Nuclear Magnetic Resonance

Nuclear Magnetic Resonance

When charged particles like protons spin on their axis, a

magnetic field is created causing the nuclei to act like
tiny magnets which are randomly oriented in space.
When charged particles like protons spin on their axis, a
magnetic field, B0 is created causing the nuclei to act like
tiny magnets which are randomly oriented in space.

However, in the presence of a B0, they are oriented with or

against this applied field.
 More nuclei are oriented with the applied B0 because this
arrangement is lower in energy. (E < 0.1 cal).

When an external energy source that matches E between these

two states is applied, energy is absorbed, causing the nucleus to
“spin flip” from one orientation to another.

The E between these two nuclear spin states corresponds to the

low frequency RF region of the electromagnetic spectrum.
Two variables characterize NMR:
• an applied B0, measured in tesla (T)
• the frequency  of radiation used for resonance, measured in
hertz (Hz), or megahertz (MHz)

A nucleus is in resonance when it absorbs RF radiation and

“spin flips” to a higher energy state.
• The  needed for resonance and the applied B0 strength are
proportionally related:

• The stronger the B0, the larger the E between the two nuclear
spin states, and the higher the  needed for resonance.
• NMR spectrometers are referred to as 300 MHz instruments,
500 MHz instruments, and so forth, depending on the  of the RF
radiation used for resonance.
• These spectrometers use very powerful magnets to create a
small but measurable E between two possible spin states.
Spectrometer
Spectrometer
Nuclear Magnetic Resonance
Nuclear Magnetic Resonance
 The  at which a particular proton
absorbs is determined by its
electronic environment.

• Protons in different environments absorb at slightly

different , so they are distinguishable by NMR.

• The size of the B0 generated by the electrons

around a proton determines where it absorbs.
• Modern NMR spectrometers use a constant B0 strength, and
then a narrow range of  is applied to achieve the resonance
of all protons.
• Only nuclei that contain odd mass numbers (such as 1H,
13C, 19F, and 31P) or odd atomic numbers (such as 2H and
14N) give rise to NMR signals.
An NMR spectrum is a plot of the intensity of a peak against its
chemical shift, measured in parts per million (ppm).
• NMR absorptions generally appear as sharp peaks.
• Most protons absorb between 0-10 ppm.
• The terms “upfield” and “downfield” describe the relative
location of peaks.
• Upfield means to the right (higher magnetic field).
• Downfield means to the left (lower magnetic field).
• An external standard, (CH3)4Si, tetremethylsilane) is added
to the sample tube prior to the NMR measurement.
• NMR absorptions are measured relative to the position of
a reference peak at 0 ppm on the  scale due to
tetramethylsilane (TMS).
• TMS is a volatile inert compound that gives a single peak
upfield from typical NMR absorptions.
• The chemical shift of the x axis gives the position of an
NMR signal, measured in ppm, according to the following
equation:

• By reporting the NMR absorption as a fraction of the NMR

operating frequency, we get units, ppm, that are independent
of the spectrometer.
 Structural Information from Features of a

• Number of signals: indicates the number of different

types of hydrogen in a molecule.
• Position of signals: indicates what types of hydrogen
the molecule contains.
• Intensity of signals: indicates the relative amounts
(how many) of each kind of hydrogen in the molecule.
• Spin-spin splitting of signals: gives further information
of the neighboring environment for the various
hydrogens in the molecule.
 Number of signals in

The number of NMR signals equals the number of

different types of protons in a compound.

• Protons in different
environments give
different NMR
signals.

• Equivalent protons
give the same NMR
signal.
 Number of signals in

0.2 ppm

All equivalent H’s

1 NMR signal
 Number of signals in

0.8 ppm

All equivalent H’s

1 NMR signal
 Number of signals in

0.8 ppm
1.4 ppm

Two types of H’s

2 NMR signals
 Number of signals in

1.3 ppm 0.9 ppm

Two types of H’s

2 NMR signals
 Position of signals in

? ppm

? ppm
Two types of H’s
2 NMR signals
 Position of signals in

3H
triplet
upfield 1.8 ppm
2H

3.6 ppm

downfield
quartet
downfield upfield
• The area under an NMR signal is proportional to the number of
absorbing protons.

• An NMR spectrometer can integrate the area under the peaks, and print
out a stepped curve (integral) on the spectrum.

• The height of each step is proportional to the area under the peak, which
in turn is proportional to the number of absorbing protons.

3H

2H
 proton
electron
Since the electron experiences a
lower B0, it needs a lower 
to achieve resonance (small δ).

The nucleus is shielded.

NMR signal appears upfield.
shielded: ↓ δ

upfield
deshielded: ↑δ shielded: ↓ δ

downfield upfield
deshielding effects shielding effects

downfield upfield
Ha Ha

Hb Hb
deshielded deshielded

deshielded shielded
 Spin-Spin Splitting in

triplet
triplet Ha
quartet
Ha
Hb

Hb
quartet
deshielded: ↑δ shielded: ↓ δ
downfield upfield
 Spin-Spin Splitting in

Spin-spin splitting occurs only between non-equivalent

protons on the same carbon or adjacent carbons.
Protons in a given environment absorb in a predictable region in an
NMR spectrum.
 triplet

quartet

singlet

3 2 1 0
PPM

3.6 3.6 1.1

singlet

3 2 1 0
PPM

3.2
 multiplet

singlet

7 6 5 4 3 2 1 0
PPM

6.7 – 7.1 5.0

 singlet

multiplet

10 8 6 4 2 0
PPM

9.9 7.5 – 7.8

 triplet

quartet

singlet

10 8 6 4 2 0
PPM

11.0 2.3 1.1

ELECTROMAGNETIC SPECTRUM