FACTORS WHICH AFFECT ACIDITY

V Effect of Resonance stabilization on acidity

Hydroxyl containing compounds in which the hydroxyl group is bonded to the carbonyl carbon
are much stronger acids than alcohols. A simple experiment in which alcohols and acids are
separately put into a solution containing bicarbonate ions can illustrate this. When the acid is
added, carbon dioxide is evolved where as the alcohol addition will not evolve carbon dioxide.

CH3COOH + HCO3- CH3COO- + H2CO3 H2O + CO2

bubbles
pKa 4.8 pKa 6.5

CH3CH2OH + HCO3- No bubbles

Comparison of alcohols, phenols and carboxylic acid shows that they have different pKa values
in spite of the fact that they are all losing a proton from the oxygen atom. The pKa of ROH,
ArOH and RCOOH are 15-19, 10 and 5 respectively. The differences in the acidity of the three
classes of compounds can be explained by resonance stabilization or the lack of it following
ionization. RO- [see CH3CH2O-] is not resonance stabilized. In RCOO- the negative charge is
shared between the two oxygen atoms i.e. the negative charge in the enolate
O O

H3C C O H3C C O

CH3 CH2O
anion is delocalised.

In ArO- the negative charge is partially delocalised by the benzene ring

- O O O
O

- -
- .

VI Effect of Solvation on acidity

The pKa of an acid varies somewhat depending on the solvent it is dissolved in and the
temperature at which the determination is carried out.
O

CH3COOH(g) +H2 O(g) H3C C O (g) + H3O+(g)

acetic acid in water in acetate anion in hydronium ion in
gas phase gas phase gas phase gas phase
pKa 130

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For example the proton transfer reaction of acetic acid with water in the gas phase takes place at
the pKa value of 130 for acetic acid. In other words it is difficult to separate the negatively
charged acetate ion from the positively charged hydronium ion unless solvent molecules are
present to stabilize the charged particles. It follows from this that the interaction of the solvent
with the undissociated acid and with anions and cations that form on dissociation contributes to
the stabilization of the various species and therefore to the position of the equilibrium. Such
interactions are particularly important in water which participates in extensive hydrogen
bonding. When an ac id is dissolved in water, the bonding between the solvent molecules is
disrupted and new hydrogen bonds are formed between water and molecules and the solute
particles.
Solvation of the anion A- stabilizes the anion. The solvent helps disperse the negative charge
through dipole-dipole interaction.
Water has greater ability to solvate ions than EtOH. Thus a water solution of RCOOH is more
acidic than an EtOH solution of the same acid.

Acid strength in substituted benzoic acid

Resonance stabilization by the aromatic ring does not play a role in the relative strength of
benzoic acids. This is because the oxygen atoms are not directly attached to the ring. The
negative charge is shared by the two oxygen atoms.
O O-

O- O

Substituents on the benzene ring can influence the acidity of benzoic acid derivatives by
inductive effect. The electron withdrawing groups enhance acidity of benzoic acids. For
example, ortho chlorobenzoic acid is more acidic than benzoic acid.

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 pKa

Ortho meta para

COOH

4.2 4.2 4.2

COOH
H3C 3.9 4.3 4.4

COOH
HO 3.0 4.1 4.5

COOH
H3CO
4.1 4.1 4.5

COOH
Br 3.8 4.0
2.9

COOH
Cl
2.9 3.8 4.0

COOH
O2N
2.2 3.5 3.4

The reasons that electronegative substituents increase the acid strength are
again,destabilization of the acid and stabilization of the anion.

Hammet (Colombia U,1939-1940) developed an equation that provides a

quantitative relationship between structure and reactivity. For a reference reaction
he used substituted benzoic acids. In order to determine the effect of a substituent
X on the acidity of benzoic acid, he used the dissociation of a family of meta and
para substituted benzoic acids.

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 COOH COO-
H2O
X + H2O + H3O+
25 0C
X
He established the fact that the magnitude of pKa is affected by the nature and
position of the substituent X. The effect of the substituent X upon the acidity of
benzoic acid was arbitrarily used as a measure of some property of the substituent.
The measure of this property was given a symbol  and defined as follows.

