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Heterolysis requires that the bond be polarized which is due to the different
electronegativities between the atoms
Double headed
arrow shows the
movement of two
electrons
The van der Waals surface electron density is indicated by the mesh
HA A¯ + H+
B C N O F
2.0 2.5 3.0 3.5 4.0
Al Si P S Cl
1.5 1.8 2.1 2.5 3.0
Ga Ge As Se Br
1.8 2.0 2.2 2.6 2.8
Te I
2.1 2.5
O δ− O
+ H+
H
Sec. 7 - Acid-base Reactions Forsey 16
What effect do alkyl groups
Which compound is more acidic?
H3C O
H3C O
C C + H+
C C
H 3C O
H3C OH CH3
CH3
O O + H+
more acidic C C
H3C OH H3C O
more stable conjugate base
resonance. We will
effects which makes the
talk more about H
anion less stable. H O sp2
this later.
only one C-H σ
bond shown Resonance
Sec. 7 - Acid-base Reactions Forsey 17
3. Resonance Stabilization
Resonance helps stabilize the negative charge by delocalizing or sharing the negative
charge with more than one atom. For example which is more acidic methanol or acetic
acid? In methanol the charge on the conjugate base is localized on a single oxygen
whereas the conjugate base of acetic acid has the charge shared or delocalized over
two oxygens. The conjugate base of acetic acid is more stable thus the equilibrium is
shifted more to the right as compared to methanol making acetic acid more acidic.
But which is more acidic acetic acid or phenol
two resonance
O O structures helps
pka = 4.74 stabilize the negative
H3C C OH H3C C O ¯ + H+
charge and shifts the
equilibrium to the right
compared to CH3OH
O O O
O
+ H+
O O
+ H+
H3C C O H3C C O
Phenol has more resonance structures than acetic acid but acetic acid is more acidic, why?
Which atom is able to handle a negative charge better, carbon or oxygen?
pka > 70 44 26
increasing acidity
increasing anion stability
C¯ C¯ C¯
sp3 sp2 sp
Al Si P S Cl
¯
CH3 ¯
NH2 CH3O¯ F¯ 1.5 1.8 2.1 2.5 3.0
+ H+ + H+ + H+ + H+ Ga Ge As Se Br
1.8 2.0 2.2 2.6 2.8
Te I
2.1 2.5
a) HCl HBr HF HI
B C N O F
2.0 2.5 3.0 3.5 4.0
Al Si P S Cl
1.5 1.8 2.1 2.5 3.0
b) CH3CH3 H2C=CH2 HC≡CH Ga Ge As Se Br
1.8 2.0 2.2 2.6 2.8
Conjugate base: CH3CH2 ¯ H2C=CH ¯ HC≡C ¯ Te I
2.1 2.5
sp3 sp2 sp
OH OH
c) OH
> >
Two resonance structures with the negative charge on two electronegative atoms
(oxygen) is more stabilizing than 3 resonance structures with the negative charge on
carbons.
e) 1) Cl OH 2) OH 3) CH3SH 4) CH3OH
Cl O
b) I¯ , F¯ , Cl¯ , Br¯
pKa+ pKb = 14
pKb = -24 pKb = -1.7
pKb = -24
The electrons on the nitrogen in compound 3 are part of an aromatic system and are
thus very stable, whereas the electrons in compound 2 are in a sp2 hybridized orbital
sticking out from the aromatic system. The electrons in compound B are more basic,
less stable, more reactive and more available than 3. Answer: A
Sec. 7 - Acid-base Reactions Forsey 26
We are always looking at an equilibrium and which way it is
shifted in a specific environment
HA A¯ + H+
∆G = −RT ln K eq
∆S° is +ve - Change from a more ordered system to less a ordered system We will come back
to this when we
∆S° is -ve - Change from a less ordered system to a more ordered system look at reactions