XXVIII. CHEMISTRY AND PHYSICS CHEMISTRY INORGANIC AND PHYSICAL ARTHUR WESLEY BROWNE Water.-In connection with a general discussion recently held by the Faraday Society upon the subject of the constitution of water, there has been published a series of five articles, by P. Walden, P. A. Guye, W. R. Bousfield and T. M. Lowry, W. Sutherland, and W. Nernst, respectively. The various lines of evidence considered seem to corroborate the theory, held for years by certain physicists and chemists, that the constitution of water must be expressed by the formula (H,O), and seem moreover to point toward the presence in liquid water and in aqueous solutions of single, double, and triple molecules, or "steam," "water," and "ice" molecules, with the formulae HO, (H2O),, and (H,O),, in proportions depending upon the temperature, the nature of the dissolved substance, and the concentration of the solution. This idea receives additional confirmation from the work of A. Rosenstiehl, who has made a statistical study of 179 salts containing water of crystallization. able to similar processes in nature. In this connection it may be of interest to cite the experiments of A. Gautier and P. Clausmann, who obtained methane and hydrogen by the action of steam upon the product obtained when magnetic iron oxide was heated in an atmosphere of carbon monoxide and hydrogen. Ferric oxide, under somewhat similar treatment, yielded a product resembling vaseline and the simpler solid hydrocarbons. Another possible theory for the formation of natural gas and petroleum might therefore be based upon the action of carbon monoxide beneath the surface of the earth upon reducible metallic oxides, with formation of carbides, which would subsequently react with steam-forming gaseous, liquid, or solid hydrocarbons. Electromerism.-In the course of an investigation upon the ionization of gases-a process for which the new name electromerism has been suggested-and chemical change, H. B. Baker has found that the rate of reaction between certain gases is greatly accelerated by the presence of electromers, which seem to facilitate condensation of the small amounts of water vapor present in the gas mixture. The catalytic action of minute amounts of water upon numerous reactions may probably be explained, in accordance with the theory of J. J. Thomson, on the ground that the water tends to condense upon the electromers, some of which are always present in ordinary gases, and that the reactions begin in the resulting drops. The behavior of water vapor toward a mixture of carbon or of a carbonaceous material with lime at a temperature of from 600° to 800° C. has been investigated by L. Vignon. Decomposition of the water was effected more rapidly and at a lower temperature by the mixtures used than by carbon alone, and resulted in the formation of hydrogen, methane, ethylene, carbon monoxide, Hydrogen Peroxide and Ozone.and calcium carbonate. It is sug- By passing a brush discharge, obsted that the formation of natural | tained with the aid of a large Wimsand petroleum may be attribut- hurst machine, between a platinum point and a platinum disk, and through air saturated with water vapor, M. Kernbaum has succeeded in effecting partial decomposition of the water, with formation of hydrogen peroxide and hydrogen. He ascribes the action to the influence of cathode radiation, rather than to that of the ultra-violet light produced by the discharge. A. Tian has shown that when water is exposed to the action of ultra-violet light, hydrogen is first evolved, and later both hydrogen and oxygen, when the hydrogen peroxide begins to decompose (see E. van Aubel, YEAR BOOK, 1910, p. 589). K. Charitschkow states that hydrogen peroxide is formed when detonating gas is burned, and when oxygen gas (but not when air) in contact with water is exposed to sunlight. Hydrogen peroxide is likewise formed in small amounts upon the surface of moist, porous substances such as wood, asbestos, and pumice. The formation of oxygen, hydrogen, hydrogen peroxide, nitric acid, and ammonia was found by A. Makowetzky to take place at the anode when a glow discharge was passed between a Nernst filament used as the anode, and a surface of water, while hydrogen alone was liberated at the platinum cathode. W. Chlopin has found that ordinary, undried air, on treatment with ultra-violet rays for a few minutes, yields very appreciable amounts of both hydrogen peroxide and ozone, and very small amounts of nitrogen oxides. An interesting contribution to the theory of thunderbolts has been made by W. M. Thornton, who concludes, on the basis of several lines of evidence, that the principal, although perhaps not the only, constituent of ball or globular lightning is an aggregation of ozone and partially dissociated oxygen expelled from a negatively charged cloud by electric