Differential pulse polarographic determination of cyanuric chloride

Cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) can be determined by fastscan differential pulse polarography in methanolic acetate buffer solution at pH 5.6 at a hanging mercury drop electrode. At positive potentials, the insoluble salt formed between cyanuric chloride and mercury(I) is adsorbed on the mercury surface and the d.p.p. current is enhanced. The detection limit is 0.2gmg ml^?1. Cyanuric chloride in air can be determined after absorption in methanol.     

An electroanalytical study of the anticancer drug dacarbazine

The electrochemical behaviour of dacarbazine [5-(3,3-dimethyl-1-triazenyl) imidazole-4-carboxamide; DTIC] was investigated by Tast and differential pulse polarography (d.p.p.) at the dropping mercury electrode, by cyclic and differential pulse voltammetry at the hanging mercury drop electrode and by anodic voltammetry at the glassy carbon electrode. Calibration graphs were obtained for 2×10^?8?2×10^?5 M DTIC by d.p.p., for 5×10^?9?1×10^?5 M by adsorptive stripping voltammetry ar a hanging mercury drop electrode, and for 1?10×10^?5 M by high-performance liquid chromatography with oxidative amperometric detection at a glassy carbon electrode. The methods are compared and applied to determine DTIC added to blood serum after a simple clean-up procedure.     

Differential pulse polarography and voltammetry with a microprocessor-controlled polarograph and a pressurized mercury electrode

The performance of a microprocessor-controlled polarograph with a pressurized mercury electrode system has been evaluated. For the technique of differential pulse polarography, the theory applying to the pressurized mercury electrode in the dropping mercury format is shown to be the same as for a conventional gravity-controlled mercury electrode system. At the short drop times used (0.2–0.4 s), faradaic distortion terms are shown to influence the shape of the observed differential pulse polarograms. A substantial decrease in sensitivity is also incurred in using these short drop times, compared with the longer ones generally employed in differential pulse polarography. Results for differential pulse anodic stripping conform to the usual expectations.     

Comparison of fundamental and second-harmonic a.c., and normal,derivative and differential pulse linear-sweep and stripping voltammetric methods

Linear-sweep and stripping a.c. and pulse voltammetric methods have been compared for a variety of electrodes and electrode processes. Each of the linear-sweep techniques is readily used systematically because, in contrast to d.c. linear-sweep voltammetry, the theory for reversible electrode processes is basically analogous to that for polarography at a dropping mercury electrode. In stripping analysis, some departures are found at a hanging mercury drop electrode because of spherical diffusion effects. For reversible electrode processes, the limits of detection for a.c. and pulse methods are comparable. However, a.c. methods offer advantages over pulse methods in discriminating against irreversible electrode processes and permit the ready use of faster scan rates. Pulse methods are more sensitive for irreversible electrode process. Normal pulse polarography is particularly favourable in minimizing undesirable phenomena arising from adsorption or deposition of material on electrodes.     

Simultaneous polarographic analysis of pyrazine and its methyl derivatives by iterative target transformation factor analysis

The polarographic waves of pyrazine and its methyl derivatives are seriously overlapping, so they cannot be determined individually by polarographic methods without a prior separation. In this paper, a chemometric approach, iterative target transformation factor analysis (ITTFA), is developed and applied to the determination of mixtures of pyrazines at trace level (2.0–9.0 × 10⁻⁶moll⁻¹) by using differential pulse polarography (DPP) and a static mercury drop electrode (SMDE). Different from the general ITTFA method, only one-dimensional measurement data of n − 1 standards and an unknown were used in this work. It produced acceptable results with average recoveries in the 96–108% range and relative standard errors in the 3.4–9.5% range.     

Fast-scan differential pulse polarography at a dropping mercury electrode

A fast-scan modification of differential pulse polarography (d.p.p.) is described, in which a dropping mercury electrode with a drop lifetime of 50 s is polarized by 100-ms pulses with a 100-ms interval between pulses; sampling and treatment of the current data are the same as in d.p.p. The method can be used to determine amalgam-forming metals at concentrations above 1 × 10^-8 mol l^-1 with good reproducibility. The technique permits a ten-fold decrease in the measuring time compared to conventional d.p.p. The method can be used for direct polarographic determinations and also advantageously replaces d.p.p. in anodic stripping.     

Direct determination of pentachlorophenol by differential pulse polarography

Differential pulse polarography at the dropping mercury electrode and differential pulse voltammetry at the carbon paste electrode are used for direct determinations of pentachlorophenol at concentrations down to 0.27 ppm. PCP is electrochemically reduced in phosphate buffers of pH 8 to produce a concentration-dependent current peak at —0.8 V vs. Ag/AgCl. The procedure requires only 15 min. Cyclic voltammetry at the hanging mercury drop electrode is used to evaluate the electrochemical reaction and to establish the reversibility of the PCP electrode reaction.     

