NUCLEAR

MAGNETIC
RESONANCE (NMR)
SPECTROSCOPY
Siti Nor Atika Baharin (Ph.D)
Syllabus
3.1 The NMR Phenomenon
3.2 Theory of NMR
3.3 Chemical Shift and its Measurement
3.4 Factors influencing Chemical Shift
3.5 Proton NMR Spectroscopy
3.5.1 Correlation Data
3.5.2 Solvents Used in NMR
3.5.3 Integrals in Proton NMR Spectra
3.5.4 Spin-Spin Coupling-Spin-Spin Splitting
3.5.5 Factors Influencing the Coupling Constant, J
3.5.6 Non-first-order Spectra
3.5.7 Simplification of Complex Proton NMR Spectra
3.5.8 Tables of Data for Proton NMR
Learning outcome
• Understand the NMR phenomenon
• Understand in how the chemical shift occurred
& its measurements
• Understand the factor that influence of chemical
shift in NMR spectra.
NMR?
Hydrogen nuclei
(1H-NMR)
NMR gives information
about the number of
magnetic distinct
atoms of the type of
being studied
Carbon nuclei
(13C-NMR)
NMR phenomenon
(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 …..
 The most abundant isotopes of C and O do not have spin.

Element 1H 2H 12C 13C 14N 16O 17O 19F

1 1 6 6 7 8 8 9

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.
NMR phenomenon
(SPIN STATE)

In applied magnetic field

- spin states are not of equivalent energy because:
i) The nucleus is a charge particle,
ii) Any moving charge generates a magnetic field
of its own
iii) Thus, the nucleus has magnetic moment (μ)
generated by its charge & spin
- In case of hydrogen all proton has magnetic
moment either aligned with the field or
opposed to the field.
NUCLEAR SPIN STATES - HYDROGEN NUCLEUS
The spin of the positively
m charged nucleus generates
a magnetic moment vector, m.

+ +

The two states

are equivalent
Low High m in energy in the
energy energy absence of a
+ 1/2 - 1/2 magnetic or an
TWO SPIN STATES
electric field.
Absorption of energy
• The NMR phenomenon occurs when nuclei
aligned with an applied field are induce to
absorb energy and change their spin orientation
with respect to the applied field

Magnetic
Absorb energy
field
+hv
direction
• Energy absorption is quantized process
• Energy absorbed must equal with the energy
difference between the two states involved.
Eabsorbed  ( E  1 / 2 state  E  1 / 2 state)  hv
The energy difference (∆E) is a function of the strength of the
applied magnetic field (B0)
Absorption of energy
N

-1/2
The stronger the unaligned
applied magnetic
field (Bo),
The greater energy DE
difference between
the possible
spin states

∆E=f (B0) +1/2

aligned
Bo S
The Larmor Equation!!!

DE = kBo = hn can be transformed into

magnetogyric
ratio g
frequency of g
the incoming n  Bo
radiation that
will cause a 2p
transition strength of the
magnetic field

g is a constant which is different for

each atomic nucleus (H, C, N, etc)
 Resonance Frequencies of Selected Nuclei
Isotope Abundance Bo (Tesla) Frequency(MHz) g(radians/Tesla)
1H 99.98% 1.00 42.6 267.53
1.41 60.0
2.35 100.0
7.05 300.0

2H 0.0156% 1.00 6.5 41.1 4:1

7.05 45.8

13C 1.108% 1.00 10.7 67.28

2.35 25.0
7.05 75.0

19F 100.0% 1.00 40.0 251.7

 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

Nuclei resonance (absorb energy & make transition)

 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
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

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
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.
IN THE CLASSICAL NMR EXPERIMENT THE INSTRUMENT
SCANS FROM “LOW FIELD” TO “HIGH FIELD”
LOW HIGH
FIELD FIELD
NMR CHART

DOWNFIELD UPFIELD
scan
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
PULSED FOURIER
N
TRANSFORM (FT):
PULSED EXCITATION

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.
FREE INDUCTION DECAY
( relaxation )

n1

O
CH2 C CH3 n2

n3

n1, n2, n3 have different half lifes

COMPOSITE FID

“time domain“ spectrum

n1 + n2 + n3 + ......

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

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

O
CH2 C CH3

“frequency domain” spectrum

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

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 …..
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
INTEGRATION

NMR Spectrum of Phenylacetone

RECALL Each different type of proton comes at a different place .
from last You can tell how many different types of hydrogen
time there are in the molecule.
 INTEGRATION OF A PEAK
Not only does each different type of hydrogen give a
distinct peak in the NMR spectrum, but we can also tell
the relative numbers of each type of hydrogen by a
process called integration.

