Application of a Power Time Current to the Study of a Catalytic Mechanism in Chronopotentiometry and Reciprocal Derivative Chronopotentiometry. Advantages of a Cyclic Stationary Response

This paper develops the theory for a pseudo‐first order catalytic mechanism in chronopotentiometry with a power time current, I(t)=I₀t^u (u≥?1/2), applied to a spherical electrode of any size, and the advantages of the use of small electrodes and ultramicroelectrodes are discussed. The advantages of using a cyclic power time current to reach a stationary response suitable for characterizing a catalytic mechanism easily and accurately are reported. The reciprocal derivative (dt/dE?E) curves, which present peaks quantitatively related to the kinetic parameters of the chemical reaction, have been obtained from the potential‐time responses. The influence of the homogeneous kinetic, the electrode radius and the power of time current in the achievement of a stationary response is analyzed. Methods for determining thermodynamic and kinetic parameters of the chemical reaction are proposed.     

Steady State Reciprocal Derivative Chronopotentiometry with Programmed Currents at Microelectrodes

Equations corresponding to the application of Reciprocal Derivative Chronopotentiometry with programmed currents to spherical and disk microelectrodes under steady state conditions have been deduced. Traditional stationary dt/dE vs. E curves for a current time function of the form I(t)=I₀t^u, u>0, and the new dI/dE vs. E curves, which do not depend on the particular characteristics of the applied programmed current I(t) are shown for any degree of reversibility of the electrode process. The evolution from transient to steady state for both derivative techniques has been analyzed. Criteria for characterizing reversible and totally irreversible stationary derivative curves, together with easy methods for determining thermodynamic and kinetic parameters of the charge transfer process from the measure of peak parameters are proposed. The validity of the theoretical predictions has been experimentally tested with hexachloroiridate(IV) reversible oxidation and with iron(III) irreversible reduction in aqueous media.     

Theoretical and Experimental Study of the Homogeneous Catalytic Oxidation of Nicotinamide Adenine Dinucleotide (NADH) at Spherical Gold Electrodes Using Linear Sweep Voltammetry and Chronopotentiometry

The homogeneous catalytic oxidation of coenzyme nicotinamide adenine dinucleotide (NADH) with dopamine at a thiolactic acid modified gold spherical electrode of radius 0.0128 cm has been studied in aqueous phosphate media (pH 7.0) using linear sweep voltammetry and chronopotentiometry with power time and exponential time currents. We have proved that, under the conditions of this study, the steady state is reached, in such a way that the expressions for the I?E and dI/dE?E responses are simplified and become independent of time and the electrochemical technique employed. Therefore, the experimental I?E and dI/dE?E curves obtained in chronopotentiometry and linear sweep voltammetry are practically superimposable and, from easy expressions for the peak parameters of the dI/dE?E curves deduced in this paper, values of the chemical and electrochemical rate constants have been obtained.     

Cyclic chronopotentiometry with non-linear current-time functions at an SMDE Amalgamation and reversibility effects and experimental verification

The general analytical equations corresponding to the potential-time response obtained for a charge transfer reaction in cyclic chronopotentiometry with power current-time functions at a static mercury drop electrode are presented. The superposition principle can be applied in this case in spite of the fact that the successive applied currents are non-linear functions of time. These theoretical equations have been tested experimentally in the following cases: (a) for reversible systems in order to quantify the amalgamation product effects; (b) for non-reversible systems pointing out that a given electrode process becomes more irreversible the lower the power of time in the applied current; (c) to analyse the influence of the electrode kinetics on the potential-time curves by using solutions of Cd²⁺ with different concentrations of n-pentanol by determining kinetic parameters of tie charge transfer reaction.The sensitivity obtained in the characterisation of amalgamation processes is similar to that of voltammetric stripping techniques. Moreover, the analysis of the different cycles of the potential-time response allows us to obtain accurate values of kinetic parameters, as well as to detect possible complications in the charge transfer reaction.     

Investigations on adsorption potentiometry Part I. Derivative adsorption chronopotentiometry of the iron(III)-2-(5′-bromo-2′-pyridylazo)-5-diethylaminophenol system

An electroanalytical method, based on derivative chronopotentiometry of the iron complex with 2-(5′-bromo-2′- pyridylazo)-5-diethylaminophenol (5-Br-PADAP) accumulated adsorptively on the surface of a hanging mercury drop electrode, for determining trace iron in food has been developed. The dependences of the peak height on the dt/dE vs. E curve on the preconcentration time, preconcentration potential and electrode area are discussed. Optimum experimental conditions include 0.005 mol 1^?1 NH₃NH₄Cl, 2 × 10^?7 mol 1^?1 5-Br-PADAP and a preconcentration potential of ?0.40 V (vs. SCE). Under these conditions, the detection limit and the linear range are 2 × 10^?9 and 6.7 × 10^?9?1.7 × 10^?7 mol 1^?1, respectively. The relative standard error of the method is 1.5% for 6.7 × 10^?8 mol 1^?1 Fe(III). The method was applied to samples of microwave digested food.     

