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A. E. Houlehan. The chemistry of nitric oxide formation in the hightension are has been investigated by F. Fischer and E. Hene. After a further investigation of the reaction between nitric oxide and liquid oxygen, F. Raschig has reached the conclusion that the green substance obtained is nitrogen hexoxide, NO,, as previously asserted (A. Y. B., 1912, p. 628), and has shown that when the substance is washed with liquid nitrogen it loses a part of its oxygen, with formation of isonitrogen tetroxide. Strong has studied the action of the corona discharge upon air, and Hausser has obtained nitric oxide by explosive combustion of coke-oven gas under pressure.

sodium, potassium, or rubidium are hydronitrogen, has been prepared by bombarded by cathode rays, there is a genuine production, as distinct from liberation of absorbed gas, of helium and X,, potassium giving the largest supply." He suggests that the emission of helium from these and other substances may be explained on the ground that "other elements besides radium, thorium, and the like make attempts to expel alpha particles (atoms of helium). In ordinary elements these particles have not enough energy to get away from the atom; they are, however, as it were, loosened, and can be detached by vigorous bombardment with cathode rays." Nitrogen.-R. J. Strutt, in the fifth of his series of articles on active nitrogen, asserts that the phenomena are not due to the presence of traces of oxygen in the gas, as has been stated by F. Comte and by E. Tiede. In this assertion he is supported by A. Koenig and E. Elöd. He has, moreover, made a further study of the chemical reactions of active nitrogen, among which are the formation of nitrogen by action upon vapor of mercury, cadmium, zinc, arsenic, so dium, and sulphur, and the production of hydrocyanic acid by action upon various organic compounds. The fixation of atmospheric nitrogen by means of boron compounds has been studied by Stähler and Elbert. W. A. Noyes has obtained some evidence in favor of the existence of a new nitrogen trichloride, containing positive nitrogen and negative chlorine, and prepared by the interaction of nitrosyl chloride and phosphorous pentachloride. Franklin has prepared potassium ammono-magnesate, Mg(NHK), .NH, a new salt belonging to his ammonia series of acids, bases, and salts, by action of potassium amide in liquid ammonia upon a halogen salt, an aquo salt, or an ammono salt of magnesium, or upon the metal itself. He has also prepared potassium Non-aqueous Solutions.-Among the ammonotitanate by a similar reac- notable contributions made, during the tion, and has studied the reaction be- year, to our knowledge of non-aquetween potassium amide and cupric ous solutions is that published by C. nitrate in liquid ammonia. Sommer A. Kraus and W. C. Bray on a genhas obtained hydrazine nitrite by in- eral relation between the concentrateraction of barium nitrite and hydra- tion and the conductance of ionized zine sulphate. An ammonated am- substances in various solvents. In the monium trinitride, NH,N,.2NH,, course of an investigation of the nature which may be regarded as a new of the metallic state, C. A. Kraus has

Piezochemistry.-During the last year an increasing interest has been shown in the influence of pressure upon chemical reactions. The decomposition of nitric oxide under pressures up to 700 atmospheres, and at various temperatures, has been studied by E. Briner. E. Cohen and his colleagues have continued their interesting piezochemical studies, and have designed and constructed an elaborate apparatus capable of maintaining pressures up to 1,500 atmospheres constant to within about one per cent. for any desired length of time. With the aid of this apparatus the influence of high pressures upon the veloc ity of inversion of cane-sugar solutions was studied, and the validity of Faraday's law for pressures up to 1,500 atmospheres was established. By using a suitable bomb, F. Bergius has been able to prepare calcium dioxide from quick-lime and oxygen under 120 atmospheres at 350 deg. He has also obtained coal-like substances by heating peat, wood, or cellulose to 340 deg. under great pressure, and is able to prepare large quantities of pure hydrogen under similar conditions by the action of iron upon water.

