离子选择性电极多次标准加入法测定氟离子电极电势

建立了选择性电极中离子传递的模型,活化后的离子选择性电极,在电极表面形成活化层,阳离子和等量的阴离子分布在电极活化层的两侧,离子由溶液与活化的界面经活化层传递到固定组成膜与活化界面,在一定的条件下,电极膜电势随时间的变化与溶液和活化层的界面离子浓度随时间的变化成正比,在控制电势随时间的变化率基本恒定的情况下,方法被用于手工测量氟离子选择性电极电势,电极斜率,溶液离子浓度直接由Gran方程求解。     

三氯乙酸根离子选择电极的研制

以长链季铵盐为活性物研制成功PVC膜三氯乙酸根离子选择电极。该电极在1×10~(-1)～2×10~(-6)M Cl_3CCOO-离子浓度范围内显示良好的Nernst响应,检测下限为1.2×10~(-6)M。用固定干扰法测定了该电极对Ac~-、Cl~-,SO_4~-、H_2PO_4~-、HCO_3~-、CO_3~-,Cl_2CHCOO~-、NO_3~-等离子的选择性系数,仅NO_3~-有明显干扰。电极适用于中性、偏碱性溶液,在1×10~(-3)M Cl_3CCOONa溶液中,pH 7.0～12.5电势读数稳定。电极连续工作五小时电势变化为±1mV,可以作为一种分析三氯乙酸盐的简便快速方法。这对控制环境污染,判断职业中毒都十分重要。     

离子浓度测定装置及离子浓度测定元件

本发明提供一种离子浓度测定装置,它可测定生物体成分中的阳离子,尤其是钠离子和钾离子的离子浓度,并可以简化离子选择性电极的结构及制作方法。在金电极（111）表面使将形成自组织化膜的绝缘性分子（例如烷硫醇）与连接体结合的阳离子捕获用配体即冠醚衍生物（109）与具有比连接体长的碳链的烷硫醇（110）共存并固定,以伴随阳离子的配位产生的电动势作为金电极表面的界面电位变化,通过电位差测量装置（104）进行测定。     

电极/离子液体界面电容

用电化学阻抗方法研究了铂片电极在BMIMPF6,BMIMBF4,BMIMClO4,BMIMTf2N,BMIMCl,BMIMBr,C3OHMIMBF4,C3OHMIMClO4和BMMIMPF6(BMIM:1-butyl-3-methylimidazolium;C3OHMIM:1-(3-hydroxypropyl)-3-methylimidazolium;BMMIM:1-butyl-2-methyl-3-methylimidazolium;Tf2N:bis(trifluoromethylsulfonyl)amide)等离子液体中的界面电容及结构.结果表明:当阴、阳离子半径相差不大且不存在特性吸附时,在零电荷电势附近,电极/离子液体界面的电容-电势曲线将出现电容单峰或者双峰.电极的零电荷电势对应于单峰的峰电势或者双峰之间的谷电势.当电极电势远离零电荷电势时,电极/离子液体界面成紧密层结构,可由紧密层理论来描述.如果存在离子的特性吸附,相应的电容峰可能不再出现,而表现为双层电容随电极电势对零电荷电势的偏离而单调增加.还研究了添加小的Li+离子对电极/离子液体界面电容的影响.通过向BMIMTf2N中加入LiTf2N,发现Li+离子可以改变电极/离子液体界面的双层结构,但无助于界面电容的提高,甚至可能引起电容的降低.最后探讨了不同条件下,尤其考虑阴阳离子特性吸附时,电极/离子液体的界面结构.     

离子选择性电极非线性测定水中氟离子的含量

利用氟离子选择性电极测定系列氟离子标准溶液的电极电位(vs.SCE),用测得的电极电位值与氟离子标准溶液的浓度数据进行非线性工作曲线拟舍,可准确测定1×10~(-6)～1×10~(-5)moL/L氟离子溶液的浓度。该法易于实现氟离子溶液的自动连续监测,适于氟离子溶液浓度的在线测量。     

基于硫氮杂冠醚离子载体的高选择性聚合物膜汞离子选择性电极

以硫氮杂冠醚化合物为离子载体,制备了一种高选择性聚合物膜汞离子选择性电极.通过对电极膜的组成及活化条件进行优化,电极在3.0×10-8～1.0×10-4 mol/L的范围内对汞离子呈能斯特响应,响应斜率为31.2 mV/dec,检出限为2.0×10-8 mol/L.该电极对大多数常见的金属离子具有良好的选择性,并可作为指示电极用于电位滴定.     

