Actinium compounds

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Actinium compounds are compounds containing the element actinium (Ac). Due to actinium's intense radioactivity, only a limited number of actinium compounds are known. These include: AcF3, AcCl3, AcBr3, AcOF, AcOCl, AcOBr, Ac2S3, Ac2O3, AcPO4 and Ac(NO3)3. Except for AcPO4, they are all similar to the corresponding lanthanum compounds. They all contain actinium in the oxidation state +3. [1] [2] In particular, the lattice constants of the analogous lanthanum and actinium compounds differ by only a few percent. [2]

Contents

Properties of actinium compounds

Formulacolorsymmetry space group No Pearson symbol a (pm)b (pm)c (pm)Zdensity,
g/cm3
Acsilvery fcc [3] Fm3m225cF4531.1531.1531.1410.07
AcH2unknowncubic [3] Fm3m225cF1256756756748.35
Ac2O3white [4] trigonal [5] P3m1164hP540840863019.18
Ac2S3blackcubic [6] I43d220cI28778.56778.56778.5646.71
AcF3white [7] hexagonal [2] [5] P3c1165hP2474174175567.88
AcCl3whitehexagonal [2] [8] P63/m165hP876476445624.8
AcBr3white [2] hexagonal [8] P63/m165hP876476445625.85
AcOFwhite [9] cubic [2] Fm3m593.18.28
AcOClwhite tetragonal [2] 4244247077.23
AcOBrwhitetetragonal [2] 4274277407.89
AcPO4·0.5H2Ounknownhexagonal [2] 7217216645.48

Here a, b and c are lattice constants, No is space group number and Z is the number of formula units per unit cell. Density was not measured directly but calculated from the lattice parameters.

Oxides


Actinium(III) oxide is the only oxide that actinium can form, with the chemical formula Ac2O3. In this compound, actinium is in the oxidation state +3. [1] [10] It is similar to the corresponding lanthanum compound, lanthanum(III) oxide. It can be obtained by heating the hydroxide at 500 °C or the oxalate at 1100 °C, in vacuum. Its crystal lattice is isotypic with the oxides of most trivalent rare-earth metals. [2]

Halides

Actinium trifluoride can be produced either in solution or in solid reaction. The former reaction is carried out at room temperature, by adding hydrofluoric acid to a solution containing actinium ions. In the latter method, actinium metal is treated with hydrogen fluoride vapors at 700 °C in an all-platinum setup. Treating actinium trifluoride with ammonium hydroxide at 900–1000 °C yields oxyfluoride AcOF. Whereas lanthanum oxyfluoride can be easily obtained by burning lanthanum trifluoride in air at 800 °C for an hour, similar treatment of actinium trifluoride yields no AcOF and only results in melting of the initial product. [2] [9]

AcF3 + 2 NH3 + H2O → AcOF + 2 NH4F

Actinium trichloride is obtained by reacting actinium hydroxide or oxalate with carbon tetrachloride vapors at temperatures above 960 °C. Similar to oxyfluoride, actinium oxychloride can be prepared by hydrolyzing actinium trichloride with ammonium hydroxide at 1000 °C. However, in contrast to the oxyfluoride, the oxychloride could well be synthesized by igniting a solution of actinium trichloride in hydrochloric acid with ammonia. [2]

Reaction of aluminium bromide and actinium oxide yields actinium tribromide:

Ac2O3 + 2 AlBr3 → 2 AcBr3 + Al2O3

and treating it with ammonium hydroxide at 500 °C results in the oxybromide AcOBr. [2]

Other compounds

Actinium hydride was obtained by reduction of actinium trichloride with potassium at 300 °C, and its structure was deduced by analogy with the corresponding LaH2 hydride. The source of hydrogen in the reaction was uncertain. [11]

Mixing monosodium phosphate (NaH2PO4) with a solution of actinium in hydrochloric acid yields white-colored actinium phosphate hemihydrate (AcPO4·0.5H2O), and heating actinium oxalate with hydrogen sulfide vapors at 1400 °C for a few minutes results in a black actinium sulfide Ac2S3. It may possibly be produced by acting with a mixture of hydrogen sulfide and carbon disulfide on actinium oxide at 1000 °C. [2]

See also

Related Research Articles

<span class="mw-page-title-main">Actinium</span> Chemical element, symbol Ac and atomic number 89

Actinium is a chemical element with the symbol Ac and atomic number 89. It was first isolated by Friedrich Oskar Giesel in 1902, who gave it the name emanium; the element got its name by being wrongly identified with a substance André-Louis Debierne found in 1899 and called actinium. Actinium gave the name to the actinide series, a group of 15 similar elements between actinium and lawrencium in the periodic table. Together with polonium, radium, and radon, actinium was one of the first non-primordial radioactive elements to be isolated.

<span class="mw-page-title-main">Lanthanum</span> Chemical element, symbol La and atomic number 57

Lanthanum is a chemical element with the symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air. It is the eponym of the lanthanide series, a group of 15 similar elements between lanthanum and lutetium in the periodic table, of which lanthanum is the first and the prototype. Lanthanum is traditionally counted among the rare earth elements. Like most other rare earth elements, the usual oxidation state is +3. Lanthanum has no biological role in humans but is essential to some bacteria. It is not particularly toxic to humans but does show some antimicrobial activity.

