CHM361

INORGANIC CHEMISTRY
Chapter 2.0
Valence Bond Theory
Che Faridah Osman
UiTM Perlis

Review the Hybridization

of Atomic Orbitals
sp, sp2, sp3, dsp3,d2sp3

What does hybridization mean?

Hybridization means mixing
Hybrid orbitals are generated by mixing
the characters of atomic orbitals.
A set of hybrid orbitals provides a
bonding picture for a molecule in terms
of localised -bonds
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The Central Themes of VB Theory

Basic Principle

A covalent bond forms when the orbitals of two atoms

overlap and the overlap region, which is between the
nuclei, is occupied by a pair of electrons.
The two wave functions are in phase so the amplitude increases
between the nuclei.

The Central Themes of VB Theory

Themes
A set of overlapping orbitals has a maximum of two
electrons that must have opposite spins.
The greater the orbital overlap, the stronger (more stable)
the bond.
The valence atomic orbitals in a molecule are different
from those in isolated atoms.
There is a hybridization of atomic orbitals to form molecular
orbitals.

Orbital shapes, Individual (isolated) Atoms

all s orbitals

all p orbitals

d orbitals

Rules for Predicting Molecular Geometry

1. Sketch the Lewis structure of the molecule or
ion
2. Count the electron pairs and arrange them in
the way that minimizes electron-pair repulsion.
3. Determine the position of the atoms from the
way the electron pairs are shared.
4. Determine the name of the molecular structure
from the position of the atoms.
5. Double or triple bonds are counted as one
bonding pair when predicting geometry.
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# Rules for writing Lewis symbol for covalent

bonding
1. Choose the most symmetry structure
2. Calculate N value. N is the number of needed
electrons for the entire atom to achieve octet
structure.
3. Calculate the A value. A is the number of
available electrons of each atom in the
compound.
4. Calculate S. S is the number of shared
electrons between the atoms by using the
following formula:
S=N-A
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Example : Lewis structure for CO2

1.
2.
3.
4.

Choose the most symmetry structure.

N= 8+ 8(2)=24 electrons needed
A=4 +6(2)=16 electrons available
S= 24-16= 8 electrons shared
..
..
: O::C: :O:
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To rationalize how the shapes of atomic orbitals

are transformed into the orbitals occupied in
covalently bonded species, we need the help of
two bonding theories:
Valence Bond (VB) Theory, the theory we will explore,
describes the placement of electrons into bonding
orbitals located around the individual atoms from
which they originated.
Molecular Orbital (MO) Theory places all electrons from
atoms involved into molecular orbitals spread out over
the entire species. This theory works well for excited
species, and molecules like O2. You will meet this theory
in advanced classes!
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COVALENT BOND FORMATION (VB THEORY)

In order for a covalent bond to form between
two atoms, overlap must occur between the orbitals
containing the valence electrons.
The best overlap occurs when two orbitals are
allowed
to meet head on in a straight line. When this occurs,
the atomic orbitals merge to form a single bonding
orbital and a single bond is formed, called a
sigma () bond.

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Dotted areas: representation of "electron cloud" for one electron

"Head-on Overlap"

Sigma Bond: merged orbital, 2 e's 13

Covalent bonds are formed when atomic orbitals

overlap.
There are two types of orbital overlap:
Sigma, s, overlap occurs when there is one bonding
interaction that results from the overlap of two orbitals.
Pi, p, overlap occurs when two bonding interactions
result from the overlap of orbitals.
single bond
sigma overlap
double bond sigma and pi overlaps
triple bond
sigma and two pi overlaps

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MAXIMIZING BOND FORMATION

In order for best overlap to occur, valence electrons
need to be re-oriented and electron clouds reshaped
to allow optimum contact.
To form as many bonds as possible from the available
valence electrons, sometimes separation of electron
pairs must also occur.
We describe the transformation process as orbital
hybridization and we focus on the central atom in
the species...
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Figure11.8

The conceptual steps from molecular formula to the hybrid orbitals

used in bonding.

