NUCLEAR MAGNETIC

RESONANCE SPECTROSCOPY
(NMR)

Introduction
2

NMR
is the most powerful tool available for organic
structure determination based on their nucleus.
is a physical phenomenon in which nuclei in a
magnetic field absorb and re-emit
electromagnetic radiation.
This ER energy is at a specific resonance frequency
which depends on the strength of the magnetic field and
the magnetic properties of the isotope of the atoms;
in practical applications, the frequency is similar to VHF
and UHF television broadcasts (601000MHz). NMR
allows the observation of specific quantum mechanical
magnetic properties of the atomic nucleus.
=>

It is used to study a wide variety of nuclei

(elements with odd atomic mass) :
1H
13C
15N
19F
31P

Al
27 Si

27

Chapter 13

Nuclear Spin
4

A nucleus with an odd atomic number or an

odd mass number has a nuclear spin. While a
nucleus with even number has zero spin
The spinning charged nucleus generates a
magnetic field.

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External Magnetic Field

5

When placed in an external field, spinning

protons act like bar magnets.

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The effect of the external magnetic field

Chapter 13

Resonant absorption by nuclear spins

will occur only when electromagnetic
radiation of the correct frequency (e.g.,
equaling the Larmor precession rate) is
being applied to match the energy
difference between the nuclear spin
levels in a constant magnetic field of the
appropriate strength.

Chapter 13

The energy of an absorbed photon is

then E = h0, where 0 is the resonance
radiofrequency that has to match (that
is, it has to be equal to the Larmor
precession frequency L of the nuclear
magnetization in the constant magnetic
field B0).

Chapter 13

Hence, a magnetic resonance absorption

will only occur when E = h0, which is
when 0 = B0/(2).

Such magnetic resonance frequencies

typically correspond to the radio frequency
(or RF) range of the electromagnetic
spectrum for magnetic fields up to roughly
20T.
It is this magnetic resonant absorption
which is detected in NMR.[citation needed]

Chapter 13

10

Two Energy States

The magnetic fields of
the spinning nuclei
will align either with
the external field, or
against the field.
A photon with the
right amount of
energy can be
absorbed and cause
the spinning proton
to flip.
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E and Magnet Strength

11

Energy difference is proportional to the

magnetic field strength.
E = h = h B0
2
Gyromagnetic ratio, , is a constant for
each nucleus (26,753 s -1gauss-1 for H).
In a 14,092 gauss field, a 60 MHz
photon is required to flip a proton.
Low energy, radio frequency or radio
wave
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12

E = hv = . Ho / I
v = . Bo / I. h
(2 ,7929) x (5,051 x 10-24) x (14092)

v = --------------------------------------------------

60 MHz
( 6,6256 x 10-27 )x

= 60 x106 Hz =

Magnetic Shielding
13

If all protons absorbed the same amount

of energy in a given magnetic field, not
much information could be obtained.
But protons are surrounded by electrons
that shield them from the external field.
Circulating electrons create an induced
magnetic field that opposes the external
magnetic field.
=>

Shielded Protons
14

Magnetic field strength must be

increased for a shielded proton to flip
at the same frequency.

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15

Protons in a Molecule
(Hydrogen)
Depending on their chemical
environment, protons in a molecule
are shielded by different amounts.
tive,
a
g
e
n
o
r
re elect o the atom
o
m
s
i
Oxygen are attracted t
s
electron

=>

16

Electrons, similar to the nucleus, are also

charged and rotate with a spin to produce a
magnetic field opposite to the magnetic field
produced by the nucleus.
In general, this electronic shielding reduces
the magnetic field at the nucleus (which is
what determines the NMR frequency).
As a result the energy gap is reduced, and
the frequency required to achieve resonance
is also reduced.
Chapter 13

17

This shift in the NMR frequency due to the

electronic molecular orbital coupling to
the external magnetic field is called
chemical shift,
Chemical shift explains why NMR is able to
probe the chemical structure of molecules,
Chemical shift depends on the electron
density distribution in the corresponding
molecular orbitals.
Chapter 13

18

If a nucleus in a specific chemical group is

shielded to a higher degree by a higher
electron density of its surrounding
molecular orbital, then its NMR frequency
will be shifted "upfield" (that is, a lower
chemical shift),
whereas if it is less shielded by such
surrounding electron density, then its NMR
frequency will be shifted "downfield" (that
is, a higher chemical shift).
Chapter 13

19

Chemical Shift

Measured in parts per million.

