Basic carbonates

Most metal carbonates are insoluble and they are precipitated either as the simple carbonate or as the basic carbonate when... 

If the normal carbonate is used, the basic carbonate or white lead, Pb(OH),. 2PbCO,. is precipitated. The basic carbonate was used extensively as a base in paints but is now less common, having been largely replaced by either titanium dioxide or zinc oxide. Paints made with white lead are not only poisonous but blacken in urban atmospheres due to the formation of lead sulphide and it is hardly surprising that their use is declining. 

The normal carbonate CuCOj is not known two naturalls occurring basic carbonates have already been mentioned. If a solution of, for example, sodium carbonate is added to a solution of a copper(II) salt, a green basic carbonate is precipitated the reactions are ... 

On heating, the basic carbonate readily yields the black copper(II) oxide. 

The metal is very effective as a sound absorber, is used as a radiation shield around X-ray equipment and nuclear reactors, and is used to absorb vibration. White lead, the basic carbonate, sublimed white lead, chrome yellow, and other lead compounds are used extensively in paints, although in recent years the use of lead in paints has been drastically curtailed to eliminate or reduce health hazards. 

Hafnium Carbonate. Basic hafnium carbonate [124563-80-0], Hf2(0H)4C02 XH20, is prepared as a wet paste by reaction of a slurry of basic hafnium sulfate [139290-14-5], Hf 02(S0 2 XH20, and sodium carbonate, then filtering. The basic carbonate has a short shelf life and is preferably prepared as needed. It is a starting material for the preparation of various hafnium carboxylates. 

Hafnium Acetate. Hafnium acetate [15978-87-7], Hf(OH)2(CH2COO)2, solutions are prepared by reacting the basic carbonate or freshly precipitated hydroxide with acetic acid. The acetate solution has been of interest in preparing oxide films free of chloride or sulfate anions. 

Lead Carbonate. Lead carbonate [598-63-0] PbCO, mol wt 267.22, d = 6.6g/cm, forms colorless orthorhombic crystals it decomposes at about 315°C. It is nearly insoluble in cold water (0.00011 g/100 mL at 20°C), but is transformed in hot water to the basic carbonate, 2PbC03 Pb(OH)2. Lead carbonate is soluble in acids and alkalies, but insoluble in alcohol and ammonia. It is prepared by passing CO2 iuto a cold dilute solution of lead acetate, or by shaking a suspension of a lead salt less soluble than the carbonate with ammonium carbonate at a low temperature to avoid formation of basic lead carbonate. 

Upon exposure to the atmosphere, magnesium hydroxide absorbs moisture and carbon dioxide. Reactive grades are converted to the basic carbonate 5MgO 4CO2 XH20 over a period of several years. Grades that resist carbonization at high temperature and humidity have been reported (71). 

The loaded organic phase is stripped of beryUium using an aqueous ammonium carbonate [506-87-6] solution, apparently as a highly soluble ammonium beryUium carbonate [65997-36-6] complex, (NH 4Be(C02)3. AU of the iron [7439-89-6] contained in the leach solution is coextracted with the beryUium. Heating the strip solution to about 70°C separates the iron and a smaU amount of coextracted aluminum as hydroxide or basic carbonate... 

Heating the ammonium beryUium carbonate solution to 95°C causes nearly quantitative precipitation of beryUium basic carbonate [66104-24-3], Be(OH)2 2BeC02. Evolved carbon dioxide and ammonia are recovered for recycle as the strip solution. Continued heating of the beryUium basic carbonate slurry to 165°C Hberates the remaining carbon dioxide and the resulting beryUium hydroxide [13327-32-7] intermediate is recovered by filtration. The hydroxide is the basic raw material for processing into beryUium metal, copper—beryUium and other aUoys, and beryUia [1304-56-9] for ceramic products. Approximately 90% of the beryUium content of bertrandite is recovered by this process. 