waves after a violent lightning discharge. By bringing together dry ethereal solutions of zinc ethyl and hydrogen peroxide E. Ebler and R. L. Krause have prepared zinc peroxide, a white amorphous solid, which is considered to be a true salt of hydrogen peroxide. Photochemistry and Actinochemistry. In a recent address P. C. Freer has summarized the researches that have been conducted in Manila with a view to ascertaining the quality of tropical sunlight and its influence upon certain chemical reactions. From this work he draws the conclusion that "tropical sunlight produces chemical changes which either take place much more slowly in temperate climates, or indeed do not take place at all." R. F. Bacon has found that tropical sunlight seems to ionize the air to a greater extent than is usual in the temperate zones. This phenomenon may, however, be due to the large amount of moisture in the tropical atmosphere, and to the luxuriant vegetation of the tropical islands. Hydrogen peroxide is rapidly formed when either water or a salt solution is exposed to direct sunlight in Manila. On the basis of this fact it is suggested that the production of hydrogen peroxide may be an essential intermediate step in the formation of clouds by the action of weak ultra-violet light. D. Berthelot and H. Gaudechon have subjected aqueous solutions of ammonia and of ammonium salts in the presence of air or oxygen to the action of ultraviolet rays with the result that nitrites are formed. Nitrates under similar treatment are reduced to nitrites. Many points of similarity between the behavior of ultraviolet rays and that of certain microorganisms were noted. These investigators have also effected several other syntheses by exposing the substances to prolonged treatment at ordinary temperatures with strong ultra-violet light. It was found possible (1) either to prepare carbon dioxide from carbon monoxide and oxygen, or to decompose it with formation of these substances; (2) either to form water from its elements, or to decompose it into its elements; (3) either to obtain formaldehyde from carbon monoxide and hydrogen, or to carry out the reverse process; (4) to prepare formamide from carbon monoxide and ammonia. The conclusion is drawn that "the synthesis of hydrates of carbon is a physico-chemical action caused by light, and can be realized in the absence of plants or chlorophyll." Nitrogen. The compounds of ni- stopper was kept for about three trogen have long been considered to weeks at room temperature. At the bear a certain relationship to the close of this time a ring of black corresponding compounds of oxygen material, subsequently shown to be (see YEAR Bоok, 1910, p. 590-1). carbon, was found near the exposed The gases themselves, however, al- end of the stopper. This carbonizathough similar in some respects, dif- tion was found to be due to the fer markedly in their chemical ac- action of mercury vapor, in the prestivity under ordinary conditions, ence of moisture, upon a gas evolved oxygen being active and nitrogen in- from the vulcanized rubber. The ert. By subjecting pure nitrogen, process, which takes place more from whatever source, to the glow rapidly at 100°, is accelerated by the discharge, R. J. Strutt has, however, presence of sulphur, but retarded by succeeded in obtaining an active mod- selenium and tellurium. Amalgams, ification of this element. The gas especially sodium amalgam, yield the after treatment glows for a short, vapor more efficiently than does time, a fact which is considered to be liquid mereury itself. Illuminating due to recombination of dissociated gas, chloroform, carbon tetrachloatoms. The active nitrogen was ride, carbon bisulphide, carbon dioxfound to convert ordinary phosphorus ide, silver bromide (in a gelatin into the red modification, to combine photographic plate), and hydrogen with sodium, and to form with gently sulphide-the last-named with liberaheated mercury an explosive com- tion of sulphur-are also decomposed pound. It acts upon nitric oxide by the action of mercury vapor. In with formation of nitrogen tetroxide, the black deposit of carbon are found attacks acetylene, and liberates halo- microscopic colorless crystals which gen from certain organic compounds, show certain of the characteristic combining with carbon to form properties of the diamond. It would cyanogen. This piece of work is un- appear, then, that certain carbon doubtedly to be regarded as one of compounds may be decomposed by the most interesting scientific ad- mercury vapor with formation of diavances of the year within the field monds. From this fact the concluof inorganic and physical chemistry. sion is drawn that the formation of The attempt made by F. Raschig to graphite and of the diamond in naprepare the hypothetical polymer ture may perhaps be attributable to (N), by means