Atkins_4e_Ch01_p56 4/24/07 2:12 PM Page 39

1.14 ELECTRONIC STRUCTURE AND THE PERIODIC TABLE

39

elements. Hydrogen occupies a unique position in the periodic table. It has one
s-electron, and so it belongs in Group 1; but it is also one electron short of a noblegas configuration, and so it can act like a member of Group 17/VII. Because hydrogen has such a unique character, we do not ascribe it to any group; however, you
will often see it placed in Group 1 or Group 17/VII, and sometimes in both.
The s and p blocks form the main groups of the periodic table. The similar
valence-shell electron configurations for the elements in the same main group are
the reason for the similar properties of these elements. The group number tells us
how many valence-shell electrons are present. In the s block, the group number (1
or 2) is the same as the number of valence electrons. This relation is also true for
all main groups when the Roman numerals (IVIII) are used to label the groups.
However, when the group labels 118 are used, in the p block we subtract 10 from
the group number to find the number of valence electrons. For example, fluorine in
Group 17/VII has seven valence electrons.
Each new period corresponds to the occupation of a shell with a higher principal
quantum number. This correspondence explains the different lengths of the periods.
Period 1 consists of only two elements, H and He, in which the single 1s-orbital of
the n  1 shell is being filled with its two electrons. Period 2 consists of the eight elements Li through Ne, in which the one 2s- and three 2p-orbitals are being filled with
eight more electrons. In Period 3 (Na through Ar), the 3s- and 3p-orbitals are being
occupied by eight additional electrons. In Period 4, not only are the eight electrons of
the 4s- and 4p-orbitals being added, but so are the ten electrons of the 3d-orbitals.
Hence there are eighteen elements in Period 4. Period 5 elements add another 18 electrons as the 5s-, 4d-, and 5p-orbitals are filled. In Period 6, a total of 32 electrons are
added, because 14 electrons are also being added to the seven 4f-orbitals. The f-block
elements have very similar chemical properties, because their electron configurations
differ only in the population of inner f-orbitals, and electrons in these orbitals do not
participate much in bond formation.
The blocks of the periodic table are named for the last orbital to be occupied
according to the building-up principle. The periods are numbered according to
the principal quantum number of the valence shell.

THE PERIODICITY OF ATOMIC PROPERTIES

The periodic table can be used to predict a wide range of properties, many of
which are crucial for understanding chemistry. The variation of effective nuclear
charge through the periodic table plays an important role in the explanation of
periodic trends. Figure 1.45 shows the variation for the first three periods. The
effective charge increases from left to right across a period and falls back sharply
on going to the next period.
7

Ar
Cl

Effective nuclear charge, Zeff

Ne
S
F

O
4

Si
Al

N
Mg

Na

B
2

Be

He
Li

9
11
13
Atomic number, Z

15

17

FIGURE 1.45 The variation of the

effective nuclear charge for the outermost
valence electron with atomic number.
Notice that the effective nuclear charge
increases from left to right across a period
but drops when the outer electrons
occupy a new shell. (The effective
nuclear charge is actually Zeffe, but Zeff
itself is commonly referred to as the
charge.)