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Chapter 15 NMR Spectroscopy

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Chapter 15 NMR Spectroscopy

Parts of Topics A5 and A9 from the IB HL Chemistry Curriculum

A5

Nuclear magnetic resonance (NMR) spectrometry (2 Hours)

A.5.1

Assessment Statement
Deduce the structure of a compound given
1
information from its H NMR spectrum.

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3

A.5.2

Outline how NMR is used in body scanners.

A9

Nuclear magnetic resonance (NMR) spectroscopy (2 Hours)

A.9.1

Assessment Statement
Explain the use of tetramethylsilane (TMS)
as the reference standard.

A.9.2

Analyze H NMR spectra.

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Teachers Notes
Students will only be assessed on their ability to deduce the number of
different hydrogen (proton) environments and the relative numbers of
hydrogen atoms in each environment. They should be familiar both with a
word description of a spectrum and with a diagram of a spectrum, including
an integration trace. The interpretation of splitting patterns will not be
assessed.
Aim 7: Data banks could be used here.
Aim 8: Protons in water molecules within human cells can be detected by
magnetic resonance imaging (MRI), giving a three-dimensional view of
organs in the human body.

Teachers Notes

Students should be able to interpret the following from H NMR

spectra: number of peaks, area under each peak, chemical shift
and splitting patterns. Treatment of spin-spin coupling
constants will not be assessed, but students should be familiar
with singlets, doublets, triplets, and quartets.

The Principles of NMR

Nuclear magnetic resonance spectroscopy, a powerful technique for finding the structure and shape of molecules,
depends on a combination of nuclear physics and chemistry. The nuclei of atoms with an odd number of protons such
as 1H, 13C, 19F, and 31P, spin and behave like tiny bar magnets. If placed in an external magnetic field, some of these
nuclei will line up with an applied field and, if they have sufficient energy, some will line up against it. This arrangement
leads to two nuclear energy levels; the energy needed for the nuclei to reverse their spin and change their orientation in
a magnetic field can be provided by radio waves.

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Chapter 15 NMR Spectroscopy

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In practice, a sample is placed in an electromagnet. The field strength is varied until the radio waves have the exact
frequency needed to make the nuclei flip over and spin in the opposite direction. This is called resonance and can be
detected electronically and recorded in the form of a spectrum.

NMR spectroscopy is non-invasive as the small quantities of the sample are recovered unharmed after the experiment.

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Chapter 15 NMR Spectroscopy

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The chemical shift

As electrons shield the nucleus from the full effects of external magnetic field, differences in electron distribution
produce different energy separations between the two spin energy levels. The technique is a very useful analytical tool,
as nuclei in different chemical environments produce different signals in the spectrum. Proton or 1H NMR is particularly
useful. The hydrogen nuclei, present in all organic molecules, effectively act as spies and give
information about their position in a molecule. The signals are measured against the standard
signal produced by the 12 hydrogen nuclei in tetramethylsilane (TMS), the structure of which is
shown on the right.
The position of the NMR signal relative to this standard is called the chemical shift of the proton. Hydrogen nuclei in
particular environments have characteristic chemical shifts. Some examples are given in the table below. A more
complete list is given in the Table 18 of the IB Data booklet.

Interpreting 1NMR spectra

The 1H NMR spectrum of ethanal is shown below.

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The spectrum trace has a peak at 9.7, which corresponds to the CHO proton and a peak at 2.1 which corresponds to the
three protons in the CH3 group. The area under the CH3 peak is three times larger than that under the CHO peak as it
indicates the relative number of protons in the different environment. The integrated trace gives this information more
directly, as it goes up in steps which are proportional to the number of protons. This spectrum is analyzed in more detail
later in the chapter.
Worked example
The NMR spectrum of a compound which has the molecular formula C3H8O is shown below.

(a)
(b)
(c)
(d)

Draw the full structural formulas and give the names of the three possible isomers of C3H8O.
Identify the substance responsible for the peak at 0 ppm and state its purpose.
Identify the unknown compound from the number of peaks in the spectrum.
Identify the group responsible for the signal at 0.9 ppm.

Solution
(a) The structures and names are:

(b) Tetramethylsilane is used as a reference standard.

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Chapter 15 NMR Spectroscopy

(c) For each structure, I-IV identifies the different environments of the H atoms in the molecule. 1-3 represents the
number of atoms in each environment. There are four peaks in the spectrum. Propan-1-ol has four peaks with the
correct areas.
(d) Peaks at 0.9 ppm correspond to the CH3 group.
Exercises
How many peaks will the following compounds show in their 1H NMR spectra?
(a) CH3COOCH3
(b) CH3OCH3
(c) C(CH3)4
(d) CH(CH3)2Cl

The NMR spectrum of a hydrocarbon with empirical formula C3H7 is shown. Use the NMR spectrum to identify the
compound.

Describe and explain the 1NMR spectrum of CH3CH2OH.

