Lanthanide divalent

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. 

In aqueous solutions, trivalent lanthanides ate very stable whereas only a limited number of lanthanides exhibit a stable divalent or tetravalent state. Practically, only Ce and Eu " exist in aqueous solutions. The properties of these cations ate very different from the properties of the trivalent lanthanides. For example, Ce" " is mote acidic and cetium(IV) hydroxide precipitates at pH 1. Eu " is less acidic and eutopium(II) hydroxide does not precipitate at pH 7—8.5, whereas trivalent lanthanide hydroxides do. Some industrial separations ate based on these phenomena. 

A series of divalent lanthanide metal metaHaborane derivatives have been prepared by the redox reaction of metallic lanthanides and boron hydrides and by the metathesis reaction of boron hydride salts with LnCl2 where Ln = Sm, Eu, Yb (181,182). The species (CH3CN)3Yb[(p.-H)2B2QH22],... 

Lewis acids are defined as molecules that act as electron-pair acceptors. The proton is an important special case, but many other species can play an important role in the catalysis of organic reactions. The most important in organic reactions are metal cations and covalent compounds of metals. Metal cations that play prominent roles as catalysts include the alkali-metal monocations Li+, Na+, K+, Cs+, and Rb+, divalent ions such as Mg +, Ca +, and Zn, marry of the transition-metal cations, and certain lanthanides. The most commonly employed of the covalent compounds include boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride. Various other derivatives of boron, aluminum, and titanium also are employed as Lewis acid catalysts. 

Monochalcogenides, LnZ (Z = S, Se, Te), have been prepared for all the lanthanides except Pm, mostly by direct combination.They are almost black and, like the monoxides, have the NaCl structure. However, with the exceptions of SmZ, EuZ, YbZ, TmSe and TmTe, they have metallic conductivity and evidently consist of Ln -t- Z ions with 1 electron from each cation delocalized in a conduction band. EuZ and YbZ, by contrast, are semiconductors or insulators with genuinely divalent cations, but SmZ seem to be intermediate and may involve the equilibrium ... 

Cyclopentadienyl derivatives of divalent lanthanides are also known [Ln ( j -C5H5)2] (Ln = Sm, Eu, Yb) might be expected to be isostructural with ferrocene but are bent ie rather than the two rings being parallel they are tilted relative to each other. 

In view of this the divalent lanthanide ions are expected to show intense optical absorption in the whole visible region in compounds containing M(d°) ions. Since these compounds are not easy to prepare, our earlier warning is relevant. Only results on well-prepared and characterized compounds may be... 

Rare earth elements are the general term for 15 kinds of lanthanide elements (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Py, Ho, Er, Tm, Yb, Lu) together with Sc and Y elements. They prefer trivalent states in the complex formation, though three elements (Eu, Sm, Yb) can assume tri- and divalent stateos and Ce a tri- or tetravalent state. Their ionic radii are fairly large (1.0-1.17 A) and their electronegativities are low (1.1-1.2). In fact, the former are much larger than those of... 

Figure 7.17 Enthalpy of formation of selected perovskite-type oxides as a function of the tolerance factor. Main figure show data for perovskites where the A atom is a Group 2 element and B is a d or/element that readily takes a tetravalent state [19,20]. The insert shows enthalpies of formation of perovskite-type oxides where the A atom is a trivalent lanthanide metal [21] or a divalent alkaline earth metal [22] whereas the B atom is a late transition metal atom or Ga/Al.

The only easily accessible divalent lanthanide is Eu2+ which is isoelectronic with Gd3+ and very similar in size to Sr2+ (260). An... 

EXAFS study on Eu2+ and Sr2+ in both solid state and aqueous solution gave coordination numbers of 8.0 for strontium(II) and 7.2 for europium(II) (228). The water exchange rate measured on the divalent europium aqua ion is the fastest ever measured by 170 NMR (Table XVI) (2). The activation volume is much more negative (—11.7 cm3 mol-1) than those determined on trivalent lanthanide aqua ions clearly indicating an a-activation mechanism which is most probably a limiting... 

For an indication of the values of the atomic radii of the different elements and of their trend along the Periodic Table, see Figs 4.5 and 4.14. Notice the variations along each period (each horizontal sequence in Fig. 4.14) and the smaller values (and their small changes) for the metals in the middle of the transition block. Notice also in the lanthanide sequence the greater dimensions of the divalent Eu andYb. 

