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KNO2 .3H20, is best known . It may be prepared by the addition of See also:potassium nitrite to an acetic See also:acid See also:solution of See also:cobalt chloride . The yellow precipitate obtained is washed with a solution of potassium acetate and finally with dilute See also:alcohol . The reaction proceeds according to the following See also:equation: 2CoC12+10KNO2+ 4HNO2=See also:Co2(NO2)6•6KNO2+4KC1+2N0+2H20 (A . Stromeyer, Annalen, 1855, 96, p . 220) . This See also:salt may be used for the separation of cobalt and See also:nickel, since the latter See also:metal does not See also:form a similar See also:double nitrite, but it is necessary that the alkaline See also:earth metals should be absent, for in their presence nickel forms complex nitrites containing the alkaline earth metal and the See also:alkali metal . A See also:sodium cobaltinitrite is also known . Cobalt nitrate, Co(NO3)2.6H2O, is obtained in dark-red mono-clinic tables by the slow evaporation of a solution of the metal, its hydroxide or carbonate, in nitric acid . It deliquesces in the See also:air and melts readily on See also:heating . By the addition of excess of See also:ammonia to its aqueous solution, in the See also:complete See also:absence of air, a See also:blue precipitate of a basic nitrate of the See also:composition 6CoO•N203.5H2O is obtained . By boiling a solution of cobalt carbonate in phosphoric acid, the acid phosphate CoHPO4.3H2O is obtained, which when heated with See also:water to 250° C. is converted into the neutral phosphate See also:Cos(PO4)2.2H20 (H . Debray, See also:Ann. de chimie, 1861, [3] 61, p . 438) . Cobalt ammonium phosphate, CoNH4PO4.12H2O, is formed when a soluble cobalt salt is digested for some See also:time with excess of a warm solution of ammonium phosphate . It separates in the form of small See also:rose-red crystals, which decompose on boiling with water . Cobaltous See also:cyanide, Co(CN)2.3H20, is obtained when the carbonate is dissolved in hydrocyanic acid or when the acetate is precipitated by potassium cyanide . It is insoluble in dilute acids, but is readily soluble in excess of potassium cyanide . The double cyanides of cobalt are analogous to those of See also:iron . Hydrocobaltocyanic acid is not known, but its potassium salt, K4Co(CN)3, is formed when freshly precipitated cobalt cyanide is dissolved in an See also:ice-See also:cold solution of potassium cyanide . The liquid is precipitated by alcohol, and the washed and dried precipitate is then dissolved in water and allowed to stand, when the salt separates in dark-coloured crystals . In alkaline solution it readily takes up See also:oxygen and is converted into potassium cobalticyanide, K3Co(CN)s, which may also be obtained by evaporating a solution of cobalt cyanide, in excess of potassium cyanide, in the presence of air, 8KCN+2Co(CN)2+See also:H2O+O= 2K3Co(CN)4+2KHO . It forms See also:monoclinic crystals which are very soluble in water . From its aqueous solution, concentrated hydrochloric acid precipitates hydrocobalticyanic acid, H3Co(CN)6, as a colourless solid which is very deliquescent, and is not attacked by concentrated hydrochloric and nitric acids . For a description of the various•salts of this acid, see P . Wesselsky, Berichte, 1869, 2, p . 588 . Cobaltammines . A large number of cobalt compounds are known, of which the empirical composition represents them as salts of cobalt to which one or more molecules of ammonia have been added . These salts have been divided into the following See also:series : Diammine Series, [Co(NH3)2]X4M . In these salts X=NO2 and M =one atomic proportion of a monovalent metal, or the See also:equivalent quantity of a divalent metal . Triammine Series, [Co(NH3)s]X2 . Here X = Cl, NO3, NO2, 4SO4, &c . Tetrammine Series . This See also:group may be divided into the •Praseo-salts [R2Co(NH3)4]X, where X=C1 . Croceo-salts [(NO2)2Co(NH3)4]X, which may be considered as a subdivision of the praseo-salts . Tetrammine purpureo-salts [RCo(NH3)4•H2O]X2 . Tetrammine roseo-salts [Co(NH3)4•(H2O)2]X3 . Fuseo-salts [Co(NH3)4]OH•X2 . Pentammine Series . Pentammine purpureo-salts [R•Co(NH3)s]X2 where X = Cl, Br, NO3, NO2, SO4, &c . Pentarntnine roseo-salts [Co(NH3)s•H2O]X2 . Hexammine or Luteo Series [Co(NH3)6]X3 . The hexammine salts are formed by the oxidizing See also:action of air on dilute ammoniacal solutions of cobaltous salts, especially in presence of a large excess of ammonium chloride . They form yellow or See also:bronze-coloured crystals, which decompose on boiling their aqueous solution . On boiling their solution in See also:caustic alkalis, ammonia is liberated . The pentammine purpureo-salts are formed from the luteo-salts by loss of ammonia, or from an air slowly oxidized ammoniacal cobalt salt solution, the precipitated luteosalt being filtered off and the filtrate boiled with concentrated acids . They are See also:violet-red in See also:colour, and on boiling or See also:long See also:standing with dilute acids they pass into the corresponding roseo-salts .
