Electrochemical generation of hydridopentamminerhodium(III) and its reaction with molecular oxygen

1969 ◽  
Vol 47 (22) ◽  
pp. 4241-4246 ◽  
Author(s):  
Leslie E. Johnston ◽  
John A. Page

The electrochemistry of Rh(NH3)5OH2+ has been studied in a buffered ammoniacal solution. The polarographic reduction wave at the dropping mercury electrode had E1/20 equal to −1.10 V (vs. saturated calomel electrode) in a 0.10 M NH3 – 0.10 M NH4ClO4 electrolyte, and gross Hg cathode electrolysis at −1.19 V produced a stable Rh(NH3)5H2+ hydride species. Both reductions were found to take place through a Rh(I) intermediate.The reaction of the Rh(NH3)5H2+ with molecular O2 in the ammoniacal electrolyte was also studied. The product was demonstrated to be a stable Rh(NH3)4(OH)(O2H)+ hydroperoxo species.

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.


1989 ◽  
Vol 54 (8) ◽  
pp. 2105-2119 ◽  
Author(s):  
Jiří Barek ◽  
Ivana Švagrová-Hauserová ◽  
Jiří Zima

The polarographic reduction of the title azodye has been studied, a mechanism was proposed and optimal conditions were found for the determination of this substance by TAST polarography in the range 5.10-5-2.10-6 mol l-1 and differential pulse polarography at a dropping mercury electrode in the range 5.10-5-2.10-8 mol l-1. The sensitivity was further increased by adsorptive accumulation of the determined substance on the surface of a hanging mercury drop electrode with linear scan voltammetry (determination limit 5.10-10 mol l-1). The selectivity was increased by prior separation of the determined azodye using thin layer chromatography and by transferring the substance adsorbed on the surface of the hanging mercury drop to a new base electrolyte solution.


2007 ◽  
Vol 32 (3) ◽  
pp. 489-495
Author(s):  
Hussein M. Fahmy ◽  
Hamed A. Daboun ◽  
Mona M Hussein ◽  
Mohamed H. Elnagdi

1987 ◽  
Vol 52 (4) ◽  
pp. 867-877
Author(s):  
Jiří Barek ◽  
Barbara Tietzová ◽  
Jiří Zima

The polarographic reduction of the bisazodye congo red has been studied, a mechanism was proposed for this process and optimal conditions were found for determination of this substance by TAST polarography and differential pulse polarography at a dropping mercury electrode and using fast scan differential pulse voltammetry and voltammetry with linearly increasing voltage at a hanging mercury drop electrode. The detection limit for the latter two techniques is about 10-8 mol l-1; a further decrease in the value can be attained by prior accumulation of the determined substance by adsorption on the surface of the working electrode.


1990 ◽  
Vol 55 (12) ◽  
pp. 2904-2913 ◽  
Author(s):  
Jiří Barek ◽  
Jana Kubíčková ◽  
Viktor Mejstřík ◽  
Oldřich Petira ◽  
Jiří Zima

The polarographic reduction of the 3'-halogen derivatives of N,N-dimethyl-4-aminoazobenzene was studied in mixed water-methanol medium and optimum conditions were found for the determination of these genotoxic substances by tast polarography in the concentration range 1 . 10-4 to 2 . 10-6 mol l-1, differential pulse polarography at a dropping mercury electrode in the range 1 . 10-4 to 2 . 10-7 mol l-1 and fast scan differential pulse voltammetry at a hanging mercury drop electrode in the range 1 . 10-6 to 2 . 10-8 mol l-1. The increase in the sensitivity resulting from adsorptive accumulation of the studied substances on the surface of a hanging mercury drop can be utilized in the determination using the latter method in the concentration range 1 . 10-8 to 2 . 10-9 mol l-1.


1993 ◽  
Vol 58 (2) ◽  
pp. 295-309 ◽  
Author(s):  
Jiří Barek ◽  
Dana Dřevínková ◽  
Viktor Mejstřík ◽  
Jiří Zima

The polarographic reduction of N,N-dimethyl-4-amino-3'-nitroazobenzene was studied by tast polarography and differential pulse polarography, constant potential coulometry and cyclic voltammetry and mechanism was proposed for the reduction. Optimal conditions were found for the determination of the test substance using tast polarography in concentration range 1 . 10-4 - 2 . 10-6 mol l-1, differential pulse polarography at classical dropping mercury electrode and fast scan differential pulse voltammetry at a hanging mercury drop electrode in range 1 . 10-4 - 2 . 10-7 mol l-1 and linear scan voltammetry at a hanging mercury drop electrode in range 1 . 10-5 - 2 . 10-8 mol l-1. A further increase in the sensitivity was achieved through adsorptive accumulation of the test substance on the surface of the working electrode, permitting the determination to be carried out in the concentration range 1 . 10-7 - 2 . 10-9 mol l-1.


1987 ◽  
Vol 52 (9) ◽  
pp. 2149-2159 ◽  
Author(s):  
Jiří Barek ◽  
Tibor J. Pastor ◽  
Simona Votavová ◽  
Jiří Zima

The polarographic reduction of N,N-dimethyl-4-amino-3'-methylazobenzene has been studied, a mechanism has been proposed and conditions have been found for the determination of this depolarizer using TAST polarography and differential pulse polarography at a classical dropping mercury electrode and using fast scan differential pulse voltammetry and linear scan voltammetry at a hanging mercury drop electrode. The detection limit at this electrode is about 10-8 mol l-1; a further decrease can be attained using adsorption accumulation of the determined azo-substance on the surface of the working electrode. In conclusion, the practical usefulness of these methods combined with extraction or thin-layer chromatography was verified.


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