Microscopic theory of chemical-reaction rate

In this paper we deduce the formulae for rate-constant of microreaction with high resolving power of energy from the time-dependent Schrdinger equation for the general case when there is a depression on the reaetional potential surface (when the depression is zero in depth, the case is reduced to that of Eyring). Based on the assumption that Bolzmann distribution is appropriate to the description of reactants, the formula for the constant of macrorate in a form similar to Eyring's is deduced and the expression for the coefficient of transmission is given. When there is no depression on the reactional potential surface and the coefficient of transmission does not seriously depend upon temperature, it is reduced to Eyring's. Thus Eyring's is a special case of the present work.

Measurement of the inelastic branch of the O-14(alpha, p)F-17 reaction: Implications for explosive burning in novae and x-ray bursters

A measurement of the inelastic component of the key astrophysical resonance in the 14O(α,p)17F reaction for burning and breakout from hot carbon-nitrogen-oxygen (CNO) cycles is reported. The inelastic component is found to be comparable to the ground-state branch and will enhance the 14O(α,p)17F reaction rate. The current results for the reaction rate confirm that the 14O(α,p)17F reaction is unlikely to contribute substantially to burning and breakout from the CNO cycles under novae conditions. The reaction can, however, contribute strongly to the breakout from the hot CNO cycles under the more extreme conditions found in x-ray bursters.

Chemical kinetics and self-ignition in a model supersonic hydrogen-air combustor

Self-ignition tests of a model scramjet combustor were conducted by using parallel sonic injection of gaseous hydrogen from the base of a blade-like strut into a supersonic vitiated airstream. The range of stagnation pressure and temperature studied varied from 1.0 to 4.5 MPa and from 1300 to 2200 K, respectively. Experimental results show that the self-ignition limit, in terms of either global or local quantities of pressure and temperature, exhibits a nonmonotonic behavior resembling the classical homogeneous explosion limit of the hydrogen-oxygen system. Specifically, for a given temperature, increasing pressure from a low value can render a nonignitable mixture to first become ignitable, then nonignitable again, This correspondence shows that, despite the globally supersonic nonpremixed configuration studied herein, ignition is strongly influenced by the intricate chemical reaction mechanism and thereby exhibits the homogeneous explosion character. Consequently, self-ignition criteria based on a global reaction rate approximating the complex chemistry are inadequate. An auxiliary computational study on counterflow ignition was also conducted to systematically investigate the contamination effects of vitiated air. Results indicate that the net contamination effects for the present experimental data are expected to be substantially smaller than contributions from the individual contamination species because of the counterbalancing influences of the H2O-inhibition and NO-promotion reactions in effecting ignition.

Studies of the Effect of a Coal Concentrator on NO Formation in Swirling Coal Combustion

To develop low-pollution burners, the effect of a coal concentrator on NO formation in swirling coal combustion is studied using both numerical simulation and experiments. The isothermal gas-particle two-phase velocities and particle concentration in a cold model of swirl burners with and without coal concentrators were measured using the phase Doppler particle anemometer (PDPA). A full two-fluid model of reacting gas-particle flows and coal combustion with an algebraic unified second-order moment (AUSM) turbulence-chemistry model for the turbulent reaction rate of NO formation are used to simulate swirling coal combustion and NO formation with different coal concentrators. The results give the turbulent kinetic energy, particle concentration, temperature and NO concentration in cases of with and without coal concentrators. The predicted results for cold two-phase flows are in good agreement with the PDPA measurement results, showing that the coal concentrator increases the turbulence and particle concentration in the recirculation zone. The combustion modeling results indicate that although the coal concentrator increases the turbulence and combustion temperature, but still can remarkably reduce the NO formation due to creating high coal concentration in the recirculation zone.

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.

Reconsideration On The Role Of The Specific Heat Ratio In Arrhenius Law Applications

Arrhenius law implicates that only those molecules which possess the internal energy greater than the activation energy E-a can react. However, the internal energy will not be proportional to the gas temperature if the specific heat ratio gamma and the gas constant R vary during chemical reaction processes. The varying gamma may affect significantly the chemical reaction rate calculated with the Arrhenius law under the constant gamma assumption, which has been widely accepted in detonation and combustion simulations for many years. In this paper, the roles of variable gamma and R in Arrhenius law applications are reconsidered, and their effects on the chemical reaction rate are demonstrated by simulating one-dimensional C-J and two-dimensional cellular detonations. A new overall one-step detonation model with variable gamma and R is proposed to improve the Arrhenius law. Numerical experiments demonstrate that this improved Arrhenius law works well in predicting detonation phenomena with the numerical results being in good agreement with experimental data.

Experimental investigation on the cavity-based scramjet model

The present work focused on improving the engine performance with different fuel equivalence ratios and fuel injections. A scramjet model with strut/cavity integrated configurations was tested under Mach 5.8 flows. The results showed that the strut may sreve as an effective tool in a kerosene-fueled scramjet. The integration of strut/cavities also had great effect on stablizing the combustion in a wide range of fuel equivalence ratio. The one-sdimensional analysis method was used to analyze the main characteristics of the model. The two-stage fuel injection should have better performance in increasing the chemical reaction rate in the first cavity region.

