α、β、γ、δ-四(4-三甲氨基苯基)卟啉与钌(Ⅲ)显色反应的研究

本文研究了α、β、γ、δ-四(4-三甲氨基苯基)卟啉(简称TAPP)和钌的显色反应。其最大的吸收波长位于436nm,表观摩尔吸光系数为5。25×10~5L·mol~(-1)·cm~(-1),钉的浓度在0～2.5μg/10ml范围内服从比尔定律,络合物的组成比为Ru:TAPP=1:1。该法用于合成矿样分析,结果满意。     

A MUSCL method satisfying all the numerical entropy inequalities

We consider here second-order finite volume methods for one-dimensional scalar conservation laws. We give a method to determine a slope reconstruction satisfying all the exact numerical entropy inequalities. It avoids inhomogeneous slope limitations and, at least, gives a convergence rate of . It is obtained by a theory of second-order entropic projections involving values at the nodes of the grid and a variant of error estimates, which also gives new results for the first-order Engquist-Osher scheme.

     

Ni selective sensors based on meso-tetrakis-{4-[tris-(4-allyl dimethylsilyl-phenyl)-silyl]-phenyl}porphyrin and (sal)2trien in poly(vinyl chloride) matrix

PVC-based membranes of meso-tetrakis-{4-[tris-(4-allyl dimethylsilyl-phenyl)-silyl]-phenyl}porphyrin (I) and (sal)₂trien (II) as electroactive material with dioctylphthalate (DOP), tri-n-butylphosphate (TBP), chloronapthalene (CN), dibutylphthalate (DBP) and dibutyl(butyl) phosphonate (DBBP) as plasticising solvent mediators have been found to act as Ni²⁺ selective sensor. The best performance was obtained with the sensor having a membrane of composition of I: sodium tetraphenyl borate: PVC in the ratio 5:5:150. The sensor exhibits Nernstian response in the activity range 2.5 × 10⁻⁶ to 1.0 × 10⁻¹ M, performs satisfactorily over wide pH range (2–5.5) with a fast response time (8 s). The sensor was found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol or ethanol and acetone and could be used over a period of 4 months. Potentiometric selectivity coefficients determined by matched potential method (MPM) indicate excellent selectivity for Ni²⁺ ions. The sensors could be used successfully in the estimation of nickel in different brand of chocolates and also as an indicator electrode in potentiometric titration.     

V-H2O体系的溶解组分优势区域图和电势-pH 图

运用浓度比较法, 对25 ℃时V-H2O体系进行热力学分析和电化学分析, 编程计算出各溶解组分浓度, 以及固相和液相、各固相间边界线, 确定固相区和液相区的位置. 在此基础上, 绘制出了总V浓度cT(V)=1.0×10-5 mol·L-1时V-H2O体系的溶解组分优势区域图和电势-pH图以及cT(V)=1.0×10-7 mol·L-1时V-H2O体系的电势-pH图. 电势-pH图结果表明在一定温度和压力下, 各相稳定区取决于体系中溶液态物质的总浓度. 随cT(V)的减小, 溶液稳定区增大, 各固相稳定区均不同程度减小.     

Gas chromatographic subsystem for fast on-line concentration profile measurements for advanced distillation column control

An automated gas chromatographic subsystem for the provision of fast and reliable concentration profile data for distillation column control is presented. The subsystem consists of a gas chromatograph, equipment for sample conditioning and a PC/AT compatible computer communicating with the supervisory process computer. A fast separation time is obtained through the use of a liquid chromatographic packing material and a high pressure drop across the column. Preliminary results show separation times below 10 s for the water-methanol-isopropanol system. Peak areas are quantified by use of parameter estimation in the frequency domain, a method that does not demand complete peak separation.     