The pentammine nitrito salts are known as the xanthocobalt salts and have the See also:general See also:formula [NO2•Co•(NH3)s]X2
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They are formed by the action of nitrous fumes on ammoniacal solutions of cobaltous salts, or purpureo-salts, or by the mutual reaction of chlorpurpureosalts and alkaline nitrites
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They are soluble in water and give characteristic precipitates with platinic and auric chlorides, and with potassium ferrocyanide
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The pentammine roseo-salts can be obtained from the action of concentrated acids, in the cold, on air-oxidized solutions of cobaltous salts
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They are of a reddish colour and usually crystallize well ; on heating with concentrated acids are usually transformed into the purpureo-salts
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Their alkaline solutions liberate ammonia on boiling
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They give a characteristic See also:pale red precipitate with sodium pyrophosphate, soluble in an excess of the precipitant; they also form arecipitates on the addition ofplatinic chloride and potassium ferrocyanide
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For methods of preparation of the tetrammine and triammine salts, see O
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Dammer's Handbuch der anorganischen Chemie, vol
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3 (containing a complete See also:account of the preparation of the cobaltammine salts)
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The diammine salts are prepared by the action of alkaline nitrites on cobaltous salts in the presence of much ammonium chloride or nitrate; they are yellow or See also: The aqueous solution, however, does not show the See also:ordinary reactions of cobalt or of ammop)a, and so it is to be presumed that the salt ionizes into [Co(NH3)s] and 3C1' . The purpureo chloride has only two-thirds of its chlorine precipitated on the addition of silver nitrate, and the electric conductivity is much less than that of the luteo chloride; again in the praseosalts only one-third of the chlorine is precipitated by silver nitrate, the conductivity again falling; while in the triammine salts all ionization has disappeared . For the constitution of these salts and of the " metal ammonia " compounds generally, see A . See also:Werner, Zeit. See also:fur anorg . Chemie, 1893 et seq., and Berichte, 1895, et seq . ; and S . Jorgensen, Zeit. fur anorg . Chemie, 1892 et seq . The oxycobaltammines are a series of compounds of the general type [Co203•H2(NH3)10]Xs first observed by L . See also:Gmelin, and subsequently examined by E . See also:Fremy, W . See also:Gibbs and G . Vortmann (Monatshefte fur Chemie, 1885, 6, p . 404) . They result from the cobaltammines by the See also:direct taking up of oxygen and water . On heating, they decompose, forming basic tetrammine salts . The atomic See also:weight of cobalt has been frequently determined, the earlier results not being very concordant (see R . See also:Schneider, Pog . Ann., 1857, 101, p . 387; C . See also:Marignac, See also:Arch . Phys . Nat . [2], I, p . 373; W . Gibbs, Amer . Jour . Sci . [2], 25, p . 483; J . B . See also:Dumas, Ann . Chim . Phys., 1859 [3], 55, p . 129; W . J . See also:Russell, Jour . Chem . See also:Soc., 1863, 16, p . 51) . C . Winkler, by the See also:analysis of the chloride, and by the action of See also:iodine on the metal, obtained the values 59.37 and 59.07, whilst W . Hempel and H . Thiele (Zeit. f. anorg . Chem., 1896, II, p . 73), by reducing cobalto-cobaltic See also:oxide, and by the analysis of the chloride, have obtained the values 58.56 and 58.48 . G . P . See also:Baxter and others deduced the value 58.995 (0 =16) . Cobalt salts may be readily detected by the formation of the See also:black sulphide, in alkaline solution, and by the blue colour they produce when fused with See also:borax . For the quantitative determination of cobalt, it is either weighed as the oxide, Co3O4, obtained by ignition of the precipitated monoxide, or it is reduced in a current of See also:hydrogen and weighed as metal . For the quantitative separation of cobalt and nickel, see E . Hintz (Zeit. f. anal . Chem., 1891, 30, p . 227), and also NICKEL . |
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Dear, Corrections for the paragraph starting with "Debray, See also: ANN Ann. de chimie, 1861, [3] 61, p . 438) . " Instead of K4Co(CN)3: K2Co(CN)4 The reaction correctly: 4 Co(CN)2 + 16 KCN + 2 H2O + O2 ---> 4 K3Co(CN)6 + 4 KOH Best Regards, Hasan Mehdi
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