Spectroscopic methods reflectance spectroscopy

Table 5-42. Other spectroscopic methods Reflectance spectroscopy.

Further structural information is available from physical methods of surface analysis such as scanning electron microscopy (SEM), X-ray photoelectron or Auger electron spectroscopy (XPS), or secondary-ion mass spectrometry (SIMS), and transmission or reflectance IR and UV/VIS spectroscopy. The application of both electroanalytical and surface spectroscopic methods has been thoroughly reviewed and appropriate methods are given in most of the references of this chapter. 

In the preceding section, we presented principles of spectroscopy over the entire electromagnetic spectrum. The most important spectroscopic methods are those in the visible spectral region where food colorants can be perceived by the human eye. Human perception and the physical analysis of food colorants operate differently. The human perception with which we shall deal in Section 1.5 is difficult to normalize. However, the intention to standardize human color perception based on the abilities of most individuals led to a variety of protocols that regulate in detail how, with physical methods, human color perception can be simulated. In any case, a sophisticated instrumental set up is required. We present certain details related to optical spectroscopy here. For practical purposes, one must discriminate between measurements in the absorbance mode and those in the reflection mode. The latter mode is more important for direct measurement of colorants in food samples. To characterize pure or extracted food colorants the absorption mode should be used. 

It is only since 1980 that in situ spectroscopic techniques have been developed to obtain identification of the adsorbed intermediates and hence of reliable reaction mechanisms. These new infrared spectroscopic in situ techniques, such as electrochemically modulated infrared reflectance spectroscopy (EMIRS), which uses a dispersive spectrometer, Fourier transform infrared reflectance spectroscopy, or a subtractively normalized interfacial Fourier transform infrared reflectance spectroscopy (SNIFTIRS), have provided definitive proof for the presence of strongly adsorbed species (mainly adsorbed carbon monoxide) acting as catalytic poisons. " " Even though this chapter is not devoted to the description of in situ infrared techniques, it is useful to briefly note the advantages and limitations of such spectroscopic methods. 

Many important heterogeneous catalytic reactions occur at the interface between a solid catalyst and liquid or liquid-gas reactants. Notwithstanding the importance of solid-catalyzed reactions in the presence of liquid reactants, relatively little attention has been paid to spectroscopic methods that allow researchers to follow the processes occurring at the solid-liquid interface during reaction. This lack can be explained in part by the fact that there are only a few techniques that give access to information about solid-liquid interfaces, the most prominent of them being attenuated total reflection infrared spectroscopy (ATR-IR) and X-ray absorption fine structure (XAFS) spectroscopy. 

One indication of the developing interest in PATs in the pharmaceutical area is the number of book chapters and review articles in this field that have appeared in the last few years. Several chapters in The Handbook of Vibrational Spectroscopy3 are related to the use of various optical spectroscopies in pharmaceutical development and manufacturing. Warman and Hammond also cover spectroscopic techniques extensively in their chapter titled Process Analysis in the Pharmaceutical Industry in the text Pharmaceutical Analysis.4 Pharmaceutical applications are included in an exhaustive review of near-infrared (NIR) and mid-infrared (mid-IR) by Workman,5 as well as the periodic applications reviews of Process Analytical Chemistry and Pharmaceutical Science in the journal Analytical Chemistry. The Encyclopedia of Pharmaceutical Technology has several chapters on spectroscopic methods of analysis, with the chapters on Diffuse Reflectance and Near-Infrared Spectrometry particularly highlighting on-line applications. There are an ever-expanding number of recent reviews on pharmaceutical applications, and a few examples are cited for Raman,7 8 NIR,9-11 and mid-IR.12... 

For the investigator who wants to study electrode processes at depth, a number of more physically oriented methods are available, such as double layer capacitance measurements19 rotating disc and ring disc techniques 25 and radio-. active tracer methods 40a Spectroscopical methods in conjunction with optically transparent electrodes can be used for the study of intermediates 40b), as can also total reflectance spectroscopy 40c). 

