Chromium(III) phosphate

Chromium(III) phosphate
Names
IUPAC name
Chromium(III) phosphate
Other names
Chromium phosphate, Chromium monophosphate, Chromium orthophosphate, Chromic phosphate
Identifiers
7789-04-0
84359-31-9 (hexahydrate)
3D model (Jmol) Interactive image
ChemSpider 56424
ECHA InfoCard 100.029.219
EC Number 232-141-0
PubChem 62673
Properties
CrPO4
Molar mass 146.97 g/mol
Density 4.236 g/cm3[1]
Melting point 1,907 °C (3,465 °F; 2,180 K)[1]
Boiling point 2,671 °C (4,840 °F; 2,944 K)
insoluble, exothermal blue solution[1]
Structure
monoclinic[1]
Hazards
US health exposure limits (NIOSH):
PEL (Permissible)
 TWA 1 mg/m3[2]
REL (Recommended)
 TWA 0.5 mg/m3[2]
IDLH (Immediate danger)
 250 mg/m3[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Chromium(III) phosphate is an inorganic compound with the chemical formula CrPO4. CrPO4 normally exists as a green crystal, CrPO4•4H2O, or a violet crystal, CrPO4•6H2O, in its hydrated form. It is insoluble in water but soluble in acids. The melting point of CrPO4 stands at a temperature of 100 °C however it is a stable compound at normal temperature and pressure. Chromium(III) phosphate undergoes thermal decomposition at a high temperature of 1450 °C to yield chromium oxide and phosphorus pentaoxide. It is used as an additive in drugs, anti-corrosive pigments, catalysts and polymer manufacture.

Synthesis

The process used in preparing Chromium phosphate depends on the intended phase of the compound.

Hydrated Phase

Tetrahydrated Chromium(III) phosphate

Chromium(III) phosphate can be prepared in the laboratory by mixing a 1M solution of trisodium phosphate with a 1M solution of chromium(III) nitrate, according to the reaction below. The suspension is equilibrated for 1 hour at 40 °C with continuous stirring to form thick green precipitates.[3] Cr(NO3)3(aq) + Na3PO4(aq) → CrPO4(s) ↓ + 3NaNO3(aq)

Hexahydrated Chromium(III) phosphate

Hexahydrate Chromium phosphate, CrPO4•6H2O, is prepared by reducing chromium trioxide, CrO3, with ethanol in the presence of orthophosphoric acid, H3PO4, at temperatures ranging from −24 °C to +80 °C.[4]

Mesoporous phase

Gel-like Chromium(III) phosphate is prepared through the reduction of ammonium dichromate, (NH4)2Cr2O7, using ethanol, CH3COOH, and nitric acid, HNO3. This process is done in the presence of ammonium dihydrogen phosphate and urea at an elevated temperature where tetradecyltrimethylammonium bromide (TTBr) is used as structure directing agent.[5]

Films

Preparation of textured Chromium phosphate is carried out by mixing equimolar solutions of aqueous chromium nitrate and diammonium phosphate in a dish placed in a sealed chamber with the low temperature ammonia vapor catalyst diffusing into the solution at a constant rate. After 24h, the resulting purple film grows out from the liquid through the hydrolysis and polycondensation occurring in the reaction environment at the air/liquid and film/liquid boundary. Surface tension makes the film compact making it easy to insert a microscope slide and lift the film from underneath the solution surface. Once obtained the solution is washed with deionized water and ethanol, then dried in a vacuum.[6]

Amorphous phase

The preparation of anhydrous chromium(III) phosphate begins by grinding a mixture of 75 mol% of chromium(III) oxide, Cr2O3, and 25 mol% of pure ammonium hydrogen phosphate, (NH4)2HPO4. This mixture is pressed into pellets and heated under air pressure at 400 °C for 24h in order to remove ammonia and water. After this, a heating sequence of 450 °C (24 h), 700 °C (3⋅24 h), 800 °C (24 h) and 850 °C (2⋅24 h) occurs. The pellet mixture is gradually cooled thereafter.[7]

Physical Properties

Crystal Structure

Chromium(III) phosphate can exist as two isoform crystals with a different arrangement of unit cell. Its β-isoform crystallizes into an orthorhombic system with the Cmcm space group. This means that its unit cell is made up of coordinated chromium, oxygen and phosphorus atoms arranged into a rectangular prism with a rectangular base of a= 0.5165 nm by b = 0.7750 nm, and height, c = 0.6131 nm. This CrPO4 isoform consists of infinite chains of trans edge-sharing CrO6 octahedra, which run parallel to the c-axis, and are linked together by PO4 tetrahedra. Above 1175 °C, β-CrPO4 is converted to α-CrPO4 which has a different crystal arrangement. The unit cell of α-CrPO4 crystallizes into a triclinic system consists of an infinite network of linked polyhedra with a CrO6 octahedron and a PO4 tetrahedron sharing a common edge. There are 12Cr3+ sites per unit cell: the four Cr(1) octahedra which are each apically linked to the four Cr(2) octahedral, while the eight Cr(2) octahedra form edge-sharing Cr(2)/Cr(2') pairs and share two corners with the four Cr(1) octahedra.[8]

