COVALENT BONDING

Introduction
• How do atoms combine to form molecules ?

• A great pioneer in the study of bonding was Gilbert N.

Lewis. In 1916, he suggested that the outer (valence)
electrons could be visualized as sitting at the corners of
an imaginary cube around the nucleus. An atom that was
deficient in the number of electrons needed to fill eight
corners of the cube could share edges with another atom
to complete its octet
Models of Covalent Bonding
• The properties of covalent compounds can best be
explained in terms of molecular orbitals. An electron in a
molecular orbital is the property of the whole molecule,
not of an individual atom.
• The simple Lewis electron-dot representations that are
taught in general chemistry

• The case of O2 molecules : double bond and

paramagnetic
A Brief Review of Lewis Structures
• The simplistic bonding representation of Lewis—that
atoms combine by sharing electron pairs—tells us nothing
in detail about the bonds themselves.
• The Lewis concept explains the driving force of bond
formation as being the attainment by each atom in the
molecule of an octet of electrons in its outer (valence)
energy level (except hydrogen, where a duet is required).
Constructing Electron-Dot Diagrams
• Draw skeletal structure of compound showing what atoms
are bonded to each other. Put least electronegative
element in the center.
• Count total number of valence e-. Add 1 for each negative
charge. Subtract 1 for each positive charge.
• Complete an octet for all atoms except hydrogen
• If structure contains too many electrons, form double and
triple bonds on central atom as needed.
Lewis structure of nitrogen trifluoride
(NF3).
Step 1 – N is less electronegative than F, put N in center
Step 2 – Count valence electrons N - 5 (2s22p3) and F - 7 (2s22p5)
5 + (3 x 7) = 26 valence electrons
Step 3 – Draw single bonds between N and F atoms and complete
octets on N and F atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?

3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons

F N F

F
Lewis structure of the carbonate ion
(CO32-).
Step 1 – C is less electronegative than O, put C in center
Step 2 – Count valence electrons C - 4 (2s22p2) and O - 6 (2s22p4)
-2 charge – 2e-
4 + (3 x 6) + 2 = 24 valence electrons
Step 3 – Draw single bonds between C and O atoms and complete
octet on C and O atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?
3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons
Step 5 - Too many electrons, form double bond and re-check # of e-

2 single bonds (2x2) = 4

O C O
1 double bond = 4
8 lone pairs (8x2) = 16
O Total = 24
 Formal Charge
An atom’s formal charge is the difference between the
number of valence electrons in an isolated atom and the
number of electrons assigned to that atom in a Lewis
structure.

formal charge total number

total number 1 total number
on an atom in
a Lewis
structure
= of valence
electrons in
the free atom
- of nonbonding
electrons
- 2 ( of bonding
electrons )
The sum of the formal charges of the atoms in a molecule
or ion must equal the charge on the molecule or ion.
Formal Charge
Practice
For each molecule or ion below, please draw the lewis
structure and determine formal number for each atom
• SO3
• HCN
• PO43-
• OF2
• NOCl
Exceeding the Octet
• In a few anomalous molecules the central atom has fewer
than 8 electrons, and in a substantial number of
molecules the central atom has shares in more than 8
bonding electrons.

• BeCl2, BF3, PCl5, SF6

Partial Bond Order
In some cases, the only structure that can
be drawn does not correlate with our
measured bond information.
Valence-Shell Electron-Pair Repulsion
(VSEPR) Rules
• Electron-dot diagrams can be used to derive the probable
molecular shape. To accomplish this, we can use a very
simplistic set of rules that tells us nothing about the bonding but
is surprisingly effective at predicting molecular shapes—the
valence-shell electron-pair repulsion (VSEPR) rules, also called
the electron domain (ED) model.

• Linear Geometry
• Trigonal Planar Geometry
• Tetrahedral Geometry
• Trigonal Bipyramidal Geometry
• Octahedral Geometry
• Greater Than Six Bonding Directions
Linear Geometry
• All diatomic molecules and ions are, by defi nition, linear.
• the few common examples of this simplest geometry with
triatomic molecules and ions.
Trigonal Planar Geometry
• The maximum separation of three electron pairs requires
an angle of 120° between each pair,
Tetrahedral Geometry
• To place four electron pairs as far apart as possible,
molecules adopt this particular three-dimensional
geometry in which the bond angles are 109,5°
Trigonal Bipyramidal Geometry
This is the only common
molecular geometry in which
the angles are not equal.
Thus, three (equatorial)
bonds lie in a single plane
and are separated by angles
of 120°; the other two (axial)
bonds extend above and
below the plane and make an
angle of 90° with it.
Octahedral Geometry
The most widely spaced possibility arises from bonds at
equal angles of 90°, the octahedral arrangement
Greater Than Six Bonding Directions
There are a few examples of molecules and ions in which
the central atom is bonded to more than six neighbors. To
accommodate seven or eight atoms around a central atom,
the central atom itself has to be quite large and the
surrounding atoms and ions quite small
The Valence-Bond Concept
The principles of the valence-bond method can be
summarized in a series of statements:
1. A covalent bond results from the pairing of unpaired
electrons in neighboring atoms.
2. The spins of the paired electrons must be antiparallel
(one up and one down).
3. To provide enough unpaired electrons in each atom for
the maximum bond formation, electrons can be excited
to fill empty orbitals during bond formation.
4. The shape of the molecule results from the directions in
which the orbitals of the central atom point.
Orbital Hybridization
Orbital Hybridization
Orbital Hybridization
Introduction to Molecular Orbitals
• When two atoms approach each other, according to the
molecular orbital concept, their atomic orbitals overlap.
• The electrons no longer belong to one atom but to the
molecule as a whole
 bonding and * bonding
• For the s orbital, the electron density between the two
nuclei is increased relative to that between two
independent atoms. There is an electrostatic attraction
between the positive nuclei and this area of higher
electron density, and the orbital is called a bonding orbital.

