Phosphates, metal

The elimination of alcohol from P-alkoxypropionates can also be carried out by passing the alkyl P-alkoxypropionate at 200—400°C over metal phosphates, sihcates, metal oxide catalysts (99), or base-treated zeoHtes (98). In addition to the route via oxidative carbonylation of ethylene, alkyl P-alkoxypropionates can be prepared by reaction of dialkoxy methane and ketene (100). 

In the double-neutralization process, Na2SiFg is precipitated and removed by filtration at a pH of 3—4 (9). Upon raising the pH to 7—9, insoluble phosphates of Fe, Al, Ca, and Mg form and separate. Iron can be precipitated as hydrous ferric oxide, reducing the phosphate loss at the second filter cake. Both the fluorosihcate and metal phosphate filter residues tend to be voluminous cakes that shrink when dewatered recovery of soluble phosphates trapped within the cakes is difficult. 

The tertiary metal phosphates are of the general formula MPO where M is B, Al, Ga, Fe, Mn, etc. The metal—oxygen bonds of these materials have considerable covalent character. The anhydrous salts are continuous three-dimensional networks analogous to the various polymorphic forms of siHca. Of limited commercial interest are the alurninum, boron, and iron phosphates. Boron phosphate [13308-51 -5] BPO, is produced by heating the reaction product of boric acid and phosphoric acid or by a dding H BO to H PO at room temperature, foUowed by crystallization from a solution containing >48% P205- Boron phosphate has limited use as a catalyst support, in ceramics, and in refractories. 

Multilayers of Diphosphates. One way to find surface reactions that may lead to the formation of SAMs is to look for reactions that result in an insoluble salt. This is the case for phosphate monolayers, based on their highly insoluble salts with tetravalent transition metal ions. In these salts, the phosphates form layer stmctures, one OH group sticking to either side. Thus, replacing the OH with an alkyl chain to form the alkyl phosphonic acid was expected to result in a bilayer stmcture with alkyl chains extending from both sides of the metal phosphate sheet (335). When zirconium (TV) is used the distance between next neighbor alkyl chains is - 0.53 nm, which forces either chain disorder or chain tilt so that VDW attractive interactions can be reestablished. 

Isomerization of ethylene oxide to acetaldehyde occurs at elevated temperatures ia the presence of catalysts such as activated alumina, phosphoric acid, and metallic phosphates (75). Iron oxides also catalyze this reaction. Acetaldehyde may be found as a trace impurity ia ethylene oxide. 

Electrochemical Process. Several patents claim that ethylene oxide is produced ia good yields ia addition to faradic quantities of substantially pure hydrogen when water and ethylene react ia an electrochemical cell to form ethylene oxide and hydrogen (206—208). The only raw materials that are utilized ia the ethylene oxide formation are ethylene, water, and electrical energy. The electrolyte is regenerated in situ ie, within the electrolytic cell. The addition of oxygen to the ethylene is activated by a catalyst such as elemental silver or its compounds at the anode or its vicinity (206). The common electrolytes used are water-soluble alkah metal phosphates, borates, sulfates, or chromates at ca 22—25°C (207). The process can be either batch or continuous (see Electrochemicalprocessing). 

Lithium orthophosphates are unimportant and differ from the other alkali metal phosphates in being insoluble. At least 10 crystalline hydrated or anhydrous sodium orthophosphates are known and these can be grouped into three series ... 

Example 5. Chromium steel (Fe-17Cr) in phosphoric acid at low concentrations shows a decreasing rate with increasing temperature (see Fig. 2.26) presumably due to surface coverage by metal phosphates. 

Awad, S. A. and Kamel, K. M. Behaviour of Tin as Metal-metal Phosphate Electrode and Mechanism of Promotion and Inhibition of its Corrosion by Phosphate Ions , Journal of Electroanalytical Chemistry, 24, 217-25 (1969)... 

Care must be taken here not to confuse acid cleaners with the high-strength, phosphoric acid-based chemical polishes and chemical brighteners, which are used specifically to obtain the surface finish which such materials produce. Also in the category of acid cleaners could be considered the lightweight alkali-metal phosphating cleaner-coater solutions, but a discussion on such materials is best left to specialist publications on metal pretreatment chemicals. 

