Cobaltous acid

Erdmann,1 in 1866, prepared the first member of this series, namely, ammonium tetranitrito-diammino-cobaltate, [Co(NH3)2(N02)4] NH4. The salt is sometimes referred to as Erdmann s salt on that account. Later, Gibbs prepared other salts of the same type, and showed that in these salts the cobalt atom, united with ammonia and acidic radicles, forms a negative radicle.2 Werner then showed that these salts form the connecting link between the neutral un-ionised complex triacido-triammino-eobalt compounds and the double salt, such as potassium eobalti-nitrite. Thus, by replacement of ammonia molecules by acid radicles a transition takes place from trinitrito-triammino - cobalt to potassium tetranitrito - diammino - cobaltate, [Co(NH3)2(N02)4]K, then to potassium pentamtrito-ammino-eobalfate. [Co(NH3)(N02)5]K, and finally to hexanitrito-cobaltate, [Co(N02)e]Iv3. Tetra-acido-diammino-cobaltates are therefore the salts of the acid tetra-acido-diammino-cobaltic acid, [Co(NH3)2R4]H. 

The best known of these compounds is potassium cobalti-nitrite, [Co(N02)6]K3.1 This salt was originally regarded as a double salt of cobaltic nitrite with potassium nitrite, and represented by the formula Co(NQ2)3.3KNOa. Such a formula, however, does not represent the reactions of the substance, as the nitrite radicle is held firmly, and nitrous aeid is not liberated when the compound is treated with cold dilute acids, as it would be if it were a double salt as the formula indicates. Molecular conductivity measurements also indicate that it is a complex salt comparable with the metal-ammines. Many compounds of cobalt of this type are known. They may be regarded as the salts of the complex acid hexanitrito-cobaltic acid, [Co (N02)6]H3. 

Cobalt Sesquioxide, Co203, results when cobalt nitrate is gently heated to 180° C.4 It is a black, amorphous powder, of density 518. Hydrogen begins to reduce it at 182° C.5 It may be regarded as the cobalt salt of cobaltous acid, namely, cobaltous cobaltile, CoCo03. 

McConnell and Hanes 1 claim to have obtained the monohydrate or cobaltous acid, H2Co03, by the action of hydrogen peroxide upon cobaltous hydroxide in aqueous suspension.2 If the acid can exist at all in the free state it is very unstable, although some of its salts are well defined. 

In 2012, Burlet et al. showed that strong spectroscopic evidence proved that the mineral structure could be better described by the chemical formula HC0O2 instead of CoO.OH [5]. The mineral should be thus considered as a cobaltic acid [12] instead of a cobalt oxy-hydroxide [3]. Heterogenite was in consequence categorized as a layered oxide with a delafossite-type structure [5]. 

Delaplane R., Ibers J., Ferraro J., Rush J., Diffraction and Spectroscopic Studies of the Cobaltic Acid System HC0O2-DC0O2 (J. Chem. Phys. 50, 1969), 1920... 

It was first described in 1608 when it was sublimed out of gum benzoin. It also occurs in many other natural resins. Benzoic acid is manufactured by the air oxidation of toluene in the liquid phase at 150°C and 4-6 atm. in the presence of a cobalt catalyst by the partial decarboxylation of phthalic anhydride in either the liquid or vapour phase in the presence of water by the hydrolysis of benzotrichloride (from the chlorination of toluene) in the presence of zinc chloride at 100°C. 

CoAsS, are also used as sources. The ore is roasted and Co is precipitated as the hydroxide and then reduced to Co with carbon (hep below 417 - C, cep to m.p.). The metal is silvery white and readily polished. It dissolves in dilute acids and is slowly oxidized in air. Adsorbs hydrogen strongly. The main use of cobalt is in alloys. Cobalt compounds are used in paints and varnishes, catalysts. Cobalt is an essential element in the diet. World production 1976 32 000 tonnes metal. 

CoS04,7H20. Few cobalt(III) oxy acid salts are known. 002(504)3,ISHjO is formed by electrolytic oxidation and forms alums Co(N03)3 contains co-ordinated nitrate (C0F3 plus NjOs). 

Besides stmctural variety, chemical diversity has also increased. Pure silicon fonns of zeolite ZSM-5 and ZSM-11, designated silicalite-l [19] and silicahte-2 [20], have been synthesised. A number of other pure silicon analogues of zeolites, called porosils, are known [21]. Various chemical elements other than silicon or aluminium have been incoriDorated into zeolite lattice stmctures [22, 23]. Most important among those from an applications point of view are the incoriDoration of titanium, cobalt, and iron for oxidation catalysts, boron for acid strength variation, and gallium for dehydrogenation/aromatization reactions. In some cases it remains questionable, however, whether incoriDoration into the zeolite lattice stmcture has really occurred. 

