Period Doubling and Chaos of Spontaneous Oscillatory Phenomena on Iron

Summary.  A new self-oscillating system introducing spontaneous oscillatory phenomena on iron in a sulfuric acid solution of hydrogen peroxide is discussed. This phenomenon can be explained by a continuous oscillation between the active and passive state of iron. Unlike other published systems that only show one-peak oscillations, the potential of iron shows highly complex dynamics: depending on the concentration of hydrogen peroxide and sulfuric acid, a period doubling and non-periodic oscillations in a self-oscillating system were observed for the first time. The reactions were analyzed by methods based on chaos theory and could finally be identified as an example of deterministic chaos. Received April 24, 2001. Accepted May 7, 2001     

Electrochemical Investigation for Cu2+ Oscillatory Phenomena at the Liquid/Liquid Interface with a Specific Adsorption of Ion Pair Model

In this paper, a novel current oscillatory phenomenon for Cu²⁺ at the water/1,2‐dichloroethane interface is reported with cyclic voltammetry and potential‐step chronoamperometry. The small irregular current spikes were only observed near the site of the oxidation peak of CuCl₂^? and were mainly related to the Cu²⁺concentration in the aqueous phase. Our experimental results demonstrated that the current oscillation is caused by specific adsorption of ion pairs at the W/DCE interface between Cu²⁺ in the aqueous phase and TPB^? in the organic phase. Therefore, a specific adsorption of ion pair model has been formulated for the current oscillation at the liquid/liquid interface. The DFT calculation method was used to explain the mechanism of ion pair formation. The calculation results suggested that the TPB^?Cu²⁺TPB^? ion pair has the lowest‐energy state, thus providing qualitative support for the ion pair model. A probable mechanism for the observed current oscillation was also discussed in this paper. At the same time, a spectrophotometric experiment was performed to evidence a strong attractive interaction between Cu²⁺ and TPB^?.     

基于现象和过程可视化的微型化学实验

设计了以“滴”为计量单位的微型化学实验,利用现象和过程可视化的技术,观察液滴中肉眼难以观察的细节。以生成气泡、生成固体、颜色变化等化学反应中最典型的3个现象为例,展示本装置的可视化效果。本实验具有可视化、微型化、家庭化、趣味化的特点,并且所需的实验仪器均可以用日常生活用品代替,特别适合作为家庭实验实施。     

Study on Frequency Doubling Scattering and Second—Order Scattering Spectra of Heparin—Methylene Blue System

Binding of heparin with methylene blue(MB) in pH5.7 Britton-Robinson buffer can result in a significant enhancement of frequency doubling scattering (FDS) and second-order scattering (SOS).Their maximum scattering wavelengths(λmax) appear at 350nm for FDS and 700nm for SOS,respectively.The optimum conditions of the reaction,the influencing factors and the relationship between the two scattering intensities and the concentration of heparin have been investigated.The new methods for the determination of trace amounts of heparin bassed on the FDS and SOS methods have been developed,which exhibit high sensitivities.The detection limits of heparin are 4.36ng/mL for the FDS method and 3.55ng/mL for the SOS method,respectively.Both of the methods have fairly godd selectivity and ware applied to the determination of heparin in sodium heparinate injection samples with satisfactory results.Moreover,the relative mechamisms have also been discussed.     

石蕊溶液与苯混合后现象的探究

为了研究苯能否从石蕊溶液中萃取出石蕊,通过用相机记录实验现象的方法,对用不同方法配制的3种石蕊溶液与苯混合振荡后经历不同时间后的现象进行研究,发现苯层不能呈现石蕊的颜色,从而得出苯不能从水中萃取出石蕊的结论。     