of the reaction of the action upon carbon dioxide of hydro-nitric acid with iodine, or with metallic vapors, such as the vapor chlorazide, N,Cl, was unsuccesful. of iron or of magnesium. By elecMercury. The pressures at which trolyzing a saturated solution of eylinders of hardened steel filled with tetramethyl ammonium chloride in mercury will burst were found by absolute alcohol at -10° between a P. W. Bridgman (see YEAR BOOK, silver-plated platinum anode and a 1910, p. 604) to be of about one- mercury cathode, H. N. McCoy and fourth the magnitude of the bursting W. C. Moore have obtained tetramepressures for cylinders filled with thyl ammonium amalgam, a crystalwater. This was explained by the line solid which is fairly stable at fact that under the conditions of the low temperatures, and have made an experiments in which mercury was extended study of its properties. The used the iron undergoes amalgama- amalgam is violently decomposed by tion. This process, however, does not water with formation of hydrogen, occur as a direct result of pressure colloidal mercury, and tetramethyl alone, but as the result of an initial ammonium hydroxide. It acts upon strain which effects a distension of aqueous solutions of ammonium, sothe pores of the iron, thereby facili- dium, potassium, and copper salts, tating union with the mercury. A and upon alcoholic solutions of copvery interesting property of mercury per and zinc salts, the tetramethyl vapor has been discovered and in- ammonium group replacing these vestigated by W. von Bolton. A metals in the salts and setting free glass test-tube containing barium the metals themselves or forming the amalgam and closed with a rubber corresponding amalgams. The au thors consider that they are warranted in concluding "that the organic radicals in our amalgams are in the metallic state and, therefore, that it is possible to prepare composite metallic substances from nonmetallic constituent elements." Solutions.- From non aqueous, non-conducting solutions it was found possible by C. B. Gates to throw out metallic copper by means of lead, zinc, cadmium, tin, bismuth, antimony, mercury, silver, iron, nickel, cobalt, aluminum, mag nesium, sodium, potassium, and calcium, but not by means of platinum or gold. Copper may also be precipitated from fused organic salts by many of the common metals. A series of the metals arranged in accordance with their relative basicity in non-aqueous solutions does not coincide with the electrochemical series. The interesting discovery was made that many metals are appreciably dissolved by oleic acid with concomitant evolution of hydrogen. Tellurium.-The work of Flint, (see YEAR BOок, 1910, p. 591), who claims to have proved the complexity of ordinarily pure tellurium, has been seriously called in question by Harcourt and Baker. These investigators have duplicated Flint's experiments with the result that the mean value for the atomic weight of tellurium was found to be 127.54. The lower results obtained by Flint are thought to be attributable to the formation of a higher nitrate. Stock and Blumenthal have prepared carbon bitelluride, an analogue of carbon bisulphide, by passing an electric are or spark between graphite and tellurium electrodes under carbon bisulphide. This substance is a very unstable brown solid which dissolves in carbon bisulphide with formation of a yellow solution. From concentrated solutions at -100° glistening brown crystals may be deposited. Carbon bitelluride possesses an unbearable odor, and is extremely irritating to the mucous membrane. Celtium. By repeated fractionation of the nitrates in connection with the isolation of lutecium (see YEAR BOOK, 1910, p. 591) from the gadolinite earths, G. Urbain obtained a mother liquor that could not be made to crystallize. From this he obtained a white oxide of magnetic susceptibility very much lower than that of lutecia. In chemical character the new element, which shows a large number of characteristic lines in the arc spectrum, is intermediate between the elements lutecium and scandium with which it is associated. The name celtium is suggested by the discoverer. as Radioactive Elements.