The Hydroxides

This compound is isostructural with brucite (Mg(OH)2) and Cdl2. The unit cell is hexagonal with a = 0.3258 nm and c = 0.4605 nm. The structure consists of sheets of corner-sharing, trigonally distorted Fe(OH)6 octahedra stacked along the [001] direction. The Fe ions occupy only half the available octahedral interstices and this results in a structure in which each filled layer of sites alternates with an empty layer of sites. The OH radical behaves as a single entity. Amakinite is a rare mineral of the composition (Fe,Mg,Mn)(OH)2, also with brucite structure. Fe(OH)2 is readily oxidized by air and even by water, upon which the colour changes from white to brownish. The structure can be maintained up to a replacement of one tenth Fe by Fe (Bernal et al., 1959). 

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Cd(OH) j. The hydroxide is precipitated from aqueous solution by OH", it does not dissolve in excess OH". Ignition of Cd(OH)2 or CdCO, gives CdO which varies in colour from red-brown to black because of lattice defects. 

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. 

Dow process The process for the extraction of magnesium from sea-water by precipitation of Mg(OH)2 by Ca(OH)2 followed by solution of the hydroxide in hydrochloric acid. 

The white solid oxides MjO and M 0 are formed by direct union of the elements. The oxides MjO and the oxides M"0 of calcium down to radium have ionic lattices and are all highly basic they react exothermically with water to give the hydroxides, with acids to give salts, and with carbon dioxide to give carbonates. For example... 

The hydroxides M OH are all soluble in water, in which they behave as strong bases, for example... 

The hydroxides M (OH)2 are generally less soluble and are of lower base strength. The Group I hydroxides are almost unique in possessing good solubility—most metal hydroxides are insoluble or sparingly soluble hence sodium hydroxide and, to a lesser extent potassium hydroxide, are widely used as sources of the hydroxide ion OH" both in the laboratory and on a large scale. 

With excess carbon dioxide, i,e, if the gas is passed through a solution of the hydroxide, a hydrogencarbonate is formed ... 

As with the hydroxides, we find that whilst the carbonates of most metals are insoluble, those of alkali metals are soluble, so that they provide a good source of the carbonate ion COf in solution the alkali metal carbonates, except that of lithium, are stable to heat. Group II carbonates are generally insoluble in water and less stable to heat, losing carbon dioxide reversibly at high temperatures. 

The hydroxide of lithium, although soluble in water, is a weak base owing to the great attraction between the Li" and OH ions (p. 74) the hydroxide of beryllium is really a neutral, insoluble... 

Aluminium oxide may be prepared in the laboratory by heating the hydroxide (p. 151) or by heating powdered aluminium in air, when the oxide is formed together with some nitride. The reaction ... 

Aqueous ammonia can also behave as a weak base giving hydroxide ions in solution. However, addition of aqueous ammonia to a solution of a cation which normally forms an insoluble hydroxide may not always precipitate the latter, because (a) the ammonia may form a complex ammine with the cation and (b) because the concentration of hydroxide ions available in aqueous ammonia may be insufficient to exceed the solubility product of the cation hydroxide. Effects (a) and (b) may operate simultaneously. The hydroxyl ion concentration of aqueous ammonia can be further reduced by the addition of ammonium chloride hence this mixture can be used to precipitate the hydroxides of, for example, aluminium and chrom-ium(III) but not nickel(II) or cobalt(II). 

Because of ammine formation, when ammonia solution is added slowly to a metal ion in solution, the hydroxide may first be precipitated and then redissolve when excess ammonia solution is added this is due to the formation of a complex ammine ion, for example with copper(II) and nickel(II) salts in aqueous solution. 

The liberated iodine is titrated with standard sodium thiosulphate(Vr) solution after acidification to remove the hydroxide ions. 

For temporary hardness due to magnesium carbonate, more lime is required, since the magnesium precipitates as the hydroxide (less soluble than the carbonate) ... 

For a cobalt(ll) salt, the precipitation of the blue->pitik cobalt(II) hydroxide by alkali, or precipitation of black cobalt(II) sulphide by hydrogen sulphide provide useful tests the hydroxide is soluble in excess alkali and is oxidised by air to the brown CoO(OH) . 

Copfierilh axUle. CuO. is a black powder, insoluble in water il is prepared by heating either the hydroxide, or the hydrated nitrate. 

It is readily dehydrated on warming, to give the black oxide CuO. It dissolves in excess of concentrated alkali to form blue hydroxo-cuprate(II) ions, of variable composition it is therefore slightly amphoteric. If aqueous ammonia is used to precipitate the hydroxide, the latter dissolves in excess ammonia to give the deep blue ammino complexes, for example [Cu(NH3)4(H20)2] ... 

Zinc(II) oxide, ZnO, is prepared by heating the hydroxide ZnlOH) or the carbonate ZnCOj. It is a white solid, insoluble in water, but readily soluble in acids to give a solution containing the zincfll) cation, and in alkalis to give a hydroxozincate(II) anion ... 

In its chemistry, cadmium exhibits exclusively the oxidation state + 2 in both ionic and covalent compounds. The hydroxide is soluble in acids to give cadmium(II) salts, and slightly soluble in concentrated alkali where hydroxocadmiates are probably formed it is therefore slightly amphoteric. It is also soluble in ammonia to give ammines, for example Of the halides, cadmium-... 

Example Solvation can have a profound effect on the potential energy profile for a reaction. Jorgensen s research group provided important insights into the role of solvation. Consider the nucleophilic addition of the hydroxide anion to formaldehyde ... 

