Percent Yield of para red dye

Extracted Content from Question Files:

Rachel Wilkinson
533-98-8568

CHM 339

Title of Laboratory: Preparation and Use of Para Red Dye

Purpose: Diazonium salts are formed from the reaction of nitrous acid and a
primary amine. You will prepare an azo dye from 2-napthol and p-nitroaniline.
The extensively conjugate double bonds of the product results in an intensely
colored product. The dye will be used to treat cotton fabric.

Goals:
• To prepare a diazonium salt
• To couple a diazonium salt with an activated aromatic ring system
• To collect, dry, weight and calculate percent yield of the para red dye.
• To treat white cotton fabric with the dye.
• To write the reactions representing the dye formation.

Materials:
• 2-Napthol
• p-Nitroaniline
• Sodium nitrate
• Concentrated H2SO4
• 2.5 M NaOH
• Glassware
• Vacuum Filtration System
• White cotton fabric
• Gloves

Procedure/Observations:
A. Preparation of Diazonium Salt
1. Mixed 0.5 mL concentrated H2SO4 in 10.0 mL water in a test tube.
2. Weighed out 0.22 g p-Nitroaniline and place it in the acid solution. Stir
until you dissolve the p-nitroaniline. Continued to add H2SO4 dropwise
until the solid is completely dissolved. Cooled it in an ice bath. Product
was yellow in color.
3. Dissolved 0.13 g NaNo2 in 5 mL water. Added it to the p-nitroaniline
solution. Mixed; recorded any observations. The solution became
foggier and became a dark yellow color.
4. The diazonium salt was placed on ice until you are ready to use it.

B. Preparation of 2-Naphthol
1. Weighed out 0.25 g 2-naphtol and placed in a test tube.
2. Dissolved 5.0 mL 2.5 M NaOH. Stirred to help dissolve into solution.
3. Added additional 5.0 mL water to the test tube.
4. Placed in crushed ice until chilled. Product was a light brown.

C. Dying Fabric
1. Measured out approximately one-half of the diazonium salt into a 250
mL beaker. Added 50 mL cold water.
2. Placed fabric to be dyed in the beaker. Stirred it around and allowed it
to sit for a few minutes.
3. Measured out approximately one-half of the alkaline 2-nathol solution
and placed it in a clean 250 mL beaker. Added about 50 mL water.
4. Grabbed the fabric with forceps and press against the side of the
beaker to expel as much liquid as possible, Placed the fabric in the 2-
napthol solution and stirred it around. Allowed to sit for several
minutes.
5. Removed the cloth sample and placed in beaker of water to rinse our
excess dye. Set the fabric on a paper towel to dry.

D. Isolating the Para Red Dye.
1. Combined the remaining diazonium salt and 2-naphthol in a clean
beaker. Stirred for a few minutes.
2. To the beaker added the contents of the two beakers from part C and
stirred as before.
3. Acidified the mixture with 1 M H2SO4 so a precipitate is formed.

E. Filtration of product
1. Pre-weighed a watch glass and small filter paper, weighing 39.4952g.
2. Filtered the product using the vacuum filtration system and the
filter paper that was weighed.
3. Washed the product with 5 mL deionixed water.
4. Using a spatula, removed the filter paper and dye to the watch glass.
5. Allowed to air dry before re-weighing. Total weight of watch glass, filter
paper and dye was 39.6330, resulting in 0.1378g of dye.

F. Disposal
1. Placed the solid dye, original filtrate, and the dye solution in the
appropriate waste containers.

Discussion:

1. Why is p-nitroaniline soluble in acid solution? Write the reaction.

p-nitroaniline (1-amino-4-nitrobenzene) is a base; therefore, it is soluble in acid.
The basic group is the amino group. When it reacts with an acid, the amino group
gets protonated. In the following reaction, the C6H4 group is the disubstituted
phenyl group. The parentheses are used to show the two substituted groups, the
nitro group and the amino group respectively.
(C6H4)(NO2)(NH2) + H+ ----> (C6H4)(NO2)(NH3+)

2. Why is 2-naphthol soluble in base solution. Write the reaction.

2-naphthol is an acid (much like phenol); therefore, it is soluble in base. The
hydroxyl group donates its proton to the base forming the anion. The C10H7
group represents the two ring system of the aromatic naphthol.

C10H7OH + OH- -----> C10H7O- + H2O

3. Write the reactions for the preparation of the diaonuim salt for the coupling of
the salt with the sodium salt of 2-napthol. See diagram below and narrative of the
complete process.

4. Write the reaction of the sodium salt of para red when treated with 1 M
H2SO4. Why does a precipitate form?

After the reaction has taken place, acidify the contents with H2SO4. The reason
we treat this with sulfuric acid at this point is to protonate the phenoxide group on
the naphthol ring portion. Remember, the 2-naphthol solution was prepared by
dissolving it in sodium hydroxide. This would have formed the naphthoxide ion as
the sodium hydroxide reacted with the phenol group on the 2-naphthol. By re-
acidifying, we protonate this O- group forming the protonated phenol again. This
makes the dye insoluble in acidic solution which forms the red precipitate, the
Para Red dye.

5. Determine the percent yield of your product para red dye. Base your
calculation on the amount of 2-naphthol that was weighed out.
6. Why is the diazonium salt kept cold during formation and storage? Write the
reaction for its decomposition to a phenol. See below

Diagram below shows how the diazonium salt decomposes to form the phenol.
You react the diazonium salt with hot aqueous acid. Nitrogen gas is released
because it is an excellent leaving group.
The following explanation covers the synthesis of Para Red from aniline.

Source: http://web.centre.edu/muzyka/organic/lab/paraRed05.htm.

1. React aniline with acetic anhydride. This forms acetanilide. Collect the product
by vacuum filtration.

2. Dissolve the acetanilide into glacial acetic acid. Add dropwise sulfuric and
nitric acid. This forms p-nitroacetanilide. Cool, and collect precipitate.

3. Convert the p-nitroacetanilide into p-nitroaniline by reaction in water with acid
catalyst. This hydrolyzes the amide bond in p-nitroacetanilide.

4. React the p-nitroaniline with sulfuric acid and sodium nitrite to form the
diazonium salt. Keep cool, of course since diazonium salts decompose rapidly
due to loss of N2 gas.

5. Prepare a cool solution of 2-naphthol in sodium hydroxide. Add the solution
which has the diazonium salt in it to the basic 2-naphthol solution.

6. After the reaction has taken place, acidify the contents with H2SO4. The
reason we treat this with sulfuric acid at this point is to protonate the phenoxide
group on the naphthol ring portion. Remember, the 2-naphthol solution was
prepared by dissolving it in sodium hydroxide. This would have formed the
naphthoxide ion as the sodium hydroxide reacted with the phenol group on the 2-
naphthol. By re-acidifying, we protonate this O- group forming the protonated
phenol again. This makes the dye insoluble in acidic solution which forms the red
precipitate, the Para Red dye.

References

http://web.centre.edu/muzyka/organic/lab/paraRed05.htm.