About Methyl Orange

By Merrene Bright D. Judan

IUPAC name: 4-[(Z)-(4-aminophenyl)diazenyl]benzene-1-sulfonic acid

Molecular Formula: C14H14N3NaO3S (National Center for Biotechnology Information, nd)
Molecular Weight: 327.334029 g/mol (National Center for Biotechnology Information, nd)
Synonyms: Orange III, Gold Orange, Eniamethyl Orange, Helianthine (National Center for Biotechnology
Information, nd)
Physical Description: Orange to Yellow odorless powdered solid (ScienceLab.com, 2005)
Solubility: Partially soluble in hot water. Very slightly soluble in cold water. Insoluble in diethyl ether.
Practically insoluble in alcohol. Soluble in Pyrimidine. (ScienceLab.com, 2005)

Uses of Methyl Orange

As pH indicator
As dye as in textiles

Preparation of Methyl Orange

Methyl orange is an azo dye prepared by the diazo coupling reaction. It is prepared from sulfanilic
acid and dimethylaniline. Sulfanilic acid is first alkalinified since it is insoluble in acid solutions. It is then
diazotized and coupled with dimethylaniline. The first product obtained is helianthin, which is the acid
form of methyl orange. In basic solutions, helianthin is converted to the orange sodium salt called methyl
orange. (Pavia, 1976, p. 245 - 247)

Reasons for Important Steps

Step
Addition of sulfanilic acid monohydrate to a
solution of sodium carbonate
Addition of sodium nitrite and pouring of the
solution in concentrated hydrochloric acid
Reason
The sulfanilic acid is dissolved in basic solution to
facilitate the reaction. Sulfanilic acid is insoluble in acid
solutions, such as nitrous acid, therefore it is
necessary to initially dissolve sulfanilic acid in sodium
carbonate solution. (Pavia, 1976, p. 246)
Formation of nitrous acid. Upon adition of the acid, the
sulfanilic acid is precipitated out of solution as a finely
divided solid which is immediately diazotized.
(Pavia, 1976, p. 246)

Addition of dimethylaniline and glacial acetic Coupling of the diazotized sulfanilic acid and
acid dimethylaniline, forming helianthin. (Pavia, 1976,
245)

Cool the mixture Methyl orange is only very slightly soluble in cold water.
(ScienceLab.com, 2005)

Addition of sodium hydroxide and heating the Addition of sodium hydroxide turns the helianthin to
mixture methyl orange and heating the mixture increases
solubility.

Addition of sodium chloride Sodium chloride reduces the solubility of methyl

orange, allowing it to recrystallize.

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Analysis of the Product

Tested
Indicator Action Methyl Orange Upon addition of acid, Methyl orange is red at
the solution turns red. pH 3.1 and below,
Upon addition of while it is yellow at pH
sodium hydroxide, the 4.4 and above.
solution turns yellow. (Block, 1974, p. 113)
(Block, 1974, p. 113)
Reduction Test Azo group Formation of colorless Azo compounds are
amine solution (Shriner, easily reduced at the
2004, p. 431) nitrogen-nitrogen
double bond by
reducing agents.
(Pavia, 1976, p. 247)
The products are
sulfanilic acid and
phenylenediamine
Spectroscopic Methyl Orange
Analysis

Answers to Guide Questions

1. Why must the diazonium salt be kept in an ice bath prior to use in coupling?

The diazonium salt is unstable at temperatures exceeding 10 degrees Celsius, and decomposes to
form nitrogen gas, hydrochloric acid and phenol.

2. Why does the dimethylaniline couple with the diazonium salt at the para position of the ring?

Dimethylaniline is ortho, para directing, but due to steric hindrance, para substitution is preferred.

3. Give the corresponding aromatic amines and/or phenols used in the synthesis of orange II, para
red, butter yellow and amaranth red via diazo coupling reaction.

Orange II: sulfanilic acid and 2-napthol

Para red: p-nitroaniline and 2-napthol
Butter yellow: N,N-dimethylaniline and benzene
Amaranth Red: 3-hydroxynapthalene-2,7-disulfonic acid and 4-aminonapthalene-1-sulfonic acid

4. Draw the structures of helianthin and methyl orange. Identify the moieties responsible or the
color change of the dye in the presence of an acid or base.

Helianthin red in color, acidic form Methyl orange yellow in color, basic form

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Moieties responsible: Benzenoid (base form) and Quinonoid (acid form)

5. Using a diagram, show the mechanism by which methyl orange exhibits its indicator action.

6. Show the products of reduction in the reduction test.

p-phenylenediamine and sulfanilic acid: