Connor LaBella

Post-Lab
3/7/2018
Abstract:
To prepare the diazonium salt of sulfanilic acid 0.06 g of anhydrous sodium
carbonate was dissolved into 5 ml of water. 0.18g of anhydrous sulfanilic acid was than
added and the solution was heated gently until dissolved. The solution was then allowed
to cool and 0.08g of sodium nitrite was mixed until completely dissolved. The flask was
then placed in an ice bath until 10 degrees Celsius. Next 0.25 ml of HLC was added and a
precipitate of dazonium salt was formed.
Next 0.14 ml of dimethylaniline and 0.10 ml of acetic acid were mixed together.
After stirring a red precipitate of heliathin was formed. The mixture was cooled on an ice
bath. 1.5ml of sodium hydroxide was slowly added to the mixture. The mixture became a
thin paste and was tested for pH. A boiling chip was added to the basic solution and
boiled for 15 min. The solution was removed from heat and 0.5g of sodium chloride was
added. The solution was then placed on an ice bath and allowed to crystallize. 5mL of
saturated sodium chloride solution was then used to rinse the solution through filtration.
The collected product and filter paper were placed in 15 ml of boiling water. The
filter paper was removed and the solution was allowed to cool. The product was then left
to dry while some moist product was used to study the effect of pH on the color of the
solution.
A dye bath of 1 mL sodium sulfate and 1 drop of sulfuric acid in 30 ml of water
was used to test 0.05g of methyl orange. The bath was heated to a gentle boil. A piece of
multifiber fabric 10A was immersed into the hot bath for 10 minutes. The bath was then
made basic with sodium carbonate. Sodium dithionite was added until the bath was
colorless. Lastly one piece of dyed fabric was placed into it and compared bleached to
unbleached.

Introduction:
This lab will synthesize the azo dye methyl orange. Methyl orange is frequently
used as a pH indicator because of its color changing properties. Methyl orange shows
orange color in acidic medium and yellow color in basic medium. Because of this it is
often used in acidic titrations. Azo compounds are known for their intense colors and are
therefore often employed as dyes. Many of these dyes are also water soluble which
makes it easy to dye fabrics such as cotton, wool, and nylon. However this compound is
known to have mutagenic properties and direct contact should be avoided.[1]
Materials:

Name Formula Structure Amt. Ref. Density Mp/Bp

Used Index g/cm3
Anhydrous Na2CO3 0.06g 1.485 2.54 851
sodium
carbonate
Anhydrous C6H7NO3S 0.18g 1.485 288
sulfanilic acid
Sodium Nitrite NaNO2 0.08g 1.65 2.168 271

Hydrochloric HCl 0.25ml 1.048 -18/

Acid 103
 Connor LaBella
Post-Lab
3/7/2018
N,N-dimethyl- C8H11N 0.14ml 0.956 2/194
aniline
Glacial acetic C2H4O2 0.10ml 1.371 1.049 16/118
acid
Sodium NaOH 1.5ml 1.3576 2.13 318/
hydroxide 1388
Sodium NaCl 0.5g 1.5442 2.165 801/
chloride 1413
Sodium sulfate Na2SO4 1 ml 2.664 884/
1429
Methyl orange C14H14N3NaO3S n/a 1.28 300 °C

Data and Calculations:

Grams of Na2CO3 used...…0.0646g
mL of water used…….. 5.0ml
grams of sulfanic acid used….. 0.1828g
grams of NaNO2 used….. 0.0827g

ml of HCl used….…0.25ml
Solution became light yellow after the addition of HCl. A white precipitate formed after
scratching the bottom of the beaker and mixing.

mL of acetic acid used…...0.10mL

mL of C8H11N used…...0.14mL
Color changed to dark espresso and become viscous after mixing the solutions together.

mL of NaOH used……..1.5ml
Color became lighter as well as more orange with creamier areas.
pH test resulted in a navy blue.

Grams of NaCl used in boiling solution......0.5144g

Mass of filter paper…..0.3445g

Mass of paper with product…..0.6539g
Mass of Methyl Orange product……0.3094g

Theoretical Yield:
(0.1828g sulfanilic acid/173.19 mm) x (327.77 g/mol Methyl Orange)......0.3460g Methyl
Orange

Percent recovery:
(0.3094g M-O exp./0.3460 M-O theo.) x 100 = 89.42%

Wavelengths 513-461 nms

Literature value 463 nms
 Connor LaBella
Post-Lab
3/7/2018

Conclusion:
A percent yield of 89.42 percent is quite high considering all the opportunities for
product to be lost. With multiple filtrations occurring there could easily be product lost
through the filter paper or stuck to the filter paper. Each step was done slowly and
carefully. The precipitate that formed after the addition of HCl was very consistent and
thicker presenting a complete reaction. The N,N-dimethyl-aniline was also added drop
wise with constant stirring which could have helped the reaction occur in a more
proportional rate which would lend itself to a higher recovery rate and a more pure
product. The solution become a very dark espresso brown and became creamy and
viscous. The drop wise addition of the sodium hydroxide also came out to the perfect pH
and was done through a slow process to keep an even distribution throughout the product.
After filtering the product had a unique golden sheen to it. When dissolved the solution
was a deep red at high temperatures and when cooled thickened and glittered with flecks
of gold and orange. The final pH test strongly demonstrated the ability of Methyl Orange
to indicate pH. The cloth dyeing process clearly illustrated how both basicity and material
type strongly affect the ability of Methyl Orange to bind and color the cloth. There was
difficulty in changing the solution with bleach to becoming colorless. It's possible that the
solution was made too basic with the sodium hydroxide. The UV spectrophotometer
recorded wavelengths of 513 - 461 nm before and after the addition of NaOH. With a
literature value of 463 nm the results are quite accurate.
 Connor LaBella
Post-Lab
3/7/2018

Questions:

1. The reaction is a nucleophilic attack by the dimethylaniline upon the diazonium salt.
a.)

b.) The attack is in the para position because there is hindrance at the ortho position by
the bulky dimethylamine substituent.

2. The proton transfer creates a much more stable product because it completes the
resonance of a benzene ring as well as eliminates the separation of charge on the azo
nitrogen.

3. Green colors are absorbed by the acidic form of methyl orange while blue and green
colors are absorbed by the basic form.

1. Sandberg, Richard G.; Henderson, Gary H.; White, Robert D.; Eyring, Edward M.
(1972). "Kinetics of acid dissociation-ion recombination of aqueous methyl orange". The
Journal of Physical Chemistry. 76 (26): 4023–4025.