摘要:

i. 122 ABSTRACTS OF CHEBECCAL PAPERS. Chemistry of Vegetable Physiology and Agriculture Butylene Glycol Fermentation of Sucrose by Bacteria of the Prodigiosus Group. M. LENOIGNE (Compt. rend. SOC. biol. 1919 82 234-236; from Chem. Zentr. 1919 iii 198).-1n addi- ticii to acid and traces of ethyl alcohol and acetaldehyde By-butylene glycol and acetylmethylcarbinol are invariably found among the product,s of the decomposition of sucrose by different varieties of B. prodiyiosus. The bacteria therefore ferment sucrose in the same manner as those of the group of B. subtilis B. l a d s aerogenes and Staphylococci (A. 1913 i 1422). H. W. The Alkali-forming Bacteria found in Milk. S. HENRY APERS PHILIP RUPP and WILLIAM T. JOHNSON jun. (U.S. D e p t . of Agricztltztre 1919 Bull. No.782).-The group of bacteriaVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 123 studied is defined as consisting of those which produce an alkaline reacticn in milk without peptoiiisation of the casein. This group produced the reaction in five days a t 30°. The reaction was not due to ammonia as ammonia was produced by a few organisms only and then not until the second week. All the citric acid in the milk was used up and an amount of carbonate corresponding with about half the citric acid was produced. The chief sources of these organisms were milk soil and water. Of the species studied six were cocci and sixty-two were bacilli; all were non-sporing and had an optimum temperature of 20-30°. The action o€ each organism on certain organic compounds was examined using cultivations in a sodium ammonium phosphate medium containing the test substance as the only source of carbon.The change in the hydrogen-ion concentration was taken as the measure of the alkalinity produced. It was found that dextrose and galactose were fermented by forty-four cultures lactose by eleven saccharose by two and raffinose by none. Ethyl propyl and amyl alcohols were more readily fermented than mannitol and glycerol. The sodium salts of many organic acids were also used with the result that pyruvic citric malic lactic succinic acetic propionic butyric valeric hexoic mucic glyceric tartaric malonic formic benzoic and salicylic acids were converted into carbonates and oxalic and glycollic acids were unacted on. n-Butyric mvaleric and n-hexoic acids were first converted into simpler acids.An investigation of the results showed that the organisms took their carbon most readily from the alkyl and primary alcohol groups provided the primary alcohol was not linked to a carboxyl group. A secondary alcohol group was less easily acted on than a primary. The carboxyl group was not split up. Some experiments were made with urea uric acid and hippuric acid as sources of both carbon and nitrogen and most of the organisms grew well in these media as also did the well-known organisms of typhoid para- typhoid and dysentery. All the organisms were able to utilise the nitrogen i n nitrates and nitrites. J. H. J. Transformation of Cyanamide into Carbamide by the Microbes of the Soil. P. MAzB VILA and M. LEMOIGNE (Compt.rend. 1919 169 921-923).-1t is shown that numerous common species of bacteria abundant in all soils in a good state of cultiva- tion can grow in the presence of cyanamide a t a concentration of 1 in 1000 and are capable of rapidly converting the cyanamide into carbamide. W. G. Solubility of Sparingly Soluble Silver Salts Demonstrated by their Nucleus-destroying Action. 13. BECHHOLD (Rolloid Zeztsch. 1919 25 158-161).-Staph~Zococcus cultures in agar- jelly were partly covered with filter paper which had been coated with various sparingly soluble silver salts and left for four days in the dark at the ordinary temperature. The preparation was then placed in an incubator for forty-eight hours and the area wasi. 124 ABSTRACTS OF CHEMICAL PAPERS. measured which was entirely free from the micro-organism. It is shown that the areas are practically proportional to the solubility of the salt employed.The experiments were carried out with metallic silver and the oxalate oxide carbonate chromate chloride cyanide thiocyanste bromide iodide and sulphide. Similar experi- ments were carried out with metallic silver and silver chloride but using cultures of various micro-organisms and from the area of the free space deductions are drawn as t o the resistance of these organ- isms to silver and silver chloride. I n the case of metallic silver B. pyocyaneus is absolutely unacted on and then follow in decreas- ing order of resistance B. coli the organism of swine erysipelas Staphylococcus paratyphoid typhoid and B. proteus. I n the case of silver chloride the order is entirely different the organism of swine erysipelas being most resistant and this is followed in order by B.pyoc?yaneu.s Staphylococcus B. proteus B. coli Paratyphoid and typhoid. Except in t-he case of the organism of swine erysipelas silver chloride is much more poisonous than metallic silver. J. F. S. Further Experiments on the Correlative Formation of Acetaldehyde and Glycerol by the Scission of Sugar and New Contributions to the Theory of Alcoholic Fermentation. CARL NEUBERG and ELSA REINFURTH (Rer. 1919 52 [Bj 1677-1703. Compare A . 1914 i 118).-As the result of the many investigations carried out by Neuberg and his co-workers in recent years the following representation of the processes occurring in alcoholic fermentation is given I.C,E,,O - 2 H,O = C,H,O the aldol of methylglyoxal 11. C,R80 = 2?X,:C(OH)-CRO or 2CH,-CO*CHO. 111. CH,:C(OH)*CHO + H20 H Glycerol + + 11 = CH, C( OH)*CHO 0 Pyruvic acid. I V . CHS-CO*CO,H = CO + Acetaldehyde. V. CH,*CO*CHO 0 Pyruvic acid + + II = CH,*CHO IT Ethyl alcohol. According to this scheme methylglyoxal and its corresponding acid Fyruvic acid are intermediate compounds and glycerol and acetaldehyde by-products in fermentation. The fact that methyl- glyoxal may be obtained from sugar by means of quite mild alka- line agents (A. 1913 i 1155) is suggestive and led the authors t o inwstigatc! the fermentation of sugar in the presence of such sub- stances especially as it had already been found that the activity of zymase is not impaired by such alkaline compounds (A.1915 i 104 3). Preliminary experiments showed that the by-products acetaldehyde and glycerol become the chief products if sodium sul- phite is t8he agent added (A. 1917 i 502). This was explained by the formation of the very stable bisulphite compound (A. 1918,VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 125 i 517) the corresponding conipoiinds of dextrose or pyruvic acid being so easily dissociated t h a t the reaction is not stopped until the acetaldehyde stage is reached. Owing to the arrest of the further reduction of the aldehyde the available hydrogen must attack some other substance leading according to the above theory to increased production of glycerol. This is now known to be actually the case having by other workers been applied to the technical production of glycerol.I n Neuberg's experiments i t was found t h a t for every molecule of acetaldehyde produced there is also one molecule of glycerol the maximum yield of aldehyde being about 73% and of glvcerol about 70% of t h a t required by the equation C6HI2O6= An important conGrmatioii of this theory o f the action of the alkaline sulphite is the fact t h a t neutral. insoluble sulphites like those of calcium magnesium and zinc. and mixtures of sodium sulphite with phosphoric acid or sodiiim dihydrogen phosphate (that is actually a feebly acid mixture) influence the course of the fer- mentation in the same wav. I n fact the use of calcium sulphite is to be preferred in all such studies. Furthermore the more dilute the solution is the less marked is the effect of the sodium sulphite even if the actual quantity present is 300% of the weight of the sugar.The same results a t any rate in the presence of calcium sulphit,e. are given by bottom veast dried veast or maceration juice. I n fact the production of acetaldehyde (sodium nitroprusside-piperidine test) may be demonstrated in less than half an hour by incubating a mixture of 20 C.C. of 10% sucrose or dextrose '2 grams of baker's yeast and 2 grams of calcium sulphite (made from sodium sulphite and calcium chloride). Scme experiments on the fermentation of the trioses in the pres- ence of calcium sulphite are also described. Dihydroxyacetone yields acetaldehyde but disproportionate amounts of glycerol some- times higher than the expect,ed quantities whilst glyceraldehyde gives no acztaldehyde a t all.CH,*CHO + C,H,(OH),+ CO,. The earlier experiments were performed with top yeast. J. C. W. The Course of Alcoholic Fermentation in the Presence of Calcium Carbonate. JOHANNES KERB (Ber. 19 19 52 rB1 1795-1 800).-Fernbach and Schiin (A. 1914 i 237 910) reported the production of a large amount of calcium pyruvate during the feiementation of dextrose or invert-sugar in the presence of calcium carbonate which seemed incredible to the author since he found t h a t pvruvic acid and its salts are more rapidly fermented by yeast than sugar itself (A. 1913 i 10'26). H e has therefore tested the question and finds that the production of alcohol by pure cultures of yeast is quite normal and that no trace of a pyruvate is present i n the Foluble calcium salts formed.These consist of the sulphate phosphate. hydrogen carbonate and acetate. The only effect is t h a t the yield of acetaldehyde and acetic acid is slightly greater. It is probable that Fernbach and Schon used an impure ferment whichi. 126 ABSTRACTS OF CHEMICAL PAPERS. produced a lactate and then pyruvate that is the normal alcoholic fermentation was very much suppressed. J. C. W. The [Course of Alcoholic Fermentation in an Alkaline Medium. 11. Fermentation with Living Yeast in Alkaline Solutions. CARL NEUBERG and Jur.rus HIRSCH (Biochem. Zeitsch. 1919 96 175-203. Compare A. 1917 i 502).-In the fermenta- tion of sugar by living yeast in the presence of sodium hydrogen carbonate a portion of the acetaldehyde which is formed as an inter- mediate product is not reduced to alcohol but is converted into an equimolecular mixture of acetic acid and alcohol.An amount of glycerol equivalent to this portion of acetaldehyde is simultaneously produced. s. s. z. The Mechanism of the 64Fixation” Method in the Degradation of Sugar into Acetaldehyde and Glycerol. The Correlation of Acetaldehyde and Glycerol during the Entire Process of Fermentation the Time Factor in this Process and its Relation to Alcoholic Fermentation. CARL NEUBERG and JULIUS HIRSCH (Biochem. Zeitsch. 1919 98 141-159).-At every stage during the process of fermentation of sugar in the presence of sodium sulphite acetaldehyde and glycerol are produced in equimolecular proportions. As ethyl alcohol and carbon dioxide are also produced independently at the same time in equivalent proportions the fermentation process can be followed by estimating the alcohol and aldehyde at the various stages.s. s. z. Utilisation of Amides by Yeast. PIERRE THOMAS (Ann. Inst. Pasteur 1919 33 777-806) .-Under suitable conditions yeash are capable of utilising carbamide and to a lesser extent ace& amide as their source of nitrogen during the fermentation of sugar. Slight utilisation of propionamide and butyramide was indicated. The mechanism of this utilisation is not clear. Although all the experiments with carbamide indicate that the organic nitrogen is converted into ammoniacal nitrogen before utilisation i t was not possible to detect any urease or other such hydrolysing ferment either in the culture liquids or in the expressed cellular juice of the yeast.W. G . Influence of Zinc Chloride on the Alcoholic Fermentation of Living and Killed Yeast. 8. KOSTYCHEV and L. FREY ( J . RUSS. Bot. Soc. 1916 1 39-47; from Physiol. Abstr. 1919 4 416).-Zinc chloride caus8s a production of acetaldehyde in “ hefanol ” and dry yeast but not in living yeast. An important part of fermented sugar forms some compounds the structure of which is not yet known; acet,aldehyde is formed only in presence of sugar; the quantity of carbon dioxide exceeds the quantity of alcohol. J. C. I).VEGETABLE PHYSIOLOQY AND AQRICULTURE. i. 127 The Action of Salts of Zinc and Cadmium on the Ferments of Yeast. S. KOSTYCHIEV and ZUBKOVA (J. Buss. Bot. SOC. 1916 1 47-56; from Yhysiol.Abstr. 1919 4 416).-The formation of acetaldehyde by dry yeast under the action of zinc salts depends on the influence of the zinc ion; a similar but more energetic effect can be produced by cadmium salts in the case of sugar fermentation but not in the autolysis in water. In the presence of cadmium salts sucrose and lzevulose produce a much larger quantity of acetaldehyde than dextrose. The reduc- tion activity of yeast is very strongly inhibited by cadmium; the proteolytic ferments on the contrary show no change in their power either in the presence or absence of that metal. Salts of calcium magnesium strontium mercury aluminium and antimony give no effects analogous to those produced by zinc and cadmium. J. C. D. The Decomposition of Lactic Acid by Killed Yeast.V. I. PALLADIN and D. A. SABYNIN (Bull. Acad. Sci. Petrograd 1916 187-194; from Physiol. Abstr. 1919 4 417).-Lactic acid is decomposed by killed yeast in the presence of methylene-blue and in a lesser degree in the presence of pyruvic acid; in the latter case acetaldehyde is not produced. The authors believe that acetaldehyde plays a r61e of an acceptor of hydrogen and is trans- iormed into alcohol. Further work is necessary to determine whether lactic acid is an intermediate compound in the course of alcoholic fermentation. J. C. D. The Influence of Alcohol and Methylene-blue on the Evolution of Carbon Dioxide by Killed Yeast. V. I. PALLADIN and E. I. LOVCHINOVSKAIA (Bull. Acad. Sci. Petrograd 1916 253; from Physiol. Abstr. 1919 4 416).-The experiments on the capacity of killed yeast to oxidise alcohol to carbon dio,xide in the presence of an hydrogen acceptor failed. J.C. D. The Yeast Saccharomyces Thermantitonum. HANS VON EULER and INGVAR UURIN (Biochem. Zeitsch. 1919 97 156-170). -The inversion capacity the catalase activity the rate of ferment- ation at 35O and 40° and the growth of Saccharomyces thermamti- towm have been studied. The culture now examined showed certain deviations in its behaviour a t the characteristic temperatures from the original culture (1905). It is suggested that adaptation may be responsible for this. s. s. z. R6le Played by Water in the Processes of Alcoholic Fermentation and of Respiration of Plants. V. I. PALLADIN (Rec. d’art. dedit a u Prof. C. 7’imiriazew 1916 1-34; from Physiol.A bstr. 1919 4 426).-The replacement of water although only partial by some other solvent such as glycerol ethylene glycol f ormamide pyridine or ethyl alcohol inhibits strongly the activity of zymase carboxylase and reductase. I n the absencei. 128 ABSTRACTS OF CHEMIOAL PAPERS. of water there is no possibility for action of either ferments of alcoholic fermentation or of those of the anaerobic phase of respir- ation. Water is assimilated during respiration and is used for an anzerobio oxidation of dextrose. The total carbon dioxide excreted a t the time of respiration is of anzrobic origin. Hydrogen which is formed in higher plants during their respiration as a result of the anaerobic decomposition of dextrose is temporarily adsorbed by some special hydrogen acceptors (respiratory pigments).The total amount of oxygen adsorbed a t the time of respiration is used exceptionally t o oxidise hydrogen bound by hydrogen acceptors. Water produced during respiration is of anaerobic origin Anthocyanins play no immediate rBle in the respiratory process. Perosydases serve for the formation of water and of pigments. The respiratory pigments play a rBle of mediators between the products of the anaerobic decomposition of dextrose and peroxydases. The oxidation of chromogens follows the scheme of a moist auto-oxidation. Oxygen adsorbed a t the time of respir- ation acts only as a hydrogen acceptor. Thus the majority of cases if not all in which the assimilation of atmospheric oxygen is accepted are in reality cases of an oxygen assimilation from water.J. C. D. Apparatus for the Study of Photosynthesis and Re- spiration. W. J. V. OSTERHOUT (Bot. Gaz. 1919 68 60-62).- A very simple apparatus is desoribed and figured in the original by means of which the air in a closed space in which is present a branch or twig with green leaves and with the stem dipping into water is caused to circulate through a solution of an indicator sensitive to carbon dioxide. By means of t.his the variation in the carbon dioxide concentration in the closed space may be followed whilst the procws of photosynthesis or the process of respiration is proceeding in the plant. W. G . Carbon Dioxide and Plants. 11. E. REINAU (Chem. Zeit. 1919 43 4 4 9 4 5 1 489491 509-512 524-525. Compare Klein and Reinau A. 1914 i 789).-From a lengthy review of the available data concerning the amount of carbon dioxide in the air its fluctuations and its effect on the growth of plants the author is led to the following conclusions.Brown’s theory of the internal pressure of carbon dioxide in plants containing chlors phyll is extended to the phenomena of assimilation under natural climatic conditions and a mathematical expression is developed which takes into consideration the effect both of water and carbon dioxide on the growth of plants. The differences in concentration of these substances witlhin and without the plant are regarded as differences of tension the value of which appears to depend mainly on temperature and atmospheric humidity. Under climatic con- ditions the amount of assimilation by green plants is not propor- tional to the absolute carbon dioxide content of the air but to the difference in tension.The internal pressure of carbon dioxideVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 129 depends on the temperature with rise of which it increases and also on the illumination with increase of which i t falls. The two functions are explained by W illstatter’s conception of the dual nature of chlorophyll; the presence of magnesium in the latter enables i t to form a dissociating compound with carbon dioxide resembling a bicarbonate whilst its chromophoric complex con- ditions its sensitiveness to light. The actual value of the carbon dioxide tension difference depends on the capacity of the air to receive water vapour and therefore indirectly on the temperature and this is explained by the close connexion which exists between the utilisation of the carbon water and salts within the plant.The generally accepted idea that the plant is only able to utilise 0-5-1.0% of the light energy falling on i t appears t o be erroneous. Assimilation of carbon must proceed simultaneously with the evaporation of water; the latter process requires from 25.5% (in full sunlight) to 92.3% (in shade) of the energy derived from the sun by the leaf; the cklorophyll in virtue of the power of selective light absorption exhibited by its chromophoric complex converts about 7% of the light energy into chemical energy and can utilise this amount completely in experimental cases and to the extent of 10-33% under climatic conditions. The carbon dioxide content of the atmosphere is regulated by the activity of terrestrial green plants and of the sea on the one hand and by that of humus (edaphon) on the other; this is rendered probable by the extreme sensitiveness of plants to alter- ation in the tension of carbon dioxide and by the fact that the action of green plants and ‘‘ edaphon ” is so nicely balanced that the actual quantity of carbon dioxide in the atmosphere is the ex- pression of the dynamic equilibrium of the results of these two factors.Consequently the absolute carbon dioxide content of the atmosphere is not a measure of the amount of carbon dioxide avail- able for vegetation but represents the proportion which cannot be lessened by plants under average conditions. It is conceivable that cases could arise in the open in which the plant suffers from too little carbon dioxide ; the agricultural aspect of this possibility and the means of preventing it are discussed in the original paper as is also the beneficent effect of ail increased concentration of carbon dioxide on diseased plants.Schloesing’s theory of the regulation of the carbon dioxide con- tent of the atmosphere by the ocean is regarded as not sufficiently firmly established and as a partial aspect of the actual case. H. W. Formation of Inositol and Hexaldehyde in the Light. P. R. KOGEL (Biochem. Zeitsch. 1919 97 21-23).-A theoretical paper. Inositol and hexaldehyde in the plant are formed by photosynthesis according to the following scheme Tetrahydroxyethylene -+ hydrate of hexaketohexamethylene + inositol.Inositol -+ cyclohexanone + hexaldehyde.i. 130 ABSTRACTS OF CHEMICAL PAPERS. I n a previous communication (A. 1919 i 471) the author put forward a scheme in which he considered that tetrahydroxyethylene was an intermediate product in the formation of formaldehyde from carbon dioxide,. s. s. z. The Hydrocyanic Acid Question. L. ROSEXTHILER (Schwezz. Apoth. Zeit. 1919 57 267-270 279-283 295-297 307-313 324-329 341-346 ; from C‘hem. Zentr. 1919 iii 274-275).- Dezani’s supposed conversion of hydrocyanic acid into ammonia by the sap of plants is erroneous; its production is due to the hydro- lysis of the cyanohydrins of sugar and occurs under conditions which could not obtain in the plant. The author has been unable to detect any formation of ammonia from hydrocyanic acid in the cold unchanged and therefore acid sap from the leaves of Cornus sanguinea Sambucus nigra etc.The presence of hydrocyanic acid which is important from the point of view of Treub’s hypothesis of nitrogen assimilation has been detected with certainty in about 360 varieties in 148 species and 41 fmilies; the varieties are enumerated in the original memoir and particular reference is made to the distribution of the acid in the various parts of the plant. Generally the presence of alkaloids and ethereal oils appears to be incompatible with the presence of hydrocyanic acid. H. W. Histological Investigations of Oxydases and Peroxydases. G. MARINESCO (Compt. rend. SOC. biol. 1919 $2 258-263; from Chem. Zentr. 1919 iv 173).-The presence of oxydases in the cells of various tissues can be detected histologically by the blue color- ation of the cell granula when treated with solutions of a-naphthol and p-phenylenedimethyldiamine. Since however fatty sub- stances give a coloration with this reagent a control with osmic acid and Nile-blue must be made in order to obtain an estimate of the actual amount of oxydase present.The presence of per- oxydase can be detelcted by Perl’s iron reaction since its action is connected with the presence of this metal. The Constituents of Wood which give Colour Reactions. 111. H. WICHELHAUS (Ber. 1919 52 [B] 2054-2056. Compare A. 1916 i 874; 1918 i 151).-The active constituents have been removed from the distillates by extraction with either and purified by distillation under greatly diminished pressure ; two fractions b.p. 8S0/0*4 mm. and 95-105°/0.4 mm. are obtained together with formic acid. Analyses of the fractions give results in agree- ment with those required by the formulae C,,H,,O and C16H22010 respectively which are simply related to the formulae of brazilin and haematoxylin. H. W. Some Components of Althaea (Marsh Mallow) Root. OSCAR VON FRIEDRICHS (Arch. Pharm. 1919 257 288-298).- Marsh mallow root contains 1.7% of an oil consisting of glycerides of palmitic and oleic acids together with butyric acid and a phyto- H. W.VEGETABLE PHYSIOLOQY AND AGBJCUL!IVJBE. i. 131 sterol apparently identical with sitosterol ; a hydroxy-acid of high molecular weight also appears to be present. The odour of the root is due to a substance of unknown composition soluble in ether insoluble in light petroleum and non-trolatile in a current of steam.The root. contains a lecithin in which palmitic and oleic acids occur and the base of which consists of choline. The sugar present is prinoipally sucrose of which the root contains 10.2% the propor- tion of invert sugar being only 0.78%. The mucilage has the formula (C,H,o05)m and consists of glucosan (64%) and xylan. No galadose is present but another saccharecolloid giving dgalactose on hydrolysis is found. The Saponins of Chenopodium quinoa Euphorbia helio- scopia (Tithymatus helioscopius) Euphorbia Peplus and Mercurialis perennis . M. GONNERMANN (Bbchem. Zeitsch. 1919 97 2440).-Preparations of the acid and neutral saponins of them plants have been investigated for their activity by hzemo- lysis of sheep's and human corpuscles.T. H. P. The titres are given. s. s. z. The Saponin in Fenugreek Seeds. H. E. WUNSCHENDOBFF (J. Phumn. Chim. 1919 [vii] 20 183-185).-The saponin may be isolated by extraction with aloohol and precipitation by ether from the alcoholic solution ; the substance consists of a semi-crystalline white powder m. p. 214-216O. On acid hydrolysis it yields a Endothia Pigments. 11. Endothin-red. L. E. SANDO (AM. J . Bot. 1919 6 242-251; from Physiol. Abstr. 1919 4 350).- This pigment was obtained from the alcoholic extract of cultures of Eltdothia 6uen.s grown on rice. Analysis and properties indicate a formula C,H,O and its probable relationship to the catechol group.J. C. D. Chemistry of Heterotropic Phanerogams . JULIUS ZELLKER (Monntsh. 1919,40 293-31 1) .-A further extension and elaboxation of the author's work on this subject (compare A. 1914 i 913). Analysis of the ash of Neottia nidus avis Monotropa hypopitys Cuscuta europaea Lathraea sqmmaria and Orobanchc grarcilis discloses a high percentage of potassium medium or small amounts of calcium normal quantities of magnwium and varying amounts of manganese which are probably connected with the pres- ence of very active oxydases. The ratio of soluble nitrogen to total nitrogen is relatively high but not the same for all parts of the plant. The question of the osmotic pressure of the cell sap is dis- cussed but unfortunately direct measurement is not yet possible. On various grounds the author is led to the conclusion that hetero- tropic plants poor in chlorophyll are richer in osmotically active substances than are the green plants.Analyses show that in all probability the concentrations of cell sap in the parasite and host do not differ widely in spite of the frequently great differences in water mntent. sapogenin and dextrose. w. P. s.i. 132 ABSTRACTS OF CHEMICAL PAPERS. The paper concludes with a critical review of the results obtained by the a.uthor and others in the study of the biochemistry of hetero- trophic phanerogams. H. W. The Honey of the Poplar. GEORGES TANRET (Compt. rend. 1919 169 873-874).-The sugary exudation on the leaves of L’opulus lziyru contains three sugars namely melizitose dextrose and lzevulose. W.G. The Colouring Matter of the Red Pea Gall. MAXIMILIAN NIERENI~TEIN (T. 1919 115 1338-1332). Function of Oxalic Acid in the Plant. The Enzymic Degradation of Oxalic Ions. MAHKUS STAEHELIN (Bzochem. Zeitsck. 1919 96 1-50).-Various plants have been examined and found to contain an enzyme which acts on oxalic ions. It appears that the enzyme is fairly widespread in the plant kingdom being also present in non-acid plants. It is found in most parts of the plant. The enzyme which is an oxydase also functions as a carb- oxylase converting a part of the oxalic ions into carbon dioxide. Its optimum temperature is 30-40° and i t is destroyed on boiling. It is ac,tive under aerobic conditions. I n the leaves of Rumex the degradation of the oxalic ions proceeds according to the formula of a unimolecular reaction whereas in the powdered leaves of Helian- thus it functions in accordance with the law of autocatalysis. Its activity is ret,arded with increased concentration of oxalates. s. s. z. Chemical Composition of Natural and Polished Italian Rice. I. GIOVANNI ISSOGLIO (Atti 22. Accad. Sci. Torino 1917- 1918 53 423-436).-The analytical results obtained by the author show that polished rice is very poor in ash and also in total phos- phoric oxide the phytin phosphoric oxide being reduced to a mini- mum. T. H. P. Chemical Composition of the Residues from the Treat- ment of Rice. 11. GIOVANNI ISSOGLIO (Atti R. Accad. Sci. ToTim 1918-1919 54 440-451).-The rice offals derived from the husk are all very poor in nutritive substances. The residues obtained by removal of the outer cortical layers of the corns are however very rich in organic and inorganic phosphorus com- pounds fat,s and proteins and contain phytin and vitamines. A third class of residues composed of small detached fragments of rice together with foreign seeds contains (1) products such as rice embryos etc. which are used only as cattle feed and (2) products which are similar in chemical composition to rice and are of value as human food. The results emphasise the necessity of reducing t o a minimum the treatment to which rice is subjected. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9201800122

