Thorium(IV) nitrate

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Thorium(IV) nitrate
Identifiers
ECHA InfoCard 100.034.090
Properties
Th(NO3)4
Molar mass 480.066 (anhydrous)
552.130 (tetrahydrate)
570.146 (pentahydrate)
588.162 (hexahydrate)
AppearanceColorless crystal
Melting point 55
Boiling point Decomposes
Soluble [1]
Hazards
Hazard O.svg O
Hazard N.svg N
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
Thorium(IV) nitrate used in a lamp. Gluestrumpf2.jpg
Thorium(IV) nitrate used in a lamp.

Thorium(IV) nitrate is a chemical compound with the formula Th(NO3)4. A white solid in its anhydrous form, it can form tetra- and pentahydrates. As a compound of thorium it is weakly radioactive.

Chemical compound Substance composed of multiple elements

A chemical compound is a chemical substance composed of many identical molecules composed of atoms from more than one element held together by chemical bonds. Two atoms of the same element bonded in a molecule do not form a chemical compound, since this would require two different elements.

Water of crystallization

In chemistry, water of crystallization or water of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization is the total mass of water in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex or a salt, which is not directly bonded to the metal cation.

Thorium Chemical element with atomic number 90

Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately hard, malleable, and has a high melting point. Thorium is an electropositive actinide whose chemistry is dominated by the +4 oxidation state; it is quite reactive and can ignite in air when finely divided.

Contents

Preparation

Thorium(IV) nitrate hydrate can be prepared by the reaction of thorium(IV) hydroxide and nitric acid:

Nitric acid (HNO3), also known as aqua fortis (Latin for "strong water") and spirit of niter, is a highly corrosive mineral acid.

Th(OH)4 + 4 HNO3 + 3 H2O → Th(NO3)4•5H2O

Different hydrates are produced by crystallizing in different conditions. When a solution is very dilute, the nitrate is hydrolysed. Although various hydrates have been reported over the years, and some suppliers even claim to stock them, [2] only the tetrahydrate and pentahydrate actually exist. [3] What is called a hexahydrate, crystallized from a neutral solution, is probably a basic salt. [4]

The pentahydrate is the most common form. It is crystallized from dilute nitric acid solution. [5]

The tetrahydrate, Th(NO3)4•4H2O is formed by crystallizing from a stronger nitric acid solution. Concentrations of nitric acid from 4 to 59% result in the tetrahydrate forming. [3] The thorium atom has 12-coordination, with four bidentate nitrate groups and four water molecules attached to each thorium atom. [4]

To obtain the anhydrous thorium(IV) nitrate, thermal decomposition of Th(NO3)4·2N2O5 is required. The decomposition occurs at 150-160 °C. [6]

Properties

Anhydrous thorium nitrate is a white substance. It is covalently bound with low melting point of 55 °C. [3]

The pentahydrate Th(NO3)4•5H2O crystallizes with clear colourless crystals [7] in the orthorhombic system. The unit cell size is a=11.191 b=22.889 c=10.579 Å. Each thorium atom is connected twice to each of four bidentate nitrate groups, and to three, and to three water molecules via their oxygen atoms. In total the thorium is eleven-coordinated. There are also two other water molecules in the crystal structure. The water is hydrogen bonded to other water, or to nitrate groups. [8] The density is 2.80 g/cm3. [5] Vapour pressure of the pentahydrate at 298K is 0.7 torr, and increases to 1.2 torr at 315K, and at 341K it is up to 10.7 torr. At 298.15K the heat capacity is about 114.92 calK−1mol−1. This heat capacity shrinks greatly at cryogenic temperatures. Entropy of formation of thorium nitrate pentahydrate at 298.15K is −547.0 calK−1mol−1. The standard Gibbs energy of formation is −556.1 kcalmol−1. [9]

Thorium nitrate can dissolve in several different organic solvents [8] including alcohols, ketones, esters and ethers. [4] This can be used to separate different metals such as the lanthanides. With ammonium nitrate in the aqueous phase, thorium nitrate prefers the organic liquid, and the lanthanides stay with the water. [4]

Thorium nitrate dissolved in water lowers it freezing point. The maximum freezing point depression is −37 °C with a concentration of 2.9 mol/kg. [10]

At 25° a saturated solution of thorium nitrate contains 4.013 moles per liter. At this concentration the vapour pressure of water in the solution is 1745.2 Pascals, compared to 3167.2 Pa for pure water. [11]

