Thermodynamics, silica-water, system

Clay minerals are present in almost all surface-water and ground-water systems, and in many instances may be controlling the concentration of aluminum, silica, iron, magnesium, or other cations in solution. The thermodynamic data necessary to evaluate the state of reaction (saturation) are not available for some clay minerals, and for those minerals with published values, the data are in disagreement by as much as 10 kilocalories per mole for the same clay mineral. A critical review of the available data for kaolinite and sepiolite, incorporating both the most recent thermodynamic data for the components in the reaction schemes and a more complete computation for the solubility data, yields the values of -907.7 +1.3 and 1105.6 +0.4 kilocalories per mole for the free energy of formation of kaolinite and sepiolite, respectively. 

The same procedure can be combined with determinations of thermodynamic and dielectric properties of the silica gel-water system. 

In this work, we review briefly the phenomenology associated to LLPTs based on results obtained from computer simulations of different systems, such as silica, water, and atomic model systems. When possible, results from computer simulations are compared to available experiments. This work is organized as follows. In the next section, we present the phase diagram of polymorphic liquids supported by many computer simulations and experiments. We review the thermodynamics of first-order phase transitions and show how it is observed in computer Simula tions of polymorphic liquids. The relationship between liquid polymorphism and anomalous properties in liquids is also discussed. The next section also includes a description of glass polymorphism, its relation to liquid polymorphism, and a close comparison between experiments and simulations. In Section III, we describe computer simulation models of systems that present liquid polymorphism, with emphasis on the molecular interactions and common properties of these models that are thought to originate LLPTs. A summary and discussion are presented in Section IV. 

Although the decomposition of ozone to dioxygen is a thermodynamically favoured process,126 it is thermally stable up to 523 K and catalysts are needed to decompose it at ambient temperature in ventilation systems, in the presence of water vapour and at high space velocity. A limited number of catalysts have been evaluated and active components are mainly metals such as platinum, palladium and rhodium, and metal oxides including those of manganese, cobalt, copper, iron, nickel and silver. Supports that have been used include 7-alumina, silica, zirconia, titania and activated carbon.125,170... 

The diversified porous patterns of diatomaceous silicas are on the nano- to submicrometer scale (< 10-300 nm) and these meso- and macropores cannot be mediated by single macromolecules, not even proteins. To mimic these meso- and macroporous structures, a different approach can be applied based on a phase separation process as in the vesicle-mediated macromorphogenesis processes extensivily reviewed in Pickett-Heaps et al.I 1 In this case oil-in-water (0/W) emulsions are applied as a model system. 0/W emulsions are isotropic and thermodynamically stable liquid media with a continuous water domain and an oil domain, which are thermodynamically stabilized by a surfactant as micrometer-sized liquid entities. 

Multicomponent systems that present polyamorphism have also been reported in computer simulation studies. For example, in Ref. [35], it is found that silica has a LLCP at very low temperature. Silica is also a tetrahedral liquid and it shares many of the thermodynamic properties observed in water. In Ref. [35], two silica models were considered. In both models, the interactions among O and Si atoms are isotropic, due to single point charges and short-range interacting sites located on each atom. Both models considered in Ref. [35] are characterized by a LLCP at very low temperature and coexistence between two liquids is observed in out of equilibrium simulations close to one of the spinodal lines (see Fig. 2b). The location of the LLCP was estimated to be below the glass transition in real silica and hence, unaccessible in experiments. We note that polyamorphism in the glass state is indeed observed in compression experiments on amorphous silica [14], and is qualitatively reproduced in computer simulations [89]. Other examples of multicomponent systems that show LLPT in simulations are presented in Refs [65,90]. In these cases, a substance that already shows polymorphism is mixed with a second component. 

Here, we review the findings of simulation studies of silica related to the phenomena of polyamorphism and LLPTs. As we discuss below, these simulation studies provide ample evidence that the thermodynamic and dynamical behavior of liquid silica follow the pattern of anomalies that are well known in the case of water. However, simulations have yet to provide unequivocal evidence for an LLPT in silica. Hence, there remains important work to be carried out on this system. 

The slow reaction process is likely due to multiple factors including (I) hindered reaction kinetics and diffusivity within the viscous gel, (2) inadequate or sluggish dissolution of precursor powder, and (3) a limited potential of iron to form a potassium-based aluminosilicate inorganic polymer. Hematite is not expected to be very soluble in concentrated alkali hydroxide solution, although it dissolution is dependent on the alkali used such that solubility is highest in NaOH, followed by KOH and LiOH. It is expected that as maghemite, magnetite and hematite dissolve, Fe and Fe ions would be released and would then be free to interact with the silica gel. Iron is versatile and can exist in multiple oxidation and coordination states in the final material. In zeolite systems, the more dilute conditions favors the diffusion of iron and other species, and a more thermodynamically stable state can be reached. The use of water-soluble iron sources such as iron nitrate and potassium ferrate in hydrothermal conditions have been shown to be an effective way to produce iron zeolites in which iron is located in tetrahedral coordination. ... 

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