Application of polydentate chiral amines within magnesium-mediated asymmetric deprotonation reactions

A set of polydentate secondary amines, each containing two stereogenic centres, were prepared. These were subsequently utilised in magnesium-mediated asymmetric deprotonation reactions and excellent enantiomeric ratios were obtained (up to 94:6 er). Furthermore, these bases tend to be highly efficient in the absence of strong Lewis base additives, which demonstrates an additional practical advantage over existing protocols.     

Temperature effects on supercritical carbon dioxide extractions of hydrocarbons from geological samples

The extraction of aliphatic and aromatic hydrocarbons from New Albany Shale by supercritical carbon dioxide at different extraction temperatures is described. The main goal of this work was to determine the effect of the temperature on the extraction process (i.e. relative extraction rate and efficiency). The data suggest that temperature changes of 20 and 40 degrees for the relatively moderate extraction temperatures tested (55, 75, and 95°C), can have significant effects on both relative extraction rates and yields. While lower molecular weight aromatics presented exponential extraction profiles, similar to those of the aliphatic hydrocarbons, higher molecular weight aromatics, such as the phenanthrenes, showed a linear extraction profile. This behavior cannot be explained by solubility differences in the supercritical fluid alone, and are, therefore, most likely based on differences in the speciation of the hydrocarbons within the sample matrix. Extractions at elevated temperatures (300°C) resulted in significant increments in the relative recoveries of all compounds, but particularly for the aromatic hydrocarbons. This may be caused by structural rearrangement of the sample matrix with subsequent release of trapped hydrocarbons and possibly by C-S and S-S bond breakage.     

Kinetics and mechanism of the iodine oxidation of hydroxylamine

Studies of the stoichiometry and kinetics of the reaction between hydroxylamine and iodine, previously studied in media below pH 3, have been extended to pH 5.5. The stoichiometry over the pH range 3.4–5.5 is 2NH₂OH + 2I₂ = N₂O + 4I^? + H₂O + 4H⁺. Since the reaction is first-order in [I₂] + [I₃^?], the specific rate law, k₀, is k₀ = (k₁ + k₂/[H⁺]) {[NH₃OH⁺]₀/(1 + K_p[H⁺])} {1/(1 + K_I[I^?])}, where [NH₃OH⁺]₀ is total initial hydroxylamine concentration, and k₁, k₂, K_p, and K_I are (6.5 ± 0.6) × 10⁵ M^?1 s^?1, (5.0 ± 0.5) s^?1, 1 × 10⁶ M^?1, and 725 M^?1, respectively. A mechanism taking into account unprotonated hydroxylamine (NH₂OH) and molecular iodine (I₂) as reactive species, with intermediates NH₂OI₂^?, HNO, NH₂O, and I₂^?, is proposed.     

Methylated antimony(V) compounds: Synthesis,hydride generation properties and implications for aquatic speciation

Reports in the literature that the compounds MeSb(O)(OH)₂ and Me₂Sb(O)(OH) are present in marine and fresh-waters need to be re-examined. The results of several synthetic strategies suggest that these methylantimony(V) compounds are either environmentally inaccessible or polymeric in nature. Pure samples of various di- and tri- methylated antimony(V) species were prepared and found to undergo molecular rearrangement reactions when subjected to hydride generation procedures typically used for aquatic speciation.     

Computer simulation of moist atmospheric convection with finite elements

A computer simulation is made of cellular convection in a moist atmosphere in an endeavour to obtain a computer model which more closely approximates the observed modes of convection. A finite element Galerkin technique, with Taylor approximation and Crank-Nicolson, is employed and comparisons are made with the author's earlier finite element models of convection in an absolutely unstable atmosphere and with finite difference models. It is found that the inclusion of the moisture effects alters the structure of a cell to that of a narrow ascending region and a wider descending region with the former of larger velocities than the latter, and also alters the preferred mode of convection by increasing the aspect ratio. This more closely resembles that which is observed in the atmosphere.     

Kinetics and mechanism of the reaction between thiosulfate and chlorite ions at 90°C

The kinetics of the oxidation of S₂O₃^2? by ClO₂^? have been studied in aqueous alkaline solution at 90⁰C using classical titrimetric methods to follow the course of the reaction. The reaction takes place according to the stoichiometry S₂O₃^2? + 2ClO₂^? + 2OH^? = 2SO₄^2? + 2Cl^? + H₂O even in large S₂O₃^2? excess. There is some indication of a complex reaction pattern, but 70% of the ClO₂^? disappearance can be best described by the autocatalytic rate equation -d[ClO₂^?]/dt = k[S₂O₃^2?] [ClO₂^?] [H⁺] with k = (1.3 ± 0.2) ×10⁸ M^?2 sec^?1. The mechanism is explained by postulating nucleophilic attack of S₂O₃^2? on HClO₂ to form a chlorine-containing intermediate.     

Fluorine in the Earth and the solar system,where does it come from and can it be found?

This review (1) presents a summary of the distribution of fluorine in different fluid (surficial, subterranean, metamorphic, and magmatic–hydrothermal–geothermal) and solid (oceanic and continental crust, mantle, and core) domains of the Earth, and various extraterrestrial materials and bodies (meteorites, planets and moons, and the Sun); (2) it provides an estimate of the total fluorine abundance for the Earth and in its dominant reservoirs contributing to the Earth's fluorine endowment; and (3) it discusses key observations that could further improve our understanding of fluorine abundances and geochemical systematics.