Names: Balo, Marielle Date Performed: October 5, 2017

Gerolaga, Winston Jake Date Submitted: October 20, 2017

EXPERIMENT 6
SYNTHESIS OF SULFANILIC ACID

I. Introduction

Sulfanilic acid (figure at the right), also known as 4-Aminobenzene-1-sulfonic acid in its
preferred IUPAC name, is an off-white crystalline solid with a molecular formula
C6H7NO3S. It has a molar mass of 173.19 g/mol and melts at 288 C. It can be
used to make dyes and various drugs and also in the quantitative analysis of
nitrate and nitrite ions by diazonium coupling reaction with N-(1-
Naphthyl)ethylenediamine. It could be synthesized by the sulfonation of aniline.
Further details about the mechanism of the reaction will be tackled in the
discussion part of this laboratory report.

The main goals for this experiment are: (a) synthesize sulfanilic acid by
sulfonating aniline (as stated earlier) with concentrated sulfuric acid as a catalyst;
(b) master techniques used in the synthesis of organic compounds; and (c)
calculate for the percent yield of sulfanilic acid synthesized.

II. Methodology

To 9 mL aniline, 12 mL concentrated H2SO4 was added with careful swirling and

cooling. The mixing was done in a 25-mL test tube. The mixture was then heated on a water bath
for 2 to 3 hours until the sample yielded no oily aniline when added to dilute NaOH. The
temperature was kept between 170 to 180 C. It was then cooled to 50 C in room temperature
and then in an ice bath. The precipitate was collected by vacuum filtration using a Buchner
funnel. The collected crude sample was then washed with cold water and decolorized by adding
activated charcoal. It was recrystallized by adding enough hot water. The crystals were dried and
weighed and was determined for the percent error.

III. Results and Discussion

Aromatic sulfonation is when benzene or substituted benzene reacts with SO3- in the
presence of H2SO4 to yield sulfonated benzene. In this experiment, substituted benzene
anilineis used as the reactant to produce sulfanilic acid. This reaction is also possible with the
use concentrated H2SO4 with the presence of heat. In this case, H2SO4 was added to aniline and
heated for about 2 hours in a sand bath to regulate the desired temperature maintaining the
temperature to be within 170C-180C. Sulfonation reaction of aniline is shown as:
 Aniline (C6H5NH2) undergoes sulfonation to form sulfanilic acid. It is benzene with an
amino group attached to it. Consequently, benzene is a stable compound. However, reactivity of
aniline increases because of the amino group present in it. This high reactivity is influenced by
the amino group. The amino group, on the other hand, is an activating group or electron-donor,
donating electrons to the ring to react to electrophiles. This high reactivity drives the reaction of
sulfuric acid to aniline.

Considering the structure of aniline; aniline is made up of two functional groups. These
functional groups are composed of an acid and a base. The HSO3 constitutes the acid part of the
sulfanilic acid. On the other hand, NH2 constitutes the basic part of the sulfanilic acid. These
partial structures are derived from H2SO3 inorganic acid and NH3 inorganic base.
Electrophilic substitution reaction refers to the reaction in which an electrophile
substitutes another electrophile in an organic compound. Anilines undergo the usual electrophilic
reactions such as halogenation, nitration and sulfonation. The functional group (-NH2) associated
with aniline is electron donating group; it is very activating towards the electrophilic substitution
reaction. Due to its various resonating structures, there is an excess of electron or negative
charge over ortho- and para- positions of the benzene ring than the meta- position. Thus, anilines
are o- and p- directive towards electrophilic substitution reaction.

The amino group in aniline is an o,p director because it is a strongly activating

substituent. Activating substituents follow the ortho and para positions when attacking the
benzene ring (with the exception of halogens adjacently attached to the benzene ring since they
are the only deactivating substituents that attack the benzene ring in an ortho, para manner) since
they are far more resonance-stabilized by the aromatic system. In addition, they are also electron-
donating substituents that donate these electrons through resonance. In electrophilic aromatic
substitution, the resonance effect of amino group is more significant than its inductive effect.

Aniline, this case, is the most activated benzene. It contains NH2 which is also the most
activating group. Strongly activated rings like aniline can open up the ring to unwanted reactions.
To avoid these unwanted reactions, the amino group undergoes reversible acetylation to make
aniline moderately activated. The base, NaOH, is used to hydrolyse the acetyl group, and aniline
with the wanted substituent is obtained.

