Lutetium earths

An early classification of the rare earths (the oxides of lanthanides) in relation to their separation from ores, was in the ceritic earths (the oxides from lanthanum to samarium) and yttric earths (from europium to lutetium, but also scandium and yttrium). A further refinement of analytical methods made it possible to split the yttric earths into terbic (europium, gadolinium, terbium), erbic (dysprosium, holmium, erbium, thulium), and ytterbic (ytterbium and lutetium) earths, along with yttrium oxide and scandium oxide. 

Reference has been made already to the existence of a set of inner transition elements, following lanthanum, in which the quantum level being filled is neither the outer quantum level nor the penultimate level, but the next inner. These elements, together with yttrium (a transition metal), were called the rare earths , since they occurred in uncommon mixtures of what were believed to be earths or oxides. With the recognition of their special structure, the elements from lanthanum to lutetium were re-named the lanthanons or lanthanides. They resemble one another very closely, so much so that their separation presented a major problem, since all their compounds are very much alike. They exhibit oxidation state -i-3 and show in this state predominantly ionic characteristics—the ions. 

Ytterby, village in Sweden) Marignac in 1878 discovered a new component, which he called ytterbia, in the earth then known as erbia. In 1907, Urbain separated ytterbia into two components, which he called neoytterbia and lutecia. The elements in these earths are now known as ytterbium and lutetium, respectively. These elements are identical with aldebaranium and cassiopeium, discovered independently and at about the same time by von Welsbach. 

Lanthanides is the name given collectively to the fifteen elements, also called the elements, ranging from lanthanum. La, atomic number 57, to lutetium, Lu, atomic number 71. The rare earths comprise lanthanides, yttrium, Y, atomic number 39, and scandium. Sc, atomic number 21. The most abundant member of the rare earths is cerium, Ce, atomic number 58 (see Ceriumand cerium compounds). 

Separation Processes. The product of ore digestion contains the rare earths in the same ratio as that in which they were originally present in the ore, with few exceptions, because of the similarity in chemical properties. The various processes for separating individual rare earth from naturally occurring rare-earth mixtures essentially utilize small differences in acidity resulting from the decrease in ionic radius from lanthanum to lutetium. The acidity differences influence the solubiUties of salts, the hydrolysis of cations, and the formation of complex species so as to allow separation by fractional crystallization, fractional precipitation, ion exchange, and solvent extraction. In addition, the existence of tetravalent and divalent species for cerium and europium, respectively, is useful because the chemical behavior of these ions is markedly different from that of the trivalent species. 

Some nut trees accumulate mineral elements. Hickory nut is notable as an accumulator of aluminum compounds (30) the ash of its leaves contains up to 37.5% of AI2O2, compared with only 0.032% of aluminum oxide in the ash of the Fnglish walnut s autumn leaves. As an accumulator of rare-earth elements, hickory greatly exceeds all other plants their leaves show up to 2296 ppm of rare earths (scandium, yttrium, lanthanum, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium). The amounts of rare-earth elements found in parts of the hickory nut are kernels, at 5 ppm shells, at 7 ppm and shucks, at 17 ppm. The kernel of the Bra2d nut contains large amounts of barium in an insoluble form when the nut is eaten, barium dissolves in the hydrochloric acid of the stomach. 

The same color variety is not typical with inorganic insertion/extraction materials blue is a common transmitted color. However, rare-earth diphthalocyanine complexes have been discussed, and these exhibit a wide variety of colors as a function of potential (73—75). Lutetium diphthalocyanine [12369-74-3] has been studied the most. It is an ion-insertion/extraction material that does not fit into any one of the groups herein but has been classed with the organics in reviews. Films of this complex, and also erbium diphthalocyanine [11060-87-0] have been prepared successfiiUy by vacuum sublimation and even embodied in soHd-state cells (76,77). 

According to this assignment the differentiating electron, that is, the final electron to enter the atom of lutetium, wss seen as an f electron. This suggested that lutetium should be the final element in the first row of the rare earth elements, in which f electrons are progressively filled, and not a transition element as had been believed by the chemists. As a result of more recent spectroscopic experiments the configuration of ytterbium has been altered to (27)... 

Between barium (Group 2, element 56) and lutetium (Group 3, element 71), the 4f orbitals fill with electrons, giving rise to the lanthanides, a set of 14 metals named for lanthanum, the first member of the series. The lanthanides are also called the rare earths, although except for promethium they are not particularly rare. Between radium (Group 2, element 88) and lawrenclum (Group 3, element 103), are the 14 actinides, named for the first member of the set, actinium. The lanthanides and actinides are also known as the inner transition metals. 

The rare earth elements (R) are those from atomic numbers 57-71, emanating as a particular series from the parent element lanthanum (atomic no. 57). The set of 14 elements from cerium (58) through lutetium (71) inclusive are commonly known as the lanthanoid (or lanthanide Ln) series. The rare earths form a bridge at the... 