Dissolve 2 g. of anthranilic acid in 12 8 ml. of 5% aqueous sodium hydroxide, or in 16 ml. of A -NaOH solution in a 50 ml. conical flask. (It is essential that the concentration of the hydroxide solution is accurately known.) Add i-6 ml. of dimethyl sulphate, and shake the securely-stoppered flask vigorously. 

Cool the reaction mixture to room temperature and add gradually a solution of 75 g. of sodium hydroxide in 125 ml. of water if the mixture boils during the addition of the alkah, cool again. The hydroxide of tin which is flrst precipitated should all dissolve and the solution should be strongly alkahne the anihne separates as an oil. Equip the flask for steam distillation as in Fig. II, 40, 1, and pass steam into the warm... 

Preparation of palladium - calcium carbonate catalyst. Prepare 60 g. of precipitated calcium carbonate by mixing hot solutions of the appropriate quantities of A.R. calcium chloride and A.R. sodium carbonate. Suspend the calcium carbonate in water and add a solution containing 1 g. of palladium chloride. Warm the suspension until all the palladium is precipitated as the hydroxide upon the calcium carbonate, i.e., until the supernatant liquid is colourless. Wash several times with... 

Sodium, like every reactive element, is never found free in nature. Sodium is a soft, bright, silvery metal which floats on water, decomposing it with the evolution of hydrogen and the formation of the hydroxide. It may or may not ignite spontaneously on water, depending on the amount of oxide and metal exposed to the water. It normally does not ignite in air at temperatures below llSoC. 

It is also used as a reducing agent in the production of pure uranium and other metals from their salts. The hydroxide (milk of magnesia), chloride, sulfate (Epsom salts), and citrate are used in medicine. Dead-burned magnesite is employed for refractory purposes such as brick and liners in furnaces and converters. 

Potassium is never found free in nature, but is obtained by electrolysis of the hydroxide, much in the same manner as prepared by Davy. Thermal methods also are commonly used to produce potassium (such as by reduction of potassium compounds with CaC2, C, Si, or Na). 

An alloy of sodium and potassium (NaK) is used as a heat-transfer medium. Many potassium salts are of utmost importance, including the hydroxide, nitrate, carbonate, chloride, chlorate, bromide, iodide, cyanide, sulfate, chromate, and dichromate. 

L. Gallia, France also from Latin, gallus, a translation of Lecoq, a cock) Predicted and described by Mendeleev as ekaaluminum, and discovered spectroscopically by Lecoq de Boisbaudran in 1875, who in the same year obtained the free metal by electrolysis of a solution of the hydroxide in KOH. 

One of the unshared pairs of the hydroxide oxygen is used to form a covalent bond to the positively polar ized proton of hydrogen fluoride The covalent bond betwen H and F in hydrogen fluoride breaks with the pair of electrons in this bond becoming an unshared pair of fluoride ion... 

Curved arrows originate at electron pairs—in this case an electron pair of the hydroxide oxygen and the shared pair in the covalent bond of HF Curved arrows terminate at an atom or between two atoms... 

Strong and Weak Bases Just as the acidity of an aqueous solution is a measure of the concentration of the hydronium ion, H3O+, the basicity of an aqueous solution is a measure of the concentration of the hydroxide ion, OH . The most common example of a strong base is an alkali metal hydroxide, such as sodium hydroxide, which completely dissociates to produce the hydroxide ion. 

Most metals will precipitate as the hydroxide in the presence of concentrated NaOH. Metals forming amphoteric hydroxides, however, remain soluble in concentrated NaOH due to the formation of higher-order hydroxo-complexes. For example, Zn and AP will not precipitate in concentrated NaOH due to the formation of Zn(OH)3 and Al(OH)4. The solubility of AP in concentrated NaOH is used to isolate aluminum from impure bauxite, an ore of AI2O3. The ore is powdered and placed in a solution of concentrated NaOH where the AI2O3 dissolves to form A1(0H)4T Other oxides that may be present in the ore, such as Fe203 and Si02, remain insoluble. After filtering, the filtrate is acidified to recover the aluminum as a precipitate of Al(OH)3. 

The pH of an NH3/NH4CI buffer (piQ = 9.24) is sufficient to ensure the precipitation of most metals as the hydroxide. The alkaline earths and alkaline metals, however, will not precipitate at this pH. In addition, metal ions that form soluble complexes with NH3, such as Cu +, Zn +, NP+, and Co +, also will not precipitate under these conditions. 

Solid Compounds. The tripositive actinide ions resemble tripositive lanthanide ions in their precipitation reactions (13,14,17,20,22). Tetrapositive actinide ions are similar in this respect to Ce . Thus the duorides and oxalates are insoluble in acid solution, and the nitrates, sulfates, perchlorates, and sulfides are all soluble. The tetrapositive actinide ions form insoluble iodates and various substituted arsenates even in rather strongly acid solution. The MO2 actinide ions can be precipitated as the potassium salt from strong carbonate solutions. In solutions containing a high concentration of sodium and acetate ions, the actinide ions form the insoluble crystalline salt NaM02(02CCH2)3. The hydroxides of all four ionic types are insoluble ... 

Magnesium oxide is an effective nonsystemic antacid, ie, it is converted to the hydroxide. It does not neutralize gastric acid excessively nor does it hberate carbon dioxide. The light form is preferable to the heavy for adininistration in Hquids because it is suspended more readily. One gram of magnesium oxide neutralizes 87 mL of 0.1 NUCl in 10 min, and 305 mL in 2 h. 

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