5.111 Lecture Summary #15 Readings for today: Sections 3.4, 3.5, 3.6 and 3.7 (Sections 3.

4, 3.5, 3.6, 3.7, and 3.8 in 3rd ed) Valence Bond Theory. Read for Lecture #16: Sections 6.13, 6.15, 6.16, 6.17, 6.18, and 6.20 (Sections 6.14, 6.16, 6.17, 6.18, 6.19, and 6.21 in 3rd ed) The Enthalpy of Chemical Change. Assignment: Problem set #5 (due Friday, October 17th at noon) _______________________________________________________________________________ Topics: Valence bond theory and hybridization I. Sigma and pi bonds II. Hybridization of atomic orbitals A. sp3 hybridization B. sp2 hybridization C. sp hybridization ________________________________________________________________________________ VALENCE BOND THEORY AND HYBRIDIZATION In valence bond theory, bonds result from the pairing of unpaired electrons in atomic orbitals. I. SIGMA AND PI BONDS (sigma) bond: cylindrically symmetric with ____ nodal plane across the bond axis. (pi) bond: a bond with e- density in two lobes, one on each side of the bond axis. A pi bond has a _______________ nodal plane along the bond axis. We can describe multiple bonds according to valence-bond theory. single bond: ____________________ double bond: one -bond plus one ____________________ triple bond: one -bond plus ___________ -bonds

1s

1s

Applying simple VB theory results in the following prediction for methane bonding:

H 2pz 2s C 2px 2pz 2py 2px

+ + C H

According to this model, the C is bonded to only two H-atoms with an H-C-H bond of _______. This is NOT what is observed for methane!

II. HYBRIDIZATION OF ATOMIC ORBITALS A. sp3 hybridization A carbon atom has four unpaired electrons available for bonding once a 2s-electron is __________________ to an empty 2-p orbital. E

2pz

2px

2py 2sp3 2sp3 2sp3 2sp3

e- promotion

2s C
(4 valence e-s)

orbitals

The sp3 hybrid orbitals are equivalent and degenerate. They differ only in their ___________________ in space.
2s 2pz 2px 2py

+ + + +

+ +

four sp3 hybrid orbitals 2

In carbon, each sp3 orbital contains a single electron, allowing four bonds.
H
C

sp3 2sp3 H H H 2sp3 2sp3 2sp3

What provides the energy for the initial electron promotion? _______________!

H 2sp3 1s

bond

Each bond is labeled based on the bond type ( or ) and atomic orbital composition. Consider ethane, C2H6.
H
C

____ (C______, H______)

109.5

H
C

H H

2sp3
bond
H

2sp3

2sp3

2sp3 2sp3

2sp3

2sp3

Two bond types in ethane: ____________________ and ____________________ . Nitrogen: Electron promotion _____________ occur with nitrogen because promotion would not increase the number of unpaired electrons available for bonding.
E

2pz

2px

sp3
2py 2sp3 2sp3 2sp3 2sp3
N

2sp3
N

2sp3

2sp3 2sp3 H

H
2s

H
N
(5 valence e-s)

hybrid orbitals

2sp3 1s

bond

N-H bond description: ________________ N-atom geometry: ____________________ 3

Oxygen: Electron promotion does not occur.

E

sp3

2pz

2px

2py 2sp3 2sp3 2sp3 2sp3

H

2sp3
O

2sp3

2sp3 2sp3 H

2s
O
(6 valence e-s)

H
hybrid orbitals

104.5

H2O geometry: ________________

B. sp2 hybridization sp2 hybrid orbitals form from the combination of one s-orbital and two p-orbitals.
2s 2pz 2px 2py
2py

+ + + +

+ +

3 hybrid orbitals 1 p-orbital Boron: Boron has 3 unpaired electrons available for bonding once a 2s-electron is promoted to an empty 2-p orbital. E

2pz

2px

2py 2sp2 2sp2 2sp2

hybrid orbitals

electron promotion

2s
B
(3 valence e-s)

The s-orbital and two of the p-orbitals hybridize to form ______________ sp2 orbitals. The three sp2-orbitals lie in a ________________ to minimize electron repulsion. 4

H sp2

2py 2sp2 2sp2 2sp2

+
x

B + +
H

, H1s)

120 trigonal planar

Carbon: Carbon can also form sp2 hybrid orbitals.

E
2s 2pz 2px 2py

+ +

2pz

2px

2py 2sp2 2sp2 2sp2

hybrid orbitals

2py

+ hybridize

2py

2s
C
(4 valence e-s) electron promotion

sp2

2py 2sp2 2sp2 2sp2

2py

trigonal planar

120 Ethylene (C2H4) has a C-C double bond, meaning one _______-bond and 1 _______-bond.
2py

+ + +

+ +
z

2py

2py

+ x

+
y looking down the x-axis

looking down the y-axis

( _________, __________)

( _________, _________)
5

+ + +

z
H

z
+
H

+
y

+ x

In addition to the C-C double bond, there are four C-H bonds: ( _______, ______)

Note: molecules cannot rotate around a double bond. Rotation would require breaking the pi bond.

H H

Benzene (C6H6)
+
2py

+
H

C H

___________ (C2sp2, C2sp2) bonds ___________ (C2sp2, H1s) bonds

H C H C C H C H C C H H H

___________ (C2py, C2py) bonds

H C C C H C C

In reality, the 6 pi-electrons are ________________ over all six carbon atoms in the benzene molecule. Each C-C bond is a ________ bond.

+ + +

+ +

C H

+
C

2sp2

+ + +

2py

H H

C. sp hybridization sp hybrid orbitals form from the combination of one s-orbital and 1 p-orbital.
E

2pz

2px

2py 2sp 2sp

hybrid orbitals

2px 2py

2s

C
(4 valence e-s) electron promotion

2s

2pz

2px

2py

2px

2py

+ +

+ -

sp z H

(2px)

2p Cy

2py

z H

2px

2px

x
180

( ______, _______ )

( ______, _______ )

+
+
z H

+ +

(2px)

C (2py) C +

2px

( ______, _______ )