Reactions

When thorium nitrate pentahydrate is heated, nitrates with less water are produced, however the compounds also lose some nitrate. At 140 °C a basic nitrate, ThO(NO3)2 is produced. When strongly heated thorium dioxide is produced. [8]

A polymeric peroxynitrate is precipitated when hydrogen peroxide combines with thorium nitrate in solution with dilute nitric acid. Its formula is Th6(OO)10(NO3)4 •10H2O. [8]

The hydrolysis of thorium nitrate solutions produces basic nitrates Th2(OH)4(NO3)4xH2O and Th2(OH)2(NO3)6•8H2O. In crystals of Th2(OH)2(NO3).6•8H2O a pair of thorium atoms are connected by two bridging oxygen atoms. Each thorium atom is surrounded by three bidentate nitrate groups and three water molecules, bringing the coordination number to 11. [8]

When oxalic acid is added to a thorium nitrate solution, insoluble thorium oxalate precipitates. [12] Other organic acids added to thorium nitrate solution produce precipitates of organic salts with citric acid; basic salts, such as tartaric acid, adipic acid, malic acid, gluconic acid, phenylacetic acid, valeric acid. [13] Other precipitates are also formed from sebacic acid and azelaic acid

Double salts

Hexanitratothorates with the generic formula MI2Th(NO3)6 or MIITh(NO3)6•8H2O are made by mixing other metal nitrates with thorium nitrate in dilute nitric acid solution. MII can be Mg, Mn, Co, Ni, or Zn. MI can be Cs, (NO)+ or (NO2)+. [8] Crystals the divalent metal thorium hexanitrate octahydrate have a monoclinic form with similar unit cell dimensions: β=97°, a=9.08 b=8.75-8 c=12.61-3. [14] Pentanitratothorates with the generic formula MITh(NO3)5xH2O are known for MI being Na or K. [8]

K3Th(NO3)7 and K3H3Th(NO3)10•4H2O are also known [4]

Complexed salts

Thorium nitrate also crystallizes with other ligands and organic solvates including ethylene glycol diethyl ether, tri(n‐butyl)phosphate, butylamine, dimethylamine, trimethylphosphine oxide. [4]

Related Research Articles

Monazite phosphate mineral series

Monazite is a reddish-brown phosphate mineral containing rare-earth metals. It occurs usually in small isolated crystals. It has a hardness of 5.0 to 5.5 on the Mohs scale of mineral hardness and is relatively dense, about 4.6 to 5.7 g/cm3. There are at least four different kinds of monazite, depending on relative elemental composition of the mineral:

Copper(II) nitrate chemical compound

Copper(II) nitrate, Cu(NO3)2, is an inorganic compound that forms a blue crystalline solid. Anhydrous copper nitrate forms deep blue-green crystals and sublimes in a vacuum at 150-200 °C. Copper nitrate also occurs as five different hydrates, the most common ones being the trihydrate and hexahydrate. These materials are more commonly encountered in commerce than in the laboratory.

Cerium(IV) sulfate a yellow to yellow/orange solid cerium salt

Cerium(IV) sulfate, also called ceric sulfate, is an inorganic compound. It exists as the anhydrous salt Ce(SO4)2 as well as a few hydrated forms: Ce(SO4)2(H2O)x, with x equal to 4, 8, or 12. These salts are yellow to yellow/orange solids that are moderately soluble in water and dilute acids. Its neutral solutions slowly decompose, depositing the light yellow oxide CeO2. Solutions of ceric sulfate have a strong yellow color. The tetrahydrate loses water when heated to 180-200 °C.

Tin(IV) chloride, also known as tin tetrachloride or stannic chloride, is an inorganic compound with the formula SnCl4. It is a colorless hygroscopic liquid, which fumes on contact with air. It is used as a precursor to other tin compounds. It was first discovered by Andreas Libavius (1550–1616) and was known as spiritus fumans libavii.

Cobalt(II) chloride chemical compound

Cobalt(II) chloride is an inorganic compound of cobalt and chlorine, with the formula CoCl
2
. It is a sky blue crystalline solid.

Iron(II) fluoride chemical compound

Iron(II) fluoride or ferrous fluoride is an inorganic compound with the molecular formula FeF2. It forms a tetrahydrate FeF2·4H2O that is often referred to by the same names. The anhydrous and hydrated forms are white crystalline solids.

