Non-Aqueous Titration

By: Rahul Malik

By: Rahul Malik
April, 2016
April, 2016

CONTENT
Introduction to Non-Aqueous Titration
Why we use Non-Aqueous Titration?
Types Of Solvents
1. Aprotic solvents
2. Protogenic solvents
3. Protophilic solvents
a. Levelling effect
4. Amphiprotic solvents
Examples of Non Aqueous Titration
Advantages and Disadvantages of Non Aqueous
Titration
Determining End Point
Reference.

Non-Aqueous Titrations
Titrations of substances is carried
out using
non- aqueous solvents.
It is the most common titremetric
procedure
used
inpharmacopoeial
assaysand serves a double purpose: it
is suitable for the titration of very weak
acidsand very weakbases, and it
provides
asolventin
which
organic compoundsaresoluble.

Such titrations can also be used for the

titration of the substances not soluble in
water.
First reported successful quantitative
titration of organic acid and base in
non-aqueous solvent: 1910.

Non aqueous titrations are

simple and accurate

Why Non- Aqueous titration?

?
?

?
?

 Non aqueous solvent are

basically used for those acid
or base
(1) Which dont give sharp end point
in titration.
(2) Which dont soluble in water.

Phenolphthalein colour fades

away at
the end point quickly.
Interference of atmospheric
CO2.

The theory is thatwater

behaves as both a weak
acid and a weak base;
thus,
in
anaqueous
environment,
it
can
compete effectively with
very weak acids and
bases with regard to
protondonation
and
acceptance

In aqueous titration, inflection in the

titration curves for weak acids and weak
bases is small, because they approach the
pH limits in water of 14 and 0
respectively, thus making end-point
detection more difficult.

General rule:

Acids with pKa > 7

Bases with pKa < 7
cannot determined accurately in aqueous
solution
Various organic solvents may be used to
replace water since they compete less
effectively with the analyte proton
donation and acceptance.

Bronsted- Lowry theory

The non aqueous titration can be
explained by the using Bronsted- Lowry
theory.
According to this theory
Acid: any substance, which can donate
proton or a substance which tends to
dissociate to yield a proton.
Base: any substance, which can accept a
proton or a substance which tends to
combine with a proton.

Solvents
The ability of substances to act as acids &
bases will depend very much upon the nature of
the solvent system which is employed.
Non-aqueous solvents are classified into the

4 groups:

Aprotic solvents
Protogenic solvents
Protophilic solvents
Amphiprotic solvents

Aprotic solvents
Chemically neutral substances
Un-reactive
Do not cause ionization of solute
No reactions with acids and bases
Used to dilute reaction mixture
Example:
Carbon
tetrachloride,
benzene, tolune.

Protogenic solvents
Acidic in nature
Readily donates protons
Strong protogenic solvents increase
the strength of weak bases
Such solvents exert a leveling effect
on all bases dissolved in them
Example: Anhydrous acid like hydrogen
fluoride & sulfuric acid

Protophilic solvents
Possess high affinity for proton
Weak acids are normally used as solute
Strong protophilic solvents convert
weak acid to strong acid-known as
leveling effect
Example: Liquid ammonia, amines, ether
and ketones

Levelling
effect
Strong protophilic solvents are used with
weak acids then they increase their acidic
strength and then become comparable to the
strength of strong acids

Amphiprotic solvents
Combine protogenic and protophilic properties
of solvent
Able to both donate and accept proton
Example: Water, alcohol & weak organic acid

Acetic acid shows acidic property by releasing

protonCH3COOH CH3COO- + H+
In presence of perchloric acid (strong acid)
acetic acid shows basic property by accepting
proton and produce onium ionCH3COOH + HClO4 CH3COOH2+ + ClO4onium ion

Examples

of non aqueous titration are:

Ephedrine preparations,
Codeine phosphate in API
formation,
Tetracycline,
Teramycin,
Antihistamines,
and various other preparations

ADVANTAGES
OF NON AQUEOUS SOLVENT
Organic acids and bases that are
insoluble in water are soluble in nonaqueous solvent.
Organic acid, which is of comparable
strength to water, can be titrated easily
in
non-aqueous
solvent. Bases also follow the same
rules.

A non-aqueous solvent may help two or

more acids in mixture. The individual acid
can
give
separate end point in different solvent.
By the proper choice of the solvents or
indicator, the biological ingredients of a
substance
whether
acidic or basic can be selectively titrated.

DISADVANTAGES
OF NON-AQUEOUS SOLVENTS

Expensive
Removal

Volatile

Toxic

of
water
is
necessary, can take water
(humidity) from the air

Potentiometric method
Potentiometric
method for the
detection of the equivalence point
The end point is determined by
using
indictor
electrode(glass
electrode)
and
reference
electrode(saturated
calomel
electrode)

Indicator method:
Indictor

Basic

Neutral

Acidic

blue-green

yellowishgreen

Crystal violet
violet

-Naphtholbenzein

blue or
blue-green

Oracet Blue B

blue

Quinaldine Red

Thymol Blue

magenta
yellow

orange

darkgreen

purple

pink

-------

almost
colour
less
blue

REFERENCE:
1 . K A Conners, A Text Book of Pharmaceutical Analysis, WileyIntersciences,
New
York.
2. A H Backett and J B Stenlake, Practical Pharmaceutical Chemistry,
Vol.I and II, The Athlone Press of The University of
London.
3. Pharmacopoeia of India, Govt.of India, Ministry of Health, Delhi.
4. J Bassett, R C Denney, G H Jeffery, J Mendham, Vogels Textbook
of
Quantitative
Inorganic
Analysis,
The
ELBS
and
Longman, London.
5. Napoleon A.A., Pharmaceutical Titrimetric Analysis
6.Watson, David G. (2005)Pharmaceutical Analysis - A Textbook
for Pharmacy 7.Students and Pharmaceutical Chemists, Churchill
Livingstone, 2nd Edition

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