The simplest and most thoroughly studied solutions are those based on phosphoric acid at low temperatures (<35°C) which alone can fulfil all three requirements of acid solvent, film former (as metal phosphate) and diffusion agent by virtue of its viscosity. Thus copper and its main alloys of brasses and bronzes can be very effectively electropolished in 60-70% orthophos-phoric acid with the temperature maintained below 35°C under other conditions copper passivates or dissolves freely under mass transfer controlled conditions, but by varying the conditions appropriately polishing can be continued under mild agitation. An annotated polarisation curve is given in Fig. 11.7 readers are referred to recent studies for more detailed 2ispects " . 

The solution of iron represented in equation 15.1 takes place at local anodes of the steel being processed, while discharge of hydrogen ions with simultaneous dissociation and deposition of the metal phosphate takes place at the local cathodes. Thus factors which favour the cathode process will accelerate coating formation and conversely factors favouring the dissolution of iron will hinder the process. 

Very thin coatings of iron phosphate can be produced by treatment with solutions of alkali metal phosphate. These serve a useful purpose for the... 

Alkali-metal phosphates have been incorporated in antifreeze solutions but there are indications of unfavourable behaviour with aluminium alloys... 

Although many ammonium metal phosphates are known, few kinetic studies of their decompositions have been reported and no systematic investigations of the influence of metal ion or structure on the deammi-nation reactions are available. Thermal analyses [971] of compounds of the type MNH4P04 xH20 (where M is a divalent metal) show that, after dehydration, there is a continuous and simultaneous evolution of NH3 and H20 [137], maintained until crystalline M2P207 is formed, e.g. 

Reference has already been made to the dehydration of alums (Sect. 1.2 and Table 10), decomposition of ammonium metal phosphates (Sect. 4.1.5) and the use of KMn04—KCIO4 solid solutions in mechanistic studies of the decomposition of potassium permanganate (Sect. 3.6). 

Nearly all transition metals are oxidized readily, so most ores are compounds in which the metals have positive oxidation numbers. Examples include oxides (Ti02, mtile Fc2 O3, hematite C112 O, cuprite), sulfides (ZnS, sphalerite M0S2, molybdenite), phosphates (CeP04, monazite YPO4, xenotime both found mixed with other rare earth metal phosphates), and carbonates (FeC03, siderite). Other minerals contain oxoanions (MnW04, wolframite) and even more complex stmctures such as camotite, K2 (002)2 ( 4)2 2 O ... 

The phosphate bonded cements described in this chapter are the products of the simple acid-base reaction between an aqueous solution of orthophosphoric acid and a basic oxide or silicate. Such reactions take place at room temperature. Excluded from this chapter are the cementitious substances that are formed by the heat treatment of aqueous solutions of acid metal phosphates. 

A gel of diesel or crude oil can be produced using a phosphate diester or an aluminum compound with phosphate diester [740]. The metal phosphate diester may be prepared by reacting a triester with phosphorous pentoxide to produce a polyphosphate, which is then reacted with an alcohol (usually hexanol) to produce a phosphate diester [870]. The latter diester is then added to the organic liquid along with a nonaqueous source of aluminum, such as aluminum isopropoxide (aluminum-triisopropylate) in diesel oil, to produce the metal phosphate diester. The conditions in the previous reaction steps are controlled to provide a gel with good viscosity versus temperature and time characteristics. All the reagents are substantially free of water and will not affect the pH. 

The pH of a medium also impacts the formation of metal-phosphate precipitates. For example, divalent ionic cadmium (Cd2+) concentrations rapidly decline as both phosphate concentration and pH increase. Sandrin and Hoffman121 determined that when no phosphate is present in a commonly used mineral salts medium, the concentration of divalent ionic cadmium remains relatively constant until an abrupt decline above pH 8. When 15 mM inorganic phosphate is added to the medium, divalent cadmium ion concentrations rapidly decline at pH values above only 6. 

This method is used to remove ionic species such as heavy metals, phosphates, or nitrates. It is the reversible exchange of ionic species between a resin and the liquid. For example, a cation resin will exchange positive ions such as hydrogen ions for copper ions that are in solution. Similarly, certain anion resins might replace phosphate ions with hydroxyl ions. 

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