Chem 5

Chapter 12

Chemical Bonding II:

Additional Aspects

Part 1

November 20, 2002

 New concepts today
• Valence bond theory
– A quantum mechanical theory of chemical bonding
• Hybridization
• σ bond

• π bond

• Polymer
Concept of covalent bond formation...

Hydrogen is the simplest molecule H2

Two H-atoms : 1s1

Imagine two H-atoms approach each other

and the wavefunctions overlap to form a
region of increased electron density between
the atoms…
 Two wavefunctions

Ψ1S Ψ’1S Ψ1S + Ψ’1S

+ +

Probability density
(Ψ1S + Ψ’1S)2
high in the middle

A covalent bond has high electron density in

between the nuclei, hence is more stable.
What about other orbitals?
Ψ1s Ψ1py py py py

+ + + +
+• _
• • + • • •
_ _ _ _
px

No bond No bond π bond

+• _ _
s +• _ px px •+ +• px

σ bond σ bond
Constructive and destructive interference of the wavefunctions
 VALENCE BOND THEORY

A covalent bond is formed by an

overlap of two valence atomic
orbitals that share an electron pair.

The greater the overlap the stronger the bond.

 Linus Pauling 1901 – 1994
Born in Portland, Oregon in 1901, Pauling was the eldest child
of a pharmacist who died while his son was young. Pauling’s
interest in chemistry began when a friend demonstrated a
reaction involving sulfuric acid and sugar. He began to study his
father’s chemistry books and set up a primitive laboratory in the
basement of his home. After high school, he attended what is
now Oregon State University. During this time, he became familiar with the work
of G. N. Lewis and Irving Langmuir on chemical bonds. In 1922 he graduated
summa cum laude and began doctoral studies at the California Institute of
Technology, later studying in Europe before returning to assume a faculty
position at C.I.T.
Like Lewis, Pauling’s interests covered a range of broad disciplines. He studied
crystal structures, chemical bonds, quantum mechanics, immunochemistry, and
DNA. In 1954, his research on the nature of chemical bonds won him the Nobel
Prize in Chemistry.
Pauling also held passionate convictions about nuclear weapons, campaigning
to educate the public about the dangers of nuclear testing. His positions made
him a controversial figure in the United States. In 1962, however, Pauling
became the only person awarded two unshared Nobel Prizes, earning the
Peace Prize for his anti-nuclear work.
 COMBINING ORBITALS TO FORM
HYBRIDS OF THE CENTRAL ATOM

The linear combination of two or more “native”

atomic orbitals on an atom to produce
“hybrid”atomic orbitals for that atom.

RULE: number of atomic orbitals that are combined

is equal to the number of resulting hybrid orbitals.

All resulting hybrid orbitals are degenerate (equal

in energy) and orthogonal (independent).
 Two sp hybrid
H-Be-H sp - HYBRIDIZATION
orbitals of Be

Atomic orbitals
Ψ(2px) Being the linear combinations
of Be, 2s & 2p of atomic wavefunctions, the sp
wavefunctions satisfy the
1
Ψ2 (sp) = (Ψ(2s) − Ψ(2p x ) ) Schrödinger equation.
2

Note sp wavefunctions are

nonzero at the nucleus!

Ψ(2s) We ignore the other two p

orbitals because they are
empty.
2px Ψ1 (sp) =
1
(Ψ(2s) + Ψ(2p x ) )
2s 2

sp sp Degenerate
 sp-HYBRIDIZATION

The s and p orbitals

The two sp-hybrids

Directed at 180o

PHH p 443
Each σ bond in BeH2 results from the overlap of a H 1s
orbital and a Be sp orbital.
Ψ(1s) Ψ1(sp)

Ψ2(sp) Ψ(1s)
 sp2 hybridization For example

Ψ(2s)

1 1 1
ψ 2 (sp 2 ) = ψ(2s) − ψ(2p x ) − ψ(2p y )
3 6 2

Ψ(2px)

1 2
+ - ψ1 (sp 2 ) = ψ(2s) + ψ(2p x )
3 3

Ψ(2py)

1 1 1
ψ 3 (sp 2 ) = ψ(2s) − ψ(2p x ) + ψ(2p y )
3 6 2

PHH P477
 COMBINE one s-orbital and two p-orbitals

sp2 - orbitals oriented at 120o

The s and p orbitals

The three sp2-hybrids

 H
METHANE: CH4

four hybrid orbitals

needed to form four C
H
bonds H
H

s + px + py + pz 4 sp3 hybrids

The four sp3 hybrid orbitals form a tetrahedral

arrangement.
When orbitals are hybridized they have the
same energy:
HYBRIDIZE

2p
E E sp3
2s

Orbitals in Hybridized orbitals of

free C atom C atom in methane

The FOUR sp3 hybrids are degenerate.

 sp3 HYBRIDIZATION

Ψ(2s) Ψ(2px) Ψ(2py) Ψ(2pz) Atomic orbitals

Four sp3 hybrid orbitals

ψ 1 ( sp 3 ) =
1
(ψ (2s) +ψ (2 px ) +ψ (2 p y ) +ψ (2 pz )), ψ 3 (sp 3 ) = 12 (ψ (2s) +ψ (2 px ) −ψ (2 p y ) −ψ (2 pz ))
2
ψ 2 ( sp 3 ) = (ψ (2s) −ψ (2 p x ) −ψ (2 p y ) + ψ (2 p z ) ), ψ 4 ( sp 3 ) = (ψ (2s ) −ψ (2 p x ) + ψ (2 p y ) −ψ (2 p z ) )
1 1
2 2
 Each bond in methane results from the overlap of a
hydrogen 1s orbital and a carbon sp3 orbital.

