One possible way to promote the bond-selective chemical-reactions by frequency-modulated lasers

It is proposed in this paper that we can use frequency-modulated (FM) lasers to realize bond-selective chemical reactions or to raise the efficiency of molecular isotope separation. Examples are given for HF molecule and the C–H bond in some hydrocarbons.

Transient flow patterns and bubble slug lengths in parallel microchannels with oxygen gas bubbles produced by catalytic chemical reactions

Transient flow patterns and bubble slug lengths were investigated with oxygen gas (O-2) bubbles produced by catalytic chemical reactions using a high speed camera bonded with a microscope. The microreactor consists of an inlet liquid plenum, nine parallel rectangular microchannels followed by a micronozzle, using the MEMS fabrication technique. The etched surface was deposited by the thin platinum film, which is acted as the catalyst. Experiments were performed with the inlet mass concentration of the hydrogen peroxide from 50% to 90% and the pressure drop across the silicon chip from 2.5 to 20.0 kPa. The silicon chip is directly exposed in the environment thus the heat released via the catalytic chemical reactions is dissipated into the environment and the experiment was performed at the room temperature level. It is found that the two-phase flow with the catalytic chemical reactions display the cyclic behavior. A full cycle consists of a short fresh liquid refilling stage, a liquid decomposition stage followed by the bubble slug flow stage. At the beginning of the bubble slug flow stage, the liquid slug number reaches maximum, while at the end of the bubble slug flow stage the liquid slugs are quickly flushed out of the microchannels. Two or three large bubbles are observed in the inlet liquid plenum, affecting the two-phase distributions in microchannels. The bubble slug lengths, cycle periods as well as the mass flow rates are analyzed with different mass concentrations of hydrogen peroxide and pressure drops. The bubble slug length is helpful for the selection of the future microreactor length ensuring the complete hydrogen peroxide decomposition. Future studies on the temperature effect on the transient two-phase flow with chemical reactions are recommended.

State-to-state dynamics of elementary chemical reactions using Rydberg H-atom translational spectroscopy

In this review, a few examples of state-to-state dynamics studies of both unimolecular and bimolecular reactions using the H-atom Rydberg tagging TOF technique were presented. From the H2O photodissociation at 157 nm, a direction dissociation example is provided, while photodissociation of H2O at 121.6 has provided an excellent dynamical case of complicated, yet direct dissociation process through conical intersections. The studies of the O(D-1) + H-2 --> OH+H reaction has also been reviewed here. A prototype example of state-to-state dynamics of pure insertion chemical reaction is provided. Effect of the reagent rotational excitation and the isotope effect on the dynamics of this reaction have also been investigated. The detailed mechanism for abstraction channel in this reaction has also been closely studied. The experimental investigations of the simplest chemical reaction, the H-3 system, have also been described here. Through extensive collaborations between theory and experiment, the mechanism for forward scattering product at high collision energies for the H+HD reaction was clarified, which is attributed to a slow down mechanism on the top of a quantized barrier transition state. Oscillations in the product quantum state resolved different cross sections have also been observed in the H+D-2 reaction, and were attributed to the interference of adiabatic transition state pathways from detailed theoretical analysis. The results reviewed here clearly show the significant advances we have made in the studies of the state-to-state molecular reaction dynamics.

Design of silicone rubber according to requirements based on the multi-objective optimization of chemical reactions

The explicit expression between composition and mechanical properties of silicone rubber was derived from the physics of polymer elasticity, the implicit expression among material composition, reaction conditions and reaction efficiency was obtained from chemical thermodynamics and kinetics, and then an implicit multi-objective optimization model was constructed. Genetic algorithm was applied to optimize material composition and reaction conditions, and the finite element method of cross-linking reaction processes was used to solve multi-objective functions, on the basis of which a new optimization methodology of crosslinking reaction processes was established. Using this methodology, rubber materials can be designed according to pre-specified requirements.

High resolution time-of-flight spectrometer for crossed molecular beam study of elementary chemical reactions

In this article, we describe an apparatus in our laboratory for investigating elementary chemical reactions using the high resolution time-of-flight Rydberg tagging method. In this apparatus, we have adopted a rotating source design so that collision energy can be changed for crossed beam studies of chemical reactions. Preliminary results on the HI photodissociation and the F atom reaction with H-2 are reported here. These results suggest that the experimental apparatus is potentially a powerful tool for investigating state-to-state dynamics of elementary chemical reactions. (c) 2005 American Institute of Physics.

Influence of compressed carbon dioxide on hydrogenation reactions in cyclohexane with a Pd/C catalyst

The potential of CO2-expanded liquid media for chemical reactions has been examined in this work, using cyclohexane as a solvent and Pd/C as a heterogeneous catalyst for hydrogenation of styrene, citral, and nitrobenzene with H-2. The rate of hydrogenation reactions is increased, and the product selectivity is altered in the CO2-expanded cyclohexane phase. In the hydrogenation of citral, the selectivity to citronellal decreases with CO2 pressure, which changes from similar to 80% in the neat cyclohexane to similar to 65% at 16 MPa.