Simple and rapid spectroscopic methods, such as front-face fluorescence, attenuated total reflectance Fourier-transform infrared and nuclear magnetic resonance spectroscopies, have a great potential for investigation of the structure of fats in dairy products and of the relation between structure and texture. Although fluorescence, infrared and NMR spectroscopies are techniques, the theory and methodology of which have been exploited extensively in studies in both chemistry and biochemistry, the usefulness of these spectroscopies for molecular studies has not been yet fully recognized in food science. Fluorescence, infrared and NMR spectroscopies coupled... 

Raman spectroscopy can provide additional information in favorable cases. Diffuse-reflectance, emission, photoacoustic, and other related spectroscopic methods also offer potential advantages, particularly in ease of sample preparation, but transmission methods are preferred when they can be used and quantitative comparisons are sought (2 4). ... 

In order to improve the fuel utilization in a Direct Alcohol Fuel Cell (DAFC) it is important to investigate the reaction mechanism and to develop active electrocatalysts able to activate each reaction path. The elncidation of the reaction mechanism, thus, needs to combine pnre electrochemical methods (cyclic voltammetry, rotating disc electrodes, etc.) with other physicochemical methods, such as in situ spectroscopic methods (infrared and UV-VIS" reflectance spectroscopy, or mass spectroscopy such as EQCM, DEMS " ), or radiochemical methods to monitor the adsorbed intermediates and on line chromatographic techniques"" to analyze qnantitatively the reaction products and by-products. 

The increasing application of spectroscopic methods in electrochemistry has characterized the last decade and marked the beginning of new developments in electrochemical science [1]. Among these methods, in-situ infrared spectroscopy provides a very useful tool for characterizing the electrode-solution interface at a molecular level. First in-situ infrared (IR) electrochemical measurements were performed in 1966 [2] using the internal reflection form [3]. However, problems in obtaining very thin metal layers on the surface of the prisms used as IR windows, delayed the extensive application of in-situ IR spectroscopy until 1980, when the method was applied in the external reflection form [4]. The importance of this step does not need to be emphasized today. 

In this context, one should bear in mind that the crystal structure may not exactly reflect the situation in solution however, it represents one possible low-energy conformation of the SO-SA complex. Other spectroscopic methods like NMR and FT-IR spectroscopy have been shown to be very helpful to study SO-SA complexation in solution and to verify the binding mechanisms found in the solid state. In this context circular dicroism spectroscopy should also be of high value. 

The reaction of water with low-loaded [Ru(bpy)3] + entrapped in zeolite Y has been reported [152]. Since translational mobility of the Ru molecules cannot occur in the zeolite, the multimolecular degradation step observed in solution is no longer possible. Instead, O2 was found to be formed from the reaction of [Ru(bpy)3] with water. It was possible to examine the evolution of this reaction at various pHs by spectroscopic methods, such as EPR, diffuse reflectance and Raman spectroscopy. Figure 30 shows the evolution of the diffuse reflectance spectra after exposure of Ru(bpy)3 +-zeolite Y to water at pH 7 [152]. Trace e is the spectrum of the... 

Surface analytical techniques. A variety of spectroscopic methods have been used to characterize the nature of adsorbed species at the solid-water interface in natural and experimental systems (Brown et al, 1999). Surface spectroscopy techniques such as extended X-ray absorption fine structure spectroscopy (EXAFS) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) have been used to characterize complexes of fission products, thorium, uranium, plutonium, and uranium sorbed onto silicates, goethite, clays, and microbes (Chisholm-Brause et al, 1992, 1994 Dent et al, 1992 Combes et al, 1992 Bargar et al, 2000 Brown and Sturchio, 2002). A recent overview of the theory and applications of synchrotron radiation to the analysis of the surfaces of soils, amorphous materials, rocks, and organic matter in low-temperature geochemistry and environmental science can be found in Fenter et al (2002). 

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