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The boundary between the two types of methods is not a sharp one, as procedures have been developed that are suitable for obtaining both types of information (eg Raman spectroscopy) A change in the amplitude of the excitation radiation occurs especially during the non-elastic interaction of photons with a substance, connected with the transfer of a defined quantum of energy; methods measuring this change are termed spectroscopic methods Relatively, the smallest energy quantum corresponds to the energy difference between two states differing in the spin of the unpaired electron, whose degeneracy has been removed by the action of an external magnetic field These processes are studied by methods termed electron spin {paramagnetic) resonance, ESR (or EPR) Of substances with an unpaired electron, transition metal compounds and free radicals can be studied.



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Electrochemistry is concerned mainly with the study of organic radicals formed during redox processes at electrodes or in subsequent chemical reactions, often in non-aqueous solvents With the ESR method, radicals in electrolytes at concentrations as low as 10~8 mol dm"3 can be detected in a wide lifetime range Very unstable radicals can also be studied indirectly, by conversion to a more stable radical by the spin-trapping method ESR measurements can readily be carried out in situ, and the term SEESR (simultaneous electrochemical ESR) is sometimes used The shape and hyperfine structure of the ESR lines also yields information on the structure of radicals, ion association, solvation, etc In practice, even the information on the mere fact that the product or intermediate in an electrode process is a radical is valuable and can be of great importance in the discussion of the mechanism of the electrode process.

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The ESR method has been quite extensively used in electrochemistry in the study of substances in the electrolyte phase, while less attention has been paid to the study of paramagnetic sites on the electrode itself Electrochemically generated products can be readily characterized by in situ measurement of their absorption spectra in the ultraviolet and visible regions Optically transparent electrodes (OTEs) prepared from thin layers.

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331 of metals or semiconductors on glass or polymer supports play a key role in these investigations. Alternatively, very fine, transparent metal mesh can be used as an electrode. Absorption spectra can be advantageously studied by means of a working electrode in a thin-layer system (with a thickness of about 0.05-0.5 mm), where electrolysis of all the bulk electrolyte lasts only a few seconds (thin-layer spectroelectrochemistry). Under certain conditions, the product of the electrode process can be studied by using electrochemically generated luminescence. This phenomenon occurs when the reactants generated at the electrode or in a subsequent chemical reaction have such high free energy that they can interact to form products in electronically excited states. If these states are capable of radiative relaxation, then they can be identified according to their luminescence spectra. Reactants for luminescence studies can be generated in two ways, either subsequently on a single electrode polarized, e.g. by a rectangular or sinusoidal voltage, or simultaneously, e.g. at a rotating ring disk electrode. Electrochemically generated luminescence finds wide application in the study of organic substances and radicals and also of some complexes of transition metals (for example, Ru(bpy) 3 2+ , where bpy = bipyridine). This method is especially useful in determining the mechanisms of electrochemical processes. The most important methods used in in-situ studies of electrode surfaces are various modifications of reflection spectroscopy in the ultraviolet through infrared regions. For electrochemical applications, the specular reflection (at smooth electrode surfaces) is much more important than the diffuse reflection from matt surfaces. The reflectivity, R, of the electrode/ electrolyte interface is defined by: R=I/I0 (5.5.41)

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