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Acids and Bases PDF
Acids and Bases PDF
Acetic acid
CH3 C OH
ttiksyra
Aniline
NH2
+ H2O
CH3 C O
+ H2O
NH3
H3O
OH
Ju starkare syra
= 1,76 x 10-5
Weakest acid
ACID
HSbF6
HCl
CH3COOH
CH3NH3+
H2O
(CH3)3COH
NH3
CH3CH3
Ex Lewis acids:
HCl, HNO3, HClO4
BF3
pKa
> -12
-7
4.8
10
Conj. BASE
SbF6ClCH3COOCH3NH2
OH-
15,7
18
33
50
AlCl3
Weakest base
(CH3)3CONH2CH3CH2TiCl4
Strongest base
ZnCl2
Examples
pKa 43
CH3 O H
pKa 16
OH
pKa 10
RCOOH
pKa 4-5
<
H-Br
-7
>
H2O <
OH - >
B-
H-Cl <
<
-9
Cl -
>
H2S
SH -
Br -
<
>
H-I
-10
>
I-
H2Se
SeH -
Increased acidity
decreased bonding strength
Increased Basicity
Higher acidity
Increased Basicity
<
NH3
<
R-OH <
HF
Ex.
CH3 C C H
pKa = 25
NH 2
NH 3
CH3 C C
NH 3
pKa = 33
pKa 3,8
OH
Phenol:
OH
O
pKa
CH3 CH2 OH
15,9
H
O
pKa 10
CH3 C OH
4,8
C
O
O
Cl CH2 C OH
2,9
O
Cl CH2 C O
The negative charge is spread by electronwithdrawing and thereby stabilising the anion
D. Polar solvent with high dielectric constant () have better ability to solvate ions
Water is extremely effective as ion solvating medium and is readily polarised, and
can thereby stabilise and solvate both cations and anions
The solvent must act as a base otherwise can not acids dissociate.
Ex. HCl is a strong acid in methanol but not in toluene.
ACIDS
Aliphatic acids
Alkyl groups can inductively decrease the acid strength
Compare: acetic acid and formic acid pKa 4,76 versus 3,77
O
O
Me
C
O
and
Go = -2.303 RT log K eq
pKa
Go
Ho
So
Acetic acid
4,76
6,5
-0,13
- 6,6
Kcal
Formic acid
3,77
5,1
-0,07
- 5,17
Kcal
Low enthalpy The energy required for dissociation of the O-H bond is canceled by
the energy evolved in solvating the resultant ions.
Entropy has a greater effect Through solvation of the ions by water molecules is
the orderliness increased. Differential solvation of the acid anions makes the acid
strength to differ. Formiat ion is stronger solvated.
For other short aliphatic acid (C3 -C5 ) are the differences in pKa small,
Minor steric effects may count for the differences (pKa 4.80 - 5,05)
pKa
4,88
sp3
CH2 CH COOH
4,25
sp2
1,88
sp
Hybridisation
HC
C COOH
Stronger acid
O
C OH
4,76
O
C OH
F CH2
Cl CH2
2,57
Cl CH2
O
C OH
Br CH2
2,86
O
C OH
Cl
Cl
1,25
I CH2
2,90
O
CH C OH
2,86
O
C OH
O
C OH
3,16
O
Cl
Cl C C OH
Cl
0,65
Inductive effects ( electron withdrawing, EW) delocalise the negative charge over
the whole of the anion. The water can be less ordered to solvate the ions.
The changes in pKa and then free energy is largely due to entropy factor also here.
Entalphy differ only little with different substituent.
The anionic charge gets more concentrated as the EW-substituent is situated further
apart increased S
Phenols
The Inductive effect falls off with distance from orto > meta > para, but is also
combined with mesomeric effect which affect primary at orto- and para-positions.
C6 H5 OH
o-O2 NC6 H4 OH
m-O2 NC6 H4 OH
p-O2 NC6 H4 OH
2,4-(O2 N)2 C6 H4 OH
2,4,6-(O2 N)3 C6 H4 OH
pKa
9,95
7,23
8,35
7.14
4,01
1,02
N
O
N
O
Methyl
pKa
C6 H5 OH
o-MeC6 H4 OH
m-MeC6 H4 OH
p-MeC6 H4 OH
9,95
10,28
10,08
10.19
Me
NO2
Cl
4,20
4,20
4,20
4,24
4,34
2,17
3,45
3,43
2,94
3,83
3,99
Br
OMe OH
2,85
3,81
4,00
4,09 2,98
4,09 4,08
4,47 4,58
N
O
EW-groups increases the acid strength, mesomeric effect may also decrease strength.
