Lecture 6

 In this type of titrations, acid base reaction takes place in a

medium completely free from water.

Advantages of non-aqueous titration:

1.If sample to be analyzed is insoluble in water, it could be
dissolved in non-aqueous solvent
2.Very weak acids or bases could be directly titrated using
leveling solvents
3.Using of differentiating solvent enables differential titration
of mixture of acids or mixture of bases as it increase the
difference between their dissociation constant (Ka) to be 104
at least
4.the low surface tension of non-aqueous solvents make the
size of droplet smaller than that of aqueous solvent, therefore
volume of the titrant taken is more accurate 2
 Bronsted Lowery theory:

An acid is defined as proton donor while a base is defined as proton

acceptor. An acid base reaction is a proton transfer from acid to
base i.e. protolytic reaction.
-
HA + B → BH+ + A
acid base conj. Acid conj. Base
►A solvent is always involved in acid base reaction for example
HCl + H2O → H3O+ + Cl-
NH4+ + H2O → H3O+ + NH3
H2O + NH3 → NH4+ + OH-
i.e. substance can react as a base in presence of more proton donor one
and as an acid in presence of a more proton acceptor.

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Role of solvent in non-aqueous titrations:
1- Relative acidity and Basicity:
According to Bronsted theory, acidity and basicity of a substance is
relative to the solvent; if a substance is more acidic than the solvent it
will behave as an acid; if more basic it will behave as a base e.g.
potassium acid phthalate

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 2- Leveling effect of solvents:
It is the ability of solvent to increase the strength of weak acids or
weak bases to reach that of strong ones.
basic solvents have a leveling effect on weak acids; Also, acidic
solvents have leveling effect on weak bases.

Example: On dissolving HCl and CH3COOH in ammonia, it will attract the

same number of protons from both acids, therefore HCl and CH3COOH have
the same acidity in ammonia. Accordingly, ammonia is described as leveling
(or non differentiating) solvent as it levels up acidity (or Ka) of CH 3COOH to
the level of Ka of HCl. i.e. will have equal strength.

3- Differentiating effect of solvents:

It is the ability of solvent to differentiate between the strength of acids
and bases.

- When HClO4, HCl and HNO3 are dissolved in glacial acetic acid, it is only
HClO4 is the strong acid i.e. acetic acid differentiates between strength of
mineral acids.

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 Factors that affect leveling and differentiating abilities of solvents

1- Acidic and basic characters of the solvent relative to solute:

 Solvents as formic, sulphuric and glacial acetic acid is proton
donor more than being proton acceptor i.e. acidic in nature and
will have leveling effect on bases
e.g. aniline is a weak base in water (Ka= 10-10) cannot be directly
titrated, however it is a strong base in glacial acetic acid and
can be directly titrated.
 Solvents as pyridine, dimethylamine and liquid ammonia is
proton acceptor more than being proton donor i.e. basic in
nature and will have leveling effect on acids
e.g. phenol is a weak acid in water (Ka= 10-10) cannot be directly
titrated, however it is a strong acid in such solvents and can be
directly titrated.
Q- Give reason: aniline (Ka= 10-10) can be directly titrated in non-
aqueous medium. 6
 2- Autoprotolysis constant (Ks):
It is the self dissociation of solvent, i.e. transfer of protons occurs
between two molecule of the solvent, one acts as proton donor and the
other as proton acceptor.
HA + HA → [A.HAH] → HAH+ + A-
Ks = [A-][HAH+]
Example:
H2O + H2O → H3O+ + OH-
CH3COOH + CH3COOH → CH3COOH2+ + CH3COO-
NH3 + NH3 → NH4+ + NH2-

It occurs in amphiprotic solvent that contain H+ liable to be donated

or accepted as e.g. H2O, alcohol and ammonia.

The smaller the autoprotolysis constant "K s" of solvent, the greater
will be its ability to be differentiating.

The smaller the Ks, the more complete the reaction because
solvents with high Ks will produce a considerable amount of ionic
species which will compete with the substance to be determined for 7
3- Dielectric constant of the solvent (D):

-It is the ability of solvent to separate positively charged ions

from negatively charged ions. In case of solvent with high D
minimum work is required for such separation.

- The higher D of solvent, the greater the separations by

decreasing force of attraction between positive and negative ions,
therefore affect the acidic and basic strength.

- Good solvent should has high D as it increases strength of

reactant. carboxylic acids in H2O (high D), have Ka = 10-5 while in
ethanol (low D) Ka = 10-10 i.e. appear as weak acids.

- H2O is a unique solvent as it has low K s and the highest D of all

solvents which allows completeness of reactions.
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Properties of best solvent for non-aqueous titration:

1- Lowest possible Ks
To decrease competition of conjugate base of the solvent
with basic sample for protons and also decrease
competition conjugate acid of the solvent and acidic sample.

