Rare earth preparation

The first isolation of plutonium was effected in room 405, Jones Laboratory, by starting with a concentrate containing the order of a microgram of plutonium in about 10 milligrams of rare earths prepared for us by Arthur C. Wahl and co-workers at Berkeley. My journal records this event as follows ... 

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... 

Conversion of a fluoride to the metal can leave areas of the metal with fluorine content much higher than the average composition. It is not uncommon in these cases for the determination of fluorine to be in error by two to three orders of magnitude. Rare earths prepared or purified in a vaporization step produce a condensed metal which, if sampled directly for analysis by SSMS, can yield erroneous data due to heterogeneous impurity content since only a few mg of sample are consumed in the analysis by SSMS (Svec and Conzemius, 1968). 

Two specific metal-ligand systems merit mention because of the comprehensive research being carried out currently in the area of transition metal complexes metalloporphyrin derivatives of the lanthanide and actinide groups (Wong et al., 1974 Wong and Horrocks, 1975 Horrocks and Wong, 1976) and phthalocyanine derivatives of most of the rare earths prepared and characterized over the last 20 years (Kirin et al., 1965). 

The element was discovered by Nilson in 1878 in the minerals euxenite and gadolinite, which had not yet been found anywhere except in Scandinavia. By processing 10 kg of euxenite and other residues of rare-earth minerals, Nilson was able to prepare about 2g of highly pure scandium oxide. Later scientists pointed out that Nilson s scandium was idenhcal with Mendeleev s ekaboron. 

Gr. aktis, aktinos, beam or ray). Discovered by Andre Debierne in 1899 and independently by F. Giesel in 1902. Occurs naturally in association with uranium minerals. Actinium-227, a decay product of uranium-235, is a beta emitter with a 21.6-year half-life. Its principal decay products are thorium-227 (18.5-day half-life), radium-223 (11.4-day half-life), and a number of short-lived products including radon, bismuth, polonium, and lead isotopes. In equilibrium with its decay products, it is a powerful source of alpha rays. Actinium metal has been prepared by the reduction of actinium fluoride with lithium vapor at about 1100 to 1300-degrees G. The chemical behavior of actinium is similar to that of the rare earths, particularly lanthanum. Purified actinium comes into equilibrium with its decay products at the end of 185 days, and then decays according to its 21.6-year half-life. It is about 150 times as active as radium, making it of value in the production of neutrons. 

The element occurs along with other rare-earth elements in a variety of minerals. Monazite and bastnasite are the two principal commercial sources of the rare-earth metals. It was prepared in relatively pure form in 1931. 

Ion-exchange and solvent extraction techniques have led to much easier isolation of the rare earths and the cost has dropped greatly in the past few years. Praseodymium can be prepared by several methods, such as by calcium reduction of the anhydrous chloride of fluoride. 

Gadolinium is found in several other minerals, including monazite and bastnasite, both of which are commercially important. With the development of ion-exchange and solvent extraction techniques, the availability and prices of gadolinium and the other rare-earth metals have greatly improved. The metal can be prepared by the reduction of the anhydrous fluoride with metallic calcium. 

L. Holmia, for Stockholm). The special absorption bands of holmium were noticed in 1878 by the Swiss chemists Delafontaine and Soret, who announced the existence of an "Element X." Cleve, of Sweden, later independently discovered the element while working on erbia earth. The element is named after cleve s native city. Holmia, the yellow oxide, was prepared by Homberg in 1911. Holmium occurs in gadolinite, monazite, and in other rare-earth minerals. It is commercially obtained from monazite, occurring in that mineral to the extent of about 0.05%. It has been isolated by the reduction of its anhydrous chloride or fluoride with calcium metal. 

Other Metals. AH the sodium metal produced comes from electrolysis of sodium chloride melts in Downs ceUs. The ceU consists of a cylindrical steel cathode separated from the graphite anode by a perforated steel diaphragm. Lithium is also produced by electrolysis of the chloride in a process similar to that used for sodium. The other alkaH and alkaHne-earth metals can be electrowon from molten chlorides, but thermochemical reduction is preferred commercially. The rare earths can also be electrowon but only the mixture known as mischmetal is prepared in tonnage quantity by electrochemical means. In addition, beryIHum and boron are produced by electrolysis on a commercial scale in the order of a few hundred t/yr. Processes have been developed for electrowinning titanium, tantalum, and niobium from molten salts. These metals, however, are obtained as a powdery deposit which is not easily separated from the electrolyte so that further purification is required. 

Calcium metal is an excellent reducing agent for production of the less common metals because of the large free energy of formation of its oxides and hahdes. The following metals have been prepared by the reduction of their oxides or fluorides with calcium hafnium (22), plutonium (23), scandium (24), thorium (25), tungsten (26), uranium (27,28), vanadium (29), yttrium (30), zirconium (22,31), and most of the rare-earth metals (32). 

Other Rea.ctlons, The anhydride of neopentanoic acid, neopentanoyl anhydride [1538-75-6] can be made by the reaction of neopentanoic acid with acetic anhydride (25). The reaction of neopentanoic acid with acetone using various catalysts, such as titanium dioxide (26) or 2irconium oxide (27), gives 3,3-dimethyl-2-butanone [75-97-8] commonly referred to as pinacolone. Other routes to pinacolone include the reaction of pivaloyl chloride [3282-30-2] with Grignard reagents (28) and the condensation of neopentanoic acid with acetic acid using a rare-earth oxide catalyst (29). Amides of neopentanoic acid can be prepared direcdy from the acid, from the acid chloride, or from esters, using primary or secondary amines. 

