Unsteady axisymmetric stagnation flow on a circular cylinder

Unsteady, axisymmetric stagnation flow about a circular cylinderis examined when the far-field flow is a periodic function oftime with a fixed time average and an oscillatory part of prescribedamplitude and frequency. Solutions are computed for arbitraryvalues of the Reynolds number, quantifying the effects of surfacecurvature, and a frequency parameter based on the period ofthe far-field flow. It is found that solutions remain regularand periodic provided that the far-field amplitude lies belowa critical value. Above this value, solutions terminate in afinite-time singularity. The blow-up time is delayed by increasingthe curvature of the surface. These results are corroboratedby asymptotic predictions valid in the limits of small and largeamplitude and frequency. For large Reynolds number, the problemreduces to the two-dimensional stagnation-point flow againsta plane wall studied by previous authors.     

Polyethylene glycol matrix reduces the rates of photochemical and thermal release of nitric oxide from S-nitroso-N-acetylcysteine

S -nitrosothiols have many biological activities and may act as nitric oxide (NO) carriers and donors, prolonging NO half-life in vivo. In spite of their great potential as therapeutic agents, most S -nitrosothiols are too unstable to isolate. We have shown that the S -nitroso adduct of N -acetylcysteine (SNAC) can be synthesized directly in aqueous and polyethylene glycol (PEG) 400 matrix by using a reactive gaseous (NO/O₂) mixture. Spectral monitoring of the S–N bond cleavage showed that SNAC, synthesized by this method, is relatively stable in nonbuf-fered aqueous solution at 25°C in the dark and that its stability is greatly increased in PEG matrix, resulting in a 28-fold decrease in its initial rate of thermal decomposition. Irradiation with UV light (λ= 333 nm) accelerated the rate of decomposition of SNAC to NO in both matrices, indicating that SNAC may find use for the photogeneration of NO. The quantum yield for SNAC decomposition decreased from 0.65 ± 0.15 in aqueous solution to 0.047 ± 0.005 in PEG 400 matrix. This increased stability in PEG matrix was assigned to a cage effect promoted by the PEG microenvironment that increases the rate of geminated radical pair recombination in the homolytic S–N bond cleavage process. This effect allowed for the storage of SNAC in PEG at −20°C in the dark for more than 10 weeks with negligible decomposition. Such stabilization may represent a viable option for the synthesis, storage and handling of S -nitrosothiol solutions for biomedical applications.     

Kinetic study of the gas-phase reaction of OH with Br2

An experimental, temperature-dependent kinetic study of the gas-phase reaction of the hydroxyl radical with molecular bromine (reaction 1) has been performed by using a pulsed laser photolysis/pulsed-laser-induced fluorescence technique over a wide temperature range of 297-766 K, and at pressures between 6.68 and 40.29 kPa of helium. The experimental rate coefficients for reaction 1 demonstrate no correlation with pressure and exhibit a negative temperature dependence with a slight negative curvature in the Arrhenius plot. A nonlinear least-squares fit with two floating parameters of the temperature-dependent k(1)(T) data set using an equation of the form k(1)(T) = AT(n) yields the recommended expression k(1)(T) = (1.85 x 10(-9))T(-0.66) cm(3) molecule(-1) s(-1) for the temperature dependence of the reaction 1 rate coefficient. The potential energy surface (PES) of reaction 1 was investigated with use of quantum chemistry methods. The reaction proceeds through formation of a weakly bound OH...Br(2) complex and a PES saddle point with an energy below that of the reactants. Temperature dependence of the reaction rate coefficient was modeled by using the RRKM method on the basis of the calculated PES.     