表面活性剂对氟离子选择电极响应时间的影响

1　引　　言根据国际纯化学与应用化学联合会推荐 ,离子选择性电极的响应时间是指从离子选择性电极和参比电极一起接触试液时 (或由试液中被测物质浓度发生改变时 )算起到电极电位值达到与稳定值相差 1mV所需的时间。电极的响应时间在理论和实际操作中都具有重要的意义 ,它提供了电极反应机理和膜内电荷传导方面的某些信息 ,决定了在测量过程中需经过多长时间才能读取和记录测量结果 ,在连续分析和自动分析中显得尤为重要。电极的响应时间很早就受到分析工作者的重视 ,提出了各种理论模式与假说 ,其中较有代表性的有扩散理论与势垒理论。有…     

伯胺N1923萃取钯(II)的动力学研究

报导了用恒界面池搅拌考察N1923-正辛烷溶液从氯化物介质中萃取Pd(II)时诸因素的影响.并用离子选择电极连续检测萃取过程中水相Pd(II)浓度随时间的变化.     

沉淀基离子选择电极对干扰离子的动力学响应研究

用活度阶梯法研究了AgI,AgBr,CuS,PbS和CdS电极对干扰离子的动力学响应.溶液中含一定浓度主要离子时上述电极对某些干扰离子响应非单一突跃型瞬时信号;溶液中不含主要离子时,除了AgBr电极响应Cl^-外,其它都响应单一瞬时信号.离子交换产物的溶解度越小,离子的水合焓差越小,瞬时信号峰高度越大.离子水合焓差对瞬时信号峰高度的影响说明,试液高速喷向电极表面时由于扩散层厚度很薄,电极对干扰离子响应瞬时信号的峰电位不决定于离子扩散速度,而决定于离子交换速度.除CuS电极外,根据其它电极非单一突跃型瞬时信号所测定的平衡电位选择性系数K_xy^e与相应化合物溶度积比值是一致的.     

Hittorf法测定离子迁移数实验的改进

以不同浓度的CuSO4溶液为电解质,Pt电极和Cu电极分别为电解电极,通过观察通电前后电解质溶液阳极区和阴极区颜色的变化,定性分析离子的电迁移现象.通过电极上产生/溶解Cu的变化量以及CuSO4溶液浓度的变化,计算了不同浓度CuSO4溶液中离子的迁移数,并对浓度等因素对迁移数的影响规律进行了探讨.本文对传统离子迁移数的实验进行了改进,旨在加深学生对离子电迁移现象的认识及对迁移数概念的理解.     

Investigation of electrochemical reactions in the solid state cell Cu/RbCu4Cl3I2/C

Using experimental potential values for a vitreous carbon electrode in contact with the RbCu₄Cl₃I₂ solid electrolyte, the concentration of Cu²⁺ ions in the electrolyte was determined. At 0.5 V, the concentration of Cu²⁺ was 1.25×10¹⁸ cm^–3. The estimated values of the Cu²⁺ ion concentration in RbCu₄Cl₃I₂ (0.8%) and the potential of the vitreous carbon electrode after electrochemical decomposition of RbCu₄Cl₃I₂ (0.606 V) correspond to experimental values of 2% and 0.58 V, respectively. This demonstrates the adequacy of the model describing the electrode potential of Cu²⁺ as a function of the concentration in RbCu₄Cl₃I₂. When the C/RbCu₄Cl₃I₂ interface was polarized, the diffusion coefficient of Cu²⁺ was 1.5×10^–8 cm² s^–1. Investigations of the interface between the copper electrode and RbCu₄Cl₃I₂ were carried out by galvanostatic and potentiostatic methods. A 1-μm layer of cuprous oxide, Cu₂O, was discovered on the interface of the copper electrode with RbCu₄Cl₃I₂. This layer blocks the course of the electrochemical reaction Cu⁰–e^–⇌Cu⁺ with participation of copper metal. The copper electrode behaves as an inert redox electrode at low overvoltages. In this case, at the Cu₂O/RbCu₄Cl₃I₂ interface an electrochemical reaction with Cu²⁺ ion participation, Cu⁺–e^–⇌Cu²⁺, takes place. The results suggest that the reaction rate is limited by slowing the Cu²⁺ diffusion in RbCu₄Cl₃I₂. The initial Cu²⁺ ion concentration in the electrolyte near this interface is about 1.4×10¹⁷ cm^–3. The exchange current density is about (4±2)×10^–6 A cm^–2. At potentials ϕ>8–10 mV, an electrical breakdown of the Cu₂O layer takes place, allowing copper metal to ionize to Cu⁺. We suggest that at 10 mV<ϕ<100 mV the rate of this reaction is limited by the formation and growth of copper nuclei and at ϕ>120 mV the reaction rate is limited by charge transfer. Electronic Publication     

