Nuclear Magnetic Resonance Spectroscopy

1. Introduction
1.1. Background
Over the past fifty year’s nuclear magnetic resonance spectroscopy, commonly referred to as
NMR, has become the preeminent technique for determining the structure of organic compounds.
Of all the spectroscopic methods, it is the only one for which a complete analysis and
interpretation of the entire spectrum is normally expected. Although larger amounts of sample
are needed than for mass spectroscopy, NMR is non-destructive, and with modern instruments
good data may be obtained from samples weighing less than a milligram. To be successful in
using NMR as an analytical tool, it is necessary to understand the physical principles on which
the methods are based.
1.1.2. History 
In 1945, Purcell, Torry and Pond (Harvard Univ.) & Bloch, Hansen and Packard (Stanford
Univ.) independently announced a far-reaching discovery about the behavior of the atomic
nucleus. Most nuclei, including p and e-, possess inherent magnetic fields, though the effects of
the nuclear fields are too small to be observed in the ambient magnetic field of the earth. Bloch
& Purcell (physicians, get Noble Price 1952) invented techniques to detect the minute amount of
energy absorbed or emitted as the nuclei jump from one energy level to another.
1.2. Definition
Nuclear Magnetic Resonance (NMR) is a spectroscopy technique which is based on the
absorption of electromagnetic radiation in the radio frequency region 4 to 900 MHz by nuclei of
the atoms.
It basically concerns the interaction of nuclear spins with radio frequency radiation in presence
of an applied magnetic field.
In analytical chemistry, NMR is a technique that enables us to study the shape and structure of
molecules. In particular, it reveals the different chemical environments of the NMR-active nuclei
present in a molecule, from which we can ascertain the structure of the molecule. NMR provides
information on the spatial orientation of atoms in a molecule. If we already know what types of
compounds are present, NMR can provide a means of determining how much of each is in the
mixture. It is thus a method for both qualitative and quantitative analysis, particularly of organic
compounds. In addition, NMR is used to study chemical equilibria, reaction kinetics, motion of
molecules, and intermolecular interactions.
1.3. Magnetic Properties of the Nucleus
It is necessary to assume that nuclei rotates about an axis and thus have the property of spin.
Furthermore, it is necessary to postulate that the angular momentum associated with the spin is a
half-integral multiple of h/2π (h=Planck’s constant). The maximum spin component for a
particular nucleus is its spin quantum number, I. I = half-integral values 0, ½, 1, 3/2… 9/2
depending on the particular nucleus. It is found that a nucleus will have (2I+1) discrete states.
The component of angular momentum for these states in any chosen direction will have values
-I, (-I+1)… (I-1), I
1.3.1. Examples
Proton has spin number of ½, thus the spin states is (2(1/2)+1)=2 and corresponding to I=+1/2
and I=-1/2. • For Chlor: I=3/2, the spin states are (2(3/2)+1)=4 and corresponding to -3/2, -1/2,
+1/2, and +3/2. In the absence of an external field, the various states have identical energies.
1.3.2. Spinning
For I=1/2, there are 2
possible levels or
orientation, with the
applied field (lower
energy) --- E= - µHo
(parallel) or against the
applied field (higher
energy) --- E=+µHo (anti-
parallel).

1.4. Chemical Shifts

The NMR spectra is
displayed as a plot of the
applied radio frequency
versus the absorption. The applied frequency increases from left to right, thus the left side of the
plot is the low field, downfield or deshielded side and the right side of the plot is the high field,
upfield or shielded side (see the figure below). The concept of shielding will be explained
shortly.
The position on the plot at which the nuclei
absorbs is called the chemical shift. Since this
has an arbitrary value a standard reference point
must be used. The two most common standards
are TMS (tetramethylsilane, (Si (CH3)4) which
has been assigned a chemical shift of zero, and
CDCl3 (deuterochloroform) which has a chemical
shift of 7.26 for 1H NMR and 77 for 13C NMR.
The scale is commonly expressed as parts per million (ppm) which is independent of the
spectrometer frequency. The scale is the delta (δ) scale.
The range at which most NMR absorptions occur is quite narrow. Almost all 1H absorptions
occur downfield within 10 ppm of TMS. For 13C NMR almost all absorptions occurs within 220
ppm downfield of the C atom in TMS.
1.5. Shielding in NMR
A spinning charge generates a magnetic field that results in a magnetic moment proportional to
the spin. In the presence of an external magnetic field, two spin states exist; one spin up and one
spin down, where one aligns with the magnetic field and the other opposes it.
Chemical shift is characterized as the difference between the resonant frequency of the spinning
protons and the signal of the reference molecule. Nuclear magnetic resonance chemical change is
one of the most important properties usable for molecular structure determination. There are also
different nuclei that can be detected by NMR spectroscopy, 1H (proton), 13C (carbon 13), 15N
(nitrogen 15), 19F (fluorine 19), among many more. 1H and 13C are the most widely used. The
definition of 1H as it is very descriptive of the spectroscopy of the NMR. Both the nuts have a
good charge and are constantly revolving like a cloud. Through mechanics, we learn that a
charge in motion produces a magnetic field. In NMR, when we reach the radio frequency (Rf)
radiation nucleus, it causes the nucleus and its magnetic field to turn (or it causes the nuclear
magnet to pulse, thus the term NMR).
1.6. Electronegativity
The electrons that surround the nucleus are in motion so they created their own electromagnetic
field. This field opposes the applied magnetic field and so reduces the field experienced by the
nucleus. Thus the electrons are said to shield the nucleus. Since the magnetic field experienced
at the nucleus defines the energy difference between spin states it also defines what the chemical
shift will be for that nucleus. Electron with-drawing groups can decrease the electron density at
the nucleus, deshielding the nucleus and result in a larger chemical shift.
As can be seen from the data, as the electronegativity of X increases the chemical shift, δ
increases. This is an effect of the halide atom pulling the electron density away from the methyl
group. This exposes the nuclei of both the C and H atoms, "deshielding" the nuclei and shifting
the peak downfield.

The effects are cumulative so the presence of more electron withdrawing groups will produce a
greater deshielding and therefore a larger chemical shift, i.e.
These inductive effects are not only felt by the immediately adjacent atoms, but the deshielding
can occur further down the chain, i.e.

NMR signal -CH2-CH2-CH2Br

δ(ppm) 1.25 1.69 3.30
1.7. Hydrogen Bonding
Protons that are involved in hydrogen bonding (i.e.-OH or -NH) are usually observed over a
wide range of chemical shifts. This is due to the deshielding that occurs in the hydrogen bond.
Since hydrogen bonds are dynamic, constantly forming, breaking and forming again, there will
be a wide range of hydrogen bonds strengths and consequently a wide range of deshielding. This
as well as solvation effects, acidity, concentration and temperature make it very difficult to
predict the chemical shifts for these atoms.