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

i. 133 Organic Chemistry. Action of Selenyl Chloride on Unsaturated Compounds. ARNO MULLER (C’hem. Zeit. 1919 43 843) .-Preliminary qualita- tive experiments show that seleiiyl chloride combines with unsatur- ated hydrocarbons and ketones to form well-defined crystalline additive compounds which are somewhat unstable towards light and air and are readily decomposed by boiling water into selenyl chloride and the corresponding hydrocarbon or ketone. Thionyl chloride also unites with olefinic substances t o give small amounts of deeply coloured additive products but the reaction is generally uncontrollably violent and the formation of by-products cannot be avoided. H. W. Removal of Aromatic Hydrocarbons from Mineral Oils by means of Trioxymethylene-sulphuric Acid. JENG TAUSZ ( J .p r . Chem. 1919 I ii] 99 276-280).-Nastkujoff’s formolite reaction (A. 1904 i 801) for aromatic hydrocarbons is also shown by diolefines such as methyl- and dimethyl-butadienes which contain conjugated double bonds owing to their condensa- tion to ring compounds under the influence of sulphuric acid. On the other hand the reaction is limited in the case of aromatic hydrocarbons t o those cmtaining a hydrogen atom in the nucleus since hexamethyl- and hexaethyl-benzenes do not answer to it. Aromatic hydrocarbons are usually completely removed from mineral oils by this method or by Herr’s modification (A. 1910 ii 904) only after a repetition of the treatment owing to gradual dilution of the sulphuric acid. The author overcomes this difficulty by the use of trioxymethylene in place of formaldehyde solution or rnethylal.[See further J . SOC. Chem. Ind. 1920 February.] J. K. Action of Fluorine on Organic Compounds. BURR HUMISTON ( J . Physical Chem. 1919 23 572-577).-The action of fluorine on organic compounds is usually violent leading to decomposition. Saturated hydrocarbons are ignited with incandescence and forma- tion of free carbon carbon fluorides and hydrogen fluoride. Filtchar ” charcoal is attacked a t the ordinary temperature a gas non-liquefiable at - 80° being the chief product accompanied by carbon tetrafluoride and tetrafluoroethylene (compare Moissan A. 1890 55). Selenium also yields as chief product a gas which escapes liquefaction a t -80O (compare Prideaux T. 1906 84 316). Acetone is ignited by pure fluorine whilst in presence of an indifferent gas charring takes place and some tetrafluoroethylene is produced.An indefinite product containing some mrbonyl chloride is obtained from chloroform. Carbonyl chloride appears t o be unathcked a t 6O but apparently some carbonyl fluoride is VOL. cxvm. i. fi. 134 ABSTRACTS OF CHEMICAL PAPERS. produced at 200O. No evidence could be obtained of a reaction with carbon monoxide. Carbon tetrachloride is only slightly attacked at the ordinary temperature but tetrachloroethylene gradually blackens even a t Oo hexachloroethane being among the products. J. K. Tetrachlorodinitroethane. W. L. ARGO E. M. JAMES and J. L. DONNELLY ( J . Physical C'hern. 1919 23 578-585. Com- pare Biltz A. 1902 i 417).-Tetrachlorodinitroethane is very soluble in liquid nitrogen tetroxide and has pronounced toxic and lachrymatory properties. The optimum temperature for its pro- duction from dry liquid nitrogen tetroxide and tetrachloroethylene is 80°.[See further J . SOC. Chem. Ind. 1920 82a.l J. K. Preparation of Ethyl Alcohol. ELEKTRIZIT~TSWERK LONZA (Brit. Pat. 134521).-In the catalytic reduction of acetaldehyde t o ethyl alcohol by means of hydrogen the excess being returned to the operation by a circulatiiig device (Brit. Pat. 120163) the pro- duction of ethyl ether as a by-product and the gradual poisoning of the catalyst by the decomposition products of acetaldehyde are avoided by circulating with the hydrogen an amount of oxygen not exceeding 0.3%. The temperature of the reaction chamber is main- tained between 90° and 170° by cooling or preferably by using the hydrogen in such excess that it absorbs and removes the super- fluous heat of the reaction.Whereas without the use of oxygen the yield of alcohol fell after thirty hours nearly t o zero an average yield of 95% of the alcohol theoretically possible was obtained in a run extending over two hundred and eleven hours in which 0.150/ of oxygen was used. 'This beneficial effect of the oxygen cannot be attributed to the complete oxidation of carbon monoxide methane etc. to the presence of which the injurious effect on the catalyst is ascribed. G . F. M. Melissyl Alcohol and Melissic Acid. A. HEIDUSCHKA and M. GAREIS ( J . pr. Chem. 1919 [ii] 99 293-311).-The formula for melissyl alcohol has been considered by some workers to be C3,H6,*OH by others C3,H,,*OH.The autlhors have therefore prepared a series of derivatives of melissyl alcohol from carnaubs wax and from beeswa?x and confirmed the view of Schwalb (A. 1885 962) that the alcohols from these sources differ. The former has the formula C3,H6,*OH whilst that of the latter is C,H,,*OH. The melting points of their respedive derivatives were as follows (those of carnauba melissyl alcohol being quoted first) acetates 7 4 O and 70°; benzoatcs 69.5" and 66O; phthalates 82O and 81.5'; monochloroncetates 79'5O and 74' ; ph enylurethanes 98O and 96O; chlorides 6 7 O and 6 5 O ; bromides 6 8 O and 6 7 O ; iodides 6 9 . 5 O and 68'. Carnauba melissyl alcohol on oxidation by Hell's process (A. 1884 1433) gave a melissic acid C30H6002 m.p. 90° (lead salt m. p. 118O) whilst the acid C31H6202 from beeswax had m. p. 88.5O (lead salt m. p. 1 1 5 O ) . The latter acid was also obtained byORGANIC CHEMISTRY. i. 135 hydrolysis of carnauba melissyl cyanide which in an impure condition melted a t 7 5 O . Stiircke's observation (A. 1884 1280) that carnauba melissyl alcohol is accompanied by an alcohol C27H5607nl. p. 76O was also confirmed. J. K. Phytochemical Reduction of Ketones. Biochemical Preparation of Qptically Active Secondary Alcohols. C. NEUBERG and F. F. NORD (Ber. 1919 52 [ B ] 2237-2248). The authors find that the phytochemical reduction of the ketonic group is frequently possible both with aromatic and aliphatic ketones and leads to the production of the corresponding secondary alcohols.Hydrogenation is more difficult than with the aldehydes since it proceeds more slowly and less completely and also requires more energetic conditions. 'The biological nature of the process is shown by the fact that the secondary alcohols are optically active an asymmetric carbon atom being developed during the process- They have been isolated in the chemically pure condition but the yields are poor (about 100,b) and a considerable portion of the original material remains unattacked and is subsequently removed by treatment with sodium hydrogen sulphite or hydrazine bases. They are not optically pure. Acetaldehyde is invariably also formed the oxidative production of which is probably the comple- mentary process of the hydrogenation of the ketone.The mixtures were generally made from conductivity water (2 litres) at 35-40' sucrose (200 grams) yeast (200 grams) and the ketone (10-15 grams) and iermentation was allowed to proceed for three to six days frequently followed by a second addition of sucrose and yeast and renewed fermentation. I n this manner met,hyl ethyl ketone1 yielded d-methylethylcarbinol b. p. 99-looo [a] + 3 * 3 4 O methyl n-propyl ketone gave d-methyl n-propylcarbinol b. p. 117-119° [u! + 6 * 3 O DIG 0-810 methyl n-hexyl ketone yielded d-methylhexylcarbinol b. p. 177-17907 [a] + 2 * 8 5 O whilst d-methylnonylcarbinol b. p. 228-229OY [a] + 2*95O and Z-phenyl- methylcarbinol b. p. 202-204O [a] - 8*0lo were prepared from methyl nonyl ketone and acetophenone respectively. H. W. Phytochemical Reduction of Diketones.C. NEUBERG and F. F. NORD (Ber. 1919 52 [B] 2248-2254. Compare preced- ing abstract).-The authors find that diacetyl can be readily hydro- genated by biochemical methods and that I-P y-butylene glycol is pxoduced in yield which is regarded as satisfactory when the diffi- culties of isolation are taken into consideration; the optical activity of the product is the more remarkable since Harden and Walpole have found that the action of bacteria on a series of carbohydrates leads to a mixture of the racemic and meso-forms of the glycol. Under similar circumstances benzil yields benzoin which in the main is optically inactive bur which contains small amounts of Lbenzoin. Attempts to reduce b e n d or benzoin to the correspond- ing glycol were unsuccessful.H. W. f 2i. 136 ABSTRACTS OF CHEMICAL PAPERS Addition Catalysis by means of Diethyloxonium Salts >O<E. OSSIAN ASCHAN (Afedd. K. Vetenskapsakad. Nobel- Et Et Inst. 1919 5 No. 8 1-32).-Reference is first made to the use of ethereal solutions of hydrogen chloride in the synthesis of hydro- chlorides in the terpene series (compare A. 1916 i 51) and it is pointed out that without. the use of ethyl ether as catalyst tertiary pineiie hydrochloride (Ofvers. Finslca Vet-Soc. forh. 1914-1915 57 [A] No. 1) could not have been prepared. The results thus obtained with the ether-additive product of hydrogen chloride led the author to investigate the addition of water to unsaturated compounds by means of a mixture of absolute ether and sulphuric acid monohydrate.When this mixture is made there is a large development of heat and when the two1 components are in equiva- lent quantities the resulting mixture is much more viscous than the' sulphuric acid. Itl is concluded that diethyloxonium sulphate OHE~-O*SO,-OH is formed although neither it nor a salt could be isolated. The method of experiment was generally t o dissolve the sul- phuric acid monohydrate in the molecular quantity of ethyl ether or if necessary in an excess of ether well cooling meanwhile and then add the unsaturated compound in small portions a t a time again well cooling. I n some experiments a further quantity of water was added to the sulphuric acid monohydrate. After keeping for some time the resulting mixture was poured into an excess of sodium carbonate solution arid the products isolated by steam distil- lation and subsequent fractionation.The normal reaction would be represented by the equations t h e aicohol being produced but in some cases possibly when the reaction mixture is poured into' the8 sodium carbonate solution fission of water takes place with reproduction of the original com- pound or an isomeride; di- and poly-terpenes may also1 be produced. Camphene hydra,te and santenol which are among the lesser sensitive alcohols are the main products of reaction from camphene and santene but some of the original substances are re-formed either as such or as diterpenes. 'The more sensitive alcohols which should result from such substances as pinene nopinene etc. are not produced either the original compound being re-formed or else a polymerisation product obtained.I n the case of P-methyl-AP- butylene the dipolymeride diamylene is readily obtained in an almost pure condition together with smaller quantities of tertiary isoamyl alcohol. Absolute ethyl ether and colourless concentrated nitric acid when mixed in small quantities give a mixture which is stable for aORGANIC CHEMISTRY. i. 137 short time. mixture. T. S. P. Diet>hyloxonium nitrate may be present in such a Kephalin. VII. The Glgcerophosphoric Acid of Kephalin. P. A. LEVENE and IDA P. ROLF (c7. Biol. Chem. 1919 40 1-16). -The generally accepted formula of kephalin presumes the exisb ence of glycerophosphoric acid in the molecule but the experi- mental evidence produced so far in support of this supposition is not ccnvincing.The presence of glyccrol in kephalin has been satis- factorily demomtrated (Foster A. 1915 ii 493). Theoretically there are only two alternative ways in which glycerol may be attached t o phosphoric acid either directly with the formation of glycerophosphoric acid or indirectly with the glycerol attached to the aminmthyl alcohol. If the latter condition existed the amino- group of the liephalin molecule would not be free. Since it ha5 been experimentally shown that the amino-group is free it follows that the presence of glycerophosphoric acid in kephalin could have been accepted before the substance was actually isolated. The glyc~rophosphoric acid isolated from the hydrolysis or” kephalin possesses an optical rotation of the same magnitude as the acid from lecithin namely [a];’ = -0.69O.This work establishes the fact that. glycerophosphoric acid exists in kephalin and that the acid is identical wit3 that present in lecithin. The crude barium d ex t r o r o t a t i on which may account for the statement made by Friinlcel and Dimihz (A. 1909 i 870) that the glycerophosphoric acids present in lecithin and kephalin are optical isomerides. The authors have now shown however that on purification the dextrorotation is lost. It is probably due to a,dmixture of the barium glycerophosphate with a dextrorotatory product of intermediary hydrolysis. The authors are unable to confirm the observations of Willstatkr and Ludecke who stated that the optical rotation of the glycerophos- phoric acid from lecithin differs according t o the mode of prepara- tion.The maximuni rotation for the glycerophosphoric acid from lecithin is found to be [alEo -0*74O a value lower than that recorded by Willstatter and Liideclce (A. 1904 i 1067). g 1 y ce r o p h os p h a t e from k ep h ali n shows J. C. D. The History of Zeise’s Mercaptan and its N a m e (1833). PAUL DIERGART ( J . pr. Cliem. 1919 [ii] 99 281-292).-Histori- cal . J. K. Preparation of Ethylene Ethylidene Disulphide. Osrran MATTER (D.R.-P. 313650; from Chem. Zentr. 1919 iv 617-618). -When the amorphous ethylene sulphides (C,H,S) m. p. 145c and 176O respectively (prepared by the action of ethylene chloride or bromide on aqueous 01- alcoholic solutions of alkali sulphides) are heated almost to dull redness in the absence of air the main portion distils as ethyleiie eth?y7itlene sulphide leaving only an unimportant charcoal-like residue.Decomposition occurs more smoothly when a solid substance such as a metallic sulphide isi. 138 ABSTRACTS OF CREMICAL PAPERS. added to the ethylene sulphide and when a slow current of hydro- gen sulphide is sent through the apparatus. After being frozen out the crude material is purified by passage through a tube loosely packed with fragments of porous pot and heated a t about 300'. The vapours are collected in a well-cooled receiver. Ehhylene ethylidene disulphide after being shaken with aqueous alkali is obtained a an almost colourless liquid b. p. 172-173O which is a good solvent for organic substances and may serve as a basis for pharmaceutical preparations. H.W. Volatility with Steam of Lower Fatty Acids in Dilute Aqueous Solution. EDGAR J. WITZENANN ( J . Awter. Chem. SOC. 1919,41,1946-1951).-The volatility in steam of formic acid acetic acid propionic acid and butyric acid has been examined by distil- ling equivalent solutions (about 1%) and analysing the distillahs. The volatility is shown to increase with increasing molecular weight. Thus the first fraction (20 c.c.) to distil over contains 6.92% of the acetic acid 3'94% of the formic acid 12.4% of the propionic acid and 19.5% of the butyric acid whilst the residue (15 c.c.) after distillatim of 180 c.c. contains 36.8% of the formic acid 18.6% of the acetic acid 5.7% of the propionic acid and 1.4% of the butyric acid.This behaviour is explained as due to the hydration of the acids to form stable complexes which lower the vapour pressure of the solution. The addition of potassium chloride or magnesium chloride to solutions of formic or acetic acid increases the volatility of the acids. The increase in volatility depends on the concentra- tion of the salt and also on its nature. Thus O.5N-potassium chloride has about the same effect as O.2N-magnesium chloride. Using a series of salts in 0.25M quantities in formic acid solution the volatility in steam is increased in every case the order being an increasing volatility with decreasing electro-affinity of the metallic ion of the salt for the chlorides of potassium sodium barium strontium calcium magnesium and aluminium. The chlorides of iron manganese and copper are irregular in their action.J. F. S. The Chlorination of Methyl Formate and Chloroformate. V. GRIGNARD G. RIVAT and ED. URBAIN (Compt. rend. 1919 169 1074-1077. Compare Kling Florentin Lassieur and Schmutz this vol. i 8).-Light exerts a marked influence on the chlorihation of methyl chloroformate. I n diffused light it is only the chloromethyl ester which is iormed bright sunlight being neces- sary for the formation of the di- or tri-chloromethyl ester. I n ultra- violet light the trichloro-ester is easily obtained. The effect of temperature is such that up to 110-112° t,he chlorination pro- ceeds smoothly but a t 113-114O it slackens very noticeably and a t 117O decomposition begins to take place with the formation of carbonyl chloride.Catalysts such as ferric chloride antimony chloride etc. are beneficial a t first in the formation of the dichloromethyl ester butORGANIC CHEMISTRY. i. 139 when a certain concentration is reached decomposition commences and may continue indefinitely as some of the perchloride becomes dissolved i n the liquid and continues its action. W. G. The Chloro-derivatives of Methyl Formate and Methyl Carbonate. V. GRIGNARD G. RIVAT and ED. URBAIN (Compt. rend. 1919 169 1143-1147. Compare this vol. i 8 and p r e ceding abstract).-A study of the properties of the chloromethyl chloroformates and of chloro-derivatives of methyl carbonate. Chloromethyl chloroformate ClCO,*CH,Cl is a lachrymatory liquid and has b. p. 106*5O 1.456 n'," 1.42857. Dichloromethyl chloroformate is a lachrymatory liquid b.p. 46O/62 mm. and 11l0 D17 1.558 T?:; 1.44322. Trichloromethyl chloroformate is less lachrymatory but more suffocating than the two preceding esters and has b. p. 125-126O/748 mm. D1" 1.644 ny; 1.45664. By moderate chlorination of methyl chloroformate in diffused sunlight trichloromethyl Carbonate b. p. 1 3 8 O DB.5 1.297 n 1.41160 is obtained as one of the products. Diclzloromethyl methyl carbonate has b. p. 45-49O/18 mm. D17 1.412 n 1.42852. Chloronaethyl dichloromethyl carbonate one of the products of the more intense chlorination of methyl chloroformate has b. p. 9 6 O / 45 mm. and 177-179O DlS 1.553 11 1.45414. Methyl trichloro- methyl carbonate has b. p . 59.5-60°/16 mm. and 161-163O D17 1.525 92 1.44964. s-Tetrachtoromethyl carbonate b.p. 8 3 O i 19 mm. or 93-94O/20 mm. D16 1.630 n 1.46396 is one of the products of the chlorination of methyl chloroformate in a leaden vessel. By carrying the chlorination still further hexachloro- methyl carbonate m. p. 7 9 O is obtained. W. G. Properties of the Chloromethyl Chloroformates. ANDRB KLING D. FLORENTIN A. LASSIEUR and E. SCHMUTZ (Compt. reild. 1919 169 1166-1168).-A study of the physical and chemical properties of the mono- di- and tri-chloromethyl chloro- formates. The purest specimen of chloromethyl chloroformate contained 8.6% of the dichloromethyl ester. It had b. p. 52.5-53°/100 mm. and 106~5-107°/700 mm. D15 1.465. It is both lachrymatory and suffocating. It is quantitatively decomposed by water according .to the equation Cl*CO,*CH,Cl+ H,O = H-CHO + CO + 2HC1.With alcohols it gives the corresponding mixed chloromethyl carbonates and with sodium phenoxide it gives phenyl chloromethyl carbonate b. p. 122-124°/13 mm. D23 1.255. Anhydrous aluminium or ferric chloride decomposes chloromethyl chloroformate at 70° giving carbonyl chloride. Dichloromethyl chloroformate has b. p. 54-55O/ 100 mm. and 110-111°/700 mm. D15 1.560. On hydrolysis it yields carbon monoxide carbon dioxide and hydrogen chloride. With alcohols it giyes the mixed dichloromethyl carbonates and with sodium phenoxide pli enyl dicliloromethyl Carbonate m. p. 14.5O b. p. 124-125O/14 mm. D15 1-34.i . 140 ABSTRACTS OF CHXMICAL PAPERS Trichloromethyl chloroformate has b. p. 49O/50 mm. and 127O/ 750 mm. D15 1.653. Its general properties resemble those of car- bony1 chloride.On hydrolysis it gives carbon dioxide and hydrogen chloride and with aniline wat,er it yields s-diphenylcarbamide. With alcohols it gives the inixed trichloromethyl carbonates and with sodium phenoxide yields p?i enyl trichloromet hyl carbon.at e m. p. 166O. Anhydrous aluminium or ferric chloride decomposes it giving carbon tetrachloride and carbon dioxide. W. G. Determination of the Position of the Double Linking and its Transposition in some Unsaturated Compounds. (MLLE.) A. C. NOORDUYN (Rev. trav. chim. 1919 38 317-344).- The method adopted was to coiivert the unsaturated compound into its ozonide and decompose this by boiling it with water the result- ing aldehydes being if necessary oxidised t o the acids for purposes of identification. By this method Goldsobel's formula for ricinoleic acid CH,*[ CH,ls* CH( OH) -CH,.CH CH*[ CHJ7*C0,H (compare A.1895 Sl) has been confirmed. Further evidence in support of this was obtained by the ozonisation of castor oil and subsequent decom- position of the ozonide. One of the products of this action after oxidation was the glyceride of azelaic acid D15 1.0377 TZ 1.4693. Similarly undecenoic acid was shown to have the formula CH,:CH*[CH,],*CO,H and one of the products of decomposition of its ozonide was the semi-aldehyde of sebacic acid m. p. 126O giving a semicarbnzone m. p. 1 6 8 O . Three unsaturated hydrocarbons octylene decylene and hepta- decylene were prepared by the method of Grosjean (compare A. 1892 691) by heating the barium salt of the next higher acid with sodium ethoxide and it was shown by the ozonide method t h a t the products in every case were mixtures of isomeric hydrocarbons.Similarly the B-octylene of Kahlbsum prepared by the action of zinc chloride on secondary octyl alcohol was shown to be a mixture of isomerides. By the fusion of oleic acid with potassium hydroxide there is formed not only acetic and palmitic acids but a number of higher homologues of acetic acid and lower homologues of palmitic acid. Under similar conditions elaidic acid also gives a mixture of acids. C,H,(O*COo[CH,]7.CO,H)~ W. G . Ghedda or East Indian Wax. 11. Its Acids. A. LIPP and EUGEN Rovbics ( J . pr. Chern. 1919 [ii] 99 243-255. Com- pare A. 1912 i 675).-The residue of potassium salts after removal from the wax of alcohols and hydrocarbons in the manner previously described furnished a mixture of acids of which one was sparingly soluble in ether (see following abstract). Froq the remainder after removal by steam of small amounts of formic and butyric acids margaric acid and a previously unknown hydroxy-ORGANIC CHEMISTRY. i.141 margaric acid were separated by fractional extraction with light petroleum. Zfydroxymuryal.ic acid C17H3-103 m. p. 5S0 could not be distilled under reduced pressure. It was characterised as a normal acid by conversion into margaric acid through t’he action of hydriodic acid successively at looo and a t 200-220O. The intermediate iodomar- garic acid was only obtained impure in the form of needles m. p. 41.5O. J.K. Gheddaor East Indian Wax. 111. Hydrocarbons and Acids. A. LIPP and E. CASINIR (J. pr. Chem. 1919 [ii] 99 256-258).-The wax contains approximately 48% of ceryl alcohol 7y4 of hydrooarbons (5% of heptacosane 2% of hentriacontane with traces of a hydrocarbon of low melting point) 24-25% of hydroxy- margaric acid m. p. 55-56O (see preceding abstract) 1.5-2% of an isomeric hydroxymargaric acid m. p. 71-72” 9-10% of margaric acid 8-9% of palmitic acid 2% of “Ghedda” acid and 1% of cerotic acid with traces of formic acetic and butyric acids and tarry matter. Cerotic and ghedda acids are present mainly in the free condition the others in the form of their ceryl esters. “ Ghedda” acid to which the formula C,,H,,O is provisionally ascribed m. p. 94.5-95O forms mossy aggregates of white needles.Its sparing solubility in ether and that of its potassium salt in alcohol permit its separation from the other acids present. It differs from melissic acid but is possibly identical with an acid obtained by Schalfeieff (this Journ. 1877 i 454; compare how- ever Nafzger A. 1884 1297). Hydroxymargaric acid CI7HMO3 m. p. 71-72O forms needles or leaflets and was isolated from the last light petroleum extracts of the mixed acids (see preceding abstract). Its calcium salt Ca( CI7H3,O3) forms small spherical nodules. The hydrocarbon previously described (Lipp and Kuhn A. 1912 i 675) as CYOHGz m. p. 70° is now found to have m. p. 68-68*5O and considered to be hentriacontane C31H64 from its resemblance to the hydrocarbon obtained by Krafft from palmitone (A 1882 1272) and its identity wit-h that prepared by Popp (Diss.Tech. Hochschde Munich 1916) by reducing myricyl alcohol which on the other hand he oxidised to nielissic acid at the same time estab- lishing the formula C31HG202 for this acid (but see Heiduschka and Gareis this vol. i 134). Also the hydrocarbon CZ6Hs4 m. p. 58O is now found to have m. p. 59*5O and considered to be hepta- cosane CZ7Hs6 from its similarity to the hydrocarbon obtained from inyristone by Krafft (loc. cit.). J. I(. Crystallographic Investigation of the Dichlorosuccinic Acids. G. ANINOFF (Arkiv Kenz. Min. Geol. 1917-18 7 No. 9 1-11) .-The optically active dichlorosuccinic acids have m. p. 166-167O and Dl5 1-820. They are monoclinic-sphenoidal [a b c = 2.3351 1 2.3754 and /3= 101°30’].Twinning takes place along the plane c(OOl) cleavage parallel with x{ TO1 1 and optical Pi. 142 ABSTRACTS OF CHEMICAL PAPERS. extinction parallel to the edges [(loo) (OOl)] and [(OOl) (Oll)]. The plane of the optical axis is parallel with b(010). The racemic acid has m. p. 174-175O and D15 1.844. The crystals are monoclinic-prismatic [a b c = 0.5846 1 0.5994 and B= 100°46/]. Cleavage takes place parallel to the axes x(101) and b { 010) and optical extinction parallel with the edges [(loo) (OOl)] and [(OOl) (OlO)]. It is not certain from the results whether the racemic acid is a true racemate. mesoDichlorosuccinic acid has m. p. 217-218O. The crystals are monoclinic and needle-shaped but they were not well enough developed to determine the crystallographic constants.The optical a.xis is parallel with h(010). T. S. P. Apparatus for the Electrolytic Decomposition of Organic Acids at Low Temperature and with Small Volumes of Liquid. Electrolytic Decomposition of the Alkali Salts of Citraconic Acid. F HENRICH and WILHELM SCKEXK (Ber. 1919 52 [ B ] 2120-2125).-The apparatus consists of a small flask the bottom of which has been removed and the neck of which is provided with a cork holding a small inverted tube. The latter serves the two-fold function of diminishing the size of the apparatus to the required extent and of allowing efficient cooling by the intro- duction of a stream of cold water into the tube. As anode a stout platinum wire or preferably a platinum gauze is placed in close proximity to the tube.The cathode consists of a piece of nickel gauze. The apparatus is conveniently kept at a temperature of 25-40°. A gas-holder of the type previously recommended by Henrich (A. 1909 ii 66) is used for collection of the anode gases and arrangements are also described which permit the analysis of these gases at. any desired moment. Electrolysis of concentrated faintly alkaline solutions of potass- ium citraconata yields a mixture of oxygen carbon dioxid-e and allylene at the anode the proportion of the latter increasing with increasing strength of current. Its production is also favoured by high concentration and low temperature and is found to depend on the particular alkali salt used; the yields increase from lithium through sodium and potassium t o rubidium and then decline to czesium.The authors consider that this behaviour supports the ccjnception of Fichter and Krummenacher (A. 1918 i 369) that electrolytic decomposition of organic acids is an oxidation process rather than the purely ionic hypothesis of Crum-Brown and Walker. H. W. Electrolytic Decomposition of Glutaconic Acid. F. HENRICH and ADOLF HERZOC (Ber. 1919 52 [R] 2126-2130).- The electrolytic decomposition of alkaline solutions of potassium glutaconate in the apparatus described in the preceding abstract leads to the f orniation of acetylene acraldehyde carbon monoxide and carbon dioxide at the anode these appearing to be the sole products of the action; the mechanism of the change has not beenORGANIC CHEMISTRY. i. 143 fully elucidated but the results appear to support the oxidation theory of electrolytic decomposition advanced by Fichter and Krummenrtcher (A.1918 i 369). Glutaconic Acid. 111 Condensation of Sodioformyl- acetic Ester with Cyanoacetic Ester. P. E. VERKADE (Vws. A7cad. Wetensch. drnsterdurn 1919 27 1130-1139).-The product of reaction of these two substances is not ethyl a-cyano- glutaconate as stated by other workers but probably ethyl ww’-di- cj-ano-1 3-dirnethylcyclohutane-w w 2 4-tetracarboxylate. H. W. CHEMICAL ABSTRACTS. Preparation of Gluconic Acid. A. HERZFELD and G. LENART (Zeitsch. Ver. deut. Zuckerind. 1919 122-128).-Kiliani and Kleemaiin’s method (A. 1854 993) has been modified in the following manner so that the use of lead compounds for the elimication of the hydrobroniic acid is obviated the object in view being the elaboration of a technical process for the preparation of a substitute for vegetable acids.One part of dextrose (from starch) dissolved in 5 parts of water is shaken in a closed vessel with 1 part of bromine until the disappearance of the latter. Oxidation is generally complete after twenty-four hours at the end of which time the excess of bromine is distilled off in a vacuuni ths temperature of the water-bath being about 50°. Heating is continued until the liquid commences to be coloured when it is diluted with about. 350 times its volume of water and the hydro- bromic acid neutralised by sodium carbonate. An excess of calcium carbonate is added gradually a t a temperature of 90° (during which operation any lactone formed during distillation is transformed) and after two or three days the calcium salt separates out and is recrpstallised.By working up the mother liquors an almost quantitative yield may be obtained. If invert sugar is used in place of dextrose the unchanged lzvulose may be either precipi- tated as its insoluble calcium salt or converted into lzvulic acid by boiling with dilute mineral acid. J. P. 0. The Hydrates of Heptaldehgde. (Mlle.) A. C. NOORDUYN (Rec. trav. chim. 1919 38 345-350).-An examination of the system heptaldehyde-water shows the existence of a monohydrate and a dihydrate. No evidence of the existeiice of the hemihvdrate described by Bussy (Annulen 1846 60 247) could be o b t a i d . W. G. The Stabilisation of Acraldehyde. IV. Compounds Acting as Stabilisers against the Formation of Bisacryl.CHARLES MOUREU CHARLES DUFRAISSE and PAUL ROBIN (Compt. rmd. 1919 169 1068-1072. Compare A. 1919 i 574; this vol. i lo).-A study of the products present in the various fractions obtained by the fractional distillation of acraldehyde prepared by the dehydration of glycerol with potassium hydrogen sulphate shows that benzoic acid exerB a marked but variable stabilising action. f” 2i. 144 ABSTRACTS OF CHEMICAL PAPERS. Phenol found in sonie of the fractions is also a stabilising agent but its activity is relatively feeble. The Stabilisation of Acraldehyde . V. Stabilising Action of Substances with a Phenolic Group. CHARLES MOUREU CHARLES DUPRAISSE PAUL ROBIN and JEAN POUGNET (Compt. rend. 1920 170 26-31.Compare preceding abstract).- It has previously been shown that both phenol and benzoio acid exert a marked stabilising action against the formation of disacryl from acraldehyde. The study has now been extended to other phenols and certain hydroxy-acids. Of the monohydroxyphenols examined a-naphthol shows the strongest stabilising action and the presence of several hydroxy- groups attached to ring carbon atoms causes a notable increase in the stabilising power except when two hydroxy-groups are in the meta-position to one another. The action of the various hydroxy- benzoic acids is intermediate between that of the phenol and that of benzoic acid itself. Unlike the phenols their methyl ethers or their acetyl derivatives show little or no stabilising action. Simi- larly the alcohols and the polyhydric alcohols do not exercise any stabilising action.Not only do the polyphenols inhibit the forma- tion of insoluble resin (disacryl) from acraldehyde but they also exercise a similar inhibiting action against the formation of soluble resin even when the phenol is only present t o the extent of 1 in 4000. W. G. Oxidation of Mannitol by Nitrous Fumes. E. VOTO~EK and C. KRAUZ (Zeitsch. Zzcckerind. Rohm. 1919 43 577-580).- In the hope of finding a reagent which will effect the oxidation of polyhgdric alcohols to either aldehydic or ketonic substances exclu- sively the authors have investigated the action of nitrous fumes on an aqueous solution of mannitol; oxidation occurs slowly (but can bo accelerated by the addition of a small quantity of a ferrous salt) and leads to the formation of a mixture of mannose and lavulose.H. W. W. G. Oximes of Rhodeose and Fucose. E. VOTO~EK (Zeitsch. Zztclcerind. Bahm. 1919 43 572-574).-RhodeoseoximeJ m. p. 188-189O is obtained in 97% yield by the action of Wohl's hydroxylamiiie solution on an aqueous solution of rhodeose ; fucose- oxime is similarly prepared and has m. p. 188-189O when rapidly heated. When treated with acetic anhydride and sodium acetate each oxime yields the same acetylrhodeononitrile m. p. 177-178O whilst in addition a substance m. p. 115-116° which does not appear to be an acetyl-nitrile is obtained as by-product from rhodeoseoxime!. isoRholdeose in sharp contrast to rhamnose rhodeose and fucose does not yield a sparingly soluble oxime.H. w. Action of Braun's Dihydrazine on certain Methyl- pentoses. E. VOTO~EK (Zeitsch. Zuckerind. Bohm. 191 9 43 574-577).-1t has been shown by von Braun that diphenyl-ORGANIC CHEMISTRY. i. 145 methanedimethylhydrazine does not react with ketonic sugars but yields hydrazones with arabinose rhamnose galactose and man- nose but not with xylose or dextlrose; in a private communication to the authcrs he has suggested that this difference in behaviour of aldoses is connected with the spatial arrangement of the hydrogen and hydroxyl g o u p s around the three asymmetric carbon atoms adjacent to the aldehydic group and that when these groups occupy alteriiate positions (annexed formula) there is no H OHH tendency towards the formation of a hydrazone. I l l This hybothesis has been tested and conkrmed a t -c-U-c-CHo I I I the instances of rhodeose fucose and isorho- bH H bII deose since the former two readily give hydr- azones in.p. 218O and 2 2 1 O (partial decomp.) respectively whilst the last-named does not react with Braun's dihydrazine. H. W. Thiodisaccharides from Galactose. WILHELM SCHNEIDER and ANNEMARIE BEUTHER (Bey. 1919 52 [B] 2135-2149).-The observation that certain saccharoses react more readily with hydro- gen sulphide in pyridine solution than does dextrose has led the authors to an exteuded examination of the behaviour of d-galactose in the hope of elucidating the constitution of the thio-derivatives. When a solution of d-galactose in ice-cold pyridine is repeatedly saturated with dry hydrogen sulphide with exclusion of air and the product is worked up as already described in the case of dextrose (A.1916 i 791) and converted into the silver salt a product is obtained which contains as in the case of the dextrose derivative more than one atom of sulphur for each atom of silver. During the course of the initial action however a crystalline pre- cipitate is observed to separate which has the composition ClzHzsOi0S3,3C5H5N and readily passes by loss of pyridine into trzthzodigalactose OH*CH,*[CH*OH],*CH( SH)=S*CH( SH) [CH*OH],*CH,-OH. The latter melts somewhat> indefinitely between 139O and 1 4 2 O and is readily decomposed even by solution in water. or aqueous pyridine. Protracted boiling with water converts it into galactose. The specific rotation could not be accurately determined on account of its instability ; solutions in aqueous pyridine are initially lzvorota- tory but rapidly change in sign probably owing to a more or less complete hydrolysis of trithiogalactose t o galactose.When an aqueous solution is treated with silver nitrate silver sulphide is immediately precipitated so that the isolation of a silver salt is impossible. Confirmation of the formula attributed to trithio- digalactose is found in its conve'rsion into a docleca-acetyt derivative leaflets m. p. 157O [a];' + The quantity of the crystalline compound which separates only corresponds with a small amount of the original ma#te,rial; further precipitations were therefore effected by the regulated addition of ether to the filtrate whereby a product needles m. p.183-184O which has also the composition of a trithiodisaccharose was isolated ; in acetylene tetrachloride solution.i. 146 ABSTRACTS OF CHEMICAL PAPERS. this is possibly either an isomeride or a disulphide oxidation product of trithiodigalactose. The isolation of a trithiodisaccharose affords an obvious explana- tion of the high sulphur content of the thio-sugars and their silver salts. The contrast between the stability of the sulphur atom in thio- isotrehalose (Schneider and Wrede A. 1917 i 540) and the insta- bility of trithiodigalactose has led the authors to prepare thio- and seleno-digalactose which are found to be perfectly st8able sub- stances ; thus octa-ace tyl t hiocli-d-gdac tose col ourless slender needles m. p. 200° [a] - 5'72O or - 6*08O in acetylene tetrachloride solu- tion is prepared by the interaction of bromoacetylgalactose on an alcoholic solution of potassium sulphide and is transformed by methyl-alcoholic ammonia into thiodi-d-galactose C,2H,2010S colourless pointed needles m.p. 230° [a]:' -41.86O in aqueous solution. The latter substance closely resembles thioisotrehalose in chemical properties ; with mercuric chloride solution it yields a white precipitate 2EIgS,HgCl,. Similarly octa-acetylselenodigalac- tose crystallises in small colourless needles m. p. 202O [u] - 13.4' or -12.5O in acetylene tetrachloride and is converted by melthyl- alcoholic ammonia into s~lenoni-d-galactose slender needles grouped in dusters. m. p. 228O [a] - 36*6O or - 3 7 . 6 O in aqueous solution. H. W.Action of Hydrogen Sulphide on Sugars. 11. WILHELM SCHNEIDER and OTTILIE STIEHLER (Ber. 1919 52 [ B ] 2131-2135).-A further study of the action of hydrogen sulphide on dextrose and other sugars in pyridine solution (compare Schneider A. 1916 i 791). The proportion of sulphur which enters t.he dextrose molecule is found to increase with the duration of the action and with increas- ing concentration of hydrogen sulphide so that it appears that the system tends towards an equilibrium between unchanged and thio-sugar water and hydrogen sulphide. Under suitable condi- tiom the dextrose molecule can combine with considerably more than one atom of sulphur. Among the hexoses d-galactose .d-mannose and d-f ructose react considerably more rapidly with hydrogen sulphide than does dextrose and absorb more than one atom of sulphur for each molecule ; the behaviour of I-rhamnosc and I-arabinose is similar.Lactose and maltose on the other hand only react very slowly whilst a-methylglucoside and. mannitol do not yield thio-com- pounds. The slight activity of pent a-scetylglucose is probably due t o the preliminary loss of one or more acetyl groups. The ability to yield thio-derivatives appears to depend on the presence of a reactive ketonic or aldehydic group in the molecule. Action of Reducing Agents on the Chloraloses. If. EhNRIoT and ANDRB KLING (Ann. Chim. 1919 [ix] 12 129-150). -When the chloraloses are heated with ammonia in solution in perfectly dry methyl alcohol in sealed tubes a t 150° for four t o H. W.ORQANIO CHEMISTRY.i. 147 six hours one of the three atoms of chlorine is replaced by hydro- gen giving products which the authors name dechlorochloraloses. With benzoyl chloride these compounds give dibenzoyl derivatives. Thus p-chloralose gives cZecJt Zoro-P-ch loralose C,H@6@I2 m. p. 156-157O [a]= - 10*57O giving a dibenzoyl derivative; a-chlor- alose gives dechloro-a-chloralose m. p. 1 6 5 O [a] +9.96O giving a dibenzoyl derivative m. p. 1 4 6 O . P-Galactochloralose gives the compound C8Hl2O6C1 occurring in two forins one having m. p. 96O the other m. p. 1 3 3 O ; both have [afD -29*20° and give a dibenzoyl derivative m. p. 11 6O. p-Arabinochloralose gives the compound C7H1,O,Cl2 m. p. 88-89O [a]= -19*72O giving a clibenzoyl derivative m. p. 90.5'. On oxidation with nitric acid dechlorefl-chloralose gives a mix- ture of a lactone and an acid from which by the action of am- monia dechloro - p - chloralamide C7H90?C1,*CO*NH m.p. 161-1 62O is obtained. Under similar conditions dechloro-P-galac- tochloralose on oxidation only yields mucic aoid. Dechloro-8-arabino- chloralose yields an acid C7H80,C1 m. p. 215O. When hydrolysed with hydrochloric acid the dechlorochloraloses simply split up giving the sugar and dichloroacetaldehyde. The dechlorochloraloses may be more easily obtained and with better yield by the reduction of the corresponding chloralose with alumin- ium amalgam in neutral or acid aqueous alcoholic solution or with a zino-copper couple or zinc and sulphuric acid or by electrolysis i n acid solution. When reduced in alkaline solution as by the action of sodium amalgam the a- and P-chloraloses derived from dextrose each lose two atoms of chlorine yielding respectively bide- chlorogluco-a-chlorulose C,H,,O,Cl m.p. 16B0 giving a dibenzoyl derivative m. p. 149O ; and bidechlorogluco-P-chloralose m. p. 1 6 6 O giving a dihenzoyl derivatik-e m. p. 1 4 6 O . On oxidation %he former of these two compounds gave oxalic and saccharic acids whilst the second gave a Zactone C7€I,0,Cl isolated as its hydr- azoae C,H70,Cl,N,H m. p. 170O. Attempts t o remove the third atom of chlorine from the chloraloses by reduction were not successful. Catalytic Hydrogenation of Lactose. J. B. SENDERENS (Compt. rend. 1920 170 47-5O).-A repetition of Ipatiev's work on the catalytic hydrogenation of lactose in aqueous alcoholic solu- tion in the presence of nickel and nickel oxide (compare A.1913 i 10). It is now shown t h a t if the cztalyst is only slightly active the reaction ceases when the aldehyde group is reduced ta the group *CH,*OH and the author has isolated the resulting compound which he calls Zactositol W. G. This compound has m. p. 7S0 [a]= +12'2O and crystallises with 1H20. On hydrolysis with dilute sulphuric acid it yields sorbitol and galactose. If in the hydrogenation a more active catalyst is used the actioni. 148 ABSTRACTS OF CHEMICAL PAPERS. proceeds further the acetal group being attacked hydrolysis occurs and the resulting products are dulcitol and sorbitol. Isolation of Inulin and Laevulose from Plant Sap. ARNOLD DANIEL (3l.R.-P. 313986; from Chern.Zentr. 1919 iv 665).-The process depends on the addition of strongly alkaline substances in the warm whereby the harmful non-inulin sub- stances are partly precipitated and partly converted into a harm- less form; the concentration of the alkali is to be so chosen that a further precipitation does not occur on treatment of the sap. The preparation of inurin from dahlia tubers by means of alkali hydroxides or carbonates or alkaline earths is described. Pure inulin may also be converted into pure laevulose and other degradation products of inulin such as caramel and dextrin. W. G . H. W. Chemical Structure of the Lignin of Spruce Wood. PETER KLASON (Arkiv Kern. Min. Geol. 1917 6 No. 15 1-21). -Spruce wood has previously been shown to consist approximately of 50% cellulose 16% other carbohydrates 30% lignin and 4% of other substances.Since the " other carbohydrates " have become of great practical importance the name " lignosans " is suggested for them. The composition of lignin has previously been derived from a study of barium lignosulphonate and found to be C4,H4,011 (com- pare A. 1908 i 717 the composition then being wrongly given as C40H42011). Calcium li.~nosz~Zphonnte CiOH4401RS2Ca has now been prepared; i t apparently contains one molecule more water than the barium salt and gives a cryoscopic molecular weight of 1628-1753 so that i t forms double molecules in aqueous solution. Lignin would then have the composition that is it results from the condensation of 1 mol. of coniferyl alcohol and 3 mols. of hydroxyconiferyl alcohol with the loss of 3 mols.of water. (This composition is apparently taken as preferable to that obtained from the barium salt.) Naphthylamine lig?tosulphonnte is readily obtained as a yellow sandy powder by precipitating a solution of the calcium salt with naphthylamine hydrochloride. When the mother liquors from which the above calcium salt has been precipitated are heated with naphthylamine hydro- chloride a naphthylamine lignosulphonnte C,,H,,01,S2N different from the above is precipitated. This can be considered as made up o f 1 mol. of coniferyl alcohol 1 mol. of hvdroxyconiferyl alcohol 1 mol. of caffeic acid 2 mols. of H2S03 and 3 mols. of naphthylamine the condensation of the first three components taking place with the loss of 3 molecules of water.The lignin form- ing the basis of this salt would thus havel the formula C,,H,,08 and contain two methoxy-groups. Assuming that the lignin of wood is made up of an equal number of molecules of the two above lignins its formula would be CcnHn809,0 with six methoxy-groups and such a composition agrees very well with analytical dat.a. C40H44018S2Ca-Ca( HS03) = c40H42012?ORGANIC CHEMISTRY. i. 149 It is suggested that the condensations above mentioned take place between the hydroxyl of an allyl alcohol group and the phenolic hydroxyl in another molecule and so on lignin thus being built up on the same principle that holds for polysaccharides and albumins. The reason for including caffeic acid in the building up of the lignin C29H2608 is that an acid residue must be present to account for the third molecule of naphthylamine in the salt the other two molecules being bound by the sulphurous acid.Plant products are of ten substituted benzeiie derivatives the first position being occu- pied by allyl alcohol or acrylic acid residues whilst the positions 3 4 and 5 are occupied by hydroxyl or metho,xyl groups; caffeic acid is such a derivative. !L"he results obtained by the dry distillation of wood are in agree- ment with the above deductions and all known facts agree with the assumption that lignin from spruce wood results from the con- densation of methylated hydroxycinnamyl alcohols or the corre- sponding aldehydes and acids which are substituted similarly t o protocatechuic acid. Combinations of lignin and sulphite have the character of tannins and lignin can be considered to be an insoluble tannin. Investigation of the molecular weight of the abovementioned calcium lignosulphonate by the ebullioscopic method gives the value 982 (theory 916) so that at the boiling point it is not asso- ciated ; the potassium salt gave similar results. Lignin prepared from spruce wood by digesting it wit.h alcoholic sulphuric acid and removing the fat and resin with light petroleum gave a molecular weight. of 650 in glacial acetic acid as compared with the theoreticaI value 714 for C40H42012 that is in agreement with the formula f o r the lignosulphonate. Experiments on the behaviour of coniferin and coniferyl alcohol towards acid sulphites gave results in agreement with the assump- tion that lignin contains aromatic nuclei of the same structure as coniferyl alcohol together with sidechains of the same constitution as allyl alcohol.The lignin reactions (compare A. 1908 i 717) which are also given by calciuni lignosulphonate after treatment with alkali point t o the samel conclusion. The final conclusion of the author is that lignin in wood is built up from pentoses. as the following equation which gives dihydroxy- cinnamyl alcohol indicates ZC',H,,O = C,H,,O + 5H,O + CO,. The methylation of the phenolic groups may be brought about by formaldehyde R-OH + CH,O = R*OCH + 0 the oxygen liberated then changing RR into R*OII and also oxidising allyl alcohol com- plexes into the corresponding aldehydes and acids thus giving the complexes shown to be present in lignin.T. S. P. Preparation of Hexamethylenetetramine Dinitrate. ZENTRAL STELLE FUR WI SSEN s CHAFTLT CH-TECHNI s CHE UNTERSUCH- UNGEN (D.R.-P. 298412; from Chem. Zentr. 1919 iv 498-499).- Solid hexamethylenetetramine is added preferably with cooling t oi. 150 ABSTRACTS OR’ CHEMICAL PAPERS. dilute aqueous nitric acid which may contain sulphuric acid. Separation of the salt occurs so completely (about 95% of that theo- retically possible) that the reaction may be applied immediately to the precipitation of nitric acid from its aqueous solution. H. W. Reduction of Methylene-blue by Glycine. FRIEDRICH HASSE (Biochem. Zeitsch. 1919 98 159-177).-Glycine reduces methylene blue in alkaline solution. Other amino-acids do not give this reaction. Quantitative estimations show that acetaldehyde and dextrose give a weaker creatine catechol and resorcinol an equal and glucosamine and to a much greater extent adrenaline and quinol a higher reduction than glycine.These observations are discussed in relation t o the Strecker-Traube reactions. s. s. z. Calcium Haloid Salts of Carbarnide and Asparagine. YUZURU OKUDA and KIYOSHI FUJIWAKA (J. Tokyo Chem. SOC. 1919 40 404-412).-Carbamide and asparagine form double com- pounds with calcium haloids which are easily crystallised. Thus the compound Ca12,6CO(NH,) m. p. 168-169O hexagonal plates having a bitter taste is obtained by passing hydrogen sulphide into a mixture of powdered calcium carbonate iodine and a little water until the iodine has dissolved removing the excess of carbonate and adding carbamide to the filtrate which is then made slightly alkaline with lime-water ; the crystals are obtained by concentrating the solution and are recrystallised from water or alcohol.Other compounds described are CaBr,,6CO(NH2) m. p. 1 4 6 O hexagonal plates ; CaC1,,4CO( NH,) hygroscopic hexagonal crystals ; CaI,,C4H80,N,,4H,0 m. p. 136O ; CaBrz,C4H,0,N,,4H,0 ; and CaCl,,C4H,0,N,,4H,0 m. p. 67O hygroscopic columnar crystals. CHEMICAL ABSTRACTS. Transformation of Asparagine into the Dipeptide of Aspartic Acid. C. RAVENNA and G. BOSINELLI (Atti R. Accad. Lincei 1919 [v] 28 ii 113-117).-When ordinary Z-asparaghe is subjected to prolonged boiling in aqueous solution ita undergoes partial racemisation (compare Pringsheim A. 1910 i 303 ; ii 437).From the inactive asparagine separable from the solution by crystal- lisation the d-isomeride may be obtained pure by dissolving a little magnesium sulphate and potassium and calcium hydrogen phos- phates in the 2% aqueous solution and leaving the latter exposed for fifteen days to the air at the ordinary temperature; the mould which develops on the liquid rapidly attacks the Z-asparagine and the d-asparagine may afterwards be crystallised out.. The mother liquors from the inactive asparagine yield no further crystals but are found to contain the dipeptide of aspartic acid (asparagylaspartic acid) (compare Fischer and Koenigs A. 1907 i 486) CO,H*CH,*CH (NH,)*CO-NH* C€I( C0,H) *CH,*CO,H. The latker may be purified by heating i t in an open vessel for some hoursORGAN10 CHEMISTRY.i. 151 a t 210° this treatment converting i t into dih.etopiperaziizediacetic anhydride which neither melts nor decomposes a t 320'; by baryta water in the cold this anhydride is transformed into asparagylaspartic acid. I n view of the widespread ocourreiice of asparagine in plants and the importance of the polypeptides in relation t o the synthesis of proteins it seems possible that the ready formation of the dipeptide of aspartic acid from asparagine may play a part in vegetable meta- bolism. T. H. P. Transformation of Ammonium Malate into the Dipeptide of Aspartic Acid. C. RAVENNA and G. BOSINELLI (Atti R. Accad. Lincei 1919 [v] 28 ii 137-139).-The composition and characters of diketopiperazinediacetic anhydride (compare preceding abstract) indicate the identity of this compound with that obtained by Dessaignes (Beilstein 3rd edition I 1389) by heating ammonium hydrogen malate and described in the older literature as fumar- imide.The conversion of the latter compound into the dipeptide of aspartia acid by the action of baryta solution in the cold confirms the identity. T. H. P. Chloroacetates of _S-Alkylthiocarbamides . JOHN TAYLOR ('I'. 1920 117 4-11). Equilibrium Conditions in the Bucher Process for the Fixation of Nitrogen. J. H. FERCUSON and P. D. V. MANNING ( J . Ind. Xng. Chem. 1919 11 946-950).-1n Bucher's process for the fixation of nitrogen the main reaction is represented by the equation 2Na,CO + 4C + N Z 2NaCN + 3C0 the iron apparently acting only as catalyst. I n order to ascertain the empirical relationships which may be taken as representing the prob- able conditions of equilibrium in practice a stream of gas of varying composition was passed over the charge which was heated in an iron boat.and the amounts of carbonate converted into cyanide a t the equilibrium points were estimated. It was found that the iron bcat was not affected in experiments a t 950° to 1000' in which the gas contained up to 80% of carbon monoxide. Curves were plotted showing the percentage formation of cyanide in relation to the pro- portion of carbon nionoxide in the initial gas. The results indicated that the temperature has relatively little influence on the conver- sion when the gas contains little carbon monoxide but would have much more influence in the case of gas such as producer gas con- taining say 30% of carbon monoxide.A t 1000° it is possible t o convert up to about 60% of the alkali carbonate by means of pro-i. 152 ABSTRACTS OF CHEMICAL PAPERS. ducer gas and the yield would be increased by the use of a higher temperature. The amount of conversion decreases with the rise in the proportion of carbon monoxide in the initial gas and in the case of gas containing 60% of carbon monoxide only half of the carbonate is converted. The results also indicated that the initial reduction of the sodium carbonate to sodium is the controlling factor in the Bucher process and that the effect of the carbon a t this stage may be to maintain the pressure of the carbon dioxide below that of the dissociation pressure of the carbonate. This view received support from the results obtained by plotting the amouiits of carbonate converted into cyanide in relation to carbon dioxide instead of carbon monoxide.[See also J . SOC. C'hem. Ind. 1920 17A .] C. A. M. Action of Mercuric Cyanide on Metallic Salts. LILANANDA GUPTA (T. 1920 117 67-73). Effect of Pressure and of Dissolved Air and Water on the Melting Point of Benzene. THEODORE W. RICHARDS EMMETT K. CARVER and WALTER C. SCHUMB ( J . Amer. Chem. SOC. 1919 41 2019-2028).-The freezing point of benzene and the effect of dissolved air and water on this quantity have been experi- mentally iwestigated. It is shown that benzene saturated with air under atmospheric pressure melts 0*003O below the true triple point. Benzene thus saturated has its freezing point but little altered by change of pressure.There appears to be no large amount of supersaturation. The effect of pressure in the absence of dis- solved air is shown to alter the freezing point 0'029O per atmosphere. Saturation with water lowers the freezing point of benzene 0.095O. The true freezing point of benzene saturated with air is probably not far from 5.493O and the true triple point not far from 5.496O. J. F. S. The Nitrotoluenes. 111. Binary Systems of the Com- ponents p-Nitrotoluene 2 4-Dinitrotoluene and 2 4 6- Trinitrotoluene. JAMES M. BELL and CHARLES H. HERTY Jun. ( J . Znd. Eng. Chem. 1919 11 1124-1128. Compare this vol. i 22 23).-The melting points of two-component systems of three of the principal nitration products of toluene have been determined by the cooling-curve method and the complete results plotted in curves.The term "melting point" is defined as the temperature a t which crystals first appear and in determining it the question of super-cooling has to be taken into consideration whilst the eutectic point is the temperatme a t which there is equilibrium ,between the solids and melted mass. The probable values found for the melting points were For p-nitrotoluene (MNT) 51.5O; 2 4-dinitrotoluene (I)A7T) 69.6O; and 2 4 6-tri- nitrotoluene ( T Z T ) 80*35O in each case with a + or - error of 0.3O. I n the binary system MNT-TNT the eutectic points were 33'85-33'95O; in the system I)N2'-TlYT 45-4-45.6O; and in the system MNT-DNT 26'44-26.54O. In 110 instance did the freez-ORGANIC CHEMISTRY.i. 153 ing-point curves intersect a t other than the eutectic temperature points and the conclusions of Giua (A. 1914 i 817) as to the exist- ence of molecular compounds in these three oases were therefore not supported by these results. C. A. M. The Nitrotoluenes. IV. The Three-component System p-Nitrotoluene 2 4-Dinitrotoluene and 2 4 6-Trinitro- toluene. JAMES M. BELL and CHARLES H. HERTY Jun. ( J . Ind. Eng. Chem. 1919 11 1128-1130).-hehe freezing points of mixtures of these compounds have been determined and plotted in the conven- tional triangular diagrams the primary freezing point being the temperature a t which the first. solid separated the second that at which the second solid separated and the eutectic point that at which all three solids were in equilibrium with the melted mass.The diagram thus consisted of three fields separated by three bow- dary curves which intersected a t the ternary eutectic point. No evidence was obtained pointing to the existence of binary moleculaI compounds as claimed by Giua (see preceding abstract). By a method of interpolation both the composition and temperature of points on the boundary curvw may be found and in this way it is possible to identify the composition of a mixture of the three com- pounds from the determination of the freezing points. p-Cymene. 111. Preparation of 2-Chloro-5 6-dinitro- p-cymene. H. A. LUBS and R. C. YOUNG ( J . Ind. Eng. Chem. 1919 1 1 1130-1133. Compare A. 1918 i 339; 1919 i 398).- The chief product formed in the nitration of 2-chloro-p-cymene is 2- chlorod 6-dinitro-p-cymene whilst an isomeric compound also appears to be formed.Another chlorodinitro-compound (m. p. 90-91O) containing less carbon than chlorodiilitrocyrnene is also formed iii small quantity together with a substance of unknown composition possibly a chloro terephthalic acid. C. A. M. C. A. M. 4-Chlorobenzene- 1 3-disulphonic Acid and its Trans- formation into the Symmetrical Compound. S. C. J. OLIVIER (Rec. trav. chim. 1919 38 351-355).-4-Chlorobenzene- 1 3-disulphonic acid gives a potassium salt C6H,C1(S0,K),,H,0 a burium salt C6I~,C1(SO,),Ba,4H,O7 and a dichloride m. p. 90-5O. When the anhydrous barium salt is heated with sulphuric acid containing some sulphur trioxide a t 300° for five hours it is partly converted into 5-chlorobenzene-1 3-disulphonic acid. The S tructura of the Chlorobenzenedisulphonic Acid prepared according to D.R.-P.260563. S. C. J. OLIVIER (Rec. trav. chim. 1919 38 356-357).-By preparation and identifi- cation of its acid chloride it is shown that the acid obtained by t#he sulphonatJon of pchlorobenzenesulphonyl chloride by the method of Meister Lucius and Briining (D.R.-P. 260563) is 4-chloro- benzene1 3-disulphonic acid. c,H3C'1( so,cl) W. G. W. G.i. 154 ABSTRACTS OF CHEMICAL PAPERS. Iodination of Aromatic Amines by means of Iodine and Persulphate. K. ELBS and H. VOLK (J. pr. Chem. 1919 [ii] 99 269-275. Compare A. 1913 i 841).-The success of this method when applied t o aromatic amines and their acyl derivatives is very limited.The yields of 2-iodo-p-nitroaniline (acefyl derivative needles m. p. 128-130') and 2 4-di-iodo-o-nitroaniline were good ; of 2-iodo-p-toluidine and 2-iodosulphanilic acid moderate ; of 2 4-di-iodoaniline (accompanied by p-iodoaniline) p-iodoaoet- anilide and 3-iodo-p-bromoaiiiline poor. Indefinite products were obtained from m-xylidine dimethylaniline diphenylamine and its acetyl derivative pchloroaniline m-bromoaniline and m-nitrcl aniline as well as from anisidinel and phenacetin although unpub- lished experiments with anisole and phenetole had given excellent results. Tribenzylamine was osidised to benzaldehyde and hexa- methylenetetramine gave its additive di-iodide. Except in the case of acetanilide the acetic acid used in the earlier experiments was replaced by concentrated hydrochloric acid.A New Modification of 3 4-Dinitromethglaniline. HERBERT SWANN (T. 1920 117 1-4). Acylvanillylamides. E. K. NELSON ( J . Amer. Chem. SOC. 1919 41 2121-2130).-Having shown capsaicin to be deceno- vanillylamide (compare A. 1919 i 543) the author has prepared a number of acylvanillylamidee and approximately determined their pungency. These amides are readily prepared by action on vanillyl- amine with the requisite acyl chloride. A cetovanillylamide has m. p. 84-85' (corr.); n 1.550; np 1.585 ; 7z7 1.685 propio- vanillylamide has m. p. 10S-llOo (corr.) ; n 1.495 ; np 1.635 ; n 1.680 ; n-butyrocnnillyla?iizde has m. p. 68-70" (corr.) ; n 1.515 ; np 1.580 ; n 1.655 ; isobzLtyrovaizillylaniide has m. p. 118-120° ; n 1.465; np 1.633 ; n7 1.635; n-he~oca?zillylanzide could not be obtained crystalline ; n-heptova"ill~lamide has m.p. 59-61 O (corr.); n 1.515 ; np 1.595 ; n 1.628 ; n-octouaizillylamade has m. p. 41-43' (cow.); n 1.56 ; n 1.57; n-no.lzovn~zillylamide has m. p. 5 2 O ; n 1.57; n 1.59; n-decovanillylanzide has m. p. 59-60° ; n 1.545; np 1.555 ; n 1.620 ; n-undecovanillylamide has m. p. 54-56O ; n 1.515 ; np 1.540; n 1,615; n-dodecoz;anillyl- amide has m. p. 60-61" (corr.) ; 72 1-58 ; np 1.540 ; n,1.60 ; crotono- vanillylamide has m. p. 119-120" (corr.) ; n 1.515 ; np 1.605 ; n 1.735 ; undecenovanillylamide has m. p. 53-55O (corr.) ; n 1.55 ; np 1.60; n 1.63 ; Ibenzovanillylanzide has m. p. 140-142'; n 1.590; np 1,675; n 1.695. Below the n-hexoamide these substances have little or no pun- gency but above this member the pungency .increases rapidly with rise in molecular weight to the nonoamide and then diminishes again.W. G . N-Methylvinylaniline. JULIUS VON BRAUN and GEORG KIRSCHBAUM ( B e y . 1919 52 [ B ] 2261-2265) .-The substance is mainly of interest because it; represents the first amine to be inveeti- J. K.ORGANIC CHEMISTRY. i. 155 gated which contains the vinyl group directly united t o the nitrogen atom. Methyl-P-bromoethylaniline is converted by trimethylamine into the quaternary bromide NMePh*CH,-CH,*NM%Br the bromine atom of which is not removed by protracted boiling with 51% potassium hydroxide solution ; the corresponding quaternary base may however be obtained by the action of silver oxide and when heated under diminished pressure yields methylvinylaniline ; the success of the operation is dependent on the purity of the bromide.The freshly distilled base forms a colourless liquid with a sharp odour resembling that of formaldehyde or acetaldehyde. It has D:795 0.9887. It differs from other anilines and bases in its in- stability and susceptibility to change ; when preserved even with exclusion of light it gradually becomes more viscous; after 48 hours it has D17’ 1.0144 after 96 hours DY3 1.0408 whilst after 144 hours i t is too viscous to allow determination of density. When distilled it boils mainly a t 98-99O/16 mm. but about one-third of the base is converted into a dark red viscous mass probably by the alkali of the glass. A further remarkable property is the ease with which the vinyl group is removed in the form of acetaldehyde by hydrolysing agents the reaction occurring even with boiling water.F o r this reason i t has not been found possible to isolate pure salts or derivatives of the base. The properties of methylvinylaniline throw doubt on the prob- ability of the presence of the vinyl group attached to nitrogen in morphine as has been postulated by Wieland and Kappelmeier. H. W. The Nitro-derivatives of Diphenylamine. M. C. F. VAN DUIN and B. C.ROETERS VAN LENNEPcRec.tmv.chim. 1919,38,358-368).- An endeavour t o determine the position of the last two nitro-groups in 2 4 6 31 ? ?-hexanitrodiphenylamine formed by nitrating 2 4 6 3l-tetranitrodiphenylamine in the cold (compare Austen this Journ. 1875 165). 2 4 6 2’ 4/-Pentanitrodiphenylamine m.p. 196-197O (corr.) is easily prepared by saturating nitric acid (D 1.49) with picryl- aniline a t a temperature not exceeding 25O. 2 4 6 21 41 6/-Hexanitrodiphenylamine may be prepared by nitrating picrylaniline in a nitric-sulphuric acid mixture or by nitrating pentanitrodiphenylamiiie a t TOo. It has m. p. 249O (decomp.). 2 4 6 2/( 1 ) 3’ 4’-Hexanitrodiphenylamine m. p. 273-274O is obtained by nitrating the 2 4 6 3/-tetranitro-compound in a nitric-sulphuric acid mixture a t the ordinary temperature. The nitro-group in the l3osition 31 is very mobile; ammonia and the amines react immediately with i t a t the ordinary temperature. Thus dimethylamine gives ?7eiLtanitl.odimethylamiszodiphenylamine m. p. 249O (corr.).2 :4 6 3’ 41-Pentanit~.odip,hen?/lamine m. p. 232O (corr.) may be prepared by heating together picryl chloride and 3 4-dinitro- aniline in a sealed tube a t 140° f o r eight hours and this may bei. 156 ABSTRACTS OF CHEMICAL PAPERS. converted into the hexanitro-derivative m. p. 273-274O given above thus establishing the position of the nitroigroup a t 4'. I n an endeavour to establish the position of the sixth nitro- group 3 4 6-trinitrodimethylaniline was heated in alcoholic solu- tion with aniline1 in a sealed tube' a t 120° the product being 4 6-da'nitl.o-3-~nilinodinzethyln~-line m. p. 1 4 3 O (corr.). This was then nit*rated but instead of the required pentanitrodimethyl- aminodiphenylamine as described above being obtained the pro- duct was 2 4 6 2' 4~-pentanitro-5-nzethylnitroaminodiphenyl- nmine m.p. 224-225O (corr.) which may also be prepared from 3-anilino-2 4 6-trinitrophenylmethylnitroamine the intermeldiate product being 2 4 6 2t-tetrunitro-5-methylnitroaminodiphenyl- nmine m. p. 200° (corr.). By the action of p-nitroaniline on tetranitrophenylmethylnitro- amine in boiling benzene solution there is obtained a mixture of a compound m. p. 235O (corr.) and 2 4 6 4I-tetranitro-5-methyl- mitroaminodiphenylamine m. p. 2 0 0 O . History of the Discovery of Oxonium Salts from Phenol Ethers. F. KEHRMANN (Bey. 1919 52 [B] 2119).-The recent publication of Meyer and Gottlieb-Billroth (this vol. i 37) on the action of nitric acid on phenol ethers leads the author to point out thatl the oxonium compound from thymol ethyl ether has been studied by Kehrmann and Messenger (Ber.1901 34 1626) and its constitut,ion has been elucidated by Decker and Solonina (A. 1902; i 767). H. W. Preparation of p-Phenetolecarbamide. J. D. RIEDEL (D.R.-P. 313965 ; from Chern. Zentr. 1919 iv 738).-Solutions of alkali cyanides are treated successively with alkaline oxidising agents and phenetidine hydrochloride ; p-phenetolecarbamide separates immediately in good yield and in a highly pure condition. Sodium hypochlorite or sodium peroxide is cited as oxidising agent H. W. J. D. RIEDEL (D.R.-P. 313413 ; from C'hem. Zeridr. 1919 iv 738-739). -0-Acetoxybenzoyl chloride is allowed t o react with cholic acid in the presence of a substaiice which will combine with halogen acid. The product obtained from these substances in the presence of pyridine is a colourless crystalline) powder insoluble in water soluble in alcohol m.p. 1 2 0 O ; it is tasteless and does not cause digestive disorders. It appears to be unchanged in the stomach but to be readily dissolved in the int,estines. It combines the pharmacological action of cholic and salicylic acids and is expected to find application in pharmacy. Molecular Rearrangement in the Acylation of certain Aminophenols. 1;. CHAS. RAIFORD (J. Anzer. Chem. Sue. 1919 41 2068-2080).-5-Bromo~-3-aminop-cresol when acetylated yielded 5-bromo-3-acetylamino-p-tolyl acetate m. p. 169O which when hydrolysed gave 5-bromo-3-acetylamimo-p-cresol m. p. 129'. W. G. Preparation of Acyl Derivatives of Cholic Acid. H. W.ORGANIC! CREMISTRY.i. 157 This compound when benzoylated yielded 5-brorno-3-benzoylanzino- p-tolyl acetate m. p. 172O molecular rearrangement thus occurring The constitution of the latter compound was proved by hydrolysing it. when 5-bromo-3-benzoylamino-p-c~esol m. p. 1 8 5 O was obtained identical with that prepared by benzoylating 5-bromo-3-amino-p- cresol by using 1 mol. of benzoyl chloride in ethereal solution with 2 mols. of the aminopheiiol. A similar series of compounds was prepared from 4 6-dibromo-2- aminophenol. On acetylation i t yielded 4 6-cZib~omo-2-acetyl- aminophenylacetate m. p. 1 9 9 O which when treated with aqueous sodium hydroxide gave 4 6-dib~onzo-2-acetylaminophenol m. p. 174-1 7 5 O (decomp.) and this with benzoyl chloride gave 4 6-dz- bromo-2-b enzoylaminophenyl acetate m .p . 195-1 9 6 O . This acetate on saponification gave 4 6-dibronzo-2-benzoylaminophe?~ol m. p. 198O identical with that obtailled by benzoylating 4:6-di- bromo-2-aminophenol in dry ether. I n both these cases therefore the diacyl derivative always had the heavier benzoyl radicle attached t o nitrogen regardless of the order in which the radicles were introduced. As this is in direct opposition to the results obtained by Ransom and Nelson (compare A. 1914 i 2 6 9 similar experiments were conducted with amino- phenol itself and regardless of the order of introduction of the acyl radicles the final product- was 2-b enzoylnminophenyl acetate m. p. 135O. Thus in these cases no differences have been observed between the behaviour in this respect of substituted and unsub- stituted aminophenols which indicates that acid-forming sub- stituents are not responsible for the rearrangement.Halogenation. XIX . The Replacement of Sulphonic Groups by Chlorine and the Preparation of Organic Chloro-derivatives . RANK LAI I)ATTA and UARAPARBUTTT KUMAR MITTER ( J . Amer. Chem. Soc. 1919 41 2028-2038).-When chlorine is passed into an aqueous solution of a sulphonic acid the sulphonic group is readily replaced by chlorine with very good yields. I n some cases additional chlorination also takes place. Aromatic substances which in addition contain an hgdroxy-group exhibit a special facility f o r this displacement of the sulphonic group by chlorine and the same has also been found true of amino- compounds such as the nitroanilines.Under these conditions anisole- and phenetole-sulphonic acids yield tetrachloroketocydo- hexadiene and some trichlorophenol. Phenolsulphonic acid gives trichlorophenol ; o-cresol-5-sulphonic acid gives 5-chIoro-o-cresol ; m-cresol-6-sulphonic acid and m-cresol-2 6-disulphonic acid both give 2 6-dichloro-m-cresol ; p-cresol-3-sulphoiiic acid gives a tri- chloro-p-crerol m. p. 85-86O which is either the 2 :3:6- or the 3 5 6-trichloro-derivative ; p-cresol-3 5-disulphonic acid gives 3 5-dichlorc~p-creso1. Thymol mono- and di-sulphonic acids both give 2 5 6-trichlorothymol ; carvacrol-5-sulphonic acid gives tri- chlorocarvacrol; orcinoldisulphonic acid gives pentachloro-orcinol [3 5-diketomethylpentachlorocyclohexane]. o- and p-Nitrophenol- sulphonic acids give respectively 4 6-dichloro-o-nitrophenol and W.G.i. 158 ABSTRACTS OF CHEMICAL PAPERS. 2 6-dichloro-p-nitrophenol ; 0- and p-nitroanilinesulphonic acids yield respectively 4 6-dichloro-o-nitroaniline and 2 6-dichloro-p nit'roaniline whereas m-nitroanilinesulphonic acid does not give any definite product. Salicylic acid on sulphonation and subsequent chlorination gives 3 5-dichlorosalicylic acid. 2 4 6-Trisulpho- m-hydroxybenzoic acid gives the corresponding trichloro-derivative and 3-sulpho-p-hydroxybenzoic acid yields 3 5-dichloro-p-hydr- oxybenzoic acid. W. G. Replacement of Sulphonic Groups by Nitro-groups by means Amer. Chem. SOC. 1919,41,2039-2048).-The sulphonic acid groups in aromatic compounds may be very easily replaced by nitro-groups by means of nitrous gases.The action is generally effected in aqueous solutions the nitrous gases being passed until saturation is reached. In the course of the action more nitro-groups frequently enter with the formation of highly nitrated compounds. Many nitrations which cannob be brought about a t all by nitric acid can be smoothly accomplished by this method. The reaction may be used for deter- mining the constitution of nitro-compounds derived from known sulphonic acids. Aromatic compounds which are already substituted by hy;roxy-groups or by halogens readily undergo replacement of the sulphonyl group by a nitro-group in some cases more nitro- groups entering the ring in suitable positions. I n the case of hydroxycarboxylic acids containing a sulphonyl group both the sulphonyl and the carboxyl groups are replaced by nitro-groups.If however the compound does not already contain substituent halogens or hydroxyl groups replacement of the sulphonyl group does not take place at all. Thus benzenesulphonic acid remains ur,acted on by treatment with nitrous gases. By this method the following compounds have been prepared 3 4-Dinitro-o-cresol from either o-cresol-3-sulphonic acid or o-cresol- 4-sulphonic acid ; 3 5-dinitro-o-cresol from the 3 5-disulphonic acid ; 2 4 6-trinitro-m-cresol from either m-cresol-6-sulphonic acid or the 2 6-disulphonic acid ; 3 5-dinitro-p-cresol from p-cresol-3-sulphonic acid ; 3 5-dinitro-o-4-xylenol from o-xylenol-4-sulphonic acid ; 5-nitro-m-4-xylenol and 2-nitro-p-5-xyleiiol from the corresponding sulphonic acids ; 6-nitrothymol from thymolsulphonic acid ; 2 4 6- trinitroresorcinol from either resorcinoldisulphonic acid m-nitro- phenolsulphonic acid or nz-hydroxysulphobenzoic acid ; 2 4-di- nitrophenol from either anisole- o r pheaetolssulphonic acid ; 2 4 6- trinitrophenol from the sulphonic acids of either 0- or p-nitrophenol or O- or p-hydroxybenzoic acid.By direct sulphonation and subse- quent treatment with nitrous gases without isolation of the sul- phonic acid 1 2 3-cresotic acid gave 3 5-diiiitro-o-cresol ; 1 3 4- cresotic acid gave 2 4 6-trinitro-m-cresol ; 1 4 3-cresotic acid gave 3 5-dinitro-p-cresol ; chloro- bromo- and iodo-benzenes gave the corresponding pnitro-derivatives; phenglacetonitrile gave p-nitrophenylacetonitrile; and anthraquinone gave B-nitroanthra- quinone.W. G . Of Nitrous Gases. ItASIK IJAL nATTAslndPIIULDE0 SAEIAYAVARMA (J.ORGANIC CHEMISTRY. i. 159 Preparation of Tetrahydro-p-naphthol. GEORG SCHROETER and WALTER SCHRAWTH (D.R.-P. 299603; from Chem. Zentr. 1919 iv 618) .-Tetrahydronaphthalene-P-sulphonic acid or its salts are fuseld with alkali. The acid is prepared by mixing tetrahydrcl naphthalene with a small excess of concentrated or absolute sul- phuric acid; i n bhe latter case the hydrocarbon dissolves immedi- ately with spontaneous warming of the solution to 80-100° and the process is completed by warming the mixture on the water-bath. On cooling the mixture solidifies to a mass of crystals from which the sulphonic acid can.be isolated by pressure; alternatively the alkali salts may be obtained by neutralising the slightly diluted mixture with alkali hydroxide and cooling or may be salted out with potassium or sodium chloride. In addition the alkali salts are prepared by the hydrolysis of tetrahydronaphthalene-/3-sulphonyl chloride (from the hydrocarbon and chlorosulphonic acid). When fused with potassium or sodium hydroxide either singly or together or with addition of milk of lime teti-ahydronaphthalene-P-sulphonic acid or its alkali salts are smoothly transformed a t 230-300° into tetrahydro-P-naphthol silky needles m. p.. 59-60° b. p. 145-146O/13 mm. 275-276O1760 mm. which is readily soluble in alkali hydroxide in solutions of salts of the fatty and sulpho-fathy acids and in concentrated sulphuric acid. The soap solutions remain permanently clear when diluted with conductivity water whilst the naphthol is again precipitated when the sulphuric acid solutions are diluted.When the sulphuric acid solution is warmed tetra- hydro-P-nnpht~~ol-a-sulphonic acid is formed and crystallises when a small quantity of water is added to the solution; it is converted into a dirnitrotetrahydronnphthol yellow prisms m. p. 112-114O when treated in aqueous solution with concentrated nitric acid. Tetrahydro-P-naphthol is intended to serve by itself or as starting material in the preparation of drugs disinfectants tanning materials dyes and explosives. Tautornerism of Phenols. I. Quinol. WALTER FUCHS and BENNO EISNER (Ber. 1919 52 [ B ] 2281-2286).-1t is found in the case of quinol that phenols can react with sodium hydro- gen sulphite in their tautomeric form as unsaturated cvclic ke'tones.Reaction slowly occurs when an aqueous solution of quinol and sodium hydrogen sulphite is heated at the temperature of boiling water whereby sodium cyclohemne-1 4-diol-1 2 4-trisulphonate colourless nee'dleis is formed. The sulphonic character of the prolduct follows from the failure t o obtain more t3han traces of sulphur dioxide from it by the action of mineral acids. The con- stitution of the substance is deduced from its oxidation by perman- ganatei to succinic o x a h and. possibly malic acids. cycloHexane- 1 4-diol-1 2 4-trisdphonic acid could not be isolated in the pure condition ; the specimens obtained consist.ed of a colour- less unstable material m. p.172-175O (decomp.) after previous darkening. The sodium salt can be used as a photographic developer; the possibility of its presence in the ordinary quinol developer is discussed. H. W. H. W.i. 160 ABSTRACTS OF CHEMICAL PAPERS. Primary Aromatic Alcohols. J. ALTWEGG (US. Pat. 1315619).-&Phenylethyl alcohol b. p. 89*/4 mm. is obtained in nearly theoretical yield by adding ethylene oxide (I mol.) to an ethereal solution of magnesium phenyl bromide (I mol.) a t Oo maintaining the temperature below loo during the addition then adding dry benzene removing the ether by distillation adding dilute sulphuric acid after cooling and separating the phenylethyi alcohol from the benzene by decantation. B-p-Tolylethyl alcohol b.p. 9B0/3 mm. is similarly obtained from magnesium p-tolyl bromide. P-p-n~et~LoxYphenylet~~yl alcohol b. p. 121°/5 mm. is prepared with the aid of toluene instead of benzene. B-3-~~ethozy-p-toZ~Zeth~Z alcohol similarly prepared is a colourless oil b. p. 129-130°/5 mm. with a faint aromatic odour. CIIEMI CAL ABSTRACTS. A New Sterol. TAKEO IKEGUCHI (J. Bid. Chem. 1919 40 175-182).-The author has previously described a sterol which he isolated from Lycoperdon geinmatum (A. 1915 i 240). He has now obtained a similar product from other fungi namely Armil- l a r k edodes Hydnum asparatum and Collybia shiitake. The crystalline sterols obtained from these sources melt a t 1 5 9 - 4 60° have [ u ] r = - 129.23O t o - 129*55O and the formula C3,H4,02. They all give the same colour reactions which differ slightly from those characteristic for cholesterol.As the author considers these crystals represent a sterol which is present in fungi generally he proposes to call it mycosterol. Mycosterol inhibits the hzemolytic action of saponin but not so powerfully as does cliolesterol. It gives a crystalline compound with digitonin C,,H,,,O,o m. p. 242O (decomp.). Mycosterol acetate C,,H,,O has m. p. 169O. Attempts t3 brominate failed so that the molecule appears to be a saturated one. It was not found possible to prepare a phenylhydrazone so that it would appear likely that the two oxygen atoms are both present as hydroxyl groups. Only one of these is however acetylated by treatment with acetic anhydride PO that the other might possibly be existent as a tertiary alcohol grouping.To gain information on this point the oxidation products of the sterol were examined. On treatment with chromic acid in acetic acid solution mycosterol yielded an oxidation product C,,H,,O m. p. 188-189O. Since this substance is neutral i t is concluded that a third hydroxyl group has been formed during tho oxidation C3,,H46(OH)2 -+ Cq,H,,(OH)2. Acetylation of the oxidation product confirmed this view for a trincetate J. C. D. C36HN06 needles m. p. 201-202° was obtained. Synthesis in the Naphthalene Nucleus. n. MADINAVEITIA and J. PUYAL (,4njnZ. Fiw. Qicim. 1919 17 125-129).-The syn- thesis of 4-methoxy-a-naphthylcarbinol is described. A current of dry hydrogen chloride was passed into a mixture of a-naphthyl methyl ether and anhydrous hydrogen cyanide in ethyl ether solu- tion in presence of powdered zinc chloride.The precipitate formedORGANIC CHEMISTRY. i. 161 gave the aldehyde OMe*C,,H,*CHO (1*4) on boiling with water. This is a liquid (b. p. 210-220°/25 mm.). On treatment with aqueous potassium hydroxide a mixture of l-nzethoxy-4-nap!itkyl- cai,binoZ (m. p. 3 5 O ) and 1-methoxy-4-naphthoic acid (m. p. 2 3 0 O ) was obtained. 4-:llethoxy - a- naphthyl cliloromethyl Jcetone On.le*C'!,II,*CO=CH,Cl is syntliesised by the action of anhydrous aluminium chloride on a mixture of a-iiaphthyl methyl ether and chloroacetyl chloride in carbon disulphidei solution ; it forms needles m. p. TOo. Tho corresponding ethoxy-derivative obtained in a similar way has m.p. 9S0 and when heated with hydrochloric acid in a sealed tube a t 120° yields a-naplbthyl chloromethyl Jcetone which after recrystallisation from alcohol has m. p. 1 3 0 O . W. S. M. Preparation of Ethylidene Esters. CIIEMISCHE FABRIK GRIESIIEIM-ELEKTRON (D.R.-P. 313696 ; from Chem. Zentr. 1919 iv 6(j4-665).-0rganic vinyl esters or mixtures of vinyl esters are heated in the presence or absence of a catalyst with organic or inorganic acids under conditions in which a molecule of the acid combines with a molecule of the ester and either at the ordinary or increased pressure until the action is complete. Thus ethylidene diacetate is obt.ained by boiling vinyl acetate with acetic acid in the presence of a sinall quantity of concentrated sulphuric acid. Vinyl benzoate b.p. 203O D20 1.065 and dry hydrogen chloride yield cliloroethpl benzoute h. p. 134O/20 mm. D"J 1.172. Vinyl acetate forms etlzylzclene acetute benzoate CH,.CH(OAc)*OBz with benzoic acid and chloroeth yl acetate OAc-CHClMe with hydrogen chloride. The products are generally liquid and excellent solvents for natural and artificial resins and cellulose nitrates and acetates; they may also be used in the preparation of varnishes films and impreg- nating mixtures. H. W. Physiological Formation of Adrenaline and Syntheses of Phenylserine. F. KNOOP (Ber. 1919 52 [B] 2266-2269).-The author criticises the views which have recently been advanced by Rosenmund and Dornsaft (this vol. i 56) on the physiological formation of adrenaline and points out that the production of many of the intermediate substances which they postulate is not in accordance with known physiological chemical process.[With ToTaNr.]-lVith the object of preparing iX-methylserine a- chloro-fl-phenyl-lactic acid was added t o a solution of niethyl- ainine; contrary to expectation the product proved to be P-methyl- ami~zo-a-hydrox?/-P-phcn~/l~ropionic acid long prisms decomposing completely a t 272O after slowly darkening at 250O; since the original acid contains the hydroxyl group in the &position it follows that it inust have migrated to the a-carbon atom probably owing to the intermediate formation of phenylglycidic acid. The constitution of the new acid is deduced from its oxidation by barium permanganate to a-methylamino-a-phen,ylacetic acid pointed prisms which sublime without melting a t 270O.The latter acid is also obtained by thei. 162 ABSTRACTS OF CHEMICAL PAPERS. action of methylamine on a-chloro-j3-acetyl-~-phenyl-lactic acid short coarse prisms m. p. 131O. H. W. Alkamine Esters of Aminotoluic Acids and Similar Compounds. E. A. WILDMAN (U.S. Pat. 1317551).-P-DzethyZ- aminoethyl 3-amino-p-toluate is obtained by reducing with tin alcohol and hydrochloric acid a t 35O the product of reaction of P-diethylaminoethyl alcohol (1 mol.) and 3-nitro-p-toluoyl chloride (1 mol.) removing the tin with hydrogen sulphide and precipitat- ing the oily ester with sodium carbonate. It forms a hydrochboride colourless crystals m. p. 157-158O. The dimethylltminoethyl ester (hydrochloride m. p. 139-140O) and various other alkamine esters of aminotoluic acids may be prepared similarly.They act as local amsthetics having but slight irritating or toxic action. CHEMICAL ABSTRACTS. Trimorphism of aZZoCinnarnic Acids. A. W'. K. DE JONG (Vers. Akad. Wetensch. Amsterdam 1919 27 1219-1231).-The residue obtained by evaporating a dilute solution of either of the allocinnamic acids m. p. 5 8 O and 68O yields the acid m. p. 42O at the ordinary temperature but this acid is never obtained when concentrat,ed solutions of the former two are used a t the ordinary temperature. Aqueous solutions of the acids m. p. 5 8 O and 68O yield only the acid m. p. 58O? at' -lo" but yield either of the acids a t - 1 6 O . Freezing experiments with special precautions to prevent inoculation by nuclei were also performed and the con- clusion is drawn that the three allocinnamic acids are trimorphous forms.CHEMICAL ABSTRACTS. Anaesthetic Alkamine Esters of Alkyloxyaminobenzoic [Aminoalkyloxybenzoic] Acids. E. A. WILDMAN (U.S. Pat. 1317250) .-These esters having properties similar t o those of the esters described above are prepared in an analogous manner. A minoethyl rn-aminoanisate is an oil which forms a h!pdrochloride m. p. 1 6 0 O . CHEMICAL ABSTRACTS. Salosalicylide and the Polymeric Salicylides . G. SCHROETER (Ber. 1919 52 [R] 2224-2237).-The salicylides which have hitherto been described hy Anschutz in particular t~hat obtained by crystallisation from chloroform show a varying molecular weight since cryoscopic determinations in phenol or nitrobenzene indicate the formula and ebullioscopic determinations in chloroform or nitrobenzene indicate (COH4<Xo>I ; the author now describes the preparation of a salicylide which undoubtedly has the constitution C,H < ~ o ~ ~ > C c H and is therefore analo- gous to the dianthranilide obtained by Schroeter and Eisleb (A.1909 i 575). The immediate cause of publication is the recentORGANIC CHEMISTRY. i. 163 communication of Anschiitz (this vol. i 48) on a new disalicylide which in many respects appears t o be identical with the author’s salosalicylide although slight discrepancies are shown in the m. p. of the two substances and of their derivatives. Salicylosalicylic acid in spite of t.he presence of the free phenolic hydroxy-group is smoothly converted by thionyl chloride into salicylosalicylyl chloride OH C,H,* CQ-0.C,H4* COCl m. p. 9 9 O which is converted in the usual manner into the corresponding an/ilzde long needles m. p. 160’5O p-phenetidide m. p. 1 5 4 O methyl ester m. p. 8 8 O and ylycine ester m. p. 90-91O; the latter substance is readily hydrolysed and on furt?her treatment with alkali yields salicylic and salicyluric acid or ethyl salicylwate OH*CGH,*CO*NH*CR,-CO,Et needles m. p. 8 8 O . Salosalicylide is most conveniently prepared by boiling salicylosalicylyl chloride dissolved in benzene with diethylaiiiline ; the dried crystalline pro- duct has m. p. 234O vhen rapidly heated but after crystallisation from nitrobenzene the rn. p. is constant a t 214-217° whilst from benzenel a product m. p. 204-208° is obtained the cause of these variations being unexplained.Cryoscopic and ebullioscopic deter- minations of the molecular weight in nitrobenzene and cryoscopic determinations in phenol show the substance t o have the formula A series of comparative experiments with salosalicylide and the so- called “ chloroform-salicylide ’’ (tetrasalicylide) is described in all of which the latter behaves as the more stable substance. Thus salo- salicylide is converted by boiling glacial acetic acid into salicylo- salicylic acid whilst “ cliloroEorm-salicylide ” remains unchanged. Similarly the f orner rapidly yields methyl salicylosalicylate with methyl-alcoholic hydrogen chloride whilst the latter is unaffected. Salicylosalicylanilide and salic-qlosalicyl-p-phenetidide are immedi- ately obtained from salosalicvlide and the recpisite amine whereas “ chloroform-salicylide ” can be boiled for hours with aniline without suffering alteration. Methyl alcohol containing sodium methoxide converts both salicylides into met<hyl salicylate.Concentrated sulphuric acid alone and also in the presence of nitrobenzene con- verts salicylosalicvlic acid salosalicylide and “ chlorof orm-sali- cylidei ” into salicylic acid ; if the action is rapidly interrupted it is found that the free’ acid is most rapidlv. the ‘‘ chloroform-salicylide ” least rapidly affected. Acetic anhydride and sulphuric acid con- vert salicylosalicylic acid into acetylsalicylosalicylic acid the same product being mainly formed from salosalicylide ; ‘( chloroform- salicylide,” however yields ncet!lltetmsalic?iZic a c z OAC*C~H,*CO*O*C,R~*CO.O*C,R,.CO*O*C6H,*C02H m. p. about 1 2 0 O . Concentrated nitric acid converts salosalicylide into nitrosalicylic acid ; under analogous conditions chloroform- salicylide is but little affected but nitration occurs wit.h a mixture of nitric and sulphuric acids nifrosalicyZZe ( NO;C,H3<x0) m. p. 265O being formed. Protracted action of nitric acid on “ chloroform-salicylidel” in the presence of nit.robenzene leads t o the formation of a nitrotetrasalicylic acid. C14H804.i. 164 ABSTRACTS OF CHEMICAL PAPERS. Nethyl tetmsalicylat e is obtained as an uncrystallisable viscouy yellow mass by the action of salicylosalicylyl chloride on the sodium compound ol methyl salicylosalicylate ; the possible conversion of the ester into a tetrasalicylide has not yet been fully studied.H. W. Phthalic Anhydride. 11. The Melting Point of Pure Phthalic Anhydride. The System Phthalic Anhydride- Phthalic Acid. I<. P. MONROE ( J . I i ~ d . E ' y . Chem. 1919 11 11 16-11 19).-Pure phthalic anhydride was prepared by subliming the product obtained by the oxidation of naphthalene in a vacuum apparatus in tho presence o€ phosphoric oxide. The melting point of the first and second sublimates agreed. estimated by a method of differential titration in which the sample was dissolved in acetone and the solution titrated with standard normal potassium phthalate wit.h bromophenol-blue (tetrabromo- phenolsulphonephthalein) as indicator. The sublimed preparations contained less than 0.1% of phthalic acid. The melting point was determined in a double-walled glass vessel immersed in a bath of sulphuric acid and after fusion the temperature was gradually lowered t o the point of incipient crystallisation.The e,quilibrium point of crystals and liquid was 130.84O. Mixtures of phthalic anhydride and acid tested in the same apparatus gave a eutectic temperature of 129'74O. By graphical interpolation the melting point of pure phthalic acid was indicated to be 2 0 8 O + 3 O . [See further J . SOC. Chem. Id. 1920 5 7 ~ . ] Phthalic Anhydride. 111. The System Naphthalene- Phthalic Anhydride. I<. P. MONROE (J. I n d . Eng. Chem. 1919 1 1 11 19-1 120) .-The freezing points of mixtures of pure naphthalene and phthalic anhydride were determined by tho method previously described (preceding abstract) the eutectic point (26.9O) corresponding with 29.0% of phthalic anhydride.There was no evidence of the existence of solid solutions. The freezing points on the phthalic anhydride curve were calculated by means of the formula C= ( - T,,T logloz)/At where C is a constant x the mol. fraction of anhydride in the mixture T the freezing point of pure phthalic anhydride T the freezing point. of the mix- ture and 4t=T0-1". The calculated values of C in this equation based on the experimental values of T averaged 1199. And since L=RC/O*4343 where L represents t.he molar heat of fusion of naphthalene (4560 cal.) and R the gas constant (1.9852 cal. per degree) the molar heat of fusion of phthalic anhydride=5480 cal. Phthalic acidwas C.A. M. C. A. M. Phloroacetophenone. KIEMUD BEHARI SEN and PRAPHULLA CHANDRA GHOSH (T. 1920! 117 61-63). Reactivity of Diphenylketen with the Nitrile Group. ADOLFO GONZ~LEZ (il72al. Fis. Quim. 1919 17 130-135).- Dipheiiyllreteii was mixed in sealed exhausted tubes with variousORGANIC CHEMISTRY. i. 165 substances containing the group *CiN. After remaining for twenty-four or forty-eight hours a t 30° or 60° the contents of the tubes were dissolved in aqueous ether. The ether then evaporated and the residue dissolved in alcohol. This solution of diphenyl- acetic acid formed by the action of the water on the residual diphenylketen was titrated with barium hydroxide solution. The nitriles of acetic benzoic and toluic acids showed only a feeble reaction with diphenylketen in the order named. Experiments with cinnamonitrile ethylcarbamine dimethylcyanamide and diethylcyanamide showed that these substances also reacted to a small extent only.With cyanogen bromide a dense liquid was obtained after evaporation of the excess of cyanogen bromide which yielded a yellow polymerisation product of diphenylketen. ydrogen cyanide and cyanogen itself did not react with diphenyl- keten. W. S. M. Some New Bicycliz Ketones. MARCEL CODCHOT and F~ZLTX TABOURY (Compt. rend. 1919 169 1168-1171).-Using the method previously described (A. 1919 i 447) with calcium hydride the authors have prepared the following bicyclic ketones. 41-Methyl-l 1~-cyclohexyZidene-3-methylcyclohexan-6-one b. p. 185O/50 mm. D16 0-9659 12.2 1.4968 gives an oxime m.p. 155O and on reduction with hydrogen in the presence of platinum using Vavon’s method gives p-methylcyclohex~l-3-methylcyclo- hexan-6-one C7HI3*C7HI10 b. p. 170-175°/50 mm. D24 0.947 rbz 1.4852 yielding an oxime m. p. 123-124O. 2’-Met h y Z- 1 l~-cyclohexyZidene-3-cyclohexan-2-one >CH CH *CHMe>C,CcCO*CHMe CH,<CH:-CH2 CH,-CH b. p. 175O/40 mm. D12 0.9926 n:” 1.500 gives an oxime b. p. 160-165°/20 mm. and a semicarbazone m. p. 177-178O. On reduction by Vavon’s method it yields 2’-methyl-1 l~-cyclohexyZ-3- methyZcyclohexan-2-me b. p. 166-16g0/35 mm. D12 0.9748 rtg 1.4974 giving an oxime difficult t o purify. Either of them ketones when reduced by sodium in absolute alcohol yields 2~-methyZcyclohexyZ-3-meth~Zcyclohexan-2-oZ b. p. 165-168O1 40 mm.D13 0.973 n’,” 1.5034 giving an aZZ,ophanatc m. p. 223O. 21 41-DimethyZ-1 l~-cyclohexylidene-3 5-dimethylcyclohexan-2- 185O/40 mm. D190-956 hg 1.493 gi;es an oxime an oil and when re’duced by sodium in absolute alcohol yields 21 4~-cZimethyLl 1’- cyclohex?/Z-3 5-dime t h yZcyclohexan-2-0 I b. p. 188-1 9 lo I 40 mm . D16 0.945 n’,” 1.496 giving.an allophanate m. p. 232O. W. G. The Constitution of D ypnopinacone and its Derivatives. MAURICE DELACRE (Ann. Chim. 1919 [ix] 12 150-178. Compare A. 1914 i 1068; 1916 i 679).-This paper which should really VOL. CXV.UI. i. 9i. 166 ABSTRACTS OR' UHEMICAL PAPERS. precede the theoretical paper previously published (cornpare A . 1918 i 539) deals with the inter-relationship and preparation of the isomeric homodypnopinacones and homodypnopinacolins and their transformations. It is an elaboration of work previously published (oompare A.1896 i 591 662). W. G . Chlorothiolanthraquinones. K. FRIES and G. SCH~RMANN (Ber. 1919 52 [B] 2170-2181).-A continuation of previous work (A. 1912 i 1005). Derivatzves of 2-Thiolanthrapuinone [with K Ross].-2-Amino- anthraquinone is diazotised in concentrated sulphuric acid solution and the diazonium sulphate is converted by potassium ethyl xanthate into ethyl 2-anthrap~inonylxanthate~ yellow needles m. p. 151° from which 2-thiolanthraquinone (Gattermann A. 1912 i 998) is obtained by the action of alcoholic potassium hydroxide solution. 2-Chlorothiolanthraguinone7 yellow prismatic crystals m. p. 136O is obtained by chlorination of the corresponding thiol or disulphide in chloroform solution and is a highly reactive sub- stance ; with alcoholic potassium hydroxide solution it appears to yield a solution of potassium 2-anthraquinouesulphenate but the corresponding acid could not be isolated.When boiled with acetone it gives 2-acetonyZthiolanthraquinone C,H,<CU>C,H co 8* 8*CH COMe yellow prisms m. p. 165O whilst with aniline in benzene or chloro- form solution it forms 2-anilinothiolanthraquinone orange needles m. p. 171O. When a solution of the chlarothiol in chloroform is shaken with water i t gives 2-ai~tZ~rayz~inosulphernic anhydride small colourless cryst'als m. p. 260° (decomp.) which is also produced when the chloride is boiled with alcohol Derivatives of l-ThioZanthrapuinone.