difference between these values,GENERAL AND PHYSICAL CHEMISTRY. 353 and on the assumption that the heat of dissociation of the chlorine molecule is - 113000 cal. the author applying Nernst's theory (Abstr. 1906 ii 727; see also Brill Abstr.1907 ii 233) deduces the formula log(1 -x3)/x2= 113000/4*57127- la7510gT+logP - 3 as applicable to chlorine above 1450". I n this formula x is the degree of dissociation of the chlorine. J. C. P. Speciflc Heat of Some Elements and Salts between the Temperature of Liquid Air and Room Temperature. PAUL NORDMEYER (Ber. deut. physikccl. Ges. 1908 6 202-206. Compare Abstr. 1906 ii 521 ; 1907 ii 432).-The specific heat values recorded for certain elements in the previous paper (loc. cit. j have been confirmed. For the other substances examined the following mean specific heats were deduced aluminium 0.182 ; phosphorus (yellow) 0.178 ; potassium 0.1 69 ; potassium bromide 0.102. H. M. D. Vapour Pressure of Dry and of Ordinary SaI Ammoniac. JOHANNES J. VAN LAAR (Zeitsch.physikal. Chem. 1908 62 194-198). -Treating this problem from the point of view of thermodynamics the author shows that the conclusions drawn by Abegg (this vol. ii 157) and Johnson (ibid.) are incorrect. It does not follow that the partial pressure of undissociated ammonium chloride above sal ammoniac must always be the same a t a given temperature whatever be the degree of dissociation of the vapour. I n the case of ordinary sal ammoniac a complete dissociation equilibrium is established ; this is not so with dry sal ammonisc and .the theory of heterogeneous dissociation equilibria is therefore not applicable to this case. Such dissociation equilibria are defined not by the partial presswe of the undissociated substance but by the total pressure of the system.J. C. P. Vapour Pressure of Aqueous Acetone Solutions. A. E. MAKOVETZKI (J. Buss. Phys. Chem. Soc. 1908 40 216-227).-The object of the research was to study complex solutions but the difference in vapour pressure of acetone and water is so great that the study of the systems acetone + water + a third substance was abandoned. Curves and tables are given showing the relation between the composition of the solutions and the refractive index at various temperatures the vapour pressure of the solutions and the partial vapour pressures of acetone and water respectively. The results are claimed to be considerably more accurate than those of previous investigators (compare Taylor Abstr. 1900 ii 529). Z. K. Condition of Substances in Absolute Sulphuric Acid. GIUSEPPE ODDO and E.SCANDOLA (Zeitsch. physikal. ChenL. 1908 62 243-255).-The authors have discovered independently the method of preparing absolute sulphuric acid lately described by Xautzsch (this vol. ii 14) and the value they find for the freezing point is 10.43". Iu the Beckmann apparatus used the tube is closed by a glass stopper into the central passage of which the thermometer is ground; another354 ABSTRACTS OF CHEMICAL PAPERS. small tube sealed into the stopper is closed at its upper end by a plugged piece of thick-walled rubber tubing in the wall of which a hole is pierced for the passage of the platinum stirrer ; with the aid of a little grease the stirrer moves easily and the acid is protected from the air. Experiments with phosphoryl chloride and sulphuryl chloride as normal solutes give 68.07' as the mean value for the molecular freezing- point depression in absolute sulphuric acid.When the value for the latent heat of fusiop of sulphuric acid (24.03") found by Picketing is inserted in the formula K=O*OZP/X K is calculated to be 66*86O a figure in better ngreernent with the authors' experimental determina- tion than with Hrtntzsch's value (70O). The numbers obtained for the molecular weight of water in absolute sulphuric acid are about two-thirds of the normal value even in solutions considerably more concentrated than those examined by Hantzsch. Using pyridine and quinoline as solutes the authors show that acid sulphates give a figure for the molecular weight which is half the normal value and not two-thirds as found by Hantzsch.The conclusions based by the latter on his experiments and his '' hydronium " theory in particular are adversely criticised. J. C. P. Heats of Vaporisation of the Liquid Halogen Hydrides and of Hydrogen Sulphide. P. H. ELLIOTT and DouaLAs MCINTOSH (J. Physical Chem. 1908 12 163-1 66).-The heats of vaporisation of the compounds in question were determined by an electrical method (compare Franklin and Kraus Abstr. 1907 ii 929). The mean values (from three to four experiments for each substance) are 14.9 17.3 15.8 and 19.6 x lo ergs. per gram-molecule for hydrogen chloride bromide iodide and sulphide respectively. The results agree well with those calculated from the variation of the vapour pressure with temperature by means of the Clausius equation except in the case of hydrogen iodide for which the calculated value is 20.7 x lozo ergs. G.S. Heat of Formation of Organic Fluoro-compounds. 11. FRSDBRIC SWARTS (Bull. Acad. voy. Belg. 1907 941-955. Compare Abstr. 1907 ii 9).-The heats of combustion of the aromatic fluoro- compounds named below have been determined. The three numbers placed after the name of each compound are the heat of combustion at constant volume the heat of combustion at constant pressure and the heat of formation (large calories) fluorobenzene 746.26 746.84 7.26 ; o-fluorotoluene 901.61 902.47 14-73 ; p-fluoro- toluene 901.86 902.72 14.48 ; fluoro-q-cumene 1206.15 1207.49 36-51 ; o-fluorobenzoic acid 739.92 739.92 108.38 ; m-fluorobenzoic acid 737.36 737.36 11 1 ; p-fluorobenzoic acid 739-43 739.43 108.87. The mean difference between the heats of formation of the above fluoro-compounds and the corresponding hydrogen compounds is approximately 14.This is considerably smaller than the mean difference of 20 which was obtained on comparing the heats ofGENERAL AND PHYSICAL CHEJIIBTRY. 355 formation of aliphatic fluoro-compounds with the corresponding hydrogen compounds. The smaller difference corresponds with tbe greater chemical activity of nuclear substituted fluorine. The above three heat values have also been determined for $-cumene ; these are respectively 1244.48 1246.5 16.24. The difference between the heat of formation of solid fluoro-$-cumme and liquid q-cumene is greater than 20 Gal. H. 3%. D. Heat of Formation of Quadrivalent Oxygen Compounds.DOUGLAS MCINTOSH (J. Physical Chem. 1908 12 167-170).