Differential pulse tensammetry: Improved response with modified timing sequence

The timing sequence of a commercially available polarograph was modified with the aim of optimizing performance of the instrument when used for the determination of surfactants. Two differential pulse modes were investigated. For both modes the optimum instrument settings were not those giving maximum peak current since the background and noise level must also be taken into account. Apart from permitting the determination of very low surfactant concentrations, the modifications greatly improve the resolution of surfactant peaks from interfering faradaic processes.     

Rapid-flow analysis using differential pulse polarography with automatic sampling

Differential pulse polarography is used in a rapid-flow analysis system for automated determination of lead, zinc and ascorbic acid in acetate-buffered sample solutions, without the need for sample deaeration. By use of a nitrogen-segmented buffer stream at high flow-rates, high-speed sampling at up to 180 samples/hr can be obtained at a flow-rate of 22.8 ml/min through a polarographic flow-cell fitted to the dropping mercury electrode. A linear calibration range of approx. 0.1 x 10(-4)-1.0 x 10(-3)M is found for lead, zinc and ascorbic acid, with respective detection limits of 4.0, 0.8 and 0.2 x 10(-6)M, limited by the high base-line current and high noise-level. Vitamin C tablets can be routinely analysed without prior separation steps, provided the sample and wash solutions are matched in electrolyte composition. A precision of better than 1% RSD is obtained at a sampling rate of 120/hr.     

Single-drop tensammetry

'Staircase' sweeps applied during the life of a single drop, and computer data processing, provide faster, more accurate determinations of surfactant (e.g. 0.05–1% (w/v) cyclohexanol) concentrations.     

Simultaneous flow injection analysis of cadmium and lead with differential pulse voltammetric detection

A flow injection (FI) method using multiple differential pulse voltammetric detection for the simultaneous determination of two metal ions was developed and applied to the resolution of Cd(II)-Pb(II) mixtures. The metals are detected by applying two sequential pulses to a three-electrode voltammetric system that uses a flow-through cell accommodating a static mercury-drop working electrode. The influence of the electrode area, flow-rate, pulse frequency, pulse width and sampling time was investigated. Under the experimental conditions used, the two metals were found to interfere with each other. The use of a neural network allows the simultaneous determination of both, in mixtures, with good accuracy. The proposed method is applicable to other complex systems involving different working electrodes and more than two electroactive species.     

Additive differential pulse voltammetry,instead of double differential pulse voltammetry

A new electrochemical double pulse potential technique called additive differential pulse voltammetry (ADPV) is proposed. This technique is inspired by the original idea of Birke et al. [Anal. Chem. 53 (1981) 852] of recording two differential pulse (DP) voltammograms and it consists of plotting the sum of these two signals versus the first pulse potential, although in this paper the proposal is to obtain the ADPV signal through just one experiment. ADPV behaves in an identical way to the triple-pulse technique double differential pulse voltammetry (DDPV) for reversible processes when diffusion coefficients are equal for spherical electrodes and for any value of diffusion coefficients in planar electrodes. In the case of reversible electrode processes with amalgamation of reaction product or other more complex processes, ADPV is more advantageous than DDPV. This is due, among other reasons, to the fact that, under these conditions, a double potential step is much simpler to analyse than a triple potential step.     

Rapid analysis for polynuclear aromatic hydrocarbons by linear-sweep differential pulse voltammetry

Rapid-scan linear-sweep differential pulse voltammetry at scan rates of up to 200 mV s^-1 is evaluated for the rapid analysis of polynuclear aromatic hydrocarbon mixtures in acetonitrile at a platinum working electrode. Three- and four-component mixtures with appropriate peak potential separation between the components can be readily separated and quantified at the 1–5-ppm concentration level. A major advantage of the method is the short time requirement. A four-component mixture which requires a 1.2-V range to cover all peaks can be scanned in only 6 s instead of the 5–10 min required by conventional differential pulse voltammetry.     

