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6.3.2 Spectroscopy

SPECIFICATION
‒ Carbon-13 NMR Spectroscopy
‒ High-resolution proton NMR
‒ Combined techniques

Source: OCR Spec

OCR A-Level Chemistry 6.3.2 Spectroscopy

Nuclear Magnetic Resonance (NMR) spectroscopy is an analytical technique used for

organic compounds. There are two types of NMR spectroscopy: Carbon-13 NMR and
Proton(1H) NMR. A sample is placed in magnetic field. This generates energy change in
nuclei of atoms. NMR spectra shows the response of a molecule to the magnetic field.
NMR spectra is analysed to find out the structures of organic molecules.
Atoms with odd mass numbers have the property of spin and behave as bar magnets
when placed in magnetic field. Only such atoms are only identified in NMR. That is why
even though carbon-12 has the highest relative abundance in an organic sample,
carbon-13 is used for NMR. The magnetic field strength of each sample is measured
relative to a reference compound. Tetramethylsilane (TMS) is used as reference
compound as it produces only one sharp peak in NMR. The peaks of the sample are
calculated from this reference peak which is known as chemical shift and is measured in
ppm (parts per million). The NMR gives the spectrum of intensity versus chemical shift.

Figure 1: Tetramethylsilane
OCR A-Level Chemistry 6.3.2 Spectroscopy

A. Carbon-13 NMR Spectroscopy

Samples used for C-13 NMR spectroscopy are dissolved in the solvent CDCl 3. Due to
the presence of carbon atoms in this solvent, a peak at 80 ppm is obtained, which can
be ignored while analysing the sample. The chemical shift values for various groups are
given in the table below.

Range of chemical
Environment of carbon atom Example
shift (ppm)
alkyl CH3─, CH2─, ─CH─ 0-50
alkene or arene ─C=C─ 110-160
alkyne ─CΞC─ 65-85
adjacent to alkene or arene ─CH2─C=C 10-40
adjacent to carbonyl or
─CH2─COR 25-50
carboxyl
adjacent to nitrogen ─CH2─NH2 30-65
next to chlorine ─CH2─Cl 30-60
next to oxygen ─CH2─OH 50-70
carboxyl R-COOH 160-185
carbonyl R-CHO 190-220
nitrile R─CΞN 100-125

The C-13 NMR spectrum of propanone is shown in the figure below. The peak at 80 ppm
is ignored. The peak at 30 ppm is due to the presence of methyl groups. Even though
there are two methyl groups, they are equivalent and produce a single peak only. The
peak at 204 ppm is due to the presence of C=O.

Figure 2: C-13 NMR spectrum of propanone

OCR A-Level Chemistry 6.3.2 Spectroscopy

An example of an aromatic compound is given in the figure below. For the benzene ring,
four peaks are formed between 110-160 ppm. The other functional groups can be
identified by using the table.

Figure 3: C-13 NMR spectrum of an aromatic compound

OCR A-Level Chemistry 6.3.2 Spectroscopy

B. High resolution proton NMR

In high-resolution proton NMR, the magnetic field strength of proton ( 1H) is analysed.
The chemical shifts for some types of proton are given in the table below.

Type of proton Range of chemical shift (ppm)

R─CH3 0.7-1.6
R─CH2─R 1.2-1.4
R3CH 1.6-2.0
N─H and R─OH 1.0-5.5
N─CH3, N-CH2R and N-CHR2 2.3-2.9
O─CH3, O-CH2R and O-CHR2 3.3-4.3
Cl or Br─CH3, Cl or Br-CH2R 3.0-4.2
and Cl or Br-CHR2
─CH=CH─ 4.5-6.0
benzene 6.4-8.0
R─CH(=O) 9.0-10.0
H3C-C(=O), RCH2─C(=O)─ 2.0-2.9
R-C(=O)-OH 10.0-12.0
Figure 4: High resolution proton NMR
Let us consider ethanol (CH3─CH2─OH). In this molecule there are three different
protons in: -OH, -CH2 and –CH3). As a result, three peaks are formed in the spectrum.
The area of the peak tells about the number of hydrogen atoms. Therefore, the area of
the peak of proton in –CH3 will be highest, followed by the peak of –CH 2 and then –OH.
The high-resolution proton NMR of ethanol is shown in figure below. . The relative
number of hydrogen atoms each peak represents is given and marked as 1H, 2H and
3H.

