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Synthesis of Methyl Orange and Its

Application to Textiles
The practice of using dyes is perhaps the most ancient art of chemistry. Dyeing substances from
plant, animal, or mineral sources has been known before written history. The accidental discovery
of the purple dye, mauve, by W.H. Perkin in 1856 is generally considered to be the birth of the
modern chemical industry. Several other synthetic dyes followed. One important group is known
as the azo dyes, which are named after their unusual N=N, azo, functional group.
Methyl orange, 4-[4-(dimethylamino)phenylazo]benzenesulfonic acid, is an azo dye that forms
orange crystals and is commonly used as an acid-base indicator, due to the fact that its anion form
is yellow and its acid form is red:
O
O

CH3
N

OH

N
CH3

Methyl orange
In this experiment, you will synthesize methyl orange from sulfanilic acid and N,Ndimethylaniline
using a diazonium coupling reaction, a common reaction for treating an aliphatic amine to yield a
carbocation. The reaction between a primary aliphatic amine and nitrous acid gives an unstable
diazonium salt that loses N2 to give a carbocation. The carbocation may then either (1) lose a
proton to give an alkene, (2) react with a nucleophile, or (3) rearrange, followed by (1) or (2).
The nucleophile we are using here is dimethylaniline. Attack is in the para position due to steric
hindrance at the ortho position by the bulky dimethylamine substituent. Because you are
synthesizing an azo dye, your product purity will easily be determined using a Spectrophotometer.
Diazontized

N,N-dimethylaniline

O
O

S
O

N
-

Methyl orange

CH3 diazonium
coupling
CH3

O
O

S
O

N
-

Na

CH3
N

sulfanilic acid

N
CH3

OBJECTIVES
In this experiment, you will

Synthesize methyl orange from the reaction of a primary amine with nitrous acid.

Calculate your product purity using a Spectrophotometer.

Observe the spectroscopic changes of methyl orange under acidic and basic
conditions.

Explore how organic chemistry is an essential component of the textile industry.

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MATERIALS
Materials Part I: Synthesis of Methyl Orange

sulfanilic acid
2% sodium bicarbonate solution
sodium nitrite
concentrated HCl
N,N-dimethylaniline
glacial acetic acid
125 mL Erlenmeyer flask
two graduated Beral pipets

10% NaOH solution


ice water bath
hot plate
glass stirring rod and spatula
Bchner funnel, filter, and filter paper
pH paper
graduated cylinders, 10 mL and 100 mL
watch glass

Materials Part II: Test the Colorimetric Absorbance of Methyl Orange

synthesized methyl orange (from Part I)


LabQuest or computer
LabQuest App or Logger Pro
SpectroVis Plus spectrophotometer

methyl orange solid


5% NaOH solution
5% HCl solution

Materials Part III: Dying Textiles

synthesized methyl orange (from Part I)


15% sodium sulfate solution

concentrated H2SO4
small fabric strips of varying materials

PROCEDURE
Procedure Part I Synthesis of Methyl Orange

1. Obtain and wear goggles. Protect your arms and hands by wearing a long-sleeve lab coat and
gloves. Conduct this reaction in a fume hood.
2. Dissolve 0.5 g of sulfanilic acid in 10 mL of 2% aqueous sodium bicarbonate solution in an
Erlenmeyer flask. Record the mass of sulfanilic acid to the nearest 0.01 g in the table below.
You can gently heat the flask for several minutes to speed up this process. Test one drop of
the solution to make sure it is alkaline; if not, add a small amount (23 mL) of 2% sodium
bicarbonate solution and check the pH again.
3. Dissolve 0.2 g of sodium nitrite in the solution of sulfanilic acid. Allow the flask to cool to
room temperature. Record the mass of sodium nitrite to the nearest 0.01 g in the table below.
4. Cool the resulting mixture in an ice water bath, and add 0.5 mL of concentrated HCl one drop
at a time with swirling. The solution should turn red-orange at this point. Allow the resulting
solution to stand in the ice bath for 510 minutes. Keep this solution cold in the ice bath at all
times. It now contains your diazonium salt, which will decompose if it becomes warm. It is
only partially soluble in the aqueous solution and will precipitate as a blue-green solid.
5. Freshly prepare the N,N-dimethylaniline solution by using the Beral pipets to combine
approximately 0.5 mL of N,Ndimethylaniline and 0.5 mL glacial acetic acid. Then slowly add
this solution to the diazonium salt suspension in the 125 mL Erlenmeyer flask. A dull, redpurple solid should appear.