Ratio of shift downfield from TMS (Hz) to
total spectrometer frequency (Hz).
Same value for 60, 100, or 300 MHz
machine.
Called the delta scale.
=>

Chapter 13

20

Chapter 13

21

Delta () and Thou ()

10
0

0 ()
10 ()
- Less shielded
More shielded

Chapter 13

22

Proton is also shielded by pi ()

electrons found in double and triple
bonds
The shielding by TB > DB > SB

The chemical shift of TB<DB<SB

Chapter 13

The NMR Spectrometer

23

sample containing protons (hydrogen

nuclei) is placed in a strong magnetic field
to produce partial polarization of the
protons.
A strong RF field is also imposed on the
sample to excite some of the nuclear spins
into their higher energy state.
When this strong RF signal is switched off,
the spins tend to return to their lower state,
producing a small amount of radiation at
the Larmor frequency associated with that
field.
The emission of radiation is associated
with the "spin relaxation" of the protons
from their excited state. It induces a radio
frequency signal in a detector coil which is
amplified to display the NMR signal.
Chapter 13

24

Photo of NMR spectrometer

Chapter 13

NMR Signals
25

The number of signals shows how many

different kinds of protons are present.
The location of the signals shows how
shielded or deshielded the proton is.
The intensity of the signal shows the
number of protons of that type.
Signal splitting shows the number of
protons on adjacent atoms.
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The NMR Graph

26

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Tetramethylsilane
27

TMS is added to the sample.

Since silicon is less electronegative
than carbon, TMS protons are highly
shielded. Signal defined as zero.
Organic protons absorb downfield (to
the left) of the TMS signal.
CH3

=>

H3C

Si CH3
CH3

Location of Signals
28

More electronegative
atoms deshield more and
give larger shift values.
Effect decreases with
distance.
Additional electronegative
atoms cause increase in
chemical shift due to the
deshielded.
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Typical Values
29

Chapter 13

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Aromatic Protons, 7-8

30

=>
Chapter 13

31

Vinyl Protons, 5-6

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Acetylenic Protons, 2.5

32

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Aldehyde Proton, 9-10

33

Electronegative
oxygen atom

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O-H and N-H Signals

34

Chemical shift depends on concentration.

Hydrogen bonding in concentrated
solutions deshield the protons, so signal
is around 3.5 for N-H and 4.5 for O-H.
Proton exchanges between the molecules
broaden the peak.
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35

Carboxylic Acid
Proton, 10+

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Number of Signals
36

Equivalent hydrogens have the same

chemical shift.

Chapter 13

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Intensity of Signals
37

The area under each peak is

proportional to the number of protons.
Shown by integral trace.

Chapter 13

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How Many Hydrogens?

38

When the molecular formula is known,

each integral rise can be assigned to a
particular number of hydrogens.

Chapter 13

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Spin-Spin Splitting
39

Nonequivalent protons on adjacent

carbons have magnetic fields that may
align with or oppose the external field.
This magnetic coupling causes the proton
to absorb slightly downfield when the
external field is reinforced and slightly up
field when the external field is opposed.
All possibilities exist, so signal is split. =>
Chapter 13

1,1,2-Tribromoethane
40

Nonequivalent protons on adjacent carbons.

Chapter 13

=>

Doublet: 1 Adjacent Proton

41

=>
Chapter 13

Triplet: 2 Adjacent Protons

42

=>
Chapter 13

The N + 1 Rule
43

If a signal is split by N equivalent protons,

it is split into N + 1 peaks.

=>
Chapter 13

Range of Magnetic
Coupling

44

Equivalent protons do not split each other.

