A method for the determination of standard potentials and rate constants of electrode reactions from cathodic waves at a dropping mercury electrode

1962 ◽  
Vol 27 (10) ◽  
pp. 2444-2446 ◽  
Author(s):  
J. M. Hale ◽  
R. Parsons
1988 ◽  
Vol 53 (4) ◽  
pp. 732-742 ◽  
Author(s):  
Anastos Anastopoulos ◽  
Anastasia Christodoulou

The influence of the adsorption of methyltriphenyl- and cyclopropyltriphenylphosphonium cations on simple deposition reactions of Cd2+ and Zn2+ at the dropping mercury electrode, is studied by polarographic techniques. The size parameters of the activated complex, r≠, and adsorbate particles, ri, are determined and discussed. It is shown that for substances undergoing interfacial rearrangements, i.e. condensation and reorientation, the values of the size ratio r≠/ri can hardly be correlated to independently determined values of r≠ and ri. Electrode coverages are related to formal rate constants and an elucidation of the inhibition mechanism is attempted.


1983 ◽  
Vol 48 (10) ◽  
pp. 2903-2908 ◽  
Author(s):  
Viktor Vrabec ◽  
Oldřich Vrána ◽  
Vladimír Kleinwächter

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.


1991 ◽  
Vol 56 (7) ◽  
pp. 1434-1445 ◽  
Author(s):  
Jiří Barek ◽  
Ivana Švagrová ◽  
Jiří Zima

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.


1996 ◽  
Vol 61 (3) ◽  
pp. 333-341
Author(s):  
Jiří Barek ◽  
Roman Hrnčíř ◽  
Josino C. Moreira ◽  
Jiří Zima

The polarographic behaviour was studied for 6-β-D-glucopyranosyloxy-7-hydroxycoumarin, a natural compound serving as an optical whitening agent. The substance can be quantitated by tast polarography, differential pulse polarography using a conventional dropping mercury electrode, and differential pulse polarography using a static mercury drop electrode over the regions of 20-1 000, 2-1 000, and 0.2-1 000 μmol l-1, respectively. The methods developed for the quantitation of the compound were applied to its direct determination in a raw product.


2006 ◽  
Vol 71 (11-12) ◽  
pp. 1571-1587 ◽  
Author(s):  
Karel Čížek ◽  
Jiří Barek ◽  
Jiří Zima

The polarographic behavior of 3-nitrofluoranthene was investigated by DC tast polarography (DCTP) and differential pulse polarography (DPP), both at a dropping mercury electrode, differential pulse voltammetry (DPV) and adsorptive stripping voltammetry (AdSV), both at a hanging mercury drop electrode. Optimum conditions have been found for its determination by the given methods in the concentration ranges of 1 × 10-6-1 × 10-4 mol l-1 (DCTP), 1 × 10-7-1 × 10-4 mol l-1 (DPP), 1 × 10-8-1 × 10-6 mol l-1 (DPV) and 1 × 10-9-1 × 10-7 mol l-1 (AdSV), respectively. Practical applicability of these techniques was demonstrated on the determination of 3-nitrofluoranthene in drinking and river water after its preliminary separation and preconcentration using liquid-liquid and solid phase extraction with the limits of determination 4 × 10-10 mol l-1 (drinking water) and 2 × 10-9 mol l-1 (river water).


1948 ◽  
Vol 26b (12) ◽  
pp. 767-772
Author(s):  
Paul A. Giguère ◽  
J. B. Jaillet

The determination of hydrogen peroxide at concentrations higher than those normally covered in polarography was studied with various electrodes. The diffusion current was found to increase linearly with the peroxide concentration up to 0.15% with the dropping mercury electrode and up to nearly 1% with a fixed platinum microelectrode. Under these conditions the limiting current was about 10 times greater than that usually observed. Although the solutions were supersaturated with oxygen, traces of strychnine sulphate were sufficient to suppress all maxima.


1965 ◽  
Vol 20 (4) ◽  
pp. 774-778 ◽  
Author(s):  
Domenic A. Maio ◽  
James R. Neville

A polarographic method was described in an earlier report which permits the accurate, rapid determination of oxygen content in small samples of blood. As with the Van Slyke technic, total oxygen capacity was formerly estimated by a separate determination of the oxygen content after complete saturation with oxygen of another portion of the blood sample. Further experience with the polarographic method has revealed the feasibility of estimating both content and capacity in a single blood sample. The capacity estimate is made possible by the polarographic observation of the quantity of potassium ferricyanide required to convert ferrohemoglobin to ferrihemoglobin. The measurement of oxygen content is performed, as previously described, by the polarographically determined increase in physically dissolved oxygen caused by the release of bound oxygen. By this means, one avoids sampling and random errors inherent in the use of two separate determinations. The method requires only a brief time for performance and ordinary technical proficiency. It is also simple in application. polarographic dropping mercury electrode; oxygen tension; digitonin; potassium ferricyanide; ferrohemoglobin; ferrihemoglobin Submitted on June 24, 1964


