Diffuse reflectance, discussion

The problems discussed above may be circumvented by eliminating the mobile phase before measuring the spectra of the eluites, as first demonstrated by Shafer et al. [379] for pSFC-FTIR. Each eluite was deposited on a moving glass plate, on which a layer of powdered KC1 or KBr had been laid down from methanol slurry for diffuse reflectance spectroscopy (SFC-DRIFTS). Solvent elimination SFC-FTIR after deposition of the eluites on to a moving ZnSe substrate is quite straightforward the window is moved to the... 

While this is not the place for a complete description of the theory, uses, and ramihcations of all possible processing treatments that can be applied to chemical imaging data, the majority of NIR chemical images recorded to date have been obtained from solid or powder samples, measured predominantly by diffuse reflectance. As such, the following discussions may serve as a general outline of the more common procedures and their applications to these types of imaging data. 

The details in the CO response continue to be the subject of many discussions and a full explanation will need further studies. These can include spectroscopy studies such as diffuse reflectance transform infrared spectroscopy (DRIFT), which can be performed under realistic conditions [43,44], and theoretical modeling [45]. However it seems likely that not only hydrogen gives rise to charged or polarized complexes on the insulator surface. Equation (2.3) may now be written as... 

The dielectric function of a metal can be decomposed into a free-electron term and an interband, or bound-electron term, as was done for silver in Fig. 9.12. This separation of terms is important in the mean free path limitation because only the free-electron term is modified. For metals such as gold and copper there is a large interband contribution near the Frohlich mode frequency, but for metals such as silver and aluminum the free-electron term dominates. A good discussion of the mean free path limitation has been given by Kreibig (1974), who applied his results to interpreting absorption by small silver particles. The basic idea is simple the damping constant in the Drude theory, which is the inverse of the collision time for conduction electrons, is increased because of additional collisions with the boundary of the particle. Under the assumption that the electrons are diffusely reflected at the boundary, y can be written... 

An approach widely used by atmospheric scientists is to infer the imaginary part of the refractive index k from measurements of the absorption coefficient a of particulate samples. Diffuse reflection, the photoacoustic effect, and integrating plates have been used for determining absorption even in the presence of considerable scattering these methods are discussed briefly in the following section. The relation (2.52) between a and k, a - 4nk/, is, of course, strictly valid only for homogeneous media. But under some circum-... 

M(lI)AlSn-LDHs with M(II) being Mg, Ni or Co were synthesized by a coprecipitation method. The influence of Sn on the thermal transformations and redox properties were investigated in detail using XRD, TG/DTA, SEM, TPR, 1 l9Sn-MAS NMR and UV-visible diffuse-reflectance (DR) spectroscopy methods. Some of these samples calcined at 450 °C were tested as catalysts in the partial oxidation of methanol (POM) reaction. In this paper we discuss briefly the effect of Sn-incorporation on the structural features and reducibility of CoAI-LDH. The catalytic performance of Co-spinel microcrystallites derived from CoAl-, and CoAlSn-LDHs was also evaluated. 

More recently, the need to analyze vinyl silane on an aluminum hydroxide (alumina trihydrate) substrate has arisen. The silanized aluminum hydroxide substrate system was investigated to determine whether quantitative diffuse reflectance measurements were practical for routine control of the vinyl silaniz-ation process. In this paper, we discuss a method to quantify the amount of silane adsorbed on the aluminum hydroxide substrate. 

Conventionally, in IR spectroscopy the measured absorptions are caused by the fundamental vibrations of the atoms within a molecule. In many cases, important information can be obtained by examining the overtones of these fundamental vibrations. This can be done in the transmission mode, but elegant work using diffuse reflectance spectroscopy is discussed by Klier. 

As illustrated by the examples discussed here, the use of FT spectrometers for the observation of surface structures is favored by situations in which the flux of radiation coming from the sample is very low or the data acquisition time is limited. Such cases arise in transmission spectroscopy using strongly absorbing or scattering samples, specular and diffuse reflectance spectroscopy from opaque samples, and emission spectroscopy from low temperature sources. FT spectroscopy is also well suited for observing the dynamics of surface species during adsorption, desorption, and reaction. 

Some of the pre-treatment methods discussed below will be illustrated using a set of NIR diffuse reflectance spectra. For reference, the uncorrected NIR spectra are shown in Figure 8.3. 

The simplifying assumptions that permit us to consider only specular reflections are no longer met when the wall surfaces contain features that are comparable in size to the wavelength of the sound. In this case, the reflected sound will be scattered in various directions, a phenomenon referred to as difjusion. The source image model cannot be easily extended to handle diffusion. Most auralization systems use another geometrical model, called ray tracing [Krokstad et al., 1968], to model diffuse reflections. A discussion of these techniques is beyond the scope of this paper. 

Hamada et al. 1992 Saito et al. 1992), this increase of absorption is caused by high-frequency conductivity of the free carriers in metallic nanotubes. Relative intensities of the spectra of Fig. 11.7 we have found as a result of the diffuse reflection measurements of powders at low wavenumbers. The discussed above Drude approximations of the low-energy part of the absorption spectra are shown by dashed curves in Fig. 11.7. Comparison of the spectra 1 and 2 shows that hydrogenation decreases high-frequency conductivity of the SWNTs by one order of magnitude. 

In this chapter, empirical rate constants were determined by following the loss of tensile strength and the decrease in diffuse reflectance of a rag and a newsprint paper buffered over a range of pH values. From the results of these experiments, the influence of acidity on both the atmospheric oxidation process and the oxygen-independent process was determined. Before describing the results of these experiments, the methodology employed to obtain the empirical rate constants will be discussed. 

A number of experimental alternatives to traditional IR transmission spectroscopy are suitable for overcoming some of these complicating experimental factors. In the technique of diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) (Hartauer et al. 1992 Neville et al. 1992) the sample is dispersed in a matrix of powdered alkali halide, a procedure which is less likely to lead to polymorphic transformations or loss of solvent than the more aggressive grinding necessary for mull preparation or pressure required to make a pellet (Roston et al. 1993). For these reasons, Threlfall (1995) suggests that DRIFTS should be the method of choice for the initial IR examination of polymorphs. He has also discussed the possible use of attenuated total reflection (ATR) methods in the examination of polymorphs and provided a comparison and discussion of the results obtained on sulphathiazole polymorphs from spectra run on KBr disks, Nujol mulls and ATR. 

Spectroscopy. - In the following paragraphs we discuss how various spectroscopy tools have been used to illuminate the rich surface chemistry of supported polynuclear metal complexes. These methods include infrared (both diffuse reflectance and transmission), ultraviolet and visible (UV-Vis), x-ray photoelectron spectroscopy (XPS), and x-ray absorption, near edge spectroscopy s (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy s. 

The adsorption property was measured by a static method at 30 °C with a conventional volumetric apparatus as well as by the temperature programmed desorption (TPD) method. The details of the pretreatment and adsorption procedures were shown in Results and Discussion section. Metal-loaded zeolite samples were characterized by XRD, diffuse reflectance UV-Vis spectroscopy (DRS) and electron spin resonance (ESR). 

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