ONLINE REFRESHER COURSE IN CHEMISTRY

FOR HIGHER EDUCATION FACULTY

(2018)

Module 25: ChemSimplified: NMR

Spectroscopy: Basic Introduction
(Month of Publication: September, 2018)

Developed at

NATIONAL RESOURCE CENTRE OF CHEMISTRY

MHRD, Govt. of India

at
Guru Angad Dev Teaching Learning Centre
A Centre of MHRD, Govt. of India
under
Pandit Madan Mohan Malaviya National Mission on Teachers and Teaching
(PMMMNMTT)
Sri Guru Tegh Bahadur Khalsa College
University of Delhi, Delhi, India
Email id: mhrdnrc.chemistry@gmail.com
 ONLINE REFRESHER COURSE IN CHEMISTRY FOR HIGHER EDUCATION FACULTY (2018)
@ SWAYAM.GOV.IN
________________________________________________________________________

CREDITS

CORE TEAM Name & Institution

Coordinator, Dr. (Mrs.) Vimal Rarh

NRC of Chemistry
Chairman,
NRC of Chemistry
Director
Module Contributors
Coordinator, National Resource Centre of Chemistry
Project Head & Joint Director, Guru Angad Dev Teaching Learning Centre (GAD-TLC)
Senior Asst. Professor, Department of Chemistry
SGTB Khalsa College, University of Delhi
Prof. A K Bakhshi
Vice Chancellor, PDM University
Ex-Chair Professor, Dept. of Chemistry, University of Delhi
Chairman, and National Resource Centre of Chemistry of MHRD
Chairman, Guru Angad Dev Teaching Learning Centre (GAD-TLC) of MHRD
Dr. Jaswinder Singh
Director, Guru Angad Dev Teaching Learning Centre (GAD-TLC)
Principal, SGTB Khalsa College, University of Delhi
Name & Institution

Key Points from Video Lecture Professor Diwan S Rawat

of FRSC, CChem (London)
Department of Chemistry
University of Delhi, Delhi-110007, India
Visiting Professor: JAIST, Japan
Associate Editor: RSC Advances

Module 25: ChemSimplified: NMR Spectroscopy: Basic Introduction

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 ONLINE REFRESHER COURSE IN CHEMISTRY FOR HIGHER EDUCATION FACULTY (2018)
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________________________________________________________________________
1. Introduction

The nuclear magnetic resonance spectroscopy was co-discovered by Purcell, Pound

and Torrey of Harvard University and Bloch, Hansen and Packard of Stanford
University.
The discovery of nuclear magnetic resonance spectroscopy occurred when the
scientist noticed that magnetic nuclei, such as 1H and 31P (proton and Phosphorus
31) were able to absorb radio frequency energy when placed in a magnetic field of a
strength that was specific to the nucleus. Upon absorption, the nuclei begin to
resonate and different atoms within a molecule resonated at different frequencies,
and hence give signals. This observation allowed a detailed analysis of the structure
of a molecule. For this discovery Bloch and Purcell got Nobel Prize in physics 1952.
This technique is so powerful that it has been applied to solids, liquids and gasses,
kinetic and structural studies, and the principle of NMR is used in the MRI, resulting
in 6 Nobel prizes being awarded in the field of NMR.

2. NMR

It is the study of interaction of electromagnetic radiation and nuclei in a magnetic

field.
1H NMR: determines the type and number of H atoms in a molecule.
13C NMR: determines the type of carbon atoms in the molecule.

3. NMR Active Nuclei

All those nuclei that have net spin are NMR active nuclei and can be studied by NMR
spectroscopy.

1H 2H 12C 13C 14N 16O 31P 32S

ELEMENT

Nuclear 1/2 1 0 1/2 1 0 1/2 0

spin
quantum
number (I)

Number of 2 3 1 2 3 1 2 1
spin states

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 ONLINE REFRESHER COURSE IN CHEMISTRY FOR HIGHER EDUCATION FACULTY (2018)
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________________________________________________________________________
The nucleus is positively charged, and if has net spin, it will behave as a bar magnet
and have a magnetic field. The magnitude and direction of such magnetic field is
determined by a vector called MAGNETIC MOMENT.
• In the absence of a magnetic field the magnetic moment points in random directions.
• In the presence of a magnetic field B0 magnetic moment will align either parallel or
anti-parallel to the magnetic field. The parallel orientation is lower in energy.
• The parallel orientation is lower in energy, but the energy difference is very small.
Therefore, both orientations are populated by almost the same number of nuclei: at
11.5 T there is an excess of ~0.05% of nuclei in the parallel orientation.

