非理想性对B-Z反应体系时间自组织的影响

从理论和实验上研究了非理想性对B-Z反应体系时间自组织行为的影响,重点考察了加入惰性电解质对B-Z反应体系振荡周期的影响,按照Oregonator模型,通过小寄生参数法动力学理论分析表明,非理想性对B-Z反应体系振荡周期的影响体现在振荡周期与铈离子的活度系数成反比,而且惰性电解质的加入使得振荡周期进一步加长.通过一系列实验观测,原则上得到了与理论分析一致的结论.     

甲酸Pt电极电化学氧化体系中时间自组织导致的可利用功耗失

在电极化学反应步骤为控制步骤的条件下,对甲酸阳极氧化体系中出现的电化学振荡的阈值及跨越阈值后状态演化的极限环路径进行了系统动力学计算.同时,根据非平衡电极过程的耗散-涨落理论,进一步对跨越振荡阈值前后的临界区与电化学震荡区的极化曲线及功耗谱进行了随机热力学分析计算.研究结果表明,跨越临界区后单位电化学反应功耗谱出现突降...     

热补偿恒温控制条件下铂电极BZ反应体系中的电化学时间自组织——从极限环型电化学振荡到环面跳跃型非连续电化学振荡

在实验室的热补偿恒温控制条件下, 理论预测的等温恒电流(电压)电化学振荡实际上将发生变异. 用慢流型上准定态的线性化稳定性分析法全面分析了此类恒温控制条件下铂电极BZ反应系在以温度为慢变参数的慢流型上的准稳定性及绕温度轴慢变轨迹的动力学行为. 发现在温度围绕控制值上下往复波动的每一个周期内, 准定态点将穿梭跨越于振荡区与非振荡区之间, 表现为间隙性的沿温度轴的环面型电化学振荡. 计算机模拟结果证实了上述理论分析.     

外控恒电流对BZ电化学反应体系动力学行为的影响

在使用探头对BZ反应体系进行观测时,原来纯粹的BZ反应系变成了由两个子系通过扩散过程耦合成的一类特殊电化学体系,所用的探头能否如实反映该体系的真实振荡行为值得探讨。本文基于FKN机理及Oregonator模型,分别对Pt电极BZ反应体系建立了动力学模型,讨论了两子系出现极限环振荡的动力学行为不一致性及外控电极电流的影响。     

利用K-L方程估算旋转圆盘电极体系反应动力学电流的误差来源分析

旋转圆盘电极（RDE）体系主要用于低溶解度反应物的电极过程动力学研究. 在利用RDE技术研究不可逆电极反应动力学时,人们常利用Koutecky-Levich方程排除传质的影响,从总电流估算反应的动力学电流. 由于K-L方程是建立在系统满足稳态扩散模型的基础上,实际运用时如果体系偏离稳态扩散,就有可能对估算的动力学参数造成很大误差. 本文以氧气在多晶铂电极上的还原反应为例系统地估算了不同氧气浓度与电极转速下的误差,结果表明低氧气浓度与低圆盘转速的情况不满足稳态扩散条件,若此时仍根据K-L方程利用外推法进行分析,误差可达30%. 因此作者建议,在RDE体系中利用K-L方程估算动力学参数时,最好忽略低浓度与低转速下的数据,直接使用较高浓度与较高转速下的数据进行计算与分析.     

光诱导约束刻蚀体系中的TiO_2纳米管阵列光电极上Cu的沉积及抑制

光诱导约束刻蚀可作为一种无应力的化学平坦化方法用于Cu的抛光。我们发现在光诱导约束刻蚀工件Cu的过程中,工具表面的TiO_2纳米管上可能出现Cu沉积。通过扫描电子显微镜及其能谱,X射线光电子能谱等方法分析其沉积形貌和成分组成,探究在工具-工件之间的微纳尺度液层中Cu光催化还原沉积的机制,并在模拟液中研究Cu沉积对刻蚀体系的影响。探究引入搅拌、加入络合剂对TiO_2纳米管表面Cu的沉积的抑制,并考察抑制措施对于工件Cu刻蚀的影响。结果表明Cu沉积会增强TiO_2纳米管光电极的光催化性能,但随着沉积量的增加,增强机制会发生变化;在尝试抑制Cu沉积时也发现改善传质以抑制Cu沉积的同时也会带来工件Cu的刻蚀增强;采用添加络合剂结合改善传质的方法有望在抑制Cu沉积的同时提高平坦化效果。所以抑制方法和条件的选择需兼顾对工具-工件之间微纳液层中的多个化学和传质过程的影响。这些研究对于进一步优化光诱导约束刻蚀体系及其在化学平坦化中的应用有重要的指导意义。     