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Magnetic resonance imaging (MRI)

NMR is the basis of the diagnostic medical tool known as magnetic resonance imaging. It is known as MRI, a label
chosen to reduce possible public concerns about nuclear technology. The water which makes up about 70% of the
human body is measured using NMR. As discussed earlier, the technique is non-invasive and unlike the medical use of Xrays, it is extremely sensitive to differences in parts of the body with high water content. It is used to study blood flow,
tissues, muscles and other soft parts of the body. Radio waves are low-energy waves with no known side-effects.
The patient is placed in a strong magnetic field chamber and bombarded with pulses of radio waves. The signals
produced are decoded by a computer to produce a two- or three-dimensional image. MRI is ideal for detecting brain
tumors, infections in the brain, spine and joints, and in diagnosing strokes and multiple sclerosis.
Exercise:
The image on the right is of the human brain. Such images are used to study soft
tissues and muscles. State how the image was produced and give one advantage of
the technique.

Tetramethylsilane (TMS) as the reference standard

As we discussed earlier, NMR signals are measured against a standard produced by the 12 hydrogen nuclei in
tetramethylsilane (TMS). Because the hydrogen nuclei are all in the same environment, one signal is recorded. And
because silicon has a lower electro negativity than carbon, TMS absorbs radio waves in a different region from that
absorbed by hydrogen nuclei attached only to carbon. This ensures that the standard signal does not overlap with any
signals under investigation. The chemical shift (represented by 0) of a proton in a molecule is defined as:
=

(f f0)
f0

106 ppm

where f and f0 are the frequencies of the radio waves absorbed by the protons in the sample and TMS respectively.
Although the absolute frequency of the signal depends on the strength of the magnetic field, the chemical shift - relative
to the standard - stays the same. This allows a standard spectrum to be produced. TMS has the additional advantages
that it is chemically inert and is soluble in most organic solvents. It can be easily removed from the sample as it has a
low boiling point.

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High resolution 1H NMR spectroscopy

The NMR spectrum of an organic compound does not generally consist of a series of single peaks as indicated by the
low-resolution spectra presented earlier. Instead, a sensitive, high-resolution NMR machine reveals a hidden structure
with the single peaks split or resolved into a group of smaller parts. For example, compare the low-resolution spectrum
of ethanal (below, left) with the high resolution figure below on the right. The figure on the right was obtained under
more carefully controlled operating conditions.

The splitting of the peaks occurs as the effective magnetic field, experienced by particular nuclei, is modified by the
magnetic field produced by neighboring protons. This effect is known as spin-spin coupling. The magnetic field
experienced by the protons in the methyl group, for example, depends on the spin of the proton attached to the carbon
atom of the carbonyl group (CHO). The local magnetic field is increased when the magnetic field of the CHO proton is
aligned with the external field and decreased when aligned against it. As the energy separation between the two spin
states of a proton depends on the local magnetic field, this results in two possible values for the energy difference
between the two nuclear energy levels for the CH3 protons. Instead of one signal corresponding to one energy
difference, E, two signals corresponding to Ea and En are produced. Each line corresponds to a different spin of the
neighboring proton. As they are both equally likely, the lines are of equal intensity. In a similar way, the low-resolution
peak corresponding to the CHO proton is split due to the different magnetic fields produced by the combinations of spin
for the three protons of the neighbouring methyl group. As there are two possible orientations for each proton, a total
of 23 combinations are possible, resulting in four different local magnetic fields. This produces four signals with relative
intensities 1, 3, 3, 1 as shown in the table below.

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Worked example:
Predict the splitting pattern produced by a neighboring CH2 group.
Solution:
There are 22 different combinations.

Three lines are produced with relative intensities of 1, 2, 1.

The splitting patterns produced from different numbers of neighboring protons can be deduced from Pascal's triangle
and are summarized in the table below.

When analysing high-resolution NMR spectra, the following additional points should be noted:
protons bonded to the same atom do not interact with one another as they are equivalent and behave as a group
protons on non-adjacent carbon atoms do not generally interact with one another
the OH single peak in ethanol does not split unless the sample is pure. Rapid exchange of the protons between
ethanol molecules averages out the different possible spins.

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Worked example:
The 1H NMR spectrum of a compound with the empirical
formula C2H4O is shown on the right.
(a) Deduce the molecular formula of the compound.
(b) Draw possible structures of molecules with this molecular formula.
(c) Use Table 18 of the IB Data booklet to identify a structure which is
consistent with the 1H NMR spectrum and account for the number of
peaks and the splitting patterns in the spectrum.
Solution
(a) The 1H NMR spectrum shows the presence of 8 hydrogens. Molecular formula: C4H8O2
(b) Possible structures CH3CH2CH2COOH, CH3CH(CH3)COOH, CH3CH2COOCH3, CH3COOCH2CH3, HCOOCH2CH2CH3, and
HCOOCH(CH3)2
(c)

Correct structure: CH3COOCH2CH3

Exercises:
(a) Draw the molecular structure of butanone.

(b) UseTable 18 of the IB Data booklet to predict the high resolution 1H NMR spectrum of butanone. Your answer
should include: the chemical shift, the number of hydrogen atoms, and the splitting pattern for the different
environments of the hydrogen atoms.

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Compare the 1H NMR spectra of ethanal and propanone. Your answer should refer to number of peaks, and the areas
and splitting pattern of each peak.

The key features of the 1H NMR spectrum of a compound with the molecular formula C3H6O2 are summarized below

(a) Draw possible structures consistent with the molecular formula.

(b) Use Table 18 of the IB Data booklet to identify a structure which is consistent with the 1H NMR spectrum and
account for the number of peaks and the splitting patterns of the spectrum.

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