NUCLEAR MAGNETIC RESONANCE

SPECTROSCOPY

Presented by
M.Ramya
2021412041
M.Tech – Food Technology

1
History
Credit for the discovery of NMR goes to
Isidor Isaac Rabi, who received the Nobel
Prize in Physics in 1944.
 The Purcell group at Harvard University and
the Bloch group at Stanford University
independently developed NMR spectroscopy
in the late 1940s and early 1950s.
Edward Mills Purcell and Felix Bloch shared
the 1952 Nobel Prize in Physics for their
discoveries
2
NMR Spectroscopy
Absorption of radiofrequency radiation
by nuclei in a magnetic field is called
Nuclear Magnetic Resonance.
Identify the presence of different
chemical and physical properties of
organic molecules due to presence of
different atoms.
To find Structure of unknown protein or
structure of any other component
3
The principle of NMR usually involves in
sequential steps
Because of its charge and spin, a nucleus can
behave like a magnet.
NMR spectroscopy operates by applying a magnetic
field to nucleus and then measuring the amount of
energy necessary to put various nuclei in resonance.
Nuclei in different electronic environments
(Shielded and deshielded) requires different amount
of energy to bring them into resonance.
An NMR spectrum provides a single or peak
representing the energy necessary to bring each
nuclei into resonance.

4
Presence of magnetic field

5
6
7
Types of Spectroscopy
Nuclear magnetic resonance spectroscopy is
possible, but the most commonly used by
organic chemists are
 Proton nuclear magnetic resonance (PNMR or 1H
NMR) spectroscopy and (Used to determine the
type and number of H atoms in a molecule)
 Carbon-13 nuclear magnetic resonance (13C
NMR) spectroscopy techniques. (Used to determine
the type of C atoms in the molecule)

8
NMR Spectroscopy instrument

9
Nuclear magnetic resonance spectroscopy, most commonly
known as NMR spectroscopy or magnetic resonance
spectroscopy (MRS), is a spectroscopic technique to observe
local magnetic fields around atomic nuclei.
The sample is placed in a magnetic field and the NMR signal is
produced by excitation of the nuclei sample with radio waves
into nuclear magnetic resonance, which is detected with
sensitive radio receivers.
The intramolecular magnetic field around an atom in a molecule
changes the resonance frequency, thus giving access to details of
the electronic structure of a molecule and its individual
functional groups.
As the fields are unique or highly characteristic to individual
compounds, in modern organic chemistry practice, NMR
spectroscopy is the definitive method to identify monomolecular
organic compounds

10
H NMR SPECTROSCOPY
1

11
Introduction
Proton Nuclear Magnetic Resonance
(1H NMR)
1H nuclei absorb (resonate) near a radiofrequency of
400 MHz
 13C nuclei absorb around 100 MHz.
Nucleus: 1H
Magnetogyric ratio: 2.68 x 108 radian/T·s
Isotopic Abundance: 99.98%
Relative Sensitivity: 1.00
Absorption Frequency: 200 MHz
at a field strength of 4.69 T

12
 1
H Chemical Shifts

C H
C C
O
C
CH3 CH3
X
O O C CH2
C H
C C
OH H Aromatic H O H CH
C C Ar CH3
TMS
H C C H

12 11 10 9 8 7 6 5 4 3 2 1 0
1H Chemical shift ( )

downfield upfield
Chemical Shift
The relative position of absorption in the NMR
spectrum defined as the chemical shift (Hz).
Chemical shift(Hz) = vsample (Hz) - vreference (Hz)
It is a unitless number (actually a ratio, in which the
units cancel), but we assign ‘units’ of ppm or d (Greek
letter delta) units.
For 1H, the usual scale of NMR spectra is 0 to 10 (or
12) ppm (or d).
The usual 13C scale goes from 0 to about 220 ppm.
The zero point is defined as the position of absorption
of a standard, tetramethylsilane (TMS):

14
Reference for H NMR 1

CH3
Tetramethylsilane (TMS) CH3 Si CH3
 Very shielded protons CH3
All the 12 protons are in the same
environment
Chemically inert
Low boiling, easily removable from the
sample.

