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Spectroscopic detection

Electronic spectra of surfaces can give information about what species are present and their valence states. X-ray photoelectron spectroscopy (XPS) and its variant, ESC A, are commonly used. Figure VIII-11 shows the application to an A1 surface and Fig. XVIII-6, to the more complicated case of Mo supported on TiOi [37] Fig. XVIII-7 shows the detection of photochemically produced Br atoms on Pt(lll) [38]. Other spectroscopies that bear on the chemical state of adsorbed species include (see Table VIII-1) photoelectron spectroscopy (PES) [39-41], angle resolved PES or ARPES [42], and Auger electron spectroscopy (AES) [43-47]. Spectroscopic detection of adsorbed hydrogen is difficult, and... [Pg.690]

With spectroscopic detection of the products, the angular distribution of the products is usually not measured. In principle, spectroscopic detection of the products can be incorporated into a crossed-beam scattering experiment of the type described in section B2.3.2. There have been relatively few examples of such studies because of the great demands on detection sensitivity. The recent work of Keil and co-workers (Dhannasena et al [16]) on the F + H2 reaction, mentioned in section B2.3.3, is an excellent example of the implementation... [Pg.2080]

This teclnhque can be used both to pennit the spectroscopic detection of molecules, such as H2 and HCl, whose first electronic transition lies in the vacuum ultraviolet spectral region, for which laser excitation is possible but inconvenient [ ], or molecules such as CH that do not fluoresce. With 2-photon excitation, the required wavelengdis are in the ultraviolet, conveniently generated by frequency-doubled dye lasers, rather than 1-photon excitation in the vacuum ultraviolet. Figure B2.3.17 displays 2 + 1 REMPI spectra of the HCl and DCl products, both in their v = 0 vibrational levels, from the Cl + (CHg) CD reaction [ ]. For some electronic states of HCl/DCl, both parent and fragment ions are produced, and the spectrum in figure B2.3.17 for the DCl product was recorded by monitoring mass 2 (D ions. In this case, both isotopomers (D Cl and D Cl) are detected. [Pg.2083]

Hefter U and Bergmann K 1988 Spectroscopic detection methods Atomic and Moiecuiar Beam Methods vol 1, ed G Scoles et a/(New York Oxford University Press) pp 193-253... [Pg.2087]

In this approach one uses narrow-band continuous wave (cw) lasers for continuous spectroscopic detection of reactant and product species with high time and frequency resolution. Figure B2.5.11 shows an experimental scheme using detection lasers with a 1 MFIz bandwidth. Thus, one can measure the energy spectrum of reaction products with very high energy resolution. In practice, today one can achieve an uncertainty-limited resolution given by... [Pg.2128]

In more dilute solutions the concentration of the nitronium ion falls below the level of spectroscopic detection, and the nature of the electrophilic species has been the subject of conjecture. [Pg.9]

Addition of water to solutions of nitric acid in 90% sulphuric acid reduces rates of nitration. Between 90% and 85% sulphuric acid the decrease in rate parallels the accompanying fall in the concentration of nitronium ions. This is good evidence for the operation of the nitronium ion as the nitrating agent, both in solutions more acidic than 90% and in weakly diluted solutions in which nitronium ion is still spectroscopically detectable. [Pg.21]

The relative abilities of nitromethane, sulpholan, and acetic acid to support the ionisation of nitric acid to nitronium ions are closely similar to their efficiencies as solvents in nitration. Raman spectroscopy showed that for a given concentration of mixed acid (i i nitric and sulphuric acids) the concentration of nitronium ions in these three solvents varied in the order nitromethane > sulpholan > acetic acid. The concentration of mixed acid needed to permit the spectroscopic detection of nitronimn ions was 25 %, 50 % and 60 % in the three solvents, respectively (see 4.4.3). [Pg.39]

Using sulpholan and acetic acid as solvents competitive nitrations were performed with solutions containing 75% and 30% of mixed acid (table 4.1, columns h, i and /, g, respectively). In the former the concentration of nitronium ions was substantial [c. 5-7 % by weight), whereas in the latter the concentration was below the level of spectroscopic detection. [Pg.70]

