Acid Strength

In general, Benzoic Acid > Carboxylic Acid > Phenol > Alcohol
i) Phenol > Alcohol
−¿ ¿
Reason: Delocalization of negative charge on O anion into benzene ring through overlap of benzene
ring orbital with p-orbital of O . Delocalization of negative charge disperses the negative charge on the
anion, and stabilizes the phenoxide anion relative to the alkoxide anion.

ii) Carboxylic Acid > Phenol

Reason: Carboxylate anion exists as a number of intermediate resonance structures, culmulating in an
overall resonance-stabilized anion.
The resonance structures alternate between
their respective forms because of the overlap
of p-orbitals of the two O and the C atoms,
such that the extra electron can move freely between the three overlapping p-orbitals. Resonance
stabilization of the carboxylic acid accords stronger stabilization on the anion structure than
delocalization of the charge in phenol.

iii) Benzoic Acid > Carboxylic Acid

Reason: The benzoate anion enjoys stabilization from both resonance and delocalization of the negative
charge into the benzene ring. Hence, the benzoate anion is more stable than the carboxylate anion,
relative to their respective undissociated acid molecules.
+ ¿¿

1) Alcohols ROH ⇌ RO−¿+ H ¿

1o >2o >3 o HO CH 3> HOC H 2 (CH 3 )> HOCH ( CH 3 )2 > HOC ( CH 3 )3
Acid strength of alcohol depends on stability of alkoxide anion. The more stable the anion, the stronger
the acid strength of the alcohol, due to shift in position of dissociation equilibrium to the right.
Alkyl (R) groups are electron-donating by inductive effect, and will intensify the negative charge on the
alkoxide anion. This destabilizes the anion relative to the undissociated alcohol molecule, and decreases
the acid strength.

Looking at 1o alcohols HOC H 3 > HOC H 2 C H 3 > HOC H 2 C 2 H 5

The larger the alkyl group, the more electron donating in character. Hence, the larger the alkyl group,
the more destabilized the alkoxide anion, and the weaker the acid strength. A similar pattern exists for
comparisons of 2o and 3o alcohols.

Looking at CH 3 OH : Cl 3 COH >Cl 2 HCOH >Cl H 2 COH > H 3 COH

Chloride atoms are electron-withdrawing because of its strong electronegative character. Hence, it
disperses the negative charge on the alkoxide anion, and increases the acid strength.
+¿¿
−¿+ H
C 6 H 5 OH ⇌ C 6 H 5 O ¿
2) Phenols
Acid strength of phenol depends on stability of
phenoxide anion. The more stable the anion,
the stronger the acid strength of the phenol,
due to shift in position of dissociation
equilibrium to the right.
Looking at ring-activating substituted phenol:

Ring activating groups generally increase the electron-density of the benzene ring, either through
delocalization of electrons into the benzene ring, or through inductive effect. These groups intensify the
electron density of the phenoxide anion, and reduce the stability of the anion, reducing the acid
strength.
The opposite trend exists for ring-deactivating substituted phenol.
+¿¿

3) Carboxylic Acids RCOOH ⇌ RCOO −¿+ H ¿

Acid strength of carboxylic acids depends on stability of carboxylate anion. The more stable the anion,
the stronger the acid strength of the carboxylic acid, due to shift in position of dissociation equilibrium
to the right.

Looking at acids HCOOH >CH 3 COOH >C 2 H 5 COOH

Alkyl groups are electron-donating by inductive effect. It will destabilize the carboxylate anion by
intensifying the negative charge of the carboxylate anion. Hence, the acid strength decreases with
increasing size of the alkyl group attached to the carboxylic acid group.

Looking at ethanoic acid C Cl 3 COOH >CH Cl 2 COOH >CH 2 ClCOOH >CH 3 COOH
Chlorine atoms are electron-withdrawing due to high electronegativity. It will stabilize the carboxylate
anion by dispersing the negative charge of the anion, and hence increase acid strength.

4) Benzoic Acid
+¿ ¿

C 6 H 5 COOH ⇌ C6 H 5 COO−¿+ H ¿

Acid strength of benzoic acids depends on stability

of carboxylate anion. The more stable the anion, the stronger the acid strength of the benzoic acid, due
to shift in position of dissociation equilibrium to the right.

Looking at ring-activating substituted benzoic acids:

Ring activating groups generally increase the electron-density of the benzene ring, either through
delocalization of electrons into the benzene ring, or through inductive effect. These groups intensify the
electron density of the benzoic anion, and reduce the stability of the anion, reducing the acid strength.
The opposite trend exists for ring-deactivating substituted benzoic acids.

Basic Strength
In general, Amine > Phenylamine (Opposite of acid strength trend)
−¿¿
+¿+OH ¿
1) Phenylamine C 6 H 5 NH 2 + H 2 O⇌ C6 H 5 NH 3
Phenylamine, as opposed to benzoic acid and phenols, do not enjoy stabilization of the
phenylammonium ion, due to the inability to form a delocalized electron cloud between overlap of the
benzene ring and the N -atom of the ammonium ion. In particular, observe that the N atom in the
 + ¿¿
ammonium group ( NH 3 ) is sp3-hybridised, and does not have a unhybridised p-orbital to overlap with
the benzene ring. Hence, the positive-charge cannot delocalize into the benzene ring.
Instead, the undissociated phenylamine molecule enjoys resonant stabilization relative to the
phenylammonium cation, due to the lone electron pair on the N atom of the NH 2 group attached to
the benzene ring. The sp2-hybridised N atom contains a p-orbital that can overlap with the benzene
ring. The greater stability of the phenylamine molecule compared to the phenylammonium cation shifts
the dissociation equilibrium to the left, favouring the undissociated molecule, and reducing its basic
strength.
−¿¿

2) Amine R NH 2 + H 2 O⇌ R NH 3+¿+OH ¿
3o >2 o> 1o RNR ' (R' ' )> RNHR ' > R NH 2 > NH 3
The basic strength of the amine depends on the stability of the ammonium cation. The more stable the
cation, the stronger the basic strength of the amine.
Alkyl groups are electron-donating by inductive effective. These groups disperse the positive charge on
the ammonium cation, and stabilize the cation. More alkyl groups attached to the N -atom of the amine
increase the dispersal of the positive charge of the cation. Hence, the 3o amine is the strongest base ,
followed by the 2o amine, the 1o amine, and finally NH 3.

Looking at 1o amines C 2 H 5 NH 2 ¿ CH 3 NH 2
The larger the alkyl group, the more electron-donating the group. Hence, the larger group accords
greater dispersal of the positive charge on the ammonium cation, and contributes to greater
stabilization of the cation.

Looking at methylamine C H 3 NH 2 >CCl H 2 NH 2 >CCl2 H NH 2>CCl 3 NH 2

Chlorine atoms are electron-withdrawing due to high electronegativity. It will destabilize the ammonium
cation by intensifying the positive charge of the cation, and hence decreases the basic strength.