Monazite And Related Minerals (df2453c2-46c2-4bf3-a8dc-059916201b18)

More than 200 minerals are known that contain the rare-earths and thorium. Monazite and bastnaesite, however, are the principal commercial sources of the rare-earths, and monazite is the principal source of thorium. Monazite was in demand in earlier years mainly for its content of thorium, which was used in the manufacture of Welsbach gas mantles; but beginning in the latter part of the nineteenth century, the rare-earths became progressively more important than thorium. Recently, however, the tenor of thorium in monazite has again become a matter of commercial interest. Rare-Earths and Thorium The rare-earths proper are defined by spectroscopists as the oxides of 14 elements with atomic numbers ranging from 58 to 71; but more commonly lanthanum, with an atomic number of 57, is also included, in which case these 15 elements are often designated as the lanthanides. Chemists also include scandium and yttrium as elements of the rare-earths. A second group of elements, beginning with actinium and including thorium, protactinium, uranium, and all the transuranium elements so far produced, with atomic numbers ranging from 89 upward, are chemically and structurally related to the lanthanides, and are known as the higher rare-earths or actinides. Berzelius discovered that the lanthanides could be separated roughly into three groups, based upon the solubility of their double salts, R2(SO4)3-K2SO4-2H2O, in excess of K2SO4. This separation, with the substitution of sodium for potassium, is still used commercially. The double salts of the cerium earths were found to be almost insoluble; the terbium earths, partly soluble; and the yttrium earths, completely soluble. Based upon the degree of solubility, scandium belongs with the cerium earths; and yttrium belongs with, and gives its name to, the yttrium earths. These three groups with their atomic numbers are shown below. [ ] The prevailing state of oxidation for the rare-earths is R2O3, but cerium may readily be oxidized to the tetravalent state, in which condition it may be separated chemically from the other cerium earths. Praseodymium and terbium may also exist with the valence IV, and samarium, europium, and ytterbium may have the valence II. Most of the elements of the rare-earths, however, are very difficult to separate, and their initial isolation required the work of many chemists over a period of 150 years.20 Fractional crystallization, fractional precipitation, and ion exchange are the principal methods so far used, and fractional precipitation is now employed commercially on a large scale. Ion exchange columns are