光促进下溴代烃在CH3OH/DMF体系中的羰基化反应

羰基化反应是有机合成中最重要的反应之一,其合成产品分别为醛、酮、酯、羧酸和酰胺等一系列化合物,可用作溶剂、增塑剂、润滑剂以及天然产物的替代品。卤代烷烃种类繁多,价格低廉,以其为底物进行羰基化反应,可以得到多种多样的羰基化合物。但常规羰基化反应往往需要高温(150-2     

Ni/Mo/N催化剂合成及其在噻吩存在体系下苯加氢反应中的应用(英文)

Ni/Mo/N间隙型催化剂具有高的加氢活性及良好耐硫性, 可应用于煤液化油加氢精制高性能喷气燃料. N原子由于只占据晶格间隙位置, 在进入Ni/Mo过程中会因不占据晶格中的特定晶位, 容易从金属晶格溢出导致无法形成稳定的Ni/Mo/N间隙型催化剂. 为此, 本文利用前驱体晶型控制的方式来实现Ni/Mo/N催化剂合成. 采用络合物分解一步法, 考察了不同结晶过程和老化时间对合成的Ni/Mo/N催化剂用于苯加氢反应活性影响, 并采用X射线衍射、X射线光电子能谱和透射电镜-能量色散X射线光谱对催化剂结构组成进行表征. XRD分析结果显示, 钼酸铵[(NH4)6Mo7O24·4H2O]、乙酸镍[Ni(CH3COO)2·4H2O]和六亚甲基四胺(HMT)添加顺序、结晶过程和老化时间直接影响催化剂组成, 并决定Ni/Mo/N晶相的形成. 结晶过程慢速搅拌速度和短老化时间有利于合成含Ni2Mo3N, Mo2C和Ni晶相的高活性Ni/Mo/N间隙型催化剂, 使苯加氢制环己烷模型反应苯的最大转化率达93%, 环己烷选择性为100%. 含0.01 wt%噻吩的存在使苯转化率由72%降至50%, XPS分析结果表明, 催化剂表面形成的MoS2是催化剂活性降低的重要因素.     

气相色谱在细胞色素P-450单充氧酶模拟体系中的应用 Ⅰ.金属卟啉催化下环己烷单充氧反应中产物的定量分析及在动力学研究方面的应用

本文研究了金属卟啉-氧化剂-烷烃仿酶体系中的气相色谱定量测定方法,获得了该体系的最佳色谱条件和产物的相对重量校正因子。该方法的相对误差小于0.2％,相对标准偏差小于0.6％。对四种类型的金属卟啉催化的环己烷充氧化反应对动力学研究结果表明:反应物的生成量与反应时间呈良好的直线关系,其相关系数大于0.99。     

Degeneration of Limit Cycle Oscillation in BZ Electrode Reaction System Controlled Externally

A dynamical model of electrode BZ reaction system was establisheed on the basis of three variables Oregonator model and kinetics of electrode process. Under weak periodical constraint approximation, dynamical stability of quasi steady state on the slow manifold of the system is analyzed by means of linearized stability analysis of three variable system. Meanwhile, the corresponding regime favorable for the appearance of limit cycle oscillation is calculated. Computer simulation shows that limit cycle oscillatory regime has degenerated because of the external periodical potential constraint in the electrode phase. In this regime the system behaves as a temporary self-organization. Whereas, outside this regime a kind of response oscillation appear, with same period as the constraint.     

Thermokinetic Behaviour Degenerated from Limit Cycle Oscillation of Isothermal B-Z Reaction System due to Temperature Controlling of Heat Compensation Type

The thermokinetic behavior of the B-Z reaction system was influenced by both the chemical reaction-heat conduction coupling and the temperature undulation due to temperature controlling of heat compensation type. Quantitative research indicated that this kind of temperature fluctuation will lead to limit cycle degeneration and the periodic or quasi-periodic response behavior of the focus near a supercritical Hopf bifurcation.     

