NMR Spectroscopy: Team D Dedicated To
NMR Spectroscopy: Team D Dedicated To
NMR Spectroscopy: Team D Dedicated To
Dedicated to
Team D
Dr. Md. Elius Hossain
Sadnan Chowdhury
Assistant Professor
Aruna Ayfar
Department of Chemistry
Md. Yeasin Arafat Tarek
Bangladesh University of Engineering &
Raisul Awal Mahmood
Technology (BUET)
Rezwan Tarek
Table of content
1. Electromagnetic radiation
2. History
3. What is Nuclear Magnetic Resonance (NMR)
4. Criteria for NMR technique
5. Instrumentation: Basic Operation of NMR Spectrometer
6. Solvents in NMR technique
7. Shielding & Deshielding
8. Chemical Shift
Electromagnetic Radiation (EMR)
NMR spectroscopy is studied
with the help of this region
History of Nuclear Magnetic Resonance (NMR)
specific orientations
Figure A Figure A
Nuclear Magnetic Resonance (NMR) Technique
A spinning 1H or 13C nucleus can orient so that its
own tiny magnetic field is aligned either with N
(parallel to) or against (antiparallel to) the external
field. The two orientations don’t have the same
energy, however, and aren’t equally likely. The
parallel orientation is slightly lower in energy by an Radio wave
amount that depends on the strength of the external
field, making this spin state very slightly favored over
the antiparallel orientation.
External
Higher energy state
magnetic
field
Absorb energy
Only nuclei with even numbers of both protons Odd Or, 𝟑𝟑 11B, 35Cl, 37Cl,
and neutrons (12C, 16O, 32S) do not give rise to Even 𝟐𝟐 79Br, 81Br
𝟓𝟓 127I, 17O
magnetic phenomena.
𝟐𝟐
Practically, field strengths in the range of 4.7 to 12C, 16O, 32S,
7.0 tesla (T) are more common. At a magnetic Even Even 𝟎𝟎 34S
NMR spectrum
NMR Chart
“Deshielded“ “Highly shielded”
protons appear protons appear
at downfield at upfield
(higher δ) (lower δ)
Deshielded
region
Deshielded
region
Acetylene protons δ̃ ≈ 2.5 ppm Vinyl (Olefinic) protons, δ = 5-6 ppm Aldehyde proton, δ= 9-10 ppm
Factors that affect Chemical Shift, 𝜹𝜹
R
Hydrogen bonding –
The chemical shift depends on how much O H H
hydrogen bonding is taking place (observed in
high concentrated solutions). Hydrogen bonding
O H O R
lengthens the O-H bond and reduces the valence
electron density around the proton R
H-bonding deshields the protons and shifts the
Alcohols vary in chemical shift from 0.5 ppm
NMR spectrum in downfield. (free OH) to about 5.0 ppm (lots of H
δ- δ+ δ- bonding).
O H O O O
-I
R C C R H 3C NH Intramolecular H-bond:
In methyl salicylate,
which has strong internal
O H O O hydrogen bonding, the
δ- δ+ δ- NMR absorption for O-H
is at about 14 ppm,
Intermolecular H-bond: Due to formation of hydrogen bonding, the (highly downfield)
protons attached to carboxylic acids forming dimer are the least
shielded protons and have a chemical shift of 10-12 ppm.
Factors that affect Chemical Shift, 𝜹𝜹
Steric hindrance
van der Waals deshielding–
In the overcrowded molecules, it is possible that
some proton may be occupying steric hindered
H
position. R
Electron crowd of a bulky group will tend to repel
the electron cloud (in over crowded molecules or
hindering groups) surrounding the proton.
CHCl3 H 0-5
3-5
NMR spectrum
sample.
Number of signals from NMR spectrum
Spin-spin coupling (Signal splitting – n+1 rule) – n+1 rule
Often a group of hydrogens will appear as a This hydrogen’s peak These hydrogens are
is split by its two split by their single
multiplet rather than as a single peak. This happens
neighbors neighbor
because of magnetic interactions with neighboring
hydrogens with nonequivalent protons on adjacent
carbons and so, is called Spin-Spin splitting.