The processes of passive oxidation, deposit-induced corrosion, active oxidation, scale/substance interactions, and scale volatility are presently studied in the case of high-purity SiC and Si3N4 in pure oxygen, giving attention to such secondary elements in the ceramics as water and CO2 oxidants, combustion environment impurities, and thermal cycling. Deposit-induced corrosion is discussed for the cases of NaSO4 as well as vanadate and oxide-slag deposits; issues associated with the active-to-passive oxidation transition are noted.

/pdf/corrosion-of-silicon-based-ceramics-in-combustion-2993joj3ia.pdf

Corrosion of Silicon-Based Ceramics in Combustion Environments

Reference LCIB-ARTICLE-2007-010doi:10.1021/cr030726oView record in Web of Science Record created on 2007-02-14, modified on 2017-05-12

Inorganic and bioinorganic solvent exchange mechanisms.

Textbooks of inorganic chemistry describe the formation of adducts by coordination of an electron donor to an electron acceptor, often using the amine-boranes, X3N → BY3, as examples. In the Lewis (electron dot) formulas of the compounds, the dative bond in H3N → BH3 and the covalent bond in H3CCH3 are both represented by a shared electron pair. In the simple molecular orbital or valence bond models the wave functions of both electron pairs would be constructed in the same manner from the appropriate sp3 type atomic orbitals on the bonded atoms; the difference between the covalent and the dative bond becomes apparent only after the orbital coefficients have been analyzed. This may be the reason why many structural chemists seem reluctant to distinguish between the two types of bonds. The object of this article is to remind the reader that the physiocochemical properties of covalent and dative bonds may be – and often are – quite different, and to show that a distinction between the two provides a basis for understanding the structures of a wide range of main group metal compounds.

Covalent versus Dative Bonds to Main Group Metals, a Useful Distinction

Publisher Summary This chapter discusses the X-ray structural analyses of organolithium compounds. Lithium compounds, perhaps the most widely used organometallic synthetic intermediates, have fascinating structures. Nevertheless, organic chemistry textbooks often treat organolithium compounds merely as “carbanions” or as monomers. The chemical behavior of lithium compounds cannot be understood without the knowledge of the structures, the degree of aggregation, and the extent and nature of solvation. “Terminally bonded” organolithium compounds afford, in principle, the simplest examples of lithium–carbon σ–bonds. This class comprises lithium compounds with a single contact between lithium and a carbon atom. The dimer of lithiobicyclo butane, and of lithiodimethylsulfide, illustrates the bridging between sp 3 -hybridized carbon atoms while phenyllithium exemplifies bridging between sp 2 carbon atoms. A few organolithium compounds crystallize in aggregates with more than four subunits. Such compounds, derived from substituted acetylenic substrates (excluding simple acetylides), form oligomeric structures involving bridging lithium atoms and possible interactions of the lithium atoms with acetylenic π system. The benzophenonedilithium compound 50, formed by the reduction of benzophenone with lithium metal, crystallizes as a dimer. A large number of mixed-metal organometallic compounds have been prepared in which the hydrocarbon ligands bridge the lithium and the other metal atoms. A number of lithium/transition-metal compounds involving metal–metal multiple bonds as well as lithium–alkyl group interactions have been structurally characterized. The structure of lithium compounds without lithium–carbon bonds summarizes the structures of some lithium compounds that do not involve Li–C contacts.

X-ray structural analyses of organolithium compounds

Chemically vapor deposited silicon carbide (CVD SiC) was oxidized at temperatures of 1000°-1400°C in H2O/O2 gas mixtures with compositions of 10-90 vol% water vapor at a total pressure of 1 atm. Additional experiments were conducted in H2O/argon mixtures at a temperature of 1100°C. Experiments were designed to minimize impurity and volatility effects, so that only intrinsic water-vapor effects were observed. The oxidation kinetics increased as the water-vapor content increased. The parabolic oxidation rates in the range of 10-90 vol% water vapor (the balance being oxygen) were approximately one order of magnitude higher than the rates that were observed in dry oxygen for temperatures of 1200°-1400°C. The power-law dependence of the parabolic oxidation rate on the partial pressure of water vapor at all temperatures of the study indicated that the molecular species was not the sole rate-limiting oxidant. The determination of an activation energy for diffusion was complicated by variations in the oxidation mechanism and oxide-scale morphology with the partial pressure of water vapor and the temperature.

Variation of the Oxidation Rate of Silicon Carbide with Water‐Vapor Pressure

/pdf/the-crystal-structure-of-tetrapyridine-copper-i-perchlorate-2d2o7di8f4.pdf

The Crystal Structure of Tetrapyridine Copper(I) Perchlorate and Tetrapyridine Silver(I) Perchlorate at 260 K.

/pdf/oxidation-of-silicon-carbide-in-oxygen-and-in-water-vapour-1vruqkxlus.pdf

Oxidation of Silicon Carbide in Oxygen and in Water Vapour at 1500 degrees C.

/pdf/on-the-crystal-structure-of-the-1-1-complex-between-lithium-4bfe6xxuaa.pdf

On the Crystal Structure of the (1:1) Complex between Lithium Thiocyanate and 1,4,7,10-Tetraoxacyclododecane at Room Temperature.

/pdf/molecular-structure-of-methylcyclopropane-and-trans-1-2-i0oaylzbrw.pdf

Molecular Structure of Methylcyclopropane and trans-1,2-Dimethylcyclopropane as Studied by Gas Electron Diffraction.

/pdf/a-refinement-of-the-crystal-structure-of-the-cadmium-sulfate-1qxqngk83b.pdf

A refinement of the crystal structure of the cadmium sulfate 3cdso4.cntdot.8h2o

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