Chap 04 Acids and Bases
Chap 04 Acids and Bases
Chap 04 Acids and Bases
H+
O H H
base
pi bonding electrons
Basicity
The position of the equilibrium is obtained by comparing the pKa values of the two acids. Equivalently, compare the pKb values of the two bases.
Note the change in formal charges. As reactant oxygen had complete ownership of lone pair. In product it is shared. Oxygen more positive by 1. Similarly, B has gained half of a bonding pair; more negative by 1.
For the moment, just note that there are two possible carbocations formed. The carbocations are conjugate acids of the alkenes.
Super acid
Aqueous Solution
Example
Recall
OH
CH3CH2OH
pKa = 9.95
Stronger acid H2O + PhOH
phenol, PhOH ethanol, EtOH
pKa = 15.9
Weaker acid H3O+ + EtO-
H3O+ + PhO-
H2O + EtOH
Ka = [H3O+][PhO-]/[PhOH] = 10-9.95
Ka = [H3O+][EtO-]/[EtOH] = 10-15.9
Ethanol, EtOH, is a weaker acid than phenol, PhOH. It follows that ethoxide, EtO-, is a stronger base than phenolate, PhO-. For reaction PhOH + EtOStronger base K= PhO- + EtOH where does equilibrium lie? Weaker base. 10-9.95 / 10-15.9 = 106.0
Increasing Increasing basicity electronegativity of of anion. atom bearing negative charge. Increasing stability of anion.
2. Size of the atom bearing the negative charge in the anion. Increasing acidity.
CH3OH CH3SH CH3O - + H+; pKa = 16 CH3S - + H+; pKa = 7.0
Increasing Increasingsize basicity of atom of anion. holding negative charge. Increasing stability of anion.
phenol, PhOH
Acidity
No resonance structures!!
Note that phenol itself enjoys resonance but charges are generated, costing energy, making the resonance less important. The more important resonance in the anion shifts the equilibrium to the right making phenol more acidic.
OH
OH
etc.
Two different bases or two sites in the same molecule may compete to be protonated (be the base).
Acetic acid can be protonated at two sites.
H
O
H
+
H+
acetic acid
H O
The more stable one! Which is that? Recall resonance provides additional stability by moving pi or non-bonding electrons.
H+
acetic acid
H O
Acidity.
H3CCH2OH
d+
F3CCH2OH
d+
F3CCH2O - + H+
Due to electronegativity of F small positive charges build up on C resulting in stabilization of the anion. Effect drops off with distance. EtOH pKa = 15.9
Increasing Basicity of A-
Increasing Acidity of HA
RCCH + LiCH2CH2CH2CH3 base acid RCCH + AgNO3 non-terminal alkyne RCCR + LiCH2CH2CH2CH3 RCCR + AgNO3 NR
HCH2CH2CH2CH3 + RCCLi
AgCCR (ppt)
No Reaction
H O H
H O O R R
pKa = 15.9
ethanol
17
propan-2-ol
18
2-methylpropan-2-ol
Example
Para nitrophenol is more acidic than phenol. Offer an explanation
OH
+ H
OH
Why? Could be due to destabilization of the unionized form, A, or stabilization of the ionized form, B.
+ H
N O O O
N O
Examine the equilibrium for p-nitrophenol. How does the nitro group increase the acidity?
O
OH
+ H
Examine both sides of equilibrium. What does the nitro group do? First the unionized acid.
N
N O O
OH
OH
OH
OH
Note carefully that in these resonance structures charge is created: + on the O and in the ring or on an oxygen. This decreases the importance of the resonance. Structure D occurs only due to the nitro group. The stability it provides will slightly decrease acidity.
N O O O
N O O
N O O
N O
Resonance structures A, B and C are comparable to those in the phenol itself and thus would not be expected to affect acidity. But note the + to attraction here
Now look at the anion. What does the nitro group do? Remember we are interested to compare with the phenol phenolate equilibrium.
O
OH
+ H
N
N O O
In these resonance structures charge is not created. Thus these structures are important and increase acidity. They account for the acidity of all phenols. Structure D occurs only due to the nitro group. It increases acidity. The greater amount of significant resonance in the anion accounts for the nitro increasing the acidity.
N O O O
N O O
N O O
N O
Resonance structures A, B and C are comparable to those in the phenolate anion itself and thus would not be expected to affect acidity. But note the + to attraction here
Sample Problem
vs
HN HN O
H2N
H2N
H2N