Metaphosphate

TrialkylPhosphates. Triethyl phosphate [78-40-0] C H O P, is a colorless Hquid boiling at 209—218°C containing 17 wt % phosphoms. It may be manufactured from diethyl ether and phosphoms pentoxide via a metaphosphate intermediate (63,64). Triethyl phosphate has been used commercially as an additive for polyester laminates and in ceHulosics. In polyester resins, it functions as a viscosity depressant as weH as a flame retardant. The viscosity depressant effect of triethyl phosphate in polyester resins permits high loadings of alumina trihydrate, a fire-retardant smoke-suppressant filler (65,66). 

The monofluorophosphates can be prepared by neutralization of monofluorophosphoric acid (1). Sodium monofluorophosphate [7631 -97-2] is prepared commercially (57) by fusion of sodium fluoride and sodium metaphosphate, and the potassium monofluorophosphate [14104-28-0] can be prepared similarly. Insoluble monofluorophosphates can be readily prepared from reaction of nitrate or chloride solutions with sodium monofluorophosphate. Some salts are prepared by metathetical reactions between silver monofluorophosphate [66904-72-1] and metal chlorides. 

The ultraphosphates are situated between P O q and the metaphosphates. These comparatively Htde-known, highly cross-linked polymers contain at least some of the phosphoms atoms as triply coimected branching points. This stmctural feature is quite unstable toward hydrolysis. Ultraphosphates undergo rapid decomposition upon dissolution. In amorphous ultraphosphates, the cross-linking is presumably scattered randomly throughout the stmctural matrix in contrast, crystalline ultraphosphates have a regular pattern. 

Several crystalline condensed phosphates may also be formed by the dehydration of monosodium phosphate (MSP). Maddrell s salt exists as Form 11 (high temperature MaddreU, NaPO -ll, insoluble metaphosphate-11) and Form 111 (low temperature MaddreU, NaPO -lll, insoluble metaphosphate-111). Both forms are highly polymerized and difficult (slow) to dissolve in water. Mixtures of the two forms are marketed as a dental abrasive for toothpaste formulations containing soluble fluoride. Maddrell s salt is also used with disodium phosphate as a cheese emulsifying aid. 

The only tme metaphosphate (ring stmcture) of significant commercial interest is sodium trimetaphosphate (STMP), Na P O. Because of the strain inherent in the small ring stmcture, STMP is more reactive toward nucleophiles than chain phosphates. In the presence of NaOH, for example, STMP forms sodium tripolyphosphate. 

Phosphate Esters. The phosphorylation of sucrose using sodium metaphosphate has been reported (78). Lyoptulization of a sodium metaphosphate solution of sucrose at pH 5 for 20 hours followed by storage at 80°C for five days produced a mixture of sucrose monophosphates. These products were isolated by preparative hplc, with a calculated yield of 27% based on all organic phosphate as sucrose monoesters. Small proportions of glucose and fmctose were also formed. 

Sohd uranium—phosphate complexes have been reported for the IV and VI oxidation states, as well as for compounds containing mixed oxidation states of U(IV) and U(VI). Only a few sohd state stmctures of U(IV) phosphates have been reported, including the metaphosphate U(P03)4, the pyrophosphate U(P202), and the orthophosphate, CaU(PO4)2. The crystal stmcture of orthorhombic CaU(POis similar to anhydrite (194). Compounds of the general formula MU2(PO4)3 have been reported for M = Li, Na, and K, but could not be obtained with the larger Rb and Cs ions (195). In the sohd state, uranium(IV) forms the triclinic metaphosphate, U(P03)4. Each uranium atom is eight-coordinate with square antiprismatic UOg units bridged by... 

Uranium(VI) phosphates have been widely investigated and can be divided in several stmcture types orthophosphates M(U02) (PO4) XH2O, hydrogenphosphates M(U02) (H P04) XH2O, pyrophosphates U 0 P202, metaphosphates (U02) (P03) XH2O, and polyphosphates (U04,(PP,).- Hp (188). 

Calcium metaphosphate [13477-39-9] is made by reaction of P2O3 in HPO3 with rock phosphate. The insoluble, polymeric product must be hydrolyzed before it can act as a fertilizer (13) ... 

An abrasive is usually chemically inert, neither interacting with other dentifrice ingredients nor dissolving in the paste or the mouth. Substances used as dentifrice abrasives include amorphous hydrated silica, dicalcium phosphate dihydrate [7789-77-7] anhydrous dicalcium phosphate [7757-93-9] insoluble sodium metaphosphate [10361-03-2], calcium pyrophosphate [35405-51-7], a-alumina trihydrate, and calcium carbonate [471-34-1]. These materials are usually synthesized to specifications for purity, particle size, and other characteristics naturally occurring minerals are used infrequently. Sodium bicarbonate [144-55-8] and sodium chloride [7647-14-5] have also been employed as dentifrice abrasives. 

Chemical Designations - Synonyms Sodium phosphate is generic term and includes the following (1) monosodium phosphate (MSP sodium phospWe, monobasic), (2) disodium phosphate (DSP sodium phosphate dibasic), (3) trisodium phosphate (TSP sodium phosphate, tribasic), (4) sodium acid pyrophosphate (ASPP SAPP disodium pyrophosphate (TSPP), (6) sodium metaphosphate (insoluble sodium metaphosphate), (7) sodium trimetaphosphate, and (9) sodium tripolyphosphate (STPP TPP) Chemical Formula (1) NaHjPO (2) Na HPO (3) NajPO (4) Na H P O, (5) Na P O, (6) (NaPOj) (7) (NaP03)3 (8) (NaP03) NaO (9) Na,P30,o. 

Modem cyclic formulation of teirametaphosphate anion suggested by A. Glatzel. (Ring structure of metaphosphate deHnitely established by L. Pauling and J. Sherman 1937.)... 

They can also be prepared in specialized cases by (a) metathesis, (b) the action of H7PO4 on an oxide, (c) thermolysis of a metaphosphate, (d) thermolysis of an orthophosphate, or (e) reductive thermolysis, e.g. ... 

These compounds were formerly called meta-phosphoric acids and metaphosphates but the lURAC cyclo- nomenclature is preferred as being structurally more informative. The only... 

The crystal structure of the cyc/<7-hcxaphos-phate anion in Nar.P OiR.fiHoO shows that all 6P atoms are coplanar and that bond lengths arc similar to those in the P Oy and p40i2 anions. See ref. 147 for the structure of the hydrated cyc/o-decaphosphate KioPit)03o.4H20. Higher cyr/r)-metaphosphates can be isolated by... 

Sodium fluoride also attacks silica, as do sodium metaphosphate and sodium polyphosphate, and to a lesser extent sodium carbonate and sodium cyanide. Attack is particularly vigorous for fused alkalis, alkali halides and phosphates. 

Also introduced was sodium metaphosphate [Hagan phosphate or Calgon , represented at the time by the formula (NaP03)6, although it tends to have a different formula today]. 

Alternatively, sodium metaphosphate (an orthophosphate that has been molecularly dehydrated by the removal of a molecule of water) may be employed because this must regain the lost water molecule before reacting with calcium as the orthophosphate. This delay may provide the time necessary to ensure that the precipitation reaction takes place solely within the confines of the bulk BW. 

---