Periodic Properties

The properties that reappear at regular intervals are called Periodic Properties.
or
The properties in which there is gradual variation (i.e. increase or drcrease) at
regular intervals are called Periodic Properties.

Cause of Peridiocity -
The cause of peridiocity is the recurrance of similar outer electronic
configuration at certain regular intervals.

1. Atomic Size or Atomic Radius

The absolute size of an atom is difficult to define because of the following two
reasons :

(i) According to wave-mechanical model of atom, there is no certainty about the

exact position of the electrons at any time. Electron at one time may be very close
to the nucleus while at other time it may be far away from the nucleus. So it is
not possible to define any boundary for an atom.

Because the electrons can be defined only in terms of probability, there is no real
boundary to an atom.

(ii) It is impossible to isolate an individual atom and determine its radius.

For practical purposes (as per Bohr model of atom), atomic radius is defined as the
distance from the centre of nucleus to the outermost electron shell.

A particular atom may have four types of radius :

1. Covalent Radius
2. Metallic Radius
3. vander Waal Radius
4. Ionic Radius

1. Covalent Radius
The atomic radius of an element may be considered to be half the interatomic
distance between two adjacent atoms. However, the interatomic distance depends on
type of bond between atoms.

Atomic radii can be defined according to the type of bonding between atoms :

1. If the bonding is Covalent, the radius is called Covalent Radius.

2. If the bonding is Metallic, the radius is called Metallic Radius.

3. If the bonding is Ionic , the radius is called Ionic Radius.

4. If the two atoms are not bonded by a chemical bond but are attracted by simply
vanderWaal forces (as in Noble Gases), the radius is called
vander Waal Radius

1. Covalent Radius -
The covalent radius is equal to one half of the internuclear distance (covalent
bond distance) between two identical atoms joined by single covalent bond.
For example, the internuclear distance (covalent bond distance) between two
identical atoms of Carbon (C-C) in diamond is 1.54A, hence covalent radius of
Carbon is 1.54/2 = 0.77 A.

Covalemt radius decreases with decreasing number of bonds, because atom approaches
closer for greater overlap. For example,

C - C Single bond Covalent Radius 0.77 A

C = C Double bond Covalent Radius 0.67 A

C = C Triple bond Covalent Radius 0.60 A

2. Metallic Radius
The Metallic Radius is defined as one half of the distance between the atoms of a
metal in a metallic close packed crystal lattice (in which metal exhibit
coordination number 12).

For example, the internuclear distance between two adjacent sodium atoms in a
metallic crystal of Sodium is 3.72 A, so the Metallic Radius of Sodium Metal is
3.72/2 = 1.86 A.

Note - The Covalent Radius of Sodium in Na2 molecule is 1.54 A . Metallic Radii are
about 10 - 15 % higher than the single bond covalent radius.

3. vander Waals Radius

The van der Waals radius of an element is half the distance between two atoms of an
element which are as close to each other as is possible
without being formally bonded by anything except van der Waals inter- molecular
forces.

The vander Waal Radius is defined as one half of the distance between the two non-
bonded atoms of two adjacent molecules in the solid state.

For example, in solid Chlorine gas, each atom is found to have one close neighbour
at a distance of 1.98 A, another at a distance of 3.60 A. Thus the Covalent radius
of Chlorine is 0.99 A whereas vander Waal's radius is 1.80 A.

The radii of Group 18 elements (Noble gases) are vertually vander Waals Radii.
Since vander Waals Radii are larger than Covalent Radii. atomic radii of Noble
gases are largest in their respective periods.

Factors Affecting Atomic Radii -

1. Number of Shell or Principal Quantum Number - If increases - Atomic radius

increases.

2. Effective Nuclear Charge - Z* - Atomic Radii are inversely proportional to Z*.

If Z* increases, Atomic radius decreases.
3. Sreening Effect, sigma, or Number of electrons in the inner shell - If Sigma
increases, Atomic radius decreases.

4. Number of Bonds - If increases, Atomic radius decreases.

5. Type of Hybridization used in concerned atom - If % S character increases -
Atomic radius decreases.

Compound Type of Hyb. % S character No. of Bond Covalent Radius

CH4 SP3 25% C - C

0.77 A

C2H4 SP2 33% C = C

0.74 A

C2H2 SP 50% C C
0.70 A

Determination of Covalent Radius -

Schomaker and Stevenson (1941) proposed following equation for calculating covalent
radius :

r A-B = rA + rB - C (XA - XB)

where r A-B = the internuclear distance between A and B.

r A = covalent radius of A
r B = covalent radius of B

XA = Electronegativities of A
XB = Electronegativities of B

C = is a constant have the value

0.08 for elements of 2nd period.
0.06 for elements of 3rd period.
0.04 for elements of 4th period.
0.02 for elements of 5th period of p- block respectively.

PERIODIC TREND

A - Along a Period -
In moving from left to right in any period, the atomic radii of elements decreases.