isolated the metallic groups CH,Hg, | phuric acid, and the cathodes were reC2H,Hg, and C2H,Hg, by electrolysis spectively of selenium and tellurium. of the respective chlorides in liquid Boron.-The synthesis of a number ammonia solution. He concludes that of borides has been effected with the "the metallic state is a molecular and aid of the vacuum electric furnace not an atomic property of matter." by E. Wedekind. Calculated amounts The behavior of silver, copper, lead, of amorphous boron and the metal and barium salts of certain organic under investigation were in each case acids, dissolved in such solvents as compressed into rods, through which benzene, toluene, and petroleum ether, the current was passed. The metals toward hydrogen chloride, has been used were zirconium, vanadium, studied by H. P. Cady and H. O. molybdenum, uranium, titanium, and Lichtenwalter. These investigators tungsten. Of these, only molybdenum note, in contradiction to the earlier and titanium presented difficulties. A. work of Kahlenberg, that each solu- Stock and C. Massenez have obtained tion giving a precipitate shows an ap- two hydrides of boron by decomposipreciable conductivity, and conclude tion of magnesium boride with acids, that every one of the reactions is in and condensation of the gaseous prodaccord with the dissociation theory. ucts with liquid air. The formula of L. Bruner and his colleagues have in- one of these, B.H10, was well estabvestigated the electrical conductivity lished by analysis and by density deof nitrobenzene solutions, and the terminations, and the properties of electrochemistry of the halogens both the substance, which melts at 116 in nitrobenzene and in liquid sulphur deg. and boils at +16 deg., were dioxide. M. E. Holmes has electro- studied. To the second substance, lyzed a solution of ammonium trini- which boils at about 100 deg., the tride in liquid ammonia, with a view formula B.H12 was assigned. Stock to ascertaining the properties of N, the and Frederici obtained a more voladischarged trinitride ion. Fritz tile compound, B,H,, which boils at Friedrichs has studied the behavior -87 deg., by decomposition of gaseof numerous substances, chiefly inor- ous B.H1. These investigators sugganic salts, in sealed tubes toward gest the use of a bath of melting carliquid ammonia and toward liquid bon bisulphide for maintaining a temsulphur dioxide at temperatures rang-perature constant at -112 deg. In a ing from -80 deg. to + 160 deg. In connection with this work he has formulated a new classification for binary systems, based upon solubility, miscibility, and critical relations.

Sulphur, Selenium, and Tellurium. -The behavior of thionyl chloride toward various oxides and dioxides when heated in sealed tubes to from 150 deg. to 200 deg. has been investigated by A. B. North and A. M. Hageman. It was found that zinc, cadmium, magnesium, and cupric oxides, for example, react under these conditions with formation of the respective metallic chloride and sulphur dioxide. From a study of the solubility of sulphur in sulphur monochloride and in other solvents, A. H. W. Aten concludes that there is evidence of the existence of a new modification of sulphur. W. Hempel and M. G. Weber describe an electrolytic method for the production of hydrogen selenide and hydrogen telluride. The electrolyte used was 50 per cent. sul

still later article, Stock, Frederici, and Priess have made a further study of B2H, and B.H10, and have investigated the solid substances obtained by decomposition of gaseous B.H10. A new compound, BH, which melts at 99.5 deg., was obtained by heating B,H,, to 100 deg. for four to five hours, or B2H to from 115 deg. to 120 deg. for 48 hours, as well as several other compounds or mixtures of which the chemical identity has not as yet been definitely established.

Miscellaneous.-A. Werner and his associates have continued their interesting researches upon the asymmetric cobalt atom. T. W. Richards and A. W. Rowe have constructed an improved apparatus for use in determining the specific heats of liquids. Known quantities of heat are liberated in this apparatus by neutralizing accurately known amounts of acid with slight excess of alkali. The specific heats of dilute solutions of hydrogen chloride, hydrogen bromide,