-Di-l-anthraquinonyl disul- phide (compare Gattermann Zoc.cat .) is most conveniently prepared by treatment of an alcoholic3 solution of l-chloroanthraquinone with aqueous sodium disulphide and is transformed into the correspond- ing thiol by the action of dextrose and sodium hydroxide. l-Bromothiolanthraquinonel reacts readily with ammonia aniline and dimethylaniline respectively yielding the correspond- ing amide orange needles which do not melt below 300° and are converted by boiling acetic acid into perd-anthraquinone-1 9-thi- azole (Gattermann Zoc. cit.) anilide shining red needles m. p. 210° and p-dimethylaminophenyE derivative red needles m. p. 285O. With ethyl sodioacetoacetate 1-bromothiolanthraquinone yields the compound C,H,<~~>C,H,*S*CH (C0,E t ) SCOMe yellow needles m.p. 163O which when boiled with mineral acid passes into the mbstance (I) yellow prismatic crystals m. p. 175O. Similar ring formation occurs when an alkali salt of l-thiolanthrztr quinone is treated with w-chloro-p-hydroxyacetophenone the pro-ORGAN10 CHEMISTRY. i. 167 duct (11) crystallising in golden leaflets m. p. 258O and yielding a red sodium salt. On the other hand sodium l-anthraquinone- COMe CO- C,H4*OH C-S C-S I I Q b (1.1 (TI.) sulphenate reacts normally with p- and o-nitrobenzyl chlorides yielding 1 -anthrapuinonyl p-nitrobenzyl szllphide orange leaflets m. p. 2 4 3 O and 1-anthraquinonyl o-nitrobenzyl sulphade orange needles m. p. 2 5 1 O ; attempts to eliminate water from these com- pc;unds with the formation of a thiophen ring w0re unsuccessful. Resorcinol and 1-bromothiolanthraquinone gave l-unthrapuinmnyl 4-resorcyl sulphide orange needles m.p. 2 3 P . 1-Anthraquinonyl phenyl sulphide m. p. 185O is formed by the action of benzene on 1-chlorothiolanthraquinone in the presence of aluminium chloride and is identical with the product obtained by Gattermann (loc. c i t . ) from a-nitroanthraquinone and phenyl mercaptan. The action of ethyl sulphate on an aqueous-alcoholic solution of sodium anthraquinonesulphenate leads to the formation of 1 -cantha- puinonyl ethyl sulphoxide yellow needles m. p. 180° (decomp.) the constitution of which follows from its conversion by acetic and hydrobromic acids into 1-anthraquinonyl et.hyl sulphide m. p. 183O (Gattermann Zoc. c i t . ) ; on the other hand the free acid when sus- pended in alcohol and treated with ethyl sulphate is transformed into the corresponding ethyl ester m.p. 149O (Fries loc. c i t . ) . H. W. 4-Aminoanthraquinone-1 -sulphenic Acid. K. FRIES and G . SCHURMANN (Ber. 1919 52 [ B ] 2182-2195).-The only sul- phenic acid which has hitherto been isolated in the pure condition is 1-anthraquinoaesulphenic acid (Fries A. 1912 i 1005); in their endeavour t o isolate further examples of this class of substance the authors now describe attempts to prepare the corresponding 4-hydroxy- 4-methoxy- and 4-amino-compounds which however are not entirely successful. 4-Bromo-l-hydroxyanthraqzcinone coarse orange-yellow needles m. p. 197O is prepared by the action of bromine on a hot solution of 1-hydroxyanthraquinone in glacial acetic acid in the presence of sodium acetate.(It forms a red sodium salt which is sparingly soluble in water.) Under similar conditions but with double the amount of bromine 2 4-dibromo-1- hydroxyanthraquinone orange needles m. p. 235O is produced. 4 4’-Dihydroxydi-l-anthraquina onyl disulphide reddish-brown flat prisms m. p. above 300° (com- pare Gattermam A. 1912 i 998) is conveniently prepared by the V 2i. 168 ABSTRACTS OF CHEMICAL PAPERS. action of an aqueous solution of sodium disulphide on 1-bromo4- hydroxyanthraquinone dissolved in alcohol and is reduced by dex- trose to 4-hydrozy-l-thiolanthrayuinone red needles m. p. 1 9 4 O (methyl thics-ether shining red leaflets m. p. 2 1 7 O whereas Gatter- mann (loc. czt.) records 1 9 4 O ; sulphoxade of methyl thio-ether orangereddish leaflets m.p. 226O). Bi-4-hydroxy-1-anthraquinonyl monosulphide crystallises in red intertwined needles m. p. above 300° whilst t.he corresponding sulphoxide forms slender yellow needles m. p. 287O. Di-4-hydroxy-1-anthraquinonyl disulphde is oxidised by hydrogen peroxide in sulphuric acid solution to 4-liydroxyanthraquinone-1-sulphowic acid yellowish-brown needles in. p. 220° (the sodium and ammonium salts are sparingly soluble in cold water and crystallise in reddish-brown leaflets with metallic glance) and by nitric acid to 3-nitro-4-hydroxyanthraguinone-l-sul- phonic acid yellow rhombic prisms m. p. 2 7 8 O after darkening above 255O (the sodium ammonium and potassium salts dissolve sparingly in cold water and form shining yellow leaflets).4-Zydr- oxyanthrapuinone-1-sulphonyl chloride golden-yellow leaflets m. p. 2 4 6 O is obtained in place of the expeoted chlorothiol when a suspension of the disulphide in chloroform or glacial acetic acid is treated with chlorine; the corresponding ardide forms shining yellow needles m. p. 199O. l-Bromo-4-methoxyanthraquinone pale yellow needles m. p. 195O is obtained by methylation of the hydroxy-compound with methyl sulpha'te and is converted by sodium disulphide into di-4- methoxy-1-anthraquinonyl disulphide yellow needles m. p. 285' (compare Gattermann loc. cit.); the latter is not attacked by bromine and is transformed by chlorine into a sulphonic chloride which was not further investigated ; 4-methoxy-l-anthraquinongl methyl sulphide orange-red needles m.p. 1 8 7 O is prepared by reduction of the disulphide followed by methylation of the thiol SO produced. Di-4-amino-1-anthraquinonyl disulphide m. p. above 300° (com- pare Gathrmann loc. c k ) is conveniently prepared from 4-cbloro- 1 -aminoanthraquinone and sodium disulphide and is readily reduced t o the corresponding thiol .which could not be isolated owing to its unusual susceptibility to oxidation. It is transformed by chlorine into 3 - chLoro - 4 - aminoanthrapuinone-1-sulphonyl chloride orange-red needles m. p. 230° when rapidly heated after darkening above 2 0 0 O ; the corresponding aczd forms slender orange-yellow needles m. p. (anhydrous) 2 1 7 O (decomp.) (the ammonium salt forms red needles m. p. about 304O whilst the anilide coarse brownish-red crystals has m.p. 2 1 0 O ) . The sulphonic group is displaced by bromine with formation of 3-chloro-l-bromo-4-aminounthraquinone m. p. 2 1 7 O . 4-Amino-1 -chlorothiolanthraquinone is obtained in an impure condition by the action of bromine on aminoanthraquinonyl disul- phide or preferably by the reduction of aminoanthraquinonesul- phinio acid by hydrobromic and acetic acids; it is thus obtained as an unstable hydrobromide orange-yellow needles which decomposeORQANIC CHEMISTRY. i. 169 above 200O; mineral acid is removed by contact with alcohol or aqueous acetic acid but the free amino-compound is too unstable to be isolated. The nature of the hydrobromide is established by the formation from i t of the sulphonanilide coarse reddish-violet needles m.p. 180° (decomp.) and of 4-amino-1-anthraquinonyl resorcyl sulphide brownish-violet leaflets m. p. 247O. Potassium 4-aminoant hraquinone-1-sulphenat e dark green needles with met,allic glance is prepared from the bromothiol but attempts to isolate the pure sulphenic acid failed; the constitution of the salt however is established bv its conversion into 4-a?nino- anthraquinonyl methyl szclphozide slender red needles m. p. 234O which is reduced by hydrobromic and glacial acetic acids to 4-amino- anthraquinonyl methyl sulphide m. p. 210° (compare Gattermann loc. cit.) and by its oxidation to 4-aminoanthrapuinonesulphinic acid red needles m. p. 191O (decomp.) which forms a sparingly soluble potassium salt. H. W. Certain Metallic Derivatives of Hydroxyanthraquinones .M. L. CROSSLEY ( J . ,4iner. Chem. Soc. 1919 41 2081-2083).- Hydroxyanthraquinones such as alizarin anthrapurpurin and flavopurpurin form copper cadmium nickel and iron salts when boiled in an organic solvent with the corresponding metallic chlorides anhydrous sodium acetate and nitrobenzene. Covnper cadmium niclcel iron cobalt and cliromium salts of alizarin have been prepared having the general formula C,,H,04M except in the case of the cobalt salt which has C,,H,IO,,Co. The copper and nickel salts of anthrapurpurin and flavopurpurin were also prepared. These alizarin salts dye wool a pale shade of the colour which alizarin gives on wool previously mordanted with the corresponding metallic salt. W. G. Oxidative Formation of Hydroxydianthraquinon~ls from Hydroxyanthraquinones .11. Experiments with Erythro- hydroxyanthraquinone and Quinizarin. R . SCHOLL E. SCHWINGER and 0. DISCRENDORFER (Ber. 1919 52 [I?] 2254-2261).-The formation of tetrahydroxydianthraquinonyl by the action of hypochlorite on an alkaline solution of alizarin (this vol. i 64) does not appear to be an example of a general reaction. Further examples however are indicated in the patent literature in the cases of erythrohvdroxyanthraquinone and quinizarin. According to D.R.-P 167461 erythrohydroxyanthraquinone when melted with potassium hydroxide yields the hydro-compound of a substance C28H1406 of unexplained con- 0 OH 1 stitution; this is now shown t o be 1 lf-di- I,,.,\, 1 hydroxy-2 2'-dianthraquinonyl (annexed for- mixla) since when distilled with zinc dust.in a I ' I I- hydrogen vacuum it gives 2:2/-dianthryl and !\e/\/ I when heated in carbon dioxide a t 5000 i t gives yellow needles. The product appear8 to be L 0 2 Z'-dknthraquinon?/lene-l If-oxide greenish-1. 170 ABSTRACWS OF OEEMICBL PAPERS. formed by the action of air on the aqueous solutioh of the melted mass and not during the process of melting. Quinizarin according to D.R.-P. 146223 is converted by salts of weak acids into two compounds C28H,,08 and C28H1808 the first of whit& is described as giving a soluble blue sodium salt whilst the latter yields a bluish-violet insoluble sodium salt. It is now shown that only the acid which forms an insoluble sodium salt is a new substance and that i t has the composition C”,H1408 whilst the other product is a mixture of this acid with quinizarin.The substance is now shown to be 1 4 1’ 4I-tetr-c~- OH /\)‘ / -/\/‘ /\ Aydroxy- 2 21 - diuntl~rayuinon,y/I I \1 I I I 1 (annexed formula) since it gives b/\/ ‘ /\/\/ 2 2/-dianthryl when distilled with zinc dust and a furan derivative when melted with zinc chloride. A. G. Perkin and W. H. Perkin (T. 1888 53 831) have described the isolation of three substances CneHJ40e C28H140 and C,,H8O4 by the diatillation of sodium anthraquinone-2-sulphonate ; the first of these has been submitted t o distillation with zinc dust whereby anthracene and 2 2’-dianthryl are obtained but the result does not throw any definite light on the constitution of the substance. H. W. OH 0 6 OH O H 8 Isomeric Carvomenthols and Scission of Inactive Carvomenthol into the Optical Antipodes.I. and 11. VINCENZO PAOLINI ( A t t i R . A c e d . Ltincei 1919 [v] 28 ii 82-85 134-137).-The author prepares pure inactive carvomenthol by reducing carvone by means of zinc dust and sodium hydroxide transforming the dihydrocarvone thus obtained into the isomeric carvenone by heating i t with dilute sulphuric acid and reducing the carvenone by means of sodium and alcohol. From this inactive carvoment.ho1 the laevo-isomaride may be isolated by crystallisation of the less soluble of the two carvomenthol strychnine phthalates and conversion of this into I-carvomenthol hydrogen phthalate and the latter into Lcarvomenthol. The carvomenthol hydrogen phthalate prepared from the mother liquors of the above strychnine salt is syrupy but when treated with the calculated proportion of ammonia and with silver nitrate it yields insoluble silver d-carvo- menthol phthalate and from this by way of sodium d-carvomenthol phthalate and d-carvomenthol hydrogen phDhalate d-carvomenthol may be isolated.forms colourless needles m. p. 155-156O [aID - 1 4 . 7 6 O (in alcohol). 1-Carvomenthol hydrogen phtltalate CO,H*CoH,*CO2*C,,H1~ forms crystals m. p. 1 2 5 O ral -3.800 (in alcohol). 1-Caruomenthd C,,R,,~OH forms an oily limpid liquid with ti faint d o u r of peppermint b. p. 2 1 8 O (corr.) D15 0.9982 nb5 1.461 1-Cawomenthol strychnine phithalate C,,R,,*CO,*C,H,*CO,*C21R,O,N [&ID -1‘82*.ORGANIU CHEMISTRY. i. 171 SiZuer d-carvomenthol phthalate is obtained a.s a voluminous white precipitate and may be purified by crystallisation from abso- lute alcohol or by precipitation from chloroform solution by addi- tion of alcohol and ether.d-Carvomenthol hydrogen phthalate forms slender colourless needles m. p. logo [a] + 4 - 6 2 O (in alcohol). d-Carvomenthol has b. p. 2 1 8 O (corr.) D15 0.9074 7tV 1,463 [a] +1*83O. T. H. P. Reduction Products of Pulegone Pulegol. I. and 11. V. PAOLINI (Atti R . Accad. Lincei 1919 [v] 28 ii 190-192 236-239).-Pulegol (compare Tiemann and Schmidt A. 1897 i 198) which previously has not been obtained free from menthol has been prepared pure by the author. The products formed by reducing pulegone by means of sodium and alcohol contain about 30% of a yellow resin C,H,O which appears to be identical with the bispulegone obtained by reducing pulegone with aluminium amalgam (compare Harries and Roeder A.1900 i 183) and is of unknown constitution although it is evidently a mixture of optical isomerides possibly of ketonio (pinacone) character. The mixture of alcoholic compounds separated from the reduction products of pulegone by distillation in a current of steam was esterified in the cold with phthalic anhydride (compare A. 1911 i 730) the various hydrogen phthalates thus formed being separated by cryst allisation and converted into the corresponding alcohols. In this way Lmenthol of peppermint oil a solid d-menthol and Z-pulegol were isolated. 1-Menthol hydrogen pht halate CO,H*C,H,*CO,*C,,H1 forms tufts of soft white needles m. p. 107-108° [alD - 1 0 7 ~ 5 ~ .The corresponding I-menthol is a crystalline solid m. p. 44O b. p. 214O (corr.) [a] - 49.7O. forms soft white needles m. p. 157-158O [a] -44.46O. d-Menthol strychnine hydrogen phthalate forms crystals m. p. 207-208O [aID - 11.7°. d-Menthol hydrogen phthalate forms crystals m. p. 107-108° [.ID +18-4O. d-Menthol C,,;R2,0 is a solid and has m. p. 88-89O b. p. 2 1 4 O and [a]? +21*8O; it is a saturated compound and is possibly identical with the a-pulego- menthol obtained by Haller and Martine (A. 1905 i 533) by reducing pulegone by Sabatier’s method. Pzdegol hydroqen phthalate Clc,HlaO crystallises in slender white needles m. p. 2120 [a] - 8 6 - 8 O . 1-Pulegol forms slender white needles with a faint d o u r of menthol m. p. 46-47O [a] -54*6O; it is an unsaturated compound and readily decolorises permanganate and bromine solution the bromide Cl,Hl,OBr~ being a dense colourless oily liquid.I-Menthol strychnine phthalate CO,H*C,H co c ,,HI 9,C21H2202N2 T. a. P. Transpositions in the Camphene Series. G. LANULOIS (Ann. Chim. 1919 [ix] 12 193-264).-1n the first part of thei. 172 ABSTRACTS OF CHEMICAL PAPERS. paper a brief r6sum6 is given of the chemistry of camphene and its derivativw. A closer study has been made of halogenation in this series and the constitutdon of the monochloroi and monobromo- derivatives of camphene has been established and a new method of synthesis for the intmduction of carbon containing substituents into the side-chain has been found. A general outline of the work is given and the experimental work is to be published later.A new method of nomenclature is advocated for the camphene series based on the hypothetical camphenylane (formula I) and the hypothetical radicles camphenylene (formula 11) and camphenylidene (formula 111). 3 4 6 I I I CH2-CH-CH CH,-~H-CH CH,-CH-C= 2 1 8 I (1- 1 11. 1 I n this system camphene becomes camphenylidene6-metohane. W. G . Chemical Investigation of Various Natural Lacquers. RIKO MAJIMA ( J . Tokyo Chem. SOC. 1919 40 91-126. Compare A. 1908 i 437; 1909 i 402 945; 1912 i 883).-Chinese lacquer (from Rhus vermkifera Dc.) is essentially the same as Japanese lacquer; both contain uruFhiol. Yunan lacquer (from R. succe- danea L. fils) Formosan lacquer (from Semecarpus vernicifera) and Ivy lacquer (from R. tozicodendrm 1 ) contain Zaccol C,,H,O a homologue of urushiol.HydroZaccoZ C,,H,*C,R,(OH) [2 31 m. p. 63-64O forms a dimethyl ether m. p. 43-44O a monon,itro- derivative m. p. 75-76O and dinitro-derivative m. p. 86-87O. Burmese lacquer contains t hitsiol C,,'R,O,. m. p. 94-96O forms a dimethyl ether m. p. 56-57O and mono- nitro-derivative m. p. 75-76O ; the dinitro-derivative is difficult to prepare. Hydrothitsiol is therefore very similar to isohydro- urushiol and probably belongs to the same group. Unlike urushiol and laccol thitsiol contains a group which is hydrogenated or ozonised only with difficulty. Siam lacquer is probably a mixture of Yunan and Burmese lacquers. Korean lacquer is assumed to be identical with Japanese lacquer. Hydrothitsiol C,~H~,.C,H,(OH) r3 41 CHEMI CAL AB s TRACT s .Bromination and Constitution of Caoutchouc. W. C. SCHMITZ (Gummi Zeit. 1919 34 167-169 193-195).-Purified rubber which has been (' depolgmerised " by heating with xylene under a pressure of 15 atmospheres forms an additive compound C20H32Brlo when brominated in carbon tetrachloride ; this product gradually eliminates hydrogen bromide with formation of a micro- crystalline compound C2,H,,Br8 which is insoluble in carbon tetra-ORGANIC CHEMISTRY. i. 173 chloride and is quite distinct from the ordinary " caoutchouc tetra- bromide." The decabromide is probably an open-chain compound and i t is uncertain whether the disruption of the cyclic caoutchouc molecule occurs during bromination or in the previous depoly- merisation. I n the bromination of solutions of ordinary rubber the chemical process is complicated by colloidal phenomena which are absent in the case of the depolymerised hydrocarbon. [See also J.soc. Chem. Id. 1920 7 3 ~ . ] D. F. T. Preparation of Double Compounds of Caffeine with Alkali Salts of Acetylsalicylic [o-Acetoxybenzoic] Acid. CHEMISCHE FABRIK J. A. WULFING (Brit. Pat. 136187). -0-Acetoxybenzoic acid (2 mols.) an alkali carbonate (1 mol.) and caffeine (1 mol.) are homogeneously mixed and the mixture is moistened with an alcohol ester ketone or chlorinated hydrocarbon of the aliphatic series t o the consistency of a viscous paste which is kneaded until a sample dissolves in water to a clear solution with- out the liberation of carbon dioxide. The solvent is then removed by evaporation a t a low temperature and the product consisting of the o-acetoxybenzoate of caffeine and the alkali metal is finally dried in a vacuum.G. F. M. Syntheses in the Cinchona Series. 11. Quaternary Salts. WALTER A. JACOBS and MICHAEL HEIDELBERGER ( J . Amer. Chem. SOC. 1919 41 2090-2120).-The authors have prepared a number of quaternary salts from the different cinchona alkaloids with a view to a study of their bactericidal or more specifically pneumo- cwcidal powers. The methochlorides the benzyl chlorides and the salts formed with the chloroacetyl derivatives of ammonia the lower aliphatic amines and benzylamine have been prepared. I n the case of the chloroacetyl derivatives of the aromatic amines the new series of salts with the alkaloids were only sparingly soluble in cold water the other salts named above being in general fairly readily soluble. Solutions of all of the salts aliphatic or aromatic gave immediate precipitates with solutions of picric acid or potassium dichromate.The quaternary salts of the alkaloids with the chloroacetyl deriv- atives of the aliphatic and aromatic amines were prepared by boil- ing equimolecular amounts of the components in dry acetone for five to seven hours. Cinchonine gives a methochloride decomposing a t 270° +225*lo; a benzylochloride m. p. 280' (decomp.) ra]g +164-8O; an iodoacetamide decomposing a t about 190°; a chloro- acetamide m. p. 110-120' (decomp.) [a] + 174'2O. Cinchonidine gives a methochloride m. p. 232-233' (decomp.) [a]g -142-7O; a chloroacetamide m. p. about 190° [u3g5 -112.5'. Quinine gives a methochloride m.p. 196-198O [alp -211.7'; a benzylochloride m. p. 183-188O [a] - 230'5O ; an iodoacetamide m. p. 175-180° ralEi-152-20; a chloroacetamide m. p. 190' (decomp.) [a] - 159~6~; a chloroacetanilide m. p. 224-225O The following sahs are described. !?*i. 174 ABSTRACTS OF CHEMICAL PAPERS. (decomp.) [u]:" - 1 3 1 ~ 5 ~ (in alcohol) giving a hydrochloride m. p. 204-206O (decomp.) and a nitrate m. p. 201-203O (decomp.); quinine-p-chloroacet ylaminophenol C2,H2~02N2,CH2C1*CO*NH*C,H4*OH m . p . 205 O (decomp . ) quinine-o- c hloroace t ylaminob enzamide C,H2,0,N,,CH,C1~Co*NH*C6H4*C0.NH m. p. 178-179O (decomp.) [a]! - 164.4O (in alcohol). Quinidine gives a methochloride m. p. 250-251O (decornp.) [a] +253*l0; a benzylochloride m.p. 180° (decomp.) + 219.9O; an iodoacetamide m. p. 190° (decomp.) [a]:"" + 166.2O (in alcohol) ; a chloroacetamide m. p. 205O (decomp.) [a]g + 207'2O; an iodoacetylcarbamide in. p. 170-175O (decomp.) and a chloro- acetylcarbamide m. p. 176-178O (decornp.) [ u ] T 5 + 170*9?. Hydroquinine gives a met.hiodide m. p. 233-235O (decomp.) - 1 0 7 ~ 6 ~ (in alcohol); a methochloride m. p. 172-173O (decornp.) [aK5 - 162-9O; a benzylochloride m. p. 202-203-5O (decomp.) [aF -196.9O; an iodoacetamide m. p. 185O -121.5O (in alcohol); a chloroacetamide m. p . 195O (decomp.) [a] - 1 2 9 ~ 1 ~ ; a chloroacetomethylamide C2,H2,02N2,CH,Cl*CO*NHMe m. p. 160O; a chloroacetoethylamide m. p. 160O; a chloroacetdi- methylamide ; a chloroacetodiethylamide m. p. 209-210° (decomp.) [u]E'~ - 84.8O; a chloroacetobenzylamide C20H2602N,,CH,C1*CO*NH CH,Ph m.p. 197-19B0 [a]2,3-42*5O; a chloroacetanilide m. p. 210° (decomp.) [a]g - 95.9O (in alcohol) giving a hydrochloride and a dinztrate ; a m-nitrochlocoacetanilide m. p. 195-200° (decomp.) ; a m-chZoroacetylaminoacetanilide m. p. 150° (decomp.) ; a p-chloro- ace t y laminoac e t anilide m . p . 205O ; a p- chl oroac e t y laminodim e t h yl- aniline C,,H,,O,N,,CH,Cl*CO*NH*C~H**NMe m. p. 200° (decornp.) - 82.9O (in alcohol) ; a p-chloroacetylaminodiethyl- aniline m. p. 190-195O [a]EO -80.5O (in alcohol); an o-chloro- acetylaminophenol m. p. 185O (decomp.) ; a m-chloroacetylamino- phenol m. p . 205O [a];; - 1 1 5 ~ 7 ~ (in alcohol) giving a hydro- chl d e m. p . 200° ; hydro quinine-p - ch Zoroa ce t y lamino phenol hydrochloride m. p.196-197O; hydroqu/inine4-~hloroacetylamino- cat e c hol hydrochloride C,,H~O,N,,CH,Cl* CO-NH*C,H,( OH),,HCl m . p . 19 6-1 98O (decomp. ) ; hydroq zcininechloroac e t y 1-o-anisidine m.. p. 185O [a3i2 - 72-5O (in alcohol) ; hydropuininechloroacetyl-m- anzszdine m. p. 190° [a] -102'9O (in alcohol) giving a hydro- chloride m. p. 170-171O; hydroquininechloroacetyl-p-anisidine m. p. 190° [a] -93.9O (in alcohol) giving a hydrochloride m. p. 180-184O ; hydroquininechloroacetyl - o - phenetidine m. p. 170-1 72O ; hydro puininech Zoroacetyl-m-phenetidine hydrochloride m. p. 173-174O; hydroquinin.echZoroacetyl-p-phenetk?ine m.. p. 210° [U]E'~ - 89. lo (in alcohol) ; hydroquinine-4-ch,loroacety~amzno- gtlaiacol C,oH,02N2,C6H,(OH)(OMe).NR.CO*CH2Cl m.p. 2 1 5 O (decomp .) ; hydropuznzne-3 4-met hylenedioxychloroacetanilide C,H,,0,N2,CH,0,:C,H,*NH*C0 CH,C1,ORGANIC CHEMISTRY. i. 176 m. p. 185O; hydropuinine-3 4-dimethoxychloroacetanilide m. p. 2 05-2 I Oo (dmom p . ) ; hydro qwinin e-m - chl or oacet y lamino b em ent- sulphonamide C2,H,,I),N2,CH2C1*CO*NH*C,H,*S0,~NHz m. p. 200-205° (decomp.). Hydroquinidine gives an iodoacetamide ; a chloroacetamide m. p. 210° (decomp.) [a12 + 179'9O; hydroquinidine-p-chloroacetylamino- phenol m. p. 285O giving a hydrochloride m. p. 245-250° (decom p . ) ; h ydr oquinidin e c h lor oace t y l-p-anisidin e m . p . 2 60-2 65O (decomp.) giving a hydrochloride m. p. 196-200° (decornp.). Hydrocupreine gives a chloroacetarvitide hydrochloride m. p. 213-214O (decomp.) and a chloroacetyl-p-anisidine hydrochloride m.p. 210° (decomp.). Ethylhydrocupreine gives a methochtoride m. p. 198-199O [u]y -176*7O and iodoacetamide m. p. 185O [u] -115'4O (in alcohol) ; a chloroacetamide m. p. 195O - 114.8O; a p-chlwo- acetylaminophenol m. p. 178-182O [u]g - 71.8O (in alcohol) giving a hydrochloride m. p. 196-197O ; ethylhydrocupreinechlmo- acetyZ-p-anisdine m. p. 200° [a] - 69*0° (in alcohol) giving a hydrochloride m. p. 204-205O (decomp.) ; ethylhydrocupreine- chtoroacetyl-p-phenetidine m. p. 210° (decornp.) [u]:'~ - 75.25O (in alcohol) giving a hydrochloride m. p. 2 0 8 O (decomp.). Most of the melting points given above are only approximate as the substances turn to jellies long before they become fluid. W. G. Synthesis in the Cinchona Series.111. Azo-dyes derived from Hydrocupreine and Hydrocupreidine. MICHAEL HEIDELBERGER and WALTER A. JACOBS ( J . Amer. Chem. Soc. 1919 41 2131-2147).-Both hydrocuprehe and hydrocupreidine behave in a normal manner as phenolic compounds and yield well-defined azo-dyes with diazotised aromatic amines and the authors assume that position 5 in the quinoline nucleus is the place of entrance of the azo-group (compare Giemsa and Halberkann A. 1919 i 342). In general the benzeneazo- and tolueneazo-dyes as well aa those with m-substituents in the benzene ring dye silk various shades of orange. 0- and p-Alkoxy-groups deepen these colours towards the red whilst the dyes from the naphthylamines dye silk a deep rose colour. These substances have the property of dyeing unmordanted cotton.Many of the substances described below are highly bactericidal in vitro. The following azo-dyes have been prepared Benzeneazohydrocupreine m. p. 1300 giving a dihydrochloride m. p. 181-183O (decornp.) ; o-tolueneazohydrocupreine m. p. 110-130° (decornp.) ; rn-tolueneazohydrocupreine m. p. 125-130° giving a dihydrochloride m. p. 195O (decornp.) ; p-toluencazohydro- cupreine m. p. 202-205O ; ccnaphthaleneazohydrocupreine m. p. 14 6-1 49O (decom p.) ; P-naph t haleneazo hy dr ocupr tine m. p. 240-244O (decornp.) ; &benzene-p- bisazohydrocupreine m. p. 204O (decornp.) ; m-nitro b enzeneazohydrocupreine m. p. 150.5-151'5° ; p-nitrobenzeneazohydrocupreine m. p. 220° (decomp.) ; m-acetyh g* 2i. 176 ABSTRACTS OF CHEMICAL PAPERS. uminobenzeneazohydrocupreine m.p. 155-180° ; m-carbamido- benzeneazohydrocupreine m. p. 165-185O (decomp,) ; p-amino- bcnzeneazohydrocupreine m. p. 155-165O ; . p-acetylaminobenzene- uzohydrocupreine m. p. 158-1 62O (decomp.) ; p-carbamidobenzene- azohydrocupreine decomposing a t 1 90° ; p-hydroxybenzeneazohydro- cupreine m. p. 150-160° * (decomp.) ; p-benzoyloxybenzeneazo- Jhydrocupreine dihydrochloride m. p. 185-195O (decomp.) ; 2-methoxy b enzeneazo hydrocupreine m. p. 1 20O ; 3-met hoxy b enzene- nzohydrocupreine M. p. 188-190° ; 4-methoxybenzeneazohydro- cupreine m. p. 213-215O (decomp.) ; 2-ethoxybenzeneazohydro- cupreine m. p. 135-140°; 3-ethoxybenzeneazohydrocupreine m. p . 90-125O ; 4ethoxybenzeneazohydrocupreine m. p. 156-161O ; 3 4-methylenedioxybenzeneazohydrocupreine m.p. 177-184O ; 3 4-vdlmethoxybenzenjeazohydrocupreine m. p. 1 1 0 O ; 3-methoxy-4- e f Ii oxy b en z e n eaz o hy drocupr e ine m. 4-met h ox y-5 - cthoxybenzeneazohydrocupreine m. p. 75-120O; 3 4-dimethoxy-6- carboxybenzeneazohydrocupreine m. p. 236O (decomp.) ; ephenyl- ylycoElic acid-p-azohydrocupreine C0,H*CHT,*O*C,H4*N:N*C,gH2302N2 m. p. 199-200° (decornp.) ; m-carboxylamidohenzeneazohyvdro- cupreine m. p. 195O (decornp.) gives a dihydrochloride ; p-sulpho- benzeneazohydrocupreine m. p. 252O (decomp.) (compare Giemsa and Halberkann loc. cit.) gives a scarlet sodium salt; m-sulphon- nmidobenzeneazohydroczcpreine m. p. 170-19Qo ; p-sulphonamido- h enzeneazohydrocupreine ni. p. 155-1 90° ; puinolyl-6azohydro- cupreine m. p. 232-234O; benzeneazohydrocupreidz'ne m.p. 183-185O giyes a dihydrochloride m. p. 220-221O (decornp.) ; a-nnpht hnleneazo h ydroczcpreicline m . p. 132-140° ; panitro b enzene- uzohydrocupreidine M. p. 135-139O ; p-sulphobenzenenzohyydro- cupreidine m. p. 2 4 7 O (decornp.) ; benzeneaz*6-hydroxyquinoline has m. p. 160-161*5°. Most of these compounds show considerable softening or sintering and darkening previous to melting. W. G . p. 100-1 35 O ; Final Report on the Alkaloids of Gelsemiurn. L. E. SAYRE ( J . Amer. Phnrnt. Assoc. 191 9 8 708-711).-The investigation was made on about 11.5 kilos. of the drug in No 20 powder. The following alkaloids isolated as salts were obtained sempervirine nitrate (about 3 grams) gelseinine hydrochloride (about 8 grams) gelsemidine hydrochloride (1 -75 grams) and an amorphous alka- loidal chloride which is named gelsemoidine hydrochloride. All of these are toxic.CHEMICAL ABSTRACTS. Ethylmorphine Sulphate. JAMES LESLIE THOMSON (Pharm. J . 1920 [iv] 50 7).-Ethylmorphine sulphate has m. p. 207O and crystallises with 5 s O ; a t 15.5O it dissolves in 9.5 parts of water Strychnine and Brucine. VI. R. CIUSA ( A t t i R. Accad. Lincei 1919 [v] 28 ii 185-187).-The action of bromine on isostrychnine in acetic acid solution and subsequent decomposition of the perbromide yields derivatives of the tribromo-base and in 111 parts of 90% alcohol. w. P. s.ORGANIC CHEMISTRY. i. 177 C21H210N2Br3 in which two bromine atoms are added a t a double linking as in strychnine while the third replaces a hydroxyl group (A 1915 i 893).This conclusion is confirmed by the behaviour of isostrychnine towards (I) alcoholic hydrogen bromide in the hot and (2) benzoyl chloride. The first of these reactions yields a crystal- line compound which appears t o have the formula C,,H,,NBr(CO,Et):NH,HBr and is to be considered later. The action of benzoyl chloride on isostrychnine suspended in 10% potassium hydroxide solution yields only a small proportion of a compound m. p. 174O. I n pyridine solution however the benzoyl- ation gives benzoylisostrychnine C,,H2,0,N2Bz which crystallises in colourless needles m. p. 174* and has the normal molecular weight in benzene solution. The benzoylation yields also the benzoate of the benzoyl derivative C2,H,,02N2Bz,RzOH,H20 which forms white needles m. p.1 2 7 O . The hydrochloride C2,H2,O2N2Bz,HC1 small colourless needles m. p. 219O ; the auricldoride yellow needles m. p. 1 9 5 O ; and the dichronaat e (C2,H2102N2B~)2,H2Cr20 slender reddish-yellow needles were prepared and analysed. The sulphate and nitrate crystallise well and are slightly soluble in water. T. H. P. Strychnine Alkaloids. XXVII. Conversion of the Methylammonium Salts from Brucine and apoMethy1- brucine into Quinones. HERMANN LEUCHS and WALTER HINTZE (Ber. 1919 52 [B] 2195-2204).-The salt of the quaternary ammonium base which is readily formed by the action of methyl sulphate on brucine shows like the alkaloid itself the red colora- tion with nitric acid which is due to the formation of quinone; the latter however could not be isolated in the pure state or a8 a salt and wa8 therefore immediately reduced to the corresponding quinol which separated from solution as a mixture of bisapomethylbruciwe methonitrate C2,H,,0,N,,MeN0,,H,0 colourless shining prisms and acid sulphat e C,,H~,0,N2Me*S04H colourless three-sided platee in which the additional molecule of water appears to be chemically united since it is not evolved in a vacuum a t 1 4 0 O .For purification the mixture of salts was transformed by 12X-hydro- chlorio acid into bisaponaet hylbrucine methochloride leaflets or prisms (+ 1H20) prisms (+ 2H20) [a]” + 6’54O for the mono- hydrated salt in aqueous solution. Oxidation of the quinol to quinone is conveniently effected with a solution of chromic acid in hydrochloric acid whereby the substance C,,H2,O4N2,MeC1,H,CrO bright red leaflets is obtained which is analogous t o the compound derived from bisapomethylbrucine itself (A.1911 i 746). A similar oxidation is effected by heating the quinol with a solutioii of hydroxylamine in hydrochloric acid when the monoxime of the quinone yellow needles is produced; this however has not the simplest formula C,,H,,O,N,Cl but contains an additional mole- cule of hydrogen chloride and according to conditions either 4H20 which may be replaced in part by hydrogen chloride or 2H,O. Cor- centrated nitria acid converts the chloride into the nitrate,i. 178 ABSTRACTS OF UHEMICJAL PBPERS. C22H2,04N3(N08) ,HNO,,Z+O yellow prisms which is hydrolysed by water la the substance CBH,404N,(N0,),H,0 + H,O red prisms which is reconverted by acid into the yellow nitrate.Simi- larly the dichloride of the monoxime yields a hydrate slender red needles when the excew of hydrochloric acid is removed preferably by addition of alkali hydroxide (1 mol.). By the aid of a second molecule of alkali hydroxide the residual chlorine atom can be removed as hydrogen chloride and a betaine-like compound C22H2505N3 orangered prisms is produced. The yellow nitrate of the oxime is only formed with gently warmed nitric acid. A t a higher temperature a more complex action occurs in which nitration is accompanied by oxidation of the quinone-oxime or nitrosophenol group to the nitrophenol group and a molecule of water is added; the nitrate C2&25O,,N5 which is thus produced is identical with the product of the oxidation of the oxime of methylcacotheline (following abstract) from which it is more readily produced.I n a similar manner bisupomethylbrucine met-hochloride is con- verted through the quinone by 5117-nitric acid a t 50-60° into methylcacotheline methonitrate. On the other hand only quinone formation unaccompanied by nitration is observed with concen- trated nitric acid a t Oo so that in this instance in contrast to that of bisapomethylbrucine itself (A. 1911 i 746) i t was not possible t o obtain a nitrated but not hydrated quinone. H. W. Strychnine Alkaloids. XXVIII . Transformations and the Violet Colour Reaction of Methylcacotheline. HERMANN LEUCHS and WALTER HINTZE (Ber. 1919 52 [B] 2204-2224. Compare A. 1919 i 35).-Previous investigation of the metho- nitrate of the cacotheline bases (now termed methylcacotheline) had established the probability that it in accordance with its mode of formation from brucine dimetbosulphate is a nitrated and hydrated quinone but the function of the added water was left unexplained.Further evidence of its quinonoid nature is now adduced by the isolation of a semicarbazone as nitratel C23H2,0,N,*N03,3H.30 the semicnrbazone of the methochloride slender pale yellow needles and the mmophenylhydruzone as nitrate C,sH,,,0GN,*N0,,3H,0 brown- ish-red oblique prisms. To determine whether water has been added in such a manner that the acid amide group *CO-N= of brucine has been converted into -C02H I R-N< attempts have been made to identify the presence of the carboxyl group in two ways.On the one hand hydrogen chloride has been removed from the semi- carbazone hydrochloride by the agency of silver oxide (or in general a molemle of acid from the salts by a molecule of alkali) whereby a crystalline betaine C2,H2,0,N has been produced which readily re-forms the original salts with acids. On the other hand the presence of the carboxyl group is shown by the conversion of the semicarbazone nitrate into its methyl ester C,,H,,O,N,Cl. The phenylhydrazone only yielded an amorphous betaine but methyl- cacotheline itself gave a crystalline betaine C2,H2,O,N3 and as no C22H2404N3C1,%0,ORGANIC CHEMISTRY. i. 179 other acidic group can be present may thus be regarded aa contain- ing the carboxyl group. The chloride of the monoxime described previousIy (loc.czt.) also yielded a crystalline betake C&?H2407Nq,4H20 ; possibly in this instance the oxime or the tautomeric nitrose phenol group could take part in the dehydration but this view is rendered improbable by the isolation of a crystalline monomet hyl and monoet hyl ester. The nitrate of the monoxime can only be obtained from the chloride by the use of metallic nitrates since the oxime is oxidised when warmed with even N-nitric acid the quinoneoxime or nitroso- phenol group being converted into the nitrophenol group a second nitro-group being thus introduced into the molecule; this ' dinitro- phenol ' also yields a crystalline betaine C2,H2,0,N4 whilst its salts can be reduced to a ' diaminophenol,' C22H290,N4C1,2HCl or 1HC1 which can be obtained less smoothly from the nitroquinonemon- oxime.According to these reactions the formula of methylcaco- theline may be resolved thus C,,H { -CO-CO- ; i C*N02 ; NMeNO ; =NH; *C02H; =CH(OH)}. The violet coloration caused by the action of stannous chloride or sulphur dioxide on methylcacotheline has been previously investi- gated and attributed to the conversion of the quinone into the corresponding quinol the necessary hydrogen being regarded as obtained by the conversion of the secondary alcoholic group of the brucine molecule into the keto-group. Further examination has now been made on the action of methylcacotheline and similar salts towards sulphur dioxide in the presence of mineral acids; methyl- cacotheline itself yields a crystalline dark violet nitrate which however contains two hydrogen atoms more than the original salt into which it is re-converted by nitric acid so2 1% NO C22=24O,,N4 f-/C22H2601ON* ; the corresponding chloride C,H240,N3Cl similarly yields a violet quinol Cz2Hz,0,N3C1 from which it is re-formed by ferric chloride.The behaviour of the acid sulphate is precisely similar the quinol sulphate re-forming the original material on treatment with ferric sulphate. The sulphite thus occupies a peculiar position in that reduction in this case only is caused by hydrogen derived from within the molecule. The presence of acid radiclea which are not ionised is not essential to the production of the violet colour since they can be removed by warming with one (or two) molecules of alkali whereby deep violet betaines are obtained C22H2,07N3*N03 C22H2507N3.With the object of demonstrating the presence of the phenol group in the violet quinols the violet chloride was boiled with acetic anhydride and sodium acetate; the product,_ however did not con- tain the acetyl group but was formed by loss of a molecule of hydrogen chloride and of water from the original substance. It appears to have a betaine structure since it readily yields additive products with acids and probably is a phenol betaine.i. 180 ABSTRACTS OF CHEMICAL PAPERS. Reduction of the betaine anhydride C,H,0,N3 with tin and hydrochloric acid yields the nminoquinol C,H2,0,N3Cl,HC1,2H,0 previously obtained from methylcacotheline and formulated with 1H20. A molecule of water appears to be eliminated during the reduction of methylcacotheline in a manner similar to that observed during the action of acetic anhydride on the violet quinol.The composition of the amine hydrochloride varies considerably and the following forms have been prepared and analysed ~BH280,N3C1,HC1 needles ; C22H,0,N3C1,2H,0 trapezoidal tables ; rectangular or quadratic tables; from t-he first of these hydrogen chloride is eliminated a t looo whilst the third is stable a t t.his temperature. H. W. The Chemical Identification of Thyroxin. 11. E. C. KENDALL and A. E. OSTERBERG ( J . Biol. Chem. 1919 40 265-334) .-Thyroxin the physiologically active constituent of the thyroid gland (A. 1919 i 497) can exist in two tautomeric forms. The keto-form (I) which is by far the more stable crystallises in long needles m.p. 250O; the en01 form (11) crystallises in rosettes of needles m. p. 204O. From a consideration of the chemical behaviour of the substance so far as it is yet known the authors suggest the formula C*,H,,O,N,C1,HC1 IH IH IH/\]==~~cH,~cH,~co,H I R/)==$WH2*CB2*C02H I H L \ / C O H N H N and lH(//\//C*OH H (1.1 (11.1 Further there is evidence that by combination with the elements of a molecule of water two further forms may exist melting at 225O’ (111) and 2 1 6 O (IV) respect.ively t.he suggested nature of which is indicated by the partial formulz \ C=C.CH,GH,~CO,H I \C==C- \c==c- I I / C &O*OH I c c-0 C C*OH ’ \/ \ N *H ’\ 0’ ‘k /\ H OH /I\ (111.) W.) (V.1 H H H Addition of an acid to the enolic form leads to fission of the ring and formation of an amino-acid (V) of which I11 is an internal salt.For the evidence on which the authors base these formuh the original must be consulted. The acetyl derivative crystallises in short curved needles m. p. 228-235O (decomp.). The sulphate has the formula C22H22010Nd6S.ORQANIC CHEMISTRY. i. 182 The hydrochloride crystallises in star-shaped plates. with cyanic acid thyroxin yields a carbamyl derivative When treated Many mono- and di-basic metallic salts of thyroxin have been pre- pared but although they are beautifully crystalline they have not been obtained in a pure condition. A dz'methyl ester has been prepared and is hydrolysed to a monomethyl ester by alkali hydroxides. When exposed to sunlight in weak alkaline solution it is very unstable. Within twenty-four hours the solution turns pink or yellow deepening to a brown and an aromatic odour is produced.The development of the pink colour is accompanied by the splitting off of iodine in the form of hypoiodous acid. Constitution of Arylanthranils Lactimides and Lact- imones. GUSTAV HELLER and HILDE LAUTH (Ber. 1919 5 2 [B] 2295-2303) .-In a previous communication (Heller A. 1915 i 844) it has been shown that acylanthranils react with hydrazine hydrate in alcoholic solution to yield 3-hydrazino-3-aryl-3 4- dihydrobenzoxazones and the reaction is interpreted as in favour Thyroxin is not easily oxidised or reduced. J. C. D. O- of the formula (? >N*COR for the acylanthr-mils the behaviour being difficult to reconcile with the alternative formula c6Hd<N= 'O.? CR' A number of somewhat similarly constituted com- C,H pounds have now been examined.Anthranoylanthranilic anhydride and acetylanthranoyl- anthranilic anhydride (Schroeter A. 1917 i 529 620) are con- verted by hydrazine hydrate in warm alcoholic solution into 3 - h y drazino- 3 -0-amino phen y l-3 ; 4dihydro h cnz oxaz on e pale yellow needles m. p. 200° (decomp.) and 3-hydrazino-3-o-ncetylamino- pltenyl-3 4-dihydrob cnzoxazone colourless thread-like crystals m. p. 216O (decomp.); these substances are decomposed by alkali and on acidification with acetic acid the lactone is re-formed in a somewhat impure condition. It appears therefore that complex acylanthranyls contain the same ring as is present in the simpler substances. Benzoylaminocinnamic lactimide and acetylaminocinnamic lact.imide react similarly with hydrazine hydrate yielding respectively. 5-keto-2-h?ytZmzino-2-phenyE-4-b enzylic?enetetrahyt~Ero-oxazole co- - '>CPh*NH*NH b( :CH Ph)*NH colourless needles m. p. 153-154O (benzylidenehydmzino-deriv- ative colourless needles m. p. about 220° aft,er darkening from 1 4 5 9 and 5-ll.eto-2-hyd~azino-2-methyl4-be~zylic2enetetralyd~-o- oxazole coarse crystals and clusters of needles m. p. about 180°i. 182 ABSTRACTS OF CHEMICAL PAPERS. (decornp.) after darkening from 160O. For reasons similar to those advanced in the case of the acylanthranils the original substances must have ths constitution CHPh:C<k .CO.R. a-Benzoylaminoisobutyric anhydride (Mohr and Geis A. 1908 i 339; 1910 i 117) is transformed by hydrazine hydrate into 5 -ket 0-2-hydrazino-2-phen y 2-4 4-dimet h y It etrahydro-oxazole slender needles m.p. 134O and must therefore have the lactam formula. The isomeric a- henzoy2aminoiso hutyric hydrazide obtained by the action of hydrazine hydrate on the acid chloride has rn. p. 248O (decomp . ) . co H. W. Dyes Derived from Ketodihydro- 1 4-benzisothiazine. W. HERZOG (Ber. 1919 52 [R] 2270-2274) .-Ketodihydrobenzo- thiazine reacts with a-isatinanilide in a solvent of high boiling point such as ethyl benzoate to yield 2(2f4ndoxyl) - 3 - ketodihydro-l 4-benz- isothiazine (annexed formula) dull co /\ brownish-violet needles with metallic I 1 7% glance m. p. above 300° which dyes cotton bluish-violet and wool reddish- ..\,.-ccy S N H violet. 2(2/ - Thionaphthen) - 3 - ketodi- hydro-l 4-benzisot hiazine yellow silky needles m.p. above 300° prepared similarly from thionaphthen- quinoneanilide has little affinity for the textile fibres. 8-Isatin- anilide yields Z(3f-indoxyl) - 3 - ketodih?ydro-l 4-henzisothiazine orangered silky needles m. p. about 270° which has very lit3tle affinity for the textile fibrB. The inferiority of the substances as dyes in comparison with indigo-blue and thioindigo-red is readily interpreted according to the Clauss hypothesis since they contain only one quinonoid indogen whilst the latter dyes contain two such groups. Certain Arylamino-derivatives of 4( 5)-Methyl-5(4bamino- methylglyoxaline and the Syntheses of 4( 5)-(P-p-Hydroxy- phenylethyl-P- aminoethyl) glyoxaline . OTTO GERNGROSS (Bey. 1919 62 [B] 2304-2318).-The anil of 4(5)-methylglyoxaline- 5(4)-aldehyde (Gerngross A.1912 i 314) is reduced by sodium in boiling isoamyl-alcoholic solution in an atmosphere of hydrogen to NH-EMe N-C*CH,*N HPh ' 4(5)-methy~ - 5(4) -anilinomethylglyoxaZine CK< slender needles from water m. p. 183O (corr.) [hydrochbride four- sided leaflets m. p. 201O (corr.) after becoming discoloured at 175O and softening a t 195O] ; the corresponding benzoyl derivative crystallises in shining four-sided plates m. p. 206O (corr.) yields a hydrochloride m. p. 2 3 5 O (corr.) and does not couple witLh diazobenzenesulphonic acid in alkaline solution. The preparation of the aniline derivative is only conveniently effected in this manner when very small quantities of material are required; for larger NH /\A\ H.W.ORGANIC CHEMISTRY. i. 183 amounts it is more conveniently produced by the action of aniline (2 mols.) on a solution of methylchloromethylglyoxaline hydro- chloride (1 mol.) in methyl alcohol (compare Ewins T. 1911 99 2054); under these conditions its formation is accompanied to a greater or less extent by that of N-phenyliminobis-4 5-dimethyl- glyoxaZi?ze NPh CHz*C<N-& small needles m. p. 199-200° (corr.) from which it can be readily separated by taking advant-age of the very sparing solubility of the latter in boiling acetone. [With HANS NAST.]-T~~ synthesis of 4(5)-(/3-p-hydrosyphenyl- ethyl- P-aminoet hyl)glyoxaline ( CMp - O N 7 NH*EH "H=%-C C,H4*NH* C,R; C,H,**H ' is described which is of pharmacological interest since it contains the active principles of Secale cornutum and tyramine united to one another.5 ($)-P-PhenyEeth ylaminomethyl-4(5 )-methylglyoxaline is obtained b y slowly adding a solution of the hydrochloride of 4(5)-methyl-5 (4)-chloromethylglyoxaline in methyl alcohol to P-phenylethylamine dissolved in slightly methyl-alcoholic water ; the crude product is converted successively into the dipicrate prisms m. p. 2 1 1 O (corr.) after softening a t 204O and the dihydrochloride shining hygroscopic crystalline leaflets m. p. 254O (corr. ; decomp.) [aurichloride yellow crystals m. p. 215O (corr.)]. Small quantities of /3-phenylethyliminobis-4 5-dimethylglyoxaline ( C3H2N2Me*CH2),N*C,H,*Ph are produced during this reaction and this substance becomes the main product when care is not taken to maintain a constant excess of the amine; the trip'crate shining yellow crystals m.p. 1 7 6 O (corr.) after softening a t 160° the hygroscopic hydrochloride and the ptatinichlwide which darkens above 200° but does not melt below 270° are described. Similarly the hydrochloride of methyl- imidazolylmethyl chloride and p-phenylenediamine yield 5 (4)-p- aminoarnilinornet hyl-4 (5)-met hylglyoxaline C,H,N,Me*CH,-NH *C,H,*NH the trihydrochloride four-sided rhombic plates m. p. 2 5 7 O (decomp.) and dip-crate large yellow crystals m. p. 219-220O (decomp.) of which are described. /3-Aminoethylglyoxaline condenses with p-hydroxyphenylethyl chloride in methyl-alcoholic solution a t looo to yield 4(5)-(B-p-hydr- ozyphen?/lethyE-P-aminoethyl~gl~~~xal~ne ; the crude product is treated with hydrochloric acid to remove the excess of the histamine base and is purified by successive conversion into the diecrate m.p. 2 0 3 ~ 5 ~ (corr. ; decomp.) the dihydrochloride colourless rods m.. p. 202-2G3O (corr.) and the free base microscopic four-sided prisms m. p. 157O (corr.); the monohydrochloride forms four- sided platelets m. p. 195O (corr.). H. W.i. 184 ABSTRACTS OF CHEMICAL PAPERS. Quinazolines. XXXIV. The Synthesis of certain Nitro- and Amino-benzoyleneureas [Diketotetrahydroquinazo- lines] and some Compounds Related Thereto. MARSTON TAYLOR BOGERT and GEORGE SCATCHARD ( J . Amer. Chem. SOC. 1919 41 2052-2068).-A supplement to and an elaboration of work previously published (compare A. 1916 i 672) certain new compounds being described.Methyl anthranilate when condensed with potassium isocyanate in acetic acid solution yielded methy2 o-carbamidobenzoate m. p 177-177.5O (corr.) 6-Nitro-2 :4- diketo-1 2 3 4-tetrahydroquinazoline7 m. p. 330-331O (corr.) gives a sodium salt which is colourless at limit 7 on the Sijrensen scale but at 7.5 and on to 11 very slowly develops a greenish-yellow colour. The development of colour is however too slow for the salt to be of any use as an indicator. 6 8-Dinitrodiketotetrahydro- quinazoline (loc. cit.) gives potassium and ammonium salts which resemble the sodium salt in general behaviour except tlhat the ammonium salt decomposes without explosion. The authors find higher m. p.’s for certain quinazoline derivatives than did Abt (com- pare A.1889 609). Thus 2 4-dichloroquinazoline has m. p. 119.5O (corr.) ; 2 4-dimethoxyquinazoline has m. p. 74O ; 2 4-diketo-1 3- dimethyltetrahydroquinazoline has m. p. 167-168O (corr.). o-Carbamidobenzoic acid when nitrated with nitric acid (D 1.5) a t - 5 O to -loo yielded 5-nitro-2-nitrocarbamidobenzoic a d NO,*NH*CO*NH~C,H,(NO,)*CO,H which it was very difficult to purify. Its methyl ester decomposing a t 184-185O (corr.) was obtained by nitration of methyl o-carb- amidobenzoate. I n an endeavour to clear up the chemistry of 5-nitro-2-acetylaminobenzoic acid the authors have prepared a specimen m. p. 218O (corr.) and its barium calCium ferric copper Zead and silver salts. Similarly they prepared 5-nitro-2-amino- benzoio acid m. p. 278O (corr. ; decomp.) and its sodium potassium and ammonium salts.The proof that the! compound obtained by Bogert and Geiger (comparef A. 1912 i 395 510) by t.he nitration of 4-quinazolone is 6-nitr0-4-quinazolone is supplied by the preparation of the same compound by fusing together 5-nitroanthranilic acid and form- amide. W. G. It gives a methyl ester m. p. 1 6 8 O (corr.). New Type of Substances Derived from Diazonium Com- pounds and Alkali Cyanides. QUSTAV HJCLLER and MARIE MEYER (Rer. 1919 52 [ B ] 2287-2294).-When an aqueous solution of a benzenediazonium salt is added t o a solution of potassium cyanide in the presence of an excess of potassium hydroxide a yellow oil is formed which immediately yields a colourless solution from which an unstable sparingly soluble red salt gradually separates ; this slowly decomposes even in thel cold liquid with evolution of nitrogen and development of the odour of isocyanide. The corre- sponding free compound however is more stable and has the formula C13H,,0N,.The colour of the substance its failure to yield hydroxylamine when treated with acids and its reduction byORGANIC CHEMISTRY. i. 185 hydrogen to a colourless derivative lead the aut,hors to consider it to be benzenediazoxydiazobenzenecarbimide PhN,-C( :NH)*O*N,Ph ; confirmatory evidence is deduced from the fact that it is only formed from syn-benzenediazonium hydrate and salt of hydro- cyanic acid and not from the anti-diazotate and substances which contain the cyano-group united to carbon or nitrogen. The potassium salt of benzenediazosydiazobenzenecarbimide forms dark red leaflets m.p. 239O (decomp.) whilst the sodium salt consists of bronze-like leaflets m. p. 2 0 9 O (decomp.). The lead mercurous manganese silver copper cobalt bismuth stannous cadmium zinc and mercuric salts are described. The corresponding free substance cryst’allises in red needles m. p. 93O with violent evolution of gas. Attempts t o obtain a benzoyl or methyl derivative were unsuccessful . p- Toluenediaz o xydiazo-p - toluenecarbimide m. p. 1 1 1 O (decomp.) is converted by phenyl- carbimide into p-toluenediazoxydiazo-p-toluenecarbimidophenyl- carbamide C,H,Me*N2*C(:N*CO*NHPh)*O*N,-C,H,Me orange- yellow crystals m. p. 148O (decomp.). o-To1uenediazoxydiazo-o- toluenecarbimide forms bluish-red rods m. p. looo (decomp.).The sodium salt of benzenediazoxydiazobeiizenecarbimide slowly decomposes in aqueous solution yielding nitrogen aniline benzo- nitrile ammonia and nitrite but not phenol. The free substance is decomposed by hot water yielding smeary products from which traces of phenol and benzonitrile could be isolated by distillation wit7h steam. The sodium salt of benzenediazoxydiazobenzenecarbimide is reduced by sodium hyposulphite in alkaline solution by alkaline stannous chloride by zinc dust- and acetic or hydrochloric acid in alcoholic solution or by phenylhydrazine in alcoholic solution to b enz enediaz oxypih en y lhydrazinocar himide PhNH*NH*C( :NH)*O*N,Ph colourless needles or crystalline aggregates rn. p. about 154O (decomp.) which is converted by methyl sulphate into the corre- sponding methyl derivative m.p. 137-138O (decomp.). Pro- tracted reductlion of benzenediazoxydiazobenzenecarbimide by zinc and acid leads to the formation of aniline whilst in a similar manner phenylhydrazine is formed when stannous chloride and hydrochloric acid act on a solution of the substance in glacial acetIc acid. Benzenediazoxyphenylhydrazinocarbimide yields practically the same products as does the unreduced compound when it decom- poses in cold alkaline solut<ion; in acid solution i t is gradually decomposed with the formation of phenol. o-Tohenediazoxy-o- tolyl~ydraz~nocarb&mide forms colourless crystals m. p. 150° (decomp .). H. W. The Special Reactions in the Transformation of the Azides of Carboxylic Acids. I.-VI. THEODOR CURTIUS ( J .pr. Chem. 1916 [ii] 94 273-382).-The ((normal ” reaction of the acid azides. and their formation are surnmarised as follows R=CO2Et + R*CO*NH*NH -+ R-COON + R*NH*CO,Et ori. 186 ABSTRACTS OF OHEMICAL PAPERS. R*NH*CO*NH*R ++ R-NH numerous examples of which have already been given in the case of mono- di- and even tri-carboxylic acids (most recent notices A 1914 i 873; 1915 i 124 169 787 872). “ Special ” reactions are given by (1) the azides of acids having two -COON groups attached to the same carbon atom (2) by hydroxy-acids and their ethers and (3) by a-amine and a-acylamino-acids. I n the first case the ultimate products are generally the aldehydes or ketones produced by the hydrolysis of the methylenediamines CHR( NH,) or CRR’( NH2)2. Examples are now given. The second section is dealt with in Parts VII.to XIII. of this series (A. 1917 i 635-639) and the third section in Parts XIV. to XVII. (A. 1918 i 44j. I. [With WILHELM Cbsm.]-Hydrazide and Azide of Methyl- and isoAmyl-malonic A cids.-Methylmalonodihydrazide CHM~(COON~H~)~ crystallises in silky needles m. p. 172-173O (compare Bulow and Weidlich A. 1906 i SSl) forms a dihydrochloride m. p. 168O a dibenzylidene compound m. p. 251O (ibid.) a disalicylidene com- pound glistening leaflets m. p. 21 6-21 7O a diisopropylidene com- pound by boiling with acetone minute needles m. p. 158-159O and a very explosive yellow diuzide CHMe(CO*N3),. This reacts with aniline to form methylmalondianilide m. p. 182O (Meyer and Bock A. 1906 i 726) and with p-toluidine to give the di-p-tolu- idide (Commanducci and Lobello A.1905 i 271). It reacts with alcohol to form an oily urethane which yields carbon dioxide and acetaldehyde on boiling with dilute sulphuric acid. isoAmylnzalono- dihydrazide forms silky crystals m. p. 140° (decomp.) and gives a dihydrochloride silky leaflets a dibenzylidene compound micre scopic leaflets m. p. 240° and a disalicylidene compound white tablets m. p. 186-187O. The diazide is a pungent-smelling oil which reacts with aniline to give isoamylmalondianilide silky needles m. p. 185O and with alcohol to form a urethane this being hydrolysed by dilute sulphuric acid to isohexaldehyde C,H,,*CHO. The aqueous distillate of the aldehyde reacts with benzhydrazide to give the benzhydrazone C,H,,*CH:N*NHBz silky needles m.p. 215O. Dimethylmalonodihydrazide crystallises in prisms m. p. 208O but gives poor results in the subsequent reactions acetone being recognised however as the ultimate product. Benzylmethyl- malonodihydrazide forms silky leaflets m. p. 260O. 11. [With HEINRICH RECHNITZ.]-TranSfOrmatiOn of Ethyl- malondiazide into Propaldehyde and Trmsf ormation of Prop- aldaziae into 4-M e t hy l- 5-e t h y 1 pyraz oline .-E thylmalonodihy dr azide forms slender needles m. p. 168O (compare Biilow and Bozen- hardt A. 1910 i 233) and gives a dihydrochloride rn. p. 180-181° a dipicrate yellow needles m. p. 187O (decomp.) a dibenzylidene compound m. p. 241-242O (decomp.) and a disali- cylidene compound m. p. 201O. The dkzide is very explosive but may be converted into the dianilide and di-p-toluidide m.p. 288O or into the diurethane CHEt(NH*CO,Et) which is hydrolysed by diluh aulphuric acid t o propaldehyde. The final yield is very poor,ORGANIC CHEMISTRY. i. 187 however as the yield of azide is only 3 5 4 0 % to begin with. Prop- aldazine N,(:CHEt) is a colourless oil with fishy odour b. p. 143-145O Dl9 0.844 n 1.379 and it reacts with maleic acid in absolute alcohol to form hydrazine maleate N2H4,C4H404 very slender needles m. p. 144O (decomp.) and 4-methyl-5-ethylpyr- azoline NH<CHEt.l,fiMe. This is a colourless liquid with the odour of peppermint b. p. 105-107°/18 mm. and is very stable in solution in dilute sulphuric acid. It gives blue and white precipi- tates with Fehling's solution and mercuric chloride respectively but does not reduce these agents. With p-toluenediazonium sul- phate it gives a brick-red compound which dissolves in concentrated hydrochloric acid with deep bluish-violet colour the solution becom- ing pale red on dilution.The yield of the pyrazoline is improved if the alcoholic mixture of propaldazine and maleic acid is heated or if hydrazine maleate is mixed with propaldehyde but the chief product in any case is a compound probably of the formula c h .CbH11N2 c6E111N2*CEt<(!ll e . ~ H N (4 - methyl - 5 - ethylpyrazoline = C6H,,N2). This is a yellowish-red viscous oil b. p. 245-250°/ 18 mm. which turns red litmus blue but only forms oily salts. It has the reactions of the simple 4-methyl-5-ethylpyrazoline and is apparently formed by the elimination of two molecules of ammonia from four of the pyrazoline. The alkaline liquid left after the extraction of the two bases contains an amount of ammonia which agrees with this view and fumaric acid is also present.111. [With OWEN E. MOTT repeated and in part amended by WILHELM SmmR.]-€Zydrazide and Azide of Benzylmalonic A cid.-Benzylmcclo.rtodihydrazi.de CH,Ph*CH(CO=N,H,) crystal- lises in slender glistening needles m. p. 164O forms a dihydro- chlorzde m. p. 1 3 5 O and a dibenzylidene compound small needles m. p. 220° and changes into secondary benzylmabonohydr- azide CH,Ph*CH <CO,NH 'O*TH glistening leaflets m. p. 241° when ( a ) its hydrochloride is kept in the moist condition or heated for some hours a t looo ( b ) it is treated with alcoholic iodine or ( c ) it is treated with sodium nitrite in the presence of a slight excess of hydrochloric acid.In the last reaction benz ylmalonyldiazide an explosive yellow oil is the chief product and the by-product can be suppressed if an excess of acid is used. The diazide may be con- verted into the dianibide CH,Ph*CH(CO*NHPh) m. p. 217O and diurethane CH,Ph*CH(NH*CO,Et) a mass of very slender needles m. p. 166O the latter being hydrolysed by 2% sulphuric acid to phenylacetaldehyde b. p. 81-8Z0/12 mm. which forms a benz- hydrazone CH2Ph*CH:N*NHBz needles m. p. 148-149O and a m-nitrobenzhydrazone m. p. 1 5 2 O . Iv. [With CARLO NARA~Go~o.]-flydrazide and Azide of rn-Xylylmalonic A cid (m-Methylbenzylmalonic A cid).-m-Xylyl- malonodihydrazidc [m-me t h y 1 b enzy lmal onodih ydrazidc] C6H,Me*CH2*CH(CO*N2H,,) N==ZCH 6 11 2i.188 ABSTRACX’S OF CHEMICAL PAPERS. crystallises in silky needles forms a hygroscopic dihydrochloride m. p. 135-136O (decomp.) a dzbenzylidene compound small glis- tening needles m. p. 219O a disalicylidene compound m. p. 185-186O a dikopropylidene compound m. p. 182O (from acetonej and a bisdiphenylmethylene compound C,HI,Me*CH,- CH (CO NH N CPh) m. p. 164O (from benzophenone). The dihydrazide changes into the secondary m-methylbenzylmalonohydrazide in. p. 236-237O when treated with alcoholic iodine. The unstable diazide may be converted into the dianilide m. p. 193O di-p-tolu- idide C,H,Me* CH,*CH( CO*NH*C,H,&~e) slender needles m. p. 190° and crude dkrethane C,H,Me*CH,-CH(NH*CO,Et) which is hydrolysed by dilute sulphuric acid to m-tolylacetaldehyde C,H,Me*CH,-CHO.This is a pleasanbsmelling pale yellow refrae tive oil b. p. 99-100°/18 mm. which forms an oily phenylhydr- azone a benzhydrazone C6H4Me*CH2-CH:N*NHBz long needles m. p. 129-130° and a m-nitrobenzhydrazone very pale yellow prismatic needles m. p. 115-116O. v. [With GOTTFRIED GR~~~E~.]-Hydrazide and Azide of Pen- tnne-aaeE-tetracarboxylic A cid and of cycloButane-1 1 -dicarb ozylic Acid.-The ethyl esters of these acids are obtained by adding a mixture of trimethylene bromide and ethyl malonate to a mass of sodium ethoxide in alcohol. If the mixture is added rapidly and the temperature is only controlled sufficiently to prevent undue violence the yield of the pentane derivative rises to about 12” but if the addition and cooling are carefully controlled the yield of cyclic compound is improved.The latter is slightly volatile in steam and may be slowly removed in this way from the non- volatile pentane compound. In any case the yields are poor and the reaction cannot be fully explained. Ethyl pentane-aaeetetra- carboxylate is a pleasant.-smelling viscous colourless oil b. p. 210-215°/12 mm. and ethyl cyclobutane-1 1-dicarboxylate is a limpid highly refractive oil with the d o u r of camphor b. p. 220-228O (compare Perkin T. 1883-1891). The esters are con- verted into the amides and hydrazides by the action of ammonia or hydrazine in the usual way. Pentane-aacx-t etracarboxylamide forms soft prisms m. p. 280° and the tetrahydrazide ( N2H,*CO),CH* C3H,*CH(CO*N2H3)2 is a snowy powder m.p. 200° (decornp.) which yields a tetrahydro- chloride m. p. ZOOo a platinocklol.ide C9Hgo04N8,2H2PtC14 and a tetrabenzylidene compound ni. p. 248O. The tetra-azide is an odourless white powder which m e h under benzene at 50-55O is comparatively stable when dry but explodes on rubbing. The tetra- nnilide is obtained from the azide as a white powder m. p. 285‘. The azide also changes into an impure carbamide derivative when boiled with water and into an oily urethane on boiling with alcohol the latter giving a distillate containing glutardialdehyde C,H,( CHO) when boiled with dilute siilphixric acid. cycloButane-ORGANIC CHEMISTRY. i. 189 1 1-dicarboxylamide crystallises in long rectangular prisms m. p. 268O and the dihydrazide CH,<CH2>C(CO*N2Hs)2 forms stout tablets or short needles m.p. 109-1100 and yields a &hydro- chloride m. p. 175-176O (decomp.) a platinochloride B,H,PtCl a dipicrate yellow needles m. p. 185O a dibenzylidene compound me p. 212-213O a disalicylidene compound m. p. 2 1 5 O and a dzisopropylidene compound m. p. 176-177O. For the conversion of the dihydrazide into the diazide the temperature of the mixture must be kept well below -50 otherwise evolution of carbon dioxide and nitrogen takes place and a deep red solution is obtained. oil which can only be'kept when moist for a short time as it is decomposed by water. cycloButane-1 1-dicarboxylanilide m. p. 214-215O and the di-p-toluidide m. p. 247O are obtained from the azide. The azide is hydrolysed to a considerable extent with the production of free hydrazoic acid when warmed with water or alcohol but it also loses carbon dioxide and nitrogen and when the product is acidified and distilled cyclobutanone is found in the distbllate.From the solution cyclobutanonephenylhydrazone a pure white light mass of felted needles or long needles from benzene m. p. 95-96O which can only be kept a few hours and the stable semicarbazone m. p. 211-212O (decomp.) (compare Demjanov and Dojarenko A. 1908 i 156) may be precipitated by adding the appropriate agents. s.-Ethanet ctracarboxylic A cid.-Et hanct ctracarboxytetrahydrazide C,H2(CO*N2H3) crystallises in slender needles m. p. 205O (decomp.) and forms a tetrahydrochloride m. p. 145-148O (decomp.) a tetrabenzylidene compound m. p. 242O a tetrasalicyl- idene compound m.p. 213-214O and a tetraisopropylidene com- pound C,,H,04N3,4H,0 m. p. 255O whioh evolvw dimethylket- azine CMe,:N*N:CM% when heated a t 110O. The conversion of the hydrazide into the tetra-azide (radiate groups of white crystals) only proceeds in the presence of an excess of hydrochloric acid which entails considerable loss of hydrazoic acid. The azide may be con- verted into the tetra-anilide m. p. 240-242O tetra-p-tolzcidide m. p. 236-237O and tetraurethane C,H2(NH*C02Et) white needles m. p. 268O the mother liquor from the latter preparation containing glyoxal. When the tetrahydrazide is warmed with water it changes into the yellow hydrazine salt of et hanetetracarboxytri- CO-Q H*CO*N,H hydrazide NH,-N< m. p. 142O which C(O*N,H,):C*CO*N2~ reach with acetone to form the trzisozvovvlidene comDound.CH2 The dkzide CH,<CH2>C(CO*N3) CH is a colourless lachrymatory F VI. w i t h HERMANN ~HIEMANN.]-HydTaZ&fC and A Z i d C Of L 1 " CO*QH*CO*NH*N CMc12 CO*CH-CO*NR-N:CMe CMe,:N*N< m. p. 138-140° (with 3H,O m. p. 90-92O). This is converted into the tribenzylidene com- pound m. p. 193-194O by means of benzaldehyde and then into the trihydrochloride m. p. 182-183O (decomp.) by rubbing withi. 190 ABS!EtAoTS OF CHEMfOAL PAPERS. conoentrated hydrochloric acid. The corresponding triazide is a very explosive viscous oil which may be converted into ethane- tricar b oxy trknilide NHP h* CO CH,* CH (CO-NHP h)2 m. p. 223-224O) and tri-p-toluidide m. p. 230O. The tetrahydrazide loses still more hydrazine residues when ground with bromine water or warmed with alcoholic iodine the product being ethanetetracarb- CO*CH*Cd v oxydihydrazide NH2*N<Coa!,H.CO>N*NH which crpstallises in highly refractive glistening scales m. p. 254-255O. This has both acidic and basic properties forming a &potassium salt pale yellow leaflets m. p. 158O a dihydrazine salt m. p. 208O a diammonilum salt m. p. 98O which loses ammonia when kept and a hydroch,Zoride m. p. 185-186O (decomp.). It also yields a dibenzyl- idene compound m. p. 240-241° a disalicylidene cornpound m. p. 231-232O a diisopropylidene compound m. p. 261° and a tetru- acetyl derivative m. p. 202-203O. When treated with sodiunl nitrite and hydrochloric acid the dihpdrazide changes into ethane- > NH which crystalliseg in CO.CH*CO tetracarboxydi-imide NH< colourless leaflets blackens a t 265-270° and forms a stable disilver salt 2H20.When boiled with water for a few hours the tetra- or tri-hydrazides lose carbon dioxide as well as hydrazine and give succinodihydrazide thus Co*yH-CO C,H,(CO*N&Q + 2H,O=C2H4(CO*N2H3) + 2NZH4 + 2C02. J. C. W. The Evolution of Proteins. E. L. KENNAWAY (Chem. News 1920 120 13-16) .-After discussing the amino-acids which have been established as occurring commonly in proteins the author draws attentqion to their very limited number but great diversity as regards structure. He then goes on to consider whether the simplest plants for example bacteria yeasts contain all these amin*acids present in the higher plants and taking the inform- ation available Bhows that with the exception of hydroxyproline the presence or absence of which is not established all the seventeen amino-acids considered are present in one or other of the five bacteria yeast and mould which have been examined.The two doubtful occurrences are serine and cystine. The author then dis- cusses the bearing of these results on evolution particularly on that of the higher animals which are dependent on plant life for some of their essential amino-acids. The Hydrolysis of Proteins in the Preseaoe of Ex- traneous Materials and on the Origin and Nature of the Humin" of a Protein Hydrosolate. R. A. GORTNER (Science 1918 48 122-124; from Physiol. Abstr. 1920 4 466). -A strong criticisni of McHargue's stntemetrts regarding protein hydrolysis (compare A 1918 ii 280).W. 0. W. G.ORGANIC CMEMISTRY 4 i. 191 Aakion of Furfuraldehyde and Dextrose on Amino- acids and Protein Hydrolysates. C. T. DOWELL and PAUL MENAUL (J. Biol. Chem. 1919 40 131-136).-1t was observed that when whole plants including the seed are hydrolysed a large amount of furfuraldehyde is given off and that an unusually high percentage of humin nitrogen is obtained. No evidence of a reaction between glycine and furfuraldehyde was obtained but there was an indication that reaction occurred with tyrosine and cystine. Only a slight amount of the humin nitrogen is due to adsorption. There is reaction between the hydrolysates of proteins and ftxrfuraldehyde which is particularly marked when the reac- tion takes place in neutral or acid solution.The greatest loss of amino-nitrogen occurs however when dextrose is present during hydrolysis and it is €herefore concluded that dextrose reacts directly with the amino-acids and not through the intermediate formation of furfuraldehyde. Complete hydrolysis of proteins may be effected by heating in 10% hydrochloric acid for three hours at 20 lb. pressure. Hydrolysis of Stizolobin the Globulin of the Chinese Velvet Bean Stizolobium niveurn. D. BREESE JONES and CARL 0. JOHNS ( J . Bio2. Chem. 1919 40 435-448).-The globulin of the Chinese velvet bean has been hydrolysed and the percentages of the constituent amino-acids determined 77.21% of the total protein was isolated as amino-acids and ammonia. Aspartic acid was determined both by the usual ester method and by Dakin’s recently published process (Dakin A.1919 i 150). The former method yielded 5.7% and the new process 9.23%. 2.81% of the recently discovered hydroxyglutamic acid was also obtained. J. C. D. J. C. D. Solubility of Casein in Dilute Solutions of Sodium Chloride and its Dependence on the Hydrogen Ion Con- centration. SIGFRID RYD (Arlciu. Kcm. Min. Geol. 1917 7 No. 1 1-15).-The solubility of casein in dilute solutions of sodium chloride has been determined for thirty-two concentrations a t 18-20O. The casein in weighed quantity was placed in a cylindrical vessel fitted with stirrer thermometer and two burettes. A quantity of a standard solution of sodium hydroxide sufficient to dissolve the casein but not an excess was added and the mix- ture stirred until solution had occurred.Then from one of the burettes standard hydrochloric acid was added until an opalescence was produced. The amount of sodium hydroxide taken in the first place was so chosen t-hat the hydrochloric acid necessary to produce opalescence was slightly more than equivalent to the sodium hydr- oxide the excess of acid was neutralised and the casein redissolved by the addition of sodium hydroxide from the other burette. This process was continued until the acid and alkali when exactly equi- valent just produced an opalescence. Hence the concentration of the solution on casein and sodium chloride was known. The solu- bility of mein in sodium chloride solution rims with increase ini. 192 ABSTRACTS OF CHEM'ICAL PAPERS. the concentration of the sodium chloride to a maximum which is reached with 0.1 150N-sodium chloride.The following are the extreme values 0-0365N-NaC1 dissolves 0.64 mg. per c.c. 0*1150N-NaCl dissolves 3.46 mg. per c.c. and 0.2725F-NaCl dis- solves 1.32 mg. per c . ~ . The hydrogen-ion concentration of each saturated solution was determined a t 21° and it is found that this quantity is practically constant a t 5.13 x 10-6N from which it follows that opalescence in solutions of casein occurs when the hydrogen-ion concentration has the above value and this lies very near the iso-electric point which has a value 1.1 x 10-4-7.9 x J. F. S. Haemocyanin . I. Recrystallisation of Oxyhaemocyanin. AUREL D. CRAIFALEANU (Boll. SOC. g a t . Napoli. 1918 3 1 88-99> .-The author describes the crystallisation of hzmo- cyanins from the blood of Octopus vulgaris 0. macrops and Eledone moschata following the methods described by Hofmeister and by Hopkins and Pinkus for the crystallisatioa of egg-albumin.The hEmocyanin derived from the1 blood of 0. vulgaris may crystallise in three different forms short needles rosettes of needles and relatively large crystals which from their appearance under the microscope the author terms '( projectile " crystals. These forms vary with the conditions of crystallisation. The hzemo- cyanin from 0. macrops was obtaineld in long needle-shaped crystals. On allowing the glass containing the crystals and mother liquor to remain for some time the crystals become insoluble and this modification is termed parahaemocyanin.The pigment from the blood of 3. moschata crystallises in needles. The so-called '( projectile " crystals are characteristic c f the haemocyanin from 0. vulgaris. J. C. D. Crystalline Salts of Uridinephosphoric Acid. P. A. LEVENE ( J . Biol. Chem. 1919 40 395-398. Compare A. 1918 i 130).-The normal ammonimz salt is readily prepared from the brucinel salt and crystlallises in heavy elongated prisms decomp. 185O (uncorr.). I n aqueous solution it has [a]kO +21.0° and crystallises with 1H,O. The ammonium hydrogen salt crystallises in long prismatic needles [a$' +13*Oo contracts a t 210° (corr.) decomp. a t 242O (corr.). Normal lead salt long needles. Brucine salt C9H1309N2P(C2sH,,0,N2),,7H,0 [a]:' - 20*0° (in very dilute solution). Air-dried substance effervesced a t 185O (corr.) and contracted and melted without further decomposition a t 195O (corr .) . J. C. D. Crystalline Guanylic Acid. P. A. LEVENE (J. Biol. Chem. 1919 40 171-174).-The crude brucine salt of guanylic acid was converted into the ammonium salt and precipitated from aqueous solution with neutral lead acetate. The solution obtained after removal of lead from the precipitate yielded on concentration under diminished pressure a crystalline substance. Analysis correflpondedORGANIC CHEMISTRY. i. 193 with the formula C,,H,,O,N,,~H,O [a]:' i n aqueous solution - 7*5O. In 5% aqueous ammonia [a]; -43'5O. In 10% hydrochloric acid i t was optically inactive. The substance had all the properties of guanylic acid. It gelatinised in the presence of mineral impurities and turned brown at 208O.The brucine salt CMH6,016N,,7H,0 contracted a t 217O melted at 233O and effervesced a t 240O; [a]:' -26-0° in 35% alcohol. The Structure of Yeast-Nucleic Acid. IV. Ammonia Hydrolysis. Y. A. LEVENE (J. Biol. Chem. 1919 40 415-424). -The original graphic representation of the entire molecule of yeast-nucleic acid had only an arbitrary schematia sense (compare Levene and Jacobs A. 1909 i 620 686; 1911 i 96 510). The views as to structural formulz advanced by Jones (A. 1917 232 233 596 597) and by Thannhauser (A. 1914 i 1015; Thann- hauser and Dorfmiiller A. 1918 i 47) and the evidence adduced in their support are considered. Nucleic acid was hydrolysed in a 2.5% aqueous ammonia solution for one hour a t looo a milder treatment than that employed by either Jones or Thannhauser.It is proved that the adenine-uridine dinucleotide is a mixture of two mononucleotides. The fraction originally regarded by Jones as a guanine-cytosine dinucleotide was found to consist principally of guanosinephosphoric acid together with a small. proportion of uridinephosphoric acid. The present findings nullify the experimental evidence in support of the theories of Jones and Thannhauser. From the theoretical point of view the theory of Thannhauser is weak because it assumes a carbon to carbon linking which is a very strong type of union whereas the polynucleotide is readily dismembered into mononucleotides. The ether linking aacepted by Jones is also a very firm union. On the basis of considerations such as these the linking of the nucleotides could be expressed most simply in the following way J.C. D. O*PO(OH) 0 0 0 $,H,O,-O-b I I 0. C I I ? 0 2 * O * ~ ~ O * ~ H ~ 0 2 ~ O * P * O * ~ ~ H . C,HON For the present this formula expresses the facts known about the structure of yeasbnucleic acid. Whether it will require alteration or not it is certain that the polynucleotide structure of yeast nucleic acid is definitely established. The Combination of Enzyme and Substrate. I. Estima- tion of Pepsin. 11. The Effect of the Hydrogen Ion Concentration. JOHN H. NORTHROP ( J . Gen. Physiol. 1919 2 113-122).-The change in the conductivity during the digestion of egg-albumin by pepsin affords a convenient and accurate method for the estimation of pepsin. The changes in conductivity do not follow the actual rate of digestion but the percentage change in conductivity is constant for a given quantity of pepsin irrespective of the absolute value of the original conductivity.It was found OH U,H,ON (1H C4H,0,N,bH C,H,N5 J. C. D.i. 194 ABSTRAUT8 OX' CJHElMIOAL PAJ?EBS. that the maximum change ocourred in strong solutions of egg- albumin titrated to p 2.6 with hydrochloric acid. By this process it is possible to determine quantitatively the amount of pepsin removed from solution by various substances. A series of experiments with substances such it8 staroh ozrlcium sulphate agar kaolin blood-charcoal caseinogen and egg-albumin gave results which indicate that the removal of pepsin from solution is not purely a matter of surface but that it is dependent in some way on the substance itself. That is the equilibrium reached is independent.of the size of the particles and therefore of their surface. This would indicate that the process is either one of solu- tion in which case the law of partition-coefficients should be found ta hold or of chemical combination in which case the law of mass action should apply. Preliminary experiments indicate that the process follows the law of pal tition-coefficients. There is a decided optimum hydrogen-ion concentration for the combination of pepsin with its substrate corresponding with the optimum reaction for digestion. It is suggested that the combina- tion of pepsin with its substrate and hence the rate of digestion is governed by the quantity of ionised protein present.The Different Actions of Pepsin and Chymosin on Acid Solutions of Syntonin. OLOF HAMMARSTEN (Medd. K. Vetenskaps- akad. A'obel-lnst. 1919 5 No. 7 1-13).-1n previous papers (compare A. 1918 i 459 510) the author has put forward evidence in support of assigning separate identities to chymosin and pepsin. Further support to his views is given by the experiments detailed in the present paper syntonin obtained from fish or horseflesh being used in place of acid and alkali legurnin (A. 1918 i 510). The method of experiment was similar to that previously detailed and all the results indicate that chymosin acts on syntonin forming albumoses a t an acid concentration a t which pepsin is inactive. J. C. D. T. S. P. Catalase. EIICHI YAMAZAKI ( J . Tokyo Chem Soc.1919 40 514-522k-The author has previously deduced an equation (ibzd. 36 and 6 ) by which it is possible to describe the course of the reaction between catalase and hydrogen peroxide a t any tempera- ture and any initial concentrations by using the temperature-coeffi- cient and the value of k a t 18O. He now finds that contrary to Evans's statement (A 1907 i 456) even with a range of concen- tration froni 1 to 80 k / E is constant provided the hydrogen-ion concentration is kept constant. Blood catalase prepared by the method of Senter (A. 1903 ii 661) is diluted to less than l% 20 C.C. of O*OZN-sodium hydrogen carbonate are added to each solution of the enzyme the volume is made up to 130 C.C. a t 25O and 20 C.C. of O.028N-hydrogen peroxide are added. The estima- tions are made in a current of carbon dioxide.The author discusses the kinetics of catalase action and is of opinion that the action is purely chemical. CHEMICAL ABSTBACTS.OROANIU OHEMISTRY. i. 195 Urease and the Radiation Theory of Enzyme Action. IV. H. P. BARENDRECHT (Yroc. K. Akad. Wetensch. Amsterdam 1919 22 126-138. Compare A. 1919 i 604; this vol. i lOZ).-A continuation and completion of previous work. The accelerating action observed with urease and attributed by previous experi- menters to carbon dioxide is shown t o be non-existent. Ammonium carbonate and carbon dioxide form a powerful buffer mixture which can maintain a constant PH value the essential condition for con- stant enzyme activity in a urea solution during hydroly~is by urease.The estimation of initial velocities of hydrolysis equal concentra- tions of urease being allowed to act on different concentrations of urea a t constant PH and T values produces results which appear inexplicable without the radiation theory. The lower the vallue oi' P the more the initial velocities increase with increase in the urea concentration. With high P values there is first an increase and then a decrease on raising the urea concentration. These facts are strictly in accordance with the radiation hypothesis. The urease radiation weakened by spreading or in any other way may effect synthesis. This is indicated by the fact that a t high P values where the urease is shown to be decaying reversion of an hydrolysis has been observed. From the last fact it is deduced that outside the sphere of hydrolytic action around a urease molecule there must be a region of radiation weakened by spreading and therefore of synthesis.This is confirmed by the fact that on diluting the urease concentration beyond a certain value its specific activity is decreased. From this it is evident that the synthetic action of urease which is not decaying can only come into play when the spheres of hydrolytic action do not intersect one another. It is shown experimentally that in any urease solution in which the enzyme is decaying through the combined action of alkalinity tem- perature and time a synthesis of urea from ammonium carbonate proportional to the urease concentration is observed. A descrip- tion of an apparatus for determining the concentration of hydrogen and hydroxyl ions is included in the paper.J. F. S. Cyanodiphenylarslipe. GIUSEPPE STURNIOLO and GIACOMO BELLINZONI (Boll. Chim. Farm. 1919 58 409-410 *).-CyanocEi- phenylarrine AsPh,.CN crystallkes in almost colourlas apparently monoclinic plates m. p. 3 5 O having the odour of both garlic and bitter almonds hydrogen cyanide being liberated readily by the action of moist air; its odour irritates the nasal mucus provoking sneezing. By treatment with aqueous or alcoholic alkali hydroxide or by heating with water or by distillation either in a current of steam or under reduced pressure (100 mm.) it is converted into diphenylarsine oxide (AsPh&O. When treated either with con- centrated nitric acid on the water-bath or with 2% hydrogen per- oxide or with bromine water in the cold it yields diphenylarsinic acid.Both cyanodiphenylarsine and diphenylarsine oxide contain- ing tervdent arsenic are transformed into diphenylarsinio acid in * and Uazzetta 1919,49 ii 326-327.i. 196 ABSTRACTS Ol?' CHEMICAL PaPERS. which the arsenia is quinquevalent by the traces of hydrogen per- oxide sometimes occurring as impurities in ether and in light petroleum. The alkali salts of diphenylarsinic acid are soluble whereas the iron salt forms a very fine white insoluble powder and decomposes when heated. T. H. P. Tetraphenyldiarsine. C. W. PORTER and PARRY BORGSTROM (J. Amw. Chem. SOC. 1919,41,2048-2051).-The authors have prepared tetraphenyldiarsine in a pure state from the oxide by the method of -Michaelis and Schulte (compare A.1883 187) and distributed it into sealed glass tubes without allowing it to come into contact with air. So prepared when exposed to air it oxidism to diphenyl- arsinic acid and tetraphenyldiarsine oxide but is not spontaneously inflammable as reported by Michaelis (compare A. 1902 i 515). In benzene solution it gradually absorbs oxygen. In similar solu- tion it rapidly absorbs iodine giving a crystalline iodo-compound m. p. 30° which is probably diphenyliodoarsine. I t s vapour pressure a t 200° is about 1 mm. and a t 300° in a vacuum it decom- poses giving arsenic and triphenylarsine and consequently its molecular weight in the state of vapour cannot be determined. Molecular weight determinations by the cryoscopio method in naphthalene indicate that tetraphenyldiarsine is associated at the freezing point of naphthalene.W. G. The Constitution of Arseno-metallic Compounds. P. KARRER (Ber. 1919 52 [B] 2319-2324).-1n reply t o Kolle (Deut. med. Woch. 1918 1177) and Binz Bauer and Hallstein (Arbb. aus Inst. exp. Therapie Georg Speyer Naus 1919 25 45) the author maintains the correctness of the views advanced by Ehrlich and Karrer (A. 1916 i 95) that the metal in complex salts such as copper- and silver-salvarsan is directly united to the arsenic atom thus H. W. Chemotherapeutic Studies on Organic Compounds containing Mercury and Arsenic. GEORGE W. RAIZISS JOHN A. KOLMER and JOSEPH L. GAVRON ( J . Biol. Ckem. 1919 40 533-552) .-The following are described 3-Nitroarsanilic acid mercuriacetate OAC-H~=C,H~(NO,)(NH~)*A~O(OH)~ bright yellow powder soluble in dilute sodium hydroxide on warming.3-Nitro-4- hydroxyphenylarsinic acid mercuriacetate C8H808NAsHg yellow powder soluble in dilute sodium hydroxide. 3 5-Dinitro-4-hydroxy- phenylarsinic acid mercuhacetnt e C8H,0,,N2AsHg bright yellow powder partly soluble in dilute sodium hydroxide. 3-Amino-4- hydroxyphenylarsinic acid mercuriacetate C,H,,O,NAsHg brawn powder soluble in dilute sodium hydroxide ; the solution decomposes on keeping with deposition of metallic mercury. 3 5-Diamino- 4- hydrox y ph eny larsinic acid mercuriace tat e C,R Q,N,AsH g dark brown powder soluble in very dilute sodium hydroxide; the solutionORGANIC CHEMISTRY. i. 197 decomposes with f orrnation of metallie mercury. 4-Carboxyphenyl- arsinic acid mercuriacetate C,H?O,AsHg cream-coloured powder insoluble in dilute sodium hydroxide soluble in dilute hydrochloric acid concentrated sodium chloride solution and in glacial acetic acid on warming.Diacetyl-3 5 -diamino-4-hydroxypF,enylarsinic acid mercuriacetate C,,H,,O,N,AsHg grFy powder soluble in dilute sodium hydroxide to form a brown solution from which mercury is deposited . C8H,05NBrAsHg white powder soluble in dilute sodium hydroxide warm glacial acetic acid and 10% hydrochloric acid. 3-Bromo-oxalylarsalziEic acid mercuriacetate C,,H,O,NBrAsHg white powder soluble in dilute sodium hydroxide ; the solution deposits metallic mercury on keeping. All the above compounds are inso'luble in the usual organic solvents. The presence of the arsinic acid group in the molecule of organic compounds appareFtly does not interfere with the entrance of the mercury group.As a class this type of compound is comparatively stable in alkaline1 solution the splitting off of mercury occurring only in compounds containing an amino-group. The toxic effectl on the animal body appears to be caused mainly by the mercury group. These new compounds were not found to be superior to the ordinary organio mercury compounds as regards curative influence in experimental trypanosomiasis and germicidal effect in vitro. 3 - Brornoarsanilic acid m ercuriace tat e J. C. D. Lead Triaryl a Parallel to Triphenylmethyl. ERICH KRAUSE and MARIA SCHMITZ (Ber. 1919 52 [B] 2165-2170).- Indications of the formation of unsaturated organo-derivatives of lead in which the metal is attached to carbon atoms by fewer than four valencies have been previously observed but the isolation of such substances has hitherto been impossible.The authors have succeeded in preparing lead tri-p-2-xylyl in the crystalline condi- tion and have shown that unsaturated derivatives are also formed to a greater or less extent by the action of magnesium phenyl or p-tolyl bromide on lead dichloride. Lead tri-p-2-xylyl Pb(C,H,Me,) is prepared by the addition of finely powdered lead dichloride to an ethereal solution of the calcu- lated quantit>y of magnesium p-2-xylyl bromide; the bulk of the dichloride dissolves to a brownish-yellow or chestnut-brown solution of the diary1 compound which gradually a t the ordinary tempera- ture but more rapidly when heated deposits lead and yields the1 lead triaryl.The substance forms a pale yellowish-green heavy crystalline powder which under the microscope appears to be formed of colourless well-developed rhombs. Determinations of the molecular weight by the cryoscopic method in benzene solution indicate the formula [(C,H,),Pb] so that the compound may possibly be regarded as hexa-p2-xylyl diplumban (C8H9) 3Pb. Pb (C*H9)3 - The d o u r of the substance however points to a feeble union of VOL. cxvm. i. hi. 198 ABSTRACTS OF CHEMICAL PAPERS. the lead atoms and to the possibility of dissociation under the influence of light. Probably the lead atoms are united in much the same manner as the methane carbon atoms of the triaryl- methyls. As is to be expected the substance is readily attacked by chemical reagents ; thus when treated with bromine in pyridine solution at -40° it gives lead tri-p-2-xylyl bromide four-sided leaflets m.p. 1 7 7 O whilst in chloroform solution at -loo it yields lead di-p-2-xylyE dibromide colourless shining rods m. p. 120O. Lead tri-p-2-xylyl is remarkably stable towards air and is not oxidised either in the solid state or in solution although in the latter condition it is rapidly and completely decomposed on exposure to light. It is not sensitive t o rise of temperature and decompoei- tion does not occur until 220O; for this reason attempts to obtain lead tetmp-Z-zylyZ by the action of magnesium p2-xylyl bromide on lead chloride a t elevated temperatures were unsuccessful but the compound was readily prepared from lead tri-p-2-xylyl bromide and the Grignard reagent; it forms colourless rectangular plates m.p. 255O which decompose above 270° with separation of lead. H. W. Mixed Lead and Tin Aryls and Aryl Alkyls and their Application to the Synthesis of Organo-compounds of Silver. Examples of the Influence of Symmetry on the Properties of Chemical Compounds. ERICH KRAUSE and MARIA SCHMITZ (Ber. 1919 52 [ B ] 2150-2164) .-The conversion of the readily accessible lead aryl monohaloids and tin aryl mono- haloids (A. 1918 i 415) into mixed aryl and aryl alkyl compounds is described. Asymmetry'in the latt.er appears to impart to. the compounds lower m. p. and greater solubility and chemical activity which is explained by the assumption that tshe metallic atom is more completely protected from contact with a reagent by the symmetrical union with for example four phenyl groups whilst with unlike groups spaces are left through which the reagent can penetrate.The lead and tin aryls or aryl alkyls react with a cold alcoholic solution of silver nitrate yielding bright yellow pre- cipitates which could not always be isolated in a pure condition but which are shown in the cases of lead and tin triphenylethyls to have the composition 2PhAg,AgN03. Mixed Lead Aryyls and A r y l A1kyZs.-The compounds are pre- pared by the addition of lead triphenyl bromide to an ethereal solu- tion of the magnesium aryl bromide and are isolated in the usual manner. Unnecessarily protracted heating and long exposure of the crude products or their solutions to light and the air of the laboratory are to be avoided.The yields are almost quantitative. The following substances are described lead triphenyl p-tolyl hair- like needles m. p. 125*5*; lead triphenyl p2-xyZyZ transparent crystals m. p. 104.50; lead tripheltyt m4-xylyl rods arranged in clusters m. p . 111.5-112°; lead triphelzyl p-phemetyl small shining needles m. p. 119-120° ; lead triphenyt a-maphthyl colour- less needles grouped in rosettes m. p. 1010; lead triphenyl cyclo-ORGANIC CHEMISTRY. i. 199 hexyl m. p. 119O; lead triphenyl ethyl needles m. p. 42O nz 1.62628 Dy (vac.) 1.5885 ; lead diphenyl di-a-naphthyl (from lead diphenyl dibromide and magnesium a-naphthyl bromide) microscopio prisms m. p. 197O ; lead di-a-naph thyl diethy2 inter- grown prisms m.p. 116O. Mixed Tin Aryls and Aryl A1kyls.-These are prepared from tin triphenyl chloride and excess of magnesium aryl or alkyl haloid in almost quantitative yield. The following substances are described tin triphenyl p - t d y l small slender needles m. p. 1 2 4 O ; t i n tri- phenyl p-2-xyt?yl coarae six-sided plates m. p. 100-5O; tin triphenyl a-naphthyl colourles prisms m. p. 125O; tin triphenyl methyl large shining rhombs m. p. 60° DF'& (vac.) 1.3113 n2iS5 1.6001 nFa5 1.60661 n"H";f" 1.62351 nz;" 1.63831 ; tan triphenyl ethyl ice-like crystals m. p. 56" DF (vac.) 1.2953 nga 1.59917 n,Q 1.60542 n& 1.62236 ; tin tetra-o-tolyl (by action of a large excess of magnesium o-tolyl bromide on a suspension of the etherate of stannic chloride) white crystalline powder m. p. 158-159'. Action of Mixed Lead and T i n Aryls on Silver Nitrate and Mercuric Chlm'de.-Silver phenyl silver nitrate 2PhAg,AgNO is prepared by the cautious addition of a solution of lead triphenyl ethyl in absolute alcohol to an alcoholic solution of silver nitrate. It forms a canary-yellow amorphous powder resembling cadmium sulphide in shade. The colour deepens rapidly when the substance is heated until decomposition occurs a t about looo the exact temperature depending both on the rate of heating and on the age of the preparation. The colour is practically unchanged after twelve hours in complete dark- ness but darkens within a few minutw on exposure to diffused light. Similarly lead triphenyl ethyl and mercuric chloride yield mercury phenyl chloride leaflets m. p. 25O0. Tin triphenyl ethyl gives silver phenyl silver nitrate and mercury phenyl chloride with silver nitrate and mercuric chloride respectively the products being identical with those prepared from the lead compound. Lead tri- phenyl p-phenetyl and silver nitrate yield a product which closely resembles the silver compound described above but does not appear to be homogeneous. Lead tetraphenyl tetra-ptolyl and tetra-p2- xylyl are not acted on by cold alcoholic silver nitrate solution but the solid compounds become grey owing to the gradual reduction of the silver nitrate on protracted boiling of the solution. Lead tri- phenyl ptolyl triphenyl p2-xyly1 and triphenyl m-4-xylyl have no action in dilute solution or only cause a yellow coloration; with excea of concentrated silver nitrate solution immediate precipitates closely resembling silver phenyl silver nitrate are formed which give a colourless solution in the boiling solvent and then yield a silver mirror and a brownish-yellow precipitate. Lead triphenyl a-naphthyl diethyl dinaphthyl and triphenyl cy clohexyl yield immediate precipitates even in dilute solution which are very similar to one another in appearance and reactions except in colour of the naphthyl compounds which is orange-yellow ; the latter sub- stancat yield naphthalene when treated with hydrochloric acid. It explodes when heated in a test-tube. h 2i. 200 ABSTRACTS OF CHEMICAL PAPERS. Lead diphenyl di-a-naphthyl does not react with alcoholic silver nitrate'. The aromatic tin compounds react less readily than the corre sponding lead compounds. Tin tetraphenyl does not react; tin triphenyl p-tolyl and triphenyl p-2-xylyl do not act in cold solu- tion and cause reduction when boiled. Tin triphenyl phenetyl gives a yellow precipitate after a few seconds whilst tin triphenyl methyl like the ethyl compound gives an immediate precipitate of silver phenyl silver nitrate which becomes black when warmed. According to the literature the lead alkyls immediately reduce silver nitrate; the authors' hypothesis that very unstable silver alkyls are formed as intermediate products is confirmed by the observation that yellow precipitates are formed which are stable a t - 30° for several seconds and at - 80° for several minutes. H. W.

