Acidic Character of Alcohols,

Phenols, and Carboxylic Acids

Review of Acids

Generally, as the strength of the acid increases,

the Ka value increases while the pKa value
decreases.

pKa= -logKa

Side note:
Ka= Acid
dissociation
constant.

Acid Review: Dissociation constants

pH

Acidic Strength

Ka

pKa

Key

= Increase

= Decrease

Acidity of Alcohols

Alcohols are very weak acids and have very large pKa values.

The oxygen in the OH group pulls electron density away from the H atom.
The following charge dispersions result:
This loss of electron density allows H to become labile and ionization can
occur.

Acidity of Alcohols

In the case of the tertiary alcohol, the methyl groups demonstrate the
positive inductive effect.

These groups donate electron density onto the -C atom.

This -C then supplies the O atom with electrons.

The polarity of the OH bon in the alcohol is therefore lowered. The oxygen
atom then has a greater tendency to be protonated or rather to stay
protonated. (This contributes to the poor acidity).

As the number of alkyl groups increase, the acidic strength decreases.

Note:
pKa of ethanol= 15.9
pKa of water= 15.73

Note:
The higher the pKa,
the weaker the acid

Acidity of Phenols

Acidity is dependent on the stability of the Phenoxide anion.

Phenol has the OH group attached directly to the benzene ring.

In the Phenoxide anion, the negative charge is delocalised and becomes a

part of the ring system.

Its acidic nature is increased because the electrons on the O in the anion are
unavailable to accept a proton.

Not acidic enough to react with Na2CO3 to evolve CO2 (g).

Acidity of Phenols: Effects of substituents

on ring

Electron-donating groups (for e.g. CH3) pushes the electron density into the ring
which reduces the extent of delocalisation of the lone pair of electrons on the
oxygen atom.
What does this mean?
The attachment group saturates the ring with edensity and the O then reduces the extent to
which it donates its electrons

The electron density on the O atom remains and it is available to accept a

proton?
What does this mean for acidity?

Therefore, the acidity of phenol with electron donating groups is reduced.

Acidity of Phenols: Effects of substituents

on ring

Electron-withdrawing groups (for e.g. Cl) have the opposite effect.

They pull electron density away from the O atom.

Note

1) This makes it easier for O to lose the H.

2) Once the anion is formed the oxygen has a
smaller negative charge and is therefore less
likely to be protonated. (This contributes to
acidity.)

Other electron withdrawing groups include NO2, COOH, and halogens.

Acidity of Carboxylic Acids

The H+ is easily lost and the negative charge is

delocalized in the available p orbitals of the Carbon and
Oxygen atoms.

The Carboxylate Ion

Acidity of Carboxylic Acids

The carboxylate anion is therefore stable since the negative

charge is equally shared by both O atoms.
The increased inability of either oxygen atom to become
protonated increases the acidic character.

Note
The carboxylate ion is less
easily protonated than the
phenoxide ion of phenol and
the alkoxide ion of an alcohol

Acidity of Carboxylic Acids:

Chlorosubstituted Acids

The electronegative Cl pulls the delocalised

electron density of the COO- group towards itself
which enables the charge cloud to be spread
throughout the anion more than in ethanoic acid.

This further loss of electron density from the

oxygen atom decreases the negative charge on
either oxygen atom and this makes the species
less like to be protonated.

Chloroethanoic acid is 80 times

stronger than ethanoic acid

Acidity of Carboxylic Acids:

Chlorosubstituted Acids

Also, chlorosubstituted acids tend to give up H

and are therefore stronger aided.

Acidity of Carboxylic Acids:

Chlorosubstituted Acids
Acids

pKa

C2H5COOH

4.88

CH3COOH

4.76

CH2ClCOOH

2.86

CHCl2COOH

1.29

CCl3COOH

0.65

Basic Character of Aliphatic Amines,

Aromatic Amines, and Amides

Base Review

A base is defined as a proton acceptor.

Amines are bases because they all contain a nitrogen atom containing a lone
pair of electrons.

This lone pair can easily form a dative bond with an H+ ion in solution.

Base Review: Dissociation constants

pH

Basic
Strength

Kb

pKb

Basic Nature of Amines

All amines do not have the same basic strength.

The strength depends on the availability of electrons
on the nitrogen atom to accept a proton.

The more available these electrons are, the greater

the basic strength.

Aliphatic Amines

Methylamine contains an electron-donating group which

pushes electron density onto the nitrogen atom (Inductive
Effect).

This intensifies the negativity on the N atom making the

lone pair more available/ready to accept a proton.

Methylamine pKb=
3.34
Ammonia pKb= 4.74

Aliphatic Amines

The positive charge created in the alkylammonium ion can

be shared between the nitrogen atom and a carbon atom.

This distribution of charge stabilizes the cation and it is

the reason why aliphatic amines are stronger than
ammonia in aqueous solutions

alkylammonium ion

Aromatic Amines

The low Kb value of phenylamine suggest that

the lone pair of electrons on the nitrogen are
not readily available to accept a proton (act as
a base).

Protonation is not as effective as in aliphatic

amines or ammonia.

The lone pair actually takes part in the

conjugative effect of the ring system. This
makes them unavailable for bonding.

Amides

Amides tend not to be very basic.

The lone pair of electrons are unavailable to accept a

proton since they are used in the delocalised electron
cloud generating greater stability.

Amides are almost neutral.

Amino Acids

Amino Acids

Amino Acids
Two functional
groups

Amino acids are chiral

(except in glycine)

Amino Acids

Zwitter:
German for
hybrid

Amino acids have a high

melting point (234 C)and
this suggests that some sort
of ionic character is
involved.
It was discovered that amino
acids exist as dipolar ions in
solution called zwitterions.
This dipolar neutral ion
results from the
deprotonation of the COOH
group and the simultaneous
protonation of the NH2
group.

zwitterion

Amino Acids

Electrostatic attractions responsible for high melting point.

Amino Acids

Zwitterions as Buffers

The possess the ability to receive protons as well as

donate them. The result is a maintained pH.

Amino Acids

Aspartic Acid

What is the IUPAC name?