Aqueous solutions. Raman spectroscopy

There have been a number of recent investigations in the field of normal Raman spectroscopy with laser excitation of proteins in aqueous solutions . Raman spectroscopy uncovers information of the peptide backbone, geometry of... 

N. A. Macleod, C. Johannessen, L. Hecht, L. D. Barron, and J. P. Simons, From the gas phase to aqueous solution Vibrational spectroscopy, Raman optical activity and conformational struc tore of carbohydrates. Int. J. Mass Spectrom. 253, 193 200 (2006). 

In the metal refining of ores, the metal is solubilized in an aqueous solution. The optical control of metal refining requires quick, accurate analysis of the major chemical species present in solution. Raman spectroscopy and resonance Raman are used to identify the amine complexes of Co, Ni, and Cu species, as well as ammonia sulfate and sulfamate, present in these industrial solutions. The Raman spectra of an industrial plant solution from mine tailings are shown in Fig. 7-15. Each solution contains one or more metal species, sulfate, sulfamate, ammonia, ammonium sulfate, and water. From a comparison with model ammine complexes, the vibrations in the spectra are identifiable. Bands were observed at 615, 980 and 1,110 cm-1 and were assigned to the sulfate ion. No bands were observed for free ammonia. A band at 376 cm-1 was assigned to the Ni(NH3)j + specie. A band at 490 cm-1 was assigned to the Co(NH3)g+ specie. 

Raman spectrum, aqueous solution. lETS spectroscopy. IR of K4[M CN)jJ in KBr disc. 

The varying actual orientation of molecules adsorbed at an aqueous solution-CCU interface with decreasing A has been followed by resonance Raman spectroscopy using polarized light [130]. The effect of pressure has been studied for fatty alcohols at the water-hexane [131] and water-paraffin oil [132] interfaces. 

In aqueous solution, all the sodium peroxoborates dissociate for the most part into boric acid, or its anion, and hydrogen peroxide. Peroxoborate species are also present in these solutions, depending on the pH and the concentration for the species type. The nature of these species has been extensively examined by classical physicochemical methods (13), by nmr, and by Raman spectroscopy (14—17). Both monomeric and polymeric species are usually present. There is some evidence (18) suggesting that these peroxoborates are more reactive than hydrogen peroxide alone under similar conditions. 

Sample preparation is straightforward for a scattering process such as Raman spectroscopy. Sample containers can be of glass or quartz, which are weak Raman scatterers, and aqueous solutions pose no problems. Raman microprobes have a spatial resolution of - 1 //m, much better than the diffraction limit imposed on ir microscopes (213). Eiber-optic probes can be used in process monitoring (214). 

Raman spectroscopy is a very convenient technique for the identification of crystalline or molecular phases, for obtaining structural information on noncrystalline solids, for identifying molecular species in aqueous solutions, and for characterizing solid—liquid interfaces. Backscattering geometries, especially with microfocus instruments, allow films, coatings, and surfaces to be easily measured. Ambient atmospheres can be used and no special sample preparation is needed. 

Lilley, T. H. Raman Spectroscopy of Aqueous Electrolyte Solutions, in Water — a Comprehensive Treatise (ed. Franks, F.), Vol. 3, chapter 6, New York, Plenum Press 1973... 

Similarly, the first-order expansion of the p° and a of Eq. (5.1) is, respectively, responsible for IR absorption and Raman scattering. According to the parity, one can easily understand that selection mles for hyper-Raman scattering are rather similar to those for IR [17,18]. Moreover, some of the silent modes, which are IR- and Raman-inactive vibrational modes, can be allowed in hyper-Raman scattering because of the nonlinearity. Incidentally, hyper-Raman-active modes and Raman-active modes are mutually exclusive in centrosymmetric molecules. Similar to Raman spectroscopy, hyper-Raman spectroscopy is feasible by visible excitation. Therefore, hyper-Raman spectroscopy can, in principle, be used as an alternative for IR spectroscopy, especially in IR-opaque media such as an aqueous solution [103]. Moreover, its spatial resolution, caused by the diffraction limit, is expected to be much better than IR microscopy. 

Transient Raman spectroscopy was also used to study charge transfer reactions across aqueous solution interfaces. One optical pulse above the band gap creates... 

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... 

IR and Raman spectroscopy have been commonly used and, for example, the effects of pressure on the Raman spectrum of a zinc compound with a N2C12 coordination sphere around the metal, have been investigated.28 IR spectroscopy has been utilized in studies of the hydration of zinc in aqueous solution and in the hydrated perchlorate salt.29 Gas phase chemistry of zinc complexes has been studied with some gas phase electron diffraction structures including amide and dithiocarbamate compounds.30-32... 

The molecular structure of Li-, Na-, and K-silicates in 0.2 to 3 mole SiOj/L aqueous solutions has been investigated by FTIR and Raman spectroscopy to help exploring their solidification process. These silicates were found to be only partially dissociated and their average molecular weight (AMW) varies with the type of the alkaline ion, the alkaline/silicon ratio, and the concentration. It is demonstrated that these differences are associated with differences in the Qn connectivity ratios of [Si04] tetrahedra and in the dominating siloxane ring structures which can be identified by their vibrational spectra. 

IR and Raman spectroscopy can fulfill these requirements and they are also robust enough for in situ silicate analysis in plant reactors [7]. Both of these techniques have been used for identifying the symmetric (s) and asymmetric (as), stretching (va, vas) and bending (5a, 5as) O-Si-O vibrations in aqueous alkaline silicate solutions which are the cheapest hence most frequently used ingredients for zeolite synthesis [8, 9 and references herein]. However, this information has to be "translated" into siloxane ring... 

Evidence for cobalt tr-butenyl and 7r-methylallyl intermediates in butadiene hydrogenations has been obtained using Raman spectroscopy (194), which could be a useful probe for catalytic reactions, especially in aqueous solutions. 

Raman spectroscopy has been used by several authors as an indent-ification method by comparing spectra of solutions with spectra of solid phases of known structure (85, 92-95). The heptamolybdate could be clearly identified (cf. below) and its spectrum in the solid state and aqueous solution is well characterized (93, 94). Other polyanions seem to be more difficult to identify because overlapping equilibria tend to conceal small changes in the spectrum upon acidification. 

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