Bismuth trioxide may be prepared by the following methods (/) the oxidation of bismuth metal by oxygen at temperatures between 750 and 800°C (2) the thermal decomposition of compounds such as the basic carbonate, the carbonate, or the nitrate (700—800°C) (J) precipitation of hydrated bismuth trioxide upon addition of an alkah metal hydroxide to a solution of a bismuth salt and removal of the water by ignition. The gelatinous precipitate initially formed becomes crystalline on standing it has been represented by the formula Bi(OH)2 and called bismuth hydroxide [10361 -43-0]. However, no definite compound has been isolated. 

Cadmium Hydroxide. Cd(OH)2 [21041-95-2] is best prepared by addition of cadmium nitrate solution to a boiling solution of sodium or potassium hydroxide. The crystals adopt the layered stmcture of Cdl2 there is contact between hydroxide ions of adjacent layers. Cd(OH)2 can be dehydrated to the oxide by gende heating to 200°C it absorbs CO2 from the air forming the basic carbonate. It is soluble ia dilute acids and solutions of ammonium ions, ferric chloride, alkah haUdes, cyanides, and thiocyanates forming complex ions. 

The carbon slurry has to be received and dewatered before feeding it to the furnace. There are two basic carbon column operating systems the batch and the intermittent or slug type. Depending on which system is used, the receiving, dewatering, and feed operations are performed differently. 

For some non-ferrous metals (copper, lead, nickel) the attack by sulphuric acid is probably direct with the formation of sulphates. Lead sulphate is barely soluble and gives good protection. Nickel and copper sulphates are deliquescent but are gradually converted (if not leached away) into insoluble basic sulphates, e.g. Cu Cu(OH)2)3SO4, and the metals are thus protected after a period of active corrosion. For zinc and cadmium the sulphur acids probably act by dissolution of the protective basic carbonate film. This reforms, consuming metal in the process, redissolves, and so on. Zinc and cadmium sulphates are formed in polluted winter conditions whereas in the purer atmospheres of the summer the corrosion products include considerable amounts of oxide and basic carbonate. ... 

In contrast with the Pb-HjO system, it can be seen in Figure 4.13 that in the presence of SO " the corrosion zone in the region of low pH no longer exists, owing to the thermodynamic stability of PbSO. The Pb-HjO-COj system has been expressed in a similar pH/potential diagram in which account has been taken of insoluble carbonates and basic carbonates of lead. 

Lead usually has excellent resistance to seawater owing to the formation of a passive film of basic carbonate and carbonate-chloride double salts , which should be compared with its behaviour in solutions of alkali chlorides (see salts p. 4 87). 

Industrial atmospheres usually accelerate the corrosion of zinc. When heavy mists and dews occur in these areas, they are contaminated with considerable amounts of acid substances such as sulphur dioxide, and the film of moisture covering the metal can be quite acid and can have a pH as low as 3. Under these conditions the zinc is dissolved but, as the corrosion proceeds, the pH rises, and when it has reached a sufficiently high level basic salts are once more formed and provide further protection for the metal. These are usually the basic carbonate but may sometimes be a basic sulphate. As soon as the pH of the moisture film falls again, owing to the solution of acid gases, the protective film dissolves and renewed attack on the metal occurs. Hudson and Stanners conducted tests at various locations in order to determine the effect of atmospheric pollution on the rate of corrosion of steel and zinc. Their figures for zinc are given in Table 4.34 and clearly show the effect which industrial contamination has on the corrosion rate. 

White rust If a fresh zinc surface is allowed to stand with large drops of dew on it, as may easily happen if it is stored in a closed place in which the temperature varies periodically, it is attacked by the oxygen dissolved in the water, owing to differential aeration between the edges and the centres of the drops. A porous form of zinc oxide builds up away from the surface and quickly takes up carbon dioxide from the air to form the basic carbonate known as white rust or wet storage stain. 

A large number of electrolytic treatments of magnesium, anodic or a.c., have been developed, in which adherent white or grey films consisting of fluoride, oxide, hydroxide, aluminate or basic carbonate are deposited from alkaline solutions containing caustic alkali, alkali carbonates, phosphates, pyrophosphates, cyanides, aluminates, oxalates, silicates, borates, etc. Some films are thin, and some are relatively thick. All are more or less absorbent and act as good bases for paint, though none contributes appreciable inhibition. All can, however, absorb chromates with consequent improvement of protective efficiency. 

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