-The amounts of heat given out when methyl alcohol acetone and ethyl ether are mixed with liquid hydrogen bromide have been measured. The apparatus used consisted of a Dewar test-tube nearly filled with liquid hydrogen chloride in which was immersed a small tube containing liquid hydrogen bromide. I n the upper part of the latter tube was a bulb containing a known weight of the organic3 liquid which Fvas ultimately dropped into the hydrogen bromide the mixing being effected by an electrical stirrer The whole apparatus was placed in a vacuum tube containing solid carbon dioxide and ether. From a com- parison of the rate of ‘‘ natural” evaporation of the hydrogen chloride with that after admixture and the known heat of vaporisation of hydrogen chloride (preceding page) the heat given out in the reactions has been calculated.The mean heats of combination of 1 mol. :of the organic oompounds with hydrogen bromide are as follows Methyl alcohol 57 x l O l o ergs. ; acetone 60 x lo1* ergs. ; ether 95 x 1O1O ergs. but the agree- ment between different observations especially in the last case is only moderate. It is considered that the heat developed is due mainly if not entirely to chemical combination but the evidence in that respect is not conclusive. G 8. Simple Demonstrations of the Gas Laws. WILLIAM M. DEHN (J. Arner. Chem. Xoc. 1908 30 578-582).-Some simple forms of apparatus are described involving the use of a moving drop of mercury (compare Abstr.1907 ii 755) by means of which the effects of heat pressure and aqueous vapour on a gas separately and conjointly may be demonstrated and calculated. Churles’ I;aw.-The apparatus consists of a calibrated bulb joined to a graduated Etem the internal diameter of which is less than 3 mm. containing a drop of mercury. A length of rubber tubing is attached to the end of the stem and the apparatus except the end of the rubber tube is then placed in a water-bath the temperature of which is known and the position of the mercury noted. The temperature of the bath is raised and the increase in temperature and volume read. Boyle’s Law.-The above apparatus is attached to a manometer by a T-tube one limb of which is fitted with a stopcock. The volume of contained air and the atmospheric pressure are noted.Air is blown into the instrument through the stopcock the drop of mercury is forced along the stem towards the bulb and the mercury rises in the manometer. The stopcock is closed and the volume of contained air356 ABSTRACTS OF CHEMICAL PAPERS. and the difference in the height of mercury in the two limbs of the manometer read off and added to the atmospheric pressure. Aqueous Tapour.-The apparatus and method employed has been described ( h e . c i t . ) . The same apparatus may be used to show the conjoint effects of heat pressure and aqueous vapour on a gas. W. H. G. Surface Tension of Dilute Aqueous Solutions. ADOLF HEYDWEILLER (Ber. deut. plysikal. Ges. 1908 6 245-248).-Thc percentage alteration of the surface tension of solutions of chlorides of lithium magnesium ammonium sodium potassium strontium and barium produced by 1 gram-equivalent of the dissolved salt can be represented by an equation of the form A = Ai + B(l - i) + Cnz in which A B and C are constants and i is the degree of dissociation of the solute. A and B represent the influence exerted respectively by the ions and the undissociated electrolyte and C is a measure of the internal cohesion pressure of the dissolved substance.In the series of chlorides examined A has a positive value which with increasing equivalent weight first diminishes and then increases. B which has a positive value for lithium and magnesium becomes negative when the equivalent weight is further increased and assumes gradually increasing negative values for the other chlorides from left to right.From the values of C numbers are calculated representing the constant a of van der Waals’ equation as applied to solutions. H. 31. D. Weight of a Falling Drop and Tate’s Laws Determination of the Molecular Weights and Critical Temperatures of Liquids by the Aid of Drop Weights. J. LIVINGSTON R. MORGAN and RESTON STEVENSON (J. Amer. Chem. Xoc. 19OS 30 360-376).-From the results of experiments on the weight of drops of water falling from a tube Tate (Phil. McLg. 1864 [iv] 27 176) deduced the following laws (1) Other conditions being the same the weight of a drop of liquid falling from a tube is proportional to the diameter of the tube in which it is formed. (2) The weight of the drop is proportional to the weight which mould be raised in the same tube by capillarity.(3) Other conditions being equal the weight of a drop of liquid is diminished by an increase of temperature. Tate used a thin-walled glass tube the lower end of which was ground t o a sharp edge so that the part of the tube in contact with the drop might be regarded as infinitely thin The present investigation was undertaken with the object of testing these laws and of ascertaining if the temperature-coeficient of drop weight of any one liquid could be employed instead of the temperature- coefficient of surface tension in a formula similar to that of Ramsay and Shields as a means of determining molecular weights and critical temperatures. An apparatus is described by means of which the volume (and hence the weight) of a single drop of a liquid falling from a tube can be accurately measured. Thick-walled capillary tubes were used the ends of which were bevelled at an angle of 45’ and were found to have theGENERAL AND PHYSICAL CHEMISTRY. 