NUCLEAR MAGNETIC

RESONANCE
T.Vishnupriya
M.Sc Chemistry
IInd – Year
Thiruvalluvar university
INTRODUCTION :
 Nuclear magnetic resonance spectroscopy is a powerful analytical
technique used to characterize organic molecules by identifying
carbon – hydrogen frameworks within molecules .
 Two common types of NMR spectroscopy are used to characterize
organic structure : 1 H NMR is used to determine the type and
number of H atoms in a molecule ; 13 C NMR is used to determine
the type of carbon atoms in the molecule .
 Under appropriate conditions in a magnetic field , a sample can
absorb electromagnetic radiation in the radio frequency ( rf ) region
at frequencies governed by the characteristics of the sample .
 The source of energy in NMR is radio waves which have long
wavelengths , and thus low energy and frequency .
 When low – energy radio waves interact with a molecule , they can
change the nuclear spins of some elements , including 1 H & 13 C .
NMR INSTRUMENT :
SCHEMATIC DIAGRAM OF NMR :
NUCLEAR SPIN STATES :

 When a charged particle such as proton spins on its own axis

It creates a magneticfield . Thus, the nucleus can be a tiny bar magnet .

 Normally , these tiny bar magnets are randomly oriented in space .

However , in the presence of a magnetic field BO , they are oriented with

or against this applied field . More nuclei are oriented with the applied

field because this arrangemet is lower in energy .

 Anything which is charged and spin then its generates a magnetism .

This is like the spin property of an electron,which can have two spins :

+1/2 & -1/2

 THE EFFECT OF EXTERNAL
MAGNETIC FIELD :
 The proton will respond to the influence of an external
magnetic field ,and will tend to align itself with that field , in
the manner of a compass needle in the earth magnetic field .
 The proton can only adopt two orientations with respect to
an external magnetic field - either aligned with the field or
opposed to the field
MAGNETIC PROPERTIES OF
NUCLEI :
 All nuclei carry a charge in some nuclei this charge spins on
the nuclear axis , and this circulation of nuclear charge
generates a magnetic dipole along the axis
 Anything which is charged and spin then it generates
magnetism
• Spin angular momentum or spin quantum number (I)
• Magnetic momentum ( ) along the axis of spin
• Electric quadrupole moment (Q)
 The spin number I can be determined from the atomic mass
And the atomic number .
 REQUIREMENTS OF NUCLEI TO BE
NMR ACTIVE :
 The nuclei that exhibits the NMR phenomenon are those for which
the spin quantum number (I) is greater than 0 : The spin quantum
number (I) is associated with the mass number and atomic number of
the nuclei

MASS NUMBER ATOMIC NUMBER SPIN NUMBER

ODD ODD OR EVEN 1/2 , 3/2 ,5/2 ,…….
EVEN EVEN 0
EVEN ODD 1,2,3,…..
 If no magnetic momentum μ > 0 then spin of proton is not
possible spin no > 0 .
 Nuclei should have high % of natural abundance
 Nuclei should have even charge distribution isotopes . That
is nucleus should be spherical in shape so as Q=0 .
 Other important magnetic nuclei that have been studied
extensively by NMR are 11B , 13C ,15N ,17O ,19F & 31P .
THE NATURE OF NMR
ABSORPTION :

 The absorption frequency is not same for all 1H or 13 C

nuclei
 Electron setup tiny local magnetic field that act in opposition
to the applied magnetic field , shielding the nucleus from the
full effect of the external magnetic field .
 The effective field actually felt by the nucleus is the applied
field reduced by the local shielding effect .

B effective = B applied – B local

PRECESSIONAL FREQUENCY :

The precessional frequency , ѵ , is directly proportional

to the strength of the external field ,BO .
ѵ ᴕ BO
As an example , a proton exposed to an external magnetic force of
1.4 Ͳ (Ξ 14 000 gauss ) will precess ≈ 60 million times per
second , so that ѵ = 600MHz .
 A magnetic nucleus can take up different orientations with
respect to that field ; the number of possible orientation is
given by (2I + 1 ), so that for nuclei with spin ½
(1H,13C,19F,etc….)
 In an applied magnetic field , magnetic nuclei like the proton
precess at a frequency ѵ, which is proportional to the strength
of the applied field .
ѵ = γ Bo /2∏
where;
Bo = applied magnetic field
γ = gyromagnetic ratio

= 60.03 MHz
Precessional frequencies (in MHz ) as a function increasing field
strength
BO /
tesla 1.4 1.9 2.3 4.7 7.1 11.7 14.1

1
H 60 80 100 200 300 500 600

2
H 9.2 12.3 15.3 30.6 46.0 76.8 92

11
B 19.2 25.6 32.0 64.2 94.9 159.8 192

13
C 15.1 20.1 25.1 50.3 75.5 125.7 151
APPLIED FIELD ,Bo FREQUENCY IN MHz

1.41 60 MHz

1.88 80 MHz

7.05 300 MHz

9.40 400 MHz

14.1 600 MHz

BOLTZ – MANN DISTRIBUTION
CONSTANT :
 It tells about the net absorption of radiation to occur , there
must be more particle in the lower energy state than in the
higher energy
 Boltzmann distribution is a probability function used in
statistical physics , with respect to temperature and energy

Nj / NO =exp( - E/KT )
Nj & NO are number of proton in higher and lower enery state
T is the absolute temperature
K is the boltzmann constant 1.381 x 10-23 JK-1
 Nj /NO = exp (-γhBO/2∏KT)

The difference in population of the two state is only on the

order of few parts . However , this difference is sufficient to
generate NMR signal .
 RELAXATION EFFECT :

There are two relaxation processes.