For example, the covalent radius of 2nd period elements :

Li Be B C N
O F Ne

1.23 0.89 0.80 0.77 0.74

0.74 0.72 1.60 S

Nuclear Charge +3 +4 +5 +6 +7
+8 +9 +10

Reason - 1 - Number of Shells remain constant.

2- Nuclear Charge (Z) or Effective Nuclear Charge (Z*)

Moving from left to right in the periodic table, the increase of nuclear charge has
an effect that generally outweighs the screening from additional
electrons.
Lanthanide Contraction -

In case of Transition or Inner-Transition elements, the covalent radius decreases

from left to right . However, in these elements decrease in size is much little.
This is called Lanthanide Contraction. For example :

2nd Period : Li------------------------F (7

elements)
1.23 0.72 A
= 0. 51 A

First Transition Series : Sc (21)-----------------Zn(30) (10

elements)
1.44 A 1.25
= 0.19 A

Lanthanides : Ce (58) ---------------- Lu (71) (14

elements)
1.65A 1.56A = 0.09
A
Actinides :

Reason :
This is because the added electron enters in inner shell, i.e., (n-1) d subshell in
case of T.E. and (n-2) f subshell in case of I.T.E. These electron tend to 'screen'
the outermost electron from the attraction of nucleus, but due to much diffused
shape of d or f orbitals , shielding is not perfrct. Consequently size decreases
with increase in nuclear charge , i.e., atomic number.

Down the Group -

On moving from top to bottom in a group, the atomic size increases.
For example, Group I - The Alkali Metals
1 H 0.30 A
3 Li 1.23 A
11 Na 1.54 A
19 K 2.03 A
37 Rb 2.16 A
55 Cs 2.35 A

Reason :
(i) In moving down the group the Number of shells increases and, therefore, the
size of the atom increases.
(ii) As we move down in a group, the nuclear charge also increases which decreases
the atomic size. However, this effect is much smaller as compared to the effect on
size of atom because of addition of new shell.
========================================
IONIC radius

Ionic radius may be defined as the distance between nucleus of an ion and point
upto which the nucleus has influence on its electron cloud.

Determination of Ionic Radius

The determination of Ionic Radii is difficult because like atoms do not form ionic
bonds. There are three imortant methods to determine ionc radii :

(a) Pauling's Method

(b) Lande's Method
(c) Bragg's Method

(a) Pauling's Method

(i) The internuclear distance between cation (c+) and anion (a-) is determined by
X-ray crystallography.

(ii) The radii are inversely proportional to the effective nuclear charges acting
on these ions.
rc+ (Z*)a-
ra- (Z*)c+
The effective nuclear charge (Z*) = Nuclear Charge (Z) - Screening Constant (sigma)

Illustration :
NaF crystal, Na+ and F- ion, sigma=4.5

rc+ 9 - 4.5 4.5

ra- 11 - 4.5 6.5 (i)

Interionic distance (Experimental value) rNa+ + rF- = 2.31 (ii)

On solving equation (i) and (ii)

rNa+ = 0.95 A
rF- = 1.36 A

Radii of Cation and Anion :

1. The radius of Cation (positive ion) is always smaller than the neutral atom from
which it is formed.
For example :
The atomic radius of Na = 1.54 A
The ionic radius of Na+ = 0.95 A

Reason - This is because with elimination of one or more electrons :

(i) Generally outer shell of electron is removed completely.
K L M
Na = 2, 8, 1
Na+ = 2, 8
(ii) The rffective nuclear charge increases. Therefore, electrons are pulled in
more towards the nucleus than before.

eg. in the number of protons in Sodium nucleus is 11.

This nuclear charge of +11 can pull 10 electrons of Na+ ion inward more effectively
than it can pull 11 electrons of Na atom. Thus Na+ is smaller than Na.

2. Radius of an anion (negative ion) is invariably larger (bigger) than that

corresponding atoms.

As for example -

The atomic radius of Cl = 0.99 A

The ionic radius of Cl- = 1.81A

Reason - In anion one or more electron are added to the valency shell of atom.
Therefore, effective nuclear charge is rduced and electrons acquire greater freedom
of getting away from the nucleus. In other words the electron clouds rxpands.

Isoelectronic Ions -

The ions which have the same number of electrons are called Isoelectronic Ions.
In Isoelectronic Ions, the ionic radius decreases with increase in atomic number
(ie nuclear charge) , eg.

Atomic No. 6 7 8 9 11 12
13 14
Ion C N O F Na Mg
Al Si
No of Eletron 10 10 10 10 10 10
10 10
Radius 2.60 1.71 1.40 1.36 0.95 0.65
0.50 0.41

PERIODIC PROPERTIES
A. Along the period -
In moving across a period from left to right, in isoelectronic ions, radii
drcreases, eg.
2nd Period : Li Be B C N O
F
0.60 0.31 0.20 0.15 0.11 0.09 0.07
Reason - Effective nuclear charge increases while shell remain constant.