4. Chemical Shift

There are two important concepts in NMR:

• Equivalent and non-equivalent protons
• Shielding and deshielding
The NMR signaling is based on the concept of nuclear shielding, which allows for
structural assignments. Nucleus of every atom is surrounded by electrons, which orbit
the nucleus. Charged particles moving in a loop will create a magnetic field which is
felt by the nucleus. Therefore, the local electronic environment surrounding the
nucleus will slightly change the magnetic field experienced by the nucleus, which in
turn will cause slight changes in the energy levels. This is known as shielding. Nuclei
that experience different magnetic fields due to the local electronic interactions are
known as non-equivalent nuclei. The change in the energy levels requires a different
frequency to excite the spin flip, which creates a new peak in the NMR spectrum.
This allows for structural determination of molecules.

5. Factors affecting Chemical Shift

• Electronegativity
• s-Character (Hybridization)
• Magnetic Anisotropic effect (-bonded electrons)
• Hydrogen bonding

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 ONLINE REFRESHER COURSE IN CHEMISTRY FOR HIGHER EDUCATION FACULTY (2018)
@ SWAYAM.GOV.IN
________________________________________________________________________
6. Magnetic Anisotropic Effect
The word "anisotropic" means "non-uniform". So magnetic anisotropy means that
there is a "non-uniform magnetic field". Electrons in π systems (e.g. aromatics,
alkenes, alkynes, carbonyls etc.) interact with the applied field which induces a
magnetic field that causes the anisotropy. As a result, the nearby protons will
experience 3 fields: the applied field, the shielding field of the valence electrons and
the field due to the π system. Depending on the position of the proton in this third
field, it can be either shielded (smaller ) or deshielded (larger ), which implies that
the energy required for, and the frequency of the absorption will change.

Magnetic Anisotropic
Effect in alkene

 = 5-6 ppm

Magnetic Anisotropic
Effect in Benzene

Magnetic Anisotropic
Effect in Alkyne

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 ONLINE REFRESHER COURSE IN CHEMISTRY FOR HIGHER EDUCATION FACULTY (2018)
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________________________________________________________________________

7. Equivalent and non-equivalent protons: Topocity

Me H Me D Me H
OR Homotopic Protons
Me H Me H Me D

H H' H' H H' H

C2 Reflect through
Enantiotopic Protons
Rotation plane of H-C-H
Me Cl Cl Me Me Cl

8. Coupling

• Homotopic Protons: Do not show coupling to each other

 Enantiotopic Protons: Do not show coupling to each other

• Diastereotopic protons: Do show coupling to each other

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 ONLINE REFRESHER COURSE IN CHEMISTRY FOR HIGHER EDUCATION FACULTY (2018)
@ SWAYAM.GOV.IN
________________________________________________________________________
9. Cis and Trans Isomerism

In case of alkenes, trans isomer has higher coupling constant than cis isomer
because steric hinderance causes de-shielding due to dispersion effect.
Ph Ph Ph H

H H H Ph
6.49 ppm 6.99 ppm

10. Summary

 Principle of NMR spectroscopy

 Only those nuclei that have spin quantum number(s) more than zero are NMR active
 Relation between nuclear spin and magnetic field
 Chemical shift and factors affecting it
 Magnetic anisotropic effect is responsible for deviation in chemical shift of protons in
case of alkene, alkyne, benzene and aldehyde
 How to calculate the number of non-equivalent protons
 Concept of coupling in cis and trans isomers
 Shielding and deshielding/equivalent and non-equivalent protons

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 ONLINE REFRESHER COURSE IN CHEMISTRY FOR HIGHER EDUCATION FACULTY (2018)
@ SWAYAM.GOV.IN
________________________________________________________________________
Reference Material
 Introduction To spectroscopy by Donald L. Pavia
 Spectrometric identification of organic compounds by Robert Silverstein
 Spectroscopy Of Organic Compounds by PS Kalsi

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