The Structure of Clusters and Jets of Pulsed Plasma Expanding into Vacuum

The space-time distribution of the basic kinetic parameters of a plasma is experimentally determined under conditions of expansion of plasma clusters and jets into vacuum. It is demonstrated that the dynamics and structure of plasmoids injected by pulsed erosion plasma accelerators of the electrothermal type are characterized by two successive stages or two modes of acceleration, namely, the Joule heating of electrons in the initial region of the path and the collisionless expansion of rarefied plasma.     

Implicit–Explicit Schemes for BGK Kinetic Equations

In this work a new class of numerical methods for the BGK model of kinetic equations is presented. In principle, schemes of any order of accuracy in both space and time can be constructed with this technique. The methods proposed are based on an explicit–implicit time discretization. In particular the convective terms are treated explicitly, while the source terms are implicit. In this fashion even problems with infinite stiffness can be integrated with relatively large time steps. The conservation properties of the schemes are investigated. Numerical results are shown for schemes of order 1, 2 and 5 in space, and up to third-order accurate in time.     

Kinetic Studies on Cocracking of Petroleum Vacuum Residue with Thermoplastics and Biomass (Petrocrop)

Cracking of petroleum vacuum residue (XVR) and its cocracking with plastics (PP or PS), Calotropis procera (CL) as a binary, ternary, and quaternary mixture of these individual plastics, and CL with XVR was carried out in a Perkin-Elmer thermogravimetric analyzer (TGA) for the purpose of comparing the process of the mixture with those of the individual components. Experiments were conducted at a heating rate of 40 K/min, in the temperature range of 30-900°C. Based on the results obtained, three temperature regimes were selected for studying the nonisothermal kinetics of TGA of individual XVR, plastics, and biomass as well as of the cocracking of these with XVR, i.e., below 400°C, between 400-500°C, and above 500°C. The kinetic studies were performed using the Coats and Redfern kinetic modeling equation. The overall activation energies obtained were 25 kJ/mole for petroleum vacuum residue, 99 kJ/mole for polypropylene, 21 kJ/mole for coal, and 35 kJ/mole for the mixture of all these materials. Thus, it has been found that there exists an overall synergy when three materials were coprocessed together. The overall orders and activation energies change during coprocessing of two or three different macromolecules, including mixed vacuum residue as presently observed. The detailed results that were obtained will be reported.     

Time and Temperature Factors in Construction of Rock Strength Criteria

Using the synthesis of the kinetic concept on solid strength and the Coulomb - Mohr strength theory as the base, the failure conditions taking into account the time and temperature factors are obtained.     

Lipase‐catalyzed dynamic kinetic resolution of (R,S)‐fenoprofen thioester in isooctane

A lipase‐catalyzed enantioselective hydrolysis process under in situ racemization of the remaining (R)‐thioetser substrate with trioctylamine as the catalyst was developed for the production of (S)‐fenoprofen from (R,S)‐fenoprofen 2,2,2‐trifluoroethyl thioester in isooctane. Detailed investigations of trioctylamine concentration on the enzyme activation and the kinetic behavior of the thioester in racemization and enzymatic reactions were conducted, in which good agreement between the experimental data and theoretical results was observed. © 2002 Society of Chemical Industry     

Moderate antioxidative efficiencies of flavonoids during peroxidation of methyl linoleate in homogeneous and micellar solutions

The relative reactivities as well as the stoichiometric coefficients for a number of flavonoids, catechols, and—for comparison—standard phenolic antioxidants were determined by analyzing the kinetics of oxygen consumption in organic and micellar systems, with peroxidation initiated by lipid- and water-soluble azo initiators. The results demonstrated that the flavonoids did not behave as classic phenolic antioxidants such as α-tocopherol, but showed only moderate chain-breaking activities. The results were in line with other structure-activity relationship studies on the importance of the B-ring catechol structure, the 2,3-double bond, and the 3,5-hydroxy groups. The data are discussed in view of possible explanations of the deviations flavonoids reveal in their behavior compared with regular phenolic antioxidants.     