ISSN:0368-1769    

DOI:10.1039/CA9201800133

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

ii. 137 General and Physical Chemistry The Optics of Disperse Systems. 111. I. LIFSCHITZ and GEORG BECK (KoZZoid Zeitsch. 1920 26 10-15. Compare A. 1918 ii 181 253).-The authors have measured the refractive index of solutions of triethylamine gelatin and phenol in water and of silicia acid stannio acid arsenic sulphide anti- inony sulphide and vanadium pentoxide sols in water by the method previously described (Zoc. cit.). The measurements were made a t a series of temperatures with the object of ascertaining the effect of change in the dispersity on the refractive index. It is shown that the degree o€ dispersion is practically without &ect on the refractive index. In the case8 of phenol and triethylamine where on lowering the temperature beyond the critical solution temperature a separation of the two liquids occurs there is only a very small ohange of refractive index shown.In the case of gelatin the value of the specific refraction varies very much with the tem- perature whether calculated by the Gladstone and Dale formula or by the Lorenz and Lorentz. formula. I n all other cases the value is approximately constant when either formula is used but the values given by the Gladstone and Dale formula are more nearly constant than the others. J. F S. The Spectrochemical Behaviour of Halogen Ethers ROfCH,],*X Halogen Hydrins HO*[CH,],-X and Acid Bromides RoCOBr . A. KARVONEN (Acad. Sea. Fennicae 19 14 A 6 1-139; from Chem. Zentr. 1919 iii 807-808).-1n con- tinuation of previous work (A. 1913 i 2) a series of halogen ethers and halogen hydrins has been ref ractometrically investi- gated.New values for the atomic refraction of chlorine bromine iodine and oxygen have been deduced from observations on normal primary alkyl monohaloids and the monclethers of normal primary alcohols. The data obtained for chlorine and iodine agree excel- lently with Eisenlohr’s figures; on the other hand the new values for bromine and ethereal oxygen differ considerably from the older results. The following figures are quoted Ha * D. q. H7. Hp-Ha. H,-Ho. Br-CHCHB- ............ 8.688 8.748 8.888 9.010 0.199 0.318 ............ 1.721 1.728 1.738 1-765 0.017 0.033 } /H2- b H 2 - The a-halogen ethers paxticularly the iodo- and bromo-deriv- atives show optical exaltations in the order Cl*CH,(OR)< Br*CH2(0R)<I*CH,(OR) whilst the behaviour of the B- and y-halogen ethers and of the fl- and y-halogenhydrins is normal.VOL. cxvm. ii. 6ii. 138 ABSTRACTS 03 CHEMICAL PAPERS. The acid bromides like the corresponding chlorides exhibit optical exaltation the order being R*COCl<R*COBr<R*COI. The atomic refraction of bromine in acid bromides is H 9.514 D 9.595 H 9.805 13 9.981 H - H 0.392 H - H 0.467. Among the corn- pounds X*CH,(OR) and R*CO*X the optical exaltatsions increase in t.h0 direction of the arrows Cl*CH,(OR) + Br*CK,(OR) + I*CH,(OR) R-COCl -+ R*COBr + R4COI When substituents such as the halogens alone or with oxygen or alkyl groups accumulate around a carbon nitrogen or phosphorus atom the optical exaltations fairly generally increase and the depression diminishes.The reverse behaviour is particularly notice- able when the atom adjacent to the central atom is at.tached to a number of substituents or is multiply linked. The accumulation of ethereal groups appears generally to have a depressing influence. H. W. Influence of Position and Accumulation of Substituents on Spectrochemical Behaviour. 11. The Spectrochemistry of Halogen and Oxygen Compounds. A. KARVONEN (Acad. Sci. Fennicae 1916 A 10 No. 4 1-22; from Chem. Zentr. 1919 iii 808. Compare preceding abstract) .-The exaltation caused by the accumulation of chlorine and oxygen atoms has been confirmed by observations on a series of chlorinated aliphatic esters. In general the optical exaltation diminishes when the halogen atoms in the chain are further removed from one another or from the oxygen atom.The esters of aliphatio acids containing a chlorine atom attached to the terminal carbon atom appear to exhibit a slight optical depression. In the annexed combinations the optical exaltations increase in the direction of the arrows Cl*[CH,],* C0,R Cl*CH,*OR RO*CO*Cl R*CO*Cl Cl*CO*Cl + J. J. J. + Br*[CH,],,*C02R --f Br*CH,*OR + RO*CO*Br -+ R*CO*Br +- Br*CO*Br J. J. + J. + I*[CH,],*CO,R H. W.GENERAL AND PHYSICAL CHEMISTRY. ii. 139 Iduence of Position and Accumulation of Substituonts on Spectrochemical Behaviour. 111. Spectrochemical Behaviour of the Esters of Normal Acids of the Oxalic Series. A. KARVONEN (Acad. Sci. Fenrbicae 1916 A 10 No. 5 1-20; from Chem. Zentr. 1919 iii 811. Compare preceding abstracts).- Optical investigation of the methyl and ethyl esters of the oxalic series shows that the exaltation diminishes uniformly as far as the succinic esters with increasing separation of the carboxyalkyl groups.The oxalic esters show slight exaltation malonio esters behave normally and the succeeding esters exhibit a slight depression with a tendency to increase in refraction towards the higher members. Esters of suberic and sebacic acids behave similarly to other esters of the oxalic series. H. W. Influence of Position and Accumulation of Substituents on Spectrochemical Behaviour. IV. Spectrochemical Behaviour of Ether-Esters ROfCH,],,- C0,R. A. KARVONEN (Acad. Sci. Fennicac 1916 A 10 No. 6 1-14; froni Chem. Zentr. 1919 iii 811. Compare preceding abstracts).-The following substances have been investigated ethyl and methyl carbonates methyl methoxyacetate ethyl ethoxyacetate propyl propoxyacetate methyl /3-methoxypropionate ethyl @-ethoxy- propionate propyl &propoxypropionate methyl a-methoxypropion- ate and ethyl a-ethoxypropionah. In the case of the lower fatty esters the optical valuw diminish when a hydrogen atom of the acid radicle is replaced by an alkyloxy-group.The optical depres- sions diminish as the ethereal oxygen atom and the carlbonyl group become more distantly separated in the alkyloxy-aliphatic esters. H. W. Secondary Spectrum of Hydrogen. T. R. MERTON (Yroc. Roy. SOC. 1920 [.4 96 382-388).-The spectrum of hydrogen a t been photographed using a concave grating 120 cm. radius of curva- ture and ruled 8000 lines per cm.It' is shown that the lines of the secondary hydrogen spectrum in the red and yellow regions are greatly enhanced in the presence of helium and that other new lines appear. In the more refrangible parts of the spectrum there is little difference in the intensity of the lines in the two cases. A second class of lines is not affected at all by the presence of helium whilst a third class diminishes in intensity and in somecases disappears entirely. It is suggested that the change in intensity under the experimental conditions may serve as a method of invea- tigation of the secondary hydrogen spectrum. Photographs of both spectra are given over the range A 4300-A 6500. A tabulated list of the lines which are not affected and of those which are enhanced in the presence of %helium together with the intensities under the two sets of conditions is appended to the paper.The lines hh5831.26 and 5703.86 are enhanced from intensity 2 to 7 h 5819.60 from 2 to 8 and A 5812.84 from 6 to 10. 1 mm. pressure an d of hydrogen in helium at 40 mm. pressure have J. F. S. 5-25. 140 ABSTRAOTS OE’ (IKEMTOAL PAPERS. Series of Multiple Lines in the Argon Spectrum. KNUD. AAGE NISSEN (Physikal. Zeitsck. 1920 21 25-28).-A theoreti- cal paper in which the lines of the argon spectrum are arranged into series. J. F. 8. Spectra of Isotopes. T. R. MERTON (PYOC. ROY. SOC. 1920 [ A ] ,96 388-395).-The specbra of ordinary lead lead from pitch- blende and lead from thorite ordinary thallium and thallium from pitchblende have been examined.An arc was produced between a tungsten button and the metal under investigation in a bell jar at a pressure of 1 mm. The respective interference fringes pro- duced by meam of a Fabry and Perot Gtalon were photographed and measured by a micrometer. It is found that the line ~ 4 0 5 8 in the case of pitchblende lead has a slightly greater wavelength than in the case of ordinary lead whilst for lead from thorite it is soniewhat shorter. The measurements in the case of thallium are not conclusive because pure thallium wm not isolated from pitchblende. J. F. S. A Relation between the Heads of Banded Spectra belonging to Different Elements of the same Group. TOKIHARU OKAYA (proc. Ph~ys. Math. sot!. Jupan 1919 [3] 1 lll-lZl).-~t is shown that for the three elements gold copper and silver the wave-lengths of the heads of bands emitted by their molecules satisfy fairly well the linear relation h=a+ Bn where a and P are constants and n is the series of natural numbers.From this it is concluded that between the heads of the band spectra elnitbed by the different molecules in similar conditions there exists a simple relation when the bands diverge toward the red side. Thus the wavelength A of the head of some band of one element with reference to the corresponding one A’ of another element is given by the relation ~=(a+pn)(.m/.?nl)n(~/y)i p and y being certain integers m and ml the atomic welghts of the elements concerned and A’ = (a + fin). Spectra of Tin Lead Antimony and Bismuth in a Mapetic Field. P. A. VAN DER HARST (Proc. K.Akad. Wetensch. Amsterdam 1920 22 300-312).-Using the light from a con- densed spark between poles of tin lead antimony and bismuth respectively the author has examined the effect of a magnetic field of about 30,000 gauss on a number of lines of these metals. The Zeeman effect is measured for 35 lines of tin 23 of lead 27 of antimony and 16 of bismuth. The measurements show deviations from those previously published by Purvis (A. 1907 ii 919) d m to uncert’ainty in the strength of the field used by Purvis. The resolutions of the lines are fairly regularly distributed between values which are 1-1.5 times the normal resolution. Incidentally it is shown that the antimony lines hh4370 4295 4287 4091 4078 4038 4024 4006 4004 3979 3721 3467 and 3460 measured by ScLppers (A.1912 ii 877) and published in Kayser’s “ €Ian& buch der Spectroscopie,” do not exist. The lines are respedively CHEMICAL ABSTRACTS.GENERAL AND PHYSICAL CHEMISTRY. ii. 141 hh2913 2863 2858 2727 2719 2692 2683 2671 2670 2653 2480 2311 and 2306. The error has arisen by Schippers mistaking lines of the third order for lines of the second order. J. F. S. Colonr of Metallic Salts. YUSI SHIBATA (J. Tokyo Chem. Soc. 1919 40 463-482).-From the spectral analysis of com- pounds of cobalt nickel and chromium the author deduces that the region of colour formation in these salts lies between the non- metallic atomic group and the metallic group which form a nucleus for the complex ions or double salts. I n no case is colour developed by metallic salts without the formation of complex ions.Colourless complex inorganic salts which show strong absorption in the ultra- violet are composed of constituents which are absolutely trans- parent in this region. A theory is developed which leads to the conclusion that the wavelength of the light absor6ed is longer the smaller is the atomia volume of the metal forming the centre of the complex. The conclusion is supported by experimental evi- dence in the case of correspondingly constituted complex salts of zinc platinum copper tin silver cadmium and mercury. The application of the theory to chromophores in organic com- pounds is disaussed. CHEMICAL ABSTRACTS. Relation between the Visible Absorption Spectra of certain Metals in their MIYX,’ and (M[,)yi X,’ Derivatives. MATHEUS D’ANDRADE ALBUQUERQUE (Revista Chim.pura appzic. 1916 1 Reprint 14 pp.).-In order to verify the law of the con- servation of even or odd valencies in derivatives of the same element evidence was sought for the existence of molecules of the type M,X,’ in salts derived from sesquioxides. A number of coloured salts with colourless anions were investigated in non-dis- sociating solvents or compounds containing complexes such as K,MX and K3MX6. Two methods were available (1) combina- tion of two different salts of the type M,X so as to obtain a mixed salt MM’X ; if the properties of the latter were different from those of M,X and (M’)?X6 the difference must be attributed to linking between M and MI; (2) spectrographic evidence for some union between M and M’. The observation of the absorption spectra proved that the normal salts derived from sesquioxides always presented absorption bands most of which were in the region where salts of the type MX4 of t-he same element show no absorption.When an element combines with another in different proportions the colour of the compounds shifts towards the red end of the spectrum as the valenay increases; and as the colour of sesquioxide salts is often abnormal this must be attributed to a radicle which can only be M,. I n the iridichlorides of silver and thallium the author assumes the presence of a complex radicle containing iridium because unlike other reddish-brown iridichlorides the salts are blue and bluish- green respectively that is approximating towards the colour of IrCls or IrpC16.It is observed that didymium gives a characteristic absorp- tion spectrum differing from those of praseodymium and neodym-ii 142 ABSTRACTS OF CHEMICAL PAPERS. ium which poinh to the existence of an atomic complex. In the majority of cases the colour of salts of the type M,X is complemen- tary to that of the salts MX of the same element a property which will be dispsed in a future paper. Absorption Bands in the Ultra-violet and Magnetic Birefraction. GUSTAVE MASSOL and A. FAUCON (BUZZ. SOC. d i m . 1919 [iv] 25 585-588).-1t is shown that the substances or groups which give absorption bands in the ultra-violet also exhibit magnetic birefraction as found by Cotton and Mouton (compare A. 1910 ii 368). W. R. S. W. G. Quinone-imide Dyes. XII. Absorption Spectra of some Cyanoacridine and Cyanopyronine Dyes.F. KEHRMANN and M. SANDOZ (Ber. 1920 53 [B] 63-66).-1n an earlier paper (A. 1918 i 313) it was shown that the substitution of the group iC-CiN for the tervalent nitrogen atom in safranines and azoxines has practically no effect on the colour. The absorption spectra for three sets of comparable dym have now been determined revealing the same feature. In fact the groups C-CN N especially may be regarded as optically equivalent. J. C. W. Determination of the Constitution of Coloured Substances from their Absorption Spectra. 11. F. KEHRMANN and MAURICE SANDOZ (Helu. Chim. -4ctn 1920 3 104-114. Compare A. 1918 ii 418).-The absorption spectra of the mono- and di-amino- and of the dianilino-phenazines have been examined.Alcoholic solutions of phenazine and aminophenazine are almost colourlms and orange respectively whilst similar solutions of 8.- and 2 3-diminophenazines are pale yellow and very light yellow ; this is in accordance with the authors’ theory that the introduction of an amino-group in the para-position t o the nitrogen of quinone- imines or in the same position with respect to the carbon atom of triphenylmethane has a hypsochromic or bathochromic influence which depends on the basicity of the group into which it enters. The introduction of the first amino-group into phenazine consider- ably increases the basicity but this is not the case with the second group. Phenylated derivatives of phenazine are slightly more red than the corresponding non-phenylated compounds but are chiefly notioeable for the augmentation of the intensity of colour effected by introduction of the phenyl group.I n general the absorption curves of the bases do not present any striking anomalies and the authors therefore attribute to them the orthoquinonoid st.ructure of phenazine ibelf,GENERAL AND PHYSICAL CHEMISTRY. ii. 143 Mono- and di-aminophenazines have very similar absor t,ion spectra when dissolved in fuming sulphuric acid which &sely resemble that of the di-acid salt of phenazine; they appear there- fore to have the orthoquinonoid structure the imino-groups having lost their auxochromic effect by conversion into amino-salts. When however the solutions are gradually diluted with concentrated sul- phuric acid the blood-red d o u r suddenly changes to green the shade differing somewhat with the individual compound.The gradual dilution of the acid appears to cause hydrolysis of the poly- acid salts and to liberate one by one the auxochrome groups the activity of which has been paralysed by saltcformation. Thus the green shade of the tri-acid salt of diaminophenazine gradually gives place to the violet tint of the di-acid salt and to the cherry coloration of the mono-acid salt. Since the successive transforma- tions take place in a continuous manner without appearance of any striking anomalies the authors ascribe the paraquinonoid consti- tution to the di-acid and mono-acid salt8 as well as to the green tri-acid compounds. The ultra-violet spectra of the bases and of the mono-acid salts have been examined.With the former an absorption band is invariably observed which becomes progressively displaced towards the visible violet as the chromogen becomes more highly substituted; it is situated at ~ = 2 5 0 ,y for phenazine at h=265 pp for the mono- and di-aminophenazmes; and a t A = 285 pp for dianilinophen- azines. The position of the anilinqroups which has such a marked influence on the position of the bands in the visible spectrum appears to have no effect on the location of the band in the ultra- violet. The mono-acid salt of aminophenazine gives two bands in the ultra-violet that of 1 2-diaminophenazine has one band in the visible violet (A= 457 p p ) whilst the second is but slightly shifted ; that of s-diaminophenazine shows only one band in the ultra- violet the second having completely disappeared.The mono-acid salta of the anilinophenazines likewise only show one band in the uItra-violet (A = 285 p p ) . It appears therefore that isomeric sub- stances with equal molecular weights give superposable spectra in the ultra-violet. H. W. Photochemical Actions produced in Crystals by means of Polarised Light. M. PADOA ( A t t i R. Accad. Lincei 1919 [v] 28 ii 372-377).-The author has studied the action of polarised light on crystals of cinnamic acid o-nitrobenzaldehyde and cinnamylidenemalonic acid (compare Weigert A. 1918 ii 344) all of which compounds undergo pronounced photochemical transformations. After exposure to the action of light crystals of cinnamic acid become dulled the dimeric u-truxillic acid being formed (compare Stobbe A.1919 i 329). Since this action is manifest only after prolongeld exposure i t may be assumed that solid solutions between the monomeric and dimeric forms are first formed; that such solu- tions are supersaturated is confirmed by the normal cryoscopicii. 144 ABSTRACTS OF CHEMICAL PAPERS. behaviour of a-truxillic acid in cinnamic acid solution and melting- point measurements indicate the concentration limit of the super- saturated solutions to be 3% of the t'ruxillic acid. No appreciably different results were obtained on exposing crystals of cinnamic acid to the action of polarised light in the one case with the plane of polarisation parallel and in the other normal to one pair of parallel edges of the crystal When two prismatio crystals of o-nit,robenzaldehyde (compare Lobry de Bruyn and Jungius A.1903 ii 531 ; Bruni and Callegari A. 1904 ii 545) are crossed normally and exposed in a polarising microscope to the influence of polarised light with the plane of polarisation at 45O to the axes of the two crystals one of the latter undergoes change more rapidly than the other. Resulk similar to but more pronounced than those obtained with o-nitrobenzaldehyde are observed in the case of cinnamylidene- malonic acid. After an exposure t o the action of polarised light varying according to the magnitude of the crystals from one and threequarters to threle hours part of the crystal with its axis per- pendicular t o the plane of polarisation is violently detached and often projected t o a distance; in some caw however only trans- verse segmentations appear in the crystals such occurring earlier and in greater number in the crystal mentioned.Subsequently crystalline nodules of the dimeride make their appearance. Here too it may be assumed that solid aolutions of the dimeride in the monomeride are first formed these solutions being so unstable as to produce a condition of tension in the crystals and consequent explosion. The partial transformation of the monomeride into the dimeride may be followed by means of the melting point which shows marked lowering even before any change in the crystal is apparent Weigert's conclusions are criticised and arguments are advanced in support of the view that photatropy is to be classed among the real photochemical phenomena.T. H. P. Behaviour of Fehling's Solution in Light. IVAN BOLIN and GUNNAR LINDER (Zeitsch. ph?y.sikal. Chem. 1919 93 721-736).- The action of light from a carbon arc on Fehling's solution in glass and quartz vessels has been studied at 1 5 O and 2 5 O . The amount of cuproua oxide precipitated was estimated by titration with potassium permanganate. The light reactions were compared with the reactions occurring in the dark. It is shown that in glass vessels the reaction has no temperature-coefficient and that there is no evolution of gas. The velocity of reaction is proportional to the time during which the solution has been illuminated and on removing the light the reaction ceases. I n quartz vessels the reac- tion has a tempsraturecoefficient 1.2 and after about three hours' illumination there is an evolution of gas.The velocity of the reaction increases with the time of illumination and when the light is removed the reaction continues for some time. The difference in the course of the reaction in glass and quartz vessels i s expl~nedGENERAL AND PHYSICAL CHEMISTRY. ii. 145 as follows. In quartz vessels in addition to the photochemical reaction an ordinary chemical reaction also takes place. This reaction is caused by substances produced in the photo-reaction. Both reactions produce cuprous oxide the chemical reaction increas- ingly more as reducing substances are produced photochemically. Consequently the total amount of cuprous oxide! produced increases progressively with the time. On shutting off the light the reaction continues until all the reducing substances have been used up.The reaction is more pronounced in quartz vessels because these allow light of smaller wave-length than 350pp to enter the liquid and i t is due to these waves that t,he reducing substances are produced from the tartrate in the solution. J. F. S. The Recoil of a-Particles from Light Atoms. L. B. LOEB (Phil. Mag. 1919 [vi] 38 533-541).-An account is given of an attempt to verify the conclusion of Rutherford namely that in collisions between a-particles and light atoms the number of atoms projected straight forward within an angle of loo from that of the a-particle is ten to thirty times that calculated from Darwin's theory of point charges by examining t.he number of a-particles recoiling after collision with light atoms.The conditions necessary t o ensure success and overcome the numerous difficulties are worked out but the results are provisional and indecisive for lack of sufficient time. They indicate that for aluminium the abnormalities found by Rutherford for nitrogen and hydrogen begin to show themselvea but the experimental difficulties were not overcome for lighter elements such as carbon. The range of the a-particle deflected at 105O from aluminium was found to be below 3.6 cm. as is to be expected if the laws of energy and momentum apply to these close encounters. F. S. Paasage of Corpuscular Rays through Material and the Constitution of the Atom. I. R. SEELIGER (Jahrb. Radioaktiv. Elektronik 1919 16 19-65).-A theoretical paper in which the author discussss the work of many investigators on the passage of a- and &rays through material.The consideration is concerned with the individual processes and changes brought about by the passage of a corpuscular ray through an atom or a molecule. These changes are subdivided into changes in the moving particle:' (i) direct conveyance of kinetic energy to the atom and (ii) emission of electromagnetic radiation; and into changes in the atom (i) direct gain in kinetic energy (ii) emission of electromagnetic radiation (iii) emission of secondary corpuscular radiation and (iv) chemical changes. J. F. S . Connexion between Collision Ionisation and the Energy of Ionisation of Neutral Molecules. J. FRANK P. KNIPPINO and THEA KRUGER (Ber. Deut. phtysikal.Ges. 1919 21 728-732). -The ionisation steps of hydrogen have been investigated. It is shown that definite ionisation occurs a t 11.5 20.7 volb 17.1 *0-25 5"ii. 146 ABSTRACTS OF CHEMICAL PAPERS. volts and 30.4k0.5 volts. The first step corresponds with the formation of H2* and the measurements show that an ion with considerably larger diameter is formed at 11.5 volk than a t 17 or 30 volts. A t 13.6*0*7 volts there is an emission of ultra-violet light the potential 17.1 f 025 volts corresponds with the ionisation of the atom into a normal and a positive ion and an electron and the potential 30.4 f 0.5 volts corresponds with ionisation of the atom into two positive ions and two electrons. Thme results go to show that the Bohr atom model of hydrogen is not strictly in keeping with the facts.J. F. S. Apparatus for the Separation of Radium Emanation and its Estimation Electroscopically . J. E. UNDERWOOD and HERMAN SCHLUNDT (Trans. Amer. Electrochem. SOC. 1918 34 203-209).-An apparatus is described by means of which radium in various ores and concentrates may be estimated. The material is either boiled with concentrated sulphuric acid or fuseld with a mixture of alkali carbonates or with sodium hydrogen sulphate in one part of the apparatus and the emanation stored in a mercury burette in anothy part of the apparatus. The emanation is kept for ten minutes in the burette to allow the thorium emanation to decay and is tchen passed into the electroscope where it is measured in the usual way. Using this method Brazilian monazite is shown to contain 0.794-0.812 x 10-7 gram radium per gram; Indian monazite 0-1017-0*1025 x lO-7gram radium per gram.J. F. S. Comparison of the Ionisation Currents due to Equal Quantities of Radium Emanation in Different Types of Electroscopes. T. H. LEAMING HERMAN SCHLUNDT and JULIUS E. UNDERWOOD (Trans. Amer. Electrochem. SOC. 1916 30 365-378). -The authors have compared the ionisation currents obtained with several types of electrwpes (Lind Wulf quartz fibre Fontacto- meter Duane and Laborde and Randall) and find that with the exception of the Randall rectangular electroscope the measured currents have lower values than the values calculated by the formula of Duane and Laborde I = E(1- C . Sl V ) . I n some cases the values were 18-22% too low. The experiments show that the reduction factor C of Duane and Laborde’s formula has mecifio valuee for ionisation chambers of definite dimensions.J. F. S. Absorption of Radium Gamma Rays. K. W. F. KOHLRAUSCH (Sitzungsber. K . Akad. IViss. Wien 1917 126 IIa 683-704).-The results of the investigation are given in the following table where RI,,K2 and R are the three c,omponents of the complex y-rays from radium Absorption Coefficients pl p2 and p3. Absorber. K1. K,. K8. Lead ........................... 0-545 1.4 4.6 Zinc ........................... 0.327 0.57 1.44 Iron ........................... 0-356 0.63 3.00 Aluminium .................. 0.127 0.23 0.67GENERAL AND PHYSICAL CHEMISTRY. ii. 147 The ratio of the energiee measured by ionisation currents is for these three components K3 K2 K = 1 6 8.The absorption measurements show that the influence of secondary radiation is extremely imp or t an t. TheHard Secondary G a m m a Rays from Radium. K. W. F. KOHLRAUSCH (Sitzungsber. K. AIcad. JViss. Wien 1917 126 Ira 705-720) .-In a previous paper (compare preceding abstract) the author made a careful series of measurements of the absorption of the y-rays of radium in various substances. I n these experiments the importance of secondary radiation was indicated. The present paper deals with this secondary radiation which is shown to have a high penetrating power. When the y-rays pass through matter a very hard type of secondary radiation (/upb=O*545 cm.-l) is pro- duced. The author compares the observed total energy of the secondary radiation with the calculated values for varying thick- ness of screen.The observations are in good agreement with theory. CHEMICAL ABSTRACTS. CHEMICAL ABSTRACTS. Absorption of Gamma Rays from Radium. K. W. F. KOHLRAUSCH (Sitzungsber. X . A Itad. TViss. TYien 1917 126 I I a 887-913).-The results are given of an extensive series of measure- ments of the absorption coefficients of radium y-rays in different substances. CHEMICAL ABSTRACTS. The Chemical Character of Protoactinium [Ekatan- talum]. I. Separation of Protoactinium from Pitchblende. OTTO HAHN and LISE MEITNER ( B e r . 1919 [B] 52 1812-1828). -The raw material for the preparation of protoactinium is the insoluble residue consisting principally of silica from pitchblende after treatment of the mineral with nitric acid.By repeated extraction with nitric acid all the radioactive substances including radium can be dissolved and the residue left with a very feeble u-actiyity due chiefly to protoactinium. It is recommended to add from 4% to 1% of tantalum oxide to the pitchblende residue and to heat it with a little concentrated sulphurio acid and excess of 40% hydrofluoric acid in a platinum capsule covered with a platinum dish containing cold water to serve as a condenser then to dilute and filter through a paraffined funnel evaporate the filtrate and ignite the residue gently which renders the tantalum oxide containing the protoactinium insoluble in acids. An addi- tion of a few milligrams of thorium and of lead nitrates to the hydrofluoric acid serves to keep traces of ionium uranium-X and radio-lead from passing through the filter with the tantalum.The ignited tantalum oxide is boiled with aqua regia to remove iron zirconium etc. leaving the tantalum undissolved. The Rutherford-Boltwood ratio of 8% f o r the actinium branch series would neglecting correction for difference of range lead to an a-activity of protolactinium 4% of that of the uranium in the mineral from which it is extracted. This is found to be much too high. The protoactinium was separated from known amounta of 6*-2E. 148 ABSTRACTS OF OHEMICAL PBPERSj pitchblende by three different methods detailed below and the a-activity of the preparation extracted per gram of mineral was found to be the same within lo% in six experiments from which after applying a correction for the range it is calculated that only 3% of the atoms of uranium disintegrating pass through the proto- actinium actinium series.The three methods consist of (1) fusion of the pitchblende with sodium hydrogen sulphate followed by treatment of the insoluble residue with hydrofluoric acid as already detailed; (2) treatment of the very finely divided mineral with hydrofluoric acid and sulphuric acid in which t,he main part of the protoactinium passes into solution directly ; (3) treatment of the mineral very similarly to that described already for the residue. Full details of the chemical operations and charts are given show- ing i n each case the distribution of the radio-elements in the successive stages of treatment. Tantalum oxide was always added to the mineral and elaborate care taken more of this material being added and separated from each of the separate parts to remove proto-actinium to ensure that all was separated. Finally itg a test a known amount of previously prepared protoactinium preparation was added to pitchblende and the result showed that no loss excwding 5% occurred in the course of the chemical treatment.The low percentage of the actinium seriea operates against sufficient protoactinium being present in uranium minerals for isolation like radium. Its period of average life can only be fixed within the limits of 1200 and 180,000 years a t present which corre- spond with weigh& in the mineral of 1.5% and 22.5% of the weight of contained radium. So far efforts to concentrate it from tantalum have failed.It is suggested that an examination of the amount of protoactinium in old uranium preparations might throw further light on the period and uranium preparations of known age of uranium not less than 100 to 200 grams are appealed for. The 3% ratio agrees with the ratio found for the relative activities of uranium-XI and uranium-P. It is pointed out that protoacthiurn with atomic weightl about 230 and place in the periodic table beyond thorium of atomic weight 232 furnishes probably another example similar to that of teIIurium and iodine. F. S. The Origin of Actinium. OTTO HAHN and LISE MEITNER (Physikal. Zeitsch. 1919 20 529-533. Compare preceding abstract) .-The paper contains some further details of the methods employed for det'ermining the relative a-activity of the preparations measured.F. S. Determination of the Half-life Periods of Thorium and Actinium Emanations. R. SCHMID (Sitzuysber. K. Akad. Wiss. Wiem 1917 126 IIa 1065-1079).-The author describes a method which is the same in principle as that used by Leslie and Perkins. Measurements were also made by Rutherford's method in which the ionisation current is measured at different points along a tubeUENERAL AND PHYSICAL CHEMISTRY. 5. 149 through which the emanation is flowing a t a known rate. A third method employed is due to Mache. The mean resultls of the investigation are as follows half-life period for thorium emanation 54.5 *Om03 sea. ; for actinium emanation 3-92 +0*015 sea. CHEMICAL ABSTRACTS. The Age of Thorium Minerals.R. W. LAWSON (Xitxungsber. K. Akad. Wiss. Wien 1917 126 IIn 721-739).-The paper deals with the end-product of the thorium series in the light of the atomic weight results of Honigschmid and others. It is shown t'hat the age determined from the1 Th/U and P b / U ratios may be betwelen 8 and 300 million years. The minelrals employed came from Devon Brevig and Norway. The poesible origin of the large discrepancy in age is discussed. Thorium minerals from Ceylon give a range from 138 to 506 million years. GEORGE SENTER (Trans. Farday SOC. 1919 15 3-9).-An introductory paper to1 a dis- cussion of The Present Position of the Thewy of Ionisation. (se'e following abstracts) in which the author summarises certain investigations o'n electrolytes in solution namely hydration deviat,ion of strong electrolytes from the law of mass action and the chemical activity of ions and non-ionised molecules.It may be regarded as established that ions and undissociated moleicules may simultaneously undergo chemical change( and thatt in the ca,talytic activity of strong acids the non-ionised molecule plays a part as well as the hydrogen ion. Electrolytic Dissociation. SVANTE ARRHENIUS (Trans. Fara- day SOC. 1919 15 10-17).-The author summarises the present evidence in favour of the dissociation theory of solution under eleven headings (1) Evidence from analyt.ica1 chemistry. (2) Addi- tive properties. (3) The diffusiosn of electrolytes. (4) The electric conduotivity of solutions. (5) Colours of solutions. (6) Ostwald's law. (7) Non-aqueous solutions.(8) Ostwald's law for salt solutions in water. (9) The freezing point of aqueous solutions. (10) Demia- tions in concentrated solutions. J. R. P. CHEMICAL ABSTRACTS. Electrolytic Dissociation Theory. J. R. P. (1 1) Velocity of reaction. Present Position of the Ionisation Theory Reactions of both the Ions and Molecules of Acids Salts and Bases. S. F. ACREE (Tram. Farday SOC. 1919 15 18-26).-Mainly an historical account of atkempts t o elucidate the so-called " abnormal salt effect" of dissolved electrolytes. Results on the inversion of sucrose and other reaction velocit-is are explained by assuming t,hat molecules as well as ions are active. The acid molecules are found to be two or three timels more active tlhan the hydrion in the case of hydrochloric hydrobromio and nitric acids as measured by the hydrolysis of sucrose.A similar conclusion was reached for the hydrolytic activity of alkalis. The activity of molecules is also deduced from a study of the action of alkyl haloids in alc~holicii. 160 ABSTRACTS OF CHEMICAL PAPERS solution on phenoxides. Another cause of abnormal salt effect is solvation studied by Lapworth. Several tables of values of the velocity constants of ions and molecules deduced from the author's results and from re-interpretation of those of other workers are given. J. R. P. TheBearing of Migration Data on Conduction in Solu- tions. The Electrochemistry of Sodium Iodide in Acetone. JAMES W. MCBAIN and F. C. COLEMAN (Trans. Faraday SOC. 1919 15 27-46).-When the sum of the movements of both ions is equal to the total current the solvent cannot be appreciably dis- sociated. Hypothesw to the contrary are therefore invalidated.The migration data for solu- tions of sodium iodide in acetone and of silver bromate in diethyl- amine show that even in highly concentrated solutions the solvent does not conduct appreciably. The evidence of the migration data shows that conduct,ivity is only an approximate measure of the degree of dissociation since the migration ratio almost invariably increases with the concentration a change ascribed to solvation. The calculation of conductivities at infinite dilution from extra- polation of dilution formulae to infinite dilutlion or from the assumption of the law of mass action a t infinite dilution are regarded with disfavour. The molecular weipht of sodium iodide This is the case in aqueous solutions.in-acetone determined by the boiling-point m&hod is normal. J. R. P. The Determination of the Ionisation of an Aqueous Solution. W. R. BOUSFIELD (Trans. Faraday SOC. 1919 15 47-73).-A summary of the methods used by the author in calcu- lating the ionisation of an electrolyte in aqueous solutions. Ion- isation is assumed to,be the result of the interaction of associated water molecules with the molecules of the salt whe'reby (H,O) and H,O molecules react with the salt to produce (H20)2 molecules and hydrated ions. The application of the law of mass action t.hen gives equations which give good results for a large class of strong electrolytes at high dilutions and in the case of the alkali chlorides give good results in concentrated so1ut)ions.On account of vary- ing hydration it is assumed that the transport numbers require correction. This however cannot a t present he carried out except by the method of trial and error. * Stress is laid on the part played by the solvent which is assumed to exist in associated forms the proportions of which vary with the concentration of the solution. J. R. P. Correction of the Transference Numbers o€ the Ions of an Electrolyte. W. R. BOUSFIELD (Trans. Paradav SOL 1919,15 74-80).-0n the assumption that the volumes of the ions in solu- tion are unequal the correction necessary in the ordinary method of calculating the relative ionic mobilities from the transport numbers is found. The corrections are inappreciable a t concentra- tions less than normal.J. R. P.GENERAL AND PHYSICAL CHEMISTRY. ii. 151 Some Aspects of the Electrolytic Dissociation Theory. NILRATAN DHAR (Trans. Faraday SOC. 1919 15 $1-93).-By a discussion of recent work on electrolytes including molecular-weight determinations Kohlrausch's rule freezing points osmotic pres- sures heats of neutralisation of acids and bases and absorption spectra the conclusion is drawn that the theory of nm-ionisation proposed by Snethlage (A. 1915 ii 615 825) is not tenable. J. R. P. The Hydration of Ions. HENRY J. S. SAND (Trans. Faraday SOC. 1919 15 94-97).-1n his calculations of the radii of ions Bousfield adopts a radius for the water molecule which leads t o a value for Avogadro's constant over twenty times that adopted in the same calculations.The values for the ionic radii deducd from Stokes's la'w do not agree with those derived from other calcula- tions. It is believed that it is incorrect to apply the law of Stokes to molecular magnitudes. Some Recent Investigations on the Dilution Law. J. R. PARTINGTON (Trans. Faruday SOC. 1919 15 98-121).-1n the case oh weak electrolytes the law of mass action applies with greater accuracy than to any other case yet investigated. The viscosity correction has been applied in a very arbitrary manner by many investigators and the author believes that in dilute solutions it is unnecemary. 'Yhe equation deduced by Szysko'wski (A. 1915 ii 616) gives very accurate results for strong electrolytes and renders unnecessary the arbitrary alterations made by Kraua and Bray (A.1913 ii 914) in the accurate experimental values of Kohlrausch and Maltby (A. 1900 ii 61). It is shown that the theory proposed by Ghosh (A. 1918 ii 348 392 423) is not in accordance with the experimental results of the latter observers since it requirea qua1 ionisations a t equal dilutions for all electro- lytes of the same type whereas differences are fuund. It is con- cluded that the law of mass action applies to strong electrolytes at great dilution. J. R. P. Variation of Electrical Conductivity of Electrolytes with Increase of Concentration. ALFRED W. PORTER (Tram. Faraday SOC. 1919 16 122-125).-The empirical equation of Kohlrausch 1 - a=const. x ci is shown by a graphical method to hold over a large range.The index n of Storch's equation a / (1 - a)" = X V-n is practically the same for potassium chloride as for sodium sulphate in spite of the difference in valency. This equation has the form required by the law of mass action for a possible reaction although the particular reaction which makes n=?j {van't Hoff has not yet been identified. The assumption of electrical action i! etween the ions would lead to diminution of the ionisation a with concentration a t a greater rate than required by the law-of mass action whereas the opposite effect is actually found. If the law of mass adion holds good at great dilution it is neces- sary to explain the transition from this to the other laws which hold J. R. P.ii. 152 ABSTRACTS OF CHEMICAL PAPERS. at increased concentrations.A possible equation is a2(1 + ba/ V ) / (1 - cc)Ll+ c(1- a)/ V ] = const. where b and c are additional con- stants. J. R. P. The Resistance of an Electrolytic Cell. EDGAR NEWBERY (Trans. Faraday SOC. 1919 15 126-136).-That part of the irre- versible resistance of an electrolytic cell which is concerned in the transfer of the current from electrode to electrolyte has been studied in a number of cells. Transfer resistance is greatest when gases are liberated a t .the electrodes considerable when gaseous ions are utilised in carrying the current although not liberated a t the electrodes and negligibly small when the current is carried by metallic cations and by anions which readily dissolve the anode. Conditions f avourable for high transfer resistance axe low current density low temperature polished surf aces and high over-voltagm.Those conditions which &ect the nature of the surfaces affect also the transfer resistance. Transfer resistance is due t o the mechani- cal resistance (pressure and frictional) which opposm the penetra- tion of gaseous ions into the surface! of the electrodes. Measure- ments of electrical conductivity are liable to serious error if transfer resistance is not perfectly eliminated and there is reason to fear that this has not been done in determining some of the conductivity data a t present available. J. R. P. Effect of Interionic Forces in Electrolytes. S. R. MILNER (Trans. Faruday SOC. 1919 15 148-151).-Chemical €orces which cause the association of two ions into a molecule diminish extremely rapidly with the distance and become negligible a t very small separations of the ions whereas electrical forces between the ions fall off comparatively slowly.The ordinary derivation of the law of mass action f o r electlrolytes assumes that interionic forces become negligible for finite separations of the ions. These forces however would cause a reduction of osmotic pressure and of molecular lower- ing of freezing point. The application of the inverse square law leads to general agreement with the observed freezing-point curves. The conductivity should be proportional to the osmotic pressure of the free ion,s that is those possessing sufficient kinetia energy to escape from their attracting neighbours. J. R. P. Ionisation and the Mass Law. H. M. DAWSON (Trans.Fura- day SOC. 1919 15 152-153).-The deviations from the law of mass action in the case of strong electrolytes are ascribed mainly to changes in the ionising power of the solvent by the highly polar solutes J. R. P. The Abnormality of Strong Electrolytes. JNANENDRA CHANDRA GHOSH (Trams. Faradag SOC. 1919 15 154-163).-The autho'r does not agree with the criticisms of Partington (see above). The deviation from his theory shown by some electrolytes is ascribed to hydration of the ions. J. R. P.GENERAL AND PHYSICAL CHEMISTRY. ii. 153 Equilibrium between Bromine and Potassium Bromide Solutions at Oo. GRINNELL JONES and MINER LOUIS HARTMANN (Trans. Amer. Electrochem. SOC. 1916 30 295-326) .-Measure- ments of the equilibrium between bromine and water and between bromine and potassium bromide solutions a t Oo and of the specific conductivity of the solutions have been made.Calculations by the method of successive approximations based on the results show that the following reactions occur (i) bromine dissolves as Br,; (ii) Br,+H,O f H'+Brl+HBrO; (iii) KBr+Br KBr,; (iv) KBr+2Br2 Z KBr,. A saturated solution olf bromine in water a t Oo has the composition Br,=0.2539 mol. per litre; H' 0*001085 ; Brl 0*000126 ; Brgl 0.000628 ; and Br5 0*000331. The hydrolysis constant XIf= (H')(Br/)(HBrO)/Br =5.7 x 10-10 the equilibrium constant I<',= Br' x Br,/Br3/ =0*051; and the equilibrium constant K5= Brl x Br,2/Br5/ = 0.0246 The partition-coefficient of Br between water and carbon tetrachloride after correcting for hydro- lysis is D =21*018 + 2*831C where C is the concentration of Br in the carbon tetrachloride. By means of these constants the concen- tration of each ion may be calculated in any solution containing known amounts of potassium bromide up t o 0*lN and bromine up to saturation.The conductivity of a series of solutions of potass- ium bromide from 0.001N to 0-1N has been determined a t 0". When extrapolated to infinity by Noyes' method these results give 83.8 for A and if the ionic conductivity of K' is 40.1 Br' has the value 43.7. From the data for the specific conductivity of solu- tions of potassium bromide containing bromine it follows that the ionic conductivity of Br,! is 23.5 and of Br5/ 16.3. Corrosion of Metals by Acids. OLIVER P. WATTS and NEWTON D. WHIPPLE (Trans.Amer. Electrochem. SOC. 1917 32 25?-284).-The rate of corrosion and solution of iron zinc zinc amalgam mercury cadmium tin lead copper gold silver tin amalgam and lead amalgam by means of hydrochloric acid sul- phuric acid peirchloric acid phosphoric acid and acetic acid and also by solution of sodium hydroxide and a series of salts has been determined. The effect of a number of oxidising agents on the rate of solution has also been investigated. The following oxidising agents were used hydrogen peroxide sodium arsenate ferric sul- phate ferric chloride potassium dichromate potassium chlorate mercuric chloride potassium permanganate potassium nitrate chromic anhydride nitric acid potassium bromide sodium nitrite and potassium iodide. The authors confirm the view previously put forward ( d i d .1912 21 340) that the protective effect of arsenio on the corrosion of iron by sulphuric acid is due to polarisation by hydrogen. This view is confirmed by the facts that the corrosion of iron by acids when the metal was protected by arsenic was greatly accelerated by oxidising agents and arsenic do= not protect iron from attack by corrosive agents which do not evolve hydrogen by their action. Amalgamation proteds zinc from corrosion by acids because the discharge potential of hydrogen on mercury exceeds the poten- tial on zinc Protection by arsenic and mercury are alike in their J. F. S.ii 154 ABSTRACTS OF CHEMICAL PAPERS nature. Tin and lead are very slowly dissolved by non-oxidising acids although their potentials are such as would cause thelr ready solution in acids if it were not for the unusually high dls- charge potential of hydrogen on them.Removal of hydrogen by an oxidising agent causes these metals to dissolve readily in acids that otherwise corrode them very slightly. Corrosion by acids of metals below hydrogen in the electrochemical series namely copper and silver has been brought about by the presence of oxidising agents. The statement that the corrosion of amalgamated zinc in dilute sulphuric acid is accelerated in a vacuum is shown t o be incorrect. By removing the depolarising oxygen of the air reduction of pres- sure retards corroeion not only of amalgamated zinc but of other metals the solution of which is hindered by a polarising film of hydrogen. With respect to their corrosion the metals examined may be classified as follows (a) Metals the potentials of which exceed the discharge potential of hydrogen on them; these dissolve readily in acids except such as form insoluble salts.( b ) Metals the potentials of which are less than the discharge potential of hydrogen on them; these dissolve readily in acids only in the presence of oxidising agents. Gold and platinum are not readily attacked by acids in general even when these contain oxidising agents. The superiority of nitric acid over other acids as a solvent for metals is due to its being a t the same time an acid and an oxidising agant which enables it to dissolve metals of the second class which non-oxidising acids are unable to do. Oxygen is necessary for success in cyaniding gold ores bemuse in dilute cyanide solutions gold is a metal of the second class.Measurements of the discharge potential of hydrogen in solutions of potassium cyanide and sodium hydroxide and experi- ments on the corrosion of metals in the latter lead to the conch- sion that the above classification the action of oxidiaing agents and protection by other metals will apply to the dissolving of any metal in any electrolyte from which it displaces hydrogen when passing into solution. The above classification of metals according to the relative magnitude of their potentials in comparison with the discharge potential of hydrogen on them applies not only to the solution of metals but also to their electrolytic deposition. Plating baths for depositing metals of the first class cannot be strongly acidified without causing the deposition of much hydrogen in place of an equivalent amount of metal; but a large proportion of acid may be added to solutions for the deposition of metals of the second class without greatly lowering the current efficienv through the deposition of hydrogen.J. F. S. K. FAJANS (Ber. Deut. physikal. Ges. 1919 21 709-713. Compare this vol. ii 12 21).-A theoretical paper in which a correction of the heat of hydration of the hydrogen ion is made; in place of the previously published figure H’=362 Cal. per gram ion the more correct but still approximate value 260 Cal. per gram ion is sub- stituteld. The term “hydration of ions” is more fully defined. Heat of Hydration of Gaseous Atomic Ions.GENERAL AND PHYSICAL CHEMISTRY.ii. 155 The term is not intended to indicate the formation of hydrates of the ions of definite st oicheiometria composition but rather that due to the electrostatic charge of the ions the oppositely charged part of the polar water molecule is turne'd toward the ion and this in its turn exerts an attractive force on the next molecule. This type of dielectric polarisation proceeds continuously in the water surrounding the ion. The heat of hydration increases with decreasing volume of the gaseous ion and reachee an exceedingly large value with the hydrogen ion. Affinity of Halogen Atoms for Electrons and the Energy of Ionisation of the Hydrogen Haloids. K. FAJANS (Ber. Deut. physilcal. Ges. 1919 21 714-722. Compare preceding abstract).-A theoretical paper in which making use of the principles previously published t h e author calculatm the energy change in the form of a development of heat which results from the com- bination of the halogen atoms with an electron. If; is shown that the combination occurs with considerable loss of energy but that the amount decreases with increasing atomic weight; the values found are in Cals. chlorine 116 bromine 87 and iodine 81. The wave-length of the spectrum line brought about by this combination is calculated by means of the formula E =hv= h x 3 x 1010/~ in which E is the1 energy change and A the wave-length in Angstrom units. The1 following values are obtained chlorine 2440 bromine 3350 and iodine 3490. By the same method. of calculation the work of ionisation of the hydrogen haloids has been obtained.The helat of combination of a gaseous hydrogen ion with a gaseous halogen ion is found to be chlorine 322 bromine 310 and iodine 300 Cal. Using the fo'rmula V = 1000?7/96,500 x 0.2388 in which B is the ionisation potential and U the energy chanqe the ionisa- tion potential has been calculated and the following values obtained hydrogen chloride 14.0 volts hydrogen bromide 13.4 volts and hydrogen iodide 13.0 volts. K. FAJANS (Ber. Deut. physikall. Ges. 1919 21 723-727. Compare preceding abstracts) .-Tn an earlier publication Franck (A. 1910 ii 817) attributes the loss of mo'bility of negative ions in the1 presence of oxygen and other cases to the combination of the gas atoms wit-h electrons and he €ormulat.es a potential series of the various gasels.This quegtion is discussed in the present paper. It is shown that the collision of an electron with a gas molecule effects the change represented by one of the equations (1) X + O = X + X - ; (2) X,+ZE)=ZX-. For the halogens the potential of the change is calculated and the following values obtained equation (l) chlorine - 0.44 volt Bromine - 1.78 volts and iodine - 1.96 volts ; equation (2) chlorine -5.47 volts bromine -5.55 volts and iodine1 -5.47 volts. I n the case of the hydrogen haloids particularly hydrogen chloride the change HX+ @=H+-X- is supposed to occur and this on calcu- lation yields the potentials hydrogea chloride + 0.39 volt hydrogen bromide -0.09 volt and hydrogen iodide -0.53 volt. J. F. S. J.F. 8. Electron Affinity of Gases.ii. 156 ABSTRAUTS OF UHEM1CM.L PAPERS. Both considerations explain the formation of gas ions from electrons and atoms without the necessity of assuming a specific electron affinity . J. F. S. Theory of Heat Change. F. HABER (Ber. Deut. physikaZ. Gas. 1919 21 750-768).-A theoretical paper in which the author discusses the theory of heat change in connexion with (i) hydration energy of gaselous ions (ii) energy of dissociation of salt vapours and ionisation potential of metal cations and (iii) lattice energy and ultra-violet characteristic frequencies. Affinity of the Halogen Atoms towards Electrons. M. BORN (Ber. Ueut. physikal. Ges. 1919 21 679-685. Compare Born A. 1919 ii 214; Fajans this vol. ii 12).-A theoretical paper in which based on the theory put forward previously by the author and Fajans (Zoc.cit.) the affinity of the halogen atoms for electrons is calculated. The values E the energy of combination of an atom with an electron 2 the energy of dissociation of an atom into ion and electron and D the heat of dissociation of a diatomic gas are calculated and the following numerical values in Cals. obtained fluorine 2 = - 26 (mean) ; chlorine 2 = - 62 (meaa) D=57 E=119 Cals. or 5.16 volts; bromine Z = -61 D=23 E=84 Cals. or 3.64 volh; iodine Z= -59 0 ~ 1 8 8 = 7 7 Cals. or 3.33 volts. It is shown also that the wave length corresponding with the energy can be calculated on the basis of the quantum thelory. The following wavelengths in Angstrom unih are obtained chlorine A = 2380 ; bromine A = 3360 ; iodine A, =3680.J. F. 8. THEODORE W. CASE (Trans. Amer. Electrochem. SOC. 1917 31 351-364) ,-The action of light on one ellectrode of the cell CulCu,Olaqueous copper formate + formic acidlCuBO ICu has been investigated. It is iound that an E.M.F. up to 0.085 volt can be obtained and a current of 0-003 ampere if the metal plates are 20 x 3.2 cm. in size. By arranging the cell on a rotating disk so thatl the copper plates are alternately illuminated an alternating current of various amplitudes and frequencies may be obtained. The action of the cell1 indioates tha,t under proper conditdons its life may be con- tinuous and that its elements will not disintegrate. The action of the cell is compared tol the resistance change of the mineral cuprite when exposed to ultraviolet light.The1 contrast betweon the E.M.F. effect of cuprous oxide and cupria oxide is discussed. The action olf the cuprous oxide photochemical cell is explained on the basis of the oxidation of cuprous oxide to cupric oxide in light. It is shown that there is no relation betwem the sign of the light action and tqhe colour of heated copper plates. Determination of Hydrogen-ion Concentration. JOHN W M. BUNKER ( J . BioE. Chem. 1920 41 11-14).-A modification of a bubbling electrode used in a closed vessel is fully deecribed. J. F. S. Cuprous Oxide Photo-chemical Cell. J. F. S.QENERAL AND PHYSICAL CHEMISTRY. ii. 157 The apparatus is dmigned to meet the requirements of quick accurate determinations in large numbers and haa given satisfactory results.J. C. D. Phenomenon after Anodic Polarisation. 11. A. SMITS G. L. C. LA BASTIDE and TH. DE CRAUW (Proc. K . Akad. Wetemch. Amsterdam 1920 22 296-299. Compare this vol. ii '8).-It was previously shown that on interrupting the current by which iron is polarised anodically the potential of the iron falls passes through it minimum and then reach= the uriginal value. This is due to diffusion changM which affect t-he ratio Fe"/Fe"'. A similar phenomenon is now observed for nickel which has been anodically polarised In solutions of nickel chloride the minimum is reached in l w than three seconds whilst in the case of nickel sulphate the change is much more prolonged. On cathodic polar- isation of iron the reverse phenomenon is observed namely the potential of the iron passes through a maximum and then falls to the normal value.This is to be expected i f the explanation offered in the case of anodically polarised iron is correct. Polarisation Tension and Constitution of Complex Cobalt Compounds. NILRATAN DHAR and G. URRAIN (Compt. refid. 1920 170 106-1OS).-The polarisation tension of a complex salt depends not only on the constitution of the complex ion but also on the nature of the ion which accompanies it. Thus in the series starting with [Co(NH,),]Cl the replacement of ammonia by water causes a diminution in the tension whereas in the seriea [COClz (NR3)4IC1 the contrary holds good. The replacement of a molecule of water by a halogen in such a compound as [Co(NH3),,H,0]C13 causes a rise in the polarisation tension.Further in the purpureo-salts the tension is higher when the purpureo-complex contains a more negative radicle. The replacement of a chlorine atom by a nitro- group or of two chlorine atams by a carbonategroup causes a lowering of the polarisation tension. The marked rise in the tension following on the substitution of an hydroxy-group for a chlorine atom is in agreement with the fact that these complex compounds are only stable in alkaline media. The Polarisation in Solutions of Iron. W. ALBERT NOYES jun. (Compt. rend. 1920 170 177-180. Compare this vol. ii 9) .-Nernst's formula A = 0.0002 T/ mpl f o r calculating the value of A in the equation Ep= A log,J + B giving the potential of an electrode traversed by a current doea not apply to the polar- isation of solutions of ferrous salts but none the less gives values proportional to the experimental values.Electrolytic Behaviour of Tungsten. WALTER E. KOERNER (Tram Amer. Electrochem. Soc. 1917 31 221-255).-The potential of tungsten in N-solutions of potassium cyanide sdium hydroxide potassium hydroxide ammonium hydroxide sulphurio J. F. S . W. G. W. G.ii. 158 ABSTRACTS OF CHEMICAL PAPERS. acid hydrochloric acid potassium nitrate nitric acid potassium fluoride potassium chloride potassium bromide potassium sulphate and potassium iodide has been measured against certain standard electrodes at 25O. The results show that tungsten doea not behave as an insoluble electrode but sends ions into the solutions with velocities which vary with the different solvents.Tungsten has a lower potential in #-alkalis than in N-acids and a lower potential in N-acids than in N-salts. The follolwing E.P. values (H=O) are calculated from the experimental results ; all solutions were normal potassium cyanide - 0.647 volt ; sodium hydroxide -0.316 volt; potassium hydroxide - 0.315 volt; ammonium hydroxide - 0,238 volt; sulphuric acid 0.193 volt; hydrochloric acid 0-256 volt; potassium nitrate 0.300 volt; nitric acid 0.311 volb; potassium fluoride 0.522 volt; potassium chloride 0.563 volt; potassium bromide 0.589 volt; potassium sulphate 0.719 volt; and potassium iodide 0.733 volt. A further series of E.M.P. measure ments were made for tungsten in saturated solutions of tungstic acid in N-solutions of hydrochloric sulphuric and nitric acid respectively.The following values are obtained hydrochlorio acid 0.317 volt; sulphuric acid 0.313 volt; and nitric acid 0.317 volt. 0.117 volt; W I W(OH),,N-HCl]IN-HCl I W 0.057 volt; and W I W(OH),,N-HNO 11 N-HNO I W 0.009 volt. The E.M.F. values obtained give the relat<ive solubilities of tungstic acid in N-acid solutions. Analytically the values were found t o be sulphuric acid 0.02281 gram WO *per litre; hydrochloric acid 0.01067 gram WO per litre; and nitric acid 0.00025 gram WO per litre. The anodic behaviour of tungsten has been investigated and it is shown that in solutions of tungsten in acids it behaves as a cation whilst in solutions of tungsten in alkalis it behaves tm an anion. Tungstic acid goes into solution in acids and alkalis as an electrolyte and not as a colloid.Tungsten dissolves anodically in aqueous and non-aqueous solutions of alkalis acids and salts. Under specified conditions tungsten becomes passive when used as anode in aqueous and non-aqueous solutions of acids bases and salts. I n aqueous solutions of alkalis and non-aqueous solutions of acids bases. and salts tungsten only becomes passive a t high current densities (2 amperes per sq. dcm.). I n aqueous solutions of acids and salts the passive condition is assumed by tungsten a t low current densities and only a t extremely low current densities will i t remain active in these solutiions. The passivity of tunqsbn is due to adherent films of hvdrated oxides of tungsten. The films may be readily dissolved and the passivity dwtroyed. The hydrated oxide films appearing on the anode vary in d o u r from lmwn through blue to yellow.The degree of passivity varies with the colour of the films. The electrochemical equivalent of tun&en was found to be 0,3173 mg. per coulomb a value very closely in agreement with the theoretical value. A number of experiments on the use of tungsten in storage cells are recorded. It is found The following combinations were also measured W I W(OH),,N-I3,SO 11 N-H,SO I W,GENERAL AND PHYSICAL CHEMISTRY. ii. 159 t?hat the potential difference between t,he brown oxide (+ ) and the blue oxide (-) is 0.75 volt. J. F. 5. Electrical Endosmose and Adsorption. T. R. BRIGQS H. L PIERSON and H. S. BENNETT (Trans. Amer. Electrochem. Soc. 1917 31 257-270).-Using a modified form of Perrin endosmo- meter which obviates the error produced by the evolution of gas a t the electrodes and permits the use of diaphragms composed of powdered solids the authors have1 determined the effect of the applied E.M.F.on the rate of flow of the liquid for the case of water with a glass diaphragm. In this case the liquid flowed to the cathode and the rake was found to be in keeping with Perrin’s law for E.M.F. values lying between 530 and 100 volts. The effect of temperature on the rate of flow using water and asbestos diaphragms and celllulose in boiled water was determined a t temperatures from 18O to 67O. It is shown that the product ratex visc~sity-~ is practically constant. The flow of liquid in acid and alkaline solutions was investigated with alundum diaphragms when sharp reversals were obtained which are in keeping with Perrin’s results. With glass diaphragms no such reversal of direction was observed.The effect of barium ions on the rate of flow to the cathode in alkaline solutions is to reduce it# much more than would an equivalent quantity of univalent ions. In acid solutions barium ions have little effect but sulphate ions reduce t.he rate’ much more than chloride nitrate or acetate ions. This with alundum and carborundum diaphragms. A number of experiments with dyes in N/500-solutions of hydrochloric acid and sodium hydr- oxide are described. It is shown that acid dyes (eosin crystal ponceau) in alkali travel t o the cathode whilst basic dyes (safranine and methylene-blue) in acids travel to the cathode; acid dyes in acids and basic dyes in alkalis give indefinite results; alundum diaphragms were used in these experiments.The relationship between dyeing and electrical endosmosis tends to confirm the adsorption theory. J. F. S. Chemistry of the Flaming Arc in Relation toluminescence. WILLIAM ROY MOTT (Trans. Amer. Electrochem. Soc. 1917 31 ‘365-390).-The light produced by flaming arcs containing various substances and the relative volatility of refractory substances have been iaveetigated. It is shown that there is no case of a blue arc shell. In every case except barium and vanadium the arc cure is blue or violet and the shell green yellow or red. Hence the light from the shell in every case but barium and vanadium is of longer wave-length than that of the arc core.The non-metallic elemenb fluorine chlorine bromine iodine oxygen sulphur and nitrogen do not give elemental spectra but fluorine chlorine oxygen and nitrogen give the spectra of compounds in a carbon arc. The elements phosphorus arsenic and boron give only a few ultra- violet lines in the carbon arc. me easily reduced metals except those of the iron group yield no arc shell. The low energy of reaeii. 160 ABSTRACTS OF CHEMICAL PAPERS. tion at high temperatures explains thk la& of light. The most eleatropositive elements give the most markedly coloured luminous shells especially where more than one valency stage is character- istic of the element a t high temperatures. With yttrium oxide the crater on the bead alone givea a green shell which replaces the usual red shell obtained with the crater partly on the bead and partly on the carbon.Zirconium oxide gives a yellowish-white shell. The colour is probably due to hot solids as zirconium carbide is less volatile than platinum and its oxidation would give an extremely non-volatile oxide. Metallic zirconium is fairly volatile. I n nearly every case with a carbon arc the flaw of material is from positive to negative. With mixture8 of salts of potassium rubid- ium and msium fluoride respectiveiy with calcium fluoride a strong blast also comes from the negative crater which causa a unique dimness near the negative part of the aro. A dim large positive crater can often be produced by nearly all salts of potass- ium rubidium m d esium and by oxy-salts of sodium.This with the effect on cyanogen bands and arc lengtlh may be explained by the reaction EF + C,N = KCN + CNF and others necessary to return by oxidation to potassium fluoride carbon dioxide and nitrogen. A dim negative crater is most easily produced by barium salts volatilised from the positive crater. Glucinum oxide is the least volatile of the oxides which are so insulating as to prevent cratering such as oxides of the alkaline earths aluminium oxide and silica. The oxides of yttrium zirconium thorium and the other rare earths allow cratering. Tungsten is by far the least. volatile of the known elements and this is followed by tantaluni. The light of a yellow flame arc is due to reactions involving calcium fluoride calcium oxide calcium carbide and metallic calcium.J. F. S. Magnetism of the Metalammine Compounds. ERNST ROSENBOHM (Zeitsch. physikd. Chem. 1919 93 693-720). -The magnetic susceptibility of a very large number of metallic ammine derivatives has been determined a t 16-20° by means of a Curie torsion balance. The metals investigated were cobalt platinum rhodium iridium ruthenium zinc nickel copper and chromium. The ammine derivatives of cobalt platinum iridium rhodium zinc and ruthenium are except in the case of some of the cobalttriammines diamagnetic. The diamagnetism is g r e a b t in hexammine salts of cobalt somewhat less in the pentammine derivatives very much less in the tetra-ammine derivativet3 and least in t'he triammine derivativa of cobalt. I n the last class of compounds it is found owasionally that para- magnetism is exhibited.The same regularity is observed when the whole or a portion of the ammonia group is replaced by ethylene- diamina or propylenediamine. The entrance of one or more ionogen residues into the sphere of the metallic atom is shown to bs followed by a decrease in the diamagnetism in the case of all the diamagnetic metallic ammines investigated. In the case of platinum it is shown that the susceptibility m d molecular magnetism ofGENERAL AND PHYSICAL CHEMISTRY. ii. 161 bivalent platinum is l e ~ ~ diamagnetic than is the case with quadri- valent platinum. Purhhelr as in the case of the electrocconductivity in passing from hexammino- to hexacido-derivatives the magnetism passw through its extreme value with those compounds which have no ionogen acid residue.The ammine derivatives of nickel copper and chromium are paramagnetic. In the case of the chromium derivatives it is shown that the magnetic susceptibility and the molecular magnetism are least in the hexammine derivatives and increase steadily t o the triammins derivatives. As in the caw of the cobalt derivatives the extreme value occurs with those deriv- atives which contain no ionogen acid group. The examination of the geometrical isomerides of the derivatives of cobalt platinum and chromium indiaates that magnetically the cis- and trans-forms of a even compound cannot be differentiated. A t the same tiine it is shown that the measurement of the magnetic susceptibility is a very sensitive method of testing the purity of these isomerides.In the case of the optiaal isomerides of cobalt and chromium it is shown that the d- and I-forms have the same susceptibility whilst the racemate has a different value. I n most cases the susceptibility of the racemate is smaller than that of the active isomerides but this is not always so. I n the case of the co-ordination isomerides of cobah and chromium it is found that the susceptibility is not alike but in most cases the two values are not very different. The greatest difference is found in the case TCo(NH,),] [Cr(C204)31.x . 106 = 13.75. The difference observed between the co-ordination isomerides and the other types of isomer- ides is probably due to the fact that the two nucleus atoms are magnetioally opposed to one another the one acting diamagnetiaally and the other paramagnetically.An examination of the magnetic influence of the nucleus atom shows that metalammines with a metal valenoy which is stable in the normal salts possess a suscepti- bility of the same order as the normal salts whilst metalammines with a metal valency which is unstable in the normal salts may have a susceptibility very different from that of the normal salts and it may even be of the opposite sign. Measurements of the poly- nuclear cobalt and chromium ammines show that these compounds are quite normal in their magnetic relatio'nships. T"he molecular magnetism is calculated frolm Pascal's formula M = XiA + 1 (A. 1911 ii 91) and the values compared with the present measure- ments. It is found that both sets of values are remarkably close. The magnetio properties are considered in connexion with the mag- netone and it is shown that in accordance with Weiss's theory the magnetone number is always a whole number.A Thermoregulator with the Characteristics of the Beckmann Thermometer. R. B. HARVEY+ (J. Biol. Chem. 1920 41 9-lO).-The instrument can be set easily at any temperature desired between -200 and +25O0. The electrical contacts are placed so that small temperature changes will make or break the circuit. When run on test in ap air-bath with a standard Beckmann [Cr(NH&l rCo(C,O,),] x . 1 O k 18.80 ; J. F. S.ii. 162 ABSTRACTS OF CHEMICAL PAPERS. thermometer and vigorous stirring the air temperature was regu- lated t,o within k0*004°. J. C. D. Specific Heat of Sulphuric Acids Nitric Acids and their Mixtures.PAUL PASCAL and M. GARNIER (Bzdl. SOC. chim. 1920 [iv] 27 S-l8).-Using an electrical method of heating the authors have determined the specific heats of binary mixtures of sulphuric acid and water containing from 10 to 100% of sulphuric acid of binary mixtures of nitric acid containing from 10 to 98% of nitric acid of binary mixtures of nitric and sulphuric acids and of ternary mixtures of nitric and sulphuric acids and water. The results are set out in detail and a graph with trilinear co-ordinates combines the data. W. G. Latent Heat and Surface Energy. G. RUDORF (Phil. Mag. 1920 [vi] 39 238-239).-A criticism of Hammick’s paper under the above title (A. 1919 ii 389) in which it is shown that using more accurate values for y (surface tension) u (molecular dia- meter) and Li (internal latent heat) the values of y V / J u and &/6 give results which are widely divergent in the case of argon.The values calculated by the author are 302 and 240 respectively instead of 226 and 214 calculated by Hammick. J. F. S. Critical Constants. Critical Temperature of Hydrogen Bromide. E. MOLES (J. Chim. Phys. 1919 17 415-424). -A criticism of Fielding’s work (compare A. 1919 ii? 45) in which t.he author support.s the law of Guldberg and Guye as to the rela- tionship between the absolute critical temperature and the absolute boiling point/ 760 mm. For hydrogen bromide the author finds experimentally the value 89*80° for the critical temperature and the value as calculated by Guldberg and Guye’s rule is in reasonably close agreement with this.He further indicates that Fielding’s formula (Eoc. cit.) for calcu- lating the critical pressure gives results considerably higher than those found by experiment in the cam of hydrogen chloride and hydrogen sulphide. W. G. Form and Regularities of the Vapour Pressure Curve. E. WERTHEIMER (Ber. Deut. physikaE. Ges. 1919 21 692-708).- A t8hwretical paper in which it is shown that the previously pub- lished vapour-pressure formula p + A 9 = C’Tn (ibid. 1919 21 435) contains in itself five approximation laws dealing with the saturation state namely Diihring’s rule of constant boiling-point difference the law of analogous &ate Trouton’s rule of normal heat of vaporisation the constancy of the van der Waals’ number ( f ) a t the critical point and the Nernst equation for calculating chemical constants.These expressions are all developed from the above formula and examined by means of a large number of previ- ously published examples. J. F. 5.C 1C.N F. RAT ANT) PHY STCAL CHEMISTRY. ii. 163 Vapour Pressure Regularities. W . HERZ (Zeitsch. Elektro- diem. 1919 25 408-409. Compare A. 1919 ii 218).-Accord- ing to the theory of corresponding s t a h the proportionality factor a in van der Waals’s equation log.rro/p=a(60/T- l) where .rro is the critical preesure 6 the critical temperature (in absolute units) and p and T corresponding values of pressure and tempera- ture should for all normal substances have the constant value 3. The value of a has been calculated for the elements hydrogen nitrogen oxygen mercury argon krypton xenon chlorine and bromine and in most cases it is nearer 2 than 3 and is always less than 3.I n vertical series the value increlases with the atomic weight of the element. The value of the constant has also been calculated for the hydrocarbons pentane to decane acetic and pro- pionic acids a number of alkyl esters of fatty acids and some alkyl chlorides in some cases for a number of different temperatures. I n all these cases its value is close to 3. It may rise or fall with increasing temperature and in most cases shows a distinct rise as a homologous serim is ascended. Associated liquids show a greater value for a than similarly constituted non-associated liquids. Thus the value for water is greater than that for hydrogen sulphide and that for ammonia greater than that for phoaphine.Relative Volatilities of Refractory Materials. WM. ROY MOTT (Tram. Amer. Electrochem. SOC. 1918 34 255-295).-Ten arc methods of ascertaining the relative volatilities of metals carbides oxides nitrides fluorides chlorides and sulphides are suggmted and to gome extent developed. The most rigid method depends on the least volatile material remaining as the residue when distilling mixtures. For materials boiling above the boiling point of iron saturated with carbon (3500O) a series of boiling points has been estimated on a triple basis of reference namely reference to the curves for iron for equal atomic amounts of material frac- tional distillation series and position of deposition at the negative arc crater.The boiling points in the series are iron saturated with carbon 3500O ; silica 3500O ; palladium 3600O ; carbon 3700O ; alumina 3700O ; chromium carbide 3800O ; vanadium carbide 3900O ; rhodium 40000; platinum 4050O ; uranium carbide 4100O ; ruthenium 4150O ; lanthanum oxide 4200O ; titanium carbide 4300O ; yttrium oxide 4300O ; columbium carbide 4300O ; zirconium oxide 4300O ; thorium oxide 4400O ; iridium 4400O ; osmium 4450O ; molybdenum carbide 4500O ; yttrium carbide 4600O ; thorium carbide 5000O ; zirconium carbide 5100O ; tantalum car- bide 5500O ; tungsten carbide 6000O. Tungsten allows carbon to distil rapidly through its molten carbide which probably surren- ders carbon vapour exactly as copper oxides surrender oxygen. The boiling point of tungsten is estimated a t 6000O and that of tantalum a5 5500O. Zirconium carbide is the least volatile carbide and is followed by thorium carbide.Thorium oxide is the least volatile oxide whilst th’e white and yellow oxides of zirconium are neyly as non-volatile. The least volatile non-cratering oxide is gluclnum oxide (b. p. 3900°) wbich is left as a final residue in fractional E. H. R.ii. 164 ABSTRACTS OF CHEMICAL PAPERS. distillation of its mixtures with barium oxide strontium oxide calcium oxide magnesium oxide silica and alumina. From the crater dilstances at positive and negative the boiling points of the more common refractory oxidm are estimated as follows:' barium oxide 2000O ; titanium oxide below 3000O ; chromium sesquioxide 3000O ; calcium oxide 3400O ; silica 3500O; magnesia 3600O ; alumina 3800O; and glucinum oxide 3900O.'* Smoke time" esti- mates of boiling points are given for several oxides sulphides and halogen salts. The figures are only roughly approximate. The volatility of oxides follows the increasing order potassium sodium lithium vanadium boron barium strontium manganese iron cobalt niukel chromium titanium silicoa calcium magnesium aluminium erbium cerium neodymium lanthanum zirconium and thorium. The characteristic oxide is intended in every case. Boron nitride sublimes at about 3000O. As an addendum to the paper is added a bibliography of work on the volatilisation of refractory mat'erials and where in these papers figures are given for boiling points and melting points them are recorded.A further addendum deals with the ratio of the melting point to the boiling point. These values are given for practically the whole of the elements and it is shown that with the exception of the metals of the first group of the periodia system the ratio abs. b. p. f abs. m. p. = cn. 1.8. J. F. S. Glass Rectifying Column especially suitable for the Rectilication of Liquid Mixtures and the Recovery of Volatile Solvents. W. ELSNER (Chem. Zeit. 1920 44 11-12).- The apparatus consists of a glass column 50 mm. in diameter and filled with glass balls the surfaces of which are ground or etched. A perforated plate a t the bolttom of the column servw as a support for the balls and the latter are of three sizes the lowelr part of the column containing the larpest balls whilst the smallest balls form the uppermost Iayers.The! top of the column is connected with a small qlass dephlegmator provideld with a water jacket which is supplied from a constant-level reservoir and above tho dephlegmator is a still-head carrying a thermometer and a side- tube. which is connect,ed with a condenser. All parts of the apparatus are connected together by means of ground-in joints. w. P. s. Saturation Pressure calculated from the Temperature Latent Heat of Vaporisation and theMolecular Volume ot the Liquid by means of Maxwell's Distribution of Velocities Law. K. K. JXRVINEN (Zeitsch. p?yikaZ. Chem. 1919 93 743-753) .- A theoretical paper wherein equations are deduced by means of which the saturation pressure may be calculated. These equations have the folrm and z=p/pa in which z is the number of molecules which have a velocity c c2 is the mean velocity of the molelcules p is the ____ _____ _____ c2=c3/c= 4/(2W,i+ 3 R T ) / M d3RT/M= d(2Wi/3RT) + 1,GENERAL AND PHYSICAL CHEMISTRY. ii.166 saturation pressure pa the intwnal pressure and Wi the internal latent heat of vaporisation. The remaining symbols have their usual significance. The expression has been tested on the sub- stances oxygen nitrogen benzene ether *pentaxle toluene and methyl butyrate and a fair agreement with fact obtained.' J. F. S. Molecular Attraction. IV. K. K. JARVINEN (Zeitsch. physikal. Chem. 1919 93 737-742. Compare preceding abstract and A. 1913 ii 293; 1915 ii 251; this vol. ii go).-A theoretical paper in which the author recalculates the constants used in the formulx previously published (Eoc.cit.). It is found for monatomic mole- cule,~ that n=5 and a=55.06. W i . v =41-30. C,v%/a. In the case of polyahmia molecules the molecular attraction is repre- sented by the expressions F = m2k/ (T - pro). = r n 2 J i j (94 - BV*)~. From this equation the following expressions are deduced - Pv$)n-l= G,(d - &,~)"/w~ . u and C J U . Wi = (n - 1)/3. d/(d - &,*). In these expressions the symbols have the meaning previously applied to them T~ is the smallest distance between the molecules and vo the smalIest volume; n = 5 and p=0-242 whence C,/u .Wi=4/3 x 1*27=1-69. A number of substances on which the formulx have been tested give the con s t m t 1-69 and agree most nearly with the value n=5.J. F. S. a = (n - 1)/3 . Method of Calculating the Limits in Physico-chemical Phenomena. MAURICE PRUD'HOMME ( J . Chim. phys. 1919 17 377-382) .-The method previously employed for calculating the critical temperature in terms of the surface tension (compare A. 1919 ii 183) is sho'wn to be applicable for calculating the density at. absolute zero as a function of the t,emperature in the case of gas@ and it is shown that as in the case of liquids the density a t absolute zero is four times the critical density. The critical pressure may also be calculated as a function of the temperature subject to a correction of So the calculated value being too high. W. G. Molecular Condition of Liquids and Solutions. ERNBT HROBER (Zeitsch. physikal. Chem. 1919 93 641-692).-Density determinations have been made a t 25O of a large number of solu- tions of liquids in organio solvent& and of a number of solid sub- stanoes in solid solvelnts.The number of molecules of solvent replaced by onel molecule of the dissolved substance in unit volume is calculated in each case. It is shown that the number of replaced molsmleis is approximat,ely equal only when the dissolved substance belongs to a closely related group for example the mono-substitu- tion derivatives of benzene. In all other cases different numbers of molecules of the solvent are replaced; the respective figures are approximately in the same proportion as the molecular volumes and the relationship is only slightly dependent on the nature of the solvent and the concentration of the dissolved substance.The 'behaviour of solutions of solids at various temperatures has been5. 166 ABSTRACTS 02' CHZMICAL PAPhlBS. investigated. The volume changm accompanying the solution of liquids is small and is not specifio either in the case of solvent or dissolved substance. In the case of solids dissolved in liquids the positive volume changes are larger and in general appear to be due t o . a change in the state of aggregation. In most cases a characteristio behaviour is observed both with the solvent and the dissolved substance. The coefficient of compressibility and the coefficient of expansion run parallel with the mean atomia concen- tration and the reciprocal of the mean atomia volume. In homo- logous series the atomic concentration corresponding with constant atomic volume is nearly constant a t the boiling point and for all substances which contain only carbon hydrogen and oxygen the value fluctuate8 only between very narrow limits. It appears possible from the properties of a mixture particularly from the coefficient of expansion to decide whether a contraction or an expansion will take place.In the very large number of cases examined only three cases were exceptional to the rules formulated and in all probability these cases were abnormal because of a chemical reaction between the components. J. F. S. Viscosity Measurements. 0. FAUST (Zeitsch. physikal. ChHn. 1919 93 758-761).-The influence of the diameter of the tube on the viscosity of liquids has been investigated in connexion with the method of viscusity measurements made by determining the time required for a bubble of air to rise through a measured length of the liquid.It is shown that Q = T ( T ~ - T ~ ~ ) in which r is the radius of the tube rl the radius of the air bubble and Q the cross- section of the liquid between the bubble and the tube. Since (T- rl) is constant and r + T ~ S ~ T Q = 2nr x C where C is a con- stant. The formula is tested with a viscid oll with tubes of various diameters and the measured time compared with the calculated time. It is shown that with wider tab= (18-24 mm.) the calcu- lated and observed results agree but with narrower tubes (16-12 mm.) there is an increasing divergence with decreasing diameter. This is due t o the fact that the error introduced by placing r+rl=2r is greater in the case of narrow tubes than in the case of wider tubes.It is also shown that in the case of wider tubw the time required for the asmnt of the bubble is independent of %he size of the bubble whilst the same is almost true with narrower tubes. J. F. S. The Welding of Solid Powders under Preseure. TONI VON EAGEN (Zeitsch. Elektrochem. 1919 25 375-386) .-An extensive series of experiments is demribed on the cohesive properties of pure powdered inorganic substances under pressure. The substancw ex- amined include the oxides sulphides sulphates halogenides nitrates and carbonatw of many metals including both anhydrous and hydrated forms of the salts. Finegrained particlw were found to cohere better than coarser and for most experiments the sub- stance was ground to pase a sie%ve of 25 meshes per sq.mm. TheGFXNERAL AND PHYSICAL CHEMISTRY. L. 167 powder was subjected for most experiments to a pressure of 560 kilos. per sq. cm. in a screw press and the tablets formed were examined by inspection and where possible by determining their hardness or crushing strength. The substances showing the best cohesion gave tablets which appeared homogeneous. Among these were the halogenides of the alkali metals and silver and hydrated calcium chloride. The next class gave tablets with smooth surfaces and pulverulent bodies this class including the hydrated sulphates of aluminium zinc cobalt and sodium many nitrates and sulphides and the oxides of lead. Most of the oxides gave powdery bodies of low crushing strength whilst the anhydrous sulphates of potassium calcium strontium barium and lead and the carbonates of cadmium barium m d lead showed no cohesion at all.Gener- ally substances of very high melting point and very hard sub stances show little cohesion. A cohesive substance mixed with a non-cohesive substance imEroves the binding properties of the latter but quantitat'ive experiments on the hardness of mixed tablets showed that this was not proportional t o the composition. I n the case of cohesive substances increasing pressure increases the density of -the tablet rapidly at first then slowly as the maximum is approached. The maximum may rise to t h e true density of the crystalline substance as in the case of gypsum or it may approach very nearly to this value as with sodium and potassium chlorides.The experiments show that there is a close relation between the crystalline form of a substance and ite behaviour under pressure. Those substances which give the most homogeneous bodies under pressure are those which have plastio crystals that is the crystals of which contain glide-planes and are deformable without losing their structure The above substances which give under high pressure tablets having almost the maximum possible density have been shown to have plastic crystals. On the other hand the crystals of such substances as quart'z and barium sulphate show no trace of plasticity and their powders show no cohesive properties. [See also J . SOC. C'hem. Tnd. 1920 189~.1 E. H. R. Absorption of Gases by Charcoal.I. Variations due to Heat Treatment Pre-equilibrium Effects. HARVEY B. LEMON (Physical Rem. 1919 14 281-292).-The rate a t which coconut- shell charcoal absorbs air and the total amount it can absorb may be widely varied by varying the heat treatment. This paper con- siders the case in which the mms of air used is leas than that required for saturation. Increase in activation is produced by repeated exhaustions a t 650° each exhaustion being followed by an absorption of air a t the temperature of liquid air. Decrease in activation resulh if a temperature of 800-900° is used. Two hypotheees to account for this (1) the clogging of the pores by heavy hydrocarbons removed by flushing out with gas and (2) the alterration in the fineneas of the carbon from the point of view of a saturated solution of carbon in liquid gas are discussed but found inconclusive particularly inasmuch as removal of the heavy hydrtlii.168 ABSTRACTS 0%’ CHEMICAL PAPERS. carbons by light petroleum alcohol and acetone causes Iw in efficiency . CHEMICAL ABSTRACTS. Absorption of the so-called Surface Active Substances by Various Absorbents. LEONOR MICHAELIS and PETER RONA (Kolloid geitscjt. 1919 25 225-229) .-Comparative absorption experiments have been carried out with charcoal kaolin osmosil (a commercial silicia acid preparation) talc amorphous silicon ferria hydroxide frmhly preoipitateld manganese dioxide calomel barium sulphats and calcium carbonate as absorbents for acetone tributyrin heptyl alcohol and octyl alcohol. It is shown that no carbon-free absorbent has a power of absorption that even approaches the absorptive power of charcoal for surface active non- eleotrolyte substances.In most cas- there is no absorption in others only the mereat trace of absorption takes place. Talc comm next to charcoal in its absorption of these substances. J. F. S. Osmosis and Diffusion of Ions through a Polarised Septum. Physical Methods for the Study of Cellular Nutrition. PIERRE GIRARD (J. Chim. Phys. 1919 17,383-4OSJ.- A r6sum6 of work already publishad (compare A 1908 ii 456; 1909 ii 463 537; 1911 ii 860; 1914 ii 718; 1919 i 419 461) and a reply to Hamburger (compare A. 1917 ii 562). w. Q. Theory of Solution and Suspension. RICHARD ZSIGMONDY (KoEZoid Zeitsch. 1920 26 1-lo).-A theoretical paper in which the significance of the terms “ solution ” and “ suspension ” is discussed a t length.J. F. S. Physical Chemical Analysis of Metallic Oxide Sols. WOLFGANG PAULI (Kolloid Zeitsch. 1920 26 20-23) .-Polemical. An answer to Zsigmondy’s theory of solutions and suspensions (pre- ceding abstract) which is based on the work of Pauli and Matula (A. 1917 ii 563). J. F. S. Nomenclature of Colloids. G. WEIBSENBERQER (Kollozd Zeitsch. 1919 25 230).-The author poinb out that the term “ gel ” is applied both to jellies and to the products of coagulation. He suggwb that the term gel should be retained and used only in connoxion with jelliw and that the products of coagulation should be termed coagels thereby implying that they belong to the group of coarse disperse colloids. J. F.S. R81e of Valencg in Coagulation by Electrolytes particu- larly in the Case of the Suspensoids. WOLFGANG OSTWALD (KolZEokZ Zeitsch.. 1920 26 28-39).-A theoretical paper in which the vazious views put forward in connelxion with the part played by the valency of the &xtmlyte ions in the coagulation of colloids is critically disoussed. J. F. 8.GENERAL AND PHYSICAL CHEMISTRY. ii. 169 Coagulation of Clay and the Protective Effect of Humic Acid. SVEN O D ~ N (J. Landw. 1919 67 177-208).-An extensive review is given of previous work on clay suspensions as regards their aggregation sedimentation disintegration swelling value and nature of individual particles. Experimenbs were made by the author witlh suspensions of two clays of different character purified by dialysis and diluted with conductlivity water t o about 1% strength.Varying amounts of colloidal humic acid were addeld to 10 c.c. of elach suspension and the effect on coagulation noted. It was found that the minimum amount required t o produce a pro- tective effect on the addition of ammonium nitlrat8e solution as coagulant was 0.065 mg. in one case and 0.14 mg. in t4hs other. On varying the coagulant it was found that much larger amounts of humic acid were required to prevelnt coagulation with barium nitrate and msium chloride than with ammonium nitrate an6 lithium chloride. The author concludes that the protective effect of humic acid is of t-he same order as that of other colloids but that it is greatly affected by the electrolyte concentration owing to1 the extreme selnsitiveness of colloidal humic acid tlof ele'ctrolytes.The effect appears t o be specific for different clays and electrolytes so that a proper explanation of the effect is still uncertain. It is clear however that itl depends on an absorption of the protective substance by the particles t o be protected. J. H. J. Non- Uni- and Bi-variant Equilibria. XIX. F. A. H. SCHREINEMAKERS (Proc. R. Akad. TVetensch. Amsterdam 1920 22 318-322. Colmpare A. 1917 ii 454).-A further theoretical paper dealing with the conditions of equilibrium in non-variant, uni-variant and bi-variant systems. The preBent paper deals with thel elquilibria of m components in m+ 1 phases. J. F. S. Characteristic Case of Rhythmic Crystal Arrangement. M. HOFSXSS (Zeitsch. physikal. Chem.1919 93 754-757).-A few drops of the N/lO-sodium hydroxide which had been used to absorb the carbon dioxide produced in the combustion of artificial graphite was allowed to evaporate on a microscope slide. The crystals formed when magnified 500 times showed a striking rhythmic concentric arrangement. Each series of rings commences from a crystal nuelelus around which circles of crystals 0*002 mm. apart are1 formed. I n all other cases of combustion of coal lignite and wood the crystals produced from the sodium hydroxide wash- bottle exhibited the usual dendritic forms. J. F. S. The Rate of Decomposition of Malonic Acid. CYRIL NORMAN HINSHELIWOOD (T. 1920 117 156-165). Mechanism of the Addition of Hydrogen to Unsaturated Glycerides in the Presence of Finely Divided Nickel.R. THOMAS ( J . Soc. Ghem. Znd. 1920 39 10-18~).-The rate of hydrogenation of olive oil (iodine value 86) by means of hydrogen VOL. cxvm. ii. 6ii. 170 ABSTRACTS OF CHEMICAL PAPERS. in the presence of finely divided nickell has beeln determined a t 1200 150° and 1 8 0 O . As the olive oil cont'ained 7% of linolin equations are deduced for the rate of addition of hydrogen by mixtures of unsaturated glycerides. The! reaction between pure hydrogen a t con- stlant prelssure and a single unsaturated glyceride takes place accord- ing to the equation for reactions of the first order. The more highly unsaturated glyceride linolin absorbs hydrogen very much faster t<han olein. The r6le played by the catalyst is discussed from the resulk of experimenh on the influence of pressure of hydrogen and of temperature on the velocity of reaction.It is found that the ratel of saturation of olelin (with threle double bonds) is pro- portional to p where p is the pressure of hydrogen. This is in keeping with the view that hydrogen becomes active through its absorption by the catalyst with a dissociation of the hydrogen molelcules into atoms. The temperature-coefficient of the velocity constant is small; an increase of 10° in temperature o'ver the range 120-180° increases the velocity 1.13 times. This suggests a photo- chemical relaction the molecules of olein being brought into an active condition by absorption of infra-red radiation emitted by t,he catalyst. The mode of action of gaseous catalyst poisons is illustratxd and discussed.Such action may be a purely physical one or it mav be chemical in the sense that the poison is capable of reacting eiiher with or in the presence of the Eatalyst. J. 3'. S. Hydrolysis of Eeters of Polyhydric Alcohols. EIICHI YAMAZAKI ( J . Tokyo Chem. SOC. 1919 40 498-514).-Denoting the five mono- di- and tlri-acetins by ( A ) OAc*CH2~CH(OAc)*CH2*OAc ( B ) OAc*CH,*CH(OH)*CH,*OAc (C) OH*CH,-CH(OAc)~CH,*OAc (D) OH*CH,*CH(OH)*CH,*OAc and ( E ) OH*CH,*CH(OAc)*CH,*OH glycerol (G) is obtained irom triacetin C - D by hydrolysis along the following rout= (amelxed formula). This apparently complicated system of hydrolysis of triacetin can be studied in a simple manne'r since all esters con- B - E taining R*CO-O* have approximately the same1 constant of velocity of hydro+ lysis which is independent of the position of tlhe acid group in the polyhydric alco'hol.The constants of velocity of hydrolysis of tri- to di-amtin ( K = 0*00638) and of di- to mono-acetin (R2= 0.00423) by hydrochloric acid calculated from Geihl's data (A. 1897 ii 547; 1898 ii 330) are co'mpared with the velocity constant (K,=0-002213) for monoacetin 4 glycerol. Assuming that each acetoxy-group is hydrolysed at the same rate R,/ 3 = Re/ 2 = R,( =R). The following equations are thus derived c = cOe-3kt ; cNKB = 3c,(l - e-gt)e-2Kt ; c = 3c,(l - e-st)%-Et ; and cY = c,(l - ~ - ~ ~ ) 3 where the concentrations of the three acetins and of /' AQENERAL AND PBYSXCAL CHEMISTRY. 5. 171 glycerol are denoted by c with suffixes HI M2 Ms and J14 respectively.If free acetic acid is denoted by c then c = c + 2 ~ ~ + 3c,w4 = 3c,,(l - e-Kt)Y. A satisfactory agreement is recorded between the calculated and the observed values of c at any instant. CHEMICAL ABSTRACTS. The Factors of Diazotisation. E. TASSILLY (Bull. SOC. chinz. 1920 [iv] 27 19-33) .-Using the method previously described (compare A. 1914 ii 256) the author has studied the rate of diazoctisation of a number of amines. The1 reaction has been p r e viously shown t o be bimolecular. Doubling the aciditly of the solution does not modify the process of diazotisation in the case1 of aniline. The diazotisation of sulphanilic acid is much more rapid when the concentration of the reacting solutdons is increase'd and i t is favoured by an excess of sodium nitritel.The1 stability of a diazo-compound with respect to time and tempeirature may be studied by this method. W. G . Colour Change of Congo-rubin under the Influence of Reactions and Neutral Salt Action. HEINRICH LUERS (KoEloid Zeitsch. 1920 26 15-20).-The time required by solutions of congwrubin (0.01%) to change from red to the! intermediate colour beltween red and blue in the presence of hydrogen ions of various concelntrations and in the preselnce of neutral salts has been dete'r- mined. It is shown that with H'=5-5 x 10-5 the change is instantlaneous but with decreasing hydrogen-ion concentration the time increasa rapidly until with the value H' = 6.8 x 10-6 it is practtically infinite. I n the presence of a neutral salt (KCl) velry small hydrogen-ion concelntrations cause the change t o take place very rapidly.The presence of large quantities of neutral salts increases the activity of the indicator toward hydroge'n ions about seventy times. I n the presence of hydroxyl ions neutral salts decrease the activity of the indicator until with OH'=10-2 i t no longer undergoes the1 colour change. These changes are explained by a change in the condition of solvatio'n of the indicator brought about5 by the electrolyte. J. F. S. Catalysis. MATHEUS D'ANDRADE ALBUQUERQUE (Reuzstac chzm. pura applic. 1918 3 reprint 22 pp.).-After reviewing the theories which have1 been formulated on the subject of catalysis the author advances the view that' catalysis is due to the format'ion of intermediate dompounds (f' catalides ") as a result of residual affinity. This does not apply to cases where the intermediate com- pound is a salt or to catalysis by solvent8 finely divided (colloidal) metals or organic ferments. W. R. S. Whole Number Isotopes and Allied Phenomena. F. H. LORING (Chem. ATeuis 1920 120 73-77).-A theoretical paper in which the experiment)al evidence supporting the idea of whole number isotopes is given together wit'h the spectroscopic elxamin- 6*ii. 172 ABSTRACTS OF CHEMICAL PAPERS. atioln of isotopes. Thel photoeleotric effect in its cmnexion with isotopes is discussed as well as the cyclio elvolut*ion of elements and isotopes. A table is given in the paper indicating the pescentage of higher mas5 isotopes of the commoner elements. The whole discussion tends t o show that the whole number isotopes are a reality and thatl the isotopic proportions may modify the ele(ctrica1 propertries of the elements. J. F. S. Deduction of the Chemical Constants of Polyatomic Gases from Planck's Theory of Probability. L ~ O N SCHAMES (PhysiAaZ. Zeitsch. 1920 21 38-39).-A mathematical paper in which a method of deducing the chemical constants of tri- and tetra-atomic gas- is deduced. The results are compared with those deduced by Sackur (A. 1913 ii 128) and Tetrode (Proc. K . A k d . TVetensch. Amsterdam 1915 17 1167). J. F. S. Chemical Constants ; Moment of Inertia of the Molecule and the Quantum Theory of Gases. L ~ O N SCHAMES (PhysikaE. l e i t s c h . 1920 21 39-42. Compare preceding abstract).-The cheLrical constant ie and the moment of inertia P. 1040= VPQR have h e n calculated by means of the equations previously deve- loped ( I L " . cit.) fpr oxygen carbon monoxide nitrogen carbon dioxide an2 water. The following values for the moment of inertia are obtained oxygen 31.2 ; carbon monoxide 10.07 ; nitrogen 9.91 ; carbon dia-ide 5.80; and water 1.365. The results are coni- pared with the valcles of other investigators particularly those of Langen (A. 1919 ii 183) and found to be in very good agreement. J. F. S. A Cheap and Simple Microbalance. J. H. SHAXBY (Proc. Z'h,t/skaZ SOC. Lmdon 1919 32 21).-A balance for loads from 5 mg. tlo 5 dcg. depelnding on the depression of a stretched thread is described. J. R. P. Condensers. FRITZ FRIEDRICHS (Zeitsch. angew. Chern. 1920 '33 29-32).-A critical discussion of the various forms of labora- tory condensers which have been described in 1iterat;ure from the time of Liebig onwards. As regards efficiency the screw-shaped condensing tube with five '' threads " and provided with an internal cooling jacket gives the best results. This form of condenser is more suitable for use as a reflux apparatus than is the spiral form. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9201805137

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 173 Oxidation of Sulphurous Acid by Ferric Salts. JULIUS MEYER (Ber. 1920 53 [B] 77-78).-In Houbeii's recent method for the estimation of ferrous and ferric iron together in acid solu- tions the assumption is made that when a ferric salt is reduced by sulphur diotxide the increased acidity corresponds with two-thirds of the acid in combination with the ferric iron according to the equation 2FeCl + SO -t 2H,O = FeSO + FeC1 + 4HC1 (this vol. ii 56). It is no'w stmated that the reductdon of a ferric salt most probably proceeds in stages; thus first' a red ferric ferrisulphite Fe[Fe(S03)3] is formed which slowly changes in the codd more quickly on warming into the ferrous salt not however with the production of sulphuric ac'id but dithionic acid thus Fe[Fe(SO,),] = FeS,O + Fe80,.Before any increasel in the acidity can take place therefore the dithionate must be decomposed thus FeS,O + 4 0 = FeSO + H2S03 and it is not quite certain whether this is completed even by vigoroas boiling. J. C. W. The Advantages of the Synthesis of Ammonia at Very High Pressures. GEORGES CLAUDE (Compt+ rend. 1920 170 174-177. Compare this vol. ii 30).-Whereas it is necessary by the German method working at a pressure of 200 atmos. to pass the reacting gases over the catalyst a considerable number of times with removal of the ammonia aEter each passage it is only neces- sary t o do this three timee a t a pressure of 1000 atmos. Other advanthga of working a t the higher pressure on an industrial scale are claimed. [See further J .SOC. Ghem. I d . 1920 187~.] W. G. Formation of Free Hydrogen in the Reversed Ammonia Flame. FRIEDRICH U. G. MULLER (Zeztsch. angezo. Chem. 1920 33 24).-The author finds t7hat the products of combustion of ammonia in oxygen contain hydrogen and nitrogen in the ratio 2 3 by volume. Since the result is unaltered by cooling the flame with cold water (Raschig A. 1919 ii 14S) it cannot be due to dissocia- tion of ammonia. On the other hand Raschig's assumption that the equation 2NH + 0 = N,H + 2H,O represents the first! stage of the reaction followed by instantaneous dissociation of N2H and partial combustion of the hydrogen does n o t account for the con- stancy of the proportion of hydrogen produced. J. K. The Velocity of Oxidation of Nitric Oxide.EUG~NE WOURTZEL (Compt. rend. 1920 170 229-231).-The oxidation of nitric oxide takes place according to t.he equation of a reaction of the third order thus - cZpNO/dt = k(pNo)2p02.. Th0 aotion does not undergo any marked modification when half the nitrio oxide is oxidised; consequelntly the exclusive and rapid 6"-2ii. 174 ABSTRACTS OF CHEMICAL PAPERS. formation of nitrites or of nitrosyl sulphate observed when the gaseous products formed at the commencement of the reaction are treated with alkali or sulphuric acid must be due t o particular conditions of absorption and not of oxidation of the nitric oxide. Nitrogen trioxide the formation of which has previously been proved (compare next abstract) is an ulterior product of the aotion and not its intermediate product.The velocity of this oxidation diminishes with rise in temperature. The Existence of Nitrogen Trioxide in the Gaseous State. EUGI~NE WOURTZEL (Compt. rend. 1920 170 109-111. Compare this vol. ii lOS).-By measuring the contraction produced when known quantities of nitric oxide and oxygen are mixed the nitric oxide being in excess the authors have shown that under a total pressure of about one-quarter of an atmosphere an almost stoicheio- metric mixture of nitric oxide and nitrogen peroxide contains about 2.5% of nitrogen trioxide. Direct Formation of Carbon Monoxide by Burning Carbon in Pure Oxygen. FRIEDRICH C. G. M~~LLER (Zeztsch. ungew. Chem. 1920 33 36).-If pure oxygen is passed downwards through a vertical quartz tube 25 cm. in length and not more than 13 mm.in diameter filleld with pieces of wood charcoal of the size of linseed the gas leaving the lower end of the tube will contain 85% of carbon monoxide. The upper part of the charcoal must be heated by a burner before the oxygen is admitted and it is essen- tial that the combustion is allowed to proceed under reduced pres- sure. This is attained by connecting the lower end of the tube with a vessel filled with water and opening the tap of the oxygen reservoir so that water flows from the lower vessel at the rate of W. G. W. G. 2 litrres per minute. w. P. s. A Reaction of Potassium Anhydrotellurate. P. HULOT (Bull. SOC. chim. 1920 [iv] 27 33).-If tellurous acid or alkali tellurit'es are brought to complete fusion with potassium nitrate and the mass after cooling'is extracted with water potassium an- hydrotdlurate K,Te4OIH is left behind as a powder which is insoluble in water or acids.I f this powder is suspended in dilute hydrochloric acid and a few pieces of zinc are added the salt gradually disappears and a black pulverulent powder which is pure tellurium is left behind. W. G. Application of the Reduction of Potassium Anhydro- tellurate by Zinc to the Treatment of Tetradymite and to the Estimation of Tellurium in this Mineral. PIERRE HULOT (BUZZ. SOC. chim. 1920 [iv] 27 100-101. Compare preceding abstract) .-The tetradymite is first treated with dilute hydrochloric acid to remove1 the calcareous gangue. The powdereld material is then dissolved in hof concentrated nitric acid the solution being evaporated to dryness and the residue fused with twice its weight of potassium nitrate.The resulting mass contains potassiumINORGANIC CHEMISTRY. ii. 175 sulphate and wlenate bismuth oxide and potassium anhydro- tellurate. The sulphate and selenate are removed with boiling water and the residue is digested with dilute hydrochloric acid whereby t>he bismuth oxide is dissolved out. The residue after washing with dilute hydrochloric acid is suspended in the same acid and some zinc is added. The whole of the tellurium is deposited in a pure state and may be collected dried and weighed after the whole of the zinc has dissolved. Reversible Oxidation of Sodium Nitrite. C. MATIGNON and E. MONNET (Compt. rend. 1920 170 180-182).-Sodium nitrite when heated in an atmosphere of oxygen at a pressure of 175 atmos.and at' a temperature gradually rising from 395O to 530° during nine hours is almost complettely oxidised t o sodium nitrate the heat of formation of the! nitrate being given by 2KaN0 sol. + 0 gas = 2NaN0 sol. + 45 Cal. The reaction is too slow to be of practical use. W. G . Calcium nitrite may similarly be converted into calcium nitrate. Some Properties of Sodium Nitrite. C. MATIGNON and (MLLE.) G. MARCHAL (Compt. rend. 1920 170 232-233).-The authors find for thel m. p. of sodium nitrite1 276.9O (con-.). Its heat of solution is expressed by NaNO sol. + Aq = NaNO. diss. - 3.52 Cal. Its heat of decomposition in aqueous solution by dilute sulphuric acid is given by 2NaN0 diss. + H,SO diss. = Na2S0 diss. + 2HN0 diss. + 2 x 4.6 Cal.From this equation and known data they deduce and Nitrous acid resembles nitric acid in its behaviour towards the following indicators phenolphthalein cochineal litmus p-nitro- phenol brazilin and iodoeosin but decomposes others like1 helianthin. Aqueous sodium nitrite is not oxidised at looo by prolonged contact with oxygen under a pressure of 50-55 atmos. even in the presence of a catalyst. Ammonium Silicate 111. ROBERT SCHWARZ and RICHARD SOUARD (Ber. 1920 53 [B] 1-17. Compa're A. 1917 ii 31; 1919 ii 283).-The authors have studied the electrical conductivi- tiss of solutions of dioxodisiloxane monosilane and silicic acid obtained from pure and technical sodium silicate silicon tetra- chloride and tetrafluoridel in ammonia in order to determine whether there are any indications of t.he elxistence of ammonium silicate or of different molecular complexity in silicic acid of various origins.The increment of the conductivity of ammonia solutions suggests that salt formation does take placel just as t.he lowering W. G . HNO disg. + NaOH diss. = NaN0 diss. + H,O + 11.1 Cat. N gas + 0 gas + Na sol. = NaNO sol. + 88.52 Cal. W. G.ii. 176 ABSTRACTS OF CHEMICAL PAPERS. of the conductivity of sodium hydroxide by silicic acid points to the same conclusion. The1 dialysis olf the preparations and the techniquel of the measurements are described. Itl was soon found that the percentage of water in the prepara- tion had a grelat influence on the conductivity partly duel to t>he diffelrent rates a t which the silicio acid entered real solution.I n order to eliminate this factor or to follow it more closecly the solutions were1 filtered through an ultra-filter after deltermining the conductivity and the1 amount of silica estimate\d. The quotient incremelnt of conductivity/dissolved SiO Ak/m = & therefore affords a clue to1 the molecular complexity of the silicic acid. The experiments show that a decrease in the proportion of water in the dioxodisiloxanel or silicic acid preparation is accompanied by a fall in the value1 Q not however gradually but apparently in three stages. I n the case of dioxoldisiloxane the value & is about 75 when the material cont-ains about 4.5% of water about 50 if the proportion of water is 2% even though the silicic acid may imbibe more water on keelping and about 25 if the1 preparation is almost dry.Similarly with the various silicic acid preparatiolns; no mattelr whatt thelir origin the nearly dry specimens give a value1 of about 25 and those rich in water about 75. After ignition how- ever silica causes no increment in the conductivity of ammonia solutions. The1 different values of Q suggest therefore that the dissolved silicic acid exists in three forms of molecular weights in the ratio 1 2 3. The simplest forms are derived from dioxodi- siloxans o r monosilane the direct hydrolysis of the1 latter in ammonia solutions being the most satisfactory way of preparing ammonium silicate sollutions. J. C. W. Silver Peroxide and the Valency of Silver. R. C. P. WEBER (Trans. Amw. Electrochem. SOC. 1917 32 391-404).- A numbefr of experiments are described which were dsigned for the prelparation of salts od silver in which the metal has a valency greatelr than unity. Except in the1 case1 of the peroxy-nit-rate the result5 were negative.This compound 2Ag,04,AgN0 is formed on the anode during the electrolysis of silver nitrate but if 15-25% of nitric acid is addetd t o t$he solution thelrei is no deposit but a brown solution is formed. This solution on e,xaminatioa is found to contain both negative and positive silver-containing ions. The valency of the silver in the oxide portion of this salt is discussed. Two formulae are put forward for the oxide part of the salt Ag,AgO (analogous tot reld lead) or Ag(AgO,) (analogous to mag- netic iroln oxide). The1 transference experiments show that one- third of the silver is cathodic and bivalent and two-t'hirds anodic and tervalent which leads t o the formula Ag(Ag0,)2.This indicates that the oxide portion of the peroxy-nitrate is the silver salt 04 an unstable1 nrgen,tic acid HAgO,. J. F. S. Lead Borates. H. V. THOMPSON (Trans. Engl. Cernm. SOC. 1918-1919 18 510-511).-The white precipitate formed by mix-INORGANIC CHEMISTRY. ii. 177 ing cold conmntrat<ed solutions of lead nitrate and borax is of in- definite composition and d m not necessarily consist of lead meta- borate Pb(B02),,H20 as stated by Rose (Ann. Phys. Ch,pm. 1833 29 455). The precipitate formed by adding an excas of a solution of borax t o a solutJon of a lead salt consists of lead me,taborate and not tlhe polybrate 2Pb0,3B20,,4H,0 as stated by Soubeiran ( J .Pharm. Chim. 1825 11 31). On boiling the metaborate with an excess of boria acid so’lution no definite chemical compound is formed in contradiction to Abegg (“Handb. aaorg. Chem.,” 1909 3 ii) who states that the com- pound Pb0,2B20,,4H,0 is produced. The author confirms a statement by Le Chatelier (BUZZ. SOC. chim. 1899 [iii] 21 35) that the compound Pb0,3B20 is formed on fusing borio acid and lead carbonate and extracting the mass with water to remove bosic acid. [See! also J. SOC. Chem. Ind. 1920 Maroh.] A. B. S. Behaviour of Cerium Carbide towards Nitrogen. FR. FICHTER and CHR. SCH~LLY (Helv. Chim. Acta 192d 3 164-172). -The requisite finely divided celrium carbide is prepared by helat- ing it mixture of cerium dioxide (1 mol.) and carbon (6 atoms) in a graphite tube in an electric vacuum-oven a t 1600O.It is found that this material in spite of its apparent similarity t o calcium carbide does not yield any compound with nitrogen ah 1250O which contains both carbon and nitrogen but that the1 carbon is replaced by nitrogen with the formation of cerium nitride. The possi- bility of the formatlion of cyanides and cyanamides from carbides appears to exist solely in the groups of the alkali and alkaline elarth metals and not in that of the1 earthy metals; it4 does not depend on the type of the carbidel but on the1 nature1 olf the metal. Cerium carbide also reacts with ammonia a t 1250° yielding the nitride but the action is slower and less complete than wheln nitrogen is used.H. W. Some Complex Compounds of Mineral Chemistry. G. URBAIN (BUZZ. SOC. chim. 1920 [iv] 27 81-94).-A lecture delivered before the’ French Chemical Society W. G . Constitution of Ultramarine. LAURENZ BOCK (Zeitsch. amgew. Chem. 1920 33 23-24. Compare A. 1915 ii 460; 1917 ii 475) .-Experiments on the action of ammoniacal silver chloride solution on arFificia1 ultlramarinee are described. It is concluded that the blue rich in silica and sulphur and based on the formula A120,,3Si02 is a definite chemical compound containing sodium sulphur aluminium and silica in definite proportions; the same1 is true of the blue poor in silica but rich in sulphur. Further the ultramarinw are analogously constituted to the aluminium silicates. A table is given showing the known ultramarines and tlheir relationship to natural and artificial silicates.J. K.ii. 178 ABSTRACTS OF CHEMICAL PAPERS. Equilibrium in Blast Furnace Reactions. ERNST TERRES and AUREL PONGRACZ (Zeitsch. Elektrochem. 1919 25 386-407). -The equilibrium of the reaction Fe + CO = FeO + CO has been studied by a' number of different obselrvers whose resulte show considelrable divergencies. A fresh investigation has theref ore been made on rather differeat elxperimental lines from those used hitherto. The reaction was studied from both sides starting on the one hand from pure iron (iron wire or ferrum limatum) and carbon dioxide and on the other from oxidised iron (prepared by oxidising pure iron witlh carbon dioxide) and carbon monoxide. The reaction was carried out in a pear-shaped glass vessel which could be1 heated t o any desired temperature in an electric furnace.For a full description of the! special apparatus used which embodied many delvices for convenience and grelater accuracy the original must be consulted. The usual procedure1 in studying such reiact,ions as the one under consideration is to allow the reading substances to remain in con- tlact' at the particular temperature until equilibrium is reached and then to analyse the products. This method was used by Baur and Glaessner (A. 1903 ii 423) who1 plotted thel composition of the gases at the end of the reaction againstl the temperature and obtained two distinct curves the1 one obtained from the starting materials iron and carbon dioxide having a well-marked minimum and the other from ferroso-ferric oxide and carbon monoxide showing an equally prominent maximum.The present authors allowed the reaction t o proceled for a definite time a t each par- ticular temperature and atl the end of this time the1 gases were analysed. The reaction was studied over the temperature range 550° t o 950O. The results are plotted in the form of four curves two showing the composition of the gas mixture aftelr seven hours starting from either side of the equation the other two after sixteen hours. Each curve is a straight line the proportion of carbon monoxide in the mixed gases increasiny steadily with the temperature. All four curves converge towards a point at about 950° with about 75% of carbon monoxide showing that in seven hours equilibrium is already attained a t this temperature.The two sixteen-hour curvels lie between the! seven-hour curves quite close together and converge at' about 810° showing that a t this temperature equilibrium is reached in sixteen hours. The true equilibrium curve evidently lies about midway beltwean the two sixteen-hour curves. Contrary to the results of Baur and Glaessner the same equilibrium point is retached from either side of the equation and the curve shows no maximum o r minimum. These results are in agreement with those1 obhained by Scheack and his co-workers (A. 1903 ii 423; 1905 ii 526; 1907 ii 470) and by Leivin (A. 1912 ii. 1176). Very careful experiments showed that the composition of the gas phase at equilibrium depefnds on the1 quantity of tlhe solid phase present the proportion of carbon monoxide increasing with increasing amounts of iron.This can be explained on the assump-INORGANIC CHEMISTRY. ii. 179 tion that the ferrous oxide phase is a solid solution of two com- ponents. A method for analysing the solid pham was; devised and it’ was shown that this always contained ferric iron. The propor- tion of ferrous to ferric oxide never corresponded with the com- position Fe,O,. It was also shown that no; other constituent was present in the solid phase. The fall in pressure always observed when carbon dioxide and iron are first heated together is due not to any chemical reaction but to absorption of the gas by the metal. [See also J . Soc. Chem”. Znd. 1920 1 9 3 ~ . ] Behaviour of Iron in Contact with Sulphuric Acid.C. E. FAWSITT and A. A. PAIN (J. Proc. Roy. SOC. A’.,!?. TVaEes 1918 52 396-405).-Differences in electrochemical behaviour show that no real similarity exists between iron which is slowly dissolving in concentrated sulphuric acid and iron rendered “ passive ” by +p- ping into nitric acid. The slowing down or cessation of the reaction is due apparently to the formation of a form of ferrous sulphate monohydrate on the surface of the iron. Although generally speak- ing increased dilution of the acid with water results in greater reaotivity certain anomalies were observed in this respect notably that 89.3% acid has considerably less solvent action than either weaker or stronger acid of 94% 90.9% 87.9% or 85% strength. The solvent eflect is in all cases noticeably increased by shaking the containing vessel.G. F. M. P. DEJEAN (Compt. reihd. 1919 169 1043-1045).-1t has previously been shown (A. 1917 ii 477). that there is a distinct discontinuity between the formation of perlite or troostite and martensite the critical point corresponding with the formation of the former being ( ( A ” and of the latter (‘ B.” It is now noted from a study of the cooling curves of a nickel-chrome-copper steel which starting from different initial temperatures was cooled from 700° to looo in about one hundred and fifty minutes that the formation of martensite apparentdy occurs in two st’ages denoted by critical poi‘nts B and B,. The point A is indicated only when the critical temperature of cooling is 790O. When this temperature rises to; 800° A is con- siderably supprwsed and the critical point B appears at about 420O.If the steel is cooled from 850° t-he second point B occurs at about 230° and if cooled from still higher temperatures B dis- appe’ars and the point B exists alone. If only the point A is in evidence during cooling the steel is relatively soft but bemmm harder when B predominates and still harder when B appears. It is concluded that for the steel studied the maximum hardness is reached in a t least two stages and that for the same steel there may be several martensitic forms. The Formula of Chromium Hydroxide. MIL. Z . JOV~TSCHITSCH (Helv. Chim. A cta 1920 3 46-49).-The solubility of chromium hydroxide in ammonia and the preparation from such solutions of complex salts which invariably contain 1 OH,O (compare E.H. R. The Critical Points of Self-hardening Steels. W. G . 6-E 180 ABSTRACTS OF CHEMICAL PAPERS. A 1913 ii 223) leads the author to assign the formula Cr4(OH)802,10H,0 or Cra(OH),,0,9H20 to chromium hydroxide. Stronger evidence in favour of such formulation is found in the absorption of carbon dioxide from the air by chromium hydroxide with the formation of a carbonate C0,,2Cr,(OH),,8H20 to which the formula Cr2(OB)~*0>C0,9H,0 or O<Cr2(0H)4* O> CO,lOH,i) Cr,( OH),*O Cr2(OH); 0 is ascribed (compare A. 1914 ii 373). EL W. Chromium Chromate CrO,,Cr,O ,7H,O. MIL. Z . JOVITSCHITSCH (Helv. Chim. Acta 1920,3,40-46).-When a solu- tion of chromium oxide in nitric acid (compare A. 1912 ii 261) is evaporated until excess of acid is removed and the residue is dis- solved in water and treated with ammonia a dark brown almost black product is obtained analyses of which are in agreement with the formula Cr2(OH),,H20 o r Cr0,,Crz0,,7H,0.The loss of 1H,O over sulphuric acid of 2H20 at 1 0 5 O and of 6 q O at 205O is mom reladily explained by the former but the chromium con- tent and particularly the possibility of the preparation of anhy- drous chromium chromatle from the substance lead the author to give preference to the latter. The substance is somewhat unstable and losm chromium trioxide when repeatedly washed even with warm water. It forms a very suitable initial material for the p r e paratdon of pure chromium hydroxide free from alkali which is effeoted by boiling a solution of the substance in concentrated hydrochloric acid with alcohol until reduction is complete and subsequent'ly adding mmonia in excess.Anhydrous chromium chromate cannot be prepared by heating the hydrated product since decomposition occurs before the last molecule of water is removed; it may however be obtained as a poro'us black mass by dissolving chromium oxide in nitric acid evaporating the solution to dryness and cautiously heating the residue t o 290°. The analytical data agree equally well with those required for the peroxide CrO but the readiness with which the tmbsbance is converted by ammonia alkali carbonate or hydroxide or by boiling water into chromium hydroxide and chromate is interpreted in f avow of a salblike constitution. H. W. Electro-deposition of Nickel.L. D. HAMMOND (Trans. Amer. Electrochem. Soc. 1916 30 103-134).-The best conditions for securing a satisf ackory mode corrosion .in the electro-deposition have been sought by studying the polarisation pressures and the ourrent efficiency obtained with anodes of cast nickel electrolyt'ic nickel a d annealed nickel in solutions of nickel sulphate contain- ing measured amounts of boric acid and niakel chloride. The experiments show tbat although cast nickel anodes corrode fairly well in simple sulphate solutions to which boric acid has been added the best results are obtained when the purest electrolytic nickel in nickel sulphate solutions containing chloride is used. Nickel chloride is to be preferred to other chlorides as its addition doesINORQANIC! CHEMISTRY.E. 181 not decrease the concentration of niakel in the electrolyte. It is shown that 6 grams of nickel chloride per litre produce a good anode corrosion and that the best resu1t.s are selcured by increasing the concentration of niokel chloride to 15 grams per litre. The con- ditions necessary for ths direct electro-depcsiticn of nickel on zinc have been investigated. It is shown that nickel can be directly deposited on zinc from the baths used to deposit nickel on more electrenegative metals if a higher initial current density is em- ployed than is usual when using these baths for their ordinary purposes. An electrolyte consisting of 120 grams of nickel sul- phate 15 grams of nickel chloride 30 grams of boric acid and 1000 C.C. of water may be used to deposit nickel on zinc copper brass or iron. To deposit on copper a current density varying from a few tenths of an ampere 60 3 or 4 amperes may be used but to deposit on zinc a current density of not lets than 3 amperes must be employed.It is suggested that whilst the above-named bath produces good deposits on flat strips of zino it will probably give a deposit with blacik streaks if irregular objects are t o be plated. The following bath composition however produces perfect deposits on irregulax objects 240 grams of nickel sulphate 15 grams of nickel chloride 30 grams of boric acid 175 grams of sodium Citrate and 1000 C.C. of water. This bath gives good deposits with current densities 0-5-7 amperm per sq. dcm. if pure nickel anodes are used. The two baths named are very rapid in their action.Nickel has been deposited directly on zinc from a N/2-solution of hydro- chloric acid containing 120 grams of nickel sulphate per litre. Sodium citrate has a beneficial effect on baths for the direct nickel- ing of zino which is not due to1 a change in the potential of zino but to a decrease in the rate of deposition by immersion. Sodium potassium tartrate and sodium rnalate have a similar action but they do not permit the use of so high a ourrent density as the citrate bath. The substitution of nickel ammonium sulphate by niokel sulphate in nickeling baths is recommended. To ensure a good deposit of nickel it is essential that the bath should be slightly acid and it is for this purpose that boric acid is added. The funo tion of the boric acid is therefore to maintain a small but fairly constant concentration of hydrogen ions in the electrolyte.J. F S. Isolation of Molybdenum and working up of Molybdenum Residues. S. MALOWAN (Chem. Zezt. 1918 42 410).-To recover molybdic acid used as a precipitant in phosphorus deter- minations the liquor is precipitated with sodium or calcium phos- phate. The yellow precipitate alter being washed and dried is heated with excess of concentrated sulphuric acid until solution is complete and the acid colourless. The cold liquid is poured into eight to ten times its volume of water and the molybdenum precipi- tated with excess of ferrocyanide. The precipitate is collected after three hours washed with dilute ferrocyanide solution until all the acid is removed dried separated from the paper and ignited at a dark red heat to incipient fusion.The cooled product is leached 6""-2ii. 182 ABSTRACTS OF CHEMICAL PAPERS. twice with hot water t.hen extracted with ammonia which dis- solves molybdic acid. The colourless solution is filtered evaporated to dryness the residue dissolved in a little water and hydrogen peroxide and the solution boiled to oxidise any lower oxides. The resulting solution of ammonium molybdate is diluted until it has D*7 1-09 (that is 10 per cent.). W. R. S. Reversible Reaction of Water on Molybdenum. GEORGES CHAUDRON (Compt. rend. 1920 170 182-185).-A study of the system water vapour-molybdenum-hydrogen-molybdenum dioxide over the temperature range 700-1100°. The values of K=pH20/pH obtained by the oxidation of the metal or the reduc- tion of the oxide agree closely. Plotting log K against 1/T the points obtained lie on a straight line within the temperature interval considered.W. G. The Violet Compounds of Uranium. J. ALOY and E. RODIER (Bull. SOC. chim. 1920 [iv] 27 101-105).-The produc- tion of violet compounds of uranium as described by Aloy (oompare A. 1901 ii 317) is not an exceptional phenomenon but quite general and does not necessarily involve the action of light. It is necessary to distinguish between salh of inorganic acids and salts of organic acids. Salts of the first type must be used in exactly neutral solution and in the presence of a readily oxidisable sub- stance. Both violet and ultra-violet rays cause the productian of violet precipitates the ultra-violet rays being the more active.The action of light is not always necessary and it is shown that these violet compounds are obtained whenever a uranous and a uranic salt are present together at the requisite temperature in a neutral 01- feebly acid medium. I n reality there exist a large number of violet compounds of uranium having an analogous constitution all of which by loss of their acid radiclss tend to become transformed into the green hydrated oxide U,O8,2&0. W. G. Soluble Metastannic Acid. HANS KREIS (Schweiz. Chem. Z e i t . 1919 389).-Spongy tin is dissolved in a solution of ferric nitrate in nitric acid D 1.23 and after the vigorous reaction has subsided hot water is added. The resulting slightly opalescent solution contains colloidal metastannic acid and may be repeatedly evaporated to dryness with or without addition of inore nitric acid without precipitation of the tin (compare Antony and Mondolfo A.1899 ii 330). The author considers that the ferrio hydroxide formed by dissociation of the ferric nitrate acts as EL protective1 colloid. A R. P. The Question of the Existence of Zirconium Monoxide. R. SCHWARZ and H. DEISLER (Ber. 1920 53 [ B ] 1. Compare %his vol. ii 42).-A recognition of similar work by Wede'kind (A. 1913 ii 225). J. C. W.INORGANIC CHEMISTRY ii. 183 Electrolysis of Aqueous Solutions of Vanadium Salts. SIEGFRIED FISCHER jun. (Trans. Amer. Electrochem. SOC. 1916 30 175-228).-Several hundred experiments are described in tabular form which have been made with the object of depositing metallic vanadium from aqueous solutions.After a resum6 of the literaturel of the deposition of vanadium the author describes fifty- five experiments made with Cowper-Coles vanadium electrolyte (1.75 vanadium pentoxide 2.00 sodium hydroxide 160-0 water and after boiling 32.0 hydrochloric acid) (A. 1899 ii 755). It is found that in no circumst'ances can metallic vanadium be obtained frotm this electrolyte. The reduction of the electrolyte is limited in mwt cases to the vanadyl state which is blue (V,O,). A reduction occurs in practically all the experiments. At temperatures of 90' or above the reduction may be taken to the lavender colour (V,O,). Lead electrodes alone give a reduction to the sesquioxide (V,O,) or green state at tempelratures below 90°; above 90° the e'lectrolyte is reduced to the lavender state.Carbon electrodes reduce the electrolyte to the green state. A t temperatures below 9Go platinum electrodes reduce the electrolyte to the blue vanadyl state only and the current density has no influence on this. A t tem- peratures above 90° the lavender state is reached only when porous cells are used. The black deposit obtained by Cowper-Coles 011 platinum electrodes is not a vanadium compound but platinum hydride. A number of experiments (112) were made with solutions of vanadium pentoxide in sulphuric acid in the presence of various concentrations of aluminium sulphate magnesium sulphate am- monium sulphate hydrofluoric acid boric acid or silicic acid using electrodes of platinum carbon lead and mercury.When platinum electrodes were used a black film was obtained which contained no vanadium. I n no case was metallic vanadium obtained. Solutions of vanadic aad in hydrochloric acid sulphuric acid nitric acid hydrofluoric acid lactic acid ethyl hydrogen sulphate and tartaric acid were electrolysed as well as a series of solutions of vanadic oxide in alkali hydroxidel but in no case could metallic vanadium be obtained. The reason for the failure to obtain metallic vanadium is the very large' heat of formation of vanadium salts. Thus the oxide V20 has a heat of formation 441000 cal.; V,O 353200 cal.; VO 104300 cal. J. F. S. Formation and Nature of Black Antimony Trisulphide. FERRUCCIO DE BACHO (Annali Chim. AppE. 1919 12 143-152). -On heating red antimony trisulphide in carbon dioxide( there is no material difference in the loss of weight a t temperatures from 150° tlo 300° tlhe change to the black modification taking place at! 2 1 2 O whilstl in a current of hydrogen sulphidel the change occurs a t 2 0 7 O .By adding ammonium chlosride to the red sulphide the temperature of the change in carbon dioxide is lowered (for examplel to 170°) whilst the presence of antimony chloride reduces the temperature1 still further. Thus in the case of a mixture of equal parts of antimony trisulphide and trichloride the blackii 184 ABSTRACTS OF CHEMICAL PAPERS. coloration appeared at 1 2 5 O . Metallic silver also has a favourable influence on the transformation. The action of ammonium chloride in boiling solution also1 promotleis the formation of the black sulphide to an extent depending on the concelritration of the solution whilst the rapidity of t'hhe transformation stands in relationship to the degree of hydrolysis of the ammonium chloride and consequent acidit,y of the solution.The presence! of antimony trichloride facilitatfes tbis conversion which is accelerat,e,d by the1 pretsence of hydrochloric acrid antimony trisulphide and potassium nitrate at high concentrations. Conceatrated solutions of e81ectrolytes such as sodium chloride ammonium sulphate or potassium nitrate alone have no elffect on the transformation which is therefore not merely the result of moletcular condensation. The coiiversion always takes place when the conditions permit of immediate contact between the rsd antimony trisulphide and a,ntimony trichloride whether addeld as such or formed in the solution. It is probable that the following reaction t'akes place 2Sb,S + 2SbC1 -+ 6Sb + 3S2C1,. It is also probable1 that the trace of frelet antimony thus formed or that produceld by dissociation of the red trisulphide when heated forms in the ccdl~idal condition a solid solution with the antimony trisulphide. This decomposition which occurs in the process of drying in analytical work is too small to be detectled gravimetric- ally. On heating the red trisulphidel there1 is a gradual increase in the specific ,gravit\y but the' conversion into the black modifi- cation is not indicated by any sudden rise in the specific gravity. C. A. M. The Action of Aqua Regia on Gold-Silver Alloys in the Presence of Ammonium Salts WILLIAM BRANCH POLLARD (T. 1920 117 99-103).

