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Spectroscopy

It is the study of interaction between matter and energy.


When energy is radiant on the matter each matter, substance, atom,
molecules or ion etc behave distinctly and in characteristic manner.
The matter can absorb energy, it can reflect energy, it can allow the
energy to pass through, any two processes or all the three processes
can occur. How the matter will behave will also depend upon type of
energy. The energy could be light energy, heat energy, magnetic
energy etc. The scientific study of all its implication involved with its
application in the study of molecular shape and size uses the
technique of spectroscopy. The techniques of nuclear magnetic
resonance, infrared spectroscopy, and ultraviolet spectroscopy are
very useful and most modern.

Nuclear Magnetic Resonance Spectroscopy.

The nuclei of many elemental isotopes have a characteristic


spin. Some isotopes of our interest have half spin. These isotopes are
1H, 13C, 19F and 31P, all of which have I = 1/2. Our discussion of NMR

will be limited to these and other having I = 1/2 nuclei.

Since these nuclei are charged positively the spinning nuclei


act like tiny bar magnet and interact with external magnetic field. In
the absence of external field, spins of magnetic nuclei are oriented
randomly. In the presence of external magnetic field these nuclei
orient themselves specifically. A spinning nucleus can orient so that
its own tiny magnetic field is either aligned with or against external
magnetic field.

The two orientations do not have the same energy.


However the difference in the energy is very small and depends
upon external magnetic field applied. If these nuclei, under the
influence of external magnetic field, are subjected to electromagnetic
radiation of proper frequency, energy is absorbed and nuclei of lower
energy state “spin- flip” to higher energy state.
When this spin-flip occurs, the magnetic nuclei are in resonance
with applied radiation. The exact frequency necessary for resonance
depends upon the strength of external magnetic field and the
identity of the nuclei. A NMR spectrometer can detect the energy
absorption of a nucleus in resonance.

In NMR spectroscopy the frequency of electromagnetic


radiation is held constant while the magnetic field is varied.

Formation NMR Spectrum

When an external magnetic field is applied to a


molecule the electrons in the molecule set up their own magnetic
field which is in the opposite direction of applied magnetic field.
Hence nucleus experience slightly less magnetic field than the
applied field. This phenomenon can be called as shielding of nuclei
from full effect of external magnetic field.

Each specific nucleus in a molecule is in slightly different


electronic environment. Each nucleus is shielded to a slightly
different extant and the effective magnetic field is different for each
nucleus. This difference in the magnetic field can be detected by the
NMR spectroscope and distinct NMR signal is available from the
instrument. Thus a complete spectrum of all the molecules in a
sample and all atoms in the molecule is possible.

The instrument will show chart of one atom of a nucleus at


a time .i.e. a different chart is available from the instrument for each
atom of nucleus. To analyze one molecule of C3H8, two sets of chart
will be given out by the NMR spectroscope one for hydrogen and one
for carbon.

NMR spectrum:
An NMR spectrum is a graph of magnetic field strength
absorbed by hydrogen atom (carbon atom also possible) of a given
compound at given frequency. The field strength is marked as parts
per million (ppm) increases from left to right.

(Although number decreases) and is indicated by “∗”. Left part of the


graph is called down field and right part is called up field. There
should be a peak at “O” ppm (not present in the graph) which is due
to reference compound.

The reference compound is tetra-methylsilane which is used to


calibrate the instrument.
Characteristics of NMR Spectrum

* Each peak represents chemically equivalent hydrogen.

* Splitting of peaks is created by neighboring hydrogen.

* Equivalent hydrogen has equal chemical shift.

* Area under the peak is proportional to number of


hydrogen

represented by the peak.

Number of peaks in the spectrum

Each peak represents a different environment for hydrogen


atoms in the molecule. In the methylpropanoate spectrum above,
there are three peaks because there are three different environments
for the hydrogens.

Remember that methyl propanoate is CH3CH2COOCH3. The


hydrogen in the CH2 group is obviously in a different environment
from those in the CH3 groups. The two CH3 groups aren't in the same
environment either. One is attached to a CH2 group, the other to
oxygen.

In the molecule there are three hydrogen atoms attached to


1st carbon. All the hydrogen atoms attached to 1st carbon are in the
same environment hence there is no separate peak for these
hydrogen. Similarly there is no separate peak for two hydrogen
atoms attached to next carbon and the three hydrogen atoms attached
to last carbon

Spin splitting of peaks

It is noticeable that there are some sub-peaks or peaks


have split. This splitting represents neighborhood carbon with
hydrogen atom. The amount of splitting tells you about the number
of hydrogen attached to the carbon atom or atoms next door. The
number of split-peaks in a cluster is one more than the number of
hydrogen attached to the next door carbon(s).

This is called as n+1 where ‘n’ is number hydrogen that is not


chemically equivalent

One peak -------- no hydrogen attached to next carbon

Doublet ------- one hydrogen attached to next carbon

Triplet -------- Two hydrogen attached to neighboring


carbon

Quartet -------- Three hydrogen attached

In the spectrum shown above the CH3 group at about 4.1


ppm shows no splitting. It means it does not have any carbon with
hydrogen attached to it. At about 2.24 ppm it shows triplet which
means it has a CH2 neighbor and lastly at about 1 ppm it shows a
quartet which means its neighbor is CH3

Chemical Shift
Chemical shift is the difference in the resonance frequency of the
hydrogen in the sample and resonance frequency of reference
compound such as tetramethylsilane.

Hydrogen which are not differentiable from other


hydrogen by way of the location on carbons are called enantiotropic.
As explained above they are represented by the same peak on nmr
spectrum. The chemical shift of all enantiotropic hydrogen is same.

The chemical shift is a constant value irrespective of


operating frequency of the instrument. The constant values of
chemical can be used to detect the alkyl group, alcohol group and
some other group. Chemical shift for R – CH3 is 0.7-0.16 ∗, for -O-
CH3, ∗ and for R-CH2 2.0-2.9 ∗.

Area under the peak

Areas under the peak are in the same ratio as the ratio of
number of hydrogen atom causing each peak. NMR spectrometers
have a device which draws another line on the spectrum called an
integrator trace (or integration trace). You can measure the relative
areas from this trace. Height of integrated curve is proportional Area
under the peak. The greater height of the peak does not mean greater
area under the peak but greater height of integrated curve mean
greater area under the peak.

An instrument known as digital tracer records the number


which corresponds to rise in line. The exact number of hydrogen is
not given by integral trace or the digital trace. It is the ratio of
hydrogen from one peak to another peak is determined.

Electron Shielding
Electron shielding phenomenon as already discussed is the
reduction of external magnetic field due magnetic effect of electron
surrounding the nucleus. The resonance magnetic field strength
increases to cause spin flip due to shielding effect. Thus there is a
lateral shift of the peak on the NMR spectrum.

Electron withdrawing group or electron donating also effect


lateral shift as these group increases or decreases electron density on
the hydrogen. Hence lateral shift can also be used to determine the
presence of electron withdrawing group and electron donating group
although not very accurately.

The discussion so far was based on the hydrogen atom.


However 13carbon also behave in the same manner. In fact the NMR
spectrum properties of hydrogen and 13 carbon are very much
similar.

It should be noted that all nuclei with odd atomic


number or mass will show NMR spectrum. The advantage of NMR
technology is that it requires very little energy, a very tiny sample can
be used for testing and it is nondestructive testing.

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