The mechanism of oxidation of 3-mercaptopropionic acid

1997 ◽  
Vol 75 (1) ◽  
pp. 9-13 ◽  
Author(s):  
Paula Forlano ◽  
José A. Olabe ◽  
Jorge F. Magallanes ◽  
Miguel A. Blesa
Keyword(s):  
Differential Pulse ◽  
Nucleophilic Attack ◽  
Differential Pulse Polarography ◽  
Acidic Ph ◽  
Mercaptopropionic Acid ◽  
Ph Dependency ◽  
Pulse Polarography ◽  
Mechanism Of Oxidation ◽  
Ph Range ◽  
Peroxide Bond

The mechanism of the oxidation of 3-mercaptopropionic acid (3-MPA) by hydrogen peroxide was studied in the acidic pH range. The nucleophilic attack by sulphur on the peroxide bond controls the rate. Extrapolation of the pH dependency suggests that the rate of attack by the deprotonated dianion is highest. Traces of Fe(III), at levels below 10−7 mol dm−3, do not catalyze efficiently the process through one-electron mechanisms; at higher concentrations, or on the surface of iron(III) oxides, this type of catalysis becomes important. The electrochemical oxidation of 3-MPA was also studied, using differential pulse polarography and cyclic voltammetry techniques. The mechanism is of the EC2E type, the second electron transfer step corresponding to the oxidation of the disulphide RS-SR. The rate constant for the dimerization of the RS• radicals was 1.8 × 103 mol−1 dm3 s−1; the slowness of this step agrees with the mechanisms observed in the course of one-electron oxidations by metal ions. Keywords: electrochemistry, kinetics, 3-mercaptopropionic acid, autooxidation.

scholarly journals Differential Pulse Polarographic Determination of Procymidone in Formulations and Wine

2002 ◽  
Vol 85 (3) ◽  
pp. 731-735 ◽  
Author(s):  
Neelam Y Sreedhar ◽  
Thommandru R Babu ◽  
Kethamreddy Samatha ◽  
Devarapalli Sujatha ◽  
Thenepalli Thriveni
Keyword(s):  
Reduction Process ◽  
Differential Pulse ◽  
Differential Pulse Polarography ◽  
Experimental Conditions ◽  
Controlled Potential Electrolysis ◽  
Pulse Polarography ◽  
Half Wave ◽  
Single Well ◽  
Controlled Potential ◽  
Ph Range

Abstract The dicarboximide fungicide procymidone was studied systematically by using direct current polarography, cyclic voltammetry, differential pulse polarography (DPP), controlled potential electrolysis, and millicoulometry in the universal buffer medium with dimethylformamide as the solvent. Procymidone exhibited a single well-defined polarographic wave in the pH range 2.0–6.0, leading to the formation of the hydroxy compound. The overall reduction process was diffusion-controlled and adsorption-free. The variation of half-wave potential with pH, the concentration of the analyte, and other experimental conditions are described. The reduction mechanism proposed is an overall 4-electron process, in which the dicarboximide group is reduced. DPP was used to determine procymidone in agricultural formulations and wine at the optimum conditions found; a detection limit of 2.4 × 10−9M was estimated. The results obtained by the proposed method were also compared with those obtained by other methods.

scholarly journals Differential Pulse Polarographic Determination of Lead in Complex Materials after Adsorption of Its N-Methylethylxanthocarbamate Complex on Microcrystalline Naphthalene or on NMethylethylxanthocarbamate–Benzyldimethyltetradecylammonium–Naphthalene Adsorbent

2002 ◽  
Vol 85 (3) ◽  
pp. 712-718
Author(s):  
Mohammad Farid Hussain ◽  
Anil Kumar Sangahi ◽  
Iqbal Ahmad ◽  
Bal Krishan Puri
Keyword(s):  
Flow Rate ◽  
Signal To Noise Ratio ◽  
Differential Pulse ◽  
Correlation Factor ◽  
Differential Pulse Polarography ◽  
Pulse Polarography ◽  
Relative Standard ◽  
Ph Range ◽  
Microcrystalline Naphthalene

Abstract Lead is quantitatively adsorbed as the lead N-methylethylxanthocarbamate (MEXC)–benzyldimethyltetradecylammonium (BDTA) ion pair complex on microcrystalline naphthalene in the pH range 4.0–11.0. The metal is desorbed with HCl and determined by differential pulse polarography. Alternatively lead can be quantitatively adsorbed on the adsorbent (MEXC–BDTA–naphthalene) packed in a column at a flow rate of 1–2 mL/min and determined similarly. Dissolved oxygen is removed by adding a few milliliters of 4% NaBH4 solution. The detection limit is 0.12 μg/mL at the minimum instrumental settings (signal-to-noise ratio, 2). Linearity was obtained over the concentration range 0.3–20.0 μg/mL with a correlation factor of 0.9998 and a relative standard deviation of ± 0.98%. Various parameters, such as the effect of pH, volume of aqueous phase, flow rate, and the interference of a large number of metal ions and anions, were studied in detail to optimize the conditions for the trace determination of lead in various standard alloys, standard biological materials, and environmental samples.