• Conversely, for the s* orbital, the electron density between

the nuclei is decreased, and the partially exposed nuclei
cause an electrostatic repulsion between the two atoms.
Thus, the s* orbital is an antibonding orbital.
General statement
MO for Period 1 Diatomic Molecules
The simplest diatomic species is that formed between a
hydrogen atom and a hydrogen ion, the H2+
MO diagram for the H2 molecule.
MO diagram for the He2+ ion
MO diagram for the 1s atomic orbitals of the
(theoretical) He2 molecule.
Bond Order
• It must be emphasized that bonding models are developed to explain
experimental observations.
• We observe that the shorter the bond length and the higher the bond
energy, the stronger the bond.
• For the Period 2 elements, bonds with energies of 200–300 kJ/mol
are typical for single bonds, those with energies of 500–600 kJ/mol
are defined as double bonds, and those with energies of 900–1000
kJ/mol are defined as triple bonds.
MO diagram for the 2p atomic orbitals of
the O2 molecule.
MO diagram for the 2p atomic orbitals of
the F2 molecule.
Changes in the energy levels of the MOs and the ground state electronic configura-
tions of homonuclear diatomic molecules involving first-row p-block elements
MO diagram for the 2p atomic orbitals of
the N2 molecule.
MO for Heteronuclear Diatomic Molecules
• When we combine atomic orbitals from different elements,
we have to consider that the atomic orbitals will have
different energies

• For elements from the same period, we find that the

higher the atomic number, the higher the Zeff and hence
the lower the orbital energies
MO diagram for the 1s atomic orbital of hydrogen and the 3p
atomic orbitals of chlorine in the HCl molecule
Simplified molecular orbital diagram for the 2s
and 2p atomic orbitals of the CO molecule.
Intermolecular Forces
• Dispersion (London) Forces
• Dipole-Dipole Forces
• Hydrogen Bonding
Dispersion (London) Forces
Dependence of the boiling points of the Group
14 hydrides on the number of electrons.
Dipole-Dipole Forces
 Hydrogen Bonding
Hydrogen bonding, then, is by
far the strongest intermolecular
force indeed, it can represent 5
to 20 percent of the strength of
a covalent bond.
The strength of the hydrogen
bond between molecules also
depends on the identity of the
non-hydrogen element.
Thus, hydrogen bond strength
decreases in the order H—F .
H—O.H—N, and this order
parallels the decrease in
electronegativity differences.
Molecular Symmetry
• In synthesis of inorganic compounds, we need to deduce
the structure, the atomic arrangement, of the product
molecule, it is first necessary to understand the basic
principles of symmetry
• Symmetry permeates the natural world
• Symmetry Operations
1. Identity
2. Proper rotation: rotation about an n-fold axis of symmetry
3. Reflection through a plane of symmetry
4. Inversion through a center of symmetry
5. Improper rotation: rotation about an axis followed by a reflection
(real or imagined) perpendicular to that axis
Identity
• The identity operator, E, leaves the molecule unchanged.
Thus, all molecules possess E. This may seem a
senseless activity
Proper rotation
• The rotation operation, symbol Cnx, involves rotating the
molecule by 360/n degrees about an axis, symbol Cn,
through the molecule. The value of n represents the
number of times the molecule can be rotated during a
complete 360° rotation while matching the original
conformation after each rotation.
Reflection through a plane of symmetry
• If a plane is constructed through
a molecule and the atoms on
one side of the plane reflect
perfectly onto the locations of
the atoms on the other side of
the plane, the molecule is said
to have a mirror plane,
represented by the symbol s.
Inversion through a center of symmetry
• If inversion of all parts of the molecule through the center
produces an indistinguishable configuration, the molecule
is said to possess a center of symmetry, also called a
center of inversion, and given the symbol i.
Improper rotation
• A so-called improper axis of rotation is the combination of
a rotation operation and a reflection through a plane
perpendicular to the axis of rotation. An improper axis of
rotation is denoted by the symbol Sn.
Point Grups
• Any particular molecular shape can possess only certain
combinations of symmetry elements. For example, the
tetrahedral shape of methane possesses four C3 axes,
three C2 axes, six v planes, three S4 improper rotation
axes, and the ubiquitous E. The collection (a group) of
symmetry elements all of which coincide at the center of a
molecule (a point) is called a point group. In the case of
methane, the point group is called Td.
ddddzzz