薄层循环伏安法研究硝基苯/水界面上离子诱导的电子转移反应

应用薄层循环伏安法研究了硝基苯/水两相界面间,且有共同离子四丁基铵TBA+存在于两相中,在有机相中的四氰化二甲基苯醌(TCNQ)与水相中的K4Fe(CN)6之间发生的反向电子转移反应。在直径为0.64cm的裂解石墨电极上用2μL硝基苯溶液使之自然扩散在电极表面形成薄层的有机相,并以此作为工作电极。对电极为铂丝(0.5mm),参比电极为Ag/AgCl电极,均置于总体积为2mL的水相中。由于共同离子TBA+的诱导,在硝基苯/水界面间,在已氧化的TCNQ+阳离子(在有机相中)与[Fe(CN)6]4-阴离子(在水相中)之间发生了反向电子转移反应。试验证明:在一定条件下,通过改变两相中共同离子的浓度,可使一些不能发生的两相界面的电子转移反应得以发生;这类电子转移反应系受界面电位差所控制。此外,还测得了在恒定的共同离子浓度比值的条件下,此两相界面电子转移反应的表观速率常数(k)为0.135cm.s-1.mol-1。     

羧基化碳纳米管修饰碳糊电极伏安法测定食盐中碘酸根

应用羧基化多壁碳纳米管(c-MWCNT)修饰碳糊电极,测定食盐中的碘酸根含量.在0.1 mol/L的NaOH电解液中,当IO3-在羧基化多壁碳纳米管修饰碳糊电极表面富集60 s,电位扫速为300 mV/s时,该修饰电极在线性扫描伏安图上能出现一灵敏的阴极溶出峰,峰电位为-0.52 V,峰电流与IO3-浓度在8.0×10-10~5.0×10-8mol/L和1.0×10-7~3.0×10-6mol/L的范围内成良好线关系,相关系数分别为0.999和0.998,检出限可达1.0×10-11mol/L;该修饰电极无汞,稳定性较好,用于加碘食盐中碘酸根含量的测定灵敏度高,平均回收率为101.1%.循环伏安(CV)测试表明,碘酸根在修饰电极上电化学反应是一不可逆过程,其电极反应标准均相速率常数为0.0109 cm.s-1.     

Equilibrium differential capacitance and electrocapillary curves within the framework of a generalized model of the surface layer

Equations that describe the equilibrium differential capacitance C and the interface tension of an electrode subjected to the adsorption of organic molecules under the conditions where this adsorption strictly follows a generalized model of the surface layer are derived. Using the developed programs, the dependences of C on the electrode potential φ are calculated at different concentrations of the organic substance. Based on these C vs. φ curves, a set of effective parameters is obtained. With these parameters, the capacitance curves can best be described by the model of two parallel capacitors combined with the Frumkin isotherm.     

电解液离子与炭电极双电层电容的关系

以酚醛树脂基纳米孔玻态炭(NPGC)为电极, 通过微分电容伏安曲线的测试, 研究了水相体系电解液离子与多孔炭电极双电层电容的关系. 结果表明, 稀溶液中, 多孔炭电极的微分电容曲线在零电荷点(PZC)处呈现凹点, 电容降低, 双电层电容受扩散层的影响显著；若孔径小, 离子内扩散阻力大, 电容下降更为迅速, 扩散层对双电层电容的影响增大. 而增大炭材料的孔径或电解液浓度, 可明显减弱甚至消除扩散层对电容的影响. 炭电极的单位面积微分电容高, 仅表明孔表面利用率高, 如欲获得高的电容量, 还要有大的比表面积. 离子水化对炭电极的电容产生不利影响, 选用大离子和增大炭材料的孔径, 可有效降低离子水化对炭电极电容性能的影响.     

