[CONTRIBUTION FROM THE
MASSACHUSETTS INSTITUTE O F TECHNOLOGY.]
REVIEW OF AMERICAN CHEMICAL RESEARCH. VOL. V.
No.
I.
ARTHURA. NOYES, Editor ; HENRYP. TALBOT, Associate Editor. REVIEWERS: Analytical Chemistry, H. P. Talbot and W. H. Walker ; Biological Chemistry, A. G. Woodman ; Carbohydrates, G. W. Rolfe ; General Chemistry, A. A. Noyes ; Geological and Mineralogical Chernistry, W. 0. Crosby ; Inorganic Chemistry, Henry Fay ; Metallurgical Chemistry and Assaying, H. 0. Hofman ; Organic Chemistry, J. F. Norris ; Physical Chemistry, H. M. Goodwin ; Sanitary Chemistry, E. H. Richards ; Technical Chemistry, A. H. Gill and F. H. Thorp.
INORGANIC CHEMISTRY. HENRYI?AY, REVIEWER.
A Reduction of Permanganic Acid by Ilanganese Peroxide. BY H. N . MORSEA N D C. L,. REESE. A m . Chem. I., 2 0 , 521535.-In a previous paper (this Rev., 2, 85) it was shown that permanganic acid decomposes in presence of manganese dioxide and a reduction of the acid takes place with the liberation of three-fifths of its active oxygen. I t was suggested later that this phenomenon might explain the evolution of oxygen which takes place when hydrogen or carbon 'monoxide is absorbed by a five per cent. acidified solution of potassium permanganate. H. Hirtz and V. Meyer maintained that the phenomenon of the evolution of oxygen observed by Meyer and Von Recklinghausen was fundamentally different from that observed by Morse, Hopkins, and Walker, because the latter experimented only with neutral solutions, and the evolution of oxygen which occurs during the absorjiion is much more rapid than that which takes place after the exhaustion of the gas. T h e authors point out that the first objection is invalid ; for out of 48 experiments 35 were made with acidified Permanganate solution. I n regard to the second objection, the suggestion is offered that the rapid initial evolution of oxygen is in some way connected with the nature of the gaseous reducing agent or that the initial peroxide molecules are of greater simplicity. Meyer and von Recklinghausen obtained about 1.9 to 2.9 cc. of oxygen when air was shaken with a five per cent. acidified solution of potassium permanganate which had been previously boiled, and they believed that there was a definite limit to the evolution of oxygen. T h e authors show that boiling with sulphuric acid produces man-
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Review of' America72 Chemical Kesearch.
ganese dioxide, which may be the cause of the decomposition, and that there is a gradual, but continuous, decomposition with continued shaking. Working with three solutions which contained respectively 2 . S 2 2 , j.614,and 5 1 milligrams of K b I n 0 , i n each cubic centimeter, and which had been filtered through two layers of asbestos, it was shown that the two weaker solutions suffered no appreciable loss of oxygen when shaken I jo to 300 hours, whether the acid added was equivalent to once or six times the potassium of t h e permanganate. In the strongest solution there was no appreciable loss of oxygen except when the acid present aiiiounted to three times that of the potassium, and even then after agitating I jo hours was not 50 large as that observed by Meyer and ron Recklinghausen. X series of experiments were made to determine the relative rates of reduction when equal volumes of permanganic acid are agitated, on the one hand with a given volume of hydrogen, and on the other with a quantity of peroxide which is equal to that produced by the absorption of all of the hydrogen. T h e same three solutions were used and were shaken at times varying from 2.1 to 300 hours and with acid equivalent to all of the potassium and to three times as much. T h e experiments sho\r that hydrogen a s a reducing agent is much more efficient during the first 24 hours than manganous sulphate with the two stronger solutions. During the period from 24 to IjO hours, the oxide produced by hydrogen acted much more rapidly in the permanganate solution containing j 1 milligrams KhlnO, than the oxide produced by the manganous sulphate. In the two more dilute solutions this order is reversed. During the period of shaking, from I j o to 300 hours, the oxide produced by hydrogen was decidedly less active than that from manganese sulphate. I n the presence of oxide there seems to be no limit to the reaction until all of the permanganic acid is used up.
On the netaphosphimic Acids ( 1 1 1 ) . BY H. N . STOKES. Am. Chenz. J . , 20, 740-760. -In two preceding papers ( t h i s Rev., 3, 4-7) t h e author has described trinietaphosphimic and tetranietaphosphimic acids obtained from the corresponding phosphonitrilic chlorides, P,?;,Cl, and P,X4Cl., H e now prepares and describes the n e s t higher members of this series, the pentainetaphosphiniic and hexametaphosphimic acids, PbN,(O H ) ,o and P , N , ( O H ) , , , by acting on the chlorides with sodium acetate. I t is found that there is a close analogy between this series of acids and t h e series of methylene ring hydrocarbons, atid that with respect to stability, power of forming lactones, and the nature of t h e decomposition-products, the properties of these acids may be explained by stereochemical considerations analogous to those of von Baeyer on the methylene hydrocarbons and of Wislicenus on t h e lactones. Assuming that t h e metaphos-
Inorganic Chemistry
.
