Praseodymium
Praseodymium | ||||||||||||||||||||||||||||
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Pronunciation | /ˌpreɪziːəˈdɪmiəm/[1] | |||||||||||||||||||||||||||
Appearance | grayish white | |||||||||||||||||||||||||||
Standard atomic weight Ar°(Pr) | ||||||||||||||||||||||||||||
Praseodymium in the periodic table | ||||||||||||||||||||||||||||
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Atomic number (Z) | 59 | |||||||||||||||||||||||||||
Group | f-block groups (no number) | |||||||||||||||||||||||||||
Period | period 6 | |||||||||||||||||||||||||||
Block | f-block | |||||||||||||||||||||||||||
Electron configuration | [Xe] 4f3 6s2 | |||||||||||||||||||||||||||
Electrons per shell | 2, 8, 18, 21, 8, 2 | |||||||||||||||||||||||||||
Physical properties | ||||||||||||||||||||||||||||
Phase at STP | solid | |||||||||||||||||||||||||||
Melting point | 1204 K (931 °C, 1708 °F)[4] | |||||||||||||||||||||||||||
Boiling point | 3403 K (3130 °C, 5666 °F) | |||||||||||||||||||||||||||
Density (at 20° C) | 6.773 g/cm3 [4] | |||||||||||||||||||||||||||
when liquid (at m.p.) | 6.50 g/cm3 | |||||||||||||||||||||||||||
Heat of fusion | 6.89 kJ/mol | |||||||||||||||||||||||||||
Heat of vaporization | 331 kJ/mol | |||||||||||||||||||||||||||
Molar heat capacity | 27.20 J/(mol·K) | |||||||||||||||||||||||||||
Vapor pressure
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Atomic properties | ||||||||||||||||||||||||||||
Oxidation states | 0,[5] +1,[6] +2, +3, +4, +5 (a mildly basic oxide) | |||||||||||||||||||||||||||
Electronegativity | Pauling scale: 1.13 | |||||||||||||||||||||||||||
Ionization energies |
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Atomic radius | empirical: 182 pm | |||||||||||||||||||||||||||
Covalent radius | 203±7 pm | |||||||||||||||||||||||||||
Spectral lines of praseodymium | ||||||||||||||||||||||||||||
Other properties | ||||||||||||||||||||||||||||
Natural occurrence | primordial | |||||||||||||||||||||||||||
Crystal structure | double hexagonal close-packed (dhcp) (hP4) | |||||||||||||||||||||||||||
Lattice constants | a = 0.36723 nm c = 1.18328 nm (at 20 °C)[4] | |||||||||||||||||||||||||||
Thermal expansion | 4.5×10−6/K (at 20 °C)[4][a] | |||||||||||||||||||||||||||
Thermal conductivity | 12.5 W/(m⋅K) | |||||||||||||||||||||||||||
Electrical resistivity | poly: 0.700 µΩ⋅m (at r.t.) | |||||||||||||||||||||||||||
Magnetic ordering | paramagnetic[7] | |||||||||||||||||||||||||||
Molar magnetic susceptibility | +5010.0×10−6 cm3/mol (293 K)[8] | |||||||||||||||||||||||||||
Young's modulus | 37.3 GPa | |||||||||||||||||||||||||||
Shear modulus | 14.8 GPa | |||||||||||||||||||||||||||
Bulk modulus | 28.8 GPa | |||||||||||||||||||||||||||
Speed of sound thin rod | 2280 m/s (at 20 °C) | |||||||||||||||||||||||||||
Poisson ratio | 0.281 | |||||||||||||||||||||||||||
Vickers hardness | 250–745 MPa | |||||||||||||||||||||||||||
Brinell hardness | 250–640 MPa | |||||||||||||||||||||||||||
CAS Number | 7440-10-0 | |||||||||||||||||||||||||||
History | ||||||||||||||||||||||||||||
Discovery | Carl Auer von Welsbach (1885) | |||||||||||||||||||||||||||
Isotopes of praseodymium | ||||||||||||||||||||||||||||
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Praseodymium (Template:Pron-en PRAY-zee-o-DIM-ee-əm or /ˌpreɪsi.ɵˈdɪmiəm/ PRAY-see-o-DIM-ee-əm) is a chemical element that has the symbol Pr and atomic number 59.
