Silicate determination, kinetic

Salah, M.S. and Magnus, U.L., A kinetic sequential injection analysis method for silicate determination in water samples containing phosphates, JFIA (2005), 22(1), 25-29. 

No attempt is made here to explain the intricate temperature dependence of the hydrations of the three calcium silicates. Work on the kinetics of these hydration processes is not complete, so the authors could give at present only highly tentative and speculative explanations. The conclusion from Figures 2 to 7 for the purposes of this paper is that the surface area development in pastes of all three silicates is determined primarily by the degree of hydration of the silicate. For a simple reaction, in which the reactants have negligible surface areas compared with the reaction products, such a conclusion would be trivial. However, for as complex... 

Because C-S-H gel is nearly amorphous. X-ray diffraction has given only very general indications of its structure. The nature of the silicate anions has been determined from the kinetics of the reaction with molybdate (S43), and, in greater detail, by trimethylsilylation (TMS) and Si NMR. In TMS methods, the sample is treated with a reagent that converts the silicate anions into the corresponding silicic acids, which then react further with replacement of SiOH by SiOSi(CH3)3. The resulting TMS derivatives can be identified and semiquantitatively determined by various procedures, of which the most widely used have been differential evaporation to isolate the... 

Experimentally determined dissolution kinetics are applicable to natural weathering processes of silicate rocks. Mass transfer from the mineral to the aqueous phase was determined to be incon-gruent under a range of experimental conditions. Transfer rates of individual species (Q) at times (t) can usually be described by one of two rate expressions ... 

High-resolution Si NMR spectroscopy was used to study the hydrolysis and condensation kinetics of monomeric and dimeric species in the silicate sol-gel system. Peak assignments for the kinetics experiments were determined by comparing add-catalyzed reaction solutions prepared with limited amounts of water with the synthetically prepared dimeric, trimeric, and tetrameric species. Si NMR peaks were assigned for 5 of the 10 possible dimeric species. The temporal evolution of hydrolysis and condensation products has been compared with a kinetic model developed in our laboratory, and rate constants have been determined. The results indicate that the water-producing condensation of dimeric species is approximately 5 times slower than the water-producing condensation of the monomeric species. The alcohol-producing condensation of dimeric species is comparable with that of monomeric species. 

Ingle and Crouch described a diflerential kinetic method for silicate and phosphate based on the faster rate of formation of heteropoly molybdenum blue from the yellow heteropoly acids in the presence of phosphate than in the presence of silicate. They found that silicon in the range of 1 to 10 ppm could be determined with 3% accuracy in the presence of 10 ppm of phosphorus, and phosphorus in the range of 1 to 10 ppm with 1% accuracy in the presence of 50 ppm of silicon. This system was also automated, with the analyses of mixtures being performed in less than 5 min. 

Field observations implicating the importance of aluminosilicates to opal diagenesis were followed by laboratory experiments to determine the effect of Al(lll) derived from detrital aluminum silicate on the solubility and dissolution kinetics of opal. Dixit et al. (2001) mixed opal-rich ( 90% Si02) sediments from the Southern Ocean with different amounts of either kaolinite or ground basalt in long-term (21 months) batch... 

Silicate is determined as a reduced silicomolybdate dye 14). The method is sensitive to the reductant used, either stannous chloride or ascorbic acid. The reaction kinetics with stannous chloride are much faster than with ascorbic acid. The analysis with stannous chloride is more sensitive, therefore, and has a detection limit of 0.5 pM compared to 1.0 pM when ascorbic acid is used. Eighty determinations can be made per hour at these detection limits. A detection limit of 0.1 pM can be obtained if the sampling rate is decreased to 50 per hour 14). The analysis with stannous chloride has a smaller salt error than with ascorbic acid, but the interference due to... 

In the acidic route (with pH < 2), both kinetic and thermodynamic controlling factors need to be considered. First, the acid catalysis speeds up the hydrolysis of silicon alkoxides. Second, the silica species in solution are positively charged as =SiOH2 (denoted as I+). Finally, the siloxane bond condensation rate is kinetically promoted near the micelle surface. The surfactant (S+)-silica interaction in S+X 11 is mediated by the counterion X-. The micelle-counterion interaction is in thermodynamic equilibrium. Thus the factors involved in determining the total rate of nanostructure formation are the counterion adsorption equilibrium of X on the micellar surface, surface-enhanced concentration of I+, and proton-catalysed silica condensation near the micellar surface. From consideration of the surfactant, the surfactants first form micelles as a combination of the S+X assemblies, which then form a liquid crystal with molecular silicate species, and finally the mesoporous material is formed through inorganic polymerization and condensation of the silicate species. In the S+X I+ model, the surfactant-to-counteranion... 

This method is also referred to as the miscible-displacement or continuous-flow method. In this method a thin disk of dispersed solid phase is deposited on a porous membrane and placed in a holder. A pump is used to maintain a constant flow velocity of solution through the thin disk and a fraction collector is used to collect effluent aliquots. A diagram of the basic experimental setup is shown in Fig. 2-6. A thin disk is used in an attempt to minimize diffusion resistances in the solid phase. Disk thickness, disk hydraulic conductivity, and membrane permeability determine the range of flow velocities that are achievable. Dispersion of the solid phase is necessary so that the transit time for a solute molecule is the same at all points in the disk. However, the presence of varying particle sizes and hence pore sizes may produce nonuniform solute transit times (Skopp and McCallister, 1986). This is more likely to occur with whole soils than with clay-sized particles of soil constituents. Typically, 1- or 2-g samples are used in kinetic studies on soils with the thin disk method, but disk thicknesses have not been measured. In their study of the kinetics of phosphate and silicate retention by goethite, Miller et al. (1989) estimated the thickness of the goethite disk to be 80 /xm. 

P. Linares, M.D. Luque de Castro, M. Valcarcel, Fluorimetric differential kinetic determination of silicate and phosphate in waters by flow-injection analysis, Talanta 33 (1986) 899. 

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