<span class="mw-page-title-main">Protactinium</span> Chemical element, symbol Pa and atomic number 91

Protactinium is a chemical element with the symbol Pa and atomic number 91. It is a dense, silvery-gray actinide metal which readily reacts with oxygen, water vapor and inorganic acids. It forms various chemical compounds in which protactinium is usually present in the oxidation state +5, but it can also assume +4 and even +3 or +2 states. Concentrations of protactinium in the Earth's crust are typically a few parts per trillion, but may reach up to a few parts per million in some uraninite ore deposits. Because of its scarcity, high radioactivity and high toxicity, there are currently no uses for protactinium outside scientific research, and for this purpose, protactinium is mostly extracted from spent nuclear fuel.

<span class="mw-page-title-main">Holmium(III) oxide</span> Chemical compound

Holmium(III) oxide, or holmium oxide is a chemical compound of a rare-earth element holmium and oxygen with the formula Ho2O3. Together with dysprosium(III) oxide (Dy2O3), holmium oxide is one of the most powerfully paramagnetic substances known. The oxide, also called holmia, occurs as a component of the related erbium oxide mineral called erbia. Typically, the oxides of the trivalent lanthanides coexist in nature, and separation of these components requires specialized methods. Holmium oxide is used in making specialty colored glasses. Glass containing holmium oxide and holmium oxide solutions have a series of sharp optical absorption peaks in the visible spectral range. They are therefore traditionally used as a convenient calibration standard for optical spectrophotometers.

<span class="mw-page-title-main">Uranium trioxide</span> Chemical compound

Uranium trioxide (UO3), also called uranyl oxide, uranium(VI) oxide, and uranic oxide, is the hexavalent oxide of uranium. The solid may be obtained by heating uranyl nitrate to 400 °C. Its most commonly encountered polymorph, γ-UO3, is a yellow-orange powder.

<span class="mw-page-title-main">Sodium metaborate</span> Chemical compound

Sodium metaborate is a chemical compound of sodium, boron, and oxygen with formula NaBO
2
. However, the metaborate ion is trimeric in the anhydrous solid, therefore a more correct formula is Na3B3O6 or (Na+)3[B3O6]3−. The formula can be written also as Na
2
O
·B
2
O
3
to highlight the relation to the main oxides of sodium and boron. The name is also applied to several hydrates whose formulas can be written NaBO2·nH2O for various values of n.

<span class="mw-page-title-main">Californium compounds</span>

Few compounds of californium have been made and studied. The only californium ion that is stable in aqueous solutions is the californium(III) cation. The other two oxidation states are IV (strong oxidizing agents) and II (strong reducing agents). The element forms a water-soluble chloride, nitrate, perchlorate, and sulfate and is precipitated as a fluoride, oxalate or hydroxide. If problems of availability of the element could be overcome, then CfBr2 and CfI2 would likely be stable.

<span class="mw-page-title-main">Berkelium compounds</span> Any chemical compound having at least one berkelium atom

Berkelium forms a number of chemical compounds, where it normally exists in an oxidation state of +3 or +4, and behaves similarly to its lanthanide analogue, terbium. Like all actinides, berkelium easily dissolves in various aqueous inorganic acids, liberating gaseous hydrogen and converting into the trivalent oxidation state. This trivalent state is the most stable, especially in aqueous solutions, but tetravalent berkelium compounds are also known. The existence of divalent berkelium salts is uncertain and has only been reported in mixed lanthanum chloride-strontium chloride melts. Aqueous solutions of Bk3+ ions are green in most acids. The color of the Bk4+ ions is yellow in hydrochloric acid and orange-yellow in sulfuric acid. Berkelium does not react rapidly with oxygen at room temperature, possibly due to the formation of a protective oxide surface layer; however, it reacts with molten metals, hydrogen, halogens, chalcogens and pnictogens to form various binary compounds. Berkelium can also form several organometallic compounds.

<span class="mw-page-title-main">Actinium(III) oxide</span> Chemical compound

Actinium(III) oxide is a chemical compound containing the rare radioactive element actinium. It has the formula Ac2O3. It is similar to its corresponding lanthanum compound, lanthanum(III) oxide, and contains actinium in the oxidation state +3. Actinium oxide is not to be confused with Ac2O (acetic anhydride), where Ac is an abbreviation for acetyl instead of the symbol of the element actinium.

Uranium trifluoride is an inorganic chemical compound with the chemical formula UF3.

<span class="mw-page-title-main">Actinium(III) fluoride</span> Chemical compound

Actinium(III) fluoride (AcF3) is an inorganic compound, a salt of actinium and fluorine.

Neptunium(III) fluoride or neptunium trifluoride is a salt of neptunium and fluorine with the formula NpF3.

