The Periodictable 17

THE PERIODICTABLE 17
period, although not quite regularly, and fall as we descend a group,

for example lithium to caesium. The fall in ionisation energy as we
descend a group is associated with the change from non-metallic to
metallic character and is very clearly shown by the Group IV elements,
carbon, silicon, germanium and tin. Here then is a link between the
physico-chemical property ionisation energy and those chemical
properties which depend on the degree of metallic (electropositive)
character of the elements in the group.
If we consider the successive (first, second, third . . .) ionisation
energies for any one atom, further confirmation of the periodicity of
the electron quantum levels is obtained. Figure 1.7 shows a graph of
Iog10 (ionisation energy) for the successive removal of 1, 2, 3 , . . . 19
electrons from the potassium atom (the log scale is used because the
changes in energy are so large). The stabilities of the noble gas
configurations at the 18 (argon), 10 )neon) and 2 (helium) levels are
clearly seen. The subject of ionisation energies is further discussed in
Chapters 2 and 3.
MELTING AND BOILING POINTS

Both melting and boiling points show some periodicity but observ-
able regularities are largely confined to the groups. In Group O, the
noble gases, the melting and boiling points of the elements are low
but rise down the group; similarly in Group VIIB, the halogens, the
same trend is observed. In contrast the metals of Group IA (and II A)
have relatively high melting and boiling points and these decrease
down the groups. These values are shown in Figure 1.8.
If we look at some of the compounds of these elements we find
similar behaviour. Thus the hydrides of Group ynB elements
(excepting hydrogen fluoride, p. 52) show an increase in melting
and boiling points as we go down the group. These are generally
low, in contrast to the melting and boiling points of the Group IA
metal chlorides (except lithium chloride) which are high and decrease
down the group. The values are shown in Figure 1.9(a) and (b).
Clearly the direction of change—increase or decrease—down the
group depends on the kind of bonding. Between the free atoms of the
noble gases there are weak forces of attraction which increase with
the size of the atom (Chapter 12) and similar forces operate between
the molecules of the hydrogen halides HC1, HBr and HI. The forces
between the atoms in a metal and the ions in a salt, for example
sodium chloride, are very strong and result in high melting and boil-
ing points. These forces decrease with increasing size of atom and ion
and hence the fall in melting and boiling points.
19
TOOr
Figure 1.8. (a] M.p. and b.p. of Group I A metals, (b) m.p. and b.p. of Group O elements,
(c) m.p. and b.p. of the halogens
Table 1.6
PERIOD 3
Group I II III IV V VI VII
Fluorides NaF MgF 2 A1F3 SiF4 PF5 SF6 C1F3

Oxides Na 2 O MgO , SiO2 (P 2 O 5 ) 2 SO3 C120,
Hydrides NaH MgH, (Am; DO
i jn ^ CTT
on 2 C1H
Table 1.7
PERIOD 4
Group I II in IV V VI VII
Fluorides KF CaF2 GaF3 GeF4 AsF5

Oxides K2O CaO Ga 2 6 3 GeO2 (As 2 O s ) 2 SeO3
Hydrides KH CaH 2 GaH, GeH4 AsHj ' SeH2 BrH
20 THE PERIODIC TABLE
300 -
a
H800
I
£
200-
1400
100 1200
HI
1000
800
LiCl NaCl KCl RbCl CsCl
Figure 1.9. (a) M.p. and h.p. of the halogen hydrides HX, (b) m.p. and b.p, of the
Group IA chlorides
VALENCY
Mendeleef based his original table on the valencies of the elements.

Listed in Tables L6 and 1.7 are the highest valency fluorides, oxides
and hydrides formed by the typical elements in Periods 3 and 4.
From the tables it is clear that elements in Groups I-IV can display
a valency equal to the group number. In Groups V-VIL however, a
group valency equal to the group number (x) can be shown in the
oxides and fluorides (except chlorine) but a lower valency (8 — x) is
displayed in the hydrides. This lower valency (8 — x) is also found in
compounds of the head elements of Groups V-VIL
CHEMICAL CHARACTER
In any group of the periodic table we have already noted that the
number of electrons in the outermost shell is the same for each ele-
ment and the ionisation energy falls as the group is descended. This
immediately predicts two likely properties of the elements in a group.
(a) their general similarity and (b) the trend towards metallic beha-
viour as the group is descended. We shall see that these predicted
properties are borne out when we study the individual groups.

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THE PERIODICTABLE 17

period, although not quite regularly, and fall as we descend a group,

MELTING AND BOILING POINTS

Group I II III IV V VI VII

Fluorides NaF MgF 2 A1F3 SiF4 PF5 SF6 C1F3

Fluorides KF CaF2 GaF3 GeF4 AsF5

Mendeleef based his original table on the valencies of the elements.

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