Characteristics
Physical
Praseodymium is a soft, silvery, malleable and ductile metal in the lanthanide group. It is somewhat more resistant to corrosion in air than europium, lanthanum, cerium, or neodymium, but it does develop a green oxide coating that spalls off when exposed to air, exposing more metal to oxidation — a centimeter-sized sample of Pr completely oxidizes within a year.[10] For this reason, praseodymium is usually stored under a light mineral oil or sealed in glass.
Contrary to other rare-earth metals, which show antiferromagnetic or/and ferromagnetic ordering at low temperatures, Pr is paramagnetic at any temperatures above 1 K.[7]
Chemical
Praseodymium metal tarnishes slowly in air and burns readily at 150 °C to form praseodymium(III,IV) oxide:
- 12 Pr + 11 O2 → 2 Pr6O11
Praseodymium is quite electropositive and reacts slowly with cold water and quite quickly with hot water to form praseodymium hydroxide:
- 2 Pr (s) + 6 H2O (l) → 2 Pr(OH)3 (aq) + 3 H2 (g)
Praseodymium metal reacts with all the halogens:
- 2 Pr (s) + 3 F2 (g) → 2 PrF3 (s) [green]
- 2 Pr (s) + 3 Cl2 (g) → 2 PrCl3 (s) [green]
- 2 Pr (s) + 3 Br2 (g) → 2 PrBr3 (s) [green]
- 2 Pr (s) + 3 I2 (g) → 2 PrI3 (s)
Praseodymium dissolves readily in dilute sulfuric acid to form solutions containing green Pr(III) ions, which exist as a [Pr(OH2)9]3+ complexes:[11]
- 2 Pr (s) + 3 H2SO4 (aq) → 2 Pr3+(aq) + 3 SO2−
4 (aq) + 3 H2 (g)
Compounds
In its compounds, praseodymium occurs in oxidation states +2, +3 and/or +4. Praseodymium(IV) is a strong oxidant, instantly oxidizing water to elemental oxygen (O2), or hydrochloric acid to elemental chlorine. Thus, in aqueous solution, only the +3 oxidation state is encountered. Praseodymium(III) salts are yellow-green and, in solution, present a fairly simple absorption spectrum in the visible region, with a band in the yellow-orange at 589-590 nm (which coincides with the sodium emission doublet), and three bands in the blue/violet region, at 444, 468, and 482 nm, approximately. These positions vary slightly with the counter-ion. Praseodymium oxide, as obtained by the ignition of salts such as the oxalate or carbonate in air, is essentially black in color (with a hint of brown or green) and contains +3 and +4 praseodymium in a somewhat variable ratio, depending upon the conditions of formation. Its formula is conventionally rendered as Pr6O11.
Other praseodymium compounds include:
- Fluorides: PrF2, PrF3, PrF4
- Chlorides: PrCl3
- Bromides: PrBr3, Pr2Br5
- Iodides: PrI2, PrI3, Pr2I5
- Oxides: PrO2, Pr2O3, Pr6O11
- Sulfides: PrS, Pr2S3
- Sulfates: Pr2(SO4)3
- Selenides: PrSe
- Tellurides: PrTe, Pr2Te3
- Nitrides: PrN
Isotopes
Naturally occurring praseodymium is composed of one stable isotope, 141Pr. Thirty-eight radioisotopes have been characterized with the most stable being 143Pr with a half-life of 13.57 days and 142Pr with a half-life of 19.12 hours. All of the remaining radioactive isotopes have half-lives that are less than 5.985 hours and the majority of these have half-lives that are less than 33 seconds. This element also has six meta states with the most stable being 138mPr (t½ 2.12 hours), 142mPr (t½ 14.6 minutes) and 134mPr (t½ 11 minutes).
The isotopes of praseodymium range in atomic weight from 120.955 u (121Pr) to 158.955 u (159Pr). The primary decay mode before the stable isotope, 141Pr, is electron capture and the primary mode after is beta minus decay. The primary decay products before 141Pr are element 58 (cerium) isotopes and the primary products after are element 60 (neodymium) isotopes.
History
The name praseodymium comes from the Greek prasios (πράσιος), meaning green, and didymos (δίδυμος), twin. Praseodymium is frequently misspelled as praseodynium.
