Qualitative Analysis

Purpose: To use qualitative analysis to determine the identity of an unknown

compound by using spectroscopy to ascertain the functional groups
and characteristics of that unknown and perform experiments to
confirm it. I am 70% confident that our unknown compound, Reese’s
19, is Benzamide.

Introduction: In this qualitative analysis lab, we first used infrared spectroscopy to get
an idea of what functional groups were present, 1H NMR spectroscopy to
find out the types of protons and 13C NMR to find the number of
carbons in our unknown compound. From the IR spec, we
discovered that we had an -NH2 group, a C=O group, and
an aromatic ring. Based on information from the spectra, I needed to
look up tests that would confirm that those functional groups were
present. I looked up tests for amines and ketones, and also for amides
because of the combination of the carboxyl group and the amine
group. Based on the results of the experiments and some background
research, I am 70% confident that our unknown compound is
Benzamide.

Physical Constants:

Name Molecular Molecular Density Melting Boiling

Formula Weight Point Point
Benzamide C7H7NO 121.4 g/mol 1.341 g/cm3 127-130 C 288 C
3
Acetone C3H6O 58.09 g/mol 0.79 g/cm -94.9 C 56.53 C
Sodium NaOH 39.997 2.1 g/cm3 318 C 1,390 C
Hydroxide g/mol
Benzenesulfo C6H5SO2 176.62 1.38 g/cm3 15 C 251 C
nyl Chloride Cl g/mol
Hydrochloric HCl 36.46 g/mol 1.189 g/cm3 -26 C 46 C
Acid
Ethanol C2H6O 46.07 g/mol 0.789 g/cm3 -114.3 C 78.4 C
2,4- C6H6N4O 150.148
Dinitrohydraz g/mol
ine
 Experiments/Procedures:

Sodium Hydroxide Hydrolysis of Amides

Procedure
1. Combine 0.2 grams of compound in a
small beaker with 5 ml of 10% sodium
hydroxide solution.
2. Shake and note if ammonia is evolved.
3. Heat the solution and note the odor.
4. Place a piece of pink litmus paper
above the beaker to test the vapor of the
solution.
Observations
Bubbles were formed in the beaker.
There was a strong burning smell once the
solution started to heat up.
The vapor from the boiling solution
caused the pink litmus paper to turn blue.

Benzenesulfonyl Chloride - Hinsberg’s Method for Characterizing Primary, Secondary,

and Tertiary Amines.

Procedure Observations
1. Add 2.5 ml of 10% sodium hydroxide
and 0.2 ml of benzenesulfonyl chloride to
150 mg of the unknown compound.
2. Stopper the test tube and shake After shaking, there were two layers of
vigorously. liquids present in the flask.
3. Test the solution to make sure that it is
alkaline
4. Once benzenesulfonyl chloride has
reacted, cool the solution and separate the
residue (if present.
5. Test the residue for solubility in 10%
hydrochloric acid.
6. (If no residue remains) treat solution
with 10% hydrochloric acid and watch for
precipitate formation.

2,4-Dinitrohydrazine

Procedure Observations
1. Add 50 mg of compound to 2 ml of
95% ethanol.
2. Add solution to 3 ml of 2,4-
dinitrohydrazine reagent.
3. Shake vigorously and look for No precipitate formed right away.
precipitate.
4. Wait 15 minutes if no precipitate forms No precipitate ever formed.
(crystallize if necessary).
 Results:

Test/Procedure Results/Observation
Appearance of Unknown White, flakey crystals (solid)
Melting Point #1 93 C -135 C
Melting Point #2 110 C - 130 C
1H NMR Solvent Deuterated Acetone
13C NMR Solvent Acetone
IR Spectroscopy (KBr pellet) 3400-3200 cm-1 - Amine group (NH2)
1700 cm-1 - Carboxyl group (C=O)
550-800 cm-1, 1900-2100 cm-1,
3000cm-1 - Aromatic
(See Spectra #1)
1H NMR Spectroscopy δ 8.00 - 8.500 ppm, multiplet - Aromatic
δ 7.00 ppm, singlet - Amide (primary)
(See Spectra #2)
13C NMR Spectroscopy δ 125.134 - 131.114 ppm - Aromatic ring
(See Spectra #3)
Sodium Hydroxide Hydrolysis of Amides Positive for Primary Amide
Hinsberg’s Method for Characterizing Negative (See Discussion)
Primary, Secondary, and Tertiary Amines
2,4-Dinitrohydrazine Negative (See Discussion)

