用交流阻抗法研究某些离子选择电极的响应特性

用交流阻抗法研究了两种液膜胆R汁酸电极和两种聚氯乙烯(PVC)膜钙离子选择电极.从体电阻R_b和电荷传递电阻R_(ct)得到膜内离子迁移活化能E_a,及电极的表观标准交换电流密度i°_0等信息.结果表明:E_a比R_b更能反映离子在膜内迁移的情况,离子在PVC膜中的迁移比在液膜中困难得多;i°_0能在一定程度上反映电极性能的优劣等。     

镉离子选择电极交流阻抗谱研究:载流子传输活化能和响应机制

研究了用相敏检测技术对以硫化镉/硫化银混晶压片膜为敏感膜的镉离子选择电极在不同温度下交流阻抗谱的测试. 提出了镉离子选择电极的等效电路及相应的电化学参数. 报导了由拟合后的阻抗谱求算不同温度下的膜本体阻抗, 并由此推断电极敏感膜片中载流子传输活化能. 比较了不同组成膜片的传输活化能的差异. 参照了固体电解质理论, 结合X衍射图谱的解析, 对其响应机理进行探讨.     

冠醚载体离子电极的选择特性研究

阴离子选择电极选择性系数随干扰离子r_j/z_j的变化规律已有报道,但冠醚为中性载体的金属离子电极的选择性系数规律未见报道。本文采用不同桥间结构的11种苯并双冠醚作为中性载体,从钾电极出发探讨了不同冠醚电极选择性系数与干扰离子r_j/z_j间的关系;并以4种烃型双冠醚为中性载体,分别考察了它们对Li~+、Rb~+、Cs~+、Ag~+、Ba~(2+)离子的响应规律。 1 实验部分     

以离子水合能解释离子选择电极响应机理

用相继切换不同浓度I^-试液的活度阶梯法研究了碘化银基离子选择电极（I^--ISE）的瞬时响应。随电位变化的离子水合自由能△Gh(I^-）显示出|△Gh（I^-）|越小，正活度阶民位跃迁越快而负活度阶梯电位变化越慢。将－△Gh(I^-）看作I（H2O）n^-与I^--ISE表面反应的活化能解释了这个现象。比起传统电位法，活度阶梯法的主要优点是ISEs响应非常快并且更灵敏，有可能实现小体积试液的快速分析。     

碳纳米管电极超大容量离子电容器交流阻抗特性

采用碳纳米管作为超大容量离子电容器的电极材料,应用交流阻抗频谱法,研究了超大容量离子电容器的频率响应特性.结果表明,用碳纳米管块作电极,超大容量离子电容器在频率250 mHz以下出现“电荷饱和”；而用活性炭块作电极, 超大容量离子电容器在频率为100 mHz时仍未出现“电荷饱和”,这说明碳纳米管电极超大容量离子电容器的频率响应特性优于活性炭电极超大容量离子电容器的频率响应特性.上述两类超大容量离子电容器的阻抗谱中均出现倾角约为45°的直线段,其相位角均远小于理想电容器的相位角90°.     

用银和铅标记人白蛋白的离子选择电极电位法研究

用离子选择电极电位法研究了银和铅与人白蛋白（ＨＳＡ）的配合平衡。明确证实银和铅都与ＨＳＡ形成了单核配合物ＭＡ和ＭＡ２．Ａｇ－ＨＳＡ配合物的稳定性积β１１＝４．４×１０＾７，β１２＝１．０×１０＾１２；Ｐｂ＝ＨＳＡ配合物的β１１＝３．１×１０＾５，β１２＝２．０×１０＾９。根据ＨＳ与人白蛋白羊抗血清（ＧＡＨＡ）的免疫反应，用银和铅分别标记ＨＳＡ时，测定ＧＡＨＡ（效价１：４０）的线性范围是０．２～２．     

溶胶-凝胶包埋法制备银离子选择电极的研究

研制了一种用溶胶 凝胶技术包埋电活性物质的银离子选择电极。研究了包埋过程的变量参数及电极的响应机理。电极Nernst响应范围为 1.0× 10 - 1～ 1.0× 10 - 5mol·L- 1,斜率为5 5 .5mV·pc- 1,检出限为 3.1× 10 - 6mol·L- 1。该电极响应快 ,体积小 ,制作简单 ,使用方便 ,具有坚固耐磨 ,可在严酷条件下使用的特点。此研究对进一步研制溶胶 凝胶ISFET化学传感器和生物传感器具有探索意义     

镍纳米线电极的交流阻抗研究

用交流阻抗法研究了一种新型电极－镍纳米线电极在碱性溶液中的电化学行为,给出了相应的等效电路和拟合效果。实验结果表明,外加电位对电极表面化学反应速度和类型有显著影响。在外加电位不高时,Ni（Ⅱ）氧化成Ni(Ⅲ)的电化学过程随着电位的升高而明显加速;当外加电位高于0．40V以后,电极表面同时发生电化学析氧反应。相同条件下,镍纳米线电极的表面电化学反应速度远远高于镍块体电极。     

Determination of Some Thiobarbiturates with Ion-Selective Membrane Electrodes

Abstract

A liquid membrane Ag⁺-selective electrode of our construction and a commercial solid membrane Ag⁺/S^2--selective electrode were used for the determination of thiobarbiturates by potentiometrie titration with AgNO₃ solution or by direct potentlometry. The potentio-setrio data correlated vd. th IR spectra allowed the elucidation of the reaction mechanism.     

