Molecular Geometry and Bonding Theories

5.4. Hybrid Orbitals

Chem 16
Module 5

1st Semester SY 2020 – 2021

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 Learning • Discuss the different types of electron groups
Objectives • Identify the electron group geometry of a covalent compound/polyatomic
ion
Now we are • Identify the molecular group geometry of a covalent compound/polyatomic
ready to talk ion
about hybrid
orbitals • Determine the polarity of a covalent compound/polyatomic ion based on
molecular geometry
• Determine the hybridization of the orbitals in the central atom of a
covalent compound
• Draw the molecular orbital diagrams for homogeneous second period
diatomic molecule/ion
• Write the molecular orbital configuration of a homogeneous second period
diatomic molecule/ion
• Determine the bond order and magnetic property of a homogeneous
second period diatomic molecule/ion
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 NUMBER OF HYBRID ORBITALS FORMED

The VSEPR Theory was

good in accounting for
molecular shapes by
saying that electron But VSEPR fail to
groups stay as far away explain how the
to minimized their orbitals interact that
repulsion is why we study
Valence bond theory

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 IS AN
APPROXIMATE
THEORY PUT
FORTH TO
VALENCE EXPLAIN THE
ELECTRON PAIR
BOND THEORY OR COVALENT
BOND BY
QUANTUM
MECHANICS
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 BOND FORMATION
4 3 2 1
1. When electrons are far grom each other they do
not interact
2. Increased overlap brings the electrons and
nuclei closer together while simultaneously
decreasing electron-electron repulsion.
3. The distance that gives the lowest energy is the
bond length. The overlap region is covalent
bond.
4. However, if atoms crash land on each other and
get too close, the internuclear repulsion greatly
raises the energy.

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 TYPES OF BONDING

Sigma (s) Bond Pi (p) Bond

 Bonds formed by end to end overlap  Bonds formed by sideways overlap
of orbitals along the orbital axes between two parallel unhybridized p-
orbitals

hydrogen, H2

orine,
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 TYPES OF BONDING

Single Bonds Double Bonds Triple bonds Bond

 All single bonds  A double bond  A triple bond is made up
are σ-bonds. consists of one σ of one σ and two π
bond and one π bonds.
bond.
s s p
s s s s s
s s s s s p
s
s p s

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 Test Yourself

 Identify if the bonds

are sigma or pi
bonds

Note that all

bonds have one
sigma bond, the
rest are pi bonds

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  A double
Test Yourself bond has 1
sigma bond  A single bond
and 1 pi bond has 1 sigma
 Identify the number
of sigma and pi
s
bonds
p p
p
 A triple bond
has 1 sigma
bond and 2 pi
bond
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 Test Yourself

 How many σ bonds are there

in the commercial insecticide,
“Sevin,” shown below? How
many π bonds?

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 Test Yourself

 How many σ bonds are there

in the commercial insecticide,
“Sevin,” shown below? How
many π bonds?
Answer
There are 27 σ bonds.
There are 6 π bonds.

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 UNPAIRED ELECTRONS ARE INVOLVED IN BONDING

In VBT, the unpaired

valence electrons are Write the electron
the ones involved in configuration of the
bonding atom and look for
the unpaired
electron

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 Recall that these are
Shapes of Orbitals the shapes of
various orbitals

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 TEST YOURSELF WRITE THE ANSWERS IN YOUR WORKSHEETS

Show the bonding in H2

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 TEST YOURSELF
Start by writing the
Show the bonding in H2 electron
configuration of the
H atoms and
determine where the
unpaired electron is
located

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 The unpaired electron is
in an s orbital which is
spherical in shape
TEST YOURSELF

Show the bonding in H2

 Electron Configuration of H  Electron Configuration of H

1s 1s
 Atomic orbital Available for bonding  Atomic Orbital Available for Bonding

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 These spherical s
orbitals combine to
TEST YOURSELF form the H2 molecule.
The overlap region is
the sigma bond.
Show the bonding in H2

 Electron Configuration of H  Combination of Atomic  Electron Configuration of H

Orbitals to form H2

1s 1s
 Atomic orbital Available for bonding  Atomic Orbital Available for Bonding

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 TEST YOURSELF WRITE THE ANSWERS IN YOUR WORKSHEETS

Show the bonding in F2

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 The unpaired electron
in F is in an p orbital
which is dumbell in
TEST YOURSELF shape

