NMR

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.
Nuclear Spin
Many atoms (e.g., 1H, 13C, 15N, 31P) behave as if the
positively charged nucleus was spinning on an axis. The
spinning charge, like an electric current, creates a tiny
magnetic field. When placed in a strong external
magnetic field, the magnetic nucleus tries to align with
it like a compass needle in the earth’s magnetic field.
Because the nucleus is spinning and has angular
momentum, the torque exerted by the external field
results in a circular motion called precession
(precessional motion), just like a spinning top in the
earth’s gravitational field
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
Schematic Diagram for NMR Spectrum
NMR is a spectroscopic technique that relies on
the magnetic properties of the atomic nucleus.
When placed in a strong magnetic field, certain
nuclei resonate at a characteristic frequency in the
radio frequency range of the electromagnetic
spectrum. 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.
In case of olefins, acetylene, aldehyde,
ketones, acids, esters, nitrile etc. if proton is
present in the positive region , it will be
shielded and absorption occur upfield.
Any group present above or below the plane
of the aromatic nucleus will be shielded and
absorption occurs upfield.
Alkynes
Relaxation processes
It involve some non-radiative transition by which a nucleus in
an upper transition state return to the lower spin state.

(Spin-lattice relaxations)

(Spin-spin relaxations)
Spin-spin relaxation: it is due to the mutual
exchange of spins by two precessing nuclei which are
in close proximity to each other. It involves the
transfer of energy from one nucleus to the other thus
there is no net loss of energy. This process results in
line broadening and makes nmr spectra of solids
comparatively more interesting.
Spin-lattice relaxation: It involves the transfer of
energy from the nucleus in its higher energy state to
the molecular lattice (as the additional translational,
vibrational and rotational energy). Total energy of the
system remains the same. An efficient relaxation
involves a short time and results in the broadening of
absorption peaks (smaller the time of excited state
greater is the line width.
Not effective in solids.
It keeps the excess of nuclei in the lower energy
state.
Spin-Spin Coupling

Coupling, also referred to as signal splitting or signal

multiplicity, is a feature of 1H NMR spectra that provides very
useful information about the structure of a compound.
Coupling is caused by the magnetic effect of nonequivalent
hydrogen atoms that are within 2 or 3 bonds of the hydrogens
producing the signal.
The effect of the nearby hydrogens is to split (or couple with)
the energy levels of the hydrogens whose signal is being
observed, and the result is a signal with multiple peaks.
e.g., ethyl bromide (CH3CH2Br), spin of two protons (-CH2-) can
couple with adjacent methyl group (-CH3) in three different ways
relative to the external field. Different ways of alignment are:

reinforcing

Not effecting

opposing B0

Thus triplet of peaks with intensity ratio of 1:2:1

Similarly spin of three protons (-CH3-) can couple with adjacent methylene
protons (-CH2-) in four different ways

Strongly reinforcing

External
field
Weakly reinforcing

Weakly opposing

Strongly opposing

Thus quartet peaks with intensity ratio of 1:3:3:1

Important to remember
All equivalent protons – No splitting and we
observe a singlet e.g., cyclobutane, benzene etc.

If a set of protons do not have another set of protons

attached with the adjacent carbon atom e.g., Butanone
C b a
(CH3CH2-CO-CH3). Here a singlet appears for
protons ‘a’ since no hydrogen is attached to the
adjacent carbon atom.
Coupling constant