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ORGANIC COMPOUNDS
COMPARING
ACIDITIES
3.1.
Ka/
moldm-3
1.7 X 10-5
4.77
1.3 X 10-5
4.89
1.3 X 10-3
2.89
Carboxylic acid
pKa
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are withdrawn from the carbon and the more the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.
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.
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.