Carbon sp3
orbitals H
These are four
σ bonds.
Hydrogen C
1s orbital H
H

Same sp3 orbitals for CH4, CCl4, CF2Cl2, NH3, NH4+, H2O, H3O+
 Cl
PCl5 Cl Cl
P
Cl Cl

Need five hybrid orbitals on the phosphorus

to fit the trigonal bipyramidal EPG.

d + s + px + py + pz 5 sp3d hybrids

Five degenerate orbitals...

PCl5 sp3d - hybrid orbitals
TRIGONAL BIPYRAMID EPG 5 PAIRS
z

+
+
1200 y
+
+

x 900
+
The small negative lobes
of the 5 sp3d not shown

overlap with orbitals on chlorine to form 5 σ bonds.

 F
F F
SF6 S
F F
F

We need six hybrid orbitals on the sulfur to

allow for the octahedral EPG and six bonds.

s + px + py + pz + d + d 6 sp3d2 hybrids

SIX degenerate orbitals...

 sp3d2- hybrid orbitals
SF6
z 900
+
+
y
+ +

900 +
+
x
The small negative lobes
of the 6 sp3d2 not shown

overlap with orbitals on flourine to form 6 σ bonds.

 VALENCE BOND MODEL
Step 1: Draw the Lewis structure(s)

Step 2: Determine the geometry of the electron pairs around each atom
using VSEPR

Step 3: Specify the hybrid orbitals needed to accommodate the electron

pairs on each atom

Geometry Example # of bonds

2

3
4

5
6
 H H
Multiple Covalent Bond
C C 120o
Ethylene C2H4
H H
VSEPR trigonal planar EPG
around each C-atom.
three hybrid orbitals on each carbon for the trigonal
planar EPG.

s + px + py 3 sp2 hybrids

The CARBON is sp2 hybridized

The 3 sp2 hybrid orbitals form a trigonal planar arrangement.

 FORMATION OF sp2 hybrids

HYBRIDIZE

2p 2p
E E sp2
2s

C atom sp2 hybridized orbitals of C

and a p orbital unhybridized
 An sp2 hydridized C atom
sp2 - hybrid orbital
z UNHYBRIDIZED
p- orbital
+
+
y
+
+
The unhybridized p
x _ orbital is
perpendicular to
sp2 plane.
 overlap two sp2 hybrids on each carbon with hydrogen
1s orbitals to form σ bonds and... H H
C C
z σ bond z H H

+ +
H H
y y

H
H _ _
x x

The two unhybridized p orbitals are left over to form a π bond.

The second part of the carbon-carbon double bond !
H H
π bond C C
z z
H H
+
H H
y
y
x H
H
_
x

Electrons are shared between the unhybridized p orbitals in

an area above and below the line between nuclei.
 BONDING IN ETHYLENE
π:C(2p)-C(2p)
σ:C(sp2)-C(sp2)

H H

σ: H(1s)-C(sp2) C C σ: H(1s)-C(sp2)

H H
The π bond is a single bond.
+ + +

_ _ _

The π orbital has a positive and a negative part, just like a

p orbital, and the entire orbital holds a pair of electrons.
 BONDING IN ACETELYNE

π:C(2p)-C(2p) two (single) π bonds!

σ: H(1s)-C(sp) σ: H(1s)-C(sp)

H C C H

σ:C(sp)-C(sp)
OVERLAP the sp hybrids from the two carbons to
form a σ bond between them.

z z

+ _ + _
y y
H C C H
+ +
x _ _
x

framework of σ bonds
 z z

+ +
_ _
y y
H C C H
+ +
x _ _ x

two π (single) bonds

Lateral overlap of p orbitals to form two π bonds

z z
+
_
y y
H C C H

+
x x
_

two π bonds and one σ bond for the C ≡ C triple bond

 Demo: Nylon

n +n

+ n H2O

Polyamide
remove H2O

Amide linkage
 Summary
• Valence bond theory considers a covalent bond in terms of the overlap
of atomic orbitals.

• Hybridized orbitals are linear combination of atomic orbitals of the

central atom, to match the molecular geometry predicted by VSEPR.

• End-to−end overlap of orbitals results in a σ bond.

• Side-to−side overlap of two p orbitals results in a π bond.

• A double bond consists of a σ bond and a π bond.

• A triple bond consists of a σ bond and two π bonds.