2- Highest possible D
As it increases the strength of reactant.

3- Acidic solvents are used to dissolve basic substances to

increase their dissociation and strength therefore allow
complete reaction while basic solvents are used for acidic
substances for the same reason.

4- Substances to be determined must be soluble in the chosen

solvent. 9
Classification of solvents used in non-aqueous titrations:
[1] Aprotic solvents:

o These are neutral inert solvents that do not accept or donate

protons

o They do not undergo autoprotolysis reaction and they have no

leveling effect

o Used in admixture with other polar solvents to suppress

ionization at end point i.e. prevent solvolysis

Examples: hexane, benzene, CH3Cl, CCl4 and nitrobenzene.

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[2] Amphiprotic solvents:

They act as acids and bases i.e. may donate or accept protons. They
undergo autoprotolysis reaction. They are classified into:

a. Neutral solvents e.g. alcohols (methanol, ethanol). They have the

same tendency to accept and donate protons with no leveling
effect.

b. Protogenic solvents e.g. acetic acid. They are more acidic than
H2O and have tendency to give protons much more than
accepting protons. They have leveling effect on weak bases with
amphiprotic properties.

c. Protophilic solvents e.g. liquid ammonia, ethylene diamine and n-

butyl amine. They are more basic than H2O with higher tendency
to accept protons than giving them. They have leveling effect on
weak acids with amphiprotic properties.
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[3] Protophilic solvents with no amphiprotic properties:
- They are basic in nature i.e. accept protons and have no acidic
character (do not donate protons).

- They do not undergo autoprotolysis reaction and they have slight

leveling effect on acids e.g. DMF (dimethylformamide) and
pyridine.

[4] Protogenic solvents with no amphiprotic properties:

- They are acidic in nature i.e. donate protons and have no basic
character (do not accept protons) e.g. HCl, HNO3, H2SO4
- They do not undergo autoprotolysis reaction and they have slight
leveling effect on bases
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 Applications of acid – base titration in non-aqueous medium

[A] [B]
Basic substances Acidic substances

[A] Determination of basic substances

1- Solvent: glacial acetic acid

2- Titrant: standard acetous perchloric acid (0.1N HClO4 in glacial acetic acid)
3- Indicator: crystal violet ( color change from violet to bluish green)

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1. Mixture of primary, secondary and tertiary amines:
1- Total amines:
are directly titrated with acetous perchloric acid using crystal
violet as indicator according to the following equations:
RNH2 + HClO4 → RNH3+ + ClO4-
R2NH + HClO4 → R2NH2+ + ClO4-
R3N + HClO4 → R3NH+ + ClO4-
2- Tertiary amine:
equal amount of the mixture used in the first step (total) is
refluxed with acetic anhydride where primary and secondary
amines are acetylated only. The remaining tertiary amine is
determined by titration against 0.1N perchloric acid in
isopropanol.
(CH3CO)2O + RNH2 → CH3CONHR + CH3COOH
(CH3CO)2O + R2NH → CH3CONR2 + CH3COOH 14
3- Secondary and tertiary amines:

equal volume of sample is heated with Salicylaldehyde which

forms Schiff's base with primary amine only. The product is
titrated with 0.1N HClO4 in isopropanol.

Calculation:
Volume of standard Perchloric in step 2 = tertiary amine
Volume of standard in (step 3 – step 2) = secondary amine
Volume of standard in (step 1 – step 3) = primary amine

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 2. Amino acids:

-Amino acids such as alanine and glycine

-They contain –NH2 group which is basic group and –COOH which is

acidic group, i.e. amino acids are amphoteric therefore we have to

dissolve in acidic solvent as glacial acetic to increase its basic

character, dissociation of -COOH group are suppressed while –NH2

group is leveled up and can be titrated with acetous perchloric using

crystal violet.

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 3. Sulfonamides:

-Sulphonamides contain –NH2 which is a basic group & –SO2–

NH– is weak acidic group. i.e., sulfonamides are amphoteric

therefore we have to add glacial acetic acid as a solvent (leveling

solvent) to increase its basic character, titrant is HClO4 using

crystal violet as indicator.

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[B] Determination of acidic substances:

1. Solvent: Pyridine, DMF

2. Titrant: sodium methoxide, sodium ethoxide in methanol
3. Indicators:
 thymol blue changes from yellow (acid) to blue (alkali)
 azo violet changes its color from red to blue

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Sulfonamides:

- Sulphonamides contain –NH2 which is a basic group & –SO2–

NH– is weak acidic group. i.e., sulfonamides are amphoteric
therefore we have to add strong basic solvent to increase its
acidic character e.g., DMF or n-butylamine, titrant is NaOCH3
using thymol blue as indicator.
- Aprotic solvent e.g. benzene is added to prevent solvolysis of
reaction product.

N.B: The same principle for amino acids. 19