SCHOOL OF CHEMICAL AND BIOMEDICAL

ENGINEERING

Nanyang
Technological
University

CH2801 Year 2/Sem 1 Lab

C3: Characterization of Aspirin Synthesis
Product Using IR and NMR Spectrometry
GP18
Aldi Stefanus Felim (U1320089H)
Date: 16th Sep 2014
Figure1SynthesizedAspirinIRSpectrum

Figure2AcetylSalicylateIRSpectrum
 Figure3SalicylicAcidIRSpectrum

InfraredSpectroscopy
1. CanyouidentifypeaksinyourAspirinSynthesisProductspectrawhicharefoundonly
inacetylsalicylicacid?

Thereis astrongpeakattheregionof1750.62cm1 inthesynthesizedaspirin

spectrumwhichcorrespondstoapeakattheregionof1754.67cm1 intheacetyl
salicylicacidspectrum.BothpeaksareresultofcarbonylIRabsorptioninester
functional group. This confirms the presence of ester functional group in both
compounds.

2. CanyouidentifypeaksinyourAspirinSynthesisProductspectrawhicharefoundonly
insalicylicacid?

There is a peak in the synthesized aspirin spectrum that can only be identified in the
salicylic acid spectrum. The peak is at the region of 2861.96 cm -1 in the synthesized
aspirin spectrum and is at the region of 2861.33 cm-1 in the salicylic acid spectrum.
The peak corresponds to the presence of a hydroxyl (-OH) group bonded to the
benzene ring. This confirms the presence of salicylic acid as impurity in the
 synthesized aspirin sample.

3. FromthisanalysisusingInfraredSpectroscopy,estimatethepurityofAspirinSynthesis
Product?

Purityofaproductcanbeestimatedbycomparingthesamplespectrumtoareference
spectrum. The presence of relatively broad peak at around 2861 cm 1 shows the
presenceofahydroxylgroupthatisbondedtoabenzenering.Thisisnotshownin
thereferenceaspirinspectrum,whichmeansthesampleisimpure.Presenceofother
peaks exhibited onlybythe synthesized aspirinspectrumalsosuggests impurities
otherthansalicylicacid.Thesampleisquitepurefromanarbitrarybasisofspectrum
comparison.

4. Arethere anymajordifferences between the IR ofsalicylicacid and youraspirin?

There are two major differences between the IR spectrum of salicylic acid and our
aspirin sample.

a. Salicylic acid has a hydroxyl OH group attached to its benzene ring hence it will produce a
broad peak at 3500-2700cm-1 range. Although our aspirin spectrum also has a peak at 2871
cm-1 frequency, it is not as broad as the peak found on salicylic acid spectrum.

b. A strong peak at 1750.62cm-1 is present in the aspirin sample spectroscopy, and the peak is
absent in the salicylic acid spectrum. This confirms the presence of an ester functional group
in aspirin

5. Which peak(s) did you use to determine if you had converted the salicylic acid to
aspirin?

The major differences between salicylic acid and aspirin are the presence of an ester
functional group in aspirin, and a free hydroxyl group that is bonded to a benzene ring
in the salicylic acid. The presence of ester group is confirmed by the presence of the
peak at 1750.62cm-1 in the aspirin spectrum, whereas this peak is absent in the
salicylic acid spectrum.

Free hydroxyl bonded to benzene will show a broad peak in the region of 3550-3200
cm-1. The presence of a carboxylic acid OH in salicylic acid will shift the peak to the
left. The peaks confirming the presence of a free OH group are present in the region
of 3200-2500cm-1 in the reference salicylic acid spectrum, whereas in the pure aspirin
spectrum, the peaks around 3200-2900cm-1 are absent. It shows that aspirin does not
 have a free hydroxyl group, and only carboxylic acid hydroxyl group. It can be used
to determine the conversion of the salicylic acid to aspirin.

6.Howdoesyouraspirinspectrumcomparetothatofthepureaspirin?

The synthesized aspirin spectrum contains the major peaks of functional groups that
signify the transformation from salicylic acid to aspirin. The ester group is present in
both of the spectrums. In the synthesized aspirin, the carbonyl ester group absorption
occurs at 1750.62 cm-1, while in the pure aspirin spectrum, the carbonyl ester group
absorption occurs at 1754.67 cm-1. Absorption of another carbonyl group that occurs
at 1684.52 cm-1 in the synthesized aspirin spectrum is also common to both pure
aspirin and salicylic acid, which might be the absorption from carbonyl group in the
carboxylic acid group contained in them.

The synthesized aspirin spectrum contains broad and relatively weaker peaks in the
region of 3200-2500 cm-1, while the pure aspirin spectrum shows narrower and
stronger peaks in the same region. Hydroxyl group is the cause of the presence of the
peaks. In pure aspirin, the only hydroxyl group present is the hydroxyl group of
carboxylic acid. As the synthesized aspirin spectrum shows broader peaks, it signifies
the presence of a free hydroxyl group. It originates from the impurities contained in
the synthesized aspirin sample. The sample is prone to salicylic acid impurities from
uncompleted reactions, and the presence of free hydroxyl group (bonded to benzene
ring) peaks confirms the salicylic impurity inside the synthesized sample.

Other peaks that are present only in the synthesized aspirin sample exist in the region
of 3900-3500 cm-1. While the identity of the compound/functional groups contributing
to the presence of the peaks cannot be pinpointed, it suggests more impurities are
contained in the sample.

