4.

NMR spectra

Interpreting NMR spectra

There are two kinds:

• Low-resolution NMR spectra

• High-resolution NMR spectra

In both cases the horizontal scale is labelled in terms of chemical shift, δ, and increases from right to left
with a small peak at 0 (if shown) due to TMS.

A low-resolution spectrum looks much simpler because it cannot distinguish between the individual peaks
in the various groups of peaks. In a high-resolution spectrum, some of the peaks are split into groups of
signals.

Low-resolution NMR spectra

There are three things to look out for:

• The number of peaks

Protons in different environments will have different chemical shifts and so each peak in the spectrum rep-
resents a different ‘type’ of proton, i.e. the number of peaks tells you the number of different environments
the hydrogen atoms are in.

• The areas under the peaks

The area under each peak is proportional to the number of protons generating that peak. This will be
shown in a number at the top of each peak or as a stepped line called an integration trace. The height of
each step corresponds to the relative numbers of each type of proton in the sample, i.e. the ratio of the
areas tells you the ratio of the numbers of hydrogen atoms in each of these environments.

• The chemical shifts

Hydrogen atoms in the same environment in a molecule will have the same chemical shift. The closer a
hydrogen atom to an electronegative atom, the larger the chemical shift, i.e. the chemical shift tells you
important information about the sort of environment the hydrogen atoms are in.

Consider ethanol, CH3CH2OH.

It has three sets of hydrogen atoms. It contains

• Three equivalent hydrogen atoms in the CH3 group

• Two equivalent hydrogen atoms in the CH2 group

• One hydrogen atom in the OH group.

Can you explain why the three hydrogen atoms of the CH3 group are equivalent?

1
4. NMR spectra

Each hydrogen atom is bonded to the same carbon atom.

Therefore its low-resolution NMR will show three peaks with relative peak areas 3:2:1.

Watch the animation low-resolution spectrum of ethanol

Consider butanone, CH3CH2COCH3

Its low-resolution NMR spectrum will contain three peaks because there are three different environments
for the hydrogen atoms.

Since the ratio of the numbers of hydrogen atoms in the various environments are 3:2:3, the ratio of the
peak areas will be 3:2:3.

The chemical shifts of the peaks will tell you how close the hydrogen atoms are to the electronegative oxy-
gen atom.

Watch the animation low-resolution spectrum of butanone

1. Butanal is an isomer of butanone.

How would its number of peaks and the ratio of the areas under the peaks differ from those
of butanone in its low-resolution NMR spectrum?

2. Deduce the number of peaks and the ratio of the areas under the peaks in the low-resolu
tion NMR spectra of the following:

a. ethanoic acid

b. propane

c. 1,4-dimethylbenzene

Draw the structure and look for hydrogen atoms in the same environment.

2
4. NMR spectra

3. An organic compound of molecular formula C3H6O2 is known to be an acid or an ester. Use its
low-resolution NMR spectrum to name the compound.

Low resolution spectrum of C3 H6 O2

(3)

(2)

(1)

• 1. Draw the possible structures.

• 2. Look at the number of peaks.

• 3. Consider the ratio of the areas under the peaks.

• 4. Look at the chemical shifts.

1. It would have four peaks with relative peak areas 3:2:2:1.

2. a) Two peaks with relative peak areas 3:1.

b) Two peaks with relative peak areas 3:1.

c) Two peaks with relative peak areas 3:2.

3. Ethyl ethanoate

3
4. NMR spectra

High-resolution NMR spectra

In a high-resolution spectrum, you find that many of what looked like single peaks in the low-resolution
spectrum are split into clusters of peaks. This splitting is caused by the influence of hydrogen atoms bonded
to neighbouring atoms, and the influence is called a coupling effect.

Each spinning hydrogen nucleus generates a magnetic field. Therefore when a particular hydrogen nucleus
resonates in an applied magnetic field, the actual magnetic field that acts on it is the sum of the applied
field and the fields from its neighbours. If the magnetic field from its neighbours is aligned with the applied
magnetic field it will absorb at a slightly lower field. Conversely, if the magnetic field from its neighbours is
aligned against the applied magnetic field it will absorb at a slightly higher field.

Protons can usually interact with other protons that are up to three bonds away. Protons in the same chem-
ical environment do not show coupling with each other.

Looking at the ethanol’s high resolution spectrum we see that the CH3 peak is split into three whilst the CH2
peak is split into four.

High-resolution spectrum of ethanol

6 5 4 3 2 1 0

We can explain why the CH3 peak is split into three by looking at ethanol’s structure.

Watch the animation explanation of splitting

The amount of splitting tells you how many hydrogen atoms are attached to the carbon atom(s) next to the
one you are interested in.

4
4. NMR spectra

The number of peaks in a cluster is one more than the number of hydrogen atoms attached to the neigh-
bouring carbon(s), i.e. if the number of adjacent equivalent protons is n; the peak will split into (n + 1)
peaks.

At A level if there is more than one carbon atom with hydrogen atoms adjacent to the carbon you are inter-
ested in; you will not be expected to calculate the number of peaks. The splitting will be shown as a multi-
plet. Also splitting patterns involving benzene rings will be shown as multiplets.

Number of adjacent
Spitting effect Name of signal Ratio of peaks
equivalent protons
1 2 peaks doublet 1:1
2 3 peaks triplet 1:2:1
3 4 peaks quartet 1:3:3:1

Can you work out why the ratio of peaks in a quartet is 1 : 3 : 3 : 1?

Think of the number of different ways that the three hydrogen atoms can align themselves.

5
4. NMR spectra

1. The high-resolution NMR spectrum of propanal can be represented as:

(3)

(2)
Multiplet
(1)

11 10 9 8 7 6 5 4 3 2 1 0

What part of the molecule is responsible for each cluster of peaks and why are the peaks split in this
way?

2. A compound of molecular formula C5H10O2 gives the following high-resolution NMR spec
trum.
(3)

(2)

(3)

(2)

5 4 3 2 1 0

Deduce the structure of the molecule, giving your reasoning.

6
4. NMR spectra

Look at the number of peak structures and the areas. Look at the splitting. What do the singlets
show?

Look at the chemical shifts. Consider structures that are not carboxylic acids or esters.

3. Draw the high-resolution NMR spectrum of methyl propanoate. Give the relative areas of
each peak and identify which protons are responsible for each peak.

7
4. NMR spectra

1. The cluster of peaks at δ = 1 ppm is caused by the hydrogen atoms in the CH3 group. The
CH3 signal is split into a triplet because it is next to a CH2 group. The cluster of groups at δ
= 2.7 ppm is caused by the hydrogen atoms in the CH2 group. The CH2 signal is a multiplet
because it is next to a CH3 group on one side and a CHO group on the other.

The cluster of peaks at δ = 9.6 ppm is caused by the hydrogen atom in the CHO group. The
CH0 signal is split into a triplet because it is next to the CHO group.

C
=
2. CH3 – CH2 – O – CH2 – C – CH3

3.

5 4 3 2 1 0

The triplet at around δ = 1.2 ppm has a peak area of 3 and is caused by the hydrogen atoms in a CH3 group
next to a CH2 group. The quartet at around δ = 2.3 ppm has a peak area of 2 and is caused by the hydrogen
atoms in a CH2 group next to a CH3 group and a C = O group.

The singlet at around δ = 3.8 ppm has a peak area of 3 and is caused by the hydrogen atoms in a CH3 group
next to an oxygen atom.