Liebrich's Inactive Space. By R. GARTENMEISTER (Annalen, 245, 230-235).-The author has repeated Liebrich's experiments on the existence of an inactive zone ("todten Raum ") surrounding the space in which chemical reaction takes place in liquids. He finds that the hypothesis of this inactive zone is unnecessary, as the phenomena in question can be easily explained without its aid. For example, a test-tube is nearly filled with a mixture of sodium carbonate and chloral hydrate solution. It is then closed with a cork and inverted; after five minutes have elapsed the mixture becomes cloudy (owing to the formation of chloroform) except at the upper surface of the liquid. This remains clear, because the chloroform evaporates into the space above the surface of the liquid. When this space is saturated with chloroform vapour, then chloroform begins to separate out in the uppermost layers of the mixture. W. C. W. Formation of Layers in Mixtures of Alcohol, Water, and Salts, or Bases. By J. TRAUBE and O. NEUBERG (Zeit. physikal. Chem., 1, 509–515).-Bodländer was the first to observe that on dissolving ammonium sulphate in mixtures of alcohol and water, at certain concentrations, the liquid divides into two well-defined layers. The authors find a similar behaviour with potassium and sodium hydroxides and carbonates, sodium phosphate and sulphate, zinc and magnesium sulphates, and other salts. They have therefore examined this change in the case of ammonium sulphate under varying conditions of temperature and concentration. With a solution containing 340 grams of salt per litre, 750 c.c. of which is mixed with 250 c.c. of alcohol (99.6 per cent.), it is found that with increasing temperature there is in the upper layer a decrease in the relative amounts of water and salt, and an increase in that of the alcohol; in the lower layer, there is an increase of water, but a decrease of salt and alcohol. The change in the composition of the lower layer is, however, so small, that within tolerably wide limits of temperature it may be looked on as constant. Keeping the temperature constant, and increasing either the amount of alcohol or salt in solution, it is found that in the upper layer there is a decrease in the relative amounts of water and salt and an increase in that of the alcohol, in the lower layer there is a decrease in the alcohol and an increase in the salt, the water first increasing and then decreasing. In this way the addition of 40 grams of salt to a litre produce about the same effect as the addition of 100 grams of alcohol. Experiments with potassium carbonate led to similar conclusions as those above quoted. It was not possible in either case to determine whether the components of the layers are present in definite molecular proportions, but this appears likely, especially in the case of the lower layer, the percentage composition of which has a great tendency to H. C. remain constant. Absorption of Gases by Grey Vulcanised Caoutchouc. By G. HUFNER (Ann. Phys. Chem. [2], 34, 1—10).-As the result of a series of observations extending over a considerable period, the author arrives at the following conclusions. Within the limits of temperature from 5° to 25°, no definite absorption coefficient of atmospheric air can be determined. An apparent absorption does take place, and during a series of experiments extending over six months this absorption was found to continue at a nearly uniform rate, but the author finds that it is due to a gradual disappearance of oxygen, caused probably by slow oxidation of the caoutchouc. Within the temperature limits from 15° to 25°, there is no perceptible absorption of nitrogen. At a temperature of about -2° grey vulcanised caoutchouc absorbs about its own volume of dry carbonic anhydride. The specific coefficient of absorption of this gas diminishes with increasing temperature. Within the limits of temperature from -2° to -13°, there was found to be no perceptible absorption of hydrogen, even after the caoutchouc had been in contact with the gas for three months. G. W. T. Inorganic Chemistry. Methods for obtaining Constant Streams of Hydrogen Chloride, Ammonia, and Nitrogen. By G. NEUMANN (J. pr. Chem. [2], 37, 342-345; compare Abstr., 1887, 769).-Hydrogen chloride can be generated in a Kipp's apparatus by the action of ordinary sulphuric acid on carnallite, and ammonia gas by allowing a solution of ammonia to react with solid potassium hydroxide. When the materials are exhausted, the solution of potash which is formed may be used for ordinary laboratory purposes after it has been boiled to expel ammonia. To prepare nitrogen in a Kipp's apparatus, it is best to employ cubes containing chloride of lime made according to Winkler's method (Abstr., 1887, 442); these are treated with a mixture of equal volumes of ammonia and water. The resulting gas contains suspended ammonium chloride and other impurities, which may be removed by passing it through water, potash, and sulphuric acid. The author describes an apparatus for obtaining constant supplies of these and other gases, which is superior to Kipp's, in that it is cheaper and that broken parts can be easily replaced. G. T. M. Hyposulphates. By K. KLüss (Chem. Centr., 1888, 215-216).