Identification of Unknown Using Spectroscopic

Methods
Aims and Objectives:

The aim of this experiment is to identify unknown compounds using spectroscopic techniques. Three
unknown compounds, an aldehyde, a ketone, and an ester are provided. Each compound is analysed
using infrared spectroscopy and an IR spectrum is obtained for each compound. The 1H NMR
spectrum and 13C NMR spectrum of each compound are provided. The identify of the compound can
be determined by calculating the molecular formula of each compound and by analysing the three
different spectrums.

Results:

Compound X =

Data:

Molecular Weight 182 amu

C 85.71% H 5.49% O 8.79%

Melting Point 49-53˚ C

Molecular Formula:

85.71 % 5.49 % 8.79 %

12 g /mol 1 g /mol 16 g/mol
7.14 5.49 0.55
0.55 0.55 0.55
13 10 1
C 13 H 10 O

IR Spectrum of Benzophenone run as ATR.

 C-H aromatic

C=C aromatic
C=O ketone

1. Table of IR Spectrum Data of Benzophenone run as ATR.

Significant frequencies (cm-1) Assignments Strength

3055.55 C-H aromatic Weak
1649.73 C=O ketone Medium
1447.38 and 1593.22 C=C aromatic weak

13
C NMR Spectrum of Benzophenone at 25 MHz Solvent: CDCl3
 2. Table of 13C NMR Spectrum Data of Benzophenone at 25 MHz Solvent: CDCl3

δ/ppm Assignment
128 C5
130 C4
132 C3
138 C2
197 C1

1
H NMR spectrum of Benzophenone at 400 MHz Solvent: CDCl3
3. Table of 1H NMR Spectrum Data of Benzophenone at 400 MHz Solvent: CDCl3
 δ/ppm Integration Multiplicity Coupled Assignment
s,d,t,q, multiplet Protons
7.4 2H T HC + HA, HC + HC
HB , HC + HA,
HC + HB
7.6 1H T HB + HC, HB + HB
HC
7.8 2H d HA + HC, HA + HA
HC

Compound Y =

Data:

Molecular Weight 132 amu

C 81.82% H 6.06% O 12.12%

Boiling Point 248˚ C

Molecular Formula:

81.82 % 6.06 % 12.12 %

12 g /mol 1 g /mol 16 g/mol
5.11 6.06 0.76
0.76 0.76 0.76
981
C9 H8 O

IR Spectrum of Cinnamaldehyde run as ATR.

 v

C-H aromatic
C-H aldehyde
v
C=C alkene
C=C aromatic
aldehyde
C=O aldehyde
v

4. Table of IR Spectrum Data of Cinnamaldehyde run as ATR.

Significant frequencies (cm-1) Assignments Strength

3028.44 C-H aromatic Weak
2741.93 C-H aldehyde Weak
1669.92 C=O aldehyde Strong
1624.83 C=C alkene Medium
1449.58 and 1605.36 C=C aromatic weak

13
C NMR Spectrum of Cinnamaldehyde at 25 MHz Solvent: CDCl3
5. Table of 13C NMR Spectrum Data of Cinnamaldehyde at 25 MHz Solvent: CDCl3
 δ/ppm Assignment
128 C7
129 C6
130 C5
131 C4
135 C3
151 C2
194 C1

1
H NMR Spectrum of Cinnamaldehyde at 400 MHz Solvent: CDCl3
 6. Table of 1H NMR Spectrum Data of Cinnamaldehyde at 400 MHz Solvent: CDCl3

δ/ppm Integration Multiplicity Coupled Assignment

s,d,t,q, multiplet Protons
6.8 1H dd HB + HA, HB + HB
HC
7.4-7.6 6H m HF + HE, HE + HD + HE + HF + HC
HD, HD + HC,
HF + HE, HE +
HD, HD + HC
9.8 1H d n/a HA
Compound Z =

Data:

Molecular Weight 136 amu

C 70.59% H 5.88% O 23.53%

Boiling Point 49-53˚ C

Molecular Formula:

70.59 % 5.88 % 23.53 %

12 g /mol 1 g /mol 16 g/mol
5.88 5.88 1.47
1.47 1.47 1.47
4 41
Empirical Formula:

C4 H4 O

Molecular Formula

C 8 H 8 O2
IR Spectrum of Methyl Benzoate run as ATR.

