Cobalt ammonium chlorides bromide

Another catalytic system which has been successfully applied to the autoxidation of substituted toluenes involves the combination of Co/Br" with a quaternary ammonium salt as a phase transfer catalyst (ref. 20). For example, cobalt(II) chloride in combination with certain tetraalkylammonium bromides or tetraalkylphosphonium bromides afforded benzoic acid in 92 % yield from toluene at 135-160 °C and 15 bar (Fig. 19). It should be noted that this system does not require the use of acetic acid as solvent. The function of the phase transfer catalyst is presumably to solubilize the cobalt in the ArCH3 solvent via the formation of Q + [CoBr]. ... 

That is, a mixture of 1-, 2-diaquo-tetrammino-cobaltic chloride and 1-, 2-diehloro-tetranimino-cobaltic chloride is formed. The aquo-salt is readily soluble in water but the diehloro-salt sparingly so. The last named forms intense blue crystals which are contaminated with small quantities of the praseo-salt, from which it may be freed by transforming it into the dithionate. The dithionate is practically insoluble, but the chloride may be regenerated from it by rubbing it with ammonium chloride. The bromide, the iodide, and the nitrate have all been prepared. 

Arsenic triiodide also dissolves, the saturated solution at 15° C. having density 3-661. Other soluble halides are potassium bromide, anhydrous ferric and aluminium chlorides 6 and tetramethyl ammonium iodide but the iodides of rubidium, cadmium, manganese and cobalt, also mercuric and stannic iodides, and cobalt and stannic bromides, are insoluble or only very slightly soluble in arsenic tribromide. The liquid also dissolves phosphoryl bromide and, very slightly, ammonium thiocyanate. In the mixed solutions of halides, the components may react chemically (cf. p. 106), but such is not always the case for example, with antimony tribromide a continuous series of solid solutions is formed.7... 

Metal Halides. Reacts explosively or violently with the following calcium bromide iron(III) bromide or chloride iron(II) bromide or iodide cobalt(II) chloride silver fluoride all four mercury(II) halides copper(I) chloride, bromide or iodide copper(II) chloride and bromide ammonium tetrachlorocuprate zinc and cadmium chlorides, bromides, and iodides aluminum fluoride, chloride, and bromide thallium bromide tin(II) or (IV) chloride tin(IV) iodide arsenic trichloride and triiodide antimony and bismuth trichlorides, tribromides, and triiodides vanadium(V) chloride chromium(IV) chloride manganese(II) and iron(II) chlorides and nickel chloride, bromide, and iodide.17,22"25... 

It separates in small violet rhombic crystals which resemble chloro-pentammino-cobaltic chloride in appearance. It is soluble in cold water to a certain extent, and only two-thirds of the chlorine is precipitated from solution by silver nitrate at ordinary temperature. In aqueous solution the salt is gradually transformed into the diaquo-salt, [Co(NH3)4(HaO)2]Cl3 dilute nitric acid, if rubbed with the substance, gives reddish-violet crystals of the nitrate, [Co(XH3)4(HaO)Cl](NOs)2 and a cold concentrated solution of ammonium sulphate yields the sulphate, [Co(NH3)4(H20)C1]S04. The corresponding bromide, [Co(NH3)4(H2Q)Cl]Br2, is obtained by filtering a cold saturated solution of the chloride into concentrated hydrobromie acid at 0° C. The precipitate formed is washed with hydrobromie acid and then with alcohol. The bromide is almost insoluble in hydrobromie acid, but more easily soluble in water than the chloride.2... 