Integration = determination of the area

under a peak

The area under a peak is proportional

to the number of hydrogens that
generate the peak.
 Benzyl Acetate
The integral line rises an amount proportional to the number of H in each peak

METHOD 1
integral line

integral
line

simplest ratio
55 : 22 : 33 = 5:2:3 of the heights
 Benzyl Acetate (FT-NMR)
Actually : 5 2 3

58.117 / 11.3 21.215 / 11.3 33.929 / 11.3

= 5.14 = 1.90 = 3.00

O
CH2 O C CH3

METHOD 2
digital assume CH3
33.929 / 3 = 11.3
integration

Integrals are
good to about
10% accuracy.

Modern instruments report the integral as a number.

 Diamagnetic Anisotropy
The applied field
induces circulation
of the valence
electrons - this
generates a valence electrons
magnetic field shield the nucleus
that opposes the
applied field.
from the full effect
of the applied field

magnetic field
lines

Bo applied B induced
(opposes Bo)
fields subtract at nucleus
PROTONS DIFFER IN THEIR SHIELDING
All different types of protons in a molecule
have a different amounts of shielding.

They all respond differently to the applied magnetic

field and appear at different places in the spectrum.

This is why an NMR spectrum contains useful information

(different types of protons appear in predictable places).

SPECTRUM
DOWNFIELD UPFIELD
Less shielded protons Highly shielded
appear here. protons appear here.
It takes a higher field
to cause resonance.
CHEMICAL SHIFT & ITS MEASUREMENT
Rather than measure the exact resonance position of a
peak, we measure how far downfield it is shifted from TMS.

CH3 reference compound

tetramethylsilane
CH3 Si CH3 “TMS”
CH3
Highly shielded
protons appear
way upfield.

TMS Chemists originally

shift in Hz thought no other
compound would
downfield
come at a higher
n 0 field than TMS.
REMEMBER FROM OUR EARLIER DISCUSSION

Stronger magnetic fields (Bo) cause

field
strength the instrument to operate at higher
frequency frequencies (n).

g
n= B
2p o
NMR Field 1H Operating
Strength Frequency
constants
1.41 T 60 Mhz
2.35 T 100 MHz
hn = ( K) Bo 7.05 T 300 MHz
HIGHER FREQUENCIES GIVE LARGER SHIFTS
The shift observed for a given proton
in Hz also depends on the frequency
of the instrument used.
Higher frequencies
= larger shifts in Hz.

TMS
shift in Hz
downfield
n 0
 THE CHEMICAL SHIFT
The shifts from TMS in Hz are bigger in higher field
instruments (300 MHz, 500 MHz) than they are in the
lower field instruments (100 MHz, 60 MHz).
We can adjust the shift to a field-independent value,
the “chemical shift” in the following way:
parts per
million

chemical shift in Hz
shift
= d = = ppm
spectrometer frequency in MHz

This division gives a number independent

of the instrument used.

A particular proton in a given molecule will always come

at the same chemical shift (constant value).
HZ EQUIVALENCE OF 1 PPM
What does a ppm represent?

1H Operating Hz Equivalent 1 part per million

Frequency of 1 ppm of n MHz is n Hz
1
n MHz ( ) = n Hz
60 Mhz 60 Hz 10 6

100 MHz 100 Hz

300 MHz 300 Hz

7 6 5 4 3 2 1 0 ppm

Each ppm unit represents either a 1 ppm change in

Bo (magnetic field strength, Tesla) or a 1 ppm change
in the precessional frequency (MHz).
 NMR Correlation Chart
-OH -NH
DOWNFIELD UPFIELD
DESHIELDED SHIELDED
CHCl3 , H

TMS

12 11 10 9 8 7 6 5 4 3 2 1 0 d (ppm)
H
CH2F CH2Ar C-CH-C
RCOOH RCHO C=C CH2Cl CH2NR2
CH2S C
CH2Br
CH2I C C-H C-CH2-C
CH2O C=C-CH2 C-CH3
CH2NO2 CH2-C-
O
Ranges can be defined for different general types of protons.
This chart is general, the next slide is more definite.
APPROXIMATE CHEMICAL SHIFT RANGES (ppm) FOR SELECTED TYPES OF PROTONS

