Principles of Chemistry 1 (KEMPRN1)

LECTURE 14
Molecular
4fz3 Polarity,
4fxz24fyz2 4fz(x2Hybridization,
–2y2) 4fxyz 4fy(3x2–y2)and
4fx(x2–3y2

Molecular Orbital Theory

Dr. Joel Garcia

Department of Chemistry
Dipole Moments and Polar Molecules

𝝁 = 𝑸×𝒓
Q is the charge.
r is the distance between charges
2
1D = 3.36×10,-. Cm
Resultant Dipole Moments in 𝑵𝑯𝟑 and 𝑵𝑭𝟑

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Resultant Dipole Moments in 𝑵𝑯𝟑 and 𝑵𝑭𝟑

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Resultant Dipole Moments in 𝑵𝑯𝟑 and 𝑵𝑭𝟑

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Resultant Dipole Moments in 𝑵𝑯𝟑 and 𝑵𝑭𝟑

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Resultant Dipole Moments in 𝑵𝑯𝟑 and 𝑵𝑭𝟑

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Resultant Dipole Moments in 𝑵𝑯𝟑 and 𝑵𝑭𝟑

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Resultant Dipole Moments in 𝑵𝑯𝟑 and 𝑵𝑭𝟑

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Example 10.2

Predict whether each of the following molecules has a dipole

moment:

(a) BrCl

(b) BF- (trigonal planar)

(c) CH?Cl? (tetrahedral)

Example 10.2 (1)
Strategy
Keep in mind that the dipole moment of a molecule depends on
both the difference in electronegativities of the elements
present and its geometry.

A molecule can have polar bonds (if the bonded atoms have
different electronegativities), but it may not possess a dipole
moment if it has a highly symmetrical geometry.
Example 10.2 (2)
Solution
(a) Because bromine chloride is diatomic, it has a linear
geometry. Chlorine is more electronegative than bromine
(see Figure 9.5), so BrCl is polar with chlorine at the
negative end Copyright © McGraw-Hill Education permission required
for reproduction or display

Thus, the molecule does have a dipole moment. In fact, all

diatomic molecules containing different elements possess a
dipole moment.
Example 10.2 (3)
(b) Because fluorine is more electronegative than boron, each
B − F bond in BF- (boron trifluoride) is polar and the three
bond moments are equal. However, the symmetry of a
trigonal planar shape means that the three bond moments
exactly cancel one another:
Copyright © McGraw-Hill Education permission required
for reproduction or display

An analogy is an object that is pulled in the directions shown

by the three bond moments. If the forces are equal, the
object will not move. Consequently, BF- has no dipole
moment; it is a nonpolar molecule.
Example 10.2 (4)
(c) The Lewis structure of CH?Cl? (methylene chloride) is

This molecule is similar to CHA in that it has an overall

tetrahedral shape. However, because not all the bonds are
identical, there are three different bond angles: HCH, HCCl,
and ClCCl. These bond angles are close to, but not equal to,
109.5° .
Example 10.2 (5)
Because chlorine is more electronegative than carbon,
which is more electronegative than hydrogen, the bond
moments do not cancel and the molecule possesses a
dipole moment: Copyright © McGraw-Hill Education permission required
for reproduction or display

Thus, CH?Cl? is a polar molecule.

Theories of Covalent Bonding
 Valence Bond (VB) Theory
A covalent bond forms when the orbitals of two atoms
overlap and a pair of electrons occupy the overlap region.

The space formed by the overlapping orbitals can

accommodate a maximum of two electrons and these
electrons must have opposite (paired) spins.

The greater the orbital overlap, the stronger the bond.

Extent of orbital overlap depends on orbital shape and direction.
 Valence Bond (VB) Theory
A covalent bond forms when the orbitals of two atoms
overlap and a pair of electrons occupy the overlap region.

The space formed by the overlapping orbitals can

accommodate a maximum of two electrons and these
electrons must have opposite (paired) spins.

The
The greater
shared the orbital
space overlap,
is occupied the stronger
by two electrons,the bond.
which
have opposite
Extent spins.
of orbital overlap depends on orbital shape and direction.
Change in Potential Energy of Two Hydrogen Atoms
as a Function of Their Distance of Separation

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Orbital Orientation and Maximum Overlap

Hydrogen fluoride, HF.