357 same effect as those used by Tate in causing all liquids to drop from one and the same area.The liquids employed were ether benzene ethyl iodide chlorobenzene guaiacol benzaldehyde aniline quinoline and water. The results show that for such tips as were employed Tate’s second and third laws are true and that the first law is also true for bevelled tips of diameters between 4-68 and 7.12 mm. It is found that for the same liquid falling drop weights can be substituted for the surface tensions in Ramsay and Shields’ relation and that molecular weights in the liquid state can be calculated with an accuracy equal to that obtained with surface tensions under the same saturated air conditions.Further from a knowledge of the molecular weight of a non-associated liquid the falling drop weight a t one temperature and the densities it is possible to calculate the weight of a drop falling from the same tip at another temperature. Critical temperatures can be calculated by the aid of Ramsay and Shields’ equation y(iU/d)%=k(~ - 6 ) by substituting a drop weight for surface tension and the molecular temperature-coefficient of drop weight for k with the same precision as is attained by using surface tensions against saturated air provided that the drop weights from which the coefficient is found are determined a t as many temperatures and a t as high a temperature as the surface tensions.A bibliography of the subject is appended. Experimental Examination of Gibbs’s Theory of Surface- concentration Regarded as the Basis of Adsorption with an Application to the Theory of Dyeing. W. C. 31. LEWIS {PM. Mag. 19OS [vi] 15 499-5226).-Adsorption effects a t liquid-liquid interfaces have been measured and the results obtained are interpreted with reference to Gibbs’s theory of surface-concentration in order to ascertain whether this theory affords an explanation of the general phenomenon of adsorption. The adsorption measurei-nenDs were made at the surface of separa- tion of a hydrocarbon oil and an aqueous solution of bile salts (‘‘ sodium glycocholate ”).The choice of these substances was determined by the fact that the hydrocarbon is chemically inert in respect of the solution and that the solute lowers the interfacial tension between the water and the hydrocarbon. By modifying Gi bbs’s fundamental expression an equation has been obtained which gives the mass of solute adsorbed per square centimetre of surface in terms of the concentration of the solution and the alteration in the interfacial tension due to the dissolved substance. Determinations of the adsorption coefficient were made (1) a t a very curved surface and (2) a t an approximately plano surface the correspond- ing interfacial tension measurements being carried out by the drop- pipette method. The values obtained in the two cases are in good agreement which appears to point to the fact that the tension even a t very great curvatures is not appreciably different from that at an approximately plane surface but these experimental values are froin twenty to eighty times greater than the values indicated by Gibbs’s theory E.G.358 ABSTRACTS OF CHEMICAL PAPERS Experiments with dyes (Congo-red and methyl-orange) gave similar results the discrepancy between theory and experiment being oE the same order of magnitude. An explanation of the observed differences has not yet been obtained. H. Rl. D. Determination of Viscosity at High Temperatures. CHARLES E. FAWSITT (Proc. Roy. Soc. 1908 80 A 290-298).-The method of determination is based on that described by Coulomb in which the viscosity is calculated from the rate of decay of the amplitude of a horizontal circular disk which is allowed to execute vibrations about a vertical suspending wire.The disk used by the author was 26 mm. in diameter and 1 to 3 mm thick. I n order to make the disk heavy enough to sink in molten metals a small iron cylinder was clamped on to the vertical stem which forms the axis of rotation The weight of the cylinder and its distance from the disk must be such as to keep tho centre of gravity of the rigid part of the apparatus as low as possible. For temperatures up t o 400° iron may be used as material for the disk ; for temperature up to a white heat fire-clay or a mixture of fire- clay and plumbago is suitable. The apparatus was found to give good results for a number of liquids at the ordinary temperature and measurements are recorded of the viscosity of mercury at temperatures up to 31fio and for sodium nitrate up to 450". Dissociation Pressures of Some Metallic Hydroxides and Carbonates.JOHN JOHNSTON (Zeitsch. phpikaZ. Chem. 19 08 62 330-358).-The dissociation pressures of calcium strontium barium lithium sodium and magnesium hydroxides of lithium and sodium carbonates and of the hydrates of barium and strontium hydroxides have been determined mostly by a statical method which is described in detail in the paper. The results obtained for sodium hydroxide are very uncertain but some of those for the other hydroxides are recorded in the following table. The figures represent the temperatures at which the hydroxide in question exerts the dissociation pressure given on the left.H. Af. D. p mm. Ca(OR),. Sr(OH),. Ba(OH),. LiOH. Ng(O?),. 9.2. 369" 452" 630" 561" 35 31.5 408 524 710 628 53 92 448 597 789 700 74 234 488 670 870 782 100 526 527 742 951 875 14'1 760 547 778 998 924 - The results obtained for the carbonates are similarly represented in the following table in which are incorporated also the results obtained by other observers (Le Chatelier Cornpt. rend. 1886,102 1243 ; Finkel- stein Abstr. 1906 ii 354 ; Brill Abstr 1905 ii 522). The values in brackets are extrapolated by means of the author's formuls p mm. CaCO,. SrCO,. BaCO Li CO MgCO,. Na,CO,. 10 [:;:I [860] '1070 783 - about 1100 50 [960] 1164 930 I 100 650 [1008] 1210 1010 - 760 825 1155 1350 [1270] 230" - 5 [480"] [814"] 1028' hOo3' - 940"GENERAL AND PHYSICAL CHEMISTRY.359 The foregoing tables show that if the elements are arranged according to the readiness with which their compounds dissociate the order is the same whether the hydroxides or the carbonates are considered and the same also as that based on the periodic classification and on the physical properties (solubility density melting point &c.) of the compounds. The author’s experiments shorn also that the dissociating tendency of the hydrates of strontium hydroxide is much greater than that of the corresponding hydrates of barium hydroxide. With the help of the equation d(log,p)/dt=Q/RT~ the heats of dissociaticn of the hydroxides of calcium strontium barium lithium and magnesium are calculated from the author’s observations. These calculated values are in good agreement with Thomsen’s direct detor- minations. The values calculated from the author’s observations by Nernst’s formula (Abstr.1906 ii 727) are not in harmony with the experimental values. A theoretical proof is given of Ramsay and Young’s equation connecting the boiling points of different substances under any pressure the same for both. When this formula is applied to fatty alcohols or acids to crystalline hydrates or to the hydroxides of calcium strontium and barium water being taken as the standard of comparison in each case the curves obtained are straight lines. On the other hand hydrocarbons benzene derivatives ethers and esters give a linear relationship when compared with fluorobenzene but not when compared with water. J. C.P. Osmotic Pressure. JOSEPH E. TREVOR (J. Physical Chem. 1908 12 141-154).