Diazoniation, or Diazotization

DIAZOTISATION TITRATION
INTRODCTION
The process of forming diazonium compounds or salts is called diazotation,

diazoniation, or diazotization
Diazonium compounds or diazonium salts are a group of organic compounds

+
sharing a common functional group with the characteristic structure of R-N2 X- where R
can be any organic residue such alkyl or aryl and X is an inorganic or organic anion such
as a halogen.
The reaction was discovered by Peter Griess in 1858, who subsequently discovered
several reactions of the new compound. This method is first used in the determination
of dyes.
Diazonium salts have been developed as important intermediates in the organic

synthesis of dyes
Diazotization titrations are carried out for the estimation of drugs containing primary
aromatic amino group.
Several drugs contain either primary aromatic amino group or they can be converted to
have such groups by simple reaction like hydrolysis orreduction.
An primary aromatic amine reacts with nitrous acid produced by the reaction of
sodium nitrite in acidic medium to form diazonium salt.
The reaction is quantitative under the controlled conditions of temp. (approx 150C) and
the end point can be detected when a small quantity of excess nitrous acid present at
the end point gives colour change with indicator or by electromerically.
It uses the titrant- Sodium Nitrite hence method is Sodium Nitrite Titration / Nitrite
Titration
CONDITIONFOR DIAZOTIZATION
RATE OF TITRATION
Different amino compound react with HONO at different rates
NaNO2 added from the burette needs time to react with amino group accumulating in
the solution
Amines are classified as rapidly, slowly diazotisable depending on the rate of

conversion into azo compounds.
TEMPERATURE
The diazonium compounds formed are unstable and readily decompose at elevated
temperature
This can lead to side reaction and give wrong result .
To eliminate this problem, this titration is carried out at lowtemperature (0-50 C).
Optimum temperature for most amine is 10-150 C, when they form relatively stable
diazocompounds.
PRINCIPLE
The first involved is addition of sodium nitrite to hydrochloric acid cause formation of
nitrous acid
NaNO2 + HCl HONO + NaCl
This nitrous acid diazotises the aromatic amino group
R − NH2 + NaNO2 + HCl R − N+ ≡ N − Cl− + NaCl
After the end point , excess nitrous acid formed is shown by instant formation of blue
colour with starch iodide paper.
KI + HCl HI+ KCl
NaNO2 + HCl HNO2 + NaCl
2HI +2HONO I2↑ +2NO +2H2O
Starch iodide paper is prepared by immersing a filter paper in starch mucilage and
potassium iodide solution
The iodine formed reacts with starch mucilage to give the blue colour.
I2 + Starch blue color (end point)
The end point can also be end point and potentiometric technique .
Method:
Weigh accurately 0.5 g sulphonamide add to it 20 ml ofhydrochloric acid and 50 ml

water, stirr, dissolve and cool to 150c. Immerse the electrode in the solution and apply the
voltage of about 50 mV. Place burette tip just below the solution to eliminate oxidation
of sodium nitrite. Stirr it gently & maintain the temp below 150c.
This method is suitable for most of the pharmacopoeial sulphonamides & its
preparations as well as the drugs which contains primary aromatic amines.
The reaction with sulphonamide can be shown as,
Slow diazotisable compounds include compounds that contain sulpha groups, nitrous oxide
group, or carboxylic group in aromatic ring or besides aromatic ring
Eg: isomeric nitro aniline, sulphanilic acid and anthranilic acid
Fast diazotisable compounds do not contain any substituent group other than amino
group but some times they may contain –CH3 or –OH group along with NH2 group.
Eg : aniline, toluidine and aminophenol
Adding KBr to the solution can increase the rate of titration.

TYPESOFDIAZOTISATIONTITRATIONS
DIRECT TITRATIONS
These are carried out by treating 1 mole of the drug with 3 moles of acid solution.
Ice can be used to lower the temperature to about 0-5°c. 0.1M sodium nitrite is added in
small amounts and titration is carried out.
The end point is determined by any one of the techniques as said before.
REVERSE METHOD
In this method a solution of amine and sodium nitrite are run into a solution ofacid.
This method is used when the diazonium salts are insoluble.
Eg: naphtylamine sulphonic acids form insolublediaonium salts due to formation of

zwitterions.
SPECIAL METHOD
Aminophenol are readily oxidized by nitrous acid to quinones
For such substances , the titration is carried out in the presence of copper sulphate
which formsdiazo-oxide
These diazo-oxides are more stable and undergo coupling reaction.

APPLICATIONS
The first use of diazonium salts was to produce water-fast dyed fabrics.
A more common process uses a paper coated with diazo.
It is also applicable in nanotechnology.
It is also used in the preparation of hydrocarbons, aryl halide, aryl cyanide and aryl
hydrazines.
It is used in the assay of sulpha drugs like dapsone, sulphonamides, sulphacetamide

sodium, sulphadiazine, sulphamethazole, sulphadoxine, sulphamethoxazole &
sulphaphenazone etc.
It is also used in the assay of various drugs like benzocaine, procainamide, procaine,
suramin, sodium amino salicylate, primaquine sulphate etc.,

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DIAZOTISATION TITRATION

The process of forming diazonium compounds or salts is called diazotation,

Diazonium compounds or diazonium salts are a group of organic compounds

Diazonium salts have been developed as important intermediates in the organic

Different amino compound react with HONO at different rates

Amines are classified as rapidly, slowly diazotisable depending on the rate of

This can lead to side reaction and give wrong result .

NaNO2 + HCl HONO + NaCl

This nitrous acid diazotises the aromatic amino group

R − NH2 + NaNO2 + HCl R − N+ ≡ N − Cl− + NaCl

Weigh accurately 0.5 g sulphonamide add to it 20 ml ofhydrochloric acid and 50 ml

The reaction with sulphonamide can be shown as,

Eg: isomeric nitro aniline, sulphanilic acid and anthranilic acid

Eg : aniline, toluidine and aminophenol

Adding KBr to the solution can increase the rate of titration.

This method is used when the diazonium salts are insoluble.

Eg: naphtylamine sulphonic acids form insolublediaonium salts due to formation of

Aminophenol are readily oxidized by nitrous acid to quinones

These diazo-oxides are more stable and undergo coupling reaction.

A more common process uses a paper coated with diazo.

It is also applicable in nanotechnology.

It is used in the assay of sulpha drugs like dapsone, sulphonamides, sulphacetamide

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