Magnetic Properties

The magnetic properties of the β-CrPO4 are a result of the cation-cation distances along the octahedral chains which give rise to strong direct-exchange interactions and even metal-metal bonding. Neutron diffraction studies reveal that the spiral moments in β-CrPO4 are collinear and anti-ferromagnetically coupled along the chains in the 001 planes, at low temperature (5K, µeff = 2.55µB).[9] Observations from a diffraction study has shown that at low temperature(2K), the α-CrPO4 octahedra CrO6 units build up an infinite, three-dimensional network expected to provide strong Cr-O-Cr magnetic superexchange linkages with exchange pathway through the phosphate group. These linkages give the structure its anti-ferromagnetic characteristic (Ɵ = -35.1 K, µeff = 3.50µB) which results in the anti-parallel magnetic spins in the plane that is perpendicular to the chains of the octahedral CrO6.[10]

Chemical Properties

Ion Exchange Reaction

At a high temperature and pH ranging from 283-383K and pH 4-7 respectively, equilibrated KOH/HCl solution, insoluble CrPO4 solid and aqueous cation solution yield a sorption reaction. Studies reveal that CrPO4 catalyzes the adsorption of divalent cations onto its amorphous surface through the cation exchange mechanism. The mechanism suggests that the H+ ions are liberated from the solid to aqueous phase as the cations become hydrolyzed and adsorb onto the catalyst surface. Thus, a decrease in the pH of the reaction is used as a direct indicator of the rate of adsorption in the reaction:

nP-OH + Mz+ ⇔ (P-O) n Mz-n + nH+ where P-O = solid

A plot of the Kurbatov equation is used to relate the release of H+ ion to the equilibrium constant of the reaction:

Log Kd = log Kex + npHeq

where Kd (l g-1) represents the distribution coefficient, and n is the slope of the straight line giving an indication of the H+/Mz+ stoichiometry of the exchange reaction. Under similar conditions, the selectivity of CrPO4 for dative cations follows the sequence: Pb2+ > Cu2+ > Ni2+ ≅ Cd2+. Increases in temperature and pH enhances the ion exchange reaction.[11]

Application

Anti-corrosive Coating

Paints containing chromium (III) phosphate have been used as corrosion resistant coating for metals. The paints consist of aqueous acidic chromium (III) phosphate solution which convert to a consistent film when applied onto metals heavily used in manufacturing and utility such as zinc, zinc alloy, aluminum and aluminum alloy substrates. Application methods include electroplating, immersing or spraying the solution on the surface of the substrate.[12]

Catalyst

Chromium (III) phosphate has various applications in the polymer industry. Combined chromium (III) aluminum phosphate is widely used as a catalyst in the alkylation of aromatic hydrocarbons using alcohols such as the methylation of toluene using methanol. The alcohol is dehydrated into ether while the alkyl substituted product could be used as an intermediate in the manufacture of synthetic fibers such as poly(ethylene terephthalate).[13]

Chromium (III) phosphate is also used to catalyze cation exchange in sorption reactions. This catalysis is widely used in the reduction of metal toxicity during environmental clean-ups. This has been applied in decreasing the concentration of lead in aquatic habitat and drinking water.[14]

Polymer

Pretreatment with chromium (III) phosphate-silicate is also used as a laminated structure to dampen vibration and noise in a motor.[15]

Medicine

The therapeutic dose of colloidal Cr(32P)O4 is radiated internally for the treatment of cavernous hemangioma. Hemangioma is among the most common benign, vascular proliferative tumor. They become problematic when they ulcerate and have massive growth thereby impacting normal function and cosmetic development[16]

Toxicity

Although chromium(III) phosphate is hardly soluble in water, overexposure to the compound from the environment, industrial location and abrasions from metal on metal implants could have harmful effects. The toxicity of chromium(III) phosphate depends on the duration of exposure, chromium(III) phosphate concentration, entry routes across a membrane barrier and release of trivalent chromium ion from the chromium(III) phosphate. Macrophage cells in the body exposed to Chromium(III) phosphate engulf or phagocytize the compound into its endosomal and lysosomal environment which is acidic. This catalyzes a proteolytic reaction yielding a dose-dependent increase in chromium(III) ion release in the affected cells. The Cr3+ ions has toxic effects on the proteins of the cytosol and mitochondria by oxidatively modifying their chemical properties thus disenabling from performing their functions. Proteins with high metal affinity such as enolase, catalase enzymes and hemoglobin, ferritin molecular transporters are affected. This may ultimately lead to nephrotoxicity, reproductive and developmental toxicity due to tissue damage, necrosis and inflammation.[17]

