Chemical Bonding
and
Molecular Structure
(Chapter 9)
Ionic vs. covalent bonding
Molecular orbitals and the covalent bond (Ch. 10)
Valence electron Lewis dot structures
octet vs. non-octet
resonance structures
formal charges
VSEPR - predicting shapes of molecules
Bond properties
polarity, bond order, bond strength
18, 20 Oct 97 Bonding and Structure 1
Forms of Chemical Bonds
There are 2 extreme forms of connecting
or bonding atoms:
Ioniccomplete transfer of electrons
from one atom to another
Covalentelectrons shared between
atoms
Most bonds are somewhere in between.
18, 20 Oct 97 Bonding and Structure 2
Ionic compounds
- essentially complete electron
transfer from an element of low
Ionic
IE (metal) to an element of high
electron affinity (EA) (nonmetal)
Bonds
Na(s) + 1/2 Cl2(g) Na+ + Cl-
NaCl (s)
- primarily between metals
(Grps 1A, 2A and transition metals)
and nonmetals (esp O and halogens)
- NON-DIRECTIONAL bonding
via Coulomb (charge) interaction
18, 20 Oct 97 Bonding and Structure 3
Covalent Bonding
Covalent bond is the sharing of the VALENCE
ELECTRONS of each atom in a bond
Recall: Electrons are divided between core
and valence electrons.
ATOM core valence
Na 1s2 2s2 2p6 3s1 [Ne] 3s1
Br [Ar] 3d10 4s2 4p5 [Ar] 3d10 4s2 4p5
Br Br
18, 20 Oct 97 Bonding and Structure 4
8A
1A
Valence Electrons
2A 3A 4A 5A 6A 7A
Number of valence electrons is
equal to the Group number.
18, 20 Oct 97 Bonding and Structure 5
Covalent Bonding
The bond arises from the mutual attraction
of 2 nuclei for the same electrons.
HA + HB HA HB
A covalent bond is a balance
of attractive and repulsive forces.
18, 20 Oct 97 Bonding and Structure 6
18, 20 Oct 97 Bonding and Structure 7
Three dimensional arrangement of the atoms
in a molecule.
Bond Angle 180o ~120o ~109o
8
Linear structure atoms in a line
Carbon dioxide
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Trigonal planar atoms in a triangle
Boron trifluoride
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Tetrahedral structure
Methane
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VSEPR Model
VSEPR: Valence Shell Electron-Pair
Repulsion.
The structure around a given atom is
determined principally by minimizing electron
pair repulsions.
12
Three Pairs of Electrons
BF3
120
Trigonal planar
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Four Pairs of Electrons
CH4
109.5
Tetrahedral
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15
2 Electron Grps = 180o
3 Electron Grps =
~120o
4 Electron Grps =
~109o
16
Bond Formation
A bond can result from a head-to-head overlap
of atomic orbitals on neighboring atoms.
H + Cl
H Cl
Overlap of H (1s) and Cl (2p)
This type of overlap places bonding electrons in a
MOLECULAR ORBITAL along the line between
the two atoms and forms a SIGMA BOND (s).
18, 20 Oct 97 Bonding and Structure 17
Sigma Bond Formation by Orbital Overlap
Two s Atomic Orbitals (A.O.s) overlap to form
an ss (sigma) Molecular Orbital (M.O.)
H H
+
sigma bond ( s)
18, 20 Oct 97 Bonding and Structure 18
Sigma Bond Formation by Orbital Overlap
H H
+ Two s A.O.s overlap to
from an s s M.O.
sigma bond ( s)
Similarly, two p A.O.s
can overlap end-on to
from a ps M.O.
e.g.
F2
18, 20 Oct 97 Bonding and Structure 19
MO Theory
Robert Mullikan won the Nobel Prize in 1966
for developing this theory.
This theory describes the electrons in orbitals
belonging to the entire molecule.
Molecular Orbitals
A molecular orbital (MO) can hold a maximum
of two electrons.
A MO has a definite energy.
We can represent an MO with an electron-
density cloud.
LCAO
Linear Combination of Atomic Orbitals
Whenever two atomic orbitals overlap, two molecular
orbitals form.
# in = # out
Energy is conserved, so
One orbital will be lower in energy
One orbital will be higher in energy
The Hydrogen Molecule
The Two Orbitals
s* Antibonding orbital
Very little electron density between the nuclei
Higher in energy
Destabilizes bond formation
s Bonding orbital
Promotes bond formation
Electron density is between the nuclei
Lower in energy
Bonding and Antibonding Orbitals
MO Diagrams
H2 and He2
Complex MO Diagrams
Bond Order
In MO theory, bond
stability of a covalent Bond # of
bond is related to its Order bonds
bond order.
0 No bond
Bond order = ( # exists
bonding electrons - #
antibonding electrons) 1 Single
bond
Bond order can be an
integer or a fraction 2 Double
bond
3 Triple
bond
Calculate Bond Order for He2+
Compare bond orders
Which would be more stable: He2 or He2+?
Justify your answer.