-A mathematical paper instigated by Porter’s recent paper (Abstr. 1907 ii 743) on the same subject. Porter’s equation connecting osmotic pressure and rapour pressure is deduced by an alternative method which shows the relation of the osmotic pressure to the reversible and irreversible work and heat of dilution. Somewhat complicated expressions are given for the rate of change of the osmotic pressure with temperature a t constant pressure and composition of the solution and with the composition at constant pressure and temperature of the solution and the assumptions made in van’t Hoff’s theory of solutions are discussed in the light of these results. The conditions for proportionality bet ween osmotic pressure and the absolute temperature are zero heat of dilution and constant specific volume of the solvent.G. S. R61e of Imbibition in the Osmosis of Liquids. G. FLUSIN (Arm. Chim. Phyls. 1908 [viii] 13 480-522. Compare Abstr. 1899 ii 204; 1901 ii 148 439).-The author’s experiments were made with the object of ascertaining whether there is in general a quantitative relation between the osmotic activity of a liquid towards a membrane and the amount of the liquid imbibed by the membrane. The membranes employed were weighed in three different conditions (1) dry before imbibition; (2) after imbibition and (3) dry after imbibition. The last weight is always less than the first and is used in the calculation of the coefficient of imbibition which is defined as360 ABSTRACTS OF CHEMICAL PAPERS the volume in C.C.of liquid absorbed by 100 grams of the membrane at a definite temperature and in a certain time; the coefficient increases appreciably but very slightly with rise of temperature. The absorptive ca.pacity of membranes such as parchment paper or pig’s bladder varies for different membranes and diminishes markedly when the same sample is used more than once. The presence in the membranes of certain substances has a great influence on the extent of absorption. The osmometer used was a modified form of that of Raoult (Abstr. 1895 ii 487) and in place of the expression velocity of osmosis the author uses (‘ osmotic debit ” (ddbit osmotique) the apparent osmotic debit being the increase in volume (c.c.) of the liquid column in the measuring tube per hour per sq.dm. of membrane. For membranes from the same source but of different thicknesses the osmotic debit is inversely proportional to the thickness. The membranes employed consisted of vulcanised caoutchouc parchment paper pig’s bladder viscose and copper ferrocyanide. As regards their absorption by caoutchouc organic liquids fall into two clearly-defined classes (1) “ active ” liquids or those which are absorbed energetically from the moment they come into contact with the membrane and (2) “ inactive ” liquids including water with which an appreciable increase in weight of the membrane only occurs after several hours. The relative value of the coefficient of imbibition depends on the duration of imbibition. The osmotic debits are in the same order as and roughly proportional to the coefficients of imbibition except for long durtttions of immersion.Apparent osmosis always takes place from the liquid with the higher towards that with the lower coeficient of imbibition. With pig’s bladder the distinction ‘ between “ active ” and ‘‘ in- active ” liquids is less clearly marked than with caoutchouc Water has the highest coefficient of imbibition and next in order is acetic acid which forms with the material of the bladder a moderately stable compound. I n this case too the osmotic debits and the initial (five minutes) coefficients of imbibition vary in the same order but the ratio has one value for the “active ” and another for the ‘( inactive ” liquids. With parchment paper or viscose the only “active” liquid is water the absorption of which is very rapid at first but almost ceases after about ten minutes.With solutions of various concentrations of sodium chloride potassium carbonate tartaric and acetic acids in contact with parchment paper the osmotic debit varies as the diminution of the coefficient of imbibition but bears no simple relation to the molecular weight of the solute even when ionisation is allowed for. Similar results were obtained with membranes of pig’s bladder. With copper ferrocyanide memhranes the osmotic debits are inversely proportional to the molecular weights of the dissolved compounds if the concentrations of the solutions are the same in each case. In order that osmosis may take place i t is not necessary for the two liquids to be miscible in all proportions,GENERAL AND PHYSICAL CHEMISTRY.361 A method is described of determining molecular weight .by nzeans of osmotic debits. T. H. P. Kinetics of the Reaction between Chloric and Hydrochloric Acids. A Reaction of the Eighth Order. ROBERT LUTHER and F. €1. MACDOUGALL (Zeitsch. piqsikal. C’hem. 1908 62 199-242. Compare Abstr. 1906 ii 436).