Electrochemical studies and differential pulse polarographic analysis of lansoprazole in pharmaceuticals

The electrochemical reduction of lansoprazole was investigated by cyclic voltammetry and direct current and differential pulse polarography. The reduction potential was -1.32 V vs. Ag/AgCl with a dropping mercury electrode in a supporting electrolyte consisting of phosphate buffer (pH 9.0)-tetramethylammonium iodide (4 + 1). The reversibility of the electrode reaction and the type of limiting current were studied. The temperature coefficient and the diffusion constant were determined. A mechanism for the electrode reaction was proposed. A new simple and sensitive differential pulse polarographic method was also developed for the quantification of lansoprazole. A linear calibration graph was obtained in the range 0.04-11.35 micrograms ml-1. The limit of detection was 0.03 microgram ml-1 and the intra- and inter-day precisions were 0.84-2.32 and 0.72-3.09%, respectively. The developed method was applied to six different commercial pharmaceutical capsule preparations containing enteric-coated granules. The relative standard deviations ranged from 1.36 to 2.85%. Recovery studies for the accuracy of the method were performed by adding a synthetic mixture to known amounts of lansoprazole and the mean recovery was 100.45%. The data obtained from commercial preparations were compared with those from a published spectrophotometric method. No difference was found statistically.     

Estimation of tungstate ion by tensammetry

It is shown that tungstate ion can be estimated quantitatively by the same experimental technique as that used for alternating current polarography. The underlying process differs, however, fundamentally from polarography in that no electron transfer takes place at the electrode and thus no d.c. polarographic steps arc obtained. The alternating current is produced solely by adsorption/ desorption processes at the electrode/solution interface, a phenomenon to which the name “tensammetry” has been given.The current-voltage curve for sodium tungstatc at pH 1.8 shows two -well defined tensammetric waves which can be used for purposes of quantitative estimation. No waves are obtained at pH values higher than 6, showing that the compound responsible for the production of the waves is not the simple WO₄^-4ion.     

The determination of ethanol by alternating current tensammetry

A method for the determination of ethanol in vodka by phase-sensitive a.c. tensammetry is described; the only prior treatment of the sample is dilution with water and addition of KCl The positive wave of the tensammetric response was used. Ethanol concentrations in the range 2–10% can be determined with a relative imprecision of 0.5%. Other species having surfactant properties, such as the fusel oils found in most distilled liquors, interfere.     

Microfluidic differential resistive pulse sensors

This study demonstrates an on-chip resistive pulse-sensing scheme with a design of symmetric mirror channels, which significantly reduces the noise and achieves better signal-to-noise ratio. Polystyrene particles of different sizes have been detected with the developed sensing scheme and a record low volume ratio of the particle to the sensing channel, or 0.0004%, has been detected with particles of 520 nm in diameter in a sensing aperture of 50x16x20 microm3. This volume ratio is about ten times lower than the lowest volume ratio reported in the literature including that specified for commercial Coulter counters.     

N-nitrosamines and differential pulse polarography

Differential pulse polarography is a versatile and sensitive technique which yields both qualitative and quantitative information about N-nitrosamines. The ability of the technique to carry out determinations in-situ permits the study of anchimeric, metabolic, and mechanistic properties in addition to phenomena such as kinetics and transnitrosation.     

Trace analysis of vanadium as pentavalent vanadium using differential pulse polarography with a coupled catalytic homogeneous reaction

The differential pulse polarographic determination of the vanadium (V) ion coupled with a catalytic homogeneous reaction was carried out in a system containing the vanadium (V)-PAR complex and an oxidant in acetic/acetate buffer. On addition of the powerful oxidant, sodium bromate, the peak current for the reduction of the vanadium (V) complex was increased significantly by about 21 times. A calibration plot was found to be linear in the concentration range 0.05–0.25 g/ml and the detection limit was 5 ng/ml.     

Determination of nitrobenzene by differential pulse voltammetry and its application in wastewater analysis

A new method for the determination of nitrobenzene (NB) by differential pulse voltammetry (DPV) based on an adsorptive stripping technique was developed. Cyclic voltammetry (CV) was used in a comparative investigation into the electrochemical reduction of NB at a glassy carbon electrode (GCE). With this electrode, the sharp peak of NB appeared at −0.71 V (vs. Ag/AgCl). The experimental parameters were optimized. Studies on the effect of pH on the peak height and peak potential were carried out over the pH range ca. 9.0–11.5 with sodium carbonate/sodium hydrogen carbonate buffer solution. A solution of pH 9.9 was chosen as analytical medium. Cathodic peak currents were found to be linearly related to the concentration of NB over the range ca. 12.3–1.23 × 10⁴ μg L⁻¹ with relative standard deviations of ca. 3.26–6.75%. The detection limit of NB in water was 5.42 μg L⁻¹. The interference of organic and inorganic species on the voltammetric response was also studied. The proposed method was applied to the determination of NB in wastewater samples with an average recovery of ca. 95.9–102.4%.     

