Energy Diagrams for Orbital Interactions

The two atomic (1s) orbitals interact to form. a new lower energy (stabilized) bonding molecular orbital (MO)
• The bonding MO contains the electron pair that defines the covalent bond

Overlap of two atomic orbitals must yield two molecular orbitals. The other MO is destabilized and is referred
to as the anti-bonding molecular orbital
• In our H2 molecule, the anti-bonding orbital is unoccupied
Bonding vs Anti-Bonding Molecular Orbitals
 Structural Representations of Organic Molecules

H H H
H H H H OH H O
H C
C
C H H C N H N
C H C C
H C C H
≡ H C C H ≡ O C SH ≡ HO SH
C H H H NH2
H H H NH2
H H

Omit H’s on carbon (mostly), show H’s on non-carbon atoms (aka, heteroatoms)
 A couple more important concepts from General Chemistry
I. Bond Polarity
Electrons in covalent bonds need not be shared equally (e.g., between atoms with significantly
different electronegativities)

–
Cl δ Cl Cl
+
Cδ C C
H H Cl
H H Cl
H H Cl
C 2.5 bond dipole No net dipole
Cl 3.2 (also a molecular dipole)

II. Formal Charge

Atomic charge resulting from electron count in a given structure (not a molecular property)

C O C O
C 4 valence e–'s C 5 valence e–'s
O 6 valence e–'s O 5 valence e–'s

H3C C N H3C C N
C 4 valence e–'s C 3 valence e–'s
N 5 valence e–'s N 6 valence e–'s
Resonance Structures
 Electron Delocalization & Resonance Structures

• Resonance structures are obtained only by delocalizing (redistributing) non-bonding electrons &
electrons in multiple bonds (p electrons)
• Redistribution of electrons that result in breaking s-bonds do not afford resonance structures
Electron Delocalization & Resonance Structures
O
O
H H
H 3C C H 3C C
H H
C–O double bond C–C double bond
neg. charge on C neg. charge on O
Energetics of Reactions: Equilibria & Bond Dissociation Energies (Ch. 2)
 Interpreting Equilibrium Constants (Keq)

K eq
H–Cl + H 2O Cl – + H 3O+

[H 3O+][Cl –] [H 3O+][Cl –] [H 3O+][Cl –]

K eq = = 56•K eq = = Ka
[HCl][H 2O] [HCl]•56 [HCl]
for dilute solutions

–log(Ka) = –7

Ka (i.e., 56•Keq) ~ 107

pKa(HCl) = –7

O O
HO S OH H OH H CH2CH3
HO CH3
O

pKa : –2.8 4.7 18 ~50

 How fast do we reach equilibrium?

Energy
ΔG

ΔG0

Rxn coord.
ΔG° < 0: Exothermic, favorable equilibrium
ΔG relatively large: "slow" to reach equilibrium

ΔG ΔG

ΔG0 ΔG0

ΔG° > 0: Endothermic, unfavorable equilibrium ΔG° < 0: Exothermic, favorable equilibrium
ΔG decreased relative to above ΔG small: rapid equilibrium