X= pKa (C6H5CO2H)-pKa (XC6H4CO2H) or

X=Log{ Ka (XC6H4CO2H/Ka(C6H5CO2H)}

A positive value for sigma indicates an acid-enhancing effect and this usually
corresponds to an electron-withdrawing capability of the substituent. Substituents
with a negative sigma values decrease the acidity of benzoic acid. The table below
shows experimental results for a selected list of substituents.

Substituent X pKa (XC6H4CO2H) X

H 4.20 0
m-OCH3 4.09 0.11
m-F 3.86 0.34
m-NO2 3.49 0.71
p-NO2 3.42 0.78
p-CH3 4.37 -0.17
p-OCH3 4.48 -0.28

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The study was extended to phenylacetic acid (C6H5CH2COOH) and 3-phenyl
propionic acid(C6H5CH2CH2COOH) and similar trends were observed. From the
studies he established the Hammet equation:
log Kx/Ko = .x or Log Kx-log Ko= .x

Ko is the equilibrium constant for the unsubstituted benzene derivative

Kx is the equilibrium constant for the meta or para X substituted benzene
derivative in its corresponding reaction.
Rho [ ] is the reaction constant indicating the relative need of a particular
reaction for electron withdrawal or electron release.

Sigma []is the substituent constant indicating the relative electron withdrawing or
electron releasing effect of a particular substituent group.
Sigma value
The sigma value is the measure of the ability of a substituent to donate or withdraw
electron density from a reaction site. For a substituent, the sigma value is the
difference between the pKa of a substituted benzoic acid and benzoic acid itself.
E.g. sigma for a nitro group =pKa (benzoic acid)- pKa (p nitro benzoic acid)= 4.2-
3.4= 0.8
Log Kpnitrobenzoic – Log KBenzoic = .x
Since pKa = - Log Ka and  =1 for benzoic acids
Then -3.4- (-4.2) = 1 . x
Thus for para substituent x = 0.8
The literature value for this group is 078

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Sigma values vary with the position of Substitution on the benzene ring. For the
Meta substitution gamma for nitro group = 0.71
A positive value for sigma implies that the substituent withdraws electron density
from the reaction site while a negative value indicates that the substituent has a
positive inductive effect.

Rho value or reaction constant

 is the measure of the sensitivity of the reaction to substituent effects or
susceptibility of the reaction to electrical effects. Reaction with a positive value of
 are helped by using compounds with known gamma values, the rho () values
can be calculated.
The rho value is calculated as a slope in the plot of rate constants of a series of
substituted compounds versus Benzoic acids substituted with the same
substituents. For example comparison of phenyl acetic acids with the
corresponding benzoic acids shows the following pKa values

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 Compound pKa
Compound pKa

CH2COOH 4.4
COOH
4.4

H3C
H3C
COOH 4.2 CH2COOH

4.3

COOH CH2COOH

4.0
4.2

Cl Cl
CH2COOH
COOH

3.4 3.9
O2N
O2 N

The plot of pKa values of phenylacetic acids against the pKa of Benzoic acids will
give a slope of 0.5
This implies that the rho value for the ionisation of phenyl acetic acid is 0.5. The
literature value for this reaction is 0.489 (compare with  for benzoic acid)
A positive rho value implies that the reaction is aided by electron withdrawing
groups. A negative rho value means that the reaction is aided by electron donating
substituents. The magnitude of rho tells us the sensitivity of the reaction to that of
the substituents.
The value of  was originally set at 1.00 for the dissociation of XC6H4COOH at
250C.

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m and p were calculated for each group (For a group x,  is different for meta
and para positions.)
Once a set of  values was obtained, gamma values could be obtained for other
reactions from the rates of two X-substituted compounds if the sigma values of the
X groups are known.
With the rho value thus calculated and the known sigma values for other groups,
rates may be predicted for reactions that have not yet been run.

The sigma values are numbers, which sum up the total electrical effects
(resonance& inductive) of a group X when attached to benzene ring.Threy indicate
the relative electron-withdrawing or electron-releasing effect of a particular
substituent. By using tables of sigma and rho values we can calculate the relative
Keq values or relative rates for thousands of individual reactions.