Attenuated total reflection mode

Fig. 8.9 Set-up for infrared measurements in attenuated total reflection mode on a planar model catalyst. The silicon ATR crystal has a top layer of SiC>2 which serves as the supported for the catalyst particles. In reality, the infrared beam undergoes 25 reflections with the surface in the crystal the evanescent waves protruding outside the crystal are used...

It has been suggested that the first step of reaction (6) may be the formation of a carboxylic species COOHads. Carboxyl radicals have indeed been observed by Zhu et al." for potentials lower than 0.65 V using Fourier Transform infrared Reflectance Absorption Spectroscopy with the Attenuated Total Reflection mode (ATR-FTtR). Moreover Anderson et al." made numerical simulation which indicated that the formation of an adsorbed carboxylic species was energetically more favorable. Here, it has to be noted that the electro-oxidation of CO being a stracture sensitive reaction (sensitive to the superficial stracture symmehy" and to the presence of surface defects) this species can be used to study the activity of a catalyst but also as a molecular probe to characterize the catalytic surface. ... 

In the present studies, a Fourier-transform infra-red spectrometer in attenuated total reflectance mode (FT-IR-ATR) was used to characterize the albuminated polymer membrane surface. FT-IR-ATR is a powerful surface analysis technique in which a spectrum of only a few micron thick surface layer is obtained. As albumin or enzymes were attached only on the surfaces of polypropylene, FT-IR-ATR technique was ideally suited for the their analysis. 

Alternatively, SFIRS can be done in the attenuated total reflection mode [341]. A gold film is evaporated onto a silicon hemicylinder. Vibrational modes of adsorbed halide ions have been detected [344],... 

Experimental studies have been few. Perhaps the most extensive study and certainly one of the few whose authors discussed their results in terms of wetting ideas was carried out by Johnson and Grannick (1991). They used Fourier transform infra-red spectroscopy in the attenuated total reflection mode to study adsorption of polystyrene from cyclohexane on to the native oxide of silicon. For relatively low relative molecular mass (43900) they found an increase in the adsorbed amount as the temperature was reduced towards the cloudpoint temperature their results (shown in figure 5.30) are consistent with... 

Fourier transform-infrared (FT-IR) spectroscopic studies on SO-SA complexation provides information that may be complementary to that of NMR and other techniques, namely, in particular, on the involvement of functional groups in intermolecular and intramolecular interactions. Attenuated total reflectance (ATR) IR spectroscopy has been used for the study of binding modes of cinchona alkaloid selectors either in solution [95] or in solid state [94], or directly on the CSP [96]. 

A majority of traditional NIR measurements are made on solid materials and these involve reflectance measurements, notably via diffuse reflectance. Likewise, in the mid-IR not all spectral measurements involve the transmission of radiation. Such measurements include internal reflectance (also known as attenuated total reflectance, ATR), external reflectance (front surface, mirror -style or specular reflectance), bulk diffuse reflectance (less common in the mid-IR compared to NIR), and photoacoustic determinations. Photoacoustic detection has been applied to trace-level gas measurements and commercial instruments are available based on this mode of detection. It is important to note that the photoacoustic spectrum is a direct measurement of infrared absorption. While most infrared spectra are either directly or indirectly correlated... 

FT Spectrometers FT spectrometers (Figure 3) differ from scanning spectrometers by the fact that the recorded signal is an interferogram [14] (see Chapter 6.2). They can be coupled to a microscope or macrochamber with an FPA detector. FT chemical imaging systems (CISs) are available for Raman, NIR, and IR spectroscopy. However, they can only be considered as research instruments. For example, most IR imaging systems are FT spectrometers coupled to microscopes. This type of spectrometer allows the acquisition of spectra in reflection, attenuated total reflection (ATR), or transmission mode. 

Nucleic acid biosensors based on optical modes of detection represent another common approach for generating analytical signals based on nucleic acid hybridization. The methods discussed herein are based on methods that are suitable for the study of materials on surfaces. There are a number of different optical methods that have been described, with the most common being attenuated total reflectance (ATR), total internal reflection fluorescence (TIRF) and surface plasmon resonance (SPR) [15]. All of these methods work... 

Attenuated total reflection FTIR is a well-established technique for obtaining absorbance spectra of opaque samples. The mode of interaction is unique because the probing radiation is propagated in a high index-of-refraction internal reflection element (IRE). The radiation interacts with the material of interest, which is in close contact with the IRE, forming an interface across which a nonpropagating evanescent field penetrates the surface of the material of interest to a depth in the order of one wavelength of the radiation. The electric field at the interface penetrates the rarer medium in the form of an evanescent field whose amplitude decays exponentially with distance into the rarer medium. 

The sample thickness in the DIT cells (25 pm) is very large in comparison with the usual thickness of samples for infrared transmission studies, and the cell itself is also thick (2.8 mm). Studies in the attenuated total reflectance (ATR) mode do not fit the experiment. For all these reasons, it was by no means certain that infrared studies could in fact be performed using the existing DIT cells. 

Fourier-transformed infrared spectroscopy (FT1R), either in the transmission mode(70), the grazing incidence reflection (GI) mode(7,5) or the attenuated total reflection (ATR) mode(7,2), has been the most widely used experimental tool for the characterization and structure determination of SA monolayers. GI-IR is especially useful in determining the molecular orientation in the film structures because it senses only the vibrational component perpendicular to the substrate surface(7,5). Polarized ATR-IR can also be used to study molecular orientation(7,77). McKeigue and Gula-ri(72) have used ATR-IR to quantitatively study the adsorption of the surfactant Aerosol-OT. 

The most commonly used technique for obtaining a spectrum is the attenuated total reflectance (ATR) method in the multiple internal reflectance (MIR) mode. In this method, the infrared beam is passed into a special crystal of a selenide (KRS-5). The angle of incidence is such that the beam will bounce along the crystal. A sample of the polyurethane is placed hard up against the crystal. The infrared just penetrates into the material before it continues down the crystal. A number of internal bounces are obtained along the crystal. Up to 25 reflectances are obtained from a 2 mm crystal. Figure 9.8 illustrates the infrared path in an ATR cell. 

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