Step 1
Molecular
formula

Step 2
Lewis
structure

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Step 3
Molecular shape
and e- group
arrangement

Hybrid
orbitals

sp Hybridization: all 2 Region

Species
BeCl2

Cl

Be

Be 2
2Cl 14

Cl

16 e's/2= 8 prs

Cl

Be

Cl

(octet violator)

Number of regions around CENTRAL ATOM: 2

Cl

Be

Cl

shape : LINEAR
bond angles: 180o
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Hybridization of Be in BeCl2
Valence es

Atomic Be: 1s2 2s2

Hybrid sp orbitals:
1 part s, 1 part p

Energy

2p

separate

2p

"hybridize"
"sp"

2s

2s

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"sp"

"arrange"
Be

Be is said to be
"sp hybridized"

(VSEPR)

FORMATION OF BeCl2:
Each Chlorine atom, 1s22s22p63s23p5 , has one
unshared electron in a p orbital.
The half filled p orbital overlaps head-on with a half
full hybrid sp orbital of the beryllium to form a sigma
bond.
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Be

Cl

Cl

Cl

Be

Be

Cl

Cl

Cl

sp hybridized, linear, 180o bond angles

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Formation of sp hybrid orbitals

The combination of an s orbital and a p orbital produces 2
2s new orbitals called sp orbitals.

These new orbitals are called hybrid orbitals

The process is called hybridization
What this means is that both the s and one p orbital are involved in
bonding to the connecting atoms
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sp2 Hybridization: All 3 Region Species

F
BF3

B 3
3F 21
24 e's/2= 12 prs

F
F

(octet violator)

Number of regions around CENTRAL ATOM: 3

F
F

shape : TRIGONAL PLANAR

bond angles: 120o
F

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Hybridization of B in BF3
Valence es

Hybrid sp2 orbitals:

1 part s, 2 parts p

Atomic B : 1s2 2s2 2p1

Energy

2p

separate

2p

"hybridize"
"sp2" "sp2" "sp2"

2s

2s

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"arrange"
B
(VSEPR)

B is said to be
"sp2 hybridized"

FORMATION OF BF3:
Each fluorine atom, 1s22s22p5, has one unshared
electron in a p orbital.
The half filled p orbital overlaps head-on with a half
full
hybrid sp2 orbital of the boron to form a sigma bond.
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sp2 hybridized, TRIGONAL PLANAR,

120o bond angles
F
F

B
B
F

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Formation of sp2 hybrid orbitals

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sp3 Hybridization: All 4 Region Species

CH4
H

C 4
4H 4
8
8 e's /2 = 4 pr

Number of regions around CENTRAL ATOM: 4

H

shape : TETRAHEDRAL
bond angles: 109.5o

C
H

H
H

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Hybridization of C in CH4
Valence es

Hybrid sp3 orbitals:

1 part s, 3 parts p

Atomic C : 1s2 2s2 2p2

Energy

2p

separate

2p

"hybridize"
"sp3" "sp3" "sp3" "sp3"

2s

2s
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"arrange"
(VSEPR)

C is said to be
"sp3 hybridized"

FORMATION OF CH4:
Each hydrogen atom, 1s1, has one unshared
electron in an s orbital. The half filled s orbital
overlaps head-on with a half full hybrid sp3 orbital
of the carbon to form a sigma bond.
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sp3hybridized, TETRAHEDRAL,
109.5o bond angles
H
H

H
H
H

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Formation of sp3 hybrid orbitals

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Unshared Pairs, Double or Triple Bonds

Unshared pairs occupy a hybridized orbital the

same as bonded pairs: See the example of NH3
that follows.
Double and triple bonds are formed from electrons
left behind and unused in p orbitals. Since all
multiple bonds are formed on top of sigma bonds,
the hybridization of the single () bonds determine
the hybridization and shape of the molecule...
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N
3H
NH3

5
3

8e's/2=4 prs

H
H

Number of regions around CENTRAL ATOM: 4

shape : TETRAHEDRAL
bond angles: < 109.5o

N
H
H

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Hybridization of N in NH3
Valence es

Atomic N: 1s2 2s2 2p3

Energy

2p

"hybridize"
"sp3" "sp3" "sp3" "sp3"

2s
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"arrange"
(VSEPR)

N is said to be
"sp3 hybridized"

FORMATION OF NH3:
Each hydrogen atom, 1s1, has one unshared
electron in an s orbital. The half filled s orbital
overlaps head-on with a half full hybrid sp3 orbital
of the nitrogen to form a sigma bond.
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sp3hybridized, TETRAHEDRAL,
~107o bond angles

H
H
H

H
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Figure11.5
continued

The sp3 hybrid orbitals in H2O.

