Silica modes

The V2 mode (bending or 8 mode) of water molecule has been used in the past to determine the quantity of adsorbed water on sihca sample [22]. However, the use of this absorption is made difficult by the absorptions of combination and overtone of network silica modes between 1500 and 1850 cm . It is easier to use the characteristic combination V2-P(vi or V3, respectively the symmetric and the asymmetric stretching modes) of water molecules as shown recently [28]. The spectral range 5000-5350 cm characterizes these combinations of water molecules. Because this range is fairly isolated from the sUica absorptions, it allows to study separately the physisorbed water molecules [2b]. Figure 26.1 shows clearly that a pure silica A pellet evacuated at 25°C under a residual of pressure of 10 " Pa does not display any absorption between 4750 and 5500 cm . Despite some controversy about this point [32], most of the silica samples are readily dehydrated by evacuation at room temperature... 

Figure 22.6 (a) Raman spectra of 8 mol% Sn02 Si02 with two different erbium contents, (b) Infrared absorption spectra normalized to the silica mode at 800cm for the same materials diluted in KBr pellets. All the spectra were measured at room temperature. (After Ref. [35].)... 

The dynamics of fast processes such as electron and energy transfers and vibrational and electronic deexcitations can be probed by using short-pulsed lasers. The experimental developments that have made possible the direct probing of molecular dissociation steps and other ultrafast processes in real time (in the femtosecond time range) have, in a few cases, been extended to the study of surface phenomena. For instance, two-photon photoemission has been used to study the dynamics of electrons at interfaces [ ]. Vibrational relaxation times have also been measured for a number of modes such as the 0-Fl stretching m silica and the C-0 stretching in carbon monoxide adsorbed on transition metals [ ]. Pump-probe laser experiments such as these are difficult, but the field is still in its infancy, and much is expected in this direction m the near fiitiire. 

In the present work low temperature adsoi ption of fluoroform and CO, were used to characterize surface basicity of silica, both pure and exposed to bases. It was found that adsorption of deuterated ammonia results in appearance of a new CH stretching vibration band of adsorbed CHF, with the position typical of strong basic sites, absent on the surface of pure silica. Low-frequency shift of mode of adsorbed CO, supports the conclusion about such basicity induced by the presence of H-bonded bases. 

BBT solution on unmodified sorbents of different nature was studied. Silica gel Merck 60 (SG) was chosen for further investigations. BBT immobilization on SG was realized by adsoi ption from chloroform-hexane solution (1 10) in batch mode. The isotherm of BBT adsoi ption can be referred to H3-type. Interaction of Co(II), Cu(II), Cd(II), Ni(II), Zn(II) ions with immobilized BBT has been studied in batch mode as a function of pH of solution, time of phase contact and concentration of metals in solution. In the presence of sodium citrate absorbance (at X = 620 nm) of immobilized BBT grows with the increase of Cd(II) concentration in solution. No interference was observed from Zn(II), Pb(II), Cu(II), Ni(II), Co(II) and macrocomponents of natural waters. This was assumed as a basis of soi ption-spectroscopic and visual test determination of Cd(II). Heavy metals eluted from BBT-SG easily and quantitatively with a small volume of HNO -ethanol mixture. This became a basis of soi ption-atomic-absoi ption determination of the total concentration of heavy metals in natural objects. 

Let us consider the separation of polymethylmethacrylate (PMMA) on a nonmodified silica column as an example. In THE (medium polar eluent) the PMMA eludes in size exclusion mode because the dipoles of the methylmethacrylate (MMA) are masked by the dipoles of the THE. Using the nonpolar toluene as the eluent on the same column, the separation is governed by adsorption because the dipoles of the carbonyl group in the PMMA will interact with the dipoles on the surface of the stationary phase. The separation of PMMA in the critical mode of adsorption can be achieved by selecting an appropriate THF/toluene mixture as the eluent. In this case all PMMA samples... 

Examples with other Pirkle-type CSPs have also been described [139, 140]. In relation to polysaccharides coated onto silica gel, they have shown long-term stability in this operation mode [141, 142], and thus are also potentially good chiral selectors for preparative SFC [21]. In that context, the separation of racemic gliben-clamide analogues (7, Fig. 1-3) on cellulose- and amylose-derived CSPs was described [143]. 

