ACID-BASE CHARACTER IN

ORGANIC COMPOUNDS

COMPARING
ACIDITIES
3.1.

explain the difference in acidity of alcohols,

phenol and carboxylic acids.
- Include chlorosubstitute acids. Reference
should be made to the relationship between
acid strength, pH and pKa.
- Inductive and conjugated effects.

Ka values of some carboxylic acids

Carboxylic acids are weak acids. They are not
completely ionised (dissociated) in solution. The position
of equilibrium is well over to the left. For example,
ethanoic acid (CH3COOH).
CH3COOH + H2O CH3COO- + H3O+
The table shows some Ka and pKa values for
diferentcarboxylic acids.

Ethanoic acid, CH3COOH

Ka/
moldm-3
1.7 X 10-5

4.77

Propanoic acid, CH3CH2COOH

1.3 X 10-5

4.89

Chloroethanoic acid, CH2ClCOOH

1.3 X 10-3

2.89

Carboxylic acid

pKa

Ka values of some carboxylic acids

The values of Ka and pKa give us information
about the position of equilibrium. The higher the
value of Ka and the lower the value of pKa:
the further the position of equilibrium is to the
right (in favor of the products).
the greater the acidity of the carboxylic acic.
We can explain these differences by referring to
two effects:
The conjugative effect (also known as the
mesomeric or resonance effect).
The inductive effect.

THE CONJUGATIVE EFFECT

The conjugative effect occurs in molecules with

multiple bonds, usually when the structure at first
sight appears to be of alternating double and
single bond e.g. benzene.
The orbitals overlap and form a delocalised
system over three or more atom centres. The effect
makes the bond lengths and bond strengths
intermediate between ordinary single bond and
ordinary double bond. The effects also makes the
structure more stable.
Other compounds showing this effect are:
the carbon-oxygen bonds in carbonate ions
the carbon-oxygen bonds in carboxylate ions
derived from carboxylic acid.

THE CONJUGATIVE EFFECT

Taking carboxylic acids as
an example:
Oxygen atoms are more
electronegative than carbon
atoms or hydrogen atoms.
The bonding pairs of
electrons tend to move
towards the oxygen atom.
The O-H bond is weakened
so that it is possible for a
proton to be lost.

THE CONJUGATIVE EFFECT

The carboxylate ion formed exist as a
resonance hybrid of two extreme forms. The
actual form is somewhere in between these
two extremes.
The carboxylate ion is relatively stable, so the
ability of the H+ ion to combine it is reduced.

THE INDUCTIVE EFFECT

Bonds between unlike atoms are polarised due to
the difference in electronegativity between the
atoms. The polarisation is represented by an arrow
pointing towards the more electronegative atom.
Groups of atoms can also exert an electronattracting or withdrawing effect on the electrons
around a particular atom such as carbon atom.
This is called the inductive effect.
Atoms or groups more electronegative
than carbon withdraw electrons from
around the carbon atom. This is
called the negative inductive effect (-I
effect). For example chlorine bonded
to carbon.

THE INDUCTIVE EFFECT

Atoms or groups less electronegative than carbon
tend to donate electrons to the carbon atom. This is
called the positive inductive effect (+I effect). For
example alkyl groups bonded to carbon.

Increasing + I effect

THE INDUCTIVE
EFFECT
As the number
of electronwithdrawing
groups on the
-COOH carbon
atom
increases, the
strength of the
acid increases.

COMPARING ACIDITY:
CHLOROETHANOIC ACIDS
The pKa of chloroethanoic acid, dichloroethanoic
acid and trichloroethanoic acid are 2.89, 1.30 and
0.64 respectively. We can explain the differences in
acidity of the chloroethanoic acids by the inductive
and conjugated effects.
The more Cl atoms that are substitute in the -CH 3
group in ethanoic acid, the greater is the electronwithdrawing (-I) effect on the C atom of the

COOH group.

COMPARING ACIDITY:
CHLOROETHANOIC ACIDS
The greater the I effect, the more the electrons
are withdrawn from the carbon and the more the
electrons in the O-H bond are drawn towards the
oxygen atom.
The more the electrons are drawn towards the O
atom in the -OH bond, the weaker the bond and
the more likely it is that a H+ ion will be formed.
The greater the I effect, the greater is the
delocalisation of the negative charge.
So the greater is the conjugative effect and the
more likely it is that a H+ ion will be formed.