Orbital Orientation and Maximum Overlap

Hydrogen fluoride, HF. Fluorine, F2.

 2s 2p
N

3H
1s 1s 1s
H N H
H
The Valence Bond Theory can be used to satisfy
the directionality of AOs.
For polyatomic molecules, directionality of AOs of the central
atom to its substituents can be an issue.
The Valence Bond Theory can be used to satisfy
the directionality of AOs.
For polyatomic molecules, directionality of AOs of the central
atom to its substituents can be an issue.
2s 2p early VBT treatment
N

3H
1s 1s 1s
H N H
H
The Valence Bond Theory can be used to satisfy
the directionality of AOs.
For polyatomic molecules, directionality of AOs of the central
atom to its substituents can be an issue.
2s 2p early VBT treatment VSEPR prediction
N

3H
Crystal structure of NH3 at 171K
1s 1s 1s
H N H
H
Formation of four sp3 hybrid orbitals can provide a
more accurate bonding picture of NH3.

2p hybridize

sp3 sp3 sp3 sp3

2s
N
2s22p3
Formation of four sp3 hybrid orbitals can provide a
more accurate bonding picture of NH3.

2p hybridize

sp3 sp3 sp3 sp3

2s
N
2s22p3
Formation of 𝒔𝒑𝟑 Hybrid Orbitals

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Formation of four sp3 hybrid orbitals can provide a
more accurate bonding picture of NH3.

2p hybridize

sp3 sp3 sp3 sp3

2s
N
2s22p3
Relationship between Hybridization and
the VSEPR Model.

sp

sp2

sp3

sp3dz2

sp3dz2dx2-y2
Relationship between Hybridization and
the VSEPR Model.

sp

sp2

sp3

sp3dz2

sp3dz2dx2-y2
Relationship between Hybridization and
the VSEPR Model.

sp

sp2

sp3

sp3dz2

sp3dz2dx2-y2
Relationship between Hybridization and
the VSEPR Model.

sp

sp2

sp3

sp3dz2

sp3dz2dx2-y2
Relationship between Hybridization and
the VSEPR Model.

sp

sp2

sp3

sp3dz2

sp3dz2dx2-y2
Method of orbital overlap by VBT does not explain
why carbon in CH4 forms four bonds.

2p

2s
C
2s22p2
Electron promotion followed by hybridization
can explain the bonding scheme in CH4.

promotion of
2p electron 2p hybridize

sp3 sp3 sp3 sp3

2s 2s
C
2s22p2
VBT can also be applied to rationalize the bond
equivalence of four C-H bonds.

promotion of
2p electron 2p hybridize

sp3 sp3 sp3 sp3

2s 2s
C
2s22p2

𝜎Csp -Hs
3

(all C-H bonds)

What about VBT treatment for multiple bonds?

2p

2s
C
2s22p2
What about VBT treatment for multiple bonds?

promotion of
2p electron 2p hybridize p
sp2 sp2 sp2
2s 2s
C
2s22p2
What about VBT treatment for multiple bonds?

promotion of
2p electron 2p hybridize p
sp2 sp2 sp2
2s 2s
C
2s22p2
 Bonding in Ethylene, 𝑪𝟐 𝑯𝟒

Sigma bond σ – head on overlap

Pi bond π – electron density above and below plane of nuclei

of the bonding atoms 41
 Bonding in Ethylene, 𝑪𝟐 𝑯𝟒

Sigma bond σ – head on overlap

Pi bond π – sideway overlap

42
 Bonding in Ethylene, 𝑪𝟐 𝑯𝟒

Sigma bond σ – electron density between the 2 atoms

Pi bond π – electron density above and below plane of nuclei

of the bonding atoms 43
 Sigma 𝛔 and Pi Bonds 𝝅

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

44
What about VBT treatment for multiple bonds?

promotion of
2p electron 2p hybridize p p
sp sp
2s 2s
C
2s22p2
Bonding in Acetylene, 𝐂𝟐 𝐇𝟐

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Bonding in Acetylene, 𝐂𝟐 𝐇𝟐

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Bonding in Acetylene, 𝐂𝟐 𝐇𝟐

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