Removal of interference in the differential pulse polarographic determination of progestogens in some combined low-dosage oral contraceptives

Previously published differential pulse methods for the determination of certain progestogens (laevonorgestrel and norethisterone) are not applicable to combined low-dosage oral contraceptives because interference from excipients in the tablets completely eliminates the polarographic response. An ultrafiltration device allows rapid prior extraction of the interfering substances before the polarographic determination in 50% ($\text{v}\text{v}$) methanol—phosphate buffer (pH 6.0). Recoveries of 100 ± 1% were obtained by the recommended method, and data for a range of formulations are in excellent agreement with expected values. Electrode characteristics of the progestogens and interfering substances are reported, based on studies employing cyclic voltammetry at a hanging mercury drop electrode, a.c. polarography and normal pulse polarography. Competitive adsorption processes seem to occur when the progestogen and excipients are simultaneously present.     

Application of reverse pulse polarography to the determination of substances which form films electrochemically on the mercury electrode

The application of reverse pulse polarography to the determination of substances which form films electrochemically on the mercury electrode is illustrated with penicillamine and cysteine. The dependence of the peak current on several variables is reported and compared with theoretical predictions. It is shown that under optimal instrumental conditions (long drop times and short effective pulses) reverse pulse polarography compares favourably with both normal pulse polarography and differential pulse polarography for the determination of penicillamine and cysteine, concentrations of penicillanline as low as 5 x 10(-8)M being readily determined in the presence of copper(II).     

Anodic behaviour of 2-mercaptoethanol at a mercury electrode

The anodic processes which occur at the mercury electrode in 2-mercaptoethanol solutions are studied by various polarographic techniques (d.c., a.c. and differential pulse), controlled-potential coulometry, cyclic voltammetry and differential capacity curves. Two steps are distinguished in the process: a one-electron charge transfer and a dismutation step leading to the formation of a mercury(II) mercaptide. The final product is isolated and analyzed. Differential-pulse polarography can be used to determine ?10^?4 M 2-mercaptoethanol with a limit of M.     

A study of the electrochemical characteristics of some thiols by differential pulse polarography and other electrochemical techniques

A study of some low-molecular-weight odorous thiols at mercury electrodes has been made by differential pulse polarography (d.p.p.), d.c. polarography, linear-sweep voltammetry, and coulometric measurement on linear-sweep reduction. Linear current versus concentration plots are found for individual thiols, in aqueous 0.2 M sodium hydroxide by using d.p.p. at thiol concentrations from ca. 2 × 10^-7 M to 10^-4 M. A linear trend between peak potential and molecular weight was found for homologous series, but the method cannot be used for qualitative identification because of peak shifts in multicomponent mixtures. The electrode reactions show quasireversible behavior. At concentrations of thiol greater than 10^-4 M, the single peak splits into two peaks and film formation occurs. Charge density versus concentration plots indicate that the quantity of adsorbed material is several monolayers.     

Electrosorption of vitamin K1 at mercury and its determination at submicrogram levels by differential pulse voltammetry at a hanging mercury electrode

The electrochemical behaviour of vitamin K₁ has been studied in ethanolic and methanolic acetate buffers by cyclic voltammetry and differential pulse voltammetry (d.p.v.) at the h.m.d.e. and differential pulse polarography at the d.m.e. Increased adsorption occurs at the mercury electrode as the percentage of water is increased. The most sensitive signal was obtained by d.p.v. with acetate-buffered 60% methanolic solutions; vitamin K₁ could then be measured down to 10 ng ml^-1.     

Determination of chloramphenicol at ultra-trace levels by high-performance differential pulse polarography: Application to Milk and Meat

High-performance differential pulse polarography (h.p.d.p.p.) is used to determine the antibiotic chloramphenicol. Optimum operating conditions are discussed. Calibration curves are linear from 10 ng ml^-1 to 1 μg ml^-1; the detection limit is about 3 ng ml^-1. Above 1 μg ml^-1, deviations from linearity occur, because of adsorption of chloramphenicol at the mercury electrode. A correction, based on variations in natural drop time, is suggested. Chloramphenicol is readily extracted from milk or minced meat with diethyl ether. The ether is evaporated, and the residue is taken up in acetate buffer pH 4.7 and filtered through a membrane filter. Recoveries from samples fortified at levels of 10–1000 ng ml^-1 are about 60% for milk and 50% for minced meat.     

