KINETICS STUDIES OF MINERAL-WATER REACTIONS IN HYDROTHERMAL FLOW SYSTEMS AT ELEVATED TEMPERATURES AND PRESSURES

This paper describes new experimental results on mlneral-water reaction kinetics obtained in plug-flow systems at high temperatures and pressures. As an example, the rates of reaction between calcite, fluorite, albite and water in the continuous flowing system have been measured in three separate studies. All experiments are carried out by suspending a sample bag in the plug-flow vessel, by pumping water at carefully controlled rates through the vessel, and by collecting and analyzing the reacted solution. In addition, the reaction mechanisms of fluorite and albite in a packed bed reactor have been studied with the aid of an axial dispersion model. The main factors controlling the effective dissolution rate with respect to temperature, solvent flow rate, and chemistry of the input solutions have been evaluated. It is also found that a non-steady state process is, in some cases, still observed, even under conditions where steady state conditions should have been attained. These results provide informatio     

Creating Reactivity with Unstable Endmembers using Pressure and Temperature: Synthesis of Bulk Cubic Mg0.4Fe0.6N

Alloy and nitride solid solutions are prominent for structural, energy and information processing applications. There are frequently however barriers to making them. We remove barriers to reactivity here using pressure with a new synthetic approach. We target pressures where the reasons for cubic endmember nitride instability can become the driving force for cubic nitride solid solution stability. Using this approach we form a novel rocksalt Mg_0.4Fe_0.6N solid solution at between 15 and 23 GPa and up to 2500 K. This is a system where, neither an alloy nor a nitride solid solution form at ambient conditions and bulk MgN and FeN endmembers do not form, either at ambient or at high pressure. The new nitride is formed, by removing endmember lattice mismatch with pressure, allowing a stabilizing redistribution of valence electrons upon heating. This approach can be employed for a range of normally unreactive systems. Mg, Fe and enhanced nitrogen presence, may also indicate a richer reaction chemistry in our planets interior.     

A step toward the wet surface chemistry of glycine and alanine on Cu{110}: destabilization and decomposition in the presence of near-ambient water vapor

The coadsorption of water with organic molecules under near-ambient pressure and temperature conditions opens up new reaction pathways on model catalyst surfaces that are not accessible in conventional ultrahigh-vacuum surface-science experiments. The surface chemistry of glycine and alanine at the water-exposed Cu{110} interface was studied in situ using ambient-pressure photoemission and X-ray absorption spectroscopy techniques. At water pressures above 10(-5) Torr a significant pressure-dependent decrease in the temperature for dissociative desorption was observed for both amino acids, accompanied by the appearance of a new CN intermediate, which is not observed for lower pressures. The most likely reaction mechanisms involve dehydrogenation induced by O and/or OH surface species resulting from the dissociative adsorption of water. The linear relationship between the inverse decomposition temperature and the logarithm of water pressure enables determination of the activation energy for the surface reaction, between 213 and 232 kJ/mol, and a prediction of the decomposition temperature at the solid-liquid interface by extrapolating toward the equilibrium vapor pressure. Such experiments near the equilibrium vapor pressure provide important information about elementary surface processes at the solid-liquid interface, which can be retrieved neither under ultrahigh vacuum conditions nor from interfaces immersed in a solution.     

The microwave-to-flow paradigm: translating high-temperature batch microwave chemistry to scalable continuous-flow processes

The popularity of dedicated microwave reactors in many academic and industrial laboratories has produced a plethora of synthetic protocols that are based on this enabling technology. In the majority of examples, transformations that require several hours when performed using conventional heating under reflux conditions reach completion in a few minutes or even seconds in sealed-vessel, autoclave-type, microwave reactors. However, one severe drawback of microwave chemistry is the difficulty in scaling this technology to a production-scale level. This Concept article demonstrates that this limitation can be overcome by translating batch microwave chemistry to scalable continuous-flow processes. For this purpose, conventionally heated micro- or mesofluidic flow devices fitted with a back-pressure regulator are employed, in which the high temperatures and pressures attainable in a sealed-vessel microwave chemistry batch experiment can be mimicked.     