<span class="mw-page-title-main">Aluminium compounds</span>

Aluminium (or aluminum) combines characteristics of pre- and post-transition metals. Since it has few available electrons for metallic bonding, like its heavier group 13 congeners, it has the characteristic physical properties of a post-transition metal, with longer-than-expected interatomic distances. Furthermore, as Al3+ is a small and highly charged cation, it is strongly polarizing and aluminium compounds tend towards covalency; this behaviour is similar to that of beryllium (Be2+), an example of a diagonal relationship. However, unlike all other post-transition metals, the underlying core under aluminium's valence shell is that of the preceding noble gas, whereas for gallium and indium it is that of the preceding noble gas plus a filled d-subshell, and for thallium and nihonium it is that of the preceding noble gas plus filled d- and f-subshells. Hence, aluminium does not suffer the effects of incomplete shielding of valence electrons by inner electrons from the nucleus that its heavier congeners do. Aluminium's electropositive behavior, high affinity for oxygen, and highly negative standard electrode potential are all more similar to those of scandium, yttrium, lanthanum, and actinium, which have ds2 configurations of three valence electrons outside a noble gas core: aluminium is the most electropositive metal in its group. Aluminium also bears minor similarities to the metalloid boron in the same group; AlX3 compounds are valence isoelectronic to BX3 compounds (they have the same valence electronic structure), and both behave as Lewis acids and readily form adducts. Additionally, one of the main motifs of boron chemistry is regular icosahedral structures, and aluminium forms an important part of many icosahedral quasicrystal alloys, including the Al–Zn–Mg class.

An yttrium compound is a chemical compound containing yttrium. Among these compounds, yttrium generally has a +3 valence. The solubility properties of yttrium compounds are similar to those of the lanthanides. For example oxalates and carbonates are hardly soluble in water, but soluble in excess oxalate or carbonate solutions as complexes are formed. Sulfates and double sulfates are generally soluble. They resemble the "yttrium group" of heavy lanthanide elements.

Actinium(III) bromide is a radioactive white crystalline solid that is a salt of actinium. It is prepared by reacting actinium(III) oxide with aluminium bromide.

Actinium(III) sulfide is the radioactive compound of actinium with the formula Ac2S3. This salt was prepared by heating actinium(III) oxalate at 1400°C for 6 minutes in a mixture of carbon disulfide and hydrogen sulfide. The result was conformed to be actinium(III) sulfide by x-ray diffraction.

Actinium(III) phosphate is a white-colored chemical compound of the radioactive element actinium. This compound was created by reacting actinium(III) chloride with monosodium phosphate. This resulted in the hemihydrate AcPO4·1/2H2O and was confirmed by x-ray diffraction. To become anhydrous, it was heated to 700°C, which resulted in a black solid due to impurities.

<span class="mw-page-title-main">Berkelium(III) chloride</span> Chemical compound

Berkelium(III) chloride also known as berkelium trichloride, is a chemical compound with the formula BkCl3. It is a water-soluble green solid with a melting point of 603 °C. This compound forms the hexahydrate, BkCl3·6H2O.

Protactinium compounds are compounds containing the element protactinium. These compounds usually have protactinium in the +5 oxidation state, although these compounds can also exist in the +2, +3 and +4 oxidation states.

References

  1. 1 2 Actinium, Great Soviet Encyclopedia (in Russian)
  2. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Fried, Sherman; Hagemann, French; Zachariasen, W. H. (1950). "The Preparation and Identification of Some Pure Actinium Compounds". Journal of the American Chemical Society. 72 (2): 771–775. doi:10.1021/ja01158a034.
  3. 1 2 Farr, J.; Giorgi, A. L.; Bowman, M. G.; Money, R. K. (1961). "The crystal structure of actinium metal and actinium hydride". Journal of Inorganic and Nuclear Chemistry. 18: 42–47. doi:10.1016/0022-1902(61)80369-2. OSTI   4397640.
  4. Stites, Joseph G.; Salutsky, Murrell L.; Stone, Bob D. (1955). "Preparation of Actinium Metal". J. Am. Chem. Soc. 77 (1): 237–240. doi:10.1021/ja01606a085.
  5. 1 2 Zachariasen, W. H. (1949). "Crystal chemical studies of the 5f-series of elements. XII. New compounds representing known structure types". Acta Crystallographica. 2 (6): 388–390. doi: 10.1107/S0365110X49001016 .
  6. Zachariasen, W. H. (1949). "Crystal chemical studies of the 5f-series of elements. VI. The Ce2S3-Ce3S4 type of structure" (PDF). Acta Crystallographica. 2: 57–60. doi:10.1107/S0365110X49000126. Archived (PDF) from the original on 2022-10-09.
  7. Meyer, p. 71
  8. 1 2 Zachariasen, W. H. (1948). "Crystal chemical studies of the 5f-series of elements. I. New structure types". Acta Crystallographica. 1 (5): 265–268. doi: 10.1107/S0365110X48000703 .
  9. 1 2 Meyer, pp. 87–88
  10. Sherman, Fried; Hagemann, French; Zachariasen, W. H. (1950). "The Preparation and Identification of Some Pure Actinium Compounds". Journal of the American Chemical Society. 72 (2): 771–775. doi:10.1021/ja01158a034.
  11. Meyer, p. 43