Show the bonding in F2

 Electron Configuration of F  Electron Configuration of F

1s 2s 2p 1s 2s 2p
 Atomic orbital Available for bonding  Atomic Orbital Available for Bonding

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 These dumbell p
orbitals combine to
TEST YOURSELF form a sigma bond in
the F2 molecule

Show the bonding in F2

 Electron Configuration of F  Combination of Atomic  Electron Configuration of F

Orbitals to form F2

1s 2s 2p 1s 2s 2p
 Atomic orbital Available for bonding  Atomic Orbital Available for Bonding

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 TEST YOURSELF WRITE THE ANSWERS IN YOUR WORKSHEETS

Show the bonding in HF by providing the following information:

 Electron Configuration of H  Combination of Atomic  Electron Configuration of F

Orbitals to form HF

 Atomic orbital Available for bonding  Atomic Orbital Available for Bonding

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 TEST YOURSELF

Show the bonding in HF

 Electron Configuration of H  Combination of Atomic  Electron Configuration of F

Orbitals to form HF

1s 1s 2s 2p
 Atomic orbital Available for bonding  Atomic Orbital Available for Bonding

hydrogen fluoride, HF

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 Problems with bonding when using pure atomic
orbitals
These problems
 Be  no two unpaired electrons in bonding was
recognized long
for BeF2 before you were
1s 2s 2p
born!

 B  no three unpaired electrons

for BH3
1s 2s 2p
 C  no four unpaired electrons
for CH4
1s 2s 2p
 N  unpaired electrons are in p
orbitals; cannot explain angle
1s 2s 2p 23
 In 1939, Linus Pauling
proposed the hybrid
Linus Pauling and Hybridization orbitals to provide a
solution to these
problems. He won a
Nobel pize for this.

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 ARE USED TO
DESCRIBE THE
BONDING THAT
IS OBTAINED BY
HYBRID TAKING
COMBINATIONS
ORBITALS OF THE ATOMIC
ORBITALS OF
THE ISOLATED
ATOMS
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 CONSERVATION OF ORBITALS
This rule says that if
four atomic orbitals
hybridize, they will
form four hybrid
orbitals

 The number of hybrid orbitals

formed equals the number of
atomic orbitals used

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COMPOSITION AND ORIENTATION OF HYBRID ORBITALS
 DETERMINING THE HYBRIDIZATION OF THE CENTRAL ATOM

# Electron-groups on
Central Atom Arrangement Hybridization
2 linear sp
3 trigonal planar sp2
4 tetrahedral sp3
5 trigonal bipyramid dsp3 or sp3d

6 octahedral d2sp3 or sp3d2

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 Again, the
number of
electron
groups DETERMINING THE HYBRIDIZATION OF THE CENTRAL ATOM
predict the
shape and
the # Electron-groups on Electron Group
hybridization Central Atom Geometry Hybridization
of the central
atom
2 linear sp
3 trigonal planar sp2
4 tetrahedral sp3
5 trigonal bipyramid dsp3 or sp3d

6 octahedral d2sp3 or sp3d2

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HOW TO DETERMINE HYBRIDIZATION

electron group
geometry

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HOW TO DETERMINE HYBRIDIZATION

electron group
geometry

Let’s follow
these steps to
determine the
hybrid orbital
used by N in
NH3.

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 HOW TO DETERMINE HYBRIDIZATION

electron group
geometry

..
H N H
H

4 electron groups  sp3 hybrid orbital

ST
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 TEST YOURSELF

Determine the hybrid orbital and molecular geometry in the ff:

1. Phosphorus pentafluoride (PF5) 3. nitrite ([NO2]-)
2. Xenon tetrafluoride (XeF4) 4. hydrogen cyanide (HCN)

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 TEST YOURSELF

Determine the hybrid orbital and molecular geometry in the ff:

1. Phosphorus pentafluoride (PF5) 3. nitrite ([NO2]-)
2. Xenon tetrafluoride (XeF4) This table
4. hydrogen cyanide (HCN) shows that
the hybrid
orbital
depends on
the number
of electron
groups
around the
atom
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 TEST YOURSELF
Determine the hybrid orbital and molecular geometry in the ff:
1. Phosphorus pentafluoride (PF5) 3. nitrite ([NO2]-)

mg: Trigonal bipyramidal mg: bent

5eg sp3d 3eg  sp2

2. Xenon tetrafluoride (XeF4) 4. hydrogen cyanide (HCN)

mg: octahedral mg: linear
6eg  sp3d2 2eg  sp
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 Although Linus Pauling
originally proposed the
formation of sp3d and sp3d2