High-pressure chemistry of nitride-based materials

Besides temperature at one atmosphere, the applied pressure is another important parameter for influencing and controlling reaction pathways and final reaction products. This is relevant not only for the genesis of natural minerals, but also for synthetic chemical products and technological materials. The present critical review (316 references) highlights recent developments that utilise high pressures and high-temperatures for the synthesis of new materials with unique properties, such as high hardness, or interesting magnetic or optoelectronic features. Novel metal nitrides, oxonitrides as well as the new class of nitride-diazenide compounds, all formed under high-pressure conditions, are highlighted. Pure oxides and carbides are not considered here. Moreover, syntheses under high-pressure conditions require special equipment and preparation techniques, completely different from those used for conventional synthetic approaches at ambient pressure. Therefore, we also summarize the high-pressure techniques used for the synthesis of new materials on a laboratory scale. In particular, our attention is focused on reactive gas pressure devices with pressures between 1.2 and 600 MPa, multi-anvil apparatus at P < 25 GPa and the diamond anvil cell, which allows work at pressures of 100 GPa and higher. For example, some of these techniques have been successfully upgraded to an industrial scale for the synthesis of diamond and cubic boron nitride.     

Organoselenium Chemistry in Stereoselective Reactions

Selenium-based methods have developed rapidly over the past few years asnd organoselenium chemistry has become a very useful tool in the hands of synthetic chemists. The different reactivity of selenium-containing compounds in contrast to the sulfur analogues has led to versatile and new synthetic methods in organic chemistry. Various functionalities can be selectively introduced into complex molecules under very mild reaction conditions. In this review, the principles of organoselenium chemistry are traced back to their origins and are highlighted with respect to stereoselective synthesis. The unique properties of selenium allow the development of new and highly selective transformations, which can be employed subsequently in new routes for the synthesis of versatile chiral building blocks and for natural product synthesis.     

Investigation on 1-Heptene/Air Laminar Flame Propagation under Elevated Pressures

The laminar flame propagation of 1-heptene/air mixtures covering equivalence ratios from 0.7 to 1.5 is investigated in a constant-volume cylindrical combustion vessel at 373 K and elevated pressures (1, 2, 5, and 10 atm). Laminar flame speed and Markstein length are derived from the recorded schlieren images. A kinetic model of 1-heptene combustion is developed based on our previous kinetic model of 1-hexene. The model is validated against the laminar flame speed data measured in this work and the ignition delay time data in literature. Modeling analyses, such as sensitivity analysis and rate of production analysis, are performed to help understand the high temperature chemistry of 1-heptene under various pressures and its influence on the laminar flame propagation. Furthermore, the laminar flame propagation of 1-heptene/air mixtures is compared with that of n-heptane/air mixtures reported in our previous work. The laminar flame speed values of 1-heptene/air mixtures are observed to be faster than those of n-heptane/air mixtures under most conditions due to the enhanced exothermicity and reactivity.     

Electric Field Enhanced Ammoxidation of Aldehydes Using Supported Fe Clusters Under Ambient Oxygen Pressure

Heterogeneous catalytic ammoxidation provides an eco-friendly route for the cyanide-free synthesis of nitrile compounds, which are important precursors for synthetic chemistry and pharmaceutical applications. However, in general such a process requires high pressures of molecular oxygen at elevated temperatures to accelerate the oxygen reduction and imine dehydrogenation steps, which is highly risky in practical applications. Here, we report an electric field enhanced ammoxidation system using a supported Fe clusters catalyst (Fe/NC), which enables efficient synthesis of nitriles from the corresponding aldehydes under ambient air pressure at room temperature (RT). A synergistic effect between the external electric field and the Fe/NC catalyst promotes the ammonia activation and the dehydrogenation of the generated imine intermediates and avoids the unwanted backwards reaction to aldehydes. This electric field enhanced ammoxidation system presents high efficiency and selectivity for the conversion of a series of aldehydes under mild conditions with high durability, rendering it an attractive process for the green synthesis of nitriles with fragile functional groups.     