hydrogen iodide, nitric acid, perchloric of the existence in the free state of acid, and of lithium, sodium, and po- compounds containing trivalent cartassium hydroxides were determined. bon atoms such as triphenylmethyl, A new proof of the material existence lends interest to the preparation of of molecules is said by N. Pihlbad to analogous compounds in the nitrohave been obtained in the course of gen series. Wieland (Berichte der his investigation of the absorption Deutsch. Chem. Gesellsch., XLV, curves of certain disperse systems con- 2600; Liebigs Annalen, CCCXCII, taining red, yellow, blue, or violet 127) found that certain ditertiary organic substances in the form of sus- hydrazines, R,N-NR,, in which the R pensions, colloidal solutions, and mo- represents positively substituted phelecular solutions. As the size of the nyl groups, dissociate to form divaparticles was diminished, the absorp- lent nitrogen compounds. For intion curves of the disperse systems stance, tetra-anisyl hydrazine dissociapproached those of the molecular ates at room temperature into colored solutions. K. A. Hofmann, O. Ehr- dianisyl nitrogen, (CH, OC,H,),N, hart, and O. Schneider have found it which is capable of adding itself to possible to "activate" solutions of various unsaturated compounds, such sodium chlorate by addition of os- as triphenylmethyl, with which it mium tetroxide. C. Boulanger and J. forms dianisy laminotriphenyl methBardet have noted the presence of ane (C,H,),CN (C,H,OCH3) 2. small amounts of gallium in commercial aluminium and in bauxite. Bearing in mind the observation, previously made by A. de Gramont, that gallium occurs in various feldspars, the investigators suggest that perhaps gallium always accompanies aluminum in nature.

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The Non-Equivalence of the Five Valences of Nitrogen.-The non-equivalence of the five valences of nitrogen in ammonium salts was demonstrated by Meisenheimer (Liebigs Annalen, CCCXCVII, 273) by means of isomeric substances of the general formula RN (OR1) (OR3). For example, two isomeric substances having the formula (CH) ¿N (OCH2) (OC2H1) were found to decompose on evaporating their aqueous solutions quantitatively as follows:

CH3

-> CHN + CH2O + C2H OH

CH3

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A number of compounds containing different alkoxyl groupings reacted similarly. Since four of the five valences of the nitrogen atom in ammonium salts have long since been shown to be equivalent, this furnishes direct experimental evidence of the different character of the fifth valence.

Optically Active Phosphorus Compounds. Wedekind (Berichte der Deutsch. Chem. Gesellsch., XLV. 2933) obtained evidence that the p-tolyl-phenyl-ethyl-methyl phosphomium grouping was resolved into optically active dextro- and levo-forms. This adds another element to those which have been found capable of

CH-N+C2H4O+ CH3OH.

CH

forming optically active isomers with asymmetric substituting groups. It also completes the evidence for such compounds of phosphorus as those presented by Meisenheimer several years ago when he resolved mixed phosphine oxides into optically active isomeric substances.

Mechanism of Reactions in Dyestuff Formation.-The chemistry involved in the synthesis of dyestuffs has always been very complicated and difficult to understand. The compounds are generally very complex and the reactions for their formation often seemingly abnormal. Recently A. G. Green (Jour. Chem. Soc., CIII, 925)

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Semmler and Rosenberg (Berichte der Deutsch. Chem. Gesellsch., XLVI, 768), in the higher boiling fractions of camphor oil, of two naturally occurring members of this class of compounds. They are a-camphoren, C2,H32, a monocyclic diterpene, and B-camphoren, C2H2, a bicyclic diterpene.

Hydrolysis of Cellulose.-Considerable attention has been given in recent years to the production of fermentable sugar from cellulose. One of the most promising methods for the hydrolysis of cellulose has been lately worked out by Willstätter and Zechmeister (Berichte der Deutsch. Chem. Gesellsch., XLVI, 2401). Ordinary concentrated hydrochloric acid (36 per cent.) will only gelatinize cellulose after acting upon it for

(2) indirect addition, under neutral some time, while stronger hydrochloric conditions,

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The benzenoid compounds thus formed can again be changed into quinones by oxidation and undergo either of the above addition reactions. This process of alternating oxidation and reduction may continue until compounds of very complicated molecular structure are formed. As examples, pararosaniline is formed through the oxidation of toluidine and direct addition of aniline, while the indulines and aniline black are formed by oxidation of aniline and both direct and indirect additions. The theory not only furnishes the chemist a means for following the course of the reactions, but also suggests new syntheses, and methods for ascertaining the constitution of many dyes heretofore unknown.

acid (40 per cent.) issolves it very rapidly and soon changes it completely into glucose. Hydrochloric acid has several advantages over sulphuric acid, which has generally been used in the past, in that it does not form any esters with the polysaccharides and the operation can be carried out without the application of heat.

