Electron spin resonance spectroscopy

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B.V.LALITHA

YELAMARTY COLLEGE OF PHARMACY PHARMACEUTICAL ANALYSIS

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What is ESR???

It is an absorption spectroscopy. is concerned with the magnetic behaviour of spinning electrons. is a branch of absorption spectroscopy in which radiation having frequency in microwave region is absorbed by paramagnetic substance to induce 4/17/12

It

It

WHAT COMPOUNDS CAN WE ANALYZE??

Applicable to species with one or more unpaired electrons.

Free radicals Transition metal compounds

Useful for unstable paramagnetic compounds generated in situ.

Electro chemical oxidation or reduction.

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Spin:

A spin s = 1/2 is an intrinsic property of electrons, characterized by quantum number 1/2 the name suggests , spin was originally conceived as the rotation of the particle around some axis. spinning of charged particle produces a magnetic field.
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As

The

Principle of esr
ESR

spectra is given only by molecules having unpaired electrons.

The

unpaired electrons are excited to a high energy state under the magnetic field by the absorption of microwave . absence of magnetic field, only one spin state of electrons exists. 4/17/12

In

Then spin angular momentum quantum number will have 2 values of m s +1/2 and -1/2. Lower energy state will have spin magnetic moment aligned with field corresponding to quantum no ,m s = -1/2. High energy state will have spin magnetic moment opposed with field corresponding to quantum no, m s = +1/2.
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The quanta of incident microwave frequency induces transition between the two states of the unpaired electrons when the energy of the quanta(hv) coincide with energy level of separation:

between the two states resonance absorption of energy takes place. 4/17/12

 The

equation describing the absorption of microwave energy between two spin states is E = hv = gH
where:

is the energy difference between the two spin states . is Plancks constant is the microwave frequency is the proportionality 4/17/12 which is factor

h v

ESR SPECTROMETER
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SCHEMATIC DIAGRAM FOR INSTRUMENTATION OF ESR

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INSTUMENTATION
Source Magnetic Sample Magnet crystal

bridge or circulator

cavity system

detector
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SOURCE:

A)klystron:
Klystron

oscillator operates in microwave band region of 3cm wave length. It is a vacuum tube which can produce microwave oscillations. It offers microwave of 9500 MHz. B)Isolator: It minimises the vibrations in the 4/17/12 frequency of microwaves produced by

C)wavemeter:
To It

measure the microwave radiation.

is usually calibrated in frequency units(MHz) instead of wavelength.

D)Attenuator:
It

adjusts the level of microwave power incident upon the sample.

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MICROWAVE BRIDGE/CIRCULATOR:
It

is made up of hollow rectangular copper or brass tubing having silver or gold plating inside to produce highly conducting flat surface.

It consists of 4arms.
The

microwave radiations enter into arm3 spits equally into two waves travelling to 1 and 2.
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MAGIC-T

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SAMPLE CAVITY:
In

ESR spectrometer the resonant cavity contaning the sample. volume: 0.15 to 0.5 ml.

Sample In

case of high dielectric constant containing samples ,flat cells with thickness of 0.25mm and sample volume of 0.05 ml are used. most, dual sample cavities are
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In

MAGNETIC SYSTEM:
It

provides a homologous magnetic field can be varied from 0 to 500 gauss. field should be stable and uniform over the sample volume. stability can be achieved by energizing the magnet with highly
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The

The

Crystal detectors:
Commonly

used detector is silicon crystal which act as microwave rectifier. It converts microwave power in to direct current output. AUTO AMPLIFIER: By this signal undergoes narrow band amplification.
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Electron Spin Resonance Spectroscopy

Crystal detector

Isolator Klystron oscillator

Wave meter

circulato r Attenuator Resonant cavity

Klystron power supply

Automatic Frequency control

Magnet power supply

Magnet
Sweep unit

Scanning unit or sweeping magnetic current

Automatic recorder

Audio amplifier and phase sensitive detector

BLOCK DIAGRAM OF ESR SPECTROMETER

Oscilloscop e

Spectra:

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 The

total area covered by either absorptive or derivative curve is proportional to the number of unpaired electrons in the sample. order to calculate the number of electrons in an unknown sample , comparison is made with standard sample. widely used standard is 1,1,diphenyl-2-picrylhydrazyl free 4/17/12

In

Most

g-FACTOR

g- factor or splitting factor is a finger print of a molecule.

The g-factor is a unit less measurement of the intrinsic magnetic moment of the electron.

Value for free electron is 2.00232

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HYPERFINE SPLITTING
Nucleus

is charged particle having spin magnetic moment. , there are chances of interaction between spinning electrons and spinning nuclei . This interactions between the spinning electrons and adjacent spinning nuclei leading to multi lined spectra is called hyperfine splitting. 4/17/12

So

IN CASE OF HYDROGEN
external field + magnetic effect of proton +1/2 -1/2 -1/2 ms= -1/2 +1/ 2

External field m s = +1/2 No field

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APPLICATIONS OF ESR
Study

of free radicals of molecules in the

Investigation

triplet state
Study

of inorganic compounds such as study of catalysts and determination of oxidation state of metal eg: copper.
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Analytical applications:
Mn+2

ions can be measured and detected even when present in trace quantities. method is convenient method for determination of Vanadium in petroleum products.

ESR

In Biological systems:
o ESR has studied the presence of free 4/17/12

ESR in molecular biotechnology :

DNA:

ESR is used to investigate the nucleotide-centered free radicals in DNA, either produced by irradiation, or indirectly by other free radicals.

Activity of enzymes:
ESR

is used in the analysis of enzymatic activity of nitric oxide 4/17/12

Miscellaneous
Used

by archeologists for dating of teeth as radiations over long period of time creates free radicals in tooth enamel. sterilized foods have been examined to determine sample irradiated to what dose.
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Radiation

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