R-CH3 0.7 - 1.3 R-N-C-H 2.2 - 2.9 R-C=C-H

R-CH2-R 1.2 - 1.4 R-S-C-H 2.0 - 3.0 4.5 - 6.5
R3CH 1.4 - 1.7
I-C-H 2.0 - 4.0
H
R-C=C-C-H 1.6 - 2.6
Br-C-H 2.7 - 4.1
O 6.5 - 8.0
R-C-C-H 2.1 - 2.4 Cl-C-H 3.1 - 4.1 O
O RO-C-H 3.2 - 3.8 R-C-N-H
5.0 - 9.0
RO-C-C-H 2.1 - 2.5
HO-C-H 3.2 - 3.8 O
O
O R-C-H
HO-C-C-H 2.1 - 2.5 9.0 - 10.0
R-C-O-C-H 3.5 - 4.8
N C-C-H 2.1 - 3.0 O
O2N-C-H 4.1 - 4.3 R-C-O-H
R-C C-C-H 2.1 - 3.0
F-C-H 4.2 - 4.8 11.0 - 12.0
C-H 2.3 - 2.7 R-N-H 0.5 - 4.0 Ar-N-H 3.0 - 5.0 R-S-H
R-C C-H 1.7 - 2.7 R-O-H 0.5 - 5.0 Ar-O-H 4.0 - 7.0 1.0 - 4.0
 YOU DO NOT NEED TO MEMORIZE THE
PREVIOUS CHART

IT IS USUALLY SUFFICIENT TO KNOW WHAT TYPES

OF HYDROGENS COME IN SELECTED AREAS OF
THE NMR CHART

C-H where C is
CH on C
acid aldehyde benzene alkene attached to an aliphatic
next to
COOH CHO CH =C-H electronega- pi bonds C-H
tive atom
X=C-C-H
X-C-H
12 10 9 7 6 4 3 2 0

MOST SPECTRA CAN BE INTERPRETED WITH

A KNOWLEDGE OF WHAT IS SHOWN HERE
DESHIELDING AND ANISOTROPY
Three major factors account for the resonance
positions (on the ppm scale) of most protons.

1. Deshielding by electronegative elements.

2. Anisotropic fields usually due to pi-bonded

electrons in the molecule.
3. Deshielding due to hydrogen bonding.

We will discuss these factors in the sections that

follow.
DESHIELDING BY AN ELECTRONEGATIVE ELEMENT

d- d Chlorine “deshields” the proton,

Cl C H that is, it takes valence electron
density away from carbon, which
d- d in turn takes more density from
electronegative hydrogen deshielding the proton.
element

NMR CHART

“deshielded“ highly shielded

protons appear protons appear
at low field at high field

deshielding moves proton

resonance to lower field
Electronegativity Dependence
of Chemical Shift

Dependence of the Chemical Shift of CH3X on the Element X

Compound CH3X CH3F CH3OH CH3Cl CH3Br CH3I CH4 (CH3)4Si

Element X F O Cl Br I H Si
Electronegativity of X 4.0 3.5 3.1 2.8 2.5 2.1 1.8
Chemical shift d 4.26 3.40 3.05 2.68 2.16 0.23 0

most TMS
deshielded
deshielding increases with the
electronegativity of atom X
 Substitution Effects on Chemical
Shift

most The effect

deshielded increases with
CHCl3 CH2Cl2 CH3Cl
greater numbers
7.27 5.30 3.05 ppm of electronegative
atoms.

most
deshielded -CH2-Br -CH2-CH2Br -CH2-CH2CH2Br
3.30 1.69 1.25 ppm

The effect decreases

with incresing distance.
MAGNETIC ANISOTROPY
Ring Current in Benzene

Circulating p electrons

Deshielded
H H fields add together

Bo Secondary magnetic field

generated by circulating p
electrons deshields aromatic
protons
ANISOTROPIC FIELD IN AN ALKENE

protons are
deshielded

H H
Deshielded
shifted
fields add downfield

C=C
H H
secondary
magnetic
(anisotropic)
field lines
Bo
ANISOTROPIC FIELD FOR AN ALKYNE

H
C
C
H secondary
magnetic
(anisotropic)
Shielded hydrogens field
Bo
are shielded
fields subtract
HYDROGEN BONDING DESHIELDS PROTONS

The chemical shift depends

R on how much hydrogen bonding
is taking place.
O H H
Alcohols vary in chemical shift
O H O R from 0.5 ppm (free OH) to about
5.0 ppm (lots of H bonding).
R

Hydrogen bonding lengthens the

O-H bond and reduces the valence
electron density around the proton
- it is deshielded and shifted
downfield in the NMR spectrum.
SOME MORE EXTREME EXAMPLES

O H O Carboxylic acids have strong

R C C R hydrogen bonding - they
form dimers.
O H O

With carboxylic acids the O-H

absorptions are found between
10 and 12 ppm very far downfield.
H3C O
O
H
In methyl salicylate, which has strong
O internal hydrogen bonding, the NMR
absortion for O-H is at about 14 ppm,
way, way downfield.

Notice that a 6-membered ring is formed.