Quantum Numbers and the Periodic Table

T H O M A S H . HAZLEHURST
Lehigh University, Bethlehem, Pennsylvania

HIS paper formulates and attempts to solve a

problem in the presentation of the Periodic Table
to elementary chemistry students. The more
modem texts (la-li) usually include a tabulation of
the distribution of electrons in shells or subshells for
each atom. In the tabulation, the shells are arranged,
quite naturally, according to the principal quantum
numbers of the electrons. Hence, when the transition
elements are reached (at Sc, No. 21), a shell already
"complete" in the sense of being chemically inert in
argon begins to find places for more electrons and actually acquires ten of them before it is "full." During
this process of completion of the third quantum shell,
there are two electrons in the fourth shell and the question inevitably arises: "Why do these two not 'fall
back' into the third shell, and, if the third shell is not
full a t argon, why is argon an inert gas?" The same
difficultiesarise for the other transition series commencing a t yttrium and lanthanum.
The question is either ignored or sidestepped in
most texts,' not, of course, because the authors did not
know the answer, but because it probably seemed a bit
beyond the comprehension of elementary students.
I t is proposed to present the actual explanation in
briefest outline and then to suggest a method of presentation suitable for elementary students and plausible
without being incorrect.
The capacities of shells with a given principal quantum number are fixed by (1) the rules governing the
permitted values of the quantum numbers and (2)
the Pauli Exclusion Principle. The permitted values
of the quantum numbers are:

quantum numbers, because 1 may have the values 0,

1, . . ., n-1, and for each value of 1 there are 21
1
values of m, and for each set of values of 1 and m there
are just two choices for s. Hence the capacity of the
nth quantum shell is

In Table 1 are listed the capacities of quantum

shells with given n. For comparison the lengths of the
periods in the Periodic Table are also inserted. There
is obviously a close relationship between the capacities
of the shells and the periods, for the numbers 2, 8, 18,
32 appear in both sets and in the same order, but the
numbers 8 and 18 appear twice in the lengtbs of the
periods. Why?
TABLE 1

Quantum shell number

Capacity
Period number
Capacity

1
2
1
2

2
8
2
8

3
4
5
18 ' 32
50
3
4
5
f
8
18
18

6
72
i
32

The nth quantum shell is actually a group of "subshells," for there are 2n3 electrons there and they do
not all have exactly the same energy. Actually, it is a
su&ciently good approximation for our purpose to
put all the electrons with the same n and 1 (but different m and s) into the same subshell, so that there
will be n subshells in the nth shell corresponding to the
n possible choices for 1. Frequently the tables showP;incipal quantum number
n
1 to m
ing electronic configurations of elements are arranged
Az~muthalquantum number
1
0 to n-1 (n values)
Magnetic quantum number
rn
-1 to +1 (21 + 1 values) by subshells.
s
-'/, or +I/, (2 values)
Spin quantum number
The order in which the shells or subshells are filled
The Pauli Exclusion Principle states that no two elec- is fixed by their relative energies, the electrons always
trons in the same atom may have the same values of all going into the available space of lowest energy. An
four quantum numbers. It follows that, for a given approximate arrangement of subshells by energies is
value of n, there are 2n2 different sets of values for the given by Pauling (2) and a modified diagram of the
same sort is shown in Figure
I t is clear that the 3d
Notable exceptions: DEMING( l h ) , FOSTERAND ALYEA * Fosren AND ALYEA(Id) have one of the same general type.
(Id).

subshell, although it belongs to the shell for which 7% =

3, lies higher in the energy scale than does the 4s snhshell and is therefore filled later.% The inert gases
come just where the largest gaps appear in the energy
diagram, that is, after the completion of subshells i s ,
2p, 3p, 4p, 5p, and Gp, respectively. The various subshells grouped together. between these positions have,
of course, exactly the capacities of the periods of the
Periodic Table, and each group might well he termed
a "valence shell" in distinction to the grouping of suhshells into "quantum shells."

the fact that there is no need to stress or, perhaps, even

to mention the designation of subshells by quantum
numbers, a bald statement that the numbering of the
suhshells "follows a convention established to facilitate
FIGURE
1.-ENERGYLEYELSOP
SHELLS
AND SUBSHELLS
OP ELECTRONS I N ATOMS. EACH
CIRCLECANHOLDTWO
ELECTRONS
Subrhrll

camcily

va
Irn<

10

14

Shr
No

SUGGESTED METHOD OF PRESENTATION

To present such material in such a fashion to firstyear students would be to create as many difficulties
as it would remove, hut there seems to he no need to
give the capacities of quantum shells a t all. It should
he feasible to start by stating that there are four types
of suhshells: s, p, d, and f,with capacities of 2, 6 , 10,
and 14 electrons, respectively. This should be followed
and illustrated by a diagram like Figure 1, in which the
arrangement of subshells according to energy levels is
shown. Each circle represents a place to put a pair of
electrons. This diagram, in connection with the intuitively plausible rule that electrons always seek the
lowest available position, justifies the locations of the
inert gases (at the wide gaps in the energy levels) and
indicates the other properties of the Periodic Table.
The group of subshells 4s, 3d, 49 would constitute the
fourth eralence shell, and the fact that several subshells
are involved will justify the variable valence of the
transition elements. Similarly, the fifth valence shell
is composed of 5s, 4 4 5p, and the sixth valence shell
of Ss, 4f, 53, Op.
Such an approach deliberately avoids the series of
numbers 2, 8, 18, 32, 50 which must be reconciled with
the Periodic Table and uses immediately the actual set
of numbers 2, 8, 8, 18, 18, 32 appropriate to the Table.
The usual tabulation of electron configurations using
subshells can still he employed if the order of the suhshells is that given in Figure 1 rather than that of the
principal quantum numbers. It is true that the question may still arise: "Why does the fourth valence
shell contain a subshell numbered '3'?" Aside from
The exact order of these energies changes in a fairly complex
manner as the nuclear charge increases (3). but the general aspects of the diagram are correct.
a

the interpretation of spectra" will probably sound sufficiently profound to be accepted and too abstruse to
be questioned further.

LITERATURE CITED

(1) Among others:

(I) HILDEBRAND,
"Principles of chemistry," The Macmillan

(a) BRINKLBY,
principle^ of general chemistry," The Mac-

millanCo.. New York City, 1941, p. 248ff.

(b) DEMING,
"Fundamental chemistry," John Wiley and
Sons, Inc., New York City, 1940, Chapter 21.
(c) ELDER,
"Textbook of chemistry." Harper and Brothers,
New York City, 1941, p. 55 ff.
(d) FOSTER
AND ALYEA,"An introduction to general chemistry," D. Van Nastrand Co., Inc., New York City, 1941,
p. 317.
(8)

GORDON
AND TROUT,
"Introductory college chemistry,"
John Wiley and Sons, Inc., New York City, 1940, p.
361 ff.

Co.,New York City, 1940,.p. 248ff.

(g)

HOPKINS,
"General chem~stry,"D. C. Heath and Co..
Boston, 1937, p. 26.

(h) MCPHERSON,
HENDERSON,
FERNELIUS,
AND MACK,
"Chemistry," Ginn and Co., Boston. 1940, p. 238.

(i) RICHARDSON
AND SCARLETT,
"General college chemistry,"

(2)

Henry Holt and Co., New York City, 1940, p. 212.

PAWLING,
"Nature of the chemical bond," 1st ed.. Cornell

(3)

RWARK
AND UREY, "Atoms, molecules, and quanta," M c -

University Press, Ithaca, N . Y., 1939, p. 26.

Graw-Hill Book Co., Inc., 1930, p. 245ff.