CHAPTER 2

NUCLEAR MAGNETIC RESONANCE

(NMR) 1
 Types of Energy Transitions in Each Region
of the Electromagnetic Spectrum

REGION ENERGY TRANSITIONS

X-ray Bond-breaking
UV/Visible Electronic
Infrared Vibrational
Microwave Rotational
Radio Frequency Nuclear and
(NMR) Electronic Spin
 THE ELECTROMAGNETIC SPECTRUM
high Frequency (n) low
high Energy low

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY

WAVE

Nuclear
Vibrational magnetic
Ultraviolet Visible infrared
resonance
2.5 mm 15 mm 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength (l) long

 • NMR is the most powerful tool available for organic and
inorganic structure determination.

• It is used to study a wide variety of nuclei:

• 1H
• 13C
• 15N
• 19F
• 31P
• Could you name other nuclei which can be studied in
NMR?
– 19F
– 31P
What is the difference between ‘typical NMR’ and solid state
NMR? And what is ‘typical NMR’? =>

4
 NUCLEAR SPIN
The nuclei of some atoms have a property called “SPIN”.

These nuclei behave as if

they were spinning.
….. we don’t know if they actually do spin!

This is like the spin property

of an electron, which can have
two spins: +1/2 and -1/2 .

Each spin-active nucleus has a number of spins defined by

its spin quantum number, I.

The spin quantum numbers of some common nuclei follow …..

5
 External Magnetic Field

When placed in an external field, spinning protons act like

bar magnets.

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Nuclear Spin
•• AAnucleus with
nucleus with an an
oddodd atomic
atomic number
number ormass
or an odd an
odd mass
number hasnumber
a nuclearhas
spin.a nuclear spin.
•• The
The spinning
spinning charged
chargednucleus generates
nucleus a magnetic
generates a field.
magnetic field.

7
Spin Quantum Numbers of Some Common Nuclei
The most abundant isotopes of C and O do not have spin.

Element 1H 2H C 13C 14N 16O 17O 19F

12

Nuclear Spin
Quantum No 1/2 1 0 1/2 1 0 5/2 1/2
(I)
No. of Spin 2 3 0 2 3 0 6 2
States

Elements with either odd mass or odd atomic number

have the property of nuclear “spin”.

The number of spin states is 2I + 1,

where I is the spin quantum number. 8
 THE PROTON

Although interest is increasing in other nuclei,

particulary C-13, the hydrogen nucleus (proton)
is studied most frequently, and we will devote
our attention to it first.

9
NUCLEAR SPIN STATES - HYDROGEN NUCLEUS
The spin of the positively
m charged nucleus generates
a magnetic moment vector, m.

+ +

The two states

m are equivalent
in energy in the
+ 1/2 - 1/2 absence of a
TWO SPIN STATES magnetic or an
electric field.10
THE “RESONANCE” PHENOMENON

absorption of energy by the

spinning nucleus

11
 Nuclear Spin Energy Levels
N

-1/2

In a strong magnetic
unaligned
field (Bo) the two
spin states differ in
energy.

+1/2
aligned
Bo S 12
 Absorption of Energy
quantized
Opposed

-1/2 -1/2

DE

DE = hn
Radiofrequency

+1/2 +1/2
Applied
Field
Aligned
Bo 13
THE ENERGY SEPARATION DEPENDS ON Bo

- 1/2

DE = kBo = hn
degenerate
at Bo = 0

+ 1/2

Bo
increasing magnetic field strength
14
 The Larmor Equation!!!
DE = kBo = hn can be transformed into

gyromagnetic
ratio g
frequency of gBg0
the incoming n =
n = Bo
radiation that
will cause a 2p
2p
transition strength of the
magnetic field

g is a constant which is different for

each atomic nucleus (H, C, N, etc)
15
A SECOND EFFECT OF A STRONG MAGNETIC FIELD

WHEN A SPIN-ACTIVE HYDROGEN ATOM IS

PLACED IN A STRONG MAGNETIC FIELD

….. IT BEGINS TO PRECESS

OPERATION OF AN NMR SPECTROMETER DEPENDS

ON THIS RESULT
16
 N

w Nuclei precess at
frequency w when
RADIOFREQUENCY
placed in a strong
40 - 600 MHz magnetic field.

hn
NUCLEAR
MAGNETIC
If n = w then RESONANCE
energy will be
absorbed and NMR
the spin will
invert. S
17
 Resonance Frequencies of Selected Nuclei
Isotope Abundance Bo (Tesla) Frequency(MHz) g(radians/Tesla)
1
H 99.98% 1.00 42.6 267.53
1.41 60.0
2.35 100.0
7.05 300.0

2
H 0.0156% 1.00 6.5 41.1 4:1
7.05 45.8

13
C 1.108% 1.00 10.7 67.28
2.35 25.0
7.05 75.0

19
F 100.0% 1.00 40.0 251.7
18
POPULATION AND SIGNAL STRENGTH
The strength of the NMR signal depends on the Population
Difference of the two spin states

Radiation
induces both
upward and
downward resonance
induced
transitions. emission

For a net positive signal excess

there must be an excess population
of spins in the lower state.

