对位叠式循环方波伏安法：Ⅰ.简单可逆电极体系

本文提出叠式循环方波伏安法和对位叠式循环方波伏安法，对简单可逆电极体系的理论作了推导和验证，经对各种电流的比较，发位叠式循环方波伏安法有较多的优点。较之其它方波伏安法灵敏。     

络合吸附催化循环叠式方波伏安法

对受前行化学反应控制的络合吸附催化体系循环叠式方波伏安法进行了理论推导和实验验证，讨论了电流的特性。结果表明，对于络合吸附催化体系的测定，循环叠式方波伏安法的灵敏度比现行方波伏安法高约２５倍。     

叠式循环阶梯脉冲伏安法：Ⅰ.简单可逆电极体系

本文提出循环阶梯脉冲伏安法和对位叠式循环阶梯脉冲伏安法，推导出简单可逆电极体系的电流方程，研究了峰电流与诸因素的关系，并进行了实验验证，发现对位叠式循环阶梯脉冲伏安法有较多的优点     

络合吸附催化不可逆循环叠式方波伏安法

研究了络合吸附催化不可逆体系受前行化学反应控制（Ｋ＜＜１）和不受前行化学反应控制（Ｋ＞＞１）两种情况下的循环叠式方波伏安法的电流理论，并进行了实验验证，讨论了电流特性，获得区分Ｋ＜＜１和Ｋ＞＞１的判据。对于上述体系的测定，循环叠式方波伏安法的灵敏度比普通差式采样方波伏安法高一个数理级以上。     

络合吸际体系叠式循环方波伏安法的理论研究

推导出不受前行化学反应控制的络合吸附不可逆过程叠式循环方波伏安法的电流及其卷积和导数方程，系统地研究了各电流一有关参数的关系，给出了峰电势表达式，并进行了实验验证。该理论同样适用于简单吸陵不可逆过程。     

络合吸附体系叠式循环方波伏安法的理论研究Ⅱ．不受前行化学反应控制

推导出不受前行化学反应控制的络合吸附不可逆过程叠式循环方波伏安法的电流及其卷积和导数方程，系统地研究了各电流峰形，各峰电流与有关参数的关系，给出了峰电势表达式，并进行了实验验证。该理论同样适用于简单吸附不可逆过程。     

络合吸附体系叠式循环方波伏安法的理论研究：Ⅰ.受前行化学反应控制

推导出受前行化学反应控制的络合吸附不可逆体系叠式循环方波伏安法的电流方程及其各阶导数卷积方程,研究了各峰电流与诸因素的关系,并推导出峰电势表达式。理论推导与实验结果一致。     

用微机电化学系统研究方波伏安法和循环方波伏安法——Ⅰ.可逆过程的理论和验证

本文应用微计算机电化学系统研究可逆过程的方波伏安法,特别是作者提出的循环方波伏安法,建立了循环方波伏安法的理论电流函数表示式。理论和实验验证都表明,循环方波伏安法正向扫描的峰电流和峰电势分别等于逆向扫描的峰电流和峰电势,这是氧化态和还原态都溶于电解质溶液的可逆电极过程体系的重要特征和判据。同时研究了参数如方波振幅(E_sw),方波周期(τ),阶梯电势增量(ΔE)的影响,理论预期与实验结果一致。     

阳极溶出催化伏安法的理论研究 Ⅰ.可逆电极溶出

本文推导了玻璃碳电极上可逆溶出催化过程的理论电流方程、峰电流及峰电势方程,得知溶出催化伏安法所得的峰电流比溶出伏安法的峰电流提高了数十倍,从而进一步提高了溶出伏安法的灵敏度。本文还用碲的溶出催化实验验证理论方程。所得实验结果均与理论方程相吻合。     

用微机电化学系统研究方波伏安法和循环方波伏安法 Ⅱ.准可逆过程的理论和应用

本文研究了准可逆过程的方波伏安法和作者提出的循环方波伏安法,建立了电流函数理论表示式。理论和实验都表明,循环方波伏安法正向和逆向扫描伏安曲线的峰电势之差(ΔE_p)严格地依存于电极反应的标准速率常数(K_s~-)和电压扫描速度(ΔE/τ)。对于完全可逆过程ΔE_p~-=0随着可逆程度的降低,△E_增加,但不受方波振幅值的影响。引入一个与K_s、ΔE/τ有关的参数K_c,经计算可以得到K_c-ΔE_p理论曲线。由实验得到ΔE_s,从理论曲线查得K_c值,便能估算K_s值。将此法初步应用于测定[Fe(CN)_6]~(3-)-H_2SO_4体系在玻碳电极上的标准反应速率常数,K_s=2.5×10~(-3)cm/s与用阶梯扫描伏安法测得值2.1×10~(-3)cm/s和文献值2.2×10~(-3)cm/s颇为接近。     

不可逆电极过程方波伏安法动力学研究 Ⅰ.平行催化体系

本文报道了在不可逆电极过程的强催化体系中，当采用快速方波扫描时，正、逆向电流将出现峰形。依据实验结果，提出了“迁出－进入”的等浓度面理论模型，推导了并讨论了电流方程式。结果表明，文中提出的理论能较好地说明实验结果。     

