Acid – Base Titrations in Nonaqueous Solvents

Advantages of Nonaqueous Solvents

Q. What are the disadvantages of carrying out titrations in aqueous

medium?

▪ It has been observed from the examinations of titration curves for

various strength acids that acid or bases with dissociation constants
less than about 1 × 10-8 cannot be titrated successfully in water at
about 0.1 M concentration
▪ This is because at lower values of the dissociation constant the
breaks in the titration curves are too small to enable observations of
the end point, reflecting incomplete titrations reactions.
▪ Some acids and bases are not soluble enough in water to produce a
0.1M solution, requiring dissociation constant higher than 1 × 10-8 to
enable end point measurement.

Q. How these problems can be overcome?

These problems can sometimes be overcome by using a solvent other

than water – that is a nonaqueous solvent.

▪ Nonaqueous solvents can be chosen that emphasize the acidity or

basicity of analytes so that the analytes can be titrated.
▪ A number of acids and bases that are not sufficiently soluble in
water to be titrated are soluble enough to titrate in properly
chosen nonaqueous solvents.
▪ Nonpolar, non-ionic species, usually organic in nature may be
much more soluble in a water-immiscible organic nonaqueous
solvent than in water, so that these species can be dissolved and
titrated at significant concentrations in an organic solvent.

Page | 1
Acid-Base Character of Solvents

The strength of weak bases is amplified in acidic solvents, whereas, the

strength of a weak acid is increased in basic solvents.

B + HCOOH ⇌ HB+ + HCOO-

This analogous to the following reaction in water

B + H2O ⇌ HB+ + OH-

Kb of the weak base in formic acid is higher than K b of the base in water.
This is because formic acid is an acidic solvent with strong proton donor
qualities.

The acidity of a weak acids is enhanced in basic solvents;

HA + en ⇌ enH+ + A-

The equilibrium is shifted towards right because of the strong tendency

for ethylenediamine to accept protons

Acidic Solvents to Enhance Basicity

For example, it is virtually impossible to carry out titration of the base,

pyridine in water because the compound is such a weak base in that
solvent with a Kb of only 1 ×10-9. However, in acetic acid solvent, the Kb
value of pyridine is greatly increased, due to the reaction

C6H5N + CH3COOH ⇌ C6H5NH+ + CH3COO-

The pyridine can be titrated in anhydrous acetic acid with perchloric acid
titrant:

C6H5N + CH3COOH2+ + ClO4- ⇌ C6H5NH+ + CH3COOH + ClO4-

Page | 2
Basic Solvents to Enhance Acidity

Acids that are very weak in water can be titrated in basic solvents. For
example phenol, which has a

OH

Ka of only 1.00 ×10-10 in water and cannot be titrated in that solvent.

However, this can be done in ethylenediamine

OH + en O- + enH+

Levelling and Differentiating Solvents

The water is a levelling solvent because of its high value of self-dissociation

constant (KW = 1.00 × 10-14) and the fact that it is neither acidic nor basic.
This quality is best seen in the strength of acids in water. Several important
acids, such as HClO4, HCl, HNO3, and the first proton from H2SO4, are
classified as strong acids in water, meaning that the reaction
HA + H2O ⎯→ H3O+ + A- lies completely to the right – that is, the acid is
completely dissociated.

In respect to these acids, however, some solvents are differentiating

solvents, in which there are differences in the strengths of a number of acids
that are all strong acids in water.

Thus, in anhydrous acetic acid solvent, HCl is not classified as a strong acid
because the acidic solvent has relatively little tendency to accept protons in
the acid dissociation reaction

HCl + CH3COOH ⎯→ CH3COOH2+ + Cl-.

An equivalent way of putting it is that in anhydrous acetic acid the conjugate

base of HCl, the Cl- ion, has a relatively strong tendency to accept protons
from the acidic proton donor solvent.

Page | 3
Cl- + CH3COOH ⇌ HCl + CHCOO-

Dielectric Constant of Solvents

In terms of solvent (liquid) properties, the dielectric constant D may viewed

as a measure of the work required to separate oppositely charged ions in the
solvent.

The higher the dielectric constant, the less work is required to separate
oppositely charged ions.

Thus, in benzene, with a dielectric constant of only 2.3, much energy must be
expended to separate oppositely charged ions, and such ions tend to exists as
ion pairs held together by their opposite charges in this solvent.

On the other hand water (D=78.5) has a very high dielectric constant, such
that oppositely charged ions in aqueous solution have a very low tendency to
be paired through purely electrostatic forces of attraction.

Solvents with intermediate dielectric constants, such as acetonitrile

(D=37.4) and ethanol (D=24.3) exhibit behavior between that represented by
benzene and water.

Nature of Ionization in Low-Dielectric-Constant Solvents

Because of ion-pair formation, it is necessary to view dissociation of acids

and bases in low-dielectric-constant solvents as two step processes. For
example, in CH3COOH (D=6.2) HClO4 exists totally as ions of CH3COOH2+
and ClO4- and is, therefore, completely ionized. However, the ions are
present almost entirely as the ion pair CH3COOH2+ ClO4-

Although this ion pair does dissociates in acetic acid according to the
following equation
CH3COOH2+ ClO4- ⇌ CH3COOH2+ + ClO4- and the dissociation constant
Ka is only about 10-5.

The tendency to form ion pairs decreases the degree of dissociation of acids
and bases. These species are relatively weaker in low-dielectric-constant
solvents.
Page | 4
This is strictly true for initially uncharged acids HA or uncharged bases B.
These react with solvents, Hsolv, that can accept or donate protons by the
following general reactions which involve formation ions.

HA + HSolv ⇌ H2Solv+ + A-
B + HSolv ⇌ HB+ + Solv-

Thus, a low-dielectric-constant solvent with little tendency to separate ion

pairs favours the formation of species such as H2Solv+ A- and HB+Solv- with
little tendency to dissociate, thus lowering the strengths of acids and
bases. For example, carboxylic acids, such as benzoic acid, typically have
Ka values around 10-5 in water, but about five orders of magnitude lower
in the low-dielectric-constant solvent ethanol.

Solvents Choice for Nonaqueous Titrations

Amphiprotic: Capable of both accepting and donating protons

Aprotic: Solvents that do not accept or donate protons.

Acidic Amphiprotic Basic

Neither predominantly acidic or basic

Page | 5
Methanol and Ethanol have been extensively studied as solvents for acid
base titrations.

1. Neither predominantly acidic nor basic

2. Low self dissociation constant
3. Low dielectric constant
4. Un-dissociated ion pairs are formed

The acid dissociation reaction of NH4+ in ethanol is

NH4+ + CH3CH2OH ⇌ NH3 + CH3CH2OH2+ in which there is a +1
charge on both sides of the reaction and the low dielectric constant of ethanol
has no effect on the dissociation reaction. In such case
(i) The low self dissociation constant of the solvent has a predominant
effect
(ii) The degree of neutralization of NH4+ by strong base in ethanol is
much higher than degree of reaction of NH4+ with strong base titrant
in water.
 NH4+ can be titrated successfully with strong base in ethanol, but not in
water.

Q. Explain that NH4+ can be titrated successfully with strong base in

ethanol but not in water.

Page | 6