Samarium earths

Samarium - the atomic number is 62 and the chemical symbol is Sm. The name derives from the mineral Samarskite, in which it was found and which had been named for Colonel von Samarski , a Russian mine official. It was originally discovered in 1878 by the Swiss chemist Marc Delafontaine, who called it decipium. It was also discovered by the French chemist Paul-Emile Lecoq de Boisbaudran in 1879. In 1881, Delafontaine determined that his decipium could be resolved into two elements, one of which was identical to Boisbaudran s samarium. In 1901, the French chemist Eugene-Anatole Demar9ay showed that this samarium earth also contained europium. 

Europe) In 1890 Boisbaudran obtained basic fractions from samarium-gadolinium concentrates which had spark spectral lines not accounted for by samarium or gadolinium. These lines subsequently have been shown to belong to europium. The discovery of europium is generally credited to Demarcay, who separated the rare earth in reasonably pure form in 1901. The pure metal was not isolated until recent years. 

Although rare-earth ions are mosdy trivalent, lanthanides can exist in the divalent or tetravalent state when the electronic configuration is close to the stable empty, half-fUed, or completely fiUed sheUs. Thus samarium, europium, thuUum, 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 stabili2ation 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 uranium ore from Elliot Lake, Canada, contains yttrium and lanthanides (see Uranium and uranium compounds). In the Jiangxi province of the People s Repubhc of China a large reserve of a rare-earth-containing clay contains over 1,000,000 t of REO. This ore is characterized by having a low cerium content (<5%) but a high content in samarium, europium, terbium, and yttrium compared to the main base REO ores (Table 6). ... 

Other catalytic uses of rare-earth compounds have not reached the same development. Neodymium salts are, however, used for mbber manufacturing (22). Divalent samarium haHdes are employed in organic synthesis (23). 

The valences of the rare-earth metals are calculated from their magnetic properties, as reported by Klemm and Bommer.14 It is from the fine work of these investigators that the lattice constants of the rare-earth metals have in the main been taken. The metals lutecium and ytterbium have only a very small paramagnetism, indicating a completed 4/ subshell and hence the valences 3 and 2, respectively (with not over 3% of trivalent ytterbium present in the metal). The observed paramagnetism of cerium at room temperature corresponds to about 20% Ce4+ and 80% Ce3+, that of praseodymium and that of neodymium to about 10% of the quadripositive ion in each case, and that of samarium to about 20% of the bipositive ion in equilibrium with the tripositive ion. 

The hexaborides for which the oxidation state of the metal is 2 -f- are CaB, SrBg, BaB5, EuB, YbB. They are diamagnetic except EuB, which is ferromagnetic (Tc = 12.5 K) . The other rare-earth hexaborides are characterized by the 3-1-oxidation state, except for SmB, in which samarium is in a mixed valence state. They exhibit antiferromagnetic order at low T except LaB, YB and SmB . ... 

All the rare earth metals except samarium, europium, and ytterbium can be prepared in a pure form by reducing their trifluorides with calcium. Magnesium fluoride is less stable than the rare earth fluorides and so magnesium does not figure as a reductant. Lithium forms a fluoride which is stabler than some of the rare earth fluorides and thus finds some use as a reductant. 

The rare earth oxides of lanthanum, samarium and gadolinium were converted into soluble nitrate salts by dissolving them in the minimum amount of concentrated nitric acid. Then two sets were prepared by adding 2.0 ml of aqueous solution of La(N03)3.6H20 [0.2 M] and 0.01 ml of (n-BuO)4Ti to 25 ml of aqueous solution of Cu(N03)2 [1.0 M]. Similarly, two sets were prepared with Co(N03)3. Same procedures were followed for Sm(N03)3 [0.2 M] and Gd(N03)3 [0.2 M], One set of all these solutions were sonicated under ultrasonic bath (Model - Meltronics, 20 kHz, 250 W) for half an hour. The solutions prepared in normal and sonicated conditions were kept in muffle furnace (Model - Deluxe Zenith) first at 100°C for 2 h and then the temperature of the furnace was raised up to 900°C and calcined for 2 h. The solid composites prepared were then cooled to room temperature and treated as catalyst for phenol degradation. 

A range of rare earth metal complexes were subsequently shown to catalyze ethylene polymerization and, on occasion, living characteristics have been reported.226-228 Dimeric hydrides such as (79)—(82) are extremely active with turnover numbers > 1800 s-1 recorded for (79) at room temperature. The samarium hydride (82) also effects the block copolymerization of methyl methacrylate (MMA) and ethylene 229 further discussion may be found in Section 9.1.4.4. 

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. 

Promethium (gjPm) was predicted to fill a space between the rare-earths neodymium (gjjNd) and samarium (gjSm) in the periodic table in 1902. Although a few scientists claimed to have produced it, separating promethium from other rare-earths proved to be difficult, and thus identifying it was elusive. Only small amounts are produced and exist. 

ISOTOPES There are 41 known isotopes of samarium. Seven of these are considered stable. Sm-144 makes up just 3.07% of the natural occurring samarium, Sm-150 makes up 7.38% of natural samarium found on Earth, Sm-152 constitutes 26.75%, and Sm-154 accounts for 22.75%. All the remaining isotopes are radioactive and have very long half-lives therefore, they are considered "stable." All three contribute to the natural occurrence of samarium Sm-147 = 14.99%, Sm-148 = 11.24%, and Sm-149 = 13.82%. 

Samarium is one of the few elements with several stable isotopes that occur naturally on Earth. 

Samarium is the 39th most abundant element in the Earths crust and the fifth in abundance (6.5 ppm) of all the rare-earths. In 1879 samarium was first identified in the mineral samarskite [(Y, Ce U, Fe) (Nb, Ta, Ti )Ojg]. Today, it is mostly produced by the ion-exchange process from monazite sand. Monazite sand contains almost all the rare-earths, 2.8% of which is samarium. It is also found in the minerals gadolmite, cerite, and samarskite in South Africa, South America, Australia, and the southeastern United States. It can be recovered as a byproduct of the fission process in nuclear reactors. 

Using a spectrometer in 1853, Jean Charles-GaUisard de Marignac (1817—1894) suspected that dydimia was a mixture of yet-to-be-discovered elements. However, it was not until 1879 that Paul-Emile Locoq de Boisbaudran (1838—1912), using a difficult chemical fractionation process, discovered samarium in a sample of samarskite, calling it samarium after the mineral, which was named for a Russian mine official. Colonel von Samarski. Samarskite ore is found where didymia is found. Didymia ( twins ) was the original name given to a combination of the two rare-earths (praseodymium and neodymium) before they were separated and identified. 

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. 

Boisbaudran obtained this rare earth element in 1892 in basic fractions from samarium-gadolinium concentrates, but it was not identified for several years. Demarcay obtained the element in the pure form in 1901. The element was named after Europe. It is found in nature mixed with other rare earth elements. Its concentration, however, is much lower than most other lanthanide elements. The principal rare earth ores are xenotime, monazite, and bastna-site. 

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