Unit 5.

UNIT 5.2

NUCLEAR MAGNETIC
RESONANCE SPECTROSCOPY

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Year:

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Unit 5.2

Topic 2: NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

Students should be able to:

demonstrate understanding of the difference between low resolution and

high resolution nmr spectra;

demonstrate understanding of the reasons for using of TMS

(tetramethylsilane) as a standard;

demonstrate recognition of chemically equivalent hydrogen atoms;

demonstrate understanding that chemical shifts depend on the chemical

environment of hydrogen atoms;

use integration curves to determine the relative number of hydrogen atoms

in different chemical environments;

apply the n +1rule to analyse spin-spin splitting, limited to doublets, triplets

and quartets where n is the number of hydrogen atoms on an adjacent
carbon atom;

deduce a molecular structure from an nmr spectrum, limited to simple

splitting patterns.

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Unit 5.2 Limit of Mass Spec – Doesn’t tell us what each fragment is bonded to

Topic 2: NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

NMR Spectroscopy helps us find out information about the structure of a

substance.

Certain nuclei with odd mass numbers, e.g. 1H, 13C, 15N, 19F, have the property of
‘spin´. These nuclei behave like tiny magnets, which can interact with
electromagnetic radiation and produce NMR spectra. We will look at hydrogen,
(or proton) NMR.

When a magnetic field is

applied the hydrogen atoms
will either align with the
magnetic field, or against it.
These opposite spin states will
have slightly different energy
levels. The hydrogen which is
aligned with the magnetic field
will be more stable, and have a
lower energy, while the
hydrogen aligned against the
field will be less stable and
have a higher energy level.

When the correct amount of energy is supplied, the hydrogen may flip to the
less stable alignment, and will later flip back to the more stable alignment,
emitting energy in the process. This flipping between alignments is known as
resonating. This resonance can be detected by NMR.

The difference in energy between the oppositely aligned hydrogen atoms will
depend on the environment of the hydrogen, as things which are bonded to it
will affect its spin.

Read C&F pg 564

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Unit 5.2

Chemical Shift

The energy at which hydrogen resonates at will depend on what it is bonded to.
For example, if a hydrogen has a relatively high electron density around it, then
it will resonate at a lower frequency. This is because the electrons shield the
nucleus from the applied magnetic field. Whereas, if a hydrogen has a relatively
low electron density around it, then it will resonate at a higher frequency, as it
will not be shielded from the magnetic field.

Chemical Environments

Ethanol has three hydrogen environments

Propanone has one hydrogen environement

An NMR spectrum shows peaks on an x-axis labelled with Chemical Shift, which
is measured in parts per million (ppm). Chemical shift is measured relative to a
reference compound known, TMS.

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Unit 5.2

Tetramethylsilane (TMS)

Tetramethylsilane, or TMS, is used as a standard for

NMR Spectroscopy. Everything else is compared to
this.

TMS is used as the standard because all twelve

hydrogen atoms are equivalent. It will therefore
only produce one peak, and because there are
twelve hydrogens, the peak will be strong.

Also, the electrons in the C-H bonds are closer to the hydrogens in this
compound than in almost any other one. That means that these hydrogen nuclei
are the most shielded from the external magnetic field, and so you would have
to increase the magnetic field by the greatest amount to bring the hydrogens
back into resonance. The net effect of this is that TMS produces a peak on the
spectrum at the extreme right-hand side. Almost everything else produces peaks
to the left of it. The more “exposed” a hydrogen is, the higher its chemical shift
from TMS, and the more it will appear to the left

The peaked caused by TMS is not always shown, but if there is a peak present at
zero on a NMR spectrum it is because of TMS

Read C&F pg 565-566

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Read L&R pg 420-422 “NMR” & “Chemical Shift”

Unit 5.2

NMR Spectrum for Ethanol

In ethanol, there are three hydrogen environments:

The hydrogen attached to the oxygen has little shielding as the oxygen
pulls the electrons away from it – it has the greatest chemical shift.

The 2 hydrogens attached to carbon 1, are more shielded as the effect of

the oxygen is less – they have smaller chemical shift.

The 3 hydrogens attached to carbon 2, are the most shielded as the

oxygen atom is now 2 atoms away – they have the smallest chemical shift

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Unit 5.2

Low Resolution NMR

This is an example of a low resolution NMR spectrum for ethanol. The area
under the curve is proportional to the number of hydrogen atoms in each
environment

This can also be indicated by an integration line, where the height of the line
indicates the area underneath the curve and hence, the number of hydrogens in
that environment

Read C&F pg 567

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Example questions in Shared Docs
Unit 5.2

Questions

Sketch the low resolution NMR spectrum you would expect:

Ethanal
Propanoic Acid

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Unit 5.2

Questions

Assign each peak in the following low resolution NMR spectrum.

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Unit 5.2

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Unit 5.2

High Resolution NMR

High resolution NMR spectrums give us extra information about the

environments of the hydrogens and hence the structure, as well as all of the
information which a low resolution spectrum is able to give us.

In a high resolution spectrum, spin-spin splitting occurs. The peaks which we

see in a low resolution spectrum, split into further peaks, caused by the
magnetic fields of other, neighbouring hydrogen environments. This gives us
information about the neighbouring groups.

Splitting follows the n+1 rule; if there are n hydrogens adjacent to a hydrogen
environment, then the peak will split into n+1 peaks.

No neighbouring hydrogens gives one peak and this is known as a singlet

One neighbouring hydrogen gives two peaks and this is known as a doublet

Two neighbouring hydrogens gives three peaks and this is known as a triplet

Three neighbouring hydrogens gives four peaks and this is known as a quartet

Each line within the split peak will have a certain height, which can be worked
out using Pascal’s triangle:
1

1 1

1 2 1

1 3 3 1

1 4 6 4 1

1 5 10 10 5 1

A doublet is a signal which appears as a pair of lines with equal intensity

A triplet is a signal which appears as three lines in the approximate intensity

ratio 1:2:1

A quartet is a signal which appears as four lines in the approximate intensity

ratio 1:3:3:1

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Unit 5.2

High Resolution NMR Spectrum of Ethanol

The CH3 peak is split into a triplet. This is due to the protons on the
adjacent CH2 group

The CH2 peak is split into a quartet. This is due to the adjacent protons on
the CH3 group.

The OH peak is a singlet. This is because the proton on the oxygen atom is
not affected by the protons on the neighbouring CH2 group.

Read C&F pg 568

Read L&R pg 422-423 “Spin-spin Splitting”

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Unit 5.2

High Resolution NMR Spectrum of Butanone

Three peaks at δ = 1: due to the protons in one of the CH3 groups, split
by the two protons on the adjacent CH2.

One peak at δ = 2: due to the protons in the other CH3 group adjacent to
C=O. No adjacent protons to cause splitting

Four peaks at δ = 2-3: due to the protons in the CH2 group, split by the
protons on the adjacent CH3 group.

The C=O group does not give a peak.

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Unit 5.2

High Resolution NMR Spectrum of a Substituted Arene

Two peaks at δ = ~ 1: due to the protons on the CH3 groups split by the
protons on the neighbouring C-H group.

Seven peaks at δ = 3: due to the protons on the CH group split by six

adjacent protons, i.e. two methyl groups.

One peak at δ = ~ 7: due to aromatic ring protons. Since these are not
adjacent to the other proton groups there is no splitting.

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Unit 5.2

Questions

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