These are practically insoluble in water, are not hydrolysed and so may be prepared by addition of a sufficient concentration of sulphide ion to exceed the solubility product of the particular sulphide. Some sulphides, for example those of lead(II), copper(II) and silver(I), have low solubility products and are precipitated by the small concentration of sulphide ions produced by passing hydrogen sulphide through an acid solution of the metal salts others for example those of zincfll), iron(II), nickel(II) and cobalt(II) are only precipitated when sulphide ions are available in reasonable concentrations, as they are when hydrogen sulphide is passed into an alkaline solution. 

Cobalt is a bluish silvery metal, exhibits ferromagnetism, and can exist in more than one crystal form it is used in alloys for special purposes. Chemically it is somewhat similar to iron when heated in air it gives the oxides C03O4 and CoO, but it is less readily attacked by dilute acids. With halogens, the cobalt(II) halides are formed, except that with fluorine the (III) fluoride, C0F3, is obtained. 

Hydrated cobalt III) sulphate, Co2(S04)3. JSHjO is obtained when cobalt(II) sulphate is oxidised electrolytically in moderately concentrated sulphuric acid solution it is stable when dry but liberates oxygen from water. Some alums, for example KCo(S04)2.12H,0 can be obtained by crystallisation from sulphuric acid solutions. In these and the sulphate, the cation [CofHjO) ] may exist it is both acidic and strongly oxidising. 

For this reaction, charcoal is a catalyst if this is omitted and hydrogen peroxide is used as the oxidant, a red aquopentammino-cobalt(lll) chloride, [Co(NH3)jH20]Cl3, is formed and treatment of this with concentrated hydrochloric acid gives the red chloro-p0itatnmino-coba. t(lll) chloride, [Co(NH3)5Cl]Cl2. In these latter two compounds, one ammonia ligand is replaced by one water molecule or one chloride ion it is a peculiarity of cobalt that these replacements are so easy and the pure products so readily isolated. In the examples quoted, the complex cobalt(III) state is easily obtained by oxidation of cobalt(II) in presence of ammonia, since... 

Cobalt(II) is also easily oxidised in the presence of the nitrite ion NO2 as ligand. Thus, if excess sodium nitrite is added to a cobalt(II) salt in presence of ethanoic acid (a strong acid would decompose the nitrite, p. 244), the following reaction occurs ... 

Addition of excess potassium nitrite acidified with ethanoic acid gives a precipitate of the potassium hexanitro-cobaltate(lll), K3[Co(N02)6] (P. 403). 

When cobalt(II) chloride was dissolved in water, a pink solution A was formed. The addition of concentrated hydrochloric acid to A gave a blue solution B. If solution A was treated with concentrated ammonia solution a blue-green precipitate was formed upon addition of further ammonia solution followed by the passage of air through the mixture, an orange-red solution C was produced. 

A compound of cobalt has the formula Co(NH3)jtCl. 0.500 g of it was dissolved in 50.00 cm M hydrochloric acid the excess acid required 40.00 cm M sodium hydroxide solution to neutralise it. Another 0.500 g portion of the compound was dissolved in water and allowed to react with excess silver nitrate solution. 0.575 g of silver chloride was precipitated. 

Carbonyiation of butadiene gives two different products depending on the catalytic species. When PdCl is used in ethanol, ethyl 3-pentenoate (91) is obtained[87,88]. Further carbonyiation of 3-pentenoate catalyzed by cobalt carbonyl affords adipate 92[89], 3-Pentenoate is also obtained in the presence of acid. On the other hand, with catalysis by Pd(OAc)2 and Ph3P, methyl 3,8-nonadienoate (93) is obtained by dimerization-carbonylation[90,91]. The presence of chloride ion firmly attached to Pd makes the difference. The reaction is slow, and higher catalytic activity was observed by using Pd(OAc) , (/-Pr) ,P, and maleic anhydride[92]. Carbonyiation of isoprcne with either PdCi or Pd(OAc)2 and Ph,P gives only the 4-methyl-3-pentenoate 94[93]. 