Implementation of a Chloride‐selective Electrode Into a Closed Bipolar Electrode System with Fluorimetric Readout

Applicability of a bipolar electrode system was tested for arrangements containing a typical ion‐selective electrode (ISE) connected with an electrode coated by a conducting polymer characterized by electroluminescence. In this case a selective response of the ISE membrane at one pole of the bipolar electrode is transduced to a fluorimetric signal obtained by reduction of the conducting polymer at the second pole. This signal transformation mode was studied on example of a simple closed bipolar electrode system composed of all‐solid‐state chloride‐selective electrode with polypyrrole transducer as the sensing pole and the reporting pole represented by electrode coated by poly(3‐octylthiophene) (POT) layer characterized by fluorescence in the neutral state. In this system selective and linear dependences of fluorimetric signal on logarithm of chloride ions concentration in turn‐on mode were recorded for optimized external voltage applied. Alternatively, a concept of cascade bipolar electrode system with incorporation of additional bipolar electrode being a polarization source for the sensing bipolar electrode with ISE and POT layer was also tested. A significant advantage of the cascade system is its possibility to work spontaneously without external polarization. For this case also linear calibration plots of fluorimetric signal vs. logarithm of analyte concentration were recorded.     

氟-铁恒电位配位滴定法测定铁离子研究

以氟离子溶液作滴定剂,氟离子选择性电极作指示电极,在pH=1.5的条件下,对恒电位配位滴定法测定铁离子进行了研究。对pH=1.5的条件下使用氟离子选择性电极的可行性,氟-铁的反应速率及电极的响应速率进行了讨论。     

多孔电极电池的循环伏安法模拟

锂离子电池的全电池建模模拟对现代新能源领域的发展至关重要。伪二维（P2D）电化学模型是最常使用的全电池模拟模型,但一直被用于输入为电流,输出为电压的模拟中。本文基于P2D模型,通过对内电位、电极电位以及电池端电压的详细讨论,首次采用电压边界条件,利用COMSOL仿真软件完成了实验中常用的两电极体系和三电极体系的循环伏安法建模和模拟。并对比分析了两/三电极体系中扫描速率、颗粒半径、电极锂扩散速率以及最大嵌锂浓度这四个参数对循环伏安曲线形状的影响。结果表明,循环伏安测试时扫描速率越大,循环伏安曲线的峰值电流越大;固相锂扩散速率越大、电活性颗粒半径越小、最大嵌锂浓度越大,峰值电流越大。在相同的测试条件下,三电极体系比两电极体系的循环伏安图对称性更好,电流响应更大,并且颗粒半径、锂扩散速率及最大嵌锂浓度这三个参数对峰值电流的影响也更为明显。     

Sensor–actuator system for dynamic chloride ion determination

Chloride is a crucial anion for various analytical applications from biological to environmental applications. In order to measure the chloride ion concentration, a measurement system is needed which can detect this concentration for prolonged times reliably. Chronopotentiometry is a technique which does not need a long term stable reference electrode and is therefore very suitable for prolonged ion concentration measurements. As the used electrode might be fouled by reaction products, this work focuses on a chronopotentiometric approach with a separated sensing electrode (sensor) and actuating electrode (actuator). Both actuation and sensor electrode are made of Ag/AgCl. A constant current is applied to the actuator and will start the reaction between Ag and Clˉ, while the resulting Clˉ ion concentration change is observed through the sensor, which is placed close to the actuator. The time it takes to locally deplete the Clˉ ions is called transition time. Experiments were performed to verify the feasibility of this approach. The performed experiments show that the sensor detects the local concentration changes resulting from the current applied to the actuator. A linear relation between the Clˉ ion concentration and the square root of the transition time was observed, just as was predicted by theory. The calibration curves for different chips showed that both a larger sensor and a larger distance between sensor and actuator resulted in a larger time delay between the transition time detected at the actuator and the sensor.