Raman typical

Raman typically provides information on a catalysts crystallinity, coordination of site structure and spatial distribution of phases through... 

Due to the rather stringent requirements placed on the monochromator, a double or triple monocln-omator is typically employed. Because the vibrational frequencies are only several hundred to several thousand cm and the linewidths are only tens of cm it is necessary to use a monochromator with reasonably high resolution. In addition to linewidth issues, it is necessary to suppress the very intense Rayleigh scattering. If a high resolution spectrum is not needed, however, then it is possible to use narrow-band interference filters to block the excitation line, and a low resolution monocln-omator to collect the spectrum. In fact, this is the approach taken with Fourier transfonn Raman spectrometers. 

Unlike the typical laser source, the zero-point blackbody field is spectrally white , providing all colours, CO2, that seek out all co - CO2 = coj resonances available in a given sample. Thus all possible Raman lines can be seen with a single incident source at tOp Such multiplex capability is now found in the Class II spectroscopies where broadband excitation is obtained either by using modeless lasers, or a femtosecond pulse, which on first principles must be spectrally broad [32]. Another distinction between a coherent laser source and the blackbody radiation is that the zero-point field is spatially isotropic. By perfonuing the simple wavevector algebra for SR, we find that the scattered radiation is isotropic as well. This concept of spatial incoherence will be used to explain a certain stimulated Raman scattering event in a subsequent section. 

We have seen that the strength of Raman scattered radiation is directly related to the Raman scattering cross-section (Oj ). The fact that this cross-section for Raman scattering is typically much weaker than that for absorption (oj limits conventional SR as a sensitive analytical tool compared to (Imear) absorption... 

The metal substrate evidently affords a huge ( 10 and even as high as 10 [84, 85]) increase in the cross-section for Raman scattering of the adsorbate. There are two broad classes of mechanisms which are said to contribute to this enhancenient [, and Ml- The first is based on electromagnetic effects and the second on cheniicaT effects. Of these two classes the fomier is better understood and, for the most part, the specific mechanisms are agreed upon the latter is more complicated and is less well understood. SERS enhancenient can take place in either physisorbed or chemisorbed situations, with the chemisorbed case typically characterized by larger Raman frequency shifts from the bulk phase. 

I CRS interferogram with a frequency of A = coj + 2c0j - cOq, where cOp is the detected frequency, coj is the narrowband frequency and coj the Raman (vibrational) frequency. Since cOq and coj are known, Wj may be extracted from the experimentally measured RDOs. Furthemiore, the dephasing rate constant, yj, is detemiined from the observed decay rate constant, y, of the I CRS interferogram. Typically for the I CRS signal coq A 0. That is, the RDOs represent strongly down-converted (even to zero... 

Figure 5.13 shows a typical experimental arrangement for obtaining the Raman spectmm of a gaseous sample. Radiation from the laser source is focused by the lens Lj into a cell containing the sample gas. The mirror Mj reflects this radiation back into the cell to increase... 

Figure 5.17 shows the rotational Raman spectrum of N2 obtained with 476.5 nm radiation from an argon ion laser. From this spectrum a very accurate value for Bq of 1.857 672 0.000 027 cm has been obtained from which a value for the bond length tq of 1.099 985 0.000 010 A results. Such accuracy is typical of high-resolution rotational Raman spectroscopy. 

Figure 6.2 shows typically how a varies with r da/dr is usually positive and, unlike d/r/dr in Figure 6.1, varies little with r. For this reason vibrational Raman intensities are less sensitive than are infrared intensities to the environment of the molecule, such as the solvent in a solution specttum. 

The use of vibrational Raman spectroscopy in qualitative analysis has increased greatly since the introduction of lasers, which have replaced mercury arcs as monochromatic sources. Although a laser Raman spectrometer is more expensive than a typical infrared spectrometer used for qualitative analysis, it does have the advantage that low- and high-wavenumber vibrations can be observed with equal ease whereas in the infrared a different, far-infrared, spectrometer may be required for observations below about 400 cm. ... 

The Aromax process was developed in the early 1970s by Toray Industries, Inc. in Japan (95—98). The adsorption column consists of a horizontal series of independent chambers containing fixed beds of adsorbent. Instead of a rotary valve, a sequence of specially designed on—off valves under computer control is used to move inlet and withdrawal ports around the bed. Adsorption is carried out in the Hquid phase at 140°C, 785—980 kPA, and 5—13 L/h. PX yields per pass is reported to exceed 90% with a typical purity of 99.5%. The first Aromax unit was installed at Toray s Kawasaki plant in March 1973. In 1994, IFP introduced the Eluxyl adsorption process (59,99). The proprietary adsorbent used is designated SPX 3000. Individual on-off valves controlled by a microprocessor are used. Raman spectroscopy to used to measure concentration profiles in the column. A 10,000 t/yr demonstration plant was started and successfully operated at Chevron s Pascagoula plant from 1995—96. IFP has Hcensed two hybrid units. 

The spatial resolution of the Raman microprobe is about an order of magnitude better than that obtainable using an infrared microscope. Measurement times, typically of a few seconds, are the same as for other Raman spectrographs. To avoid burning samples, low (5—50-mW) power lasers are employed. 

Special Raman Spectroscopies. The weakness of Raman scattering results typically in the conversion of no more than 10 of the incident laser photons into a usable signal, limiting the sensitivity of conventional spontaneous Raman spectroscopy. This situation can be improved using alternative approaches (8,215,216). 

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