The compounds of the rare earth elements are usually highly colored. Neodymium s compounds are mainly lavender and violet, samarium s yellow and brown, holmium s yellow and orange, and erbium s rose-pink. Europium makes pink salts which evaporate easily. Dysprosium makes greenish yellow compounds, and ytterbium, yellow-gold. Compounds of lutetium are colorless, and compounds of terbium are colorless, dark brown, or black. 

Rare earth. One of a group of 15 chemically related elements lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. 

ISOTOPES There are a total of 59 isotopes of Lutetium. Only two of these are stable Lu-175, which makes up 97.41% of all the natural abundance found on Earth. The other is a long-lived radioisotope (Lu-176) with such a long half-life (4.00x10+ ° years) that it is considered stable Lu-176 contributes 2.59% to the natural abundance of lutetium. 

In the last (17th) position in the lanthanide series, lutetium is the heaviest and largest molecule of all the rare-earths as well as the hardest and most corrosion-resistant. It has a silvery-white color and is somewhat stable under normal atmospheric conditions. 

Lutetium is the 60th most abundant element on Earth, and it ranks 15th in the abundance of the rare-earths. It is one of the rarest of the lanthanide series. It is found in monazite sand (India, Australia, Brazil, South Africa, and Florida), which contains small amounts of all the rare-earths. Lutetium is found in the concentration of about 0.0001% in monazite. It is difficult to separate it from other rare-earths by the ion-exchange process. In the pure metallic form, lutetium is difficult to prepare, which makes is very expensive. 

An interesting bit of history is that the American chemist Charles James, of the University of New Hampshire, and his students also discovered lutetium in 1907. They processed many tons of ore, and by using the crystallization process, produced a small sample of lutetium. James s work was recognized in 1999 by the ACS (American Chemical Society). This is the only example of a rare-earth being discovered in the United States. 

Lutetium fluoride is a skin irritant, and its fumes are toxic if inhaled. The dust and powder of the oxides of some rare-earths, including lutetium, are toxic if inhaled or ingested. 

Recently, rare-earth metal complexes have attracted considerable attention as initiators for the preparation of PLA via ROP of lactides, and promising results were reported in most cases [94—100]. Group 3 members (e.g. scandium, yttrium) and lanthanides such as lutetium, ytterbium, and samarium have been frequently used to develop catalysts for the ROP of lactide. The principal objectives of applying rare-earth complexes as initiators for the preparation of PLAs were to investigate (1) how the spectator ligands would affect the polymerization dynamics (i.e., reaction kinetics, polymer composition, etc.), and (2) the relative catalytic efficiency of lanthanide(II) and (III) towards ROPs. 

Lutetium is produced commercially from monazite. The metal is recovered as a by-product during large-scale extraction of other heavy rare earths (See Cerium, Erbium, Holmium). The pure metal is obtained by reduction of lutetium chloride or lutetium fluoride by a alkali or alkaline earth metal at... 

The metallophthalocyanines which have found application as elecfiochromes are mainly the rare earth derivatives, especially lutetium, and second row fiansition metals such as zirconium and molybdenum. Synthesis of these molecules follows the fiaditional routes, e.g. condensation of 1,2-dicyanobenzene with a metal acetate in a high boiling solvent (see Chapter 2). These compounds have structures in which the rare earth element is sandwiched between two phthalocyanine rings, e.g. zirconium bisphthalocyanine (1.92 M = Zr) and lutetium bisphthalocyanine (192 M = Lu), the latter protonated on one of the meso N atoms to balance the charge. 

The rare earths have ion radii that vary 1.5% from one element to the next - the size decreases while the atomic number increases from lanthanum to lutetium. This is what is commonly called the "lanthanides contraction", see Figure 10. 

Charles James, 1880-1928. Director of the chemistry department at the University of New Hampshire. Author of many papers on the rare earths. Independent discoverer of lutetium. He was born in England and studied under Sir William Ramsay. 

Moseley s work not only shed much fight on the periodic system and the relationships between known elements and the radioactive isotopes, but was also a great stimulus in the search for the few elements remaining undiscovered (11). One of the first chemists to utilize the new method was Professor Georges Urbain of Paris, who took his rare earth preparations to Oxford for examination. Moseley showed him the characteristic fines of erbium, thulium, ytterbium, and lutetium, and confirmed in a few days the conclusions which Professor Urbain had made after twenty years... 

However, when Moseley and Urbain examined the rare-earth residues supposed to contain the new element, they found only about ten lines, all of which could he attributed to lutetium and ytterbium. In 1922, after a long period of interruption because of military duties, Professor Urbain resumed his search for element 72 in the same rare-earth.residues which he and Moseley had examined before the war. At his suggestion M. A. Dauvillier used de Broglie s improved method of X-ray analysis and observed two faint lines which almost coincided with those predicted for element 72 (15, 16). 

The lanthanides proper do not include lutetium, element 71, although this is considered a rare-earth element. 

---