The electrochemical oxidation of 2,5-dihydroxybenzoic acid on a mercury electrode in aqueous solutions

1986 ◽  
Vol 64 (1) ◽  
pp. 11-14 ◽  
Author(s):  
D. Sazou ◽  
N. Papadopoulos

The electrochemical behaviour of 2,5-dihydroxybenzoic acid (2,5-DHBA) has been studied in the pH range 5.5–12.7 at a hanging mercury drop electrode (HMDE). Voltammograms show the existence of one reversible wave of 2,5-DHBA governed by diffusion conditions. In the oxidation process a two-electron transfer takes place, as shown by the controlled potential electrolysis. From the calculation of the voltammetric parameters (peak width Ep − Ep/2, peak current function [Formula: see text]and from the other experimental data, a mechanism for the overall reaction in two different pH ranges, 5.5–9.5 and 9.5–12, is proposed.


1989 ◽  
Vol 54 (1) ◽  
pp. 42-52 ◽  
Author(s):  
Dimitra Sazou ◽  
Ioannis Poulios

Electrochemical investigation of 2,5-dihydroxyanisole (2,5-DHA) has been carried out in aqueous solutions in pH range 2-11 on hanging mercury drop electrode (HMDE). The oxidation process in pH range 2-6 is a quasi-reversible electrode reaction which involves the transfer of two electrons and two protons. By use of semi-integration a dependence of the heterogeneous rate constant on the potential has been appreciated. Thus, the variation of peak current with pH changes can be explained. In more basic solutions the electrooxidation is complicated by subsequent chemical reactions as indicated from the calculated voltammetric and chronoamperometric parameters.



2012 ◽  
Vol 9 (4) ◽  
pp. 1864-1874
Author(s):  
V. Nagaraju ◽  
R. Sreenivasulu ◽  
P. Venkata Ramana

The electrochemical behaviour of N′-(p-toluenesulphonyl)-3-methyl-4-(4′-substituted arylhydrazono) pyrazolin-5-ones has been investigated at dme and gc electrodes in buffer solutions of pH 2.0, 4.0, 6.0, 8.0 and 10.0 using dc polarography and cyclic voltammetry and coulometry. The compounds exhibit one well defined wave in the entire pH range of study. The process is irreversible and diffusion controlled. Controlled potential electrolysis indicates the involvement of four electrons in the reduction process. The effect of solvent, cations and anions, temperature and substitutents on the mechanism of reduction has been studied. Based on the results obtained the mechanism of reduction has been suggested.



2002 ◽  
Vol 85 (3) ◽  
pp. 731-735 ◽  
Author(s):  
Neelam Y Sreedhar ◽  
Thommandru R Babu ◽  
Kethamreddy Samatha ◽  
Devarapalli Sujatha ◽  
Thenepalli Thriveni

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.



1965 ◽  
Vol 18 (5) ◽  
pp. 619 ◽  
Author(s):  
TM Florence

Solutions of 4-aminoazobenzene-4'-sulphonic acid were reduced by controlled potential electrolysis at a mercury cathode, and the disproportionation rate of the hydrazo derivative determined by spectrophotometry and polarography. The kinetics of the reaction were found to be first-order with respect to both hydrazo and hydrogen ion concentrations, although the overall reaction involved two molecules of the hydrazo compound. In the rate law, -d[hydrazo]/dt = k[H+][hydrazo], k was calculated to be (5.0�0.3) x 106 l. mole-1 sec-1 from spectrophotometric measurements, and (4.5�0.5) x 106 l. mole-1 sec-1 by polarography (25�). A reaction mechanism based on a rate determining step involving a quinonediimine intermediate has been proposed. Another value of the disproportionation rate constant was obtained from the effect of drop time on the limiting currents of 4-aminoazobenzene-4'-sulphonic acid at the dropping mercury electrode. A value of k of (22�5) x 106 l. mole-1 sec-1 was determined by this method. Reasons for the discrepancy between this result, and those found by direct measurement, are discussed.



1996 ◽  
Vol 74 (1) ◽  
pp. 95-102 ◽  
Author(s):  
A. Safavi ◽  
M. B. Gholivand

Electrochemical techniques of polarography, cyclic voltammetry, and controlled potential electrolysis at mercury electrodes have permitted a detailed investigation of the reduction reactions associated with mercury 2-aminocyclopentene dithiocarboxylate complexes, Hg(ACD)2, in dimethyl sulphoxide (DMSO). As a complementary study, the electrochemistry of the ligands themselves was investigated in DMSO solutions and at mercury electrodes. The lability of mercury(II) complexes and their rapid interaction with elemental mercury strongly influence the nature of the redox processes observed at mercury electrodes. Reduction of Hg(ACD)2 at a mercury electrode occurs in an overall two-electron step as:[Formula: see text]although mercury(I) is implicated as an intermediate. Key words: reduction, electrochemical techniques, mercury complexes.



