Silica thermodynamic

Koopal and co-workers [186] have extended this thermodynamic analysis to investigate the competitive wetting of a solid by two relatively immiscible liquids. They illustrate the tendency of silica to be preferentially wet by water over octane, a phenomenon of importance in oil reservoirs. 

Gu Y and Fluang Z 1989 Thermodynamics of hemimicellization of cetyltrimethylammonium bromide at the silica gel/water interface Colloids Surf. 40 71-6... 

Normally, a slight excess of sulfuric acid is used to bring the reaction to completion. There are, of course, many side reactions involving siHca and other impurity minerals in the rock. Fluorine—silica reactions are especially important as these affect the nature of the calcium sulfate by-product and of fluorine recovery methods. Thermodynamic and kinetic details of the chemistry have been described (34). 

The full explanation of solute retention on silica, bonded phases or for that matter in liquid/liquid systems is still elusive and controversial. The thermodynamic approach... 

Adsorption of hard sphere fluid mixtures in disordered hard sphere matrices has not been studied profoundly and the accuracy of the ROZ-type theory in the description of the structure and thermodynamics of simple mixtures is difficult to discuss. Adsorption of mixtures consisting of argon with ethane and methane in a matrix mimicking silica xerogel has been simulated by Kaminsky and Monson [42,43] in the framework of the Lennard-Jones model. A comparison with experimentally measured properties has also been performed. However, we are not aware of similar studies for simpler hard sphere mixtures, but the work from our laboratory has focused on a two-dimensional partly quenched model of hard discs [44]. That makes it impossible to judge the accuracy of theoretical approaches even for simple binary mixtures in disordered microporous media. 

Dove, P. (1995). Kinetic and thermodynamic controls on silica reactivity in weathering environments. In "Chemical Weathering Rates of Silicate Minerals" (A. F. White and S. L. Brantley, eds), Mineralogical Society of America Washington, DC, Reviews in Mineralogy 31, 235-290. 

There are very few examples of asymmetric synthesis using optically pure ions as chiral-inducing agents for the control of the configuration at the metal center. Chiral anions for such an apphcation have recently been reviewed by Lacour [19]. For example, the chiral enantiomerically pure Trisphat anion was successfully used for the stereoselective synthesis of tris-diimine-Fe(ll) complex, made configurationally stable because of the presence of a tetradentate bis(l,10-phenanthroline) ligand (Fig. 9) [29]. Excellent diastereoselectivity (>20 1) was demonstrated as a consequence of the preferred homochiral association of the anion and the iron(ll) complex and evidence for a thermodynamic control of the selectivity was obtained. The two diastereoisomers can be efficiently separated by ion-pair chromatography on silica gel plates with excellent yields. 

Ethanol can be derived from biomass by means of acidic/enzymatic hydrolysis or also by thermochemical conversion and subsequent enzymatic ethanol formation. Likewise for methanol, hydrogen can be produced from ethanol with the ease of storage/transportation and an additional advantage of its nontoxicity. Apart from thermodynamic studies on hydrogen from ethanol steam reforming,117-119 catalytic reaction studies were also performed on this reaction using Ni-Cu-Cr catalysts,120 Ni-Cu-K alumina-supported catalysts,121 Cu-Zn alumina-supported catalysts,122,123 Ca-Zn alumina-supported catalysts,122 and Ni-Cu silica-supported catalysts.123... 

The book focuses on three main themes catalyst preparation and activation, reaction mechanism, and process-related topics. A panel of expert contributors discusses synthesis of catalysts, carbon nanomaterials, nitric oxide calcinations, the influence of carbon, catalytic performance issues, chelating agents, and Cu and alkali promoters. They also explore Co/silica catalysts, thermodynamic control, the Two Alpha model, co-feeding experiments, internal diffusion limitations. Fe-LTFT selectivity, and the effect of co-fed water. Lastly, the book examines cross-flow filtration, kinetic studies, reduction of CO emissions, syncrude, and low-temperature water-gas shift. 

As in the previous example (Fig. 26.1), silica concentration in the calculations asymptotically approaches a single value, regardless of the initial concentration. The final silica concentration, however, does not represent a thermodynamic equilibrium, since (as we can see in Fig. 26.2) it is supersaturated with respect to quartz and undersaturated with respect to cristobalite. 

Ostwald s step rule holds that a thermodynamically unstable mineral reacts over time to form a sequence of progressively more stable minerals (e.g., Morse and Casey, 1988 Steefel and Van Cappellen, 1990 Nordeng and Sibley, 1994). The step rule is observed to operate, especially at low temperature, in a number of min-eralogic systems, including the carbonates, silica polymorphs, iron and manganese oxides, iron sulfides, phosphates, clay minerals, and zeolites. 

Figure 26.7. Only after the mineral has almost disappeared does the silica concentration begin to decrease. Since the surface area and rate constant for cristobalite are considerably greater than those of quartz, the fluid remains near equilibrium with cristobalite until it in turn nearly disappears. Finally, after several hundred thousand years of reaction, the fluid approaches saturation with quartz and hence thermodynamic equilibrium.

Pure silica zeolites or molecular sieves are metastable with regards to the thermodynamic stable polymorph at ambient conditions, a-quartz. However, they are... 

In many cases, however, the silicas are formed under kinetic control,16 and not thermodynamic, resulting often in living materials that undergo structural modifications, and thus changes in reactivity, even months after preparation (Figure 5.5). 

If a surface precipitate of metal hydroxy-polymer has formed on an adsorbent, the -pH relationship for the coated adsorbent should resemble closely that observed for particles consisting purely of the hydroxy-polymer or the hydrous oxide of the metal (15). This kind of evidence for Co(ll), La(lII), and Th(lV) precipitation on silica colloids was cited by James and Healy (15). It should be noted, however, that the increase in C toward a maximum value often occurs at pH values well below that required thermodynamically to induce bulk-solution homogeneous precipitation of a metal hydrous oxide (15, 16). If surface precipitation is in the incipient stage under these conditions, it must be a nucleation phenomenon. James and Healy (15) argue that the microscopic electric field at the surface of a charged adsorbent is sufficiently strong to lower the vicinal water activity and induce precipitation at pH values below that required for bulk-solution precipitation of a metal hydrous oxide. 

C. P. Fitzsimmons, C. B. Knkbnde.d Precision Enthalpy of Solution Calorimeterfor Slow Rates of Solution. The Enthalpy of Solution of Vitreous Silica in Hydrofluoric Acid. J. Chem. Thermodynamics 1970, 2, 265-273. 

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