Thorium dioxide

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Thorium dioxide
Fluorite-unit-cell-3D-ionic.png
Identifiers
CAS number 1314-20-1 YesY
PubChem 14808
Jmol-3D images Image 1
Properties
Molecular formula ThO2
Molar mass 264.04 g/mol
Appearance white solid
Odor odorless
Density 10.00 g/cm3
Melting point 3,390 °C (6,130 °F; 3,660 K)
Boiling point 4,400 °C (7,950 °F; 4,670 K)
Solubility in water insoluble
Solubility insoluble in alkali
slightly soluble in acid
Refractive index (nD) 2.200 (thorianite)
Structure
Crystal structure Fluorite (cubic), cF12
Space group Fm3m, No. 225
Lattice constant a = 559.74(6) pm[1]
Coordination
geometry
Tetrahedral (O2–); cubic (ThIV)
Thermochemistry
Std molar
entropy
So298
65.2(2) J K−1 mol−1
Std enthalpy of
formation
ΔfHo298
−1226(4) kJ/mol
Hazards
EU Index Not listed
Flash point Non-flammable
LD50 400 mg/kg
Related compounds
Other cations Hafnium(IV) oxide
Cerium(IV) oxide
Related compounds Protactinium(IV) oxide
Uranium(IV) oxide
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Thorium dioxide (ThO2), also called thorium(IV) oxide, is a crystalline solid, often white or yellow in color. It was formerly known as thoria or thorina. It is produced mainly as a by-product of lanthanide and uranium production.[1] Thorianite is the name of the mineralogical form of thorium dioxide. It is moderately rare and crystallizes in isometric system. The melting point of thorium oxide is 3300 °C – the highest of all known oxides. Only a few elements (including tungsten and carbon) and a few compounds (including tantalum carbide) have higher melting points.).[2]

Chemistry[edit]

The compound is radioactive due to the radioactivity of thorium. Thorium dioxide can be used as a nuclear fuel. (Refer to the article of thorium for more information on this application.) The high thermal stability of thorium dioxide allows applications in flame spraying and high-temperature ceramics. Thorium dioxide was the primary ingredient in the X-ray contrast medium Thorotrast. Use of Thorotrast was abandoned when it was found to be a carcinogen, sometimes causing cholangiocarcinoma. Today, barium sulfate is the standard X-ray contrast agent. Thoria has the fluorite crystal structure. This is uncommon among binary dioxides (other examples include cerium dioxide, hafnium dioxide, uranium dioxide and plutonium dioxide). The band gap of thoria is about 6 eV.

Applications[edit]

Thorium dioxide is used as a stabilizer in tungsten electrodes in TIG welding, electron tubes, and aircraft engines. As an alloy, thoriated tungsten metal is not easily deformed because the high-fusion material thoria augments the high-temperature mechanical properties, and thorium helps stimulate the emission of electrons (thermions). It is the most popular oxide additive because of its low cost, but is being phased out in favor of non-radioactive elements such as cerium, lanthanum and zirconium.

A major use in the past was in gas mantles of lanterns, which were frequently composed of 99 percent ThO2 and 1% cerium(IV) oxide. Even as late as the 1980s it was estimated that about half of all ThO2 produced (several hundred tonnes per year) was used for this purpose.[3] Some mantles still use thorium, but yttrium oxide (or sometimes zirconium oxide) is used increasingly as a replacement.

Thorium dioxide was formerly added to glasses during manufacture to increase their refractive index, producing thoriated glass with up to 40% ThO2 content. These glasses were used in the construction of high-quality photographic lenses. However, the radioactivity of the thorium caused both a safety and pollution hazard and self-degradation of the glass (turning it yellow or brown over time). Lanthanum oxide has replaced thorium dioxide in almost all modern high-index glasses.

Thorium dioxide is a Welsbach material. It has been suggested[4] that these chemicals could be sprayed into the upper atmosphere to reflect sunlight and thus lower the global temperature.

Thorium dioxide is a catalyst in many chemical reactions, including the Ruzicka large ring synthesis, petroleum cracking, conversion of ammonia to nitric acid and preparation of sulfuric acid.[5]

Thoria dispersed nickel finds its applications in various high temperature operations like combustion engines because it is a good creep resistant material. It can also be used for hydrogen trapping.[6][7]

References[edit]

  1. ^ a b Yamashita, Toshiyuki; Nitani, Noriko; Tsuji, Toshihide; Inagaki, Hironitsu (1997). "Thermal expansions of NpO2 and some other actinide dioxides". J. Nucl. Mat. 245 (1): 72–78. doi:10.1016/S0022-3115(96)00750-7. 
  2. ^ Emsley, John (2001). Nature's Building Blocks ((Hardcover, First Edition) ed.). Oxford University Press. p. 441. ISBN 0-19-850340-7. 
  3. ^ Greenwood, Norman N.; Earnshaw, Alan (1984). Chemistry of the Elements. Oxford: Pergamon Press. pp. 1425, 1456. ISBN 0-08-022057-6. 
  4. ^ Chang, David B; Shih, I-fu "Stratospheric Welsbach seeding for reduction of global warming", US Patent No. 5003186.
  5. ^ Patnaik, Pradyot (2003). Handbook of Inorganic Chemical Compounds. McGraw-Hill. p. 931. ISBN 0-07-049439-8. Retrieved 2009-06-06. 
  6. ^ Mitchell, Brian S (2004). An Introduction to Materials Engineering. and Science for Chemical and Materials.. p. 473. ISBN 978-0-471-43623-2. 
  7. ^ Robertson, Wayne M. (1979). "Measurement and evaluation of hydrogen trapping in thoria dispersed nickel". Metallurgical and Materials Transactions A 10 (4): 489–501. doi:10.1007/BF02697077.