Protons bonded to the same carbon will
split each other only if they are not
equivalent.
Protons on adjacent carbons normally will
couple.
Protons separated by four or more bonds
will not couple.
=>
Chapter 13

Splitting for Ethyl Groups

45

=>
Chapter 13

46

Splitting for
Isopropyl Groups

=>
Chapter 13

Coupling Constants
47

Distance between the peaks of multiplet

Measured in Hz
Not dependent on strength of the
external field
Multiplets with the same coupling
constants may come from adjacent
groups of protons that split each other.
=>
Chapter 13

48

Values for
Coupling Constants

=>
Chapter 13

Complex Splitting
49

Signals may be split by adjacent

protons, different from each other,
with different coupling constants.
Example: Ha of styrene which is split
by an adjacent H trans to it (J = 17 Hz)
and an adjacent H cis to it (J = 11 Hz).
=>

a
H

H
C C

Hb
Chapter 13

Splitting Tree
50

a
H

H
C

Hb

Chapter 13

=>

Spectrum for Styrene

51

=>
Chapter 13

Stereochemical
Nonequivalence

52

Usually, two protons on the same C are

equivalent and do not split each other.
If the replacement of each of the protons
of a -CH2 group with an imaginary Z
gives stereoisomers, then the protons are
non-equivalent and will split each other.
=>
Chapter 13

53

Some Nonequivalent
Protons
a
H

H
C C

c
H OHa

dH

Hb

CH3
H

Cl
Hb

aH
Cl

Chapter 13

=>

Hb

Time Dependence
54

Molecules are tumbling relative to the

magnetic field, so NMR is an averaged
spectrum of all the orientations.
Axial and equatorial protons on
cyclohexane interconvert so rapidly that
they give a single signal.
Proton transfers for OH and NH may occur
so quickly that the proton is not split by
adjacent protons in the molecule.
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Chapter 13

55

Hydroxyl
Proton

Ultrapure samples
of ethanol show
splitting.
Ethanol with a
small amount of
acidic or basic
impurities will not
show splitting.
Chapter 13

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N-H Proton
56

Moderate rate of exchange.

Peak may be broad.

=>
Chapter 13

57

Identifying the O-H

or N-H Peak

Chemical shift will depend on

concentration and solvent.
To verify that a particular peak is due to
O-H or N-H, shake the sample with D 2O
Deuterium will exchange with the O-H
or N-H protons.
On a second NMR spectrum the peak
will be absent, or much less intense.
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Chapter 13

Carbon-13
58

C has no magnetic spin.

13C has a magnetic spin, but is only 1% of
the carbon in a sample.
The gyromagnetic ratio of 13C is onefourth of that of 1H.
Signals are weak, getting lost in noise.
Hundreds of spectra are taken, averaged.

12

=>
Chapter 13

Fourier Transform NMR

59

Nuclei in a magnetic field are given a

radio-frequency pulse close to their
resonance frequency.
The nuclei absorb energy and precess
(spin) like little tops.
A complex signal is produced, then
decays as the nuclei lose energy.
Free induction decay is converted to
spectrum.
=>
Chapter 13

60

Hydrogen and Carbon

Chemical Shifts

Chapter 13

=>

61

Combined 13C
and 1H Spectra

Chapter 13

=>

62

Differences in
13
C Technique

Resonance frequency is ~ one-fourth,

15.1 MHz instead of 60 MHz.
Peak areas are not proportional to
number of carbons.
Carbon atoms with more hydrogens
absorb more strongly.
=>
Chapter 13

63

Spin-Spin Splitting

It is unlikely that a 13C would be adjacent

to another 13C, so splitting by carbon is
negligible.
13C will magnetically couple with
attached protons and adjacent protons.
These complex splitting patterns are
difficult to interpret.
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Chapter 13

Proton Spin Decoupling

64

To simplify the spectrum, protons are

continuously irradiated with noise, so
they are rapidly flipping.
The carbon nuclei see an average of all
the possible proton spin states.
Thus, each different kind of carbon gives
a single, unsplit peak.
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Chapter 13

65

Off-Resonance Decoupling
C nuclei are split only by the protons
attached directly to them.
The N + 1 rule applies: a carbon with N
number of protons gives a signal with
N + 1 peaks.
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13

Chapter 13

Interpreting

13

C NMR

66

The number of different signals indicates

the number of different kinds of carbon.
The location (chemical shift) indicates the
type of functional group.
The peak area indicates the numbers of
carbons (if integrated).
The splitting pattern of off-resonance
decoupled spectrum indicates the number
of protons attached to the carbon. =>
Chapter 13

Two

13

C NMR Spectra

67

=>
Chapter 13

MRI
68

Magnetic resonance imaging, noninvasive

Nuclear is omitted because of publics fear
that it would be radioactive.
Only protons in one plane can be in
resonance at one time.
Computer puts together slices to get 3D.
Tumors readily detected.
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69

End of Chapter 13