Fractionated crystallization main effects

Yttrium and lanthanum are both obtained from lanthanide minerals and the method of extraction depends on the particular mineral involved. Digestions with hydrochloric acid, sulfuric acid, or caustic soda are all used to extract the mixture of metal salts. Prior to the Second World War the separation of these mixtures was effected by fractional crystallizations, sometimes numbered in their thousands. However, during the period 1940-45 the main interest in separating these elements was in order to purify and characterize them more fully. The realization that they are also major constituents of the products of nuclear fission effected a dramatic sharpening of interest in the USA. As a result, ion-exchange techniques were developed and, together with selective complexation and solvent extraction, these have now completely supplanted the older methods of separation (p. 1228). In cases where the free metals are required, reduction of the trifluorides with metallic calcium can be used. 

Stable isotope fractionation was predicted and calculated by Urey and coworkers as early as 1932. Bigeleisen (1961) dealt with the statistical mechanics of isotope effects. Hydrogen isotope fractionation is mainly connected with the processes in the hydrosphere, but its equilibrium and kinetic effects were also studied for water of crystallization, ore-forming fluids, as represented by liquid inclusions, and biological cycles. 

Preparation.—The main source of rubidium compounds is the residual mother-liquor obtained in the extraction of potassium chloride from carnallite. The solution contains rubidium-carnallite, RbCl,MgCI2, a substance transformed by addition of aluminium sulphate into rubidium-alum, RbAl(S04)8,12H20. Separation from the potassium and caesium salts also present is effected by fractional crystallization of the alum,8 of the chloroplatinate 8 Rb2PtCl8, of rubidium-iron-alum,4 and of the double chloride with stannous chloride5 or with antimony trichloride.6... 

The technique of self-nucleation can be very useful to study the nucleation and crystallization of block copolymers that are able to crystallize [29,97-103]. Previous works have shown that domain II or the exclusive self-nucleation domain disappears for systems where the crystallizable block [PE, PEO or poly(e-caprolactone), PCL] was strongly confined into small isolated MDs [29,97-101]. The need for a very large number of nuclei in order to nucleate crystals in every confined MD (e.g., of the order of 1016 nuclei cm 3 in the case of confined spheres) implies that the amount of material that needs to be left unmolten is so large that domain II disappears and annealing will always occur to a fraction of the polymer when self-nucleation is finally attained at lower Ts. This is a direct result of the extremely high number density of MDs that need to be self-nucleated when the crystallizable block is confined within small isolated MDs. Although this effect has been mainly studied in ABC triblock copolymers and will be discussed in Sect. 6.3, it has also been reported in PS-fc-PEO diblock copolymers [29,99]. 

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