Calcium pyrophosphate

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Calcium pyrophosphate refers to any member of a series of inorganic compound with the formula Template:Chem2. They are white solids that are insoluble in water. They contain the pyrophosphate anion, although sometimes they are referred to as phosphates. The inventory includes an anhydrous form, a dihydrate (Ca2P2O7·2H2O), and a tetrahydrate (Ca2P2O7·4H2O). Deposition of dihydrate crystals in cartilage are responsible for the severe joint pain in cases of calcium pyrophosphate deposition disease (pseudo gout) whose symptoms are similar to those of gout.[1] Ca2P2O7 is commonly used as a mild abrasive agent in toothpastes because of its insolubility and nonreactivity toward fluoride.[2]

Preparation

Crystals of the tetrahydrate can be prepared by treating a solution of sodium pyrophosphate with calcium nitrate with careful control of pH and temperature:[3]

Na4P2O7(aq)+2 Ca(NO3)2(aq)→ Ca2P2O7·4 H2O + 4 NaNO3

The dihydrate, sometimes termed CPPD, can be formed by the reaction of pyrophosphoric acid with calcium chloride:Script error: No such module "Unsubst".

CaCl2 + H4P2O7(aq) → Ca2P2O7·2 H2O + HCl.

The anhydrous forms can be prepared by heating dicalcium phosphate:[2]

2 CaHPO4 → Ca2P2O7 + H2O

At 240-500 °C an amorphous phase is formed, heating to 750 °C forms β-Ca2P2O7, heating to 1140 - 1350 °C forms the α-Ca2P2O7.

Structure of anhydrous and hydrated forms

The stable tetrahydrate was originally reported to be rhombohedral but is now believed to be monoclinic. Additionally there is an unstable monoclinic form.[3]

The dihydrate is triclinic, with hydrogen bonding between the two water molecules and hydrogen bonds to the O atoms on the anion.Script error: No such module "Unsubst". An hexagonal dihydrate has also been reported.[4]

The anhydrous form has 3 polymorphs, α-, β-, and metastable γ[5] (Tα/β=1140ºС[6]). The high temperature form α- is monoclinic (P21/n, a=12.66(1)Å, b=8.542(8)Å, c=5.315(5)Å, Z=4, ρα=2.95 g/cm3), with 8 coordinate calcium, the lower temperature form β- is tetragonal (P41, a=b=6.684Å, c=24.144Å, V=915.40Å3, Z=8, ρβ=3.128 g/cm3), with calcium in four different coordination environments, 2 that are 7 coordinate, one eight and one 9. In both the pyrophosphates are essentially eclipsed.[7][8][9]

References

Template:Reflist Template:Calcium compounds

ja:ピロリン酸カルシウム

  1. Calcium Pyrophosphate Deposition Disease at eMedicine
  2. a b Template:Ullmann
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