-The method employed in studying this reaction was to pass a rapid current of an indifferent gas through the mixture and so sweep away the chlorine and chlorine peroxide the substances concerned in the intermediate equilibrium. By this procedure these substances were kept permanently a t a small concentration arid this permitted a quantitative study of the primary reaction.The necessary data for this study mere obtained by absorbing the chlorine and chlorine peroxide in potassium iodide solution ; the velocity of the reaction was thus ascertained as well as the ratio C10 Cl,. The velocity of the primary reaction is proportional to the fourth power of the H’ concentration to the second power of the ClO,‘ concentration and to the second power of the C1’ concentration that is the reaction as a whole is one of the eighth order. The net change may be represented by the equation but consideration of the experimental data shows that the separate stages are probably Secondary { 4H’ + 2C10,’ + 2C1’ = 2C10 + C1 + 2H20 Primary ; 4H’ + 2C10,’ + 2Cl’ t 2H2C10 + (21,. H,CIO -+ C1O2+H,O 4H’ + 4Cl’ + H2C10 -+ :Cl2 + 3H,O Among the experimental facts which support the foregoing representation of the reaction are the following the reaction is not noticeably retarded by chlorine peroxide ; the ratio C10 C1 in the products is practically independent of the intensity of the gas current and the total reaction is retarded proportionally t o the square root of the chlorine concentration.I n discussing the results from a general point of view the authors point out that in oxidation-reduction reactions the primary product is probably always that compound which is in the next jstage of oxidat ion. J. C. P. Influence of Slow Dissociation on the Equilibrium between Phases. C. VAN ROSSEM (Zeitsch. physikal. Chenz. 1908 62 257-283).-Ramsay and Young have found (Phil. Trans. 1886 177 i 82) that in certain cases the statical and dynclmical methods of determining the vapour pressure of a solid lead to divergent and irregular results the substances which exhibit this behaviour being all capable of dissociation namely aldehyde-ammonia phthalic and succinic acids and chloral hydrate and alcoholates.The author adopts Bancroft’s explanation (Abstr. 1899 ii 411) that when zt solid sublimes rapidly there is not sufficient time for the establishment of the dissociation equilibrium. This interpretation is considered in detail in connexion with Ramsay and Young’s experiments.362 ABSTRACTS OF CHEMICAL PAPEKS. These investigators found also (Zoc. cit.) that in the case of the chloral alcoholates the vapour pressure of the supercooled liquid was smaller than that of the solid phase at the same temperature.Bancroft's explanation (Zoc. cit.) of this is rejected and the author points out that the phenomenon was probably due to these alcoholates being contaminated with the alcohol from which they were crystal- lised. Again Ramsay and Young found (Zoc. cit.) that the statically- determined vapour pressure of succinic acid varied with the amount of the solid phase. Bancroft's oxplanation of this is rejected and the author suggests that this phenomenon also is due to the slowness with which the dissociation equilibrium is reached. Increase of the quantity of the solid phase would involve increase of the subliming surface and mould therefore accelerate the establishment of the equilibrium J. C. P. Ammonia Equilibrium. F. JOST (Zeitsch. ccnorg. Chem.1908 57 414-430. Compare Haber and van Oordt Abstr. 1905 ii 159 384 814; Haber and Le Rossignol Abstr. 1907 ii 454).-The equilibrium N + 3H2.2NH has been investigated between 685' and 1040' by means of the special electric furnace designed by Nernst (Zeitsch. EZektrochem. 1907 11 521) which admits of the investiga- tion of gas reactions under high pressures. The furnace is described and figured. A mixture of hydrogen and nitrogen at partial pressures of FiO and 20 atmospheres respectively was passed slowly through the apparatus arid the composition of the resulting mixture determined and the equilibrium was also reached from the other side with a mix- ture containing excess of ammonia. Platinum iron and manganese mere used as catalytic agents. Between 700' and 1 040° the equilibrium is represented satisfactorily by the equation l o p = 3065/T - 6-9 18 where x is the partial pressure of the ammonia.At 685" 876' and 1040° the partial pressure of the ammonia is only 0*0178% 0.0055% and 0.0026% respectively. The heat equivalent of the reaction calculated from the measnrcments by van't Hoff's equation is 28,000 cal. a t 1150° compared with 24,400 cal. found by Berthelot a t the ordinary temperature. The results are in moderate agreement with those calculated by Nernst's formula connecting equilibrium and temperature but the data are not sufficient to allow of a satisfactory comparison. The agreement between the author's results and those of Haber and Le Rossignol (Zoc. c k ) is also only moderate. G. S. Equilibrium of Ammonia under Pressure.FRITZ HABER and ROBERT LE XOSSIGNOL (Zeitsch. EZektrochem. 1908 14 181-196).- Nernst and Jost (Zeitsch. EZektrochem. 1907 13 521) have made determinations of the equilibrium condition of ammonia a t tempern- tures between 685' and 1040' and pressures of 12 to 70 atmospheres. The results do not agree with those obtained by the authors at atmospheric pressure (Abstr. 1907 ii 454) and they have therefore made further experiments a t 30 atmospheres pressure. The essential part of the apparatus used is a quartz tube containing iron o rGENERAL AND PHYSICAL CHEMISTRY. 363 manganese asbestos; the tube (5 mm. internal diameter and 3 mm. thick) withstood the pressure of 30 atmospheres a t 980'. Full details are given of the methods used to eliminate errors; the authors believe that the quantities of ammonia found are correct to within 2Pk. Equilibrium is attained from both sides.The final results are % NH at 30 atmos. 700" 0.654 6.80 801 0.344 3-56 901 0 '207 2.13 974 0.144 to 0'152 1.48 to 1.56 The equilibrium constant K is defined by the ratio of the partial pressures of the gases p(NH,)/p(N,)! x p(H,)*. These numbers agree very well with the authors' previous experiments at atmospheric pressure ; they do not agree with Nernst's theoretical calculations. The discrepancy is possibly due to an error in the heat of formation of ammonia or to an increase in the specific heat of ammonia at high temperatures. T. E. Temperature. (IT, H a z l 3). K x 104. Theory and Practice of the Iodometric Estimation of Arsenious Acid.EDWARD W. WASHBURN (J. Amw. Chem. Xoc. 1908 30 31-46).