CHM 111 LECTURE NOTE FIVE

PERIODICITY OF ATOMIC PROPERTIES

We learned that physical and chemical properties of the elements vary periodically
with the atomic number. The periodic table therefore provides an organized
structure to the knowledge and understanding the chemistry of the elements. Apart
from this, there is also a variation of atomic properties of elements in the periodic
table. Some of these properties are; atomic and ionic sizes, ionization energy,
electron affinity and electronegativity.
Atomic Size
The size of an atom is defined in terms of its atomic radius, which is one-half the
distance between the two nuclei in two adjacent metal atoms or in a diatomic
molecule. This definition implies that there two types of atomic radius commonly
used to describe atomic size, viz:
1. Metallic radius: This is used mostly for metals, it is one-half the shortest
distance between nuclei of adjacent, individual atoms in a crystal of the
element.
2. Covalent radius: this used for elements occurring as molecules, mostly
nonmetals, it is one-half the shortest distance between nuclei of bonded atoms.
Atomic radii increase down a group and decrease from left to right across a
period. Across a period, as a result of the joint effects of penetration and shielding,
there is an increase in effective nuclear charge. This increase pulls the electrons
closer to the nucleus and results in a smaller atom. On descending a group,
electrons occupy successive shells outside a completed core and the radii increase.
For the elements the d block element, the increase in atomic size is not as expected.
For example, although there is a substantial increase in atomic radius between
C (77 pm) and Si (118 pm), the atomic radius of Ge (122 pm) is only slightly
greater than that of Si.
Ionic Radius
Ions of elements are formed when atoms lose or gain electron. The size of an ion
called ionic radii is different from atomic sizes. Ionic sizes are measured in
electrovalent compounds. The ionic radius of a given compound is the distance
between the centre of one ion and the centre of its nearest neighbour of opposite
charge.
A positive ion is formed by removing one or more electrons from an atom. When
this happens, the number of positive nuclear charge is more than the number of
negative electronic charge; hence the electrons are pulled in. A positive ion is
therefore smaller than the corresponding atom and the more electrons removed
(that is, the greater the charge on the ion), the smaller it becomes e.g.
Atomic radius Na = 0.186nm Atomic radius Fe = 0.139nm
Ionic radius Isle = 0.116nm Ionic radius Fee' = 0.090tun
Ionic radius Fe31- = 0 076nm
When a negative ion is formed, one or more electrons are added to an atom. The
number of positive nuclear charge is now less than the numbers of negative
electronic charge hence the pull on the electrons is reduced. In general, ionic radii
of negative ions are greater than the corresponding atomic radii i.e. negative ions
are bigger than the corresponding atom e.g.
Atomic radius CI = 0.099
ionic radius CI = 0.128
Ionization Energy
Is the minimum energy (in kJ/mol) required to remove an electron from a gaseous
atom in its ground state. In other words, ionization energy is the amount of energy
in kilojoules needed to strip 1 mole of electrons from 1 mole of gaseous atoms.
Gaseous atoms are specified in this definition because an atom in the gas phase is
virtually uninfluenced by its neighbors and so there are no intermolecular forces
(that is, forces between molecules) to take into account when measuring ionization
energy.
Na (g) + IE → Na+ (g) + e− where IE is the ionization energy
Ionization energy increases across a period and decreases down a group. Ionization
energies are directly related to atomic radii. Elements that have small atomic radii
generally have high ionization energies. Therefore, as the atomic radius increases
down a group, the ionization energy decreases. Likewise, the decrease in radius
across a period is accompanied by an increase in ionization energy. There are
variations in this trend: in particular, high ionization energies occur when electrons
are removed from half-filled or full shells or subshells. Thus the first ionization
energy of nitrogen ([He]2s22, 2p3) is 1402 kJ mol-1, which is higher than the value
for oxygen ([He]2s22p4, 1314 kJ mol-1). Similarly, the ionization energy of
phosphorus (1011 kJ mol-1) is higher than that of sulfur (1000 kJ mol-1)
Factors influencing the ionization energy
 Size of the atom which is a measure of the outermost electron from the
nucleus.
 Charge on the nucleus - as nuclear charge increases, the attraction for
outermost electron increases, and so more energy is required to ionise .
 screening effect of inner electron shells - the outermost electrons are
repelled by all the other inner shell electrons and prevented from
experiencing the full attraction of the positively charged nucleus:
Across a period, the first ionization energy increases as atomic number increases
since the atomic radius decreases. As the distance decreases, the attraction of the
positive nucleus for the electron will increase; hence more energy is required to
remove the outermost electron hence the ionization energy will increase. Note that
the screening effect remains almost the same across a period since electrons are
added to the same shell.
Electron affinity
The electron affinity (EA) is the energy change (kJ/mol) accompanying the
addition of 1 mol of electrons to 1 mol of gaseous atoms or ions. The first electron
affinity (EA1) refers to the formation of 1 mol of monovalent (12) gaseous anions:
X (g) + e− → X− (g) ΔE = EA.
As with ionization energy, there is a first electron affinity, a second, and so forth.
The first electron is attracted by the atom’s nucleus, so in most cases, EA 1 is
negative (energy is released), analogous to the negative ΔH for an exothermic
reaction. But the second electron affinity (EA2) is always positive because energy
must be absorbed to overcome electrostatic repulsions and add another electron to
a negative ion.
Moving from left to right across a period, electron affinities decreases (i.e. increase
in negative value), expect for the noble gases which have positive values. Down a
group of the periodic table, electron affinities increase (i.e. decrease in negative
value). The reason for the observed trend is that atoms with smaller atomic radii
tend to have a stronger attraction for electrons and thus form negative ions more
readily.
Electronegativity
The tendency of an atom in a molecule to attract bonded electrons to itself is
termed the electronegativity of the atom. Generally, small atoms attract electrons
(due to closeness of the nucleus) more than large ones and are therefore more
electronegative. Atoms with nearly filled shells of electrons will tend to have
higher electrcnegativity (because of the desire to have a stable filled shell) than
those with sparsely occupied shells.
The electronegativities of elements decrease down a group and increase across a
period. The reason for the trend is that, down the group, atomic size increases and
effective nuclear charge decreases hence electron attracting power
(electronegativity) of the atom decreases. From left to right of a period, the
opposite effect is observed, atomic size decreases and effective nuclear charge
increases, these combine to increase electronegativity. The most electronegative
elements are the reactive non-metals (e.g. Fluorine) at the top right-hand corner of
the periodic table while the least electronegative elements are the reactive metals
(e.g. caesium) at the bottom left-hand corner of the period table.