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SynthesisofMethylOrangeandItsApplicationtoTextiles
6. While the solution flask is still on ice, very slowly, two to three drops at a time, add 5 mL of
10% aqueous NaOH, with constant stirring with your glass stirring rod. This process should
take 1015 minutes. If the NaOH is added too quickly, then free dimethylaniline will separate
out as an oily phase. This then leaves an equivalent amount of the diazonium salt unreacted.
7. Make sure the solution is basic using the pH paper, adding more NaOH if necessary. At the
end of the coupling reaction a yellow-orange or golden color should be observed.
8. To recrystallize the product, heat the reaction mixture at a low setting on the hotplate for
about 30 minutes. Everything should dissolve and the solution should be translucent (though
colored). Gently stir the mixture periodically to prevent bumping.
9. Allow the mixture to cool slowly to room temperature to crystallize and then place the flask in
an ice bath to get it as cold as possible. Important: Do not stir or shake the solution when it
is cooling. Allow the crystals to form in an undisturbed flask. The crystals will have a higher
purity if they form slowly in a motionless flask.
10. Filter the resulting gold-orange plates of methyl orange by suction.
a. Set up a vacuum filtration using a Bchner funnel. Be sure to weigh and record the mass of
the filter paper to the nearest 0.01 g before filtering the solid.
b. Transfer the contents of the flask to a Bchner funnel assembly. Filter the mixture with
vacuum suction.
c. When most of the liquid has been drawn through the funnel, turn off the suction and wash
the crystals with 5 mL of cold, distilled water.
d. Gently transfer the filter paper with your product onto the watch glass to air dry. As
directed by your instructor, either direct a gentle stream of air (low flow) to help dry the
solid, or let them air dry until the next lab period.
e. Weigh the dried recrystallized product on the filter paper and record the mass to 0.01 g
11. Weigh out and quantitatively dilute a small crystal of your synthesized methyl orange in
water. Depending on purity, 510 mg of synthesized methyl orange in 500 mL of water should
be sufficient. Record your mass and volume in the table below. You will need to know exactly
how much of each you are measuring with the Spectrophotometer to determine the purity. Set
this solution aside.
Procedure Part II Test the Colorimetric Absorbance of Methyl Orange

You will analyze several samples to determine the amount of methyl orange in your synthesized
sample. You can use this information to calculate its purity. Follow Steps 1217 to prepare a set
of methyl orange standard solutions and conduct testing to develop your own Beers law plot of
the standards. Steps 18 and 19 will guide you through the testing of your synthesized methyl
orange sample.
12. Quantitatively prepare a 4.0 10-5 mol/L stock methyl orange solution in water.
13. Prepare four dilutions of the methyl orange stock solution with the following
concentrations: 3.0 10-5, 1.5 10-5, 8.0 10-6, 5.0 10-6 mol/L. Summarize the volumes and
concentrations for the trials in the data table below.
14. Connect the SpectroVis Plus spectrophotometer to the USB port of LabQuest or a
computer. Start the data-collection program, and then choose New from the File menu.

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15. Calibrate the Spectrophotometer.


a. Place the blank cuvette of water in the Spectrophotometer. To prepare a blank cuvette,
rinse the cuvette twice with ~1 mL amounts and then fill it 3/4 full. Wipe the outside with a
tissue and place it in the Spectrophotometer.
b. Choose Calibrate from the Sensors menu of LabQuest or the Experiment menu of
Logger Pro.
c. When the warmup period is complete, select Finish Calibration. Select OK.
16. Determine the optimal wavelength for creating the standard curve and set up the mode.
a. Empty the blank cuvette. Using the first methyl orange solution, rinse the cuvette twice
with ~1 mL amounts and then fill it 3/4 full. Wipe the outside with a tissue and place it in
the Spectrophotometer.
b. Start data collection. A full spectrum graph of the solution will be displayed. Stop data
collection.
c. Change the mode to Events with Entry (absorbance vs. concentration) and select a
wavelength for analysis:

InLabQuestApp,thedisplayedwavelengthofmaximumabsorbance(max)is
automaticallyidentifiedonyourgraphwithapointprotector.TaptheMetertab,thentapMode.
ChangethemodetoEventswithEntry.EntertheName(Concentration)andUnits(mol/L).Tap
OK.