scholarly journals Voltammetric Behavior of Zaleplon and Its Differential Pulse Polarographic Determination in Capsules

2005 ◽  
Vol 88 (4) ◽  
pp. 1135-1141 ◽  
Author(s):  
Gipsy Larenas ◽  
Soledad Bollo ◽  
Marcelo Rodriguez ◽  
Igor Lemus ◽  
Luis J Nuñez-Vergara ◽  
...  
Keyword(s):  
Column Liquid Chromatography ◽  
Differential Pulse ◽  
Differential Pulse Polarography ◽  
Content Uniformity ◽  
Reduction Peak ◽  
Buffer Solution ◽  
Pulse Polarography ◽  
Voltammetric Behavior ◽  
Ph Range ◽  
The Individual

Abstract In this work both the electrochemical behavior and the analysis of the hypnotic pyrazolopyrimidine derivative zaleplon were studied. Zaleplon in ethanol–0.1M Britton Robinson buffer solution (30–70) showed 2 irreversible, well-defined cathodic responses in the pH range of 2–12 using differential pulse polarography (DPP), tast polarography, and cyclic voltammetry. From chronocoulometric studies, it was possible to conclude that one electron was transferred in each reduction peak or wave. For analytical purposes, the DPP technique working at pH 4.5 for peak I was selected, which exhibited adequate repeatability, reproducibility, and selectivity. The recovery was 99.97 ± 1.52%, and the detection and quantitation limits were 5.13 × 10−7M and 1.11 × 10−6M, respectively. The DPP method was applied successfully to the individual assay of capsules in order to verify the content uniformity of zaleplon. Treatment of the sample is not required because the excipients do not interfere, the method is not time consuming, and it is less expensive than column liquid chromatography.

Determination of platinum in biological material by differential pulse polarography: Analysis in urine, plasma and tissue following sample combustion

1983 ◽  
Vol 48 (10) ◽  
pp. 2903-2908 ◽  
Author(s):  
Viktor Vrabec ◽  
Oldřich Vrána ◽  
Vladimír Kleinwächter
Keyword(s):  
Biological Material ◽  
Biological Fluid ◽  
Mercury Electrode ◽  
Differential Pulse ◽  
Differential Pulse Polarography ◽  
Linear Calibration ◽  
Catalytic Current ◽  
Pulse Polarography ◽  
Dropping Mercury Electrode

A method is described for determining total platinum content in urine, blood plasma and tissues of patients or experimental animals receiving cis-dichlorodiamineplatinum(II). The method is based on drying and combustion of the biological material in a muffle furnace. The product of the combustion is dissolved successively in aqua regia, hydrochloric acid and ethylenediamine. The resulting platinum-ethylenediamine complex yields a catalytic current at a dropping mercury electrode allowing to determine platinum by differential pulse polarography. Platinum levels of c. 50-1 000 ng per ml of the biological fluid or per 0.5 g of a tissue can readily be analyzed with a linear calibration.

Polarography of N,N-dimethyl-4-amino-4'-hydroxyazobenzene in water-methanol mixtures

1985 ◽  
Vol 50 (3) ◽  
pp. 712-725 ◽  
Author(s):  
Jiří Barek ◽  
Lubomír Kelnar
Keyword(s):  
Differential Pulse ◽  
Differential Pulse Polarography ◽  
Polarographic Reduction ◽  
Reduction Mechanism ◽  
Pulse Polarography ◽  
Methanol Medium

The polarographic reduction of N,N-dimethyl-4-amino-4'-hydroxyazobenzene in water-methanol medium was investigated. Evidence is presented for adsorption of the depolarizer on the electrode, and a reduction mechanism is proposed. Conditions are indicated for the determination of this compound in the concentration range 10-4-10-6 mol/l by d.c. polarography, 10-5 to 3 . 10-7 mol/l by Tast polarography, and 10-5-3 . 10-8 mol/l by differential pulse polarography.

Polarographic and voltammetric determination of 6-mercaptopurine and 6-thioguanine

1986 ◽  
Vol 51 (11) ◽  
pp. 2466-2472 ◽  
Author(s):  
Jiří Barek ◽  
Antonín Berka ◽  
Ludmila Dempírová ◽  
Jiří Zima
Keyword(s):  
Detection Limit ◽  
Differential Pulse Voltammetry ◽  
Detection Limits ◽  
Differential Pulse ◽  
Voltammetric Determination ◽  
Differential Pulse Polarography ◽  
Hanging Mercury Drop Electrode ◽  
Pulse Polarography ◽  
Pulse Voltammetry

Conditions were found for the determination of 6-mercaptopurine (I) and 6-thioguanine (II) by TAST polarography, differential pulse polarography and fast-scan differential pulse voltammetry at a hanging mercury drop electrode. The detection limits were 10-6, 8 . 10-8, and 6 . 10-8 mol l-1, respectively. A further lowering of the detection limit to 2 . 10-8 mol l-1 was attained by preliminary accumulation of the determined substances at the surface of a hanging mercury drop.