C-H

C-H
C=C aromatic

C-O ester
C=O ester

7. Table of IR Spectrum Data of Methyl Benzoate run as ATR.

Significant frequencies (cm-1) Assignments Strength

2998.33 sp2 C-H stretch Weak
2951.94 sp3 C-H stretch weak
1718.09 C=O ester Strong
1451.63 and 1601.03 C=C aromatic Weak-medium
1272.52 C-O ester strong
13
C NMR Spectrum of Methyl Benzoate at 25 MHz Solvent: CDCl3
 8. Table of 13C NMR Spectrum Data of Methyl Benzoate at 25 MHz Solvent: CDCl3

δ/ppm Assignment
52 C1
128 C6
130 C5
131 C4
134 C5
168 C2

1
H NMR Spectrum of Methyl Benzoate at 400 MHz Solvent: CDCl3
 9. Table of 1H NMR Spectrum Data of Methyl Benzoate at 400 MHz Solvent: CDCl3

δ/ppm Integration Multiplicity Coupled Assignment

s,d,t,q, multiplet Proton
3.9 3H s n/a A
7.4 2H T HB + HC, HB + C
HC
7.5 1H T HD + HC, HD + D
HC
8.1 2H D B
Discussion:

Firstly, the melting point of the solid compound, compound X was determined to be 49-53˚ C. Using
the elemental analysis provided the molecular formula of the compound was determined to be
C13H10O, eliminating the possibility of the compound being an ester as it only contains one oxygen. In
the IR spectrum of compound X a stretch was observed at 1649.73 cm -1 which corresponds to a C=O
bond of a ketone and IR stretches at 1447.38 cm -1 and 1593.22 cm-1 indicate the presence of
aromatic rings. The 1H NMR spectrum had three signals, the first a triplet, at 7.4 ppm with a total of 2
equivalent protons responsible for the signal, indicating 2 equivalent neighbouring protons, and the
second a triplet at 7.6 ppm with 1 proton responsible for the signal, indicating 2 neighbouring
protons. The third signal a doublet appeared at 7.8 ppm with a total of 2 protons responsible for the
signal indicating 1 neighbouring proton. This suggested that the only protons present in this
compound are protons from an aromatic group. As there are 5 hydrogens, this means only one
substituent can be attached to the ring. The 13C NMR spectrum confirmed this as 4 signals appeared
between 128-138 ppm also indicating an aromatic group. The only other signal observed was at 197
ppm, this signal correlates with a carbon of a conjugated ketone, this confirms that the only types of
groups present are aromatic groups and a ketone. The double bond equivalent (DBE) for compound X
is 9 DBE this suggests that more than one benzene ring is present in the structure. It was suggested
that the compound was benzophenone, and this was confirmed by comparing the experimental
melting point range of 49-53˚ C to the literature melting point of 48.5 ˚ C [1].

Compound Y could either be an aldehyde or ester. The molecular formula was determined to be
C9H8O, therefore compound Y is an aldehyde as it only has one oxygen so cannot be an ester. In the IR
spectrum of compound Y, a strong stretch was observed at 1669.92 cm -1 and the stretch at 2741.93
cm-1 confirmed the presence of an aldehyde as these stretches correlated to a C=O and C-H stretch of
an aldehyde. Stretches were also observed at 1624.83 cm -1 indicating an alkene was present and
stretches at 1449.58 cm-1 and 1605.36 cm-1 suggested the presence of an aromatic group. The 1H
NMR spectrum had three signals, starting upfield the first signal at 6.8 ppm with an integration value
of 1 indicated that there is one proton responsible for the signal and the doublet of doublet peak
indicated that the proton had two non-equivalent neighbouring protons. The second signal a
multiplet between 7.4-7.6 ppm with a total of 6 protons responsible for the signal suggests an
aromatic group is present. The third signal at 9.8 ppm with an integration value of 1 indicated that
there was 1 proton responsible for the signal indicating 1 neighbouring proton. This suggested an
aromatic ring with a substituent attached. As the third signal only had 1 neighbouring proton this
suggested that this was attached to a terminal carbon and that the first signal was attached to a
carbon in between the aromatic group and terminal carbon. The 13C NMR spectrum confirmed this as
4 signals appeared between 128-131 ppm also indicated an aromatic group, a signal at 135 ppm
indicated a carbon double bond and a signal at 151 ppm indicated another carbon double bond, the
slight downfield shift of the protons can be explained by its close proximity to the electronegative
and electron withdrawing oxygen atom. The final signal observed at 194 ppm indicated the presence
of a carbon of a conjugated aldehyde. The double bond equivalent (DBE) for compound Y is 6 DBE
this suggests a benzene ring. From all this analysis and the molecular formula compound Y was
proposed to be cinnamaldehyde. The boiling point of 248˚ C stated in the provided data matched the
boiling point of 248˚ C researched online, this confirmed the identification of the compound was
correct [2].