方波伏安法评估聚苯胺膜修饰电极的电荷传输速度

研究导电聚合物的电荷传输机制与速度对于其在应用方面的研究极为重要［‘］．例如在电池的研究中，充放电的速度决定于导电聚合物的电荷传输速度；在电致变色器件的研究中，响应时间也是决定于导电聚合物在氧化还原态间的变化速度，即电荷传输速度．显然较低的电荷传输速度不利于器件的实用化，因此人们必须找到一种能够迅速准确评价电荷传输速度的方法，由于导电聚合物是一个特殊的体系，用一般的电化学方法对其电荷传输速度进行测定时常常遇到这样或那样的问题［‘j．一般说来，导电聚合物的氧化还原过程中均伴随着抗衡离子的运动．体系…     

Study on the Electrochemical Behavior of Melatonin with an Activated Electrode

It was found that melatonin could be incorporated and accumulated on the surface of the glassy carbon electrode which was activated electrochemically by pretreatment in sodium hydroxide solution by means of cycling the potential well into the positive limit of the solvent. In Britton‐Robinson buffer solution (pH 6.7), melatonin gave a sensitive oxidation wave at a potential of +0.65 V (vs.Ag/AgCl) by using Osteryoung square‐wave stripping voltammetry (OSWSV). The oxidation process has been shown to be irreversible and adsorption‐controlled at this electrode by means of cyclic voltammetry and linear sweep voltammetry. A chronocoulometric characterization of the adsorption characteristics of melatonin at this electrode is also presented. The factors affecting the peak current were optimized, and the dependence of peak currents on the concentration of melatonin was found to be linear in the range 8.0×10^?7?1.0×10^?5 mol L^?1. A detection limit of 5.0×10^?8 mol L^?1 was obtained (signal‐to‐noise ratio of 3). This method was applied to the assay of melatonin in tablets and capsules with good recoveries (98–100%).     

Cyclic Square Wave Voltammetry: Theory and Experimental

Abstract

The voltage wave form of cyclic square wave voltammetry (CSWV) and its theory are presented, and experimental verification of theoretical work for CSWV is given. Indications are that the peak potential difference, E_p, of the differential current between the forward sweep and the reverse sweep is zero. Their peak heights have the same value for a reversible electrode reaction, zero, a different value for a reversible electrode reaction with stripping process, not zero, and the same value for a quasi-reversible electrode reaction. According to this property, the reversibility of an electrode reaction can be easily determined.     

The catalytic adsorptive stripping voltammetric determination of chromium with TTHA and nitrate

A sensitive voltammetric method is presented for the determination of trace amounts of total chromium (Cr(III) and Cr(VI)) in natural waters, employing the square wave mode. The method is based on the preconcentration of the Cr(III)-TTHA complex by adsorption at the HMDE at the potential of –1.0 V vs. Ag/AgCl. The adsorbed complex is then reduced producing a response with a peak potential of –1.29 V and the peak height of the Cr(III) reduction is measured. The catalytic action of the nitrate ions on the Cr(III)-TTHA reduction has been elucidated using cyclic voltammetry. The adsorption of chromium complexes at the HMDE was investigated using out-of-phase a.c. voltammetry and the potential range of adsorption was determined.Based on these investigations optimal conditions for the determination of the total chromium concentration in the range 155–2000 ng 1^–1 have been established. The determination limit is 15 ng 1^–1 and the RSD is 3.5% for chromium concentrations 200 ng 1^–1.The usefulness and wide scope of this method for reliable and highly sensitive chromium analysis down to the ultra trace levels existing in various types of natural waters is demonstrated by determinations of the total chromium content in lake, sea and rain water.     

氧氟沙星在乙炔黑修饰电极上的电化学行为及测定

本文制备了一种乙炔黑修饰电极,研究了氧氟沙星(OFL)在该修饰电极上的循环伏安行为。结果表明,在pH=5的PBS缓冲液中,氧氟沙星在该修饰电极上出现一不可逆的氧化峰,在40～360 mV/s扫速范围内,氧化峰电流与扫速呈线性关系,表明该电极过程受吸附控制。计算了电极过程的部分动力学参数:反应电子数为2,电极有效面积为0.067 cm2。讨论了修饰剂用量、缓冲液种类、溶液pH值对测定的影响。用方波溶出伏安法对OFL进行测定,在2.5×10-6～2.5×10-4mol.L-1的浓度范围内与氧化峰电流(Ipa)呈线性关系,Ipa(μA)=-1.6148+0.2169c(10-6 mol.L-1),相关系数为0.9951,检出限为1.332×10-7 mol.L-1,回收率为90.40%～101.06%。     

Facilitated ion transfer of protonated primary organic amines studied by square wave voltammetry and chronoamperometry

The transfer of the protonated forms of heptylamine, octylamine, decylamine, procaine and procainamide facilitated by dibenzo-18-crown-6 from water to a solvent polymeric membrane has been investigated by using cyclic square wave voltammetry. The experimental voltammograms obtained are in good agreement with theoretical predictions. The values of the standard ion transfer potential, complexation constant and diffusion coefficient in water have been obtained from these experiments, and have been used to draw some conclusions about the lipophilicity of these species and the relative stability of the organic ammonium complexes with dibenzo-18-crown-6. The results have been compared with those provided by linear sweep voltammetry. Calibration graphs were obtained with both techniques. An interesting chronoamperometric method for the determination of the diffusion coefficient of the target ion in the membrane has been developed and applied to all these protonated amines.