Kinetics and mechanism of polymerization of methyl methacrylate initiated by stibonium ylide

Homopolymerization of methyl methacrylate (MMA) was carried out in the presence of triphenylstibonium 1,2,3,4-tetraphenyl-cyclopentadienylide as an initiator in dioxane at 65°C±0·l°C. The system follows non-ideal radical kinetics (R _p ∝ [M]^1·4 [I]^0·44 @#@) due to primary radical termination as well as degradative chain-transfer reaction. The overall activation energy and average value ofk ₂ ^p /k _t were 64 kJmol⁻¹ and 0.173 × 10⁻³ 1 mol⁻¹ s⁻¹ respectively     

HCHO-(DL-苹果酸)-BrO-3-Mn2+-H2SO4体系化学振荡反应动力学研究

研究了HCHO参与下的(DL-苹果酸)-BrO-3-Mn2+-H2SO4化学振荡反应体系的非线性动力学行为,考察了该体系中各反应物的初始浓度范围及主要影响因素. 结果表明,在5.0×10-5～1.0×10-2 mol·L-1范围内, HCHO对振荡反应的诱导期和周期有较大影响,且HCHO浓度的对数lnc(HCHO)与诱导期倒数的对数ln(1/tin)及周期倒数的对数ln(1/tp)均存在线性关系. 诱导期和周期的表观活化参数分别为70.87,55.71 kJ·mol-1. 另外还对HCHO参与下的可能振荡反应机理进行了探讨.     

Kinetics and mechanism of free-surface vaporization of zinc, cadmium and mercury oxides analyzed by the third-law method

On the basis of critical comparison of experimental and theoretical values of the E parameter and investigation of the retardation effect of oxygen on the evaporation rate of ZnO, CdO and HgO, it was concluded that the dissociative evaporation of ZnO and HgO proceeds with releasing of atomic oxygen (O) as a primary product of decomposition. By contrast, the mechanism of dissociative evaporation of CdO corresponds to the equilibrium reaction with releasing of molecular oxygen (O₂) as a primary product of decomposition. As was shown, this difference in mechanisms is not related with interatomic OO distances in these oxides. From the analysis of crystal structure for 12 different oxides, which evaporate with releasing of atomic oxygen, and for 13 compounds, which evaporate with releasing of molecular oxygen, it was revealed that the first mechanism is observed for all oxides with the cubic crystal structure. It was proposed that a decisive role in this difference belongs to a local symmetry in the position of O atoms.     

机械结构因素对光电跟踪伺服系统性能的影响

为克服机械结构因素对光电跟踪伺服系统性能的不良影响,分析了转动惯量、结构谐振频率、摩擦力矩等伺服机械结构因素与伺服系统性能的关系,包括分析转动惯量与伺服系统性能的关系、结构谐振频率与伺服系统性能的关系、摩擦力矩与伺服系统性能的关系,探讨了消除或减小机械谐振的措施.该分析方法可应用于设计和制造响应速度快、跟踪精度高的光电跟踪伺服系统.     

CO（ a）+ NO（X）传能体系中的新传能通道

在相对碰撞平动能为 0 .0 5eV的分子束实验条件下 ,研究了亚稳态CO(a) +NO(X)的E E传能通道 .通过测量和分析交碰区的传能发射光谱 ,在 780和 860nm处观测到了NO(b -a)跃迁Ogawa带的△v =+ 4和△v =+ 3序的发射光谱 .从而首次在实验上直接证实了传能过程中第四通道的存在 (CO (a) +NO(X)→CO (X) +NO(b) ) .这一通道的发现解释了前人测量到的在CO(a)与NO(X)碰撞传能过程中CO(a)的猝灭速率远大于NO(A ,B)生成速率的实验结果 ,并进一步证实了这一“经典”E E传能体系为电子交换机理的传能观点     

Formation of metallic NbSe2 nanotubes and nanofibers

We succeed in synthesizing NbSe₂ nanotubes along with nanofibers by chemical vapor transportation. They are stable crystalline systems and can be synthesized reproducibly in a nearly equilibrium reacting process. We have investigated these nanosize structures of NbSe₂ by transmission electron microscopy and electron diffraction. Both of the structures have a similar size of 100–200 nm in diameter. While nanotubes consist of rolled-up NbSe₂ layers, nanofibers are a pile of thin flat layers. We propose a mechanism of the formation of NbSe₂ nanotubes and nanofibers on the basis of deseleniditive transition from a NbSe₃ fiber-shaped crystal. We also measured electrical resistance of the nanofibers with conductive atomic force microscopy and demonstrated that the material show metallic behavior at room temperature.     

掺Perylene的PVK薄膜荧光谱及发光机理

用高荧光效率的有机染料芘(perylene)掺杂聚乙烯咔唑(PVK),其荧光光谱与芘的发射光谱基本一致,而且亮度比纯芘发光提高十多倍,说明发光主要来自芘分子,并在PVK和perylene之间存在十分有效的能量传递或电荷转移过程,荧光谱强度随掺杂浓度的变化关系说明存在一个最佳的掺杂浓度比.分析PVK和perylene之间可能发生的能量转移过程,认为从PVK到perylene这种能量转移与实验不符;分析PVK和perylene薄膜的光致发光过程,认为从(PVK+)→(perylene+)和从(PVK-)→(p     

The samarium(II)-mediated intermolecular couplings of ketones and β-alkoxyacrylates: a short asymmetric synthesis of an antifungal γ-butyrolactone

The samarium(II) iodide-mediated coupling of ketones with β-alkoxyacrylates gives β-hydroxy-γ-butyrolactones in moderate yield. The process has been applied to the asymmetric synthesis of an antifungal, γ-butyrolactone natural product.     

Quantum-Chemical Study of the Profiles of Reactions that Form Pyrrole Anion N-Adducts with CS<Subscript>2</Subscript> and CO<Subscript>2</Subscript>

The profiles of reactions leading to pyrrole anion N-adducts with CO₂ and CS₂ have been studied by the ab initio (RHF/6-31+G*, MP2/6-31+G*) and density functional (B3LYP/6-31+G*) methods. Addition of the pyrrole anion to the carbon disulfide molecule is accompanied by the appearance of a minimum corresponding to a pre-reaction complex. The transformation of the complex to the N-pyrrolyldithiocarboxylate anion occurs via a low activation barrier, which is due to repolarization of the C=S bonds. The profile of the reaction leading to the pyrrole anion N-adduct with CO₂ does not contain any intermediate stationary points throughout the whole route from reagents to products.Original Russian Text Copyright © 2004 by V. B. Kobychev, N. M. Vitkovskaya, I. L. Zaitseva, and B. A. Trofimov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 990–993, November–December, 2004.     

Mechanism of the thermal decomposition of nitrates from graphite furnace mass spectrometry studies

A basically new mechanism of the thermal decomposition of solids is proposed to explain the mass spectral observations of gaseous molecules of CoO, CuO, Cu₂O, NiO, PbO and Mg(OH)₂ during the low-temperature decomposition of the anhydrous and hydrated nitrates of these metals. The mechanism consists of two stages: congruent gasification of all reaction products irrespective of their saturated vapor pressure and subsequent condensation of the low-volatility species (oxides and hydroxides). The partial pressures of these species at the appearance temperatures calculated from this theory for the first stage of the process (1–50 mPa) are in agreement with the detection limits of the quadrupole mass spectrometers used in these experiments. The proposed mechanism is supported by other available data obtained by thermal analysis.