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Calcium pyrophosphate

Topic: Chemistry

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Calcium pyrophosphate
Names
IUPAC name
Calcium diphosphate
Other names
Diphosphoric acid, calcium salt (1:2); Dicalcium diphosphate; Dicalcium pyrophosphate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
MeSH Calcium+pyrophosphate
UNII
Properties
Ca2O7P2
Molar mass 254.053 g/mol
Appearance White powder
Density 3.09 g/cm3
Melting point 1,353 °C (2,467 °F; 1,626 K)
insoluble
Solubility soluble in HCl, nitric acids
1.585
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondFlammability code 0: Will not burn. E.g. waterHealth code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
0
2
0
Flash point Non-flammable
Related compounds
Other anions
 Calcium phosphate
Other cations
 Magnesium pyrophosphate
Sodium pyrophosphate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Calcium pyrophosphate (Ca2P2O7) is a chemical compound, an insoluble calcium salt containing the pyrophosphate anion. There are a number of forms reported: 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,[citation needed] because of its insolubility and nonreactivity toward fluoride.[2]

Preparation

Crystals of the tetrahydrate can be prepared by reacting sodium pyrophosphate, Na4P2O7 with calcium nitrate, Ca(NO3)2, at carefully controlled 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:[citation needed]

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

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

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.[citation needed] 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

  1. ↑ Calcium Pyrophosphate Deposition Disease at eMedicine
  2. ↑ Klaus Schrödter; Gerhard Bettermann; Thomas Staffel; Friedrich Wahl; Thomas Klein; Thomas Hofmann (2012). "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_465.pub3. 
  3. ↑ 3.0 3.1 Christoffersen, Margaret R.; Balic-Zunic, Tonci; Pehrson, Søren; Christoffersen, Jørgen (2000). "Growth and precipitation of a monoclinic calcium pyrophosphate tetrahydrate indicating auto-inhibition at pH7". Journal of Crystal Growth 212 (3–4): 500–506. doi:10.1016/S0022-0248(00)00231-1. Bibcode: 2000JCrGr.212..500C. 
  4. ↑ Mandel, Gretchen S.; Renne, Kathleen M.; Kolbach, Ann M.; Kaplan, Wayne D.; Miller, Jay D.; Mandel, Neil S. (1988). "Calcium pyrophosphate crystal deposition disease: Preparation and characterization of crystals". Journal of Crystal Growth 87 (4): 453–462. doi:10.1016/0022-0248(88)90093-0. Bibcode: 1988JCrGr..87..453M. 
  5. ↑ Parodi, J. A.; Hickok, R. L.; Segelken, W. G.; Cooper, J. R. (1965). "Electronic Paramagnetic Resonance Study of the Thermal Decomposition of Dibasic Calcium Orthophosphate" (in en). Journal of the Electrochemical Society 112 (7): 688. doi:10.1149/1.2423665. Bibcode: 1965JElS..112..688P. https://iopscience.iop.org/article/10.1149/1.2423665. 
  6. ↑ Hill, W L; Reynolds, D S; Hendbicks, S B; Jacob, K D (1945-02-01). "Nutritive Evaluation of Defluorinated Phosphates and Other Phosphorus Supplements. I. Preparation and Properties of the Samples". Journal of AOAC International 28 (1): 105–118. doi:10.1093/jaoac/28.1.105. ISSN 0095-9111. https://doi.org/10.1093/jaoac/28.1.105. 
  7. ↑ Calvo, C. (1968-07-01). "Crystal structure of .alpha.-calcium pyrophosphate". Inorganic Chemistry 7 (7): 1345–1351. doi:10.1021/ic50065a019. ISSN 0020-1669. https://doi.org/10.1021/ic50065a019. 
  8. ↑ Parodi, J. A.; Hickok, R. L.; Segelken, W. G.; Cooper, J. R. (1965). "Electronic Paramagnetic Resonance Study of the Thermal Decomposition of Dibasic Calcium Orthophosphate". Journal of the Electrochemical Society 112 (7): 688. doi:10.1149/1.2423665. Bibcode: 1965JElS..112..688P. 
  9. ↑ Webb, N. C. (1966). "The crystal structure of β-Ca2P2O". Acta Crystallographica 21 (6): 942–948. doi:10.1107/S0365110X66004225. 

ja:ピロリン酸カルシウム



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