The effects of reaction kinetics upon the instabilities in cathodic electrodeposition

This article deals with a linear stability analysis of electrodeposition. The surface energy is disregarded in order to focus on the possible effects of the finite width of the electric double layer and the finite electrode reaction rate upon the wavelength selection. It is found that in the absence of electroconvection the fastest growing perturbation mode is that with a wavelength equal to the geometric average of the Debye length and the reaction diffusion length, which is the ratio of diffusivity to the electrode reaction rate. This wavelength is one–two orders of magnitude greater than that selected by the capillarity mechanism based on the surface energy estimates. This shift of the selected wavelength towards long waves is enhanced by another order of magnitude by electroconvection in the regime of the nonequilibrium electroosmosis developing upon the emergence of the extended space charge.     

Estimation of Coupling Rate Constant of L‐Cysteine Radical Studied by Concentration‐Step Coulometry Using Porous Carbon Felt Electrode Impregnated with an Electrolyte

Controlled potential coulometry using carbon felt electrode impregnated with electrolytic solution realizes very rapid complete electrolysis and can be used to measure the faster reaction rate constant than that using conventional electrolytic cell. In this research, concentration step method was adopted to investigate coupling reaction rate of L ‐cysteine radical. The coupling reaction rate of L ‐cysteine radical becomes much larger than further electrode reaction rate of L ‐cysteine radical at high L ‐cysteine concentration, because the coupling reaction rate is proportional to the second order of L ‐cysteine radical concentration although the further electrode reaction rate is proportional to the first order of L ‐cysteine radical concentration. At a low constant potential value, apparent number of electrons (n_app) increased from 1 (L ‐cystine is produced) to 2 (L ‐cysteine sulfenic acid, RSOH, may be produced) according to decrease in concentration of L ‐cysteine to be electrolyzed. The second order rate constant of coupling reaction was estimated to be about 1200 dm³ mol^?1 s^?1 at 20 °C by curve fitting method for n_app vs. logarithm of L ‐cysteine concentration. Apparent number of electrons (n_app) consumed in the electrode oxidation of L ‐cysteine gradually increased as an applied potential increases, because the consecutive electrode reaction steps with different electrode reaction rates were involved in the electrode oxidation of L ‐cysteine. In the present method, the constant limited electrolytic current was observed at high electrode potential range, which suggests that electrode oxidation rate of L ‐cysteine is kinetically controlled.     

人尿中多胺的离子交换富集和气相色谱测定

以离子交换法对尿样中的多胺进行预分离富集，确定了最佳的离子交换条件，同时比较了三种不同酰化剂的酰化效果，确定了最佳酰化条件，并用毛细管气相色谱法测定了尿中腐胺，尸胺，精脒，精胺的含量，结果表明癌症病人尿中多胺含量高于正常人。     

Cesium Ion-Selective Electrode

The membrane material was prepared by mixing 40% of cesium-triphenyl-cyanoborate and 60% of PVC powder. The mixture was pressed at a pressure of 20tons/cm² for 1hours to make the membrane. Then, the membrane was mounted on a self-constructed electrode body. Nernstian slope of 60 mv/decade was obtained throughout the concentration range 10^?1～2×10^?5M. Selectivity coefficients were presented. The life time of the electrode is longer than 6 months.     

坡面侵蚀形态转变过程的REE示踪法研究

利用REE元素示踪法，采取沿坡面垂直分层布设的新的试验布设方法，通过室内模拟降雨试验，研究了次降雨条件下坡面侵蚀形态的转变过程和细沟的发育发展过程。研究结果表明，降雨初期坡面以面蚀为主，细沟出现后，坡面侵蚀将加快加剧；随着降雨时间的延续，累积面蚀量和细沟累积侵蚀量都将逐渐增加，后者的增加速率大于前者，面蚀所占总侵蚀量的百分比随降雨时间呈曲线形式逐渐递减，细沟侵蚀则逐渐增加；试验结束时细沟侵蚀量分别为面蚀量的4—5倍。本研究为定量区分片蚀和细沟侵蚀量以及坡面侵蚀过程中片蚀向细沟侵的转变以细胞侵蚀发生、发育提供了新的思路和解决途径。