7.Aretherepeakspresentwhicharenotfoundineitheracetylsalicylicacidorsalicylic
acid?Whatcouldthesepeaksrepresent?

Peaks present in the region of 3900-3500 cm -1 are the most noticeable difference
contained only in the synthesized aspirin spectrum. Other small differences in the
fingerprint region are also present, yet the exact contributor of the absorption at those
peaks cannot be identified. It can be guessed that the peaks may represent other
impurities from the reaction procedure such as acetic acid, acetic anhydride and
ethanol that are used throughout the reaction and re-crystallization procedure.
Figure4SynthesizedAspirinNMRSpectrum

NMRSpectroscopy

1. Can you identify any of the patterns of the reference compounds in your sample
spectrum? If so, which of these compounds can you identify in your sample?
From the NMR spectrum of the sample, there are no peaks or patterns that correspond to the
reference molecule (TMS) which is auto-set to be at 0 ppm by the computer. It is used as a
reference to identify other substances in the spectrum.

2. On your spectrum, identify all peaks associated with the correct product, aspirin
(acetylsalicylic acid).
The peaks on the spectrum that correspond to the correct product aspirin is shown in the table
below.
 Chemical Shift ( Type of Number of Associated
ppm) Splitting protons Proton
shown on our (Integration)
spectrum
10.5 Singlet 1
(labile
proton)

6.5 - 8 Doublet 1

Triplet 1

Triplet 1

Doublet 1
8.154-
8.158 ppm

2.377 Singlet 3

3. On your spectrum, identify all peaks associated with salicylic acid or acetic
anhydride (starting materials), if any.
If salicylic acid exists in the NMR sample, it should give peaks occurring at the same region
of chemical shift as the aspirin table above for the 4 protons from the benzene ring. Purified
aspirin should only give 4 peaks with 2 doubles and 2 triplets respectively, thus our aspirin
sample contains a presence of salicylic acid as impurities. This is because our NMR spectrum
shows with the presence of an extra doublet, triplet and quintet peaks respectively in the 6.5-
8ppm region. These peaks correspond to the peaks of salicylic acid.
A tiny peak was also found at 2.157 ppm which most probably signals the presence of acetic
anhydride, an impurity of synthesized aspirin.

As these impurities' peaks are relatively small (intensity) as compared to the aspirin peaks,
this shows that the amount of impurities present is not very significant.

4. On your spectrum, identify all peaks associated with acetic acid (by product), if
any.
Acetic acid has two different types of hydrogen. One is from the methyl group attached to the
carboxyl carbon while the other is the acidic hydrogen. The hydrogen in the methyl group
would give a peak of 2-3 ppm, which we are unable to differentiate if the tiny peak at
2.157ppm belongs to acetic anhydride or acetic acid. The acidic hydrogen from acetic acid
would give a peak between 10 to 12 ppm. Thus the tiny peak present in chemical shift 10.485
ppm could also be due to acetic acid, indicating the presence of acetic acid in our sample.

5. Based on the intensities of these patterns, roughly estimate the % of each of the
above components in your product.
The intensities of the peaks are related directly to the concentration of products in the sample.
Using the height of the peaks to represent the concentration, the percentage of aspirin and
salicylic acid is calculated as:
The % of aspirin present in the sample
=
Peak height of Aspirin
Peak height of Aspirin+ Peak height of Salicylic Acid + Peak Height of Acetic Anhydride

10 cm
100
= 10 cm+0.9 cm +0.5 cm

= 87.7%

The % of salicylic acid present in the sample

=
Peak height of Salicylic Acid
Peak height of Aspirin+ Peak height of Salicylic Acid + Peak Height of Acetic Anhydride

0.9 cm
100
= 10 cm+0.9 cm +0.5 cm

= 7.89%

The % of acetic anhydride present in the sample = 100% - 87.7% - 7.89%

= 4.41%
 6. From this analysis, how pure is your Aspirin Synthesis Product? What is the
percentage of aspirin in your product?
The purity of the Aspirin Synthesis Product is estimated to be about 87.7% pure as calculated
in Question 5.

7. Are there any peaks in your spectrum that you cannot identify? If so, what do
these peaks represent, and how could you get rid of them?
There is a singlet at 7.282 ppm. This peak correspond to CHCl3 which is present due to the
incomplete deuteration of the solvent, CDCl3 which is used in this experiment. In order to get
rid of this peak, we have to ensure complete deuteration of the solvent. However, producing
100% pure CDCl3 is very difficult or expensive with current technology.

8. Which peak(s) did you use to determine if you had the converted SA to aspirin?
The singlet at 2.377 ppm is used to determine whether we have converted the salicylic acid to
aspirin. This peak correspond to the hydrogen (protons) on the ester group of the aspirin
which is not present in the NMR of salicylic acid.

9. Why would you find acetic acid, ethanol or water in your product?
Most of acetic acid should be gone with the filtrate during the recrystallization but acetic acid
could still be found because it is both the by-product from the synthesis of aspirin and the
product of hydrolysis when aspirin comes into contact with water.

Ethanol is being used as the solvent to dissolve salicylic acid during the recrystallization
process for aspirin synthesis. The failure to remove the excess ethanol added would result in
ethanol being found in the final aspirin product.

Water is present because the aspirin product may not be completely dry via the vacuum
filtration. Also, the exposure of product to humid air during the experiment period would also
give rise to the presence of water molecules in the synthesized product.
1.