HO and MeO- groups may have both inductive (EW) and mesomer effect (ED)
depending on position. The effect can give a weaker acid also.
O
O
H
O
- H+
C
H
HOOC-COOH
HOOC-CH2 -COOH
HOOC-CH2 -CH2 -COOH
Maleic acid has a low pK a1 compared with fumaric acid due to intra molecular Hbonding, which on the other hand also makes pKa2 higher due to stabilisation.
O
H
C
C
O
O
H
C
H
C
O
-H
C
C
C
Maleic acid
C
O
pKa1= 1,92
pKa2= 6,23
COOH
C
O
H
H
O
C
HOOC
Fumaric acid
pKa1= 3,02
pKa2= 4,38
For malic and succinic acid is pKa2 higher as the first COO- group is Elect. Donating.
As the entropy has a major effect on pKa:s also temperature influences the value of
pKa.
BASES
More convenient to use pKa also for bases
Ka =
[B] [ H3 O+ ]
[ BH+ ]
NH3
Go
12,6
pKa
9,25
Ho
12,4
+ H3 O+
So
0,2 Kcal
pKa:
NH3
Me NH 2
Me
NH
Me
9,25
10,64
10,77
Me
Me N
Me
9,80
Et NH 2
Et
NH
Et
10,67
10,93
Et
Et N
Et
10 88
Alkyl groups on ammonia increases the base strengthThe first one markedly, the
second slightly but the third actually decrease base strength.
Not only electron availability on the nitrogen also solvation of the cation must be
stabilised. Tertiary amines less easily solvated.
The more hydrogen atoms attached on nitrogen the more powerful solvation via Hbonding between these and water.
H2O
H2O
O2H
>
H2O
H2O
>
H2O
In solvent where ions are not solvated by H-bonding is the order of base strength
the same as the inductive effect of the alkyl groups.
In chlorobensen or gas phase:
But NH2
<
But 2 NH
<
But 3 N
O
R C
O
C
N
C
O
O
NH 2
R C
NH 2
H
acidic H
Amide nitrogens are non basis due to mesomeric EW effect (pKa 0,5).
Pthalimide, with two carbonyls , is acidic and non-basic.
R4 N+ OH- as a ion pair has a base strength alike alkali bases
Guanidine has pKa of 13,6 and protonation gives three exactly equal resonance
structures.
Anilines
NH 2
NH 2
NH 2
NH 2
NH 2
H NH 2
+
Alkyl groups
C6 H5 NH 2
4,62
4,38
o-Me-C6 H4 NH 2
C6 H5 NHMe
4,84
4,67
m-Me-C6 H4 NH 2
C6 H5 NMe2
5,15
5,10
p-Me-C6 H4 NH 2
Alkyl groups do only effect little whatever position, and the main effect on the base
strength is the mesomeric stabilisation of the aniline molecule with respect to the
cation.
O2 N-C6 H4 NH 2
o- - 0,28
m- 2,45
p- 0,98
NH 2
N
O
HO-C6 H4 NH 2
MeO-C6 H4 NH 2
o- 4,49
m- 4,20
p- 5,29
o- 4,72
m- 4,17
p- 5,30
NH 2
NH 2
NH 2
OMe
OMe
Orto position gives greatest effect due to strongest inductive effect but also by
direct interaction by steric and H-bonding.
H
O
N
O
N
CH3
O
N
N
N
O
CH3
O
N
O
Stronger base
2,4,6-trinitro-N,N-dimethyl aniline is much more stronger base than N,N-dimethylaniline or 2,4,6-trinitro-aniline, because the orto groups inhibit resonance
interaction by steric reason.
Hetrocyclic bases
Pyridine (A) aromatic (sp2) pKa 5,2 less basic than ex. triethylamine (sp3)
As nitrogen becomes more multiply bonded its lone pair of electrons is
accommodated in an orbital with more s character., the electron are drawn closer to
the nitrogen nucleus. Compare also MeCN pKa -4,3 (sp).
Hybridisation
+
N
N
R3 N >
> RC N
N
(A)
N
H
H
N
H
(B)
N
H
(C)
Base strength
Pyrrole (B) have aromatic character, the electron pair is incorporated in the aromatic
6 -system, which gives a weaker base. -Carbons is more basic.
Pyrrolidine (C) on the other hand have pKa 11,3 resembling of diethylamine.