The 3.8-nonadienoate 91, obtained by dimerization-carbonylation, has been converted into several natural products. The synthesis of brevicomin is described in Chapter 3, Section 2.3. Another royal jelly acid [2-decenedioic acid (149)] was prepared by cobalt carbonyl-catalyzed carbonylation of the terminal double bond, followed by isomerization of the double bond to the conjugated position to afford 149[122], Hexadecane-2,15-dione (150) can be prepared by Pd-catalyzed oxidation of the terminal double bond, hydrogenation of the internal double bond, and coupling by Kolbe electrolysis. Aldol condensation mediated by an organoaluminum reagent gave the unsaturated cyclic ketone 151 in 65% yield. Finally, the reduction of 151 afforded muscone (152)[123]. n-Octanol is produced commercially as described beforc[32]. 

Although this experiment is written as a dry-lab, it can be adapted to the laboratory. Details are given for the determination of the equilibrium constant for the binding of the Lewis base 1-methylimidazole to the Lewis acid cobalt(II)4-trifluoromethyl-o-phenylene-4,6-methoxysalicylideniminate in toluene. The equilibrium constant is found by a linear regression analysis of the absorbance data to a theoretical equilibrium model. 

Chemical ingenuity in using the properties of the elements and their compounds has allowed analyses to be carried out by processes analogous to the generation of hydrides. Osmium tetroxide is very volatile and can be formed easily by oxidation of osmium compounds. Some metals form volatile acetylacetonates (acac), such as iron, zinc, cobalt, chromium, and manganese (Figure 15.4). Iodides can be oxidized easily to iodine (another volatile element in itself), and carbonates or bicarbonates can be examined as COj after reaction with acid. 

Manufacture. Furan is produced commercially by decarbonylation of furfural in the presence of a noble metal catalyst (97—100). Nickel or cobalt catalysts have also been reported (101—103) as weU as noncatalytic pyrolysis at high temperature. Furan can also be prepared by decarboxylation of 2-furoic acid this method is usually considered a laboratory procedure. 

Adiponitrile undergoes the typical nitrile reactions, eg, hydrolysis to adipamide and adipic acid and alcoholysis to substituted amides and esters. The most important industrial reaction is the catalytic hydrogenation to hexamethylenediarnine. A variety of catalysts are used for this reduction including cobalt—nickel (46), cobalt manganese (47), cobalt boride (48), copper cobalt (49), and iron oxide (50), and Raney nickel (51). An extensive review on the hydrogenation of nitriles has been recendy pubUshed (10). 

Oxidation. Acetaldehyde is readily oxidised with oxygen or air to acetic acid, acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal product depends on the reaction conditions. Acetic acid [64-19-7] may be produced commercially by the Hquid-phase oxidation of acetaldehyde at 65°C using cobalt or manganese acetate dissolved in acetic acid as a catalyst (34). Liquid-phase oxidation in the presence of mixed acetates of copper and cobalt yields acetic anhydride [108-24-7] (35). Peroxyacetic acid or a perester is beheved to be the precursor in both syntheses. There are two commercial processes for the production of peracetic acid [79-21 -0]. Low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or osone yields acetaldehyde monoperacetate, which can be decomposed to peracetic acid and acetaldehyde (36). Peracetic acid can also be formed directiy by Hquid-phase oxidation at 5—50°C with a cobalt salt catalyst (37) (see Peroxides and peroxy compounds). Nitric acid oxidation of acetaldehyde yields glyoxal [107-22-2] (38,39). Oxidations of /)-xylene to terephthaHc acid [100-21-0] and of ethanol to acetic acid are activated by acetaldehyde (40,41). 

Butane-Naphtha Catalytic Liquid-Phase Oxidation. Direct Hquid-phase oxidation ofbutane and/or naphtha [8030-30-6] was once the most favored worldwide route to acetic acid because of the low cost of these hydrocarbons. Butane [106-97-8] in the presence of metallic ions, eg, cobalt, chromium, or manganese, undergoes simple air oxidation in acetic acid solvent (48). The peroxidic intermediates are decomposed by high temperature, by mechanical agitation, and by action of the metallic catalysts, to form acetic acid and a comparatively small suite of other compounds (49). Ethyl acetate and butanone are produced, and the process can be altered to provide larger quantities of these valuable materials. Ethanol is thought to be an important intermediate (50) acetone forms through a minor pathway from isobutane present in the hydrocarbon feed. Formic acid, propionic acid, and minor quantities of butyric acid are also formed. 

The Acetaldehyde Oxidation Process. Liquid-phase catalytic oxidation of acetaldehyde (qv) can be directed by appropriate catalysts, such as transition metal salts of cobalt or manganese, to produce anhydride (26). Either ethyl acetate or acetic acid may be used as reaction solvent. The reaction proceeds according to the sequence... 

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