Radiation, electromagnetic refraction

In the second broad class of spectroscopy, the electromagnetic radiation undergoes a change in amplitude, phase angle, polarization, or direction of propagation as a result of its refraction, reflection, scattering, diffraction, or dispersion by the sample. Several representative spectroscopic techniques are listed in Table 10.2. 

Specular reflection of electromagnetic radiation at the (electrochemical) interface is generally described by Fresnel equations. Supposing the most simple case that both the electrolyte and electrode are transparent and differ only in their refractive indexes, nx and n2, the reflectivity for normal incidence of the radiation equals ... 

Electromagnetic radiation has its origins in atomic and molecular processes. Experiments demonstrating reflection, refraction, diffraction and interference phenomena show that the radiation has wave-like characteristics, while its emission and absorption are better explained in terms of a particulate or quantum nature. Although its properties and behaviour can be expressed mathematically, the exact nature of the radiation remains unknown. 

Theory The initial understanding of the refraction of light dates back to Maxwell s study of electromagnetic radiation. Ernst Abbe invented the first commercial refractometer in 1889 and many refractometers still use essentially the same design. 

Interactions with electromagnetic radiation determine the UV, IR, and NMR spectra, refractive index, etc. For such properties, conjugated systems, including aromatic systems, are particularly significant. 

In diffuse reflection spectroscopy, the spectrometer beam is reflected from, scattered by, or transmitted through the sample, whereas the diffusely scattered light is reflected back and directed to the detector. The other part of the electromagnetic radiation is absorbed or scattered by the sample [124,125]. Changes in band shapes or intensity as well as signal shifts can be affected by morphological and physicochemical properties of the sample or combinations thereof (e.g., chemical absorptions, particle size, refractive index, surface area, crystallinity, porosity, pore size, hardness, and packing density [126]). Therefore, NIR diffuse reflection spectra can be interpreted in dependence of various physical parameters [127]. 

The effect of electromagnetic radiation on matter is to induce a dipole. In a transparent dielectric medium, only the velocity of electromagnetic radiation is reduced, depending on the refractive index of the medium, which is determined by its density. The propagation constant of electromagnetic waves is given by... 

There are numerous properties of materials which can be used as measures of composition, e.g. preferential adsorption of components (as in chromatography), absorption of electromagnetic waves (infra-red, ultra-violet, etc.), refractive index, pH, density, etc. In many cases, however, the property will not give a unique result if there are more than two components, e.g. there may be a number of different compositions of a particular ternary liquid mixture which will have the same refractive index or will exhibit the same infra-red radiation absorption characteristics. Other difficulties can make a particular physical property unsuitable as a measure of composition for a particular system, e.g. the dielectric constant cannot be used if water is present as the dielectric constant of water is very much greater than that of most other liquids. Instruments containing optical systems (e.g. refractometers) and/or electromechanical feedback systems (e.g. some infra-red analysers) can be sensitive to mechanical vibration. In cases where it is not practicable to measure composition directly, then indirect or inferential means of obtaining a measurement which itself is a function of composition may be employed (e.g. the use of boiling temperature in a distillation column as a measure of the liquid composition—see Section 7.3.1). 

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