Periodicity and Some Graphical Insights on the

Tendency toward Empty, Half-full, and Full Subshells

Ronald L. Rich and Robert W. Suter
Blumon College, Bluffton. OH 45817

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.

702 Journal of Chemical Education

Figure 3. Energies (schematic) and occupancies (entries in Ib figure) of the
outer orbitals of isolatedatoms of the 3dand 4d elements in their groundstates
VS. atomic number. The two big d m in each graph show the intersectionsthat
are not adjustable.
other n electrons. Successive electrons do reauire additional
energ;, but this increase is remarkably reguiar for a given p
subshell, and reflects essentially the increased effective nu-
clear charge. T o the precision shown on this plot there is no
extra stability for a filled p subsbell, compared with the pS
configuration, that cannot be accounted for by factors influ-
encing the energies of the other p electrons. Likewise, when
one c&npares the energy required to remove an electron
from the half-filled p subshell with that needed for a p2
structure, nothing sperial is found.
There is something special about the difference between
the ionization enerw for o4and that for n'. but this is clearlv
~~~ ~ ~
due to the ~oulomcinteiactionof two eieitrons in the sank
orbital in a n4 confieuration. Similarlv. the large energv
difference between el&trons in 3s' and i p 6 config&ations%
readily explained by the difference in principal quantum
number; this again indicates no more "extra" stability of a
filled n subshell than i t does for ap5or any other structure in
whichthe electron being removed is at the lower principal
quantum level.
We turn next to the d orbitals, using a slightly different
approach toward similar goals. Figure 3 shows, with minor
modifications, two of six related graphs presented earlier (6)
hut perhaps not known to many readers. Here we plot the
enereies schematicallv versus atomic number in such a way
as tolead to the correct configuration within each neutrai,
isolated atom. while remainine aware that most chemistrv
does not startaith such atom:
The extra Coulomb energy for electrons that are paired in
orbitals has already been mentioned. Partly for clarity in the
figure we assign all of the extra energy of pairing to the
"second" of the two electrons. This gives us two approxi-
mately parallel curves for the energies in each subsbell, the
lower one for unpaired electrons and the higher for the
paired ones. I t also reflects the fact that when one electron
leaves, i t does carry with i t essentially all of the pairing
energy. (We note, incidentally, that only two intersection
noints in each - eranh -
. in Fieure 3 must be set without anv
leeway in order to interpret the electronic configurations for
10 elements in each case.) We consider, then, that the pair-
ing energy effectively divides each subshell into a low-energy
half and a hieh-enerev half. This seuaration, though illus-
trated differently here, is of the same-sort as brought out for
p electrons in Figure 2.
What does this mean for electron configurations? Elec-
trons will occupy the lowest available energy levels. Because
Figure 4. Energies (schematic) and occupancies (entries in the figure) of the
outer orbitals of MZt and M3+of the 41 elements in their ground states, but not
isoiated, VS. atomic number. The dashed lines sloping gently down to the right
represent the negative energy that can be overcome by an oxidant-iigand
combination in the medium: this is more negative for the smaller ions to the
right. The upper dashed line represents water as the oxidant: the lower one.
any aqueous oxidant with a standard potential of at least 1.7 V.
there are five such vacancies before the energy rises sharply,
five electrons, or a tendency toward five in a d subshell,
should occur frequently, buttbere is clearly nothing magical
about the group of five.
Figure 4 deals with the ions of the 4 t elements, and again
has a somewhat different basis, partly in order again to bring
out some additional points. (Boldface symbols here desig-
nate regions of the periodic chart (6), as opposed to regular
roman type for types of orbitals.) The spectra of these ele-
ments are complex, and not all the relevant energies are well
known. Therefore, and because the ions are here assumed to
be surrounded by other species, for example, in an aqueous
solution. the eneraies are given onlv schematically.
The sioping dashed lines represent the energies above
which an electron is lost to the strongest oxidant(s) in the
medium. These lines reflect lower energies toward the right
as the smaller 4 f ions with greater effective nuclear charge,
and hence smaller radii (7,8), interact more strongly with
the ligands after oxidation. The upper dashed line corre-
