3
96
Review of Arr2ericaiz CJiewzical Kcseaich. 75
--I
co11st.
(71
P
----! =: const. - const.
ill
p,
2t) where#, tlie osmotic pressure of the kation, is proportional to its concentration (c) ; hence it follows that if x is plotted as ordinates and 1~p , or its proportional quantity (71 c, as abscissae that t h e points should lie along a straight line. T h e metals zinc, copper, gold, silver, lead, mercury, and iron lyere investigated, and the results discussed in conjuction n-it11 those of 1-011 Oettingen. I n general, the potential decreased with increasing dilution, according to the logarithmic formula up to dilutions of 1,000 to 10,000 liters. Beyond this dilution the potential decreaed very much less rapidly. T h e order of the metals in nortiial cyanide solutions n-as found to be zinc, copper, gold, silver, lead, mercury. iron. I n very dilute solutions the order became zinc, lead. iron, copper, silver, gold, mercury-. T h e last part of tlie paper is devoted to a consideration of the question of the variation of the solvent power of cyanide solutions for gold, with the concentration, and with the amount of air or oxygen dissolved. Experiments on the solubility of similar gold strips rotated twenty-four hours under like conditions in cyanide solutions of various strengths showed no appreciable solvent action when the solution contained less than 0.001 per cent. T h e solubility increased rapidly at concentrations greater than 0.0005 normal. T h e saiiie was true when a large amount of air was present in the bottles containing the metal and solution. Experiiiients show that the solvent action of the cyanide is utiquestionably increased b y the presence of dissolved oxygen, and that the reason w h y the solvent action becomes a maximum in a j to roper cent. solution is, that a t this concentration the combined effects of the dissolved oxygen, and of t h e potential difierence between the metal and the solution attains its greatest value. T h e effect of the presence of hydrogen peroxide in solution was also studied. T h e experinients described suggest several interesting line.; of work for further inyestigation.
INORGANIC CHEflISTRY. HESKT F a x R E V I L X Q E K
Potassium Perselenate-Preliminary Note. BY I,. ?rf. DES0. lv. BROWS. y. A?IZ. rhein. Sac., 23, 3 j 8 ~ 3 5 9 . Potassium perselenate was prepared by the electrolysis of a cold saturated solution of potassium selenate containing free selenic acid. T h e product separates upon the anode as a white powder. TT'hen hot, potassium perselenate oxidizes manganese dioxide to potassium permanganate, and oxidizes thallous and ferrous sulphate in the cold. NIS h3D
hiorganic Chemistvy.
I97
The Reaction between Chlorine and Ammonia. RY WILA. NOYESAND ALBERTC. LYON. J. A m . Chem. SOC., 23, 460-463. -The authors have shown by quantitative experiments that the reaction between chlorine and ammonia takes place according to the reaction : 12NHs 6C1, = N, NCl, 9NH,C1, when the ammonia is used very nearly in the proportion indicated. If an excess of ammonia is used it reacts with the nitrogen trichloride, giving free nitrogen and ammonium hypochlorite. LIAM
+
+
+
On the Decomposition of Sodium Nitrate by Sulphuric Acid, 11. BY C. W. VOLNEY. J. Am. Chem. Soc., 23, 489-492.-The author considers that the reaction between sulphuric acid and sodium nitrate takes place in two phases. T h e first takes place below IOO', according to the reaction :
+
+
NaNO, 2H,SO, = XaH,(SO,), HNO, ; on raising the temperature the second phase takes place according to this reaction : NaH,(SO,), WaSO, =.NaH(SO,), "0,.
+
+
The Sulphohalides of Lead. BY I'ICTOR LENHER. J . Am. Chem. Soc., 23, 680-682.-The sulphohalides of lead are readily prepared by dissolving lead sulphide in the halogen acid and diluting this solution with water. T h e chlor- and bromsulphide separate immediately a s red precipitates. An excess of water converts this precipitate into black lead sulphide. The Crystallization of Copper Sulphate. BY ARTHVRJ O H N HOPKISS. Am. Chem. J . , 25, 413-4rg.-In the preparation of crystals of copper sulphate from 20-30 mm. in length, the author was guided by the following principles : I. I n the process of crystallizing copper sulphate, at constant room temperature, the solubility is a constant and the concentration, minus this constant, is t h e total weight of crystal deposit. 11. ( a ) I n a solution, supersaturated in absolute quiet, no crystals will form. ( 6 ) I n a solution supersaturated in absolute quiet, the number of crystal points formed by the first disturbance is the same as the number of crystals formed. (c) T h e ratio between the number of crystals formed and the weight of crystal deposit determines the size of t h e crystals. 111. For a given volume of solution and given size of crystals and weight of crystal deposit, the diameter of the crystallizing dish determines the space between the crystals. Experiments showed that the best conditions were obtained when 171 grams of copper sulphate were dissolved in water and 15 cc. of normal sulphuric acid, and the whole evaporated to less than 340 c c . , and then diluted to exactly that volume with boiling water. As the ratio of the volume of solution to the horizontal surface of the crystallizing dish is identical with the depth of solution, a dish 26 cm. in diameter was selected so a s to have a depth of
I g8
Reaiew a t Ainericn)i Chemical Research.