TO HYBRID OR NOT TO hybrid orbitals, newer

studies show evidence that
the energy of the d-orbital is

HYBRID – THAT IS THE too high to be involved in

hybridization with s and p
orbitals

QUESTION
So let’s focus on the
formation of sp, sp2
and sp3 hybrid
orbitals
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 FORMATION OF SP HYBRID ORBITAL IN BE
 2 Atomic Orbitals in  2 Hybrid Orbitals in Be  2 Atomic Orbitals  2 Hybrid  2 Combined
Be Combine formed Combine Orbitals Hybrid orbitals
Formed in one axis
 Molecular
Geometry:
Linear

 Angle: 180 o

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 Sigma bonds are
formed from the
head on overlap
of the sp hybrid
TEST YOURSELF orbitals in Be
and the p
orbitals in F
 Show the bonding between Be and F in BeF2

 Orbital Used by Be  Orbital Overlap in by BeF2  Orbital Used by F

(Two sp hybrid (Two p orbitals)
orbitals)

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 FORMATION OF SP2 HYBRID ORBITAL IN B
 3 Atomic Orbitals in B  3 Hybrid Orbitals in B  3 Atomic Orbitals  3 Hybrid  3 Combined
combine formed Combine o Orbitals Hybrid orbitals
Formed in one axis
 Geometry:
Tetrahedral
 Angle: 120 o

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 TEST YOURSELF
 Show the bonding between B and F in BF3

 Orbital Used by B  Orbital Overlap in by BH3  Orbital Used by F

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 FORMATION OF SP3 HYBRID  4 Combined
ORBITAL IN THE C OF CH4  4 Hybrid Hybrid orbitals
Orbitals in one axis
 4 Atomic Orbitals in C  4 Hybrid Orbitals in C  4 Atomic Orbitals Formed  Molecular
Combine Formed Combine Geometry:
tetrahedral
 Bond Angle:
109.5 o

 Four orbitals
for bonding
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 TEST YOURSELF
 Show the bonding between C and H in CH4

 Orbital Used by C (four  Orbital Overlap in by CH4  Orbitals Used by H’s

sp3 hybrid orbitals) (Four s orbitals)

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 FORMATION OF SP3 HYBRID
 4 Combined
ORBITAL IN THE N OF NH3  4 Hybrid Hybrid orbitals
Orbitals in one axis
 4 Atomic Orbitals in N  4 Hybrid Orbitals in N  4 Atomic Orbitals Formed  Molecular
Combine Formed Combine Geometry:
tetrahedral
 Bond Angle:
<109.5 o

 One orbitals
with lone pairs,
three orbitals
for bonding
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 The lone pair of
electrons are
also in a sp3
TEST YOURSELF hybid orbital

 Show the bonding between N and H in NH3

 Orbital Used by N (four  Orbital Overlap in by NH3  Orbital Used by H

sp3 hybrid orbitals) (Three s orbitals)

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 FORMATION OF SP3 HYBRID  4 Combined
ORBITAL IN THE O OF H2O  4 Hybrid
Hybrid orbitals
in one axis
Orbitals
 4 Hybrid Orbitals in O  4 Atomic Orbitals Formed  Molecular
 4 Atomic Orbitals in O
Formed Combine Geometry:
Combine
tetrahedral
 Bond Angle:
<109.5 o

 Two orbitals
with lone pairs,
two orbitals for
bonding
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 TEST YOURSELF
 Show the bonding between O and H in H2O; where are the lone pairs in the molecule?