Application of ionic liquids in organic reactions

Room-temperature ionic liquids are good solvents for a wide of organic, inorganic and organometallic compounds. Typically consisting of nitrogen-containing organic cations and inorganic anions, they are easy to recycle, nonflammable, and have no detectable vapor pressure. More recently, ionic liquids have been found to be excellent solvents for a number of chemical reactions, e. g. hydrogenation, alkylation, epoxidation, Heck-vinylation, Suzuki cross-coupling reactions and enzyme catalyzed organic reactions. This paper focuses on the recent development of using ionic liquids as solvents for transition metal and enzyme catalyzed reactions.

Dynamic Characteristics of Spherically Converging Detonation Waves

The spherically converging detonation wave was numerically investigated by solving the one-dimensional multi-component Euler equations in spherical coordinates with a dispersion-controlled dissipative scheme. Finite rate and detailed chemical reaction models were used and numerical solutions were obtained for both a spherical by converging detonation in a stoichiometric hydrogen-oxygen mixture and a spherically focusing shock in air. The results showed that the post-shock pressure approximately arises to the same amplitude in vicinity of the focal point for the two cases, but the post-shock temperature level mainly depends on chemical reactions and molecular dissociations of a gas mixture. While the chemical reaction heat plays an important role in the early stage of detonation wave propagation, gas dissociations dramatically affect the post-shock flow states near the focal point. The maximum pressure and temperature, non-dimensionalized by their initial value, are approximately scaled to the propagation radius over the initial detonation diameter. The post-shock pressure is proportional to the initial pressure of the detonable mixture, and the post-shock temperature is also increased with the initial pressure, but in a much lower rate than that of the post-shock pressure.

Numerical Simulation of the Flow Field and Concentration Distribution in the Bulk Growth of Silicon Carbide Crystals

The physical vapor transport (PVT) method is being widely used to grow large-size single SiC crystals. The growth process is associated with heat and mass transport in the growth chamber, chemical reactions among multiple species as well as phase change at the crystal/gas interface. The current paper aims at studying and verifying the transport mechanism and growth kinetics model by demonstrating the flow field and species concentration distribution in the growth system. We have developed a coupled model, which takes into account the mass transport and growth kinetics. Numerical simulation is carried out by employing an in-house developed software based on finite volume method. The results calculated are in good agreement with the experimental observation.

Numerical Investigation On Detonation Cell Evolution In A Channel With Area-Changing Cross Section

The two-dimensional cellular detonation propagating in a channel with area-changing cross section was numerically simulated with the dispersion-controlled dissipative scheme and a detailed chemical reaction model. Effects of the flow expansion and compression on the cellular detonation cell were investigated to illustrate the mechanism of the transverse wave development and the cellular detonation cell evolution. By examining gas composition variations behind the leading shock, the chemical reaction rate, the reaction zone length, and thermodynamic parameters, two kinds of the abnormal detonation waves were identified. To explore their development mechanism, chemical reactions, reflected shocks and rarefaction waves were discussed, which interact with each other and affect the cellular detonation in different ways.

Optimization of tried wave-function in quantum monte-carlo method

A method for optimizing tried wave functions in quantum Monte Carlo method has been found and used to calculate the energies of molecules, such as H-2, Li-2, H-3+, H-3 and H-4. Good results were obtained.

化学反应和球面聚心爆轰波的相互作用

考察球面爆轰波聚心传播过程中，波阵面附近压力和温度不断升高引起化学反应进程的改变；对比氢氧可燃气体与氮气的数值模拟结果，分析化学反应对波面温度和压力的影响，从而考察Zeldovich理论预测聚心爆轰波后参数的精确性．数值结果表明，爆轰波聚心传播初期，放热的燃烧反应对波后热力学参数起主导作用；传播后期，波阵面趋近于对称中心时，吸热的气体解离反应变得非常活跃，解离反应对后期的汇聚压力影响不大，但会在很大程度上限制汇聚温度的升高．

Control of Large-size SiC Growth Process Using Modeling tool

Large size bulk silicon carbide (SiC) crystals are commonly grown by the physical vapor transport (PVT) method. The PVT growth of SiC crystals involves sublimation and condensation, chemical reactions, stoichiometry, mass transport, induced thermal stress, as well as defect and micropipes generation and propagation. The quality and polytype of as-grown SiC crystals are related to the temperature distribution inside the growth chamber during the growth process, it is critical to predict the temperature distribution from the measured temperatures outside the crucible by pyrometers. A radio-frequency induction-heating furnace was used for the growth of large-size SiC crystals by the PVT method in the present study. Modeling and simulation have been used to develop the SiC growth process and to improve the SiC crystal quality. Parameters such as the temperature measured at the top of crucible, temperature measured at the bottom of the crucible, and inert gas pressure are used to control the SiC growth process. By measuring the temperatures at the top and bottom of the crucible, the temperatures inside the crucible were predicted with the help of modeling tool. SiC crystals of 6H polytype were obtained and characterized by the Raman scattering spectroscopy and SEM, and crystals of few millimeter size grown inside the crucible were found without micropipes. Expansion of the crystals were also performed with the help of modeling and simulation.