B. Down the Group :

In moving down a group the ionic radius increases both for cations and anions.

For example, Group I - The Alkali Metal Ions

1 H+ 0.29 A
3 Li+ 0.60 A
11 Na+ 0.95 A
19 K+ 1.33 A
37 Rb+ 1.48 A
55 Cs+ 1.69 A
Fr+ 1.76 A

Reason -
Number of shell increases.
======================================================================

may be considered to be one half of

the covalent bond distance of a molecule such as C1-, (equal to its
atomic radius in this case), where the atoms concerned are participating in
single bonding.

4.3.1 Estimates of Atomic Size

There are four different modes by which sizes may be assigned to any
particular atom in its elementary or combined states.

Atomic Radius
The atomic radius of an element may be considered to be half the
interatomic distance between two adjacent atoms. T

his may apply to iron,

say, in its metallic state, in which case the quantity may be regarded as
the metallic radius of the iron atom, or to a molecule such as CI,. In the
latter case the quantity is the covalent radius of the chlorine atom. If
applied to the multiply bonded O, and N, molecules, the radii would
only be appropriate for oxygen and nitrogen atoms participating in
multiple bonding in their compounds. The differences between these
examples is sufficient to demonstrate that some degree of caution is necessary
when comparing the atomic radii of different elements. It is best to limit
such comparisons to elements with similar types of bonding, metals for
example. Even that restriction is subject to the drawback that the
metallic elements have at least three different crystalline arrangements with
possibly different coordination numbers: the number of nearest
neighbours for any one atom.
Covalent Radius
The covalent radius of an element may be considered to be one half of
the covalent bond distance of a molecule such as C1-, (equal to its
atomic radius in this case), where the atoms concerned are participating in
single bonding.

Covalent radii for participation in multiple bonding are

also quoted in data books. In the case of a single bond between two
different atoms, the bond distance is divided up between the participants
by subtracting from it the covalent radius of one of the atoms, whose
radius is known. A set of mutually consistent values is now generally
accepted and, since the vast majority of the elements take part in some
76 Atomic Structure and Periodicity
form of covalent bonding, the covalent radius is the best quantity to
consider for the study of general trends. Only atoms of the Group 18
elements (except Kr and Xe) do not have covalent radii assigned to them,
because of their general inertness with respect to the formation of
molecules. The use of covalent radius for comparing the sizes of atoms is
subject to the reservation that its magnitude, for any given atom, depends
on the oxidation state of that element.

Ionic Radii
As indicated above, the covalent radius of an element depends on its
oxidation state. In a binary ionic compound, MX, containing the
positive ion, M*, and the negative ion. X , the minimum distance between
them is measurable with considerable accuracy by the method of X-ray
diffraction. The problem is to divide such a distance into the ionic radii
for the individual ions. That ions behave like hard spheres with a
constant radius whatever their environment might be is an approximation
to the real situation. In compounds which do not exhibit much cova-
lency the approximation is reasonable, and led Shannon-* and Prewitt to
assign radii to O- and F of 140 and 133 pm respectively after their study
of many oxides and fluorides. Ionic radii are not assignable to every
element, and the generalizations described apply only to those elements
which do form ions in compounds, and are subject to their oxidation
states (discussed in Chapter 5) and coordination numbers (i.e. the
number of nearest neighbours they have in the ionic compound).

Van der Waals Radius

The van der Waals radius of an element is half the distance between two
atoms of an element which are as close to each other as is possible
without being formally bonded by anything except van der Waals inter-
molecular forces. Such a quantity is used for the representation of the
size of an atom with no chemical bonding tendencies; the Group 18
elements. That for krypton, for instance, is half of the distance between
nearest neighbours in the solid crystalline state, and is equal to the atomic
radius. Van der Waals radii of atoms and molecules are of importance
in discussions of the liquid and solid states of molecular systems, and in
the details of some molecular structures where two or more groups
attached to the same atom may approach each other.
There are three types of van der Waals forces:
(i) interactions between molecules with permanent dipole moments;
these are called dipole-dipole forces;
(ii) dipole-induced-dipole forces, where a molecule with a permanent
dipole moment induces a dipole in a neighbouring molecule; and
Periodicity i: Some Atomic Properties; Relativistic Effects 77
(iii) London dispersion forces which operate between atoms.
The first two interactions are not relevant to elementary cohesion, but
the third and weakest force is that which holds the Group 18 elements
in their solid state. The London force arises because of a transitory and
ever-changing deviation from spherical symmetry of an atom because
the uncertainty principle forbids the accurate placement of the nucleus
in the surrounding electronic configuration. The very small transient
dipoles of atoms interact to give some cohesion to the Group 18
elements. Of course, the forces operate between all atoms, but if any kind
of chemical bonding is present they represent an almost insignificant
contribution to the overall cohesion.