Chemical Analysis. The presence of siUcones in a sample can be ascertained quaUtatively by burning a small amount of the sample on the tip of a spatula. SiUcones bum with a characteristic sparkly flame and emit a white sooty smoke on combustion. A white ashen residue is often deposited as well. If this residue dissolves and becomes volatile when heated with hydrofluoric acid, it is most likely a siUceous residue (437). Quantitative measurement of total sihcon in a sample is often accompHshed indirectly, by converting the species to siUca or siUcate, followed by deterrnination of the heteropoly blue sihcomolybdate, which absorbs at 800 nm, using atomic spectroscopy or uv spectroscopy (438—443). Pyrolysis gc followed by mass spectroscopic detection of the pyrolysate is a particularly sensitive tool for identifying siUcones (442,443). This technique rehes on the pyrolytic conversion of siUcones to cycHcs, predominantly to [541-05-9] which is readily detected and quantified (eq. 37). [Pg.59]

Although the most sensitive line for cadmium in the arc or spark spectmm is at 228.8 nm, the line at 326.1 nm is more convenient to use for spectroscopic detection. The limit of detection at this wavelength amounts to 0.001% cadmium with ordinary techniques and 0.00001% using specialized methods. Determination in concentrations up to 10% is accompHshed by solubilization of the sample followed by atomic absorption measurement. The range can be extended to still higher cadmium levels provided that a relative error of 0.5% is acceptable. Another quantitative analysis method is by titration at pH 10 with a standard solution of ethylenediarninetetraacetic acid (EDTA) and Eriochrome Black T indicator. Zinc interferes and therefore must first be removed. [Pg.388]

Kinetic investigation of the reaction of cotarnine and a few aromatic aldehydes (iV-methylcotarnine, m-nitrobenzaldehyde) with hydrogen eyanide in anhydrous tetrahydrofuran showed such differences in the kinetic and thermodynamic parameters for cotarnine compared to those for the aldehydes, and also in the effect of catalysts, so that the possibility that cotarnine was reacting in the hypothetical amino-aldehyde form could be completely eliminated. Even if the amino-aldehyde form is present in concentrations under the limit of spectroscopic detection, then it still certainly plays no pfi,rt in the chemical reactions. This is also expected by Kabachnik s conclusions for the reactions of tautomeric systems where the equilibrium is very predominantly on one side. [Pg.177]

Sample concentration, and hence enrichment, is certainly a key issue in this area of analysis, since complementary information obtained from NMR or IR spectroscopic detection is often desirable in conjunction with mass spectrometry. Detection methods such as these have far higher concentration thresholds than MS and obtaining adequate quantities of material for detection becomes a significant challenge. [Pg.63]

This is a frequently postulated species (Olah and Kuhn, 1964 Ciuhandu and Dumi-treanu, 1970) which so far has escaped spectroscopic detection (Hogeveen et al., 1967). [Pg.50]

The results described in this review show that matrix stabilization of reactive organic intermediates at extremely low temperatures and their subsequent spectroscopic detection are convenient ways of structural investigation of these species. IR spectroscopy is the most useful technique for the identification of matrix-isolated molecules. Nevertheless, the complete study of the spectral properties and the structure of intermediates frozen in inert matrices is achieved when the IR spectroscopy is combined with UV and esr spectroscopic methods. At present theoretical calculations render considerable assistance for the explanation of the experimental spectra. Thus, along with the development of the experimental technique, matrix studies are becoming more and more complex. This fact allows one to expect further progress in the matrix spectroscopy of many more organic intermediates. [Pg.56]

Interactions. Formic acid is often more effective but is limited In general use by its instability and difficulty of purification. Commercially available samples of formic acid have a rather poorly defined composition. Methanol is an effective modifier for masking iUnophilic interactions with polar functional groups when spectroscopic detection is used [22,28,84]. In this case... [Pg.827]