Kinetics of the gas-phase reaction of OH with HCl

The reaction of hydroxyl radicals with hydrogen chloride (reaction 1) has been studied experimentally using a pulsed-laser photolysis/pulsed-laser-induced fluorescence technique over a wide range of temperatures, 298-1015 K, and at pressures between 5.33 and 26.48 kPa. The bimolecular rate coefficient data set obtained for reaction 1 demonstrates no dependence on pressure and exhibits positive temperature dependence that can be represented with modified three-parameter Arrhenius expression within the experimental temperature range: k1 = 3.20 x 10(-15)T0.99 exp(-62 K/T) cm3 molecule(-1) s(-1). The potential-energy surface has been studied using quantum chemical methods, and a transition-state theory model has been developed for the reaction 1 on the basis of calculations and experimental data. The model results in modified three-parameter Arrhenius expressions: k1 = 8.81 x 10(-16)T1.16 exp(58 K/T) cm3 molecule(-1) s(-1) for the temperature range 200-1015 K and k1 = 6.84 x 10(-19)T2.12 exp(646 K/T) cm3 molecule(-1) s(-1) for the temperature dependence of the reaction 1 rate coefficient extrapolation to high temperatures (500-3000 K). A temperature dependence of the rate coefficient of the Cl + H2O --> HCl + OH reaction has been derived on the basis of the experimental data, modeling, and thermochemical information.     

广义Bethe树上奇偶马尔可夫链场上的若干极限性质

通过构造两个非负鞅证明了一个强极限定理,然后把它应用到本文所定义的广义Bethe树上的奇偶马尔可夫链场上,从而获得了此马氏链场上的一类强极限定理.     

Suppression of plasma turbulence during optimized shear configurations in JET

Correlation of density turbulence suppression and reduced plasma transport is observed in the internal transport barrier (ITB) region of JET tokamak discharges with optimized magnetic shear. The suppression occurs in two stages. First, low frequency turbulence and ion transport are reduced across the plasma core by a toroidal velocity shear generated by intense auxiliary heating. Then with the ITB formation, high frequency turbulence and electron transport are reduced locally within the steep pressure gradient region of the ITB.     

Oxidation of Rich Propane Mixtures in a Temperature Range of 773–1023 K at Pressures of 1–3 atm

Kinetics and Catalysis - The results of an experimental study of the oxidation of rich propane mixtures in a temperature range of 773–1023 K at pressures of 1–3 atm obtained in a flow...     

Nuclear orbiting and anomalies in nuclear reactions

In this paper, we report our measurements of back-angle oxygen and carbon particle yields from ¹⁶O+⁸⁹Y, ¹²C+⁹³Nb reactions forming the same compound nucleus ¹⁰⁵Ag at the same excitation energy and spin distribution. We find anomalously large oxygen yield and entrance channel dependence at high excitation energies from ¹⁶O+⁸⁹Y reaction implying formation of a dinuclear orbiting complex. Possible connection between nuclear orbiting and fast fission is also discussed.     

Temperature-dependent kinetics study of the gas-phase reactions of OH with n- and i-propyl bromide

An experimental, temperature-dependent kinetics study of the gas-phase reactions of hydroxyl radical with n-propyl bromide, OH+n-C3H7Br-->products (reaction 1), and i-propyl bromide, OH+i-C3H7Br-->products (reaction 2), has been performed over wide ranges of temperatures 297-725 and 297-715 K, respectively, and at pressures between 6.67 and 26.76 kPa by a pulsed laser photolysis/pulsed laser-induced fluorescence technique. Data sets of absolute bimolecular rate coefficients obtained in this study for reactions 1 and 2 demonstrate no correlation with pressure and exhibit positive temperature dependencies that can be represented with modified three-parameter Arrhenius expressions within their corresponding experimental temperature ranges: k1(T)=(1.32x10(-17))T1.95 exp(+25/T) cm3 molecule(-1) s(-1) for reaction 1 and k2(T)=(1.56x10(-24))T4.18exp(+922/T) cm3 molecule(-1) s(-1) for reaction 2. The present results, which extend the current kinetics data base of reactions 1 and 2 to high temperatures, are compared with those from previous works. On the basis of the present data and available data from previous studies, the following bimolecular rate coefficient temperature dependencies can be recommended for the purpose of kinetic modeling: k1(T)=(1.89x10(-19))T2.54exp(+301/T) cm3 molecule-1 s-1 for reaction 1 in a temperature range 210-725 K, and k2(T)=(2.83x10(-21))T3.1exp(+521/T) cm3 molecule(-1) s(-1) and k2(T)=(4.54x10(-24))T4.03exp(+860/T) cm3 molecule(-1) s(-1) for reaction 2 in temperature ranges 210-480 and 297-715 K, respectively.