Acid base indicators

NON AQUEOUS
TITRATION
Mahaveer singh

INTRODUCTION
Non- aqueous titrations are the titrations in which
weakly acidic or basic substances are carried out
using nonaqueous solvents to get sharp end point.
The moisture content in nonaqueous titrations
should not be more than 0.05%.
Moisture and carbon dioxide are to be avoided in
non aqueous methods

THEORY
Lowry-Bronsted theory
HB H+ + B(ACID)

(CONJUGATE BASE)

B + H+ HB+
(BASE)

(CONJUGATE ACID)

The ability of substances to act as acids or

bases depend on the choice of solvent
system.

Colorless to yelllow
H2N
O

OH

O
+

O
+

SOLVENTS

Protogenic solvents: Are acidic substances, exert levellling effect,

on dissociation yield a H+,
Ex:H2SO4,,CH3COOH

Protophilic Solvents: basic in nature, react with acids to form

solvated protons , high affinity for H+
Ex:(CH3CO)2O,ether,pyridine
Amphiprotic Solvents : donate protons and accept protons
Ex:H2O,alcohols
Aprotic Solvents: no tendency to yield and accept H +
Ex:CCl4,hydrocarbons, toluene, CHCL3 do not react with acid or
bases, dont favor ionization

ASSAY BY NON-AQUEOUS

TITRATIONS
Acidimetry in Non-aqueous TitrationsIt can
be further sub-divided into two heads, namely :
(i) Titration of primary, secondary and tertiary
amines, and
(ii) Titration of halogen acid salts of bases.

Alkalimetry in Non-aqueous Titrations

titration of acidic substances

ACIDIMETRY IN
NON AQUEOUS TITRATIONS
Example : Primary amines
METHODOLOGY: four steps

(i) Preparation of 0.1 N Perchloric acid,

(ii) Standardization of 0.1 N Perchloric Acid,
(iii) Choice of Indicators, and
(iv) Effect of Temperature on Assays

PREPARATION OF 0.1 N PERCHLORIC

ACID
Materials Required : 8.5 ml of perchloric acid (70.0 to 72.0%) ;
1 Litre of glacial acetic acid ; 30ml of acetic anhydride.
Procedure : Gradually mix 8.5 ml of perchloric acid to 900 ml of
glacial acetic acid with vigorous and continuous stirring. Now
add 30 ml acetic anhydride and make up the volume to 1 litre
with glacialacetic acid and allow to stand for 24 hours before use.
The acetic anhydride reacts with the water (approx. 30%) in
perchloric acid and some traces in glacialacetic acid thereby
making the resulting mixture practically anhydrous. Thus, we
have :
H2O + (CH3CO)2O 2CH3COOH
Acetic anhydride
Acetic acid

STANDARDIZATION OF 0.1 N
PERCHLORIC ACID
Weigh accurately about 0.5 g of potassium hydrogen
phthalate in a 100 ml conical flask.
Add 25 ml of glacial acetic acid and attach a reflux
condenser fitted with a silica-gel drying tube. Warm until
the salt gets dissolved completely. Cool and titrate with
0.1 N perchloric acid by making use of either of
the following two indicators :
(a) acetous crystal violet-2 drops, end point Blue to BlueGreen (0.5% w/v)
(b) acetous oracet blue B-2 drops, end point Blue to Pink.

REACTIONS
RCOOM

RCOO + M+

CH3COOH2++RCOO
Onium ion
KHC8H4O4 +

RCOOH+ CH3COOH
Acetic acid
HClO4

POTTASSIUM HYDROGEN PTHALTE

C8H6O4+KClO4
PTHALIC ACID

204.14 g C8H5O4K HClO4 1000 ml N

or 0.02041 g of C8H5O4K 1 ml of 0.1 N HClO4
Strength of 0.1N Perchloric acid = wt. of potassium hydrogen phthalate taken
____________________________________
Vol. of Perchloric acid X 0.02042

CHOICE OF INDICATORS
S.No.