ISSN:0368-1769    

DOI:10.1039/CA9201805173

出版商:RSC    

年代:1920

数据来源: RSC

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ii. 184 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Colloid Colour Substances in Minerals. C. DOELTER (Kolloid Zeitsch. 1920 26 23-27) .-A theoretical paper in which it is shown that the colours of many minetrals are due to small quantitim of impurities which may be the same in differently coloured minerals. The natjure of the colour depends on the size of the particles of the pigment. Change in the colour effected by helating or by the action of radium rays is due to a change1 in the dimensions of the particles. J. F. S. I. BELLUCCI and I;. GRASSI (Gozzetta 1919 49 ii 232-246).-A nodule included in the1 building stone known as ((peiperino,” occurring in a cave in the Ariccia district is found to1 consist principally of olivine and biotite together with iiumerous small shining crystal- line aggregatm having a radiating fibrous structure and a pale emerald-green colour.This greeii mineral D 3.23-3-29 A Markedly Ceritic Fluoapatite from Latium.MINERALOGICAL CHEMISTRY. ii. 186 m 1-63-1.65 is a fluoapatite containing comparatively large pro- portions of rare earths; analysis gave, Rare earth CaO. oxides. FeO. p205. SO3. F. Total. 50.86 5.24 1.92 35.5 2.59 3.37 99.48 The rare earths present are ceritdc and not yttric in character the presence of cerium didymium and lantihanum beJng demonstrated. A summary is given of the literature dealing with apatites con- taining rare earths. I n the apatite of Narsarsuk Flink (A. 1900 ii 410) found 3.36% of ytkric oxidw and 1.52% of ceritic oxides. T. H. P. The Origin of the Beds of Sodium Carbonate in Peru.EMM. POZZI-ESCOT (BUZZ. SOC. chim. 1919 [iv] 25 614-617).- It is suggested that the sodium sulphate of the soil dissolve8 in the water which gradually collects in natural deprmsions forming salt marshes with an abundance of vegetat!ion suited to the conditioqs. The sulphate in contact with the plants and a l p becomes reduced tot sulphide which is then in its turn decomposeid by carbon dioxide elithelr atmospheric or that resulting from local vegetative1 combus- tion with the resulting formation of sodium carbonate or soldium hydroge’n carbonate. The industrial possibilities of these deposits are discussed. W. G. GUST. FLINK (Arkiu Kemi Min. Geol. 1917 6 No. 21 1-149).-1n Part IV of his “Mineralogy of Sweden,” the author gives detailed dmcriptions of forty-five Mineralogy of Sweden Si02.I ........................ 16.61 I1 ........................ 16.50 I11 ........................ 17.74 IV.. ...................... 17.21 V. ................ ...:. . 39.84 VI ........................ 40.00 VII ........................ 37.53 VIII ........................ 45.53 IX ........................ 43-54 X ........................ 43.40 MnO. I.. ...................... 0-35 I1 ........................ 2.83 111 ........................ 2-88 IV ........................ 2.78 V ........................ 26.82 VI ........................ 7.05 VII ........................ 0.48 VIII.. - IX.. - X ........................ trace ...................... ...................... Al,03. - - - - L - 23.79 23-07 22-62 23-05 CaO.1.75 0.52 10.42 7-31 15-67 37.82 21.97 25.48 26-56 26.49 Fe,O,. - - - - - - 7.73 1-93 1-79 1.27 MgO. 0.4 1 0.10 0-45 0-95 0.55 0.94 0-34 - - 0-40 FeO. - - - - 0.15 trace 3-85 - I - H,O. 0-40 0.08 0.60 0-54 2-48 3.14 4-48 4-81 4.89 - PbO. 77.63 77.70 66-53 70.14 - - - - - - Total. 99-95* 99-82? 99.11 98.395 100*10 99.931) 99*63** 100.49 99.32 99.50 G10. - - - - 16.53 11.49 - - - - Sp. gr. 6.53 6.706 5.576 3-404 3.16 3.189 2.914 2.906 - - * Including Fe 0.10 C1 trace. p Including ZnO 0.90 K,O 0.09 Ne,O 0-40 SO 0.63 C1 0.12. 11 Including F 0.15. Including Na,O 0.06 K,O 0-17 CO 0.26. 5 Including CI 0.10. ** Including TiO 0.11 K,O 0-24 Na,O 0-45.ii. 186 ABSTRACTS OF CHEMICAL PAPERS. species belonging to tlhe silicate group. Analysm are given of tlhe following I and 11 barysilit'e of different types from Jakobsberg ; formula Pb,S&O,. Ganomalite 111 from Jakobsberg IV from L%ngban. V trimerite from Jakobsberg ; formula Gl,SiO (Mn,Ca),SiO,. VI harstigite from Harstig mine; formula Gl,Ca,Si,O,,. VII epidote from Noh felspar quarry Gota. Prehnite VIII from Uppsala dist'rict IX from Hastberp estate near Falun X from Sjosa iron mine near Svarta. L. J. 8. Presence of Lithium in the Salts of Vesuvian Fumaroles. L. DE LUISE (Gazzetta 1919 49 ii 328--329).-The salts from the fumaroles of the crater of Vesuvius have thet composition potassium chloride 20.521% ; sodium chloride 79.458% ; iron and aluminium traaes. Sometimes lithium is present in small propor- tion and in one instance 180 grams of the mixed chlorides were found t o contain lithium chloride correaponding with 0.07 gram of lithium sulphate. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9201805184

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

ii. 186 ABSTRACTS OF CHEMICAL PAPERS. Qualitative Analysis in the Presence of Phosphoric Acid. HEINRICH REMY (Zeitsch. anal. Chem. 1919 58 385-392).-The following procedure is recommended for the qualitative analysis of a solution cont'aining various metals etc. and phosphoric acid. Heavy metals are first separated by means of hydrogen sulphide; the filtrate from the sulphide precipitate is boiled to expel hydrogefn sulphide filtered heated with the addition of a small quantity of nitric acid then nearly neutraliseld with ammonium carbonate treated with an equal volume of concent'rated ammonia and an excess of ammonium phosphate is added. Aluminium chromium iron calcium strontium barium manganese and magnesium are prelcipitated whilst zinc nickel cobalt and alkali metals remain in solution.The precipitate is dissolved in warm dilute hydro- chloric acid pot*assium sulphate solution is added and the precipi- tated alkali earth sulphates are collected on a filter and sepasated and identified in the usual way. The filtrate from the sulphates is boiled wit,h the addition of sodium acetate and ammonium chloride ; iron chro'mium manganese and aluminium are1 precipi- tated whilst magnesium and a small quantity of calcium remain in solution. The precipitate is dissolved in hydrochloric acid boiled nelarly ne(utza1ised with sodium carkonate and then poured into a mixture of hydrogen peroxide and 20% sodium hydroxide solution. Iron and manganese are precipitated whilst chromium and aluminium are converted into soluble chromate and aluminate rmpectively. The filtrate from the first phosphate1 precipitate andANALYTICAL CHEMISTRY.ii. 187 containing the zino etc. is heated treated with ammonium sulphide the precipitate is collected (the filtrate from this pre- cipitate contains the alkali metals) and the zinc sulphide is dis- so3ved in dilute hydrochloric acid in which nickel sulphide and cobalt sulphide are insoluble. The hydrochloric acid solution is t.hen rendereld strongly alkaline) with sodium hydroxide heated diluted and filtered; zinc is precipitated from the filtrate as sulphide after the addition of acetic acid. Nickel and cobalt are A. THIEL (Chem. Zeit. 1920 44 81-82).-A discussion advocating the use of equivalent unit8 in expressing the results of analysis. separated and identified in the usual way.w. P. s. Method of Stating Analytical Results. W. P. S. Influence of Temperature on the Strength of Standard Solutions in Quantitative Analysis. YUKICHI OSAKA (J. Tokyo Chem. SOC. 1919 40 424-449) .-The tables previously published (ibid. 1911 32 450) showing the changes in the concentratioz of standard solutions a t different temperatures taking 1 5 O as the st'andard temperature have belen extended for temperatluree from 5 O to 30° each being compared with three standards a t 1 5 O 20° and 2 5 O . Nineteen tables are given for N - and N/lO-oxalic acid AT-hydrochloric nitric and sulphuric acids N- and N / 10-sodium carbonate N / 10-sodium hydroxide N / 10- and N /lOO-sodium chloride N/10- and AT/lOO-silver nitrate N / 10- and N/100- potassium permanganate N / 10-ammonium thiocyanate and water.The change in the concentration of the solution and in the volume of the flask produced at different temperatures is recorded. The results are summarised in the following table] Standard temp. 13". * Solution temp. 5". 30". NaOH (N) ............... 1.00245 0.99508 NhC0 (N) ............ 1.00230 0.99521 HNO ( N ! ............... 1.00227 0.99516 HzS04 (N) ............... 1.00231 0.99516 H,C,O (N) ............... 1.00160 0.99580 HC1 (N) .................. 1,00153 0.99608 NaCl (0.1N) ......... 1.00108 0.99642 AgNO (0.1N) ...... 1.00105 0.99640 NH4CNS (0.1N) ...... 1*00104 0.99639 KMnO (0.1N) ...... 1.00096 0.99613 Na,CO (0.1N) ...... 1.00095 0.99675 H,C,O (0.1N) ...... 1.00078 0.99674 NaCl (0-01N) ......... 1.00089 0.99649 AgNO (0.01N) ......... 1.00089 0.99655 KMn04 (0.0137) ......1.00087 0.99653 H,O ..................... 1.00083 0.99661 20". +-. 5". 30". 1.00393 0.99655 1-00374 0.99664 1.00371 0.99658 1-00365 0.99659 1.00279 0.99698 1.00264 0.99718 1.00201 0.99735 1.00202 0-99737 1.00199 0.99734 1.00193 0.99737 1-00177 0.99757 1-00161 0-99757 1.00178 0-99738 1.00177 0.99743 1.00181 0.99745 1.00174 0.99751 25". * 5". 30'. 1.00559 0.99819 1.00534 0.99820 1.00534 0.99822 1.00526 0.99818 1.00422 0.99840 1.00395 0.99849 1.00321 0.99854 1.00321 0.99856 1.00322 0.99856 1.00312 0.99856 1.00287 0.99866 1.00270 0.99866 1.00295 0.99853 1-00294 0.99858 1-00294 0.99858 1.00288 0.99864 The a;velrage from all equinormal solutions is given in the final table for elach temperature from 5 O to 30° against threel standard temperatures.This table could be used for any iV-solution within error of 5 in 10,000. Another table is given which could be applied for any solution lelss than 0.1N within error of 5 in 10,000. It isii. 188 ABSTRACTS OF CBEMICAL PAPERS. pointed out that maximal errors for two solutions of equal strength made at two extreme tempmatures (5O and 30°) is 7:lOOO for N and 5 1000 for solutions less than 0.1N. CHEMICAL ABSTRACTS. The Effect of a Change in Temperature on the Colour Changes of Methyl-orange and on the Accuracy of Titrations. HENRY THOMAS TIZAED and JOHN REGINALD HARVEY WHISTON (T. D. J. DE JONG (Pharm. Weekblad 1919 66 465-467).-An extension and amplification of previous COM- munications (ibid. 179 238 328 404 405).I f a drop of acid is placed on ordinary filter paper and tested with methyl-orange a weak reaction will be indicated in a ring surrounding the drop and beyond this will exist a neutral (‘water ring.” I f the paper is previously treated with hydrogen chloride washed and dried it becomes saturated with hydrogen ions and further absorption of these from the drop will be prevented. A stronger coloration will thus result and will be produced in the whole moistened portion. Addition of acid to methyleno-blue similarIy increases its sensitive- ness. W. J. W. Use of the Electrometer for Titrations. J. PINKHOFF (Pharm. Weekbbad 1919 56 1218-1234).-The author givee a description of the apparatus and mode of operation in carrying out titrations by the potential method.A difference of potential of 1 millivolt should be detected by a suitable electrometer. The scope of the method and its special applications are discussed a t some length. W. J. W. Use of Arsenious Anhydride in Namias’ Method of Volumetric Analysis. FERRUCCJO DE BACHO (Annuli Chim. Appl. 1919 12 136-142).-1n Namias’s method (A. 1892 1374) any given oxidising agent is treated with an excess of arseai- om anhydride in the presence of ammonium acetate and the boiling liquid titrated with iodine solution after the additioin of acetic acid. Critical experiments have shown that this method is untrusb- worthy. No blue coloration is given by starch paste with iodine at 60-70° and it is therefore uselless to pmploy i t as an indicator in a boiling solution. The presence oE ammonium chlolride formed from the ammonium acetate when the solution contained hydro- chloric acid also influences the results. Equilibrium between the reacting substances is then only very slowly attained. Contrary to the assertion of Namias the reaction between arsenious anhydride and chromic acid is only complete after prolonged action and the results obtained are invariably too high and not concordant.1920 117 150-156). Indicator Papers. C. A. M. New Volumetric Reduction Method with Arsenious An- hydride. FERRUCCIO DE BACHO (ATMLCEIZ Chim. Appl. 1919 12 15;-3-174).-An oxidising agent is treated with excess of arsenioasANALYTICAL CHEMISTRY. ii. 189 acid solution in the presence of hydrochloric acid and the solution subsequently titrated with standard potassium bromate solution methyl-orange being used as indicatolr. To prelvent loss through volatilisation of arsenic chloride the proportion of hydrochloric acid must not exceed 12*8% a distinct loss occurring when it reaches 15%.In many cases the reduction is completle at the ordinary temperature but as a rule it is preferable to boil the liquid beneath a reflux condenser. The method gives good reaulk in the analysis of per- manganates in the estimation of manganese dioxide in pyrolusib and the analysis of chlorates and chromates including lead chromate. In the case of mixtures of hypochlorita and chloraw the hydrochloric acid is reduced to 5% t o retard the action of t-he chlorate during the estimation of the hypochlorites. The acid is then increased to 12% and the reduction effected at boiling point when both chlorates and hypochlorites react and the amount of the former is found by difference.[See also J . SOC. Chem. Ind. 1920 March.] C. A. M. Improved Electro-analysis Apparatus. J. L. JONES (Trans. Amer. Electrochem. SOC. 1917 32 329-334).-A description of a six- and a ten-unit electrically stirred electrolytic apparatus for the quantitative analysis of non-ferrous alloys. The electrodes and beakers are fixed; stirring is effected by revolving tungsten rods. Each electrolysis receives a separate current which may be varied between 0.5 and 6.0 amps. A switch and push-button before each unit enable the current and E.M.P. to be read at any molmant. J. F. S. Use of Lead as a Substitute for Platinum in Analysis. CARL H~TTER (Zeitsch.angew. Chem. 1919 32 380).-Platinum basins may be replaced by lead basins for certain quantitative esti- mations. Thus in the case of chrome iron ore the mineral may be heated with concentrated sulphuric acid in a lead basin on the water-bath and any lead sulphata formed removed without inter- fering with the subsequent analysis. The method is suitable €or the estimation of silicon aluminium potassium and sodium for which silica or silver basins cannot be used. Any alteration in the stage of oxidation is prevented by introducing a current of carbon dioaide through a porcelain tubs inserted intol a hole in the middle of the lead mver of the basin. C. A. M. Catalytic Reduction of Organic Halogen Compounds. M. BUSCH (Zeitsck. angew. Chem. 1918 31 232).-In the catalytic reduction of organic halogen compounds by means of palladium hydrazine may be substituted with advantage for a current of puri- fied hydrogen. 0.2 Gram of the organic compound is dissolved in 40-50 C.C.of alcohol; 2 grams of palladinised calcium carbonate or barium sulphat'e 2.5 O.C. of 50% potassium hydroxide and 10 drops of hydrazine hydrate are added. The liquid is boiled under reflux for thirty minutes after which the bulk of the alcoholii. 190 ABSTRACTS OF CHEMICAL PAPERS. is expelled on the water-bath. The catalyst is filtered of€ and the halogen dete,rmined in the filtrate after acidification with nitric acid. W. R. S. Estimation of Organic Chlorine or Bromine by the Chromic Acid Method. P. W. ROBERTSOX (Chem. News 1920 120 54).-To ovelrcome minor difficulties encountered in the chromic acid method of estimating organic chlorine or bromine (T.1915 107 902) the following modifications are suggested. A freshly prepared cold solution of sodium peroxide is used as absorb- ing medium instead of sodium hydroxide solution containing hydro- gen peroxide. The chromic anhydride may be replaced by halogen- free potassium dichromate and N / 20-solutions of silver nitrate and ammonium thiocyanate are relcommended instead of N / 10-solu- tions. Finally in the case of compounds particularly liquids which react explosively with the oxidising mixture the best procedure is to cover the substance with a large amount of powdered dichromate and run the previously cooled sulphuric acid very rapidly into the reaction vessel through a wide funnel by means of a suction pump connected with the absorption tube.The reactdon vessel is coded in ice until the initial violence of the oxidation has moderated. G. F. M. Iodometric Estimation of Chloric Acid. I. M. KOLTHOFF (Pharm. Weekblad 1919 56 460-465).-The direct iodometric estimation of chlorate in a strongly acid medium gives high results owing to oxidation of hydrogen iodide by atmospheric oxygen. Rupp’s method (A. 1918 ii 125) is satisfactory. It is sufficient however to use hydrochloric acid to the extent of one and a-half times the volume of the chlorate solution and only 100 C.C. of potassium iodide need be added. By using ferrous sulphate still smaller quantlit4ies of reagents may be employed. The chlorats solu- tion is boiled with 10 C.C. of 4.Y-hydrochloric acid and ferrous sul- phate; 1 gram of potassium iodide is added at 50° and the solution then titrated with slight heating towards the end.Estimation of Iodide. I. M. KOLTHOFF (Phnrm. Weekblad 1919 56 1029-1035) .-Estimations were made by several known methods with the same preparation of potassium iodide (0.098N) in each case. Winkler’s method (Zeitsch. anal. Chem. 1914 53 20) gives good results only in absence of bromide. The presence of bromide in small quantities does not affect the results in the easel of thoee methods in which hydrogen iodide is oxidised to iodine and the latter sstimated for example Volhard’s Vincent’s (A. 1900 ii 166) and Richard’s (Pharm. Weekblad 1903 40 157). I n the lastrmentioned method it is advisable to let the solution remain for two to three minutes aftm addition of the tartaric acid.Iodide may be estimated in presence of bromide by adding benzoic acid and potassium iodate boiling until thel iodine has disappeared then adding potassium iodide and sulphuric acid and titrating back wi tqh t hiosulp hate. W. J. W. W. J. W.ANALYTICAL CHEMISTRY. ii. 191 Estimation of Oxygen with Cuprammonium Compounds. W. HAEHNEL and M. MUGDAN (Zeitsch. angew. Chem. 1920 33; 35)-In the preparation of ammoniacal copper solution for the absorption of oxygen the usual ammonium carbonate solution em- ployed may with advantage be replaced by saturated ammonium chloride solution. The rate of absorption of oxygen is not affected but the residual gas is free from carbon dioxide derived from the The Volumetric Estimation of Sulphates by Oxidation of Benzidine Sulphate with Potassium Permanganate.9. L. HIBBARD (Soil Sci. 1919 8 61-65).-A moldification of the method of Raiziss and Dubin (compare A. 1914 ii 671) full details being given. It is shown that both temperature and volume are important factors which shonld be kept constant. The1 solu- tion for the precipitation of benzidine sulphate should be free from organio matter iron the heavy metals nitrates and phosphates and should cont'ain between 0.5 and 4.0 mg. of SO,". It is advisable to use an excess of standard permanganat'e solution the oxidation flask being heated in a boiling-water bath for ten minutes. A t the end of tlhis time$ a slight' excess of standard oxalic acid solution is run in and this is then titrated back with the perman- ganate solution.W. G. Estimation of the Non-protein Nitrogen in Blood. B. ALBERT (Biochem. Zeitsch. 1918 92 397-412).-A modifi- cation of the micro-method for estimating the non-protein nitrogen in blood. The blood or serum is freed from its protein by the addition of colloidal iron and 10% pot?assium sulphate. The filtrate is oxidised with " micro-sulphuric acid," consisting of 15 grams of nitrogeln-free potassium sulphate 5 grams of pure copper sulphate 100 C.C. of distilled water and 400 C.C. of pure concen- trated sulphuric acid. The distillation is carried out in an apparatus described by the author. The distillesd ammonia is received in S / 200-sulphuric acid and estimated iodometrically.ammoniacal copper solution. w. P. s. s. s. 2. Estimation of Urea Nitrogen in Blood (and Urine). B. ALBERT (Biochenz. Zeitsch. 1919 93 82-89) .-The Lesser- Siebeck micro-method for the estimation of urea nitrogen is con- sidered a very suitable one. Some modifications are recommended. s. s. 2. Estimation of Small Quantities of Arsenic. W. VAN RIJN (Pharm. Weekblad 1919 56 1072-1083).-Various methods od estimatdon of small quantities of arsenic as in urine have been investigated. Separation of the arsenic from the material under test is accurately effected by several methods as follows ( a ) Treat- ment with potassium chlorate and hydrochloric acid (Fresenius and Babo) ; ( b ) absorption by ferric hydroxide (Lockemann and Paucke A. 1911 ii 720); (c) acidification of the sample withii.192 ABSTRACTS OF CHEMICAL PAPERS. sulphuria add addition of solutiou of bromine in potassium bromide then ammonia and magnesia mixture; ( d ) treatment with ammonia and magnesia mixture and addition of sodium phosphate (Berntrop). Bloelmendaal's apparatlus was used for obtaining the mirror; final estimation of this by comparison with a standard mirror was not accurate and the titration method (Berntrop A. 1906 ii 706) was useld. Quantitiee as small as 1 mg. oif arsenic pelr litre were estimated. The estimations were also carried out with wallpapers paintl and blind materials. Precision Method for the Estimation of Gases in Metals. H. M. RYDER (Trans. A m e r . Electrochem. Soc. 1918 33 197-204).-The metal to be inve5tigated is mountsd as a thin ribbon or filamelnt in an electric light bulb which is connected to a.Toepler pump and exhausted. The temperature of the fils ment is then raiseld by an elelctric currelnt and the pump set work- ing so that the gas= are continuously removed. The tempera- ture is raiseld in steps of 50° up to the melting point and the gases evolved a t each temperature are measured and analysed. The bulb is watter-coold to prevent the evolution of gases by the glass on heating. Silicon steel was found to give off large volumm of gas a t 730O. I n the analysis the water vapour and carbon dioxide are frozeln out by metans of liquid air and the remaining gases removed. The carbon dioxide1 is then removed by substituting carbon dioxide snow for the liquid air. The volume1 of carbon dioxide is measured by reading the preasure existing in the apparatus by melans of a MacLeod gauge.It is then pumped out and the water vapour released into the vessel1 by removing the refrigerant. The pressure due to this is read by means of a mercury U-tube mana- meter with optical levelr attachmeat. Oxygein is added to the residual gases and the hydrogen methane and carbon monoxide are burnt to carbon dioxide and waher which a're eatimated as before. Carbon monoxide is added to the residual gases and servw after combustion to estimab the excm of oxygen and any which may have been there originally. Nitrogen is estimated by difference. 5. F. S. New Absorption Apparatus for Elementary Analysis FRITZ FRIEDRICHS (Zeitsch. amgew. Ckenz. 1919 32 388).-A compact form of absorption apparatus is described in which the carbon dioxide is absorbed by means of potassium hydroxide solu- tion in a helical tube which is fixed within the1 bend of a U-tube.The lattelr is charged with calcium chloride instead of soda-lime. The use of calcium chloride as a drying agent is preferable to that of sulphurio acid when it is a question of equilibrium being attained. The binary system CaCl,-H,O in which the phases CaCl CaC1,,2H20 H,O occur is univariant and the tension therel- fore depends on t-he t'emperaturel but not on the1 concentration whereas the system H,SO,-H,O in which only two phaxs H,SO H,O are formed is bivariant and its telnsion delpends on the con- centration its well as on the temperature. The use of both drying W. J.W.ANALYTICAL CHEMISTRY. ii. 193 agents as hitherto? is unsuitable since the tension of sulphuric acid is lower than that of CaC12,2H,0. The gas must therefore be moistened not dried in the calcium chloride tube following the sulphuric acid vessel or the results for hydrogen will be too low; under these conditions calcium chloride dihydrate must be used instelad of anhydrous calcium chloride. It is therefore advisable t o discard the sulphuric acid and replace it by 50% potassium hydroxide solutioa and calcium chloride. C. A. M. Estimation of Combustible Matter in Silicate and Carbonate Rocks. A. C. FIELDNER W. A. SELVIG and U. B. TAYLOR (U.S. Bureau of Mines 1919 Tech. Paper 212).-The melthod described is a modification of that devised by Lissner (Chem. Zeit.1910 34 37-38) involving digestion of the silicate material with hydrofluoria and hydrochloric acids and combustion of the insoluble residue. Carbonate rocks are treated with dilute hydrochloric acid to remove calcium carbonate etc. and the process is applied t o 1 the insoluble residue. [See further J . SOC. Chem. znd. 1920 155A.I W. E. F. P. The Estimation of Calcium and Magnesium in Different Saline .Media. E. CANALS (BUZZ. SOC. chim. 1919 [iv] 25 655-658. Compare A. 1919 ii 34 477).-For the volumetric estimation of small quant%ities of magnesium it is recommended that the magnesium should first be precipitated as magnesium ammonium phoephate and then one of two methods adopted. (1) The precipitate is washed centrifugally with dilute ammonium hydroxide and then dissolved in just sufficient 5% hydrochloric acid the phosphoric acid in the solution being estimated by titra- tion with an uranium solution (1 O.C.=0*5 mg. P,O,) using cochineal as an indicator. The reaults are accurate t o 0.2 gram of magnesium. (2) The precipitate is washed with a saturated aqueous solution of sodium phosphate and then dissolveld in hydrochIoric acid the ammonia present being estimated colorimetrically by means of Nessler’s reagent. The results are accurate to 0.01 gram of magnesium. W. G. Spectroscopic Estimation of Small Amounts of Lead in Copper. C. W. HILL and Gt. P. LUCHEY (Trans. Amr. Electroehem. SOC. 1917 32 335-343).-A method is desoribed for the rapid estimation of small quantities of lead in copper. A known weight (0-1-1-0 gram) of the sample in the form of a shot is placed in a m a l l cavity in the lower positive graphite electrode of a carbon arc and a fixed or rotating negative electrode used above. The arc is struck the light focussed on to the slit of a grating spectroscope and the time required for the1 complete disappearance of the1 bright lead line (405-8pp) from the spectrum or for its reduction to a definite feeble intensity is measured by means of a stop-watch.With careful adjustment of the arc the times varyji. 194 ABSTRACTS OF CHBMICAL PAPERS. regularly with the amount of copper used and with its percentage of lead. Thus 0.2 gram of copper containing 0.004% of lead required 14 secs. whilst 1.0 gram of copper containing 0.038% of lead required 227 se(m. A series of experiments made with 0-4 gram samples show that the1 analyses are sufficiently accurate for use in a copper refinery.Estimation of Mercury. H. B. GORDON (ArtaZyst 1920 45 41-46).-For the1 estimation of small quantities of mercury a coil of copper gauze is suspended in the solution which has previously received the addition of a small amount of hydrochloric acid and of coppelr sulphate; the gauze is kept in motion by a motor and aftelr a suitable1 time is removeid from t,hel solution washed dried. and weighed. It is then heated in a current of hydrogen cooled in the same gas and rekweighed; the1 loss in weicht is due to the vola>tilisation of the depositeld mercury. The volatilised mercury may be collected in a constricted portion of the heating t8ube and identifield bb the iodine test.As little as 0.1 mg. of mercury may be detected by the method. Nitrate6 do1 not interfere but antimomny arselnic bismuth and silver should not be premnt as they are liable t o cause error unless the copper gauze is heated at such a temperature that the mercury alone volatilises. [See Detection and Estimation of Very Small Quantities of Chromium in Minerals and Ores containing Silicates and Carbonates. 0. HACKL (Chem. Zeit. 1920 44 63).-0ne gram of the minelral is fused with eight times its weight of a mixture of sodium carbonatel and potassium carbonate the fused mass is t.related with water a drop of alcohol is added the mixture heated to reduce and precipitate any manganese compounds prwent and the solution is filtered. The filtrate is evaporated but not so far that alkali salts crystallise out again filtered.and dilute'd to a definite volume which should be from 20 to 50 c.c. according to the quantity of chromium present. The chromium is then estimated colorimetrically using as a standard a potassium chromate solution co;ntlaining 0.0511 gram of the salt and a small quantity of sodium carbonate per 200 c.c.; eaah C.C. of this solution is equivalent to J. F. S. furthelr J . SOC. Chem. Ind. 1920 March.] W:P. s. 0.1 mg. of Cr,O,. w. P. S'. A Very Sensitive Reagent for Cobalt. I. BELLUCCI (Gazzetta 1919 49 ii 294-298).-0ne mg. of cobalt in solution may be detectad colorimetrically in 1-2 litres of water by means of u-nitroso-j3-naphtho17 and in about 17 litres of water by means of P-nitroso-a-naphthol (compare1 Atack A.1915 ii 652 ; Jones A. 1918 ii 410; Bellucci and Chiucini this vol. ii 54). One mg. of nickel in 4-5 litres of water may be detected by means of dimethylglyoximel. T. H. P. The Theory of Colour Lakes. C. BRENNER (HeZw. Chirn. Acta 1920 3 90-103).-The author has endeavoured to baseANALYTICAL CHEMISTRY. ii. 195 melthods for the detection and e8timation of minimal amounts of cobalt and copper on the colorations which the metallic ions give with nitrosonaphthols. a-Nitroso-&naphthol is found to be un- suitable for this purpose in aqueous solution since the lake is too easily precipitated whilst chlorof o m or carbon disulphide solutions (in which cobalt "nitrosite" is readily soluble) are only adapted to the detection but not to the estimation of cobalt.On the other hand the solubility of the lake in water can be sufficiently increased by introducing one or morel sulphonic groups into the napht'hol molecule. The colour of the lake depends on the number and posi- tion of the hydroxy- and sulphonic groups; the yellowest shade is given by the1 nitlroso-derivative of " R "-acid the deepest reid with nitrosocl-naphthol-5-sulphonic acid and the darkest shade with nitroso-1 8-dihydrolxynaphthalene-3 6-disulphonic acid (chromo- tropic acid). I n ammoniacal solution the latter gives a lake when metal and acid are in the proportion of 1 atom to 2 molecules whilst in sodium hydroxide solution thelarequisite proportion is 1 6 ; attempt8 to base a colorimetric process f o r estimating cobalt on these data were1 unsuccelssful the! results being 10-40% high.On the other hand the acid can be1 used for the micro-titration of cobalt since the yellow ammoniaoal solution of nitrosdromotropic acid yields an immediate intense blue coloration with the cobalt ion in the formation of which 2 molecules of the acid react with an atom of cobalt; when the cobalt' ions have1 been completely con- verteld into this compound further addition of the acid causes a change in shadel from blue to red. Test analyses show the1 method tor be fairly accurate but it cannot be used for cobalt in the presence of nickel although the latter alone1 mag also be estimated by the reagent. The micro-titra8tion of copper can be effected similarly but a larger excess of the reagent is required to give a definite end- point.Other substances with propert'iee similar to those of nitroso- chromotropic acid are1 found among azocdyes which are used with metallic mo'rdants and among those which in dyeing are subjected t o after-chroming. Thus Diamond Black F gives a deep blue solution in aqueous alkali which yields differently coloured lakes with ammoniacal solutions of the1 most various metals ; when the metallic ion is completely united with the1 dye addition of a further quantity of the lat,ter causes a change in shade towards blue. The possible utility of the method is illustrated at the instance of copper. The possibilities of the formation of diff elrentlV coloured complex compounds have been investligated for twenty different metals and sixteen dyes; such compounds appear to be formed most frequently with magnesium the1 alkaline earth metals and those of the iron group.It is interesting to note thatl chromium which is so largely used in mordanting is allied in this respectl with thel least reactive metals of the nitrogen family. The capabilit?y of the dye! to form differently coloured complex compounds which are soluble in ammonia appears to depelnd on the presence of a hydroxyl groupii. 196 ABSTRACTS OF CHEMICAL PAPERS. --- -1 alkali metal in an alkaline solu- 0 ,* z .- .-. .. in the orthoc or para-position to the azocgroup and as a result of extensive experiments with a number of dyes it is pmsible t'o give methods for the1 microchemical estimation of copper silver mag- nesium zinc cadmium calcium strontium barium iron nickel and cobalt.The constitution of the lakes and the colour change8 involved in tqhe titrations are discussed with particular reference to Diamond Black. I n acid sollutlion the quinonoid formula (I) is ascribeld to the dye in which two strong partial valencies amre associateld with the oxygen grotups whilst the other partial valencies of the azcqroups satisfy each othelr. The former valencies are taneously thel parhial valeiicies of the azo-groups are satisfied by those of the alkali metal. When however metallic ions are present in the solution the subsidiary valencies of which are stronger than thma of the alkali met'als the adaal lake is produced as indicated in formula (11). H. W. LUDWIG LOWY (Zeitsch. angew. Chern. 1919. 32 379-380) .-Ferrotungsten is completely decomposed when fused with ammonium sulphate and concentrated sulphuric acid without the porcelain or platinum crucible being attackeld as when the fusion is elffected with pot4assium hydrogen sulphate.The fuwd mass is dissolved in water the solution trelated with a little nitric acid and then boiled with dilute (1 5) hydrochloric acid. The precipitated tungstic acid is separated and washeld wit?h dilute hydrochloric acid the1 filtrate freeld from iron by prelcipitation with ammonia then acidified and evaporated to dryness the1 residue boiled with dilute hydrochloiric acid and the fresh precipitate of tungs,tic acid separateid. For very accuratle analyseis a third precipitation may be made. The1 unitled precipitates are1 ignited until constant in weight evaporated with hydrofluoric acid and again ignited and weighed.Any remaining iron may be separated by fusing the relsiduel with sodium carbonatel extractling thel mass with water and weighing the1 residue of felrric oxide. Estimation of Tungsten in Ferrotungsten. [Seel further J . Soc. Chem. Tnd. 1920 1 5 8 ~ ~ 1 C. A. M,ANALYTICAL CHEMISTRY. ii. 197 Estimation of Uranium and its Separation from Other Rare Elements. C. A. PIERLE (J. Ind. Eng. Chem. 1920 12 60-63).-1t is shown that good results may be obtained by pre- cipitating uranium with ammonium hydroxide washing the p r s cipitate with ammonium nitrate solution and igniting it. Pre- cipitation as uranyl ammonium phosphate1 by means of ammonium dihydrogen phosphate is also trustworthy but has the drawback that the ignited uranyl pyrophosphate rapidly absorbs moisture.Precipitation as uranium sulphide and subsequent ignition invari- ably gives too high results owing tIo part of the sulphur being oxidised to sulphate during the ignition. Volumetiric estimation of uranium by means of potassium permanganate is inaccurate owing to1 oves-redudion taking place and it is not possible to eliminate this or to cont-inue the reduction to a definite point below the uranous condition. A method of separating uranium from vanadium mollybdenum and tungsten has been based on Peligot's observation (Ann. Chim. Phys. 1842 riii] 5 I) that uranyl nit3rate is reladily sofluble in ether. The solution is evaporateld to dryness and the residue of uranyl nitlrate etc.is extracted with ether in which vanadium pentoxide molybdenum trioxide and tungstic tri- oxide are1 insolublel. The dry residue should be moistened with nit4ric acid immediately before the extraction and shortly after the procem has b q u n t'o reconvert into1 nitrate the partly decompoaed uranpl nitrate. Anothe'r method of separating uranium from vanadium has been based on the1 fact that uranyl nitrate is readilv soluble whereas vanadium pentoxide is insoluble in acetic acid of 95% strength or above to which nitric acid has been added in the prolpostion of 1 20. The solution of uranyl nitrate and sodium met,avanadab is evaporated tqo drynew with nitric acid and the uranium extracted from the residue by metans of the mixed acids. [See further J. s o c .Chem. Tnd. 1920 209~.] C. A. M. Reaction of Tin Salts. A. MAZUIR (Ann. Chim. anal. 1919 [ii] 2 9).-The reaction depends on the insolubility of stannous or stannic iodide in sulphuric acid. Two C.C. of the neutral or slightly alkaline solution containing the tin salt are treated with 2 C.C. of 10% potassium iodide solution and 1 to 2 C.C. of concen- trated sulphurio acid. A yellow crystalline precipitate of tin iodide forms at once if the solution under examination contains not l a than 0.1 gram of tin per litre; the precipitate is soluble in chloroform alcohol and dilute hydrochloric acid. It is decom- posed by ether iodine being liberated. Arsenic gives a similar reaction but the arsenic iodide formed is insoluble in dilute or concentrated hydrochloric acid. I n the case of antimony the iodide obtained is flocculelnt and brick-red in colour.w. P. s. Separation and Estimation of Lead and Bismuth. G. LUFF (Chem. Zed. 1920 44 71).-A nitric acid solution of the two metals is neutralised with ammonia saturated ammonium nitrite solution and sodium nitrite solution amre added the rnixbure isii. 198 ABSTRACTS OF CHEMICAL PAPERS. diluted to about 200 c.c. and boiled. When the evolution of nitrogen celasels the1 precipitate1 (bismuth hydroxide or basic bismuth nitrate) is collected on a filter washed with hot water then dis- solved in nitric acid the! solution evaporated and the residue ignited and weighed as Bi,O,. The filtrate is acidifield with acetic acid and the lead precipitated and weigheld as had chromate. The bismuth oxide after weighing should be treated with nitric acid and hydro- fluorio acid again ignited and washed to remove traces of silica and alkali respectivelly.w. P. s. The Estimation of Acetylene in Gaseous Mixtures J. A. MULLER (RuU. SOC. chim. 1920 [iv] 27 69-71).-The acetylene is absorbed in ammoniacal cuprous chloride using a volume of gas containin? atl the most 10-1 1 C.C. of acetylene ; the) solution is acidified with acetic acid and the cuprous acetylide is collected and washed. The paper and precipitate are transferred to a platinum crucible! and sulphuric acid is added drop by drop until a homogeneous fluid mass is obbained. The excess of acid is gelntly evaporated and when fuming has ce'ased the crucible is heated t o a red heatl cooled and weighed.W. G. Determination of the Composition of Mixtures of Alcohol and Water by Measurements of Electrical Conductivity. T. M. KOLTHOFF (Rec. trav. chim. 1920 39 126-134) -For the determination of the alcohol content of beer or wine the following procedure1 is relcommended. The excess of carbon dioxide is removed from the liquid by bubbling air through it and the liquid is then distilled with magnesium oxide. Fifty C.C. of the distillate are mixed with 10 C.C. of approximately W / 2 - oxalic acid solution and t.he mixture is made up to 100 C.C. with water. The specific conductivities 1 and 302 of the mixture and of the original oxalic acid solution diluted to one-tenth with water are then determined. Then f t = l O O x xI/x2. This can then be1 corrected to f,8 by melans of the temperature-coefficient and a table is given showing the relationship between f I 8 and the alcohol content of the distillate.W. G . SpecificReaction of Butylene &t-Glycol and of Acetylmethyl- carbinol Products of Butyleneglycallic Fermentation. LEMOIGNE (flowapt. rend. 1920 170 131-132) .-The character- isation of acetylmet,hylcarbinol in the products of microbic decom- position of sugars servea to) diff erentiats certain groups of similar microbes and the1 following method affords a ready means of detecting tracm of this compound. The carbinol is oxidised to diacetyl by means of ferric chloride the diacetyl beinq distilled off and detected by precipitation in ammoniacal solution as nickel dimethylglyoxime with a nickel salt and hydroxylamins. Bv this method it is possible to detect acettylmethylcarbincd at' a dilution of 1 in 1,000,000.The reaction is not given by any other of the products of fermentation W. G.ANALYTICAL CHEMISTRY. ii. 199 Microchemical Method of Estimating Dextrose. 11. IVAR BANG (Biochem. Zeitsch. 1918 92 344-347. Conipare A 1918 ii 279).-It is found that the potassium iodate employed by the author in his modified method for the micro-estimation of sugar in blood does not keep well. He therefore uses free iodic acid instead. The solution is prepared by dissolving 0.3567 gram of pure1 pot<assium iodate in 10 C.C. of 20% sulphuric acid. 2.5 Grams of coppes sulphate (CuSO + 5H,O) may also be added to i t a t the same time and the solution is made up t o 1 litre. The author finds that by means of Willstatter and Schuchl’s method 0.1-0.5 mg.of sugar can be estimated. However this method cannot be employed in the estimation of sugar in blood. Blood containing 0.107% of sugar showeld a content of 0.22% and 0.23% by t’his method. s. 5. z. Adsorption Compounds and Adsorption. V. The Adsorption Compounds of Cuprous Oxide. L. BERCZELLER (Biochem. Zeitsch. 1919 93 230-237) .-In precipitating cupric hydroxide from cupric salts with sodium hydroxidel some of the alkali is adsorbed by the cupric hydroxide. Thel black hydroxides adsorb more of i t than the blue on=. Iodate ions are also adsorbed by cupric hydroxide but in this case the blue hydroxides adsorb more of it than the black. The presence of sugar prevents the adsorption of sodium hydroxide by cupric hydroxide. S.S. Z. Estimation of Small Quantities of Sugar in the Presence of the Higher or Lower Products of Protein Degradation. ERWIN LAST (Biochem. Zeitsch. 1919 93 66-82).-The higher products of protein degradation such as albumoaes and peptones the prcsence of which interferes with the estimation of sugar can be removed by means of mercuric chloride in neutral solution. The sugar can then be estimated by Bertrand’s method. I n the presence of acids the precipitation of these products is incomplete. An excess of mercuric chloride must also be avoided in order to ensure good results. Two grams of mercuric chloridel per gram of peptone are found to be a suitable quantity. The presence of monoamino- acids does not affect the accuracy of the sugar estimation by Bertrand’s method ; ereptone however does influence the results.This is due to the special atomic grouping in elreptone which on boiling with alkali hydroxide liberates ammonia and this dissolves some of the cuprous oxide. Ereptone can be removed from sugar solutions also by precipitation with mercuric chloride in neutral solut*ion. The removal of both the higher and lower products of protein degradation with mercuric nitrate according to the Patein- Dufau method conduces to accurate results. 5. s. z. Estimation of Lactose in Altered Milks. E. HECDT (Bull. Sac. chim. 1919 [iv] 25 617-621).-A more detailed account of work already published (compare A 1919 ii 84). W. G.ii. 200 ABSTRACTS OF CHEMICAL PAPERS. Modifhation of the Phenylhydrazine Method of Estimating Pentosans. PAUL MENAUL and 0.T. DOWELL ( J . I d . Emg. Chem. 1919 11 1024-1025).-The material is distilled with sulphuria acid instead of hydrochloric acid and the furfuraldehyde is estimated in the distillate by precipitating with a known excess of phenylhydrazine filtering off the hydrazone and determining the excess of phenylhydrazine in the filtrate. F o r this purpose an aliquot part of the filtrate1 is heated with ammoniacal copper sulphate solution and the nitrogen evolved is measured the reaction previously employed by Ebler f o r the determination of hydrazinei (A. 1906 ii 53) being quantitative also1 in the case of phenylhydrazine. [See further J . Soc. Chem. Ind. 1920 170~.1 J. H. L. A Microchemical Method for the Estimation of Acetone.M. RICHTER-QUITTNER (Biochem. Zeitsch. 1919 93 163-172).-A microchemical method in which 1-2 C.C. of urine and 1.5-3 O.C. of alkali need only be used. The urine is distilled once with steam in the presence of acetic acid and a second time with dilute sulphuric add. Blood or plasma need only ba distilled once and instead of the steam air is passed through the heated flask. The tdtration of the distilled acetone is carried outl with N / 100-iodine and iV/ 100-sodium thiosulphate. 0.1 Mg. of acetone1 in 100 C.C. can be estimated with accuracy by this method. The’ quantity of urine and blood used must contain not less than 0.04 mg. od acetone. s. s. z. Microchemical Reactions of Veronal Luminal and Pro- 1919 56 1112-1117; J . Pharm. Chim. 1919 [vii] 20 337-343).-Small trace6 of the derivatives of barbituric acid separated from urine by treatment with lead acetate and hydrogen sulphide may be oonverted into an easily identifiable crystalline form by sublimation. Veronal may be separated as monoclinic crystals from its solution in sodium hydroxide1 by the addition of an acid potassium dichromatel or ammonium phoslphate. Lead acetate gives an amorphous mass which becomes crystalline on boiling. Ammoniacal silver nitrate gives an irregular crystallinel mass of large simple crystals o f veronal-silver . With thallium nitrate crystals of veronal-thallium are formed. Luminal and proponal have only to1 be separated in the uncombined state. A crystal of ammonium phosphate introduced into a drop of a solution of tqhese in soldium hydroxide causes the separation of the free acids in the form of drops which only gradually change intlo crystals probably rhombic. W.J. W. POnal. L. VAN ITALLIEand A. L. w. E. VAN DER VEEN (Pharrn. Weekblad Estimation of t 1 Saccharin ’’ in Urine. GEORUE S. JAMIESON ( J . BioZ. Chem. 1920 41 3-8).-Urine is treated with lead aceltate and filtered. After a,oidifying with hydrochloria acid the ‘‘saccharin” is extracted by ether the ether removed by evapor-ANALYTICAL CHEMISTRY. ii. 201 ation and the ‘‘saccharin” extracted from the residue by ether. The ether is removed and the resulting residue is fused with sodium carbonate. From an estimation of sulphur in the fused product the amount of “saccharin” may be deduced. J. C. D. The Estimation of Aniline in Commercial Anilines.WILLIAM JAMES SANDERSON and WILLIAM JACOB JONES ( J . SOC. Chem. Ind. 1920 39 ~T).-A method of estimation is given which is based on a determination of the freezing point of the sample. The purity is deduced by reference to a table which is provided showing the freezing points of dry mixtures of aniline with varying proportions (1-7% by weight of the mixture) of each of benzene phenylhydroxylamine nitrosobenzene paminophenol nitrobenzene o- or p-toluidine m-phenylenediamine and xylidine. J. K. Formaldehyde Titration of Amino-acids in Aqueous Solutions or in Urine. W. MESTREZAT (Bull. SOC. Chim. Biol. 1919 1 107-113).-The me,thods employed by Ronchh (cited by Maillard Compt. rend. SOC. BioZ. 191 1 61 653) are insufficiently accurate. J. C. D. Urea and Hypobromite.L. LESC(EUR ( J . Pharm. Chim. 1919 20 305-314 343-351 374-381) .-Tho volume of nitrogen liberated by the action of alkaline hypobromite solution on urea is always less than that required by theory; too low results are also found i f the urea is calculated from the amount of carbon dioxide formed or of the hypobromite used in the reaction. The deficit is to some extent dependent on the proportion of free alkali present and decreases but never quite disappears as the quantity of free alkali is increased; i t appears to be due to the conversion of a part of the urea into sodium cyanate. w. P. s. Ureometer. P. SEYOT (Ann. Chim. anal. 1920 [ii] 2 11-13). -The apparatus consists of a graduated tube open a t its lower end whilst the upper end above the zero point is bent over and down- wards for a short distance where it is blown out to form a bulb.A short side-tube with a tap is provided at the top of the bend. The bulb has a tubulure a t the side into which is ground the neck of a small cylindrical bulb. The latter contains the hypobromite solution whilst the urine or other liquid under examination is placed in the larger bulb. The whole apparatus is placed in a cylinder of water the level of the latter then adjusted to the zero point by manipulating the tap and the smaller bulb then turned (by means of the ground-in joint) so that the hypobromite solution mixes with the urine in the larger bulb. The evolved nitrogen displaces water from the graduated tube and the volume of the nitrogen is noted afte’r the water-level has been adjusted.If 1.3 C.C. of urine is taken for the estimation each C.C. of nitrogen is equivalent t o 1 gram of urea per litre of urine. w. P. s.ii. 202 ABSTRACTS OEl CHEMICAL PAPERS. Identification of Traces of Hydrocyanic Acid. L. CRELLL (Bz~ll. SOC. Pharm. Bordeaux 1919; from Ann. Chim. anal. 1920 [ii] 2 21-24. Compare A. 1919 ii 529).-The following tests may be used for the identification of traces of hydrocyanic acid Phthalein test.-A red coloration is obtained when a cyanide solution is treated with a drop of alkaline phenolphthalein solution reduced previously with zinc and a drop of 0.1% copper sulphate is added. isoPurprate test.-If a cyanide solution is heated with the addition of alkaline picric acid solution an orange coloration develops after a few hours.Ammoniacal silver iodide test.-The reagent is prepared by diluting a mixture of 10 C.C. of N/1000- silver nitrate solution 2 C.C. of ammonia and five drops of 19% potassium iodide solution to 100 c.c.; this reagent gives a turbidity with a cyanide solution. For instance if a turbidity is obtained when 1 C.C. of the cyanide solution is treated with 0.2 C.C. of the reagent less thin 0.001 mg. of hydrocyanic acid is present; with 0.005 mg. of hydrocyanio acid 1 C.C. of the reagent is required. Ferrocyanide test.-This is the most characteristic reaction of hydrocyanic acid; it may be used for the identification of hydro- cyanic acid in silver cyanide and mercuric cyanide. W. P. S. Sensitiveness of some Cyanide Reactions. JOHN B. EKELEY and ICIE C. MACY (Proc.Colorado Sci. SOC. 1919 11 269-274) .-Working directly with solutions of potassium cyanide the Prussian blue test gives positive results (a blue precipitate on keeping) at a dilution of 1 7 x 104 (at about 1:17 x 104 for hydrogen cyanide). One hundred C.C. of potassium cyanide solu- tJon (1 7 x 105) give a definite result after acidifying with 10 C.C. of 1% tartaric acid and distilling off about 2 c.c.; this corresponds with a dilution of hydrogen cyanide about 1 1.7 x 106. The hang- ing-drop method with silver nitrate give positive result8 with solu- tions of potassium cyanide (1 8 x 106 corresponding with hydrogen cyanide a t a dilution of about 1 19 x 106) when 100 C.C. are exposed t o the drop of silver nitrate for fifteen minutes.The Schonbein test gives positive results with potassium cyanide solutions at a dilution of 1 18 x 106 in the light and 1 23 x 106 in tohe dark (equivalent) to 1 43 x 106 and 1 55 x 106 respectively for hydrogea cyanide). This test should be performed in closed vessels in the dark to secure trustworthy results and only a t extreme dilutions does it indicate the presence of hydrogen cyanide and exclude the presence of other substances (chlorine bromine hydrogen peroxide hydrogen chloride) which are known to respond a t high concentra- tions. CHEMICAL ABSTRACTS. Estimation and Separation of Pyridine and Ammonia. E. B. R. PRIDEAUX (Trans. Faraday Soc. 1919 15 137-147). -Precise information as t o the conditions for the titration of pyridine and of ammonia in the presenc,e of pyridine and of the separation of the two by distillation has been obtained by appli- cation of the electrochemical theory.Congo-red is the correctANALYTICAL CHEMISTRY. ii. 203 indicator for pyridine and nitric acid the best acid. A correct indicator for the titration of ammonia in the presence of pyridine is a-naphtholphthalein . Both ammonia and pyridine are estimated with sufficient accuracy provided that pyridine is not present in excess. Rosolic acid may be used if the bases are titrated directly and the pyridine is present in amount considerably less than the ammonia. Ammonia and pyridine may be partly separated by distillation from a solution of which the acidity is maintained at about p H = 3 to 4 (reddish-brown to Congo orange to methyl- orange).The first part of the distillate contains most of the pyridine the second most of the ammonia so that the titrations just described may be used. J. R. P. Estimation of Indole in Biological Media. HARPER F. ZOLLER ( J . Biol. Chem. 1920 41 25-36).-The usual preliminary steam distillation of the indole solution is abandoned and replaced by direct distillation care being taken to have the solution adjusted to a hydrogen-ion concentration of p 9.2 (see this vol. i 250). The distillation is continued until all but about 10 C.C. have been driven over the distillate beinq collected in a 100 C.C. volumetric flask and made up to the mark. A portion of the distillate con- taining not more than 0-20 mg. of indole is measured into a test- tube of convenient size and two drops of 1.0% solution of sodium nitrite and five drops of concentrated sulphuric acid are added.The tube is shaken and left for five minutes for the nitroso-reaction to approach equilibrium. The contents are then extracted with three portions of 3 C.C. of isobutyl or isoamvl alcohol each portion being drawn off with a pipette and placed in a test-tube having a 10 C.C. graduation. .li.oButyl or isoamyl alcohol is then added to bring the conbnts of the tube up t o 10 c.c. and the colour is matched against a series of standards prepared by similar treat- ment of solutions containing a known amount of pure indole. The method is stated to be simple trustworthy and rapid. The relative sensitivities of Herter’s naphthaquinone reaction and the nitroso-reaction were found to be 1 2,000,000 and 1 1,500,000 respectively .A warning is sounded against the use of the vanillin test pro- posed by Steensma (A. 1906 ii 315). The rate a t which the equilibrium of the nitroseindole react.ion is reached depends on the factors of concentration and temperature At temperatures from 30-90° the full depth of colour is obtained in a few seconds but higher temperatures tend to destroy the coloured compound when in aqueous solutions. I n pure isobutyl alcohol the colour is not dest,royed by heating for several hours a t looo. I n actual analvses the test should not be carried out at temperatures above 30°. J. C. D. Detection of other Cinchona Alkaloids in Salts of Quinine. I. M. KOLTHOFF (Phamz. Weekblnd 1919 56 451-459).-Kerner and Weller’s method has many disadvantages and only givesii. 204 ABSTRACTS OF CHEMICAL PAPERS.accurate results under certain conditions. The following method is suitable for quinine sulphate but is inapplicable to other salts. 0.5 Gram of quinine sulphate is boiled gently for one minute with 250 mg. of sodium sulphab and 10 C.C. of water. Water is then added to restore the original volume and the mixture cooled to 1 5 O with shaking. The liquid with the precipitate is kept below 1 8 O for twenty-four hours and then filtered through glass wool. Three drops of 4N-sodium hydroxide are added to the filtrate which is then heated on the water-bath for half an hour. After twelve hours the solution is examined for the presence of a precipitate. The test is sensitive to 1% of cinchonidine.I n regard to the nitroprusside test the author does not confirm Kruysse’s opinion of its sensitive- ness and failed t o devise a means of increasing this. De Vrij’s chromate test is considered to be a suitable substitute for Kerner and Weller’s method. For quinine hisulphate 0-5 gram is boiled with 20 C.C. 2N-sodium acetate until the liquid is clear. Then 3 C.C. of 10% potassium chromate are added and further treatment is carried out by de Vrij’s method. For quinine 0.5 gram is taken together with 3 C.C. of 11T-sulphuric acid and 20 C.C. of 2N-sodium acetate and the test continued as above. Quinine hydrochloride may be tested exactly as described by de Vrij. W. J. W. Estimation of Albumin in Urine. OTTO MAYER (Zeitsch. anal. Chem. 1919 58 337-346) .-A reagent described previously by the author (A. 1914 ii 80) for the estimation of albumin in urine is a l t e r d in composition in order to render it more sensitive. Ten grams of mercuric chloride 65 grams of sodium chloride and 25 grams of citric acid are dissolved in 500 C.C. of hot water and the solut.ion is filtered after a few days. This solution wilI give a ring reaction in about ten minutes with as little as 0.0002% of albumin whilst 0.001% of albumin is denoted by ths appearance of a turbid zone within three m i n u b . If the urine contains more than 0.001% of albumin the test is repeated after dilution until the reaction is just observable and the quantity of albumin present then calculated Estimation of Catalase in Blood. MEYER BODANSKY (J. RWZ. Chem. 1919 40 127-130).-1n making estimations of cata- lase by the method employed by B u r p (Amer. ,7. Ph?/sioZ. 1916 41 153) i t was found that different samples of hydrogen peroxide often gave results which differed by 15-350/n. It was experiment- ally shown that the reaction of the medium is one important factor in determining the activity of catalase. Consequently caution must be exercised in maintaining uniform conditions when a series of determinations are being made. from the degree of dilution. w. P. s. J. C. D.

ISSN:0368-1769    

DOI:10.1039/CA9201805186

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

i. 200 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. Analyses of Blood Gases. 111. The Permeability of Human Erythrocytes to Chlorions. H. STRAUB and KLOTHILDE MEIER (Biochem. Zeitsch. 1919 98 205-228. Compare A. 1919 i 53) .-Blood corpuscles suspended in a physiological sodium chloride solution were subjected to the influence of various concen- trations of carbon dioxide. It was found that the corpuscles acted as " buffers " towards carbon dioxide. The hydrion concentration of the inside of the cells exceeded PH=7*O0 only when the sodium chloride solution in which the corpuscles were suspended reached an hydrion concentration of Y,=6-67. This is no doubt brought about by the alteration in the colloidal condition of the cell mem- brane. The change in the hydrion concentration was found to be independent of the concentration of C1 and Na ions of the solution in which the corpusclw are suspended as long as a certain minimum of these ions was assured and the solution made isotonic.In hyper- tonio 0.2 molar salt solutions the change in the corpuscles was brought about a t the same hydrion concentration namely PH = 6-67. In a hypertonic 0.102 molar solution on the other hand the change Analyses of Blood Gases. IV. The Influence of Alkali Ions on the Haemoglobin and Cell Membrane. H. STRAUB and KLOTHILDE MEIER (Biochem. Zeitsch. 1919 98 228-256) .- The influence of alkali ions on the electrical charge of haemoglobin and on the permeability of the membrane of human erythrocytes to these ions has been studied. The membrane becomes permeable to the various ions at the following hydrion concentrations Li and Na at P,=6-67 K a t P,=6*8 Rb atq PH=6.92 Cs a t PH=7.06.The hzmqglobin loses its charge on the addition of the alkali ions took place earlier. S..S. z.PHYSIOLOGICAL CHEMISTRY. i. 201 a t the following hydrion concentrations Na and K a t Y,=7-00 Rb at. P,=7-22 Cs at P,=7*34. The membrane becomes per- meable to ammonium ions in low concentrations a t P,=7*48. Higher concentrations of these ions require a higher hydrion con- centration before the membrane becomes permeable to them. The action of ammonium ions on the charge of the hzmoglobin is similarly influenced by the concentration of the ions. The analogy between the permeability of the cell membrane to the alkali ions. and the precipitation of colloids by means of these ions is pointed out.The bearing of the adsorption theory on the permeability of the cell membranes to alkali ions is also discussed. s. s. z. Influence of High Temperatures and Dilute Alkalis on the Antineuritic Properties of Food. AMY L. DANIELS and NELLEE I. MCCLURC ( J . Biol. C'licm. 1919 37 201-213).-The results obtained by these authors are not in accord with those reported by McCollum and Simmonds (ibid. 1918 33 55). It appears improbable that the commercial canning of foods is responsible for a serious destruction of the antineuritic vitamine and the warning sounded by Chick and Huma (Proc. R0.y. SOC. 1917 [R] 90 60) is regarded as unfounded. The Vitamines of Green Foods. THOMAEI B. OSBORNE and LAFAYETTE B.MENDEL (with ceoperation of EDNA L. FERRY and ALFRED J. WAKEMAN) (d. Bid. Chem. 1919 37 187-200).-Dried yeast is somewhat more than four times as efficient as dried spinach leaves when used as a source of the water-soluble vitamine. These leaves howeve? appear to be a rich source of fat-soluble - 2 . The values of cabbage lucerne clover and timothy plants in supplying the water-soluble accessory substance are of the same order as that of spinach but the experiments are not regarded as complete. Very small amounts of lucerne clover and timothy plants will supply sufficient fat-soluble .I for the growth of young rats. Em- phasis is therefore laid on the importance of fresh green vegetables in the human dietary. Identity of the Water-soluble Growth-promoting Vitamines and the Antineuritic Vitamine.H. H. MITCHELL (.I. RioZ. Chem. 1919 40 399-413).-The author reviews the literature dealing with the distribution properties and character of these two substances and f o r m the opinion that there is as yet insufficient evidence to assume that they are identical. Formation of Urea by the Placenta. FREDERICK S. HAMMETT (?7. Bid. f'hem. 1919 37 105-112).-Formation of urea by the placenta may be conclusively demonstrated although the processes leading up to its production can only be surmised. J. C. D. J. C. D. J. C. D. J. C. T). Physical Properties and Chemical Composition of Human Amniotic Fluid. DOKO UYENO (J. Biol. Chem. 191 9 37. 77-101).-The human ariiniotic fluid at the end of pregnancyi. 202 ABSTRACTS OF CHEMICAL PAPERS.always contains coagulable albumins (an average of 0.226% inclu- sive of mucin). The quantity of mucin was too small to be estim- ated. Peptones add proteoses were not found. Approximately 0.003% of ammonia and 0.0323% of urea were found together with very small amounts of uric acid and creatine but creatinine and hippuric acid were absent. Cholesterol is also a component of the human amniotic fluid. J. C. D. The Effect of Pyretics and Antipyretics on Catalase Production. W. E. BURGE ( J . Phnrm. expt. Ther. 1919 14 121-130) .-Tetrahydro-8-naphthylamine adrenaline caffeine and sodium chloride stimulate the alimentary glands particularly the liver to an increased output of catalase; this fact is offered in explanation of the increased oxidation produced by these sub- stances and hence of the accompanving fever in so far as the increased heat production is involved in this. Chloroform decreases catalase both by decreasing itng output from the liver and by direct destruction of this enzyme.Ether decreases catalase principally by direct destruction of the enzyme without disturbing the liver func- tion so much as does chloroform. Acetanilide quinine and phen- acetin produce a slight decrease in catalase by decreasing its output from the liver. Chloroform and ether lower temperature in so far as decreased oxidation is involved in this by decreasing catalase the enzyme principally responsible for oxidation in the body. The fact that acetanilide quinine and phenacetin have little or no effect in decreasing catalase suggests that their mode of action in lowering temperature is not due to a decrease in oxidation.The Carnosine Content of Normal and Pathological Human Cardiac Muscles. F. BUBANOVI~ (Biochem. Zeitsch. 1918 92 125-129).-The carnosine content of the human heart is very constant and is not influenced either by hypertrophy or atrophy of the muscles. The average content is 0.25%. The carno- sine was determined when possible both by the diazo and the copper colorimetric methods. s. s. z. J. C. D. Bioluminescence. X . Production of Carbon Dioxide during Luminescence of Cypridina Lueiferin. E. NEWTON HARVEY ( J . Gem. Physiol. 1919 2 133-135).-All luminous animals require oxygen for luminescence but there has previously been some doubt as to whether carbon dioxide is given off as a result of this phenomenon.A brilliant luminescence results when a small amount of luciferase solution is added to a solution of Cypridina luciferin (A. 1919 i 299) so that it. should be possible to ascertain whether this process is accompanied by a liberation of carbon dioxide. The results of experiments indicate that the oxida- tion. of luciferin which is responsible for luminescence is not t o be compared with the reactions in cells giving rise to the carbon dioxide of respiration. As previously suggested by the author the process is probably similar to the oxidation of a leuco-dye (A. 1919 i 299). J. C. D.PHYSIOLOGICAL CHEMISTRY. i. 203 Bioluminescence. XI. Heat Production during Lum- inescence of Cypridina Luciferin. E. NEWTON HARVEY ( J . Gen.Physiol. 1919 2 137-143).-The heat change during tho oxidation of luciferin by luciferase was investigated in order to ascertain the nature of the luminescent reaction. The change observed was so small that i t is estimated that 1 gram of luciferin develops less than 0.1 cal. during the oxidation process accompany- ing luminescence. This clearly differentiates this type of reaction from those such as the oxidation of dextrose 1 gram of which will give 4000 cal. It therefore appears probable that no carbon dioxide is produced during the oxidation of luciferin and that the process is one more closely resembling the oxidation of leuco- methylene-blue (compare preceding abstract). Physiology of Phosphorus and Calcium Metabolism as Related to Milk Secretion. EDWARD B.MEIGS N. R. BLATHERWICK and C. A. CARY ( J . Biol. Chem. 1919 37 1-75). -Normal blood plasma contains no phosphorised protein and prob- ably no phosphorus compounds other than phosphatides and inorganic phosphates. The phosphorus of these two classes of com- pounds certainly comprises more than 97% of all that exists in normal plasma. The precursor in plasma of milk fat and milk phosphorus is of a phosphatide nature. The concentration of calcium in the plasma of cows is quite constant. Small variations can be induced by varying the amount supplied with the rations but the chief controlling factor is probably the concentration of bicarbonate in the plasma. It is probable that the concentration of calcium tends to vary inversely with that of the bicarbonate. The concentrations of phosphatide and inorganic phosphates in the plasma are highly variable.Both can be made to vary by changing the amount of phosphorus supplied with the rations though the variations in’ducFd in this manner show themselves most markedly in the inorganic phosphate. Both undergo variations as the accompaniment of increasing age and of the later stages of preg- nancy. The phosphatide of the plasma shows a marked tendency to rise during the first month of lactation and to remain high until lactation has ceased. This phenomenon is largely independent of the diet and is thought to be connected with the fact that near the beginning of lactation there is a tendency for the body fat t o be released from its stores and thrown out into the blood. J. C. D. J.C. D. Pyrrole and Melanuria. PIETRO SACCARDJ (Atti R. Accad. Zincei 1919 [v] 28 ii 85-89) .-Administration of pyrrole leads to the formation of melanin in the urine in the case of the rabbit but not in that of the dog ; the latter being essentially a carnivorous animal appears easily to oxidise those products of the scission of proteins which lead to the formation of pyrrole whereas with herbivorous animals the oxidation proceeds only a5 far as melanogen. Melanins have been obtained from rabbits’ mine from cuttlefish from black hair from the choroid and from a melanotic tumour,i. 204 ABSTRACTS OF CHEMICAL PAPERS. the properties and reactioiis of the different products being described. These melanines all resemble closely pyrrole-black obtained by the chemical oxidation of pyrrole; when heated in a test-tube they yield crystalline sublimates in the form of black orthorhombic lamella whereas precipitat,ion of the melanines gives amorphous masses.The glandular oxidation of pyrrole in aqueous suspension con- taining a few drops of toluene has been studied in vitro at about 40° the glands used being the mamma liver testicles thyroid kidneys and spleen of the ox. The glandular tissue gradually turns brown and assumes the appearance of an ordinary melanotic tumour; the most intense blackening is shown by the liver and spleen the testicles kidneys and thyroid following in order. The mamma exhibits 110 blackening after six days and even undergoes putrefaction in spite of the presence of toluene. Addition of adrenaline accelerates the blackening of the glandular organs.T. H. P. The Physical Theory of the Action of Drugs and Poisons. I. TRAUBE (Biochern. Zeitsch. 1919 98 177-197) .-A theoretical paper. The pharmacological action of drugs and toxins is attributed mainly t o their physical properties. It is urged that more attention ought to be given to the physical side of these prin- ciples in the study of chemotherapy. s. s. z. The Biological and Pharmacological Properties of Chlorophyll. EMIL B ~ R G I and C. F. VON TRACZEWSKI [with (FRL.) SCHEINA BASS A . BRAUNSTEIN and (FRL.) s. FRIDKISS] (Biochem. Zeitsch. 1919 98 256-284) .-The hamoglobin-forming capacity of chlorophyll was studied in a series of esperiments in which the latter was administered to rabbits made anamic by means of bleeding and by the action of phenylhydrazine.It was found that chlorophyll as well as iron when given in large doses possessed a blood-forming capacity. Both chlorophyll and iron were equally effective whether the experimental anzmia was induced by bleeding or by the administration of phenylhydrazine. Small doses of chlorophyll were found t o possess a “sensitising ” effect on the action of iron in the production of blood. s. s. z. Blood-forming Properties of Chlorophyll. R. GRIGORIEW (Biochem. Zeitsch. 1919 98 284-294).-Chlorophyll in the form of phEophytin possesses a higher blood-forming capacity than iron when given t o normal o r naturally anaemic rabbits. The best results are achieved with these animals by the administration of a combination of iron and chlorophyll.s. s. z. Maximum Production of Glutamine by the Human Body as Measured by the Output of Phenylacetylglutamine. 1919 37 11 3-2 19).-No marked increase i i i siilphur metabolism CARL P. SHERWIN. MAX JVOLF and WILT.IAM %‘OLP (./. UiOl. Chenz..,VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 205 followed the ingestion of phenylacetic acid by man. This does not agree with the experimental results of E. and H. Salkowski working with rabbits (A. 1879 662). Intestinal putrefaction as measured by the excretion of ethereal sulphates is decreased after administration of phenylacetic acid. About half of the acid administered was excreted in combination with glutamiiie. J. C. D. Comparative Metabolism of certain Aromatic Acids - 111. Fate of p-Nitrophenylacetic Acid in the Organism of Fowl Dog and Man.CARL P. SHERWIN and MAX HELFAND ( J . Biol. Chem. 1919 40 17-27).-The human organism eliminated 68-77! of the ingested p-nitrophenylacetic acid in the urine in the un- changed condition. Attention is drawn t o the peculiar fact that this acid although toxic to the body is excreted without havinq been rendered innocuous by combination with some substance such as glycine in its passage through the tissues. When administered to the dog the greater part is excreted unchanged b u t some is found to be present in the urine as 17-iiitropheiiylaceturic acid. I n the case of the fowl a certain amount of the 11-nitrophenylacetic acid is excreted unchanged. but the greater part is combined with ornithine in the body and excreted as p-?titrophen.~?ncpt.~lornithinic ucid C'L,H2,0RN4 short thick irregula; needles m. p. 184-185O. J. C. D. Behaviour of Sudan I11 in the Animal Organism. B. E. READ (t7. Rid. Chem. 1919 37 121-135).-Sudan I11 dissolved in oil and administered intraperitoneally subcutaneously or by the mouth is absorbed and may be traced in the lymph blood and bile. It is transported t o the fatty tissue of the body being deposited particularly in the omentum. It is excreted in the faxes and is not found in the urine of normal animals. Ordinary com- inercial preparations of Sudan I11 contain more or less impurity of a toxic nature. The foreign substances are excreted in the urine which is deeply coloured and may cause death. J. C. D.

