Chapter 9

Molecular Geometry &

Bonding Theories
Overview
Molecular Shapes
VSEPR Model
Predicting Shapes
Effect of Nonbonding Electrons
Polarity of Molecules
Covalent Bonding
Hybrid Orbitals
sp, sp
2
, sp
3

hybrids containing d orbitals
Multiple Bonds
sigma (s) & pi (p)
localized & delocalized
Molecular Orbitals
electron configurations & bond order
diamagnetism & paramagnetism
Molecular Shapes & VSEPR
Shapes defined by bond angles
linear, 180 angles
trigonal planar, 120 angles
tetrahedral, 109.5 angles

VSEPR
Valence Shell Electron Pair Repulsion theory
electron pairs are arranged symmetrically with
maximum separation
Two electron pairs
180 apart
linear geometry

180
Three electron pairs
120 apart
trigonal planar geometry


120
Four electron pairs
109.5 apart
tetrahedral geometry




109.5
Five electron pairs
angles of 90 and 120
trigonal bipyramidal (TBP) geometry


120
90
Six electron pairs
angles of 90
octahedral geometry

90
Geometries
Electron pair geometry
arrangement of electron pairs around a central
atom
Molecular Geometry
arrangement of atoms around a central atom
When all electron pairs are bonding pairs
electron pair geometry = molecular geometry
When there are unshared electron pairs
electron pair geometry molecular geometry
To determine electron pair geometry
draw Lewis dot structure
count shared & unshared electron pairs around
central atom
a multiple bond is counted as only one bonding pair when
predicting geometry
determine electron pair geometry based on the
number of electron pairs
2 pair = linear
3 pair = trigonal planar
4 pair = tetrahedral
5 pair = trigonal bipyramidal
6 pair = octahedral
Molecular Geometries with One or More
Unshared Pairs
Two Pairs

electron pair geometry linear

bonding pairs 2

non-bonding pairs 0

molecular geometry linear
Two electron pairs

180
electron pair geometry
molecular geometry


Three Pairs

electron pair geometry trigonal planar

bonding pairs 3 2

non-bonding pairs 0 1

molecular geometry trig. pl. bent
Three electron pairs


120

trigonal planar
bent
electron pair geometry
molecular geometry
trigonal planar
Four Pairs

electron pair geometry tetrahedral

bonding pairs 4 3 2

non-bonding pairs 0 1 2

molecular geometry tet. trig. pyr. bent
Four electron pairs




109.5
electron pair
geometry



bent
trigonal pyramid
tetrahedral
molecular
geometry
Five Pairs

electron pair geometry trigonal bipyramid

bonding pairs 5 4 3 2

non-bonding pairs 0 1 2 3

molecular geometry tbp seesaw T-shp. Lin.
Five electron pair


120
90
electron pair
geometry
molecular geometry

TBP
seesaw
T-shaped
linear
Six Pairs

electron pair geometry octahedral

bonding pairs 6 5 4 2

non-bonding pairs 0 1 2 4

molecular geometry oct sq.pyr. sq. pl. lin.
Six electron pairs

90

square
pyramid

linear
square
planar
octahedral
electron pair geometry
molecular geometry
Molecular Polarity
Molecules are always non-polar if all covalent
bonds are non-polar
N
2
, P
4
, Cl
2

Molecules with polar bonds can be polar or non-
polar
H - Cl polar bond, polar molecular
O=C=O two polar bonds but total molecule is
non-polar
H Cl
d+ d-
O C O
d+
d- d-
equal but opposite
forces cancel out
non-polar molecule
O
H H
d+
d+
d-
are these dipole moments equal & opposite?
no
is this molecule polar?
yes
C
Cl Cl
d- d-
d+
Cl Cl
d-
d-
are these bond dipole moments equal & opposite?
yes
is this molecule polar?
no
C
Cl Cl
d- d-
H H
d+
d+
are these bond dipole moments equal & opposite?
no
is this molecule polar?
yes
Single and Multiple Bonds
s (sigma) bonds
always the first bond between two atoms
single bonds are localized between two atoms
orbitals from two atoms overlap, allowing electrons to be shared
electron density is on the internuclear axis
C C

localized electrons
p (pi) bonds
the second & third bonds between two atoms
p bond electrons can be delocalized over
several atoms to form resonance structures
electron density is above & below the internuclear axis
C C C C
internuclear axis
electron
density above
& below--p
bond
C C C C
electron density can move
or delocalize

Hybridization
allows for greater number of bonds
types of hybridization
sp mixing of one s orbital & one p orbital

2s 2p sp p
sp
2
mixing of one s orbital & two p orbitals

2s 2p sp
2
p
sp
3
mixing of one s orbital & three p orbitals

2s 2p sp
3

in sp hybridization
the two sp hybrid orbitals form two s bonds
with linear geometry
remaining two p orbitals form p bonds
in sp
2
hybridization
the three hybrid orbitals form three s bonds
with trigonal planar geometry
the remaining one p orbital forms a p bond
in sp
3
hybridization
the four hybrid orbitals form four s bonds
with tetrahedral geometry
sp
3
hybrid atoms can form no p bonds as they
have no unhybridized p orbitals
Molecular Orbitals
mathematical combinations of atomic orbitals
delocalized over whole molecule
n atomic orbitals produce n molecular orbitals
are bonding orbitals and are antibonding orbitals

bond order
# bonding electrons - # antibonding electron
2
electron configuration of diatomic, homonuclear
molecules

s *
p *
p
s

s *
s
MOs from s orbital
combination
MOs from p orbital
combination
electron configuration of diatomic, homonuclear
molecules with interaction of the 2s and 2p
orbitals

s *
p *
s
p

s *
s
relative positions
switched
s *
p *
s
p

s *
s
s *
p *
s
p

s *
s
H
2
N
2

2 electrons 10 electrons
B.O. = 1 B.O. = 3
s *
p *
s
p

s *
s
s *
p *
p
s

s *
s
He
2

4 electrons
B.O. = 0
O
2

12 electrons
B.O. = 2