Valence elemental lanthanides

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. 

As a group of typical metal elements, lanthanide elements can form chemical bonds with most nonmetal elements. Some low-valence lanthanide elements can form chemical bonds in organometallic or atom cluster compounds. Because lanthanide elements lack sufficient electrons and show a strong repulsive force towards a positive charge, chemical bonds between lanthanide metals have not yet been observed. Table 1.4 shows that 1391 structure-characterized lanthanide complexes were reported in publications between 1935 and 1995 and these are sorted by chemical bond type. 

FIGURE 4 Total energy differences between divalent and trivalent elemental lanthanide metals (open circles) and their sulphides (solid circles). The dashed line shows the experimental values for the lanthanide metals. The calculated energy differences have been uniformly shifted upwards by 43 mRy to reproduce the valence transition pressure of 6 kbar in SmS. 

FIGURE 5 The energy differences between the divalent and trivalent valence states of the elemental lanthanides (open circles) and their sulphides (solid circles) versus the difference between the fractional numbers of itinerant f electrons in the two valence states. 

There is no single best form of the periodic table since the choice depends on the purpose for which the table is used. Some forms emphasize chemical relations and valence, whereas others stress the electronic configuration of the elements or the dependence of the periods on the shells and subshells of the atomic structure. The most convenient form for our purpose is the so-called long form with separate panels for the lanthanide and actinide elements (see inside front cover). There has been a lively debate during the past decade as to the best numbering system to be used for the individual... 

A technologically important effect of the lanthanide contraction is the high density of the Period 6 elements (Fig. 16.5). The atomic radii of these elements are comparable to those of the Period 5 elements, but their atomic masses are about twice as large so more mass is packed into the same volume. A block of iridium, for example, contains about as many atoms as a block of rhodium of the same volume. However, each iridium atom is nearly twice as heavy as a rhodium atom, and so the density of the sample is nearly twice as great. In fact, iridium is one of the two densest elements its neighbor osmium is the other. Another effect of the contraction is the low reactivity—the nobility —of gold and platinum. Because their valence electrons are relatively close to the nucleus, they are tightly bound and not readily available for chemical reactions. 

The rare earth elements (REE) are the lanthanides (defined as those elements with valence electrons in 4/orbitals), La, Ce, Pr, Nd, (Pm), Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb. Often included for analysis, because they behave in a chemically similar way, although strictly not REE, are the Group 3 transition metals Y and Lu. The radioactive lanthanide element promethium (Pm) is excluded from analysis, since it is not found in samples because of its short half-life. 

Quantum chemists have developed considerable experience over the years in inventing new molecules by quantum chemical methods, which in some cases have been subsequently characterized by experimentalists (see, for example, Refs. 3 and 4). The general philosophy is to explore the Periodic Table and to attempt to understand the analogies between the behavior of different elements. It is known that for first row atoms chemical bonding usually follows the octet rule. In transition metals, this rule is replaced by the 18-electron rule. Upon going to lanthanides and actinides, the valence f shells are expected to play a role. In lanthanide chemistry, the 4f shell is contracted and usually does not directly participate in the chemical bonding. In actinide chemistry, on the other hand, the 5f shell is more diffuse and participates actively in the bonding. 

Zintl phases remarks on their definition. We have seen that the Zintl phases may be considered as a group of compounds formed by an electropositive (cationic) component (alkali, alkaline earth metal, lanthanide) and an anionic component (for instance a main group element of moderate electronegativity). The anionic part of the structure may be described in terms of normal valence combination. 

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... 

The atomic spectra of the actinides are very complex and it is difficult to identify levels in terms of quantum numbers and configurations (6). The chemical behaviour of the elements is dictated by the configurations of the electrons around the nucleus and in the case of the actinides it is the competition between the 5/ 1 7 s2 and the 5 /n 1 6 d 7 s2 levels that dictates these chemical properties. A comparison of the /-energy levels of the lanthanides and the actinides shows that less energy is required for the promotion of the 5 / -> 6 d levels than for the 4/ -> 5 d levels in the lanthanides. As a result of this lower energy requirement by the actinides they have the tendency to display higher valences since the bonding electrons are more readily available. It is only at the commencement of the second half of the actinides that there is commencement of properties which echo those of the lanthanides. 

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. 

As mentioned, all of the elements in the lanthanide series possess similar physical properties and chemical characteristics. One of the major properties of these elements is that their valence electrons are not in their outer shells. In all 15 of the lanthanides, the outer shell is the sixth, or P, shell, which contains two electrons. For most of the 15 lanthanides, the fifth, or O, shell contains eight electrons (with three exceptions). It is the fourth, or N, shell (third... 

Symbol Ce atomic number 58 atomic weight 140.115 a rare-earth metal a lanthanide series inner-transition /-block element metaUic radius (alpha form) 1.8247A(CN=12) atomic volume 20.696 cm /mol electronic configuration [Xe]4fi5di6s2 common valence states -i-3 and +4 four stable isotopes Ce-140 and Ce-142 are the two major ones, their percent abundances 88.48% and 11.07%, respectively. Ce—138 (0.25%) and Ce—136(0.193%) are minor isotopes several artificial radioactive isotopes including Ce-144, a major fission product (ti 284.5 days), are known. 

Symbol Ho atomic number 67 atomic weight 164.93 a lanthanide series rare earth element electron configuration [Xe]4/ii6s2 valence state +3 metallic radius (coordination number 12) 1.767A atomic volume 18.78 cc/mol ionic radius Ho3+ 0.894A one naturally occurring isotope. Ho-165. 

Symbol Lu atomic number 71 atomic weight 174.97 a lanthanide series element an /-block inner-transition metal electron configuration [Xe]4/i45di6s2 valence -1-3 atomic radius (coordination number 12) 1.7349A ionic radius (Lu3+) 0.85A two naturally-occurring isotopes Lu-176 (97.1%) and Lu-175(2.59%) Lu-172 is radioactive with a half-life of 4xl0i° years (beta-emission) several artificial isotopes known, that have mass numbers 155, 156, 167—174, 177—180. 

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. 

Symbol Tb atomic number 65 atomic weight 158.925 a lanthanide series element an inner-transition rare earth metal electron configuration fXe]4/96s2 valence states -i-3, +4 mean atomic radius 1.782A ionic radii, Tb3+... 

Symbol Tm atomic number 69 atomic weight 168.93 a lanthanide series element a rare earth metal electron configuration iXe]4/i36s2 valence +2, -i-3 atomic radius 1.73 A ionic radius, Tm " " 1.09 A for coordination number 7 one stable, natural isotope Tm-169 (100%) thirty radioisotopes in the mass range 146-168, 170-176 ty, 1.92 years. 

Most transition metals of the three d-series in all their valency states exhibit ionic radii within the limits of 0.55 and 0.86 A, favourable to octahedral coordination. In fact higher coordination numbers are observed only in fluorides of the largest transition ions, above all in compounds of the lanthanide and actinide series. Therefore fluorides of those elements, though sometimes isostructural with compounds of the d-series, will not be discussed here. For information the books and reviews written by Spedding and Daane (291), Katz and Seaborg (181) and Kaiz and Sheft (182) may be consulted. 

In Fig. 1, the valences of the transition 3d-, 4d-, 5d-series are also plotted. As for what regards the spread of valences, an interesting observation is that, at least for the hght actinides (if not for the whole series), there is more similarity between the actinides transition elements than the actinides and lanthanides. 

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