Oscillatory Dynamics of CO Oxidation on Platinum-Group Metal Catalysts

Rate oscillations are theoretically studied for the CO + O₂ reaction proceeding according to a modified Langmuir-Hinshelwood mechanism on a platinum-group metal catalyst. A new hierarchical system of consistent mathematical models is suggested for the identification of oscillatory regimes in the stochastic model. This system includes the stochastic model based on the Monte Carlo method and a point deterministic model in the medium field approximation. Three fundamentally different types of oscillatory behavior of the stochastic model are revealed and studied. These are kinetic oscillations corresponding to autooscillations of the point model, fluctuation-induced oscillations occurring in an excitable medium in the region of the unique stable stationary solution of the point model, and fluctuation-induced random phase transitions between stable stationary solutions of the point model in the bistability region. The effect of internal fluctuations (which are inherent in stochastic models) on the oscillatory dynamics of the reaction is studied.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 485–496.Original Russian Text Copyright © 2005 by Kurkina, Semendyaeva.     

Spontaneous Resolution by Crystallization of an Octanuclear Iron(III) Complex Using Only Racemic Reagents

The P and M enantiomers of the octanuclear [Fe₈(μ₄‐O)₄(μ‐4‐Cl‐pz)₁₂Cl₄] complex, having T symmetry, were resolved by temporary substitution of chloride ligands by racemic 4‐^sBu‐phenolates and subsequent crystallization, where the (S)‐ and (R)‐phenolates coordinate selectively to the M and P complexes, respectively. The complexes were characterized by circular dichroism analysis and X‐ray structure determination. This work constitutes a rare example of enantiomeric recognition resulting in spontaneous resolution upon crystallization.     

论“异常实验现象”的教学功能

在调查研究的基础上,从创设教学情境、培养问题意识、发展学科能力和强化心理素质等方面对“异常实验现象”的教学功能进行了探讨,论述了“异常实验现象”的教学价值,并提出了相关教学措施。     

Segregation Phenomena on the Crystal Surface of Chemical Compounds

The current state of the theoretical and experimental studies of changes in the chemical structure and composition caused by segregation phenomena on the surface of chemical compounds was reviewed. The review considers the experimental data obtained exclusively on single crystals, which were studied by modern instrumental methods, including in situ Auger electron spectrometry, X-ray spectral microanalysis, high-resolution scanning and transmission electron microscopy, secondary electron emission, and atomic force microscopy. The models that suggest the crystal-chemical diffusion and liquid-phase mechanisms of segregation were described. The parameters of the theory include the type of chemical bond, elastic constants, and crystal-chemical characteristics of substances. The models make it possible to predict the nature of changes in the surface composition: segregation tendency, segregant type, and degree of nonstoichiometry. A new direction in surface segregation was considered, which is promising for nanoelectronics and emission electronics.     

Electrovectorial Effects of Electrically Polarized Hydroxyapatite on Biological Phenomena

Electrically polarized hydroxyapatite ceramics have chemical, physical, and biological effects upon their surrounding constituents in vivo as well as in vitro as electrets, independent solids irradiating electrostatic force. Using the polarized hydroxyapatite, we have observed that crystal growth from a simulated body fluid can be accelerated or decelerated, and microorganisms can be manipulated on the surfaces of hydroxyapatite, depending upon the electric signs.     

基于现象和过程可视化的化学实验——以“化学花园”为例

通过改变观察方式来实现实验过程和现象的可视化。通过在手机后置摄像头夹上手机微距镜头来实现微距摄影功能，通过录像捕获试管内硅酸钠溶液与绿豆大的金属盐反应画面，用"拍大师"视频编辑软件按需设置"播放倍数"，以及使用教学多媒体展示来观察实验现象。结果表明，此方法能够捕获反应全过程，得到清晰、放大的画面，实验现象明显。对实验细节现象做出了更准确的描述，了解到更丰富的细节信息。     

环糊精-苯丙氨酸超分子体系的包合现象与分子识别

通过紫外-可见光谱探讨了水溶液中α-环糊精(CD 1),β-CD 2,七(2, 6-二-o-甲基)-β-CD 3和γ-CD 4与D-、L-、D,L-苯丙氨酸(Phe)形成超分子包合物的稳定常数(K)。手性或外消旋苯丙氨酸与同一主体结合能力的强弱顺序为:L- >D,L- >D-Phe,各体系的K_L/K_D值在1.65～3.01之间,给出了较好的异构体分离。但三种形式的苯丙氨酸与这些主体的缔合常数均较小(K< 3×10²mol·L^-1)。就不同主体而言,K值的次序为:3 >1 >4 >2,并不完全等同于K_L/K_D的顺序:2 >1 >3 >4。     