2010 ◽  
Vol 75 (11) ◽  
pp. 1201-1216
Author(s):  
Funda Öztürk ◽  
Zehra Durmuş ◽  
Öznur Ölmez Uçkan ◽  
Emine Kiliç ◽  
Esma Kiliç

2-[(8-Hydroxyquinoline-5-yl)azo]benzo[c]cinnoline (HQAB) was prepared and characterized by elemental analysis, MS, FTIR and 1H NMR techniques. The electrochemical reduction of HQAB has been investigated by cyclic voltammetry, chronoamperometry and controlled potential electrolysis at mercury pool electrode in the pH range 3.5–9.4. The number of electrons transferred in the electrode reaction, diffusion coefficients and standart rate constants were calculated. In acidic medium, cyclic voltammograms display four cathodic peaks, with the total exchange of 6 e– and 6 H+. By contrast, the reverse scan displays two anodic peaks. Constant potential electrolysis at –1.0 V and TLC analysis of the product reveals that the reduction of azo group (in the bridge) in HQAB does not stop at the hydrazo stage but goes further through the cleavage of –NH–NH– linkage to give amino compounds as the final products. The voltammograms recorded in basic medium exhibit two cathodic peaks corresponding to 4 e–, 4 H+ and two reverse anodic peaks, and thus the reduction stopped at hydrazo stage. A tentative mechanism for the reduction has been suggested.



1969 ◽  
Vol 47 (12) ◽  
pp. 2123-2135 ◽  
Author(s):  
Leslie E. Johnston ◽  
John A. Page

The polarography and coulometry of Rh(III) has been studied in an aqueous pyridine–pyridinium chloride–sodium chloride electrolyte at pH 5.30 and ionic strength 0.30 M at 25.0 °C. Two distinct types of polarographic behavior were noted as the total Py concentration was varied between 0.05 and 0.45 M, a "normal" wave with E1/2 of −0.43 V vs. a standard calomel electrode, and a second catalytic wave which under some conditions masked the normal wave.For both types of behavior, controlled potential electrolysis gave a well-defined two electron reduction but there was a definite H+ consumption in the electrolyses. It is postulated that hydride species are involved in the reduction according to the scheme[Formula: see text]surface reaction at dropping mercury electrode[Formula: see text]slow, bulk solution in controlled potential electrolysis



2010 ◽  
Vol 7 (1) ◽  
pp. 166-170 ◽  
Author(s):  
N. Y. Sreedhar ◽  
M. Sankara Nayak ◽  
K. Srinivasa Prasad ◽  
P. R. Prasad ◽  
C. Nageswar Reddy

Electrochemical behaviour of anticancer drug zileuton was investigated by direct current polarography (DCP) and differential pulse polarography using a dropping mercury electrode (DME) as working electrode and Ag/AgCl reference electrode in universal buffer of pH range from 2.0 to 12.0. The drug was extracted from the dosage forms in dimethyl formamide (DMF). Kinetic parameters such as diffusion co-efficient (D) and heterogeneous forward rate constants (k0f,h) are evaluated and reported. The differential pulse polarographic method has been developed for the determination of this drug in pharmaceutical formulations.



1995 ◽  
Vol 73 (2) ◽  
pp. 176-180 ◽  
Author(s):  
Rajeev Jain ◽  
M. Damodharan

Electrochemical behaviour of the medicinally important 4-(4′-sulphonamoyl)hydrazono-1-phenyl-3-methyl-2-pyrazolin-5-ones has been studied at d.m.e. and glassy carbon electrodes. At d.m.e., all six compounds exhibited a single, well-defined, four-electron wave in the pH range 2.5–12.0. Polarographic four-electron wave was found to be diffusion-controlled and irreversible. Similarly, cyclic voltammetry of these compounds at glassy carbon electrode exhibited a single peak. Peak potential shows shifts towards negative potential with pH, with linear segments up to pH 8.2 and are practically pH independent at higher pH values. An anodic peak at far-off positive potential was observed in the reverse scan, indicating the irreversible nature of the electrode process. Controlled potential electrolysis and coulometric studies gave the value of n as 4.0 ± 0.1 in the pH range 2.5 to 10.0. Out of the two major end products formed, one was identified as sulphanilamide and the other as 1-phenyl-3-methyl-4-amino-2-pyrazolin-5-one on the basis of IR and NMR studies. On the basis of DCP, LSV, CV, CPE, coulometry and spectral analysis, a mechanism has been postulated for the reduction of these compounds at d.m.e. and glassy carbon electrodes. Keywords: polarography, cyclic voltammetry, antibacterials, pyrazolin-5-ones.



Sign in / Sign up

Export Citation Format

Share Document