Close-coupling time-dependent quantum dynamics study of the H+HCl reaction

The paper presents a theoretical study of the dynamics of the H + HCl system on the potential energy surface (PES) of Bian and Werner (Bian, W.; Werner, H. -J., J. Chem. Phys. 2000, 112, 220). A time-dependent wave packet approach was employed to calculate state-to-state reaction probabilities for the exchanged and abstraction channels. The most recent PES for the system has been used in the calculations. Reaction probabilities have also been calculated for several values of the total angular momentum J > 0. Those have then been used to estimate cross sections and rate constants for both channels. The calculated cross sections can be compared with the results of previous quasiclassical trajectory calculations and reaction dynamics experimental on the abstraction channel. In addition, the calculated rate constants are in the reasonably good agreement with experimental measurement.

Theoretical studies of product polarization and state distributions of the H+HCl reaction

The angular momentum polarization and rotational state distributions of the H-2 and HCl products from the H + HCl reaction are calculated at a relative translational energy of 1.6 eV by using quasiclassical trajectories on two potential energy surfaces, one from G3 surface [T.C. Allison et al., J. Phys. Chem. 100 (1996) 13575], and the other from BW2 surface [W. Bian, H.-J. Werner, J. Chem. Phys. 112 (2000) 220]. Product rotational distributions obtained on the G3 potential energy surface (PES) are much closer to the experimental results (P.M. Aker et al., J. Chem. Phys. 90 (1989) 4795; J. Chem. Phys. 90 (1989) 4809) than the distributions calculated on the BW2 PES. The distributions of P(phi(r)) for the H-2 and HCl products obtained on the G3 PES are similar, whereas the rotational alignment effect of the H-2 product is stronger than that of the HCl product. In contrast to the polarization distributions obtained on the G3 PES, the rotational alignment effect of the two products calculated on the BW2 PES is similar. However, the abstraction reaction is dominated by out-of-plane mechanisms, while the exchange reaction is dominated by in-plane mechanisms. The significant difference of the product rotational polarization obtained on the G3 and BW2 PESs implies that the studies of the dynamical stereochemistry can provide a sensitive test for the accuracy of the PES. (C) 2002 Elsevier Science B.V. All rights reserved.

The influence of variant PE-b-PEO segments on physical properties of LLDPE graft copolymers

A method was adopted to fix a series of polymers of PE-b-PEO with different PEO/PE segments on the chains of LLDPE. Maleic anhydride (MA) reacting with hydroxyl group of PE-b-PEO (mPE-b-PEO) was used as the intermediate. The structures of intermediates and graft copolymers were approved by H-1 NMR and FTIR. XPS analysis revealed a great amount of oxygen on the surface of grafted copolymers although the end group of PEO was fixed on the LLDPE chains through MA. Thermal properties of the graft copolymers as determined by differential scanning calorimetry (DSC) showed that PE segments in the grafted monomers could promote the heterogeneous nucleation of the polymer, increase T., and crystal growth rate.

Kinetics of Y(III) stripping for the system Y/HCl/Cyanex 272-P507/heptane with constant interfacial area cell with laminar flow

Kinetics and mechanism of stripping of yttrium(III) previously extracted by mixtures of bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272, HA), and 2-ethylhexyl phosphonic acid mono-2-ethylhexl ester (P507, HB) dissolved in heptane have been investigated by constant interfacial-area cell by laminar flow. The corresponding equilibrium stripping equation and equilibrium constant were obtained. The studies of effects of the stirring rate and temperature on the stripping rate show that the stripping regime is dependent on the stripping conditions. The plot of interfacial area on the rate has shown a linear relationship. This fact together with the strong surface activity of mixtures of Cyanex 272 and P507 at heptane-water interfaces makes the interface the most probable locale for the chemical reactions. The stripping rate constant is obtained, and the value is compared with that of the system with Cyanex 272 and P507 alone. It is concluded that the stripping ability with the mixtures is easier than that of P507 due to lower the activation energy of the mixtures. The stripping rate equation has also been obtained, and the rate-determining steps are the two-step interfacial chemical reactions as predicted from interfacial reaction models.

响应曲面法应用于RECl_3-HCl-P507-煤油体系的研究

应用响应曲面法研究盐酸体系中P507萃取稀土元素的分配比与初始酸度、稀土初始浓度的关系及在盐酸、硝酸体系中P507对Dy~(3+)的萃取情况。结果表明,在盐酸介质中,体系中Dy~(3+)的初始浓度和初始酸度均较低时,有利于P507对Dy~(3+)的萃取,且硝酸体系优于盐酸体系。

UO_2-HF-HCl-H_2O体系中介稳溶液的研究

铀是基本的核燃料,是重要的能源资源,UF_4则是生产金属铀工艺中的重要化合物。湿法生产UF_4又是重要手段之一。但在工业上如何用水法生产合格的UF_4,有不少值得研究的问题,其中对湿法生产UF_4中生产工艺条件的控制是关键,因此必须深入了解和掌握UF_4的生成和结晶的平衡条件。本文研究了UO_2-HF-HCl-H_2O四元体系80℃相平衡,平衡75h,盐酸浓度150g/l载面中介稳溶液的性质,测定了它的区域,分解时间和组成的关系,找到了能够生成良好的UF_4晶体的条件和区域。

A NOVEL SHELL COLOR VARIANT OF THE PACIFIC ABALONE HALIOTIS DISCUS HANNAI INO SUBJECT TO GENETIC CONTROL AND DIETARY INFLUENCE

Molluscan shells may display a variety of colors, which formation, inheritance, and evolutionary significance are not Well understood. Here we report a new variant of the Pacific abalone Haliotis discus hannai that displays a novel orange shell coloration (O-type) that is clearly distinguishable from the Wild green-shelled abalone (G-type). Controlled mating experiments between O- and G-type abalones demonstrated apparent Mendelian segregations (1:1 or 3:1) in shell colors in F-2 families, which support the notion that the O- and G-types are under strict genetic control at a single locus With a recessive o (for orange shell) allele and a dominant G (for green shell) allele. Feeding with different diets caused modifications of shell color within each genotype, ranging from orange to yellow for O-type and green to dark-brown for the G-type, without affecting the distinction between genotypes. A previously described bluish-purple (B-type) shell color was found in one of the putative oo X oG crosses, suggesting that the B-type may be it recessive allele belonging to the same locus. The new O-type variant had no effect on the growth of Pacific abalone on the early seed-stage. This Study demonstrates that shell color in Pacific abalone is subject to genetic control as well as dietary modification, and the latter probably offers selective advantages in camouflage and predator avoidance.