Formation of a high coverage (3 x 3) NO phase on Pd(111) at elevated pressures: interplay between kinetic and thermodynamic accessibility

Using in situ polarization modulation infrared reflection absorption spectroscopy and density functional theory calculations, a new high-coverage monomeric NO adsorption state on Pd(111) was observed and proposed to have a (3 x 3)-7NO structure. Formation of this high coverage NO phase was found to take place only at elevated pressure and temperature conditions showing that some of the accessible thermodynamic equilibrium states at elevated temperatures and pressures are thermodynamically unfavorable or kinetically hindered at lower temperatures and pressures. Our results emphasize the danger of extrapolating results from traditional surface science experiments performed under ultrahigh vacuum to elevated temperature and pressure conditions encountered in heterogeneous catalysis.     

Un siècle de Hautes Pressions : Développements technologiques et scientifiques

A century of high pressure: technological and scientific developments. This paper is devoted to the development of high pressures during approximately one century and the main scientific domains concerned by such a development.Roughly three main periods have been considered: (i) the early period at the beginning of XX^th century (1900 → 1970), the second period (1970 → 2005) taking into account some important technical developments (the high pressure vessels with a large volume, the diamond anvil cell associated with the laser heating…), and a prospective concerning, on the basis of recent results, the possible developments during the next 10 years.The early period was mainly characterized by some industrial problems: the improvement of the mechanical properties of alloys and consequently the requirement for performant cutting and machining tools (leading to the diamond synthesis), the synthesis of ammonia (initiated both by the development of explosives and the requirement of fertilisers), the preservation of foods (correlated to a new organization of the Society), the elaboration of single crystals characterized by specific physical properties with functional properties for the development of some industrial sectors (telecommunications, computer science…).The more recent period (1970–2005) has been characterized by the development of new performant tools able to improve the development of scientific domains (diamond-anvil-cell and Geosciences, Belt-type, multi-anvils and toroïd equipments and the Chemistry of Materials, high pressure vessels and Food-Science…).During these last years roughly three main tendances have been observed: (i) the investigation of researches at extreme (P, T) conditions, (ii) the improvement of researches involving mild (P, T) conditions mainly in liquid phase (hydrothermal and solvothermal synthesis), (iii) the development of high pressures in Biology and Biotechnology.During the next years the extension of high pressure level and also the development of the next scientific domains would improve research involving different planets. In parallel the development of chemical reactions in mild P, T conditions in a liquid phase would allow to prepare new hybrid nano-systems at the interface between inorganic and organic chemistry, inorganic and biological chemistry or new supramolecular systems. The applications of high pressures in Biotechnology – due in particular to the low energy conveyed by pressure – would lead to new research domains or industrial processes involving either the inactivation of pathogen microorganisms with the development of new vaccines or the domain of the proteins…     

Trends in non-polluting organic surface coatings chemistry

Paint application is a sector of human activity, where the common use according to product determination by the end user or small craftmans business contributes most obviously to environment pollution, In first instance of course by solvent evaporation. There is a steadily increasing pressure by governmental authorities on the plant industry to reduce solvent emission from its products. At the same time, more integral approaches of environmental impact assessments - so called life cycle analysis - become more and more important. The paint industry answers these challenges by development of new types of coatings, which mainly means new types of binder polymers and new types of crosslink chemistry. Advances in the understanding of polymer physical chemistry as well as the advent of new synthesis concepts lead to a number of emerging technologies expected to contribute significantly to reduction of pollution by paint application. While in industrial paint application end-of-the-pipe technology is still economically favourably competing with the advanced paint chemistry concepts (e.g. high-solids, waterborne, UV-curing, electrocoating, powder coating and supercritical CO₂-application), the situation in the large sector of end-user and craftsman application of paint is much more difficult, at least in the sector of high performance and particularly high gloss coatings. End-of-pipe-technology is unapplicable and, on the other hand, degrees of freedom in application equipment and curing conditions are limited. Furthermore, labour safety requirement further restrict the scope of applicable new chemistry.     

