Raman traces

K. M. Gough and H. K. Srivastava, J. Phys. Chem., 100, 5210 (1995). Electronic Charge Flow and Raman Trace Scattering Intensities for CH-Stretching Vibrations in n-Pentane. 

K. M. Gough, H. K. Srivastava, K. Belohorcova. Analysis of Raman trace scattering intensities in alkanes with the theory of atoms in molecules. J. Chem. Phys. -, 98, 9669 9677 (1993). 

The general task is to trace the evolution of the third order polarization of the material created by each of the above 12 Raman field operators. For brevity, we choose to select only the subset of eight that is based on two colours only—a situation that is connnon to almost all of the Raman spectroscopies. Tliree-coloiir Raman studies are rather rare, but are most interesting, as demonstrated at both third and fifth order by the work in Wright s laboratory [21, 22, 23 and 24]- That work anticipates variations that include infrared resonances and the birth of doubly resonant vibrational spectroscopy (DOVE) and its two-dimensional Fourier transfomi representations analogous to 2D NMR [25]. 

Siebert D R, West G A and Barrett J J 1980 Gaseous trace analysis using pulsed photoacoustic Raman spectroscopy Appl. Opt. 19 53-60... 

Figure Bl.22.6. Raman spectra in the C-H stretching region from 2-butanol (left frame) and 2-butanethiol (right), each either as bulk liquid (top traces) or adsorbed on a rough silver electrode surface (bottom). An analysis of the relative intensities of the different vibrational modes led to tire proposed adsorption structures depicted in the corresponding panels [53], This example illustrates the usefiilness of Raman spectroscopy for the detennination of adsorption geometries, but also points to its main limitation, namely the need to use rough silver surfaces to achieve adequate signal-to-noise levels.

When acetic anhydride was in excess over nitric acid, acetyl nitrate and acetic acid were the only products. When the concentration of nitric acid was greater than 90 moles %, dinitrogen pentoxide, present as (N02+)(N0a ), was the major product and there were only small traces of acetyl nitrate. With lower concentrations of nitric acid the products were acetic acid, acetyl nitrate and dinitrogen pentoxide, the latter species being present as covalent molecules in this organic medium. A mixture of z moles of nitric acid and i mole of acetic anhydride has the same Raman spectrum as a solution of i mole of dinitrogen pentoxide in 2 moles of acetic acid. 

Raman measurements [INFRARED TECHNOLOGY AND RAMAN SPECTROSCOPY - RAMAN SPECTROSCOPY] (Vol 14) -trace analysis of [IHACE AND RESIDUE ANALYSIS] (Vol 24)... 

The sodium hydroxide is titrated with HCl. In a thermometric titration (92), the sibcate solution is treated first with hydrochloric acid to measure Na20 and then with hydrofluoric acid to determine precipitated Si02. Lower sibca concentrations are measured with the sibcomolybdate colorimetric method or instmmental techniques. X-ray fluorescence, atomic absorption and plasma emission spectroscopies, ion-selective electrodes, and ion chromatography are utilized to detect principal components as weU as trace cationic and anionic impurities. Eourier transform infrared, ft-nmr, laser Raman, and x-ray... 

Selected physical properties of chloroprene are Hsted in Table 1. When pure, the monomer is a colorless, mobile Hquid with slight odor, but the presence of small traces of dimer usually give a much stronger, distinctive odor similar to terpenes and inhibited monomer may be colored from the stabilizers used. Ir and Raman spectroscopy of chloroprene (4) have been used to estimate vibrational characteristics and rotational isomerization. 

Raman spectroscopy is primarily a structural characterization tool. The spectrum is more sensitive to the lengths, streng ths, and arrangement of bonds in a material than it is to the chemical composition. The Raman spectmm of crystals likewise responds more to details of defects and disorder than to trace impurities and related chemical imperfections. 

NMR and visible spectra have established that a number of S-N anions are present in such solutions.The primary reduction products are polysulfides Sx, which dissociate to polysulfur radical anions, especially the deep blue 83 ion (/Imax 620nm). In a IM solution the major S-N anion detected by NMR spectroscopy is cycZo-[S7N] with smaller amounts of the [SSNSS] ion and a trace of [SSNS]. The formation of the acyclic anion 5.23 from the decomposition of cyclo-Sjl is well established from chemical investigations (Section 5.4.3). The acyclic anions 5.22 and 5.23 have been detected by their characteristic visible and Raman spectra. It has also been suggested that a Raman band at 858 cm and a visible absorption band at 390 nm may be attributed to the [SaN] anion formed by cleavage of a S-S bond in [SSNS]. ° However, this anion cannot be obtained as a stable species when [SsN] is treated with one equivalent of PPhs. 

