XXIV. CHEMISTRY AND PHYSICS

CHEMISTRY

INORGANIC AND PHYSICAL
CHEMISTRY

ARTHUR WESLEY BROWNE

Water and the Hydrates.-The saponification of methyl acetate and of methyl formate (1) by water alone, (2) by aqueous solutions of nonhydrated salts, and (3) by aqueous solutions of strongly hydrated salts, has been studied by H. C. Jones and J. E. L. Holmes in order to ascertain whether or not there is a detectable chemical difference between "free water" and "combined water." It was found that certain salts of calcium, strontium, barium, and magnesium, which are strongly hydrated in solution, produce the greatest increase in the velocity of the reaction. To account for the greater chemical activity of combined water the authors venture the suggestion that "combined water is more highly ionized than free water." A detailed investigation of numerous compounds containing two molecules of water of crystallization has been prosecuted by I. Guareschi. By compressing arsine with water at 0°, a crystalline solid, of which the formula was calculated to be AsH,. 6H,O, was obtained by de Forcrand. The pressure temperature curve of this hydrate was measured up to 28.3°, at which temperature the curve was found to intersect the curve for arsine itself.

pound of the formula 3MgO,.MgCO,. H2O, may be obtained. The increase in the solubility of various salts in water effected by addition of hydrogen peroxide may be explained by the formation of perhydrates, in which hydrogen peroxide behaves similarly to water of hydration. J. D'Ans and A. Kneip have prepared performic acid, HCO.O.H, of high concentration by the action of pure hydrogen peroxide upon formic acid in the presence of sulphuric acid. Peracetic acid, CH,.CO.O,H, in concentrated form was found to be most readily obtainable by the interaction of acetic anhydride and pure hydrogen peroxide.

Hydrogen. The solubility of hydrogen in the solid alloys of palladium with gold, silver, and platinum has been determined by A. Sieverts, E. Jurisch, and A. Metz, over a range of temperatures from 138° to 820° C., and of pressures up to one atmosphere. The amount of gas absorbed in the case of each of the three series of alloys was found to be approximately proportional to the square root of the pressure. The evidence is considered to indicate the formation of true ternary solid solutions between the hydrogen and the binary alloys. V. Ipat'ev and A. K. Starynkevitch have found that metallic mercury is deposited from a saturated solution of mercurous nitrate by the action of hydrogen gas at 225° Hydrogen Peroxide. The behavior C. under a pressure of 130 atmosof hydrogen peroxide toward vari- pheres, and from mercuric nitrate at ous salts has been investigated by 240°-250° under 120 atmospheres. UnP. V. Kazanetzkii. Treatment of ce- der suitable conditions both cadmium sium carbonate with 30 per cent. and zinc were displaced from their hydrogen peroxide, for example, was salts by hydrogen. Continuing his found to yield the crystalline solid earlier researches (4. Y. B., 1912, p. Cs2CO3.2H2O2. Carbonates of the 629), I. Langmuir has further studied other alkali metals behave similarly. the conditions under which the dissoBy dissolving basic magnesium car-ciation of hydrogen into atoms takes bonate in hydrogen peroxide a com- place. The active modification is

formed when the gas at low pressures in the presence of sulphuric acid, J. is brought into contact with metallic W. Turrentine and J. M. Olin have wires at temperatures above 1,300°K. It can react with oxygen at room temperature, or with many reducible substances, and can dissolve in metals, such as platinum. The dissociation of the hydrogen is not considered to occur in the space around the wire, nor by the impact of molecules against its surface, but takes place only among the hydrogen molecules that have been absorbed by the metal of the wire.

obtained hydronitric acid. Small amounts of hydrazine were obtained by electrochemical oxidation of ammonium hydroxide solutions that contained sodium chloride and glue. Turrentine has prepared the new compound hydrazine diperchlorate. By working with nonaqueous solutions L. Chugaev and M. Grigoryev have been able to obtain complex compounds containing both platinum and hydrazine. J. Lifschitz has effected the synthesis of a pentazole compound containing a group of five nitrogen atoms linked together by cautiously warming cyanotetrazole in alcoholic solution with hydrazine hydrate. As a product of a series of reactions a silver salt apparently of the composition represented by the formula AgN, was obtained.

