Pyrophosphate phosphors

Synonyms Ethyl pyrophosphate phosphoric acid tetraethyl ester TEPP Tetron NIFOS TEP... 

Olefins can also be conveniently polymerized by means of an acid catalyst. Thus, the treated, olefin-rich feed stream is contacted with a catalyst (sulfuric acid, copper pyrophosphate, phosphoric acid) at 150 to 220°C (300-425°F) and 150-1200 psi (10-81 atmospheres), depending on the feedstock and product requirement. 

Defect Reactions Occurring in Calcium Pyrophosphate Phosphor... 

Strontium pyrophosphate, Sr2P207, doped with Eu + -I- Mn +, will produce yellow fluorescence. Reported pyrophosphate phosphors include those of types... 

In solution, both heptaoxodiphosphoric(V) acid and the hepta-oxodiphosphates(V) (pyrophosphates) are slowly converted (more rapidly on heating) to phosphoric(V) acid or its salts, for example... 

Phosphoric Acid and Phosphorothioic Acid Anhydrides. The aUphatic organophosphoms esters originally developed by Schrader (27) are extremely toxic to mammals and are largely of historic interest. Tetraethyl pyrophosphate [107-49-3] (40) (bp 104—110°C at 10.7 Pa, d 1.185, vp 6.1 mPa at 30°C) is miscible with water and hydrolyzes very rapidly with a half-life of 6.8 h at 25°C. The rat LD qS ate 1.1 (oral) and 2.4 (dermal) mg/kg. 

The catalyst used in the production of maleic anhydride from butane is vanadium—phosphoms—oxide (VPO). Several routes may be used to prepare the catalyst (123), but the route favored by industry involves the reaction of vanadium(V) oxide [1314-62-1] and phosphoric acid [7664-38-2] to form vanadyl hydrogen phosphate, VOHPO O.5H2O. This material is then heated to eliminate water from the stmcture and irreversibly form vanadyl pyrophosphate, (V(123,124). Vanadyl pyrophosphate is befleved to be the catalyticaHy active phase required for the conversion of butane to maleic anhydride (125,126). 

Thermal polymerization is not as effective as catalytic polymerization but has the advantage that it can be used to polymerize saturated materials that caimot be induced to react by catalysts. The process consists of the vapor-phase cracking of, for example, propane and butane, followed by prolonged periods at high temperature (510—595°C) for the reactions to proceed to near completion. Olefins can also be conveniendy polymerized by means of an acid catalyst. Thus, the treated olefin-rich feed stream is contacted with a catalyst, such as sulfuric acid, copper pyrophosphate, or phosphoric acid, at 150—220°C and 1035—8275 kPa (150—1200 psi), depending on feedstock and product requirement. 

Phosphates are the principal catalysts used in polymerization units the commercially used catalysts are Hquid phosphoric acid, phosphoric acid on kieselguhr, copper pyrophosphate pellets, and phosphoric acid film on quartz. The last is the least active and has the disadvantage that carbonaceous deposits must occasionally be burned off the support. Compared to other processes, the one using Hquid phosphoric acid catalyst is far more responsive to attempts to raise production by increasing temperature. 

Silver Phosphates. Silver phosphate [7784-09-0], or silver orthophosphate, Ag3P04, is a bright yellow material formed by treating silver nitrate with a soluble phosphate salt or phosphoric acid. Silver pyrophosphate [13465-97-9], is a white salt prepared by the addition of a soluble... 

Titanium pyrophosphate [13470-09-2] TiP20y, a possible uv reflecting pigment, is a white powder that crystallizes ia the cubic system and has a theoretical density of 3106 kg/m. It is iasoluble ia water and can be prepared by heating a stoichiometric mixture of hydrous titania and phosphoric acid at 900°C. 

FIGURE 3.10 (a) Electrostatic repnlsion between adjacent partial positive charges (on carbon and phosphorns, respectively) is relieved upon hydrolysis of the anhydride bonds of acetic anhydride and phosphoric anhydrides. The predominant form of pyrophosphate at pH values between 6.7 and 9.4 is shown, (b) The competing resonances of acetic anhydride and the simnltaneons resonance forms of the hydrolysis product, acetate. 

The situation with phosphoric anhydrides is similar. The phosphorus atoms of the pyrophosphate anion are electron-withdrawing and destabilize PPj with respect to its hydrolysis products. Furthermore, the reverse reaction, reformation of the anhydride bond from the two anionic products, requires that the electrostatic repulsion between these anions be overcome (see following). 

The concepts of destabilization of reactants and stabilization of products described for pyrophosphate also apply for ATP and other phosphoric anhydrides (Figure 3.11). ATP and ADP are destabilized relative to the hydrolysis products by electrostatic repulsion, competing resonance, and entropy. AMP, on the other hand, is a phosphate ester (not an anhydride) possessing only a single phosphoryl group and is not markedly different from the product inorganic phosphate in terms of electrostatic repulsion and resonance stabilization. Thus, the AG° for hydrolysis of AMP is much smaller than the corresponding values for ATP and ADP. 

Compounds with similar functions are sodium carbonate, sodium EDTA, phosphoric acid, pentasodium pentetate, tetrasodium etidronate, and tetrasodium pyrophosphate. 

The explanation lies in the defect reactions controlling the formation of the phosphor itself. The defect reactions occurring were found to be the substitution of a trlvalent cation on a divalent site and the defects reactions thereby associated. This is shown in the following table which compares these two methods of preparing such materials. In this case, the increase in brightness was found to be related to the amount of activator actually being incorporated into the lattice. It is well known that phosphor brightness is proportional to the numbers of Sb3+ ions (activators) actually incorporated into cation sites of the pyrophosphate structure. 

When AMP is heated under reflux in DMF, the 2, 3 -cyclic phosphate is formed, and cyclic phosphates can also be obtained from nucleosides and ortho-, pyro-, or poly-phosphoric acids under the same conditions. Promotion of phosphorylation by DMF is well known and the reaction with AMP is probably intermolecular as no 3, 5 -cyclic AMP can be detected. Minor products in the latter reaction are the 2, 3 -cyclic 5 -diphosphate and the 2 (30,5 -diphosphate. The synthesis of adenosine 2 (3 )-phosphate 5 -pyrophosphate has been achieved by the phosphoromorpholidate method used in a synthesis of Co A. ... 

---