Acids and

Bases
Lewis Acids and Bases

O
H + O H H
H H H
Lewis Lewis Adduct
acid base
Electron Electron New
deficient rich covalent
bond
 Acids and
Bases
Lewis Acids and Bases

Examples of Lewis Acids:

Fe3+ AlCl3
H3O+
Examples of Lewis Bases:
−
NH3 H2O Cl
Acids and
Bases
 Acids and
• pH = – Bases
log[H3O+]
HA + H2O A + H3O

A H3O
Ka =
HA

pKa = – log (Ka)

 Acids and
Bases
Acid Strength
HA + H2O H3O+ + A-

- WEAK ACID
A Has a strong
E conj. base
N (∴higher energy)
E - STRONG ACID
A
R ionization Has a weak conj.
G easier base
Y HA (∴lower energy)
Acids and
Bases
 Acids and
Bases
Acid Strength
• Factors that influence stability
of the conjugate base include:
– Resonance
– Electronegativity
– Atomic Size
– Hybridization
– Inductive Effects
 Acids and
Bases
Resonance Effects
increasing quality
of resonance pKa Values

R OH 18 R CH3 45 R NH2 28

CH3 30

10 NH2 25
OH
O
CH3O C CH3 25
O O O
R C OH 5
R C CH3 20 R C NH2 15

O O
R C CH2 C R 9
 Acids and
• The Acetate Ion Bases
O O

CH3 C OH -H+ CH3 C O

Base
acetic acid

O
CH3 C O
acetate ion

Resonance Stabilized
Equivalent structures (charges on oxygens)
 Acids and
• The Phenolate Ion Bases
O O O O O

-
More resonance structures, but not more stable than acetate
Nonequivalent structures (note charges on carbon and oxygen)
 Acids and
Bases
increasing
Electronegativity
pKa Values
electronegativity
O
CH4 >45 RCH3 45
R C CH3 20
NH3 34 RNH2 35

H2O 16 ROH 18 O
15
3.5 R C NH2
HF

O 5
R C OH
 Acids and

increasing
ElectronegativityBases
pKa Values
size
O
HF 3.5 F– 1.36 Å H2O 16
R C OH
HCl –7 1.81 Å H2S 7
Cl– O
H2Se 4
HBr –9 1.95 Å
R C SH
H2Te 3
Br–
HI –10 2.16 Å S
I– R C SH
 Acids and
Bases
Inductive Effects
Electron-withdrawing Groups Electron-donating Groups

δ− δ+ δ+ δ−
Cl C CH3 C

F, Cl, Br, O, N R, CH3, B, Si

electronegative elements alkyl groups and elements

pull electron density away less electronegative than carbon
from carbon push electron density toward carbon
 Acids and
Bases
Inductive Effects
Chlorine helps to stabilize – δ− δ+O
CO2– by withdrawing
electrons Cl C
O
This effect diminishes with distance—it extends for about 3 bonds

O
δ − δ + δ−δ+ δ− δ+
Cl C C C
O
 Acids and
Bases
increasing Inductive Effects increasin
electronegativity pKa Values
g
substitut
ion
I CH2COOH 3.13 CH3 COOH 4.75

Br CH2COOH 2.87 Cl CH2 COOH 2.81

Cl
Cl CH2COOH 2.81 1.29
Cl CH COOH
Cl
F CH2COOH 2.66
Cl C COOH 0.65

Cl
 Electrophiles
 e- pair acceptor
 electron poor R R.
 may possess formal positive charge R C+
 incomplete octets R X.
 greatly reduced e- density
 those that can yield e- poor species
: CH2 NO2+

+
CO2 R C+
X2 in protic solvent X AlCl3 O
H2O
O SO3 δ+ δ−
C OH + CH3 AlCl4 BF3
R O SO3H
H+ FeBr3
 Nucleophiles

 e- pair donor
 excess negative charges
OH-
 fractional negative charges CN-
 may have a lone pair e- RO-

R NH2-
O X-
R C: - C
R -
O N3-
R
O-