On the curing of a vinylester-urethane hybrid resin

Curing kinetics of a vinylester-urethane hybrid (VEUH) resin consisting of vinylester resin (VE) diluted in styrene and novolac type polyisocyanate (NPI) have been studied by differential scanning calorimetry (DSC). As VEUH is crosslinked via free radical polymerisation between the vinyl functions of styrene and VE, and polyaddition reaction between the secondary -OH groups of VE and -NCO of NPI, it was necessary to study these reactions separately. This was achieved by studying the curing with and without incorporating the NPI. The curing reaction was monitored by measuring the heat of reaction under isothermal and dynamic temperature conditions. Models describing the curing were developed, which are in good agreement with the experiments. A comparison between the curing of the VEUH and the VE resin without NPI leads to the conclusion that the curing of the VEUH as accessed by DSC is dominated by the radical polymerisation of styrene with VE although the two reactions are not time separated.     

A new approach to the mechanism of chlorine evolution: Separate examination of the kinetic steps using ac impedance on a rotating thin ring electrode

In the absence of a bulk diffusion effect, it is shown for the first time that the impedance spectra for the chlorine evolution reaction on a rotating thin ring electrode comprise three consecutive semicircles in the capacitive half of the complex plane. The first (highest frequency) semicircle is due to the charge-transfer resistance for chloride discharge and the simultaneous chlorine adsorption coupled to the double-layer capacitance. The second semicircle (around 5 Hz) is due to the adsorption and desorption of a chlorine intermediate. The third (lowest frequency, around 0.5 Hz) semicircle is due to the relaxation of surface oxygen species. The impedance data allow the steps of the overall reaction to be examined individually. On a Pt surface the rate of chloride discharge and simultaneous chlorine adsorption (the admittance of the first semicircle) is first order with respect to chloride concentration and has a potential-dependence close to 58 mV/decade. The rate of the adsorption and desorption process (the admittance of the second semicircle) is second order with respect to chloride concentration, and has a potential dependence close to 30 mV/decade. The time constant for the adsorption/desorption processes is ca 20 ms, independent of electrode potential in the range studied. These features are consistent with a mechanism in which a faster discharge reaction (Cl⁻ Cl_ad + e) is followed by a slower surface combination reaction (2Cl_ad → Cl₂), but inconsistent with mechanisms in which ion + atom desorption is predominant, the initial chloride discharge is slow, or a unipositively charged chlorine species is involved.     

On the kinetics of the autoxidation of fats: influence of pro‐oxidants,antioxidants and synergists

The influence of minor amounts of pro‐ and anti‐oxidants on the kinetics of the autoxidation of fat has been evaluated. The reaction rates of oxygen with the substrates were found to follow the same basic equation, hitherto established for pure substrates. There is evidence that the surface of the reaction vessel also acts as a reaction catalyst and its effect is proportional to the area of glass in contact with lipids. Oxidation is enhanced by trace metal ions as well as by surface‐active compounds (e.g. hydroperoxides and sterols). Antioxidants such as α‐tocopherol and butylated hydroxyanisole inhibit the oxidation by delaying the start of oxygen consumption (the induction period) while retarders like amino acids only decrease the rate of oxidation. Thus pro‐ and anti‐ oxidants affect either the start or the rate of oxygen consumption. The empirical formula dx/dt = k [O₂] (1‐x/n) f′(t) was found applicable to the different stages of oxidation.     

明渠湍流床面附近跃移层面颗粒浓度垂线分布

本文以动理学理论的Boltzmann方程为基础，考虑明渠湍流床面附近猝发喷射和清扫运动对跃移层内运动颗粒的不同作用，分析了明渠中泥沙颗粒浓度垂线分布问题，得到了适用于包括跃移层、悬移层在内的统一浓度垂线分布公式。文中着重研究了跃移层内运动颗粒的浓度垂线分布，并将本文结果与实测跃移层内浓度垂线分布及实测跃移层顶部浓度进行了对比，结果表明理论与实验两者符合较好。