-E. Ebler has succeeded in preparing a small sample of metallic radium (see YEAR Book, 1910, p. 592) by carefully decomposing in vacuo perfectly dry crystals of radium trinitride, Ra (N,), Although the resulting product was contaminated with metallic barium, the work will probably stand an interesting confirmation of Mme. Curie's discovery that pure radium is a metallic element, with properties analogous with those of metallic barium. The electrochemistry of polonium and other radioactive elements has been investigated by A. R. Johnson. In order to separate polonium from bismuth the oxychloride was dissolved in hydrochloric acid. By rotating a copper disc in the resulting solution, deposition of the radioactive element was effected. Polonium seems to be a metal that is less electropositive than copper or bismuth, but more than mercury. By passing a slight current between copper electrodes through a solution containing polonium it was found possible to effect the deposition upon the cathode of nearly all of the polonium present. The element therefore moves with the current in solution, as do real metals. The chemistry of mesothorium, the first product of the thorium disintegration series, and the parent of radiothorium, has been independently investigated during the past year by W. Marckwald and by F. Soddy. The latter investigator inclines toward the opinion that thorium-X, mesothorium, and radium form a trio inseparable by chemical means. He also propounds the question "whether some of the common elements may not, in reality, be mixtures of chemically non-separable elements in constant proportions, differing step-wise by whole units in atomic weight. This would certainly account for the lack of regular re- but complete expression for the chemlationships between the numerical values of the atomic weights." De Forcrand has attempted to predict some probable chemical properties of radium and its compounds, basing his statements upon certain relationships that exist between radium and the metals of the alkali and the alkaline earth groups. (See also infra, Phys ics.) ical nature of compounds. In this way it is possible to point out the difference between isomeric substances, and also to understand their having different chemical properties. At first atomic weights and valence were considered as sufficient for this purpose, but as the number of organic compounds studied carefully by the chemist increased, need for some new means became apparent. For the idea of stereochemistry or spacial arrangement of the atoms and groups within the molecule. Then tautomerism was added to the list to account for differences which could be explained in no other way. Even with all this, many isomeric substances, like the two benzophenones or the three different cinnamic acids, could not be distinguished from each other by means of their structural formulae. Falk and Nelson (Journal of the American Chemical Society, vol. 32, 1911, p. 1,637) have now sug. gested another addition, that of giv ing valence direction. By means of this it is possible to write structural formulae for compounds like those mentioned above in such a way that their differences are expressed in their formulae. Miscellaneous.-Brief mention at least should be accorded to the work this reason Van't Hoff introduced of A. C. Vournasos, who has de-. scribed a method for the synthesis of volatile hydrides. This consists in heating the element in question with sodium formate. E. Bentel has studied the behavior of certain gold compounds toward potassium ferrocyanide solution and finds that finely divided metallic gold slowly dissolves under certain conditions in this reagent. J. Novak has prepared two magnesium carbides, MgC2 and Mg,C,. He states that these substances furnish the only example of two simple and well defined carbides formed from the same metal. J. Meunier has found that by holding a piece of copper in the reducing flame of a gas burner and then thrusting it into the interior of the burner, the metal continues to glow, thus furnishing an illustration of the rapid combustion of gases without flame. Wolfgang Ostwald has confirmed the experimental data of Kossonogov, who recently investigated with the ultramicroscope the phenomena of electrolysis, but offers a new explanation of the facts. The luminous points supposed by Kossonogov to be ions are regarded by Ostwald charged colloidal particles. W. v. Lepkowski has investigated critical mixtures of aniline and amylene with the aid of the ultramicroscope and with especial reference to the interesting opalescence phenomena characteristic of liquids in the neighborhood of the critical state. ORGANIC CHEMISTRY J. M. NELSON as Structural Formulae.-The main object in the use of structural formulæ, especially in organic chemistry, has been to give a very short Falk (Journal of the American Chemical Society, vol. 33, 1911, p. 1,140) has applied this idea to explaining the difference between ethylenic isomers like maleic and fumaric acids, in place of the older way of stating that they differ in a stereochemical sense. He considers the difference between the acids as due to the difference in direction of certain valencies. This might be more clearly shown by means of the following formula: HO2C.CHCH.CO2H Fumaric Acid HO.C.CHCH.CO2H Maleic Acid Cinnamic Acids. In his investigation of the three cinnamic acids Stobbe (Berichte der Deutschen chemischen Gesellschaft, vol. 44, 1911, p. 2,753) has come to the conclusion that all three acids belong |