Thulium properties

The brittle, silvery, shiny metal was long considered the last stable element of the Periodic Table. In 2003 it was unmasked as an extremely weak alpha emitter (half-life 20 billion years). Like thulium, there is only one isotope. Bismuth alloys have low melting points (fuses, fire sprinklers). As an additive in tiny amounts, it imparts special properties on a range of metals. Applied in electronics and optoelectronics. The oxichloride (BiOCl) gives rise to pearlescent pigments (cosmetics). As bismuth is practically nontoxic, its compounds have medical applications. The basic oxide neutralizes stomach acids. A multitalented element. Crystallizes with an impressive layering effect (see right). 

Silver-colored, ductile metal that is attacked slowly by air and water. The element exhibits interesting magnetic properties. Found in television tubes. Laser material such as YAG (yttrium-aluminum garnet) doped with holmium (as well as chromium and thulium) can be applied in medicine, especially in sensitive eye operations. 

Swedish physicist, astronomer, and spec-troscopist. He mapped the spectra of yttrium, erbium, didymium, lanthanum, scandium, thulium, and ytterbium, and in 1866 wrote a histoncal review of spectrum analysis. He also studied the magnetic properties of iron and iron ores. 

Ionic radius Tm3+ 0.880 A. Metallic radius 1.746 A. First ionization potential 6.18 V second 12.05 V. Odier physical properties of thulium are given under Rare-Earth Elements and Metals. 

Important scientific and industrial applications for thulium and its compounds remain to be developed. In particular, the photoelectric, semiconductor, and thermoelectric properties of the element and compounds, particularly behavior in the near-infrared region of the spectrum, are being studied. Thulium has been used in phosphors, ferrite bubble devices, and catalysis. Irradiated thulium (169Tm) is used in a portable x-ray unit. 

Although rare-earth ions are mosdy trivalent, lanthanides can exist in the divalent or tetravalent state when the electronic configuration is dose to the stable empty, half-filled, or completely filled shells. Thus samarium, europium, thulium, and ytterbium can exist as divalent cations in certain environments. On the other hand, tetravalent cerium, praseodymium, and terbium are found, even as oxides where trivalent and tetravalent states often coexist. The stabilization of the different valence states for particular rare earths is sometimes used for separation from the other trivalent lanthanides. The chemicals properties of the di- and tetravalent ions are significantly different. 

The behaviour of lanthanum in dimethyl formamide (DMF) is quite different from that in methanol and acetonitrile. While perchlorate forms inner sphere complexes with lanthanides in acetonitrile [31], no such complexes are formed in DMF [32]. The coordination properties in DMF solutions were studied by NMR and UV-Vis spectroscopy techniques [33,34], The rate of DMF exchange in the system ytterbium perchlorate-DMF-CD2CI2 was slow enough that 1H NMR resonances permitted the determination of the mean coordination number to be 7.8 0.2. Similar determination in the case of thulium(III) gave a mean coordination number of 7.7 0.2. Thus it was concluded that the predominant species in heavy lanthanides is Ln(DMF)g+ in DMF solutions. In the case of lighter lanthanides, the following equilibrium exists... 

Lanthanide elements (referred to as Ln) have atomic numbers that range from 57 to 71. They are lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu). With the inclusion of scandium (Sc) and yttrium (Y), which are in the same subgroup, this total of 17 elements are referred to as the rare earth elements (RE). They are similar in some aspects but very different in many others. Based on the electronic configuration of the rare earth elements, in this chapter we will discuss the lanthanide contraction phenomenon and the consequential effects on the chemical and physical properties of these elements. The coordination chemistry of lanthanide complexes containing small inorganic ligands is also briefly introduced here [1-5]. 

In 1961 Hayes and Twidell (8) found that if calcium fluoride crystals containing trivalent thulium were irradiated with x-rays, some of the thulium was converted to the divalent state. This discovery was the first of many in the study of dilute solutions of divalent rare earth ions. Most workers prefer to study the alkaline earth fluorides since these materials are stable with respect to air and have more attractive mechanical properties than the alkaline earth chlorides, bromides, and iodides. Enough work has been carried out in these softer materials to show that reactions similar to those in the fluorides do occur. 

The materials derived from YBa2Cu307 by replacing yttrium with other rare earth elements (lutetium, ytterbium, thulium, erbium, hohnium, dysprosium, gadolinium, europium, samarium, neodymium, lanthanum) are also superconductors, with r, s of 88 to 96 K. The crystal structures of RBa2Cu307 are almost the same as those of YBa2Cu307. The lattice constant is slightly different for the different ionic radii of the rare earth elements, and yet their chemical and physical properties are almost the same as those of YBa2Cu307. 

Treatment of thulium diiodide with substituted phospholide and arsolide salts afforded stable bis(phospholyl)- and bis(arsolyl)thulium(ll) complexes (Scheme 201) as green solids, that were characterized by multinuclear NMR and X-ray crystal structures. The latter clearly revealed the beneficial effects of the steric and electronic properties of crowded phospholyl and arsolyl ligands for the stabilization of divalent thulium.727 Several other homoleptic samarium(ll) and thulium(n) phospholyl sandwich complexes containing the 2,5-di-/-butyl-3,4-dimethylphospholide (=dtp) or 2,5-bis(trimethylsilyl)-3,4-dimethylphospholide (=dsp) ligand have been synthesized and structurally characterized. X-ray studies revealed that [Sm(dtp)2]2 and [Sm(dsp)2]2 are both dimeric in the solid state due to... 

Bisphthalocyanines based on rare earth metals lutenium (45j) and thulium (45k) were studied as early as 1990.[267] These compounds had a field-effect mobility of 10 cm V- s- under vacuum, but the electronic properties degraded rapidly upon exposure to ambient conditions. 

The lanthanide or rare earth elements (atomic numbers 57 through 71) typically add electrons to the 4f orbitals as the atomic number increases, but lanthanum (4f°) is usually considered a lanthanide. Scandium and yttrium are also chemically similar to lanthanides. Lanthanide chemistry is typically that of + 3 cations, and as the atomic number increases, there is a decrease in radius for each lanthanide, known as the lanthanide contraction. Because bonding within the lanthanide series is usually predominantly ionic, the lanthanide contraction often determines the differences in properties of lanthanide compounds and ions. Lanthanide compounds often have high coordination numbers between 6 and 12. see also Cerium Dysprosium Erbium Europium Gadolinium Holmium Lanthanum Lutetium Praseodymium Promethium Samarium Terbium Thulium Ytterbium. 

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