Complex Formation Studies with Cupric Ion-Selective Membrane Electrodes

Abstract

A cupric ion-selective electrode of the liquid-liquid membrane type is shown to respond selectively to Cu⁺⁺ activity over the range of pCu⁺⁺ = 2–5 in aqueous solutions of pH 3.5–6.5. Cupric ion activity measurements in the presence of complexing ligands have yielded a reliable estimate of formation constants for a number of soluble copper complexes.     

四苯硼酸盐PVC膜锂离子选择电极的研究

四苯硼酸盐与介体溶剂所组成的PVC膜对碱金属离子的选择性同溶剂的性质有关^[1]。因此,可选择适当的溶剂研制碱金属离子选择电极。本工作研究了以DOPP(苯基膦酸二辛酯)或TBP(磷酸三丁酯)为介体溶剂,NaTPB(四苯硼钠)或KTPB(四苯硼钾)为活性物质的PVC膜对金属离子的选择响应。结果表明,DOPP为溶剂、KTPB为活性物质可制备性能良好的PVC膜Li⁺选择电极。该电极的电化学性能接近或优于新近报道的几种Li⁺选择电极^[2~7]。     

Ion-Selective Electrodes Prepared with Polyaniline Membranes

Polyaniline is a conductive polymer that has electrochemical activity. For this reason, it has many different uses in electrochemical area. In this study, polyaniline was prepared by electrochemical oxidation of aniline in concentrated H₂SO₄ and HCl solutions. Then, membranes were obtained from a mixture of these polymers and paraffin at a weight ratio of 50%. Ion-selective electrodes were prepared with these membranes and AgCl/Ag electrodes. Properties of prepared membranes were investigated with potentiometric measurements made in HCl, KCl, H₂SO₄, and HClO₄ solutions of different concentrations. The E–logc plots obtained with these ion-selective electrodes were found to be linear in a distinct concentration range. Their slopes depend on the membrane type and the doping ion in the test solution. The difference between these membranes was explained according to the morphological structures of polyaniline membranes.     

Application of Ion-Selective Electrodes as Reference Electrodes

Abstract

Reference electrodes limiting interfering effects of conventional reference electrodes on the measurement involving ion-selective electrodes have been developed. They are constructed of a plastic body with porous plug or sleeve junction. Solid state, low impedance, ion-selective electrodes (cupric, cadmium, fluoride) in the equilibrium of corresponding ion solution are used as the half-cells. The absence of interfering ions in the electrolyte allows the determination of the ion of interest at extremely low levels without interference. The electrodes have good reproducibility and stable intercomparison potentials of ± 0.2 mV. The performance of the electrodes has been tested for the measurement of sub-ppm halide levels. Data on stability, reproducibility, effects of temperature, ionic strengthand pH is presented and compared to that of conventional reference electrodes.     

Arginine Determination with Ion-Selective Membrane Electrodes

Abstract

A new method for the determination of the amino acid arginine utilizes a dual enzyme catalyzed reaction monitored with an ammonium ion selective membrane electrode of the antibiotic type. The technique gives a linear correlation between arginine concentration and electrode response over the 3 × 10^?3 M to 3 × 10^?5 M range and a useful, but non-linear, response over a wider range. Major interferences are urea, K⁺, and NH₄ ⁺, but Na⁺ does not interfere in the physiological concentration range.     

Determination of Antiseptic Dyes with Ion-Selective Electrodes

The possibility of determining Methylene Blue and Brilliant Green antiseptic dyes in solutions with the use of ion-selective electrodes based on trioctyl oxybenzosulfonic acid was examined. Data on application of the electrodes fabricated to analysis of powdered dyes are presented. A gravimetric method for analysis for Brilliant Green was suggested and used as a comparative technique.     

Some Characteristics of Ion-Selective Electrode Membrane Surfaces

Abstract

Some studies of the features of surfaces of PVC based liquid ion-exchanger and neutral carrier membranes, and of solid-state membranes of ion-selective electrodes are reviewed with respect to the application of X-ray fluorescence (XRF), Auger spectroscopy and scanning electron microscopy (SEM), Among the membranes discussed are those responding to (i) calcium for organophosphate type membranes, (ii) barium and polyalkoxylate non-ionic surfactants for PVC membranes based on complexes of barium with polyalkoxylate s, (iii) copper(II) for solid-state membranes of mixed copper(II) sulphide and silver sulphide, and (iv) sulphide and thiols for membranes of silver sulphide.