Principles of General Chemistry, 2nd ed. By M.

Silberberg
Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.

Exercises
1. Identify the type of bond/s that exist/s in the
Chemical Bonding following compounds:
a. SO2 b. FeCl2 c. Ca(OH)2
2. Use orbital diagrams to depict the formation
of MgO.
3. Draw all possible structures for NCO- and
determine the most stable structure.
4. Draw all resonance structures for NO3-.

Answers
Answers
3. NCO-
1. a. SO2
Covalent Bond
-2 0 +1 -1 0 0 0 0 -1
b. FeCl2
Ionic Bond –
N C O
– –
N C O N C O
c. Ca(OH)2
Ionic and Covalent Bonds
A B C

4. NO3 -
2. Mg: [Ne] 3s2 O: [He] 2s2 2p4
– – –
for MgO to form, 2e-s are transferred from Mg to O resulting to: O O O

Mg2+: [Ne] N N N
O O

O2-: [He] 2s2 2p6 O O O O

Principles of General Chemistry, 2nd ed. By M. Silberberg

Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.

Lecture topics…
Molecular Structure &
1. Stereochemistry
Covalent Bonding 2. Valence Shell Electron Pair Repulsion
Theories (VSEPR) Theory
3. Polar Molecules: The Influence of
Molecular Geometry
4. Valence Bond (VB) Theory
5. Molecular Shapes and Bonding

Stereochemistry
• the study of the three
dimensional shapes of
molecules.
• can be used to explain
chemical properties associated
with intermolecular attractions
Basic approach
for molecular structure prediction:
3. Determine the electronic geometry
around the central atom.
– VSEPR is a guide to the geometry.
4. Determine the molecular geometry
around the central atom.
– Ignore the lone pairs of electrons.
5. Adjust molecular geometry for effect
of any lone pairs.
In summary of the approach…
Basic approach
for molecular structure prediction:
1. Draw the correct Lewis dot structure.
– Identify the central atom.
– Designate the bonding pairs and lone
pairs of electrons on central atom.
2. Count the regions of high electron
density on the central atom.
– Include both bonding and lone pairs in
the counting.
Basic approach
for molecular structure prediction:
6. Determine the hybrid orbitals on
central atom.
7. Repeat procedure if there is more
than one central atom in molecule.
8. Determine molecular polarity from
entire molecular geometry using
electronegativity differences.
Two Simple Theories
of Covalent Bonding
• Valence Shell Electron Pair Repulsion
Theory (VSEPR)
– Principal originator: R. J. Gillespie in the 1950’s
• Valence Bond Theory (VBT)
– Principal originator: L. Pauling in the 1930’s-40’s
 VSEPR Theory VSEPR Theory
• Regions of high electron density around • two regions of high electron density
the central atom are arranged as far apart around the central atom
as possible to minimize repulsions.
= 2 electron groups
• There are five basic molecular shapes based
on the number of regions of high electron
density around the central atom.

note: regions of high electron density =

electron groups = bonding + lone pairs

VSEPR Theory VSEPR Theory

• three regions of high electron density • four regions of high electron density
around the central atom around the central atom
= 3 electron groups = 4 electron groups

VSEPR Theory VSEPR Theory

• five regions of high electron density • six regions of high electron density
around the central atom around the central atom
= 5 electron groups = 6 electron groups
Balloon Analogies of the
Electron (Group) Geometries
Angular Consideration
VSEPR Theory
two geometries for each molecule:
• electronic group geometry (EGG) is
determined by the locations of regions of
high electron density around the central
atom(s).
• molecular group geometry (MGG) or
molecular shape is determined by the
arrangement of atoms around the central
atom(s).
Balloon Analogies of the
Electron (Group) Geometries
Angular Consideration
VSEPR Theory
• lone pairs of electrons (unshared pairs)
require more volume than shared pairs.
– consequently, there is an ordering of repulsions of
electrons around central atom.
• Ordering of the repulsions:
– lone pair to lone pair is the strongest
– lone pair to bonding pair is intermediate
– bonding pair to bonding pair is the weakest
• note: lone pair to lone pair repulsion results to a
109.5º bond angles in water
 the single molecular shape of the
VSEPR Theory linear electron group arrangement
• consider: methane (CH4) and water (H2O)
CH4 – an example of a molecule that has the
same electronic and molecular geometries
– electronic and molecular geometries are
both tetrahedral
H2O – an example of a molecule that has
different electronic and molecular geometries
– electronic geometry is tetrahedral &
molecular geometry is bent or angular

the two molecular shapes of the the three molecular shapes of the
trigonal planar electron group tetrahedral electron group
arrangement arrangement

the four molecular shapes of the

the three molecular shapes of the
trigonal bipyramidal electron group
octahedral group arrangement
arrangement
polar molecules: the influence polar molecules: the influence
of molecular geometry of molecular geometry
• molecular geometry affects molecular
polarity.
– Due to the effect of the bond dipoles and how they
either cancel or reinforce each other.