Cobalt(II) fluoride chemical compound

Cobalt(II) fluoride is a chemical compound with the formula (CoF2). It is a pink crystalline solid compound which is antiferromagnetic at low temperatures (TN=37.7 K) The formula is given for both the red tetragonal crystal, (CoF2), and the tetrahydrate red orthogonal crystal, (CoF2·4H2O). CoF2 is used in oxygen-sensitive fields, namely metal production. In low concentrations, it has public health uses. CoF2 is sparingly soluble in water. The compound can be dissolved in warm mineral acid, and will decompose in boiling water. Yet the hydrate is water-soluble, especially the di-hydrate CoF2·2H2 O and tri-hydrate CoF2·3H2O forms of the compound. The hydrate will also decompose with heat.

Sodium metasilicate chemical compound

Sodium metasilicate is the chemical substance with formula Na
2
SiO
3
, which is the main component of commercial sodium silicate solutions. It is an ionic compound consisting of sodium cations Na+
and the polymeric metasilicate anions [–SiO2−
3
–]n. It is a colorless crystalline hygroscopic and deliquescent solid, soluble in water, but not in alcohols.

Cadmium nitrate chemical compound

Cadmium nitrate describes any of the related members of a family of inorganic compounds with the general formula , the most commonly encountered form being the tetrahydrate. The anhydrous form is volatile, but the others are colourless crystalline solids that are deliquescent, tending to absorb enough moisture from the air to form an aqueous solution. Like other cadmium compounds, cadmium nitrate is known to be carcinogenic.

Nickel(II) nitrate chemical compound

Nickel nitrate is the inorganic compound Ni(NO3)2 or any hydrate thereof. The anhydrous form is not commonly encountered, thus "nickel nitrate" usually refers to nickel(II) nitrate hexahydrate. The formula for this species is written in two ways: Ni(NO3)2.6H2O and, more descriptively [Ni(H2O)6](NO3)2. The latter formula indicates that the nickel(II) center is surrounded by six water molecules in this hydrated salt. In the hexahydrate, the nitrate anions are not bonded to nickel. Also known are three other hydrates: Ni(NO3)2.9H2O, Ni(NO3)2.4H2O, and Ni(NO3)2.2H2O. Anhydrous Ni(NO3)2 is also known.

Cobalt(II) nitrate chemical compound

Cobalt Nitrate is the Inorganic compound with the formula Co(NO3)2.xH2O. It is cobalt(II) salt. The most common form is the hexahydrate Co(NO3)2·6H2O, which is a red-brown deliquescent salt that is soluble in water and other polar solvents.

Chromium(III) nitrate chemical compound

Chromium(III) nitrate describes several inorganic compounds consisting of chromium, nitrate and varying amounts of water. Most common is the dark violet hydrated solid, but an anhydrous green form is also known. Chromium(III) nitrate compounds are of a limited importance commercially, finding some applications in the dyeing industry. It is common in academic laboratories for the synthesis of chromium coordination complexes.

Ferric oxalate chemical compound

Ferric oxalate, also known as iron(III) oxalate, is a chemical compound composed of ferric ions and oxalate ligands; it may also be regarded as the ferric salt of oxalic acid. The anhydrous material is pale yellow; however, it may be hydrated to form several hydrates, such as potassium ferrioxalate, or Fe
2
(C
2
O
4
)
3
 • 6H2O, which is bright green in colour

Bismuth(III) nitrate chemical compound

Bismuth(III) nitrate is a salt composed of bismuth in its cationic +3 oxidation state and nitrate anions. The most common solid form is the pentahydrate. It is used in the synthesis of other bismuth compounds. It is available commercially. It is the only nitrate salt formed by a group 15 element, indicative of bismuth's metallic nature.

Cerium nitrate family of chemical compounds

Cerium nitrate refers to a family of nitrates of cerium in the three or four oxidation state. Often these compounds contain water, hydroxide, or hydronium ions in addition to cerium and nitrate. Double nitrates of cerium also exist.

Zirconium nitrate chemical compound

Zirconium nitrate is a volatile anhydrous transition metal nitrate of zirconium with formula Zr(NO3)4. It has alternate names of zirconium tetranitrate, or zirconium(IV) nitrate.