-A study has been made of the equilibria involved in this analytical process and the proper conditions to be observed a t the end-point have been deduced from the results. It is shown that the success of the titration depends on maintaining the hydrogen-ion concentration a t a sufficiently small value. Calcula- tion of the limits of the hydrogen-ion concentration gives loF4 as the upper limit and 10-9 as the lower limit. If an accuracy of 0.00 1% is desired the hydrogen-ion concentration must lie between these limits the best value being their geometrical mean which is almost identical with the concentration of the hydrogen ions in pure water. It follows therefore that at the conclusion of a titration of an arsenious acid solution with iodine the solution should be neutral.A solution will maintain itself a t any desired hydrogen concentration even although small quantities of acid or base are added if it contains something which will remove both hydrogen and hydroxyl ions. A solution containing the salt of a weak acid or base together with an excess of the acid or base has this property. I t is shown that the ionisstion constant of the acid should be numerically equal to the desired hydrogen-ion concentration. From theoretical considerations it is found that phosphoric carbonic and boric acids are capable of meeting the requirements. I n the case of phosphoric acid it is shown that a t the end of the titration the solution should contain about 2 mols.of Na,HPO to 1 mol. of NaH2P0 in order that neutrality may be preserved. A 0.12 molar solution of sodium hydrogen carbonate saturated with carbon dioxide and a solution saturated with borax and boric acid are also capable of achieving the desired result. Experiments have proved that these conclusions are justified.364 ABSTRACTS OF CHEMICAL PAPERS. It is recommended that for accurate work the solutions should be weighed instead of measured and a convenient form of weight-burette is described. Methods of proparing the standard solutions are given and the mode of carrying out the titrations and the precautions to be observed are described. The results of the investigation show that under the proper conditions iodine can be quantitatively reduced to iodide by arsenious acid and that a definite permanent and exceedingly delicate end-point is obtained.E. (2 Mutual Solubility of Piperidines and Water. OTTO FLASCHNER (Zeitsch. physiknl. Chem. 1908 62 493-49S).-Piperidine is miscible with water in all proportions between 0' and 250° but some experi- ments in which potassium chloride WRS added to the mixed liquids indicate that the hypothetical lower critical solution-temperature (see Timmermans Abstr. 1907 ii 229) for the system piperidine + water is about 277'. The lower critical solution-temperature for methyl- piperidine + water is 48*3' the critical mixture containing 23% of the base. I n this case indications are obtained that the complete mutual solubility crirve would be a closed one but i t is not fully rea!ised.The lower critical solution-temperature for ethylpiperidine + water is 7-45" the critical mixture containing 27% of the base. In the system n-propylpiperidine + water the lower critical solution-tempera- ture could not be reached owing t o the formation of solid ; it appears to lie about - 2 O O . The author suggests a relationship between mutual solubility and dielectric constant. J. C. P. Stability of Colloidal Solutions. 11. THE SVEDBERG (Clhena. Zenfr. 19OS i 88; from Zeitsch. Chem. Id. liolloide 1907 2 142-149. Compare Abstr. 1907 ii 535).-By further studying the behaviour of slightly ionising solvents on colloidal solutions the author's view that the phenomena of coagulation are dependent on other factors than those considered by Billitzer (Abstr. 1907 ii 5 3 5 ) is confirmed.If the activity of the ions is made as small as possible by using a medium having a small ionising effect and a colloidal substance with very small solubility pressure such as platinum in ether the following regularities are found. Concerning the temperature there exist well-defined '' critical points "(sharp coagulation points) and these are elevated on the addition of a small quantity of a non-colloidal substance. The '' critical curves," which show the relation between the temperature of coagulation and the amount of added material are asymptotic to the negative temperature axis. An increase of solubility pressure of the colloid or an increase of the ionising power of the solvent causes in each case a decrease in the sharpness of the critical point." J.V. E. Process of F o r m a t i o n of Hydrosol and Hydrogel. 11. Adsorption of Silver N i t r a t e and Potassium Iodide by Amorphous Silver Iodide. ALFRED LOTTERMOSER and A. ROTHE (.%itsch. physikal. Chew,. 1908 62 359-383. Compare Abstr. 1907 ii 851 ; also Abstr. 1905 ii 586; 1906 ii 429 ; 1907 ii 7S).-YureGENERAL .4ND PHYSICAL CHEMISTRY. 365 silver iodide was prepared by precipitating ammoniacal potassium iodide with ammoniacal silver nitrate the product being successively washed with ammonia water nitric acid and water again. When such amorphous silver iodide is shaken with a solution of silver nitrate some of the latter substance is adsorbed and the adsorption is i n harmony with the usual formula x / m = /3.c1/p. The equilibrium is established very rapidly when a series of silver nitrate solutions of gradually increasing concentration is used but very slowly when the concentration is changed in the opposite direction.It is therefore practically impossible to free silver iodide completely from adsorbed silver nitrate by mere washing with water. When a solution containing Ag’ ions is added to a solution contain- ing I’ ions so that the latter are always in excess a negative hydrosol is formed provided the concentration is below a certain maximum value. SimiIarly when a solution containing I‘ ions is added to one containing Ag’ ions so that the latter are always in excess a positive hydrosol is formed provided the concentration is less than a certain maximum value. This maximum concentration a t which formation of hydrosol can take place is much lower in the latter case than in the former.The maximum concentration is markedly lowered by multi- valent cations where a negative hydrosol is being formed and by inultivltlerit anions where a positive hydrosol is being formed. Multi- valent cations are without influence on a positive hydrosol and multi- valent anions have no effect on a negative hydiosol. Moist amorphous silver iodide can be converted into a hydrosol by I’ ions. This effect reaches a maximum for a certain concentration oE the iodide ; the higher the valency of the metal in the iodide the lower is the concentration which gives the maximum effect. The structure of amorphous silver iodide is altered by I’ ions and this is probably the reason why the adsorption of potassium iodide by moist amorphous silver iodide does not take place in accordance with the usual adsorption law.J. C. P. [Action of Some Electrolytes on Colloidal Silver Solutions. The Process of Coagulation.] ALFRED LOTTERMOSER (Zeitsci.. physikat. Chem. 1908 62 284-286).