ISSN:0368-1769    

DOI:10.1039/CA9201800200

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

ii. 205 General and Physical Chemistry. The Optics of Disperse Systems. I V . I. LIFSCHITZ and GEORG BECK (li'olloid Z & t d . 1920 26 58-66. Compare A 1918 ii 181 253; this vol. ii 137).-The chernid proloesses occur- 'ring during change in the colloidal state and their effect on the change in the light absorption is theoretically considered. An attempt is made to use the published work on the refractometrio measurements of colloids to explain the r81e of the change in the colloidal state in the ohange in light absorption. The density refractive index molecular and specific refractivitiea for the C D and F lines have been measured for solutions of twenty organic aoida and their sodium saltsl in methyl alcohol a t 2 5 O . It is shown that the increase in refraction from acid to sodium salt is different in the different cases but with acids which form salts accompanied by a reanangement o r by exercising subsidiary valenciw there is an extraordinarily large change.The increase in refraction in salt formation is independent of simultanesus peptisation or colloid formation and m abnormally large increase in the refraction cannot be explained by a change in the dispersity. It is also shown that a very large percentage of case8 of vario-chromism and polychromism are to be explained by intramolecular action of subsidiary valencies and that chromoisomerism is to be similarly explained. J. F. S. Influence of Position and Accumulation of Substituents on Spectrochemical Behaviour . V. Alkyloxyacetic Acids. A. KARVONEN (Acad. Sci. Ferznicae 1916 [ A ] 10 No.8 1-7; from Chem. Zentr. 1919 iii 987. Compare this vol. ii 129).- The alkyloxyacetic acids exhibit optical values slightly lower than that of acetic acid itself. H. W. Influence of Position and Accumulation of Substituents on Spectrochemical Behaviour . VI. Esters of Keto- alcohols COMe-[CH,],- OeCO-Me. A. KARVONEN (Acad. Sci. Fencnicae 1916 [ A ] 10 No. 8 1-7; from Chem. Zmtr. 1919 iii 987) .-Further investigation with fresh materials shows that the optical values increase somewhat with increase in the relative distance between the carbony1 group and that of oxygen con- nected to two carbon atoms in the cam af esters of the lower alkyloxy-aliphatic acids and keto-alcohols. Influence of Position and Accumulation of Substituents on Spectrochemical Behaviour .VII. Ether-Alcohols ROo[CH,],*OH. A. KARVONEN (Acad. Sci. Fennicae 1916 [ A ] 10 No. 9 1-43; from Chem. Zentr. 1919 iii 981).-Spectro- chemical investigation of the monomethyl ethyl and prolpyl ethers H. W. VOL. CXVIII. ii. 7ii. 206 ABSTRACTS OE' CHEMICAL PAPERS. of ethylene glycol and of the monomethyl and ethyl ethers of tri- methylene glycol shows these compounds to be closely related optically. H. W. Influence of Position and Accumulation of Substituents on Spectrochemical Behaviour. VIII. Mutual Spectro- chemical Action of Hydroxyl Groups. A. KARVONEN (Acad. Sci. Fenwicae 1916 [ A ] 10 No. 10 1-10; from Chem. Zentr. 1919 iii 981).-Investigatim of ethylene and trimethylene glycols showed that two hydroxyl groups in direct union with one another cause marked exaltation which is progressively diminished by the successive introduction of methylene groups between the hydroxyls.Certain atoms or atomic groups directly united with one another cause optical exaltation (HO + + OH O t +O -S+- +S- - S e t +Se-) whilst others bring about depression a third section being neutral or nearly 80 (H,N Oil). This action cannot readily be ascribed to supplementary valencies and not invariably to the existenoe of double bonds between the atoms. (C-t +(OR),. d,H,N+ t s H N+ +-N) H. W. Effect of an Electric Field on the [Spectrum] Lines of Argon and Oxygen. E. BijTTCHER and F. TUCZEK (Ann. Physik 1920 [iv] 61 107-112).-The effect of an electric field of 26,000 V / c m on the spectrum lines of argon and on both the spark and arc lines of oxygen has been investigated.I n the case of argon the lines are absolutely unaffected by the field; the same result was obtained with the spark lines of oxygen. Of the arc lines the 3-7 members of the I subsidiary triplet series showed a dis- placement towards the red which increased with increasing member number. The four lines hh4846 4743,4634 and 4559 are observed in the spwtrum under the influence of the field and have not before been observed. They are displaced toward the violet. The intensity increases with increasing wavelength and the scrim ceasea with the most intensive member without any indication of a further less intensive member. The p-components are considerably more intensive than the s-components. With increasing strength of field the intansity of the lines with longer wave-lengths increases more rapidly than that of those with shorter wavelengths.The lines are regarded as belonging to a sharp subsidiary series of the I triplet subsidiary series. Spectro-analytical Investigation of the Luminosity of Decomposing Ozone. KARL STUCHTEY (Zeitsch. wiss. Photochem. 1920 19 161-197).-The spectrum of the luminosity of an oxygen-nitrogen mixture in an ozoniser has been photographed and shown to be made up of the second positive group of the nitrogen spectrum the emission spectrum of the Y-oxide of nitro- gen (Warburg and Leithiiuser A. 1906 ii 743; 1907 ii 342; 1909 ii 226 227) and the visible emission spectrum of ozone. The emission spectra agree absolutely with the well-known absorption J.F. S.GENERAL AND PHYSICAL CBEMISTRY. ii. 207 spectra. On heating ozone a t 400° in a specially constructed oven a strong luminosity is observed. The light shows both the visible and the ultra-violet spectra of ozone. A mixture of nitrogen and ozonised oxygen heated in the same furnace shows in addtion to the emission spectrum of ozone also the emission spectrum of the Y-oxide of nitrogen. An explanation of the mechanism of the luminosity is given and it is shown that the luminosity does not depend on preclence of oxidisable substances. J. F. S A Helium Series in the Extreme Ultra-violet. THEODORFI LYMAN (Nature 1919 104 314; Science 1919 50 481-483).-By using a powerful disruptive discharge in helium a fairly strong line in addition to those previously reported for the helium spec- trum was found to appear a t wavelength 1640.2 and a fainter line a t about 1215.1.dxperimental evidence is thus afforded for the existence of the lines 1640.1 and 1214.9 as calculated from theoretical considerations. CHEMICAL ASS TRACTS. Some New Spark Spectra in the Extreme Ultra-violet. LEON BLOCH and EUGENE BLOCH (C'mpt. rend. 1920 170 320-322) .-Using the spwtrograph with a fluorspar prism previ- ously described (&id. 226) the authors have studied the spectra from a condensed spark between metallic electrdes in hydrogen in the case of four metals. Cadmium gave a spark spedrum extend- ing to A = 1500 and the rays have been measured down to A = 1600. Bismuth gave a spectrum to h=1500 the rays being measured to A = 1550.The spark spectrum of nickel is very rich in rays in the extreme ultra-violet these being measured to A=1540. Down to h=1650 there is a great similarity between the arc and spark spectra. For silver the rays were measured down to ~=1496. Nickel gave a doublet h=1550'7 and 1548.2 and silver gave a doublet A = 1551.3 and 1548'7. W. G . Line Spectra of Cadmium and Zinc in the Electrodeless Ring Discharge. A. HAGXNBACH and H. SCHUMACHER (Zeztsch. wiss. Yhotwhem. 1919 19 129-142).-The spectra of zinc and cadmium prcduced from an electrodeless discharge have been measured and compared with the arc and spark spectra of these elements. It is shown that the spectrum coincides neither with the aro spectrum nor with the line spectrum in either case but contains lines of both spark and arc spectra as well as a number of new lines.The intensity of the various lines is also very different from that of the lines in the arc and spark spectra. In the case of cadmium lines are measured from h6467.4 to 2183.1 and forty-four new lines lying between ~5511.0 and 2436.25 are recorded both in the international system and in Rowland's system. In the case of zinc the lines measured lie between ~6362.58 and 2252.87 and thirteen new lines lying between ~3186.24 and 2246.88 are recorded. It is also shown that under suitable conditions a band spectrum can also be obtained. J. F. S. 7-2Z. 208 ABSTRACTS OF CHEMICAL PAPERS Band Spectrum of Zinc from the Electrqdeless Ring Discharge. A. HAGENBACH and H. SCHUMACHER (Zeitsch. wks. Photochem. 1919 19 142-148.Compare preceding ab- stlract).-The band spectrum of zino obtained from an electrodeless discharge has been measured over the range ~4894.9-3469’5 and compared with existing measurements. A large number of new bands are recorded. J. F. S. Measurement of the Arc Spectrum of Iron below 2373 according to the International System. H. SCHUMACHER (Zeitsch. w&s. Photochem. 1919 19 149-158).-The iron spec- trum of smaller wavelength than ~ 2 3 7 3 has been photographed and measured. The wavelengths are given on the international system and an accuracy of about 0.03 A. is claimed for the values. As source of light an iron arc burning with 4 amperes and 220 vollts was used. The valuB are compared with those of Kayser and Runge. J. F. S. Theory of Absorption Spectra.I. LIFBCHITZ (Schweiz. Chem. Zeit. 1918 2 58; from Chem. Zentr. 1919 iii 970).-A reply to KaufFmann’s miticisms (A. 1917 i 391) of the author’s views (A. 1917 ii 435). The Chromophore Function. V. Optical Properties of some Heavy Metal Complexes. I. LIFSCHITZ and ERNST ROSENBOHM (Zeitsch. wks. ,Photochem. 1920 19 198-214. Com- pare K. 1917 ii 62 435).-The absorption spectra of the heavy metal complexes consist in general of at least three bands which lie between ~ 6 0 0 0 and ~ 2 0 0 0 A . units. Of these that with the longest wavelength depends mainly on the nature of the oentral atom; the next band depends on the nature of the ccwrdinated groups if the oentral atom is the same. The band with shortest wave-length is not so completely investigated because in many cases i t lies so far in the ultra-violet as to be unmeasurable with the apparatus employed.All the work on the subject tends to show that this band is displaced more toward the longer wave- lengths in the presence of bivalent co-ordinated groups than in the presence of univalent groups. H. W. J F. S. Calculation of the Frequency Limits of Absorption K and L of the Heavy Elements. LOUIS DE BROOLIE (Compt. rend. 1920 170 585-587) .-For tungsten platinum gold lead bismuth thorium and uranium examined Vegard’s formula gives results for the frequenoy limits of absorption K and L which are much more nearly in agreement with the mean of the observed results than those calculated by Bohr’s formula. W. G . Absorption Coefficients of Solutions for Monochromatic Radiation.E. 0. HULBURT anci J. F. HUTCHINSON (Carnegie Inst. Pub. 1918 260 6-69) .-The absorption-coefficient of solu- tions of inorganio sdts in water and in difEerent alcohols has beenQENERAL AND PHYSICAL CHEMISTRY. ii. 209 measured at intervals of 2 0 p p to 40pp throughout the spectrum region from 600pp to 1300pp. For each salt a series of solutions varying in concentration from saturation t o moderate dilution ,was prepared and the absorption curve drawn for each solution. The molecular absorption-coefficient A of the salt was calculated for each wave-length and plotted against c the concentration of the salt in gram-molecules. Solutions of cobalt chloride in water ethyl propyl isobutyl and isoamyl alcohols were examined by the phote graphio method; the valuw of A changed with the concentration and the absorption curves for the higher alcohols were similar to those for ethyl alcohol.The following solutions were also examined cobalt nitrate and sulphate nickel chloride (anhydrous and the hexahydrate) nitrate and sulphate in methyl ethyl and propyl alcohols ; ammonium ferric alum in water ; chromic chloride nitrate and su1phat.e ; and pot,assium permanganate. The relation between A and c has been determined from the data thus obtained. I n general A is not constant. Sometimes it deoreases with dilu- tion i n other cases increases with dilution and also passes through a minimum; a maximum was not obtained. The deviations of A from a constant value were usually small except at mrtain points in the spectrum which in general were situated at the edges of absorption bands.No theory adequately explains the observations. CHEMICAL ABSTRACTS. Colour Antagonism or Chemical and Electrical Polarity of the Spectrum. GABRIELE RABEL (Zeitsch. wiss. Photochem. 1919 19 69-128).-The long-wave half of the spectrum from the yellowish-green to the infrsred is termed positive light whilst the short-wave half from bluish-greea to ultra-violet is termed negative liqht. It is shown that phosphorescent light is produced by nega- tive light and extinguished by poaitive light. Phosphorescent substances and certain classes of orqanio substances change their colour when subjected to negative light but in positive light regain the original d o u r . Silver salts are reduced by negative light but are oxidised by positive light. Certain biological and chemical reactions occur in the reverse direction in negative light from that in positive light.Electrodee which are sensitive to light undergo opposite mtential changes in negative light from those in positive light. The retina of the eye belongs to the light sensitive elec- trodes. The movements of lower organisms are influenced in oppo- site ways by Dositive and negative Iight. I n high-tension discharqe in hvdroqen in the red hydroqen layers the maximum potential lies in the luminous layer the minimum in the dark space between the lavers whilst with the blue hydroqen layers the maximum is in the dark space and the minimum in the luminous layer. In the bluish-red douhle layers the dark space shows neither maximum nor minimum but is positive to the blue laver and nerrative to the red laver.If a plate covered with sodium chloride is brought into a luminous layer discharge reduction (that is formation of a blueii. 210 ABSTRACT’S OF CHEMICAL PAPERS. coloration) occurs in the luminous layer in the blue discharge and in the dark space in the red discharge. Fluorescence and Absorption of the Uranyl Sulphates. E. L. NICHOLS and H. L. HOWES (Physical Rev. 1919 [2] 14 293-305) .-The fluorescenoe spectrum of the uranyl sulphates con- sists of eight equidistant bands. the first and eighth of which disappear at the temperature of liquid air. The remaining bands are resolved into groups of narrow line-like bands the homologous members of which form series having constant frequency intervals ranging from 85.7 in UOoSOI,CsoS0,,2~R,0 to 83.0 in The fluorescence groups are dist>inguished by a strong pair of bands about eight frequency units apart and several weak bands some of which are doublets.There is a shift of all bands towards the 1-iolet with increasing molecular weights of about fifteen frequencv units in passin? from the spectrum of uranyl su1phat.e to that of the msium double salt. The absorption spectra of the sulphates are made up of seriea of bands having a frequencv interval of 70.3 on an average. These absorption series eytend into group 7 of t h p flaorescencs without break of interval. There are many reversals where fluorescence and absorption overlap. The reversing region is. therefore one group further towards the red than in most snectra of the uranyl compounds. Fluorescence and Absorption of the Uranvl Acetates.E. L. NICHOLS H. L. HOWES and FRANCES G. WICK (Physica7 Rev. 1919 r2] 14 201-221).-The paper deals with the fluores- cence and absomtion spectra of the t3wo known forms of ura.nv1 acetate and of thirteen double uranvl acetates as thev amear when wcited a t the temperature of liquid air. The essential identity of the spe’dra of t-he double acetates of lithium tmtassium. calcium manganese and strontium both as reEards the location of thhs princinal bandq and the structure of t h e fluorescence groups. is established and the deviations from this t y m occurring in the spectra of the uranyl acetates containin? barium ammonium rubidium sodium mapnesium zinc silver and lead are considered.The anproximate identitv of frenuency intervals for all ceries and for all salts is likewise established the interval being 84-76. J. F. S. UO?SO~,K~SO~,2H~O. CHEMICAL ABSTRACTS. CHEMICAL ABSTRACTS. Quanten Theorv Basis of Photochemistry. E. WARBURG (Zeitwh B7e?~fmc7tem. 1920 26 54-59).-A theoretical paner in which i t is shown that every photochemical reaction is character- ised by the specific photochemical adion +. that is. by the number of cram cals. of heat ahsorhed per mol. The fundamental law of nhottochemieal readion ic. thpt enerqg of freouencv v is absorbed in quanta by the reacting moledes. The molecules which absorb the liqht radiation are termed photochemical reserved mole- ciilefi.” and from the law Stated. the number of thwe may be calcu- lated.VaIency radiation is the radiation which in the reservingGENERAL AND PHYSICAL CHEMISTRY. ii. 211 of 1 mol. of the photolyte is absorbed by it. The indicated photo- chemical equivalent ( p ) is the number of rnols. which are reserved in the absorption of 1 gram-cal. The effective photochemical equi- valent is the number of mols. which are decomposed or changed by the absorption of 1 gram-cal. It is equal to the specifio photcl chemical action + when this is calculated on the number of decom- posed o r changed molecules. + / p is the efficiency relationship. Einstein’s photochemical equivalent law says that every absorbing o r reserved molecule is by the act of absorption decomposed or changed and when the secondary processes are known it determines the efficiency relationship for which values >= 1 are obtained.The law is rigidlv held in iFolated cases only because in general the reserved molecules o r a t least a part of t4hem do not undergo primary change for the following reasons (1) the valency radia- tion is smaller than the molecular decomposition energy; (2) energy is lost during the absorption of the radiat.ion; and (3) the ohemi- cal change only takes place as a secondary process as in the case of photolytic isomerisation. Photochemical Studies. VIII. Periodic Light Reactions. JOH. PLOTNIKOTV (Zeitsch. wiss. Photochem. 1919 19 22-39). -The action of chlorine on a-cyanocinnamic acid in carbon tetrachloride solution under the influence of light of wave- length A=436p,u has been investigated a t 1 7 O .It is shown that there is no formation of a chlorine additive compound and that the nitrile concentration has no influence on the reaction but chlorine is used up linearly with time and its use is due t o a hitherto unknown reaction between carbon tetrachloride and chlorine. The reaction between carbon tetrachloride and chlorine was therefore investigated. It is shown that the absorp- tion of chlorine is linear both with blue light h=436pp and ultra- violet light A = 366 ,upL. Using the whole of the light from a uviol lamp a periodio change in the concentration of the chlorine is observed. Further experiment8 show that in light pure carbon tetrachloride yields free chlorine. The reaction is discussed and the possibility of periodic light reactions shown. Two types of such reactions are indicated (1) Periodic light reactions are a neces- sary consequence of the stationary condition of photochemical pre cmes and must occur periodically so long as light of various wave lengths acts. (2) Periodic light reactions are the result of the combination of different opposing reactions which are brought into existence by light of different wavelengths and are influenced by $fferent catalysts and consequently tend to an equilibrium condition.J. I?. S. Photochemical Studies. VII. Equilibria in Photo- chemical Addition of Bromine. Jon. PLOTNIKOW (Zeitsch. u4.s.c. Photochem. 1919 19 1-21).-Reactions of the type CR1R2:CR3R4 + Br = CRlR2Br-CR3314Br are reversible and are of such a nature that the equilibrium posi- tion in the dark as well as in the light depends on the temperature J.F. S.ii. 212 ABSTRACTS OF CHEMICAL PAPERS. concentration nature of the solvent intensity of light) and the nature of the radiclesl R1 R2 R3 and R4. The reaction between bromine and a-cyanocinnamio acid in light has been investigated CHPh:C(CN)*CO,H + Br CHPhBr*CBr(CN)*CO,H. The reac- tions were carried out in carbon tetrachloride solution using light of wave-length 1 = 4 3 6 p p at 7". It is shown that bromine dow not read as Br but as 2Br and the r e d i o n taking place is pro- portional to the square of the absorbed light energy. The displace- ment of the equilibrium is proportional to the light intensity. The equilibrium formula for the react'ion has the form where y is the equilibrium constant of the dibromide p the thick- nem of th0 layer of solution a the initial concentration of the nitrile b the initial concentration of the bromine i the normal light absorption constant of bromine (for h=436 pp i t is 0-2156 per millimol.concentration) and J the light intensity. The tempera- ture-coefficient of the dark reaction of the dibromide decomposition is determined from the correspondinq equilibrium displacement and found to be 2.14. It is suggested that the extreme ultra-violet rays have the opposite action t o the! long waves on this reaction. J. F. S. )lP% Q = J( 1 - e - iP(b - 9)2(a - Y) Spectral Photoelectric Sensitivity of Silver Sulphide and ereveral other Substances. W. W. COBLENTZ and H. KOHLIER (Bull. Bur. Standards 1919 15 231-249; Sci.Paper 1919. No 344).-Data are given of the change1 in the electrical resistance of the sulphides of silvelr and bismuth when exposed to radiations from 0.6 EL in the visible spectrum to 3 p in the infr+red. Galena cvlindrite pyrites and jamesonite did not show photoelectric sensitivity for the highest spectral radiation intensitiM available. The sulphides of silver and bismuth are sensi- tive from 0 . 6 ~ to 1 . 8 ~ . The photoelectric response for silver sulphide becomea fatigued at the ordinary temperature. The ohange in resistlance of the crystal when exposed to radiation is first negative and then positive. the resultant change being nega- tive and approximately onefifth of the original change. A t - 1 5 8 O this polarisation phenomenon disappears and t b response to radiation is the same as that of other substances such as selenium or molybdenih.Ths smsitivitv is greatlv increased when the temperature is lowered to -158O. The sensitivity curve is quite symmetrical and shows a maximum a t 1 . 2 ~ . An increase in the intensity of the exciting radiation shifts the maximum towards the lonq wavelengths. A spectral photoelectrio sensitivity curve of bismuthinite was obtained at -166* maxima occurring atl 0 . 6 4 ~ and 1.08p. CHEMICAL ABSTRACTS. Photo-oxidation of Organic Compounds by Chromates . JOH. PLOTNIKOW (Zeitsch. ?&w. Photochem. 1919 19 40-56) .- The photo-oxidation of ethyl alcohol o f various concentrations by ammonium chromate and ammonium dichromate in light of wak've-QEXERAL AHb PHXSlCAL CEEUlSTRY.ii. 213 length h=436 p p has been studied at 20°. It is shown that the velocity constant may be calculated by means of a linear equation and that it is proportional to the concentratiou of the alcohol. Increase in the salt concentration causes the reaction velocity t o approach a m+ximum. The absorption constants of the salt solutions have been measured and are found to be a iunction of the alcohol concentration and show a maximum. The dichromate follows Beer’s Law but the chromate does not. The absorption changes brought about by the alcohol do not affect the reaction veloaty. The velocities of oxidation are the same with chromate as with dichromate. The temperature-coefficient of the reactions is 1.02. These reactions in general exhibit a perfectly normal p hotochemical behaviour .F. SCHANZ (PJEiiger’s Archiv 1918 170 646-676; from Physiol. B b s t ~ . 1918 3 552).-Ob- servations on the lens of the eye have shown that the effect of light is to render protein l a soluble. Some authors have attributed this change to certain substancw accompanying the protein. The presence of acetone in diabetes coupled with the frequent occur- rence of lenticular opacity suggested a series of experiments in which equal amounts of a protein solution in a series of quartz tubes were treated with increasing amounts of acetone. Series 1 and 2 were placed in the sunshine whilst series 3 was incubated in the dark a t 38O. After four days the contents of the various tubes were equalised by appropriate additions of aoetone the only dis- tinction being that in series 1 and 3 the added acetone had been previously treated with light whereas in series 2 it had not.The amount of preoipitation after the addition of ammonium sulphate sodium chloride and acetio acid by the method previously dewribed was then noted in each case. The results showed that. the change from a more to less soluble condition of the protein was due to the effect of light on the protein itself; the reaction was however increased by the presence of acetone. The amount of acetone breakdown (amount of gas formed) was tested after exposure to a quartz lamp of acetone (1) in ordinary glass (absence of shorter rays than A 30 ,up); (2) in quartz (absence of shorter rays than h200pp); and (3) shaded with a ((euphos” glass screen (rays shorter than A 400 pp).The results showed that acetone absorbed and was acted on by the ultra-violet rays alone. The author main- tains that chemically pure organic salts are quickly broken down by the action of light in the absence of iron. Some quartz spectro- graphs figured in the text show absorption of the violet rays by protein and other substances the greatest absorption being exhibited by acetaldehyde and acetone. Certain coloured sub- stances such as eosin haematoporphyrin and chlorophyll act as optical sensitisers; eosin is non-toxic u n l w the organism is exposed to intense light. Mice die suddenly i f exposed to daylight after previous injection of hzmatoporphyrin and various lesions of the skin occur in sub-acute cases. It is suggested that the brilliant J.F. S. Biochemical Action of Light. 7*ii. 214 ABSTRACTS OF CHEMICBf; PAPERS. colourings of flowers etc. is to enable the organism to select the particular light rays required. Othar experiments show that the growth of plants is dfected by ultra-violet rays. J. C. D. The Reaction of Proteins to Light. F. ~ C H A N Z (P’uger’s Archiv 1917 169 82-86; from L’hyszol. Abstr. 1917 2 534).- The author refers to hw previous work on the lens proteins and also to Neuberg’s work. Proteins are more sensitive to light than Neuberg con&ers and experiments are given which show that quartz lamp rays can effect in them changea in solubility etc. so that albumins then show the characters of globulins. 3 . C. D. Some Observations on the Action of Coal on a Photo- graphic Plate.ERIC SINKINSON (T.y 1020 117 165-170). Chemical Actions of Radiation. EUQBNE WOURTZEL (Le R h m 1919 11 289-298 332-347. Compare A. 1914 ii 18 238).-l’he chemical action of a-rays from radium emanation on hydrogen sulphide ammonia nitrous oxide and carbon dioxide has been investigated. When the reaction is not accompanied by secondary reactions it is found that the amount oi decomposition under the same conditions of volum~ pressure and temperature 1s proportional to the amount of emanataon present. This is the ca58 with the reactions H,S= H,+ S and NH3= N + 3H. The effect i n c r m with the dimensions of the vessel and the volume but tends to a maximum value corrBponding with the total utilisa- tion of the energy of the radiation. If A K x are the velocity constants for particular colnditions and for total utilisation of energy respectively R is the radius of the vessel and p the prea- sure then when K>0*5Ka it i s found that K = K X ( l - C / & p ) where C is a constant.the relation is repre- sented by a line tangent to the above curve and passing through the origin. The decomposition of nitrous oxide is complicated by a secondary reaction namely the formation of nitric peroxide from the nitric oxide and oxygen set free in the initial reactions N,O= N + 0 ; N,O =NO + N. Contrary to the statement of Ramsay and Cameron carbon dioxide is on,ly very slowly decomposed by a-rays. No theoretical conclusions are drawn from the results beyond the statement that the decompositions do not follow Faraday’s law. A full account of the apparatus used is given.When K<0*5Kz J. R. P. New Arrangement for the Rontgen [Ray] Crystallo- graphic Investigation of Crystalline Powders. HELGE BOHLIN (Ann. Physik 1920 [iv] 61 421-439).-8 new arrange- ment is described in which by means of a cylindrical arc-shaped scattering surface made of a compressed crystalline powder inter- ference lines can be produced. One edge of the linee is sharp and may be geometrically defined whereby an increased accuracy over that of the previously described methods is rendered possible. It is shown that the sharpness and the position of the line edge is in-QENERAL AND PHYSICAL CHEMISTRY. ii. 215 dependent of the width of the slit and of the depth to which the radiation penetratea. By means of photographs of the interfewnce lines the space grating of thorium nickel and magnesium has been determined by this method.It is shown that thorium and nickel have face-centred cubic lattices whilst magnesium has a lattice made up of two simple interpenetrating hexagonal lattices. J. F. S. An Experimental Determination of the Critical Electron Velocities for the Production of the Ionisation and Radia- tion on Collision with Argon Atoms. FRANK HORTON and ANN CATHERINE DAVIES (Proc. Roy. Soc. 1920 [ A ] 97 1-23. Compare A. 1919 ii 210).-In the conclusion of Franck and Hertz that ionisation occurred in argon when the velocity of the colliding electrons was raised to 1 2 volts the ionisation of the gas could not be distinguished from photoelectric effects of radiation produced by the collisions.By methods similar to those previously employed for helium it has been shown that when electrons bom- bard argon atoms a radiation is produced when the electrons attain a velocity corresponding with 11-5 volts which is not accompanied by ionisation of the argon but a t 15.1 volts ionisation of the argon takes place. The latter potential corresponds according to the quantum relation with a wavelength of 817 A.U. which is in accord with the spectroscopic investigation of the extreme ultra- violet spectrum of argon by Lyman which he found terminated abruptly at 800° A.U. Evidence has been obtained that at 15.1 volts not all the collisions are fruitful in producing ionisation and that the fraction of fruitful collisions is increased greatly by intense 11-5 volt radiation.The minimum ionisation velocity 15.1 volts however is the same whether the argon is exposed to weak or intense 11.5 volt radiation. F. S. Investigation of the Effects of Electron Collisions with Platinum and with Hydrogen to ascertain whether the Production of Ionisation from Platinum is due to Occluded Hydrogen. FRANK HORTON and ANN CATHERINE DAVIES (Proc. Roy. SOC. 1920 [ A ] 97 23-43).-During the investigation of electron collisions with helium it was found that positive ions were produced from a positively charged platinum gauze bombarded with electrons of minimum velocity corresponding with 11 volts and this has been more fully inveatigatsd to determine whether it is due to the metal or to attached hydrogen. This voltage is subject to a correction f o r the velocity at which the electrons leave the tungsten filament and the mean of all the corrected results gives 13-0 volts as the critical electron velocity for the production of the ionisation which docs not agree with the usually accepted value of the “ionisation potential ” of hydrogen (11 volts).In the same apparatus the production of ionisation in hydrogen was investigated hydrogen being introduced through a palladium tube heated in a flame and the conclusion was reached that the first- critical velocity (13 volts) is not due to hydrogen at all but probably 7+-2ii. 216 ABSTRACTS OE CIXEMICAL PAPERS. to the platinum itsdf. In hydrogen it was found that a radiation is produced at an electron velocity of 10.5 volts a second type of radiation at 13.9 volts an ionisation at 14.4 volts and a second type of ionisation at 16.9 volts.These four velocities correspond probably with radiation from the hydrogen atom and molecule and ionisation of the hydrogen atom and molecule respectively the values calculated from Bohr’s theory be’ing 10.2 instead of 10.5 for the first 13:6 instead of 14.4 for the third and 16.3 instead of 16.9 for the fourth. It is desirable that these critical velocities be further examined in an apparatus specially designed for the purpose. F. S. M. E. LEMBEHT (Zeitsch. EZektrochem. 1920 26 59-60).-The melting points of pure lead chloride and lead chloride containing Ra-G chloride have been determined and shown to agree to within 0*06% that is to within 0.5O. The material used for the determination was that used by Richards and Lembert for atomic-weight determinations and from which the values 207.15 and 206-57 respectively were obtained (A.1914 ii 683). The present results confirm the assumption of Fajans (A. 1915 ii 206) that v2m is constant for isotopes as against the view of Lindemann (A’ature 1915 95 7) that v is constant. J. F. S. Melting Pointiof Lead Isotopes. The Radioactivity of Bavarian Rocks and Waters and of the Fluorspar of Wolsenberg. F. HENRICH (Zeitsch. angcw. Chem. 1920 33 5-8 13-14 20-22).-An investigation of the distribution of radioactivity in the springs rocks and minerals of Bavaria including also French Switzerland the Fichtelgebirge and the Oberpfalz is dacribed with details of the activity of a large number of springs expressed in Mache units ( M .U .) . The springs in the chalk mountains of French Switzerland were but feebly active but in tho granitic areas of ths Fichtelgebirge most of the springs had an activity between 10 and 100 H.U. and four were over 100 M.U. The minerals tobernite and autunite occurred in these districts in the granite A special examination of the gases from one of the springs showed the unusual composition of about 12% of oxygen and the rest “ unabsorbable.” A description is given of ths fluorspar of Wolsenberg (“Stink- flus’’) in which the dark blue and violebcoloured varieties emit a p d i a r odour on being crushed which is undoubtedly due to the evolution of free fluorine. The origin of this is considered to be due to the action of rays of radioactive substancea dissociating the calcium fluoride with coloration of the mineral due to colloidal calcium and evolution of free fluorine. By acting on fluorspar with radium rays the colour is easily produced but not the odour of fluorine.I?. s. Dependence of the Dielectric Constants of Water Ethyl Alcohol Methyl Alcohol and Acetone on Pressure. G. FATARENBERG (Ann. Physik 1920 [iv] 61 145-166) .-The dielec-QENERAL AND PHYSICAL CHEMISTRY. ii. 217 tric constant of water. ethyl alcoho1 methyl alcohol and acetone has been determined a t temperatures (16.3-20°) Over the pressure range 7-200 atms. The mean change in tshe dielectric constant per atmosphere inmease in preasure is found tQ be 0.0046% f o r water 0.0097% for ethyl alcohol 0.0102% for methyl a h h o l and 0.01 60L for acetone.The refraction constants (n - 1) Id (n*- 1) 117. and ( n 2 - 1) / ( n 2 + 2) .I Id are calculated f o r the above-named liquids at the pressures named. I n the case of water and both alcohols a rood acreement is found for the expression ( n 2 - - l ) / d . both a t low and hiph pressixres. I n the case of acetone owinc to insufficient lrnnw1edvfi of +ha ccmm-essihilitv. concliisinnq are not arrived a t . 7Tcinw thQ rwults of Ortvav ( A . . 1913 ii. 9M). t.he values of ( n z - l ) / d and (m-l)Id are calculated for benzene and ethvl alcohol. I n the case of benzene the value of ( n 2 - l ) / d is constant over the ranpe 1-500 atmospheres but with ethyl alcohol all three vnliiea show considerable irrepularity over the same pressure ran?@ The verv large vaIues of the Wiener number u for water and the two alcoholls confirm the sucrqestion of Rijntpen that the ratio of polymerised to non-polymerised molecules chanyw with increase of pressure.[Electricall Condnctivitv of Solid S a l t s and Mixtiires nf $ a h . ROBERT KFTZFR (Zeitsch. E7~ktrocham.. 1 920 26 77-84). T h e specific cmductivitv of naqtilles of lead chloride. lead hromide. and rniyt1n-w of these qubstancw with varvinu amounts of sodium and potawium chloride and bromide respectively has been determined a t 37O. Electrical contacts were made with amal- gamated copper plates. and it is shown that differences in conduc- tivity amounting to 12% may he occasioned by variations in the nressure employed in making the pastille. It is shown that the large inorease in conductivity found by Fritsch (A.1897 ii 301) on mixing the haIoids of lead and mercury with alkali haloids does not occur if moistme is completely removed and i f the mixture is not heated to a high temperature. It is shown that the previous treatment of Iead chIoride has a marked influence on the conduc- tivity. In the case of the mixtures it is found that heating before pressing increases the conductivity to a considerable extent. Thus 2% of sodium chloride in lead chloride i n c r e w the conduc- tivity of the lead chloride 109-170 times if the previous heating was carried out in moist air in a vacuum or in chlorine; on heat- ing in dry air the increase was 41 times. The very smallest addi- tions to lead chloride produced a considerable increase in conduc tivity ; thus 0.001% of sodium chloride increased the conductivity 45 times if the mixture was melted in chlorine before pressing.No proportionality was found between the concentration of the alkali chloride and the increase in conductivity. Form of the Conductivity Function in Dilute Solutions. CHARLES A. KRAUS ( J . Amer. Chem. Soc. 1920 42 1-18).-A theoretical paper in which the method adopted by Washburn (A. 1918 ii 5 5 ) for cdculation of the value of k is examined J. F. S. J . F. S.ii. 218 ABSTRACTS OF CHEMICAL PAPERS. The author is not able to agree either with Washburn's conclusions or with his interpretation as to the limiting character of. the law of mass action. J. F. S Conductivity and Viscosity of Organic and Inorganic Salts in Formamide and in Mixtures of Formamide with Ethyl Alcohol.P. B. DAVIS and H. I. JOHNSON (Camegie Inst. Pub. 1918 260 71-96).-The conductivity and the viscosity in formamide solution of ( a ) metallic nitrates and formates (common anion) and ( b ) sodium salts of organic acids (common cation) have been measured and also the behaviour of certain representative salts in mixtures of formamide and ethyl alcohol has been studied. The molecular conductivities of ammonium potassium sodium calcium strontium and barium nitrates in formamide which has a greater dissociating power than water are much smaller than in aqueous solution. Evidence of complex solvent formation is obtained with the calcium strontium and barium salts in form- amide and in water. From the conductivities and viscosities of the formates of rubidium ammonium lithium sodium barium and strontium in formamide a t 15O 25O and 35O the conclusions are drawn that these salts like the nitrates are more strongly disso- ciated at low dilutions in formamide than in water that the tem- perature-coefficients of the conductivities are of the same order of magnitude for the alkali formah but are greater for the alkaline- earth formates and that rubidium and ammonium formates increase the viscosity less than sodium and lithium formates.From conductivitv and viscosity measurements in formamide a t 15O 25O and 35O of sbdium m-bromo- m-amino- and 3 5-dinitroe benzoate benzoate salicylate benzenedphonate and succinab the conclusions are drawn that (a) the conducting capacity of the first three salts is approximately the same and the same is true of the next three.All monobasic salts have nearly the same conduct- ance which is about half that of the dibasic salt; ( 6 ) no relation exists between the conductivity and the constitution of the organic salts and the same is true of the viscosity. Data were also obtained on the molecular conductivity and the viscosity of tetramethylammonium iodide rubidium iodide. lithium nitrate and calcium nitrate in mixtures of formamide and ethvl alcohol. The first three salts show an increase in molecular conductivity up to a concentration of 25% formamide and 75% ethyl alcohol. where a maximum is reached a f a c t explicable by an increase of ionic mobility at this point. Caesium rubidium and potassium salts lower the viscosity of water but increase that of f ormamid e.CHEMICAL ABSTRACTS. Electrical Conductivity of the Sodium Salts of certain Organic Acids in Absolute Alcohol at 15" 25" and 3 5 O . H. H. LLOYD and A. M. PARDEE ( C m e g i e In&. Pub. 1918 260 99-118).-An extension of previous work on the electrical conduc- tivity and dissociation of Various organic acids in dcoholic soh-ii. 219 QENERAL AND PHYSICAL CHEMISTRY. tion. involvinq a studv of the sodium salts of the orqanic acids in ahsolute alcoholic solution to obtain first the A( values for these salts and then the A( values for the acids. Absolute alcoholic solu- tions of thirtv-two sodium salts were prepared. and the conductivi- tiw a t 150. 25O. and 35O over the ranye 37/50 to N/20.000 were rleterrmined.Goldschmidt's lorevious rwults were confirmed. The 1 vahles were obtained by extranolation usinr the function 1 I A = I /A,%+ R(CXV-1 develoned by Noves and Johnston. The Rohlraiisch formula did not pive satisfactory results. The h valiies a t 2 5 O were obtained for all the salts and bv comhinntion with the x vahies for hvdroren and sodium chlorides the limitin? condii,t,ivitv at 950 of thirtv-one oreanic acids in a h l u t e alcoholic mliition w a q ca1.nlato.J. Thp iiiwociation and affinitw constants of tqheSe acids in such soliition can be calculated from the A values. There is a preat similaritv in the conductivitv of these orgranic acids in alcohol. Lit,tln can be said of the relation betweep rhpmical cnmnocition and conrluct~vit~v.No diffarence was found hptwwn alinhatic and aromatic derivatives. and t h e position of sicllbstitnmts in the latter appeared to be wit,hoiit influeneel on the conductivity. CHEMICAL ABSTRACTS. T h e Positive Influence which +he nv-Diols Exercise on tho Canrlurrtivitv of Boric Arrirl. J. B~RRRKRN (Rec. tmm. et,hvlmalonic arid F a 4 K-=2.8 x 10-3. and i p notablo much stronrer than diplvcollic acid (comnare A . . 1916. ii. 595\ It mbht hn eunected. therefore. to have a feebl~lr neyative influence on the mnductivit,v of boric acid but the diminution found is almost the same in the two cases. W i t h w. F. Th. HF,NDRTKSZ.1-MeasUrementS with B-nitro-B- metholnronnn~Lav-di~l give re~ults almost eclual to those of glvcerol and much less than those of pentaerpthritol.T h e cvcZoHexan-X 2-diols and the Flexihilitv of -+,he Penzeno Rina. .T. R~~RSRKEN and J. VAN GIFFEN (Rcc. f m w . chim. 1970. 39. 183-lPf;\ -Mpasiirt.ments have hem made with the ci.7- 2nd fm.nc-r~ir7ruh~~anprl 9-diolc to determine their influence on the condiidivitn of horic arid. The infliimce of both isomerides is mnnifwtlv nwqtive hiit the influence of the cis-immeride i q qliphtlv mow fwhJe thqn thnt nf the fmnc-isomeride. The &-&l shnvq a Vreater tplnrlencv to form comnlmes than the trans-diol. The authors exnlain the difference of hehnviour of these two isomeridw on the hvDot+hesis that the flexibility of the c?yrZohexane ring per- mit. of thp hvijr0-1 rroiins of the cis-form obyinq mora easily their natnral repulsion. W. G. Increase in the Conductivity of the a-Keto-acids by Boric Acid as a Consequence of the Formation of a-Hydroxv- acids by Hydration R-C(OH);CO,H.J. BOESEREN and W. ROST VAN TONNINGEN (Rec. trm. chim. 1920 39 187-190\.- Trimethylpyruvic acid like pyruvic acid i b 1 f (compare A. 1916 fh;mr . 1920 39.178-1 89) -pxrith w R,OST V4N TONNTWTcFN.1-T);- W. G.ii. 220 ABSTRACTS OF CHEMICAL PAPERS. ii 209) exerts a marked positive influence on the conduct'ivity of boric acid itself. thus confirming; the view previously expressed (loc. &.) that- the a-ketto-acids in aqueous solutions are1 hydrated and behave like dihydroxy-compounds. Trimethvlpyruvic acid is notablv much weaker than pyruvic acid and the dehydrat*ion take3 place more easilv so that it apparently exerts a negative influence even a t moderate dilutions.W. G. Overpotential and Catalytic Acfivit,v. ERTC K. RIDEAT (7. Amm. Chem,. Snc. 1920. 42 94-105).-The influence of temperature on overpotential has been determined at a series of temmratures for nlatinum. conper and zinc. I n the case of zinc. there1 is no rdat,ionshin between the calciilated and ohs~rvd tem~erature-coeffi~~nt the latter only amountinc to 0-31 millivolt per depree a t 3 7 O . I n the case of conper and nlatinum. a hipher coefficient is observed. the values beinp 2.2 millivolts ner dwree and 0.17 millivolt per deqres respectivelv. TheFel values are1 three t o four times a? larye as the calculated values. It is suqqwted that overpotential is a measure of the enerqy relquird for the desorntion of hydroaen from a metal surface.Metals with low latent heats of desorption are1 catalyt.ically activel. the activity increasinc with decreasiny overpotentials. Metals with over- potelntials excedinq 0.455 volt are catalvticallv ineil-t.. and no metal can pmss an overvoltage exceeding 1-80 volts. The cdcu- lated values of t h e catalytic activitim of the metals are in agree ment with Sabatier's qualitative observations. A suqgestion is made for the mechanism of the process of desorption on the radiation hypothesis. J. F. S. Resemblances between the Properties of Surface Films in Passive Metals and in Living Protoplasm. II. RALPH S. LILLIE (Science 1919 50 416-421. Compare A. 1919 i 606). -Most ions activate passive iron a t varviiig rates and the stabilitv of the surface film in any solution and hence the prmrvation of the passive state is dependent on the osidising properties of the dissolved substance.Continued oxidation seems t o be necessary for preservation of passivity. Ions of strong oxidising properties tend to stabilise regardIees of charge for example the dichromate per- manganate silver gold and platinum ions. The haloid ions have a strong activat>ing influence the rate being proportional to the concentration. Salts with terminal oxygen in union activate only very slowly. The cation has not so large an effect but passivity is retained longer in solutions of heavy metal salts. Any condition that confers increased stability on the surface film prevents or retards its destruction in an activating solution. Hence oxidising anions or cations more noble than the experimental metal anta- gonise the activating effects of other ions.The antagonism between sodium and calcium so charaderistic in biological systems is not exhibited by passive iron. Anasthetics except ethyl nitrate show no retarding effect towards activation as they do in protoplasm butGENERAL AND PRYSTCAL CKEMISTRP. ii. 221 this is nolt to be expected since solutsion in the organic solvents of the protonlasm. particularly lipdds is not paralleled bv any process of solution in the metals. CHEMT CAI> AB s TRACT s . Simple Hvdrogen Electrode. C. H. BAILEY ( J . Amer. Chm. SOC.. 1920 42 4548).-The vessel and electrode for preparing a simple hydroqen cell may be constructed as follows. A piece of 7 mm. bore tube is blown out a t one end to form a bulb 15 mm.diam.; the tube is then bent to form an anqle of about 45* a t a distance of 50 mm. from the top of the bulb. The other limb of the tube is about 80 mm. long and is fitted with a ground-glass stopper. The metal electrode is a thin gold disk 5 mm. diam. welded to a piece of thin platinum wire and fused into the side of the shorter limb of the tube about 5 mm. above the bend. The gold foil is platinised in the usual way. The tube is filled with the liquid under investigation and then by means of a fine tube the bulb is filled with pure hydrogen thus expelling some of the liquid. T t is then stoppered care being taken to exclude all air and vieorously shaken until the solution is saturated with hyarogen. Connexion is made with the standard electrode by removing the stopper and placing the syphon tube well down the longer limb. The electrode is stated to give trust.worthy results and to be very rapid in its action.J. F. S. A Gas Collecting Tube. ERTCH M~LLER (Zeitsch. E'JeJcfrochem. 1920 26 76-77\.-A gas burette for collectin? the gases evolved a t electrodes durinrf electrolysis is described. The novelty of the apparatus lies in the tap which is attached a t the bottom of the burette; this is a heavy tap with a key bored in T-shape so that the horizontal bore will give access to the burette and the vertical bore to a side-tube to which the levelling tube is attached. J. F. S. New Cadmium Vapour Arc Lamp. FREDERICK. BATES (PhiE. Ma//. 1920 [vi] 39 353-358).-A small quartz cadmium vapour lamp is deacribed.The lamp is in the form of an inverted U-tube of 10 C.C. capacity and is fitted with two long quartz capillaries at its ends by means of which the tungsten wire electrodes are admitted. The electrodes are fastened into the capillaries by means of lead seals. The lamp is filled by distilling from a quartz bulb attached a t the bend of tho U-tube a gallium-cadmium alloy containing 2-3% of gallium. The prmence of the gallium renders the cadmium soft and so prevents breakage of the lamp when the metal solidifies. The distillation is carried out at 0.001 mm. pres- sure and when sufficient has been distilled into the lamp the narrow tube by which the bulb is connected is sealed. The- lamp will burn with 110 volts and 3 amperes with a drop of 14 volk across the terminals but is more efficient with a current of 7 amperes and a drop of 25 volts.To start the lamp one limb must be heated with a bunsen flame. The spectrum of the light thus p r o d u d is prao-ii. 222 ABSTRACTS OF CHEMICAL PAPERS. tically that of pure cadmium; the lamp is durable and requires little attention and furnisheq an intense monochromatic source of red light by means of the line 16439A. J. F. S. Magnetic Susceptibilities of Hvdrogen and some other Gases. T A K ~ SONB (Phil. Mag. 1920 [vil. 39 305-350 and Sci. Rep. Tohoku. Imp. Univ. 1919 8 115-167).-The magnetic sus- ceptibility of air oxygen carbon dioxide atmospherio nitrogen chemicallv pure nitlrogen arqon and hvdrown hay been deter- mined with reference to water = -0-720 x 10-6.The following specific susce1r)tibilities ( x lo6) a t ZOO. and volume susceptibilities (K . lo6) a t Oo and 760 mm. are found air y=23*85. ~=0*03084 ; oxygen x = 104.1. K = 0.1488 ; carbon dioxide x = - 0.423 K = - 0.000836 ; chemically pure nitrogen x = - 0.265 K = - 0.000331 ; atmospheric nitrogen x = - 0.360 K = - 0*000452 ; arpon. Y = - 5.86 K = 0.0104 ; hydrogen x = - 1.982 K = -0.0001781. The susceptibility of air as determined is very close to that calculated from the values for the constituent cases. which indicates that the additive1 rule holds for the susceptibilitv of gases. The susceptibility of nitroeen is foiind t o he diamacnetic. a fad which is omwed to the values of all other ohservers except Pascal who found it had a vahie about 50% prelater than the present value.The specific susceDtibi1it;w of qaseous and solid carbon dioxide have the same value. The nrecelnt results are considered in the light of Bohr’s at’omic model for hydrogen. J. F. S. Moment of TnePtia of the Magneton. R. GANS (Ann. Ph?/sik. 19?0. riv1. 61 396-397).-A theoretical paDer. in which the moment of inertia of the magneton of a number of elements is calculated. This value is of the same order in most cases and lies between 0-761 x 10-43 and 60.2 x 10-43. The moment of inertia of nlatinum i s 67-7 x 10-40 and of anhydrous manganous sulphate 12.4 10-40. J. F. S. Magneto-chemistry of the Chromic Chlorides. Josi B A r.TA ELIAS (Anal. Fis. Ouim. 1918 16. 467483).-The magnetic SUR- cwtihilitv of aqueous solutions of the green and the violet chromic chloride was determined at different degrem of concentration tern- nerature and acidity and during transformation of either modifi- cation into the other.Quincke’s method was employed for dilute and the solenoid method for conwntrated solutions. The suscepti- bility of the solutions of Pither salt was found t o be independent of +he concentration. hence thev comply with Wiedemann’s law (that i.1 the siisceptibilitv is an additive promrtv obtained as the sum of those of its components). The conversion of the green into the violet solution and vice versa was not marked bv any change in thp maqnetic constant within the intemals in which the measurements were made (im to e k h t hundred and eighty-six hours). Hence the two modifications have the same magnetic constant where% theirGENERAL A N D PHYSICAL CHEMISTRY. ii.223 other physical properties are different. It is inferred that-unlike cobalt the magnetic properties of which undergo profound changes in certain co-ordination compounds-the linking between chromium and the other atoms or radicles in its co-ordination sphere is effected through the more external electronic orbits of the atom. The existence of nineteen mametons in the chromium aton is confirmed (compare Cabrera and Marquina. A. 1917 ii. 355). The maqnetic constant of both salts decrease~s in dilute solutions but in preaence of hvdrochloric acid hydrolysis is repressed and the (stable) green chloride repenerated. The figures obtained for the molecular susceptibilities (y(M)) of the two compounds are sziven below together with those obtained by Feytis (A.1913 ii 381) rcrfH',m61cl" . ..... ... ...... 6lQl .lO-R 5920.10-~ E1ia.w. Fevtk [CrCl,(FI;O) ,1C1.2R2O . . . 6179. 6100.10-6 W. R. S. Establishing of the Absolute Temperature Scale. FREDERICK G. KEYES ( J . Amer. Chem. Soc.. 1920 42. 54-59).-A trheoretical paner. in which the work of Buckinwham and of Chanpuis on the absolute temperature scale is considered from the mint of view of the author's new muation of state. which iq hmed nn the Bohr conception of the atom (Proc. Nat. Acnd. Rci.. 1917 3 323). J. F. S. Characteristics of the Gouy Themno-remlator. T. S. ST,TW-T jun. (.7. Amw. Chem. Roc.. 1920. ;42 60-68).-The paper iteqcriheq a. morlification of tphe usual tvpe of electrical thermo- remilator in which the fiyed rontact element i s renIaced by an oacillatina contact element.. and Shows that such a repulator will reduce the periodic variations of the bath temperature and the erratic variations due to variations of the mercury surface to a fraction of the valnw obtainable with the usual form of thermo- remulator.A neriodic variation in bath ternneratm-e of lws t$han T)*OT)T)lO. as indicated bv a temneratiire indicator havinq a natural ppn'n? nf ahoiit Fve seconds is essilv ohtained. Rv t h e use of an twrillatincr contact recrulator. w~riatinna of mean h t h temneratiire due to variations in external conditions are reduced below tbe valnes usuallv obtained. Characteristic equations are derived for both the fixed and oscillating. tvpe of thermclreplator.amd these equations. towther with exnerimental data have been used to draw a comparison between the two types of regulator. Variation of Thermal Conductidfv during +.he Fudan of Matah. SETREI RONNO (Sci. Ren. Tohokv.. Imp. Univ. 1919 8 169-1 79\.-The thwmnl roniiiictivit,v has been determined for tin (1 8-4989 lead (1 8-601 O'I. hiqmuth (18-584O). zinc (18-5780) aluminium (1&-800°\ and antimony (0-692O). The thermal ccm- ductivity of tin lead. zinc. and aluminium decreases with rise of temperature up to the melting point. On melting the thermal J. F. S.ii. 224 ABSTRACTS OF CHEMICAL PAPERS. conductivity of these metals decreases abruptly and to a consider- able extent. The thermal conductivity of bismuth and antimony decreases t o a minimum. which lies at 1 6 0 O and 182O respectively and then slowlv rises to the melting point.On melting the thermal conductivity of bismuth increases considerably whilst that of anti- mony appears t o decrease sliqhtly. The thermal conductivity of the molten metals in all cases decreases slightly with increase in temperature. The chanqes in thermal conductivity run parallel with the changes in electrical conductivity with rise in tempera- ture. J. F. s. Variation of Atomic Heats as a Function of the MATHEUS D'A. ALBUQUERQUE (Pamphlet [Portu- Temperature. guese] 1919 1-19) .-A theoretical discussion. Melting Points of Pure Metals. W. GUERTLER and M. PIRANI (Zeitsch. Metallkunde 11 1-7 ; from Chem. Zentr. 1919 iii 910-911).-The following are given as the mosts trustworthy figures for the melting p0int.s of the elementa Ag 961O; Al 658O; As 850° ( 1 ) ; Au 1063O; B.2400O; Ba 850O; Gl. 1300O ( 1 ) ; Bi 270O; C >3600°; Ca 809O; Cd 321O; Ce 700O; C1 -101-5O; Co 1490O; Cr 1520O; Cs 26O; Cu 1084O; Fe 1530O; F -223O; Ga 30°; Ge 958O; H -259O; Hg -39.7O; I 113.5O; In 155O; Ir 2350O; K 62.4O; La 8 1 0 O ; Li 186O; Mg 651O; Mn 1210O; Mo 2410O ( 1 ) ; N - 2 1 0 O ; Na 97-5O; Cb 1700O ( 1 ) ; Nd 840O; Ni 1452O; 0 - 2 1 8 O ; Os 2700O (?); P 930O; Pb 3 2 7 ~ 4 ~ ; Pd 1545O; Pr .940° ( 1) ; Pt 1760O; Ra 700O; Rb 38O; Rh 1960O; Ru 2450O ( 2); S 119'2O; Sa 1300O; Sb 630O; Se 2 1 7 O ; Si 1420'; Sr<Ca<Ba; Sn 232O; Ta 2800O; Te 450O; Th>Pt 1800O; Ti 2000O ( 1 ) ; T1 301O; U >1850°; V 1800O; W 3030O; Y 1490O; Zn 4 1 9 ~ 4 ~ ; Zr 1700O ( 2).The dependence of the melting. point on the Dosition of the element i& the periodic system isoal$o graphically illustrated. H. W. Thickness of the Capillary Layer between the Homo- geneous Liquid and Vapour Phases particularly for Carbon Dioxide. G. BAKKER (Ann. Physik 1920 [iv] 61 273-302. Compare A. 1919 ii 12; this vol. ii 19).-A theoreti- cal paper in which the thermodynamic equation ( E l E2) / 2 - E = Tz{Id(H/[T)/dt} is deduced by t w o methods H is the surface tension 3 the thickness of the capillary layer T the absolute tem- perature and E E and E are the energy densities' (energy per unit volume) of the liquid vapour and unstable phases respec- tively. The thermodynamic potential of the unstable phase has the same value as the homogeneous liquid and vapour phases.Making use of the formulae of Gauss-van der Waals and Mills the following thicknesses are calculatsd for the capillary layer of carbon dioxide -25O 1 . 5 2 ~ ~ ; -loo 1 . 5 1 ~ ~ ; Oo 1-87pp; loc 2 . 1 3 ~ ~ ; 200 3-11 pp; 28O 5-86 pp; 30° 13-66 pp; snd 31'12O 193pp. Mak-GhBJERAL AND PBXSlCAL CBEMStkY. ii. 226 ing u88 of a different method of calculation the values for the number of layers in the capillary layer R and the total number of layers rL of gas and liquid w h c h form the capillary layer are calculated. B'or carbon dioxide the values are t = -25" -lo" O" lo" 20" 28". R = 3.0 8-6 4.2 5.1 7-0 11.4 n = 2.7 8.4 4.0 4.9 6.9 11-3 = 1.6 2 4 2.3 %.8 3.2 6-1 ~ p . The value of R has also been calculated for benzene and ether. Thetie a m based on the van der Wads's equation of state and are as follows (1) benzene 5.4O 2.4; SOo 3; looo 3.4; 150° 3.5; 200° 4.0; 250° 10.8; and 280° 16; (2) ether Oo 2-4; 20° 3.3; 50° 3.3; 80° 4.2; 120° 5 ; 170° 7.8; 190° 16.4; and 193O 21.5.J. F. S. Certain Binary and Ternary Mixtures of Liquids having W ILLIAM KINGROSE GELSTON ATKXNS Constant Boiling Points. (T.) 1920 117 218-220). Brown's Formula for Distillation. SYDNEY YOUNG (Sci. Proc. Roy. Dubl. Soc. 1920 15 667-672).-Brown's formula M'A/&'b = c . & A / & - (where Ad'.,) and fU. MB are the relative number of molecules of A and B in the vapour and liquid phase respeotively and c is a constant depending on the relative vapour preesures of the pure substances a t the boiling point of the mixture) is applicable without serious error to mixtures of benzene and toluene of which the vapour preasure P approximately equals MP + (I - fklc)Y Y and k" being the vapour prwswes of the two pure substances at the same temperature and M the molar fraction of the substance A.Further for benzene and toluene the best value of the constant c differs but slightly from the ratio PA/PB namely 2.591. G. F. M. Thermodynamics and Probability. A. BERTHOUD ( J . Chim. Phys 1919 17 589-624).-A mathematical discussion of the relationship between entropy and probability in which a formula is given by means of which it is possible (1) to determine the most probable distribution of the mollecules of a monatomic or diatomic gas according to their velocity or energy this distribution being expressed by the generalised Maxwell formula; (2) to find the rela- tionship which express= the entropy of a monatomic or diatomic gas in terms of its temperature and its volume this relationship agreeing with the thermodynamic expression of entropy.W. G . Free Energy and the Hypothesis of Nernst. A. BOUTARIC (Le Radium 1919 11 257-262,298-305,348-356).-The author directs attention to the well-known looseness of terminolog of writers on the free energy equation A - V = T(dA /dT). He d ecs ucegii. 226 ABSTRAOTS OF CHEMICAL PAPERS. this and numerous other equations by familiar methods and con- siders their application to some special examples. J. R. k'. Heats of Dilution of Certain Aqueous Salt Solutions. ALLEN EDWIN STEARN and G. McP. SMITH (J. Amer.Chem. Soc. 1920 42 18-32).-The reversible molecular heat of dilution has been determined tor the chloridee of sodium potassium and stron- tium at various concentrations ranging from 3.2 weight N to 0.2 weight N and also for solutions of mixtures of pairs of the above- named salts in equivalent and molecular quantities. The heats of dilution of sodium and potassium ahlorides are negative. 'I'his faot in the light of the equation L u = b 2 ' ~ . (d log,p/p,)/dT in which L is the molecular heat of dilution indicates an increase in the degree of ionisation with t,emperature which is contrary to the experimental results of Noyes (A. 1912 ii 526) unlws they are explained on the basis of decompoeition of complexes which exist in solution but are decomposed on dilution. 'l'he heats of dilution for the solutions of mixed salts bear no simple additive relation to the heat effects of the single componenb at equivalent concentrations. The results are explained on the basis of higher order compounds as put forward by Werner.J. F. 8. Heats of Dilution of Solutions of Barium Chloride and Barium-Sodium Chloride Mixture. G. McP. SMITH ALLEN E. STEARN and R. F. SCHNEIDER (J. Amer. Chem. Soc. 1920 42 32-36. Compare preceding abstract).-The reversible molecular heat of dilution has been determined for solutions of barium chloride of 3.2 2.8 and 1.6 weight N and for solutions of the mixed salts in equivalent proportions of 3.2 1.6 0.8 and 0.4 weight N . It is shown that the heat of dilution of the mixture of salts bears no simple additive relationship to the heat of dilution of the components a t equivalent dilutions.The behaviour of barium ohloride in this respect is therefore analogous to that of strontium chloride (Em. I+.). The experimental resulk citn be explained on the same basis as the results obtained with the mixed strontium salts namely on the assumption of the formation of compounds of a higher order. J. F. S. Relations between Relative Densities Absolute Density and Apparent Weight of Solutions. 0. CHENEAU (Bull. Assoc. Chim. Sum-. 1919 37 175-181).-For the interconversion of s p d o gravity results at 15O from one basis of reference to another a table has been compiled showing absolute densities (that is 15O in vacuum/water at 40 in vacuum) and in parallel columns the corrmtions to b added or subtracted to arrive a t corresponding valum referred to any of the following bases 15' in airlwater at 15O in air 15O in vacuum/water at 15O in vacuum 15O in vacuum/water at 15'5O in vacuum and 15O in air/water at 4 O in vacuum.The values are given to five places of decimals and range from 0.7 to 1.8. J. H. L.GENERAL AND PHYSICAL CHJZMISTRY. ii. 227 Investigation of Mewes’ Law of the Relation between the Volume of a Gas and the ‘l’emperature. ~ C ’ D O L F MEWES (Zeitsch. Sauerstoff. Stickstoff. Znd. 1919 11 73-75 91-93 ; from Chem. Zentr. 1920 i 104 278. Compare Mew= and Neu- mann A. 1919 ii 493).-(a) The errors observed in the previous ezperiments are to be ascribed in part to the presence of impuri- ti= and consequent liquefaction. In the second paper the author shows that Landolt’s expression (ntp - I) (1]10.~~- 1) =dtp is valid for low temperatures i f errors due to partial condensation of the gas by surfwe actim and partial liquefaction are eliminated.H. W. Electrical Nature of the Cohesive Forces of Solid Sub- stances. M. BORN (Ann. Yhyszk 1920 Liv) 61 87-1061.-A mathematical paper in which relationships are deduced for the molecular forces existing in crystals of the alkali haloids. It was shown by Born and Land6 (A. 1919 ii 188) that the compressi- bility of these salts can be explained by the assumption that the ions exercise attractive and repulsive forcm on one another in the sense of Coulomb’s law and that two ions exercise a repulsive force the potential of which is inversely proportional to the ninth power of the distance between the ions.The present calculations are based on this assumption. Surface Tension of Mixtures of Water and Alcohol. JAMES BRIERLEY FIRTH (T. 1920 117 268-271). The Adhesion of Starch at Fluid Surfaces. I. Experi- ments with Starch Grams. F. U. HOFMANN (P$iLyer’s drchzv 1917 167 267-279; from PhyswJ. Abstr. 1917 2 541).-Potato- starch has been used to study the adhesion of solids when distributed between two immiscible liquids and the conditions which influence this adhesion. J. C. D. The Viscosity of Caesium Salts in Glycerol-Water Mixtures. P. B. DAVIS (C‘arnegie Inst. Pub. 1918,260 97-98).- An extension of previous studiw by Jones and others on the vis- cosity of solutions in glycerol and in binary mixtures containing glycerol with special reference to those salts known to decrease the viscosity of water and of glycerol.Rubidium and a s i u m iodides produced phenomenal lowering of the viscosity of glycerol. I n these experiments the viscosities of CBeSium nitrate and cesium chloride were measured at 2 5 O and 3 5 O . Caesium salts decrease the viscosity of glycerol-water mixtures more than rubidium salts. When salts of both rubidium and csesium increase the solvent vis- cosity as for example water and acetone or water and the alcohols the miurn salt produca a smaller increment than the rubidium salt. CHEMICAL ABSTRACTS. The Sorption of Hydrogen by Palladium at Low Temperatures. JAMES BRIERLEY FIRTH (T.? 1920 11 7 J. F. S. 171- 183).ii. 228 ABSTRACTS OF CHEMICAL PAPERS.The Effect of Heating on the Absorptive Power of Sugar- charcoal for Sulphur Dioxide. KAMSAY MIDDLETON WINTEH and HERBERT BRERETON BAKER (T. 1920 117 319-321). Influence 01 Temperature on the Adsorbability the Colloid-yrecipitatrng Power of somu Narcotics. R. BIERICH (Pfliiyer's ATC~L'LU 1919 174 202-217; from Yhyszol. nlbstr. 1919 4 184).-The observation of Meyer and Overton of the partition-cdcients between oil and water was confirmed for the partition between cod-liver oil and water in the case of salicyl- amide and benzamide. The adsorption of naraotics by animal charcoal was found to be almost unafEeoted by alteration of tem- perature. In the investigation of the colloid-precipitating power it waa found that with isobutyl alcohol ethylurethane propyl- urethane benzamide and salicylamide the precipitation of serum albumin by cobalt chloride is strengthened more at high than a t low temperatures; the same applied for some of the narcoticv with the spdium chloride precipitation of colloidal ferrio hydroxide.The narcotic power as tested on tadpoles wa4 always increased by rise of temperature. As regards bmzamide and salicylamide this is opposed to the observation of Meyer that the threshold strength of the narcotio varies in the opposite direotion to the oil-water parti- ti on- coefficient. J. C. D. Adsorption by Precipitates. 11. HARRY 13. WEISEH and EDMUND B. MIDDLETON ( J . PhyskzJ Chem. 1920 24 30-73. Compare A. 1919 ii 269).-The amount of adsorption of phos- phate citrate tartrate oxalate sulphate iodate and dichromate ions by definite quantitiw of precipitated ferrio oxide from a ferric oxide sol has been determined.It is shown that since the first procw in the preoipitation of a colloid by an eleotrolyte is the neutralisation of the ohage by the adsorption of an ion of opposite charge it follows that two adsorbing media are concerned in the process the electrically charged particlw and the eleotrically neutral particles. Accordingly the total amount of a given ion carried down by a precipitated colloid is determined by (a) the adsorption by the electrically charged particlw during the process of neutraliGation and ( b ) the adsorption of the electrically neutral particlea during the process of agglomeration and settling. The failure to take the second cause into consideration has led to the erroneous conclusion that the amounts of all precipitating ions carried down by a precipitated colloid are equivalent. The adsorp- tion of equivalent amounts of precipitating ions will neutralise a given amount of colloid provided the stabilising effect of the ion having the same charge as the colloid is kept constant; but the amounts adsorbed by the neutralised particles will vary with the nature of the adsorbing medium the nature of the adsorbed ion and the concentration of the ion in the solution. The determina- tion of adsorption values a t the precipitation concentration as a rule will not give comparable results because of the variability inQENERAL AND PHYSICAL CHEMTSTRY.ii. 229 the latter and the consequent variability in the degree of satura- tion of the adsorbent in the adsorbed phase.The variations from strict equivalence in the adsorption values of Freundlich are prob- ably due quite as much to the varying concentration and adsorba- bility of the ions as to the analytical errors. The ions mentioned above are strongly adsorbed by hydrated ferric oxide. The adsorp- tion of univalent ions was relatively weak so that the precipitate was readily peptised by washing. The amounts of the ions adsorbed are not even approximately equivalent. The phosphate ion is most strongly adsorbed and the others follow the order phosphate>cit.rate>tartrat.e > oxalate > sulphate > iodate > di- chromate. The order of adsorption determined by analysis is entirely different from the order dedumd from precipitation values on the assumption that the most strongly adsorbed ion precipi- tates in the lowest concentration.The latter order is dichromate> tartrate>sulphate>citrate>oxalate>iodate>ph~~phate. I n addi- tion to the effect of the valencv and the adsorbabilitv of precipi- tating ions the precipitating values are influenced by differencm in the degree of ionisation of electrolytes the hydrolysis of certain salts the stabilisinq effect of the ion having the same charge as the colloid the mobility of the ions which in certain cases decreases with dilution owing. to increased hvdration the rate of coagulation and the method of determining the critical concentrations. The order of preqipitation values is the same f o r the acids as for their Dota-ssium salts except that the former preciDitate in somewhat higher concentration than the latter owing to the stabilising effect of the strongly adsorbed hydrogen ion.There is apparently no connexion between the precipitation values and the ionisation consitants of the acids investigated probably because precipitation takes place at such small concentrations (0.0002-0-0008N). The order of precipitation values of the potassium salts is ferro- cvanide<ferricyanide<dichromate<tartrate < sulphate < oxalate <chromate<iodate<bromat.e < thiocyanate < chloride < chlorate <nitrate<bromide<iodide<formate. There is a tendenov for ions of the highest valency to be most stronTlv adsorbed. That there are exceptions to this rule and that ions of the same valency are frequently adsorbed in widely varying amounts may be expected since adsorbability is a specific property of the ions. J.F. S. Attempt to Extend Planck’s Theory of Dilute Solutions. P. BOEDKE ( A m ) . Ph71.d. 1920 h 1 61 334-352).-A theoretical paper in which Planck’s thermodynamical function is considered in connexion with binam liquid mixtures with the object of obtainino. expressions which shall represent the equilibrium conditions of such liquid pairs and give the saturation conditions. [See also Jahn A. 1902 ii 597.1 J. F. S. Polymerism a€ Dissolved Binary Salts. P. WALDEIQ ( Z e i t s c h . K7ektrochem. 1920. 26 60-65).-The molecular weight of a number of binary salts has been determined by the cryascopicii.230 ABSTRACTS OF CHEMICAL PAPERS. method a t a series of concentrations in non-ionising solvents. AS solvents acetia acid naphthalene and diphenylamine were used and as dissolved substances tetra-amylammonium iodide triphenyl- amylphosphonium iodide tetrapropylammonium iodide ammonium thiocyanate tetramethylammonium thiocyanate tetraethylam- monium bromide ethylammonium chloride and tetraethylammon- ium iodide. From the results it is shown that depolymerisation occurs according to the expression x = c* . const. that is the degree of association is directly proportional to the linear ooncentration or to the distance between the molecules. The molecular weight ill of the dissolved salt conditions the dimensions of the constant since z=O-305iW/ V* or s=0-305M8.C3. The influence of the nature of the solvent is shown by the fact that the degree of association x is inversely proportional to the dielectric constant E of the solvent as shown by the expression x=1*92J%/EV* or x=1.92.MfC*/E. In view of the influence of the dielectric constant in the depolymerisation the author puts forward t-he question Are the products of depolymerisation oppositely electric- ally charged according to the scheme (MX) (MX)’ + ( VX)’ z= (M,X)’ + X’ Z 2hI’ + 2X’? J. F. S. Influence of the Molecular Size of Electrolytes on the Conductivity and the Ionic Velocity of the Ions Solvation of Ions in Non-aqueous Solutions. P. WALDEN (Zeitsch. Elektrochem. 1920 26 65-71).-It is shown that a large number of binary salts mainly iodides in a number of non-aqueous solvents follow the relationship A qa 1 d/=const.= 11.1 5 where A is the limiting conductivity of a salt with molecular weight 2cI in the solvent under investigation and ym is the viscosity of the solvent. If these salts are regarded as normal that is neither associated nor solvated it becomes possible to determine the degree of solvation of other salts with a fair degree of accuracy. As a control of the values obtained from the formula deduced by Herzog from Einstein’s relationship (A. 1911 ii 23) A v3) V+=const. may be used. Both equations give solvation values which are practically identical for the ions examined. Is the Migration Velocity of the Ions of an Electrolyte Extremely Large when the Solvent is Capable of Forming Similar Ions 3 P. WALDEN (Zeitsch.Elektrochem. 1920 26 72-76).-A theoretical paper in which the conductivity and mobility of the ions of salts which furnish one ion similar to one of the ions of the solvent have been considered. The solvents con- sidered are pyridine formic acid acetic acid aniline m-chloro- aniline nitromethane methyl thiocyanate hydrocyanio acid ammonia formamide and niti-ic acid. The results show that the titular question is to be answered in the negative and that if there is any influence of the solvent on the dissolved substance in this respect it only occurs in a few exceptional cases. J. F. S . J. F. S.GENERAL AND PRYSTGAL CHEMISTRY. 2. 231 Dissociating Powers of Free and Combined Water. G. FRED ORDEMAN (Camevie Inst. Pub. 1918 260 119-127).- The conductivities of two isohvdric solutions were measured. and the measurements repeaked after the addition of a third salt (in three different concentrations).The followin,g series of salts were iised ( a ) isohvdric solutions of M-Dotassium chloride and 0.695M- czlcinm chloride. before and after the addition of sodium motassiiim. ammonium. macrnesium. calcium or strontium chloride ; ( h ) iqohydric solutions of M-sodium chloride and 0.597M-calcium chloride the addendum beinq sodium. ammonium magnesium calcium or strontium chloride. or potassium nitrate; ( c ) isohydric solutions of M-sodium nitrate and 0*681M-calcium nitrate the addendum being sodium potassium ammonium magnesium or calcium nitrate or potassium chloride ; (d) isohydrio solutions of O.5M-sodium nitrate and 0.31OM-calcium nitrate the addendum beintr as in ( c ) ; (e) isohvdric solutions of M-potassium nitrate and O.698M-calcium nitrate the addendum being sodium potassium or strontium nitrate or potassium or sodium chloride.For every pair of solutions. the suppression of the conductivity is more pro- nounced in the hydrated solutions showing that the added salt dissociates more in the non-hydrated solutions than in the com- parable isohydrio solutions of the hydrated salts. The repression of the ionisation of the hydrated salts added is much greater than that of comparable quantities of non-hydrated salts in both iso- hydric solutions of every pair studied. A few added salts having no common ion show irregular results. The combined water (of hydration) in the solution of a hydrated salt is assumed to possess less ionising power than the uncombined water hence the salt added would be less dissociated. The hydrated salts used as addenda are less dissociated than the other addenda because the water of hydration now exists in both of any pair of solutions. The dissociation however is always less in the solution of the hydrated salt of any pair because of the smaller dissociating power of the water of hydration already present in that solution.CHEMICAL ABSTRACTS. The Ultimate Structure of Isomorphous Substances. F. RINNE (Celttr. Mim. 1919 161-172).-From the results of the X-ray analysis of the crystal structure of a number of substances the author has calculated the absolute atomic or molecular volumes of the substances comprising a number of iromorphous seria.The substancw dealt with are the cubic elements aluminium coppe'r silver gold and lead the rhombohedra1 carbonates of magnesium. calcium manganese iron zinc and cadmium and the haloids of lithium sodium potassium rubidium and msium. From a comparison of t.he Riintgen-ray diagrams of a large number of minerals which are usually isomorphous mixtures with those of pure substances i t is concluded that there is no essential difference between their structures; that is the X-ray evidence favours the view that in isomorphous mixtures the dispersity is so great t.hatii. 232 ABSTRACTS OF CHEMICAL PAPERS. it is highly probable that the vicarious constituents replace one another atom for atom or group for group in the lattice structure of the crystal.The importance for isomorphism of the chemical nature and especially of the valency of the vicarious atoms or atomic groups is insisted on. This factor is often of more import- anm in determining isomorphism o r miscibility t’han molecular volume. Thus in the case of the above elements although the edge of the fundamental lattice is practically of equal length for aluminium silver and gold and considerably less for copper silver and gold are perfeldly miscible together but only slightly so with aluminium. I n the case of the haloids of the alkali metals the miscibility variw with the temperature t o a much greater extent than would be expected were the dimensions of the funda- mental lattices the ruling factor. The author recards the mixed crystal state as one intermediate between a physioal mixture and a true chemical compound.E. H. R. Van Weimarn’s Theory of the Colloidal State. E. R. RUCHNER and J. KALFF (Rec. trm. chim,. 1920 39 135-1441.- The authors consider that von Weimarn’s thmry of corresponding states in the formation of precipitates is untenable. They show that his law giving the relationship between “the coefficient of precipitation,” on which the form of the precipitate depends the solubility of the substance precipit,atd and the amount of the precipitate formed is incorrect in the cases of such precipitates as calcium fluoride barium fluoride. and calcium sulphate in com- parison with barium sulphate and in the cases of silver chloride bromide and iodide and lead iodide. Further that in the case of such precipitates as aluminium hydroyide.the conditions cannot be expressed by anv formula. Whilst his theory may have some value qualitatively his law of corresponding states is not confirmed by quantitative experiments. W. G. Swelling and Solution of Aleuron. MARIAN 0. HOOKER and MARTIN R. FISCHER (Ro7loid Zeitsch. 1920. 26 49-58).-The amount of swelling of aleuron (a mixture of plant probinc;) ocoasioned bv water dilute solutions of hydrochloric nitric. sulphuric. lactic formic and tartaria acids. hvdrochloric acid mixed with various quantit-ia of the chlorides of sodium potassium. iron aluminium ammonium copper. magmsium. calcium and strontium respectively ; hydrochloric acid mixed with potawium bromide nitrate iodide acetate. thiocvanate.tartrate and citrate respec- tively and hvdrochlorio acid mixed with carbamide. methyl alcohol ethvl alcohol dextrose. and sucrose respectively. has been measured. The amount of aleuron dissolved by the above-named solutions has also been determined. A similar series of experi- ments has been carried out with sodium hydroxide solutions and with sodium hydroxide solution to which the above-named sub- stanoes have been added It is shown that aleuron behaves asGENERAL AND PHYSICAL CHEMISTRY. ii. 233 regards its swelling and solution in much the same way as gelatin fibrin blood serum and gluten. It swells more in mid and alkali solutions than in watsr but the amount of swelling d m not run parallel with hydrogen- or hydroxyl-ion concentration. The swell- ing is reduaed not only by neutralisation of the acid or alkali but also by the addition of neutral salta. The greater the concentra- tion of the added salt the greater the reduction of the swelling.Non-electrolytes do not influence the swelling in either acid or aIkali solution. The solubility of aleuron in acids and in alkalis is also greater than in water but it do- not run parallel with the swell- ing. Some salts increase the solubility whilst others reduce it in both acid and alkaline solutions but there is no parallelism between solubility and swelling. The results indicate that hydration and solution of an albuminous substanoe or mixture of albuminous substan- although often connected and often occurring in the same sense yet are not identical processes. Each follows its own particular laws.J. F. S. Influence of the Concentration of Electrolytes on some Physical Properties of Colloids and Crystalloids. JACQUEB LOEB ( J . Gem. Physiol. 1920 2 273-296).-When alkali Qr neutral salt is added to a 1% solution of dim gelatinate separated from distilled water by a collodion membrane the rate of diffusion is diminished. This depressant action is greater when the cation of the added electrolyte is bivalent than when it is univalent. When a neutral M/256-solution of a salt with univalent cation is separated from distilled water by a oollodion membrane and an alkali or neutral salt is added the diffusion of water is also depressed in proportion to the amount added. It can be shown that under these conditions water diffuses through the membrane in the form of positively charged particles.In the cam of the diffusion of water into a neutral salt with univalat or bivalent cation the effect of the addition of electrolyte on the rate of diffusion can be explained on the basis of the influence of the ions on the electrification and the rate of diffusion of the electrified particles of water. Since the influenoe of the addition of electre lyte seems to be the same in the case of solutions of metal gelatinate the question arises whether this influence cannot also be explained in the same way and if this be true the further question can be raised whether this depressing effect necessarily depends on the colloidal character of the gelatin solution or whether in both cases the same property of matter is not being dealt with namely the influence of ions on the electrification and rate of diffusion of water through a membrane.The ourve representing the influence of the conoentration of the electrolyte on the initial rate of diffusion of water from solvent into the solution through the membrane is similar to the curve representing the permanent osmotia pressure of the gelatin solution. The diffusion of water as negatively charged particles into a solu- *ion of gelatin chloride is depressed by addition of an acid orii. 234 ABSTRAUTS OE UHliMICAL PAPERS. neutral salt. This is also found to be true when the diffusion takes place into a solution of M/5l2-Al2C4. Influence of a Slight Modification of the Collodion Membrane on the Sign 01 the Electrification ot Water.JACQUES LOEB (J. Gen. Physid. 1920 2 255-271).-Collodion membranes which have received one treatment with 1% gelatin solution show for a long time afterwards a different osmotic behaviour from untreated membranes. This difference shows itsell' only towards solutions of those electrolytes which have a tendency t o induce a negative electrification of the water particles diffusing through the membrane. When solutions of ~alb with tervalent cation are separated from water by collodion membranes treated with gelatin water diffuses rapidly into the solution whilst no water diffuses when the collodion membrane has received no gelatin treatment. Solutions of acid separated from water by treated membranes show negative osmosis where= with untreated mem- branes positive osmosis occurs.These differences only occur in that range of ooncentrations of electrolytes inside of which the forces determining the rate of diffusion of water through the membrane are predominantly electrical that is from 0 to about M/16. The differences in the osmotic behaviour of the two types of membrane are not due to differences in permeability but are rather due to the fact that water diffuses into solutions of tervalent cations ur acids through gelatin-treated membranes as negatively charged par- ticles whilst in the case of non-treated membranes the charge is positive. Treatment of the membranes with caseinogen egg- albumin blood-albumin or edestin has the same effect but treat- ment with peptone from egg-albumin alanine or starch has no such effect.J. C. D. Colloidal Electrolytes. Soap Solutions and their Consti- tution. JAMES W. MCBAIN and C. S. SALMON (Proc. Roy. SOC. 1920 [ A ] 97 44-65; J. Amer. Chern. Soc. 1920 42 426-460) .-Colloidal electrolytes are solutions of salts in which an ion has been replaced by a heavily hydrated multivalent micelle carrying an equivalent sum total of electric charges and also serving as an excellent conductor of electricity. This new class of electrolytes probably includes most organio compounds con- taining more than eight carbon atoms and capable of forming ions also acid and alkali solutions of proteins dyes indicators sulphonates soaps alkali tungst a h zincates tellurates and silicatea. The constitution of solutions of the sodium and potassium salts of behenic stearic palmitic myristic lauric decoic octoic hexoic and acetic acids has been investigated.The vapour pressure and elevation of the boiling point have been ascertained by the dew- point method for solutions of the above-named salts at' concentra- tions 0*2N-3-ON'. From the results coupled with osmotic and conductivity data previously published (T. 1914 105 435) the concentration of crystalloid constituents and the concentration of colloid constituents are deduced. It is shown that in N-solutions J. C. D.GENERAL AND PHYSIC& CHEMISTRY. ii. 235 in evary m e colloid material is present; in the case of the hexoate 15% is present as colloid whilst with potassium stearate 99% is colloid. The amount of colloid decreases rapidly with decrease in ooncentration and it apparently becomes inappreciable with N l 5 - laurate solutions. The ionic micelle are regarded as either (in the cam of palmitate) an agglomeration of palmitate ions heavily weighted by water as a complex solvate (P’) .(H,O) or and more probably a collection of all or nearly all the colloid in the ionic micelle (Nap)%. (P’>,(H@),. Penetration of Electrolytes into Gels. I. Penetration of Sodium Chloride into Gels of Agar-agar containing Silver Nitrate. WALTER STILES (Bzochem. J. 1920 14,58-72)- The penetration of sodium chloride from solutions of various con- centrations (5h’-O*05~V) into agar gels has been followed by the indicator method. When silver nitrate is present in the gel the entranoe of sodium chloride into the gel is marked by the form- ation of silver ohloride and the progress of the chloride into the ge,l is indicated by the forward movement of the sharp line of demarcation between the silver chloride in the gel and the unpre- cipitabd silver salt.The distance this line of demarcation has moved forward in any time is termed the penetration. It marks the position of a definite concentration of chloride namely the saturation concentration of silver chloride. The penetration of sodium chloride into agar gels containing silver nitrate is within wider limits proportional to the square root of the time. If P is the penetration in a time t P/ Jt =constant for any particular gel and any particular concentration of penetrat.ing salt and is termed the penetration factor. The rate of penetration is dependent on the initial concentration of the penetrating salt the higher the concentration of the salt the more rapid the penetration.The concentration of the gel itself appears to exercise little influence on the rate of penetration but owing to the probability of actions between the silver salt and the gel and hence doubt as to the true active concentration of the silver salt in the gel the influence of concentration of the gel must be left an open question. In any case the influence cannot be great in gels containing between 1 and 4% agar. The expression obtained by von Fiirth and BubanoviE (A. 1919 ii 13) to indicate the relationship between the penetration time and concentration of the penetrating salt only holds in very special cases and between narrow limits and is even then only very approximate.The following more general empirical relationship. is deduced P/ JT= k log c + k f where is the initial concentration of the penetrating salt k a constant depending on the nature of the penetrating salt and also although to a slight extent on the nature of the gel content and k/ a second constant depending mainly on the concentration of silver nitrate in the gel. Adsorptive Stratification in Gels. 111. SAMUEL CLEMENT BRADFORD (Biochem. J. 1920 14 29-41. Compare A. 1919 ii 139).-A discussion of the supersaturation and the adsorption J. F. S. J. F. S.ii. 236 ABSTRACTS OF CHEMICAL PAPERS. theory of the Liesegang phenomenon in gels. The author supports the adsorption theory by a number of experimental facts. The formation of bands usually oeases long before the bottom of a tube is reached.The hypotonic reagent is invariably so strong that this effect can only be due to the solub in the gel having been exhausted from the lower regions of the tube. This fact also controverts the deduction from the supersaturation theory that the diffusion of the solute in the gel is negligible. With certain colloidal precipitates such as manganese sulphide in agar a tendency is observed to form large spherical aggregates which have much the same structure and density as the bands except that they frequently show concentric banding. When one of t h s e spherical aggregatw begins to form in the zone where a band will shortly appear the band do% not extend to join the sphere b u t a spherical cavity 2-3 mm.wide is left surrounding the concretion from which the surface of the cavity is everywhere equidistant. This effect must be due to the solute having been exhausted from the neighbourhod of the aggregate. Its spherical form implies that nutrient material has a m e d equally from all directions. J'. F. S. Mutual Action of Sols. WILDER D. BANCROFT (J. Physical Chem. 1920 24 21-29).-A theoretical paper in which it is shown that when positively charged gelatin is mixed with a negatively charged sol or negatively charged gelatin with a posi- tively charged sol there may be precipitation over a range of relative concentrations. When two sols peptised by water are mixed the mutual adsorption may decrease the adsorption of water to such an ext,eat that precipitation takea place.There may be and often is mutual adsorption when two sols having the same elsctrical charge are mixed. The mutual adsorption of positively charged ferric oxide and positively charged gelatin in ammonia solution gives a different product from the mutual adsorption of positively charged ferrio oxide and positively charged gelatin to which ammonia is subsequently added inasmuch as in the first case preoipitation is brought about whilst in the second there is no precipitation. J. F. S. [Physical Chemical Analysis of Metal Hydrosols .] An Explanation. RICHARD ZSIQMONDY (Kolloid Zeitsch. 1920 26 67-69) .-Polemical ; an answer t o Pauli's criticism (this vol. ii 168) of certain parts of a paper by Varga J. F. S. R6le of Valency in the Coagulation of Suspensoids by Electrolytes.WOLFGANG OSTWALD (Kolloid Zeitsch. 1920 26 69-81. Compare this vol. ii l68).-The various theories which have been put forward to explain the function of valency in the coagulation of suspensoids are summarised and the precipitation values of a large number of electrolytes are collected from various sources and tabulated. From the absorption theory of Freundlich,GENERAL AND PHYSIOAL CHEMISTRY. ii. 237 an expression is deduced which gives a quantitative relationship between valency and precipitating power. This has the form l / c l/% 1/c3 . . . = 1 2% 3n . . . in which cl c2 and c3 are the precipitating values of mi- bi- and ter-valent electrolybx and rn is a constant. It is shown that none of the theorim hitherto put forward satisfactorily accounts for the coagulation of electrolytes. It is shown that the r81e of valency as the determining factor in coagulation processes has been considerably overestimated.This follows from the facts that (1) the precipitating valum of electro- lytes of the same valency differ considerably (2) univalent electro- lytes in some oasm have smaller precipitating values than bivalent electrolytes and (3) salts of different valencies fall into the same group with respect t o their precipitating valum. J. F. S. Precipitation of Congo-rubin by Electrolytes. WOLFGANG OSTWALD (Koll. chem. Beihefte 1920 26 92-102. Compare A. 1919 ii 187 400).-A continuation of previous work (Eoc. &t.). It is shown that the behaviour of Congo-rubin toward electrolytes in respect of Schulze’s rule is exactly the same as that of inorganic hydrosuls.The behaviour of Congerubin in respect of its colour changea in the presence of electrolytes is of the same nature and depends on the same causes as the oolour changes of inorganic hydrosols for example the d o u r changes of gold sols or in other words the phenomenon is of colloidal chemical character. J. F. S. Equilibria in Solutions containing Mixtures of Salts. The System Water and the Chloride$ and Sulphates of Sodium and Magnesium at 2 5 O . W. C. BLASDALE ( J . Ind. Eng. Chem. 1920 12 [ii] 164-167).-Previous work on this sub- ject indicates that the solid phases to be expected at 25O are MgS04,7H,0 MgS04,6H20 MgSO,,H,O N~SO,,lOH,O Na@O MgC1,,6H20 NaC1 and MgS0,,Na2S0,,4H,0 (blodite). I n ascertaining the limits of the fields reprwenting the composition of all the solutions which can be in equilibria with each of the eight solid phases the composition of solutions saturated with respect to MgS0,,7H20 N~S0,,10H20 MgC1,,6H2O and NaCl was determined and the ends of two axee at right angles one to represent the relative proportions of MgSO and NaC1 and the other of N+S04 and MgCl were fixed.The solubility of each of the former four salts in solutions containing increasing concentrcsr tions of a second salt which yields a common ion was determined up t o the point a t which a second solid phase appeared and thereby a number of points intermediate between the extremities of the two axes repreaenting solutions in equilibrium with two solid phases were fixed.Further starting with solutions saturated with respect to two solids the composition of solutions saturated with respect to each pair of solids in the presence of increasing concen- trations of that salt which yielded a fourth ion was determined up VOL. CXVTII. ii. 8ii. 238 ABSTRACTS OF CHEMICAL PAPERS. to the point at which a third solid separated. The results are shown in a curve in which the horizontal axis is used to represent the number of mols. of MgSO and NaCI and the vert%ical axis the number of mols. of MgCl and Na$O per 1000 mols. of water and tables b e given showing the composition of all these solutions which represent critical points. S. S. A. Reaction Iaochore and Velocity of Reaction from the Statistical Point of View. M. POL~NYI (Zeztsch. Eiektrochem.1020 26 49-54).-A theoretical paper in which it is shown that the velocity constant of it reaction of the type A +B zz A B + B in the endothermic direction is given by the product of the number of collisions and the equilibrium constant and in the reverse direction it is the same as the number of collisions. These results are deduced from the assumption that i t is just as likely after a collision between A and B that the particles react or that they are dis- persed without a reaction taking place. The results of the theoretical investigation are tested by means of the experimental rmults of Bodenstein and Lind on the reaction Br + H2+ BrH + H (A. 1907 ii 76) and found to be in accordance with the experi- mental facts. J. F. S. Influence of Pressure on the Temperature of Explosion.G . TAMMANN (Nach. Ges. Wiss. Gottingem 1919 220-224; from Chem. Zentr. 1920 i 146).-The explosive material is contained in a small glass tube open a t one end and is placed in a steel cylinder filled with mercury; the latter is connecteld with a spring manometer and pressure pump. The cylinder is heated in an oil- bath provided with an efficient stirrer the te'mperature of the bath being observed from minute to minute. Tables are given showing the rate of heating in degrees per ten minutes before attaining the temperature of explosion the weight of explosive the pressure and temperature a t which explosion occurs the differences in pressure before and after the explosion and the sudden rise of pressure during the explosion.The temperature of explosion of moist glyceryl nitrate varied somewhat considerably at constant pressure ; increase of the latter by 2500 kilos. per sq. cm. appeared to depress the temperature of explosion by 8*4O but the variation lies within the limits of experimental error. With d r y glyceryl nitrate the variations are less marked but a disthct influence of the pressure on the temperature of explosion is not observed; a similar effect is still less certain in the case of a mixture of tetranitromethane (2 mols.) and benzene (1 mol.). With tetranitromethane (2 mols.) and naphthalene (1 mol.) an increase in pressure of about 2000 kilos per sq. cm. causes an elevation of 5*7O in the temperature of explosion. The influence of pressure on the temperature of ex- plosion of Iiquid explosives is determined by the effect of pressure on the conductivity for heat of the material itself and its environ- ment and by alteration in the chemical-kinetic conditions such as the increase in the number of molecular collisions caused byGENERAL AND PHYSICAL CHEMISTRY.ii. 239 isothermal increase in pressure as a consequence of the incream in volume of the explosive. H. W. Difference in Chemical Activity of Free and Semi-com- bined Water as Illustrated by the Effect of Neutral Salts on the Hydrolysis of Acetic Anhydride. GERALD C. CONNOLLY (Carnegie Z n s t . Pub . 1918 260 131-143).-1n extension of the work of Holmes and Jones (ibid. 1915 230) on the effect of salts on the hydrolysis of methyl acetate and methyl formate the action of strongly hydrated and of slightly hydrated salts on the hydro- lysis of acetic anhydride has been studied with the object of deter- mining whether any chemical difference exists between free and combined water.Care being taken always to keep the water con- tent constant M - 0*5M- and 0*25M-solutions of various salts (potassium sudium calcium magnesium barium and strontium chlorides sodium and magnesium sulphates potassium and sodium nitrates) a t 15O and at 25O were treated with acetic anhydride aliquot portions were removed a t various intervals and the acetic acid estimated. The amount of acetic acid present in mixtures of the acid and its anhydride was estimated by adding aniline and titrating the total acetic acid with sodium hydroxide. The con- centration of the anhydride was 5% and in no case did the time exceed sixty minutes a t 15O and forty minutes a t 2 5 O since the hydrolysis by water was practically complete.All the salts examined excepting sodium and magnesium sulphates have in the case of the greater concentrations a retard- ing influence on the hydrolysis the ret’ardation diminishing with increasing salt dilution. The four non-hydrated salts have prac- tically the same retarding effect on the hydrolysis. The hydrated salts excepting magnesium chloride produce greater hydrolysis than the non-hydrated salts and with the more dilute solutions there is an appreciable acceleration of the hydrolysis of the anhydride over that due to water alone. Sodium and magnesium sulphates a t all concentrations have a marked accelerating effect on the hydrolysis. Calcium strontium and barium chlorides also exert an accelerating influence in the more dilute solutions.The results with magnesium chloride and sulphate were inconclusive the former resembling tho non-hydrated salts in retarding the hydrolysis a t all dilutions. CHEMICAL ABSTRACTS. The Alkaline Hydrolysis of Tartaric Ester. ANTON SKRABAL and ERNA SINGER (Monatsh. 1919 40 363-375).-The rate of hydrolysis of methyl tartrate by a mixture of sodium carbonate and sodium hydrogen carbonate has been measured after the procedure necessary for the attainment of satisfactory remlts had been worked out in the case of methyl acetate. Referred to [OH]’=l and at 25O the constants for the first and second stages in the hydrolysis OF methyl tartrate are k,=206 and L,=14-7 respectively whilst for methyl acetate k = 5.4.J. K. 8 - 2ii. 240 ABSTRACTS OF CHEMICAL PAPERS. Catalysis of Hydrogen and Oxygen Mixture8 at the Ordinary Temperature by Moistened Contact Substances. XI. The Platinum Metals as Hydrogen Carriers. K. A. HOFMANN and LOTTE ZIPFEL (Ber. 1920 53 [B] 298-314. Com- pare Hofmann and Ebert A. 1917 ii 25)-The results may be summarised in the following manner. Mixtures of oxygen and hydrogen are catalysed a t palladium platinum or iridium surfaces a t very different rates depending on the exact extent a t the moment to which they are charged with gas. Pre-treatment with oxygen is thirty to fifty times as effective in the case of palladium three times with platinum and three to ten times with iridium as is pretreatment with hydrogen.The greater activity caused by charging with oxygen is not brought about by the adsorbed or occluded gas serving as a source for the formation of water since the amount of metal required for catalysis is insufficient to produce this effect but depends on the production of a “fresh” hydrogen-metal combination which in the cases of palladium and platinum is far more active than an “aged” pre- paration. The catalyst shows greater activity in proportion as this “ fresh ’’ condition is more rapidly and completely developed. I n the case of iridium another factor is involved since the metal in presence of gases containing excess of oxygen can function as an active oxygen electrode. The close parallelism between catalytic and electromotive activity indicates that both effects are to be ascribed to the same cause.This probably depends on the presence of free or metallically- dissolved hydrogen atoms which cause the hydrogen potential and ultimately combine with the oxygen of the gas mixture to form water. Under the experimental conditions adopted an active oxygen electrode is only formed with finely divided iridium when the oxygen concentration is high ; platinum and palladium behave entirely as hydrogen elwtmdes. The maximal velocity of formation of water is not invariably observed when the gases are used in the proportion of hydrogen (2 vols.) to oxygen (1 vol.) but according to conditions may occur a t a greater or smaller oxygen concentration according as the catalyst becomes more or less rapidly saturated with hydrogen.If the catalyst can also function as an oxygen electrode as in the case of finely-divided iridium a second maximum may occur with a higher oxygen content in the gas. It may be generally stated that the surface does not show its greatest catalytic activity when hydrogen and oxygen are absorbed according to the measure of their combination at an electrically neutral electrode but that the maximum possible hydrogen or oxygen potential must be “freshly” developed in order to react witth the gaseous mixture at the maximum rate. H. W. A Relation among the Atomic Weights of Chemical Elements. SUMINOSUKE h o (Proc. Fhys. Math. SOC. Japan 1919 [3] 1 231-236).-The atomic weight ( A ) may be given by aii. 241 GENERAL AND PHYSICAL CHEMISTRY.formula A ="'I where q=1*204 and N' is roughly equal to Moseley's atomio number + 2 or Rydberg's ordinals. For the more exact calculation of the atomic weight i V l V may become a more complicated function and N' may be identica.1 with neither the atomic numbers nor the ordinals. CHEMICAL ABSTRACTS. The Derivation of Molecular and Atomic Weights from Vapour Densities in Chemical Teaching. W. MARCHOT (C'hem. Z e i t . 1920 44 153-154).-An academic discussion on the most suitable formula for expressing the relation between mole- cular weights and gas densities with respect to water air and hydrogen in teaching chemistry. E. H. R. The Law of the Harmonic Triangle in Chemical Re- actions. EDUARD SCHMIZ (Ber. Deut. pharnt. Ges. 1920,30 27-33).-The numerical relationships shown in a previous paper to hold between the atomic weights of a number of the elements (A. 1919 ii 460) are now shown to hold also between the atomic and mole- cular weights of substances taking part in simple inorganic reac- tions. These relationships are those holding bet'ween the sides and hypotenuse of an isosceles right-angled triangle the radius of the inscribed circle and that of the circle circumscribed about the squares erected on the sides of the triangle. It is claimed that in simple cases u n l w such a relationship holds between the molecular weights of substances interaction between them cannot take place. E. H. R. Structure of the Atomic Nucleus. E. GZBHRCRE (Ber. Deut. p'hyysikkd. Ges. 1919 21 779-784) .-A theoretical paper in which the author formulates the constitution of the nucleus of the helium lithium gIucinum boron nitrogen and carbon atoms.The helium nucleus consists of two eleotrons and four hydrogen ions. I n the case of lithium the nucleus consists of four electrons situated at the corners of a regular tetrahedron and seven hydrogen ions situated one at the centre of gravity of the tetrahedron one a t each corner of the tetrahedron and two in an orbit close to the tetrahedron and a t some distance from the outer electron ring. This nucleus is capable of accounting for the doublet series of the lithium spectrum. Glucinum possesses a nucleus consisting of five electrons situated one a t the centre of gravity and one at each of the corners of a regular tetrahedron and nine hydrogen ions situated one in the middle of each of the edges of the tetrahedron and the remaining three in an orbit surrounding the tetrahedron.This nucleus is capable of explaining triplet seriee of the glucinum spectrum. Boron has a nucleus composed of six electrons situated one in the middle of each of the edges of a regular tetrahedron and eleven hydrogen ions situated one a t the centre of gravity of the whole one on the outside of each of fhe nuclear electrons and one at each of the corners of the tetrahedron. The nuclem of carbon consists of six electrons situated aa in the case of boron one inii. 242 ABSTRAEL'S OF OREMICAL PAPERS. the middle of each of the edges of a regular tetrahedron and twelve hydrogen ions two of which are attached to each of the electrons.A nucleus so constructed accounts for the tetrahedral directions of the carbon valencies since it will possess four electrostatic lines of force in these directions. Nitrogen is regarded as having a nucleus composed of seven electrons and fourteen hydrogen ions which are grouped into three helium nuclei in an orbit surrounding one electron with two hydrogen ions attached t o it. Constructing further after the manner of nitrogen the nucleus oxygen is regarded as a ring of four helium nuclei fluorine as four helium nuclei in a ring round an H,+ ion and neon as a ring of four helium nuclei round a single helium nucleus. J. F. S. Condition of Dissociation of the Gases of the Fixed Stars. JOHN EGGERT (Physikn2. Zeitsch. 1919 20 570-574).-A theoretical paper in which on the basis of the Nernst heat theorem the relationship between the dimensions of the chemical constants deduced by Sackur Tetrode and Stern and the Bohr atomic theory the degree of dissociation of the atoms into nucleus and electrons possible at temperatures between 106 and lo'* and pressures of lo7 atm.is investigated. Thel calculations show that considering only one type of atomic model the maximum dis- sociation would consist in the separation of the two outermost rings of electrons that is of sixteen electrons. From this it follows that the mean atomic weight of the gases of the fixed stars is 3.3 a value which is very near that (2.8) deducdd by Eddington in his theory of the structure of the fixed stars. J. F. S. Atomic Nuclei and a-Radiation.HANS TIT. WOLFF (Ann. Physik 1919 [iv] 60 685-700).-A theoretical paper in which a theory of the structure of the atomic nucleus and the forces oper- ative in the nucleus is put forward. The nucleus has a disk-like form and is made u~ of concenbric rings. With the exception of the outermost ring thev consist of sinqly charged hydrogen atoms and doubly charged helium atoms which are rotating round the middle noint. Outside these charged atoms in the outermost ring rotate the electrons. The positive charges are assumed to exert an attraction on one another when thev are a t certain distances apart and thereby effect the stability of the nucleus. At small distances however a repulsive force becomes operative. On this assumption i t is shown that one of the two potential formulze and P=L(l /R - A,/R3+ ,4,,/R5) represents the reciprocal action of the positive charqes in the atomic nucleus.Expressions are deduced for calculating the potential and field of force which a rotating charge will generate in a point in the same plane but in a ring outside itself. The conditions of stability after movement are worked out for a point which attracts a rotating charge accord- ing to either of the above formulz. Both potential formulae are applied to the atomic nucleus of the radium atom and the constants P = L (1 R - A / R2 + RY)GENERAL AND PHYSICAL CHEMISTRY. ii. 243 det,ermined so that they are in keeping with the expulsion of an a-radiation of the experimentally determined velocity. J. F. S. Analysis of an Electron-transference Hypothesis of Chemical Valency and Combination. JOHN MARSHALL (Proc.Roy. SOC. Edin. 1919 39 131 209-233).-A mathematical in- vestigation of refractive indices based on the Thomson model atom in which account is taken of the effect of the positive electrification as well as of the electrons and of the fields of electrical action between the atoms of a molecule. The results are in moderate agreement with experiment,. J. R. P. The Octet Theory of Valence and its Applications with Special Reference to Organic Nitrogen Compounds. IRVING LANGMUIR ( J . Amer. Chem. Soc. 1920 42 274-292).- The octet theory of valence which has been described in previous papers (Lewis A. 1916 ii 310; Langmuir A. 1919 ii 506) is here applied particularly to organic nitrogen compounds although the general application of the theory to inorganic nitrogen com- pounds and to salts is discussed.The number of availa,ble electrons in the outside shell of any atom is usually given by the ordinal number of the column of the periodic table in which the element is found. The number which may be represented by 3 corresponds with the maximum positive valence of the ordinary valence theory and is one for sodium four for carbon five for nitrogen six for oxygen and seven for chlorine. It is readily proved that the octet theory is entirely in agreement with the ordinary valence theory whenever the ordinary formulae are based on valences of unity for hydrogen and 8-E for each other element. Thus the ordinary formulze agree with those of the octet theory whenever the following valences are adopted hydro- gen one; carbon four; nitrogen and phosphorus three; oxygen and sulphur two; chlorine bromine etc.one. On the other hand all formulz in which valencies different from t.hese have been used require modification according to the octet theory. The appli- cation of the octet theory to the following compounds among others the formulze of which require modification is particularly discussed sodium chloride Na+Cl- (the co-valence of both atoms is zero) ; ammonium chloride (NH,)+Cl- (the nitrogen is quadri- covalent) ; triphenylmethyltetramethyl ammonium (NMe,)+[CPhJ - (the nitrogen is quadricovalent whilst the central carbon atom in the anion is tercovalent) ; diazophenol R<r;:N ; dinzonium corn- pounds (R-NZN)+OH- or R-N=N*OH ; triazo-compounds R-N = N=N ; hydroxylamine H,N.OH or H,N-0. According to this theory all salts are completely ionised even before they are brought into solution. This conclusion is more- over in agreement with the recent work of Milner Ghosh and 0ii. 244 ABSTRACTS OF CHEMICAL PAPERS. others; it explains why there are weak akds and weak bases but no weak salts. The known cases of isomerism including stereoisomerism of nitro- gen phosphorus and sulphur compounds are in full accord with the octet theory. The fact that organic cyanates cyanides and nitrites exist in two isomeric forms whilst the corresponding inorganic salts exist in only one form is explained since the nulcovalent atoms of the metals in the inorganic compounds are not attached to definite atoms of the acid radicles. The available data on phosphonium arsonium sulphonium and oxonium compounds are in full accord with the octet theory which givea for these compounds constitutions closely resembling those previously assigned by Werner. H. W. Accelerated Filtration through Filter-paper . G. BRUEINS (Chem. Zeit. 1920 44 207).-A filter-paper folded in the usual way is placed in a funnel and the l m e end of the thrmfold layer is turned back and pressed against the side of the funnel; this folding back is repeated several times so that the greater part of the interior of the funnel is covered by only one thickness of paper. I n the ordinary way of using a filter one-half of the funnel is covered by a threefold layer of paper. w. P. s. Small Generator for Acetylene Bunsen Burners. P. ASKENASP (Zeitsch. Elektrochem. 1920 26 32).-An acetylene generator is deeigned which with one charge of carbide will feed a large bunsen burner with acetylene for six hours. J. F. S. [Lecture Experiment.] .A Chemical Model of the Excitation Process. MAX VERWORN (Pfliiger’s Archiv 1917 167 289-308) .-A mixture of pure vacuum-distilled nitrio acid and 40% formaldehyde solution possesses considerable lability and will react with explosive violence by the action of certain stimuli. The reaction is an oxidative decomposition of the formaldehyde to carbon dioxide and water. The mixture will remain unchanged a t ordinary temperatures but on addition of nitrous oxide colloidal platinum or on warming there is first a latent period during which no change occurs which is followed by the violent reaction. Cool- ing the mixture or the addition of water or a carbamide solution will inhibit the process. If the mixture is placed in a long tube and one part is locally stimulated the reaction will proceed along the whole tube in the form of a wave. The mixture is an ‘‘iso- bolic ” system and obeys the “ all or nothing ” law. J. C . D.