Fig. 21. Raman spectra showing improvement of signal-to-noise using multiple scans with computer time averaging over single scan. Lower traces single scan upper traces multiple scans (10 scans) and computer output, (a) i of CCU (b) Hg emission line and n of LiCh (c) n of Na02 with oxygen isotopic counterparts (89).

Detection of an Intermediate. In many cases, an intermediate cannot be isolated but can be detected by IR, NMR, or other spectra. The detection by Raman spectra of NOj was regarded as strong evidence that this is an intermediate in the nitration of benzene (see 11-2). Free radical and triplet intermediates can often be detected by ESR and by CIDNP (see Chapter 5). Free radicals [as well as radical ions and EDA complexes] can also be detected by a method that does not rely on spectra. In this method, a doublebond compound is added to the reaction mixture, and its fate traced. One possible result is cis-trans conversion. For example, cis-stilbene is isomerized to the trans isomer in the presence of RS- radicals, by this mechanism ... 

According to the Raman spectrum the product contains traces of Se in solid solution which could not be removed by repeated recrystallization. If the oxidation is carried out at -25 °C in a CS2/CH2CI2 mixture and the molar ratio is increased to 1 2.2, PS O is obtained [59] isolated in 10% yield [60]. 

Raman spectra (for both the solid state and aqueous solution) provide better fingerprints for heparins than their i.r. spectra.79 However, the application of Raman spectroscopy to glycosaminoglycans is less routine than with i.r., both for instrumental reasons and because of possible interference from traces of fluorescent impurities.77... 

Analytical Raman Spectroscopy. Edited by Jeanette Graselli and Bernard J. Bulkin Trace and Ultratrace Analysis by HPLC. By Satinder Ahuja... 

Typical X-ray diffraction patterns of three different carbon powder samples are shown in Fig. 3. Two 00/ and two hkO diffraction peaks can be distinguished in the patterns of samples produced at 800°C and 1000°C. The 002 (26 26.9°) and 004 (26 54.9°) peaks correspond to the parallel graphene layers. The 100 (26 43°) and 110 (26 77.8°) diffraction peaks are characteristics of the 2D in-plane symmetry along the graphene layers. Based on its XRD pattern, the powder synthesized at 500°C is not graphitized, which is in agreement with Raman analysis. This low temperature sample also contains traces of iron chlorides. 

For trace analysis in fluids, some Raman sensors (try to) make use of the SERS effect to increase their sensitivity. While the basic sensor layout for SERS sensors is similar to non-enhanced Raman sensors, somehow the metal particles have to be added. Other than in the laboratory, where the necessary metal particles can be added as colloidal solution to the sample, for sensor applications the particles must be suitably immobilised. In most cases, this is achieved by depositing the metal particles onto the surfaces of the excitation waveguide or the interface window and covering them with a suitable protection layer. The additional layer is required as otherwise washout effects or chemical reactions between e.g. sulphur-compounds and the particles reduce the enhancement effect. Alternatively, it is also possible to disperse the metal particles in the layer material before coating and apply them in one step with the coating. Suitable protection or matrix materials for SERS substrates could be e.g. sol-gel layers or polymer coatings. In either... 

Vo-Dinh T., Hiromoto M.Y.K., Begun G.M., Moody R. L., Surface-enhanced Raman spectrometry for trace organic-analysis, Anal. Chem. 1984 56 1667-1670. 

As in the previous case of infrared transitions, one wants to calculate the line strengths S(v,J —> v, J ) defined in Eq. (2.127). For Raman transitions there are two contributions, as discussed in Chapter 1. The so-called trace scattering is induced by the monopole operator... 

Experiments at high pressure have shown that the P-T phase diagram of butadiene is comparatively simple. The crystal phase I is separated from the liquid phase by an orientationally disordered phase II stable in a narrow range of pressure and temperature. The strucmre of phase I is not known, but the analyses of the infrared and Raman spectra have suggested a monoclinic structure with two molecules per unit cell as the most likely [428]. At room temperature, butadiene is stable in the liquid phase at pressures up to 0.7 GPa. At this pressure a reaction starts as revealed by the growth of new infrared bands (see the upper panel of Fig. 25). After several days a product is recovered, and the infrared spectrum identifies it as 4-vinylcyclohexene. No traces of the other dimers can be detected, and only traces of a polymer are present. If we increase the pressure to 1 GPa, the dimerization rate increases but the amount of polymer... 

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