THE ACIDITY OF COMPOUNDS

WITH OH GROUPS
Ethanol and ethanoic acid are soluble in water. This is
because they can form extensive hydrogen bonding
with water. Phenol is only sparingly soluble in water
and is a solid at room temperature. Its higher molar
mass and large aryl ring reduce the hydrogen bonding
capacity with water. Phenol, however, although less
acidic than ethanoic acid is more acidic than ethanol.
AN ACID is "a substance which donates hydrogen
ions (protons) to other things

THE ACIDITY OF COMPOUNDS

WITH OH GROUPS
The strengths of weak acids are measured on
the pKa scale.
The smaller the number
stronger the acid is.

on this scale, the

THE ACIDITY OF COMPOUNDS

WITH OH GROUPS
Phenol is a very weak acid. It ionises slightly in water
to form the phenoxide ion.
C6H5OH(s) + aq C6H5O-(aq) + H+(aq)
Phenol is a much weaker acid than ethanoic acid but it
is more acidic than water or ethanol.
An aqueous solution of phenol has a pH just below 7
whereas alcohol and water appear neutral with narrow
range universal indicator paper.
Phenol is too weak an acid to libarate carbon dioxide
from carbonates whereas ethanoic acid will libarate
carbon dioxide.
Neither ethanol nor water will neutralise sodium
hydroxide but phenol does.

ETHANOL
The charge on any ethanoate
ions formed is concentrated on
the oxygen atom because of
the positive inductive effect of
the ethyl group and the
electronegativity of the O atom.
This increases the negative charge on the oxygen atom.
So any ethoxide ion formed is more likely to accept a H+
ion.
There is not conjugative effect to stabilise the
ethanoate ion since ethanol does not have a C=O
group.
The position of equilibrium is so far over to the left that
the ethanol exist as undissociated molecules with
hardly any ethanoate ions.

PHENOL
In the phenoxide ion, one of the lone pairs of
electrons in a p-orbital on the oxygen atom
overlaps with the delocalise electrons in the
phenol ring.
An extended delocalised system is formed which
includes the oxygen.
The conjugate(resonance) effects is increased because
the delocalised electrons can move over a large area.
The
extra
delocalisation
reduces the electron density
on the oxygen. The charge is
spread over the whole ion
rather than being confined to
the oxygen.

PHENOL
The increased conjugative effect stabilises the
phenoxide ion.
The conjugated effect is greater than the inductive
effect, so the movement of the electrons in the C-O
bond is towards the phenol ring rather than towards
the oxygen.
The position of equilibrium is further to the rigth
compared with ethanol.
H+ ions are not as strongly
attracted to the phenoxide
ion. So the phenoxide ion is
less
likely
to
form
undissociated
molecules
than is the ethoxide ion.

ETHANOIC ACID
Some of the p-electrons in the COO- group are delocalised.
This delocalisation reduces the electron
density on the oxygen (the charge is
spread over the whole ion rather than
being confined to the oxygen of the O-H
group.
The conjugative effect stabilises the
ethanoate ion.
The conjugative effect is greater than in phenol, so the
stabilisation of the ion is greater.
The position of equilibrium is further to the right
compared with phenol.
H+ ions are not strongly attracted to the ethanoate ion.
So the ethanoate ion is less likely to form undissociated
molecules than is the phenoxide ion.

ACIDIC CHARACTER IN ORGANIC COMPOUNDS

Two of the factors which influence the ionisation of an
acid are: - the strength of the bond being broken,
- the stability of the ions being formed.

CARBOXILIC ACID > PHENOL > ALCOHOL

Carboxilic acids: the negative charge is delocalized in the
available p orbitals of the carbon and oxygen atoms,
then the carboxylate anion is more stable.
Phenol: in the phenoxide anion the negative charge is
delocalized and becomes a part of the ring system, it
is therefore a very weak acid since the electron on the
O in the anion is unavailable to accept a proton.
Alcohols: the negative charge is entirely located at the O, then,
that intense negative charge will be highly attractive
towards hydrogen ions, and so the ethanol will
instantly re-form. Alcohols are poor acids

KEY POINTS
The COO- ion in carboxylic acids is stabilised
by the conjugated (mesomeric) effect.
The acid strength of carboxylic acids increases
in the C next to the -COOH group has electronwithdrawing atoms bonded to it.
Carboxylic acids are stronger acids than
alcohols because of the effect of the conjugative
and inductive effects on the COOH group.
The greater the number of Cl atoms substituted
on the carbon atom next to the COOH group,
the greater the acidity of the carboxylic acid.

KEY POINTS
Phenol is a weakly acidic but more acidic than
ethanol or water.
Phenol is less acidic than carboxylic acids.
The acidity in phenols is due to the
delocalization of charge on the phenoxide ion
with the delocalised electrons in the phenol ring.
The alkoxide ion does not have delocalised
charge associated with the O atom. So the O readily accepts a hydrogen ion to form a
molecule.

CHEMISTRY FOR CAPE

PAGE 323
QUESTIONS 1 AND 2
1.a. Explain the acidic nature of the O-H bond in propanoic acid.
b. Place the following molecules in order of increasing acidic
strength. Explain your answer.
C2H5OH
CH2ClCOOH
C6H5OH
C2H5COOH
CH3COOH
2.The pKa values of ethanoic acid and chloroethanoic acid are
4.76 and 2.86 respectively.
a. State the meaning of the term pKa and explain the
significance of this value.
b. Account for the difference in pKa values of ethanoic acid
and chloroethanoic acid based on the structure of the molecules.