The solubility of sodium chloride in aq. acetone at 20° falls to 27"18 with 10 c.c. of acetone per 100 c.c. of solvent to 0 25 with 90 c.c. of acetone per 100 c.c. of solvent at 0°, 100 grms. of acetone dissolve 4"6 grms. of lithium chloride, and at 58°, 214 grms., so that the solubility is diminished by a rise of temp. The solubility of potassium in aq. soln. of acetone increases from almost zero with 100 per cent, acetone at 20° to 8"46 with 50 per cent, acetone and to 21 "38 with 20 per cent, acetone. At 30°, 100 grms. of a soln. with 696 per cent, acetone carries 23 42 per cent, potassium chloride and the remainder is water 8"06 per cent, of this salt is present in a soln. with 45 98 per cent, acetone and 0-13 per cent, of this salt in a soln. with 89"88 per cent, of acetone. At 40°, a soln. with 15"75 per cent, acetone carries 21 "28 per cent, of potassium chloride and with 79"34 per cent, of acetone there is 0"58 per cent, of potassium chloride. At 40°, therefore, for cone, of acetone between 20 and 80 per cent., the sat. soln. separates into two layers the upper layer has 55 2 per cent, water, 31 "82 acetone, and 12"99 KC1, when the lower layer has 28"14 per cent, water, 69 42 acetone, and 2"44 KC1. Similarly, when the upper layer has water, acetone, and potassium chloride in the respective ratio 46 49, 45"34, and 8 17 the lower layer has 38 68, 56"17, and 5 25. The separation into two layers with sat. soln. of potassium chloride containing 26 per cent, acetone, occurs at 46"5° and the temp, of separation with other proportions of acetone is indicated in Fig. 22. C. E. Linebarger (1892) and J. E. Snell (1898) 34 found the phenomenon also occurs with the chlorides of lithium, ammonium, sodium, rubidium, calcium, strontium, cobalt, and many other radicles also with bromides, sulphates, cyanides, and numerous other salts with aq. acetone,... 

Concentrated hydrochloric acid also dissolves the trichloride, about 100 g. of the latter dissolving in 1 litre of acid at 100° C.7 Dissolution in hydriodic acid is accompanied by evolution of heat and the triiodide is formed.8 Ethyl iodide reacts similarly.9 Double decomposition reactions occur w hen arsenic trichloride is heated with phosphorus triiodide, stannic iodide or germanium iodide, the reactions being complete.10 Similarly, potassium iodide heated with arsenic trichloride in a sealed tube at 210° C., and potassium bromide at 180° to 200° C., form respectively arsenic triiodide and tribromide.11 Stannous chloride, added to the solution in hydrochloric acid, causes reduction to arsenic (see p. 29). Arsenic trichloride may be completely separated from germanium chloride by extraction with concentrated hydrochloric acid.12 Ammonium, sodium and cobaltic chlorides react with arsenic trichloride to form additive compounds with magnesium, zinc and chromic chlorides there is no reaction.13... 

Nitrosylpentaamminecobalt(II) chloride, synthesis 49 cts-Bromoamminebis (ethylenediamine) cobal t (111) bromide, CIS- and trans-aquoamminebis(ethylenediamine)cobalt(IIl) bromide, and cis- and triphenylphosphine)rhodium and chloro-carbonylbis(triphenylarsine)rhodium, synthesis 56 Sodium hexachlororhodate(III) 2-hydrate and potassium hexachlororhodate(III) 1-hydrate, synthesis 57 Ammonium hexachloroiridate(IV), synthesis 58 Resolution of the tris(l,10-phenanthroline)nickel(II) ion, synthesis 59... 

Write formulas for the following compounds, using brackets to enclose the complex ion portion (a) tri-amminebromoplatinum(II) nitrate (h) dichlorobis(ethylenediamine)cobalt(Il) monohydrate, (c) penta-amminesulfatocobalt(III) bromide, (d) potassium hexafluoroplatinate(IV), (e) tetraaquadibromochro-mium(lll) chloride, (/) ammonium heptafluorozirconate(lV). 

Ammonium bifluoride Barium acetate Benzyltriethyl ammonium bromide Cobalt perchlorate (ous) Indole Lead nitrate Nickel chloride (ous) Phenylhydrazine Tributyl phosphate Zinc cyanide... 

The formation of (II) provides a quite selective spot test for palladium. Gold must be removed prior to the test because it will cause the development of a deep ruby red in the spot plate test and a diffused violet spot on the paper, apparently due to the reduction of the gold ions to the colloidal metal. Interference may also arise from 0s04 , Os+, Ru+, and RuCle ions because they have distinct self-colors. Mercurous ion causes partial interference by the reduction of part of the palladium to the elementary state, but a positive response can still be seen. It is possible to detect I part of palladium in the presence of 200 parts of platinum or 100 parts of rhodium. Less favorable ratios should be avoided because of the color of these salts. No interference is caused by mercuric and iridic chloride, but free ammonia, ammonium ions, stannous, cyanide, thiocyanate, fluoride, oxalate, and tetraborate ions do interfere. Lead, silver, ferrous, ferric, stannic, cobaltous, nickel, cupric, nitrite, sulfate, chloride, and bromide ions do not interfere. 

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