The Positions of Lanthanum (Actinium] and Lutetium (Lawrencium] in the Periodic Table William B. Jensen University of Wisconsin-Madison. Madison, WI 53706

The debate as to whether lanthanum and actinium or lu- tetium (and, more recently, lawrencium) should be placed in erouo IIIB of the neriodic table alone with scandium and vt- .. . trium (or rquiv:ilintly, in electronic tirrns, which pair ihodd he considered as r he iirsr memhrrs ofthe d block ior periuds 6 and 7) has a long, but poorly publicized, history. or quite some time i t has been known that yttrium, and, to a lesser degree, scandium are closer in their chemical properties to lutetium and the other heavy rare earths than they are to lanthanum (1,2) and on this basis alone a number of chemists in the 1920's and 1930's assigned lutetium rather than lan- thanum to erouo IIIB (3). The current consensus. which olaces ,. . . . lanrhanum and actinium in this position instead, appears to have evolved during the 194O's a h , : with the u s e d oeriodic tahles based on electronic configurkion and the concept of the differentiating electron.

Early spectroscopic work on the rare earths seemed to in- dicate that the ground states of their atoms had, with few exceptions, an electronic configuration of the form [Noble Gas](n - 2)fx-'(n - l)d'ns2. Indeed, this was thought to conform to the "ideal" electronic configuration for the f-block elements in general (2). Thus, ytterbium was assigned the

ground state [Xe]4f135d16s2 and lutetium the ground state [Xe]4f145d16s2, resulting in a 4f differentiating electron for lutetium and firmly establishing it as the last member of the f-block for period 6. Barium, on the other hand, had the con- figuration [Xe]6s2 and lanthanum the configuration [Xe]. 5d16s2, thus giving lanthanum a 5d differentiating electron and establishing it in group IIIB as the first member of the d block for period 6. This assignment for lanthanum appeared to be further justified by the analogy between its configuration and the configurations of the other members of group IIIB: Sc = [Ar]3d14s2 and Y = [Kr]4d15s2.

More recent spectroscopic work, however, has revised the earlier electronic configurations (4). Only three of the rare earths in period 6 (La, Gd, and Lu) are now known to have the ground state [Xe]4p-'5d16s2, all of the rest having the con- figuration [Xe]4fx6s2. In period 7 only six of the actinides (Ac, Pa, U, Np, Cm, and Lr) have the old configuration. Thorium has the configuration [Rn]6d27s2 and the remaining eight the configuration [Rn]5f*7s2. This strongly suggests [Noble Gas] (n - 2)fis2rather than [Noble Gas](n - 2)fX-Vn - l)dlns2 as the ideal ground state configuration for the f-block elements in general. Ytterbium and nobelium now have the configu-

Revised version of the currently popular medium-length block form of the periadictable.

634 Journal of Chemical Education

ration [Nohle Gas](n - Z)P4ns2 and lutetium and lawrencium the configuration [Nohle Gas](n - 2)f14(n - l)d1ns2, resulting in a d rather than an f differentiating electron for both lute- tium and lawrencium and makine them eouallv valid candi- . . dnws for the first memhers of the d block in periods ti and 7. On the other hand. the IRn16d27s%onfirurati#tn for thorium. which no one doubts is'au )-block element with an irregula; configuration, strongly sul,pc,rts the supposition that both lanthanum and actinium should be cons~dered as f-t~lock PI- ements with irregular configurations derived from the ideal configuration [Nohle Gas](n - 2)f1ns2. In other words, lan- thanum and actinium should be considered the first memhen of the f hlock (rather than Ce and Th), ytterbium and nohel-

Atomic Radiis

l Al

1. Periodlc Trends in Various P

Sum of the First TWO Ionization

POtentiaI~* (eV)

1 9 . z \ y 1 8 . 6 1 1 ~

17.04 versus

ium should he considered t1.e last members of the f hlock (rather than Lu and Lr), and lutetium and lawrencium (rather than La and Ac) should be considered the first memhen of the d hlock in periods 6 and 7 and assigned to Group IIIB along with scandium and yttrium.

The argument that the total (i.e., core plus valence) elec- tronic configurations of lanthanum and actinium are closer to those of scandium and vttrium than are the confieurations - ~ ~~

of lutetium and l a w r e n c h (due to their filled (n - 2)f'4 suhshells) is misleadins. One must consider intraoeriod as well as intragroup analog&. Thus, the remaining kine d-block elements of period 6 (Hf - Hg) all have the complete [Xe]4f14 core like lutetium and not just the [Xe] core of lanthanum.

lrtles tor the First Part of the d-BI(

Melting Pointb

(OK)

F m m ref. (I). 'Data hom ref. (f8)

Volume 59 Number 8 August 1982 635

Likewise, in oassine down the columns of the d hlock from Table 2. A Comparlson 01 Vartous Prowrttes of Sc and Y versus Ti-Zn one alkavs t:&,uniers the addition of the 4f1'subshell on passinr from period 5 to period 6. In short, if one wishes to usi analogies hased on trehds in the configurations of the cores, eighteen of these analogies favor the assignment of lu- tetium and lawrencium to Group IIIB and only one favors the assignment of lanthanum and actinium.