Macrocyclic glycopeptides. The first of these CSPs - based on the cavity of the antibiotic vancomycin bound to silica - was introduced by Armstrong [25]. Two more polycyclic antibiotics teicoplanin and ristocetin A, were also demonstrated later. These selectors are quite rugged and operate adequately in both normal-phase and reversed-phase chromatographic modes. However, only a limited number of such selectors is available, and their cost is rather high. 

This relatively new class of CSPs incorporates glycopeptides attached covalently to silica gel. These CSPs can be used in the normal phase, reversed phase, and polar organic modes in LC [62]. Various functional groups on the macrocyclic antibiotic molecule provide opportunities for tt-tt complexation, hydrogen bonding, and steric interactions between the analyte and the chiral selector. Association of the analyte... 

Studies on hot water tank enamelsin media of varying pH demonstrate a minimum corrosion rate at pH value of 4. In citric acid (pH 2), IR measurements indicate that ion exchange is the principal mode of corrosion. Distilled water (pH 7) showed evidence of a bulk dissolution mechanism with no silica enrichment of the surface layer. In neutral solutions, the first stage of attack is leaching of alkali ions, raising the pH of solution, which subsequently breaks down the glass network of the acidic oxides. 

Modifying the mode of boiler operation to reduce boiler startups and wide load swings. Boilers are far less prone to silica vapors when operating at continuous load (provided, of course, that the basic pretreatment and water chemistry controls are in place). 

Naphthalenedisulfonate-acetonitrile as the only mobile phase with a silica column coated with a crosslinked aminofluorocarbon polymer has proven to be an effective combination for the separation of aliphatic anionic surfactants. Indirect conductivity and photometric detection modes are used to monitor these analytes. The retention of these surfactants is found to depend on both the ionic strength and the organic solvent content of the mobile phase. The mechanism of retention is considered to be a combination of both reverse phase and ion exchange processes. Selective separation of both alkanesulfonates and... 

It is important for the analyst to be able to select the best stationary phase to use for a particular chromatographic analysis. Silica gel can be used in two modes of chromatographic separations as a stationary phase in normal elution development or as a stationary phase in exclusion chromatography. 

FIGURE 12.10 Tapping mode atomic force microscopy (AFM) images of the section analyzes of ethylene-propylene-diene monomer (EPDM) rubber-melamine fiber composites. A, composite containing no dry bonding system B, composite containing resorcinol, hexamine, and silica in the concentrations 5, 3, and 15 phr, respectively. 

Zhong, Q., Innis, D., Kjoller, K., and Elings, V., Fractured polymer/silica fiber surface studied by tapping mode atomic force microscopy. Surf. Sci. Lett., 290, 688, 1993. 

Adsorption and ion exchange chromatography are well-known methods of LC. In adsorption, one frequently selects either silica or alumina as stationary phase for separation of nonionic, moderately polar substances (e.g. alcohols, aromatic heterocycles, etc.). This mode works best in the fractionation of classes of compounds and the resolution of isomeric substances (J). Ion exchange, on the other hand, is applicable to the separation of ionic substances. As to be discussed later, this mode has been well developed as a tool for analysis of urine constituents (8). 

Another example of the use of small particle silica is in the analysis of theophylline in plasma, as shown in Figure 5 (40). The clean-up procedure is simply a single extraction of the plasma with an organic solvent. This analysis has also been achieved by reverse phase chromatography (41), and this points out the fact that in some separations (e.g. with components of moderate polarity) either the adsorption or reverse phase mode can be used. 

Capillary electrophoresis (CE) has several unique advantages compared to HPLC, snch as higher efficiency dne to non-parabolic fronting, shorter analytical time, prodnction of no or much smaller amounts of organic solvents, and lower cost for capillary zone electrophoresis (CZE) and fused-silica capillary techniques. However, in CZE, the most popular separation mode for CE, the analytes are separated on the basis of differences in charge and molecular sizes, and therefore neutral compounds snch as carotenoids do not migrate and all co-elute with the electro-osmotic flow. 

An aerosil sample was methoxylated at 400 C to examine the effect of surface composition on the infrared spectrum. The difference spectrum between the methoxylated silica and the dried silica is shown in Figure 2b. Comparing this with the difference spectrum for hydroxylated silica (2a) several changes are apparent. First, the band due to the hydroxyl stretches at 3744 cm is diminished and replaced by bands at 2958 and 2856 cm" due to the asymmetric and symmetric CH stretching modes of the adsorbed methoxy. 

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