Figure 4.17. The binary phase diagrams of the magnesium alloy systems with the divalent metals ytterbium and calcium (Ca is a typical alkaline earth metal and Yb one of the divalent lanthanides). Notice, for this pair of metals, the close similarity of their alloy systems with Mg. The compounds YbMg2 and CaMg2 are isostructural, hexagonal hP12-MgZn2 type.

Within the lanthanides the first ones from La to Eu are the so-called light lanthanides, the other are the heavy ones. Together with the heavy lanthanides it may be useful to consider also yttrium the atomic dimensions of this element and some general characteristics of its alloying behaviour are indeed very similar to those of typical heavy lanthanides, such as Dy or Ho. An important subdivision within the lanthanides, or more generally within the rare earth metals, is that between the divalent ones (europium and ytterbium which have been described together with other divalent metals in 5.4) and the trivalent ones (all the others, scandium and yttrium included). 

The 3rd group metals a summary of their atomic and physical properties 5.5.5.1 The rare earth metals. A summary of the main atomic and physical properties of the rare earth metals has been collected in Tables 5.11-5.13. To complete the information and the presentation of the entire series of lanthanides the data relevant to Eu and Yb have been included in these tables. However, the same data are reported also in Table 5.7 in comparison with those of the other typical divalent metals (the alkaline earth metals). As for the properties of liquid rare earth metals and alloys see Van Zytveld (1989). 

The rare earth metals. The rare earth metals are extremely reactive elements especially with respect to the normal atmospheric gases. The light trivalent lanthanides oxidize with air at room temperature they should be stored (and handled) in vacuum or under He or Ar. Divalent Eu oxidizes much more readily than any of... 

Europium and ytterbium di-valence. The oxidation state II for Eu and Yb has already been considered when discussing the properties of a number of divalent metals (Ca, Sr, Ba in 5.4). This topic was put forward again here in order to give a more complete presentation of the lanthanide properties. The sum of the first three ionization enthalpies is relatively small the lanthanide metals are highly electropositive elements. They generally and easily form in solid oxides, complexes, etc., Ln+3 ions. Different ions may be formed by a few lanthanides such as Ce+4, Sm+2, Eu+2, Yb+2. According to Cotton and Wilkinson (1988) the existence of different oxidation states should be interpreted by considering the ionization... 

Figure 5.8. Lanthanide Ln203 oxides (cubic cI80-Mn2O3 type, on the left side) and Pb alloys (LnPb3, cubic cP4-type, on the right). The trends of the lattice parameter and of the heat of formation are shown (see the text and notice the characteristic behaviour of Eu and Yb). A schematic representation of the energy difference between the divalent and trivalent states of an ytterbium compound is shown. Apromff represents the promotion energy from di- to trivalent Yb metal, A,//11, and Ar/Ynl are the formation enthalpies of a compound in the two cases in which there is no valence change on passing from the metal to the compound the same valence state (II or III) is maintained.

Figure 5.14. Compound formation capability in the binary alloys of Sc, Y, light trivalent lanthanides (as exemplified by La), heavy trivalent lanthanides (exemplified by Gd) and of the actinides (exemplified by Th, U and Pu). The different partners of the 3rd group metals are identified by their position in the Periodic Table. Notice that a sharper subdivision between compound-forming and not forming metals will result from a shifting of Be and Mg from their position in the 2nd group towards the 12th group (see 5.12.3). The behaviour of the divalent lanthanides Eu and Yb is shown in Fig. 5.7 where it is compared with that of the alkaline earth metals.

The rare earth (RE) ions most commonly used for applications as phosphors, lasers, and amplifiers are the so-called lanthanide ions. Lanthanide ions are formed by ionization of a nnmber of atoms located in periodic table after lanthanum from the cerium atom (atomic number 58), which has an onter electronic configuration 5s 5p 5d 4f 6s, to the ytterbium atom (atomic number 70), with an outer electronic configuration 5s 5p 4f " 6s. These atoms are nsnally incorporated in crystals as divalent or trivalent cations. In trivalent ions 5d, 6s, and some 4f electrons are removed and so (RE) + ions deal with transitions between electronic energy sublevels of the 4f" electroiuc configuration. Divalent lanthanide ions contain one more f electron (for instance, the Eu + ion has the same electronic configuration as the Gd + ion, the next element in the periodic table) but, at variance with trivalent ions, they tand use to show f d interconfigurational optical transitions. This aspect leads to quite different spectroscopic properties between divalent and trivalent ions, and so we will discuss them separately. 

Table 4.17 Comparison of the Extraction Constants Aei for the Ilh-Suhgroup Divalent Ions, and inh Lanthanide Ions, with Sulfur or Oxygen Dialkyl Phosphoric Acids ...

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