— The following hyposulphates (dithionates) are described:-Bismuth, Bi2O,,S205 + 5H2O; stannous, 8SnO,S2O, + 9H2O; thorium, Th(S2O6): + 4H2O; normal and basic chromium salts, Cr2(S2O6)18H2O and 3Cr203,4S20, + 24H2O; uranium salts of the composition 7UO2,S2O5 + 8H2O, 6U02,S2Os + 10H2O, and 8UO2,S2O5 + 21H2O; an ammonium salt, (NH4)2, S206, H2O; a beryllium salt, 5BeO, 2S2O, + 14H2O; ferrous hyposulphate, FeS2O + 7H2O, and the following basic ferric salts, 8 Fe2O3, S205 +14H2O, and 3Fe2O3, S2O, + 8H2O. The normal ferric salt is unstable in the solid state. Normal copper hyposulphate, CuS2O + 5H2O, and several basic salts, 4CuO,S2O, + 3 and 4H2O, a mercury salt, 5HgO,2S,O,, and an aluminium salt, Al2O3,3S2O5 +18H2O, were also prepared. Attempts to prepare hyposulphate of zirconium and vanadium failed. Hyposulphuric acid is without effect on cerium dihydroxide and thallium hydroxide at the ordinary temperature; on heating, the acid decomposes with evolution of sulphur dioxide, which reduces the hydroxide. In the second part of the paper, the author discusses the isomorphism of the hyposulphates, and describes the preparation of different double salts. Double salts of ammonium hyposulphate with hyposulphates of magnesium, zinc, cadmium, ferrous oxide; manganous oxide, nickel, cobalt, aluminium, and copper are described. The following isomorphous mixtures were analysed: barium with lithium and silver salts, and thallium with sodium, lithium, silver, and barium salts. There does not appear always to be such a sharply defined line between double salts and an isomorphous mixture as has hitherto been supposed. J. P. L. Nitrous Anhydride and Nitrosyl Chloride. By A. GEUTHER (Annalen, 245, 97-99).-The mixture of nitrogen sesquioxide and peroxide obtained by the action of nitric acid (sp. gr. 1·4) on arsenious oxide, may easily be separated by distillation, if the vapours are first passed into a flask at 30° before entering the receiver, which is surrounded by ice and salt. The sesquioxide boils at 35°. Its specific gravity has been determined at different temperatures The peroxide boils at 26°. Its specific 1-5035 at -5° to 1·4935 at 0°, and 1.474 at 15°. The specific gravity of nitrosyl chloride is At 18° 1·433 Nitryl chloride does not appear to exist. 0° 1·449 +1 1.4485 +2 1.447 gravity varies from W. C. W. Action of Carbon Tetrachloride on Inorganic Oxygen Compounds free from Hydrogen. By H. QUANTIN (Compt. rend., 106, 1074—1076).—The various oxygen compounds were heated at different temperatures in the vapour of the tetrachloride. Barium and sodium carbonates at dull redness are completely converted into chlorides with evolution of carbonic anhydride and carbon oxychloride. Geuther obtained a mixture of carbonate and chloride by the action of the tetrachloride on the oxides of these metals, but probably the chloride which was formed melted and protected the carbonate from the action of the vapour. Carbonic anhydride, boric anhydride, and silicic anhydride offer similar resistances to the reducing action of carbon tetrachloride, and hence it was of interest to compare the behaviour of carbonates, borates, and silicates. Ferric and aluminium borates are completely volatilised at a red heat, the boric acid being partially converted into boron trichloride and partially volatilised as the anhydride. Kaolin is distinctly attacked under the same conditions. Silicates rich in silica yield a small quantity of silicon tetrachloride, the amount increasing with the proportion of alumina in the silicate. Barium and potassium sulphates at a red heat are partially converted into chlorides, with formation of pyrosulphuryl chloride, carbonic anhydride, and carbon oxychloride. Calcium phosphate at a red heat yields calcium chloride and phos. phorus pentachloride. By the action of chlorine and carbonic oxide on the phosphate at a lower temperature, Riban obtained phosphorus oxychloride. It follows that the interaction of carbon tetrachloride and phosphorus oxychloride at a red heat yields phosphorus pentachloride. Tungstic anhydride at dull redness yields the oxychlorides WOC and WOCI,, whilst molybdic and uranic anhydrides yield mixtures of chloride and oxychloride. From these results it follows that oxygen compounds which contain no hydrogen are attacked by carbon tetrachloride at a high temperature, the metal and the non-metal being converted into oxychloride, if the latter can exist in presence of excess of carbon tetrachloride. The tetrachloride is converted into carbonic anhydride and carbon oxychloride. If the temperature is so high that the oxychlorides are reduced by the excess of the tetrachloride, metallic and non-metallic chlorides only are obtained. C. H. B. Sodium Potassium Carbonate. By L. HUGOUNENQ and J. MOREL (Compt. rend., 106, 1158-1160).