Chemistry:Curium(III) oxide

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Curium(III) oxide
Unit cell, ball and stick model of curium(III) oxide
Names
IUPAC name
Curium(III) oxide
Systematic IUPAC name
Curium(3+) oxide
Other names
Curic oxide

Curium sesquioxide

Curium trioxide
Identifiers
3D model (JSmol)
Properties
Cm2O3
Molar mass 542 g·mol−1
Melting point 2,265 °C (4,109 °F; 2,538 K)
Structure
Hexagonal, hP5, Body-Centered Cubic, Monoclinic
P-3m1, No. 164
Related compounds
Other cations
 Gadolinium(III) oxide, Curium hydroxide, Curium trifluoride, Curium Tetrafluoride, Curium Trichloride, Curium Triiodide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Curium(III) oxide is a compound composed of curium and oxygen with the chemical formula Cm
2O
3. It is a crystalline solid with a unit cell that contains two curium atoms and three oxygen atoms. The simplest synthesis equation involves the reaction of curium(III) metal with O2−: 2 Cm3+ + 3 O2− ---> Cm2O3.[1] Curium trioxide can exist as five polymorphic forms.[2][3] Two of the forms exist at extremely high temperatures, making it difficult for experimental studies to be done on the formation of their structures. The three other possible forms which curium sesquioxide can take are the body-centered cubic form, the monoclinic form, and the hexagonal form.[3][4] Curium(III) oxide is either white or light tan in color and, while insoluble in water, is soluble in inorganic and mineral acids.[5][6] Its synthesis was first recognized in 1955.[7]

Synthesis

Curium sesquioxide can be prepared in a variety of ways.

  • Ignition with O2: Curium(III) oxalate is precipitated through a capillary tube. The precipitate is ignited by gaseous oxygen at 400 °C, and the resulting product is thermally decomposed via 600 °C and 10−4 mm of pressure.[8]
  • Aerosolized Curium Sesquioxide: The aerosolization process of Cm2O3 can be done through multiple experimental processes. Typically, Cm2O3 is aerosolized for experimental procedures which set out to discover the effects of curium metal within a biological system.[6][9]

Route 1: The traditional aerosolization reaction utilizes curium metal as the starting material. While curium metal has been discovered to naturally exist as a mixture of 87.4% 244Cm, 8.4% 243Cm, 3.9% other curium isotopes, and ~0.3% of the daughter nuclide, plutonium, in most aerosolized syntheses of curium(III) oxide, curium metal is purified through solvent extraction of curium nitrate and bis(2-ethylhexyl) phosphoric acid in toluene to remove the plutonium.[6] NH3OH is then added to the purified curium nitrate, and the resulting precipitate is collected and rinsed with deionized water. The precipitate (Cm2O3) is resuspended in solvent and aerosolized with some sort of high output aerosol generator (ex: Lovelace nebulizer).[6]

Route 2: In other aerosolizations, instead of the addition of NH3OH to the purified curium nitrate, ammonium hydroxide is utilized to adjust the pH value of the solution to 9. The increased basicity of the solution creates a curium hydroxide precipitate. This precipitate is then collected through filtration and resuspended in deionized water, and a nebulizer is then used to aerosolize the product.[9]

  • Reduction by Hydrogen Gas: A solution of curium trichloride is evaporated to dryness with pure nitric acid to produce curium nitrate. The curium nitrate is then ignited in air, producing curium oxide, believed to be an intermediate structure between CmO2 and the formation of Cm2O3. The intermediate is scraped into capillary tubes attached to a vacuum system and reduced with gaseous hydrogen - the result of the combustion of UH3.[8]
  • Obtaining Curium-244: For many of the reactions described above, curium metal is provided by an outside retailer. In order to obtain curium metal, 239Pu metal can be sent through the pile irradiation process described by the radioactive decay processes below (note that neutrons are indicated by the letter "n" and beta-minus particles by "β−"):

239Pu + n ---> 240Pu + n ---> 241Pu + n ---> 242Pu + n ---> 243Pu+ β− ---> 243Am + n ---> 244Am + β− ---> 244Cu.[10]

However, 244curium is one of the more unstable curium isotopes, so any structural data obtained for compounds containing 244Cm may deviate from the expected as a result of structural damage.[3] It has been experimentally determined that, within one day, 244CmO2's lattice parameter increases by a factor of 0.2%.[3] This has been hypothesized to be a result of the weakening interatomic interactions between curium(IV) and the neighboring oxide groups as a result of alpha-decay. This affects the thermal conductivity of curium oxides, causing it to exponentially decrease over time as the effects of alpha-decay strengthen.[11] Abnormal phase transitions have also been reported and have been theorized to be a result of induced self-irradiation, either by 244Cm or the presence of leftover 244Am from incomplete radioactive decay.[3][11]

