Negative Apparent Electrochemical Enthalpy of Activation: The Reduction of Bromate at the Dropping Mercury Electrode in Alkaline Solutions

1994 ◽  
Vol 141 (5) ◽  
pp. 1183-1190 ◽  
Author(s):  
E. Kirowa‐Eisner ◽  
M. Schwarz ◽  
M. Rosenblum ◽  
E. Gileadi
Keyword(s):  
Mercury Electrode ◽  
Alkaline Solutions ◽  
Enthalpy Of Activation ◽  
Dropping Mercury Electrode

The "Presodium" Hydrogen Evolution at the Dropping Mercury Electrode Catalysed by Simple Cysteine Peptides

2001 ◽  
Vol 66 (3) ◽  
pp. 397-410 ◽  
Author(s):  
Pavel Mader ◽  
Věra Veselá ◽  
Vlastimil Dorčák ◽  
Michael Heyrovský
Keyword(s):  
Catalytic Activity ◽  
Reduced Glutathione ◽  
Mercury Electrode ◽  
Alkaline Solutions ◽  
Common Mechanism ◽  
Solution Ph ◽  
Weakly Alkaline ◽  
Dropping Mercury Electrode ◽  
Hydrophilic Character ◽  
Blank Solution

"Presodium" catalytic currents at dropping mercury electrode of cysteine, cysteinylglycine, γ-glutamylcysteine and reduced glutathione were systematically studied in weakly alkaline solutions. They consist in shifts to positive potentials of current due to reduction of the blank solution, and, under some conditions, also in formation of "catalytic prewaves". The two cases have been qualitatively interpreted as based on a suggested common mechanism, differing by the occurrence of weak catalyst adsorption in the prewave case. The catalytic activity depends on the catalyst itself (concentration, structure, conformation at the electrode, partial protonation/ionisation, partial hydrophobic/hydrophilic character) as well as on the solution (pH, ionic strength, nature and concentration of components).

Reduction and tensammetric pulse-polarographic currents of polynucleotides

1987 ◽  
Vol 52 (11) ◽  
pp. 2810-2818 ◽  
Author(s):  
Emil Paleček ◽  
František Jelen ◽  
Vladimír Vetterl
Keyword(s):  
Diagnostic Criteria ◽  
Pulse Width ◽  
Mercury Electrode ◽  
Pulse Amplitude ◽  
Single Strand ◽  
Pulse Polarography ◽  
Dropping Mercury Electrode ◽  
Adenylic Acid ◽  
Drop Time

The behaviour of electrochemically reducible single-strand polynucleotides (poly(adenylic acid)) and poly(cytidylic acid)) was studied by the differential (derivative) pulse polarography (DPP) and by other methods. Measurements were performed with the help of the dropping mercury electrode under various conditions specified by the pulse width, pulse amplitude, drop time etc. For the faradaic and tensammetric DPP peaks the diagnostic criteria were proposed which make it possible to classify even very small DPP peaks of double helical polynucleotides.

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.

The reduction of cobalt (II) ion in thiocyanate media by pulse polarography

1983 ◽  
Vol 48 (2) ◽  
pp. 544-549 ◽  
Author(s):  
Jorge Alfredo Bolzan ◽  
Robert Tokoro
Keyword(s):  
Mercury Electrode ◽  
Thiocyanate Complex ◽  
Catalytic Wave ◽  
Pulse Polarography ◽  
Dropping Mercury Electrode ◽  
Thiocyanate Concentration

The electroreduction of cobalt(II) in aqueous thiocyanate solutions at the dropping mercury electrode depends on the thiocyanate concentration. At [SCN-] = 0.3 mol/l the intermediate cobalt(I)-thiocyanate complex does exist electrokinetically and may be responsible for the appearance of a peaked catalytic wave. The predecessor species of this intermediate may be CoSCN+ and Co(SCN)2 in similarity to the behaviour of cobalt(II) with cyanide and azide ions.

Oxidation of hydrogen peroxide at the dropping mercury electrode

1984 ◽  
Vol 49 (10) ◽  
pp. 2320-2331 ◽  
Author(s):  
Miroslav Březina ◽  
Martin Wedell
Keyword(s):  
Hydrogen Peroxide ◽  
Superoxide Anion ◽  
Ph Value ◽  
Mercury Electrode ◽  
Electrode Process ◽  
Electrochemical Processes ◽  
Dropping Mercury Electrode ◽  
Oxidation Of Hydrogen ◽  
Decreasing Ph ◽  
Rate Controlling Step

Reduction of oxygen and oxidation of hydrogen peroxide at the dropping mercury electrode are electrochemical processes strongly influenced both by the pH value and the anions in solution. With decreasing pH, both processes become irreversible, especially in the presence of anions with a negative φ2 potential of the diffusion part of the double layer. In the case of irreversible oxygen reduction, the concept that the rate-controlling step of the electrode process is the acceptance of the first electron with the formation of the superoxide anion, O2-, was substantiated. Oxidation of hydrogen peroxide becomes irreversible at a lower pH value than the reduction of oxygen. The slowest, i.e. rate-controlling step of the electrode process in borate buffers at pH 9-10 is the transfer of the second electron, i.e. oxidation of superoxide to oxygen.

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