Nonaqueous Solutions. E. C. Franklin has investigated the be

Nitrogen.-W. Jevons has obtained the band spectrum characteristic of boron nitride as a result of the interaction of active nitrogen and boron trichloride or methyl borate. A. Koenig has effected the electrical activation of nitrogen by means of the high-tension direct-current arc. The gas after this treatment can react with ethylene, acteylene, pentane, nitric oxide, and metals, but not with hydrogen, methane, water, oxy-havior of potassium amide toward gen, or ozone. It is now conceded by various metallic amides in liquid amR. J. Strutt that the purest nitrogen monia solution (see A. Y. B., 1913, will not give more than a little ac- p. 645), and has succeeded in obtive nitrogen when subjected to the taining potassium ammonoargenate, action of the electric discharge, but potassium ammonobarate, potassium on the other hand it is maintained ammonostrontiate, potassium amby him that the presence of oxygen monocalciate, and potassium ammonoor an oxygen compound is not es- sodate. He has also prepared two sential to the production of a good ammonobasic iodides of aluminium, yield, since the presence of small as well as numerous metallic salts amounts of almost any foreign gas of ammono acids, and of acid ammono will greatly increase the yield of esters. The reaction between potasactive nitrogen. A curious luminous sium amide and certain salts of cadexplosive phenomenon was observed mium, nickel, and chromium in liquid in oxygen-free, rarefied nitrogen by ammonia has been studied by G. S. J. Kowalski subsequent to an inter- Bohart. The molecular conductivity ruption of the current. This was at- of acetylene in liquid ammonia has tributed to the decomposition of an been determined by M. Skossarewsky, explosive nitride of mercury. F. who also electrolyzed a solution of Haber has made a study of the am- primary sodium acetylide, C,HNa, in monia equilibrium at ordinary pres- ammonia. Metallic sodium was desures, and has redetermined this posited upon the cathode, and a numequilibrium under a pressure of 30 ber of complexes were formed at the atmospheres. Haber and Tamaru anode. T. W. B. Welsh has electrohave determined the heat of formalyzed a solution of sodium hydrazide tion of ammonia at high tempera- in anhydrous hydrazine, and with H. tures. W. Schlenk and Th. Weichsel- J. Broderson has studied the behavior felder have succeeded in preparing of anhydrous hydrazine as a solvent and analyzing the very explosive so- toward a large number of substances. dium derivative of hydrazine, NH. It was found that reactions take NHNa, obtained by interaction of place in hydrazine that are similar sodium and hydrazine in an atmos- to those in water or in ammonia. In phere of nitrogen. By electrochemi- the seventh of his researches upon cal oxidation of hydrazine sulphate reactions in nonaqueous solutions A.

to carbon monoxide and water by rays of long wave length, and to carbon dioxide and hydrogen by rays of short wave length, has been shown by D. Berthelot. This seems to indicate that radiant energy is of a lower form than thermal energy, and that frequency of vibration in the former corresponds to temperature in the latter.

Silicon. The preparation of the chlorides SiCl, Si,Cl, and Si,Cl, was accomplished by G. Martin, who brought chlorine into contact with 50 per cent. ferrosilicon. It is assumed by the investigator, in explanation of these results, that free silicon and the metallic silicides contain silicon atoms directly united in chains. The preparation of silico-oxalic acids has also been made the subject of a research by Martin, who has moreover discussed in still another article the constitution of silica and of these acids.

Naumann has investigated the solu- | action of aluminium upon CCl, was bility of numerous substances in ben- found to contain 12 atoms per molezonitrile, and various reactions that cule. That the photolysis of oxalic take place in this solvent. The die- acid involves initial decomposition lectric constants of 21 organic solv-into carbon dioxide and formic acid, ents at their melting or boiling with subsequent change of the latter points have been determined by J. D. Cauwood and W. E. S. Turner. Carbon. As a result of their study of the heats of combustion of graphite, diamond, and amorphous carbon, W. A. Roth and H. Wallasch conclude that two varieties of graphite may now with certainty be differentiated: the alpha variety, including the natural graphites, which were probably formed at moderate temperature and high pressure; the beta variety, including all artificial graphites, formed at high temperature and low pressure. The fact that diamond has a higher heat of combustion than graphite has been confirmed, and the conclusion is reached that pure, thermally well defined amorphous carbon cannot be prepared. The thermal properties of commercial carbon dioxide at low temperatures have been described by C. F. Jenkin and D. R. Pye. The general assumption that aqueous solutions of carbon dioxide contain the hydrate H,CO, is seri- Lead. Considerable interest has reously questioned by E. Wilke. Car-cently been taken in the atomic bonic acid was found to be a much weight of lead obtained from various stronger acid in salt solutions than sources. T. W. Richards and M. E. in pure aqueous solution. It is con- Lembert have determined the atomic cluded that while in salt solutions weight of lead of radioactive origin H2CO, may exist, in aqueous solu- obtained from different localities, tions there is probably a higher hy- with the amazing result that values drate, such as C(OH). The molec- lower than that of ordinary lead ular weight of sodium carbonate and were invariably obtained. For the the atomic weight of carbon referred lead obtained from pitchblende 0. to silver and bromine have been deter- Hönigschmid and Mlle. St. Horowitz mined by T. W. Richards and C. R. obtained a value 0.4 lower than that Hoover. G. N. Lewis and W. N. of ordinary lead. F. Soddy and H. Lacey have studied the equilibrium Hyman have made a preliminary exbetween carbon oxysulphide, carbon amination of the lead from Ceylon monoxide, and sulphur. It was thorite, while G. P. Baxter, F. L. found that "when carbon monoxide Grover, and T. Thorvaldson have deand sulphur are heated together at termined the atomic weight of lead 250° to 300° C., carbon oxysulphide, obtained from ten widely distributed carbon dioxide, carbon disulphide, sources. Some indication of the ex; and carbon monosulphide are formed istence of an allotropic modification by the reactions: CO+S=COS; of lead has been obtained by H. Hel2COS CO2+CS1; CS2=CS+S." The ler, who observed that lead electrodes action of aluminium and certain slowly change, in a nitric acid soluother metals upon such chlorides of tion of lead acetate, into a gray, carbon as CC, CCl, CaCl, and powder-like substance. CoCl was investigated by E. V. Zappi. The carbon obtained by the

