[CONTRIBUTIONFROM THE MASSACHUSETTS INSTITUTE OF TECHNOLOGY.]
REVIEW OF AMERICAN CHEMICAL RESEARCH. VOL. V.
No. 4.
ARTHUR A. NOYES,Editor ; HENRY P. TALBOT, Associate Editor. REVIEWERS : Analytical Chemistry, H . P. Talbot and W. H. Walker; % ' . Rolfe ; Biological Chemistry, A. G. Woodman ; Carbohydrates, G. 1 General Chemistry, A. A. Noyes ; Geological and Mineralogical Chemistry, W. 0. Crosby; Inorganic Chemistry, Henry Fay ; Metallurgical Chemistry and Assaying, H. 0. Hofman ; Organic Chemistry, J. F. Norn s ; Physical Chemistry, H. M. Goodwin ; Sanitary Chemistry, E. H. Richards ; Technical Chemistry, A. H . Gill and F. H. Thorp.
INORGANIC CHEMISTRY. HENRYF A Y , REVIEWER.
Presidential Address. BY WOLCOTTGIBBS.PYOC.A m . Assoc. Advancement Sci., 1898, 1-16. Science, 8, 233-243.-The author attempts to work out the theoretical relations existing between the complex derivatives of molybdic and tungstic acids with the acids of silicon and phosphorus.
On Some Relations a m o n g the Hydrates of the Metallic Nitrates. BY J. H. KASTLE. A m . Cltem.]., 20, 81~+-81g.-The author has found that practically all of the salts of nitric acid may be referred to one of the hypothetical nitric acids, and that the nitrates can be grouped under five general classes. T h e first class, which includes all of the anhydrous nitrates, is regarded as an addition-product of the anhydride of nitric acid and the metallic oxide, M',O+N,O, = 2M1N0,. T h e second class includes a few nitrates, HgNO,.H,O and T h (NO,),.qH,O, which are formed by the addition of ordinary nitric acid to a metallic base M(OH)+HNO,=MNO,.H,O. T o the third class belong a large number of nitrates of the bivalent and trivalent metals which are addition products of ortho-nitric acid and the metallic base derived as follows : MI1(O H ) , f 2 H s N 0 , = MI1'( NO,),.qH,O; M"'(OH),+3H,N0,=~1''(N0,),.6H,0. Examples of this class are Ca(N0,),.4H,O, F e ( N 0 , ) , . 6 H a 0 , and a large number of double nitrates of which 2Ce(NO3),.3Co(NO,),,24H,O is a type. T h e fourth class is formed by the addition of a base to the acid H,NO,, as M"(OH), 2H,NO,= M"(N0,),.6H20, M"'(OH), 3H,NO, = M'I'(NO,),.gH,O, and MIT(OH)rv 4H,NO,= M'"(NO,),. 12H,O. Rytheaddition of pyronitric acidto a metallic
+
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Review of Ainericaiz Chemical Research.
base the fifth class is formed : M (OH),+H,N,O, = M1r(NOz)9. 3H,O of which Cu(N0,),.3H,O is an example. Including a number of cases of doubtful composition, 7 j per cent. of all the normal nitrates described fall under one of these five classes. hIost of the basic nitrates may also be classed under these headings as salts of some of the hypothetical nitric acids.
Liquid Ammonia as a Solvent. BY E. C. FRANKLIN A N D C. A. KRAUS. Am. Chewz. J . , 20, 820-836.-The authors have extended the mort of Gore, Weyl. and Seeley on the solubility of various inorganic and organic substances in ammonia. Liquid ammonia was drawn off into a vacuum-jacketed tube and the substance to be tested was introduced into this tube in small quantity at a time and in case the substance was a solid, in the form of fine powder. Where there was any doubt about the solubility a measurement of the electrical conductivity was made. Tables are given which show the solubility of I j 7 inorganic salts and 250 organic substances.
Metathetic Reactions between Certain Salts in Solution in A N D C. A . KRAUS.A m . Liquid Ammonia. BY E. C. FRANKLIN Chem. J . , 21, I-8.-On account of the close relationship between liquid ammonia and water in solvent power, and in the power of dissociating many salts, it was supposed that metathetic reactions would take place in liquid ammonia as in water. This has been shown to be true. Sixteen nitrates were used to furnish the metallic ions ; and the sulphide, chloride, bromide, iodide, chromate, and borate of ammonia were used as precipitants. T h e tests were made by bringing the nitrates and the precipitants together in small vacuum-jacketed tubes and observing whether or not a precipitate was formed. Using ammonium chloride as precipitant no precipitates were produced in solutions of sodium and mercuric nitrates ; and from solutions of lithium, potassium, lead, silver, and copper, precipitates were produced only in concentrated solutions ; other nitrates gave precipitates at once. With ammonium bromide the results were the same except that here in addition potassium gave no precipitate and the other precipitations took place more slowly. Ammonium iodide produced precipitations only in solutions of strontium and barium salts. All the metals tested, with the exception of the alkalies, precipitatedwith ammonium sulphide. Judging from the color only a few of these substances were identical with the sulphides produced in water solution. T h e magnesium precipitate was found to be a double salt, zMgS.(NH,),S.xNH,, which evolved amnionia and hydrogen sulphide in the air. Ammonium chromate produces precipitates with all metals tested except lithium and sodium ; ammonium borate acts similarly with the exception that the potassium salt is soluble.