-A criticism of Woudstra’s recent paper (this vol. ii 160). J. C. P. M u t u a l Flocculation of Colloids. OSCAR TEAGUE and BERNARD H. BUXTON (Zeitsch. physikal. Chem. 1908 62 287-307).-The rule that the degree of flocculation and the extent of the region of optimal concentration (Abstr. 1907 ii 933) depend on the degree in which the substances are colloidal (rule of colloidal flocculation) vras first ,observed t o hold for aniline dyes and is now found t o apply to a number of other colloids. The mutual flocculation of an acid and a basic dye is greatest when the two are mixed in equivalent proportions -An inorganic salt (sodium chloride) is formed by double decomposition and extends the flocculation zone.Histological experiments indicate that highly colloidal dyes are more firmly united than the less definitely colloidal ones. G. B. YOL xciv ii. 26366 ABSTRACTS OF CHEMICAL PAPERS. Parallel Growths of Crystals and Isomorphous Miscibility. THOMAS VIPOND BARKER (&in. Mug. 1908 15 42-53).-The experi- ments on the parallel growth of soluble salts on each other (Abstr. 1907 ii 240) are continued with the sulphstes and chromates of the alkali metals. Although isomorphous miscibility and the formation of parallel growths of crystals are favoured by the same factor namely similarity in molecular volume and crystal-structure yet these two properties do not always go hand in hand for many immiscible or only slightly miscible substances readily form parallel growths.Mixed crystals cannot therefore be regarded as being built up of alternating parallel layers. The bearing of parallel growths on questions of iso- morphism and the limitations of the term isomorphism are discussed. L. J. S. Isomorphism. B. GOSSNER (Zeitsch. Kryst. Min. 1908 44 4 17-518).-A lengthy dissertation on isomorphism in general. L. J. 8. Supposed Alteration in the Total Weight of Substances taking part in a Chemical Reaction. HANS LANDOLT (Siteungsber K. Aknd. Berlin 1908 354-387. Compare Abstr. 1906 ii 528).- The author gives the final results of his extensive investigttions on the question whether changes in total weight take place when substances undergo chemical change.The fact that in the majority of the changes previously investigated a small loss of weight was found has led the author to examine whether this might not be due to the circumstance that these changes take place with development of heat resulting in a diminu- tion of the amount of water condensed on the surface of the glass vessels and also in an increase of volume of the apparatus. The recovery from these disturbances was examined by determining the weights of the reaction vessels from day to day over much longer intervals of time than those during which observations were made in the earlier experi- ments.As a result of these new measurements the supposed pre- ponderance of the reactions which take place with loss of weight dis- appears and in nearly all of the forty-eight experiments the changes in weight fall within the estimated limits of experimental error The final conclusion drawn by the author is that in none of the fifteen different chemical changes which have been examined can a change in the total weight of the reacting substances be recognised. H M. D. Deduction of the Stoicheiometric Laws. 0. DE TRIES (Zeitsch. pluysiknl. ClLenz. 1908 62 30S-329).-The author criticises a t length the attempt made by Walti (Abstr. 1897 ii 311 400; 1898 ii 64 159 327; 1S99 ii 276; 1907 ii 755) to provide an cc priori foundation for the stoicheiometric laws as well as the similar attempts made by Ostwald (Trans. 1904 85 506) Benedicks (Abstr.1.906 ii 530) and Baur (Abstr. 1906 ii 661). It is con- sidered that the proofs given by these writers are either faulty in themselves or are bssed on facts which are equivalent to those involved ia the stoicheiometric laws. These laws should be regarded as purelyGENERAL AND PHYSICAL CHEXIISTRT. 569 experimental in character. [For other papers bearing on this subject see Nasini Abstr. 1905 ii 514; Kuhn Abstr. 1907 ii 678; this vol. ii 98.1 J. C . P. Are the Stoicheiometrical Laws Intelligible without the Atomic Hypothesis? F. WALD (Chem. &it. 1908 32 299-301. Compare Abstr. 1907 ii 678 755).-Polemical. A further reply t o Kuhn. P. €I. Choice of the Most Probable Value for an Atomic Weight Atomic Weight of Hydrogen.WILLIAM A. NOYES (J. Amer. Chem. Soc. 190S 30 4-8).-The following suggestions a r e made as a guide t o the selection of the most probable value for a n atomic weight. (1) When a n observer discovers sources of error in the work of a n earlier observer and succeeds i n avoiding them in his own work the later work should be accepted and the earlier work regarded as of only confirmatory value. (2) When the results obtained by two independent observers agree whilst those of a third are discordant much greater weight should be given to the former than to the latter ; and further values obtained by one author which differ markedly from those obtained by several authors should be rejected. (3) After eliminating certain results by (1) and (2) the remainder shonld be arranged in the order of their probable errors.Arty result with a pro- bable error more than five times t h a t of the smallest probable error should be excluded and the values remaining for a given ratio should be combined by weighting them inversely as the squares of their pro- bable errors. The ratios thus selected should be weighted not by the mathematical probable error but by the deviation of the results of different observers from the value selected. The combination of the experimental ratios for the calculation of atomic weights should be carried out by the application of the same general principles. On applying these principles t o the determinations which have been recorded of the atomic weight of hydrogen the value 1.00775 is obtained (0 = 16) (compare this vol.ii 100). E. G. Number of Corpuscles in the Atom. J. BOSLER (Compt. Ye?ad. 1908 146 686-687).