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Simple oxoacids: the simplest oxoacids are the mononuclear acids that
contain one atom of the parent element E
E(O)p(OH)q pKa
e.g. H2CO3, HNO3, H3PO4 and H2SO4
OH OH
p=0 H-O-Cl HO OH OH
Si Te HO B
OH HO OH OH
HO OH
OH
7.2 10 7.8, 11.2 9.1
O O- O
OH HO OH HO Se
p=1 O Cl I + OH OH
P HO I O
OH OH OH HO OH OH
HO OH
2.1, 7.4, 12.7 3.6 OH 1.6, 7.0 OH 2.6, 8.0
O
p=2 O
O N S Cl+ Cl
OH OH OH OH
O O O- O
-1.4 OH O
O -2.0, 1.9 -1.0
O
p=3
Cl Cl+
OH OH
O
O O -10
O-
The first dissociation constant of oxoacids pKa(1)
pKa(1) decreases as the number of “hydrogen free” oxygen
atoms (p) increases
Formula of acid E(O)p(OH)q n pKa(1)
•The greater the number of the oxygen atom in the conjugated base
[E(O)p+1(OH)q-1]-, the more the negative charge of the anion can be
spread out.
e.g. the negative charge of nitrate ion is delocalized uniform over via
the π-bonding system
H δ- H First hydration
O shell
H H
δ- O O δ-
H H
Na+
Ion-dipole δ-
interactions H O H
δ- O
H δ- H
O
H H
For many transition metal salts, the cations Mn+ form covalent
bonds with H2O
H H
H H H O H
H O H O O
H H
O O Cu 2+
H n+
H H
M O O H
H O H H H
O O
H H
H O H
H H Hexaaquacopper(II) ion
Covalent bond
Complex/ Distorted octahedral
Coordination/dative adduct
/metal-ligand bond
The metal-H2O complexes can act as Brønsted
Acids by loss of H+ from a coordinated H2O
molecule:
Hydrolysis/
deprotonation
[M(H2O)5(OH)](n-1)+(aq) + H3O+(aq)
δ+ H H δ+ O O Hydroxide ion
O H
e- density
Mn+
M
+ H
H O
H
pKa Values of Metal Cations
O δ-
H -H+ O
O C δ+ C
H HO O-
O δ-
Metal-OH has stronger nucleophilicity
Hydrophobic region
pKa = 7
δ+
Coordinated water δ+ H
H
O
Zn2+
Active site
O
H2 O H
C
O
O
- Zn
HCO3
(b) Lewis Concept
•Lewis Acid – electron pair acceptor
•Lewis Base – electron pair donor
Lewis Acid + Lewis Base Acid – base adduct
H+ + OH- H2O
e--acceptor e--donor Adduct
+
N + H Cl N H + Cl -
acid base
Lewis base Adduct Adduct Lewis base
Metal ion 2+
N
4 N + Ni2+ N Ni2+ N
H O H
O
H H
O
H H
+
Ag+ + 2 NH3 H3N Ag NH3
Lewis acid Lewis base Adduct/complex
Identify the acids and bases
H3N NH3 H3 C
Pt S Au Cl
H3C
Cl Cl
Metal-carbon bond
Cl CH3
H3C CH3
Cl Cl
W
W
H3C CH3
Cl Cl
CH3
Cl
Hexamethyltungsten
An organometallic complex
Examples of Lewis Acids: Group 2
Cl Be Cl 4-e-
Beryllium dichloride
2-
Cl
2 Cl- Be
Cl
Cl Cl
BeCl2 +
Et Et
CH2CH3 O
2O
Be
CH2CH3 Cl
O Cl
Et
Et
Examples of Lewis Acids: Group 13
X = halides, alkyl 6-e-
X X X
B Al Ga
X X X X X X
X X
In Tl
X X X X
Acid-Base Reactions Involving Group 13 Acids
CH3
CH3 H3C CH3
N
N CH3
F + CH3 B
F
trimethylamine F
F
B
F F H3CH2C CH2CH3
+ CH2CH3 O
O
B
CH2CH3 F
F
F
diethyl ether
Acid-Base Reactions Involving Group 13 Acids
CH3
C
Cl N
Cl Cl
Al Al + 2 N C CH3 2
Al
Cl Cl Cl
Cl Cl
Cl
Me3N
H Ga
H + NMe3 H
H
Ga NMe2
H H H
+ 2 NMe3 H Ga
H
NMe3