InLoggerPro,clicktheConfigureSpectrophotometerbutton, .ClickAbsvs.
ConcentrationastheCollectionMode.Thewavelengthofmaximumabsorbance(max)willbe
selected.ClickOK.
17. You are now ready to collect data for the five standard solutions.
a. Retain the cuvette in your Spectrophotometer. Start data collection.
b. When the value displayed on the screen has stabilized, select Keep and enter the molar
concentration. Select OK. The absorbance and concentration values have now been saved
for the first solution.
c. Discard the cuvette contents as directed by your instructor. Using the next methyl orange
solution, rinse the cuvette twice with ~1 mL amounts, and then fill it 3/4 full. Wipe the
outside, place it in the device, wait for the absorbance to stabilize and select Keep. Enter
the molar concentration, and select OK.
d. Repeat the procedure for the remaining methyl orange solutions that you prepared.
e. Stop data collection to view a graph of absorbance vs. concentration.
f. Record the absorbance and concentration values in your data table. You can determine
these values by examining your data points along the curve, or by viewing the data table.
g. Choose Curve Fit from the Analyze menu.
h. Select Linear as the Fit Equation and select OK.
18. Retrieve the synthesized methyl orange sample dissolved in water you prepared for
testing.
19. Measure and record the absorbance of the sample:
a. Rinse and fill the cuvette 3/4 full with the sample. Cap the cuvette and place it in the
Spectrophotometer.

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SynthesisofMethylOrangeandItsApplicationtoTextiles
b. Read the absorbance value. If the absorbance value falls within the range of the methyl
orange standard solutions, record it in your data table. If it does not, prepare a more dilute
or more concentrated sample, depending on the absorbance value from your first test.
20. To determine the concentration of your methyl orange sample, interpolate along the
regression line to convert the absorbance value of the unknown to concentration.
a. Choose Interpolate from the Analyze menu.
b. Click or tap any point along the regression curve (or use the or keys on LabQuest) to
find the absorbance value that is closest to the absorbance reading you obtained in Step 19.
The corresponding methyl orange concentration, in mol/L, will be displayed to the right of
the LabQuest graph, or on your Logger Pro graph.
c. Record the concentration of methyl orange in your data table.
21. Discard all solutions as directed.
22. Test the use of methyl orange as an acid-base indicator by dissolving a few crystals in
several milliliters of water in a test tube. Add a few drops of 5% HCl solution to one part of
the solution and a few drops of 5% NaOH solution to another part of the solution until the
color changes are apparent in each case.
23. Obtain spectra for both the acidic and basic forms of methyl orange.
Procedure Part III Dying Textiles

24. To test the use of methyl orange as a fabric dye, take 0.1 g of methyl orange and place it
into a 250 mL beaker. Add 50 mL of water to the beaker, 2 mL of 15% aqueous sodium
sulfate, and 3 drops of concentrated H2SO4.
25. Add a stir bar and heat the mixture on a hot plate until it boils.
26. Remove from the heat and place the test fabric strip into the dye solution for 10 minutes.
27. Remove the sample with tongs and rinse well with water.
28. Repeat the procedure for as many different types of fabrics as provided.

DATA TABLE
Part I Synthesis of Methyl Orange
Mass of sulfanilic acid used (g)
Mass of sodium nitrite used (g)
Mass of methyl orange and filter paper (g)
Mass of filter paper (g)
Mass of methyl orange synthesized (g)

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Part II Standard Methyl Orange Absorbance


Trial
number

Volume of 4.0 10-5


M methyl orange
stock (mL)

Volume of water
(mL)

Concentration
(mol/L)

Absorbance

1
2
3
4
5
Part II Synthesized Methyl Orange Absorbance
Mass of synthesized
methyl orange used
(g)

Volume of water
used in dilution
(mL)

Concentration
(mol/L)

Absorbance

DATA ANALYSIS
1. Determine your product yield.
2. Determine your product purity based on your spectroscopy results.
3. How did the color of methyl orange change with pH? What is the structure of methyl orange
at low pH? What is the structure of methyl orange at high pH? What property of methyl
orange and related dyes gives them such intense color?
4. Comment on the results of the dying of the test fabric strip. Did all of the materials dye equally
well? Explain in terms of the molecular structure of the test fabrics.

