Valence lanthanide oxides

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... 

Oxides of the lanthanide rare earth elements share some of the properties of transition-metal oxides, at least for cations that can have two stable valence states. (None of the lanthanide rare earth cations have more than two ionic valence states.) Oxides of those elements that can only have a single ionic valence are subject to the limitations imposed on similar non-transition-metal oxides. One actinide rare-earth oxide, UO2, has understandably received quite a bit of attention from surface scientists [1]. Since U can exist in four non-zero valence states, UO2 behaves more like the transition-metal oxides. The electronic properties of rare-earth oxides differ from those of transition-metal oxides, however, because of the presence of partially filled f-electron shells, where the f-electrons are spatially more highly localized than are d-electrons. 

The lanthanide oxides find important applications in the catalysis, lighting, and electronics industries. In particular, the design of advanced devices based upon the integration of lanfhanide oxides with silicon and other semiconductors calls for a defailed undersfanding of the bonding, electronic, and dielectric properties of fhese materials (Scarel et al., 2007). Here, we use the SIC-LSD to address the issue of the lanthanide valence in the dioxides RO2 and sesquioxides R2O3, for R = Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, and Ho. 

Lanthanides Luminescence Applications Lanthanides in Living Systems Lanthanide Oxide/Hydroxide Complexes Lanthanides Coordination Chemistry Sustainability of Rare Earth Resources The Electronic Structure of the Lanthanides Variable Valency. 

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. 

Lanthanides with fractional valences have II, III and IV valences, as well as mixed II/III and III/IV valences. Depending on temperature and pressure, the degree of oxidation can change. This effect may result in a change in the different properties of nanoparticles, such as the stability, heat capacity, conductivity and magnetic susceptibility [218]. Valence fluctuation phenomena have been reported to occur... 

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.

Transition metah—found in the groups located in the center of the periodic table, plus the lanthanide and actinide series. They are all solids, except mercury, and are the only elements whose shells other than their outer shells give up or share electrons in chemical reactions. Transition metals include the 38 elements from groups 3 through 12. They exhibit several oxidation states (oxidation numbers) and various levels of electronegativity, depending on their size and valence. 

SYMBOL Eu PERIOD 6 SERIES NAME Lanthanide ATOMIC NO 63 ATOMIC MASS 151.964 amu VALENCE 2 and 3 OXIDATION STATE +2 and +3 NATURAL STATE Solid ORIGIN OF NAME Named for the continent of Europe. 

Symbol Nd atomic number 60 atomic weight 144.24 a rare earth lanthanide element a hght rare earth metal of cerium group an inner transition metal characterized by partially filled 4/ subshell electron configuration [Xe]4/35di6s2 most common valence state -i-3 other oxidation state +2 standard electrode potential, Nd + -i- 3e -2.323 V atomic radius 1.821 A (for CN 12) ionic radius, Nd + 0.995A atomic volume 20.60 cc/mol ionization potential 6.31 eV seven stable isotopes Nd-142 (27.13%), Nd-143 (12.20%), Nd-144 (23.87%), Nd-145 (8.29%), Nd-146 (17.18%), Nd-148 (5.72%), Nd-150 (5.60%) twenty-three radioisotopes are known in the mass range 127-141, 147, 149, 151-156. 

In Fig. 1, we have plotted the oxidation numbers of the actinides and of the lanthanides. We see that for the lanthanides the valence 3 is the most stable valence throughout the series. There are exceptions Ce displays for instance tetravalency in many compounds Eu and Yb display divalency. These exceptions are understood e.g., Eu and Yb are at the half-filling and at the filling of the 4f shell, which are stable electronic configurations. There is a tendency for both to share just the two outer 5 s electrons in bonding, displaying therefore, divalency, and preserve these stable configurations. 

Let us assume that the metallic valence is three for most lanthanides, and two for Eu and Yb. This is consistent with the chemistry of these elements, since (Fig. 1) three is their most common oxidation number. Trivalency has been explained in the proceeding chapter, by assuming the easy promotion of one 4 f electron to a 5 d level. The conduction quasi-free electrons are therefore of 5d and 6 s origin. We may say that the conduction band has a prevalent (s, d) character. 

When the itinerant state is formed, a volume collapse AV/V is always encountered, as predicted by the theory of the preceding sections. In one of the lanthanides, cerium, this volume collapse is particularly accentuated for its isostructural transition from the y to the a form, possibly associated with a change in metallic valence from three to four (both oxidation numbers are stable in cerium chemistry) (see Fig. 1 of Chap. A),... 

RARE-EARTH ELEMENTS AND METALS. Sometimes referred to as the fraternal fifteen," because of similarities in physical and chemical properties, the rare-earth elements actually are not so rare. This is attested by Fig. 1, which shows a dry lake bed in California that alone contains well in excess of one million pounds of two of die elements, neodymium and praseodymium. The world s largest rare earth body and mine near Baotou, Inner Mongolia, China is shown in Fig. 2. It contains 25 million tons of rare earth oxides (about one quarter of the world s human reserves. The term rare arises from the fact that these elements were discovered in scarce materials. The term earth stems from die tact that the elements were first isolated from their ores in the chemical form of oxides and that the old chemical terminology for oxide is earth. The rare-earth elements, also termed Lanthanides, are similar in that they share a valence of 3 and are treated as a separate side branch of the periodic table, much like die Actinides. See also Actinide Contraction Chemical Elements Lanthanide Series and Periodic Table of the Elements. 

The striking characteristics of the lanthanide higher oxides are rooted in the electronic structure of Ce, Pr, and Tb atoms. The lanthanide elements located in the third group of the periodic table have a normal 3+ valence state and the normal oxides have the R2O3 formula. Due to the special electron configurations of Ce... 

Module type and average valence state of the lanthanide higher oxides... 

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