Saturation = equal populations = no signal 19

CLASSICAL INSTRUMENTATION
typical before 1960
field is scanned

20
 A Simplified 60 MHz
NMR Spectrometer
RF (60 MHz) hn
Oscillator absorption RF
Recorder
signal Detector
Transmitter
Receiver

MAGNET MAGNET
~ 1.41 Tesla
N S (+/-) a few ppm

Probe
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 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.

22
 E and Magnet Strength
• 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. =>

23
 Magnetic Shielding
• 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.

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 Shielded Protons
Magnetic field strength must be increased for shielded proton
to flip at the same frequency.

25
 Protons in a Molecule
Depending on their chemical environment, protons in a
molecule are shielded by different amounts.

26
 NMR Signals
• 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 integration/intensity of the signal shows the number of
protons of that type.
• Signal splitting pattern shows the number of protons on
adjacent atoms.
• The coupling constant, J value (Hz) shows the environment
interaction between protons

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The NMR Spectrometer

28
The NMR Spectrum

=>
29
1
H NMR

30
13
C NMR

31
 CH3
Tetramethylsilane
H3C Si CH3
CH3

• TMS is added to the sample as internal standard apart from

the solvent used.
• 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.

32
 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 NMR instrument.
• Called the delta scale.

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Delta Scale

34
=>
Location of Signals
• More electronegative atoms
deshielded more and give larger
shift values.
• Effect decreases with distance.
• Additional electronegative atoms
cause increase in chemical shift.

35
Typical Values

36
 Fortunately, different types of protons precess at
different rates in the same magnetic field.

N Bo = 1.41 Tesla

EXAMPLE: 59.999995 MHz

59.999700 MHz
O
CH2 C CH3

hn
To cause absorption
60 MHz 59.999820 MHz of the incoming 60 MHz
the magnetic field strength,
Bo , must be increased to
S a different value for each
type of proton.
Differences are very small,
in the parts per million range. 37
IN THE CLASSICAL NMR EXPERIMENT THE INSTRUMENT
SCANS FROM “LOW FIELD” TO “HIGH FIELD”

LOW HIGH
FIELD FIELD
NMR CHART

Bo
s i ng
ea
incr

DOWNFIELD UPFIELD
scan
38
NMR Spectrum of Phenylacetone

O
CH2 C CH3

NOTICE THAT EACH DIFFERENT TYPE OF PROTON COMES

AT A DIFFERENT PLACE - YOU CAN TELL HOW MANY
DIFFERENT TYPES OF HYDROGEN THERE ARE 39
MODERN INSTRUMENTATION

PULSED FOURIER TRANSFORM

TECHNOLOGY

FT-NMR
requires a computer
 PULSED EXCITATION
N

n2
n1
O
BROADBAND
RF PULSE CH2 C CH3
contains a range
of frequencies n3
(n1 ..... nn)

S
All types of hydrogen are excited
simultaneously with the single RF pulse.
41
FREE INDUCTION DECAY
( relaxation )

n1

O
CH2 C CH3 n2

n3

n1, n2, n3 have different half lifes

42
COMPOSITE FID

“time domain“ spectrum

n1 + n2 + n3 + ......
time 43
 FOURIER TRANSFORM
A mathematical technique that resolves a complex
FID signal into the individual frequencies that add
together to make it. ( Details not given here. )

converted to DOMAINS ARE

TIME DOMAIN FREQUENCY DOMAIN MATHEMATICAL
FID NMR SPECTRUM TERMS

FT-NMR
computer

n1 + n2 + n3 + ......
COMPLEX
SIGNAL
Fourier
Transform

individual
a mixture of frequencies
frequencies
decaying (with time)
44
converted to a spectrum
The Composite FID is Transformed into a classical
NMR Spectrum :

O
CH2 C CH3

“frequency domain” spectrum 45

 COMPARISON OF
CW AND FT TECHNIQUES

46
CONTINUOUS WAVE (CW) METHOD
THE OLDER, CLASSICAL METHOD

The magnetic field is “scanned” from a low field

strength to a higher field strength while a constant
beam of radiofrequency (continuous wave) is
supplied at a fixed frequency (say 100 MHz).

Using this method, it requires several minutes to plot

an NMR spectrum.

SLOW, HIGH NOISE LEVEL

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PULSED FOURIER TRANSFORM
(FT) METHOD FAST
THE NEWER COMPUTER-BASED METHOD LOW NOISE

Most protons relax (decay) from their excited states

very quickly (within a second).

The excitation pulse, the data collection (FID), and

the computer-driven Fourier Transform (FT) take
only a few seconds.

The pulse and data collection cycles may be repeated

every few seconds.

Many repetitions can be performed in a

very short time, leading to improved signal …..
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 IMPROVED SIGNAL-TO-NOISE RATIO
By adding the signals from many pulses together, the
signal strength may be increased above the noise level.

signal enhanced
noise signal

1st pulse

2nd pulse
add many
pulses

noise is random
nth pulse etc. and cancels out

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