liquid of 6 . 3 inin. for tlie above coiicentration. In order to obtain the proper number of crystal points, a blast of air was blown on the surface of the solution until the desired number of crystals mere started. T h e dish was tlien allowed to stand at constant temperature over night. O n crystallization at z ~ O ,27 j cc. of mother-liquor and 7s grains of crystals, ZC--30 nim. in length, u-ere obtained. I n order to concentrate the mother-liquor to such a volume as to produce a proportioilate crop of crystals, it x i s calculated that any saturated solution of copper sulphate must be evaporated to 6 7 . I per cent. of its volume. On the Formation of Platinum Tetrachloride from Aqueous liydrochloric Acid by Atmospheric Oxidation in Contact with Platinum Black. BY J . IT-.Jlar,I.Fx'. A i r r . Cheiu. J . , 25,.430. --It was found that wheii platinum black was washed with a fairly strong aqueous solutioii of hydrochloric acid i t was dissolred to a small extent with the formation of platinum tetrachloride.
On the Purification of Caesium Ilaterial. BY H. L. ~VELLS. Cheui. 26, 26j-268.-The use of the double salt, 2CsC1. PbCl,, has been found. very convenieiit for the separation of caesium, particularly after a large part of the caesium has been removed by some other means. To accoinplish this, the author separates the greater portion in the form of the salt 3CsCl.2SbCI,, as recommended by Godeffroy, except that a much less concentrated hydrochloric acid is used. T h e filtrate then carries a small amount of caesium-, which is precipitated as zCsC1.PbC14when 2 or 3 grams of lead nitrate per liter are added, and the solution is saturated with chlorine gas. T h e caesium in the antimony double salt is recovered by treating the salt with boiling dilute animonium hydroxide. I n the filtrate from the antinionious hydroxide, the large amount of animouiuni chloride is removed by several evaporations with strong nitric acid. T h e caesium nitrate can be further purified by recrystallization, or by dissolving the nitrate and an equivalent weight of iodine in I O parts of I : I hydrochloric acid at a temperature just below boiling. On cooling, the salt CsC1,I separates, practically free from rubidium, lithium, sodium, and potassium. Alii.
I.,
On a Salt of Quadrivalent Antimony. BY H. I,.WELLSA X D -4711. C h i t , J . , 26, 268-271.-The double salt zCsCl.SbCI,. which had been previously made by Setterberg by boiling a solution of antimony trichloride in strong hydrochloric acid, with antimony pentachloride and caesium chloride in excess, was found to be isomorphous with the salt 2CsCl.PhC1,. T h e color of the octahedral crystals is black, but the powdered crystal is dark blue.
F.J . METZGER.
Imrganic Chemistry.