Compounds of thorium any chemical compound having at least one thorium atom

Many compounds of thorium are known: this is because thorium and uranium are the most stable and accessible actinides and are the only actinides that can be studied safely and legally in bulk in a normal laboratory. As such, they have the best-known chemistry of the actinides, along with that of plutonium, as the self-heating and radiation from them is not enough to cause radiolysis of chemical bonds as it is for the other actinides. While the later actinides from americium onwards are predominantly trivalent and behave more similarly to the corresponding lanthanides, as one would expect from periodic trends, the early actinides up to plutonium have relativistically destabilised and hence delocalised 5f and 6d electrons that participate in chemistry in a similar way to the early transition metals of group 3 through 8: thus, all their valence electrons can participate in chemical reactions, although this is not common for neptunium and plutonium.

Europium(III) nitrate chemical compound

Europium(III) nitrate is an inorganic compound with the formula Eu(NO3)3. Its hexahydrate is the most common form, which is a colorless hygroscopic crystal.

References

  1. New Jersey Department of Health. Thorium Nitrate. Hazardous Substance Fact Sheet, 1987
  2. Bogus hydrates include 12, 6, 5.5, 2 and 1 water molecules.
  3. 1 2 3 Benz, R.; Naoumidis, A.; Brown, D. Th Thorium: Supplement Volume C 3 Compounds with Nitrogen. Springer Science & Business Media. pp. 70–79. ISBN   9783662063309.
  4. 1 2 3 4 5 6 Katz, Joseph j.; Seaborg, Glenn t. (2008). "Thorium". The Chemistry of the Actinide and Lanthanide Elements. Springer. pp. 106–108. ISBN   1-4020-3598-5.
  5. 1 2 Herrmann, W. A.; Edelmann, Frank T.; Poremba, Peter (1999). Synthetic Methods of Organometallic and Inorganic Chemistry, Volume 6, 1997: Volume 6: Lanthanides and Actinides (in German). Georg Thieme Verlag. p. 210. ISBN   9783131794611.
  6. JR Ferraro, LI Katzin, G Gibson. The Reaction of Thorium Nitrate Tetrahydrate with Nitrogen Oxides. Anhydrous Thorium Nitrate. Journal of the American Chemical Society, 1955, 77(24):139-140
  7. Ueki, T.; Zalkin, A.; Templeton, D. H. (1 November 1966). "Crystal structure of thorium nitrate pentahydrate by X-ray diffraction". Acta Crystallographica. 20 (6): 836–841. doi:10.1107/S0365110X66001944.
  8. 1 2 3 4 5 6 7 Brown, D. (1973). "Carbonates, nitrates, sulphates, sulfites, selenates, selenites, tellurates and tellurites". In Bailar, J.C. (ed.). Comprehensive inorganic chemistry (1. ed.). Oxford [u.a.]: Pergamon Press. pp. 286–292. ISBN   008017275X.
  9. Cheda, J.A.R.; Westrum, Edgar F.; Morss, Lester R. (January 1976). "Heat capacity of Th(NO3)4·5H2O from 5 to 350 K" (PDF). The Journal of Chemical Thermodynamics. 8 (1): 25–29. doi:10.1016/0021-9614(76)90146-4. Open Access logo PLoS transparent.svg
  10. Apelblat, Alexander; Azoulay, David; Sahar, Ayala (1973). "Properties of aqueous thorium nitrate solutions. Part 1.—Densities, viscosities, conductivities, pH, solubility and activities at freezing point". Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases. 69 (0): 1618. doi:10.1039/F19736901618.
  11. Kalinkin, A. M. (2001). "Calculation of Phase Equilibria in the Th(NO3)4-HNO3-H2O System at 25°C". Radiochemistry. 43 (6): 553–557. doi:10.1023/A:1014847506077.
  12. Bagnall, Kenneth W. Th Thorium: Compounds with Carbon: Carbonates, Thiocyanates, Alkoxides, Carboxylates. Springer Science & Business Media. p. 82. ISBN   9783662063156.
  13. Bagnall, Kenneth W. Th Thorium: Compounds with Carbon: Carbonates, Thiocyanates, Alkoxides, Carboxylates. Springer Science & Business Media. pp. 66, 73, 74, 105, 107, 113, 122. ISBN   9783662063156.
  14. Šćavničar, S.; Prodić, B. (1 April 1965). "The crystal structure of double nitrate octahydrates of thorium and bivalent metals". Acta Crystallographica. 18 (4): 698–702. doi:10.1107/S0365110X65001603.
Salts and covalent derivatives of the nitrate ion