The polarographic and voltammetric determination of 2,6-dicyano-4-nitro-2'-acetylamino-4'-diethylaminoazobenzene

1990 ◽  
Vol 55 (6) ◽  
pp. 1508-1517 ◽  
Author(s):  
Jiří Barek ◽  
Dagmar Civišová ◽  
Ashutosh Ghosh ◽  
Jiří Zima
Keyword(s):  
Azo Dye ◽  
Differential Pulse ◽  
Differential Pulse Polarography ◽  
Determination Limit ◽  
Polarographic Reduction ◽  
Hanging Mercury Drop Electrode ◽  
Optimal Conditions ◽  
Pulse Polarography ◽  
Pulse Voltammetry

The polarographic reduction of the title azo dye was studied and optimal conditions were found for its analytical utilization in the concentration range 1 . 10-6 - 1 . 10-7 mol l-1 using differential pulse polarography and 1 . 10-6 - 1 . 10-8 mol l-1 using fast scan differential pulse voltammetry or linear scan voltammetry at a hanging mercury drop electrode. When the latter technique is combined with adsorptive accumulation of the studied substance on the surface of the hanging mercury drop, the determination limit can be further decreased to 3 . 10-9 mol l-1.

Electroanalytical chemistry of vanadium complexes: Electrochemical oxidation of [V(IV)O(nta)(H2O)]-

1989 ◽  
Vol 54 (1) ◽  
pp. 64-69 ◽  
Author(s):  
Roland Meier ◽  
Gerhard Werner ◽  
Matthias Otto
Keyword(s):  
Cyclic Voltammetry ◽  
Electrochemical Oxidation ◽  
Ph Dependence ◽  
Differential Pulse ◽  
Nitrilotriacetic Acid ◽  
Reduced Form ◽  
Vanadium Complexes ◽  
Differential Pulse Polarography ◽  
Electroanalytical Chemistry ◽  
Ph Range

Electrochemical oxidation of [V(IV)O(nta)(H2O)]- (H3nta nitrilotriacetic acid) was studied in aqueous solution by means of cyclic voltammetry, differential pulse polarography, and current sampled DC polarography on mercury as electrode material. In the pH-range under study (5.5-9.0) the corresponding V(V) complex is produced by one-electron oxidation of the parent V(IV) species. The oxidation product is stable within the time scale of cyclic voltammetry. The evaluation of the pH-dependence of the half-wave potentials leads to a pKa value for [V(IV)O(nta)(H2O)]- which is in a good agreement with previous determinations. The measured value for E1/2 is very close to the formal potential E0 calculated via the Nernst equation on the basis of known literature values for log Kox and log Kred, the complex stability constants for the oxidized and reduced form, respectively.

Polarographic and voltammetric determination of N,N’-dinitrosopiperazine

1991 ◽  
Vol 56 (7) ◽  
pp. 1434-1445 ◽  
Author(s):  
Jiří Barek ◽  
Ivana Švagrová ◽  
Jiří Zima
Keyword(s):  
Mercury Electrode ◽  
Linear Sweep Voltammetry ◽  
Differential Pulse ◽  
Differential Pulse Polarography ◽  
Polarographic Reduction ◽  
Concentration Region ◽  
Pulse Polarography ◽  
Chemical Efficiency ◽  
Dropping Mercury Electrode

Polarographic reduction of the genotoxic N,N’-dinitrosopiperazine was studied and its mechanism was suggested. Optimum conditions were established for the determination of this substance by tast polarography over the concentration region of 1 . 10-3 to 1 . 10-6 mol l-1 and by differential pulse polarography on the conventional dropping mercury electrode or by fast scan differential pulse voltammetry and linear sweep voltammetry on a hanging mercury drop electrode over the concentration region of 1 . 10-3 to 1 . 10-7 mol l-1. Attempts at increasing further the sensitivity via adsorptive accumulation of the analyte on the surface of the hanging mercury drop failed. The methods are applicable to the testing of the chemical efficiency of destruction of the title chemical carcinogen based on its oxidation with potassium permanganate in acid solution.

Determination of Organic Bases by Ion-Pair Extraction Polarography Using Orange II as Counter Ion

1992 ◽  
Vol 57 (11) ◽  
pp. 2272-2278 ◽  
Author(s):  
Václav Koula ◽  
Daria Kučová ◽  
Jiří Gasparič
Keyword(s):  
Model Compound ◽  
Differential Pulse ◽  
Ion Pair ◽  
Differential Pulse Polarography ◽  
Orange Ii ◽  
Organic Bases ◽  
Counter Ion ◽  
Pulse Polarography ◽  
Ammonium Compounds

The combination of ion-pair extraction and differential pulse polarography is shown to be a method suitable for the determination of 10-7 mol l-1 concentrations of organic bases of quaternary ammonium compounds. Orange II (4-[2-hydroxy-1-naphtyl]azobenzenesulfonic acid) was found to be an appropriate polarographically active counter-ion. The proposed method was used for the determination of tetrapentylammonium bromide (as model compound), Septonex ([1-(ethoxycarbonyl)-pentadecyl]trimethylammonium bromide) and codeine.

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