Table 1. Data for the masses

Mass of the filter paper 1 (g) 0.5321

Mass of the crude sulfanilic acid (g) 4.0934
Mass of the filter paper 2 (g) 0.5858
Mass of crystalized sulfanilic acid + filter 0.9822
paper (g)
Mass of crystalized sulfanilic acid (g) 0.3964
Mass of filter paper 3 (g) 0.5387
Mass of crystallized sulfanilic acid from waste 1.2683
+ filter paper (g)
Mass of crystallized sulfanilic acid from waste 0.7296
(g)

The reaction between aniline and sulfuric acid to form the aniline hydrogen is
exothermic. The heat of the exothermic reaction causes the temperature of the reaction mass to
rise. To cause water to be split off and to promote the para-rearrangement of reaction at a slow
but measurable rate, the minimum temperature must be about 165 C.-170 C. At this
temperature, the aniline hydrogen sulfate is slowly converted, by an endothermic reaction, to
sulfanilic acid. Sulfanilic acid, (in contrast to the aniline hydrogen sulfate salt) is stable and does
not melt up to its decomposition temperature which is about 280 C. When the temperature is
raised to the rearrangement temperature, the conversion starts.

Sulfanilic acid is insoluble in molten aniline hydrogen sulfate. This result to the
formation of molten mass becomes a pasty, sticky mass of a liquid phase and a dispersed solid
phase. When water is present in the aniline hydrogen sulfate, the mixture forms a liquid or pasty
mass at temperatures below 160 C. By maintaining the temperature of at least 160 C, the
sample is converted into salicylic acid. During the water elimination the sample turns into a
grayish or deep purplish product with indefinite composition. To purify this colored product and
to remove the undesirable colored intermediates which affect the purity of the sample, a
generous amount of activated carbon was mixed with the sample. It was then vacuum-filtered
using Buchner funnel. The filtrate which contains the sulfanilic acid was placed in an ice bath to
allow fast rate of recrystallization. After that, it is vacuum-filtered again and dried. At this
instant, the dried sample is the purified solid sulfanilic acid. Compared with the grayish powder-
like solid crude sample recovered, the recrystallized sample appears to be white crystals.

Figure 1 shows all the data for the masses of the sample obtained all throughout this
experiment. During the experiment; however, the filtrate for recrystallization was mixed with the
filtrate of the other group. This leads to the recollection of the excess sulfanilic acid remaining
from the filter paper. This is subjected again to filtration. Due to this error, two data for the mass
of the crystallized sulfanilic acid was recorded. For the second trial, 0.3964g was obtained, and
0.7296g was crystallized from waste. This implies that a large amount of sulfanilic acid was
discarded in the first trial.

Table 2. Percent yield

Trial 2 (%) 4.22

From waste (%) 7.77

Table 3. Percent error

Trial 2 (%) 95.78

From waste (%) 92.23
 As seen in table 2, greater amount of percent yield which is about 7.77% was obtained
from waste than from trial 2 which is 4.22%. Overall, the total percent yield from this
experiment is significantly low. The errors computed for this experiment are found to be 95.78%
and 92.23% for trial 2 and from waste, respectively.

IV. Conclusion

Sulfanilic acid was successfully synthesized from aniline. Two different masses of
purified sulfanilic acid0.3964 g for the second trial and 0.7296 g from the waste product
were obtained due to the human error committed. Overall, the original sample had 4.22% yield
and the recrystallized sample from waste had a percent yield of 7.77% sulfanilic acid.

For the next synthesis experiments it is recommended to familiarize the basic methods
used for synthesis to avoid any errors that can affect the purity of the product or the product
yield.

V. References

Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013

(Blue Book). (2014). Cambridge: The Royal Society of Chemistry

Hauptmann, S. (1985). Organische Chemie (2nd Ed.). Leipzig, Germany: VEB Deustcher Verlag
fr Grundstoffindustrie

A Dictionary of Chemistry. (2000). Oxford University Press: Oxford Reference Online)s

Jerffery, G. H., Bassett, J.H, (1989) Vogels Textbook of Quantitative of Chemical Ryan

Capio, B.T., Lacson, D. & Estandarte, J. D. (2016). Synthesis of sulfanilic acid. Retrived October
15, 2017 from https://www.scribd.com/document/328097892/Preparation-of-Sulfanilic-
Acid

Lund, M. C., & Pass, M. C. (1989). U.S. Patent No. US4808342 A. Washington, DC: U.S. Patent
and Trademark Office.

Census data revisited. (2016, February 5). Electrophilic substitution of anilines. Retrived from
byjus website, https://byjus.com/chemistry/electrophilic-substitution/