Covalent and Metallic Bonds

Covalent Bonds
 Sharing of electrons

 Examples - F2, Cl2, N2, H20, Diamond, Polymers

 Prerequisite: Each participating atom must have at least one partially filled
orbital

 Only then energy can be substantially lowered by having bonding electrons in

orbitals of two atoms simultaneously

 The more the orbitals overlap, the more is the lowering of energy, and
stronger is the bond

 Often, the orbitals can overlap directionally, i.e., along specific directions,
(except s, which is spherically symmetric). It gives directionality to the bond,
and makes the bond stronger

 Overlapping can also occur in end-to-end fashion (sigma bond) or by lateral

overlapping (pi bond)
 The CH4 molecule
 C: 1s2 2s2 2p2

 One electron from 2s orbital promoted to 2p orbital.

 But if this were the case, we should have 1 weak non-directional bond (s
overlapping), and 3 stronger, directional, bonds (p overlapping)

 Instead, we have 4 bonds of equal strength !!

 Answer: SP3 hybrids: Mathematically, an equivalent set of solutions to the

time-independent wave equation for n = 2. Each hybrid orbital has a larger
maximum value of ψ2 and therefore, overlap other orbitals to a greater extent,
resulting in even lower bond energies for overlapping p orbitals.

 Some inert gases (Xe, Kr) can react with Flourine to form stable bonds.
Similar explanation: But in these cases, the electrons are promoted from p
to d levels, rather than from s to p levels
 Covalent bonding (contd.)
 Detailed quantification of electron wavefunctions can be done by the LCAO
model (Linear Combination of Atomic Orbitals)

 Attractive and Repulsive Forces:

- Attraction: Electron of one atom and nucleus of other
- Repulsion: 1) Electron-electron electrostatic repulsion
2) Pauli Exclusion principle repulsion

 Properties of covalently bonded materials:

- High bond energies: Strong, but some materials which have three-
dimensional network bonding are stronger.
Eg: Diamond, Bakelite

- No mobile electrons: Poor electrical conductivity

- Directional bonding: Difficult to crystallize, not close packed.
 Metallic bonding
 Majority of the elements are metals ! (91 out of 118)

 Metallic bonding, even in the elemental state

- Eg: Na, Li, Cu, Fe …………..

 Similar principle as in covalent bond of lowering electron energy by bringing

it closer to more than one nucleus.
But, here 1) the electrons a donated to a common pool.
2) Metallic bonds can exist only between a large aggregate of
atoms
 Metallic bonding (Energy considerations)
 Loosely held valence electrons: Electron wavefunctions are more spread out
in space - Mobile electron clouds.
 Lowering of potential energy: Electrons are always closer to one or another
nucleus than they are in a free atom - Source of attractive force is the
electron – nuclei electrostatic attraction.

 Lowering of kinetic energy: Wavefunctions are more spread out, effectively

“increased wavelength” of electrons.

 Repulsion: Between metal ions. This repulsion is screened by the electron

clouds. Very difficult to show that the total energy is minimized.

 A quantitative treatment depends on

- Electron (charge) density,
- Charge state of ion cores
- Dielectric constant
 Metallic vs Covalent bonding
 What determines whether the nature of bond is covalent or metallic?

ANS: Looseness with which the valence electrons are held.

The fewer the valence electrons, and the more loosely they are held, the
more metallic the bonding.
 Metallic vs Covalent bonding (contd).
 What determines whether the nature of bond is covalent or metallic?

ANS: Looseness with which the valence electrons are held.

The fewer the valence electrons, and the more loosely they are held, the
more metallic the bonding.

 Transition metals (having incomplete d shells,) have significant fraction of

covalent bonding - High melting points !!

 Competition evident in the fourth column of periodic table:

C (Diamond) - covalent
Si, Ge - partly covalent, partly metallic
Tin - Exists in two forms - one covalent, one metallic
Lead - Metallic
 Metallic bonding (properties)
 Mobile valence electrons - High electrical and thermal conductivity

 Electrons are more or less free to move throughout the solid: Gives rise to
the important phenomenon called “slip” – Permanent plastic deformation
possible

 Opaque - Absorb light photons and get excited to higher energy levels

 Lustrous – Re emit photons as they fall back to lower energy levels

 Close packed, isotropic materials - Non directional bonding