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The kevs to understandine ohvsical ~rooertiesand ther- Before discussing this further let us review the relative
modynamic and kinetic aspeck df reac;iviiy clearly include energies of s and p electrons for several second- and third-
(11 knowledge of the energy levels availahle to electrons in a period elements. Figure 1 is a plot of differences between
species and 72) the extentto which these levels are populat- successive ionization energies (5)for atoms of Ne through P.
ed. Virtually every introductory text, whether at the second- (Other elements for which ionization energies are availahle
ary or college level, therefore describes the quantization of can be used without any substantial difference in the inter-
atomic energy levels; many, if not most, also a t least refer to pretation.) Figure 2 is a plot of differences between first
molecular orbitals. In fact, inadvisable as i t is, even some ionization energies for successive second- and third-period
seventh and eighth graders are being required to memorize elements. The striking thing illustrated in these is that the
eround-state electron confieurations for common elements. difference between the energy required to remove an elec-
- Two recent articles in t&s Journal have contributed to tron from a filled p subshell and that needed for the fifth
readers' knowledee of certain seeminelv anomalous oxida- electron is part of a regular series of such differences for the
tion states of thetransitional (1) a n d h t h a n o i d (1-3) ele-
ments. "The calculation of formation enthalpies", however,
cannot serve as "the key to understanding the relative stabil-
ities of lanthanide oxidation states." Thermodynamics al-
ways yields predictions, albeit precise ones, of one kind of
thermodynamic data from related thermodynamic data,
never from the fundamental keys to understanding in atom-
ic and molecular structure. Certainly we need both the pre-
cise thermodynamics and these other really basic consider-
ations. However, the promise of the usefulness of electronic
structures for a deeoer anoroach to chemistrv is still severelv
limited by thecompleni;i& of evaluatingen& levels to thk
rewired r recision. Thus. at the introductorv level. we show
what canbe done with cl'assical thermodynakics and kinet- +
ics; then we try to give students a "feeling" for the underly- g 2, ,
u.-"
ing reasons by qualitative reference to the character of the 1.5
fundamental particles. (2d-2$) (z$-z~I (~$2~3 (zp2-2;) (2p'-2pZ)
The broadest concept for relating the nature of those
particles and their behavior is chemical periodicity. The Configurations compared
success of the correlation is so apparent that it serves as the
Figwe 1. Differences between lonlznilon energies far successive elecmrns
framework for discussing the descriptive chemistry of the within the same atom.
elements, and hence is familiar to practically every begin-
ning student. There are "problems", however, with the sim-
plest efforts a t correlation using the periodic chart alone, for
example, Why do Cr and Nb have s1 ground states? Why is
3+ chemistry so much less prominent with Mn than with Cr
and Fe? Or why are Sm2+,Eu2+,and Yb2+the only stable 2+
lanthanoid ions found in water?
The "explanation" for these ohservations is often given as,
for example, "the tendency for one electron to be present in
each of the five 3d orbitals" and as "the relative stahility of
systems in which each of the f orbitals is 'half filled"' (1).
The following more extreme example from a contemporary
freshman chemistry textbook (4) is not really unique: "This
anomalous behavior is partly due to the special stability
associated with precisely half-filled sets of degenerate orbi-
tals" (our italics).
Related statements would in fact be quite legitimate and
useful if presented only as summaries of ohservations, with
the real reasons possibly to be examined later. There is a
correlation between filled or half-filled subshells and stable
oxidation states, but an emphasis on these configurations Configurations compared
alone may convey to the student the impression, whether
intended or not, that there is a tendency toward such struc- Figure 2. Differencesbetween first ionizationenergies for successive serond-
tures per se. and third-period elements.