ISSN:0368-1769    

DOI:10.1039/CA9201805205

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

i. 213 Organic Chemistry. Oxidation of Methane. R. K. BAILEY (US. Pat. 1319748). -Methane or natural gas is mixed with twice its volume of nitric oxide and with sufficient oxygen or air to form nitrogen peroxide. This mixture is passed through a porcelain or other inert tube heated to redness. Oxidation products including formaldehyde are obtained. The oxidation is prevented from being carried too far by conducting the reaotion produds as quickly as possible into a cooling chamber where they are brought into contact with a sludge of calaium carbonate which unites with the oxides of nitrogen except nitric oxide. Formaldehyde is recovered from the solution after separating the solids from the sludge. Instead of using calcium carbonate the hot reaction gases may be brought into contact with calcium oxide to effect absorption of water thus preventing formation of nitrous and nitric acids which if present would oxidise the formaldehyde. Reaction temperatures a8 low as 450° may be employed.Methyl Sulphate. T. H. DURRANS (U.S. Pat. 1317648).- Methyl sulphate is produced together with methyl hydrogen sulphate and methyl chloride by treating methyl alcohol prefer- ably with cooling with chlorine and sulphur dioxide the latter preferably being in slight ex- throughout the reaction. Methyl chloride is removed by distillation a t the ordinary pressure and the methyl sulphate under reduced pressure or the products may be used together as alkylating agents. Improvements in the Manufacture of Aliphatic Nitrites. PAUL RENE DE WILDE (Brit. Pat.133304).-Nitrites of aliphatic alcohols are produced by the reducing action of sulphur dioxide on solutions of the alcohols in pure or diluted nitric acid or altern- atively a saturated alcoholic solution of sulphur dioxide may be mixed with nitric acid. As an example 74 grams of isobutyl alcohol dissolved in 100 grams of nitric acid (D 1.375) yield on treatment with sulphur dioxide 85 grams of isobutyl nitrite. CHEMICAL ABSTRACTS. CHEMICAL ABSTRACTS. G. F. M. ANDR~ KLING D. FLORENTIN and E. JACOB (Compt. rend. 1920 170 111-113. Compare this vol. i 139 and Grignard Rivat and Urbain this vol . i 139) .-By the successive chlorination of methyl carbonate mono- di- tri- tetra pent* and hexa-chlorederivatives are obtained the most symmetrical derivative being obtained in each case. Properties of the Chloromethyl Carbonates.ANDRh KLING D. FLORENTIN and E. JACOB (Compt. r e d . 192% 1709 234-236) .-The physical properties of the nine possible chlorinated voc. OXVTTI. i. 2 Preparation of Chloromethyl Carbonates W. G.i. 214 ABSTRACTS OF OHEWCAL PAPERS. methyl carbonates the preparations of which have previously been described (preceding abstract) are given as below Formula,. M. p. CH2Cl*O*C0,Me . . . - CO(O-CH,Cl) . . . - CHCl,.O-CO,Me - CHCl,*O*C0,*CH2CI' ' - CC1,-O.COBMe ... - 70" (viscou) CC1,.0*C02-CH2Cl . . . - 70" (viscous) C0(O*CClI) ... ... 78" CO(O*CHCl,)2 ... - 40" CCl,*O*CO,.CHClp ... - 30" B. p./760 mm. B. p.150 mm. D15. 139-140" 67 " 1.303 176" 99" 1.480 147" 72" 1.421 178' 102" I *562 165" 86" 1.535 160" (decomp.) 110" 1.631 196" S? 115" 1.686 203" 124" - 182-183" 105-106" 1.618 9 Y The substances which contain the group *O*CCl are particularly b X i C .W. G. Organic Derivatives of Tellurium. I. Dimethyl- telluronium Dihaloids. RICHARD HENRY VERNON (T. 1920 117 86-98). The Industrial Chloromethyl Formates and their Analysis. MARCEL DELBPINE (Bull. SOC. chim. 1920 [iv] 27 39-45) .-The mono- and di-chloromethyl chlorof ormates are decomposed by dilute alkali according to the equations C1*C02*CH,C1 + H20 =2HC1+ C02+ H*CHO C1.COz*CHClz + H20 = 3HC1+ CO + CO. H*C02*CH2C1 + H20 = H*CO,H + H*CHO + HCI H*CO,*CHCL+ HzO = 2HC1+ 2CO + H,O. The formaldehyde formed may be estimated by Romijn's method (compare A. 1897 ii 166) the formic acid by Pean de St. Gilles's method (compare Ann.Chim. Phys. 1859 55 374) and the carbon monoxide by direct measurement of its volume after decomposing t,he material with sodium hydroxide. These results together with the percentage of chlorine enable an idea to be formed as to the different esters present in industrial chlorinated methyl f ormates. [See further J . SOC. Chem. Znd. 1920 205~.] Manufacture of Esters of Ethylenic Halogenhydrins. SOCII~TS CHIMIQUE DES USINES DU RH~NE (Brit. Pat. 128911).- Ethylene halogenhydrin esters of the general formula R*CO,*CH,*CH,X where R is an alkyl or aryl group and X a halogen are prepared by the interaction of ethylene oxide and an acidyl haloid in equi- molecular proportions a t a suitable temperature depending on the particular acid chloride or bromide used.The reaction is con- veniently brought about by passing gaseous ethylene oxide through the acidyl haloid a t ordinary atmospheric pressure and quantitative yields are obtained. Examples are given of the preparation of &chZoroethyE acetate b. p. 143-144O from acetyl chloride at its boiling point 8-chloroethyl chloroacetate b. p. 94-95*/12 mm. The oorresponding mono- and di-chloromethyl f ornates give W. G .ORGANIC CHEMISTRY. i. 215 from chloroacetyl chloride at looo &chZoroeth.yl benzoate b. p. 120-122*/5 mm. from benzoyl chloride a t 190-240° &chZoro- ethyl p-nitrobewzoute yellow crystals m. p. 56O from p-nitro- benzoyl chloride at 190-240° and 8-bromoethyl acetute b. p. 1 6 3 O from a mixture of equimolecular proportions of ethylene oxide and acetyl bromide kept for several hours a t the ordinary temperature.G. F. M. Colloid-chemical Studies on Soaps. Non-aqueous Lyophilic Soap Colloids. MARTIN H. FXSCHEER (C hem. Eng. 1919 2'7 184-193) .-The solvation capacities of various sodium soaps of the acetic series were determined. One gram-mol. of sodiuni arachidate will take up 27.5 litres of ethyl alcohol and still form a non-syneretic gel. The capacity of the lower members of the series becomes lees as the molecular weight of the soap decreases. When a given soap is employed with different alcohols the solvation capacity increases as the molecular weight of the alcohol becomes greater. The aut,hor has elaborated his theory of lyophilic and lyophobic colloids. The theory of soap gels is also dealt with. According to this soaps form ( A ) true solutions in a solvent a t higher temperatures.On the other hand (D) a gel when the temperature is low is a true solution of the solvent in the solvated soap. Between these two extremes there exist two stages ( B ) solvated soap dispersed in the solvent (C) dispersed solvent in the solvated soap. If the temperature of A is lowered all these stages are obtained. This is also true when the temperature of D is raised. The ranges of temperature in which B or C exists are not necessarily the same when the temperature of A is being lowered as when the temperature of D is being raised because of a hysteresis effect. There exists therefore a region of ambiguity which depends on the previous history of the system. Gelation capacity is for these reasons not synonymous with solvation capacity. The latter is the phenomenon generally known as swelling which is a different process from liquefaction.CHEMICAL ABSTRACTS. Colloid-chemical Studies on Soaps MARTIN H. FISCHER and MARION 0. HOOKER (Chem. Eng. 1919 27 223-232. Compare preceding abstract.)-Solutions of sodium or potassium hydroxide of various concentrations are added to a standard aqueous solution of potassium oleate having the consistency of a syrup. As the concentration of the base is increased the viscosity becomes greater until a gel is formed. Further addition of the base causes the soap to separate and the viscosity to fall rapidly. The separation of the soap occurs a t a lower concentration for sodium hydroxide than for potassium hydroxide.The addition of aqueous ammonia always lowers the viscosity the. authors' explanation being that ammonium soaps are more soluble in water and are better solvents for water. Similar results are obtained when a sodium or potassium salt is added in place of the hydroxide except that potassium acetate has a much greater salting-out && than the chloride nitrate etc. Ammonium salts on the other hand emulsify ths i 2i. 216 ABSTRAOTS OR' OHEMIOAL PAPEBS. soap but do not salt it out. Calcium or magnesium salts form insoluble or less hydrated soaps and therefore the viscosity steadily decreases as more of the salt is added. Sallts of the heavy metals such as copper or iron cause the soap to separate in hard lumps. The effect is additive when potassium hydroxide or a potassium salt is also added.Oleates and Stearates of certain Metals. MATHEUS D'ANDRADE ALBUQUERQUE (Revista Chim. p r a a p p l 1916 [ii] 1 reprint 8 pp.).-The o l e a h and stearates of a number of metals were prepared by double decomposition of solutions of their salts with alkali soaps. The ethereal solutions of some of the metallic soaps oxidised on exposure to air; the action of hydrogen peroxide on the ethereal solutions was also ascertained. CHEYI CAL ABSTRACTS. Colour of Metal. ethereal solution. colourIess amber-yellow colourless colourless Ag cu Cu" bluish-green Mn" almost colourless CO" red Pb" colourless Cr" pink Cr'" violet Hg' Hg" V' violet (?) Oxidation Oxidation Stability of by air by H,O peroxidised to- to- solution. - pale yellow - bluish-green - - - no colour change - - no change - - yellowish-brown unstable - dark chestnut stable dark green dark green stable - orange-yellow very unstable violet violet - - no change I green (at once) not given - Titanium soaps could not be obtained.The cuprous compounds were made from cupric soaps by reduction with hydrazine sulphate as well as by the action of alkali stearate and oleate on moist cuprous chloride. The silver compounds were darkened by light. By means of the ethereal soap solutions it was possible to observe the absorption spectra of the various metals in the non-ionised state. The chromic compounds showed a strong absorption in the yellow. W. R. S. [Preparation of] Maleic Acid from Benzoquinone by Catalytic Oxidation. J. M. WEISS and C. R.DOWNS (U.S. Pat. 1318632) .-Maleic acid is produced by dissolving benzoquinone in benzene and subjecting the mixture in the vapour phase to catalytic oxidation under conditions as described in U.S. Pat. 1318631 (this vol. i 236). Inert diluent gases may be employed to control the reaction. In the condensate obtained from the reaction products there is usually present benzoquinone maleic acid benzene form- aldehyde water and various other by-products. CHEMICAL ABSTRACTS. [Preparation of] Maleic Acid by Catalytic Oxidation of Benzene. J. M. WEISS and C. R. DOWNS (U.S. Pat. 1318633).- The patent relates to a method of the same character as that described above (preceding abstract) preferably operating a t 300-550° with subsequent recovery of maleic acid as the mainORGANIC CHEMISTRY.i. 217 product. When equal weights of benzene vapour and air are passed over vanadium oxide as a catalyst a t such a velocity that the mixture stays in contact with the catalyst about 0.25 sec. a maximum yield of maleic acid is obtained by maintaining the catalyst a t 400-450° CHEMICAL ABSTRACTS. The Mode of Pyrogenic Decomposition at High Tem- perature of Acetaldehyde Metacetaldehyde and EthyI Alcohol. (MLLE.) EGLANTINE PEYTRAL (Bull. SOC. chim. 1920 [iv] 27 34-39).-When acetaldehyde is submitted to a high tempera- ture for a very short time the main decomposition is its conversion into carbon monoxide and methane the molecule thus undergoing the least deformation possible. A second reaction proceeding at. the same time but to a less extent yields carbon monoxide ethylene and oxygen.I f the time of heating is prolonged other secondary products such as acetylene and benzene appear. Metacetaldehyde under similar conditions is first depolymerised to give acetaldehyde which then undergoes the changes given above. I n the case of ethyl alcohol the principal reaction is its oxidation to acetaldehyde which then undergoes pyrogenic decom- position as described. A second reaction proceeding simul- taneously but to a lesser extent results in the conversion of the alcohol into ethylene and water. A Keto-glycol Derived from Mesityl Oxide. J. PASTUREAU and CH. LAUNAP (Bull. Soc. chim. 1919. [ivl 25 593-597).-The crystalline compound m. p. 123O obtained by PlTolffenstein (com- pare A. 1895 i 644) by the action of hydrogen peroxide on mesityl oxide is shown to be not a glycol as described by him but a W.G . peroxide of mesityl oxide CH,*CO*CH<-? and on hydr+ CMe.,*O lysis it loses oxygen and gives the glycol of meiityl oxide described by Harries and Pappos (compare A 1901 i 673). Lactoare. J. GILLIS (Rec. trav. chim. 1920 39 88-1 25).-A more detaiIed account of work already published (compare A . 1918 i 101 155). W. G. ERIK HAGGLUND (Arkiv. Kern. Min. Geol. 1918-191 9 7 No. 8 1-20).-Reviewing the results of previous workers the author attaches most importance to those of Klason (A. 1908 i 717 and Suensk Papperstidnhg 1916 No. 17) derived from a study of the ligninsulphonia acids; but the regeneration of lignin from these derivatives by means of 70% sulphuric acid a method also used by Koenig (Chem.Z e i t . 1912 36 1101) requires one to two hours and is accompanied by considerable decomposition of the lignin. The author now finds that 28% by weight of the wood of (‘ hydrochloric acid-lignin ’’ is obtained by shaking 1 part of finely powdered pine wood with 10 parts of 43% hydrochloric acid for fifteen minutes rapidlv filtering and wash- ing the residue free from hydrochlorio acid. The product is a W. G . Lignh.i. 218 ABSTRAOTg OF CHEMTCAL PAPERS. pale brown powder with a strong odour of vanillin and contains 1.63% of combined chlorine. It gives a deep purple colour with phloroglucinol in hydrochloric acid solution a pale yellow colour with aniline sulphate a dark red colour with p-phenylene- dimethyldiamine sulphate a dark blue colour with equal parts of potassium ferricyanide and ferric chloride but no precipitate with Maule's reagent.A comparison of its methoxyl content with that of the original wood shows that about 20% of this is split off during the hydrochloric acid treatment. After introducing a correspond- ing correction the author's analytical results agree 1vit.h Klason's formula (C,,,H 0 ) for lignin but not with those of Cross and Bevan (" Ce1lu"M:'" iii) or of Green (Schwalbe '' Chemie der Cellulose," 1911 448). Protocatechuic acid was identified among the products of fusion of hydrochloric acid-lignin with potassium hydroxide and lead peroxide but acetic acid oxalic acid and catechol could not be detected. The formation of these products from wood (Lange.A. 1890 228) is therefore due to other con- stituents than lignin. The author also investigated his product in regard to its furfuraldehyde content solubility in bisulphites and in alkalis the action of chlorine and bromine its oxidation with alkaIine permanganate and with potassium chlorate and nitric acid. and the results of dry distillation. .J. R. Salts of ~-Hydroxytrimethvlenedig~~cine and of N-Hydr- oxvmethylglycine. Huao KRAUBR (Bey. 191 9 52 [I?] 1211-1222).-"he peculiarity (A.. 3918. i 156) attending tho formation of the barium salt (t 3U,O\ of B-hvdroxvtrimethvlene- diglycine (the barium salt containinp 1-5H?O TA.. 1918. i 3371 is now stated t o be non-existent) has been examined. It is diw'to supersaturation which however is not alwavs operative in many experimenk a noteworthv retardation of the crystallisation was never observed when technical formalin reacted with a freshly prepared solution of barium glvcine or when a solution of the latter which had been kept,.in the cold for an hour or longer was treated with formaldehyde solution containing or not containing methvl alcohol.The initiation of crysttallisation hv the addition of a little methyl alcohol (Zoc. c i t . ) cannot be regarded therefore. as a proof that the alcohol plays a part in the reaction. A second 6arrizum salt of the same composition C,H,,O&B a,3H90 which is amorphous and extremelv soluble in water is obtained bv treating a 25% solution of B-hydroxytrimethylenediglycine in formalin which has been kept for a few days with the theoretical quantity of a 15% paste of barium hydroxide and adding 8 vols.of 80% methyl alcohol to the resulting almost clear solution. Some experiments on the simultaneous formation of the barium salts of P-hydroxytrimethylenediglycine and N-hydroxymethyl- glycine indicate that the production of the latter is favoured by working at low temperatures with pure formaldehyde any con- siderable excess of which is to be avoided.ORGANIC CHEMISTRY. i. 219 In addition to the salts of N-hydroxymethylglycine already described (Zoc. cit.; A. 1919 i 67) the following have been pre- pared by the action of piire 33% formaldehyde solution on the metallic glycine salt potnssium OH*CH,*NH*CH,*CO,K amorphous brittle mass which is obtained in a purer form by treating the normal lead salt with potassium sulphide; sodium (at 80° in a vacuum these two salts r2 mols.] appear to lose water [l mol.] with the formation of anhydro-salts) ; bariim (+ 2H,O) microscopic rods ; calcium ( -+ lH,O) hygroscopic amorphous powder.The copper and lead salts must be dried over calcium chloride not over sulphuric acid (loc. c i t . ) which causes loss not Behavioar of Carbamide towards Hydrogen Peroxide and a Simple Procems for its Purification and Decoloration. HERMANN KUNZ-KRAUSE (R'oZZm'd Zeitsch. 1919 25 240-241). -Carbarnid0 is not affected in the slight.est degree by boiling it in aqueous solution with hydrogen peroxide but colloidal colouring matter which is generally present in carbamide is destroyed. Carbamide made from potassium cyanide which has teen obtained from potassium ferrocyanide often exhibits a blue to green tint.which cannot be removed by remystallisation. The colour is due to Prussian-blue and is destroyed by boiling the carbamide with hydrogen per oxide. only of water but also of a little formaldehyde. c. s. J. F. S. Carboalkyloxythiocarbamides . AUGUSTUS EDWARD DIXON and RAYMOND THOMAS JOACHTM KENNEDY (T. 1920 117 80-85). Preparation and Separation of Cyanates Soluble in Water. J. D. RIEDEL (D.R.-P. 314629; from Chem. Zentr. 1919 iv 913).-Chlorine or bromine is directly added to highly concen- trated alkaline solutions of cyanides; formation of cyanogen haloid only occurs t o a subsidiary extent. Sodium cyanate is smoothly formed by this reaction and is deposited in the solid state from its solution as the process goes forward.The product is applicable to technical and pharmaceutical purposes. H. W. Free Thiocyanogen. ERIK SODERBACK (Annulen 191 9 4 19 217-322) .-The author discusses the unsuccessful attempts of ?&big (1829 and 1844) Linnemann (1861) and Schneider (1866) to prepare thiocyanogen. Klason's compound (CN),S3-S,(CN) obtained in 1886 is a cyanuric derivative. Quite recently Bjerrum and Eirschner have detected small quantitiea of t h i e qanogen in aqueous solutions of complex gold thiocyanates MAu ( SCN)4. When an ethereal N - or N/lO-solution of iodine is shaken with silver thiocyanate in excess the colour of the iodine rapidly fades and yellow silver iodide is formed. The reaction however appears to reach a state of equilibrium.As it is imDossible to separate completely the excew of iodine from the soluble product of thei. 220 ABSTRACTS OF CHEMICAL PAPERS. reaction the halogen is removed as far as possible by mercury and the pale yellowish-brown solution examined. As the author expected it to be a dilute solution of thiocyanogen and to behave analogously to the halogens it was treated with (1) chloridw and bromides whereby no appreciable effect was produced; (2) aqueous or alcoholic solutions of iodides (of cadmium lead silver and mercury) whereby iodine was liberated ; (3) iron powder whereby ferric thiocyanat'e was produced in such quantity that the solution became opaque ; (4) mercury whereby mercurous thiocyanate was formed ; (5) cuprous thiocyanate whereby black cupric thiocyanate was formed; and (6) water which slowly decomposed the thio- cyanogen producing thiocyanic acid hydrogen cyanide and sulphurio acid.The solvent ether can be replaced by acetone absolute ethyl alcohol chloroform carbon tetrachloride benzene ethylene dibromide or carbon disulphide. The reaction proceeds very slowly in the last solvent but almost reaches completicm in chlore form; in every case however a state of equilibrium appears to be attained. The thiocyanates of potassium zinc cadmium copper and lead do not react appreciably with a solution of iodine but mercuric thiocyanate reacts in the same way as silver thiocyanate. Much better results are obtained with bromine. A solution of bromine in dry ethyl ether ethyl chloride ethyl bromide carbon disulphide carbon tetrachloride chloroform benzene or ethylene dibromide reacts completely with the thiocyanates of silver lead cadmium mercury zinc thallium and copper in accordance with the equation 2MSCN + Br,= 2MBr + 2CNS since the resulting solu- tion (in carbon disulphide or tetrachloride) is completely free from bromine and in experiments with silver lead and mercury t h i e cvanates in which an excess of bromine was used the solid product of the reaction is the pure metallic bromide.The velocity of the reaction is influenced by the solvent. A N-solution of bromine in carbon disulphide is decolorised by lead thiocyanate in slight excess within a few minutes whilst about half an hour is necessary when the solvent is drv ether. A solution of bromine in carbon disulphide dried with phosphoric oxide is not decolorised by lead thiocyanate after one hour but is almost instantly decolorised by silver or mercury thiocyanate.The solutions of thiocyanogen obtained above are usually faintly yellow but are occasionally quite colourless. The more concen- trated solutions have a stinking odour resembling that of thiocyanic acid and stain the skin pale red changing to yellow. The solu- tions become turbid on keeping and deposit yellow or yellowish-red amorphous products. The decomposition proceeds slowly in ethyl chloride or bromide or ether and very rapidly in carbon disulphide. The amorphous products which are diff went from different solvente appear to be mixtures consisting chiefly of polythiocyanogen (CNS),; about 1% of hydrogen is also present.Chlorine in carbon tetrachloride solution does not react with lead thiocyanate but yields a solution of thiocyanogen and the corre-ORGANIC CHEMISTRY. i. 221 sponding metallic chloride by shaking with an excess of silver or mercury thiocyanate ; sulphur chloride and cyanogen chloride are not present in appreciable quantities in the resulting solution. The author's usual practice for the preparation of a solution of thiocyanogen is to treat lead thiocyanate with a dry ethereal solu- tion of bromine cooled by ice-water. The evaporation in a vacuum over sulphuric acid of an approxim- ably N / 2-solution of thiocyanogen in ethyl chloride bromide or ether left a clear viscous unstable yellow oil. By cooling an approximately I\i / 2-solution in carbon disulphide to - 70° thio- cyanogen CNS is obtained in cruciform aggregates of almost colourless crystals m.p. - 3O t o - 2O. The molten substance can be supercooled to -20° but always resolidifies a t -30° giving well-defined rhombic plates. By allowing it to warm to the ordinary temperature thiocyanogen becomes reddish-brown and more viscous; finally a yellow smoke is evolved and a dark brick red amorphous solid is formed. Thiocyanogen dissolves extremely rapidly in ethyl alcohol or ether but only slowly in carbon disulphide or tetrachloride. Thiocyanogen is a t least as strongly electronegative as iodine. A solution of thiocyanogen reacts with zinc and cadmium (solvent carbon disulphide mixed with about one-fifth the volume of absolute ethyl alcohol) to form the respective thiocyanates; with mercury (solvent carbon tetrachloride) to form mercurous thio- cyanate; with aluminium (solvent dry ether) to form an etherute of aluminium thiocyanate Al(SCN),,2EhO extremely hygroscopic colourless plates which become friable and ultimately a syrup in air; with tin (solvent carbon disulphide mixed with a small quantity of dry ether) to form an etherate of stannic thiocyanate Sn( SCN),,2E&O yellow apparently prismatic hygroscopic crystals which change into a syrup in air; with arsenic (solvent carbon disulphide) to form nrsen,iazts thiocyanate As(SCN) almost colourlees crystals; with antimony (solvent dry ether) to form an extremely hygroscopic antimony thiocyanate (not isolated) ; with an excM of iron (ferrum reductum) (solvent dry ether) to form ferrous thiocyanate and with a deficit of iron to form anhydrous ferric thiocyanate dark violet crystalline powder ; with manganese (solvent ether and alcohol) to form manganous thiocyanate; with nickel (solvent carbon tetrachloride) cobalt (solvent carbon di- sulphide and alcohol) and silver (solvent ether) to form the respective metallic thiocyanates and with gold (solvent none) to form apparently a mixture of aurous and auric thiocyanates (not isolated).Many of the experiments with metals are of a qualitative nature only. The molecular weight of thiocyanogen cannot yet be determined. It does not yield well-defined products by treatment with organo- magnesium compounds. I n order to ascertain which of its three atoms is the reactive one a solution in dry ether was treated wit) mercury diphenyl.whereby phenyl thiocyanate and phenyl mercun- thiocyanate Ph*Hg(SCN) m. p. 231-232'5O (Otto in 1870 gave m. p. 226-227O) were obtained; the latter was also obtained from i"i. 222 ABSTRACTS OF CHEMICAL PAPERS. phenyl mercuri-iodide and thiocyanogen in carbon disulphide solu- tion. Ethereal solutions of thiocyanogen and zino ethyl react to form zinc thiocyanate and ethyl thiocyanate. Thiocyanogen in solution does not yield well-defined products with ammonia or aliphatic amines but in cold ethereal solution it reacts with aniline in accordance with the equation 2PhNH,+ 2CNS = NCS*c,H,*NH + PhNH,,HSCN to form aniline thio- cyanate and p-thiocyanoanibine colourless odourless needles (from water) m. p. 57-57'5O.When twice the quantity of thiocyanogen is used the product is p-thiocyanoaniline thiocymate faintly red crystals. By reduction with hydrochloric acid and zinc dust pthio- cyanoaniline yields paminophenyl mercaptan which was identified by oxidation to the corresponding disulphide. I n a similar manner thiocyanogen and dimethylaniline react in ethereal solution to form dimethylaniline thiocyanate and p-t hiocyanodimet hylaniline NM%*C,H,*SCN colourless odourless crystals m. p. 73-74O which yields p-dimethylaminophenyl mercaptan by reduction. Diphenylamine and thiocyanogen in ethereal solution yield thio- cyanic acid and ? ?-dithiocyanodiphenyhmine NH(C,H,-SCN) faintly greenish-yellow needlecj m. p. 120° whilst triphenylamine under similar conditions yields thiocyanio acid and ? 3-dithio- cyanot&phenytamine needles m.p. 115-116O. Phe'nol and t*hiocyanogen in carbon disulphide solution react to form thiocyanio acid (which was not detected however being appar- ently converted by a secondary reaction into an insoluble yellowish- brown substance) and p-t hiocyanophenot colourless odourless plates of rhombic habit m. p. 53-54O the constitution of which was proved by its conversion through p-hydroxyphenyl niercaptan into pp'-dihydroxydiphenyl disulphide and also by its formation from p-thiocyanoaniline by the diazo-reaction . Some experiments on the competition of iodine and thiocyanogen in solution for a metal show that the equilibrium MSCN+I M I + CNS is largely dependent on the nature of the metal; in the case of cadmium the reaction from right to left is practically irreversible.Stannous thiocyanate produced by the interaction of lead thio- cyanate and stannous sulphate in aqueous solution and obtained in colourless crystals from the hot filtrate after removing lead sulphate is converted into the etherate of staniiic thiocyanate by a solution of thiocyanogen in a mixture of carbon disulphide and ether. An ethereal solution of thiocyanogen reacts with mercuric cyanide (and also with silver or zinc cyanide) to form mercuric thiocyanate and a substance which is identical with the cyanogen sulphide (CN),S described by Linnemann and by Schneider; from this method of preparation the substance might be cyanogen thiocyanate CN-SCN. Several investigators have recorded the production of a ver;y unstable blood-red substance when a concentrated aqueous solution of potassium thiocyanate is acidified with sulphuric acid and treatedORUANIU UHEMISTRY.i. 223 with a solution of sodium nitrite. This substance which almost immediately decomposes with the evolution of nitric oxide can also be obtained by treating a solution of nitrosyl chloride in carbon tetrachloride with silver thiocyanate at the ordinary temperature. It appears to be nitrosy2 thiocyanate NO*SCN since its solution which is re!atively stable at - 1 7 O converts cuprous thiocyanate into cupric thiocyanate and metallic mercury into mercurous thio- cyanate and reacts with aqueous sodium hydroxide to form sodium thiocyanate and sodium nitrite. The author has performed some preliminary experiments in which the substance is produced from nit,ric oxide and thiocyanogen in well-cooled carbon disulphide.The substance allies itself with the nitrosyl haloids in iIx3 properties its position falling between those of the bromide and iodide. Although its molecular weight cannot yet be ascertained the author is of opinion that the molecular magnitude and the con- stitution of thiocyanogen in solution are represented by the formula CN*S.S.CN. I n accordance with this nitrile structure a dry ethereal solution of thiocyanogen reacts with dry ethereal hydrogen chloride cooled with ice-water to form a precipitate of a colourless crystalline substance 2CNS,2HC1 (which becomes yellow above looo and changes gradually t o a brown substance without melting) and a solution of a substance 2CNS,HC1 pale yellow prisms or plates of rhombic habit m.p. 69-70°. I n contrast to the former the latter substance which is not formed when carbon disulphide carbon tetrachloride chloroform or benzene is employed as solvent is easily soluble in organic solvents and is unaffected by hot water. The substance 2CNS,2HC1 is converted by water into a substance pale yellow rhombic leaflets or needles which decomposes without melting when heated and has the composition of thiocyanogen hydrate (CNS),,H,O. The latter substance is regarded as 2-imino- 5-keto-l 3 4-dithioazolidine several points of analogy to perthiocyanic acid (2-imino-5-thi+ 1 3 4-dithioazolidine; Hantzsch and Wolvekamp A. 1904 i 718) particularly in its behaviour with cold aqueous potassium hydr- oxide whereby sulphur is liberated and a colourless crystalline substance C,0N,SK2 (potassium cyanoiminot hiocarb mat e CN*N:C[SK]*OK) analogous to potassium dithiocyanate (cyanoiminodithiocarbonate) produced.The substance 2CNS,2HC1 is probably 5 5-dichloro-2- When suspended in iminel 3 4-dithioazolidine NH< benzene i t reacts with aniline to form the hydrated hydrochloride of Fromm's thiuret (A. 1893 i 575) C,H,N3%,HCl,3H20. NH<~(:.~). co-y since it presents CCI,-~ c( N H ~ ' c. s Photochemical Oxidation of Potassium Thiocyanate. DOMENICO GANASSINI (Boll. Chim. Farm. 1919 58 457-463).- Under the influence of sunlight aqueous potassium thiocyanate solutions undergo change in which the atmmpherio oxygen takes i* 21.224 ABSTRACTS OF CIEEMIOAL PAPERS. part. With solutions of medium concentration this change takes place with great rapidity an amorphous yellow precipitate of pseudocyanogen sulphide separating in most cases ; if the concen- tration is either above or below a certain limiting value the change is either entirely prevented or proceeds only very slowly. The concentration of the thiocyanate most favourable t o the separation of pseudocyanogen sulphide is about 50% in the summer and about 10% in the winter. The purer potassium thiocyanates especially those quite free from traces of ferrous salts are more sensitive to this reaction than less pure preparations. I n addition to pseudocyanogen sulphide the photochemical decomposition of potassium thiocyanate yields as constant products hydrocyanic and sulphuric acids carbon dioxide and ammonium salts 12KCNS + 120 + 6H,O = 6K2S04 + 3HCN + 3C0 + 3NHR,+ 2(CNS),.Further there is always formed an unstable inter- mediate peroxygenated compound which imparts a blue colour to fresh guaiacum tincture and is possibly analogous to Caro's acid. Normal decinormal and centinormal solutions of potassium thio- cyanate undergo these alterations but only with the first of these does separation ,of pseudocyanogen sulphide take place. Although decomposed in this way the deci- and centi-normal solutions show within certain limits of time no sensible diminution in titre prob- ably owing to the re,placement a t least in the early stages of the change of the thiocyanate by an equivalent proportion of the cyanide.T. H. P. Direct Passage from the Nitrous Esters and Nitro- compounds to Nitriles by Catalysis. ALPH. MAILHE and (MME) M. L. BELLEGARDE (Buzz. Soc. chim. 1919 [iv] 25 588-593) .-By the catalytic hydrogenation of isoamyl nitrite by means of reduced nickel at 280° primary secondary and tertiary amines result with a small amount of isovaleronitrile. If the temperature of hydrogenation is increased to 300-320° the yield of nitrile is considerably increased a t the expense of the amines. At the same time a certain amount of isoamyl alcohol is obtained owing to hydrolysis of some of the nitrite and a portion of the alcohol then undergoes dehydrogenation giving the corresponding aldehyde. Similar results were obtained with propyl isobutyl and heptyl nitrites.I n the same way at temperatures above 300° nitromethane gave some hydrogen cyanide and nitropentane some isovaleronitrile. W. G. Fixation of Nitrogen in the 'Form of Hydrogen Cyanide by means of an Electric Arc. E. BRINER and A. BAICRFUSS (HcZv. Chim. Acta 1919 2 663-666).-Mixtures of hydrocarbons and nitrogen when submitted to the action of an electric arc pro- duce hydrogen cyanide in yields much superior to the yield of ammonia obtained from nitrogen and hydrogen. The method employed is similar to that previously described (A. 1919 ii 338).ORGANIC CITEMISTRY. i. 225 The mixture of gases circulates a t the rate of 8-10 litres per hour in a chamber where an arc of 0.020 amp. is burning betcveen platinum electrodes 7 mm. apart. Using 12 parts of methane 23 of nitrogen and 65 of hydrogen under G35 mm.pressure O-OB? by volume of hydrogen cyanide is obtained. This gives a yield of 0.46 gram of hydrogen cyanide per kilowatt hour in addition to a yield of 0.14 gram of ammonia per kilowatt hour. I n this ctise the E.M.F. applied was 1020 volts. With the same mixture but with an E.M.F. of 420 volts 0.12% by volume of hydrogen cyanide was obtained which is 1-75 gram per K.1V.H. and 0.44 gram of ammonia per K . W . H . The best case examined is with a mixture of 1 part of methane and 5 of nitrogen a t 505 volts where a yield of 0.75% by volume of hydrogen cyanide was obtained which is 7.39 grams of hydrogen cyanide per K.W.H. and 0.48 gram of ammonia per K . W.H. J. F. S. Action of Carbon Monoxide on Sodium Alkyls. WALTER SCHOELLER WALTER SCHRAUTH and WALTER ESSERS (Ber.1920 53 [B] 62-63) .-In reference t.o Schlubach’s communication on this subject (this vol. i 19) reference is given to earlier work by t,he authors on the action of carbon monoxide on mercury acetate (A. 1913 i 1162). J. C. W. Preparation of o-Divinylbenzene. JULIUS VON BRAUN and LUDWIG NEUMANN (Ber. 1920 53 [B] 109-113).-The pule methiodide of o-di(-/3-dimethy laminoethyl) benzene NM~*C2H4*C6H4*C2H4*NMe,I has m. p. 196O and not 175-185O as previously stated (A. 1917 i 130). When boiled with sodium hydroxide in a current of steam the salt is decomposed into an amorphous pale yellow poly- meride of o-divinylbenzene C6H4(CH:CH,)2 m. p. 206-207O and also /3- 0- vin y lphe nyle t h yldime t h ylamine CH2:CH*C,H4*C13,*CH,*NMe which passes over in the steam.The base has b. p. 123-124O/ 13 mm. and forms a picrate yellow leaflets m. p. 137O a platini- chloride m. p. 167O and a silvery methiodide m. p. 209O. The corresponding quaternary ammonium hydroxide is stable in solu- tion but yields the above polymeride on evaporation. Seeing that the isolated unsaturated base is so stable i t appears t h a t the extensive decomposition which i t suffers in the above reaction is “ induced ” by the decomposition of the other group. J. C. W. The Two Isomeric Diphenylindenes. A. OREKHOFF (BuZZ. SOC. chim. 1919 [iv] 25 598-600).-The author shows that the diphenylindene obtained by him by the action of heat on aSy-tri- phenylpropene dibromide (compare A. 1914 i 265) is really the aSdiphenylpropene and that during the formation of its benzyl- idene derivative or its oximino-derivative i t undergoes isomerisa- tion to the By-diphenylindene described by Thiele and Ruggli (compare A.1912 i 866). W. G .i. 226 ABSTRAOl'8 OF UHEMI(YAL PAPERS. Action of Light on 1-1 O-Brornophenanthrene-3( or 6)-sd- phonic Acid. H%KAN SANDQVIST (Arkiv Kern. Min. Gsol. 19 17-1 8 7 No. 4 1-14).-1n a previous paper (A 1915 i 795) the author has shown that the action of light on aqueous solutions of 10-bromo- phenanthrene-3 (or 6 ) -sulphonic acid in hydrochloric acid decreases the viscosity of the solution and has explained this as being due t o the light changing an a-form of the acid into the b-form. Each form was supposed to give salts with different solubilities water of rtrystallisation etc.but the further experiments of the author with the barium salt have not led to the isolation of two such isomerides. However from the more soluble fractions of the barium salt which had been exposed to an intense light a reddish- brown to black varnish-like acid was obtained which immediately lowered the viscosity of a sulphonic acid-hydrochloric acid mixture when added to it. From this dark acid the dimethyl ester was prepared and analysis showed it to be dimethy2 monobromodi- phenanthryldisdphonate (annexed formula) ; the harium salt was C,H,,Br(SO,),Ba. It is the pro- duction of this acid by the action (') c14H7<i6SMe (3 or 6) of light (oxidation) on the original sulphonic acid which causes the (lo') C14H8-s03Me (3' Or ") decrease in viscosity ; the addition of 0.02% to the sulphonic acid-hydrochloric acid solution lowers the viscosity to one-third of its former value.From the mother liquors of t>he above-mentioned barium salt another substance was isolated but not identified which lowered the viscosity but not to such a great extent. Phenanthra- qninone-3-sulphonic acid exerts a still less effect. The product formed together with II-lO-bromophenant~hrene-3(or 6)-sulphonic acid in the bromination of phenanthrene-3-sulphonic acid (ihirl. 1917 6 No. 13 13) has exactly the same effect as the above- mentioned product of the action of light and is therefore probably the same substance. It is shown experimentally that the presence of monobromodi- phenanthyldisulphonia acid or its barium salt accounts for the differencea in solubility etc.described in the previous paper (Zoc. cit .) . I T. S. P. Amine Oxidation. I. Oxidation of Aniline STEFAN GOLDSCRMIDT (Ber. 1920 63 [B] 28-44) .-In Bamberger's interpretation of the oxidation of aniline phenylhydroxylamine is regarded as the initial product. WhiIst this compound mag ve,ry well lead ultimately to nitrobenzene it does not offer a satisfactory explanation of the formation of the polynuclear oxidation products since it is not sufficiently reactive. It has been shown however that benzoquinonephenyldi-imine which is regarded as the p r e cursor of aniline-black and azobenzene are the first demonstrable products of the oxidation by alkaline permanganate o r bleaching powder whereas these are not formed under conditions appropriate to tho production of phenylhydroxylamine and illtimately nitro-ORGANIC CHEMISTRY i. 227 benzene.It appmrs therefore that there are two different initial products varying according to the conditions. Agents which readily yield atomic oxygen such as Caro's acid or hydrogen per- oxide produce aniline oxide and further developments follow as in the scheme PhNH + PhNH,:O + PhNH*OH + PhNO + PhNO and PhNO + PhNH-OH + PhN-NPh and PhNO + PhNH = PhN:NPh. Under other conditions however the initial stage is represented by the removal of two atoms of hydrogen subsequent changes being due to the activity of the PhN residue (compare A 1913 i 1173). This radicle may for example polymerise to azobenzene benzoquinonephenyldi-imine NPh:C,H,:NK or emeraldine.This assumption is based on the fact that azo-compounds and quinonearyldi-imines can be isolated when aniline and especially its nuclear-substituted methyl homoi logues having free para-positions are oxidised by lead peroxide. The theory is considerably strengthened by the further fact that mixe'd azoicompounds and mixed quinonearyldi-iminea are produced when two amines are oxidised together. The methylated quinonearyldi-imines are easily hydrolysed by acids t o the original amine and the quinone and may thus be identified. They differ therefore from unsubstituted benzoquin- onephenyldi-imine which mainly polyrnerises to emeraldine. This explains therefore why Willstatter obtained only duroquinone in an attempt t o oxidise aminodurene in acid solution to a methylated emeraldine (A 1909 i 899).I n the oxidation of aniline itself the base is dissolved in ether and shaken with lead peroxide and anhydrous sodium sulphate. The filtered oxidation products are then shaken with alcohol ammonium chloride and zinc dust to reduce the benzoquinone- phenyldi-imine to p-aminodiphenylamine. A current of steam removes unchanged aniline and azobenzene whilst the diamine is isolated as the sulphate. I n the other cases the ethereal solution is oxidised by lead peroxide and glacial acetic acid the di-imine is then reduced by zinc dust and the colourless solution is shaken with sodium carbonate to remove acetic acid. The dry ethereal solution is finally mixed with alcoholic oxalic acid to precipitate the oxalate of the aminodiarylamine.A minodidurylamine C2nH28N2 cry~tallises i n concentric groups of needles m. p. 157O and may be oxidised by lead peroxide t o duropuinon eduryldi-imine C,H Me4*N C6Me4 1 NH druses of reddish- brown needles m. p. 155-156O which yields aminodurene and p-duroquinone m. p. llOo when mixed with an excew of hydro- chloric add. 1-Amino-2 3 5-cumene gives rise to azocumene [2 3 5 21 31 51- hexamethylazobenzene] m. p. 152-153O aminodicumylamine C,8H24N2 m. p. 138-1390 and cumoquinonecumyldiimine C,H,M%*N:C,HMe&NH stout prisms m. p. 103O. From m4-xylidine are prepared azoxylene (2 3 21 3'-tetra- methylazobenzene) m. p. 11l0 aminodkylylnrnine [4-amino- 'o/i 228 ABSTRAOTS OF (JREMIUAL PAPERS. 2 3 21 3f-tetramethyldiphenylamine] m. p. 74-75O and xylo- quinonexylyldi-imine brown rosettes m.p. 67-5-68.5O. The oxidation of a mixture of aminodurene and m-4-xylidine is described. The isolation of the products presents some difficulties but xylylaminodurylamine [4-amino-2 3 5 6 21 31-hexamethyldi- phenylamine] m. p. 153-154O is certainly identified by its oxida- tion to duroquinonexylyldi-imine m. p. 83-8401 and hydrolysis of this to duroquinone and the xylidine. Azodurene is also present; it forms reddish-yellow tablets m. p. 80-81O. J. C. W. Intramolecular Rearrangement of the Alkylarylamines Formation of 4-Amino-~butylbenzene. JOSEPH REILLY and WILFRED JOHN HICKINBOTTOM (T. 1920 117 103-137). JIRO TAKBDA and SATURO KURODA ( J . Pharm. Japan 1919 449 561-608).-Stvrene dibromide and carbamide react a t 120-130° New Method for the Preparation of Alkylamines.I .I CH,-Q HPh CfNH,KN ' to form 2-amino-4-phenyl-4 5-dih ydro-oxazole O< the hydrolysis of which by alcoholic potassium hydrhxidi' a t 150° yields ammonia and fl-hydroxy-a-phenylethylamine NH,*CHPh*CH,*OH the dibenzoyl derivative m. p. 155O of which has also been pre- pared by the following series of reactions which prove its constitu- tion COPh*CH,Br + COPh*CH,*OAc + COPh*CH,*OH + NOH:CPh*CH,*OH -j. NH,*CHPh*CH,*OH + NRBz*CHPh*CH,*OBz. On the assumption that the reactions proceed analogously to the preceding anethole dibromide heated with half its weight of carb amide at 1 20-130° yields 2-amino-4-p-anisyl-5-methyl4 5-dihydro- oxazole O M ~ . C H * C H < ~ ~ ~ ~ . ~ N1=-Q.NH* rectangular columns m.p. 165O the hydrolysis of which by alcoholic potassium hydroxide produces ammonia and P-hydroxy-a-p-anisylpropylamine OH*CHMe=CH (NH,) *C,H,*OMe (hydrochloride m. p. 193O; copper derivative m. p. 113O). Bromo- anethole dibromide and isosafrole dibromide also react with carb amide yielding corresponding oxazolines m. p. 20° and 175O respectively. CHEMICAL ABSTRACTS. Ketens. XXX. Preparation of a Keten-imine Derivative from Diphenylketen. H STAUDINGER and JULE~ MEYBR (Ber. 1920 53 [ B ] 72-76) .-Triphenylphosphinephenylimine (this vol. i 107) reacts with diphenylketen in benzene solution in an atmo- sphere of nitrogen to form triphenylphosphine oxide (I) and diphenylketenphenylimine (11) thus PPh,*N Ph 0-C C Ph . PPh,:NPh + CPh,:CO = I I + O:PPh and NPh:C:CPh,ORQANIC CHEMISTRY.i. 229 The same products are formed when triphenylphosphinediphenyl- methylene (ihid. 106) is treated with phenylcarbimide thus PPh,*CPb 0-C:NPh PPh,:CPb,+NPh:CO = I I (I.) and (11.) In either case the oxide is precipitated by the addition of light petroleum. Diphenylketenphenylimine crystallises in transparent pale yellow tablets m. p. 55-56O b. p. 190-195°/abs. vac. It has been sought for some time in order to compare its properties with those of compounds with other systems of twin double linkings such as ketens -C:C:O and carbimides -N:C:O. Quite unexpectedly the ne.w compound with the system -N:C:Cz is very stable and resistant to air water alcohol and bases. When warmed with concentrated hydrochloric acid however i t yields diphenylacet- anilide. J.C. W. Certain Completely Substit'uted Aromatic Iminosulphides. H. RIVIER and CH. SCHNEIDER (Hetv. Chim. Acta 1920 3 115-134).-The authors give an extended review of the literature relating to the formation of substances containing the group C-S-CzN and their isomerides with the group C-N-C-S. The possibility of assigning definite formulze to the substances is based on the fact that the chromophore CZ8 is much more active than the group C-S-C. From this point of view the authors have revised and extended the work of Jamieson (A. 1904 i 396) and have prepared a series of compounds which are either yellow or red and which are therefore held to cont,ain the groups -C-S-C- and CIS respectively I n only one case has the direct conversion of one form into the other proved possible but a general consideration of the constitution of the products which have been isolated appears to justify the conclusion that stability is conditioned bv symmetry of the molecule.It is however. remarkable that in the sole instance of actual transformability conversion is from the symmetrical to the less symmetrical form. Benzanilide sulphide NPh:CPh* S*CPh:NPh intenselv yellow prisms m. p. 211-212O (Jamieson Zoc. c i t . ; Raffo and Rossi A. 1915 i 86 give 202-204°). is most conveniently prepared by the action of benzanilideiminochloride on the potassium salt of thio- benzanilide. It is converted by hvdrogen chloride in ethereal solu- tion into the correspondinq chloride an amorphous red mas3 which is decomposed on exposure to moist air.a-Thiobenznaphthalide yellow crystals m. p. 149-150° and B-thioberrzn.aphtha~~~e yellow leaflets m. p. 160-162O. are pre- pared by the action of phosphorus pentasulphide on a solution of the corresponding benznaphthalides in solvent naphtha. a-Renz- naphthatide sulphide S(CPh:N*C,,,H7)2 yellow crystalline powder m. p. 130-131° is formed in the same manner as benzanilidei. 230 ABSTRACTS OF CHEMICAL PAPERS. sulphide; when its solutions are boiled f o r some time or u e evaporated it becomes transformed into t hiob enzoyZ&a-naphthyL benzen&m*e C,,E7*N:GPh*N(C,,H7)*CPh:S red crystals m. p. 156-157O but the reverse change could not be effected. Hydrogen chloride and concentrated sulphuric acid convert the yellow substance into red salts which are decomposed by excess of acid whilst the red material is decomposed by acid with formatioll of benznaphthalide and thiobenznaphthalide.The action of benz- anilide iminochloride on potassium a-thiobenznaphthalide or of a-benznaphthalide irninochloride on potassium thiobenzanilide yields the substance NPh:CPh*S*CPh:N*C,,H7 yellow crystals m. p. 176-177O which yields an unstable red hydrochloride which IS decomposed by excess of acid into thiobenzanilide and a-benz- naphthalide showing that in the transformation which precedes the decomposition it is the group NPh and not N*C,,H7 which has exchanged places with the sulphur atom. Attempts to prepare fl-benznaphthalide sulphide or the sulphide of benzanilide and B-benznaphthalide were unsuccessful. p-Dimet hylaminobenz- aniZide s d p h i d e S[C(C,R,*NM%):NPh] yellow needles or prisms m.p. 155-156O is best prepared by the action of potassium sulphide on p-dimet~hylamino;benzanilideiminochloride hydro- chloride; it yields a yellow crystalline hydrochloride C,,H,,N4S,2HC1. Excess of hydrochloric or sulphuric acid does not decompose the salts which thus appear t o have the same constitution as the free base. The action of thiobenzciyl chloride Ph*CSCl on diphenylbenzenyl- amidine on di-a-naphthylbenzenylamidine pale yellow leaflets m. p. 160-1 61° and on di-P-naphthylbenzenylamidine colourless crystals m. p. 154-155O has been investigated; in the first case benzanilide sulphide was obtained whilst positive results were not given by the naphthalene derivatives. Benzoyfthiobenzanilide COPh*NPh*CSPh red prisms m.p. 108-109° (compare Jamieson Zoc. &t.) benzo?~l-a-t?Liobenz- naphthaZi.de red crystals m. p. 145-146O and henzoyl-P-thiohenz- m p h t h d i d e red crystals m. p. 129-130° were prepared by the gradual addition of a solution of benzoyl chloride in chloroform to the requisite thioanilide or thiobenznaphthalide dissolved in the calculated quantity of alcoholic pot-assium hydroxide. They are decomposed by hydrogen chloride in ethereal solution even if only one molecular proportion of the acid is used yielding benzoyl chloride and the corresponding thioanilide. They are soluble in concentrated sulphuric acid without decomposition but addition of water precipitate5 the thioanilide. H. W. [Preparation of] Phenolic Compounds. E. H. ZOLLINUER and H.ROEHLING (U.S. Pat. 1321271).-Lead compounds which form insoluble or sparingly soluble compounds with phenols are made to react with aromatic halogen compounds and a hydroxide of an alkali or alkaline earth metal. The reaction is facilitated bycaklyste such as copper or copper compounds iodides of dkali or alkaline earth metals iodates vanadium titanium molybdenum and rare earths and their salts. Thus *chlorophenol is heated for about forty-five minutes at 250° with an aqueous solution of lead acetate and sodium hydroxide (alternatively lead sulphate or hydr- oxide at 260° with copper iodide as catalyst) whereby the lead salt of oatecho1 is formed which crystallises on cooling. Among the examples recorded is the formation of cresolsulphonic acid from &lore or bromo-toluenesulphonic acids orcinol from bromocreeol or dibromotoluene catechol-4-sulphonia acid from sodium 1 2-dichlorobenzene-4-sulphonate 3 5-dihydroxybenzoic acid from 3 5-dihalogenobenzoic acids salicylaldehyde from o-chlorobenzaldehyde a- and &naphthols from the respective &lore naphthalenes and alizarin from 1 2-diohloroanthraquinone. CHEMICAL ABSTRACTB.The Preparation of 2 4-Dinitrophenetole and 2 4 6- Trinitrophenetole. M. MARQUEYROL and SCOHY (Bull. SOC. chim. 1920 [iv] 27 105-107).-2 4-Dinitrophenetole may readily be prepared by the action of aqueous sodium hydroxide on an alcoholio solution of 1 -chIoro-2 4-dinitrobenzene a t 36O gradually rising to 55O. I f this phenetole is then nitrated in sulphuric acid solution at 3040° an excellent yield of 2 4 6-trinitrophenetole is obtained.W. G. The Synthesis of Aldehydes and Hydroxy-acids by meam of Secondary aaa-Trichloro-dcohols. PIERRE H~BBRT (BUZZ. SOC. chim. 1920 [iv] 27 45-55).-Bossneck’s method for the pre- paration of aldehydee or hydroxy-acids by the action of potassium hydroxide on aaa-trichloro-secondary alcohols (compare A. 1885 976; 1886 458) is shown to be generally applicable in the aliphatic cyclic aromatic naphthalene and aryl aliphatic. seriee. The pohsium hydroxide may be replaced by the hydroxides of sodium calcium magnesium or barium or advantageously by sodium carbonate. The trichloro-alcohols of the aliphatic sene8 do not give such good yields as do the aromatic alcohols where the *CH(OH)* group is directly attached to a ring carbon atom.The activity in the aromatic series is diminished if this group is separated from the nucleus by one or more carbon atoms. The following new compounds are described. By condensing magnesium p-bromophenyl bromide with anhydrous chloral 8-p- b romoph en y Ztric hloromet h ylcarbind CGH,Br*CH (OH)*CCl b. p. 183-187O/18 mm. is obtained giving an acetate m.. p. 145-147O and this on decomposition with sodium carbonate grvee pbromobenzaldehyde and p-bromophenylglycollic acid. Magnesium benzyl bromide reacts with chloral to give phelcyl- trichloroisopropyl alcohol CH,Ph-CH(OH)*CCl b. p. 15&160°/ 18 mm. giving an acetate m. p. l l O - l l l o . o-4~Xylyltrichloromethylcarbinol is decomposed by sodiumi. 232 ABSTRAWS OF CHEMICAL PAPERS.carbonate giving 3 4-dimethylbenzaldehyde and 3 4-dimethyl- phenyZgZycolZic acid C,H,Ma,-CH(OH)*CO,H m. p. 115-1 16O. Ethyl a-naphthylglycollute C,,H,*CH(OH)*CO,Et has m. p. 68-69'. W. G . Mercury Benzoate. ROBERT WOOD TERRY (Midl. Drug. and Pharm. Rev. 1919 53 222-225; from Chem. Zentr. 1919 iii 866).-A 1% solution of mercury benzoate is obtained by dis- solving 2-715 parts of mercuric chloride and 2.880 parts of sodium benzoate in 442 parts of water and filtering after a week. H. W. Abietic Acid. . DAVID JOHANSSON (Arkiv Kern. 1Min. Geol. 1917 6 No. 19).-Very little is known as to the derivatives and decomposition products of abietic acid. The author has therefore sought evidence of its unsaturation and of the presence in its mole- oule of the aromatic and hydroaromatic nuclei postulated by previous investigators (compare Easterfield and Bagley T.1904 1238; Levy A. 1913 i 620). The acid prepared from American colophony by Hunt and Pochin's process had m. p. 168-173O (sintering a t 155O) and in alcoholic solution [u1 -28.60. Both the Hiibl-Waller and the Winkler iodine numbers increased with the duration of the determination respective values of 102-171 and 150-357 being obtained. Since approximately the same values were obtained from the dihydro-derivative (below) and this behaviour was reproduced by the congener d-pimaric acid and its dihydro-derivative it would appear that the unreduced acids contain a t least two double bonds which are not equivalent or that substitution takes place. Halogenated compounds could not however be isolated.Dihydroabietic acid C,R,O m. p. 173-178O (sintering a t 156O) was obtained by hydrogenation in ethereal solution in presence of platinum-black. Unlike abietic acid i t is unchanged after long exposure. Treated with chlore form and glacial acetic and sulphuric acids it gives a reddish-violet colour changing to yellowish-brown whilst abietic acid gives a deep blue colour which becomes brownish-green. From sulphonation experiments a very smaIl proportion of a mixture of acids was obtained. Dinitronbietic acid C,H,,O,(NO,) produced by nitra- tion with fuming acid below loo separates from acetone in needles m. p. 178-184O [u] +44*26O whioh on exposure to sunlight turn red in a felw seconds and eventually brownish-green. Tho sodi?cm salt C,,,H1,O2(NO,),Na,l iH,O needles the pota.ssiztm salt and the barizim salt [C2,,Hzt0,(N0,),1,Ba,4K,0 yellowish- white needles crystallise much better than those of abietic acid ; the silver salt C,,,H,,O,(NO,),Ag is a flocculent precipitate.I n contrast with abietic acid its dinitro-derivative is esterified by treatment with alcohol and hydrochloric acid. The methyl ester forms needles m. p. 178-182O. needles m. p. 156-158O is best prepared from the silver salt and The ethyl ester C,,Hy(NO,),*CO,Et,ORGANIC CHEMISTRY. i. 233 is only hydrolysed by alkali with difficulty. Molecular compounds of the dinitro-derivative with in some cases four and in others six molecular proportions of naphthalene anthracene phen- anthrene and retene separate from alcohol in white needles stable to light which respectively melt a t 110-117° (decomp.) 244-246O 235-236O) and 234-238O. Diamino-abietic acid &hydrochloride C,H,,0,(NH2,HC1) is a brown amorphous powder m.p. 280° and very hygroscopic. A tarry product was obtained in an attempt to remove the amino-group by diazotisation. Crystalb graphic data are given for abietic dihydroabietic and dihydro- dextropimaric acids. The prmence of an aromatic or hydroaromatic nucleus in the molecule of abietic acid is regarded as now definitely determined. J. K. The Action of Nitrites on some Imino-ethers. A. BERNTON (,4rkiu Kern. Min. Geol. 1918-1919 7 No. 13 1-Zl).-The product of the action of nitrous acid on ethyl benzoyliminoacetate is not a nitrosederivative (Haller A 1887 826) but is identical with ethyl oximinobenzoylacetate (Perkin T.1885,47,243). Ethyl imino-oximinobenzoybacetate COPh*C(NOH)*C(NH)*OEt leaflets m. p.. 1 1 2 O is obtained as the intermediate product when a cold solution of ethyl iminobenzoylacetate is added to a cold solution of sodium nitrite and passes into ethyl oximinobenzoylacetate on warming or when treated with acids. Further chloro-oximinoaceto- phenone by treatment with potassium cyanide and hydrochloric acid furnishes oximinobenzoylacetonitrile (E. v. Meyer A. 1885 582) which is converted by hydrochloric acid in alcoholia solu- tion into the hydrochloride of ethyl imino-oximinobenzoylacetate. The hydrochloride C,,H,,03N,Cl m. p. 114O is precipitated by leading dry hydrogen chloride into its ethereal solution. It can also be similarly obtained from the product of the action of amyl nitrite on an ethereal solution of ethyl iminobenzoylacetate whilst by passing dry ammonia into a similar solution or a solu- tion of ethyl imino-oximinobenzoylacetate in alcohol oximino- b enzoylacetamidine C,'HQO~N~ sulphur-yellow crystals m.p. 227-229O is produced. Its hydrochloride C,H,,,O,N,Cl is faintly yellow and begins to lose hydrochloric acid a t 200O. The sulphate CQH,,05N& melts at 195O. The action of nitrous acid on ethyl iminophenylacetate leads to the formation of ethyl phenylacetate and phenylacetamidine nitrite CH,P h- C (NH ) *NH ,H NO (Lossen Diss . Koenigsberg 1890; Kammer ibid. 1893)) ni. p. 147O. This compound was further identified by the preparation of its acetate m.p. 195O and its nitrate m. p. 166-167O and its conversion into phenylacet- amide by the action of sodium hydroxide. I n agreement with Knorr's view (A. 1917 i 255) that the form- ation of amidines by the action of ammonia on the hydrochlorides of imino-esters is conditioned by ammonium chloride it is shown that the nitrate of ptolylacetamidine is produced by the action of ammonium nitrate on ethyl imino-ptolylacetate. J. K.i. 234 ABSTRAUTS OF CHEMICAL PAPERS. Electrochemical Oxidation of Benialdehyde and Beazoic Acid. FR. FICHTER and ELDOR UHL (Helv. Chzm. Acta. 1920 3 22-39) .-According to the literature the anodic oxidation of toluene and pnitrotoluene a t platinum electrodes appears to lead only to the formation of benzaldehyde and p-nitrobenzyl alcohol respect,ively; these results do not appear to harmonise with the powerful oxidising action usually associated with anodic oxygen.Since also Fichter and Stocker (A 1914 i 947) have found tolu- quinone among the products of the electrolytio oxidation of toluene the whole question has been re-examined with particular reference to the substances formed in minor quantity. The electrolytic oxidation of a suspension of benzaldehyde in 2N-sulphuric acid at platinum anodes gave much unchanged material and benzoic acid as the only isolable substances but the discrepancy between the amounts of original and final material pointed to a further oxidation of the benzoio acid formed. Direct experiment with the latter substance showed that it is actually con- verted into catechol quinol 2 5-dihydroxybenzoic acid and a hydroxyquinolcarboxylic acid.The latter substances possibly owe their origin to the intermediate production of 0- and p-hydroxy- benzaio acids and under the experimental conditions salicylic acid was found to yield quinolcarboxylic acid whilst p-hydroxybenzoic acid gave protocatechuic acid. The production of quinolcarboxylic acid is also observed in the electrolytic oxidation of benzaldehyde and toluene. Measurements. of potential with toluene benzyl alcohol benz- aldehyde and benzoic acid respectively show a rapid and remark- able increase of anodic polarisation in the case of the aldehyde; the same phenomenon is observed to a much smaller degree with benzyl alcohol and toluene whilst with benzoic acid anodic polarisation is very feeble; the results show that i t is impossible so t o control electrolytic oxidation that only benzyl alcohol is produced and also that benzoic acid can be further oxidised even in the presence of an excess of toluene. The peculiar behaviour of benzaldehyde is attributed to the formation of a peroxide presumably either dibenzylidene peroxide hydrate or dibenzylidene peroxide since evidence of the production of the volatile benzoic peracid Ph*CO,H Ph*CH Ph*CH,*OH + Ph*CHO + Yh*CH<OH HO O>CH*Ph O-- I C,H,*CO,H -+ C6H,( OH) *CO,H + C,H,( OH)2*C02H- C,H,(OH)* CO,H -+ C,H,( OH),*CO H- 2 1 2.5 1 1 '-+ %:4 1 I + CgH2(0H),C02H + 24:5 1ORGANIC CHEMISTRY.i. 235 could not be obt-ained. follows t-he lines of the scheme on the previous page. The electrolytic oxidation of toluene thus H.W. A New Method of Synthesis of Indenic Ketones. A. OR~KHOFF (Bull. SOC. chim. 1919 [iv] 25 597-598).-An appli- cation of the method previously described for the synthesis of indene derivatives (compare A. 1914 i 265). When benzylidene- deuxybenzoin dibromide is heated at 140-145O it lose two mole cules of hydrogen bromide and gives diphenylindone m. p. 151-152O; this yields a phenylhydrazone m. p. 175-176O. W. G. Action of Cyanogen and its Haloids on Mixed Organo- magnesium Derivatives. New Methods of Synthesis of Nitrilee and Ketones. New Method of Introduction of a Halogen into an Organic Molecule. V. GRIGNARD E. BELLET and CH. COURTOT (Ann. Chim. 1919 [ix] 12 364-393. Compare A. 1916 i 487).-The first part of the paper is a more detailed account of work already published (compare A.1911 i 292; 1912 i 623; 1914 i 391). By using 2 mols. of the mag- nesium alkyl or aryl haloid to 1 mol. of cyanogen chloride a ketimine results which when hydrolysed with water or dilute hydro- chloric acid gives the corresponding ketone (A. 1914,. i 391). I n this way the authors have prepared benzophenone 4 41-dimethyl- benzophenone 2 2f-dimethylbenzophenone m. p. 72O giving an oxime m. p. 105O aa-dinaphthyl ketone 2 4-dimethylbenzophen- one and phenyl a-naphthyl ketone. W. G . Derivatives of Naphthyl-/3-ethylamine. ANTONIO MADINA- VEITIA (Bull. SOC. chim. 1919 [iv] 25 601-610; A d . Fis. Quim. 1918 16 543-545).-The author has prepared a number of naphthalene derivatives having a side-chain with an amino-group in the 6-position with the view of studying their aation on the sympathetic nervous system in comparison with that of &methyl- aminou-phenylethane and its derivativea.a-ChloreP-bromcm-methoxyethane when added t o a solution of magnesium in bromobenzene and ether gives 6-brom+a-methoxy- a-phenylethane b. p. 125-127O/15 mm. which when heated with methylamine in benzene solution a t looo for three hours giva P-methylamino-a-methoxy-a-phenylethme b. p. 105-106O/ 22 mm. giving a hydrochloride and a platinichloride m. p. 189O (decomp.). P-Methylamino-a-methoxy-a-naphthylethane is similarly prepared with the intermediate formation of /3-bromea-methoxy-a-naphthyl- ethane b. p. 185-190°/14 mm. and gives a htydrochZoride and a platinichloride. a-Naphthyl methyl ketone when acted on by amyl nitrite in the presence of sodium ethoxide gives a-naphthyl nitrosomethyl ketone giving a sodium salt and this nitrosederivative when reduced with stannous chloride and hydrochloric acid yields a-naphthyl aminomethyl ketone C,,H,*CO*CE,*NH giving a hydrochloride.i.236 ABSTRACTS OF CHEMIOAL PAPERS. Similarly 4-methoxy-a-naphthyl methyl ketone gives a nitruso- derivative which on reduction yields 4-methoxy-a-mphthyl amino- methyl ketone isolated as its hydroclaloride which when heated in a sealed tube for four hours at looo with fuming hydrochloric acid gives 4-hydro~y-a-n~aphthyl aminomethyl ketone isolated as its hydrochloi-ide. The vaso-constrictive action of these substancm has been studied by Trendelenburg’s method.It is shown that the introduction of a methoxy-group into the sidechain has little o r no influence on the physiological action of the substance but the replacement of the phenyl nucleus by a naphthyl nucleus has a very marked effect increasing the vaso-constrictive action about forty timw in the case of the substances studied. 4-Hydroxy-a-naphthyl aminomethyl ketone posseses a very marked vaso-constrictive action which is much greater than that of the corresponding derivative without the hydroxyl group or than that of the corresponding derivative without the carbonyl group in the side-chain. W. G. The Constitution of Dypnopinacone and its Derivatives. IV. The Lnteo-dypnopinacones. MAURICE DELACRE ( A m . Chtim. 1919 [ix] 12 394-425. Compare A. 1914 i 1068; 1916 i 479; 1918 i 539; this vol.i 165).-A more detailed account of work already published (compare A. 1891 456; 1896 i 662). W. G . [Preparation of] p-Benzoquinone from Benzene. J. RI. WEISS and C. R. DOWNS (U.S. Pat. 1318631).-A mixture of benzene and oxygen or air in the form of vapour or spray is passed over pumice impregnated with vanadium oxide and heated at 300-700°. p-Benzoquinone maleio acid and by-products are obtained together with unchanged benzene. As substitutes for the catalyst vanadium or vanadium compounds molybdenum tungsten gold ruthenium cobalt or the oxides of copper manganae cobalt lead chromium antimony cadmium and thorium may be used. The reaction may be carried out a t pressures greater than equal to or less than atmospheric pressure. After removal of maleic acid by crystallisation or by solution in water the remaining liquid products may be again passed over the catalyst to effect further oxidation with the production of additional p-benzoquinone and maleic acid.CHEMICAL ABSTRACTS. A Novel Degradation in the Anthraquinone Series. K. FRIES and E. AUFFENBERG (Ber. 1920 53 [ B ] 23-28).-When the hydrochloride of 1-aminoanthraquinone is exhaustively chlorinated in glacial acetic acid it yields 2 2 3 4 4-pentachloro- 1-keto-l 2 3 4-tetrahydroanth?.aqz~inone which crystallises in rhombic tablets m. p. 166-168O (slight decomp.) and may be reduced by stannous chloride to 2 4-dichloro- 1-hydruxyanthrupwhone slender orangecoloured needles m. p.ORGANIC CREMISTRY. i. 237 2 4 2 O . The compound may also be reduced by boiling an acetic acid solution with ammonium chloride the product being 2 3 4- trichloro-T-hydroxyanthrapuinone which crystallises in orange needles m.p. 2 1 4 O forms sparingly soluble brilliant red alkali salts and is remarkably stable towards chlorine or concentrated nitrio and sulphuric acids. The pentachloro-derivative undergoes a novel hydrolysis when warmed with concentrated sulphuric acid the product being 0-2 3 4 6-tetrachloro-5-hydroxybenzoylbenz&c acid formed by the rupture of the middle ring according to the equation CI4H5O3Cl5 + H20 = C,,H,O,Cl + HC1. It crystallises in minute druses m. p. 277-278O forms a sparingly soluble sodium salt and an acetate m. p. 2 1 3 O and is hydrolysed by heating at a higher temperature with sulphuric acid to phthalic acid and 2 3 4 5-tetrachlorophenol. The same derivative of benzoylbenzoic acid is formed as a by-product when the original crude chlorination product containing ammonium chloride is boiled with acet,ia acid but it is not given by the main product of this reaction namely the above trichlorohydroxyanthFaquinone.J. C. W. Stereoisomeric Derivatives of Aminomethylenecamphor . I. HANS RUPE MAX SEIBEBTH and WALTER KUSSMAUL (HeEu. Chim. Acta 1920 3,50-70) .-Aminomethylenecamphor and many of its derivatives are found to exist in two forms characterised by lower melting point and generally greater solubility and higher melting point and usually more sparing solubility ; these are designated 8- and a-compounds respectively. In general they are readily mutually transformable.Since a new asymmetric carbon atom is not developed during the formation of these substances optical isomerism is out of the question and it appears certain that instances of cis-trans-isomerism (annexed formula) are being dealt with although direct experi- R*NH*CH HC-NHR mental evidence on this Doint is lacking. The optical iniestiga- tion of these substances promises results of considerable II C and CO CbH,4< I interest since but few optically active cis-trans-isomerides have been examined ; the sparing solu- bility of the products at the ordinary hmperature and the ease with which they undergo transformation when the temperature is raised have prevented an extended examination and the results which have been obtained so far do not allow any general con- clusions to be drawn.A considerable improvement in the preparation of hydroxy- methylenecamphor is effected if the sodium camphor is prepared by the interaction of camphor and sodamide in benzene solution ; under these conditions the formation of borneol is avoided and any unattacked camphor can be recovered. a-A min om ethyl enecamp h or is conveniently prepared by heatingi. 238 ABSTRACTS OF CEIEMICAL PAPERS. hydroxymethylenecamphor with saturated aqueous ammonia under pressure at looo; it forms colourless shining leaflets m. p. 1 5 6 O DY 0.81'76 [a]? + 191*37O [u] + 257.32' + 323*41" [a]? + 417*19O [aIF/[a] 2-48 in alcoholic solution. When distilled under diminished pressure i t is quantitatively converted into the &form m.p. 103-104° DT 0.8159 [UI:? + 236*57O [a]:' + 313-76O [a) + 388.23' [a]? 553*99O [U]./[U}~ 2.34. The latter is very labile but can be preserved unchanged in substance even i f ex- posed to sunlight; it is Converted into the a-form if its solution in alcohol or benzene is evaporated when the benzene solution is exposed to sunlight or when the alcoholic solution is boiled. a-Benzoyluminomethylenecamphor is the sole product of the action of benzamide on hydroxymethylenecamphor in glacial acetic acid solution and is formed together with the 8-isomeride by the benzoylation of aminomethylenecamphor in pyridine solution ; it forms slender colourless needles m. p. 208O DF 0.9838 [a]:o + 164.28' [alp + 219*29O [a]& + 273.15O [a] + 393*06O [alF/[a]c 2.39 in pyridine solution.The &modification crystallises in monoclinic prisms Ta b c=0.96402 1 1.0501 1 ,p= 11 0'40'1 m .p. 11 2O DY 0.983 5 Talc" + 166.44O [a]? + 228*29O [u]& + 392*67O [a] + 453.11° [a]F([u]c 2.72; it is converted into the a-variety when its solution in light petroleum is exposed to ultra-violet light. but not by treat- ment with hydrogen chloride in alcoholic or light petroleum solution. The reverb0 transformation is effected by boiling a solution of the a-form in pyridine. a- and fl-p-Nitroandinomet hylenecamphor are simultaneously formed by the action of p-nitroaniline on hyclr- oxymethylenecamphor in glacial acetic acid solution and are separated by taking advantage of the greater solubility of the j3-isomeride in cold benzene. The a-form crystallises in canary- yellow leaflets m.p. 180-151° and slowly passes into the B-isomeride at the ordinary temperature rapidly at 200° ; the 8-isomeride forms orange-ydow needles with a violet reflex m. p. 151-152O and is converted into the a-form when its solution in boiling alcohol is exposed to direct sunlight. p- Phen~lened~~naEinzethyle,2.ecanaphor pale yelIowish-green microscopic needles m. p. 276-277O appears to be the sole product of the action of p-phenylenediamine on hydroxymethylenecamphor ; i t could only be obtained in one form. p -A c e t y lamin onnilin om e t h y ?en e c m phor,ORGANIC CHEMTSTRY. i. 239 forms pale yellowish-green leaflets m. p. 226-227O and exists in one form only. p-Aminmnilinomet hylenecamphor could not be obtained by the reduction of the corresponding nitro-compound by iron and acetic acid; alt-hough reduction appears t o occur the amino-derivative is immediateIy hydrolysed and condensation then occurs between the p-phenylenediamine and hydroxymethylene- camphor which are t,hus formed with the ultimate production of p- phenvl enedi aminodim ethyl enecamphor ; reduction could not be effected with ammonium sulphide whilst with sodium suIphide either form of the nitro-compound yields the same aminederivative i n poor yield.The pure amine m. p. 163O is however obtained by the action of ethyl-alcoholic potassium hydroxide on the corre- sponding acetyl derivative. The h?/drochZoride is sparingly soluble in water and cannot be diazotised. p- P h e n e t idinom e t h y 1 e n e camph or (P- f orm coarse pl a h and prisms m.p. 111-112°; a-form pale yellowish-green leaflets m. p. 166-167O) is prepared by the action of p-phenetidine on hydroxy- met,hylenecamphor in alcoholic solution and is separated into its isomerides by fractional crvstallisation from benzene. The &variety is very labile and is converted into the &variety when attempts are made to recrystallise it from alcohol; it has not been found possible to effect the reverse transformation. H. W. Stereois omeric Derivatives of Aminamethylenecamphor . 11. HANS RUPE MAX SEIBERTH and WALTER KUSSMAIJL (ReZv. Ghim. Acta 1920 3 71-89).-A continuation of the work described in the preceding abstract. Diethylaminomet hylenecamphol C s H 4 ~ ~ H * N E t 2 is obtained as a pale yellow viscous oil b.p. 175-175*5*/11 mm. which solidifies when cooled to a mass of transparent plates m. p. 20-22O by the act-ion of diethylamine on hvdroxymethylenecamphor or chloromethylenecamphor. The h?/drochZoride is slowly decomposed in aqueous solution. yielding hydroxymethylmecamphor and diethylamine hydrochloride. Piperklinomethylenecamphor is a pale yellow viscous oil b. p. 203-204°/11 mm. m. p. 60° after softening a t 58O; the hvdrochloride slender needles suffers first dissociation and then hvdrolysis in aqueous solution. Tetrahydro- qzcinolinmet7~y1enecamphor forms coarse transparent prisms m. p. :CH*NH*CO*NH logo. Carbamidomethylenecamphor C8H,,<go prepared by melting the components together or by condensation in glacial acetic acid solution cryst.allises in needles m.p. 197O; a second modification which does not melt below 280° possibly exists. j3-Ethylurethanomethylenecnmphor is exclusively obtained when its components are heated together a t l l O o and forms a colourless odourless highly refractive oil which does not solidify in a mixture of ice and salt and rapidly becomes yellow or red when preserved; it has b. p.. 178-1f9°/i0 mm. DF0.9835 [a] + 145.93' [a] + 197*17O + 247.62' [a]? + 366*69O [aJF/[a]ci. 240 ABSTRACTS OF CHEMIOAL PAPERS. 2.51 in pyridine solution. When however the components are mixed in glacial acetic acid solution the a-variety is mainly formed at the ordinary temperature but the reaction is very incomplete whilst at a higher temperature reaction proceeds quantitatively but yields more of the P-variety.The a-isomeridc forms colourlese many-sided sryatals m. p. 162' l.) 0.95352 + 149*4Z0 [alp" + 198*52O [a]& + 245.11° [a]$' + 347*35O [alF/[a]c 2.32. Transformation of the 8- into the a-variety can be effected by hydrogen bromide hydrogen chloride concentrated sulphuric acid nitrous fumes iodine in ethereal solution by exposure t o direct sunlight and by preserva- tion in the dark. The reverse action is effected by boiling a solution of the a-variety in glacial acetic acid with exclusion of light. The two forms of ethyl methylenecamphor-paminobenzoate are simultaneously formed by the condensation of the components in glacial acetic acid solution and are separated with the aid of light petroleum; the a-variety crystallises in minute needles m.p. 176O whilst the @-form has m. p. 1 0 5 O . The former modification is exclusively formed when a mixture of the components is gently heated; it appears to be exceptionally stable but undergoes partial transformation when its solution in formic acid is boiled during a protracted period in direct sunlight and in the presence of iodine. The methylenecamphorant hran&c acids are simultaneously formed from hydroxymethylenecamphor and anthranilic acid in glacial acetic acid solution and can be separahed to some extent mechanically owing to the difference in their crystalline forms. Separation by means of solvents is impracticable owing to their very similar solubilities. Isolation of the 8-variety is best effected by boiling the mixture of isomerides with benzene when the a-variety passes into the &form almost colourless needles which rapidly become brown and have m.p. 112O and 176O after re solidifying. The a-variety is conveniently obtained by boiling a solution of the @form in toluene and forms pale brown many- sided crystals m. p. 1 7 6 O ; the latter isomeride is exclusively formed when the components are heated torether the result being attribu- table to the high temperature of the reaction. Attemph to con- vert the methylenecamphoranthranilic acids into indole or indigo- derivatives were unsuccessful. Acetic anhydride however converb the &derivative into methylenecamphor-N-acetylanthrandic acid C,B,,<~~H"Ac~c6H4'c02R colourless shining needlea united _ _ in clusters m. p. 185O to an intensely green liquid which gradu- ally becomes reddish-brown.Either variety is transformed by phosphoryl chloride into the &lactam of methylenecamphor- anthranilic acid C,H,< I > C8H,4 colourless crystals which immediately become discoloured on exposure to air and have m. p. 1 6 5 O . The substance is converted by boiling water into methylene camphoranthranilic acid and by cold alkali into a mixture of the sodium salts of the two forms of the acid. N*CH:Q co ocORGAN10 CHEMISTRY. i. 241 Met h y lenecamplb or- p-aminoplt en ylarsinic acid C C H *N H C H ,*AsO,H C8H14<& Y is best obtained as sodium salt by heating hydroxymethylene- camphor with atoxyl at 110O; it forms slender colourlw needles which decompose at 220° and melt indistinctly at 250O; anilino- methylenecamphor m.p. 168-170° and a substance CnH4202 slender yellow needles m. p. 188O are formed as by-producta during the condensation. H. W. Transpositions in the Camphene Series. G. LANGLOIS (Ann. Chim. 1919 [ix] 12 265-363. Compare this vol. i 171). -By the direct bromination of camphene in anhydrous ether w-bromwamphene b. p. 115-120°/15 mm. 225-226°/760 mm. D16 1.265 [a]D + 68.85O is obtained its constitution being proved by its behaviour on oxidation either by nitrous vapour or by potassium permanganate camphenylone being the product in either case. In the preparation of a magnesium derivative from bromocamphene some dehydrodicamphene C10H15*C10H15 m. p. 181° is obtained. The magnesium derivative when acted on by carbon dioxide gives an acid C,,H,,*CO,H m.p. 124-125O which on oxidation also gives camphenylone and oxalia acid. w-Bromocamphene is stable towards Beckmann’s oxidising mixture and with hydrogen bromide yields 2-w-dibromocamphane the latter change being reversible. Attempts to replace the bromine in bromocamphene with a phenyl group by means of magnesium phenyl bromide were not very successful whilst with magnasium methyl iodide the product was cymene. On chlorination in ether bromocamphene gives dichloro- bromocamphene C,,H,,Cl,Br m. p. 74O. Hydrogen chloride in the cold is without action on bromocamphene but when passed into an acetia acid solution ata looo it yields dibromocamphane. As compared with camphene bromocamphene only undergoes very slow acetylation and the product is not characterised.By carefully restricted chlorination of camphene a certain amount of chlorocamphene b. p. 95-9g0/15 mm. D15 1.016-1*017 [aID + 37O is obtained which is not acted on by any hydrogen chloride or by Beckmann’s oxidising agent. With potassium permanganate it is oxidised to camphenylone. With hydrogen bromide it gives o-chloro-2-bromocumphane m. p. 1 0 3 O and on further chlorination it gives trichlorocamphene m. p. 104O. On bromination it gives chlorodibromocamphene C,,H,,ClBr m. p. 64-65O. When oamphene is heated on an oil-bath for two days with a mixture of trioxymethylene and acetic acid it gives an acetate C,,H,,*CO,*CH b. p. 130-135°/20 mm. which on hydrolysis gives a primaFy alcohol camphenylidene-6-ethano1 C,H,,:CH*CH,*OH b. p. 125-126O/8 mm. 135O/17 mm. 234-23g0/760 mm.D16 0*987-0*988 [aID +45O which is best purified through its hydrogen phthalate CO~H°C,H,oC0,*C,,H,7 m. p. 124-125’. If the alcohol is subjected to prolonged heating with alcoholic potassiumi. 242 ABSTRACTS OB CHEMICAL PBPERS. hydroxide it gives an ether O(CH,*CH:C,H,,) b. p. 235-240°/ 25 mm. D20 0.983. The alcohol C,,H,,*OH when oxidised with potassium permanganate in the presence of aqueous sodium carbonate gives camphenylone hydroxycamphenylanic acid and oxalic acid. In the presence of sodium hydroxide the products of oxidation are camphenylone camphenecamphorio acid and oxalic acid. By a similar study of the oxidation of camphene it is shown that the endocyclic transposition is not due to t*he permanganate but rather t o the isomerising action of the free alkali used in excess.Certain derivatives of camphenylidene-6-ethanol have been pre- pared. It gives a diphelzylurethane difficult to purify and a pyrwvate b. p. 150-155°/10 mm. giving a semicarbazolw m. p. 167O. The ether (CllH17)20 when oxidised by sodium dichromate and sulphuric acid givee first an aldehyde$ and then camphenyl- idene-ethanoic acid. A chloride C1,H17C1 corrmponding with camphenylidene-6- ethanol may be obtained either by the action of hydrogen chloride on the alcohol in toluene solution at 140-150° or by the action of phosphorus pentachloride either on the alcohol or the correspond- ing ether. This chloride has b. p. 100-102°/6 mm. 110°/15 mm. D15 1.020 [.ID +27.38O. On oxidation with potassium perman- ganate it yields camphenylone.Unlike o-chlorocamphene it is oxidised by sodium dichromate +nd sulphuric acid giving first an aldehyde and then camphenylideneacetia acid. The chloride is quite stable towards either hydrogen chloride or hydrogen bromide undergoing no transposition. Further it is not reduced by sodium in absolute alcohol but under these conditions simply gives an ethyl ether C,,H17*OEt b. p. 125-130°/8 mm. 230°/760 mm. This ether when oxidised by the chromic acid mixture gives camphenylidene,acetic acid. If the reduction of the chloride is carried out by zinc and hydrochloric acid the product is o-methyl- camphene b. p. 178O D15 0.884 [a]= +4*2B0. The chloride C,,H,,Cl when acted on by sodium or magnesium in anhydrous ether gives a terpenic hydrocarbon CllH17:CllH17 b. P.210'1 25 mm. D*5 0.952 [aID +67-30° which is remarkably stable towards aqueous potassium permanganate. By the action of sodium ethoxide the chloride yields the corresponding ether (C,,H,7)20 described above. With sodium cyanide the chloride yields the nitrile C,,H,,*CN b. p. 140°/12 mm. D15 0.959 D2O 0.963 [a]r + 61.20° which is readily oxidised t o cmphenylone and on hydrolysis gives the corresponding acid CllH,7*C02H m. p. looo CH CKORGANIC CHEMISTRY. i. 243 b. p. 185O/24 mm. [a] +41*16O. From its behaviour on oxidation it is suggested that this acid is redly a mixture of two a- and /3-isomerides (see formuls on previous page). When camphenylidene- 6-ethanol is oxidised by Beckmann's mixture in the cold it yields camphenylidene-6-acetaldehyde C9H14:CH*CH0 b.p. 130°/ 12 mm. l24"/8 mm. D15 1.002 [.ID +72'58O which gives a sodium bisulphite compound a semicarbazone m. p. 233O and an oxime b. p. 160°/15 mm. The oxime gives a hydrochloride and on dehydration yields camphenylideneacetoaitrile CgH,,:CH-CN b. p. 132O/6 mm. 140°/10 mm. D16 0.987 D20 0.983 [ u ] ~ + l l O o which when boiled with alcoholic potassium hydroxide gives the come sponding amide CloH15*CO*NH2 m. p. 192O. This amide is very stable and is not hydrolysed by sulphuric acid. Camphenylidene- acetaldehyde gives a diacetate C,H,,:CH*CH(CO,Me) m. p. 54-5 5O. If the oxidation of camphenylidene-6-ethanol with Beckmann's mixture is pushed further the product is camphenylideneacetic acid m. p. 124-125O b. p. 18l0/19 mm. the same acid being obtained by the action of carbon dioxide on the magnesium deriv- ative of o-bromocamphene.It gives an ethyl ester b. p. 150°/ 22 mni. DZo 1.008 and an acid chloride b. p. 145O/15 mm. which by the action of ammonia is converted into the amide m. p. 192O (see above). When heated o? an oil-bath f o r several hours camphenylideneacetic acid loses carbon dioxide and gives a camphene m. p. 45-46O b. p. 158-160° which on oxidation yields camphor. On oxidation with potassium permanganate the acid yields camphenylone and on reduction with sodium in amyl alcohol it gives isocamphanecarboxylic acid which when oxidised gives r-canaphenylanic acid m. p. 75-76O. o-Methylcamphene may be obtained by the reduction of camphenylideneacetaldehyde by zinc and hydrochloric acid its con- stitution being shown by its behaviour on oxidation with potassium permanganate when it yields camphenylone oxalic acid and camphenecamphoric acid. It is not oxidised by sodium dichromate and sulphuric acid or by hydrogen chloride but with hydrogen bromide it gives a hydrobromide CIIHl9Br b.p. 108-110°/17 mm. D15 1-175. Camphenylideneacetaldehyde is capable of condensing with ketones. CQH14 CH- CH :CH*COMe b. p. 160°/12 mm. D15 0.980 giving a semicarbazme m. p. 220-2210. With methyl et.hyl ketone the aldehyde gives the ketone C,H,,:CH*CH:CH*COEt b. p. 172-175°/12 mm. D15 0.968 giving a semicarbuzone m. p. 209-210°. Owing to the presence of three conjugated double linkings neither of these ketones is oxidised by chromic acid mixture and the firsbnamed is not acted on by hypochlorites.Camphenylideneacetaldehyde also reacts with magnesium alkyl haloids of low molecular weight to give unstable secondary alcohols which when distilled in a vacuum give diethylenic hydrocarbons. Thus with magnmium methyl Thus with acetone it yields the ketme,i. 244 ABSTRAUTS OF OHEMICUL PAPEBS. iodide the final product is camphenylideneproylelte b. p. 85-90°/10 mm. 203-205°/760 m. D15 0.921 DZo 0.917 [ajD +76*39O. With magnesium ethyl bromide the product is camphenylidenebztylene CQH14:CH CH CHMe b. p. 95-97O / 12 mm. and 230-232O/760 mm. D15 0.919 [alD + 70°. With mag- nesium propyl bromide the product is camphenylidenepentene CQH,:CH*CH:CHEt b. p. 110-120°/ 15 mm. and 238-240°/ 760 mm. D15 0-905 [alD +80° and with magnesium butyl bromide the product is camphenylidenehexene CQH14 CH CH CHPr b.p. 140°/10 mm. and 255O/760 mm. D15 0.900 [a] + 73.5O. All these diethylenic hydrocarbons when oxidised with chromic acid mixture give the original aldehyde or camphenylideneacetic acid. They also undergo spontaneous oxidation giving camphenylidene- acetaldehyde and formaldehyde acetaldehyde propaldehyde and butaldehyde respectively. W. G. Chemistry of the Terpenes. XIX. Synthesis of a mMenthadiene from m-isoCymene . GEOHGE GERALD HENDERSON and THOMAS FREDERICK SYEATON (T. 1920 117 144-149). Occurrence of the Terpene Terpinene in the Oil of Eucalyptus megacarpa. HENRY G. SMITH (J. Proc. Roy. SOC. N.S. Wales 1918 52 529-533).-The oil of Eucalyptus mega- carp contains pinene limonene and dipentene about 30% of cineole and possibly as much as 10% of terpinene.The latter was detected in the fraction boiling from 170-190° by the formation of its nitrosite m. p. 155O and by its rapid oxidation in the cold with Beckmann’s chromic acid mixture as evidenced by the increased optical rotation of the residual oil (consisting mainly of limonene) after the removal of the inactive terpinene. C,Hi,:CB CH:C& G. F. M. The Vulcanisation of Caoutchouc with Agents other than Sulphur. HENRY Y. STEVENS (J. SOC. Chem. Ind. 1917 35 107). -Vulcanisation of caoutchouo with from 1 to 4% of dinitrobenzene or trinitrobenzene at 140° is possible in the additional presence of a considerable proportion (for example 8 to 30%) of lead oxide or magnesium oxide; the trinitro-compound is more effective than its dinitro-analogue whilst with nitrobenzene itself satisfactory results are not obtainable. The nitrecompound enters almost entirely into combination with the caoutchouc and is not removable by acetone.The products possess poor mechanical qualities relative to caoutchouc vulcanised in the ordinary way with sulphur. Benzoyl peroxide also effects vulcanisation and in this case^ no third sub- stance is necessary; from 4 to 6% of the peroxide is required and a vulcanisation period of ten to fifteen minutes at 130-135O. The products are weak and have a remarkably pale colour. [See also Bunwhoten A. 1918 i 503; Ostromisslenski A. 1916 i 278.1 D. F. T.ORGANIC CHEMISTRY. i. 245 The Nature of Vulcanisation. I. The Combination of Rubber with Sulphur. 11. The Action of Solvents on Vulcanised Rubber.H. P. STEVENS ( J . SOC. Chem. lnd. 1919 38 192-196~).-The results on which Harries and Fonrobert (A. 1916 i 659 733) base their opinion that vulcanisation of caout- chouc is essentially a physical procms and may occur without any appreciable combination with sulphur are probably explained by unsuitable conditions of experiment. Under similar conditions but with the additional precaution of vulcanising the mixture of caoutchouc and sulphur in thin sheets so as to ensure greater uniformity of heating and consequently of vulcanisation the author obtained a product which after exhaustive extraction with acetone retained more than 1% of combined sulphur. It is therefore not possible to effect ordinary vulcanisation without the concurrent fixation of an appreciable proportion of sulphur.With an increasing proportion of combined sulphur caoutchouc becomes less and less soluble in solvents such as ben!ene; freshly vulcanised samples containing 0.27% and 0.39% of combined sulphur could be dissolved in benzene whereas 0.45% prevented solution ; after storage for three months none of these samples would pass com- plet.ely into solution. The extract obtained on treating more highly vulcanised caoutchouc with hot benzene contains the same proportion of combined sulphur as the undissolved residue. D. F. T. Autoxidation of Colophony. LUDWIG PAUL (Kolloid Zeitsch. 1919 25 241-246).-The constituents of colophony are investi- gated and some of t.he products examined and characterised. When a solution of colophony in alkali is treated with hydrochloric acid a voluminous precipitate of y-pinic acid is obtained; this sub- stance has m.p. 75-76O which in eight months rises to about 88O. a-Pinic acid has a constant m. p. 81-83O and shows a tendency to form liquid crystals. It is soluble in water and petroleum as also is y-pinic acid. 8-Pinic acid melts at 98-looo (compare A. 1918 i 411). J. F. S. Compounds of High Molecular Weight. I. Synthesis of some Acylglucosides of High Molecular Weight. SVEN ODEN (Arkiv Kern. &€in. GeoE. 1917 6 No. 18).-Almost all known organic compounds of high molecular weight are natural products of indefinite constitution and extremely difficult to purify circumstances which are great obstacles to the study of their physicechemical properties.The author has now synthesised a series of esters of 2 4 6-tribromophenol-d-glucoside with a view to a study of the variation of their properties with molecular weight. The esters were prepared by E. Fischer’s procew for which the most suitable conditions in this case consist in treating a suspension of the finely divided glucoside in dry chloroform with excess (about onethird) of the acid chloride and quinoline a t a b u t 50°. The product was usually isolated by precipitation from the solution by VOL. CXVTII. i. ki. 246 ABSTRAUM OF CHEMICIAL PAPERS. alcohol and purified by repetition of the treatment the bromine content furnishing an effective criterion of purity. The constancy of melting point of the products renders it improbable that the use of quinoline caused any stereoisomeric change during the reac- tion.All the products were stable indifferent substances and slightly laevorotatory . With the exception of the tetrapropionate the tetrabenzoate and the tetra-pbromobenzoate which are crystal- line they were amorphous substances resembling stearin or fats and in their aspect and solubility relationships lipoid in character. It is noteworthy that the tetrabenzoate exists in two intercon- vertible forms an amorphous form m. p. 94O and a crystalline m. p. 147O the difference in m. p. being apparently conditioned by the variation in granular size (compare Pawlov A. 1910 ii 1033). The following derivatives of 2 4 6-tribromophenol-d-glucoside are described the tetra-acetat e C,H,O,,Br needleshaped crystals m.p. 195-196O ; the tetraproportate CaH2Q010Br3 prisms m. p. 89-5O; the tetrdaurate C60H101010Br3 resembling fat m. p. 48-49O; the tetramyristate C,,H,,,01.$3r m. p. 56-57O; the tetrapalmitate c76Hl&luBr3 resembling stearin m. p. 61-62O ; the tetrastearate CsaH149010Br3 resembling stearin m. p. 70-71° in tetqrachloroiithane solution [a]iO - 3-6O; the tetra- hexabromosfcarnte CNH12501,Br27 fairly hard m. p. 1 5 2 O ; the tetracerotate C,,6fl,,,oloBr3 solid m. p. 80-81O; the tetra- benzoate C,,H2,O1,Br m. p. as above; the tetra-p-bromobenzwte C40H25010Br7 m. p. 115O amorphous 214O crystalline (aggregates of needleshaped crystals) ; the tri-P-mphthoate C45HS109Br3 m. p. 175O; the tetra-P-naphthoate C,H,,O,,Br m. p. 218O. In addition the following were prepared from a-methyl-d- glucoside the tripdmitate C6,H1,40 amorphous m.p. 77O; the tristearate c61H1(&9 amorphous m. p. 82O ; the tetrastearate C79H150010 amorphous m. p. 68O ; the tetruip-bromob enzoate C,H,OloBr4 needles m. p. 148O. J. K. Compounds of High Molecular Weight. 11. Some Acyl Derivatives of Natural Glucosides of High Molecular Weight. SVEN ODEN (Arlciv Kern. Min. GeoE. 1918-1919 7 No. 15 1-22) .-The method of acylation previously described (see previous abstract) gives good results when applied to natural glucosides and has the advantage over older methods of giving completely acylated products. In several casa t9he products were crystalline with a sharp melting point but the granular size was again observed to have a distinct influence on the melting point; in all cases this was depressed by precipitation of the amorphous or microcrystalline form by alcohol from a solution of the crystalline form in chloro- form.The chlorides of /3-naphthalene- and a-bromocamphor-r- sulphonic acids were also used this being the first occasion on which sulpho-derivativw of members of the sugar group have been pre- pared. I n these oases however a temperature above 50° was necewary for the condensation the reaction proceeded less smoothly,OBGANIO OHEMISTRY. i. 247 the resulting compounds were impure and the yields only about 30%. The products were very friable and appeared under the microscope as small strongly refractive glassy spheres. In the impure condition they are not dissimilar from the oxidation pro- ducts of sulphite liquors.The following derivatives are described. Salicin :-pentacinnamate C58H430,2 needles m. p. 173O [a] + 46*5O Pentaphenylpropionate C58H58012 long needles m. p. 58O. [u]? - 3*5O and penta-p-bromobenzoate C,8Hs301&3r needles m. p. 15B0 [a]:. + 30.2O. Helicin :-tetracinnumate C4&!&1 prisms m. p. 176O [a] + 7 7 ~ 3 ~ (p- bromophenylhydrazone C,,H,,O,,N,Br amorphous m. p. 118-120° decomp.) tetrapalmitate C77H136011 amorphous m. p. 68O (p-bromophenylhydrazone CBH14101,N2Br amorphous m. p. ca. 45O). Coniferin -pentacinnamat e C61H52013 amorphous m. p . ca 145O and tetrastearate C85H158012 amorphous m. p. 69-70°. Amygdalin :-heptabenzoate C,gH,,Ol,N small needles m. p. 2 1 8O [a] - 1 0 *5 O h epta-p - ch 1 or o b en z oat e C,$?,,O 18NC17 crystal,s m.p. 234O slightly kevorotatary heptep-bromobenzoate C69H48018NBr7~ needles m. p. 229O hepta-anisate C,6H69025K amorphous m. p. 117-119° [a]io + 13.2O and heptmtea?-ate C,~,I~E~O,~N amor- phous m. p. 92O [a]:”5 - 8.40°. Phlwidzin :-heptu-p-bromobenzoat e C70H4 j01?Br7 amorphous m. p. 130-132O [a]:‘ + 19.5O and heptapalmztate C,33H231017 amorphous m. p . 51° [a]:”” - 9 ~ 5 5 ~ . a-Met hyl-d-glucoside -t e tm-P-naph t hdenesulphonat e C47H35014S4 snow-white powder m . p . 14 7 O tetra- a-b rom o camph or-T -sul ph o 11 ate C47H,,0,8Br4S4 glassy spheres m. p. 150° [alD +12S0 and tetra- palmitate C,1H131010 needles m. p. 69O [a) + 46.9O. 2 4 6-Trzbromophenol-d-$ucos~e :-tetra-a-hromocamphor - m - sulphonate C,2H650,8Br7S4 amorphous m. p. 18l0 [a] + 75.1O. All optical data refer to solutions in chloroform.Compounds of High Molecular Weight. 111. Derivatives of Raainose and of some other Sugar Derivatives of High Molecular Weight. SVEN ODLN (Ad& Kern. Mzn. Gcol. 1918-1919 7 No. 15 23-38).-The eleven hydroxyl groups of raffinose render this compound a very suitable starting point for the synthesis of derivatives of high molecular weight. The method of acylation already described was successfully applied in this case and gave completely acylated products (contrast Stoll6 A. 1901 i 189) ; but the reaction took place more slowly and some material was always recovered unchanged ; sulphonyl chlorides react still less readily than those of carboxylic acids. The products were all amorphous and definitely uniform except possibly the hendecahexabromostearate.Amorphous derivatives were also obtained from saccharose but mannitol and dulcitol furnished crystalline products. From inositol only the hexa-pbrornobenzoate could be obtained. J. K. The following derivatives are described. k 2i. 248 ABSTRAOTS OF CHEMICIAL PAPERS. kufinose :-hendecabenzoate CQ$~@ m. p. 113O [ a j f 5 + 106.8* I~erLdecu-p-chlorobenzoate CQ5H65~27Clll m; p. 130-132O hendeca- p-bromo6enzoute CQ5H6502713rll m. p. 136-138O [a;:' + 85.2' lLe?idecapalmitate Clg4h&2 m. p. 53O [a]:' i- 31*8° hendeca- stearate C216H406027 m. p. 62O [a] + 28*3O hendecacerotate c&&8208 m. p. 6B0 hendecahexubronaostearate C216H340027BrS6 m. p. 147-14B0 [ a ] D ca. + 1 Z0 and hendecanaphthalenesuiphmte c128~g8o~Sl1 m.p. ca. 126O. Sucrose :-octacinnamate C84H70019 m. p. 87-88O [a]? + 12-5O and octa-p-bromobenzoate C68H4601gBr8 m. p. 116-118° [alD + 2 7 O . ihdcitol -hexa-p-chlorobenzoate c4,H,o,,c16 m. p. 238O and hexapalmitate Cl@H,Q& m. p. 74O both optically inaotive. d-Mannit ol -hexa-p-bromob enzoat e C4sHz0,,BF6 prisms m. p. 96O La] +.29*6O. lnositol :-hexa-p-bromobenzoate C4,Ha0,,Br6 prisms m. p. 264O optically inactive. All optical data refer to solutions in chloroform. Diastereomeric Acyl Derivatives of some Sugars. J. K. SVEN ODEN (Arkiv Kern. Min. Geol. 1918-1919 7 No. 16 1-16).-- The acylation of d-glucose by treatment with acid chlorides and yninoline required some days for completion at temperatures of 30-70°. I n all cases the product corresponding in its sparing solubility in alcohol with those obtained in other instances (see pre- ceding abstracts) was accomp'anied by an isomeride easily soluble in alcohol and differing in m.p. and specifio rotation. The less soluble modifications were also obtained as sole products by the acylation of P-&glucose usually a t rather higher temperatures and are therefore to be derived from &?-glucose whilst the more soluble forms correspond with ad-glucose. Similar results were obtained with &galactose and 2-arabinose. In these cases the author designates the parent sugar of which only one solid form is known and that modification of the acylated sugar which is andogous in respect of melting point specific rotation and solubility. The following com- pounds are described pemta-anisoyl-d-glucose C4(&@16 a-form m.p. 98O [ a ] ~ ' * +103O and the &form amorphous m. p. 1 7 5 O [a]zo + 110 ; penta-p-nitrobenzoyl-d-glucose C41H27021N5 a-form m. p. 235O (decomp.) [a] +176O soluble in chloroform and the @-form m. p. ca. 2 6 5 O (decornp.) insoluble in chloroform; penta- p-bromobenzoyl-d-glucose C41H,70,,Br5 a-form crystals m. p. 1 9 7 O [aID +110° and the &form amorphous m. p. 220° [a] + 83O ; penta-p-bromob enzoyl-d-galuctose C41H27011Br5 a-form needles m. p. 130° [ a ] D +45O and the &form prisms m. p. 207-5O [a] + 1 0 7 O ; tetra-p-bromobenzoyl-I-arabinose a-form m. p. 205O [a]? +383O and the &form m. p. 118O [a]; + 228O ; hexa-p-nitrobenzoyldulcitol C48H32024N6 crystals m. p. 2 65-268O ; oct clrp-nitro b enzo ylsucrose CS8H460~5N8 amorphous m. p.150° (dwomp.) ; tetra-p-nitrobenzoyg2 4 6-tribromophenoh d-ghcoside C,oH,,013N,Br amorphous M. p. %To r a ] D - 39'; C33H,O,Br,,ORGANIC CHEMISTRY. i. 249 and tetrapuZmity2-1-arubinose C69H,3409 amorphous m. p. 69*5O [a]; +4O. All optical data refer to solutions in chloroform. The Theory of Colour Lakes. Catalytic Reduction of Furfuraldehyde. J. K. C. BRENNER (Helv. Chim. Acta 1920 3 90-103).-See t'his vol. ii 194. HANS PRINGSHEIM and HARTMUT NOTH (Ber. 1920 53 [ B ] 114-118).-The hydro- genation of furfuraldehyde has already been studied by Padoa and Ponti (A. 1907 i 146) and that of furan by Bourguignon (A. 1908 i 280). A new study of this subject has now supplied a con necting link between the earlier results. By arranging that the furfuraldehyde is exposed to the reduced nickel as much as possible the authors have obtained furan 1-methylfuran and a dihydro- furan bmides the products described by Padoa and Ponti. It appears therefore that the hydrogenation of furfuraldehyde proceeds in three ways concurrently (I) reduction of the aldehyde group as far as methyl and then hydrogenation of the ring; (11) expulsion of the aldellyde group with the formation of furan and further hydrogenation; and (111) rupture of the ring and formation of pentan-P-ol and methyl propyl ketone.Some Reactions of Calcium Hydride. SIGISMOND REICH and H. 0. SERPEK (Heh. Chim. Acta 1920 3 138-144).-The present investigation was undertaken on account of the importance of calcium hydride as a reducing agent particularly in organic chemistry and also because the data recorded by Moissan by Erd- mann and van der Smissen (A.1908 ii 587) and by Mayer and Altmayer (A. 1908 i 845) are discordant in many respects. Carbon monoxide is reduced by calcium hydride heated to dull redness with the formation of hydrogen methane and form- aldehyde rather more than 16% of the carbon monoxide being converted into the latter. When a mixture of the hydride with sodium hydrogen carbonate is gently heated formic acid is pro- duced the yield being 13.2% of that theoretically possible; a similar result is obtained when normal sodium carbonate is used. Ammonia is formed in small amount when nitrogen is passed over calcium hydride a t about 500° but the main reaction appears to consist in the formation of calcium nitride 3CaH + N f C%N + 3H2. J.C. W. Acetone reacts energetically with finely divided calcium hydride giving mesityl oxide b. p. 128-130° and 0 the mbstance (annexed formula) b. p. 226-236O ; acetophenone also yields con- MeR G*CBMe densation products with calcium hydride CHMe,*C CMe a t 240° but these have not been fully investigated. Quinoline is converted at 220° into BP-diquinolyl needles m. p. 190° whilst pyridine at 160-165O yields a small quantity of crystalline matter /\ \/ 0i. 260 ABSTRACTS OF CHEMICAL PAPERS. m. p. 54-56O which does not appear to be identical with any known dipyridyl. Other organio compounds such as ethyl acetate benzene nitro- benzene and anthraquinonel did n o t appear to react with calcium hydride under varying conditions of temperature.Calcium hydride therefore only appears to react as a reducing agent at very high temperatures and its use in the hydrogenation of organia compounds must be very limited the more so since its action when it does occur appears t o lead preferably to condensations. When calcium hydride is added to an ethereal solution of ferric chloride hydrogen is evolved and a brown precipitate is produced which is soluble in water to an acid solution; its composition is represented by the formula Ca3FeCl,(C,H,,0)3. Dipicrates of Arginine and Histidine. L. HUGOUNENQ and G . FLORENCE (Bull. SOC. Chem. Biol. 1919 1 102-106).-The dipicrates have been prepared by the action of picric acid on the monopicrates in ethereal solution. H. W. A r,qinine dipicrate C,H,?O,N,,(C,H,O,N3)2 m.P. 156O (corn.) forms spherules of fine needles and histidine di&rate C,H,0,N~,(C,B30;N,),,5H~07 long needles; m. p. T A ~ 80°. J . b. u. Synthesis of some Purine Glucosides . BURCRHARDT HELFERICH and MALTE VON K~~RLEWEIN (Ber. 1920 53 [B] 17-22. Compare Fischer and Helferich A. 1914 i 333).-By the interaction of the silver salts of purines with acetobromo- galactose and acetobromoarabinose followed by hydrolysis of the acetates with methyl-alcoholic ammonia further purineglucosides have been obtained as follows. Tetraiace tylt h eophylline-d -galacto- side C,H7O2N4*C,H70,Ac4 has m. p. 135-137O (corr.) [al; - 13*97O 12*96O in toluene and thpophy2Zin ed-,qntncfoside forms long needles m. p. 251O (corn.; decomp.). [a],” +23.45O in water.Tetra-acetyltheohromine-d-galactoside crystallisps in microscopia needles m. p. 208O (decomp.) [a]:’ +9*76O in chloroform and theobromine-d-palactoside forms minute needles with 2R,O decomp. above 150° and is very speedily decomposed by water. Triacetyl- theophylline-l-arabinos2e forms thin rhombic plates m. p. 214-216O [a] + 43*34O in s-tetrachloroethane. and theophylline- 1-arabinoside crystallises in slender needles m . p. 276-277O r.1” +34*08O in water. The Condensation of Ethyl Acetoacetate with p-Dimethyl- aminobenzaldehyde and Ammonia. LEONARD ERIC HINKEL and HERBERT WILLIAM CREMER (T. 1920 117 137-140). Influence of Hydrogen-ion Concentration on the Volatility of Indole from Aqueous Solution. HARPER F. ZOLLER (J. BioE. Chem. 1920 41 37-44) .-The range of most rapid volatilisation of indole from the aqueous solutions studied is from p 8.0 to 10.5.This has led t o the adoption of direct distillation in the separation of indole (this vol. ii 203). J. C. W. J. C. D.ORGANIC CHEMISTRY. i. 251 Ring Closure in the Meta-position in the Benzene Series. 11. Reduction of m-Xylylene Dicyanide. J ULIUS VON BRAUN (FRL.) L. RARPF and W. VON GARN (Ber. 1920 53 [B] 98-109. Compare this vol. i 87) .-When m-xylylene dicyanide is reduced by means of sodium in alcohol the normal product the primary diamine forms only about oneseventh of the yield. The chief product is a saturated secondary amine of the formula (I) or (IT). It yields isophthalic acid on oxidation and the quaternary ammonium hydroxide obtained from it after treatme'nt with methyl iodide losea not only water but also dimethylamine on distilla- tion giving an unsaturated hydroca.rbon (111) or (IV).This may ( > - C H ~ ~ H ~ - CII CH (III.1 (W.1 be reduced to a saturated hydrocarbon and both compounds yield isophthalio acid on oxidation. This result indicates theref ore that contrary to all experience the two meta-carbon atoms in the benzene ring may be connected not only by a chain containing nitrogen but by a simple carbon chain also. m-Di-8-aminoethylbenzene C,H,(CH,*CH2*NH2)2 is a colourless liquid with b. p. 165-170°/20 mm. It absorbs carbon dioxide from the air forms a dihydrochloride m. p. 290° a platinichloride m. p. 238O and a picrate m. p. 238O. Unlike the corresponding diamine of the ortho-series (A.1917 i 130) i t reacts with methyl iodide to form a bispuat ernary iodide C,H,( CH2-CH,*NMe31)2 m. p. 212O. The secondary amine (I) or (11) has b. p. 97-98O116 mm. and forms a hydrochloride m. p. 160° a platinichloride m. p. 232O a sulphur-yellow picrate m. p. 176O a benzoyl derivative leaflets m. p. 72O a phenylthiocurbamide C,,H,,N*CS*NHPh leaflets m. p. 8 7 O an oily nitroso-compound and a quaternary methiodide C,,H,,NMe$ leaflets m. p. 236O (corresponding chloride and platinichloride C,H,,N,Cl,Pt m. p. 228O). It also - reacts _ _ with o-xylylene dibromide to form the compownd c?,,R,,N<~ H2>C6HI I CH Br m. p. 168-169O. The unsaturated hydrocarbon (111) or (IV) is a mobile liquid with intense characteristic odour b. p. 62-63O/ 18 mm. Dig 0.900 (unusually low compared with t*he isomerio hydrocarbons C,,H,,) n:" 1.54029.It polymerises like styrene and forms a dibrmide m. p. 48O. On reduction by means of colloidali. 252 ABSTRACTS OF UHEMICAL PAPERS. palladium it yields the hydrocarbon Cl0Rl2 which is a mobile liquid with pleasant odour and abnormally low density b. p. 50.5-51.5°/14 mm. D:7'3 0,852 n?.' 1.4968. J. C. W. Preparation of 3 6-Diaminoacridine. POULENC FR~RES and ROBERT MEYER (Brit. Pat. 137214).-m-Pheaylenediamine is melted a t 130° with formic acid or oxalic acid and glycerol o r other polyhydric alcohol and a condensing agent such as anhydrous zinc or calcium chloride; when the evolution of carbon dioxide has ceased the temperature is raise'd to and maintained for two hours at 150-170° and the diminoacridine is isolated from the resultant almost solid mass by treat>ment with water and ammonia. It may be purified through its sulphate which is sparingly soluble in very dilute sulphurio acid.[See further J . SOC. Chem. Znd. 1920 March.] C. F. M. Rhodanines. CH. GRANACHER (BeZu. Chim. Acta 1920 3 152-163).-The author hw attempted to elucidate the constitu- tion of Nencki's rhodanine red but great difficulty has been ex- perienced in purifying the dye since it could not be caused to crystallise; analyses of the product moreover show it to be more complex than was anticipated. It has however been shown that the imino-hydrogen of the rhdanine is not concerned with its oxidation by ferric chloride since N-substituted rhodaninea such as 3-phenylrhodanine also yield red dyes under suitable conditions.On the other hand benzylidenerhodanine is not affected by ferric chloride so that the presence of a free methylene group appears ewential t o the production of a dye. Rhodanine appears to be tautomeric with 4-hydroxy-2-thiol- thiazole. since i t can be readilv transformed in alkaline solution into C(SBz)r whilst if the s<cH=c *OBz' the colourless benzoyl derivative methylene hydrogen atoms are substituted as in benzylidene- rhodanine the yellow monobenzoyl derivative S<c( CIIPh). 6 o is produced. Alkylidenerholdanines react with aniline and phenyl- hydrazine to yield the corresponding phenylhydrazones and anilides the sulphur of the thi*keto-group being removed as hydrogen sulphide. Since aniline is comparatively readily re'moved from these anilides they can be employed for condensing the rhdanine molecule with compounds containing a reactive methylene group ; in this manner benzylidenerhodanineanilide can be con- densed with a second molelcule of NH-Co I NH-Co I 1 rhodanine to yield 5-benzylidene-5'- S6 C-=C C:CHPh rhodanylidene - 2 - rhodanine (annexed formula). Reaction with aniline or phenylhydrazine proceeds in a totally different manner with rhodanines such as N-phenylrhodanine which contain the free methylene group ; in C(SBz)==N \/ S \/ SORGANIC CHEMISTRY.i. 253 this case the sulphur of the thio-keto-group remains unaffected aiid complete fission of the rhodanine ring occurs with formation of thiocarbamides or thiosemicarbazides reaction occurring so readily that the process is conveniently used for the preparation of the latter class of substances.The following individual substances are described dibenzoyl- rhodanine colourless needles m. p. 126O ; 5-benzylidene-2-henzoy/- n2ercnptothiazoline deep yellow leaflets m. p. 151-152O ; 5-benz?yl- idenerhodnnine-2-pken?/Th?/dmzolle orange#-red leaflets m. p. 219O after softening at 21 Oo ; 5-p-di?,teth?/lamino~)enzyli~?en erhodanin e- 2-phenylhydrazone red leaflets m. p. 282O (decomp.) ; 5-henz?yl- iden erhodnnine-2-nnilide pink leaflets m. p. 252-253O after softening at 248O ; 5-p-dimet hylnmin obenzyliden erhodanine-2- anilide. dark yellow leaflets m. p. 308O (hydroslysis of the two sub- stances last! named leads to the formation of 2 4-diketod-benzyl- idenethiazolidine yo-S>C:CHPh m.p. 238-240° and of 2 4-diket 0-5-p-dime thylaminoh en zylidene t hiazolidin e long orange- yellow needles m. p. 296O respectively) ; 5-benzylidene-5/- ?*hocZan?ylidene-2-~hodn;nin e brown leaflets ; ~iphen?~lthiocnrhnn~i~?e colourless leaflets m. p. 151-152O ; diphenylthiosemiccwbazide long colourless needles m. p . 176-177°. ?JH*CO H. W. Acyl Substituted isoThiohydantoins . AUGUSTUS EDWARD DIXON and RAYMOND THOMAS JOACHIM KENNEDY (T. 1920 117 74-79). p-Cymylene-2 6-diamine and the Formation of 2 4-Di- nitrotoluene by the Nitration of p-Cymene. J. ALFTHAN (Ber 1920 53 [B] 78-98).-With a view to the utilisation of the large quantities of pcymene which accumulate in the sulphite-cellulose industry (1 kilo. per ton of cellulose) Aschan has studied the nitra- tion of the hydrocarbon (Fin ska K em Gt sum ficnde ts M eddelnnde n 1916 25 122).The conditions finally adopted and now described are the gradual addition of one part of cymene t o a mixture of t,wo parts of nitric acid (D 1.5) and four parts of sulphuric acid (1.84)) the temperature being kept below Oo. The main product is a crude dinitro-derivative which may be reduced to a crude diamine. When this is examined it is found to consist of some 2 4-tolylenediamine but chiefly p-cymylene-2 6-diamine a new base. Thel occurrence of the toluene derivative theref ore suggests t h a t 2 4-dinitrotoluene is present in the nitration product the isopropyl group having been expelled by a nitro-group. The mechanism of this displacement is discussed but various probable suggestions are negatived by experience and the question is left open.There also seems to be little hope of making the dinitro- toluene the main prodixct and so utilising cymene as a source of trinitrotoluene. The separation of the products of nitration is a difficult matter xs"i 254 ABSTRACTS OF CHEMICAL PAPERS. distillation under reduced pressure being the be& method. The crude product is partly oily and partly solid the latter yielding 2:4-dinitrotoluene m. p. 70° b. p. below 161°/6 mm. and 2 6-dinitr*p-cymene m. p. 54O b. p. 161-163O'/6 mm. The oil contqins in addition cymene p-tolyl methyl ketone and it mono- nitrocymene which can be converted into the above dinitro- cymene. The crude dinit'ro-compounds are relduced by means of tin and zinc and hydrochloric acid (tin a t ths commence'ment zinc after the reaction ha5 set in) and the crude diamines separated by fractional distillation under 15 mm.preissure. 2 4-Tolylenediamine purifield by crystallisation from benzene! forms pale yellow very hard needles m. p. 98-99O b. p. 160-168°/15 mm. and p-cymylene-2 6-&mine [Me Prb NH2 NH,=1 4 2 61 separates from 20% alcohol in glistening tlhin leaflets m. p. 95-96O b. p. 300-300.5°/768 mm. 158-162°/10 mm. 0.7469 gram dissolving in 100 grams of watelr at 25O. The following salts of pcymylelne-2 6-diamine are described hydrochloride needles delcomp. 180-200° ; characteristic zincichlwide decomp. 250° ; ktrate long' l&fIe& decomp. 170° ; hydro!jen oxaylate B,2H2C204 rods m. p.188-189O (decomp.); and thio- cyannte neidles m. p. 137O. crystallism in thin needles m. p. 254O and yietlds a 3-nitro-com- pound neledles m. p. 280-282O which may be hydrolysed to 3-nitro-p-cymyylerce-2 Gdiamine yellow needles m. p. 1 8 7 O . The dihenzoyl derivative forms needles m. p. 246-247O. Condensation products of the . cymylenediamine are as follows with formaldehyde 2 6-bismethyleneimino~p-cymene m. p. 170-180° (decomp.); from the ohloride and potassium cyanate or thiocyanate 2 6-dicarhnmido-p-cymene needles m. p. 270-280O (decomp.) and 2 6-dithiocarbamdo+p- cymene m. p. 165-175O (decomp.); with carbon disulphide and alcoholic potassium hydroxide 2-methyl-5-isopopyl-1 S-phenylene- t hiocarb m i d e CH*C-NH CPrP/ >CMe )09 m. p. 157-158O; and with alcoholic oxalia acid m-amircocymyl- oxamic acid NH,*C,,H,,*NH*CO*CO,H m.p. 217-218O (decolmp .) . The following dyes havel also' been prepared a dark red hydrolxyazo-dye C,oH,0,4N4S4Na4 by diazotising a t a low tempera- ture to avoid the production of a Bismarck-brown and coupling wlth sodium &naphthol3 6-disulphonate ; a chrysoidine of the The diacetyl desivative CIO'HdNHA42 CIOH12(N:CH2)2 C:loH,z( NH CO-NH,) \CH C-NHORGANIC CHEMTSTRY. i. 255 formula (I) reddish-yellow cubes m. p. 114-115° by coupling with diazotised o-toluidine ; and a brownish-yellow eurhodine m. p. Me N Me N C8H7 (11.1 NH (1.1 177-17S0 of the formula (11) by condensation with p-nitroso- dimethylaniline. J. C. W. 2-Nitro-4-cyanobenzaldehyde and 6 6'-Dicyanoindigotin. S. REICH and E.LENZ (Helv. Chim. Acta 1920 3 144-151).- 2-Nitro-p-toluonitrile colourless shining needles m. p. 107O is prepared from 2-nitreptoluidine~ by a modification of the method of Niementowski and Noyes and is converted by pnitrosodimethyl- aniline in alcoholic solution in the presence of sodium carbonate into p - c~~methylnminophen,~Z - 2 - nitro - 4 - cyunophenylazomethine [2 -nitr0-4-cym.nob enzy Zidene- p-ph my Ten edimet h yldinmine] NM%*C,H,*N:CH *C,H,(CN) (NO,) almost black needles m. p. 182.5-183O (decomp.) which is hydro- lysed by hydrochloric acid yielding 2-nitro-4-cyanahenzaldeh?yde red needla m. p. 110'. The latter yields an oxime red needles m. p. 142-143' and a phenylhydrazone bright red crystals m..p. 202-203' (decomp.) which could not be converted by potassium hydroxide in aqueous-alcoholic solution into an isoindazole deriv- ative a fact which is interpreted as further evidence in favour of Reich's views on the influence of the accumulat>ion of atoms and atomic groups round the aldehydic carbon atom on such condensa- tions (compare Reich and Nicolaeva A.1919 i 171). The aldehyde when dissolved in benzene is converted by exposure to sunlight into 2-nitroso-4-cyanob enzoic acid small yellow crystals which begin to darken at about 210° and have m. p. 250° (decomp.). When a solution of the aldehyde in acetone is treated with dilute sodium hydroxide solution 6 6'-dicyan&digotin is deposited as a bluish-violet powder with metallic lustre ; when heated i t does not sublime but decomposes with evolution of reddish-violet vapours.When reduced with sodium hyposulphite i t dyw wool and cotton from an alkaline bath in reddish-purple shades which become blue with a tinge of violet on exposure to air oxidation proceeding more slowly than with indigotin. The1 shades are fast to light and milling. Preparation of Easily Soluble Compounds of the CC-Di- alkyl- CC-Diallyl- and CC-Alkylaryl-barbituic Acids F. HOFFMANN LA ROCHE & Co. (Brit. Pat. 122778).-Easily soluble compounds of these acids are obtained by combining them with alkylamines for example diethylamine or dimethylamine by add- H. W. E' 2i. 256 ABSTRACTS OF CHEMICAL PAPERS. ing rather more than the theoretical amount of alkylamine to the free acid so that the latter is dissolved and then evaporating off the excess of amine.The products are more powerful hypnotics than the fre,e acids and much more stable in aqueous solution than their sodium salts. Action of 0- Amino thiophenol on Orthopinones. I . 5-Imino-7 12-naphthaphenthiazine. KNUT SrmRFoss (Heh. Chinz. A cta 1920 3 134-138) .-o-Aminothiophenol hydrochloride reacts with 4-amino-1 2-naphthaquinone in boiling 80% acetic acid solution with formation of 5-imino-7 12- napht haphen,t hiazine ltydroc hloride a choco- late-brown powder which is stable in air and was analysed. The free bdse (annexed //\/\/\/ formula) is an unstable yellow substance. HN S The constitution of the substance follows from the conversion of the hydrochloride by con- centrated sulphuric acid into a naphtllaphenazthione identical with that formed from o-aminothiophenol and 4-hydroxynaphtha- quinone.H. W. readily soluble in water. The pzatinichlode New Bases for the Preparation of Mordant Dyes. HEINRICH BAMBERGER (Zeitsch. otegew. Chem. 1920 33 i 8).-The chlorides of o-nitrophenol-psulphonic acid 6-nitro-o-cresol-psulphonic acid and 6-nitrosalicyl-p-sulphonic acid obtained by treatlment of their potassium salts with chlorosulphonic acid react quantitatively with aromatic amines diamines amino-carboxylic acids or amino-phenols and with amino-sulphonic acids or amino-phenolsulphonic acids of the benzene or naphthalene series. By reducing the resulting sulphamidc-compounds with sodium sulphide valuable bases are produced for mono- and bisazo-mordant dyes which give colours raaging from yellow t o bluish-violet (compare Swiss Pat.81249-81256; Fr. Pat. 490177 [1918] ). J. I(. Certain Salts with para- ortho- and meta-Quinonoid Structure. R. CIUSA (Atti R. Accad. Lincsi 1919 [vl 28 ii 366-371).-1n contact with alkali best in acetone solution p-nitrophenylhydrazones are turned violet addition of water to the solution o r acidification yielding t,he initial hydrazones unchanged. That t3he corresponding salts which are easily obtainable differ in structure from the nitrohydrazones themselves is shown by their diffe'rent colour in solution and by their different absorption spectrum. To explain the intense d o u r of these salts the simple auinonoid constitution is insufficient the assumption of the more I NO M ..................... complex formula CsH~~Nr.SN:CHPhl.,,..l in which the metal M is united by secondary vale&ies to the rest of the molecule being necessary; the position a t which the secondary valencies act is still uncertain.Similar complex formulae are attributed to all theORQANIC CHEMISTRY. i. 257 quinonoid salts dealt with in the paper. The foilowing salts have been prepared the potassium salt of benzaldehyde-y-nitrophenyl- hydrazone CHPh:N*N:C,H,:NO,K ; the disodium salt of benzyl ide,nepyruvic acid-pnitrophenylhydrazone *CHPh:CH*C(CO,Na) :N*N:C,H,:NO,Na ; the dipotassium salt of benzoylglyoxylic acid-pnitropheiiylhydr- azone CO,K*CBz:N*N:C,H,:NO,K. I n alcoholic or acetone solution 0-nitrophenylhydrazones also dissolve in alkali the solutions assuming a blue coloration. Crystal- line salts of benzaldehyde-o-nitrophenylhydrazone have not been obtained although the sodium salt (I) certainly exists in solution CO~K-CB~:N-N:/-\ \J CH Ph :N*N :/\ N 0,K \J N0,Na (1.1 (11.) but the dipotassium salt of benzoylglyoxylic acid-o-nitrophenyl- hydrazone (11) has been prepared in shining bronze-coloured crystals or as a blue powder.It has been stated that benzophenonem-nitrophenylhydrazone does not undergo salt formation in contact with alcoholic potassium hydroxide. The author finds however that a very slight change of colour does take place under these conditions and that in acetone solution m-nitrophenylhydrazones give a green coloration with the alcoholic alkali addition of water then resulting in the formation of the unaltered nitrophenylhydrazones. The absorp- tion spectaum of such an alkaline solution differs from that of the original hydrazone and persists even on dilution of the liquid I n this case i t has not been found possible to obtain crystallised salts but it may be assumed that the salt formation occurs with change from the benzenoid to the m-quinonoid structure CHPh:N*N:C,H,:NO,M ; such m-quinonoid saline compounds are certainly readily hydro- lysable and the tendency to their formation small.The experimental results are to be published elsewhere. T. H. P. Amine-oxidation. 11. Bivalent Nitrogen. Triphenyl- hydrazyl. STEFAN GOLDSCHMIDT (Ber. 1920 53 [B] 44-62).- When an ethereal solution of triphenylhydrazine (Wieland A. 1915 i 797) is shaken with lead peroxide a fugitive deep blue solution is formed which has the characteristics of solutions of compounds with bivalent nitrogen (Wieland ibid.848). This suggests that oxidation to hexaphenyltetrazane has taken place this being dissociated in solution into triphenylhyCTrazyZ thus By carrying out the oxidation in methyl ether a t - 5 5 O to - 60° tho tetrazan may actually be isolated as a very pale green crust which is sparingly soluble in chilled ether or light petroleum but more soluble in toluene or chloroform. The solutions are deep blue and 2NPh,*NHPh + NPh,*NPh*NPh*NPh + 2NPh2*NPh-... .... .....i. 258 ABSTRAOTS OF CHEMICAL PAPERS. do not obey Beer's dilution law thus confirming the idea of dis- sociation. The dissociation depends on temperature and on the solvent. For example ethereal solutions which are only pale greenish-blue a t -80° are deep blue a t the ordinary temperature and chloroform solutions are darker than ethereal solutions under the same conditions.The substance may be analysed by means of quinol this causing reduction to triphenylhydrazine when the liberated quinone can be titrated iodometrically. Triphenylhydrazyl is not sensitive to oxygen but combines with nitric oxide a t low temperatures to form N-nitrosotriphenylhydr- mine golden prisms m. p. 115O (Busch A. 1907 i 552). It also co'mbines with triphenylmethyl but this agent react8 too slowlx to permit of the isolation of a pure product before the tdphenyl- hydrazyl has decomposed. The decomposition of triphenylhydrazyl is accompanied by change of colour through green to reddish- brown the products being diphenylamine and quinoneanildiphenyl- hydrazone NPh,*N:C6H4:NPh (Wiedand A.191 1 i 82). Ethereal solutions of triphenylhydrazine also develop the blue colour of tri- phenylhydrazyl on exposure to sunlight and then yield the same decomposition products. When a mixture of aniline and triphenylhydrazine in ether is oxidised by lead peroxide benzoquinoneanildiphenylhydrazone is again formed. This is interpreted as the fusion of the two radicles NPh,*NPh* + :NPh + NPh2*N:C,H4:NPh (compare this vol. i 226) and is confirmed by the fact that a mixture of cumidine and triphenylhydrazine gives a homologous compound (annexed formula) which crystallises in the form of its hqdrochlorzde in bluish- Me Me<\-N:c,H4:N.Nph violet stout spikes m.. F. 152-153O. Both comDounds exhibit onlv one absorption band the aniline dehvative at 465-65Opp and the new one a t 475-525pp. The identity of the new compound is established by reduction to diphenylamine and p-amin~phenylcz~mylumine NH,*C6H,*NH-C,H2Mq concentric groups of needles m. p. 86-87O. These facts are discussed in connexion with Wieland's views on the decomposition of triphenylhydrazine. It is suggested that the products are best interpreted by assuming an initial dissociation into H and NPh,*NPh*. When triphenylhydrazine is treated with ethereal hydrogen chloride a t - 20° i t yields N-phenylbenzidine (Busch loc. c i t . ) . This is oxidised by lead peroxide in ether to diphenoquinonephenyl- di-imine NPh:C,H,*C,H,:NH yellowish-red needles m . p. 180-1 81 '. v Me J. C. W. Haemoglobin. I. Optical Constants. WILLIAM H. WELKER and CHARLES SPENCER WILLIAMSON ( J . B i d . Chem. 1920 41 75-79).-By employing the method of Marshall and Welker (A. 1913 ii 568) for removing small amount.$ of other colloids fromPHYSIOLOCIICAL CHEMISTRY. i. 259 haemoglobin solutions the authors were able to prepare purer speci- mens of crystallised hzmoglobin which could be used for the study of the absorption coefficients of the pigment from various specie. The results obtained indicate that there is not sufficient difference in the absorption coefficients of the hzmoglobin of various species to serve as a means of identification of the species. The Structure of Yeast-nucleic Acid. V. Ammonia Hydrolysis. P. A. LEVENE (J. Biol. Chem. 1920 41 19-23).- The fourth nucleotide cytidinephosphork acid C9H,,0,N3P m. p. 225O (corr.; decomp.) [a] +40-43O has now been obtained in a crystalline condition. There is a danger of error in assuming the existence of di- or tri-nucleotides on t,he basis of the resulh of elementary analysis for i t is shown that the free nucleotides as well as their brucine salts are capable of forming mixed crystals which may furnish analytical data very nearly approaching those required by polynucleotides. Crystalline Uridinephosphoric Acid. P. A. LEVENE (J. Biol. Chem. 1920 41 1-2) .-The crystalline diammonium salt of uridinephosphoric acid was converted into the lead salt which was decomposed by hydrogen sulphide. From the concentrated filtrate the free1 uridinephosphoric acid CgH,,OgN,P was obtained in a crystalline condition m. p. 202O (corr. ; decomp.) [a] + 10.5O. This research marks an important step in the chemistry of yeast- nucleic acid as every one of the four constituent nucleotides has now been prepared in crystalline form. J. C. D. J. C. D. J. C. D.