High pressure chemistry in a Fourier transform ion cyclotron resonance mass spectrometer using a split-pair magnet

A new experimental method has been developed to probe ion/molecule reactions at gas pressures up to 0. 1 torr. A Fourier transform ion cyclotron resonance (FTICR) mass spectrometer has been constructed to trap ions within the trapped ion cell at these pressures for time intervals up to several hundred milliseconds, allowing the ions to undergo several million collisions. Multiple pulsed valves inject the gaseous reagents in brief, high pressure bursts. A unique, high conductance vacuum chamber rapidly reduces the gas pressure from as high as 0.01 torr to near background pressures in 2–5 s for optimum operation of the FTICR for identifying the ionic products. A pressure of 0.1 torr is attainable but results in slower gas evacuation. High pressure operation of this instrument is demonstrated for ion chemistry in silane, argon, and silicon tetrafluoride. Pressures are sufficiently high to allow termolecular formation of adducts with the trapped ion cell. Negative ion formation in silane has greatly improved efficiency due to the high pressure ionization. Trace impurities at the ppm level in argon and silicon tetrafluoride are detected through chemical ionization afforded by the large number of ion/molecule collisions.     

The chemical imagination at work in very tight places

Diamond-anvil-cell and shock-wave technologies now permit the study of matter under multimegabar pressure (that is, of several hundred GPa). The properties of matter in this pressure regime differ drastically from those known at 1 atm (about 10(5) Pa). Just how different chemistry is at high pressure and what role chemical intuition for bonding and structure can have in understanding matter at high pressure will be explored in this account. We will discuss in detail an overlapping hierarchy of responses to increased density: a) squeezing out van der Waals space (for molecular crystals); b) increasing coordination; c) decreasing the length of covalent bonds and the size of anions; and d) in an extreme regime, moving electrons off atoms and generating new modes of correlation. Examples of the startling chemistry and physics that emerge under such extreme conditions will alternate in this account with qualitative chemical ideas about the bonding involved.     

Carbon Dioxide as an Alternative C1 Synthetic Unit: Activation by Transition-Metal Complexes

The carbon dioxide molecule has been of limited importance as a synthetic unit in organic chemistry. When it is coordinated to transition metals, however, completely new possibilities arise; CO₂ can bond to metal complexes in a variety of ways and can enter into insertion and coupling reactions, or become catalytically attached to other substrates. The formation of C? C bonds between carbon dioxide and unsaturated hydrocarbons under conditions of homogeneous catalysis makes available new synthetic routes to industrially interesting organic compounds.     

Rhodium(0) nanoparticles supported on nanocrystalline hydroxyapatite: highly effective catalytic system for the solvent-free hydrogenation of aromatics at room temperature

The hydrogenation of aromatics under mild conditions remains a challenge in the fields of synthetic and petroleum chemistry. Described herein is a new catalytic material that shows excellent catalytic performance in terms of activity, selectivity, and reusability in the hydrogenation of aromatics in solvent-free systems under mild conditions. The catalyst, consisting of rhodium nanoparticles supported on nanocrystalline hydroxyapatite, can quantitatively hydrogenate neat benzene to cyclohexane with exceptionally high rates (initial TOF > 10(3) h(-1)) at 298 K and 3 bars of initial H(2) pressure. This new material maintains its inherent catalytic activity after several reuses. Importantly, catalyst preparation does not require elaborate procedures because the active metal nanoparticles are readily formed from the in situ reduction of Rh(3+)-exchanged hydroxyapatite while submerged in the aromatic solvent at room temperature under 3 bars of H(2) pressure.     

Impact of a pressure drop on a monolithic capillary column on the efficiency and separation ability of the column

The impact of inlet and outlet column pressures on column separation properties was investigated for monolithic capillary column in gas chromatography. It was demonstrated that the classical Van Deemter equation does not allow us to make a clear choice of the optimal separation conditions. More relevant data can be obtained from the dependence of the height equivalent to a theoretical plate (HETP) on the inlet and outlet column pressures. The dependence ensures that the minimum HETP value can be achieved at high values of inlet and outlet column pressures, but the ratio of the pressures must approach 1. The efficiency of the column under these optimal conditions can exceed by 25–35% the column efficiency under the optimal conditions found using the classical Van Deemter plot. It was shown that a decrease in inlet and outlet column pressures even at a relative pressure close to 1 leads to an increase in HETP and the loss of column separation ability.     

