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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
Basic approach
Stereochemistry for molecular structure prediction:

• the study of the three


1. Draw the correct Lewis dot structure.
dimensional shapes of – Identify the central atom.
molecules. – Designate the bonding pairs and lone
• can be used to explain pairs of electrons on central atom.
chemical properties associated 2. Count the regions of high electron
density on the central atom.
with intermolecular attractions – Include both bonding and lone pairs in
the counting.

Basic approach Basic approach


for molecular structure prediction: for molecular structure prediction:
3. Determine the electronic geometry 6. Determine the hybrid orbitals on
around the central atom. central atom.
– VSEPR is a guide to the geometry. 7. Repeat procedure if there is more
4. Determine the molecular geometry than one central atom in molecule.
around the central atom. 8. Determine molecular polarity from
– Ignore the lone pairs of electrons. entire molecular geometry using
5. Adjust molecular geometry for effect electronegativity differences.
of any lone pairs.

Two Simple Theories


In summary of the approach…
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 Balloon Analogies of the
Electron (Group) Geometries Electron (Group) Geometries

Angular Consideration Angular Consideration

VSEPR Theory VSEPR Theory


two geometries for each molecule: • lone pairs of electrons (unshared pairs)
require more volume than shared pairs.
• electronic group geometry (EGG) is
determined by the locations of regions of – consequently, there is an ordering of repulsions of
high electron density around the central electrons around central atom.
atom(s). • Ordering of the repulsions:
• molecular group geometry (MGG) or – lone pair to lone pair is the strongest
molecular shape is determined by the – lone pair to bonding pair is intermediate
arrangement of atoms around the central
atom(s). – 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 Double Bonds
Valence Bond Theory (Hybridization) • a proper orientation of the orbitals are
consider each central atom necessary for the formation of the bond
C atom has four electrons. • an sp2 hybridized C atom has this shape.
> remember there will be one electron in each of
Three electrons from each C atom are in sp2 the three sp2 lobes and one in the p orbital.
hybrids.One electron in each C atom remains
in an unhybridized 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 Triple Bonds
• thus a C=C bond looks like this and is made • Ethyne or acetylene, C2H2, is the simplest
of two parts, one σ and one π bond (& is the triple bond containing organic compound.
same for all double bonds). • 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

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Delocalization and Shapes of Delocalization and Shapes of


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

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Delocalization and Shapes of Delocalization and Shapes of


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

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

questions?