Chemical Bonding II: Molecular Geometry and...
Transcript of Chemical Bonding II: Molecular Geometry and...
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Chapter 10
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Chemical Bonding II:
Molecular Geometry and
Hybridization of Atomic Orbitals
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Valence shell electron pair repulsion (VSEPR) model:
Predict the geometry of the molecule from the electrostatic
repulsions between the electron (bonding and nonbonding) pairs.
AB2 2 0
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
linear linear
B B
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Cl ClBe
2 atoms bonded to central atom
0 lone pairs on central atom
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AB2 2 0 linear linear
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB3 3 0trigonal
planar
trigonal
planar
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AB2 2 0 linear linear
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB3 3 0trigonal
planar
trigonal
planar
AB4 4 0 tetrahedral tetrahedral
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AB2 2 0 linear linear
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB3 3 0trigonal
planar
trigonal
planar
AB4 4 0 tetrahedral tetrahedral
AB5 5 0trigonal
bipyramidal
trigonal
bipyramidal
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AB2 2 0 linear linear
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB3 3 0trigonal
planar
trigonal
planar
AB4 4 0 tetrahedral tetrahedral
AB5 5 0trigonal
bipyramidal
trigonal
bipyramidal
AB6 6 0 octahedraloctahedral
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bonding-pair vs. bonding
pair repulsion
lone-pair vs. lone pair
repulsion
lone-pair vs. bonding
pair repulsion> >
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Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB3 3 0trigonal
planar
trigonal
planar
AB2E 2 1trigonal
planarbent
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Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB3E 3 1
AB4 4 0 tetrahedral tetrahedral
tetrahedraltrigonal
pyramidal
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Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB4 4 0 tetrahedral tetrahedral
AB3E 3 1 tetrahedraltrigonal
pyramidal
AB2E2 2 2 tetrahedral bent
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Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB5 5 0trigonal
bipyramidal
trigonal
bipyramidal
AB4E 4 1trigonal
bipyramidal
distorted
tetrahedron
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Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB5 5 0trigonal
bipyramidal
trigonal
bipyramidal
AB4E 4 1trigonal
bipyramidal
distorted
tetrahedron
AB3E2 3 2trigonal
bipyramidalT-shaped
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Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB5 5 0trigonal
bipyramidal
trigonal
bipyramidal
AB4E 4 1trigonal
bipyramidal
distorted
tetrahedron
AB3E2 3 2trigonal
bipyramidalT-shaped
AB2E3 2 3trigonal
bipyramidallinear
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Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB6 6 0 octahedraloctahedral
AB5E 5 1 octahedralsquare
pyramidal
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Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
VSEPR
AB6 6 0 octahedraloctahedral
AB5E 5 1 octahedralsquare
pyramidal
AB4E2 4 2 octahedralsquare
planar
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Predicting Molecular Geometry
1. Draw Lewis structure for molecule.
2. Count number of lone pairs on the central atom and
number of atoms bonded to the central atom.
3. Use VSEPR to predict the geometry of the molecule.
What are the molecular geometries of SO2 and SF4?
SO O
AB2E
bent
S
F
F
F F
AB4E
distorted
tetrahedron
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Dipole Moments and Polar Molecules
H F
electron rich
regionelectron poor
region
d+ d-m = Q x r
Q is the charge
r is the distance between charges
1 D = 3.36 x 10-30 C mC: is coulomb & m is meter
Dipole moments are usually expressed by: D (debye units named for Peter Debye
عزم ثنائي القطب والجزيئات القطبية
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Behavior of Polar Molecules
field off field on
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Bond moments and resultant dipole moments in NH3 and NF3.
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Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CF4
O
dipole moment
polar molecule
S
CO O
no dipole moment
nonpolar molecule
dipole moment
polar molecule
C
F
FFF
no dipole moment
nonpolar molecule
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Does BF3 have a dipole
moment?
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Does CH2Cl2 have a
dipole moment?
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Bond Enthalpy Bond Length
H2
F2
436.4 kJ/mol
150.6 kJ/mol
74 pm
142 pm
Valence bond theory – bonds are formed by sharing
of e- from overlapping atomic orbitals.