Inorganic Chemisf ry
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On the Solubility of Argentic Bromide and Chloride in Solutions of Sodic Thiosulphate. BY THEODORE WILLIAM RICHARDS AND HENRY BURNELLFABER.A m . Chem.]., 21, 167172.-The authors have examined the solubility of silver bromide and chloride in sodium thiosulpjate by agitating an excess of the pure silver salts with solutions of varying strength of the thiosulphate. After thorough agi‘ation 5 cc. portions were drawn off and analyzed for silver. With increasing strength of the thiosulphate solutions the quantity of silver salt going into solution increased more rapidly than the increase in the quantity of thiosulphate used. T h e molecular ratio of the sodium thiosulphate to the dissolved salts at 35’ C. for 2 0 0 gramsof the crystallized salt to the liter of water was I : 0.78 for silver chloride and I : 0 . 5 2 for silver bromide. Evidence for the existence of a complex ion in such solutions was obtained by observing the change in the freezing-point ; it was found that by the addition of silver bromide the freezing-point was raised indicating the formation of a complex salt. A New Gas. BY CHARLESF. BRUSH. /. A m . Chem. Soc., 899-9 I 2 .-During an investigation of the heat conductivity of various gases at extremely low pressures, it was found that gases were evolved from the glass on heating, which were only partly reabsorbed on cooling. Supposing the gas to come from the surface, some powdered glass was placed in the tube, and from this the gas seemed to be more freely evolved. On exposure to the air more of the gas was absorbed by the glass. On slight diminution of pressure the gas begins to come off, and the amount rapidly increases with the diminishing pressure. It is readily absorbed by soda-lime and phosphorus pentoxide. T h e heat conductivity at a pressure of 0.96 millionths of an atmosphere was found to be twenty times as great as that of hydrogen, and that of the pure gas would be IOO times that of hydrogen. If the inference is correct that the heat conductivity and the molecular velocity of gases are directly related, then the molecular velocity of the new gas is also one hundred times that of hydrogen. From this value of the molecular velocity, the density was found to be 0.0001, and the molecular weight, 0.0002. T h e author suggests that at anything like this molecular velocity, it would be quite impossible for a gas to remain in the atmosphere unless fhe space above aZso contained it, and therefore that the gas must fill all celestial space. On this assumption h e has named the gas “etherion,” and suggests that it may have some of the properties of the ether of the physicist.-Various investigators, notably Crookes, have recently claimed that all the phenomena described by Brush can be explained by the presence of a small quantity of water vapor in his apparatus. 20,
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Review o f American Chemical Research.
Commercial Iron Silicides with a High Percentage of Silicon: Their Properties, Manufacture, and Uses. BY G. DE CHALMOT. J . A m . Chem. SOC., 21, 5g-66.-The authorhas produced in the electric furnace iron silicides containing from twenty-five to fifty per cent. of silicon and probably consisting of the two compounds FeSi, and Fe,Si,. These silicides are crystalline, white or gray, hard and brittle, unalterable in the air, and can be cast well with sharp outlines and corners. These alloys are recommended for castings, on account of the smooth finish and high luster they are capable of taking ; for anodes for electrolysis in aqueous baths ; and for abrasives. Their manufacture is carried out by heating iron ore, river sand, and coke, in a special form of electric furnace. The Preparation of Zirconium Nitrides. BY J. MERRITT MATTHEWS. J . Am. Chem. Sac., 20, 843-846.-The compound ZrCl,.SNH, heated in a current of nitrogen decomposes and leaves as a gray residue the nitride Zr,N,. By heating zirconium tetrachloride in ammonia gas there is decomposition with the formation of the nitride Zr,N,. Ilethod of Preparing a Strictly Neutral Ammonium Citrate Solution. BY A. D. COOK. J . Am. Chem. SOC., 20, j85-jB6.T h e author recommends stirring the citric acid solution after adding ammonia, the heat of neutralization being sufficient to drive off the excess of ammonia. On the Segregation of Carbon in a Piece of Boiler Plate. BY J . A m . Chem. SOC., 20, HEKRY Far A N D HENRPP. TALBOT. 614-617.-The authors have examined a piece of boiler-plate steel which, after having been twice annealed, cracked on flanging. On polishing and etching the surface, it was found that the steel was highly crystalline, and that the crystalline layer extended only part way into the plate on either side. Microscopical examination showed the carbon to be much segregated, and analysis of the borings taken from different parts of the plate varied from 0.03 to 0. I j 6 per cent, of carbon. T h e probable cause of the brittleness was due to the annealing which was done at a temperature, 600"-7 50' C., at which granulation of mild steel takes place, as has been shown by the experiments of Stead. ORGANIC CH EAISTRY. j. F. h-ORRIS, REVIEWER.
On Some Double Halides of Mercury. BY J . N . SWAN. AWL.Chem. J., 20, 613-633.-The double chlorides of mercury with aniline and the toluidines were prepared and studied. Aniline, a-toluidine, and $-toluidine gave salts of the composition, zHgCl,.BHCl, HgCl,.BHCl, and HgC1,.2BHC1 where B repre-