Perhaps the most revolutionary development has been the application of on-line mass spectroscopic detection for compositional analysis. Polymer composition can be inferred from column retention time or from viscometric and other indirect detection methods, but mass spectroscopy has reduced much of the ambiguity associated with that process. Quantitation of end groups and of co-polymer composition can now be accomplished directly through mass spectroscopy. Mass spectroscopy is particularly well suited as an on-line GPC technique, since common GPC solvents interfere with other on-line detectors, including UV-VIS absorbance, nuclear magnetic resonance and infrared spectroscopic detectors. By contrast, common GPC solvents are readily adaptable to mass spectroscopic interfaces. No detection technique offers a combination of universality of analyte detection, specificity of information, and ease of use comparable to that of mass spectroscopy. [Pg.375]

The most important area for packed column use involves modified mobile phases (MPs). Consequently, pSFC needs detection systems in which the MP modifier and possible additive(s) do not interfere, and in which detection of low or non-UV-absorbing molecules is possible in combination with pressure/modifier gradients. The disadvantage of adding even small amounts of modifier is that FID can no longer be used as a detector. In the presence of polar modifiers in pSFC the detection systems are restricted basically to spectroscopic detection, namely UVD, LSD, MSD (using PB and TSP interfaces as in LC). ELSD can substitute FID and covers the quasi-universal detection mode, while NPD and ECD cover the specific detection mode in pSFC on a routine basis. As ELSD detects non-UV absorbing molecules dual detection with UV is an attractive option. [Pg.208]

In this chapter, spectroscopy is an umbrella term for a variety of complementary methods such as tJV/VIS, IR, luminescence, and NMR, with the object of examining mainly polymer additives in solution after extraction but usually before a chromatographic separation. On-line spectroscopic detection hyphenated to chromatography is dealt with in Chapter 7. [Pg.299]

Domcke W, Stock G (1997) Theory of ultrafast nonadiabatic excited-state processes and their spectroscopic detection in real time. Adv Chem Phys 100 1—170... [Pg.328]

The density here refers to the spatial coordinate, i.e. the concentration of the reaction product, and is not to be confused with the D(vx,vy,vz) in previous sections which refers to the center-of-mass velocity space. Laser spectroscopic detection methods in general measure the number of product particles within the detection volume rather than a flux, which is proportional to the reaction rate, emerging from it. Thus, products recoiling at low laboratory velocities will be detected more efficiently than those with higher velocities. The correction for this laboratory velocity-dependent detection efficiency is called a density-to-flux transformation.40 It is a 3D space- and time-resolved problem and is usually treated by a Monte Carlo simulation.41,42... [Pg.13]

Palladium(II) complexes possessing bidentate ligands are known to efficiently catalyze the copolymerization of olefins with carbon monoxide to form polyketones.594-596 Sulfur dioxide is an attractive monomer for catalytic copolymerizations with olefins since S02, like CO, is known to undergo facile insertion reactions into a variety of transition metal-alkyl bonds. Indeed, Drent has patented alternating copolymerization of ethylene with S02 using various palladium(II) complexes.597 In 1998, Sen and coworkers also reported that [(dppp)PdMe(NCMe)]BF4 was an effective catalyst for the copolymerization of S02 with ethylene, propylene, and cyclopentene.598 There is a report of the insertion reactions of S02 into PdII-methyl bonds and the attempted spectroscopic detection of the copolymerization of ethylene and S02.599... [Pg.607]

Fig. 2.8. (a)On-line mass spectroscopic detection of HD (m/e = 3) produced by application of a potential step to 0.97 V vs. PdH to a Pt electrode in 10 2 M CD3OH/10 4 M/HClO4/0.1 M NaC104/H20 during 0.5 s, followed by a potential step to —0.44 V vs. Pd-H. For comparison HD signal without methanol oxidation when switching the potential from open circuit to H2 evolution at — 0.44 V (b). Upper part recording of current. [Pg.146]


See other pages where Spectroscopic detection is mentioned: [Pg.2116]    [Pg.2135]    [Pg.312]    [Pg.334]    [Pg.129]    [Pg.85]    [Pg.398]    [Pg.305]    [Pg.414]    [Pg.449]    [Pg.200]    [Pg.213]    [Pg.106]    [Pg.426]    [Pg.27]    [Pg.252]    [Pg.254]    [Pg.149]    [Pg.46]    [Pg.90]    [Pg.99]    [Pg.332]    [Pg.375]    [Pg.559]   
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