Overlap Of
2 1s
2 2p
How does Lewis theory explain the bonds in H2 and F2?
Sharing of two electrons between the two atoms.
Valence bond theory
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Change in Potential Energy of Two Hydrogen Atoms
as a Function of Their Distance of Separation
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Change in electron density as two hydrogen atoms
approach each other.
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Valence Bond Theory and NH3
N – 1s22s22p3
3 H – 1s1
If the bonds form from overlap of 3 2p orbitals on nitrogen with
the 1s orbital on each hydrogen atom, what would the molecular
geometry of NH3 be?
If use the
3 2p orbitals
predict 90o
Actual H-N-H
bond angle is
107.3o
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Hybridization – mixing of two or more atomic
orbitals to form a new set of hybrid orbitals.
1. Mix at least 2 nonequivalent atomic orbitals (e.g. s
and p). Hybrid orbitals have very different shape
from original atomic orbitals.
2. Number of hybrid orbitals is equal to number of
pure atomic orbitals used in the hybridization
process.
3. Covalent bonds are formed by:
a. Overlap of hybrid orbitals with atomic orbitals
b. Overlap of hybrid orbitals with other hybrid
orbitals
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Formation of sp3 Hybrid Orbitals
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Formation of Covalent Bonds in CH4
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Predict correct
bond angle
sp3-Hybridized N Atom in NH3
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Formation of sp Hybrid Orbitals
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Formation of sp2 Hybrid Orbitals
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# of Lone Pairs+
# of Bonded Atoms Hybridization Examples
2
3
4
5
6
sp
sp2
sp3
sp3d
sp3d2
BeCl2
BF3
CH4, NH3, H2O
PCl5
SF6
How do I predict the hybridization of the central atom?
1. Draw the Lewis structure of the molecule.
2. Count the number of lone pairs AND the number of
atoms bonded to the central atom
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sp2 Hybridization of Carbon
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Unhybridized 2pz orbital (gray), which is perpendicular
to the plane of the hybrid (green) orbitals.
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Sigma bond (s) – electron density between the 2 atoms
Pi bond (p) – electron density above and below plane of nuclei
of the bonding atoms
Bonding in Ethylene, C2H4
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Another View of p Bonding in Ethylene, C2H4
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sp Hybridization of Carbon
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Bonding in Acetylene, C2H2
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Another View of the Bonding in Ethylene, C2H4
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Describe the bonding in CH2O.
CH
OH
C – 3 bonded atoms, 0 lone pairs
C – sp2
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Sigma (s) and Pi Bonds (p)
Single bond 1 sigma bond
Double bond 1 sigma bond and 1 pi bond
Triple bond 1 sigma bond and 2 pi bonds
How many s and p bonds are in the acetic acid (vinegar)
molecule CH3COOH?
C
H
H
CH
O
O Hs bonds = 6 + 1 = 7
p bonds = 1
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Molecular orbital theory – bonds are formed from
interaction of atomic orbitals to form molecular
orbitals.
O
O
No unpaired e-
Should be diamagnetic
Experiments show O2 is paramagnetic
molecular orbitals Theory
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Energy levels of bonding and antibonding molecular
orbitals in hydrogen (H2).
A bonding molecular orbital has lower energy and greater
stability than the atomic orbitals from which it was formed.
An antibonding molecular orbital has higher energy and
lower stability than the atomic orbitals from which it was
formed.
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Constructive and Destructive Interference
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Two Possible Interactions Between Two Equivalent p Orbitals
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General molecular orbital energy level diagram for the
second-period homonuclear diatomic molecules Li2, Be2, B2,
C2, and N2.
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1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.
Molecular Orbital (MO) Configurations
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bond order = 1
2
Number of
electrons in
bonding
MOs
Number of
electrons in
antibonding
MOs( - )
bond
order½ 1 0½
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Delocalized molecular orbitals are not confined between
two adjacent bonding atoms, but actually extend over three
or more atoms.
Example: Benzene, C6H6
Delocalized p orbitals
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Electron density above and below the plane of the
benzene molecule.
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Bonding in the Carbonate Ion, CO32-