Lanthanide series atomic radii

As one traverses through the lanthanide series, there is a reduction in the cation size as the atomic number increases. This results in small differences in the strength of interactions of the ligand with the lanthanide ions. These trends are reflected in the IR spectra of these complexes in a few cases. Cousins and Hart (203) have observed an increase in Pp Q with decreasing lanthanide ion radius for the complexes of TPPO with lanthanide nitrates. This observation has been attributed to an increase in the Ln—O bond strength with an increase in the atomic number of the lanthanide ion. 

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 Dy atomic number 66 atomic weight 162.50 a lanthanide series, inner transition, rare earth metal electron configuration [Xe]4 5di6s2 atomic volume 19.032 cm /g. atom atomic radius 1.773A ionic radius 0.908A most common valence state +3. 

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 La atomic number 57 atomic weight 138.91 a rare-earth transition metal, precursor to a series of 14 inner-transition elements known as the lanthanide series electron configuration [XejSdiGs oxidation state -i-3 atomic radius 1.879A ionic radius (LaS+) 1.061A electronegativity 1.17 two natural isotopes are La-139 (99.911%) and La-138 (0.089%). 

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 Pm atomic number 61 atomic weight 145 a lanthanide series inner-transition metal electron configuration [Xe]4/56s2 partially filled f orbitals valence states -i-3 ionic radius Pm " 0.98A aU isotopes of promethium are radioactive twenty-two isotopes in the mass range 134-155 longest-lived isotope Pm-145, ti/2 17.7 year shortest-bved isotope Pm-140, ti/2 9.2 sec. 

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. 

The atomic radii of the second series of d-metals (Period 5) are typically greater than those in the first series (Period 4). However, the radii in the third series (Period 6) are about the same as those in the second row and smaller than expected. This effect is due to the lanthanide contraction, the decrease in radius along the first row of the f block (Fig. 16.4). This decrease is due to the increasing nuclear charge along the period coupled with the poor shielding ability of -electrons. When the d block resumes (at lutetium), the atomic radius has fallen from 224 pm for barium to 172 pm for lutetium. 

One property of a transition metal ion that is particularly sensitive to crystal field interactions is the ionic radius and its influence on interatomic distances in a crystal structure. Within a row of elements in the periodic table in which cations possess completely filled or efficiently screened inner orbitals, there should be a decrease of interatomic distances with increasing atomic number for cations possessing the same valence. The ionic radii of trivalent cations of the lanthanide series for example, plotted in fig. 6.1, show a relatively smooth contraction from lanthanum to lutecium. Such a trend is determined by the... 

The decrease in radius in moving from La3+ to Lu3+ is 117.2 to 100.1 pm which is less than 114-88 pm for elements Ca2+ to Zn2+. In the case of Sc3+ to Ga3+, the radius decreases from 88.5 to 76 pm. This comparison shows that the percent contraction is greater in the case of Sc3+ to Ga3+ and Ca2+ to Zn2+ series than lanthanides series. The fact is that the magnitude of the lanthanide contraction is small and the usual interpretation of magnetic and spectroscopic properties of the lanthanides are inconsistent with the idea of considerable shielding of 4/ electrons from the chemical environment of the ion by the 5s25p6 configuration. Thus the implication that the size of lanthanide atoms or ions is determined by the 4 fn subshell must be incorrect. 

These are listed in Table 2.3 and shown in Figure 2.4. It will be seen that the atomic radii exhibit a smooth trend across the series with the exception of the elements europium and ytterbium. Otherwise the lanthanides have atomic radii intermediate between those of barium in Group 2A and hafnium in Group 4A, as expected if they are represented as Ln + (e )3. Because the screening ability of the f electrons is poor, the effective nuclear charge experienced by the outer electrons increases with increasing atomic number, so that the atomic radius would be expected to decrease, as is observed. Eu and Yb are exceptions to this because of the tendency of these elements to adopt the (+2) state, they have the structure [Ln +(e )2] with consequently greater radii, rather similar to barium. In contrast, the ionic radii of the Ln + ions exhibit a smooth decrease as the series is crossed. 