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sp3d Hybridization: All 5 Region Species

F
PF5

P
5
5F 35
40
40 e's /2 = 20 pr

P
F

F
F

P
F

F
F

Number of regions around CENTRAL ATOM: 5

F
P

shape : TRIGONAL BIPYRAMIDAL

bond angles: 90, 120, 180o
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Hybridization of P in PF5

P: 1s2 2s2 2p6 3s2 3p3

Energy

3d

3d
separate

3p

3p

3s

3s
"hybridize"
3
39 d"
"sp3d" "sp3d" "sp3d" "sp

"sp3d"

"arrange"
(VSEPR)

P is said to be
"sp3d hybridized"

FORMATION OF PF5:
Each fluorine atom, 1s22s22p5, has one unshared
electron in a p orbital. The half filled p orbital
overlaps head-on with a half full hybrid sp3d orbital
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of the phosphorus to form a sigma bond.

sp3d hybridized, TRIGONAL BIPYRAMIDAL,

90, 120, 180o bond angles
F

F
P

F
F

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sp3d2 Hybridization: All 6 Region Species

F
SF6

S
6
6F 42
48
48 e's /2 = 24 pr

F
F

F
F
F

F
F

Number of regions around CENTRAL ATOM: 6

S
F

shape : OCTAHEDRAL
bond angles: 90, 180o

F
F

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Hybridization of S in SF6

S: 1s2 2s2 2p6 3s2 3p4

Energy

3d

3d
separate

3p

3p

3s

3s
"hybridize"
43
3 2

"sp d "

"arrange"
(VSEPR)

S is said to be
"sp3d2 hybridized"

FORMATION OF SF6:
Each fluorine atom, 1s22s22p5, has one unshared
electron in a p orbital. The half filled p orbital
overlaps head-on with a half full hybrid sp3d2 orbital
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of the phosphorus to form a sigma bond.

sp3d hybridized, TRIGONAL BIPYRAMIDAL,

90, 120, 180o bond angles
F
F

F
F

S
F

F
F

F
F
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The bonds in ethane(C2H6).

Figure11.9
both C are sp3
hybridized

s-sp3 overlaps to
bonds

sp3-sp3 overlap to form a

bond

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relatively even
distribution of
electron density over
all bonds

Figure11.10

The and bonds in ethylene (C2H4).

overlap in one position

p overlap -

electron
density

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Figure11.11

The and bonds in acetylene (C2H2).

overlap in one position

p overlap -

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Summary: Regions, Shapes and Hybridization

#, regions

shape

linear

3
4
5
6

hybridization
sp

trigonal
planar
tetrahedral

sp

sp

trigonal
bipyramidal
octahedral

sp3d
sp3d2
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50

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52

53

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Overlap of Orbitals

56

The degree of overlap is determined by the systems potential energy

equilibrium bond distance

The point at which the potential energy is a minimum is

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called the equilibrium bond distance

Hybrid orbitals can be used to explain bonding and molecular

geometry

58

Multiple Bonds

Everything we have talked about so far has only dealt with

what we call sigma bonds

Sigma bond () A bond where the line of electron

density is concentrated symmetrically along the line
connecting the two atoms.

Hybridization of atomic orbitals

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Pi bond () A bond where the overlapping regions

exist above and below the internuclear axis (with a
nodal plane along the internuclear axis).

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Example: H2C=CH2

61

Example: H2C=CH2

62

Example: HCCH

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Conclusion
IF you can draw a Lewis structure for a species,
and count electronic regions around central atom,
you can immediately determine:
the shape of the species about the central atom
the hybridization of the species based on the
central atom

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