Phosphorous acid fluoride

Chromates, vanadates, and cerium salts give colour reactions with the reagent and should therefore be absent. Iron salts give a yellow colour with hydrogen peroxide, but this is eliminated by the addition of syrupy phosphoric acid. Fluorides bleach the colour (stable [TiF6]2 ions are formed), and large amounts of nitrates, chlorides, bromides, and acetates as well as coloured ions... 

Environmentally sound phosphate fertilizer plants recover as much of the fluoride value as H2SiFg as possible. Sales for production of AIF. -3H20 is one of the most important markets (see Fertilizers Phosphoric acid and the phosphates). 

The large amount of fluorine values released from phosphate rock in the manufacture of fertilisers (qv) gives a strong impetus to develop fluorine chemicals production from this source (see Phosphoric acid and the phosphates). Additional incentive comes from the need to control the emission of fluorine-containing gases. Most of the fluorine values are scmbbed out as fluorosiUcic acid, H2SiPg, which has limited useflilness. A procedure to convert fluorosihcic acid to calcium fluoride is available (61). 

Alternative Processes. Because of the large quantity of phosphate rock reserves available worldwide, recovery of the fluoride values from this raw material source has frequently been studied. Strategies involve recovering the fluoride from wet-process phosphoric acid plants as fluosiUcic acid [16961-83-4] H2SiFg, and then processing this acid to form hydrogen fluoride. 

The majority of the fluorine ia the earth s cmst is present in the form of the phosphoms fluoride fluoroapatite [1306-05 ] Ca (P0 2F- Phosphate rock deposits contain an average concentration of 3.5 wt % fluorine. During phosphate processing these fluorine values are partially recovered as by-product fluorosihcic acid. The amount of fluorosiUcic acid recovered has grown steadily, in part because of environmental requirements (see Phosphoric acid and THE phosphates). 

Isopropylnaphthalenes can be prepared readily by the catalytic alkylation of naphthalene with propjiene. 2-lsopropylnaphthalene [2027-17-0] is an important intermediate used in the manufacture of 2-naphthol (see Naphthalenederivatives). The alkylation of naphthalene with propjiene, preferably in an inert solvent at 40—100°C with an aluminum chloride, hydrogen fluoride, or boron trifluoride—phosphoric acid catalyst, gives 90—95% wt % 2-isopropylnaphthalene however, a considerable amount of polyalkylate also is produced. Preferably, the propylation of naphthalene is carried out in the vapor phase in a continuous manner, over a phosphoric acid on kieselguhr catalyst under pressure at ca 220—250°C. The alkylate, which is low in di- and polyisopropylnaphthalenes, then is isomerized by recycling over the same catalyst at 240°C or by using aluminum chloride catalyst at 80°C. After distillation, a product containing >90 wt % 2-isopropylnaphthalene is obtained (47). 

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. 

Aluminum fluoride is also made by the reaction of fluosiUcic acid [16961 -83-4] H2SiFg, a by-product from phosphoric acid production (see Phosphoric ACID AND THE PHOSPHATES), and aluminum hydroxide from the Bayer process. 

The vapor-phase conversion of aniline to DPA over a soHd catalyst has been extensively studied (18,22). In general, the catalyst used is pure aluminum oxide or titanium oxide, prepared under special conditions (18). Promoters, such as copper chromite, nickel chloride, phosphoric acid, and ammonium fluoride, have also been recommended. Reaction temperatures are usually from 400 to 500°C. Coke formed on the catalyst is removed occasionally by burning. In this way, conversions of about 35% and yields of 95% have been reported. Carba2ole is frequently a by-product. 

Titanium corrodes very rapidly in acid fluoride environments. It is attacked in boiling HCl or H2SO4 at acid concentrations of >1% or in ca 10 wt % acid concentration at room temperature. Titanium is also attacked by hot caustic solutions, phosphoric acid solutions (concentrations >25 wt%), boiling AlCl (concentrations >10 wt %), dry chlorine gas, anhydrous ammonia above 150°C, and dry hydrogen—dihydrogen sulfide above 150°C. 

Hot oleum (>50°C), strong alkalis, fluoride solutions, sulphur trioxide Strong alkalis, especially >54°C, distilled water >82°C, hydrofluoric acid, acid fluorides, hot concentrated phosphoric acid, lithium compounds >1 77°C, severe shock or impact applications Strong oxidizers, very strong solvents... 

This input to design refers to the long-term stability of the raw material sources for the plant. It is only of importance where the raw materials can or do contain impurities which can have profound effects on the corrosivity of the process. Just as the design should cater not only for the norm of operation but for the extremes, so it is pertinent to question the assumptions made about raw material purity. Crude oil (where HjS, mercaptan sulphur and napthenic acid contents determine the corrosivity of the distillation process) and phosphate rock (chloride, silica and fluoride determine the corrosivity of phosphoric acid) are very pertinent examples. Thus, crude-oil units intended to process low-sulphur crudes , and therefore designed on a basis of carbon-steel equipment, experience serious corrosion problems when only higher sulphur crudes are economically available and must be processed. 

There are, however, certain acid-based materials which can primarily be construed as cleaners. One such type of material is used in the cleaning of aluminium cans prior to treating and lacquering. Such cleaners are normally based on sulphuric or phosphoric acid, with, generally, additions of hydrofluoric acid and surfactants. These materials are sprayed on to pre-formed cans to remove the lubricant used during the can-forming operation. The fluoride is present to enhance the removal of fines of metal swarf in the cans as well as to remove the oxide film. 

Both acids form compounds of silicon as a result of attack on the network, silicon fluoride from hydrofluoric acid and silicyl phosphate from phosphoric acid. 

There are some means for synthesis of defined primary or secondary esters. Monoester salts of phosphoric acid, for instance, are prepared by addition of alcohol or ethoxylated alcohol, alkali fluoride, and pyrophosphoryl chloride (C12P0)20 in a molar ratio of 0.9-1.5 0.05-1 1.0 at -50 to +10°C and hydrolysis of the Cl-containing intermediates with base. Thus, 32.3 g (C12P0)20 was treated at -50°C with 23.9 g lauryl alcohol in the presence of 0.7 g KF and the mixture was slowly warmed to room temperature and hydrolyzed with H20 and 40% NaOH to give 83% sodium monolauryl phosphate. The monoester salts showed comparable or better washing and foaming efficiency than a commercial product [12]. 

C21-0082. Calcium dihydrogen phosphate is a common phosphoras fertilizer that is made by treating fluoroapatite with phosphoric acid. Hydrogen fluoride is a by-product of the synthesis. Write a balanced equation for the production of this fertilizer and calculate the mass percent of phosphorus in the fertilizer. 

Akitt, J. W., Greenwood, N. N. Lester, G. D. (1971). Nuclear magnetic resonance and Raman studies of aluminium complexes formed in aqueous solutions of aluminium salts containing phosphoric acid and fluoride ions. Journal of the Chemical Society, A, 2450-7. 

Trichloroacetyl fluoride, 45, 6 2-(Trichloromethyl)bicyclo[3.3.0]octane, from reaction of chloroform and cib,o i-l,5-cyclooctadiene, 47,10 hydrolysis with phosphoric acid to c.ro-m-bicyclo[3.3.0]octane-2-carboxylic acid, 47, 11 1,1,3-Trichloro- -nonane, 46,104 Tricyclo[2.2.1,02 6]heptan-3-ol, 46,... 

---