Name of Indicator

Colorchang
e
Basic

Observed

Acidic

Neutral

Crystal violet (0.5% w/v

in glacial acetic acid)

Oracet Blue B(0.5% in

glacial acetic acid)

Blue

Purple

Pink

-Naphtholbenzein
(0.2% in glacial acetic
acid
Quinalidine Red
(0.1% in methanol

Blue

Orange

Dark-green

Violet

Magenta

Bluish
green

Yellowish
green

Almost
colourless

EFFECT OF TEMPERATURE ON
ASSAYS
Non-aqueous solvents possess greater coefficients of
expansion as compared to water, so there is effect of
temperature.
The volume of titrant may be corrected by the
application of the following formula :
Vc = V [1 + 0.001 (tl + t2)]
Vc = Corrected volume of titrant,
V = Volume of titrant measured,
tl = Temperature at which titrant was standardized,
t2 = Temperature at which titration was performed.

Titration of primary amines

Ex: Methlyldopa
R.NH2 + HClO4 [R.NH3]+ + ClO4 Specific reaction between methyldopa and perchloric
acid is expressed by the following equation
HCLO 4
RN

CH 3COOH

CH 3COOH 2

HCLO 4

CH 3COOH 2

CH 3COOH

CH 3COO

RN

RNH
-

CH 3COO

CLO 4
-

2CH 3COOH

RNH

CLO 4

PRECAUTIONS
(a) Perchloric acid is usually available as a 70 to 72% mixture with water .It
usually undergoes a spontaneous explosive decomposition and, therefore, it is
available always in the form of a solution.
(b) Conversion of acetic anhydride to acetic acid requires 40-45 minutes for its
completion. It being an exothermic reaction, the solution must be allowed to
cool to room temperature before adding glacial acetic acid to volume,
(c) Avoid adding an excess of acetic anhydride especially when primary and
secondary amines are to be assayed, because these may be converted rapidly
to their corresponding acetylated non-basic products :
RNH2 + (CH3CO)2O R.NH.(CH3CO) + CH3COOH
Primary amine
Acetylated product
(d) Perchloric acid is not only a powerful oxidising agent but also a strong
acid. Hence, it must be handled very carefully.

ADVANTAGES OF NON AQUEOUS

TITRATIONS
1) Organic acids and bases that are insoluble in water are soluble
in non-aqueous solvent.
2) Organic acid, which is of comparable strength to water, can be
titrated easily in non-aqueous solvent. Bases also follow the same
rules.
3) A non-aqueous solvent may help two are more acids in mixture.
The individual acid can give separate end point in different solvent.
4) By the proper choice of the solvents or indicator, the biological
ingredients of a substance whether acidic or basic can be selectively
titrated.
5) Non aqueous titrations are simple and accurate, examples of non
aqueous titration are: Ephedrine preparations, codeine phosphate in
APC, tetracycline, teramycin, Antihistamines and various piperazine
preparations.

Titration of Halogen Acid Salts of Bases

In general, the halide ions, namely: chloride, bromide and
iodide are very weakly basic in character so much so that
they cannot react quantitatively with acetous perchloric acid.
In order to overcome this problem, mercuric acetate is
usually added (it remains undissociated in acetic acid
solution) to a halide salt thereby causing the replacement of
halide ion by an equivalent amount of acetate ion, which
serves as a strong base in acetic acid as shown below:

Assay of Amitriptyline Hydrochloride:

Materials Required: Amitriptyline hydrochloride : 1.0 g ;
mercuric acetate ; crystal violet; 0.1 N perchloric acid ; glacial
acetic acid.
Procedure: Weigh accurately about 1.0 g of sample and dissolve it
in 50 ml of glacial acetic acid, warm slightly, if necessary, to affect
the solution. Cool, add 10 ml of mercuric acetate solution, two
drops of crystal violet solution and titrate with 0.1 N perchloric
acid to a green end-point. Perform a blank determination and
make any necessary correction.