膜电极上并联电容和控制电流示波电位滴定法

本文研制了几种含聚氯乙烯（ＰＶＣ）膜的选择性电极，使用两种克服电极上交流噪音的方法即并联电容和控制电流示波电位滴定法测定Ｃｕ＾２＋、Ｎｉ＾２＋等金属离子以及ＴＰＢ＾－、Ｍｎｏ４等阴离子并对盐酸左旋咪唑，盐酸阿米替林，心得安等药物含量进行了测定，文中还对这两种方法消除交流噪音的机理进行了探讨，获得满意的结果。     

Estimation of non-ionic, surface-active substances in aqueous solutions by means of the Controlled Growth Mercury Electrode

In this paper, a quick and simple tensammetric method of estimation of non-ionic surfactants (NS) in aqueous solutions is proposed. The method makes use of the variation in the differential capacity of double layer in relation to the time of accumulation (C(d)-t(acc)) of non-ionic surfactants at the hanging mercury drop electrode, generated by a single, very quick opening of the valve. Under such conditions, the capacity current measured at the potential of maximum adsorption diminishes with accumulation time of non-ionic surfactants. The proposed method, which was verified for model surfactant (Triton X-100), may also be applied in the determination of other NS. Modifications in construction of the CGME electrode and its improved metrological parameters played an important role in the presented procedure. In addition, other measurements were performed using standard electrochemical techniques, whereby current-time and differential capacity-potential curves were recorded. Satisfactory results were obtained in the determination of Triton X-100 in the range from 0.05 to 20 mg L(-1) (R.S.D.=6%, recovery=94-103%, r=0.999, DL=0.15 mg L(-1)). Applicability of the method was presented using the water samples from Bia?ka and Dunajec rivers, from which NS were removed by addition of fumed silica.     

Identifying Diffusion Limiting Current to Unravel the Intrinsic Kinetics of Electrode Reactions Affected by Mass Transfer at Rotating Disk Electrode

Rotating disk electrode systems are widely used to study the kinetics of electrocatalytic reactions that may suffer from insufficient mass transfer of the reactants. Kinetic current density at certain overpotential calculated by the Koutecky-Levich equation is commonly used as the metrics to evaluate the activity of electrocatalysts. However, it is frequently found that the diffusion limiting current density is not correctly identified in the literatures. Instead of kinetic current density, the measured current density normalized by diffusion limiting current density (j/j_L) has also been frequently under circumstance where its validity is not justified. By taking oxygen reduction reaction/hydrogen oxidation reaction/hydrogen evolution reaction as examples, we demonstrate that identifying the actual diffusion limiting current density for the same reaction under otherwise identical conditions from the experimental data is essential to accurately deduce kinetic current density. Our analysis reveals that j/j_L is a rough activity metric which can only be used to qualitatively compare the activity trend under conditions that the mass transfer conditions and the roughness factor of the electrode are exactly the same. In addition, if one wants to use j/j_L to compare the intrinsic activity, the concentration overpotential should be eliminated.     

Electrode Kinetics and Complex Formation of [Zn‐Antibiotics‐Cephalothin] System vis a vis Kinetics of Electrode Reactions

Charge transfer reactions between a dropping mercury electrode and a [Mn‐antibiotics‐cephalothin] system were studied at pH = 7.30 ± 0.01, μ = 1.0 MNaClO₄ at 298 K. The antibiotics were doxycycline, chlortetracycline, oxytetracycline, tetracycline, minocycline, amoxicillin and chloramphenicol used as primary ligands and cephalothin as secondary ligand formed 1:1:1, 1:1:2 and 1:2:1 complexes with Zn². Electrode kinetics was discussed on the basis of kinetic parameters viz. transfer coefficient (α), degree of irreversibility (λ), diffusion coefficient (D) and rate constant (k). The values of α varied from 0.40 to 0.57 (0.50) confirm that ‘transition state’ behaves between reactant and product response to applied potential and it lies always between d.m.e. and solution interface. A small variation in potential affects the rate and rate constant greatly.     

The Effects of the Electrode System Geometry on the Properties of Contactless Conductivity Detectors for Capillary Electrophoresis

The basic analytical parameters of contactless conductivity detectors with planar, semi‐tubular and tubular electrodes have been compared. It has been found that the differences in the analytical parameters of the detectors are not significant for analytical use. The mean values of baseline peak‐to‐peak noise of 0.27, 0.35 and 0.33 mV, sensitivities of 0.97, 2.08 and 2.27 mV/pg (for K⁺ ion), limits of detection of 0.93, 0.65 and 0.53, and the heights equivalent to a theoretical plate of 2.83, 2.39 and 2.40 μm were obtained for the detectors with planar, semi/tubular and tubular electrodes, respectively. Modifications of the basic detectors, namely a detector with thinned capillary wall and planar electrodes, and a detector with semi‐tubular electrodes placed one against the other on the opposite sides of the capillary were also tested. The configuration with the electrodes placed one against the other permits detector construction with zero gap between the electrodes without increasing the noise; when the electrodes overlap, the detector begins to operate as a permittivity detector.