Figure 4: High resolution proton NMR of ethanol

It can be noticed that the peaks of 2H and 3H are split. This is due to the interference of
the magnetic field of neighbouring nuclei, which is called spin-spin coupling. The number
of splits is equal to n+1 where n is the number of 1H atoms in the neighbouring carbon
OCR A-Level Chemistry 6.3.2 Spectroscopy

Using this rule, the NMR of ethanol can be explained in detail:

a) The peak of CH3(3H) is split into 3. This is because of the neighbouring CH 2 group
(n=2). n+1= 3.
b) The peak of CH2(2H) is split into 4. This is because of the neighbouring CH 3 group
(n=3). n+1= 4.
c) In general, the OH(1H) peak does not split. Even though the OH group in ethanol
has a neighbouring carbon atom with two protons, the peak of the OH group does
not split into three as per the n+1 rule. This is because its protons are constantly
being exchanged with protons in water and other ethanol molecules. As a result, a
single average peak is produced. This phenomenon also occurs in amines and
amides that consist of the –NH group. The chemical shifts of –OH and –NH groups
overlap with the peaks of other functional groups, which makes it difficult to analyse
the NMR spectrum. This problem is solved by adding deuterium oxide (D 2O) to the
sample. The deuterium atom has two protons ( 2H) and does not appear the same
spectrum as hydrogen(1H) atoms and the peaks of –OH and –NH groups do not
appear. Therefore, to confirm the presence of –OH and –NH groups, the original
NMR is compared with the NMR that is obtained by adding D 2O to the sample.
The splitting pattern and its relative intensities are summarised in the table below.
Figure
Number 4: HighRelative
resolution proton NMR
Number of
of intensities
adjacent Shape
splits in splitting
protons (n)
(n+1) pattern

0 1, singlet 1

1 2, doublet 1:1

2 3, triplet 1: 2: 1

3 4, quartet 1: 3: 3: 1
OCR A-Level Chemistry 6.3.2 Spectroscopy

The high-resolution proton NMR of ethanal (CH 3-CHO) is shown in figure below.

The peak at 9.7 is due to hydrogen in R–CHO group. It is split into four due to the
neighbouring hydrogen atoms in –CH3 group. The peak at 2.2 is due to hydrogen atoms
in –CH3. This peak is split into 2 by the neighbouring hydrogen atom in –CHO.
The high-resolution proton-NMR spectra of propanoic acid (CH 3CH2COOH) is given.

Figure 4: High resolution proton NMR

• The peak at 2.4 could be due to RCH2─C(=O)─ or H3C-C(=O). Because there are
only 2 hydrogen atoms, the peak at 2.4 can be confirmed to be of RCH2─C(=O)─.
• The peak at 11.7 is due to –RCOOH. It is not split because its neighbouring carbon
atom does not have hydrogen bonded to it (-COOH).
• The peak at 2.4 is split into four, because its adjacent carbon atom has 3 hydrogen
atoms. Therefore, R in RCH2─C(=O)─ must be CH3.
• The peak at 1.1 is due to R─CH3. It is split into three, because its adjacent carbon
atom consists of 2 hydrogen atoms. Therefore, R in R─CH3 must be CH2.
Using the above information, it is concluded that the proton-NMR spectra represents
propanoic acid.
OCR A-Level Chemistry 6.3.2 Spectroscopy

C. Combined techniques
The structures of organic compounds are found out using different analytical data:
elemental analysis (Article 3), mass spectra (Article 21), IR spectra (Article 21) and NMR
spectra. In the example below, the percentage composition, mass spectra and proton
NMR spectra are combined to find out the structure of an unknown compound.
Example 1: A compound has the composition of 62.1% carbon, 10.3 % hydrogen and
27.6 % oxygen. Its mass spectra and proton NMR spectra are given below.

Figure 5: Mass spectra

Figure 4: High resolution proton NMR

Figure 6: High resolution proton NMR

a) What is the empirical formula of this compound?

b) Using the mass spectra, find the molecular formula.
c) This compound consists of carbonyl group. Using the NMR spectra, deduce the
structure of this compound.
OCR A-Level Chemistry 6.3.2 Spectroscopy

Solution:
a) To find the empirical formula,

Number of
Composition Divide by the
Element Ar moles=Composition
by mass smallest
by mass/Ar

C 12 62.1 5.175 3
H 1 10.3 10.3 5.971=6
O 16 27.6 1.725 1

The empirical formula for this compound is C 3H6O.

b) The highest mass-to-charge ratio in mass spectra gives the molecular mass. The
molecular mass of this compound is 58.
Mass of C3H6O=58
Therefore, the molecular formula
Figure of this
4: High compound
resolution is NMR
proton C 3H6O.

c) The peaks in the NMR are:

i. 3H at 1.1 ppm
Using the table for 1H NMR, this could be due to a –CH3 group. This peak is a triplet.
It means the neighbouring carbon atom has two hydrogen atoms.
ii. 2H at 2.4 ppm
This could be due to a CH2 group bonded to C=O. This is a quartet, and this shows
that the neighbouring carbon atom has three hydrogen atoms.
iii. 1H at 9.8 ppm
This could be due to the hydrogen in –CH=O group. This is again a triplet but with
smaller area which means that the neighbouring carbon atom has two hydrogen
atoms.
The structural formula for this compound is H 3C─CH2─CH(=O). This is propanal.