Oxoacids

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)

HNO2 N(O)(OH) 1 3.37

HNO3 N(O)2(OH) 2 -1.40

H2SO3 S(O)(OH)2 1 1.82

H2SO4 S(O)2(OH)2 2 ≈-2

HOCl Cl(OH) 0 7.2

HClO2 Cl(O)(OH) 1 2.0

HClO3 Cl(O)2(OH) 2 -1.0

HClO4 Cl(O)3(OH) 3 ≈-8

•After the first dissociation, the number of “hydrogen free” O atoms
increases to p+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

-1/3 Empirical rules devised by Linus Pauling

O
•For the oxoacids EOp(OH)q. pKa ≈ 8 – 5p
N
-1/3 -1/3 •The successive pKa values of polyprotic
O O acids (those with q > 1) increases by 5 units
for each successive deprotonation
Aquated Cations as Brønsted Acids – Aqua Acids

•When a metal salt dissolves in H2O, the cation and

anion are hydrated
e.g. Aqueous solution of NaCl

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:

[M(H2O)6]n+(aq) + H2O (l)

Hydrolysis/
deprotonation

[M(H2O)5(OH)](n-1)+(aq) + H3O+(aq)

The position of the equilibrium depends on the degree of the

O-H bonds are polarized
 When H2O coordinates to M with n+ positivecharge,
charge is withdrawn towards the metal center, leaving
the H more δ+ than in bulk water
n+
H H (n-1)+

δ+ H H δ+ O O Hydroxide ion
O H
e- density

Mn+
M
+ H
H O
H
 pKa Values of Metal Cations

Ion Radius (a) pKa (a) = Z2/r

K+ 152 0.007 14.5
Na+ 116 0.009 14.2
Li+ 90 0.011 13.6 a pKa
Ba2+ 149 0.027 13.5
Sr2+ 132 0.030 13.3
Ca2+ 114 0.035 12.8
Mg2+ 86 0.047 11.4
 Harnessing the Acidity of Metal Cations in
Biology
e.g. Carbonic anhydrase
An enzyme located in RBC that catalyzes conversion of CO2
to bicarbonate ion

Carbonic anhydrase bicarbonate

- +
CO2 (aq)+ H 2O (l) HCO 3(aq)+ H(aq)
•In the absence of enzyme, this reaction is very slow: ~ 10-2 s-1
in the presence of enzyme: 106 s-1

•The active site of this enzyme is composed of a Zn2+ ion

bonded to the backbone of the enzyme
• One of the reasons for the slow rate constant is the
poor nucleophlicity of H2O. Hydroxide is a strong
nucleophile but its concentration at pH = 7 is only 10-7 M

O δ-
H -H+ O
O C δ+ C

H HO O-
O δ-
 Metal-OH has stronger nucleophilicity

Coordination of a water molecule to Zn2+ in the

enzyme increases its acidity to 107 times!

Hydrophobic region
pKa = 7
δ+
Coordinated water δ+ H
H
O

Zn2+

Active site

Hydrophobic region – binding of CO2

 H
H δ-
O
δ- O
O H3O+ δ+
δ+
δ+ C
δ+ H H
C O
H
O O
O δ-
δ- Zn
Zn

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

Lewis base Lewis acid Adduct/complex

 Examples of Lewis Acids and Bases
Acid
•Alkali metal ions
•Alkaline earth metal ions
•Transition metal ions
(e.g. Fe3+, Cu2+, Zn2+, Ni2+, Au+1,
Ti4+, Co3+)
•Main group metal ions (e.g. Tl+,
Pb2+, Al3+)
•Neutral molecules
(e.g. BF3, BeCl2)
Base
•Anions i.e. OH-, O2-
Halides, S2-, Se2-, NH2-,
S-R-, O-R-, alkyl & aryl
ions
•pseduohalides,
•Neutral molecules i.e.
H2O, amines, ammonia,
phosphines, arsines,
ethers, thioethers,
heterocyclics, (many of
them contain group 15,
16 or 17 elements as
their donor atoms)
Examples of Lewis Acids: Transition Metals

Different Oxidation States

e.g. Fe0, Fe+1, Fe+2, Fe+3, Fe+4

Different ionic radii

e.g. Fe0 > Fe+1> Fe+2> Fe+3> Fe+4

Ru+2 > Fe+2; Au+1> Au+3

Acid-Base Reactions Involving Metal Ions
H H 2+
H O H
O O
H H
Cu2+ + 6 H2O Cu 2+

H O H
O
H H
O
H H

Cu2+ + 4 Cl- CuCl42-

+
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