Discussion: Based on the spectra of our unknown compound, qualitative tests, and
some background research, I am 70% confident that our unknown, Reese’s 19, is the
compound Benzamide. From the first week of lab, when we did the IR spectroscopy of
our compound (see Spectra #1), we were able to deduce that the broad, medium peak at
3400 cm-1 told us that there was an -NH2 group; the skinny, sharp peak at 1700 cm-1
told us that there was a C=O group; and the very short, sharp peaks at 3100 cm-1, the
peaks from 1900-2100 cm-1, and peaks in the fingerprint region 550-800cm-1 indicate an
aromatic ring. These results tell me that I have either a ketone, an amine, or an amide (the
combination of C=O and NH2) along with an aromatic ring. When we did our 1H NMR
spec, we dissolved our compound in deuterated acetone because it was insoluble in
deuterated CDCl3 or deuterated DMSO. From the 1H NMR spectrum (see Spectra #2),
the multiplets at 8-8.5 ppm indicate that there are aromatic protons present. The broad
singlet at 7 ppm indicates that there are amide protons, and the broadness of the singlet
indicates hydrogen bonding, which lead me to believe that there was a primary amide.
The quintet at 2 ppm are the proton peaks of our solvent, deuterated acetone. I was
unsure about the singlet peak at 3.4 ppm because it did not fit in with our proposed
structure. We did not get to do a 13C NMR spec until the following week, so it was
unclear exactly how many and what type of carbons were in our compound. Because of
this, I needed to look up experiments to test over the next two labs for the three different
functional groups we thought we had based on our IR spec - an amine, a ketone, and an
amide.
The second week, we did the 13C NMR spectrum (see Spectra #3) by
dissolving our unknown in acetone because it was the only solvent that dissolved our
compound. The cluster of six peaks in the range 125.134-131.114 ppm are those of the
aromatic ring. The peak at 204.994 ppm is a ketone peak, and the peak at 28.992 ppm is
an alkane peak. These two peaks are from the acetone solvent, but I did not know that at
the time when I first got these results; I believed that the singlet at 28.992 ppm was
related to the mysterious singlet peak in the 1H NMR spectrum.
When I saw the ketone peak, I thought that I could do a test for a ketone
because I thought one R group of the ketone could be the aromatic ring and the other R
group could be the amide group. So I proceeded to do the following tests. The first test I
did was an amide test by an experiment called The Sodium Hydroxide Hydrolysis of
Amides. During the reaction, if ammonia was formed, it would indicate that the
compound was a primary amide by turning pink litmus paper blue when the solution was
heated. When I did the test, the vapor did indeed turn the litmus paper blue, which told
me that I did have a primary amide, which confirmed my previous thoughts based on my
1H NMR results. I probably did not have to do any more tests if I had interpreted all of
my data correctly. Because I did not know that the ketone peak on my 13C NMR was
from acetone and thought that amides were part of a ketone, I did a ketone test titled 2,4-
Dinitrohydrazine. After I mixed my compound with ethanol, then added the 2,4-
dinitrohydrazine reagent, no precipitate ever formed. That’s when I realized that amides
are not part of ketones. I looked up the 13C NMR peaks for acetone and they matched
those on my spectrum. That’s when I realized that the singlet peak at 3.4 ppm in the 1H
NMR spectrum mentioned earlier might be a discrepancy. Then I proceeded to do an
amine test, called Hinsberg’s Method for Characterizing Primary, Secondary, and
Tertiary Amines. I did this test because I thought that the -NH2 group of an amide and of
an amine were the same because of hydrogens on the nitrogen, and I did it to confirm that
I do have a primary amide. After I added sodium hydroxide and benzenesulfonyl
chloride to my unknown, two distinct layers were formed. Then I realized that amides
and amines are two completely separate functional groups.
After we had finished all of our tests, we were absolutely positive that we
had an primary amide group attached to an aromatic ring. Once that was figured out, I
was able to narrow it down to two possible identities: Benzamide or Phenylacetamide. I
went to the Spectral Data Base of Organic Compounds online to compare the spectra of
benzamide and phenylacetamide and see how they compare to the ones that we collected.
As a result, phenylacetamide looked very similar to all of the spectra we collected, but
benzamide did not. However, the true melting point of phenylacetamide (156-157 C)
does not match with the melting point we collected twice, which is about 110-130 C.
This melting point does match with benzamide. The 13C NMR of phenylacetamide
looks exactly like the one we collected, but I strongly believe that the two outer peaks
belong to acetone, and not our compound. Therefore, I believe that our unknown
compound is Benzamide.
If I were to perform this type of analysis again in the future, I would do all
of the spectroscopy methods first so as to get a stronger idea of what I have so I can look
for the correct types of experiments to perform. This would allow me to rule out the
peaks of my solvents so as to not get them confused with peaks from my compound. I
would also look up more tests to perform that help distinguish what type of amide (1, 2,
3) is present, and also some aromatic tests just to confirm that an aromatic is definitely
present. As a final confirmation of our unknown, I would like to perform a TLC test so
as to compare my compound with that of what I think it is.