Stripping Chronopotentiometry with Dry‐Preservable Supporting Electrolyte

The determination of some toxic metals by stripping chronopotentiometry with a supporting solution having an unconventional composition has been investigated with the aim of using such components in disposable measuring cells preservable in dry state and quite ready for use, only needing addition of a small volume of sample. The new supporting solution is prepared with a solid strong acid, p‐toluenesulfonic acid, in the place of the inorganic acids commonly used to improve the cation availability. The other components are, as usual, sodium chloride, which fixes the potential of the screen‐printed silver – silver chloride reference electrode, and mercury(II) chloride as the plating agent. This supporting solution has been tested in batch measurements with the mercury film glassy carbon electrode as well as with screen‐printed carbon‐ink electrodes, either with mercury film or bare. The physical shape of the mercury layer electrolytically deposited on screen‐printed carbon‐ink electrodes from a supporting solution containing 0.1 M p‐toluenesulfonic acid and 0.1 M sodium chloride has been investigated by scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) microanalysis. In chronopotentiometric stripping p‐toluenesulfonic acid performs as well as the usual inorganic strong acids, particularly in terms of sensitivity. At 0.1 mol dm^?3 it proved very suitable for the determination of toxic metals, in particular lead(II), at levels down to a few μg dm^?3. The overall results appear promising and can open new avenues for preparing disposable cells for on‐field stripping chronopotentiometric determination of toxic metals.     

Non-linear perturbation functions in the study of electrode kinetics: Part IV. Instrumentation

The construction of a digital function generator with the capability of generating voltage-time functions of the form E=E₀t^?1/2 is described. Some applications of such a device for fast chronopotentiometric measurements employed for the study of the mechanism of electrode reactions and superimposed non-faradaic charging processes are suggested.     

A unified treatment of reversible electrode processes in voltammetric techniques and chronopotentiometric techniques with programmed current

In this paper we demonstrate the existence of a total analogy between the potentiostatic and chronopotentiometric responses when a constant potential E and a programmed current of the form I(t)=I₀t^u, u≥−1/2 , respectively, are applied to planar and spherical electrodes, and also to hemispherical microelectrodes. From the above analogy, we also compare differential pulse voltammetry (DPV) and a new reciprocal derivative chronopotentiometric technique proposed in this paper.     

Electrochemical dissolution of chalcopyrite studied by voltammetry of immobilized microparticles

The characteristics of anodic electrochemical dissolution of chalcopyrite (CuFeS₂) powder in hydrochloric acid medium with sodium chloride have been studied. Cyclic voltammetry and chronopotentiometry of immobilized microparticles using paraffin-impregnated graphite electrode was employed. Present work is focused on electrochemical identification of chalcopyrite cathodic and anodic reaction products within the potential range of −0.7 to +0.8 V (vs. SCE) in hydrochloric acid solution containing sodium chloride and/or copper(II) chloride.     

Determination of chloride by stripping chronopotentiometry with silver-film electrode

The experimental parameters of cathodic stripping chronopotentiometry of chloride at a silver-film electrode are investigated and optimized. The chloride preconcentration is achieved in the form of silver chloride by a controlled potential oxidation of the working electrode under vigorous stirring. Cathodic stripping of the deposit is obtained by the constant current, under the condition of diffusive mass transfer. Deaeration of the solution is not necessary. A detection limit of 35 μ dm⁻³ (10⁻⁶ mol dm⁻³) is obtained at a deposition time of 180 s, with a reproducibility of 6.7 % (expressed as relative standard deviation, RSD).     