ISSN:0368-1769    

DOI:10.1039/CA9201800213

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

INOL1GANIC CHEMISTRY. ii 246 lnorganie Chemistry. Heat of Vaporisation of Hydrogen. W. H. KEESOM (Zeitsch. Sauerstoff Stickstoff I d . 1919 ii 83; from Chem. Zentr. 1920 i 147).-Dewar has determined the heat of vapor- isation of hydrogen to be 123WE; the author however gives the values 108.5-113.2 the greater probability of which is supported by theoretical considerations. H. W. Crystallography of Ice. F. RINNE (Ber. Verh. Sachs. Ges. IYiss. Math.-gat. Kl. 1917 69 57-62; from Jahrb. Man. 1919 Ref. 25-27).-The X-ray photograph of ice on the basal plane shows dihexagonal symmetry with a:c=1:1*678 but does not decide whether the crystal is hemimorphic or not. Ice belongs to the magnesium type of the author’s “isotypea” (A. 1916 ii 29) of which a tabulated list is given. L. J.S. TE~FILO ISNARDI (Ann. Physik 1920 [iv] 61 264-272).-The vapour preesure of solid bromine has been determined a t Oo - 10*9O - 1 5 * 5 O and -21*l0 by two methods (I) a manometric method and (2) by allowing the vapour of bromine a t measured temperature to fill a globe of known volume condensing and weighing the liquid. The values obtained are considerably higher than those determined by Ramsay and Young (T. 1886 49 453) except in the case of the value at Oo which lies vary near to that of Ramsay and Young. The following values are obtained Oo 65-83 mm.; -loago 35.37 mm.; -15.5O 24-95 mm.; and -21.l0 15.75 mm. Extrapolation of the vapour- pressure curve to -41.3O gives values which agree very closely with those obtained by Cuthbertson by his optical method (A.1911 ii 582). The triple point is calculated to lie a t - 7-3O and 46.4 mm. pressure. The vapour pressure of solid bromine is given by the formula log p= a/ T + b log T + c where the constants have the values a= -7109.142 b= -43.33195 and c=133*46929. The heat of sublimation is calculated t o 60.7 cal. per gram. J. F. S. Revision of the Atomic Weight of Fluorine. E. MOLES and T. BATUCCAS ( J . Chim. Phys. 1919 17 537-588).-See this vol. i 283. Vapour Pressure of Solid Bromine. Mass of the Litre of Air and Gas Mixtures. A. LEDUC (Engineering 1919 108 569).-A re‘sum6 of the more important of the results published by Leduo (Trav. Mem. Bureau Internat. Poids et Mesures 16). Two gases A and B both a t pressure P and of equal volume when mixed in double the volume have not the same pressure as before mixing but a pressure P+ E + where E and depend on the nature of the gasea.If the two gases are similar chemically (E. + EJ is immeasurable as for =ample is the 8*ii. 246 ABSTRACTS OF CHEMIOAL PAJ?ERS. case with a mixture of carbon dioxide and nitrous oxide but in the case of hydrogen and sulphur dioxide the mixture has a pressure 3 mm. greater than the pressure of the constituents. As regards the mixture of oxygen and nitrogen in the atmosphere E may be disregarded. The density of air has been determined by direct weighing of air and from the weight of the constituent gases. Paris air has the follo'wing composition by volume (carbon dioxide and water vapour having been removed) oxygen 0*2100 ; nitrogen 0.7806; argon 0.0094; neon 15 x 10-6; helium 5 x 10-6; hydrogen 1 x 10-6; krypton 50 x 10-9 and xenon 6 x 10-9; by weight oxy- gen Cl.2321; nitrogen 0-7549; argon 0.0130; neon 8.4 x 10-6; helium 0.7 x hydrogen 0.07 x 10-6; krypton 140 x 10-9; and xenon 30 x 10-9.The rare gases with the exception of argon only affect the density of air in the fifth decimal place. A litre of air at Oo and 760 mm. weighs 1.2928 grams when g=980*665; under a pressure of 1 megabar if g is 980.97 and the density of mercury is 13.5951 the weight is 1.2759 grams. Samples of air collected all over France and Algiers and a t various altitudes show a weight per- centage of oxygen varying between 23.05 and 23.25%. The oxygen percentage is lower in the north of France and there is generally lets oxygen close to the soil than at the height of foliage.J. F. S . Equilibrium in the System Ammonia-Ammonium Thiocyanate. H. W. FOOTE and M. A. HUNTER ( J . Amer. Chem. Soc. 1920 42 69-78).-With the object of finding an absorbent other than water for f re,e ammonia the system ammonia-ammonium thiocyanate has been invsstigated. The vapour pressure of ammonia-ammonium t hiocyanate mixtures has been determined by passing ammonia a t known pressure through a known weight of ammonium thiocyanate until no further increase in weight occurred; in this way the vapour pressure of ammonia is known. This was carried out a t temperatures O-40°. A further series of vapour-pressure measurements was made for saturated aqueous solutions of ammonia and ammonium thiocyanate a t temperatures - 78O to + 20° and the following values obtained - 78O 1 mm.; -65O 4 mm.; -50° 9 mm.; -34O 21 mm.; -23O 34 mm.; -20° 41 mm.; Oo 107 mm.; and +20° 225 mm. The solubility of ammonium thiocyanate in ammonia has been determined a t tem- peratures from Oo to 50° and the following composition of satur- ated solutions is obtained Oo 23.3% ammonia 76.7% thiocyanate; loo 22.65% ammonia 77.35% thiocyanate; 20° 21.6% ammonia 78.4% thiocyanate; 30° 20.15% ammonia 79.85% thiocyanate; 40° 18.4% ammonia 81.6% thiocyanate; 50° 16.65% ammonia 83.35% thiocyanate. The specific conductivity of several solutions a t Oo has been measured and the following values obtained 75 mol. % ammonia 0-1979 ohms-1; 68.9 mol. % ammonia 0.1640 ohms-'; 63.3 mol. % ammonia 0.1395 ohms-'; 59.7 mol.% ammonia 0.1246 ohms-1; and 57.1 mol. % ammonia 0*1110 ohms-'. The vapour pressures found are much lower than Raoult's law requires. The practical application of ammonium thiocyanate as an absorbentINORGANIO CHEMISTRY. ii. 247 for ammonia has bean considered and it is shown that such an absorbent could be used in casw where it is necessary to eliminate water and that a very large amount of the ammonia (98.1-99*6%) would be easily recoverable. J. F. S. Catalytic Oxidation of Ammonia to Nitric Acid. B. NEUMANN and H. ROSE (Zeitsch. angew. Chem. 1920,33,41-44 45-48 51-55) .-The authors have summarised the numerous processes and research in connexion with the catalytic oxidation of ammonia and contribute some further results of investigations. Highest yields are obtained with platinum at 500° (96%) ferric oxide a t 670° (go%)) and iron-bismuth oxide at 600° (95%).The influence of the ammonia concentration of the velocity of the gases and of the temperature is discussed. Curves are given for the gas composition with various catalysts between 300° and 700O. Under definite conditions the oxidation will proceed continuously without external heat. W. J. W. Vapour Pressure of Arsenious Oxide in Sulphuric Acid Solutions. F. S c a w ~ ~ s ( J . SOC. Chcrn. Ind 1920 39 33-34~).- I n the contact prmess for the manufacture of sulphuric acid the sulphur dioxide is washed by bubbling through sulphurio acid. Experiments were made to determine to what extent arsenious acid is removed from the sulphuric acid by the sulphur dioxide since any appreciable amount so carried forward would have a serious poisoning effect on the catalyst..In the experimenh it measured volume of air was bubbled through sulphuric acid at 60° containing a known amount of arsenious oxide and was then passed through a series of sodium hydroxide absorption tubes to collect any vola- tilised arsenic. The acid used contained in two experiments 0.015% and 0.001% of arsenious acid and in each case small but appreciable amounts of arsenic were found in the absorption tubes the amount carried forward being proportional to the amount present in the acid and more than sufficient to have a poisoning effect on the catalyst. E. H. R. Atomic Weights of Boron and Fluorine. EDGAR F. SMITH and WALTER K. VAN RAAGEN (Carmegie Inst. Pub.1918 267 1-63) .-Methyl alcohol obtained by the hydrolysis of methyl oxalate was used to prepare methyl borate from which b r i o acid wag produced by hydrolysis. The acid thus obtained and sodium carbonate gave borax which was completely dehydrated by pro- longed fusion. The anhydrous borax by treatment with the appropriate acid and repeated evaporation with methyl alcohol was converted into sodium chloride sulphate nitrate and carbon- ate from the weights of which the atomic weight of boron was calculated. The anhydrous borax was a130 indirectly converted into sodium fluoride through the formate the direct conversion being impracticable. The valuee obtained are 10-900 for boron and 19.005 for fluorine. 8*- 2ii. 248 ABSTRAOTS OF OHEMICAL PAPERS The boron value is 1% lower than the accepted d u e whioh is erroneous owing chiefly to the retention of water by borax glass.CHEMICAL ABSTRACT s . The Combustion of Wood Charcoal with Nitric Acid. FRIEDRICH C. G. MULLER (Zeitsch. acrtgew. Chem. 1920 33 40).- Wood charcoal wits heated in a current of nitrio acid vapour and the resulting g w were collected and analysed. The gases had approximately the following composition C O 57.2% ; CO 13*3% ; H 4.6%; N 24.9%. The high wbon monoxide content and the presence of free hydrogen are noteworthy. It was observed that a conaiderable quantity of ammonia was present in the condensate. The production of ammonia is difficult t o account for as the reac- tion temperature was at least 1000°. Adiabatic Compression of Carbon Dioxide at High Temperatures.KURT NEUMANN (Zeitsch. VeT. deut. Ing. 63 1002-1007; from Chem. Zentr. 1919 iii 989).-The author has iavestigatd the expansion of carbon dioxide which enclosed in an insulated cylinder had previously been heated to such a tempera- ture that partial dissociation into carbon monoxide and oxygen had ocaurred (a phenomenon which is observed in internal combus- tion engines). During the expansion combination of carbon mon- oxide and oxygen to carbon dioxide (after combustion) takes place which has an importmt influence on the adiabatics. Expressions have been developed which permit the calculation of gaseous com- position preasure and volume at a definite temperature. H. W. Aqueous Solutions of Carbon Dioxide. KOBERT STROHECKER (Inaug.-D.tss. Marburg 44 pp.; from Jahrb.Min. 1919 Ref. 1).- Carbon dioxide solutions are important agents in geological pro- cwam. The slow neutralisation of such solutions by various bases was invatigated with the idea of gaining some idea as to their constitution. It appears that carbonia acid is not such a weak acid as is generally supposed the dissociation constant being much higher than is usuallv stated. The acid constant was determined E. H. R. aswk =44-10-5; i t behives therefore as an hydroxyformic acid. L. J. S. Fall in Pressure Density and Heat of Vaporisation of Argon. iC. A. CROMMELIN (Zeitsch. Sauerstoff Stickst08 Ind. 1919 11 81-83; from Chem. Zentr. 1920 i 147).-The latent heat of vaporisation of argon a t -185-5O is found to be 69.4WE. Values for the fall in pressure and density a t numerous tempera- tures are given in tabular form.Surface Colours of Metals. G. TAMMANN (Nachr. K Ges. W k s . GGttiyen 1919 225-236; from Chem. Zerctr. 1920 i 148). -Metals which yield surface colours become coated with a film of oxide the rate of thickening of which with the time can be esti- mated by the alteration of the surface colours. Certain metals yield similar collours with iodine vapour at the ordinary tempera- H. W.INORGCAKIC OHEMISTRY. ii. 249 ture and these are particularly suitable for the experimental investigation of the laws governing the rate of formation of the surface layer. The isothermal rate depends solely on the cwffi- cient of diffusion of iodine into the layer of silver iodide covering the silver and hence there is a parabolic dependence of thickness on time of action.The author's theory which is confirmed by experiment is based on the same fundamental ideas as Nernst's thmrv of solution. The actual chemical action occurs far more rapidly than the diffusion process which in the one case leads to an attack of the reagent on the metal through a layer of con- stantly increasing thickness whilst in the other case action occurs through a layer of constant thickness since the deposit becomes detached. The quantitative relationships therefore depend on the different properties of the layers of reaction products. I f crystals of iodine are placed in a desiccator over sulphuric acid iodine vapour is observed which rive surface colours with silver copper lead and thallium; bismuth and antimony rapidly darken and a fine dark dust is deposited on their surfacm.Tin behaves simi- larly but yields a yellow incoherent layer. Small patches are formed within a few minutes on iron cobalt nickel and manganese and these when removed from the desiccator rapidly form droplets since the iodides are hygroscopic. Zinc and cadmium are more regularly but much more slowlv attacked ; with chromium act.ion is doubtful. With metals which give surface colours the rate of increase of the layer which causes the coloration can be determined if care is taken to keep the concentration of iodine'vapour con- st'ant. For this purpose air is drawn through a definite iodine solution and the surface colour is compared at definite intervals with a table which gives the relationship between surface colour and thickness of film.A strip of silver shows three different types of behaviour towards iodine accordinq t o whether it has been rolled and cleaned has been melted and thus covered with large crystal- lites or has been left unworked and thus covered with multitudin- ous small dendritic crystals. The surface colorations on copper are similar to those on silver which has been similarly treated. Since however the index of refraction of copper iodide haa not been determined the thickness corresponding with the colours of the mmesponding layers of air cannot be calculated to actual thick- n w m of iodide film. I n many regions of temperature the rate of increase of the superficial layer is independent of the tempera- ture; this is true in the case of steel for which the author Eives calculations based on Lowenherz's experiments.H. W. Segregation Dispersaids in Anisotropic Media. WILHELM EITEL (Centr. Milt. 1919 173-183).-When homogeneous mix- tures of sodium and potassium chlorides are cooled rapidlv from a high temperature metastable homogeneous mixed crystals can be obtained which however when maintained for som0 time at a suit- able temperature decompose into the constituent salts the crystals becoming opaque. This phenomenon has been investigated bjr theii. 260 ABSTRACTS OF CHEMICAL PAPERS. ultramicroscopia method used by Lorenz and Eitel for the exam- ination of metallic fogs in crystals of the correBponding chlorides (A. 1915 ii 260 261). A complete series of mixtures of the two salts was examined and it was shown that the segregation of the mixture can be optically demonatrated under the ultramicroacope through the gradual formation of a fog or fine disperaoid phase a t a temperature of about 250O.A number of photographs are reproduced. E. H R. Solidification Points of Mixturedl of Metallic Chlorides. FRED. C. A. H. LANTSBERRY and R. A. PAGE ( J . SOC. Chem. Id. 1920 39 37--41~).-The authors have determined the freezing- point curvm of the three binary mixtures and one ternary mixture comprised in the system sodium chloride-potassium chloride-calcium chloride by the cooling method that is plotting the cooling curve of a mixture of known composition and noting the arrest point. In the sodium chloride-potassium chloride series the components form a continuous series of solid solutions; the lowest melting mix- ture contains 55% KC1 and 45% NaCl and solidifies a t 650O.The curve for the sodium chloride-calcium chloride series shows a very sharp minimum at 72.5% CaCl and 27.5% NaC1; the correspond- ing freezing point is 5 0 5 O . The potassium chloride-calcium chloride seriee is more complicated. The curve shows two distinct eutectic points and a maximum between them at about 70% CaC4. The maximum corresponds with a freezing point of 725O and repre- sents the formation of a compound 2KC1,3CaC4. The eutectic between the compound and CaCl freezes at 608O and contains 17.5% KCI whilst that between the compound and KCI freezes at 590° and contains 60% KCl. The remlts do not confirm the work of Menge (A.1911 ii 982) who reportd the formation of a com- pound 4NaCl,CaCl in the sodium chloride-calcium chloride series. Freezing-point determinations were made on a series of forty-one ternary mixtures and the results are plotted on a triangular diagram in which the isothermal lines are shown. There are two ternary eutectics one containing 70% CaCl 25% NaC1 and 5% KC1 freezing at 495O the lowest in the series the- other contain- ing 30% CaCl 20% NaCl and 50% KC1 freezing at 530O. E. H. R. Additive Products of Sulphur Dioxide and Alkali Iodides (Alkali iodide Sulphones) . FRITZ EPHRAIM (Ber. 1920 53 [B] 118).-The alkali iodides absorb varying proportions of sulphur dioxide (A. 1916 ii 614) whereas Forcrand and Taboury have recently stated that sulphones of the type MI,SSO are produced (A.1919 ii 341). J. C. W. The Dissociation of Ammonium Carbamate. C. MATIGNON and M. FE~JACQUES (Compt. rend. 1920 170 462464).-The values obtained by Naurnann (this Journ. 1871 1195) for the dis-INORGANIC CHEMTSTRY. ii. 261 sociation pressures of ammonium carbamate over the temperature range - 15O to + 60° may be expressed by two equations log p = - 3,635 / T - 7.045 log T + 28.692 log p= - 4.821 / T - 154 log T + 53.3586. and Measurements made a t 8 1 O and 9 3 O where the pressures are several atmospheres confirm the accuracy of these equations. Calculations made by means of these equations give the heat of dissociation of ammonium carbamate a t constant pressure as -39.0 cal. which is in close agreement with the value previously found by experiment (compare Matignon A.1908 ii 465). W. G . Growth Phenomena of Copper Silver and Gold. A. BEUTELL (Centr. Min. 1919 14-28).-When natural or arti- ficial silver sulphide is heated in an evacuated sealed tube for several days at a temperature of 350-600° a certain amount of decomposition takes place. The small amount of silver formed mams to wander through the silver sulphide appearing a t the cooler end of the tube in the form of hair silver. A number of experiments which were made showed that neither silver foil nor hair silver is attacked by sulphur vapour in a vacuum at 450O; the metal re4mained bright after forty-eight hours. Silver foil heated alone in a vacuum for a long period a t 450-585O showed no trace of the growth of hair silver but when silver foil and silver sulphide were heated together a t 450° remarkable growths were obt-ained in a comparatively short time.To obtain these growths it is necessary for the silver and the silver sulphide to be actually in contact. Similar growths of copper were obtained by heating together copper and cuprous sulphide but the process was much slower. When silver selenide or telluride was used in place of the sulphide similar growths of silver were obtained and hair copper was obtained to a certain extent with copper selenide and telluride. With gold the best results were obtained when gold telluride containing silver was heated with silver foil. After seven days’ heating at 500° growths of “moss” gold containing silver had appeared a t the cooler end of the tube. E.H. R. Action of Water on Strontium Sulphide. E. TERRES and K. BRUCKNER (Zeitsck. EEehtrochem. 1920 26 25-32) .-The action of water on strontium sulphide has been investigated. It is shown that the reaction in this case differs materially from the reaction in the case of barium sulphide (see following abstract). I n the present case t.he reaction takes place between two molecules of water and two molecules of sulphide with the formation of equi- molecular quantities of strontium hydroxide and stront,ium hydro- sulphide 2SrS + 2H20 = Sr(SH) + Sr(OH),. The hydroxide and hydrosulphide in consequence of their widely differing solubility may be completely separated by crystallisation. When strontium sulphide is extracted with hot water and the clear filtrate cooled pure strontium hydroxide crystsllises.The solubility of strontiumii. 262 ABSTRACTS OF CHEMICAL PAPERS. hydrosulphide has been determined a t temperatures 0-looo and the following values obtained in grams of the anhydrous compound per 100 grams of water Oo 27.5; 20° 29.7; 40° 31.6; 60° 33.2; 80° 35.6; looo 37.8. The solubility of strontium hydroxide and strontium hydrosulphide in the same solution has been determined over the range O-lOOo and it is shown that no mixed compound is formed and that the hydroxide and hydrosulphide are in equili- brium with one another a t all temperatures. Hence strontium hydroxide may be prepared by direct crystallisation of the solution obtained by the aotion of water on strontium sulphide. J. F. S. Action of Water on Barium Sulphide.E. TERRES and K. BR~~CKNER (Zeitsch. Elektrochem. 1920 26 1-24) .-The con- ditions influencing the formation of barium hydroxide from barium sulphide are experimentally investigated. A long list of patents and investigations is given with short critical remarks. A number of processes are repeated which are based on the action of water on barium sulphide and in which the crystalline product is worked up to barium hydroxide either by crystallisation or by treatment with metallic oxides. The reaults confirm in many cases the pub- lished accounts. The concentration of the solution and the com- position of the residue obtained by extracting barium sulphide with water a t various temperatures are investigated. The content of the solution of barium hydroxide and barium hydrosulphide increases rapidly with increasing temperature.The solid residue consists to the extent of 4-2 of barium oxide. The solutions contain equal molecular quantities of hydroxide and hydrosulphide so that it would appear as though in the presence of one another these s u b stances had the same solubility in water. The action of barium hydroxide solution on barium sulphide shows however that the solution is not saturated with barium hydroxide. Hence i t would seem that the solution is saturated with an intermediate compound either an hydroxyhydrosulphide or a double compound of barium hydroxide and barium hydrmulphide but it is not saturated with the components of this double compound. The solubility of barium hydrosulphide is determined from - 1 5 O to looo.It is shown that the intermediate compound is formed when barium hydroxide and barium hydrosulphide are mixed in definite proportions and that the maximum quantity of the compound is precipitated when twenty-seven molecules of the hydrosulphide are mixed with one molecule of the hydroxide; also the greater t-he exce-ss of hydro- sulphide the purer the precipitated double compound The double compound may be expressed by one of the formula OH*Ba*SH,5H20 or Ba(O~),,Ba(SH),,10H2O. Experiments on the solubility of the intermediate compound show that the solution contains the com- ponents in very different proportions to the solid substance that is the undissolved residue contains an excms of hydroxide. The inter- mediate compound is shown to possess a considerable stability except towards oxidising agents and there is no considerable decom-INORGANIC CHEMISTRY. 5.253 position by water either with or without pressure or even by alkalis. The compound in relation to the hydrcwulphide possesses a very small hydrogen sulphide pressure. For these and other reasons the author allots the formula OH*Ba*SH,5H,O to this compound. The solubility of barium hydroxide and barium hydro- sulphide simultaneously has been determined from the cryohydric point to looo. A t all temperatures the region of existence of the double compound lies between those of barium hydroxide and barium hydrosulphide. The two simple compounds therefore can never exist together in the same solution but must combine to form the intermediate product.It also follows that pure barium hydroxide can never be crystallised from the solution obtained by the action of water on barium sulphide. Solubility of Zinc in Cyanide Solutions. H. A. WHITE ( J . Chem. M e t . Min. SOC. S. Africa 1919 20 97-101).-From the results of an investigation made t o determine the effect of various practical conditions on the solution of zino during the precipitation of gold from cyanide solutions i t is concluded that close regulation of cyanide strength alkalinity and aeration of the auricyanide solution is necessary if the consumption of zinc is to be kept within reasonable limits. The ideal of a zinc consumption corresponding even approximately with the amount of gold precipitated appears unlikely to be attained. LFor further details see J .Soc. Chem. Znd. 1920 April.] Attempt to Determine if Common Lead could be Separated into Isotopes by Centrifuging in the Liquid State. J. JOLY and J. H. J. POOLE (Phil. Mag. 1920 [vi] 39 372-375). -Molten lead has been centrifuged at a rate of 9000 revolutions per minute in electrioally heated steel tubes for periods of one hour. The top and bottom layers were then withdrawn and cast into pellets and the density determined. Although small differ- ences between the density of the two layers are observed they lie inside the experimental error so that the experiments furnish no evidence that a separation of the isotopes has been effected. J. F. S. W. E. F. P. J. F. S. Effect of Centrifuging certain Alloys while in the Liquid State. J. JOLY and J.H. J. POOLE (Phil. Mag. 1920 [vi] 39 376).-Using the method described above (see pre- ceding abstract) it is found that silver-lead alloys could not be appreciably separated by centrifuging but lead-tin alloys could be to some extent separated. Thus with an alloy containing 82% of lead and 18% of tin the top layer was 1.8% lighter than the bottom layer after centrifuging. J. F. LIVERSEEGE and A. W. KNAPP ( J . Soc. Chem. Id. 1920 39 27-33~).-The experiments here recorded on the action of water on lead were made with the waters colleoted in the Caban reservoir Elan Valley Wales for J. F. S. The Action of Water on Lead.ii. 254 ABSTRACTS OF CHEMICAL PAPERS. the use of Birmingham. These waters have a slight alkalinity due to hydrogen carbonates etc. equal to about 0.3 part CaC03 per 100,000.The action of such waters and generally of waters the alkalinity of which does not exceed 1.5 is erosive. The whole surface of the lead is attacked and a flocculent precipitate forms which becoming detached leaves the surface of the lead bright but mottled. When the alkalinity is increased to 1.5-2.5 the action becoma corrosive and a loosely-held white opaque crust forms here and there on the surface. With still greater alkalinity the lead almost invariably becomes covered with a dull white film which appears t.o act as a protective coating. The erosion tats were made by the method of Houston in which a clean strip of lead of standard size is immersed in the water in a test-tube air having free warn. The amount of lead eroded is determined colorimetrically as sulphide.It proved possible to carry out the test in one day. It waa found that such variations as occurred naturally in the amount of oxygen present in the water had no appreciable effect on the erosion. Variations in the amount of water used did not affect the amount of erosion but the greater the depth of immersion of the lead the smaller was the velocity of attack. Exposure to glass lowered the ermive ability of the water. Erosion readily occurred in waters free fron carbon dioxide and small variations in the carbon dioxide content had no appreciable effect,. The presence however of from 1 to 2% of carbon dioxide by volume caused a sudden change from erosion to “ plumbc+solvency,” that is the lead precipitate no longer appwrs but soluble lead hydrogen carbonate is formed.Carbon dioxide dissolves lead more rapidly in presence of oxygen than alone. It is concluded that given oxygen present the principal factor in determining both amount and kind of erosion is the alkalinity of the water. The addition of small quantities of calcium hydroxide carbonate or hydrogen carbonate or of potassium permanganate decreases erosion but calcium hydrogen carbonate is most effective ; erosion occurs in absence of bacteria. It was observed that the baoteria in the water are not all destroyed by exposure t o lead for six hours. E. H. R. The Alloys of Copper Zinc and Nickel. LBON GUILLET (Cmnpt. r e d . 1920 170 460-462) .-Brasses containing nickel in which the copper content falls to 40% and even less and the nickel content rises to 15% are of particular interest because of their mechanical properties. Their breaking strain varies from 45 to 75 ki1os.lrnm.z with elongations of 45-18%.They are readily malleable at high temperatures and in colour and resist- ance to oxidation they are comparable to German silver. W. G. Compressibility of Indium. THEODORE W. RICHARDS and JITSUSABURO SAMESHIMA ( J . Amer. Chem. Soc. 1920 46 49-54). -The compressibility of indium has been determined over the pressure range 100-500 megabars. The measurements were madeINORGANIO OHEMISTRY. ii. 256 a t 25O. The measurementg were carried out by the usual method but instead of a steel piezometer as previously used a small glass one was made use of in the present work. It is found that the compressi- bility of indium over the range examined is 0-0000027 or about two-thirds that of mercury.A t thie temperature indium has a density 7.318. J. F. S. The Limits of the Combining Power of Silicon with certain Metals of the Iron Group. A. SANFOURCHE (Rev. M i t . 1919 16 239-245 ; from Chem. Zmtr. 1920 i 149-150) .- The uncertainties in the literature concerning the combining power of silicon with members of the iron group are frequently to be ascribed t>o faulty methods of analysis consisting in the treatment of the alloy with alkaline reagents t o effect removal of the excess of silicon and isolation of the alloy richest in silicon from the residue. Actually the persilicated compounds are frequently attacked in the circumstances whilst removal of the free silicon enclosed in the alloy is frequently incomplete.I n addition the combining power of silicon with iron and related substances is not a constant quantity but depends on various factors notably on the excess of free silicon. In ferrosilicons the lower limit of combining power lies a t 55.55% Si corresponding with the formula FeLSi the upper limit a t 60% Si corresponding with FeSi,. With manganese-silicon alloys the limit lies between 46-70 and 50.11% Si; the upper value is here obtained with 8% of free silicon whilst for iron in similar circumstances a 2% excess of silicon suffices. The higher limit approximates to the formula MnSi2 so that this com- pound may be regarded as having the highest possible silicon con- tent; the lower limit does not correspond with a definite compound whilst the substance MnSi appears t o require the presence of a sufficient excess of silicon to prevent its dissociation with liberation of this element. The influence of silicon is also very noticeable with cobalt silicon alloys; as it increases from 0% to 6% the com- bining power increases from 50% to about 53%.Neither limit correeponds with a definite chemical compound; the simple formulz to which they most closely approximate are CoSiz (48.7% Si) and Co.@i (54.26% Si). With nickel-silicon alloys the limits of com- bining power are most widely separated (3945%); in this case also a definite compound is not indicated. The upper limit is only attained in the presence of at least a 10% excw of free silicon. The method of analysis consists in the estimation of total silicon by treatment with alkali carbonate and of uncombined silicon by removal of the combined element as silicon tetrafluoride by treat- ment with pure hydrofluoric acid.Combined silicon is estimated by difference. The author is led to the conclusion that compounds of the iron group rich in silicon tend to dissociate partlv into f r w silicon and a more o r less well-defined compound of silicon and the metal M,Si = M&3iv - z + Si . St'abilisation oocum in the presence of a sufficient excess of silicon but if this is present in quantity onlyii. 266 ABSTRAOTS OF CHEMICAL PAPERS. sufficient to form the compound a certain amount of it passes into the free condition (in solutioni and so depresw the combining power. H. W. Form of Ultra- microscopic Platinum Particle. RICHARD GANS and RICARDO CALATRONI (Ann. Physik 1920 [iv] 61 465-470).-Using platinum sols prepared bot,h by the Bredig process and by reduction of chloroplatinic acid with hydrazine hydrate in the presence of the sodium salt of protalbic acid as protecting colloid t'he authors have measured the absorption for the four helium lines Xh6678 5877 5010 and 4472 A. units. To ensure uniformity of the particles and to remove aggregates the solutions were filtered through collodion ultra-filters which con- tained 0.5-1*0% of acetic acid. The results show that as in the case of silver and gold amicrons (A. 1912 ii 508; 1915 ii 390) the platinum amicrons are spherical in form (see also Diesselhorst and Freundlich Physikd. Z e i f s c h . 1916 17 117). J . F. S.

ISSN:0368-1769    

DOI:10.1039/CA9201805245

出版商:RSC    

年代:1920

数据来源: RSC