See also

References

  1. 1 2 3 4 Brauer, Georg (1965) [1962]. Handbuch Der Präparativen Anorganischen Chemie [Handbook of Preparative Inorganic Chemistry] (in German). 2. Stuttgart; New York, New York: Ferdinand Enke Verlag; Academic Press, Inc. p. 1341. ISBN 978-0-32316129-9. Retrieved 2014-01-10.
  2. 1 2 3 "NIOSH Pocket Guide to Chemical Hazards #0141". National Institute for Occupational Safety and Health (NIOSH).
  3. ↑ Mustafa, S.; Murtaza, S.; Naeem, A.; Farina, K. (2010). "Ion Exchange Sorption Of Pb2+ Ions On CrPO4". Environmental Technology. 26 (4): 353–359. doi:10.1080/09593332608618544.
  4. ↑ Vasovic, Dusanka D.; Stojakovic, Djordje R. "Preparation and properties of some amorphous chromium(III) phosphates". Journal of Non-Crystalline Solids, 2003, 101, 1, pp 129-132.
  5. ↑ Tarafdar, A.; Biswas, S.; Pramanik N.K; Pramanik P. "Synthesis of Mesoporous Chromium Phosphate through an unconventional sol-gel route." Microporous and Mesoporous Materials, 2006, 89, 1-3, pp 204-208.
  6. ↑ Gomm, J.R; Schwenzer B.; Morse D.E. "Textured films of chromium phosphate synthesized by low-temperature vapor diffusion catalysis." Solid State Sciences, 2007, 9, 5, pp 429-431
  7. ↑ Bosacka, M.; Jakubus P.; Rychowska-Himmel I. "Obtaining Of Chromium(III) Phosphates(V) In The Solid-State And Their Thermal Stability." Journal of Thermal Analysis and Calorimetry, 2007, 88, 1, pp 133–137.
  8. ↑ Attfield, J.P; Battle, P.D; Anthony, K.C; Johnson, D.C. (1988). "Magnetic Structures and Properties of alpha-CrPO4 and alpha-CrAsO". Inorganic Chemistry. 28 (7): 1207–1213. doi:10.1021/ic00306a004.
  9. ↑ Attfield, J.P; Battle, P.D; Anthony, K.C; Johnson, D.C. (1988). "Magnetic Structures and Properties of alpha-CrPO4 and alpha-CrAsO". Inorganic Chemistry. 28 (7): 1207–1213. doi:10.1021/ic00306a004.
  10. ↑ Attfield, J.P; Battle, P.D; Anthony, K.C. "Spiral Magnetic Structure of β-chromium(III) Orthophosphate(β-CrPO4)." Journal of Solid State Chemistry, 1985, 57, pp 357-361
  11. ↑ Mustafa, S.; Murtaza, S.; Naeem, A.; Farina, K. (2010). "Ion Exchange Sorption Of Pb2+ Ions On CrPO4". Environmental Technology. 26 (4): 353–359. doi:10.1080/09593332608618544.
  12. ↑ Ludwig, R.; Recker, A. "Chromium(VI)-free, aqueous acidic Chromium(III) conversion solutions." US20070243397 A1, 2007. Columbia Chemical Corporation, Ohio, https://www.google.com/patents/US20070243397 (accessed April 12, 2015)
  13. ↑ Johnson, M.M.; Nowack, G.P. "Chromium phosphate as an alkylation catalyst." U.S Patent 4543436 A, September 24, 1985.https://www.google.com/patents/US4543436 (accessed April 12, 2015)
  14. ↑ Mustafa, S.; Murtaza, S.; Naeem, A.; Farina, K. (2010). "Ion Exchange Sorption Of Pb2+ Ions On CrPO4". Environmental Technology. 26 (4): 353–359. doi:10.1080/09593332608618544.
  15. ↑ Swanson, R.; Hufnagel, A. "Laminated Viscoelastic Damping Structure and Method of making the same." US 20090252989 A1, October 8, 2009. https://www.google.com/patents/US20090252989?dq=Laminated+viscoelastic+damping+structure&hl=en&sa=X&ei=u3QqVd0mg6uiBLWzgVA&ved=0CB4Q6AEwAA (accessed April 12, 2015); SciFinder Scholar 2009: 20090252989 A1
  16. ↑ Shi, C.; Yuan B.; Lu J.; Xu J.; Yang W.; Deng J.; Wang J. "Continuous Low-Dose-Rate Radiation of Radionuclide Phosphorus-32 for Hemangiomas." Cancer Biotherapy and Radiopharmaceuticals, 2012, pp 198-203.
  17. ↑ Scharf, B.; Clement, C.C.; Zolla, V.; Perino, G.; Yan, B.; Elci, S.G.; Purdue, E.; Goldring, S.; Macaluso, F.; Cobelli, N; Vachet, R.W; Santambrogio, L. "Molecular Analysis of Chromium and Cobalt-related toxicity". Nature. 2014: 5729.
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