3
phimic acids are phosphorus-nitrogen ring conipounds, and that the mean angle for an eight-membered ring, which is the most stable condition, is 135', the properties of theother acids may be deduced from this. From the following table it will be seen that a s we ascend in the series there is a very rapid increase of stability to a maximum, followed by a gradual decrease. T h i s is in accordance with the experimental data. P,N,(OH),, is less stable than P,N,(OH),, but markedly more stable than P , N , ( O H ) , , corresponding to the difference of only 9' from 135' in one case against 15' in the other. Ring.
Number of sides.
Mean angle.
PN PZNZ
2
OC
4 6
90°
Difference from 135'.
-135O -49
-
I200
I
T h e acids containing I and 2 atoms of phosphorus are unknown ; those containing 3, 4, 5 , and 6 atoms of phosphorus have been isolated and exist in two atoms, the lactam form, (PNO,H,),, where n is either 3, 4, 5 , or 6 , which is formed only in neutral or acid solution and the openchain form (PNO,€I,),f H,O formed under the influence of alkali. T h e acid corresponding to the chloronitride, P,N,Cl,,, and possibly those from the higher members, exist only in the open chain form. T h e higher members of the series break down into the more stable form containing four atoms of phosphorus. Pentametaphosphimic acid breaks down under the influence of mineral acids into tetrametaphosphimic acid, triimidotetraphosphoric acid, diimidotriphosphoric acid, and orthophosphoric acid. T h e sodium and silver salts of penta- and hexametaphosphimic acids in which the metals replaced one-half of the hydrogen, were prepared. Unsuccessful attempts were made to prepare the amides of the metaphosphimic acids by treating the chloronitrides with strong ammonia. On the Claims of Davyum to Recognition a s a Chemical Element. BY J. W . MALLET. A m . Chem. 2 0 , 776-783.Davyuin has been described by Kern as having been obtained from platinum ores. H e found its atomic weight to be 154,and one of its characteristics was the insoluble double sodiuni salt. T h e material investigated by the author was obtained from a London manufacturer of platinum : the filtrate from the aqua regia solution, after decantation from osmiridium and separation of the platinum by means of ammonium chloride, had been evaporated to dryness with sodium chloride. On taking this up in a small quantity of water, the insoluble residue, where davyum
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Review of American Chemical Research.
should be found, was proved by the author to be a mixture of finely divided quartz, zircon, and osmiridiulri. I n the precipitation of platinum from certain liquors, ammonium chloride saturated with sodium chloride is used. By evaporation of the filtrate there was formed a buff-colored powder consisting of octahedra. T h e metal was reduced by pure zinc, dissolved in aqua regia, the sodium double salt again made, dried, weighed, and reduced in hydrogen. Assuming the formula for t h e double salt to be Sa,hlCl,, the atomic weight of the metal was deduced as I j I . j , which agrees closely with Kern’s value. T h e properties of the metal obtained were similar to those described for davyum, but it was shown to consist of iridium and rhodium in about equal amounts and of a trace of iron. The Formation of Alums by Electrolysis. BY JAS. LEWIS HOWEA N D E. A . O’NEAL. J . A m . Chem. Sol., 2 0 , 7j9-76j.Solutions of metals in the lower state of oxidation were electrolyzed in a platinum dish, which formed the positive electrode, in presence of sulphuric acid and the different alkali sulphates. T h e rubidium and caesium iron alums and the rubidium and caesium cobalt alums were prepared in this way. Derivatives of the Tetrachlorides of Zirconium, Thorium, and Lead. BY J. MERRITT MATTHEWS. J . Am. Chem. SOC., 2 0 , 815-839.--By bringing together ethereal solutions of t h e tetrachlorides of zirconium, thorium, and lead, with different substituted ammonias, direct addition takes place. Four molecules of methyl, ethyl, and propyl amines are added to each of the tetrachlorides. Zirconium tetrachloride combines with four molecules both of aniline and toluidine ; thorium tetrachloride with four of aniline and three of toluidine ; and lead tetrachloride with three of aniline, decomposing toluidine. Two molecules each of pyridine, quinoline, and naphthylamine combine with zirconium tetrachloride, one each with thorium tetrachloride, while lead tetrachloride combines with one of pyridine atid naphthylamine, and two of quinoline. Under different conditions eight, six, and two molecules of ammonia add directly to zirconium tetrachloride ; eight and six to thorium tetrachloride ; and foiir to lead tetrachloride. Derivatives of the Tetrabromides of Zirconium and Thorium. BY J . MEKRITT MATTHEITS. /. A m .Chem. soc., 20, 839-843.Zirconium tetrabromide adds itself directly to four molecules of ammonia, ethylamine, and aniline, and to three of pyridine ; thorium tetrabromide adds directly to one molecule of pyridine, three of ammonia, and four of ethylamine and aniline. Review and Bibliography of the MetallicCarbides. BY J . A. MATHEWS. Smithsonian Miscellaneous CoZZectiom, N o . 1090, 1-32.