sponds to water itself as an oxidant, the lower one to any of
several strong oxidants in water, or to a standard electrode
potential (IUPAC) of a t leastC+1.7 V.
We see that SmZC,EuZf, and Yb2+ are the only stable M2+
ions in water, and we note that E u ~ and
+ Yh2+have exactly
half-full or full subshells, while Sm2+is sometimes said to
show a tendency toward the former configuration. The fig-
ure shows all values of occupancy of each half subshell from 1
to 7 on a straight line, analogously to Figure 3. At the same
time we see again that starting a new half subshell would
indeed lead to (suddenly) higher energies for the "highest"
electron of the next several elements. hence to that elec-
tron's easy removal by aqueous oxidants.
Readers will notice the chanee of slooe at the point of half
filling a subshell. After this point we have Ghat can be
considered the normal slope for a constant configuration.
Before this we have the effect of increased lowering of ener-
gies due to the rising number of electrons of the same spin,
yielding greater (negative) quantum-mechanical "exchange
Volume 65 Number 8 August 1986 703
energies". This is less significant in the p and d suhshells,
which have fewer electrons. (Still, additional exchange even
between singly occupied s and d orbitals, together with the
other factors, helps stabilize 4s13d5in Cr and 5s14d4in Nb,
for example.) T o rationalize the important results even for f
electrons, however, does not require us to consider this phe-
nomenon further.
On related aspects of periodicity, the periodic chart re-
cently recommended by the IUPAC has provoked much
discussion. The present authors originally shared the fre-
quent impression that the new form was being adopted as
the only official one. Actually, however, the purpose is sim-
ply to eliminate the amhiguity-costly for all of us directly
or indirectly-especially for abstracting and indexing pur-
poses, of the A and B suhgroups, and to have a way of doing
this consistent with the widely used tables that have gaps in
the middle and have the inner-transition elements a t the
bottom (9).
Also in connection with the problem of placing some ele-
ments into periodic charts it is stated ( I ) that "The one
characteristic Zn possesses in common with Co2+, Ni2+,
Cu2+,etc., is approximate size." We note, however, various
chemical similarities of Zn2+ (not shared with ions from
other regions of the periodic chart), including the tendency
to form stable complexes with ammonia, cyanide ion, and so
forth. These justify, hut of course do not by themselves
necessitate, classifying the zinc group as transitional.
Summary
On the one hand there is no magic in empty, half-full, or
full suhshells, or in empty or filled shells, for that matter. On
the other hand there are certainly far more such structures
than would he expected randomly. The abundance of such
704 Journal of Chemical Education
configurations is not the result of a special driving force
toward precisely these configurations per se. The d5 struc-
tures occur more frequently than the d6 (or higher interme-
diate) ones because the sixth or subsequent electrons in such
configurations have additional energies as a result of the
Coulomb repulsion. These higher energies cause such elec-
trons to be readily lost to another subshell or to even mild
external oxidants. The d5 configurations also occur more
often than the d' (or lower intermediate) ones mainly be-
cause the absence of the Coulomb repulsion in any empty
orbitals helm such orbitals accept an electron, perhaps from
an s2pair or a surrounding reductant. The exchangeenergy
is a smaller contributor. Analogous arguments
- can he made
for f electrons.
We thus need to explain the observed tendencies in elec-
tron structures by stressing the energy differences due to one
or more of the following:
1. occupancy of differing shells,
2. occupancy of differing suhshells within a given shell,
3. double occupancy vs. single occupancy of an orbital,
4. quantum-mechanicalexchange.
Literature Cited
1. Fcmeiius, W. C. J. Chem Edue. 198463,263;on the periodic table.
2. Smith. 0. W. J. Chem. Educ. 1986.63, 228: on ".. . the Enthaipi~sof Formation of
LsnthenideHalides and Oxides':
3. Chriatianaen,J.A. J. Am. Chem. Sot. 1960,62,5526.Hare theAm.Chem. Soe. r m m -
mended the term "lsnthanoid", avoiding the "ide"e"ding for this vasge.
4. Bmvn,T. L.: Lemqv, H.E., Jr. Chrmlalry:The CentrolScionea,3rdod.;Prcatiee-Hall:
Englewaod Cliffs. NJ. 1965; p 162.
5. Mwre, C. E. "Ionizstion Potentials and Ionization LimitsDerivedfmm the Analyaisof
OpticslS~tra:'NSRDS-NBS,34.NationaiBumauofStandsds:U.S.Governmenl
p;intin6omee:waahingtan, IWO.
6. Rich, R. Periodic Correlonions; Benjamin: New York. 1965; 0 9 (some unex~iained
. .
9. simn,~.
E., Chemical Ahstrads Service. personal communication, 1986