Electrochemical determination of N,N-dimethyl-4-amino-4′-aminoazobenzene

N,N-Dimethyl-4-amino-4′-aminoazobenzene has been determined using differential pulse polarography. Fast-scan modification and linear-scan voltammetry at a hanging mercury drop electrode was used with a detection limit of less than 10⁻⁸ mol liter⁻¹. Differential pulse polarography was then used to analyze mixtures of the above depolarizer with azobenzene and N,N-dimethyl-4-aminoazobenzene, either directly, or after a TLC separation.     

Absorptive accumulation in stripping voltammetry

A critical evaluation of adsorptive accumulation in stripping analysis, with differential pulse polarography for the measurement step, is described. Generally applicable conditions for this method are given. Adsorptive accumulation at a static mercury drop electrode is discussed for some alkaloids, local anaesthetics, surfactants and inorganic ions. Concentrations of 10^-6—10^-8 M are usually measurable.     

Potentiometric stripping analysis

The analytical possibilities of potentiometric stripping analysis are outlined. The technique comprises reduction of metal ions at a stationary mercury drop or thin-film electrode. The amalgamated metals are then re-oxidized with mercury(II) ions, and the time—potential behaviour of the mercury electrode is recorded. The technique is compared with d.c. and differential pulse anodic stripping analysis.     

Polarographic and liquid chromatographic methods for the determination of sulfur residues on grapes and wheat

Sampled d.c. and differential pulse polarography are used, in batch mode, to determine sulfur in methanol/0.1 M ammonium acetate (pH 5.0). A two-electron reaction (reduction of sulfur to sulfide) is shown to be involved. Differential pulse polarography is sensitive for the determination of sulfur in relatively clean solutions; the detection limit is 7.2 μg l^?1. The interference of heavy metals (Pb and Cd) is avoided by addition of EDTA. For complex matrices, such as extracts of wheat and grapes, matrix effects are serious. For such samples, reversed-phase liquid chromatography with amperometric detection (dropping mercury electrode) gives excellent results. A relatively simple procedure is described for the determination of sulfur residues in wheat and grapes at levels ? 0.5 mg kg ^?1; linear response is obtained up to ca. 7 mg kg^?1.     

Determination of pseudouridine at submicromolar concentrations by cathodic stripping voltammetry at a mercury electrode

Pseudouridine (5-ribosyluracil), uridine (N,1-ribosyluracil), deoxyuridine (N,1-deoxyribosyluracil) and uracil are investigated by means of d.c. polarography and by differential and normal pulse polarography. Pseudouridine, which is known to be a cancer marker, yields anodic polarographic currents in the pH range 7–11, whereas uridine and deoxyuridine are inactive under the same conditions. The polarographic response of pseudouridine obtained is due to the formation of a sparingly soluble mercury compound. Pseudouridine can be determined by differential pulse polarography in the concentration range 2–6 × 10^?6 M and by differential-pulse cathodic stripping voltammetry at concentrations two orders of magnitude lower. Small excesses of uridine, deoxyuridine or proteins do not interfere with the determination.     

Modified normal pulse polarography of alkali-metal ions in acid solution

Well-defined polarograms of five alkali-metal ions in 0.01M hydrochloric acid were obtained by means of modified normal pulse polarography. The method uses the procedure of anodic stripping chronoamperometry during the life-time of a drop from a dropping mercury electrode, namely preparation of electrode, accumulating step and anodic stripping step of a metal. The instantaneous polarographic currents were sampled only once per mercury drop after the fall of each pulse. The wave heights for alkali-metal ions by the present method are free from the interference caused by 0.01M hydrochloric acid. The present method is applicable to monitoring of alkali-metal ions in fluid acid streams.     

A direct differential pulse anodic stripping voltammetric method for the determination of thallium in natural waters

A dual direct method for the ultratrace determination of thallium in natural waters by differential pulse anodic stripping voltamrnetry (d.p.a.s.v.) is presented. D.p.a.s.v. at the hanging mercury drop electrode and at the mercury film electrode is used in the concentration ranges 0.5–100 μg Tl l^-1, and 0.01–10 μg Tl l^-1, respectively. Quantification is aided by the technique of standard additions. The response of the method is optimized for typical natural surface water matrices. An intercomparison of thalium determinations performed by the two anodic stripping methods and electrothermal-atomization atomic absorption spectrometry on normal and thallium-spiked surface water samples demonstrates equivalent accuracy within the range where atomic absorption is applicable. The method appears free from serious interferences.