15
16
Classification of protons
Homotopic hydrogens are those that upon
replacement one at a time with some group
(G) in separate models creates identical
structures.
If replacement of one hydrogen at a time in
separate models creates enantiomers, the
hydrogens are enantiotopic.
If replacement of hydrogens in separate
models creates diastereomers, the hydrogens
are diastereotopic
17
 G H H
CH3CH2CH2CH3 CH3CH2CH2C CH3CH2CH2C CH3CH2CH2C
H G H
H H G

G H H G
CH3CH2CH2CH3: C C
CH3CH2 CH3 CH3CH2 CH3

H H H G G H
C CH3 C CH3 C CH3
CH3 C CH3 C CH3 C
H Br H Br H Br

18
Spin-spin splitting (Coupling)
Proton NMR spectra are often much more
complex.
Because of its nuclear spin, each proton exerts a
slight effect on the localized magnetic field
experienced by its neighboring proton(s).
The result is that proton signals in the NMR
spectrum are typically split into multiplets. This
phenomenon is called coupling; the consequence
is signal splitting.
The type of multiplet (doublet, triplet, quartet,
etc.) depends on the number of protons on the
next carbon.
19
Spin-Spin Splitting

20
The n+1 rule
The multiplicity of a proton or a group of protons is given
by the n+1 rule, where n = the number of protons on
the adjacent (adjoining) carbon atom (or atoms)

n n+1 multiplet name (abbrev) intensity pattern

1 2 doublet (d) 1 : 1
2 3 triplet (t)1 : 2 : 1
3 4 quartet (q) 1 : 3 : 3 : 1
4 5 quintet/pentet - 1:4:6:4:1
5 6 septet - 1 : 5 : 10 : 10 : 5 : 1
6 7 septet/heptet - 1 : 6 : 15 : 20 :15 : 6 : 1

21
Some Common Splitting Patterns

22
23
24
 CH3 CH3

O
OCH2 CH2
CH3CH2COCH2CH3

CH3 CH3

OCH2 CH2

25
Continuous-Wave NMR
“Block diagram of Continuous-Wave NMR.”

26
FT-NMR
Free Induction Decay
◦ all of the nuclei will re-emit RF radiation at
their respective resonance frequencies
◦ interference pattern in the resulting RF
emission versus time
◦ frequencies are extracted from the FID by a
Fourier transform of the time-based data.

27
28
Application of H1NMR
Identification verification of vegetable
oils
Monitoring of oxidation
Reaction monitoring (mixtures of
vegetable oils with other fatty
compounds)
Solid fat content (SFC)
Non-fatty (extraneous) materials

29
Determination of free fatty acids in vegetable oils
  A 1H NMR method to quantitatively determine FFA in
vegetable oils, animal fats and bio diesel.
 It is based on the integration of the signal corresponding to
the α-carbonyl methylene protons of FFA (the methylene
group directly adjacent to the COOH group) and the α -
carbonyl-CH2 signal of esterified fatty acids.
 In vegetable oil and biodiesel, α-CH2 peaks of fatty acids
appear at chemical shift (δ) values higher than those of the
ester, as a consequence of the stronger deshielding effect of
the carboxylic group with respect to the ester group.
 Hence, one of the peaks of the triplet of FFA is visible
outside the α-CH2 region of the ester, while the other two
peaks overlap with those due to the ester.

30
This means that a sample of vegetable oil or biodiesel
containing both FFA and ester shows a pseudo-quartet
signal in the α-CH2 region of the proton NMR spectrum
and that the intensity of the peaks depends on the
content of FFA in esters.
Two 1H NMR methods, based on the integration of the
α-carbonyl methylene protons or of the carboxyl proton
signal of FFA (free fatty acid) were reported.
The main drawbacks are related to
(i) the narrow spectral width and the following
risk of signal overlap,
(ii) sensitivity issues in the first method, and
(iii) the need for some effort in the sample
preparation in the second method
31
Reference
https://www.youtube.com/watch?v=_HL2IFEFpWU

THANK YOU

32