Monazite lanthanum

Lanthanum is found in rare-earth minerals such as cerite, monazite, allanite, and bastnasite. Monazite and bastnasite are principal ores in which lanthanum occurs in percentages up to 25 percent and 38 percent respectively. Misch metal, used in making lighter flints, contains about 25 percent lanthanum. 

As with other rare-earth metals, except for lanthanum, europium ignites in air at about 150 to I8O0C. Europium is about as hard as lead and is quite ductile. It is the most reactive of the rare-earth metals, quickly oxidizing in air. It resembles calcium in its reaction with water. Bastnasite and monazite are the principal ores containing europium. 

Gr. neos, new, and didymos, twin) In 1841, Mosander, extracted from cerite a new rose-colored oxide, which he believed contained a new element. He named the element didymium, as it was an inseparable twin brother of lanthanum. In 1885 von Welsbach separated didymium into two new elemental components, neodymia and praseodymia, by repeated fractionation of ammonium didymium nitrate. While the free metal is in misch metal, long known and used as a pyrophoric alloy for light flints, the element was not isolated in relatively pure form until 1925. Neodymium is present in misch metal to the extent of about 18%. It is present in the minerals monazite and bastnasite, which are principal sources of rare-earth metals. 

Scandium is very widely but thinly distributed and its only rich mineral is the rare thortveitite, Sc2Si20v (p. 348), found in Norway, but since scandium has only small-scale commercial use, and can be obtained as a byproduct in the extraction of other materials, this is not a critical problem. Yttrium and lanthanum are invariably associated with lanthanide elements, the former (Y) with the heavier or Yttrium group lanthanides in minerals such as xenotime, M "P04 and gadolinite, M M SijOio (M = Fe, Be), and the latter (La) with the lighter or cerium group lanthanides in minerals such as monazite, M P04 and bastnaesite, M C03F. This association of similar metals is a reflection of their ionic radii. While La is similar in size to the early lanthanides which immediately follow it in the periodic table, Y , because of the steady fall in ionic radius along the lanthanide series (p. 1234), is more akin to the later lanthanides. 

In situ densitometry has been the most preferred method for quantitative analysis of substances. The important applications of densitometry in inorganic PLC include the determination of boron in water and soil samples [38], N03 and FefCNfg in molasses [56], Se in food and biological samples [28,30], rare earths in lanthanum, glass, and monazite sand [22], Mg in aluminum alloys [57], metallic complexes in ground water and electroplating waste water [58], and the bromate ion in bread [59]. TLC in combination with in situ fluorometry has been used for the isolation and determination of zirconium in bauxite and almnimun alloys [34]. The chromatographic system was silica gel as the stationary phase and butanol + methanol + HCl -H water -n HF (30 15 30 10 7) as the mobile phase. 

Experimental work was carried out on black sand in which the effect of sodium oxalate on monazite activation was examined. It should be noted that monazite is essentially a phosphate of cerium and lanthanum, where the possibility exists that sodium oxalate has an activating effect on monazite [11]. The use of sodium oleate as activator was studied with different sulphonate collectors (Table 24.12). 

Lanthanide, as a pure metal, is difficult to separate from its ores, and it is often mixed with other elements of the series. It is mosdy obtained through an ion-exchange process from the sands of the mineral monazite, which can contain as much as 25% lanthanum as well as the oxides of several other elements of the series. The metal is malleable and ductile and can be formed into many shapes. Lanthanum is considered the most basic (alkaline) of the rare-earth elements. 

The main ore in which lanthanum is found is monazite sands, and it is also found in the mineral bastnasite. Monazite sands contain all of the rare-earth elements as well as some elements that are not rare-earths. Its ores are found in South Africa, Australia, Brazil, and India and in California, Florida, and the Carolinas in the United States... 

The element was discovered by Klaproth in 1803 and also in the same year by Berzelius and Hisinger. It is named after the asteroid Ceres. Cerium is found in several minerals often associated with thorium and lanthanum. Some important minerals are monazite, aUanite, cerite, bastnasite, and samarskite. It is the most abundant element among aU rare-earth metals. Its abundance in the earth s crust is estimated to be 66 mg/kg, while its concentration in sea water is approximately 0.0012 microgram/L. 

Lanthanum is most commonly obtained from the two naturally occurring rate-earth minerals, monazite and bastnasite. Monazite is a rare earth-thorium phosphate that typically contains lanthanum between 15 to 25%. Bastnasite is a rare earth-fluocarbonate-type mineral in which lanthanum content may vary, usually between 8 to 38%. The recovery of the metal from either of its ores involves three major steps (i) extraction of all rare-earths combined together from the non-rare-earth components of the mineral, (ii) separation or isolation of lanthanum from other lanthanide elements present... 

Extraction of lanthanum from monazite is discussed below first, followed by that from bastnasite. 