Structure

The body-centered cubic and monoclinic forms are the most common polymorphic forms of curium trioxide, produced by the chemical reactions detailed above. Their crystalline structures are very similar. One of the polymorphs of curium trioxide - the body-centered cubic form - spontaneously transforms to the hexagonal form after several weeks.[8] This transformation is undergone upon spontaneous 244Cm alpha decay, which produces radiation damage effects within the cubic crystal lattice to distort it to that of hexagonal.[3] Although not experimentally proven, there is speculation that monoclinic curium trioxide may be an intermediate form in between the transformation of the cubic form to that of the hexagonal. The body-centered cubic form of curium trioxide exists below temperatures of 800 °C, the monoclinic form between 800 °C and 1615 °C, and the hexagonal form above 1615 °C.[8]

Crystallography

The lattice parameters for three of the polymorphic structures of curium sesquioxide are given below.

Hexagonal:

Hexagonal

Data Table[8][12] Temperature (°C) Lengths of a (Å) Uncertainty (Å) Lengths of c (Å) Uncertainty (Å)
1615 3.845 0.005 6.092 0.005
--* 3.496 0.003 11.331 0.005

(*: No specific temperature has been stated to produce the lengths listed in the second row.[8][12])

Monoclinic:

Monoclinic

Data Table[13] Temperature (°C) Lengths of a (Å) Lengths of b (Å) Lengths of c (Å)
21 14.257** 8.92** 3.65**

(**: None of these lengths contained given uncertainties.[13])

Cubic:

Lattice body centered cubic

Data Table[8] Temperature (°C) Lengths of a (Å) Uncertainty (Å)
21 10.97 0.01

Data

Ever since the discovery (and isolation) of 248Cm, the most stable curium isotope, experimental work on the thermodynamic properties of curium sesquioxide (and other curium compounds) has become more prevalent. However, 248Cm can only be obtained in mg samples, so data collection for 248Cm-containing compounds takes longer than that for compounds which predominantly contain other curium isotopes.[3] The data table below reflects a large variety of data collected specifically for curium sesquioxide, some of which is purely theoretical, but most of which have been obtained from 248Cm-compounds.[3][4][7][14][15][16]

Ground State F-Configuration for Metal Approximate Melting Point (°C) Magnetic Susceptibility (μb) Uncertainty (μb) Enthalpy of Formation (kJ/mol) Uncertainty (kJ/mol) Average Standard Molar Entropy (J/molK) Uncertainty (J/molK)
f7 (Cm3+) 2265* 7.89** 0.04** -400** 5** 157*** 5***

(*: Different syntheses of curium trioxide have been shown to produce compounds with different experimental melting points. The melting point given in this data table is merely an average of those collected from the references.[15][16])

(**: Characteristic of the monoclinic form.)

(***: Various experiments have calculated different estimates of the standard molar entropy for curium trioxide: Moskin has reported a standard molar entropy of 144.3 J/molK (no given uncertainty). Westrum and Grønvold have reported a value of 160.7 J/molK (no given uncertainty), and Konings’ value is reported to be 167 +/- 5 J/molK.[14])

Toxicology

Curium metal is a radionuclide and emits alpha particles upon radioactive decay.[14] Although it has a half life of 34 ms, many curium oxides, including curium sesquioxide, have half lives nearing thousands of years.[7] Curium, in the form of curium sesquioxide, can be inhaled into the body, causing many biological defects. The LD50 of curium is 3 micro-Ci through ingestion and inhalation and 1 micro-Ci through absorption through the skin.[17] In one experiment, rats were introduced to aerosolized particulates of curium(III) oxide. Although the experiment proved that inhaled 244Cm2O3 is half as carcinogenic as compared to inhaled 239PuO2, the rats still suffered from many biological deformities, such as skin lesions, malignant tumors, and lung neoplasms.[9] A small amount of the rat population was able to clear particulate curium sesquioxide from the lungs, suggesting that curium sesquioxide is partially soluble in lung fluid.[9]

Applications

Curium(III) oxide is heavily used in industrial grade-reactions and reagents.[15] As recently as 2009, actinide oxides, such as curium sesquioxide, are being considered for storage uses (in the form of heavily durable ceramic glassware) for the transportation of the light-and-air sensitive fission and transmutation target substances.[15]

