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JUPEB 003 M2
Anaomalous behavior of Period II elements in the periodic table

Diagonal Relationship
It has been observed that Lithium, Beryllium, Boron, Carbon, Nitrogen, Oxygen, and Fluorine have slightly
different periodic properties than the rest of the elements belonging to Group 1, 2, 13-17 respectively. For
example, Lithium and Beryllium form covalent compounds, whereas the rest of the members of Groups 1 and 2
form ionic compounds. Also, the oxide that is formed by Beryllium when it reacts with Oxygen is amphoteric
in nature, unlike other Group 2 elements that form basic oxides. Yet another example is that of Carbon which
can form stable multiple bonds, whereas Si=Si double bonds are not very common.
So, it has clearly been established that the second-period elements are different. In fact, they display periodic
properties that are similar to the second element of the next group (i.e. Lithium is similar to Magnesium and
Beryllium to Aluminium) or in other words, they have a diagonal relationship.

Reasons for Anomalous Periodic Properties

The reasons for differences in periodic properties and hence in chemical behaviour are:
 Small size of these atoms
 High electronegativity
 Large charge/radius ratio
 These elements also have only 4 valence orbitals available (2s and 2p) for bonding as compared
to the 9 available (3s, 3p, and 3d) to the other members of the respective groups, so their
maximum covalency is 4. (This is why Boron can only form [BF4]– whereas Aluminium can form
[AlF6]3-).

Structure of Solids

Crystalline solids have regular ordered arrays of components held together by uniform
intermolecular forces, whereas the components of amorphous solids are not arranged in regular
arrays. With few exceptions, the particles that compose a solid material, whether ionic, molecular,
covalent, or metallic, are held in place by strong attractive forces between them. When we discuss
solids, therefore, we consider the positions of the atoms, molecules, or ions, which are essentially
fixed in space, rather than their motions (which are more important in liquids and gases). The
constituents of a solid can be arranged in two general ways:

(i) they can form a regular repeating three-dimensional structure called a crystal lattice,
thus producing a crystalline solid, or
(ii) they can aggregate with no particular order, in which case they form an amorphous
solid (from the Greek ámorphos, meaning “shapeless”).

Crystalline solids, or crystals, have distinctive internal structures that in turn lead to distinctive flat
surfaces, or faces. The faces intersect at angles that are characteristic of the substance. When
exposed to x-rays, each structure also produces a distinctive pattern that can be used to identify
the material. The characteristic angles do not depend on the size of the crystal; they reflect the
regular repeating arrangement of the component atoms, molecules, or ions in space. When an ionic
crystal is cleaved (Figure 1), for example, repulsive interactions cause it to break along fixed
planes to produce new faces that intersect at the same angles as those in the original crystal. In a
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covalent solid such as a cut diamond, the angles at which the faces meet are also not arbitrary but
are determined by the arrangement of the carbon atoms in the crystal.

Figure 1: Cleaving a Crystal of an Ionic Compound along a Plane of Ions. Deformation of the ionic crystal
causes one plane of atoms to slide along another. The resulting repulsive interactions between ions with
like charges cause the layers to separate.

Crystals tend to have relatively sharp, well-defined melting points because all the component
atoms, molecules, or ions are the same distance from the same number and type of neighbors; that
is, the regularity of the crystalline lattice creates local environments that are the same. Thus the
intermolecular forces holding the solid together are uniform, and the same amount of thermal
energy is needed to break every interaction simultaneously.
Amorphous solids have two characteristic properties.
 When cleaved or broken, they produce fragments with irregular, often curved surfaces; and
 They have poorly defined patterns when exposed to x-rays because their components are not
arranged in a regular array.
An amorphous, translucent solid is called a glass. Almost any substance can solidify in amorphous form if
the liquid phase is cooled rapidly enough. Some solids, however, are intrinsically amorphous, because either
their components cannot fit together well enough to form a stable crystalline lattice or they contain
impurities that disrupt the lattice. For example, although the chemical composition and the basic structural
units of a quartz crystal and quartz glass are the same—both are SiO2 and both consist of linked
SiO4 tetrahedra—the arrangements of the atoms in space are not. Crystalline quartz contains a highly
ordered arrangement of silicon and oxygen atoms, but in quartz glass the atoms are arranged almost
randomly. When molten SiO2 is cooled rapidly (4 K/min), it forms quartz glass, whereas the large, perfect
quartz crystals sold in mineral shops have had cooling times of thousands of years. In contrast, aluminum
crystallizes much more rapidly. Amorphous aluminum forms only when the liquid is cooled at the
extraordinary rate of 4 × 1013 K/s, which prevents the atoms from arranging themselves into a regular array.

Crystals

Because a crystalline solid consists of repeating patterns of its components in three dimensions (a
crystal lattice), we can represent the entire crystal by drawing the structure of the smallest identical
units that, when stacked together, form the crystal. This basic repeating unit is called a unit cell.
For example, the unit cell of a sheet of identical postage stamps is a single stamp, and the unit cell
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of a stack of bricks is a single brick. In this

section, we describe the arrangements of
atoms in various unit cells.

Fig 2: Unit Cells in Two Dimensions. (a–

c) Three two-dimensional lattices illustrate the
possible choices of the unit cell. The unit cells
differ in their relative locations or orientations
within the lattice, but they are all valid choices
because repeating them in any direction fills the
overall pattern of dots. (d) The triangle is not a
valid unit cell because repeating it in space fills
only half of the space in the pattern.

Fig 3: Unit Cells in Three Dimensions. These

images show (a) a three-dimensional unit cell and
(b) the resulting regular three-dimensional lattice

The Unit Cell

There are seven fundamentally different kinds of unit cells, which differ in the relative lengths of
the edges and the angles between them (Figure 11.7.611.7.6). Each unit cell has six sides, and
each side is a parallelogram. We focus primarily on the cubic unit cells, in which all sides have
the same length and all angles are 90°, but the concepts that we introduce also apply to
substances whose unit cells are not cubic.
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Figure 4: The General Features of the Seven Basic Unit Cells. The lengths of the edges of the
unit cells are indicated by a, b, and c, and the angles are defined as follows: α, the angle between
b and c; β, the angle between a and c; and γ, the angle between a and b.

If the cubic unit cell consists of eight component atoms, molecules, or ions located at the corners
of the cube, then it is called simple cubic (Figure 5a). If the unit cell also contains an identical
component in the center of the cube, then it is body-centered cubic (bcc) (5b). If there are
components in the center of each face in addition to those at the corners of the cube, then the unit
cell is face-centered cubic (fcc) (Figure 5c).

Figure 5: The Three Kinds of

Cubic Unit Cell. For the three
kinds of cubic unit cells, simple
cubic (a), body-centered cubic
(b), and face-centered cubic (c),
there are three representations for
each: a ball-and-stick model, a
space-filling cutaway model that
shows the portion of each atom
that lies within the unit cell, and
an aggregate of several unit cells.