Phosphoric formation

Potassium chlorate Red phosphorous Formation of explosive mixture sensitive to shock and friction... 

The solid state reactions which occur and the stages of development which occur during phosphor formation are remarkably alike from system to system. These stages are shown for both Srs F(P04)s Sb and Sr5Cl(P04)3 Sb. The emission colors for these phosphors is blue-green. 

The formation of an insoluble film of barium sulphate soon causes the reaction to cease, but addition of a tittle hydrochloric acid or better phosphoric(V) acid to the sulphuric acid allows the reaction to continue. 

There are numerous variations of the wet process, but all involve an initial step in which the ore is solubilized in sulfuric acid, or, in a few special instances, in some other acid. Because of this requirement for sulfuric acid, it is obvious that sulfur is a raw material of considerable importance to the fertilizer industry. The acid—rock reaction results in formation of phosphoric acid and the precipitation of calcium sulfate. The second principal step in the wet processes is filtration to separate the phosphoric acid from the precipitated calcium sulfate. Wet-process phosphoric acid (WPA) is much less pure than electric furnace acid, but for most fertilizer production the impurities, such as iron, aluminum, and magnesium, are not objectionable and actually contribute to improved physical condition of the finished fertilizer (35). Impurities also furnish some micronutrient fertilizer elements. 

Hexafluorophosphoric Acid. Hexafluorophosphoric acid (3) is present under ambient conditions only as an aqueous solution because the anhydrous acid dissociates rapidly to HF and PF at 25°C (56). The commercially available HPF is approximately 60% HPF based on PF analysis with HF, HPO2F2, HPO F, and H PO ia equiUbrium equivalent to about 11% additional HPF. The acid is a colorless Hquid which fumes considerably owiag to formation of an HF aerosol. Frequently, the commercially available acid has a dark honey color which is thought to be reduced phosphate species. This color can be removed by oxidation with a small amount of nitric acid. When the hexafluorophosphoric acid is diluted, it slowly hydrolyzes to the other fluorophosphoric acids and finally phosphoric acid. In concentrated solutions, the hexafluorophosphoric acid estabUshes equiUbrium with its hydrolysis products ia relatively low concentration. Hexafluorophosphoric acid hexahydrate [40209-76-5] 6 P 31.5°C, also forms (66). This... 

The typical acid catalysts used for novolak resins are sulfuric acid, sulfonic acid, oxaUc acid, or occasionally phosphoric acid. Hydrochloric acid, although once widely used, has been abandoned because of the possible formation of toxic chloromethyl ether by-products. The type of acid catalyst used and reaction conditions affect resin stmcture and properties. For example, oxaUc acid, used for resins chosen for electrical appHcations, decomposes into volatile by-products at elevated processing temperatures. OxaUc acid-cataly2ed novolaks contain small amounts (1—2% of the original formaldehyde) of ben2odioxanes formed by the cycli2ation and dehydration of the ben2yl alcohol hemiformal intermediates. 

Commercial condensed phosphoric acids are mixtures of linear polyphosphoric acids made by the thermal process either direcdy or as a by-product of heat recovery. Wet-process acid may also be concentrated to - 70% P2O5 by evaporation. Liaear phosphoric acids are strongly hygroscopic and undergo viscosity changes and hydrolysis to less complex forms when exposed to moist air. Upon dissolution ia excess water, hydrolytic degradation to phosphoric acid occurs the hydrolysis rate is highly temperature-dependent. At 25°C, the half-life for the formation of phosphoric acid from the condensed forms is several days, whereas at 100°C the half-life is a matter of minutes. 

Phosphoms(V) sulfide is a mild skin irritant and may cause dermatitis in sensitive individuals. The primary health ha2ard results from the Hberation of hydrogen sulfide after contact with moisture. Contact with moisture also forms phosphoric acid. A secondary ha2ard is the formation of sulfur dioxide when phosphoms(V) sulfide bums. The oral LD q of in rats is 389 mg/kg the OSHA standard time-weighted average (TWA) is 1 mg /m (33). 

Phosphorus(III) Oxide. Phosphoms(III) oxide [12440-00-5] the anhydride of phosphonic acid, is formed along with by-products such as phosphoms pentoxide and red phosphoms when phosphoms is burned with less than stoichiometric amounts of oxygen (62). Phosphoms(III) oxide is a poisonous, white, wax-like, crystalline material, which has a melting point of 23.8°C and a boiling point of 175.3°C. When added to hot water, phosphoms(III) oxide reacts violentiy and forms phosphine, phosphoric acid, and red phosphoms. Even in cold water, disproportionation maybe observed if the oxide is not well agitated, resulting in the formation of phosphoric acid and yellow or orange poorly defined polymeric lower oxides of phosphoms (LOOP). 

Phosphoric acid [7664-38-2] and its derivatives are effective catalysts for this reaction (60). Reverse alcoholysis and acidolysis can, in principle, also be used to produce polyamides, and the conversion of esters to polyamides through their reaction within diamines, reverse alcoholysis, has been demonstrated (61). In the case of reverse acidolysis, the acid by-product is usually less volatile than the diamine starting material. Thus, this route to the formation of polyamide is not likely to yield a high molecular weight polymer. 