Author(s):  
Yuri V. Polenov ◽  
Gleb A. Shestakov ◽  
Elena V. Egorova

A stoichiometric mechanism for full thiourea dioxide decomposition in aqueous solution under pH of 4.0 is proposed based on dependences of concentrations of thiourea dioxide and its decomposition products on the time and literature data. The concentration of thiourea dioxide was measured via iodometry, while the intermediates were quantified using the polarography. Polarography was carried out in glass two-electrode electrochemical cell by means of PU-1 polarograph in differential mode. Dropping mercury electrode was used as working one and silver chloride as a reference one. Rate constants for individual stages are obtained via mathematical modeling, presented a system of differential equations. Absolute errors of rate constants, correlation coefficients, and F-factors were also calculated. Verification of supposed kinetic model was conducted using the comparison between experimental and calculated concentrations, F-test and the calculated values of correlation coefficients of the individual stages of the process. Supposed kinetic model of decomposition consists of a number of consequent stages including various compounds such as sulfur monoxide, thiosulfuric, sulfuric, dithionic, hydrosulfuric acids as intermediates was used for previously obtained data for pH of 8.85. To test the universality of supposed model, we simulated kinetics of thiourea dioxide decomposition reaction at pH of 8.85. Experimental kinetic data were taken from literature. The initial approximations of the individual stages constants were taken from previous calculations. Analysis of calculated data: concentration values, F-test, correlation coefficients allowed to conclude about the applicability of proposed mechanism for the process of thiourea dioxide decomposition in a weakly alkaline medium.


2011 ◽  
Vol 76 (12) ◽  
pp. 1991-2004 ◽  
Author(s):  
Vlastimil Vyskočil ◽  
Ivan Jiránek ◽  
Aleš Daňhel ◽  
Jiří Zima ◽  
Jiří Barek ◽  
...  

Electrochemical behavior of genotoxic nitro derivatives of quinoline, namely 5-nitroquinoline (5-NQ), 6-nitroquinoline (6-NQ) and 8-nitroquinoline (8-NQ), was investigated by DC tast polarography (DCTP) and differential pulse polarography (DPP), both at a classical dropping mercury electrode (DME), and by differential pulse voltammetry (DPV) and adsorptive stripping differential pulse voltammetry (AdSDPV), both at a miniaturized hanging mercury drop minielectrode (HMDmE), in buffered aqueous (for 5-NQ) or aqueous-methanolic (for 6-NQ and 8-NQ) solutions. Optimum conditions were found for the determination of 5-NQ, 6-NQ and 8-NQ by DCTP at DME (with limits of quantification, LQ ≈ 9 × 10–7, 3 × 10–7 and 2 × 10–6 mol l–1, respectively), by DPP at DME (LQ ≈ 1 × 10–8, 9 × 10–8 and 1 × 10–7 mol l–1, respectively), by DPV at HMDmE (LQ ≈ 2 × 10–8, 1 × 10–7 and 1 × 10–7 mol l–1, respectively), and by AdSDPV at HMDmE (LQ ≈ 1 × 10–8 mol l–1 for 8-NQ; an attempt at increasing the sensitivity using AdSDPV at HMDmE was not successful for 5-NQ and 6-NQ). Practical applicability of the developed methods was verified on the direct determination of the studied compounds in model samples of drinking and river water in submicromolar concentrations and on the determination in model samples of drinking and river water using preliminary separation and preconcentration by solid phase extraction (SPE) in nanomolar concentrations.


1978 ◽  
Vol 56 (5) ◽  
pp. 703-708 ◽  
Author(s):  
Jacques Devynck ◽  
Bernard Tremillon ◽  
Hugues Menard ◽  
Germain Comarmond

The electrochemical behaviour of Sb(III) and Sb(V) in water–HF mixtures (2.5 to 50% HF) and in anhydrous HF is described. A Teflon capillary dropping mercury electrode is proposed for polarographie investigations in these fluorinated media. It is shown, by classical or puise polarography, that Sb(III) can be reduced to Sb(0), as in acidic non-fluorinated media. The electrochemical reaction becomes reversible by addition of Cl−, Br− or I−. Sb(V) is not electroactive in the various HF-media, except when it is introduced as the SbCl5. In this case, the two polarographie waves of Sb(V) disappear with time because of SbF6− formation. Analytical applications to the determination of Sb(III) in water–HF and in anhydrous HF are discussed.


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