环丙沙星-钨硅多金属氧酸盐的制备及热分解动力学

A new polyoxometalate （CPFX·HCl）3H4SiW12O40·10H2O was prepared from ciprofloxacin hydrochloride and H4SiW12O40·nH2O in aqueous solution, and characterized by elemental analysis, IR spectra and DTA-TG-DTG techniques. The IR spectrum confirmed the presence of Keggin structure and the characteristic functional group for ciprofloxacin in the compound. The TG-DTA-DTG curves showed that its thermal decomposition was a four-step process consisting of simultaneous collapse of Keggin type structure. The residue of decomposition was the mixture of WO3 and SiO2, confirmed by X-ray diffraction and IR spectroscopy. The decomposition mechanism and nonisothermal kinetic parameters of the polyoxometalate were obtained from an analysis to the TG-DTG curves by the single scanning methods （the Achar method and Coats-Redfern method） and the multiple scanning methods （the Kissinger method, Flynn-Wall-Ozawa method and Starink method）. The results indicate that the kinetic equationswith parameters describing the thermal decomposition reaction are dα/dt=6.65×10^6[3（1-α）^2/3]e^-10495.5/T with E=87.26 kJ/mol and A=6.65×10^6 s^-1 for the second step,dα/dt=7.01×10^9（1-α）e^-18770.7/T with E=156.06 kJ/mol and A=7.01×10^9 s^-1 for the third step,dα/dt=9.77×10^43[（1-α）^2]e^-88980.0/T with E=739.78 kJ/mol and A=9.77×10^43 s^-1 for the fourth step.     

Catalytic Adsorptive Stripping Chronopotentiometry of Co(II)‐DMG‐Bromate System at an In Situ Plated Lead Film Electrode

A novel catalytic adsorptive stripping chronopotentiometric (CC‐CAdSCP) procedure for the determination of Co(II) traces was developed using a lead film electrode (PbFE). The PbFE was generated in situ on a glassy carbon support from a 0.1 M ammonia buffer containing 1×10^?5 M Pb(II), 6.5×10^?5 M DMG and the target metals. An addition of 0.2 M NaBrO₃ to the solution yielded an 11‐fold catalytic enhancement of chronopotentiometric response of the Co(II)‐DMG complex. The CC‐CAdSCP curves were well‐developed, sharp and reproducible (RSD 5.0 % for 5×10^?9 M Co(II)). The limit of detection for Co(II) for 210 s of accumulation time was 4×10^?10 M (0.024 µg L^?1). In addition, the elaborated method allowed the simultaneous quantification of Co(II) and Ni(II) simultaneously.     

Investigations on if-E Curve in Cyclic Derivative Chronopotentiometry(Ⅵ)——Theoretical Equations of if-E Curves in the Case of Quasi-reversible and Irreversible Electrode Reactions

The theory of if-E curve in cyclic derivative chronopotentiometry is presented. Theoretical equations of if-E curves in the case of quasi-reversible and irreversible electrode reactions are deduced respectively.     

Dissolved iron analysis in estuarine and coastal waters by using a modified adsorptive stripping chronopotentiometric (SCP) method

An electrochemical method based on adsorptive stripping chronopotentiometry (SCP) with a rotating mercury film electrode has been developed for the determination of dissolved iron (III) at subnanomolar concentrations in estuarine and coastal waters. The detection limit was 0.11 nM after adsorption time of 60 s. Compared to the other chronopotentiometric methods available for dissolved iron measurement in natural and estuarine waters, the procedure described here exhibits a 15-fold better sensitivity. Therefore, it allows one to accurately quantify concentrations commonly found in estuarine and coastal waters. Moreover, by using the speciation scheme proposed by Aldrich and van den Berg (Electroanalysis 10 (1998) 369), several forms could be measured, i.e. reactive iron (Fe R) and reactive iron (III) (Fe^III R), or estimated, i.e. complexed iron (Fe C) and reactive iron (II) (Fe^II R). The method described here is reliable, fast, inexpensive and compact. It was applied successfully to the study of the chemical speciation of dissolved iron along the salinity gradient of the Aulne estuary (Brittany-France).     

Chronopotentiometry of systems involving follow-up chemical reactions: Application of convolution and finite difference procedures

Distortion of polarization curves by double layer charging severely limits the standard application of chronopotentiometry to mechanism and rate constant analysis of systems involving fast follow-up chemical reactions. A procedure is proposed to overcome these difficulties in the case of irreversible electrochemical-chemical processes (pure kinetic conditions). It starts with the extraction of the faradaic component, i_f, of the imposed current and the computation of its convolution integral, I, with the function (πt)^?1/2. The i_f-E and I-E are then simultaneously treated by a logarithmic analysis the form of which depends upon the expected mechanism. The efficiency of the method in mechanism and rate determination is illustrated experimentally on the example of the electrohydrodimerization of p-methylbenzylidene malononitrile for which discrimination between 32 possible limiting mechanisms has to be carried out. The same reaction is also used to test another type of analysis to be applied to partially reversible systems. Data processing then combines finite difference approach and convolution. It amounts to fitting the formal kinetics with the experimental data automatically in a small size computer avoiding tedious manual fitting with a priori calculated working curves. It is shown that the rate constants can be thus determined with a good accuracy even from single-step experiments.     