Areuments of this nature were nut forward hv Luder in - favor of the reassignmellt of lutetium and lawrencium over a decade ago but appear to have gone unnoticed (5,151. Like- wise, the Russian chemist Christyakov, using periodic trends in ionization potentials and atomic radii, arrived a t the same conclusion ( f a ) . One may also add to this list trends in ionic radii, redox potentials, and electronegatives, as well as the chemical hehavior of scandium and yttrium mentioned earlier. The most compelling evidence, however, has heen presented by the physicists ( s13) . This includes comparisons of trends in the melting points of the elements (11,J2), their crystal structures at room temoerature (11). the crvstal structures of their oxides and various intermktaiiic compounds ( l l ) , the structures of their excited state soectra (11 ).their suoercon- ductivities (10, 11), and the strukures of t'heir condktivity hands as revealed by X-ray isochromats (13). All of these properties unanimously favor the placement of lutetium and lawrencium, rather than lanthanum and actinium, in group IIIB. Some example data are summarized in Tables 1 and L.

In fact, so overwhelming is the evidence for this assignment that Mazurs adopted i t in the 1974 edition of his classic monoeranh on the oeriodic tahle (14). However. a auick ex- amination of over gfteen freshman chemistry tektsind four popular inorganic texts published since 1975 revealed that none of them had revised their periodic tables (15). Indeed, in talking with his fellow chemists, the author discovered that none of them was aware of the evidence favoring the reas- signment of lutetium and lawrencium or indeed that there ever was any question about their placements (a category in which the author must include himself until very recently). As chemists, the periodic tahle is presumed to he-our special province; surely its about time we pay attention to what the physicists have to tell us ahout its arrangement. A revised version of the currently popular medium-length hlock form of the table is shown above.

Literature Cited

. . -. . . . . .. .. New York. 1961. Chap. 2.

(3) See, forexampie, Shemyskin, F. M.,Zh. Obshch. Khim.2.62 11932) andHury, C.R., J. Amer Chem Soc., 43,1602 (1921). Further examples can he found in reference 114).

~ ~~~-

thore 01 Lu and La

Propew

Highest common oxidation state

Precipitation of sulfate in fractional crystallization'

Stlllcture of metal at r m m temperatureb

Shlcture of oxide (M20s)"'

Y group Y group Y group Ce group

special hCP hCP hcp double hcp

:[AB~,.]C %%NIc S ~ A B ~ ~ ~ I C special hex. CN-7

A-MIOO

Presence of low-lying No NO No Yes nonhydrogenic I-orbitals

&Block-like structure Yes Yes Yes NO for conduction bandd

S u p e r ~ o n d u c t i v i t y ~ ~ ~ NO No No Yes (4.g°K)

Ref. (1) "el. (17) ORel. (11) 'Ref. (13) . R~I . (14 ' Ms~trchk ln igg l l m a d i ~ t i o n f m u l a s

(1968). His count far the lanthanides, however.bifferswith regard to Ce fmh <hat i n Moore. I. C.. "Inorganic Potentlala and Ionization Limits Derived from t h e Analyses of Optical Spectra,(' NSRDS-NBS 34, National Bureau of Standards, Washington, DC, 1970.

(5) Luder. W. F.."TheElwtron-RopulsionThmmof QeChemiealBond,('&inhold,Ncw York, 1967,Chap. 2.

(6) Luder, W. F.,Con. Chem. Edue.,513), 13(1970). (7) Christyakov, V. M., Zh. Obshch. Khim., 38(2), 2W (1968): Engl. Ed., 38(2), 213

(1968). Christyskov. V. M., Vests; Akad. N o d &lore. SSR, Sol. Khim Nouuk, 13, 50

(1968): Chem. Abst., 70.61016h (1970). Landau.L. D.,sndLibhitz,E. M.."QuantumMeohsnies,((Pugamon.London. 1959,

p. 245, footnote Hamiltan, D. C., and Jenaon, M. A,, Phys. R m Letter?, 11,205 (19631. Hamiltan, D. C.,Amer. J Phys, 33,637 (1965). Matthias, B. T.. Zaehariscn. W. H., Webb, G. W., and Ewdhardt. J. J.. Phya. Re".

~, ~~, ~- , - ~ ~ , Mcrz, H., and Ulmer, K.,Phw Letters, 2646 (1967). MUUS, E. G.. "GraphieRepresentstionaof thcPariodieSystemDuring One Hundred

Years" Uniu. Alabama Press, University, Alabama, 1974. oneexaption to thislist is theinoreanictelt by Lsgmki.which, however,waspub-

lishad before 1975. Heme8 the long formof t h e periodictable pmposed by Werner and places bath Lu and Lr in group I I l B See Legomki. J. J., "Madem lnowanic Chemistry,"Dekker. NcwYork, 1978, p. 38and pp.602605.

Ball, M. C., and Norburg, A. H., "Physical Data for Inorganic Chemists," Longman, London. 1974.

Weiis, A. F., "Structural Inorganic Chemistry:' 4th Ed.. Clanndon P-, Oxford, 1975.

636 Journal of Chemical Education