Phosphoric acid cations

Phosphoric acids and the phosphates maybe defined as derivatives of phosphoms oxides where the phosphoms atom is in the +5 oxidation state. These are compounds formed in the M2O—P20 system, where M represents one cation equivalent, eg, H", Na", 0.5 Ca ", etc. The molecular formula of the phosphoms(V) oxide [1314-56-3] is actually P O q, but this oxide is commonly referred to in terms of its empirical formula, P2O5. StmcturaHy, four phosphoms—oxygen (P—O) linkages are arranged in an approximate tetrahedral configuration about the phosphoms atom in the phosphate anion. Compounds containing discrete, monomeric PO ions are known as orthophosphates or simply as phosphates. 

Solvent extraction—purification of wet-process phosphoric acid is based on preferential extraction of H PO by an organic solvent vs the cationic impurities present in the acid. Because selectivity of acid over anionic impurities is usually not sufficient, precipitation or evaporation steps are included in the purification process for removal. Cmde wet-process acid is typically concentrated and clarified prior to extraction to remove post-precipitated sludge and improve partition of the acid into the solvent. Concentration also partially eliminates fluoride by evaporation of HF and/or SiF. Chemical precipitation of sulfate (as Ba or Ca salts), fluorosiUcates (as Na salt), and arsenic (as sulfides) may also be used as a prepurification step preceding solvent extraction. 

Orthophosphate salts are generally prepared by the partial or total neutralization of orthophosphoric acid. Phase equiUbrium diagrams are particularly usehil in identifying conditions for the preparation of particular phosphate salts. The solution properties of orthophosphate salts of monovalent cations are distincdy different from those of the polyvalent cations, the latter exhibiting incongment solubiUty in most cases. The commercial phosphates include alkah metal, alkaline-earth, heavy metal, mixed metal, and ammonium salts of phosphoric acid. Sodium phosphates are the most important, followed by calcium, ammonium, and potassium salts. 

Many orthophosphate salts, in particular those of polyvalent cations, exhibit incongment solubihty where disporportionation occurs in solution to yield a more basic orthophosphate salt and phosphoric acid. This hydrolytic disproportionation of orthophosphates should not be confused with the... 

Alkali Meta.IPhospha.tes, A significant proportion of the phosphoric acid consumed in the manufacture of industrial, food, and pharmaceutical phosphates in the United States is used for the production of sodium salts. Alkali metal orthophosphates generally exhibit congment solubility and are therefore usually manufactured by either crystallisation from solution or drying of the entire reaction mass. Alkaline-earth and other phosphate salts of polyvalent cations typically exhibit incongment solubility and are prepared either by precipitation from solution having a metal oxide/P20 ratio considerably lower than that of the product, or by drying a solution or slurry with the proper metal oxide/P20 ratio. 

For solvent extraction of a tetravalent vanadium oxyvanadium cation, the leach solution is acidified to ca pH 1.6—2.0 by addition of sulfuric acid, and the redox potential is adjusted to —250 mV by heating and reaction with iron powder. Vanadium is extracted from the blue solution in ca six countercurrent mixer—settler stages by a kerosene solution of 5—6 wt % di-2-ethyIhexyl phosphoric acid (EHPA) and 3 wt % tributyl phosphate (TBP). The organic solvent is stripped by a 15 wt % sulfuric acid solution. The rich strip Hquor containing ca 50—65 g V20 /L is oxidized batchwise initially at pH 0.3 by addition of sodium chlorate then it is heated to 70°C and agitated during the addition of NH to raise the pH to 0.6. Vanadium pentoxide of 98—99% grade precipitates, is removed by filtration, and then is fused and flaked. 

Hydration and dehydration employ catalysts that have a strong affinity for water. Alumina is the principal catalyst, but also used are aluminosihcates, metal salts and phosphoric acid or its metal salts on carriers, and cation exchange resins. 

Phosphoric acid forms several series of salts in which the acidic H atoms are successively replaced by various cations there is considerable commercial application for many of these compounds. 

Examples of liquid cation exchangers are alkyl and dialkyl phosphoric acids, alkyl sulphonic acids and carboxylic acids, although only two appear to have been used to any extent, viz. di-(2-ethylhexyl)phosphoric(V) acid and dinonylnaphthalene sulphonic acid. 

The neutral surfactant is measured after fixing of the ionic substances on a combined anionic/cationic ion exchange column. Volatile substances in the eluate are determined by gas chromatography and nonvolatile substances are measured gravimetrically. In the bulk of the neutral compounds phosphoric acid triesters may be present. This part is additionally determined by atom emission spectroscopy. 

Use chemical behavior and electronegativities to assess the reasonableness of the assignments. Phosphoric acid can be viewed as the phosphate anion (-3 charge) associated with three H ions. Sodium, an alkali metal, readily forms cations with +1 charge, hi KH, the assignments are consistent with the electronegativities (jjf) of the two elements — 0.8, = 2.1. 

This concept covers most situations in the theory of AB cements. Cements based on aqueous solutions of phosphoric acid and poly(acrylic acid), and non-aqueous cements based on eugenol, alike fall within this definition. However, the theory does not, unfortunately, recognize salt formation as a criterion of an acid-base reaction, and the matrices of AB cements are conveniently described as salts. It is also uncertain whether it covers the metal oxide/metal halide or sulphate cements. Bare cations are not recognized as acids in the Bronsted-Lowry theory, but hydrated... 

Apart from the alkyl halide-Lewis acid combination, two other sources of carbo-cations are often used in Friedel-Crafts reactions. Alcohols can serve as carbocation precursors in strong acids such as sulfuric or phosphoric acid. Alkylation can also be effected by alcohols in combination with BF3 or A1C13.37 Alkenes can serve as alkylating agents when a protic acid, especially H2S04, H3P04, and HF, or a Lewis acid, such as BF3 and A1C13, is used as a catalyst.38... 

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