Subtractive Fourier-transform

Figure 4. Magnitudes of the phase-shift subtracted Fourier transform of calcite-rich bituminous coal (A), the Fust seam lignite (B), and calcium acetate (C).

QCMB RAM SBR SEI SEM SERS SFL SHE SLI SNIFTIRS quartz crystal microbalance rechargeable alkaline manganese dioxide-zinc styrene-butadiene rubber solid electrolyte interphase scanning electron microscopy surface enhanced Raman spectroscopy sulfolane-based electrolyte standard hydrogen electrode starter-light-ignition subtractively normalized interfacial Fourier transform infrared... 

Dc correction is a process by which the contribution of the receiver dc is omitted from the FID. The dc level is generally determined by examining the last (one-fourth) portion of the FID (tail), which is more likely to have the maximum dc contribution of the receiver. The level is then subtracted automatically from each FID of the data set before Fourier transformation. 

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. 

For infrared spectroscopy, 20-50 mg of the cobalt-exchanged zeolite was pressed into a self-supporting wafer and placed into an infrared cell similar to that described by Joly et al. [21], Spectra were recorded on a Digilab FTS-50 Fourier-transform infrared spectrometer at a resolution of 4 cm-i. Typically, 64 or 256 scans were coadded to obtain a good signal-to-noise ratio. A reference spectrum of Co-ZSM-5 in He taken at the same temperature was subtracted from each spectrum. 

Figure 6.18 Subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS) spectra of a polished polyciystaUine Pt electrode, immersed in 0.1 M HCIO4, + 5 M CH3OH electrolyte. All spectra were normahzed to the base spectrum collected at 0 mV vs. RHE. (Reproduced from Iwasita and Vielstich [1988].)...

Mrad/h). Films were stored at -20° until analysis could be carried out. Oxidized films and derivatized, oxidized films were characterized by iodometry (reflux with Nal in isopropanol/acetic acid) and by transmission Fourier Transform (FT) IR (Perkin Elmer 1500), using the spectral subtraction technique (3, 14). Free radicals were measured by the electron spin resonance technique (e.s.r., Varian E4 spectrometer). 

Figure 14. Fourier transform of (A) the oxygen isotope ratio vs. time in C. japonica and (B) deuterium isotope ratio vs. time in C. japonica, transformed into power vs. reciprocal period (average slope subtracted) (26).

The Fourier transforms were performed in the standard way. No smoothing nor filtering was employed. Subtraction of the data from the least squares fit removes the constant or linear term characterizing a Markovian process. Fourier transform of the differences from the linear fit suppresses the enhancement of both the power and amplitude spectra at low frequencies. 

Transmission infrared spectra of species adsorbed on the catalyst were taken with a Digilab FTS-10M Fourier-transform infrared spectrometer, using a resolution of 4 cm-l. To improve the signal-to-noise ratio, between 10 and 100 interferograms were co-added. Spectra of the catalyst taken following reduction in H2 were subtracted from spectra taken in the presence of NO to eliminate the spectrum of the support. Because of the very short optical path through the gas in the reactor and the low NO partial pressures used in these studies, the spectrum of gas-phase NO was extremely weak and did not interfere with the observation of the spectrum of adsorbed species. 

Subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS), has been used extensively to examine interactions of species at the electrode/electrolyte interface. In the present work, the method has been extended to probe interactions at the mercury solution interface. The diminished potential dependent frequency shifts of species adsorbed at mercury electrodes are compared with shifts observed for similar species adsorbed at d-band metals. 

Subtractively normalized interfacial Fourier transform infrared spectroscopy has been used to follow the reorientations of isoquinoline molecules adsorbed at a mercury electrode. Field induced infrared absorption is a major contribution to the intensities of the vibrational band structure of aromatic organic molecules adsorbed on mercury. Adsorbed isoquinoline was observed to go through an abrupt reorientation at potentials more negative than about -0.73 V vs SCE (the actual transition potential being dependent on the bulk solution concentration) to the vertical 6,7 position. 

The SNIFTIRS approach. The acronym SNIFTIRS means Subtractively Normalized Interfacial Fourier Transform Infrared Spectroscopy. The basic concept of this method involves the fact that the raw data obtained directly from the Fourier Transform process contain components which are undesirable. Firstly, there is material in the solution which may have affected the spectrum. Secondly, unwanted information on certain material on the electrode (adsorbed water, for example) is best eliminated. 

It can be readily seen from the above discussion that a simplistic version of the polarization modulation method for using Fourier Transform Infrared method would be to say that if one subtracted the message obtained from the vertical light from that obtained from the parallel light, the result will be information from the surface only. The relevant equation is shown below. 

The right panel of Figure 1.3 displays the radial function obtained by Fourier transformation of the -weighed background-subtracted EXAFS data from the solid heated to 420°C [31], This spectrum shows two major peaks, one at about 1.5 A associated with backscattering from O neighbors, and a second at 3 A related to the Nb-Mo pairs. The measured distances are consistent with a combination of niobium oxo species and heteropolymolybdate fragments, presumably the catalytically active phase. 

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