--The total potential energy of 1 gram of hydrogen is 11;(72e)2-n21013 ~- ergs where N is the number of atoms (about 10z4) i n 1 gram n the number of electrons in the atom e their charge (about 3.2 x 10-lo) and ct the radius of the atom ( ; the corresponding value in the case of radium is (%25/3) x 7i21Ol3 or n21U15 ergs whilst the observed value calculated from Curie’s measure- ment of the heat emanation and Rutherford’s estimate of the life of radium is 3 x 1016 ergs ; i t follows therefore t h a t the number n of corpuscles in the atom of hydrogen is of the order of units and this result is in agreement with the results of J.J. Thornson’s later experiments from which he concluded that t h e number of corpuscles of the atom is of the order of greatness of the atomic weight. a M. A W. 25-2368 ABSTRACTS OF CHEMICAL PAPERS. Chemical Elements. Periodicity Weight and Valency. GEORGE WOODIWISS (Chefi2. ATews 1908 97 122-124).-An attempt t o find relationships between the specific gravities of the elements in the solid state and their atomic weights. It is assumed that the valency of the elements in the long series of Mendel6eff’a table increases uniformly from the first to the eighth group the elements i n which have a valency of eight and then decreases uniformly. The elements of the copper and zinc groups are thus septa- and sexa-valent respectively. When the specific gravities of the elements are divided by these hypothetical valencies numbers are obtained which in the case of the metals increase uniformly with the atomic weights and when plotted on a diagram with atomic weight as abscissa these numbers fall approximately on a straight line.The numbers for the non-metallic elements do not correspond a t all with this relationship. H. AI. D. Theory of Valency and Constitution of Salts. GR~GOIRE N. WYROUBOFF (Ann Chinz. Phys. 19OS [viii] 13 523-561).-The author advances a new theory of the formation and constitution of salts which comprehends the so-called molecular compounds as well as the ordinary atomic compounds. H e also applies the notion of mixed functions generally used only in connexion with organic compounds t o inorganic substances.The ideas involved in the terms partial valency crypto-valency pseudo-valency and secondary valency are crit,icised. All theories of valency confound the chemical energy inherent in a n atom with its valency or in other words the sum of the chemical actions which it can exert according to the laws of definite and multiple proportions with the number of atoms of a certain kind with which i t can combine directly. By separating these two notions the problem of valency becomes greatly simplified as also does that of molecular compounds. The valency of a molecule is regarded as being independent of the atomicity of the atom from which it originates and the combination of a molecule M(OH) with nHC1 is represented not by the equation M(OH) + nHC1= MCI + mH,O but by M(OH) + nHCl= M(OH),,nHCl. So that salts are produced by the neutralisa- tion of two different functions without elimination of water and are characterised by being electrolytes and by being capable of taking part in double decompositions. The following considerations are brought forward in support of this hypothesis. A large number of hydrated salts are known from which it is impossible to remove all the water without decomposing them or at any rate completely changing their character. This is the case for exa,mple with magnesium sulphate and chloride and with the chlorides of the alkaline-earth metals and the stable hydrates generally represented as MgSO,,H,O and MCl2,2H,O are regarded as containing water of constitution M(OH),,H,S04 and &I(OH),,2HC1. Thermochemical data are quoted to shorn that the water in such stable hydrates is present in a form different from that in which any further water absorbed exists Thus 1 mol. of calcium sulphate in taking up 28,O t o form gypsum Oa(OH),H,SO evolves 4.4 Gals. whilst 1 mol. of gypsum dissolves in water with absorptionINORGANIC CHEMISTRY. 369 of 0.3 Gal. When dehydrated compounds dissolve in water they are regarded as combining with water and passing from the condition of anhydrides t o that of true salts Salts which are always anhydrous in the solid state are looked on as resulting from the instability of the hydrated salts in the solid form. The formation of organic salts without elimination of water is cited in support of the above theory of salt formation. The author also discusses the compounds Pt(OH),C12,2HCl,2H20 and PtC1,,2HC1,2H20 which he regards as derived from the non- existent or unstable normal salt Pt(OH),,4HCl; the compound Cr2(C,0,),(OH)6 ; the compound Cr2(0H) which presents itself under four distinct aspects with exclusively (1) basic or (2) alcoholic functions ; (3) with functions partly acid and partly basic as in the green chromium compounds and (4) in a form in which the hydroxgls are acid and alcoholic a t the same time. Colson’s work (this vol. ii 45) is criticised. Apparatus for the Centrifugal Draining of Small Quantities of Crystals. GREGORY P. BAXTER (J. Amer. Chem. Xoc. 1908 30 286-288. Compare Richards Abstr. 1905 ii 238).-The apparatus consists of an aluminium cup containing a platinum crucible and fitted with a rubber sleeve which in turn holds a platinum Gooch crucible. The aluminium cup is attached by means of trunnions to the centrifugal machine. The crystals are placed in the Gooch crucible and the mother liquor drains into the platinum crucible beneath. The removal of the platinum crucible is facilitated by a hole situated at the bottom of the aluminium cup. A full description and diagram of the apparatus are given. T. H. P. E. G.

ISSN:0368-1769    

DOI:10.1039/CA9089405333

出版商:RSC    

年代:1908

数据来源: RSC