I99
On the Acid Nitrates. BY 11, I,.WELLSAND F. J . METZGER. Am. Chem.]., 26, 271-275.-1n addition to the acid nitrates described by Ditte, the authors have prepared and studied the properties of the new salts, RbNO,.HNO,, RbN0,.2HN03, CsNO,.HNO,, CsNO,. 2HNO,, TlNO,. 2HN0,. T h e monacid salts are readily prepared by saturating nitric acid, of sp. gr. 1.42, with the normal nitrates at a gentle heat and cooling till crystallization occurs. For the diacid salts, it was necessary to use nitric acid of I . jo sp. gr. and to cool in a freezing-mixture. Investigations on Double Nitrates. BY H. I,. WELLS, H. P. BEARDSLEY, G. s. JAMESON,AND F. J . METZGER. Ant. Chem. ]., 26, 275-278.-It was found impossible to prepare double nitrates of ,caesium and the bivalent metals ; but with ferric nitrate, caesium nitrate forms a yellow deliquescent salt, melting at 33'-36', having the composition represented by the formula Cs.N0,.Fe(N0,),.7H20, and with bismuth nitrate, colorless, prismatic crystals of caesium bismuth nitrate, zCsXO,.Bi( NO,),, were obtained by evaporating a nitric acid solution of the two nitrates. When thallous nitrate is dissolved in concentrated nitric acid by the aid of heat a part of the salt is oxidized, and a thallons thallic nitrate of the composition 2TlSO,.Tl( NO,), separates 0x1 cooling. On Caesium Periodate and Iodate-Periodate. BY H. I,. WELLS. Ani. Chenz. ]., 26, 278-281 .-caesium periodate was formed by adding caesium carbonate to a concentrated solution of periodic acid. There was no evidence of the formation of any other than the normal periodate. By dissolving caesium iodate and periodate in dilute periodic acid, the iodate-periodate, HCsIO,. 10,.2H,O, crystallizes out in white prisms on evaporation. On the Caesium-Antimonious Fluorides and Some Other Double Halides of Antimony. BY H. L. WELLS AND F. J. METZGER. A m . J . Sei., 161, 451-456.-By bringing together solutions of antimonious fluoride and caesium fluoride with some free hydrofluoric acid in varying proportions the following double salts were isolated : CsF.3SbF,, CsF.2SbF3, +CsF,7SbF,, CsF. SbF,, 2CsF.SbF,. T h e 3 : 2 type of salt hasnot been made, and this seems the more remarkable since this type is prominent among the chlorides, bromides, and iodides. T h e I : 3 and 4 : 7 type of caesium antimonious fluoride salts are not found among the other double halide salts, and the 3 : 4, 3 : 2 , 7 : 3, 3 : I , and 4 : I types have not been found for the double fluorides. Caesium-antimonious iodide, Q C S I . ~ S ~has I , , been found to exist in a brick-red, octahedral form, and in yellow, hexagonal plates. T h e octahedral salt separates from solutions strongly acidified with hydriodic acid and the hexagonal salt from weakly acidified solutions. T h e composition of Setterberg's double chloride, CsCl.
200
Review qf A m e r i c a n Chemical Research.
SbCl,, has been confirmed, but the corresponding double fluoride does not seem to exist. T h e only double fluoride of caesium and quinquivalent antimony which has been found is the one having the composition represented 11y the formula CsF. SbF,OH.
On a Caesium-Tellurium Fluoride. BY H. I,.V'ELLS ASD J. M. WILLIS. A H ZJ .. Sci., 162, I9o.-IJnder the widest range of conditions only one double fluoride of caesium and tellurium could be prepared. T h e salt, CsF.TeF,. crystallizes in large transparent, colorless needles, and is readiiy decomposed by water. On the Double Chlorides of Caesium and Thorium. BY H. L. WELLS .4SD J. &I. \YILLIS. / ? I / l . f. S C i . , 162, 191-192.-011 bringing together thorium aiid caesium chlorides in varying proportions, two new salts, 3CsCl.ThC1,. I zH,O and zCsCl.ThC1,. I IH,O, were prepared. Attempts to prepare the double fluorides were not successful on account of the great insolubility of thor i iini fluoride. ORGANIC CHETIISTRY. J. F. S O R I U S , K E ~ I I : ~ ~ E I 4
The Composition of a W6od Oil. BY G. S.FRAPS.Ani.Chem. material used in the investigation wasobtained from a hard-wood tar. T h e tar, after distillation, was treated with caustic potash and again distilled. T h e distillate so obtained, whichboiled from 54' to z IO', was fractionated into portions which were collected at intervals of 3'. X s a result of a careful investigation of the separate fractions, the following conclusions are drawn : T h e oil probably contains the series of aldehydes C,,H,,,O u p to caproic aldehyde. T h e quantity of these compounds is so small, however, that valeric aldehyde only was positively identified. Furfural is also present in small quantity. T h e following ketoues were detected in the oil : dimethyl-, methylethyl-, niethylpropyl-, and probably methyl-n-butyl- and diethyl ketones. Cyclopentanone and other ring ketones are also present. It contains nitriles in minute quantities and the methyl esters of acetic, propionic, 12-butyric, and 72-valerianic acids. Methyl caproate, heptoate, and isobutyrate are also probably present. Esters of unsaturated acids, which were not identified, were also found. T h e oil contains methyl-, dimethyl-, trimethyl-, and higher furanes. No dimethylacetal or appreciable quantities of pyridines or alcohols were discovered. Unsaturated compounds which unite with hydrochloric acid and bromine were shown to be present. T h e oil contains toluene and xylene, and probably cuinene and cymene. I t also contains creosote and minute quantities of phenol ethers. T h e higher-boiling oil, freed from ke-
I., 25,26-j3.--The