The monazite sand is heated with sulfuric acid at about 120 to 170°C. An exothermic reaction ensues raising the temperature to above 200°C. Samarium and other rare earths are converted to their water-soluble sulfates. The residue is extracted with water and the solution is treated with sodium pyrophosphate to precipitate thorium. After removing thorium, the solution is treated with sodium sulfate to precipitate rare earths as their double sulfates, that is, rare earth sulfates-sodium sulfate. The double sulfates are heated with sodium hydroxide to convert them into rare earth hydroxides. The hydroxides are treated with hydrochloric or nitric acid to solubihze all rare earths except cerium. The insoluble cerium(IV) hydroxide is filtered. Lanthanum and other rare earths are then separated by fractional crystallization after converting them to double salts with ammonium or magnesium nitrate. The samarium—europium fraction is converted to acetates and reduced with sodium amalgam to low valence states. The reduced metals are extracted with dilute acid. As mentioned above, this fractional crystallization process is very tedious, time-consuming, and currently rare earths are separated by relatively easier methods based on ion exchange and solvent extraction. 

There are in fact fourteen, and they became known as the rare earths - a misnomer, for some are not particularly rare at all, and they are metals, not earths . A better name is the lanthanides, since they all follow after lanthanum in the Periodic Table. They form an entirely new group, which cannot economically be fitted into Mendeleyev s scheme and is usually depicted as floating freely below it. The lanthanides are, broadly speaking, all rather similar in their chemical behaviour, which is why they were so hard to separate. They are found in minerals such as monazite and bastnasite, the main sources of which are in China and the USA. 

Mischmetal is produced commercially by electrolysis, The usual starting ingredient is the dehydrated rare earth chloride produced from monazite or bastnasite. The mixed rare earth chloride is fused in an iron, graphite, or ceramic crucible with the aid of electrolyte mixtures made up of potassium, barium, sodium, or calcium chlorides. Carbon anodes are immersed in the molten salt. As direct current flows through the cell, molten mischmetal huilcls up in the bottom of the crucible. This method is also used to prepare lanthanum and cerium metals. 

The principal sources of ytterbium are euxenite, gadolinite, monazite, and xenotime. the latter being the most important. Ytterbium is separated from a mixture of yttrium and the heavy Lanthanides by using the sodium amalgam reduction technique. Ytterbium metal is obtained by heating a mixture of lanthanum metal and ytterbium oxide under high vacuum. The ytterbium sublimes and is collected on condenser plates whereas the lanthanum is oxidized to the sesquioxide. 

To evaluate the factors affecting the structural stability of some crystalline materials that are potential hosts for radioactive wastes, the crystal structures of a series of 3+p5 xv5+o compounds, where A is lanthanum or a member of the rare-earth series, were determined. The end-member phosphates (APO4) have the monoclinic Monazite structure (P2 /n) for A La, Ce-Gd, and the tetragonal Zircon structure (l4]/amd) for A Tb - Lu. The corresponding vanadates have the Monazite structure only for LaVO, and the Zircon structure for A = Ce - Lu. When the end members are iso-structural, e.g., LaPO /LaVO, Monazite, YbPC /YbVOA,... 

Praseodymium, separation of mixtures with lanthanum from monazite, as magnesium nitrate double salt, 2 56, 67 Praseodymium (III) nitrate, analysis of anhydrous, 5 41 Praseodymium (III) oxide, for synthesis of nitrate, 5 39w. Precipitates, apparatus for removing liquid from, 8 16 Purpureochromic chloride, 2 196 6 138... 

Scandium, yttrium, and lanthanum, in group Ilia of the periodic table, usually occur in nature with the fourteen rare-earth elements, cerium (atomic number 58) to lutetium (atomic number 71). All of these elements except promethium (which is n ade artificially) occur in nature in very small quantities, the principal source being the mineial monazite, a mixture of rare-earth phosphates containing also some thoriurn phosphate. 

A fraction of Ce, La. Nd and Pr derived from bastnasite or monazite is a typical feedstock in the recovery process of cerium on a commercial scale. Separation of the rare-earth elements may be achieved by splitting the mixed rare-earth elements into a cerium/lanthanum and didymium (Nd/Pr) fraction first. The cerium/lanthanum fraction may be used as a further feedstock in a second extraction stage and will yield high pure cerium and lanthanum solution respectively. Cerium can then be precipitated as. for example, an oxalate or a carbonate which may be used as precursor for cerium derivatives. 

The principal source of thorium is monazite (p. 425), a phosphate of cerium and lanthanum with up to 15% of thoria. It is dissolved in concentrated sulphuric acid and the thorium phosphate precipitated with magnesium oxide. The washed phosphate heated with sodium carbonate gives crude thoria, ThOg, which is converted to the soluble oxalate and separated from the insoluble oxalates of cerium and lanthanum. After ignition to oxide the nitrate is made, purified by recrystallisation, and again calcined to thoria. 

Monazite (white)—RARE EARTHS cerium, lanthanum, neodymium, thorium... 

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