BONDING AND MOLECULAR

SHAPES
Experiment 6
THEORIES OF COVALENT BOND
Valence Bond Theory (VBT)
the build up of electron density between two nuclei is
visualized as occurring when a valence atomic orbital
of one merges with that of another atom.
covalent bond consists of a pair of electrons in atomic
orbital
can be described by the concept of hybridization
tries to explain the bonding process; merging of
valence atomic orbitals to form an overlap region; the
overlap region can accommodate maximum of 2
electrons of opposite spins to form a covalent bond.

Valence-Bond Hybridized Orbitals
Hybridization
the process of mixing of atomic orbitals of the
same atom to form degenerate orbitals
the number of hybrid orbitals formed is equal
to the number of pure atomic orbitals that
combine.


Types of hybrid orbitals:
sp hybrid orbital: mixing one s and one p orbital
Consider BeCl
2
:
the ground state orbital diagram for Be should be
but this indicates that Be does not form covalent bonds
with Cl since Bes electrons are already paired
one of Bes electrons must be promoted to 2p:


Now there are two Be atoms for bonding, but this indicates
that the two BeCl bonds are different since one forms
from a 2s orbital and other from the 2p orbital.
But experiments indicates that the two BeCl bonds are
equivalent
the 2s and 2p orbital hybridizes to form two equivalent sp
hybrid orbital:
sp
2
hybrid orbital: mixing one s and two p orbitals

Consider BF
3
:
the ground state orbital diagram for B should be:
and promoting one of Bs 2s electrons to 2p gives
Now there are three B orbitals for bonding, but this
indicates that two of the BF bonds (from 2s) should be
the same but one (from 2s) should be different.
But experiment indicates that the three BF bonds are
equivalent
the 2s and 2p orbital hybridizes to form three
equivalent sp
2
hybrid orbital:

sp
3
hybrid orbitals: mixing one s and three p
orbitals
Consider CH
4
. (Draw the ground state orbital
diagram and show the hybridization process)

sp
3
d hybrid orbitals: mixing of one s orbital,
three p orbitals, and one d orbital
sp
3
d
2
hybrid orbital: mixing of one s orbital,
three p orbitals, and two d orbitals



Predicting what hybrid orbitals form:
Draw Lewis structure to determine total
number of bonds on central atom
Given the Lewis structure, we can determine
what hybrid orbitals must be involved by
counting the number of bonds around each
atom (counting multiple bonds as one) and
number of lone pairs:

Number of bonds + Lone
Pairs
Hybrid Orbitals
2 sp
3 sp
2

4 sp
3

5 sp
3
d
6 sp
3
d
2

Valence Shell Electron Pair Repulsion Theory
The BEST arrangement of a given number of e

pairs is
the one that minimizes the repulsion among them.
The valence electron pairs (electron domains)
surrounding an atom repels one another so the orbitals
containing those electrons are oriented as far apart as
possible.

Types of valence electron pairs:
bonding pairs shared electrons
nonbonding pairs lone pairs
Types of electron repulsions:
lone pair lone pair (lp-lp)
lone pair bonding pair (lp-bp)
bonding pair- bonding pair (bp-bp)
Rules on Electronic Repulsion
Types of Repulsion
Bonding pair bonding pair < lone pair bonding
pair < lone pair lone pair
The increasing size and lower electronegativity
of the central atom permits the lone pairs to
be drawn out farther, thus decreasing
repulsion between bonding pairs.
decreasing bond angle (dec electronic repulsion):
H
2
O > H
2
S > H
2
Se

Repulsions exerted by bonding pairs decreases
as the electronegativity of the bonded atom
increases
decreasing bond angle (decreasing repulsion): H
2
O
> F
2
O
Presence of multiple bonds increases
repulsion between bonding pairs
decreasing bond angle: HC CH > H
2
C = CH
2
> H
3
C
CH
3


In trigonal bipyramidal
double bonds prefer equatorial position
lone pairs occupy equatorial position
least electronegative atoms prefer equatorial
position
In octahedron
Any lone pair occupies any position
If 2 lone pairs are present, it must be opposite to
each other
Multiple bonds do not affect the gross
geometry of the molecule because the
geometry is primarily determine by the
number of sigma bonds and lone pairs.


Terms:

electron pair geometry arrangement of
electrons pairs around an atom
molecular geometry arrangement of atoms
in space; may be predicted from the electron
pair geometry

Steps in predicting the Molecular
Geometry:
Write down the Lewis structure.
Count the total number of electron pair
around the central atom. (Note: Double bonds
and triple bonds counted as one electron
pair.)
Arrange electron pairs such that repulsion is
minimized.
Predict molecular geometry based on the
arrangement of bonding pairs/atoms.
Note:
Nonbonding (lone pairs) electron pairs and
electrons in multiple bonds exert greater
repulsive forces on adjacent electron pairs and
thus, tend to compress the angles between
bonding pairs.
lone pairs occupy hybrid orbital
multiple bonds do not occupy hybrid orbital

Writing a Lewis Structure
1. Sum the valence electrons from all the atoms
in the molecule.
For polyatomic anions, add the number of
negative charges to that total.
For polyatomic cations, we subtract the
number of positive charges from this total.
Writing a Lewis Structure
2. Choose the central atom and write the
skeletal structure of the compound, using
chemical symbols and placing bonded atoms
next to one another.
Least electronegative atom occupies the
central position.
Hydrogen and fl uorine usually occupy the
terminal (end).
Writing a Lewis Structure
3. Draw a single covalent bond between the
central atom and each of the surrounding
atoms.
For every used electron, subtract it from the
total number of valence electrons.
Writing a Lewis Structure
4. Complete the octets of the the central atom.
For every used electron, subtract it from the
total number of valence electrons.
Writing a Lewis Structure
5. Distribute the remaining electrons in the
surrounding atoms.
For every used electron, subtract it from the total
number of valence electrons.
Remember to satisfy the octet rule.
Carbon, Nitrogen, Oxygen and Fluorine (CNOF)
will never violate the octet rule, other elements
can.
-If an atom violates the OCTET Rule, it usually is the
central atom.

Writing a Lewis Structure
6. if the atom has fewer than eight electrons
(except H and He), try adding double or triple
bonds between the surrounding atoms and the
central atom.