Fuels and Lubricants. Rare-earth neodecanoates have been claimed as additives for diesel fuels that reduce the precipitation of particles and gum (108). Neodecanoic acid has also been used in the preparation of ashless detergent additives for fuels and lubricants that reduce engine deposits in internal combustion engines (109). 

The cerium concentrate derived from bastnasite is an excellent polish base, and the oxide derived direcdy from the natural ratio rare-earth chloride, as long as the cerium oxide content is near or above 50 wt %, provides an adequate glass poHsh. The polishing activity of the latter is better than the Ce02 Ln0 ratio suggests. Materials prepared prior to any Ln purification steps are sources for the lowest cost poHshes available used to treat TV face plates, mirrors, and the like. For precision optical polishing the higher purity materials are preferred. 

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). 

Polyisoprenes of 94—98% as-1,4 content were obtained with lanthanum, cerium, praseodymium, neodymium, and other rare-earth metal ions (eg, LnCl ) with trialkyl aluminum (R3AI) (34). Also, a NdCl 2THF(C2H3)3A1 catalyst has been used to prepare 95% <7j -l,4-polyisoprene (35). <7j -l,4-Polyisoprene of 98% as-1,4 and 2% 3,4 content was obtained with organoalurninum—lanthariide catalysts, NdCl where L is an electron-donor ligand such as ethyl alcohol or butyl alcohol, or a long-chain alcohol, and is 1 to 4 (36). 

Investigated is the influence of the purity degree and concentration of sulfuric acid used for samples dissolution, on the analysis precision. Chosen are optimum conditions of sample preparation for the analysis excluding loss of Ce(IV) due to its interaction with organic impurities-reducers present in sulfuric acid. The photometric technique for Ce(IV) 0.002 - 0.1 % determination in alkaline and rare-earth borates is worked out. The technique based on o-tolidine oxidation by Ce(IV). The relative standard deviation is 0.02-0.1. 

The rare earth composition of commercial electrodes is also related to electrode corrosion. This was noted by Sakai et. al. [44], who found that the presence of Nd or Ce inhibited corrosion when substituted in part for La in La, fZt(NiCoAl)5 (Z = Ce or Nd) electrodes. However no explanation for the effect was noted. Willems [22] prepared an electrode of La0XNd02Ni25Co24 Si0l which retained 88% of its storage capacity after 400 cycles. He attributed its long cycle life to a low VH of 2.6 A3. 

This method of analyzing rare-earth samples is rapid and reliable. An oxide sample may be prepared and completely analyzed in 35 minutes. Two persons, one preparing samples and the other operating the x-ray machine, can fully utilize the x-ray machine and analyze a maximum of about 40 samples per day for 7 elements each. 

The average error of analysis has been established to be about 3 per cent of the quantity present in the range from 5 to 100 per cent and about 7 per cent of the quantity present from 0.2 to 5 per cent. This accuracy, which is satisfactory for the present purposes of the rare-earth project, might be improved by preparation of more standards. 

In a similar manner, treatment of anhydrous rare-earth chlorides with 3 equivalents of lithium 1,3-di-ferf-butylacetamidinate (prepared in situ from di-ferf-butylcarbodiimide and methyllithium) in THF at room temperature afforded LnlMeCfNBuOils (Ln = Y, La, Ce, Nd, Eu, Er, Lu) in 57-72% isolated yields. X-ray crystal structures of these complexes demonstrated monomeric formulations with distorted octahedral geometry about the lanthanide(III) ions (Figure 20, Ln = La). The new complexes are thermally stable at >300°C, and sublime... 

Binary phase diagrams indicate that the rare-earth dodecaborides do not melt congruently . Owing to the difficulty in preparation of single-phase and single-crystal dodecaborides, little information is available on their physical properties. 

The problems raised by the preparation of some rare-earth borides such as SmB4, YbB4 and TmB2 are comparable to those found for the alkali borides from the point of view of the volatility of the metals. They dissociate through metal evaporation, yielding boron-rich borides as indicated in 6.7.2.4. 

In this method " - the melt eontains boric oxide and the metal oxide in a suitable electrolyte, usually an alkali or alkaline-earth halide or fluoroborate. The cell is operated at 700-1000 C depending on electrolyte composition. To limit corrosion, the container serving as cathode is made of mild steel or of the metal whose boride is sought. The anode is graphite or Fe. Numerous borides are prepared in this way, e.g., alkaline-earth and rare-earth hexaborides " and transition-metal borides, e.g, TiBj NijB, NiB and TaB... 

This method is used extensively in the laboratory because it is particularly suitable for preparing borides of rare or expensive metals, e.g., the transition-metal-rich borides CrB, Cr3B4, CrB2 (except Cr3B2 and Cr4B), the diborides ScB2, TiB2 the rare-earth hexaborides, dodecaborides and MB -type borides. 

The reduction of a metal oxide by a mixture of B and C is easier than the reduction by the borothermic process described above. The rate of reduction depends on the removal of CO, so operation under vacuum increases the rate and allows the reaction to proceed at a lower T than the borothermic process. The metal oxide may be volatile and the borides can be contaminated by C. Accordingly, this method is not suitable for preparing pure alkaline-earth and rare-earth hexaborides because in all cases borocarbides of formula MBg C, (e.g., M = Sr, Eu, Yb) are formed . 

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