Filling of the inner 4f electron shell across the lanthanide series results in decreases of ionic radii by as much as 15% from lanthanum to lutetimn, referred to as the lanthanide contraction (28). While atomic radius contraction is not rmique across a series (i.e., the actinides and the first two rows of the d-block), the fact that all lanthanides primarily adopt the tripositive oxidation state means that this particular row of elements exhibits a traceable change in properties in a way that is not observed elsewhere in the periodic table. Lanthanides behave similarly in reactions as long as the mnnber of 4f electrons is conserved (29). Thus, lanthanide substitution can be used as a tool to tune the ionic radius in a lanthanide complex to better elucidate physical properties. 

The lanthanide or rare earth elements (atomic numbers 57 through 71) typically add electrons to the 4f orbitals as the atomic number increases, but lanthanum (4f°) is usually considered a lanthanide. Scandium and yttrium are also chemically similar to lanthanides. Lanthanide chemistry is typically that of + 3 cations, and as the atomic number increases, there is a decrease in radius for each lanthanide, known as the lanthanide contraction. Because bonding within the lanthanide series is usually predominantly ionic, the lanthanide contraction often determines the differences in properties of lanthanide compounds and ions. Lanthanide compounds often have high coordination numbers between 6 and 12. see also Cerium Dysprosium Erbium Europium Gadolinium Holmium Lanthanum Lutetium Praseodymium Promethium Samarium Terbium Thulium Ytterbium. 

Excepting effects which are clearly 4f configuration/redox in origin, reactivity trends across the lanthanide series are usually associated with differences in Lewis acidity/electrophilicity and steric interactions. Each of these effects, in turn, is necessarily sensitive to the falling metal ionic radius with increasing atomic number. The quantity D(I M-H) - D(I M-alkyl) is a crucial thermodynamic determinant for a number of important homogeneous catalytic reaction components, such as )9-H elimination (Equation... 

Abstract This chapter discusses the chemical and physical properties of the lanthanides, some of which are in a certain way peculiar. It discusses the oxidation states of the REE, and the phenomenon called the lanthanide contraction (meaning that the atomic radius decreases with increasing atomic number in the series lanthanum-lutetium). It lists the isotopes known per element, and explains the radioactivity of promethium, the only element of the rare earths that has only radioactive isotopes and no stable isotopes. Magnetism and luminescence also are discussed. 

In the periodic system, the lanthanide group of elements also gives rise to a peculiar phenomenon, called the lanthanide contraction. This phenomenon is the important and progressive decrease in atomic radii and in radii of ions when going from lower to higher atomic numbers in the lanthanide series. Thus lanthanum has the largest atomic radius, and lutetium has the smallest. In Table 3.3, the ionic radii for the lanthanides are given, and the effect described above can be clearly seen in Fig. 3.2. 

Also as a result of the lanthanide contraction, yttrium has an ionic radius comparable to that of the heavier REE species in the holmium-erbium region. If the effective ionic radius (Shannon 1976) of is plotted (0.90 A)., it plots in between element 67 (Ho) and 68 (Er). Scandium (effective ionic radius is 0.745 A), plots outside of the Lanthanide series. As also the outermost electronic arrangement of yttrium is similar to the heavy rare earths, the element behaves chemically like the heavy rare earths. It concentrates during (geo)chemical processes with the heavier REEs, and is difhcult to separate from the heavy REEs. Scandium, on the other hand, has a much smaller atomic radius, and the trivalent ionic size is much smaller than that of the heavy rare earths. Therefore, scandium does not occur in rare earth minerals, and in general has a chemical behavior that is significantiy different from the other rare earth elements (Gupta and Krishnamurthy 2005). 

The experimental lattice parameters as a function of lanthanide atomic number show the famous lanthanide contraction, the decrease of the lattice parameter across the lanthanide series, with the exception of the two anomalies for Eu and Yb, as seen in Figure 1 (top panel). What is plotted there b actually the atomic sphere radius S (in atomic units) as a function of the lanthanide element A similar behaviour is abo observed, for example, for lanthanide monochalcogenides and monopnictides, whose lattice parameters are abo shovm in Figure 1 (middle and bottom panels). 

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