Thermal cracking of aviation kerosene for scramjet applications

Thermal cracking of China No.3 aviation kerosene was studied experimentally and analytically under supercritical conditions relevant to regenerative cooling system for Mach-6 scramjet applications. A two-stage heated tube system with cracked products collection/analysis was used and it can achieve a fuel temperature range of 700-1100 K, a pressure range of 3.5-4.5 MPa and a residence time of approximately 0.5-1.3 s. Compositions of the cracked gaseous products and mass flow rate of the kerosene flow at varied temperatures and pressures were obtained experimentally. A one-step lumped model was developed with the cracked mixtures grouped into three categories: unreacted kerosene, gaseous products and residuals including liquid products and carbon deposits. Based on the model, fuel conversion on the mass basis, the reaction rate and the residence time were estimated as functions of temperature. Meanwhile, a sonic nozzle was used for the control of the mass flow rate of the cracked kerosene, and correlation of the mass flow rate gives a good agreement with the measurements.

Kinetic study of the 2-methyl-3-methoxy-4-phenylbutanoic acid produced by oxidation of microcystin in aqueous solutions

Microcystins (MCs) are a family of related cyclic hepatotoxic heptapeptides, of which more than 70 types have been identified. The chemically unique nature of the C20 beta-amino acid, (2S, 3S, 8S, 9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca4,6-dienoic acid (Adda), portion of the MCs has been exploited to develop a strategy to analyze the entirety. Oxidation of MCs causes the cleavage of MC Adda to form 2-methyl-3-methoxy-4-phenylbutanoic acid (MMPB). In the present study, we investigated the kinetics of MMPB produced by oxidation of the most-often-studied MC variant, MC-LR (L = leucine, R = arginine), with permanganate-periodate. This investigation allowed insight regarding the influence of the reaction conditions (concentration of the reactants, temperature, and pH) on the conversion rate. The results indicated that the reaction was second order overall and first order with respect to both permanganate and MC-LR. The second-order rate constant ranged from 0.66 to 1.35 M/s at temperatures from 10 to 30 degrees C, and the activation energy was 24.44 kJ/mol. The rates of MMPB production can be accelerated through increasing reaction temperature and oxidant concentration, and sufficient periodate is necessary for the formation of MMPB. The initial reaction rate under alkaline and neutral conditions is higher than that under acidic conditions, but the former decreases faster than the latter except under weakly acidic conditions. These results provided new insight concerning selection of the permanganate-periodate concentration, pH, and temperature needed for the oxidation of MCs with a high and stable yield of MMPB.

CO2置换开采天然气水合物研究进展

介绍了近年来CO2置换开采天然气水合物技术的研究进展；论述了CO2与天然气水合物中CH4置换反应在热力学上的可能性；认为正确理解置换反应机理、探索新的反应技术并提高反应速率是置换开采技术走向产业化的关键。

The Deposition and Burning Characteristics During Slagging Co-Firing Coal and Wood: Modeling and Numerical Simulation

Numerical analysis was used to study the deposition and burning characteristics of combining co-combustion with slagging combustion technologies in this paper. The pyrolysis and burning kinetic models of different fuels were implanted into the WBSF-PCC2 (wall burning and slag flow in pulverized co-combustion) computation code, and then the slagging and co-combustion characteristicsespecially the wall burning mechanism of different solid fuels and their effects on the whole burning behavior in the cylindrical combustor at different mixing ratios under the condition of keeping the heat input samewere simulated numerically. The results showed that adding wood powder at 25% mass fraction can increase the temperature at the initial stage of combustion, which is helpful to utilize the front space of the combustor. Adding wood powder at a 25% mass fraction can increase the reaction rate at the initial combustion stage; also, the coal ignitability is improved, and the burnout efficiency is enhanced by about 5% of suspension and deposition particles, which is helpful for coal particles to burn entirely and for combustion devices to minimize their dimensions or sizes. The results also showed that adding wood powder at a proper ratio is helpful to keep the combustion stability, not only because of the enhancement for the burning characteristics, but also because the running slag layer structure can be changed more continuously, which is very important for avoiding the abnormal slag accumulation in the slagging combustor. The theoretic analysis in this paper proves that unification of co-combustion and slagging combustion technologies is feasible, though more comprehensive and rigorous research is needed.

Gasoline-range hydrocarbon synthesis over cobalt-based Fischer-Tropsch catalysts supported onSiO2/HZSM-5

Two types of SiO2 with different mesopore size and HZSM-5 zeolite were used to prepare hybrid supported cobalt-based catalysts. The textual and structural properties of the catalysts were studied using N-2 physisorption, X-ray diffraction (XRD), and H-2 temperature-programmed reduction (TPR) techniques. Fischer-Tropsch synthesis (FTS) performances of the catalysts were carried out in a fixed-bed reactor. The combination effects of the meso- and micropores of the supports as well as the interaction between supports and cobalt particles on FTS activity are discussed. The results indicate that the catalyst supported on the tailor-made SiO2 and HZSM-5 hybrid maintained both meso- and micropore pores during the preparation process without HZSM-5 particles agglomerating. The mesopores provided quick mass transfer channels, while the micropores contributed to high metal dispersion and accelerated hydrocracking/hydroisomerization reaction rate. High CO conversion of 83.9% and selectivity to gasoline-range hydrocarbons (C-5-C-12) of 55%, including more than 10% isoparaffins, were achieved simultaneously on this type of catalyst.

Bleaching kinetics of indoly-benzylfulgimide in PMMA

Indoly-benzlfulgimide belongs to the photochromic fulgide family and follows photochemical first order kinetics. Its bleaching kinetics is investigated at 633 nm and 640 nm by spectroscopy, by the time dependence of transmission and of diffraction from holographically induced gratings. The non-exponential decay law resulting for diffraction experiments with a Gaussian beam profile is calculated and verified experimentally. For a quasi-homogeneous beam profile the time constant determined from diffraction decay is half the one for absorbance decay. The photochemical reaction rate of indoly-benzylfulgimide in PMMA is (3.9 +/- 0.3) cm(2)/J at 650 nm. (c) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.