 Thenmr has become the

preeminent technique for

determining the structure of
organic compounds. it is the
only one for which a complete
analysis and interpretation of
the entire spectrum is normally
expected.
 The physical principles on which the NMR
methods are based.

 The nuclei of many elemental isotopes have a

characteristic spin (I).

 Some nuclei have integral spins (e.g. I = 1, 2, 3

....), some have fractional spins (e.g. I = 1/2,
3/2, 5/2 ....), and a few have no spin, I = 0 (e.g.
12C, 16O, 32S, ....).
 Isotopes of particular interest and use to
organic chemists are 1H, 13C, 19F and 31P, all
of which have I = 1/2.
Thefollowing features lead to the nmr
phenomenon:
 1. A spinning charge generates a magnetic field, as
shown by the animation on the right.

 The resulting spin-magnet has a magnetic moment ( μ)

proportional to the spin.
 2. In the presence of an external
magnetic field (B0), two spin states exist,
+1/2 and -1/2.
The magnetic moment of the lower energy +1/2 state is
aligned with the external field, but that of the higher
energy -1/2 spin state is opposed to the external field.
Note that the arrow representing the external field
points North.
 3. The difference in energy between the two
spin states is dependent on the external
magnetic field strength, and is always very
small. The following diagram illustrates that
the two spin states have the same energy
when the external field is zero, but diverge
as the field increases.
 Modern NMR spectrometers use
powerful magnets having fields of
1 to 20 T. Even with these high fields,
the energy difference between the two spin
states is less than 0.1 cal/mole.

For NMR purposes, this small energy difference (ΔE) is

usually given as a frequency in units of MHz (106 Hz),
ranging from 20 to 900 Mz, depending on the magnetic
field strength and the specific nucleus being studied.
 Strong magnetic fields are necessary for
NMR spectroscopy.
 Irradiation of a sample with radio
frequency (RF) energy corresponding
exactly to the spin state separation of a
specific set of nuclei will cause excitation
of those nuclei in the +1/2 state to the
higher -1/2 spin state. Note that this
electromagnetic radiation falls in the
radio and television broadcast spectrum.

 The energy calculation:
 Since the magnetic moment increases as the spin angular
momentum increase so
µ=ɤJ
Where ɤ is the proportionality constant which
magnitogyric ratio it is a characteristis property
of the nuclei
E=µβ β is the applied magnetic field
E= ɤJβ
Since J=(h/2π)I where I is the spin angular mom

E= ɤβI (h/2π)
 Then the energy difference
 = ɤβ(h/2π)=hѴ

Ѵ= ɤβ/2π
ω=2πѴ=Ѵ= ɤβ
This is lamor frequency
So we use two external magnetic field the first one
to increase the energy difference between the
two spin states and the other has the same
frequency of lamor by which the nucleus can
change its spin state
 Thereare two major
relaxation processes:-

1-Spin - lattice (longitudinal)

relaxation

2-Spin - spin (transverse)

relaxation
1-Spin - lattice relaxation
Nuclei in an NMR experiment are in a sample. The
sample in which the nuclei are held is called the
lattice. Nuclei in the lattice are in vibrational and
rotational motion, which creates a complex
magnetic field. The magnetic field caused by
motion of nuclei within the lattice is called the
lattice field. This lattice field has many components.
Some of these components will be equal in
frequency and phase to the Larmor frequency of
the nuclei of interest. These components of the
lattice field can interact with nuclei in the higher
energy state, and cause them to lose energy
(returning to the lower state). The energy that a
nucleus loses increases the amount of vibration and
rotation within the lattice (resulting in a tiny rise in
the temperature of the sample).
 The relaxation time, T1 (the average lifetime of
nuclei in the higher energy state) is dependant
on the magnetogyric ratio of the nucleus and the
mobility of the lattice. As mobility increases, the
vibrational and rotational frequencies increase,
making it more likely for a component of the
lattice field to be able to interact with excited
nuclei. However, at extremely high mobilities,
the probability of a component of the lattice field
being able to interact with excited nuclei
decreases.
2-Spin - spin relaxation

Spin - spin relaxation describes the interaction

between neighbouring nuclei with identical
precessional frequencies but differing magnetic
quantum states. In this situation, the nuclei can
exchange quantum states; a nucleus in the
lower energy level will be excited, while the
excited nucleus relaxes to the lower energy
state. There is no net change in the populations
of the energy states, but the average lifetime of
a nucleus in the excited state will decrease. This
can result in line-broadening.
 Chemical shift
 In nuclear magnetic resonance (NMR), the chemical
shift describes the dependence of nuclear
magnetic energy levels on the electronic
environment in a molecule.[1][2][3] Chemical shifts
are relevant in NMR spectroscopy techniques
such as proton NMR and carbon-13 NMR.
 The magnetic field at the nucleus is not equal to the
applied magnetic field; electrons around the nucleus
shield it from the applied field. The difference between
the applied magnetic field and the field at the nucleus is
termed the nuclear shielding.
 Consider the s-electrons in a molecule. They have spherical
symmetry and circulate in the applied field, producing a magnetic
field which opposes the applied field. This means that the applied
field strength must be increased for the nucleus to absorb at its
transition frequency. This upfield shift is also termed diamagnetic
shift.
 Electrons in p-orbitals have no spherical
symmetry. They produce comparatively
large magnetic fields at the nucleus, which
give a low field shift. This "deshielding" is
termed paramagnetic shift.
 Chemical shift is defined as nuclear
shielding / applied magnetic field.
Chemical shift is a function of the nucleus
and its environment. It is measured
relative to a reference compound. For 1H
NMR, the reference is usually
tetramethylsilane, Si (CH3)4.
 How many types of H ? Indicated by how
many groups of signals there are in the spectra .
 What types of H ? Indicated by the chemical
shift of each group
 How many H of each type are there? How
many H of each type are there? Indicated
by the integration (relative area) of the
signal for each group.
 What is the connectivity ?

Look at the coupling patterns. This tells you what

is next to each group
 Integration
 The area of a peak is proportional to the number
of H that the peak represents
 The integral measures the area of the peak
 The integral gives the relative ratio of the
number of H for each peak
 Coupling
 The proximity of other "n" H atoms on
neighbouring carbon atoms, causes the signals
to be split into "n+1" lines.
 This is also known as the multiplicity or splitting
of each signal.
The advantages of the NMR
In chemistry for the study of chemical
structure:
1- The one-dimensional NMR spectroscopy used to
study chemical bonds.
2- Two dimensional approaches have been
developed for the determination of the structure
of complex molecules like proteins.
3-Time domain NMR spectroscopy is used to study
molecular dynamics in solutions.
4- NMR of solid samples can help determine
molecular structures. There are NMR methods
for measuring diffusion coefficients.
 The Disadvantages of NMR
 1. we have lots of atoms and a lot of
extracted data from a system.
 2. This is good for the more accurate
determination of the structure, but not for
the availability of higher molecular
masses.
 3. the resolving power of NMR is less than
some other type of experiments (e.g.: X-
ray crystallography) since the information
got from the same material is much more
complex
 4. the highest molecular mass which
was examined successfully is just a
64kDa protein-complex
 5. there are lots of cases when from
a given data-set - a given type of
experiment - we could predict two or
more possible conformations, too
 6. unfortunately we are just able to
determine the degree of probability
of being of the protein segment in
the given conformation
 7. The cost of the experimental
implementation is increasing with
the higher strength and the
complexity of the determination