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 Two H-atoms : 1s1 H2

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 + _ • + • px
_

py py + •
_

+ •
_

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).

H-Be-H

Two sp hybrid orbitals of Be

sp - HYBRIDIZATION

Atomic orbitals Ψ(2px) of Be, 2s & 2p
Ψ2 (sp) =

Being the linear combinations of atomic wavefunctions, the sp wavefunctions satisfy the 1 (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.
Ψ1 (sp) = 1 (Ψ(2s) + Ψ(2p x ) ) 2

2s

2px

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
Ψ(2s)

For example

ψ 2 (sp 2 ) =
Ψ(2px) + -

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

ψ1 (sp 2 ) =

1 2 ψ(2s) + ψ(2p x ) 3 3

Ψ(2py)

ψ 3 (sp 2 ) =

1 1 1 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

METHANE: CH4 four hybrid orbitals needed to form four bonds

H

C H 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 2s Orbitals in free C atom E sp3

Hybridized orbitals of 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
1 1 ψ 3 ( sp 3 ) = (ψ (2s) + ψ (2 p x ) −ψ (2 p y ) −ψ (2 p z ) ) ψ 1 ( sp ) = (ψ (2s ) + ψ (2 p x ) + ψ (2 p y ) + ψ (2 p z ) ), 2 2 1 1 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 ) ) 2 2
3

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 1s orbital

C H H

H

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

PCl5

Cl 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 EPG 5 PAIRS z
+

TRIGONAL BIPYRAMID

1200

+ + +

y

x

+

900
The small negative lobes of the 5 sp3d not shown

overlap with orbitals on chlorine to form 5 σ bonds.

SF6

F F

F 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

Multiple Covalent Bond Ethylene VSEPR C2H4

H C H C

H 120o H

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 E 2s C atom E 2p sp2

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 orbital is perpendicular to sp2 plane.

x

overlap two sp2 hybrids on each carbon with hydrogen 1s orbitals to form σ bonds and... H H C C H H z z

σ bond

H

+

+

H y H

y 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 ! z H y H x x
_

π bond
+

H

H C C H

z

H

H y

H

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) H σ: H(1s)-C(sp2) H + _ + _ C C H σ: H(1s)-C(sp2) σ:C(sp2)-C(sp2)

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) H C C H σ: H(1s)-C(sp)

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 x
+

C
_

C x
_

H

framework of σ bonds

z
+ _

z
+ _

H
+

C x
_

y
+

y

C
_

H x

two π (single) bonds

Lateral overlap of p orbitals to form two π bonds

z + _ H x C y + _ y

z

C

H

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.

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