PATEL SANJEEVKUMAR MSC SEM (2013-14) INORGANIC CHEMISTRY PAPER 3 RAMNIRANJAN JHUNJHUNWALA COLLEGE

INTRODUCTION
It is a branch of absorption spectroscopy in which radiation having frequency in microwave region is absorbed by paramagnetic substance to induce transition between magnetic energy level of electron with unpaired spins. Magnetic energy splitting is done by applying a static magnetic field. Absorption spectroscopy, operate at microwave frequency 104 106MHz. It is also called as electron paramagnetic resonance spectroscopy.

ESR Phenomenon is shown by:

Atoms having odd number of electrons. Ions having partly filled inner electron shells Other molecules that carry angular momentum of electronic origin. Free radicals having unpaired electrons. Molecules with paired electrons and zero magnetic field.

In ESR the energy levels are produced by the interaction of magnetic moment of an unpaired electron in a molecule ion with an applied magnetic field. The unpaired electrons are excited to a high energy state under the magnetic field by the absorption of microwave radiations. The excited electron changes its direction of spin and relaxes in to the ground state by emitting its energy.

PRINCIPLE

The transition between two different energy levels takes place by absorbing a quantum of radiation of frequency in the microwave region. Microwave absorption is measured as a function of the magnetic field by ESR Spectroscopy. The energy of transition is given by,

E = hv = gH

E is the energy difference between the two spin states . h is Plancks constant v is the microwave frequency g is the proportionality factor which is a function of electrons environment. H is the applied magnetic field. is the electron Bohr magneton, Where = eh/4mc

INSTRUMENTATION
Source Circulator or Magic -T Sample Cavity Magnet System Crystal Detector Auto amplifier and Phase sensitive Detector Oscilloscope and Pen Recorder

 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 minimizes the vibrations in the frequency of microwaves produced by klystron. It isolates the narrow range of microwaves C)wavemeter: To measure the microwave radiation. It is usually calibrated in frequency units(MHz) instead of wavelength. D)Attenuator: It adjusts the level of microwave power incident upon the sample. It is similar to filter in spectrophotometer.

MAGIC T OR 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 arm1. Arm2 is connected to resonant cavity and sample. Arm3 having terminating load which absorbs any power reflected from detector. Arm4 is attached to the detector.

SAMPLE CAVITY:
In ESR spectrometer the resonant cavity contaning the sample. Sample volume: 0.15 to 0.5 ml.

It is constructed in such a way to maximize the applied magnetic filed along the sample dimension.
In most, dual sample cavities are used for the simultaneous observation of sample and reference.

MAGNETIC SYSTEM:
sample cavity is placed between the pole pieces of an electromagnet .
It provides a homologous magnetic field can be varied from 0 to 500 gauss. The stability can be achieved by energizing the magnet with highly regulated power supply.

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.

OSCILLOSCOPE: Signal from detector and sweep unit is recorded by oscilloscope.

Presentation of ESR Spectrum

The ESR spectrum is obtained by plotting intensity against the strength of a magnetic field. The total area covered by either the absorption or derivative curve is proportional to the number of unpaired electrons in the sample. In order to find out the number of electron in an unknown sample, comparison is made with a standard sample having a known number of unpaired electrons and possessing the same line shape as the unknown. The most widely used standard is 1,1-diphenyl-2-picrylhydrazyl free radical(DDPH)

Hyperfine Splitting
Hyperfine splitting in ESR spectra is similar to the chemical shift in the NMR spectra. It is caused by the interaction between the spinning electrons and adjacent spinning magnetic field. When a single electron is interacting with one nucleus the number of splitting will be 2I+ 1, where I is the spin quantum number of nucleus. In general a single electron interacts magnetically with n equivalent nuclei the electron signal is split up to (2nI+1) multiplet.

Determination of g value
The best method of measurement of g value is to measure the field separation between the center of the unknown spectrum and that of reference substance whose g value is already known. DDPH is generally used a standard whose g value is 2.0036. In the spectrometer standard sample is placed along with the unknown sample in the same chamber of dual cavity cell. The spectrum will show signals with a filed separation of H. The g value of unknown sample is given

g=g s(1-H/H)
H is resonance frequency H is field separation between standard and sample.

APPLICATIONS
Study of Free radicals
Even in very low concentrations also we can study the free radicals by using ESR spectroscopy. Structure of organic and inorganic free radicals can be identified. Investigation of molecules in the triplet state. The ESR studies may be used in knowing the exact structures of solvated metal ions. ESR is used in the study of catalysts. ESR is used in the determination of oxidation state of metal. eg. Copper is found to be divalent in copper protein complexes whereas it is found to be monovalent in some biologically active copper complexes. Like, Spin labels, Structural determination, and Reaction velocities and reaction mechanisms

Study of inorganic compounds

Analytical applications: Mn+2 ions can be measured and detected even when present in trace quantities. ESR method is convenient method for determination of Vanadium in petroleum products. Biological systems: ESR has studied the presence of free radicals in healthy and diseased tissues. Functioning of most of the oxidative enzymes can be conformed.

REFERENCE
P. Atkins, T. Overton, J. Rourke, M. Weller, F. Armstrong, "Inorganic Chemistry", Fourth Edition, OUP, 2006 Chatwal G.R, Anand S.K. Instrumental Methods Of Chemical Analysis,(Analytical Chemistry) , 5th Revised And Expended Edition Reprint 2005

Willard Hobart H. Et Al, Instrumental Methods Of Chemical Analysis, 7th Edition,

www.slideworld.com/pptslides.aspx/ESR-spectroscopy

Analytical applications:
Mn+2 ions can be measured and detected even when present in trace quantities. ESR method is convenient method for determination of Vanadium in petroleum products. ESR can also be used to estimate Cu(II), Cr(II), Gadolinium(III), Fe(III) and Ti(III). The ESR spectroscopy has been used to estimate polynuclear hydrocarbons, which are first, converted in to radical cations and then absorbed in the surface of an activated silica-alumina catalyst.

Biological systems:
ESR has studied the presence of free radicals in healthy and diseased tissues. Functioning of most of the oxidative enzymes can be