In 1841, Mosander extracted the rare earth didymium from lanthana. In 1874, Per Teodor Cleve concluded that didymium was in fact two elements, and in 1879, Lecoq de Boisbaudran isolated a new earth, samarium, from didymium obtained from the mineral samarskite. In 1885, the Austrian chemist baron Carl Auer von Welsbach separated didymium into two elements, praseodymium and neodymium, which gave salts of different colors.
Leo Moser (son of Ludwig Moser, founder of the Moser Glassworks in what is now Karlovy Vary, Bohemia, in the Czech Republic, not to be confused with Leo Moser, a mathematician) investigated the use of praseodymium in glass coloration in the late 1920s. The result was a yellow-green glass given the name "Prasemit". However, a similar color could be achieved with colorants costing only a minute fraction of what praseodymium cost in the late 1920s, such that the color was not popular, few pieces were made, and examples are now extremely rare. Moser also blended praseodymium with neodymium to produce "Heliolite" glass ("Heliolit" in German), which was more widely accepted. The first enduring commercial use of purified praseodymium, which continues today, is in the form of a yellow-orange stain for ceramics, "Praseodymium Yellow", which is a solid-solution of praseodymium in the zirconium silicate (zircon) lattice. This stain has no hint of green in it. By contrast, at sufficiently high loadings, praseodymium glass is distinctly green, rather than pure yellow.
Using classical separation methods, praseodymium was always difficult to purify. Much less abundant than the lanthanum and neodymium from which it was being separated (cerium having long since been removed by redox chemistry), praseodymium ended up being dispersed among a large number of fractions, and the resulting yields of purified material were low. Praseodymium has historically been a rare earth whose supply has exceeded demand. This has occasionally led to its being offered more cheaply than the far more abundant neodymium. Unwanted as such, much praseodymium has been marketed as a mixture with lanthanum and cerium, or "LCP" for the first letters of each of the constituents, for use in replacing the traditional lanthanide mixtures that were inexpensively made from monazite or bastnäsite. LCP is what remains of such mixtures, after the desirable neodymium, and all the heavier, rarer and more valuable lanthanides have been removed, by solvent extraction. However, as technology progresses, praseodymium has been found possible to incorporate into neodymium-iron-boron magnets, thereby extending the supply of the much in demand neodymium. So LC is starting to replace LCP as a result.
Occurrence
Praseodymium is available in small quantities in Earth’s crust (9.5 ppm). It is found in the rare earth minerals monazite and bastnäsite, typically comprising about 5% of the lanthanides contained therein, and can be recovered from these minerals by an ion exchange process, or by counter-current solvent extraction. Misch metal, used in making cigarette lighters, contains about 5% praseodymium metal.[12]
Applications
Uses of praseodymium:
- As an alloying agent with magnesium to create high-strength metals that are used in aircraft engines.[13]
- Praseodymium forms the core of carbon arc lights which are used in the motion picture industry for studio lighting and projector lights.
- Praseodymium compounds give glasses and enamels a yellow color.[14]
- Praseodymium is used to color cubic zirconia yellow-green, to simulate mineral peridot.
- Praseodymium is a component of didymium glass, which is used to make certain types of welder's and glass blower's goggles.[14]
- Silicate glass doped with praseodymium ions has been used to slow a light pulse down to a few hundred meters per second.[15]
- Praseodymium alloyed with nickel (PrNi5) has such a strong magnetocaloric effect that it has allowed scientists to approach within one thousandth of a degree of absolute zero.[16]
- Doping praseodymium in fluoride glass allows it to be used as a single mode fiber optical amplifier.[17]
- Praseodymium oxide in solid solution with ceria, or with ceria-zirconia, have been used as oxidation catalysts.[18]
- Modern ferrocerium firesteel products, commonly referred to as "flint," used in lighters, torch strikers, "flint and steel" fire starters, etc., contain around 4% praseodymium.[14]
Precautions
Like all rare earths, praseodymium is of low to moderate toxicity. Praseodymium has no known biological role.
References
- ^ "praseodymium". Oxford English Dictionary (Online ed.). Oxford University Press. (Subscription or participating institution membership required.)