微分吸附计时电位法测定痛力克

非成瘾性高效镇痛新药痛力克在硫酸底液中产生一灵敏的微分吸附计时电位溶出峰，峰电位在－１．０Ｖ。利用该峰测定痛力克的线性范围为０．０２－２．０ｍｇ／Ｌ，检测限为０．００４ｍｇ／Ｌ。用线性扫描，循环伏安等方法研究了该体系的电化学行为和电极反应机理，认为所研究体系属于有吸附性的不可逆还原过程，电极反应的电子转移数为２，参与电极反应的质子数为２。用该方法测定了片剂中痛力克的含量，结果满意。     

The renovated silver ring electrode

In this preliminary note, a new type of working electrode – the renovated silver ring electrode (RSRE) – is presented. The main constituents of the RSRE: a specially constructed silver ring electrode, a silver sheet used as silver counter/quasi-reference electrode and a silicon O-ring are fastened together in a polypropylene body. The renovation of this electrode is carried out through mechanical removal of solid contaminants and electrochemical activation in the electrolyte which fills the RSRE body. The effectiveness of the renovation procedure was tested by designating the RF and E_pzc and by recording C_d–t curves. As shown on selected examples, RSRE exhibits good performance in underpotential deposition stripping voltammetry (UPD-SV) applied for the determination of Pb(II) traces in certified reference materials.     

Kinetic model of induced codeposition of Ni-Mo alloys

The kinetic model of induced codeposition of nickel-molybdenum alloys from ammoniun citrate solution was studied on rotating disk electrodes to predict the behavior of the electrode-position. The molybdate (MoO42-) could be firstly electro-chemically reduced to MoO2, and subsequently undergoes a chemical reduction with atomic hydrogen previously adsorbed on the inducing metal nickel to form molybdenum in alloys. The kinetic equations were derived, and the kinetic parameters were obtained from a comparison of experimental results and the kinetic equations. The electrochemical rate constants for discharge of nickel, molybdenum and water could been expressed as k1(E) = 1. 23 × 109 CNi exp( - 0.198FE/RT) mol/(dm2·s), k2(E) =3.28× 10-10 CMoexp( - 0. 208FE/ RT) mol/(dm2·s) and k3(E) = 1.27 × 10-6exp( - 0.062FE/ RT) mol/(dm2 · s), where CNi and CMo are the concentrations of the nickel ion and molybdate, respectively, and E is the applied potential vs. saturated calomel electrode (SCE). The codeposition p     

Potentiometric stripping analysis of antimony based on carbon paste electrode modified with hexathia crown ether and rice husk

An electrochemical method based on potentiometric stripping analysis (PSA) employing a hexathia 18C6 (HT18C6) and rice husk (RH) modified carbon paste electrode (HT18C6–RH-CPE) has been proposed for the subnanomolar determination of antimony. The characterization of the electrode surface has been carried out by means of scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy and chronocoulometry. By employing HT18C6–RH-CPE, a 12-fold enhancement in the PSA signal (dt/dE) was observed as compared to plain carbon paste electrode (PCPE). Under the optimized conditions, dt/dE (s V⁻¹) was proportional to the Sb(III) concentration in the range of 1.42 × 10⁻⁸ to 6.89 × 10⁻¹¹ M (r = 0.9944) with the detection limit (S/N = 3) of 2.11 × 10⁻¹¹ M. The practical analytical utilities of the modified electrode were demonstrated by the determination of antimony in pharmaceutical formulations, human hair, sea water, urine and blood serum samples. The prepared modified electrode showed several advantages, such as simple preparation method, high sensitivity, very low detection limit and excellent reproducibility. Moreover, the results obtained for antimony analysis in commercial and real samples using HT18C6–RH-CPE and those obtained by inductively coupled plasma-atomic emission spectrometry (ICP-AES) are in agreement at the 95% confidence level.     

Determination of α-tocopherol in Cosmetic Products by Chronopotentiometry

Abstract

In the present study, a rapid chronopotentiometric method was developed for the determination of α-tocopherol in various cosmetic products. Determination of α-tocopherol is based on its irreverse oxidation by constant current at the planar glassy carbon electrode. The influence of the most important experimental parameters of chronopotentiometry was investigated. After optimization, an appropriate procedure for the sample preparation was developed. Under the defined experimental conditions, a detection limit of 7.5 mg L^?1 of α-tocopherol was obtained. The accuracy of the defined method was confirmed by means of recovery assay. The developed method was successfully applied to quantitation of α-tocopherol in various cosmetic products.