What is it?

Nuclear Magnetic Resonance (NMR) spectroscopy is the most powerful tool available for
determining the structure of organic compounds. This technique relies on the ability of atomic
nuclei to behave like a small magnet and align them with an external magnetic field. When
irradiated with a radio frequency signal the nuclei in a molecule can change from being aligned
with the magnetic field to being opposed to it. Therefore, it is called “nuclear” for the instrument
works on stimulating the “nuclei” of the atoms to absorb radio waves. The energy frequency at
which this occurs can be measured and is displayed as an NMR spectrum.

Basic Principle:
The nucleus of a hydrogen atom behaves as a spinning bar magnet because it possess both
electric and magnetic spin. Like any other charged body, the nucleus of hydrogen atom also
generates a magnetic field.
NMR involves the interaction between an oscillating magnetic field of EMR and the magnetic
energy of the hydrogen nucleus or some other type of nuclei when these are placed in an external
static magnetic field. The sample absorbs the EMR in radio wave region at different frequencies
since absorption depends on the type of protons or certain nuclei contained in the sample.
All nuclei carry a charge. So, they will possess a spin angular momentum. The moment of spin
angular momentum is quantized that is only those nuclei which have a finite value of spin
quantum number (I > 0) will precess along the axis of the rotation. It is known that the spin
quantum number I is associated with the mass number and the atomic number of the nuclei.

The circulation of the nuclear charge generates a magnetic moment along with the axis. This
intrinsic magnitude of the generated dipole is expressed in terms of magnetic moment .
If a proton is placed in a magnetic field, then it starts precessing at a certain frequency in the
radio wave region and thus, will be capable of taking up one of the two orientations with
respect to this axis of the external field –
a. Alignment with the field,
b. Alignment against the field.
If a proton is precessing in the aligned orientation it can pass into the open orientation by
absorbing energy. From the high energy orientation, it comes back to the low energy aligned
orientation by losing energy. The transition from one energy level to another is called flipping of
the proton. The transition between two energy states can be brought about by the absorption of
a quantum of EMR in the radio wave region with energy, E = h . The energy to bring about the
transition or to flip the proton depends upon the strength of the external field. Stronger the field
greater will be the tendency of nuclear magnet to remain lined up with it and higher will be the
frequency of the radiation needed to flip the proton to the higher energy state. If we irradiate
the precessing nuclei with a beam of EMR of a desired frequency then the low energy will absorb
it and move to higher energy state. The precessing proton will absorb the energy from the radio-
frequency source only if the precessing is the same as the frequency of the radio frequency beam,
i.e. when the quantum energy of the EMR matches up the energy differences between two
energy states at the field strength H0. When this occurs the nucleus and the radio frequency
beam are said to be in resonance. Hence, the term ‘Nuclear Magnetic Resonance’. This technique
consists in exposing the protons in an organic molecule to a powerful field. This proton will
precess at different frequencies. Now, we irradiate these precessing protons will steadily changes
frequencies and observe the frequency at which absorption occurs. It is generally more
convenient to keep the radio frequency constant and the strength of the magnetic field is
constantly varied. At some value of the field strength, the energy required to flip the protons
matches the energy of the radiation. Absorption occurs and a signal is observed. Such a spectrum
is called NMR spectrum.
All protons do not absorb the same applied field but absorption depends upon the magnetic field
which a particular proton feels. The effect field strength is different for different sets of proton
as one set of protons will have slightly different environment for any other sets of proton. Thus,
at a given radio frequency different protons will require slightly different applied strength which
causes absorption. In the NMR spectrum, we measure applied field strengths for each sets of
protons and absorption peaks are plotted. The number different signals at different applied field
strength are equal to the different sets of equivalent protons.

Instrumentation:
There are four main parts of an NMR spectrometer. They are
1. A magnet,
2. A radio frequency source,
3. A detector,
4. An amplifier.
The detection system of the NMR spectroscopy is use to note that energy is being transferred
from the radiofrequency beam to the nucleus
 .

The sample under investigation is taken is a glass tube which is placed between the pole faces of
the magnet. A radiofrequency source is made to fall on the sample. It can be done by feeding
energy into a coil wound round the sample tube. A signal is detected if the nuclei in the sample
resonate with the source, i.e., delta E energy required to flip the proton is the same as that of the
source.Energy is transferred from the source via nuclei to the detector coil. The output from the
detector can be fed to a cathode ray oscillograph or to a strip chart recorder after amplification.
Now, this record is printed out by using a proton and the NMR spectrum of the sample is
obtained. The sample is identified by comparing this spectrum with a given data or a standard
sample.

Solvents used in the NMR studies:

A substance free of protons should be used of a solvent, i.e. which does not give absorption
of its own in NMR spectrum. Moreover, the solvent should be capable of dissolving at least
10% of the substance under investigation. Following solvents are commonly used in NMR
spectroscopy.
a. Carbon Tetra chloride (CCl4),
b. Carbon disulphide (CS2),
c. Deuterochloroform (CDCH3),
d. Hexachloroacetone (CCl3-CO-CCl3).

Characteristics of solvent used in the NMR studies:

a. It should be chemically inert and magnetically isotropic,
b. It should be devoid of hydrogen atom,
c. It should dissolve the sample to a reasonable extent,
d. It should be easily removable from the sample,
e. It should have a very simple NMR spectrum or preferably should have no spectrum,
f. It should easily available.

(n+1) rule:
The number of peaks that are observed for a hydrogen nucleus in a particular environment
is depended upon the number of hydrogen atoms that are attached to the adjacent carbon
atoms. Each equivalent group protons split the resonance of its neighbor into (2nI + 1)
multiplates where n is the number of the multiple nuclei in the coupling and I is the spin of
the coupling nuclei.
In case of protons, I = ½
Therefore, 2 × n × I + 1 = 2 × n × ½ + 1 = n + 1
So for protons, the number of peaks ‘p’ that are observed for a particular type of hydrogen
nuclei in a multiplate are equal to the number of equivalent protons (n) an adjacent carbon
atom plus one that is (n+1).

Coupling constant:
The distance between the centers of the adjacent peak in a multiplate is usually constant and is
called the coupling constant. The value of the coupling constant is independent of the external
field. It is measured in Hertz (Hz) or in cycle per second (cps). It is denoted by the latter ‘J’. if we
work the spectrum of a particular compound at different ratio frequencies, the separation of
the two signals due to different chemical shifts change but the separation of two adjacent
peaks in a multiplates remain always constant.

Types of coupling:
There are three types of coupling. They are as follows:
a. Germinal coupling,
b. Vicinal coupling,
c. Long range coupling.

Decoupling:
Sometimes a single peak is split into several peaks. This phenomenon is called decoupling.
By decoupling a triplet split double doublet is found, same way a doublet is split into two
singlets. It is the opposite of the coupling.
Application of NMR Spectroscopy:
The NMR spectroscopy is widely used for the detailed investigation of an unknown
compound. Some of its importances are given below:
a. Identification of structural isomers,
b. Detection of hydrogen bonding,
c. Detection of aromaticity,
d. Distinctions between cis-trans isomers and conformers,
e. Detection of some double bond character due to resonance,
f. Detection of electronegative atom or group,
g. Importance of quantitative analysis.