Bibliography.-Among the more important books on organic chemistry published during the year may be mentioned the following: Auschütz and Schroeter's Richter's Organische Chemie, 11th edition, two volumes; Allen's Commercial Organic Analysis, 4th edition, Volume VII, covering alkaloids, animal bases and acids, glucosides and cyanogen; James Walker'a Organic Chemistry for Medical Stu dents; Julius B. Cohen's Organic Chemistry for Advanced Students, Volume II; Ettore Molinari's General and Industrial Organic Chemistry, translated by Thomas H. Pope; and T. A. Henry's The Plant Alkaloids.

BIOLOGICAL AND FOOD

CHEMISTRY

CARL L. ALSBERG

Fats and Lipoids.-Much study has been given fats and fat-like subNatural Diterpenes.-Up to the stances, or lipoids, particularly plant present time the only known diter- lipoids. Since plants consist largely penes have been those synthesized in of fibrous skeleton the quantity of the laboratory. It is, therefore, in- lipoid obtainable from them is relateresting to note the discovery by tively too small to have invited at

Since the lipoid theory of the nature of cell-membranes and the lipoid theory of the action of narcotics are interdependent, the latter is also being discredited. Instead of making the action of the indifferent narcotics such as alcohol and chloroform dependent upon their solubility in fat and lipoids, their effect upon surface tension is being offered in explanation. Indeed, pharmacologists are inclined to explain various poison effects as manifestations of surface tension. However, the theory that narcosis is dependent upon the inhibition of oxidation (Verworn) has found little acceptance (Winterstein, J. Loeb and Wasteneys).

tention until studies on animals the permeability of these membranes showed that lipoids must be as im- is dependent upon surface tension. portant to plants as to animals. It By "surface tension" is meant the has been found that the lipoids, of peculiar phenomena observed at surboth animal and vegetable origin, faces. "Capillary attraction" is one contain a variety of basic nitrogenous of these phenomena. Biologists at substances other than cholin, the present seem inclined to ascribe great simplest of these being colamin, or importance to surface tension. amino-ethylalcohol (4. Y. B., 1912, pp. 634-5), which may be regarded as intermediary between the sugars and the amino-acids or proteins. The occurrence of substances of this type has furnished Trier with a basis for an interesting hypothesis of protein formation in plants, which correlates protein formation with lipoid formation and offers an explanation of the genesis of many bases and alkaloids, as well as of the interdependence of the metabolism of nitrogen and phosphoric acid, both constituents of many lipoids. In this connection it is important to note that sulphur may occur in lipoids as well as in protein and that the lipoid containing sulphur, or sulphatid, described from impure preparations first by Thudichum and then by Koch has finally been obtained in the pure state and found free from phosphoric acid (Levene). Lignoceric acid has been obtained from the brain lipoid, sphingomyelin (Levene). This acid, the structure of which is now known, had been found only in plants. Its discovery in the brain extends the list of substances with large molecules of the type common in plants now known to occur in animals (A. Y. B., 1912, p. 634). Methods have been devised for the determination in tissues and blood of cholestearin, a substance related to the terpenes and found in practically all tissues associated with true lipoids. In consequence it has been possible to study its distribution in the tissues and to correlate it with disease, though these studies have not as yet been brought to any definite conclusion.

Nutrition, Proteins. It has long been known that the mere ingestion of food increases heat production. Zuntz assumed this to be due merely to the mechanical processes of digestion, such as the muscular work of the intestines, the activity of the glands and the like. Rubner, on the contrary, held that chemical processes produced the heat without benefit to the cells. Benedict and Pratt have now practically proved Rubner's theory. Further study has magnified the importance of the "vitamines" (A. Y. B., 1912, p. 631). Thus normal life can be maintained on a diet of pure protein, sugar and butter, but not if lard be substituted for butter, apparently because butter, like milk, contains "vitamines" (Osborne and Mendel). It has been shown that by the use of such restricted diets the susceptibility of rats and mice to tumors and the rate of growth of tumors may be influenced (Sweet, Corson-White and Saxon). London The prevalent theory of the nature has shown that dogs may be kept in of cell-membranes, namely that they good condition on a bread and milk are composed of lipoids, has been diet after removal of the stomach losing ground. It was based largely and all the intestines except the on observations by Overton that these duodenum and ileum. Valuable new membranes permitted the passage of methods have been devised for the substances soluble in lipoids. Ruh- determination of uric acid (Folin and land, however, endeavors to show that Denis) and of urea (Marshall). Ac

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