- ^ "Standard Atomic Weights: Praseodymium". CIAAW. 2017.
- ^ Prohaska, Thomas; Irrgeher, Johanna; Benefield, Jacqueline; Böhlke, John K.; Chesson, Lesley A.; Coplen, Tyler B.; Ding, Tiping; Dunn, Philip J. H.; Gröning, Manfred; Holden, Norman E.; Meijer, Harro A. J. (2022-05-04). "Standard atomic weights of the elements 2021 (IUPAC Technical Report)". Pure and Applied Chemistry. doi:10.1515/pac-2019-0603. ISSN 1365-3075.
- ^ a b c d Arblaster, John W. (2018). Selected Values of the Crystallographic Properties of Elements. Materials Park, Ohio: ASM International. ISBN 978-1-62708-155-9.
- ^ Yttrium and all lanthanides except Ce and Pm have been observed in the oxidation state 0 in bis(1,3,5-tri-t-butylbenzene) complexes, see Cloke, F. Geoffrey N. (1993). "Zero Oxidation State Compounds of Scandium, Yttrium, and the Lanthanides". Chem. Soc. Rev. 22: 17–24. doi:10.1039/CS9932200017. and Arnold, Polly L.; Petrukhina, Marina A.; Bochenkov, Vladimir E.; Shabatina, Tatyana I.; Zagorskii, Vyacheslav V.; Cloke (2003-12-15). "Arene complexation of Sm, Eu, Tm and Yb atoms: a variable temperature spectroscopic investigation". Journal of Organometallic Chemistry. 688 (1–2): 49–55. doi:10.1016/j.jorganchem.2003.08.028.
- ^ Chen, Xin; et al. (2019-12-13). "Lanthanides with Unusually Low Oxidation States in the PrB3– and PrB4– Boride Clusters". Inorganic Chemistry. 58 (1): 411–418. doi:10.1021/acs.inorgchem.8b02572. PMID 30543295. S2CID 56148031.
- ^ a b Jackson, M. (2000). "Magnetism of Rare Earth" (PDF). The IRM quarterly. 10 (3): 1.
- ^ Weast, Robert (1984). CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber Company Publishing. pp. E110. ISBN 0-8493-0464-4.
- ^ Kondev, F. G.; Wang, M.; Huang, W. J.; Naimi, S.; Audi, G. (2021). "The NUBASE2020 evaluation of nuclear properties" (PDF). Chinese Physics C. 45 (3): 030001. doi:10.1088/1674-1137/abddae.
- ^ "Rare-Earth Metal Long Term Air Exposure Test". Retrieved 2009-08-08.
- ^ "Chemical reactions of Praseodymium". Webelements. Retrieved 2009-06-06.
- ^ Gschneidner, K.A., and Eyring, L., Handbook on the Physics and Chemistry of Rare Earths, North Holland Publishing Co., Amsterdam, 1978.
- ^ L. L. Rokhlin (2003). Magnesium alloys containing rare earth metals: structure and properties. CRC Press. ISBN 0415284147.
- ^ a b c C. R. Hammond (2000). The Elements, in Handbook of Chemistry and Physics 81st edition. CRC press. ISBN 0849304814.
- ^ "ANU team stops light in quantum leap". Retrieved 18 May 2009.
- ^ Emsley, John (2001). Nature's building blocks. Oxford University Press. p. 342. ISBN 0-1985-0341-5.
- ^ Jha, A; Naftaly, M; Jordery, S; Samson, B N; Taylor, E R; Hewak, D; Payne, D N; Poulain, M; Zhang, G (1995). Pure and Applied Optics: Journal of the European Optical Society Part A. 4: 417. doi:10.1088/0963-9659/4/4/019.
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(help)CS1 maint: multiple names: authors list (link) - ^ Borchert, Y.; Sonstrom, P.; Wilhelm, M.; Borchert, H.; Baumer, M. (2008). "Nanostructured Praseodymium Oxide: Preparation, Structure, and Catalytic Properties". Journal of Physical Chemistry C. 112: 3054. doi:10.1021/jp0768524.
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Books
- R.J. Callow, "The Industrial Chemistry of the Lanthanons, Yttrium, Thorium and Uranium", Pergamon Press, 1967.
External links
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