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SynthesisofMethylOrangeandItsApplicationtoTextiles

INSTRUCTOR INFORMATION
1. Do not attempt to take the melting point of your methyl orange as it decomposes on heating.
2. Be familiar with the MSDS information for each compound and follow safe handling and
disposal practices.
3. Preparation of solutions:
2% sodium bicarbonate should be prepared 2% weight of sodium bicarbonate to volume
water. This is also a 0.25 M NaHCO3 solution.
10% sodium hydroxide should be prepared 10% weight of sodium hydroxide to volume
water. This is also a 2.5 M NaOH solution.
5% sodium hydroxide should be prepared 5% weight of sodium hydroxide to volume
water. This is also a 1.3 M NaOH solution.
5% HCl should be prepared 5% volume HCl to volume of water. This is also a 0.6 M HCl
solution.
5. Methyl orange has a low solubility in water and students will find it hard to dissolve. This is all
right since it is also a strong chromophore; therefore, it is desirable for it to be very dilute.
Depending on purity, 510 mg of synthesized methyl orange in 500 mL of water will give an
absorbance of about 1.2.
6. We suggest cotton, wool, polyester and/or a polyester blend as testing fabric strips.

HAZARD ALERTS
Acetone: Fire hazard (flash point 17.0C). Store in dedicated flammables cabinet. Moderately
toxic by inhalation or ingestion. Moderately toxic by ingestion. Vapor causes weakness, fatigue,
nausea and headache. Skin and eye irritant. HMIS Classification: Health hazard2,
Flammability3, Physical hazard0.
Sulfanilic Acid: Body tissue irritant. Avoid all body tissue contact. Combustible solid. HMIS
Classification: Health hazard2, Flammability0, Physical hazard0.
Sodium Bicarbonate: Slightly toxic by ingestion. Dust may be irritating to respiratory system.
Slowly decomposes in moist air. HMIS Classification: Health hazard1, Flammability0, Physical
hazard0.
Hydrochloric acid: Highly toxic by ingestion or inhalation; severely corrosive to skin and eyes;
wear gloves and eye protection when using this substance. HMIS Classification: Health hazard3,
Flammability0, Physical hazard0.
N,N-dimethylaniline: Serious fire hazard. Irritating to body tissues. Severe eye irritant. Avoid all
body tissue contact. Slightly toxic by ingestion. Vapor causes weakness, fatigue, nausea and
headache. Skin contact causes dermatitis. HMIS Classification: Health hazard4, Flammability2,
Physical hazard0.
Glacial Acetic Acid: Corrosive to skin and tissue; moderate fire risk (flash point 40C);
Moderately toxic by ingestion and inhalation. Causes eye burns. HMIS Classification: Health
hazard3, Flammability2, Physical hazard0.

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Sodium Nitrite: May intensify fire; oxidizer. Toxic if swallowed. Causes eye irritation. Fatal if
inhaled. Very toxic to aquatic life. Toxic to aquatic life with long-lasting effects. HMIS
Classification: Health hazard2, Flammability0, Physical hazard1.
Methyl Orange: Highly toxic by ingestion. Health hazard2, Flammability0, Physical hazard0.
The hazard information reference is: Sigma-Aldrich Co., 1-800-325-3010,
www.sigmaaldrich.com/safety-center/msds-search.html

COMPOUND INFORMATION
Molar mass
(g/moL)

Density
(g/mL)

Sulfanilic acid

173.19

Solid

N,Ndimethylaniline

121.18

0.956

Sodium
bicarbonate

84.01

Solid

270

Sodium nitrite

69.00

2.168

271

Acetic acid

60.05

1.049

116117

Methyl orange

306

Solid

Decomposes

Boiling point
(C)

Melting
temperature (C)

Compound

288
193194

1.52.5

1516
>300

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SynthesisofMethylOrangeandItsApplicationtoTextiles

SAMPLE RESULTS

Beers law analysis of pure methyl orange

Absorbance spectrum of lab-synthesized methyl orange

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