Sahcyhc acid can be converted to sahcyloyl chloride [1441 -87-8] hy reaction with thionyl chloride in boiling ben2ene. The formation of acyl haUde may also extend to reaction with the phenoHc hydroxyl. The reaction with phosphoms tri- and pentachlorides is not restricted to the formation of the acid chloride. Further interaction of the phosphoms haUde and the phenoHc hydroxyl results in the formation of the phosphoric or phosphorous esters. 

A method suitable for analysis of sulfur dioxide in ambient air and sensitive to 0.003—5 ppm involves aspirating a measured air sample through a solution of potassium or sodium tetrachloromercurate, with the resultant formation of a dichlorosulfitomercurate. Ethylenediaminetetraacetic acid (EDTA) disodium salt is added to this solution to complex heavy metals which can interfere by oxidation of the sulfur dioxide. The sample is also treated with 0.6 wt % sulfamic acid to destroy any nitrite anions. Then the sample is treated with formaldehyde and specially purified acid-bleached rosaniline containing phosphoric acid to control pH. This reacts with the dichlorosulfitomercurate to form an intensely colored rosaniline—methanesulfonic acid. The pH of the solution is adjusted to 1.6 0.1 with phosphoric acid, and the absorbance is read spectrophotometricaHy at 548 nm (273). 

Synthetic pine oil is produced by the acid-catalyzed hydration of a-pinene (Fig. 1). Mineral acids, usually phosphoric acid, are used in concentrations of 20—40 wt % and at temperatures varying from 30—100°C. Depending on the conditions used, alcohols, chiefly a-terpineol (9), are produced along with /)-menthadienes and cineoles, mainly limonene, terpinolene, and 1,4- and 1,8-cineole (46—48). Various grades of pine oil can be produced by fractionation of the cmde products. Formation of terpin hydrate (10) from a-terpineol gives P-terpineol (11) and y-terpineol (12) as a consequence of the reversible... 

For extraction of uranium from sulfate leach Hquors, alkyl phosphoric acids, alkyl phosphates, and secondary and tertiary alkyl amines are used in an inert diluent such as kerosene. The formation of a third phase is suppressed by addition of modifiers such as long-chain alcohols or neutral phosphate esters. Such compounds also increase the solubihty of the amine salt in the diluent and improve phase separation. 

Silver [7440-22-4]—The coloi additive silvei (EEC No. E 174) is a crystaUine powdei of high purity silver prepared by die reaction of silver nitrate with ferrous sulfate in the presence of nitric, phosphoric, and sulfuric acids. Poly(vinyl alcohol) is used to prevent the agglomeration of crystals and the formation of amorphous silver. 

Under certain conditions hydrogen cyanide can polymerize to black soHd compounds, eg, hydrogen cyanide homopolymer [26746-21-4] (1) and hydrogen cyanide tetramer [27027-02-2], C H N (2). There is usually an incubation period before rapid onset of polymer formation. Temperature has an inverse logarithmic effect on the incubation time. Acid stabilizers such as sulfuric and phosphoric acids prevent polymerization. The presence of water reduces the incubation period. 

Phosphorus Pentoxide. This compound, P2O55 (Class 1, nonregenerative) is made by burning phosphoms ia dry air. It removes water first by adsorptioa, followed by the formation of several forms of phosphoric acid (2). Phosphoms peatoxide [1314-56-3] has a high vapor pressure and should only be used below 100°C. Its main drawback is that as moisture is taken up, the surface of the granules becomes wetted and further moisture removal is impeded. For this reason, phosphoms pentoxide is sometimes mixed with an iaert material (see Phosphoric acids and phosphates). 

In laboratory preparations, sulfuric acid and hydrochloric acid have classically been used as esterification catalysts. However, formation of alkyl chlorides or dehydration, isomerization, or polymerization side reactions may result. Sulfonic acids, such as benzenesulfonic acid, toluenesulfonic acid, or methanesulfonic acid, are widely used in plant operations because of their less corrosive nature. Phosphoric acid is sometimes employed, but it leads to rather slow reactions. Soluble or supported metal salts minimize side reactions but usually require higher temperatures than strong acids. 

Examples are given of common operations such as absorption of ammonia to make fertihzers and of carbon dioxide to make soda ash. Also of recoveiy of phosphine from offgases of phosphorous plants recoveiy of HE oxidation, halogenation, and hydrogenation of various organics hydration of olefins to alcohols oxo reaction for higher aldehydes and alcohols ozonolysis of oleic acid absorption of carbon monoxide to make sodium formate alkylation of acetic acid with isobutylene to make teti-h ty acetate, absorption of olefins to make various products HCl and HBr plus higher alcohols to make alkyl hahdes and so on. 

Treatment of a nylon with formaldehyde leads to the formation of A-methylol groups but the polymers are unstable. If, however, the nylon is dissolved in the solvent such as 90% formic acid and then treated with formaldehyde and an alcohol in the presence of an acidic catalyst such as phosphoric acid a process of alkoxymethylation occurs Figure 18.19). 

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