Determinations of citric acid by differential pulse polarography with immobilized enzymes

Summary Citrate lyase and oxaloacetate decarboxylase can be rapidly and simply immobilized in polyacrylamide gel to provide a selective and sensitive reactor. Conversion ratio of citric acid to pyruvic acid comes up to 90% under the optimal conditions. Generated pyruvic acid can be determined by differential pulse polarography. The bioreactor can be used for thirty determinations over several weeks. Samples of sports drinks and wine were successfully tested without pretreatment; the relative standard deviation with 1.0×10^-5 mol l^-1 citric acid in polarographic solutions was 1.17% and the detection limit was 6.6×10^-7 mol l^-1 (=2).     

对苯二酚和邻苯二酚的DPV法同时检测

利用电化学还原的方法制备了4-氨基吡啶共价修饰玻碳电极,通过循环伏安法研究了对苯二酚和邻苯二酚在此修饰电极上的电化学行为.结果表明,4-氨基吡啶修饰电极对对苯二酚和邻苯二酚有较好的电催化活性和电分离作用.利用微分脉冲伏安法,用4-氨基吡啶修饰电极可同时及定量检测对苯二酚和邻苯二酚,在2.5×10~(-6)~1.1×10~(-4)mol/L范围内,二者的微分脉冲伏安响应与浓度呈良好的线性关系.     

Carbon paste electrodes modified with cation-exchange resin in differential pulse voltammetry

Chemically modified carbon paste eletrodes are prepared by incorporating appropriate quantities of a cation-exchange resin directly into the paste mixture. Ionic analytes can be preconcentrated on these electrodes by an ion-exchange reaction rather than electrolytic plating. Differential pulse voltammetry is used to quantify the accumulated ions. The response is characterized with respect to preconcentration period, bulk concentration, pH, paste composition, reproducibility, and other variables. Copper ion is used as a test system. The procedure exhibits good linearity for 6.25 × 10^?5?3.0 × 10^?4 M copper(II) ions and the peak current varies linearly with preconcentration time between 1 and 7 min for the conditions used.     

Effects of surfactants in differential pulse polarography

Differential pulse polarograms of surfactants exhibit tensammetric peaks at the adsorption and desorption potentials of the surfactant. In the potential range where adsorption occurs the base current is depressed. The heights of the tensammetric peaks are nonlinear functions of the bulk concentration of the surfactant. Differential pulse polarograms of reducible substances are greatly affected by the presence of surfactants, the effect being similar to that observed in a.c. polarography. Surfactants with the same charge as the depolarizer act as electrochemical masking agents, whereas peak currents may be enhanced by oppositely charged surfactants.     

High-performance pulse and differential pulse polarography: Part I. Theoretical considerations

A theoretical approach is given for complete elimination of the charging current caused by drop growth in modified normal and differential pulse polarography (n.p.p. and d.p.p.). Maximum sensitivity can be obtained in modified n.p.p., but the resolution of waves is better in modified d.p.p. or can be increased in differential modified n.p.p. The best overall performance can be achieved with modified d.p.p., considering sensitivity and wave resolution together. Preliminary results for the determination of chloramphenicol are described.     

The analytical performance of direct current,normal pulse and differential pulse polarography with static mercury drop electrodes

The recently developed static mercury drop electrode (SMDE) provides a fundamentally new approach to electrodes for polarography. An analytical evaluation of the electrode is presented. For a range of electrode processes, current-sampled d.c. polarography at the SMDE is useful down to at least the 10^-7 M concentration level when short drop times and fast potential scan rates are used. The improvement in the limit of detection for d.c. polarography is therefore very substantial. Improvements in sensitivity associated with normal pulse and differential pulse polarography at the SMDE compared with the dropping mercury electrode (DME) are marginal. It is concluded that at the SMDE, the analytical performance and response characteristics of d.c., normal pulse and differential pulse polarography tend to converge.