The Rare Earths.-L. M. Dennis and B. J. Lemon have effected by

the action of chlorine and bromine upon the hydrides B.H. and BH149 and has ascertained the conditions under which chlorination and bromination will take place. The derivative B,H,Cl is apparently a spontaneously inflammable gas. The corresponding bromine compound, B,H,Br, was isolated and carefully studied. A. C. G. Egerton, after an attempt to reproduce the results obtained by Collie and Patterson (4. Y. B., 1913, p. 644; 1914, p. 615), concluded that in his opinion, from the viewpoint of both theory and experiment, the source of the neon and helium ob

electrolysis the separation of lanthanum from neodymium, praseodymium, lanthanum, and samarium, as well as from praseodymium alone; and the separation of erbium from yttrium. Dennis and Van der Meulen have subjected various solutions of the rare earths to fractional electrolysis, with the result that the hydroxides of the metals are precipitated in the order of the basicities of the earths. Certain derivatives of perceric oxide have been described by C. C. Meloche. A revision of the atomic weight of praseodymium has been made by G. P. Baxter and O. J. Stewart, on the basis of their analy-tained, aside from the possibility of sis of the chloride of this metal.

their entrance as the result of atmosHalogen Compounds. The vapor pheric contamination, must be sought pressures of the halogen hydrides in some action upon the solids comand of hydrogen sulphide have been posing the discharge tube, rather measured at low temperatures by O. than upon the gases in the tube. W. Maass and D. McIntosh. The densi- D. Harkins and E. D. Wilson in a ties and degrees of dissociation of series of articles upon atomic structhe saturated vapors of the am-ture have presented and discussed the monium halides and of phosphorus theory that the various chemical elepenta-chloride have been determined ments are to be regarded as atomic by A. Smith and R. H. Lombard. (not chemical) compounds of hydroA. Gutbier has described various gen and helium. The electrical concompounds of iridium chloride with ductivity of various mixtures of organic bases, and in collaboration fused salts has been measured by C. with his associates has prepared Sandonnini. Several contributions to numerous hexachloroiridates, hexa- the theory of emulsification and the chlorosmates, and pentachlororutheni- theory of dyeing have been made durates. A. Rosenheim and E. Dehn ing the year by W. D. Bancroft and have studied the cyanides of tungsten his associates. T. C. Choudhri has and molybdenum. An approximate described a new crystalline variety determination of the boiling points of silver obtainable by treatment of of the alkali halides has been made spongy silver, prepared by ignition by L. H. Borgström. Ammonium di- of silver tartrate, with concentrated chloroiodide, NH ̧Cl,I, and ammonium nitric acid (free from lower oxides chlorobromoiodide, NH,CIBRI, have of nitrogen) at ordinary temperabeen prepared by F. D. Chattaway by tures. The silver that did not disthe action under proper conditions of solve was slowly converted into the the respective halogens upon am- long needle-shaped crystals of the monium chloride. The activation of new variety. No evidence of the exchlorates by formic acid has been istence of an alkali element of higher noted by K. A. Hofmann and K. atomic weight than cesium was obSchumpelt (see A. Y. B., 1913, p. tained by G. P. Baxter in connection 647). This influence of formic acid with a series of fractional crystallizais not attributable to its acidity, but tions of cesium nitrate obtained from to the property, possessed also by Paris (Maine) pollucite. T. W. Richother reducing activators, of acting ards and E. P. Bartlett have investiupon an oxidizing agent to form a gated the compressibilities of mermore actively oxidizing substance. cury, copper, lead, molybdenum, tantalum, tungsten, and silver bromide at 20° C., over a range of 100 to 500 megabars pressure. A valuable résumé of the work done by Richards and his co-workers in support of the

Miscellaneous.-A. Stock has continued his interesting researches upon the hydrides of boron (A. Y. B., | 1913, p. 646). With his associates E. Kuss and O. Priess he has studied