Amine‐Catalyzed Direct Photoarylation of Unactivated Arenes

Constructing biaryls through direct aromatic C? H functionalization of unactivated arenes has become a popular topic in organic chemistry. Many efficient methods have been developed. In this Communication, a direct arylation of unactivated arenes with a broad range of aryl iodides is reported. This reaction proceeds through a new type of amine‐catalyzed single electron transfer initiated radical coupling procedure to form biaryls in high yields under UV irradiation at room temperature. Only 20 mol% of TMEDA is used as the catalyst. No other additives are required for this transformation, thus avoiding the use of toxic transition metal catalysts, strong bases, or large amounts of other organic additives. This greener protocol provides a new strategy to achieve direct aromatic C? H functionalization and offers a new example of cost‐effective and environmentally benign access to biaryls.     

Mechanochemie: Chemie mit dem Hammer

Mechanochemistry offers a wide spectrum of possible applications. The standard preparation methods of solid state chemistry often require high temperatures or pressures, well defined gas atmospheres or special reactants' conditions. In the mechanochemical process not more than an adequately powerful ball mill with accessories is required. With this method, a lot of chemical reactions can be carried out via a non-thermal, sustainable reaction pathway.     

High-pressure study of lithium azide from density-functional calculations

The structural, electronic, optical, and vibrational properties of LiN(3) under high pressure have been studied using plane wave pseudopotentials within the generalized gradient approximation for the exchange and correlation functional. The calculated lattice parameters agree quite well with experiments. The calculated bulk modulus value is found to be 23.23 GPa, which is in good agreement with the experimental value of 20.5 GPa. Our calculations reproduce well the trends in high-pressure behavior of the structural parameters. The present results show that the compressibility of LiN(3) crystal is anisotropic and the crystallographic b-axis is more compressible when compared to a- and c-axes, which is also consistent with experiment. Elastic constants are predicted, which still awaits experimental confirmation. The computed elastic constants clearly show that LiN(3) is a mechanically stable system and the calculated elastic constants follow the order C(33) > C(11) > C(22), implying that the LiN(3) lattice is stiffer along the c-axis and relatively weaker along the b-axis. Under the application of pressure the magnitude of the electronic band gap value decreases, indicating that the system has the tendency to become semiconductor at high pressures. The optical properties such as refractive index, absorption spectra, and photoconductivity along the three crystallographic directions have been calculated at ambient as well as at high pressures. The calculated refractive index shows that the system is optically anisotropic and the anisotropy increases with an increase in pressure. The observed peaks in the absorption and photoconductivity spectra are found to shift toward the higher energy region as pressure increases, which implies that in LiN(3) decomposition is favored under pressure with the action of light. The vibrational frequencies for the internal and lattice modes of LiN(3) at ambient conditions as well as at high pressures are calculated from which we predict that the response of the lattice modes toward pressure is relatively high when compared to the internal modes of the azide ion.     

Hydrophobic interaction electrophoresis under high hydrostatic pressure: study of the effects of pressure upon the interaction of serum albumin with a long-chain aliphatic ligand

Hydrophobic affinity electrophoresis under high hydrostatic pressure has been developed to study the interaction between fatty acid-free bovine serum albumin and a long-chain aliphatic ligand physically immobilized within the gel matrix. From apparent association constants at various pressures and temperatures, apparent thermodynamic parameters including the volume change in binding were calculated. The results are as expected for hydrophobic interactions between the long-chain alkyl ligand and a high-affinity long-chain fatty acid binding site. The feasibility of high-pressure affinity electrophoresis is demonstrated. This new high-pressure technique provides a direct means for studying quantitatively the effects of pressure upon protein-ligand interactions. It could become a suitable tool for the investigation of protein binding sites' topography.