BZ反应系非理想性对化学振荡动力学区域的影响

基于Debye-Huckel强电解质溶液活度系数理论、反应速度的活化络合物理论以及三变量微分方程奇点理论,探讨了非理想性对BZ反应体系振荡动力学区域的影响。以Oregonator为模型建立了均匀体系非理想BZ反应的系统动力学方程,计算并绘制了化学振荡的临界"溴酸钠浓度-离子强度"阈值图谱,划分了不同的动力学区域,并进行了一系列实验研究,得到了与理论分析一致的结论.     

混沌系统的变量变化率反馈控制方法研究

设计了一种控制连续非线性系统中混沌的新方法--变量变化率脉冲反馈(VRPF)方法.介绍了VRPF方法的控制原理以及反馈系数和脉冲间隔的选择技巧.将此方法应用到BZ反应3D模型系统混沌的控制中,计算机仿真模拟显示,通过恰当地选择反馈系数和脉冲间隔,可以将系统稳定在1p、2p、3p、4p、…、2n×3mp (n、m为整数)这样不同的周期轨道,从而使系统的功率谱也由混沌态时的连续谱转变为具有分立单峰的分立谱.此外,仿真模拟还发现VRPF方法具有极宽的控制域.     

Mechanism and Kinetics of the Induction Period in Nitroxide Mediated Thermal Autopolymerizations. Application to the Spontaneous Copolymerization of Styrene and Maleic Anhydride

Recently we reported an experimental and theoretical (simulation) investigation on the mechanism of the induction period and the initial polymerization stages in the nitroxide mediated autopolymerization of styrene. In this paper we extend some of the results presented there and perform preliminary induction period experiments for the study of the mechanism and kinetics of the spontaneous copolymerization of styrene (S) and maleic anhydride (MA) in the presence of TEMPO and 4-OH-TEMPO. With even small amounts of MA (2% wt) the induction period is dramatically reduced by a factor of about 20 in comparison with the nitroxide-mediated styrene autopolymerization at 120 °C. Our results suggest that the initiation mechanism involves a first step of reaction between S and MA. We speculate that this reaction is a Diels-Alder cycloaddition followed by hydrogen abstraction through a monomer or TEMPO assisted homolysis to form a radical pair (monomer case) or a single radical (TEMPO case), which either initiates polymerization or is trapped by TEMPO depending on the conditions. Hall and Padias have studied similar electron donor-acceptor co-monomer pairs and favor the formation of a tetramethylene diradical as the initiating species for spontaneous copolymerization. In any case, the rate-limiting step would be the initial reaction of S and MA. These induction experiments allow us to obtain an initial estimate of the order of magnitude for the kinetic constant of the rate-limiting step, as 10⁻⁶ Lmol⁻¹s⁻¹.     

Texture and Stability of Emulsions: Role of Oscillatory Structural Forces

A digitized optical imaging technique was used to obtain the droplet size distribution, texture, and the radial distribution function which determines the inter-droplet interactions in emulsion systems. The effects of sucrose ester and polyglycerin stearic acid ester as emulsifiers on the stability (i.e., creaming) of oil-in-water food emulsions were investigated, ft was observed that as the concentration of the emulsifier was increased, the droplet size decreased, and the emulsion became more monodispersed and the stability increased. This was confirmed by the experimentally determined radial distributions and the structure factors. It was found that the emulsion made with the fatty acid ester was more stable than that with sucrose ester, and was less polydisperse with better texture. A statistical thermodynamic model was applied which accounts for the droplet-droplet interaction forces, i.e., oscillatory structural forces, and the polydispersity effect to predict the creaming velocity of an oil-in-water emulsion. Good agreement was found between the experimentally determined creaming velocity and the model predictions.