Thermodynamics hydrothermal synthesis

Diaspore, which is thermodynamically more stable than boehmite, can also be obtained by hydrothermal transformation of gibbsite or boehmite, but its formation is slow. Higher temperatures (i.e., >200 °C) and pressures (>15 MPa) are required for the synthesis, and the presence of diaspore seed crystals helps to avoid boehmite formation. Methods to produce weU-crystaUized diaspore have been reported these include hydrothermal synthesis at 300 °C and 3.45 x 10 Pa (5000 psi) over a 72-h period (67) or high-pressure calcination of boehmite (68). 

Lencka, M.M., Riman, R.E. Thermodynamic modeling of hydrothermal synthesis of ceramic powders. Chem. Mater. 5,61-70 (1993)... 

Lencka, M.M. and Riman, R.E. (1995) Thermodynamics of the hydrothermal synthesis of calcium titanate with reference to other alkaline-earth titanates. Chem. Mater., 7 (1), 18-25. 

Low-temperature solid-state synthesis is preferred in most cases, where appropriate, for obvious reasons such as energy and cost economy and process safety or for critical concerns regarding the accessibility of compounds that are stable only at low temperatures or non-equilibrium phases, i.e., compounds thermodynamically unstable with respect to the obtained phase (e.g., a ternary instead of binary phase). The use of low-temperature eutectics as solvents for the reactants, hydrothermal growth... 

The synthesis of chalcogenides such as those of the rare earth elements has traditionally been performed through the reaction of rare earth metals or oxides with a molten or vaporous chalcogen source in a high-temperature environment. Soft synthetic methods utilizing lower temperature conditions, such as hydrothermal or flux syntheses, can allow access also to thermodynamically metastable phases. Flux syntheses of R chalcogenides via an alkali poly-chalcogenide flux have been shown to be extremely versatile for the preparation of many new structures, some of which cannot be obtained by direct synthesis from the elements. 

Theoretical calculations [43] based on first principles molecular dynamics discussed in Sect. 3.2.6 have suggested that Mg Al LDHs are most stable for n = 3 (i.e. x = 0.25) and indeed many minerals, including hydrotalcite itself, have this stoichiometry [4]. It has been reported that the synthesis of LDHs (with benzoate or terephthalate anions in the interlayers) from solutions containing Mg/Al = 2, leads to LDHs having the same composition when the synthesis is carried out at moderate temperatures but LDHs with Mg/Al = 3 (plus AlOOH) when the reaction is carried out under hydrothermal conditions [44]. It was proposed that the latter ratio represents the thermodynamically most favorable product. A similar observation has been reported [45] for solutions with Ni VPe = 2, where hydrothermal preparation led to segregation of an LDH with Ni VPe = 3 and Ni Fe 204. An attempt to synthesize a Co sAl LDH resulted in partial oxidation of the Co and formation of a Co o.yCo o.s LDH with complete migration of Al " from the layers to generate interlayer aluminum oxy-species [46]. 

In the absence of oxygen and in the presence of H2, reduced carbon is thermodynamically preferred. That is certainly true deep in the ocean, for example, near hydrothermal vents, where the synthesis of reduced organic compounds is thermodynamically favored. Shock, Cody, and others have exploited that fact to propose net synthesis of organic molecules in anoxic environments.14,15... 

Hybrid framework compounds, including both metal-organic coordination polymers and systems that contain extended inorganic connectivity (extended inorganic hybrids), have recently developed into an important new class of solid-state materials. We examine the diversity of this complex class of materials, propose a simple but systematic classification, and explore the chemical and geometrical factors that influence their formation. We also discuss the growing evidence that many hybrid frameworks tend to form under thermodynamic rather than kinetic control when the synthesis is carried out under hydrothermal conditions. Finally, we explore the potential applications of hybrid frameworks in areas such as gas separations and storage,... 

Celsian. One of the compounds important for ceramic materials science is monoclinic celsian, BaAljSijO, a compound with a feldspar structure. Flowever, its formation during solid phase synthesis occurs in several stages with the formation of a very stable hexagonal modification of BaAljSijO as an intermediate phase. Its subsequent transition into thermodynamically stable monoclinic celsian is hindered and requires calcination at elevated temperatures ( 1600°C) either the hydrothermal treatment, or the use of mineralizers [12-14]. 

Similar to the porosils, the dense, thermodynamically stable Si02 modification a-quartz is also prepared under hydrothermal conditions. However, in the industrial process for the production of quartz, the temperatures are rather high (around 400°C). In this process, NaOH is added as a mineralizer to the aqueous solution to promote dissolution of the silica precursor. The reaction mixtures for the preparation of porosils and other zeotype materials also generally contain a mineralizer, but the reaction conditions are much milder. Synthesis temperatures are below 200°C, typically between 140 and 180°C. Some zeolites can even be prepared from aqueous solutions under reflux at normal pressure. These mild synthesis conditions provide the kinetic control necessary to form metastable products [5-9]. 

The discussion of hydrothermal diamond synthesis is divided into two sections, dealing with synthesis from C-H-0 liquids and synthesis based on decomposition of silicon carbide, respectively. Both start with thermodynamic calculations in order to demonstrate the theoretical possibility of carbon formation before the experimental findings are summarized. Naturally, equilibrium calculations do not consider kinetic limitations. 

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