Other reactions

Curium sesquioxide will spontaneously react with gaseous oxygen at high temperatures.[12] At lower temperatures, a spontaneous reaction will occur over a period of time. Curium trioxide reacted with water has been hypothesized to afford a hydration reaction, but little experimentation has been done to prove the hypothesis.[12] Curium sesquioxide has been shown to not react with nitrogen gas, spontaneously or non-spontaneously.[12]

See also

References

  1. ↑ 8. N.A. (2010). "Study of oxychloride compound formation in chloride melt by spectroscopic methods." Radiochemical Division/Research Institute of Atomic Reactors. pp. 1-17.
  2. ↑ Cunningham, B. B. (1964). "Chemistry of the Actinide Elements". Annual Review of Nuclear Science 14: 323–346. doi:10.1146/annurev.ns.14.120164.001543. Bibcode: 1964ARNPS..14..323C. 
  3. ↑ 3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 Milman, V., Winkler, B., and C.J. Pickard (2003). “Crystal Structures of Curium Compounds: An Ab Initio Study.” Journal of Nuclear Materials (322): 165-179.
  4. ↑ 4.0 4.1 Petit, L., Svane, A., Szotek, Z., Temmerman, W.M., and G. M. Stocks (2009). “Electronic structure and ionicity of actinide oxides from first principles calculations.” Materials Science and Technology Division, Oak Ridge National Laboratory. pp. 1-12.
  5. ↑ Norman M. Edelstein; James D. Navratil; Wallace W. Schulz (1984). Americium and curium chemistry and technology. D. Reidel Pub. Co.. pp. 167–168. 
  6. ↑ 6.0 6.1 6.2 6.3 Helfinstine, Suzanne Y., Guilmette, Raymond A., and Gerald A. Schlapper (1992). “In Vitro Dissolution of Curium Oxide Using a Phagolysosomal Simulant Solvent System.” Environmental Health Perspectives (97): 131-137.
  7. ↑ 7.0 7.1 7.2 Morss, L. R., Fuger, J., Goffart, J. and R.G. Haire (1983). “Enthalpy of Formation and Magnetic Susceptibility of Curium Sesquioxide, Cm203.” Inorganic Chemistry (22):1993-1996.
  8. ↑ 8.0 8.1 8.2 8.3 8.4 8.5 8.6 Wallmann, J.C. (1964). “A Structural Transformation of Curium Sesquioxide.” Journal of Inorganic and Nuclear Chemistry (26): 2053-2057.
  9. ↑ 9.0 9.1 9.2 9.3 Lundgren, D. L. , Hahn, F. F., Carlton, W. W., Griffith, W. C., Guilmette, R. A., and N. A. Gillett (1997). “Dose Responses from Inhaled Monodisperse Aerosols of 244Cm203 in the Lung, Liver and Skeleton of F344 Rats and Comparison with 239Pu02.” Radiation Research (5): 598-612.
  10. ↑ Stevens, C. M., Studier, M. H., Fields, P. R. , Meck, J. F., Sellers, P. A., Friedman, A. M., Diamond H., and J. R. Huizenga (1954). “Evidence for Quadrivalent Curium: X-Ray Data on Curium Oxides.” Communications to the Editor (7): 1707-1708.
  11. ↑ 11.0 11.1 S.E. Lemehov *, V. Sobolev, and P. Van Uffelen (2003). "Modelling thermal conductivity and self-irradiation effects in mixed oxide fuels." Journal of Nuclear Materials (320): 66–76.
  12. ↑ 12.0 12.1 12.2 12.3 12.4 Lumetta, Gregg J., Thompson, Major C., Penneman, Robert A., and P. Gary Eller (2006). The Chemistry of the Actinide and Transactinide Elements. “Curium: Chapter Nine.” Springer Pub. Co. Vol.3. pp. 1397-1443.
  13. ↑ 13.0 13.1 Rimshaw, S. J., and E. E. Ketchen (1967). “Curium Data Sheets.” Oak Ridge National Laboratory - Union Carbide Corporation. pp. 42-102.
  14. ↑ 14.0 14.1 14.2 Konings, R.J.M (2001). “Estimation of the Standard Entropies of some Am(III) and Cm(III) Compounds.” Journal of Nuclear Materials (295): 57-63.
  15. ↑ 15.0 15.1 15.2 15.3 Smith, Paul Kent (1969). “Melting Point of Curium Trioxide (Cm2O3).” Journal of Inorganic and Nuclear Chemistry (31): 241-245.
  16. ↑ 16.0 16.1 Smith, Paul Kent (1970). “High-Temperature Evaporation and Thermodynamic Properties of Cm2O3.” The Journal of Chemical Physics (52): 4964-4972.
  17. ↑ “Radionuclide Data Sheet: Curium.” University of California, San Diego. n.d.1.

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