 Orbitals Used by O (four  Orbital Overlap in H2O  Orbital Used by H

sp3 hybrid orbitals) (Two s orbitals)

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 FORMATION OF SP3 HYBRID  4 Combined
ORBITAL IN THE C OF CH4  4 Hybrid Hybrid orbitals
Orbitals in one axis
 4 Atomic Orbitals in C  4 Hybrid Orbitals in C  4 Atomic Orbitals Formed  Molecular
Combine Formed Combine Geometry:
tetrahedral
 Bond Angle:
109.5 o

sp3
sp3 sp3

sp3

 Four orbitals
for bonding
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 A sigma bond is
formed between
two C sp3 hybrid
TEST YOURSELF orbitals

 Show the bonding between C and H in C2H6

 Orbitals Used by C (four  Orbital Overlap in C2H6  Orbital Used by H

sp3 hybrid orbitals each) (Two s orbitals)

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 FORMATION OF SP2 HYBRID ORBITAL OF C IN C2H4
 3 Atomic Orbitals in C One s and two p orbital  3 sp2 Hybrid  3 Combined
 3 Hybrid Orbitals in C 
Combine; 1 p orbitals Combine and one p Orbitals Hybrid orbitals
formed; 1 p orbital kept orbitals left unhybridized
not involved in hybrid Formed; 1 p in one axis plus
as unhybridized
orbitals as is 1 unhybridized
p orbital
 Molecular
Geometry:
Linear
 Angle: 120 o
p
sp2
sp2

sp2

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 A sigma bond is
formed between
two C sp2 hybrid
orbitals and a pi
bond is formed
TEST YOURSELF by the sideways
overlap of two p
 Show the bonding between C and H in C2H4 orbitals

 Orbitals Used by C (three  Orbital Overlap in C2H6  Orbital Used by H

sp2 hybrid orbitals and 1 (Two s orbitals)
p orbtal each)

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 Here’s the pi
bond formed by
the sideways
PI BINDING IN C2H4 overlap of two p
orbitals

 The two unhybridized p orbitals are involved in sideways overlap to form a pi bond

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 FORMATION OF SP HYBRID ORBITAL OF C IN C2H2
 2 Atomic Orbitals in C One s and one p orbital  2 sp Hybrid  2 Combined
 2 Hybrid Orbitals in C 
Combine; 2 p orbitals Combine and two p Orbitals Hybrid orbitals
formed; 2 orbitals kept orbitals left unhybridized
not involved in hybrid Formed; 2 p in one axis plus
as unhybridized p
orbitals as is 2 unhybrizied p
 Molecular
Geometry:
Linear
 Angle: <180 o
p
p

sp sp

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 A sigma bond is
formed between
two C sp hybrid
orbitals and two pi
bonds are formed
TEST YOURSELF by sideways overlap
of p orbitals and
 Show the bonding between C and H in C2H2 two

 Orbitals Used by C (Two sp  Orbital Overlap in C2H2  Orbital Used by H

hybrid orbitals and 2 p
orbitals each) (Two s orbitals)

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 Recall that in
C2H4, a pi bond
is formed by the
PI BINDING IN C2H4 sideways overlap
of two p orbitals.
Some pi
 The two unhybridized p orbitals areelectrons
involvedcanin sideways overlap to form a pi bond
move to many p
orbitals they
delocalize

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 If I were an ELECTRONS
electron, I
would love to
THAT ARE
delocalize SPREAD OVER A
because I
NUMBER OF
am free to
wander
around
DELOCALIZED ATOMS IN A
MOLECULE
ELECTRONS RATHER THAN
LOCALIZED
BETWEEN PAIR
OF ATOMS
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IC UPD 1st Sem 2021

 Figure a shows the
resonance structures of
NO3-. The pi electrons are
TEST YOURSELF not permanently between
the N and one of the
oxygens. Instead, the pi
 Show the boding in nitrate, NO3- electrons are delocalized
throughout the ion. Figure b
is a model showing the
localized electrons staying
between the N and one O.
We can also see in figure b
that there are two other p
Figure a. Resonance structures of nitrate orbitals that are in the same
plane as the pi bond. In
figure c, the pi electrons
delocalize between the
three oxygens

Fig. b. localized p electrons

Figure c: delocalized p electrons
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 A requirement to
delocalize is to have
TEST YOURSELF p orbitals all in one
plane

 Show the boding in benzene, C6H6

Resonance structures

Sigma bonds P orbitals

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 The ring inside the
hexagon shows that
the pi electrons
delocalize and can
TEST YOURSELF freely move around
the ring and
delocalize
 Show the boding in benzene, C6H6

localized p electrons localized p electrons delocalized p electrons

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 Congratulations for finishing Module 5. Make sure
to finish your worksheet as a review for the
upcoming exam! Good luck!

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