On process of elimination based on the above analysis, compound Z is an ester. The molecular
formula of compound Z is C 8H8O2. In the IR spectrum strong stretches are observed at 1718.09 cm -1
and 1272.52 cm-1. These stretches correspond to the C=O and C-O of an ester group. IR stretches
observed at 1451.63 cm-1 and 1601.03 cm-1 indicated the compound contains an aromatic group. The
1
H NMR spectrum had four signals, starting upfield the first signal at 3.9 ppm with an integration
value of 3 indicated that there are three equivalent protons and the singlet peak indicated that each
proton had no neighbouring protons. The second signal a triplet at 7.4 ppm with a total of 2 protons
indicating that each proton had 2 neighbouring protons The third signal a triplet at 7.5 ppm with an
integration value of 1 indicated that there was 1 proton responsible for the signal with 2
neighbouring protons. The fourth signal a doublet at 8.1 ppm with an integration value of 2 had each
1 neighbouring protons. The second, third and fourth signals all between 7.4-8.1 ppm indicated the
presence of an aromatic group. As there are 5 hydrogens this means that there is only one
substituent attached to the ring. The first signal had 3 equivalent protons suggesting a terminal
methyl group is present. The 13C NMR spectrum confirmed this analysis as 4 signals appeared
between 128-134 ppm also indicating an aromatic group, a signal at 52 ppm indicated a methyl
group that had been deshielded and pushed downfield due to the carbon’s close proximity to an
electronegative atom and a signal at 168 ppm indicated an ester group is present. The double bond
equivalent (DBE) for compound Z is 5 DBE this suggested a benzene ring is present. It was suggested
that compound Z is methyl benzoate. This is confirmed by comparing the data provided about
compound Z to literature values for methyl benzoate. It is stated that the boiling point of compound
Z is 198-199˚ C and it is researched that the boiling point of methyl benzoate is 199˚ C. This confirms
that compound Z is methyl benzoate.

Conclusion:

The aim of this experiment was to identify unknown compounds using spectroscopic techniques.
Infrared (IR), 1H NMR and 13C NMR spectroscopy was employed to determine the identity of
compound X, Y and Z. This was successfully achieved by analysing the spectrums of the compounds
and the data provided. Compound X was identified as benzophenone, compound Y was identified as
cinnamaldehyde and compound Z was identified as methyl benzoate.

References

[1] PubChem (n.d.). Benzophenone. [online] pubchem.ncbi.nlm.nih.gov. Available at:

https://pubchem.ncbi.nlm.nih.gov/compound/Benzophenone#section=Melting-Point.
[2] PubChem (n.d.). Cinnamaldehyde. [online] pubchem.ncbi.nlm.nih.gov. Available at:
https://pubchem.ncbi.nlm.nih.gov/compound/637511#section=Boiling-Point [Accessed 22 Oct.
2023].
[3] PubChem (n.d.). Methyl benzoate. [online] pubchem.ncbi.nlm.nih.gov. Available at:
https://pubchem.ncbi.nlm.nih.gov/compound/Methyl-benzoate#section=Boiling-Point.

‌Spectrum Links

Benzophenone 1H NMR and 13C NMR: https://www.chemicalbook.com/SpectrumEN_119-61-

9_13CNMR.htm

Cinnamaldehyde 1H NMR and 13C NMR: https://www.chemicalbook.com/SpectrumEN_14371-10-

9_1HNMR.htm
Methyl Benzoate 1H NMR and 13C NMR: https://www.chemicalbook.com/SpectrumEN_93-58-
3_13CNMR.htm