 The spin lattice or longitudinal : (T1)
Involves transfer of energy from the excited protons to the
surrounding protons .
 The spin – spin or transverse relaxation : (T2)
It involves transfer of energy among the processing protons .
CONTINUOUS WAVE – NMR

 To obtain a spectrum the oscillator frequency ѵ1 is scanned

over the proton frequency range ; alternatively , the oscillator
frequency may be held constant and the field B0 scanned.

 Each different kind of proton must be brought into resonance

one by one .this mode is called continuous wave
spectrometry
FOURIER TRANSFORM
SPECTROMETRY :

 In FT –NMR all nuclei are excited at the same time by a radio

frequency pulse

 All frequencies are measured in a rapid scan

 SCALE

 Chemical shift is measure in three major

spectra scale .

1. Delta scale ( δ )
2. Tau scale ( τ )
3. Hertz (Hz )
 up field shielding

down field deshielding

 5 4 3 2 1 0 δ-
SCALE

5 6 7 8 9 10 τ
SCALE

800 400 100 Hz

1000 scale
 CHEMICAL SHIFT :
 The chemical shift in absolute terms Is defined by the
frequency/ magnetic field of the resonance expressed with
reference to a standard compound which is defined to be at
0 ppm .
 The change in resonance frequency (or field ) is vey very low
for proton i.e ppm ,
 The scale is made more manageable by expressing it in parts
per million (ppm) and is independent of the spectrometer
frequency .
We can adjust the shift to a field – independent value ,the
chemical shift in the following way :
 δ value is dimensionless and is NOT PROPORTIONAL to B0 or
Osc frequency
 Δ value is same in all the different instruments
universal scale in NMR
Higher the value of HZ or δ – deshielded is the proton .

Lower the value of chemical shift in Hz or δ –shielded is the

proton
 SHIELDING :
 Shielded mean that nucleus whose chemical shift has been
decreased due to more electron density , magnetic induction ,
or other effects .
 Shielded proton is surrounded by electrons which oppose the
external magnetic field.
 Due to opposing of external magnetic field , it require high
magnetic strength to bring proton in resonance .
 Shielding decreases the δ value i.e . Require high field
strength.
 DESHIELDING

 When we say that an atom is deshielded , we mean that a

nucleus whose chemical shift has been increased due to
removal of electron density , magnetic induction , or other
effects .”
 In deshielded proton is not surrounded by electrons or due to
other effects
 Deshielding increase the δ value i.e require low field strength
HIGH FIELD (SHIELDING)
• More electron density ,
electron oppose the
external magnetic field
(shield) hence these proton
require higher external field
to come in resonance
LOW FIELD (DESHIELD)
• Less electron density (or)
anisotropic effect .electron
not oppose the external
magnetic field (deshield)
hence these proton require
lower field to come in
resonance
 REFERENCE STANDARD FOR 1H
– NMR :

 Tetra methyl silane (TMS) used as reference compound or

internal standard for NMR .
 The chemical shift of TMS is lower than most proton in
organic molecule , so it is take as zero.
 It should be readily volatile .
 TMS is chemically inert .
 In NMR spectra is plotted by considering TMS as 0.0 δ value .
 It should be miscible with organic solvents ..
FACTORS AFFECTING
CHEMICAL SHIFT (δ):

 Electronegativity
 Effect of magnetic anisotropy
 Resonance effect
 conjucation
ELECTRONEGATIVITY :
EFFECT OF MAGNETIC ANISOTROPY :
• Due to the presence of ∏ bond .
The protons are less sheilded
δ = 6.5 to 8.5
18 – ANNULENE

The applied and induced magnetic

fields are opposite and inner fee
weaker net field – lower ppm
(upfield ).

The applied and induced magnetic

fields are aligned and outer hydrogen
feel stronger net field – higher ppm
(down field )

INNER HYDROGEN : - 3.0 (SHIELDED)

OUTER HYDROGEN : 9.3
(DESHEIDED)
RESONANCE EFFECT :

 Electron donating
resonance effect increases
electron density at the
carbon and in turn to
hydrogen - sheilding of
proton

 Electron withdrawing
resonance effect decreases
electron density at carbon
and in turn to hydrogen -
deshielding of proton
CONJUCATION :
CHEMICAL SHIFT : Resonance effect
MULTIPLICITY – (SPLITTING OF
NMR SIGNALS )
 Peaks are often split into multiple peaks due to magnetic
interactions between nonequivalent protons on adjacent
carbons , The process is called spin – spin splitting .

multiplicity = 2nI + 1

n = number of adjacent hydrogens involved in splitting , number

of NMR active nuclei involved in splitting
I = spin quantum number of of the atom involved in splitting
Integration value – intensity
COUPLING CONSTANT (J)

The coupling constant (j) is the distance between two adjacent

peaks of a split NMR signal in hertz

Generally fall into range 0 to 18 Hz

RULES FOR SPIN – SPIN
SPLITTING:
 Equivalent protons do not split each other

Cl-CH3 Cl-CH2-CH2-Cl
 protons that are greater than two carbon atoms apart do not
split each other
Vicinal coupling :
aliphatic saturated coupling with the adjacent
hydrogen
 An important factor in vicinal coupling is the angle between
the C-H sigma bonds and whether or not its fixed .

J=0 to 8Hz
strictly 3-5Hz
Geminal coupling :

 Non equivalent H on the same carbon will couple and cause

signal splitting , this type of coupling is called geminal
coupling .

J= 12-18 Hz
Cis and trans coupling :