A B A A B
A
linear molecule angular molecule
nonpolar polar

Valence Bond (VB) Theory Valence Bond (VB) Theory

• Covalent bonds are formed by the Regions of Electronic Hybridization

overlap of atomic orbitals. High Electron Geometry
Density
• Atomic orbitals on the central atom can 2 Linear sp
mix and exchange their character with 3 Trigonal sp2
other atoms in a molecule. planar
– process is called hybridization. 4 Tetrahedral sp3
• Hybrid Orbitals have the same shapes as 5 Trigonal sp3d
predicted by VSEPR. bipyramidal
6 Octahedral sp3d2

Linear EGG: sp hybridized central Linear EGG: sp hybridized central

atom atom

Electronic Structures Lewis Formulas Dot Formula Electronic & Molecular

1s 2s 2p Geometry
B e ·· ·· ··
Be ↑↓ ↑↓ · Cl · Be · Cl ·
· · · ·
3s 3p ·· ··
··
·· C l .
Cl [Ne] ↑↓ ↑↓ ↑↓ ↑ ··
Linear EGG: sp hybridized central Linear EGG: sp hybridized central
atom atom
Orbital Box Diagram
for Hybridization of Be

Trigonal Planar EGG: sp2 Trigonal Planar EGG: sp2

hybridized central atom hybridized central atom

Electronic Structures Lewis Formulas Dot Formula Electronic & Molecular

·· ·· Geometry
1s 2s 2p B. ·· Cl ··
B ↑↓ ↑↓ ↑
··
3s 3p ·· ·· B ·· Cl Cl
Cl [Ne] ↑↓ ↑↓ ↑↓ ↑
·· Cl . ·· Cl ·· ·· Cl ·· B
·· Cl
·· ··
120o-trigonal planar

Trigonal Planar EGG: sp2 Trigonal Planar EGG: sp2

hybridized central atom hybridized central atom
Orbital Box Diagram
for Hybridization of B
Tetrahedral EGG: sp3 hybridized Tetrahedral EGG: sp3 hybridized
central atom central atom
Electronic & Molecular
Dot Formula Geometry
Electronic Structures Lewis Formulas
2s 2p H
.. ..
.. ..
[He] ↑↓ ↑ ↑ .C . H C
C
.. H
1s H
H ↑ H.

Tetrahedral EGG: sp3 hybridized Tetrahedral EGG: sp3 hybridized

central atom central atom
Orbital Box Diagram
for Hybridization of C

Tetrahedral EGG: sp3 hybridized Tetrahedral EGG: sp3 hybridized

central atom (with lone pairs) central atom (with lone pairs)
Trigonal Bipyramidal EGG: sp3d Octahedral EGG: sp3d2 hybridized
hybridized central atom (e.g. PCl5) central atom (e.g. SF6)

Compounds Containing Compounds Containing

Double Bonds Double Bonds
• with VSEPR or VBT, a double bond (& • VSEPR Theory suggests that the C
even a triple bond) is considered as ONE
electron group
atoms are at center of trigonal planes.

H H
Ethene or ethylene, C2H4, is the simplest
organic compound containing a double
bond. C C
H · · H H H
·
C ·· ·· C · or C C
H ·· · H H H
· H H

Compounds Containing Compounds Containing

Double Bonds
Valence Bond Theory (Hybridization)

consider each central atom
C atom has four electrons.
Three electrons from each C atom are in sp2
hybrids.One electron in each C atom remains
in an unhybridized p orbital
Double Bonds
• a proper orientation of the orbitals are
necessary for the formation of the bond
• an sp2 hybridized C atom has this shape.
> remember there will be one electron in each of
the three sp2 lobes and one in the p orbital.

2s 2p three sp2 hybrids 2p

C ↑↓ ↑ ↑ ⇒ ↑↑↑ ↑
Top View Side View
Compounds Containing Compounds Containing
Double Bonds Double Bonds
• the portion of the double bond formed from • the other portion of the double bond,
the head-on overlap of the sp2 hybrids is resulting from the side-on overlap of the p
designated as a σ bond. orbitals, is designated as a π bond.

Compounds Containing Compounds Containing

Double Bonds
• thus a C=C bond looks like this and is made
of two parts, one σ and one π bond (& is the
same for all double bonds).
Triple Bonds
• Ethyne or acetylene, C2H2, is the simplest
triple bond containing organic compound.
• Compound must have a triple bond to obey
octet rule.
• VSEPR suggests a linear geometry

H ·· C ·· ·· ·· C ·· H or H C C H

Compounds Containing Compounds Containing

Triple Bonds Triple Bonds
Valence Bond Theory (Hybridization) A σ bond results from the head-on overlap
Carbon has 4 electrons. of two sp hybrid orbitals.

Two of the electrons are in sp hybrids.

Two electrons remain in unhybridized p
orbitals.

2s 2p two sp hybrids 2p
C [He] ↑↓ ↑↑ ⇒ ↑↑ ↑↑
Compounds Containing Delocalization and Shapes of
Triple Bonds Molecular Orbitals
• The unhybridized p orbitals form two π bonds. • Valence bond theory discusses
note: a triple bond consists of one σ and two π resonance formulas.
bonds. – Carbonate ion (CO32-) is an example.

2- 2- 2-
O O O
C C C
O O O O O O

62

Delocalization and Shapes of Delocalization and Shapes of

Molecular Orbitals Molecular Orbitals
• Molecular orbital theory describes
shapes in terms of delocalization of
electrons.

63 64

Delocalization and Shapes of Delocalization and Shapes of

Molecular Orbitals Molecular Orbitals
• Resonance structure of Benzene- VB • Molecular orbital theory
theory.

65 66
“Genius ain’
ain’t anything
more than elegant
common sense.”
sense.”

questions?