-A solution containing per litre 495 9 grams of potassium iodide, 10.3 grams of potassium carbonate, 773 grams of sodium carbonate, 420 grams of disodium phosphate, and 58.3 grams of sodium chloride, when allowed to evaporate spontaneously, yields large, transparent, prismatic crystals containing the two carbonates together with water of crystallisation. They are slightly efflorescent, begin to melt at about -40°, and dissolve in their own weight of water. The crystals are monoclinic prisms, the dominant face being me', and the ratios of the axes a b c = 07104 10: 0-78, with an inclination of 75° 35'. When dissolved in water and recrystallised, the crystals have not the same composition, but contain a higher proportion of potassium, and approximate more closely to Margueritte's salt, K,CO,,6H,O + 2(NaCO3,6H,O). The composition of the original crystals agrees fairly well with the formula K2CO3,6H2O + 3(Na2CO3,6H2O), but only when they have been formed under the particular conditions described above. There can be little doubt that the crystals are not true double salts, but mixtures of isomorphous salts. C. H. B. Compound of Zinc Oxide with Sodium Hydroxide. By A. M. COMEY and C. L. JACKSON (Ber., 21, 1589-1590).—When a solu tion of zinc or zinc oxide in strong aqueous soda is shaken with alcohol, the liquid separates into two layers. The lower, aqueous, layer is again treated two or three times with alcohol, when it solidifies to a crystalline mass. The alcoholic solution, under circumstances not yet determined, deposits lustrous needles in conical or spherical groups. The crystals have the composition expressed by the formula 2NaOZnOH + 7H2O. They do not melt at 300', and are decomposed by alcohol, and by water when free alkali is not present. The composition of the crystals first mentioned was not determined, but they seem to differ from the other crystals only in having a larger amount of water of crystallisation; they melt below 100°. N. H. M. Action of Sodium Thiosulphate on Cupric Salts. By G. VORTMANN (Monatsh., 9, 165-179) -The compound obtained when a solution of sodium thiosulphate is added to a solution of copper sulphate has been investigated by many experimenters, and various formulæ have been assigned to it. The author's results are as follows. A greenish-yellow salt, Cu,S2O3, Na,S,O,+ 3H2O, separates in the form of microscopic prisms when saturated solutions of copper sulphate and sodium thiosulphate in the proportion of 1 mol. of copper sulphate to 2 mols. of sodium thiosulphate are mixed and allowed to stand at the ordinary temperature. Sodium tetrathionate is also formed. When, however, the solutions are previously heated to 40° and then mixed, the temperature rises 5-7, and on standing in water at 40° an intensely citron-yellow salt, 3Cu2S2O3,2Na2S2O3 + SH2O, separates in the form of microscopic prisms. When this salt is washed with alcohol and dried over sulphuric acid, it loses 3 mols. H2O, but if left too long it gradually decomposes. citron-yellow salt can also be prepared from the greenish-yellow one by continued washing with cold water, and it is always formed when the solutions of copper sulphate and sodium thiosulphate are warm or dilute. It is unstable, decomposes, and becomes black on standing. When boiled with water or dilute sulphuric acid, it is decomposed: 3Cu,S,O,,2Na2S2O3,8H2O = 3Cu2S + 2Na2SO, + H2SO, + S2+2SO2 + 7H2O. Attempts to prepare copper thiosulphate were unsuccessful. This Salts containing more than 1 mol. of sodium thiosulphate to 1 mol. of copper thiosulphate, such as Cu2S2O3,2Na2S2O3 + 4H2O; Cu2S2O3,3Na2S2O3 + 2H2Ö, and Cu2SO,,4Nа2S,O3 + 6H2O, are best obtained by mixing a solution of the citron-yellow salt with a solution of the calculated quantity of sodium thiosulphate and adding alcohol. The double salts separate as oily liquids which solidify when treated with fresh quantities of absolute alcohol. They are yellow to white. crystalline compounds, which are more stable and less readily decomposed when boiled with water than the salts described above. They do not decompose on keeping, and are readily soluble in water, but are not deliquescent. With barium salts, their aqueous solutions give a white precipitate, Cu2S2O3,2BaS2O3 + 7H2O, which is soluble in hydrochloric acid, but almost insoluble in water. F. S. K. |